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Setting a g-mail account is an easy option. You will begin a task once you have created a Google account, and you can use a quick sign-up process through which you can use your Gmail account name. In this blog, we will learn how to set a Google account for Gmail and how you can edit the contacts, mail settings, and sending mail. Setting a Gmail account To create a g-mail address, you first need to set a Google account. From there, you will be redirected to the Gmail account sign up page. From there, you must learn some basic information like birth, name, gender, and date. Also, from there, you need to choose your name for the new Gmail address. Once you have created an account, then you can adjust your mail settings. Creating an account  First, you must go to the google website and then create an account that you prefer.  From the sign-up form. Follow all the directions that are important for every required information.  Next, you must enter your cell phone number to verify your account. Moreover, Google can use the two-step verification process for your security.  Furthermore, you can get the verification code from google. After then, you can also use the entering code to know about the account verification.  Moreover, some other brands can also see personal information like the birthday and your name.  After then you can use the google terms of services and the privacy policy, then you must be agreeing about it.  Then your account will be created Moreover, it is important to get a strong password, and in order words, it is difficult for someone else to guess. Your password must contain the upper case and the lower-case letters with the symbols as well. You should focus on creating a strong and easy-remembered password when meeting common errors when logging in. Sign in to your account When you have created your account, you will automatically be signed in to your account. Moreover, you also need to sign in and sign out when you are done. Signing out is one of the important parts to share on the computer because it will preview your emails. To sign in Go to the Gmail account Type the name you want to mention there and the password as well, then you can click on next. Sign out From the top right of the page, you can enter the option of locating the circle to sign out. You can click on the sign out option on the page. Mail settings Sometimes you wish to make changes in the mail's behavior and appearance. You can create the vacation reply or the signature, but you can change the theme and edit your labels. These settings can be made from the mail settings. Adding contacts Like every other major setting, you can easily have complete control over the address book provided by google. However, you can also memorize the contact information like phone, physical addresses, and others. Adding a contact From the drop-down of the contacts menu, you can click on the contacts you wish to have. From the add new contact, you can get the from the lower right corner, and from there, you can enter the save option. To edit contact From google, click on the drop-down menu, then you can select the option of the contact. After then you can edit the change you want to make I the connection. However, by default, you can edit all the changes into your contacts as the person needed. Important contacts and mail You must have the contact list from all the email addresses, and there would be the re-enter of the information that you can already be working on manually. Gmail allows all the essential information you wish to have manually. Gmail can also import the information from the email messages from the account. Several email providers like AOL, Hotmail, and Yahoo. Adding another account From the top right corner, click on the settings on the page. Then go to the add a mail account. From there you can follow every important information to your mail. However, you might feel challenge you do not have a Gmail account. If it is the issue, then you must create one Gmail account. After then, you must Navigate the Gmail settings and then set the preferences in the Gmail settings. After then you can set the new contact you wish to have. Sending an email When you have written the email, then from the compose window, you will get the email recipient's option of the email address, and there you enter from the subject and the body of the email message itself. From there, you can get the various formatting of the texts and even more attachments. Then enter the send option and send the task. Conclusion All in all, sending an email and making an account on Gmail is the easiest option. Therefore, there are millions of ids in Gmail. Hence, you only need to have some seconds to learn about how to make your own Gmail id.  

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Drilling And Blasting Of Rocks Lengkap.pdf

DRILLING ÄND BLASTING OF ROCKS CARLOS LOPEZ JIMENO Project Director for EPM, SA

EMLIO LOPEZ JIMENO FRANCISCO JAVIER AYALA CARCEDO Project Director for ITGE Translated by

YVONNE VISSER DE RAMIRO

A.A. BALKEMA / ROTTERDAM / BROOKFIELD / 1995

This work has been totally financed by the Geornining Technological Institute of Spain under contract with the E.F?M.,S.A. Cornpany (Estudios y Proyectos Mineros, S.A.).

Authorization to photocopy iterns for internal or personal use, or the internal or personal use of specific clients, is granted by A.A.Balkerna, Rotterdarn, provided that the base fee of US$1.50 per copy, plus US$O.lO per Page is paid directly to Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, USA. For those organizations that have been granted a photocopy license by CCC, a separate systern of payrnent has been arranged. The fee code for users of the Transactional Reporting Service is: 90 5410 199 7/95 US$1.50 + US$O. 10. Original text: Manual de perforacion y voladura de rocas O 1987 Instituto Geologico y Minero de Espaila Revised and updated edition in English: O 1995 A.A. Balkerna, PO. Box 1675,3000 BR Rotterdarn, Netherlands (Fax: +3 1.10.4135947)

Distributed in USA & Canada by: A.A. Balkema Publishers, Old Post Road, Brookfield, VT 05036, USA (Fax: 802.276.3837) Printed in the Netherlands

Contents

FOREWORD PREFACE ACKNOWLEDGEMENTS 1 ROCK DRILLING METHODS 1.1 Introduction 1.2 Types of drilling operations used in rock breakage 1.3 Fields of application for the different drilling methods 1.4 Classification of the rocks and their principal physical properties References 2 ROTARY PERCUSSIVE DRILLING 2.1 Introduction 2.2 Fundamentals of rotary percussive drilling 2.3 Top hammer drilling 2.4 Drilling with down the hole harnmer 2.5 Advance systems 2.6 Mounting systems 2.7 Dust collectors 2.8 Inclination instruments 2.9 Penetration rate 2.10 Average penetration rate 2.1 1 Calculation of drilling 'costs References 3 ROTARY PERCUSSIVE DRILLING ACCESSORIES 3.1 Introduction 3.2 Types of threads 3.3 Shank adaptors 3.4 Dnll steel 3.5 Couplings 3.6 Dnll bits 3.7 Calculation of the necessary drilling accessories 3.8 Care and maintenance of the bits 3.9 Care and maintenance of drill steel 3.10 Guide for identifying accessory failure and its causes References

4 ROTARY DRILLING WITH ROLLING TRICONE BITS 4.1 Introduction 4.2 Mounting and propulsion systems 4.3 Power sources 4.4 Rotation systems 4.5 Pulldown/hoisting systems 4.6 Mast and pipe changer 4.7 Control cabin 4.8 System for flushing drill cuttings 4.9 Dnll string 4.10 Auxiliary elements 4.1 1 Operative practice. Drilling parameters 4.12 Penetration rate 4.13 Calculation of drilling costs References 5 ROLLING CONE ROCK BITS 5.1 Rolling cone rock bits 5.2 Major components and design features 5.3 The metallurgy of rolling cone rock bits 5.4 Types of rolling cone bits 5.5 Bit type selection 5.6 Effects of the operating parameters on the rolling cone bits 5.7 Nozzle selection 5.8 Evaluation of du11 rolling cones 5.9 Example of roller iricone bit selection 5.10 IDAC Codes References

6 ROTARY DRILLING WITH CUTTING ACTION 6.1 Introduction 6.2 Fundamentals of drilling with cutting action 6.3 Flushing of drill cuttings 6.4 Cutting tools References 7 SPECIAL DRILLING METHODS AND MOLINTING SYSTEMS 7.1 Introduction 7.2 Drilling through overburden 7.3 Shaft sinking 7.4 Raise driving

Contents

7.5 Jet piercing 7.6 Water-jet drilling 7.7 Drilling ornamental rock References

12.2 Explosive cost 12.3 Charge diameter 12.4 Rock characteristics 12.5 Volume of rock to be blasted 12.6 Atmospheric conditions 12.7 Presence of water 12.8 Environmental problems 12.9 Fumes 12.10 Safety conditions 12.11 Explosive atmospheres 12.12 Supply problems References

8 COMPRESSORS 8.1 Introduction 8.2 Types of compressors 8.3 Drive 8.4 Auxiliary elements 8.5 Calculating pressure drops References 9 THERMOCHEMISTRY OF EXPLOSIVES AND THE DETONATION PROCESS 9.1 Introduction 9.2 Deflagration and detonation 9.3 Detonation process of an explosive 9.4 Thermochemistry of the explosives 9.5 Heat of explosion 9.6 Oxygen balance 9.7 Volume of explosion 9.8 Minimum energy available 9.9 Temperature of the explosion 9.10 Pressure of the explosion References

92 92 92 93 94 94 95 95 96 96 96 97

10 PROPERTIES OF EXPLOSIVES 10.1 Introduction 10.2 Strength and energy 10.3 Detonation velocity 10.4 Density 10.5 Detonation pressure 10.6 Stability 10.7 Water resistance 10.8 Sensitivity 10.9 Detonation transmission 10.10 Desensitization 10.11 Resistance to low temperatures 10.12 Fumes References

98 98 98 101 102 102 102 102 102 103 104 104 104 105

11 INDUSTRIAL EXPLOSIVES 11.1 Introduction 11.2 Dry blasting agents 11.3 Slurries 11.4 Emulsions 11.5 Heavy ANFO 11.6 Gelatin dynamites 11.7 Granular dynamite 11.8 Permissible explosives 11.9 Blackpowders 11.10 Two-component explosives 11.11 Explosives cornmercialized in Spain References

106 106 106 110 111 113 115 115 116 116 117 117 117

12 EXPLOSIVE SELECTION CRITERIA 12.1 Introduction

119 119

13 BLASTING ACCESSORIES 13.1 Introduction 13.2 Nonelectric initiation systems 13.3 Electric initiation systems 13.4 Sources of energy 13.5 Other accessories References

123 123 123 127 130 132 135

14 INITIATION AND PRIMING SYSTEMS 14.1 Introduction 14.2 Priming and boostering bulk ANFO-type blasting agents 14.3 Priming cartridge ANFO type blasting agents 14.4 Priming pumped or poured slurry and emulsion blasting agents 14.5 Priming cartridged watergel and emulsion blasting agents 14.6 Location of primers 14.7 Priming conventional cartridged explosives References

136 136

15 MECHANIZED SYSTEMS FOR CHARGING AND DEWATERING BLASTHOLES 15.1 Introduction 15.2 Mechanized blasthole charging Systems 15.3 Blasthole dewatenng Systems References 16 MECHANISMS OF ROCK BREAKAGE 16.1 Introduction 16.2 Rock breakage mechanisms 16.3 Transmission of the strain wave through the rock mass 16.4 Energetic yield of the blastings References 17 ROCK AND ROCK MASS PROPERTIES AND THEIR INFLLTENCE ON THE RESULTS OF BLASTING 17.1 Introduction 17.2 Rock properties 17.3 Properties of the rock mass References

136 138 139 140 140 143 143 144 144 144 152 153 154 154 154 156 157 159

V11

Contents

18 CHARACTERIZATION OF THE ROCK MASSES FOR BLAST DESIGNING 18.1 Introduction 18.2 Diamond drilling with core recovery and geomechanic testing 18.3. Characteristics of the joint systems 18.4 Seismic survey 18.5 Geophysical techniques to obtain rock mass data 18.6 Logging of production blastholes 18.7 Characterization of the rock mass during blasthole drilling 18.8 The attempt to correlate drilling indexes with the blasting design parameters 18.9 System of drilling data management in actual time References 19 CONTROLLABLE PARAMETERS OF BLASTING 19.1 Introduction 19.2 Blasthole diameter 19.3 Height of bench 19.4 Blasthole inclination 19.5 Sternrning length 19.6 Subdrilling 19.7 Burden and spacing 19.8 Blasthole patterns 19.9 Geometry of the free face 19.10 Sizeandshapeof the blast 19.11 Available expansion volume 19.12 Charge configuration 19.13 Decoupling of the charges 19.14 Explosives 19.15 Distribution of explosives in the blastholes 19.16 Powder factor 19.17 Initiation and priming 19.18 Delay timing and initiation sequences 19.19 Influence of loadiniequipment on the design of the blasts 19.20 Specific dtilling 19.21 Blasthole deviation References

167 167 167 167 170 170 170 171 174 177 178 179 179 179 181 181 182 182 183 183 184 185 186 186 186 187 187 188 188 188 189 189 190 190

20 BENCH BLASTING 20.1 Introduction 20.2 Small diameter bench blasting 20.3 Large diameter blasting 20.4 Bench blasting with horizontal blastholes 20.5 Rip-rap production blasting 20.6 Cast blasting Appendix 1: Formulas to calculate bench blasting patterns References

199 203

21 BLASTING IN OTHER SURFACE OPERATIONS 2 1.1 Introduction 2 1.2 Excavations for highways and railways

205 205 205

191 191 191 193 195 195 196

21.3 Trench blasting 2 1.4 Ramp blasting (sinking cut) 2 1.5 Blasting for ground leveling 21.6 Blastings for foundations 21.7 Mini-hole blasting 2 1.8 Preblastings References

208 210 212 213 2 14 215 216

22 BLASTING FOR TUNNELS AND DRIFTS 22.1 Introduction 22.2 Advance systems 22.3 Blasting Patterns for tunnels 22.4 Types of cuts and calculation of the blasts 22.5 Equipment for marking out dtilling patterns References

217 217 217 218 219

23 SHAFT SINKING AND RAISE DRIVING 23.1 Introduction 23.2 Shaft sinking 23.3 Raise driving References

23 1 23 1 23 1 232 237

230 230

24 UNDERGROUND PRODUCTION BLASTiNG IN MINING AND CIVIL ENGINEERING 239 24.1 Introduction 239 24.2 Crater retreat method 239 24.3 Longhole method 243 24.4 Sublevel stoping with blastholes in fan pattern 245 24.5 Room and pillar mining 248 24.6 Cut and fill mining 248 24.7 Underground chambers in civil engineering projects 249 References 25 1 25 CONTOUR BLASTiNG 25.1 Introduction 25.2 Mechanisms responsable for overbreak 25.3 The theory of contour blasting 25.4 Types of contour blasts 25.5 The parameters that intervene in a contour blasting 25.6 Tendencies in the field of contour blasting 25.7 Evaluation of the results 25.8 Exarnple 25.9 Extraction of ornamental rock with contour blasting References 26 UNDERWATER BLASTiNG 26.1 Introduction 26.2 Methods of execution 26.3 Calculations for charges and drilling patterns 26.4 Charging the blastholes and priming systems 26.5 Types of explosives 26.6 Environmental effects associated with underwater blastings

252 252 252 253 254 256 264 267 268 268 270 272 272 272 247 275 276 276

V11

Contents

18 CHARACTERIZATIONOF THE ROCK MASSES FOR BLAST DESIGNING 18.1 Introduction 18.2 Diamond drilling with core recovery and geomechanic testing 18.3- Characteristics of the joint systems 18.4 Seismic survey 18.5 Geophysical techniques to obtain rock mass data 18.6 Logging of production blastholes 18.7 Characterization of the rock mass during blasthole drilling 18.8 The attempt to correlate drilling indexes with the blasting design parameters 18.9 System of drilling data management in actual time References 19 CONTROLLABLE PARAMETERS OF BLASTING 19.1 Introduction 19.2 Blasthole diameter 19.3 Height of bench 19.4 Blasthole inclination 19.5 Sternming length 19.6 Subdrilling 19.7 Burden and spacing 19.8 Blasthole patterns 19.9 Geometry of the free face 19.10 Size and shape of the blast 19.11 Available expansion volume 19.12 Charge configuration 19.13 Decoupling of the charges 19.14 Explosives 19.15 Distribution of explosives in the blastholes 19.16 Powder factor 19.17 Initiation and prirning 19.18 Delay timing and initiation sequences 19.19 Influence of loadingequipment on the design of the blasts 19.20 Specific drilling 19.21 Blasthole deviation References

167 167 167 167 170 170 170 171 174 177 178 179 179 179 181 181 182 182 183 183 184 185 186 186 186 187 187 188 188 188 189 189 190 190

20 BENCH BLASTING 20.1 Introduction 20.2 Small diameter bench blasting 20.3 Large diameter blasting 20.4 Bench blasting with horizontal blastholes 20.5 Rip-rap production blasting 20.6 Cast blasting Appendix 1: Formulas to calculate bench blasting patterns References

199 203

21 BLASTING IN OTHER SURFACE OPERATIONS 21.1 Introduction 21.2 Excavations for highways and railways

205 205 205

191 191 191 193 195 195 196

21.3 Trench blasting 21.4 Ramp blasting (sinking cut) 21.5 Blasting for ground leveling 21.6 Blastings for foundations 21.7 Mini-hole blasting 2 1.8 Preblastings References

208 210 212 213 214 215 216

22 BLASTING FOR TUNNELS AND DRIFTS 22.1 Introduction 22.2 Advance systems 22.3 Blasting Patterns for tunnels 22.4 Types of cuts and calculation of the blasts 22.5 Equipment for marking out drilling patterns References

217 217 217 218 219 230 230

23 SHAFT SINKING AND M I S E DRIVING 23.1 Introduction 23.2 Shaft sinking 23.3 Raise driving References

23 1 23 1 23 1 232 237

24 UNDERGROUND PRODUCTION BLASTING 239 IN MINING AND CIVIL ENGINEERING 24.1 Introduction 239 24.2 Crater retreat method 239 24.3 Longhole method 243 24.4 Sublevel stoping with blastholes in fan pattern 245 24.5 Room and pillar mining 248 24.6 Cut and fill mining 248 24.7 Underground chambers in civil engineering projects 249 References 25 1 25 CONTOUR BLASTING 25.1 Introduction 25.2 Mechanisms responsable for overbreak 25.3 The theory of contour blasting 25.4 Types of contour blasts 25.5 The parameters that intervene in a contour blasting 25.6 Tendencies in the field of contour blasting 25.7 Evaluation of the results 25.8 Example 25.9 Extraction of ornamental rock with contour blasting References 26 UNDERWATER BLASTING 26.1 Introduction 26.2 Methods of execution 26.3 Calculations for charges and drilling patterns 26.4 Charging the blastholes and priming systems 26.5 Types of explosives 26.6 Environmental effects associated with underwater blastings

252 252 252 253 254 256 264 267 268 268 270 272 272 272 247 275 276 276

V111 26.7 Shaped or concussion charges References 27 INITIATION SEQUENCE AND DELAY TIMING 27.1 Introduction 27.2 Single-row delayed blast 27.3 Multi-row sequenced bench blastings 27.4 Bench blasting sequences for underground stopes 27.5 Delay timings 27.6 Underground blasts in tunnels and drifts References 28 EVALUATION OF BLAST RESULTS 28.1 Introduction 28.2 Fragmentation and swelling of the muckpile 28.3 Geometry of the muckpile, its height and displacement 28.4 Condition of the remaining mass 28.5 Analysis of the bench floor 28.6 Boulders in the muckpile 28.7 Vibrations and airblast 28.8 Profiles of underground excavations 28.9 Conclusions References 29 SECONDARY FRAGMENTATION AND SPECIAL BLASTINGS 29.1 Introduction 29.2 Pop shooting 29.3 Secondary breakage by mechanical means and special methods 29.4 Special blastings References 30 PLANNING THE WORK OF DRILLING \ AND BLASTING 30.1 Introduction 30.2 Factors that have influence on the planning of drillling and blasting 30.3 Planning the Stages of excavation References 31 STRUCTURE AND BUILDING DEMOLITION 3 1.1 Introduction 3 1.2 Drilling diameters and types of explosive 3 1.3 Demolition of structural elements 3 1.4 Demolition of structures 31.5 Demolition of buildings 3 1.6 Demolition of steel structures References

Contents 32 OPTIMIZING COSTS OF FRAGMENTATION WITH DRILLING AND BLASTING 323 32.1 Introduction 323 32.2 Econornical aspects of drilling and blasting 323 32.3 Model for determining cost optimization 325 32.4 Predicting the fragmentation 326 32.5 Probabilistic analysis optimization model 331 References 33 1 33 LAND VIBRATIONS, AIR BLAST AND THEIR CONTROL 33.1 Introduction 33.2 Parameters which affect vibration characteristics 33.3 Characteristics of ground vibrations 33.4 Air blast charactenstics 33.5 Instrumentation for recording and analyzing vibrations and air blast 33.6 Calculators of propogation laws for land and air vibrations 33.7 Studies of vibration and air blast 33.8 Damage prevention critena for buildings 33.9 Effects of vibrations and air blast on people 33.10 Effects of vibrations on rock masses 33.11 Effect of vibrations on freshly poured concrete 33.12 Recommendations for reducing ground vibration and air blast levels References 34 FLYROCKS AND THEIR CONTROL 34.1 Introduction 34.2 Models to calculate the throw of flyrock 34.3 Coverings 34.4 Recommendations for carrying out bench blastings References

333 333 333 337 339 340 342 346 350 357 358 360 36 1 364 366 366 366 368 370 370

35 SAFETY MEASURES FOR DRILLING AND BLASTING OPERATIONS 35.1 Introduction 35.2 Blasthole drilling 35.3 Blastings References

37 1 37 1 37 1 375 38 1

CONVERSION FACTORS

382

GENERAL INFORMATION, WEIGHT OF MATERIALS

383

GLOSSARY

385

SUBJECT INDEX

389

Foreword

During the past two decades, there have been numerous technical contributions which have brought a better understanding of rock fragmentation with explosives, an improvement in drilling equipment and a noticeable evolution in the development of new explosives and blasting accessones. The Geomining Technological Institute of Spain (ITGE), aware of this Progress and of the importance which the breakage process has acquired in mining and civil engineering projects, has considered the publication of a 'Rock Drilling and Blasting Handbook' of great interest. This handbook was conceived with integration in mind, as the Systems and machines of drilling, the types and characteristics of explosives and the methods for calculating the blasts are treated together, without ever forgetting that these breakage operations form part of a

macrosystem and that the results obtained by them influence the production and economy of the whole exploitationor construction process. At the Same time, the objectives and contents of this handbook contribute to improved safety in mining. There are very few similar works in other languages, and certainly none other in Spanish. We sincerely hope that this handbook, which brings together practical and theoretical aspects, will be of use to all engineers who work with drilling and blasting as a rock breakage method. Camilo Caride de Liiian Director of the Geomining Technological Institute of Spain

Preface

'\

Rock breakage with explosives has existed since the XVII century when black powder came into use in mining, rapidly becoming one of the most popular methods. The important historical events which have marked an era were the invention of dynamite by Alfred Nobel in 1867, the use of ANFO starting in 1955, the development of slumes from the late fifties on and, lastly, the preparation of blasting agents such as emulsions, heavy ANFO, etc., which are still in evolution. At the Same time, blasthole drilling progressed with such decisive events as the the use of compressed air as the source of energy in rotary percussive rigs in 1861, the use of large rotary drills and of down-the-hole hammers in the fifties and the development of hydraulic hammers in the late seventies. However, rock blasting was always considered, until recently, as an art bom from the skill and experience of the blasters. Now it has become a technique based on scientific principles derived from knowledge of the action of explosives, the mechanisms of breakage and the geomechanic properties of the rock masses. The purpose of this handbook is to give basic knowledge of the drilling Systems, the types of available explosives and accessaries and the Parameters that intervene in blast designing, whether controllable or not. The handbook is primarily meant for students of the Technical Schools, to be useq as a textbook, and for all professionals who are involved with explosives in mining operations and civil engineenng projects. Carlos and Emilio Lopez Jimeno

This handbook was written by the following engineers: Carlos Lopez Jimeno, Doctor of Mining Engineering, Project Director for EPM., S.A. Emilio Lopez Jimeno, Doctor of Mining Engineering. Francisco Javier Ayala Carcedo, Doctor of Mining Engineering, Project Director for ITGE. Translated by: Yvonne Visser de Ramiro This work has been totally financed by the Geomining Technological Institute of Spain under contract with the EPM, S.A. Company (Estudios y Proyectos Mineros, S.A.).

Acknowledgements

The authors wish to express their most sincere gratitude to the following experts, companies and official organisms for their collaboration and release of technical material as well as permission to reproduce certain data and figures. Amerind-Mackissic,Inc.: G. J. Knotts Amos L. Dolby Co.: J. Petrunyak App1ex:S.O. Olofsson Atlas Copco S.A.E.: E Menendez Atlas Powder Company: VA. Sterner, L. Osen & PM. Miller Atlas Powder International: J. Garcia Milla Bauer, Calder & Workman, Inc.: J.L. Workman & A. Bauer (T) Bill Lane Inc.: W.C. Lane Blasting & Mining Consultants, Inc.: J. Ludwiczak Bucyrys Erie Co.: J.D. Nelmark & G. Rekoske Bendesanstalt für Geowissenschaften und Rohstdffe: R. Lüdeling Canmet: G. Larocque Ci1 Inc.: S. Chung, B. Mohanty, K.C. Joyce, PR. Day, W.K. Webster, D. Dayphinais, I. Huss & K.R. Sharpe Cominco Ltd.: W Russe11 Crowsnest Resources Ltd.: R.A. Reipas David, S. Robertson & Associates Inc.: C. Davenport Dupont Canada: D. Tansey E. I. Du Pont De Nemours & Co.: P D. Porter, B. L. Glenn, J. R. Knudson & A. B. Andrews Entrecanales y Tavora, S.A.: J. Aznar Gardner Denver Mining and konstruction Group Geovanca: R. Ucar Golder Associates: T. N. Hagan, E. Hoek & Guy Le Bell Hullera Vasco Leonesa: E. Castells Hydro-Quebec: F! Lacomte Iberduero, S.A.: J. Fora ICI Australia Operations Pty Ltd.: G. Harries, J. K. Mercer & G.G. Paine Ilmeg: S. Johansson Ingersoll Rand Instituto Tecnologico Geominero de Espaiia: EJ. Ayala & M. Abad Instituto Superior Tecnico de Lisboa: C. Dinis Da Gama Ireco Canada Inc.: L. de Couteur Irish Industrial Explosives, Ltd.: J. P Higgins Julius Kruttschnitt Mineral Research Centre, University of Queensland: C. K. Mckenzie & K. E. Mathews Kaiser Engineers, Inc.: G.V. Borquez

Kemira Oy Kenneth Medearis Associates: K. Medearis Kometa Oy: R. Ikola Kontinitro A.G. L.C. Lang & Associates, Inc.: L.C.Lang Lewis L. Oriard, Inc.: L.L.Oriard LKAB: L. Hermansson Martin Marietta Laboratories: D.A. Anderson & S. R. Winzer McGill University: R.E Favreau, R.R. MacLachlan, W. Comeau & J.C. Leighton Michigan Technological University: F.O. Otuonye New Jersey Institute of Technology: W. Konon Nitro Consult, A.B.: I. Hansson Nitro Nobel AB: B. Larsson, PA. Persson, M. Landberg & G. Lande Nobel's Explosives Company Limited: M. J. Ball The Norwegian Institute of Technology: K. Nielsen The Ohio State University: R.G. Lundquist Oy Forcit Palabora Mining Co.: G. P Fauquier Petromin: \! Cobeiia Precision Blasting Services: C.J. Konya Queen's University: P N. Calder Reed Mining Tools, Inc.: M. Suiirez Richard L. Ash & Associates: R. L. Ash Rietspruit Mining Co.: K. I. Macdonald Societa Esplosivi Industriali S.PA.: G. Calarco & G. Berta Strornrne: A. M. Heltzen Thermex Energy Corporation: R.C. Paddock T Peal, S.A.: J. Alonso & R.Arnaiz Union Espaiiola de Explosivos: R. Blanco University of Missouri Rolla: P N. Worsey, R. R. Rollins & N.S. Smith U.S. Bureau of Mines Twin Cities. Research Center: L. R. Fletcher At the Same time we would also like to acknowledge the drawings and photography done by Jose Maria de Salas and the corrections made by Carlos Ramiro Visser.

CHAPTER 1

Rock drilling methods

1.1 INTRODUCTION Rock drilling, in the field of blasting, is the first operation carried out and its purpose is to Open holes, with the adequate geometry and distribution within the rock masses, where the explosive charges will be placed along with their initiating devices. The systems of rock drilling that have been developed and classified according to their order of present day applicability are: - Mechanical: Percussion, rotary, rotary-percussion. - Themzal: Flame, plasma, hot fluid, Freezing. - Hydraulic: Jet, erosion, cavitation. - Sonic: High frequency vibration. - Chemical: microblast, dissolution. - Electrical: Electric arc, magnetic induction. - Seismic: Laser ray. - Nuclear: Fusion, fission. Even though there is an enormous variety of possible rock drilling systems, in mining and civil engineering drilling is presently canied out, almost exclusively, by mechanical energy. Therefore, in this handbook only the mechanical means will be discussed, reviewing the fundalmentals, tools and equipment for each of them. The main components of a drilling system of this type are: the drilling rig which is the source of mechanical energy, the drill steel which is,the means of transmitting that energy, the bit which is the tool that exercises that energy upon the rock, and the flushing air that cleans out and evacuates the drilling cuttings and waste produced. 1.2 TYPES OF DRILLING OPERATIONS USED IN ROCK BREAKAGE Within the large variety of excavations using explosives, numerous machines have been developed which can be classified in two types of drilling procedures: - Manual drilling. This is canied out with light equipment that is hand held by the drillers. It is used in small operations where, due to the size, other machinery cannot be used or its cost is not justified. - Mechanized drilling. The drilling equipment is mounted upon rigs with which the Operator can control all drilling Parameters from a comfortable position. These structures or chasis can themselves be mounted on wheels or tracks and either be self-propelled or towable. On the other hand, the types of work, in surface as well

as in underground operations, can be classified in the following groups: - Bench drilling. This is the best method for rock blasting as a free face is available for the projection of material and it allows work tobe systemized. It is used in surface projects as well as in underground operations, usually with vertical blastholes, although horizontal holes can be drilled on occasion. - Drilling fordrifting and tunnelling. An initial cavity or cut must be opened towards which the rest of the fragmented rock from the other charges is directed. Blasthole drilling can be carried out with hand held drills, but the trend is towards total mechanization, using jumbos with one or various booms. - Production drilling. This term is used in rnining operations, fundamentally underground, to describe the labors of ore extraction. The equipment and methods used v a q with the exploitation systems, having the common factor of little available space in the drifts for blasthole drilling. - Drilling for raises. In many underground and civil engineering projects it is necessary to Open raises. Although there is a tendency to apply the Raise Bonng method, still today the long blasthole method is used as well as other special drilling systems combined with blasting. - Drilling rocks with overburden. The drilling of rock masses which are covered with beds of unconsolidated materials calls for special drilling methods with casing. This method is also used in underwater operations. - Rock supports. In many underground operations and sometimes in surface ones it is necessary to support the rocks by means of bolting or cementing cables, in which drilling is the first phase. 1.3 FiELDS OF APPLICATION FOR THE DIFFERENT DRILLING METHODS The two most used mechanical drilling methods are rotary-percussion and rotary. - Rotary-percussive methods. These are the most frequently used in all types of rocks, the top harnrner as well as the down-the-hole hammer. - Rotary methods. These are subdivided into two groups, depending upon if the penetration is canied out by crushing, with tricones or by cut with drag bits. The first system is used in medium to hard rocks, and the second in soft rocks.

2

Drilling and blasfing of rocks

By taking into account the compressive strength of the rocks and the drilling diameter, the fields of application of the different methods can be defined as refiected in Fig. 1.1. On the other hand, depending upon the type of mining or civil engineenng surface project, the most comrnon equipment and diameters for bench blastings are indicated in Fig. 1.2.

In the Same manner, the most frequently used equipment for the different underground mining methods and the charactenstic drilling data are indicated in Fig. 1.3. Other criteria to be accounted for in the selection of drilling equipment are: cost, mechanical design, maintenance and semice, operative capacity, adaptability to equipment of the exploitation, and the work area conditions (accessability, type of rock, sources of energy, etc.).

DOWN TUE HOLE

I

DIAMETER (Inch)

3"

2"

11/2"

I "

3 1/2"

6"

5"

9,'

12"

15"

"OLE

mOOUCTIOH.-1HO

HUO HEL0 DRLLS

I

N 1mGE SCUE. W A C E W

Fig. 1.1 Fields of application for drilling methods as function of the compressive strength of the mcks and the diameters of the blastholes.

APLlCATlON RANGE L

W BE-

H E A W -B

4

-W

L

METHODS OF BENCH BLASTING

1

1

ROTARY PERCUSSIVE DRILLING

1

DOWN THE HOLE HAMMER

I

I

ROTARY DRILLING CRUSHING

180-200 mm not "."aI)

1

CUTTMG

I

I

(80-200 mm. not "sunll

CONSTRUCTION WORK

SURFACE MlNlNG

I

Fig. 1.2 Drilling methods for surface operations (Atlas Copco).

U B q 1aMOl UaqM fCllsI?lPUE '3!s~q U1 '3!WqEflIil S! J! '%ZS pue SV uaaMiaq 'ale!pawalu! s! I! '%ZS PUB pue anleA ieql uaarnlaq 'p13~paleuyuiouap A1le3p1aq3oa8 s! I! '%z9 ueqi ~aq8rqs! leqliuaiuo3 z o !e~ seq 3301aqijI -13eduio3pue pnq ~ l ae n 'sao8 8u!lp.q se nj SE 'pazuoa~auiuaaq 1ou aAeq 1eql s y m ~ snoaug! q8noqile f p a p aq ~ ue3 uoyiezuoalaui JO naM '8uyin3 'uo!ieiuaui8eg q i ! ~paiuoquo3 uaqM JoIAeqaq qaqi 'aJojaJaqjd-snoaua8o~alaqA J ~ Aa n s3!is! - ~ a i ~ n le3yaq3 q3 pm 1e3!sAqd lyaql l e q %u!aq iInsaJ aql 'SLBM aslaA!p U! padno~8a n pue sazrs snopA jo ' s l e ~ a u yiua~ajj!pAq pawoj a n A a q ~'sy30~snoau81JO A l a p a%nl ~ aqi a~!8eur8euijo uo!ie3y!pqos 8uunp lsyxa ieql suog!puo3 1e3!uiaq3 pue 1eqsAqd asJaA!p aqL -ma~ajj!ph r a ~uaaq aAeq ue3 seui8eui aql jo uo!i!sod -uo3 le3yaq3 leuy8uo aql 'upA3e 'pue lualuo3 le3yaq3 ~!aq)a8ueq3 pm pay!p!Ios Apea~lea n leql slelauy aqi q i ! ~13ea-r ue3 prnbg lenp!saJ aqi 'oslv wauioui q3ea jo a~nle~adwal pue a ~ n s s a ~aqi d uodn Ourpuadap pa3npo~ds! uopez!lle1su3 pauo!13eq asnwaq ssa3o~d 8~11003SI! 8uunp sapA eui8eui jo uog!soduio~ aqL .unu 5 01 I w o ~' j ~ ~ az!s 1 8uinypaui E q i ! ~sseui 3301e sa3npo~dq 3 y aw!] ~ 8u!loo3 aieJapoui e jo 1eq s! puuou lsoui aqL .sJaiaui jo suazop 01 auo uioq 08 ieqi sq8ua~ls q i ! ~uuoj aI!p U! punoj Alpnsn a n sadAi aaJqi asaqL .xuieui 10 sseui pau.18 auy e U!~I!M pahiasqo a n sp1

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4

Drilling and blasting of rocks

the same sense that igneous rocks are poorer in silica, they are richer in ferromagnesian silicates. The acids are more abrasive and harder than the basic ones, but they are also more dense and resistant to impact.

1.4.1.2 Metamorphic rocks Metamorphic rocks are derived from other pre-existing endogenic or exogenic rocks through important transformations of their mineral components. These marked changes are produced by the necessity of stabilizing their minerals under the new conditions of temperature, pressure and chemism. These rocks are intermediate in physicai and chemical characteristics, between the igneous and the sedimentary, because they have associations of minerais that pertain to the two types. Thus, minerals such as quartz, feldspars, rnicas, amphiboles, and olivines, essential in igneous rocks, are also found in metamorphic rocks; however they do not contain aikali feldspars. As in sedimentary rocks, they can have calcite, dolomite, silica and hematites; but they do not contain evaporites. Minerals comrnon to the two other types also appear such as tourmaline, zircon, magnetite, topaz and corundum; all of which are very stable in any exogenous or endogenous medium. There is a series of minerals that are very specific to metamorphic rocks, which can form part of the grains of detrital rocks, owing to their stability in exogenous medium~,and others are at the same time products of meteoric alteration of the minerals in endogenic rocks. Actually, meteorization is a mineralogical transformation that is both a physical and chemical process, but at low temperature and pressure. 1.4.1.3 Sedimentary rocks Sedimentary rocks are formed by accumulation of broken and decomposed rock material, by chemical precipitation of solubilized minerals or by accumulation of shells or other organic material: animal or vegetable. In the first case, detritic sediments are produced such as gravels, conglomerates or sands in which gravity has played a role in their precipitation. In the second case one

Fig. 1.4. Geological cycle of rocks.

Table 1.1 Classification Very hard Hard Medium hard Medium soft Soft Very soft

Mohs' scale of hardness +7 6-7 4.5-6 3-4.5 2-3 1-2

Compressive strength (MPa) +200 120-200 60- 120 30-60 10-30 -10

can find, as an example, the evaporites or saline rocks precipitated by over-saturationof a brine that is subjected to intense evaporation. The third type are accumulations of shells, skeletons of animals or remains of plants, such as the conchiferous limestones. This last group is subdivided into organogenous biochemistry and mineral biochemistry depending upon whether their components are of organic or inorganic nature. For the first we have coal and petroleum, and for the second the limestones, dolornites and phosphatic rocks. For an initial classification of sedimentary rocks, their formation process is taken into account, later the grain size, the characteristics of their bonding, apart from the types and quantities of their rninerai components. 1.4.2 Rock properties that affect drilling The principal physical rock properties that have influence upon penetration mechanisms and, as a consequence, on choice of the drilling method are: hardness, strength, elasticity, plasticity, abrasiveness, texture, structure, characteristics of breakage. 1.4.2.1 Hardness Hardness is considered to be the resistance of a surface layer to be penetrated by another body of harder consistency. In rock, it is a function of the hardness and composition of its mineral grains, the porosity, degree of humidity, E etc. The hardness of rocks is the principal type of resistance that must be overcome during drilling, because once the bit has penetrated, the rest of the operation is easier. Rocks are classified as to their hardness by using Friedrich von Mohs' Scale of Hardness (1882), in which the concept is that any mineral can scratch anything that has a lower or equai number to it, numbering from 1 to 10. As can be seen from Table 1.1, there is a certain correlation between hardness and compressive strength of the rocks. 1.4.2.2 Strength Mechanical strength of a rock is the property of opposing destruction by an extemal force, either static or dynarnic. The rocks give maximum resistance to compression, normally, as the tensile strength is not more than 10 or 15% of the compressive strength. This is due to the fragility of rocks, to the large quantity of local defects and irregularities that exist and to the small cohesion between the particles of which they are constituted.

Rock drilling rnethods

5

stratification sense or schistosity is larger than in a parallel sense. The quotient that is usually obtained between both strength values varies between 0.3 and 0.8, and it is equal to 1 only for isotropic rocks. In Fig. 1.5, the most frequent compressive strengths for different types of rock are indicated.

The rock strength fundamentally depends on its mineralogical composition. Among the integrating minerals, quartz is the most solid with a strength that goes over 500 MPa, while that of the ferromagnesian silicates and the aluminosilicates vary between 200 and 500 MPa, and that of calcite from 10 to 20 MPa. Therefore, the higher the quartz content, the more the strength increases. The mineral strength depends upon the size of the crystals and diminishes with their increase. This influence is significative when the crystal size is under 0.5 mm. In rocks, the size factor has less influence on strength as the intercrystallinecohesion force also intervenes. For example, the compressive strength of a fine grained arkose sandstone is almost double that of a coarse grained; that of marble composed of 1 rnrn graines is equal to 100 MPa, whereas a fine grained limestone - 3 to 4 mm - has a strength of 200 to 250 MPa. Amongst the sedimentary rocks the ones with highest strength are those that contain silica cement. With the presence of clay cement, the strength is drastically reduced. Porosity in rocks with the Same lithology also reduces strength proportionately, more porosity - less strength; as it simultaneously reduces the number of contacts of the mineral particles and the force of reciprocal action between them. The depth at which rocks were formed arid the degree of metamorphism also have influence upon their strength. Therefore, the strength of clay beddings near the ground surface can be of 2 to 10 MPa, whereas in clay rocks that went through a certain metamorphism the strengths can reach 50 to 100 MPa. On the other hand, the strength of ansiotropic rocks depends upon the sense of action of the force. The compressive strength of rocks in the perpendicular to

1.4.2.3 Elasticity The majonty of rock minerals have an elastic-fragile behavior, which obeys the Law of Hooke, and are destroyed when the strains exceed the limit of elasticity. Depending upon the nature of deformation,as function of the Stresses produced by static charges, three groups of rocks are taken into consideration: 1) The elastic-fragile or those which obey the Law of Hooke, 2) The plasticfragile, that have plastic deformation before destruction, 3) The highly plastic or very porous, in which the elastic deformation is insignificant. The elastic properties of rocks are charactenzed by the elasticity module 'E' and the Poisson coefficient ' V ' . The elasticity module is the proportionality factor between the normal Stress in the rock and the relative correspondant deformation, its value in most rocks varies between 0.03 X 104and 1.7 X 1o5 MPa, basically depending upon the mineralogical composition,porosity, type of deformation and magnitud of the applied force. The values of the elasticity modules in the majority of sedimentary rocks are lower than those corresponding to the minerals in their composition.The texture of the rock also has influence on this Parameter, as the elasticity module in the direction of the bedding or schistosity is usually larger than when perpendicular. Poisson's coefficient is the factor of proportionality between the relative longitudinal deformations and the transversal deformations. For most rocks and minerals it is between 0.2 and 0.4, and only in quartz is it abnonnally low, around 0.07.

0

I0

20

30

40

60

SO

DEFORMATION (mm x 108) Fig. 1.6. Curves of stress-deformationfor different types of rocks.

6

Drilling und blasting of rocks

1.4.2.4 Plasticity As indicated before, in some rocks the plastic deformation preceeds destruction. This begins when the Stresses exceed the limit of elasticity. In the case of an ideally plastic body, that deformation is developed with an invariable stress. Real rocks are deformed and consolidated at the Same time: in order to increase the plastic deformation it is necessary to increase the effort. The plasticity depends upon the mineral composition of the rocks and diminishes with an increase in quartz content, feldspar and other hard minerals. The humid clays and some homogeneous rocks have plastic properties. The plasticity of the stony rocks (granites, schistoses, crystallines and sandstones) becomes noticeable especially at high temperatures. 1.4.2.5 Abrasiveness Abrasiveness is the capacity of the rocks to wear away the contact surface of another body that is harder, in the rubbing or abrasive process during movement. The factors that enhance abrasive capacities of rocks are the following: - The hardness of the grains of the rock. The rocks that contain quartz grains are highly abrasive. - The shape of the grains. Those that are angular are more abrasive than the round ones. - The size of the grains. - The porosity of the rock. It gives rough contact surfaces with local stress concentrations. - The heterogeneity. Polymineral rocks, although these are equally hard, are more abrasive because they leave rough surfaces with hard grains as, for exarnple, quartz grains in a granite. This property has great influence upon the life of drill steel and bits. In Table 1.2, the mean arnounts of quartz for different types of rock are indicated.

Table 1.2 Rock type Amphibolite Anorthosite Diabase Diorite Gabbro Gneiss Granite Greywacke Limestone Marble Mica gneiss Mica schist Nori te Pegmatite Phyllite Quartzite Sandstone Shale Slate Taconite

Quartz content %

1.4.2.6 Texture The texture of a rock refers to the structure of the grains of minerals that constitute it. The size of the grains are an indication, as well as their shape, porosity etc. All these aspects have significative influence on drilling performance. When the grains have a lenticular shape, as in a schist, drilling is more difficult than when they are round, as in a sandstone. The type of material that makes up the rock matrix and unites the mineral grains also has an important influence. As to porosity, those rocks that have low density and, consequently, are more porous, have low crushing strength and are easier to drill. In Table 1.3 the classification of some types of rocks is shown, with their silica content and grain size.

Table 1.3. Cornmon rock names and their geological definitions (based on Dearman, 1974;ISRM, 198la). W

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Rock drilling methods

7

Table 1.4. Properties of rock types according to origin-based classification. Rock type

Specific gravity (m3)

Grain Swell Compressive size factor strength (mm) (MPa*)

TntruDiorite sive Gabbro INGENOUS Granite Andesite Extrusive Basalt Rhyolite Trachyte

2.65-2.85 2.85-3.2 2.7 2.7 2.8 2.7 2.7

1.5-3 2 0.1-2 0.1 0.1 0.1 0.1

..-.-

Congomerate 2.6 Sandstone 2.5 SEDIMEN- Shale 2.7 TARY 2.7 Dolomite Limestone 2.6 Limerock 1.5-2.6

1.5

170-300

2 0.1-1 1 1-2 1-2 1-2

Gneiss 2.7 2 Marble 2.7 0.1-2 METAMOR- Quartzite 2.7 0.1-1 PHIC Schist 2.7 0.1-L Serpentine 2.6 Slate 2.7 0. L * 1 MPa = 1 MN/^^ = 10 kg/cm2 = 142.2 psi

In Table 1.4, the characteristic properties of different types of rocks are indicated, according to their origin. 1.4.2.7 Structure The stmctural properties of the rock masses, such as schistosity, bedding planes, joints, diabases and faults, as well as their dip and strike affect the allignment of the blastholes, the drilling performance and the stability of the blasthole walls.

SPACING OF JOINTS A) B) C) D)

lOOOcm

105

10

1

0.1

STRONG ROCK MEDIUM ROCK WEAK ROCK VERY WEAK ROCK

Fig. 1.7. Classification of the rock masses.

In Fig. 1.7, the rock masses are classified from the spacing between joints and the strength of the r o c h material. REFERENCES Atlas Copco: Manual atlas copco, 4th edition. 1984. Heinz, W. F.: Diamond drilling handbook. 1989. Hunt, R.E.: Geotechnical engineeßng techniques und pracdces. McGraw Hill. 1986. Sandvik-Coromant: Manual de perforacibn de rocas. Teoria y tkcnica. 1983.

Tamrock: Handbook of surface drilling. 1989.

CHAPTER 2

Rotary percussive diilling

2.1 INTRODUCTION Drilling by rotary percussion is the most classic system for drilling blastholes, and its chronological appearance coincides with the industrial development of the ninteenth century. The first Prototype machines made by Singer (1838) and Couch (1848) were run by steam, but it was when compressed air was used as the source of energy, in the execution of the tunnel of Mont Cenis in 1861, that this system evolved and was put into extensive use. This event, along with the arrival of dynamite, was decisive in the rapid development of rock breakage in mining and civil engineering at the end of the last century. The drilling pnnciple of these rigs is based upon the impact of a steel piece (piston) that hits a utensil which transrnits at the Same time that energy to the bottom of the blasthole by means of the final element called the bit. The rotary percussive rigs are classified in two large groups, depending upon where the hammer is located: - Top hammer. In these drills, two of the basic actions, rotation and percussion, are produced outside the blasthole, and are transmitted by the shank adaptor and the dnll steel to the dnll bit. The hamrners can be driven hydraulically or pneumatically. - Down the hole hammer. The percussion is delivered directly to the drill bit, whereas the rotation is performed outside the hole. The piston is driven pneumatically, while the rotation can be hydraulic or pneumatic. Depending upon the fields of application of these drilling ngs, surface or underground, the most comrnon range of diameters are shown in Table 2.1. The main advantages of rotary percussive dnlling are: - It can be applied to any type of rock, from soft to hard. - Wide range of diameters; - Versatile equipment, it adapts well to different operations and is very Mobile; - Only requires one Operator; - Easy, quick maintenance, and - The capital cost is not high. In view of these advantages and characteristics, the type of operations where it is used are: - Underground civil engineering; tunnels, underground hydraulic plants, residual deposits, etc., and in surface operations; roads, highways, indusirial excavations, etc.

- In underground mines and in small to medium sized surface operations.

2.2 FUNDAMENTALS OF ROTARY PERCUSSIVE DRILLING Rotary percussion drilling is based upon the combination of the following: - Percussion. The impacts produced by repeated blows of the piston generate shock waves that are transmitted to the bit through the drill steel (in top harnmer) or directly upon it (down the hole). - Rotation. With this movement, the bit is turned so that the impacts are produced on the rock in different positions. - Feed, or thrust load. In order to maintain the contact of the dnll bit with the rock, a thrust load or feed force is applied to the drill siring. - Flushing. aushing removes the drill cuttings from the blasthole. The indentation forming process with which penetration is achieved in this drilling system is divided into five times, as indicated in Fig. 2.2. a) Crushing of the rough edges of the rock upon bit contact. b) Radial cracks appear from the points of Stress concentration and a V shaped wedge is formed. C) The rock of the wedge is pulverized. d) The larger fragments are chipped in the zones next to the wedge. e) The drill cuttings are flushed away. This sequence repeats itself with the Same impact rhythrn of the piston upon the system of energy transmission to the bit. The yield of this process increases proportionally with the size of the rock chippings. 2.2.1 Percussion The kinetic energy E, of the piston is transmitted from the hammer to the drill bit, through the dnll steel, in the form of a shock wave. The wave travels at high speed and its shape depends basically on the design of the piston. When the shock wave reaches the drill bit, part of the energy is transformed into work, causing the bit to penetrate, and the rest is reflected and returns through the drill steel. The efficiency of this transmission is difficult to

Rotary percussive drilling Tahle 2.1. Drilling method Top hammer Down the hole

Drilling diameter (mm) Surface Underground 38- 65 50- 127 75-200 100- 165

The percussion mechanism consumes from 80 to 85%of the total power of the equipment.

ROTATION

2.2.2 Rotation

FEED FORCE

Fig. 2.1. Basic actions in rotary percussive drilling.

Fig. 2.2. Sequence of rock failure during Center formation (Hartman, 1959).

evaluate as it depends upon many factors such as: type of rock, shape and size of piston, drill steel characteristics, bit design, etc. Another thing to take into account is that energy is lost through the sleeves of the rod couplings, due to reflection and fricton which is converted into heat and wear on the drill steel threads. In the first coupling the losses oscillate between 8 and 10%of the shock wave energy. In down the hole drilling the piston energy is transrnitted directly to the bit, giving greater performance. In these drilling Systems, percussion force is the parameter that most influences the penetration rate. The energy freed per hammer stroke can be estimated from the following equations:

where: m, = Mass of the piston, V = Maximum piston speed, p, = Pressure of the work ffuid (oil or air) inside the cylinder, A, = Surface area of the piston face, I, = Stroke of the piston. In the majority of hydraulic hammers, the manufacturers indicate the impact energy value, but this is not the case with the pneumatic hammers. Special care should be taken in estimating the p, for these, as it is 30 to 40% lower in the cylinder than in the compressor, owing to charging and expansion losses of air with each stroke of the piston. Thus, the hamrner power is the energy per stroke multiplied by the frequency of strokes n,:

.

.

and taking into account the previous equations, the following can be stated:

Rotation, which tums the dnll bit between consecutive blows, has the function of making the bit stnke upon different points of the rock in the bottom of the blasthole. In each type of rock there is an optimum rotation speed which produces larger sized cuttings taking advantage of the free area of the hole created with each impact. When drilling with insert bits, the most common rotation speeds oscillate between 80 and 150 r.p.m. with angles between indentations of 10 to 20°, Fig. 2.3. For button bits from 51 to 89 mm, the speeds should be lower, between 40 and 60 r.p.m., that bring turning angles between 5 and 7". Bits of larger diameters require even lower speeds.

2.2.3 Thrust load The energy generated by the mechanism of hammer blows should be transfered to the rock, for which it is n e c e s s q to have the dnll bit in permanent contact with the bottom of the hole. This is achieved with the thrust load or pull down, supplied by a pull down motor, which should be adapted to rock type and drill bit. Insufficient thrust load has the following negative effects: lower penetration rates, greater wear of rods and sleeves, loosening of drill steel threads and heating of the Same. On the contrary, if the pull down is excessive the penetration rate is also diminished, there is increased

INSERT BIT

BUTTON BIT

Fig. 2.3. Rotation speed between consecutive blows as a function of penetration rate and bit diameter.

10

Drilling und blasting of rocks FLUSHING FLUID

FEE0

Fig. 2.4. The effect of thmst load upon penetration rate in top hammer dnlling.

rotation resistance, drill steel can become jammed, the wear on the bits increases as well as the rotation rate and equipment vibrations, and the blastholes can be deviated. As occurs with rotation, this Parameter does not have decisive influence on the penetration rates, Fig. 2.4. Pnnciple of fiushing.

2.2.4 Flushing In order to have efficient drilling, the bottoms of the blastholes must be maintained clean by evacuating drill cuttings as soon as they appear. If this is not done, a large quantity of energy will be consumed in regrinding with the consequent wear on drill bits and decrease in penetration, apart from the risk of jamming. Blasthole flushing is carried out with a flow of air, water or foam that is injected by pressure to the bottom through an opening in the Center of the drill steel and flushing holes in the dnll bits. The cuttings are removed up through the space between the rod and the blasthole walls, Fig. 2.5. Fiushing with air is used in surface operations, where the dust produced can be eliminated by means of dust collectors. Water flushing is mostly used in underground drilling, which also keeps dust down, although it reduces performance by about 10 to 20%. , Foam is used as a complement to air as it helps bring large particles up to the surface and also acts as a seaier for blasthole walls when drilling through loose material. The velocity of air flow for efficient cleaning with air goes from 15 to 30 mls. The minimum velocities for each case can be calculated from the following equation:

where: V , = Velocity of air flow (mls), pr = Rock density (g/cm3),d, = Diameter of the particles (mm). Therefore, the flow that should be supplied by the compressor is:

where: Qa = Fiow (m3/min), D = Blasthole diameter, d = Diameter of the rods (m). When water is used for flushing, the velocity of air

flow should be between 0.4 and 1 m/s. In these cases the pressures are maintained between 0.7 and 1 MPa, to keep the flow from entering into the hammer. When using air with top hammers, it is not common to have a high pressure compressor for flushing alone. Only in down the hole hammer drilling is a high pressure compressor used (1 - 7 MPa) because the percussion power is increased along with the flushing of cuttings. An important factor to remember when estimating the flushing flow is that of charging losses produced due to the narrow conducts through which the fluid must pass (flushing needle, drill steel holes) as well as along the dnll stnng. In Table 2.2, the flushing velocities for top hammer drilling are indicated as function of air compressor flow and drill steel diameter. 2.3 TOP HAMMER DRILLING This drilling System can be qualified as the most conventional or classic, and although its use by pneumatic drive was limited by the down the hole and rotary equipment, the appearance of the hydraulic hammers in the sixties has given a new boost to this method, complementingand widening its field of application. 2.3.1 Pneumatic drilling rigs Hammers driven by compressed air basicaily consist in: - A cylinder with a front Cover that has an axial opening where the rotation chuck goes, as well as a retaining device for the drill rods. - The piston that altemately strikes the dnll steel shank through which the shock wave is transmitted to the rod.

Rotarypercussive drilling - The valve that regulates the passage of compressed air in a pre-set volume and in alternating form to the front and back of the piston. - A rotation mechanism, that can be a spirally fluted nfle bar or of independent rotation. - A flushing System that consists in a tube that allows the passage of air to the inside of the drill steel. These elements are cornrnon to all the types of hammers on the market, with only a few design charactenstics that differ: diameter of the cylinder, length of the piston stroke, distribution valves, etc. The following describes the working pnnciple of a pneumatic harnrner, Figs. 2.6 to 2.12. 1. The piston is at the end of its return stroke and is ready to Start its working stroke. The air, at line pressure, fills the backhead (1) and passes through the back supply port (2) into the cylinder (3). The air pushes the piston fonvard, beginning the working stroke. Meanwhile, the cylinder front end (5) is at atmospheric pressure since the exhaust port (6) is Open. 2. The piston (4) continues to accelerate forward, driven by the line pressure, until the leading edge (7) of the pistons control head shuts off the entrance of compressed air. The air confined in the back end of the cylinder (3) starts to expand and contiunes to drive the piston forward. Note that the piston flange (4) closes the exhaust port (6) and that the front end is still at atmospheric pressure. 3. The air confined at the back of the piston (3) continues to expand until the back edge of the piston flange starts to uncover the exhaust port (6). Remember that the piston control head (7) has already shut off the compressed air entrance, so that no compressed air will be wasted when the exhaust port is opened. Up front, the piston has trapped air that was a atmopheric pressure (5), and has now compressed it to slightly above atmospheric pressure. 4. The piston continues to move forward because of its momentum until it strikes the drill shank steel. Now, the back edge of the piston flange (8) has uncovered the exhaust port (6) and the air in the back end is exhausted into the atmosphere. While this was going On, the back edge (10) of the control head opened the front supply port adrnitting compressed air to the front end (5) driving the piston back on the return stroke. During this Stage there is compressed air pushing against the piston from the front end (5) and also pushing against the back end (10). The front surface area is much larger than the back (10) so the piston moves towards the rear. 5. The piston is accelerated back on the return stroke, until the back edge of the control head (10) Covers up the front air supply port. The air up front then continues to push the piston back. 6. The piston continues to accelerate backwards while the air in the front end (5) expands until the front end of the piston flange (11) uncovers the exhaust port, trapping the air in the back end of the cylinder and compressing it to a pressure slightly more than atmospheric. Note than the front edge of the control head (7) is just about to Open the back supply port.

11

W

Fig. 2.6. Piston at the end of its return stroke.

I Fig. 2.7. The piston accelerates forward.2.

W-

Fig. 2.8. The backedge of the piston flange uncovers the exhaust port.

w-

Fig. 2.9. The piston compresses the air in front of it.

I Fig. 2.10. The piston is accelerated back.

7

Fig. 2.1 1. The front edge of the piston flange uncovers the exhaust port.

Fig. 2.12. Return stroke of the piston finishes.

CHAPTER 6

Rotary drillling with cutting action

6.1 INTRODUCTION Rotary drilling by cutting action was at its peak in the forties, in American coal mines, for blastholes in overburden and in the ore itself. With growing use in surface operations using rotary rigs with rolling tricone rock bits, this method has been limited to soft rocks, usually with small to medium diameters, clearly competing with direct breakage Systems. In underground jobs, rotary percussive drilling has taken over most of the work, leaving only low to medium strength rocks that are non-abrasive (potash, coal, etc.) to the rotary rigs. Drilling by cutting action in production blastholes is carried out with bits whose stnictures have elements of tungsten carbide or other materials such as synthetic diamonds or polycrystalines, which vary in shape and angle and can be classified in the following types: a) Two-wing drag bits, with diameters from 36 to 50

mm. b) Three and four-wing drag bits with diameters from 50 to 115 mm. C) Three replaceable blade bit with fluted reamers in diameters that go from 160 to 400 mm.

of cut. This force is divided into two, one tangential N, and another vertical E, Fig. 6.4. The tangential force is the one that overcomes the compressive rock strength when confronted with the bit. The resisting torque T,., measured in the axis of the drilling element, is the product of the tangential force multiplied by the radius of the bit. The resisting torque on the total cutting area, supposing that it is a circularcrown, is given by:

where: T, = Resisting torque, p = Coefficient of friction, E = Thrust on the bit, r, = Outside radius of the bit, r, = Inner radius of the bit. This resisting torque is determined by the rninimum torque of the rock drill that allows the rock to be penetrated. Calling r, the effective radius of the bit, which is equal to

6.2 FUNDAMENTALS OF DRILLING W H CUTTING ACTION

the previous equation is transformed into

The cutting actions of a' rotary drag-bit on rock are, according to Fish, the following: 1. Beginning the cycle immediately after the formation of a large fragment, elastic deformations by stresses owing to the angular deflexion of the bit and to torsional strain in the drill rod. 2. Strain energy is released, with consequent impact of the cutting edge against the rock surface, and comrninution of rock fragments. 3. Build up of stresses at the bit-rock contact area, with further crushing and displacement of rock debris, until the cutting edge is effectively bearing on a step of unbroken rock which subsequently parts to create a large fragment or chip which, once bailed out, allow a new cycle to start, Fig. 6.2. The field tests carried out by Fairhurst (1964) show that the pulldown load and the rotary torque upon the bit undergo great variations owing to the discontinuous nature in chip formation, Fig. 6.3. The cutting force is in function with the geometry of the bit, the compressive strength of the bit and the depth

It is deduced that if p is constant, the torque is proportional to the thrust load on the cutting tool. In reality, the coefficient p is not constant, as it oscillates with the thickness of the cut and with the feed force itself. The index that determines the penetration in the rock is obtained by the relationship between the energy consumed by the drill and the specific rock energy. The total energy consumed by the equipment is 2xNrTr?where Nr is the rotary speed, which gives the following:

where: E, = Specific rock energy, Ar = Area of the blasthole Cross section. From this relationship it can be deduced that the penetration rate for a given rock and for a determined drilling diameter is linearly proportional to the thrust and rotary speed, although this is not completely true in practice, as it has been indicated that the friction coefficient of the rock varies with the Uinist. In Fig. 6.5, it can be obsemed

Rotary drilling with cutting action

73

-THRUST N W 667 -

DARLEY DALE SANDSTONE 229mm/min CUTTING SPEED

---TORQUE

1 150

0 III

2 445-

100

222-

50

a) TWO WlNG DRAG BIT

oL

J

I

o

25

1

I

0

6

o5

, 12

5

I

I

I

o 75

1 0

I 25

I

I

I

19

25

y)

in

mm

DISTANCE CUT

Fig. 6.3. Drag-bit force - displacement curves (Fairhurst, 1964)

CUTTING EDGE CHIP

I

b) THREE AND FOUR WlNG DRAG BIT

CRACKS

v / / t ; 3

NEW SURFACE

Fig. 6.4. Forces that act upon the cutting tool.

Q

LT

LINEAR PORTION BY CLOGGING AT THE BITS C)

THREE REPLACEABLE BLADE BIT

W

Z

Fig. 6.1. Rotary drag bits.

W

a

DEPARTURE FROM LlNEARlTY DUE T 0 EXCESSlVE WEAR ON BIT

APPLIED THRUST

Fig. 6.5. Basic th~st-penetrationrate curve for rotary drag-bit drilling (Fish and Barker, 1956).

ACCUMULATION TNEw: OF ; R*FINE ....!::;CuTTINGs ::::.,... ?. ,...:.::.:: :,

s u m E N FRACTURE

.::.... .L.

..... ::;,,..:,.,; :.'.'..::. .. ...............:::. ..'.'.'.. ...... ........: ...'{..'. ..... ........ ........... . .:,:. ,.,...:.. . .:.. :::;

',,.',>,',.. , , *,',,.,.,;,,;.

, I'.

;

.

U-

--

......... . '.: ,/,,',,',!,, , .,.,,,,, , ,, ,, ,4;&,j2,:,,!:;,);:,:,);<;,:, ,;, , >,,.,:.',< .. ' . '

l.,~,'l',

- -- -I'.

(C)

(,

Fig. 6.2. Drag-bit cutting sequence (Fish and Barker, 1956)

that there is a thrust value under which a theoreticai penetration rate is not achieved, only excessive wear, and a limit vaiue which, if surpassed, will produce clogging of the bit. The rotary speed is limited by the growing frictional wear on the bits as the number of revolutions increases. Apart from the abrasiveness of the rocks, it must be taken into consideration that the wear increases with higher feed loads and the frictional forces between the rock and bit become higher. In Table 6.1, the recornrnended thrusts and rotary speeds are given in function with blasthole diarneter and compressive rock strength.

74

Drilling und blasting of rocks

Table 6.1. Cornpressive rock strenth IMPa)

Unitary thmst (Nimm)

Blasthole diameter (mm)

Rotary speed (rlrnin)

Two practical limits of rotary drilling can be given: compressive rock strength, which should be under 80 MPa, and the siliceous content, which should be less than 8% because, if not, the wear could be uneconomicai. Eimco-Secoma has developed a test for measuring the drillability and abrasiveness of the rocks. It consists of drilling a hole in a rock sample with constant thrust and rotary speed. The bit is of tungsten carbide and the flushing is carried out with water. A penetration-time curve is obtained and, from this, the drillability index or hardness expressed in 1110 mm of advance and, by measuring the wear undergone by the calibrated tool during 30 seconds, the abrasiveness is determined in tenths of mm of bit edge wear. The rocks are clasified in four groups or zones, in function with the two parameters, which define the most adequate drilling methods.

Zone I Zone with soft formation and low abrasiveness. Dry, low-thrust rotary drilling is suggested with low air presSure. Zone II Medium hard formation and low abrasivity. Dry mediumthrust rotary drilling with medium pressure air injection. Zone III Fairly hard rock, low abrasiveness. High-thmst rotary drilling and high pressure water flushing. The thrust can reach 20 kN.

O V)

0.9

Zone IV Very hard formation and high abrasiveness. Use rotary percussive dnlling with air or water flushing. The dnlling parameters for each Zone, for drilling diameters between 30 and 51 rnm are, according to Secoma, the following: Zone I Rotary dnlling with little thrust. - Thrust: From 1 to 8 kN. - Rotary speed: 800 to 1.100 rlmin. - Dry drilling - Types of rock: coai, potash, salt, gypsum and soft phosphate. - Tools: Spiral rods; Two wing drag-bits, 6 = 110125", ß = 75", y = 0-14". - Drilling rates = 3.5 to 5 mlmin. - With humid air the penetration rates are multiplied by 1.5 and 2.

Zone I1 Thrust: 8 to 12 kN. - Rotary speed: 550 to 800 rlrnin. - Drilling with humid air injection. - Types of rock: Limestone and soft bauxites, soft iron ores. - Cutting bits: 6 = 125", ß = 75-80", y = 0-2". - Penetration rate: 2 to 3.5 mlrnin. Zone III Thrust: 12 to 18 kN. - Rotary speed: 300 to 550 rlmin. - Drilling with water injection. - Types of rock: Bauxites and medium limestones, schists without quartzites, hard gypsums and hard phosphates. - Cutting bits: 6 = 125-140°, ß = 80°, y = -2-6" - Penetration rate: 1 to 1.8 mlmin. The rotary power, in HP, necessary to make a drag-bit rotate, is calculated with the following equation:

ROTARY PERCUSSIVE-DRILLING

ROTARY DRILLING

75

Rotary drilling with cutting action

where: D = Diameter (mm), N, = Rotary speed (rlmin), E = Thrust load (W). The necessary rotary torque is deterrnined from the equation:

T, =

HP,

X

7.14

Y

Table 6.2. Type of rock Hard gypsum Limestone, bauxite Soft iron ore Soft gypsum Phosphate, coal, salt, potash

Penetration rate (m/min) 1.5-2 1.5-2.5 1.5-3 3.8-6 3.5-10

Flushing System Water Water Water or dry Humid air or dry Humid air or dry

where: T, = Rotary Torque (kN.m). 6.3 FLUSHING OF DRLLL CUTTINGS Drill cuttings are eliminated with a flushing fluid that can be air, in surface operations, or water or humid air in underground jobs. The advantages that the use of air with water injection brings are the following: - It facilitates upward bailing, thus increasing the advance rate. - It cools the dnll bit, reducing wear. - It avoids blasthole filling. - It eliminates dust which is very important in abrasive formations. According to Eimco-Secoma, in order to inject humid air around 1.000 to 1.500 llmin of air are necessary and, for each rock drill, about 250 cm3/minof water. In very soft rocks, from 30 to 40 MPa, helicoidal dnll steel can be used, with larger pitch as the penetration rate increases for efficient removal of the drill cuttings, Fig. 6.7. In Table 6.2, apart from the typical penetration rates in different types of rocks, the most commonly used flushing systems are indicated. 6.4 CUTTING TOOLS The cutting efficiency of a to?l depends largely upon its

design, according to the type of rock that is to be drilled. Fig. 6.8. The attack angle 6 usually varies between 110" and 140°, becoming increasingly obtuse in harder rock: if not, the hard meta1 would splinter. On occasions bits have been designed with rounded contours. The angle of the cutting wing ß varies between 75 and 80" and that of the cut y between -6 and 14", being positive in soft rocks and negative in hard rocks. Lastly, the backing-off angle or clearance angle is 6 = 90' - ß = Y. During drilling, a point on the cutting bit located at a distance r advances along a helical path. The angle of inclination of this helix is: 0.l

= arc tan

(&)

wherep is the advance of the bit per revolution. Owing to the movement of the bit along the helix, the effective clearance angle is reduced: For points near the center of the bit the effective clearance angle is Zero, as in these zones the tool compresses the rock. For this reason, drag-bits designed with a central gap usually reach higher drilling speeds. At the end of the seventies, General Electric manufactured the first Compact Diamond Polycrystalline-PDC,

CUTTER HEAD ASSEMBLY LEAD ASSEMBLY

-

...

REVERSIBLE LOCKING TYPE

I) HOLLOW STEM AUGER. 1.6m LENGTH 2) HEX DRIVE CAP 3) ROD T 0 DRIVE CAP ADAPTOR 4) LOCKING PIN 6) LOCKING PIN BOLT 6, CENTRE DRILL ROD , 7) PLUG 8) PLUG BOLT

9) 10) 11) 12) 13) 14) 16)

BIT TYPE CUTTER HEAD BODY CARBIDE INSERT BIT BIT LOCK RING BLADE TYPE CUTTER HEAD CARBIDE INSERT BLADE BLADE BOLT TUNGSTEN CARBIDE PILOT BIT

Fig. 6.7. Helicoidal drill rod and bits with differentconfigurations.

16) PlLOT BIT SHANK

17) 18) 19) 20) 21) 22)

BOLT. PILOT BIT SHANK TUNGSTEN CARBIDE PILOT BIT. LARGE SlZE PILOT BIT, SOFT FORMATION HEX QUICK BREAKOUT ADAPTOR LOCKlNG WEDGE WEDGE PUNCH

Drilling and blasting of rocks

7r

NEGATIVE SIDE RAKE ALL CUTTERS '6

,TER FLUSH HOLES

3- DIAMETER

-E F O R AIR W A T E R FLUSt 7-C2542 STRATAPAX BLANKS

(0)

BIT ROTATION

CORE CRUSHER (TUNGSTEN CARBIDE) SECTION X-X

Fig. 6.10. Drill bit with diarnond cutting elernents. Fig. 6.8. Sorne characteristics of a cutting tool (Fish and Barker, 1956).

RAKE ANGLE ECTIVE DEARANCE W -HELIX ANGLE

"-z

MOVEMENT

BIT AXlS

Fig. 6.9. Direction of a point on the the bit (Fairhurst, 1964).

obtained from a mass of very fine diamond particles that are sinterized under extreme pressure and embedded in tungsten carbide bases that are shaped at high pressures and temperatures. The resulting alloy has exceptional abrasion resistance along with the high resistance of tungsten carbide to impacts. The present day diamonds are thermically stable up to 1200°C in non oxidizing atmospheres and are available in sizes that range from 0.005 to 0.1 8 g (0.025 to 0.9 carats) in triangular prism, parallepiped or cylinder shape. Apart from their use in exploration drilling, diamond bits are used in underground mining for coal, potash, salts and gypsums to drill small diameter blastholes, from 35 to 110 mrn. In many instances, the penetration rates obtained and the Service lives of these bits are quite Superior to their conventional Counterparts.

Atkins, B.C.: Drilling Application Successes Using Stratapax Blank Bits in Mining und Construction. Australian Drilling Association Symposium, 1982. Bemaola, J.: Petforacibn Rotativa. 11 Serninario de Ingeniena de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundacibn Gbrnez-Pardo. 1987. Morales, V.: La Seleccibn y el Funcionamiento de los Triconos. Canteras y Explotaciones. Septiembre, 1984. Roberts, A.: Applied Geotechnology. Pergamon Press, 1981. Rodriguez, L.: Petforacibn Hidrbuiica Rotativa en Proyectos Subterrbneos. I Seminario de Ingenieria de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundacibn Gornez-Pardo, 1986. Tandanand, S.: Principles of Drilling. Mining Engineering Handbook. SME. 1973.

Photo 6.1. Rotaiy drilling equiprnent with heicoidal drill steel in a potash mine.

CHAPTER 7

Special drilling methods and mounting systems

7.1 INTRODUCTION Apart from the standard drilling equipment, there are units and mounting systems on the market for special or very specific applications. Among these jobs, a few can be mentioned such as: drilling rock masses with overburden of a nonconsolidated material andlor sheets of water, drilling rigs for shafts and raises, thermal and water jet drilling, etc. 7.2 DRILLING THROUGH OVERBURDEN These drilling methods were developed to solve problems that appeared when drilling in rocky ground, unconsolidated or alterated masses, overburdens, etc., that require continuous casing tubes to maintain blasthole stability. Some of the applications for these systems that are in use at present are: - Drilling for underwater blasting - Drilling for rock rnass blasting with overburden that has not been removed previously. - Anchonng - Foundations - Water wells - Soil and core sampling, etc. The overburdens can be b ~ d sof natural clay, sand, gravel, etc., as well as of fill with compact or noncompact materials, rock fill, etc. Drilling can be canied out, as will be noted later on, with top hammer or down-the-hole hammer, and consists of drilling through the overburden at the Same time that the casing tube is passed down into the hole, to keep loose material from caving in and blocking the hole, so that drilling can proceed into solid rock. One important feature of these techniques is that the flushing, or bailing out, of the debris be very effective. It can be canied out centrally through the shank adaptor or through a separate flushing head, in which case the fluid pressure should be higher. The two methods that have been developed are known as OD and ODEX. 7.2.1 OD (Overburden Drilling) Method In this method, the descent of the casing tube is canied out by percussion and rotation. The equipment consists of an outer casing tube with a tungsten carbide ring bit

mounted on the lower end. The casing tube encloses an inner drill stnng of standard drill steel which is extended by use of coupling sleeves that are independent from those of the casing tube. The casing tubes as well as the drill steel is connected to the hammer by a special shank adaptor, which transmits impact force and rotary force to both, Fig. 7.1. The basic operations for application of the System are: - The casing tubes, with or without the inner drill steel, proceed simultaneously through the overbur-den. - The outer ring bit advances a few centimeters when it reaches the bedrock. - Drilling is carried out with the inner drill steel unless decomposed or sand beds are encountered, in which case the casing tube would descend at the Same time. - The extension rods are drawn up. - The plastic casing tubes are allowed to remain in the hole to serve as channels for charging the explosive, or plastic tubes are inserted for this purpose, and - The casing tubes can be removed. As between the casing tube and the blasthole walls there is friction which increases with depth, the rock drills should be used with high rotary torque. Water is usually the flushing fluid in these cases, or compressed air with or without foam. If the upward bailing of the cuttings is insufficient with central flushing, then lateral flushing can be added. 7.2.2 ODEX Method (Overburden Drilling with Eccentric) In this method, based on the principle of underreaming, the casing tube is driven into place by vibrations from the drill and its own weight. Very little rotation is necessary. The equipment consists of an eccentric reamer bit that drills a hole with a larger diameter than the casing tube which descends as drilling advances. Once the required depth has been reached, the drill string reverses and the reamer bit becomes concentric, loosing diameter, and can then be drawn up through the casing tube. The standard drill steel is then introduced and drilling continues, Fig. 7.3. The rotary percussive rigs can be top or down-the-hole hammers. If top hammers are used, the percussion impacts are transmitted to the casing tube by means of a driving cap and shank adaptor which make the tube rotate slightly and vibrate. The flushingcan be central or lateral, Fig. 7.4.

78

Drilling und blasting of rocks

1 ii L

CHANK ADAPTER

CASING TUBE

Fig. 7.3. The ODEX method (Atlas Copco).

CASlNG TUBE

7.1. The OD Equipment (Atlas Cop-

4

5

6

Fig. 7.2. Operations in the OD System.

Table 7.1. Data

For-down-the-hole-drilis XD X 90 115 Min. inside diameter (mm) 115 90 123 152 Diameter of reamed hole (mm) Normal max hole depth in overburden (m)* 60 100 3"DTH 4"DTH Inner equipment Weld thread Weld thread Casina tube *ODEX 90 at 1.2 MPa, ODEX 115-215 at 1.8 MPa. Source: Atlas Copco.

i5' Fig. 7.4. ODEX top hammer equipment (Atlas Copco).

For top hamrners ODEX OD 140 165 215 127 72 127 72 140 165 215 76 187 212 162 108 278 96 100 40 40 40 100 100 5"DTH 6"DTH 7-8"DTH R38 R38 R38 Weld Weld thread Weld thread Thread Weld Weld X

ODEX 76

Special drilling methods and mounting Systems

Photo 7.1. ODEX drill bit. DTH

Table 7.2.

BIT TUBE

ODEX 90 115 0 X 0 0

GUlDE REAMER

Fig. 7.5. ODEX down-the-hole drilling equiprnent (Atlas Copco).

When down-the-hole hammer is used, the unit has only one wing coupling, as drill tubes are used instead of extension rods. The string of casing tubes is pulled down by means of a specially designed bit tube, and the flushing is carried out through the rotary head, Fig. 7.5. In both methods the cuttings are swept upwards through the annulus that remains between the casing and the drill steel, going out through the headstocks. The flushing fluid can be air up to a depth of 20 m, below which the addition of a foam is recommended to increase the bailing efficiency, wall stability, lower wear and increase penetration rate. This method has numerous advantages, although some important aspects that should be studied are: the sizes of the casing tubes, the flushing and the drilling System. The depth of the blastholes must be taken into account when choosing the equipment. In Table 7.1, a selection guide for both drilling methods is given. On the other hand, as to the applications for these drilling methods, aside from the one described for rock fragmentation blastholes, Table 7.2 indicates other possibilities.

140 165 X X 0 0

76

OD 127 72

Water well drilling Roadembankrnent 0 0 Underwatter drilling O O Blasthole drilling 0 0 X Anchoring X X X Injection X X X O Pros~ectine X X X O X = Suitable, 0 = Cm be used. Source: Atlas Copco.

X X X X X X

7.3 SHAFT SINKING When excavating long, large section shafts or metal structures pneumatic or hydraulic jumbos are used with three or four booms with the Same number of feeds and rock drills. When working, these rigs rest on the bottom of the shaft and are anchored to the walls with horizontal hydraulic cylinders. The central supporting column can turn 360°, and the booms, which are similar to the jumbos used for tunnelling, can vary their inclination withrespect to the vertical and lengthen themselves if they are telescopic. Once each round is drilled and charged, the rig is folded and moved to a safe position, later carrying out the mucking operation with twin valve ladles or hydraulic clam shells, as shown in Fig. 7.6. There are also platforms that have been designed to widen shafts.

80

Drilling und blasting of rocks

1. DRILLING

3. VENTILATION

2. BLASTING

4. SCALING

Fig. 7.7. Work cycle with an Alimak platform.

7.4 RAISE DRIVING 7.4.1 Alimak raise climber This excavation method for raise driving was introduced in 1957 and since then, due to its flexibility, economy and Speed, it is one of the most widely used in the world, especially in cases when there is no other access to the upper level. This equipment consists of a cage, the work platform, the driving motors, the guide rail and auxiliary elements. In Fig. 7.7, a complete work cycle is shown. The platform climbs along a pin rack welded to a guide rail and driven by either compressed air, electric or dieselhydraulic motors. The guide rail is bolted to the wall with Special Alimak design expansion bolts. The air and water pipes, which supply the necessary ventilation and water Spray, are placed on the inside of the guide rail for their protection. During work, the drillers are on a Safe platform, as it is covered and has a protective railing. Men ride up to the face safely in the cage, which is under the platform. In each work shift two drillers can advance from 2.2 to 3 m. Air engines are adequate for lengths under 200 m, the electric for up to 800 rn, and from these distances On, diesel-hydraulicengines are recornrnended. The main benefits of these rigs are: - They can be used for raises of any length and inclination. - Different lengths and geometries of the raises can be achieved by changing the platforms. It is possible to drive cross sections from 3 to 30 m2, Fig. 7.8.

- In the Same operation it is possible to change the direction and inclination of raises by using side-bent (curved) guide rails. - The length or height of the raises is practically unlirnited. Up to the moment, the longest raise driven is 1.040 m long with a 45O inclination. - It can be used as production equipment in some ore beds by applying the Alimak Raise Mining method, Fig. 7.9. - The enlarging of pilot raises for excavation of large cross section shafts can be aided by using horizontal drilling units. - The basic equipment can be used to Open various raises simultaneously. - In poor ground the platforms can be used as supports with bolting, injection, etc. - The investment is lower than with the Raise Borer System. - The labor does not have to be highly specialized. - The initial preparation of the work area is minimum. On the other hand, there are a few disadvantages: - Poor quality work environment. - 'The walls are very rough which is a problem for ventilation raises and an advantage in ore Passage outlets. - The remaining rock mass is left in poorer condition than with the Raise Boring method.

7.4.2 The Jora method This rnachine is manufactured by Atlas Copco and can

Special drilling methods und mounting Systems

Fig. 7.8. Different platforrn configurations.

PILOT HOLE

HORIZONTAL BLAST AND LOADNQ DRILLING

Fig. 7.9. Exploitation method in narrow and inclined beds.

Fig. 7.10. Jora method for vertical and inclined raises (Atlas Copco).

Photo 7.2. Work on Alimak platform.

81

82

Drilling and blasting of rocks

also be used in raising and ore outlets, whether vertical or inclined. The principal difference when compared to the previous equipment is the drilling of a pilot hole with a diameter between 75 and 100 mm through which the cable which holds the lifts is lowered. The main components are the work platform, the lift basket, the hoisting mechanism and, in inclined raises, the guide rail, Fig. 7.10. During drilling, the platform is anchored to the raise walls by a system of telescopic booms. The main inconvenience of this method, against the former, is the pilot hole drilling, as the maximum raise height will depend upon the accuracy of its alignment. Its practical and economical field of application is between 30 and 100 m. For each round it is necessary to remove the cage from the hoisting cable, because, if not, the cable would be damaged during blasting. The central blasthole serves as expansion space for parallel cuts, obtaining advances per round of 3 to 4 m, and also as an entrance for fresh air. 7.4.3 Raise Boring (Full-face)method This method, which has become increasingly popular over the past 20 years, consists of the cutting or reaming of the rock with mechanical equipment. Its main advantages are: - Excellent personnel safety and good work conditions. - Higher productivity than in conventional methods of rock breakage with explosives. - Smooth walls, with minimum losses due to air friction in the ventilation circuits. - Overbreak does not exist. - High advance output. - Possibility of drilling inclined raises although it is better adapted to vertical ones. The most important disadvantages are: - Very high investment. - High excavation costper lineal meter. - Lack of flexibility, as the sizes and shapes of the raises cannot be varied nor the direction changed. - Gives problems in rocks that are in poor condition. - Requires highly specialized personnel and previous preparations of the work area. At the moment there are over 300 rigs in operaton around the world, with the following subsystems of Raise Boring: standard, reversible and blind hole raising. a) Standard raise boring This is the most widely used system and consists of setting up the equipment on the upper of the two levels to be intercomected, or even outside the mine, so that a pilot hole can be drilled down to a previously opened level. Aftenvards, the reamer head is attached to the drill string and the raise is drilled upwards to the rig. b) Reversible raise boring The Same operations are carried out as before, with the difference of placing the equipment on the lower level and inverting the pilot hole and raising execution, which

are ascending and descending, respectively. C) Blind hole raise boring Once the rig has been erected on the lower level, the drilling is done upwards in full section, without the pilot hole, as there is no access to a second level. The basic elements to cany out the work, apart from the rig itself which exerts the rotation and feed force from its point of installation are, for the blasthole, the tricone bit, the roller stabilizers and the drill rods; and for the reaming, the axis, base, Cutters and their sockets, Fig. 7.12. The heads can be integral, segmented or extensible. The first are used for diameters from 1 to 3 m with pilot holes of 200 to 250 mm, the segmented for raise diameters that are between 1.5 and 3 m, and the Same pilot holes as before, and, lastly, the extensible heads are for sections that range from 2 to 6.3 m with pilot holes up to 350 m. The power for the equipment is usually over 600 kW with rotary speed, rotary torque and thrust loads on the rock having values that oscillate between: 15 and 30 r.p.m., 150 and 820 kNm and 4 and 12.5 MN, respectively.

CHAPTER 14

Initiation and priming systems

14.1 INTRODUCTION ries and emulsions in rock breakage has brought about an important development of initiation and priming techniques. This is due to, on one hand, the relative insensitivity of these compounds and, on the other hand, a desire to obtain maximum performance from the energy released by the explosives. The detonation process requires initiation energy so that it can develop and majntain stable conditions. The most frequent tenninology used in initiation is: Primer: High strength, sensitive explosive used to initiate the main column in the blasthole. They are cap and detonating cord sensitive, including ones of low core load. Booster. Powerful explosive charge with no initiation accessory that has two functions: I. Complete the initiation work of the pnmer in the explosive column, and 2. Create zones of high energy release along the length of the column. Since the seventies, various theories have been devel.oped on initiaTion, ~~~~~~~~~~~i~creätIng-sömc confusion amongst operetors. In the following paragraphs present day knowledge is discussed and a series of practical recommendations are given in order to obtain maximum yield from the explosives.

14.2 PRIMING AND BOOSTERING BULK ANFO-TYPE BLASTING AGENTS When blastholes have a length of under 10 in and are kept dry, initiation of ANFO can be carried out safely with only one bottom primer. However, if the bench is very high and the holes pass through zones of different lithological charactenstics and fracture frequency, water can appear and there is the possibility of separation of the explosive column during charging, due to dnll cuttings and loose rock that can fall into the blasthole. In these cases, multiple priming is recommended with an initiator every 4 or 5 m, which, although slightly more costly, would eliminate the risk of incomplete detonation in any of the holes.

14.2.1 Initiation by aprimer In the priming of ANFO, the efficiency of a primer is detined by its detonation pressure, dimensions and -shape. The higher the detonation pressure PD, the greater its initiating ability. The effect of the 'PD' on the detonation velocity VD of ANFO is shown in Fig. 14.1. As can be observed, with detonation pressure that is less than a certain value, a partial reduction in VD is produced, and the contrary is true when PD is above the mentioned value. Following the Same procedure, the effect of the diarneter of the pnmer has alio been studied, Fig. 14.2. Therefore, the conditions that a primer should comply with in order to eliminate low VD zones in the ANFO are: the highest possible detonation pressure and a diameter above 213 that of the charge, - approximately. -The length of the primer is also imkrtant, as the primer itself is initiated by a blasting cap or detonating cord and they have a run-up distance in the VD. For exarnple, for a slurry to reach the detonation velocity regime it usually has a characteristic run-up distance of 3 to 6 times that of the charge. In Table 14.1, the minimum dimensions of pentolite boosters for different blasthole diameters are shown. As to the shape of the primers, the latest investigations have demonstrated that it has a significative effect upon performance, which means that it is a field Open to study. Although it is generally believed that the energy produced by ANFO increases with the transient velocity of the charge, this concept is false because the total energy releasedby an explosive is constant and independent of that velocity. An increase in VD brings about an increase in Strain Energy ET, thus lowering that of the gases EB -butthesum of-both remains constant. The relationship ETIEB is lower in zones of VD reduction and higher when the primer produces a raise in VD. The increase in Strain Energy is only beneficial for fragmentation when hard, fragile and massive rocks are being blasted. In sedimentary bedding planes or highly fissured rocks, the bubble energy should be increased in order to take advantage of the fractures and planes of weakness and obtain adequate rock displacement. Finally, it has been found that the VD steady-state in ANFO is independent of type, weight and shape of the primers (Junk, 1972).

Initiation und priming systems

137

DETONATMG CORD

-

Y

C ~ V E

f

DETONATION PPESSURE OF PRIMER !MP!l

24.000

b 0

$! 7W 4.000-

Fig. 14.3. Conventional primers. STEADY-STATE VOD

3CGU-

P M E R MAMETER- W O MAMETER- 7Omi

2000ASBESTOS TVBE C W N E K N T

K M

200

3m

I

500

400

Fig. 14.4. Primer cartridges with Detaprime primer (Du Pont)

MSTANCE FROM WTlATlON P W T (mm)

Fig. 14.1. Effect of primer's detonation pressure on initial VD of ANFO (Junk, 1972)

14.2.2 Types of primers und boosters

At present time, the most used primers are those made of pentolite as they have numerous advantages, such as: - Insensitivity to impacts and frictions. - High physical strength, therefore dimensionally stable. - They have one or two longitudinal tunnels through which the detonating cord can be threaded and re-ained, or into which a detonator can be inserted, Fig. 14.3. - They are small, compact and easy to handle, and they do not have adverse physiological effects. - They are not alterated by age. ~ e s l u r r i e s a n d e m d s ~ h a ~ e e a ~ ive can be used as primers or primer cartridges, with the advantage that they occupy the entire cross-section of the blasthole and are very efficient. When these explosives require a primer for initiation, they can only be used as boosters (secondary primers) unless special accessories are used such as Detaprime by Du Pont, Fig. 14.4.

STEADY-STATE VOO

M

O

DULIETER- 7

h

ASBESTOS TVBE C O H - N K N T

14.2.3 Initiation by downline P -

iia

k 3 .

350

Sb0

Sb0

MSTANCE FROM MTIATIOW PONT (mnl

Fig. 14.2. Effect of primer's diameter on initial VD of ANFO (Junk, 1972).

Table 14.1 Blasthole diameter (mm) -50 50-1 15 115-160 160-320

Size of pentolite booster (Mass X diameter X length) 3 0 g x 2 3 m m x 52mm 60gx28mmx70mm 150g X 40mm X 79mm 400 e X 80 mm X 59 mm

W e n a d e t o n a t i i ~ i i n s u f f i c i e n core t loadto initiate a charge of ANFO, the detonation of said cord creates a pressure front that expands in cylindrical shape and a chimney of gas inside the ANFO. If the crosssection of the blasthole is small then the lateral pressure can compress and desensitize the explosive. According to Hagan, in blastholes of 75 to 125 mm, a downline with core loads of 10 glm that lies along or near the axes densifies and desensitizes at least some of the ANFO. If the downline is along the blasthole wall, there is very little risk of desensitization with a properly rnixed ANFO, but it is possible in blastholes with water where the explosive is alterated.

138

Drilling und blasting of rocks

1 ANFO DETONATION VELOCITY(VERY LOW)

combustion or deflagration of part of the explosive charge.

3/8 RADNS OF TUE CHARGE

\

14.2.4 Initiation by primer and detonating Cord REACTION FRONT. C

o

+ Z

BLASTHOLE WALL

W

o

-

1B

I

G -

U

DETONATION V E L ~ ~ lrnlsl l ~ y

I

W t- -

4000

DETONATING CORD

4200

DETONATION PRESSURE (MP4

When the detonating cord does not completely initiate ANFO charges, the following Situations may appear: - In blastholes with diameters larger than 200 rnrn and cords with core loads under 10 g/m, the detonation of the cord has an insignificant effect and the ANFO is only affected by the primer. - When a cord of 10 g/m lies along or near the axis of a 75 to 125 mm blasthole, the detonation of the downline, as indicated before, compresses and desesitized the ANFQ 0 . . are not dose to the primer. When this occurs, the fraction of ANFO that detonates decreases as the detonation wave propagates into the ANFO. In practice, above all in angled blastholes, as the downline lies along the blasthole wall and not the charge axis, this situation is not produced. If the downline side-initiates the charges, the primers have little influence on the effect of the ANFO detonation, unless they are very close together.

'"Mo 1300 500

1000

RACMAL DISTANCE (-1

Fig. 14.5. Detonation effect of a downline lying along the axis of a blasthole upon the VD of ANFO.

14.3 PRIMING CARTRIDGE ANFO TYPE BLASTING AGENTS If the covering of an ANFO charge has been damaged, permitting its contents to be alterated by water, the propagation of the detonation can be interrupted unless several primers are placed along the colurnn of cartriged explos-

DOWNLME

0

2

4

6

8

-

X)

gIrn

ALL CARTROGES EXCEPT TWS ONE OETONATE

Fig. 14.6. Energy losses provoked by the downline in ANFO columns (K0nya-&Walter,-1-9-~0>.-

If the downline side-initiates the ANFO, the initial VD is slower and incieases gradually while the detonation wave front passes through the section of the explosive colurnn. With axial initiation an increase in Bubble Energy is produced at expense of the Strain Energy, which can be quite advantageous in soft and highly fissured rocks, and when a controlled trajectory blast is desired with maximum displacement. On the other hand, in Fig. 14.6, the energy losses are shown for ANFO when it suffers damagefrom the downline, owing to the pre~0mpreSSi0nbrought On by the

al I N A o E o U A T E

b) S A T I S F A C T o R Y

Fig. 14.7. Inadequate and satisfactory pnming for cartridged loosepoured ANFO in wet Blastholes (Hagan, 1985).

Initiation und priming Systems ives, Fig. 14.7, and there is certainty that they are in contact. In blastholes with 150 m diameters, pnmers of 125 g weight are recommended, and in larger holes of 500 g. When ANFO has been pressure-packed in cartndges at the factory, the densities reached (1.1 g/cm3) are higher than when the explosive is loose-poured (0.8 g/cm3). Thus, although water is present in the blastholes, it is more probable that the cartridges will come into contact with the pnmers and, apart from this, the wrappings are usually more water and abrasion resistant, requiring less number of primers than in the previous cases. 144 P R T 4 ? Y AND EMULSION BLASTING AGENTS Generally speaking, slumes and emulsions are less sensitive to initiation than ANFO. These blasting agents tend to be more easily compressed and can be desensitized by cord detonation inside the explosive column. Less porosity and the presence of a liquid phase reduce the atenuation of the shock wave produced by the detonating cord and prolong the action of the high pressured gases after the shock wave passes. In order to minimize the risk of cut-offs originated by the detonating cord, in large diarneter blastholes (150 to 381 mm) a multiple pnming system is used. The number of equidistant boosters n, inside a blasthole of D diameter with a column length L is deterrnined, according to Hagan, with the following equation:

Photo 14.1.Placing a booster to initiate a column of poured slurry.

In a 20 m high bench with a diameter of 229 mm, a stemming of 5.70 m and a subdcilling of 1.80 m, the number of cast pnmers required will be:

In order to be certain that the boosters are correctly placed, a weight or heavy rock should be put on the end of the detonating cord to tense the line, and the first boosters should be placed at the calculated depth. When the density of the multiple pnmers is not more -thrthat-of-t~ti~igagentsused-0-that-f-tk mud itself that can exist in the hole, there could be a nsk of inadequate positioning of the pnmers as a consequence of their flotation or being pushed upwards. In these cases it is recomrnended that the downline be prepared for multiple prirning outside the hole, threading twice each of the pnmers, Fig. 14.8.

Fig. 14.8. Recommended priming system for pumped watergel and emulsion changes (Hagan, 1985).

140

Drilling und blasting of rocks

In some place the accessories are lowered with clips in the shape of tweezers that avoid their rising towards the surface. 14.5 PRIMING CARTRIDGED WATERGEL AND EMULSION BLASTING AGENTS Watergels and emulsions have high water resistance, which allows primers to be widely spaced within charges if it were not for the potential problem of desensitization by the downline. The multiple initiation system is recommended, as shown in Fig. 14.9. In blastholes with diameters under 150 mm, the recommended weights of the 13< n

should be increased to 500. As with pourable slurries and emulsions, if two lines of detonating cord are used in the blasthole, only one of these should reach the top of the column to avoid nsk of desensitization.

PACKAGED WATE OR EMULSION

14.6 LOCATION OF PRIMERS 14.6.1 Bottom priming Bottom priming gives maximum use of explosive energy, increasing fragmentation and displacement of the rock with a minimum of flyrock. This is due to the fact that the detonation Progress towards the stemming while the gases of the explosion are entirely confined within the rock mass, until the stemrning material is ejected and allows their escape. This time of confinement is usually around 3 to 4 ms, according to detonation velocity and length of column. The subsequent fall of pressure through escape on bench toe level takes place much later, Fig. 4 4 e ~ a ~as well . e as~a lower vibration level due to shock wave propagation towards the top part of the bench. In bench blasts, as the breakage at floor level is extremely important, the priming should be such as to produce maximum strain at that point. If the priming takes place at floor level and not at the bottom of the blasthole, an increase in peak strain of 37% is obtained (Staxiield, 1966) due to simultaneous detonation of the two parts of the charge that are equidistant from that point, Fig. 14.11. In the Same manner, a 37%greater peak strain can be generated in any strong bed if the primer is placed centrally within the bed. In blastholes without subdrilling, the bottom primer should be located as low as possible but never upon the drill cuttings or in mud, recommending that there be a distance of approximately 4D above the effective base. Apart from the cited advantages, bottom priming has much less chance of cut-offs than top or multiple priming. In Fig. 14.12, two 270 mrn diameter and 20 m long blastholes are shown as an example, where the spacing between explosive columns and sternming height is 7 m. The detonation velocities are 70OCCiKäKand mis in the cord and in the ANFO, respectively, and between both blastholes there is a milisecond delay interval of 25 ms. As blasting failures are produced by cut-off of the cord through ground movement, the larger the difference in

B

W

0

O

T INITIATION

I-

Q W

a

3

V) V)

t'

W

CAST PRIMER

h

(VENTING BEGINS AT COLLAR)

Y1

nN I

I I

VENTlNG REACHES TOE

(RAPID DROP DUE T 0 VENTlNG BEHIND DETONATION WAVE)

\ r

TIME

Fig. 14.9. Priming system for packaged watergel or emulsion blasting agents (Hagan, 1985).

Fig. 14.10. Effect of the position of the pnmer upon the pressure-time profile in the blasthole.

Initiation und priming Systems /: RESULTANT STRAIN r

\PULSE AT POHT P

I

I I

:

RESULTANT STRAIN PULSE AT POINT P

,i

I I

--

TIME

TIME

Fig. 14.11. Strain pulses at point P for charges pnmed (a) at their bases and (b) at bench floor level (Hagan, 1974).

A bottom priming pattern called safety is the one indicated in Fig. 14.13. In this case, if the low core load cord of the detonator N failedfor some reason, at the end of a time equal to the nominal intewal of the series of milisecond delay the top primer would initiate, producing the detonation of the

iai

(b)

Fig. 14.12. The reduced probability of cut-offs where charges arebottom pnmed.

Up until a short time ago, Operators were not interested in bottom priming because the use of detonators inside the blastholes had certain risks, but nowadays nonelectric accessories are available such as low core load downlines and those of very low energy that offer a wide field of possibilities for this initiation System.

14.6.2 Toppriming

Fig. 14.13. Safety Pattern with bottom pnming.

In bench blasts where top priming is used, a high strain wave is propagated towards the subdrilling Zone where, of course, its energy is dissipated and therefore wasted. In blasting overburden for a dragline, this strain energy can be more usefully employed in fragmenting the rock between the bottom of the blasthole and the top of the coal, but not the coal itself, especially if there is a strong bed irnrnediately above the coal andlor a well defined Zone between the waste and the ore. If peak strain is to be maximized along the rock that surrounds the stemming column, the top primer should be atleastl~M-af-the-hurden-be1~~_thetop-af-the~ (Starlield, 1966). If the explosive is initiated with a primer at the highest point, the superposition of the strains generated by adjacent charge elements gives a lower result in any point of the stemming, Fig. 14.14. The elimination of premature escape of the gases into the atmosphere, with adequate stemming height, improves fragmentation and rock displacement by Bubble Energy. For elongated charges, the efficiency of the stemming with top priming is less because the inerte stemming material, as well as the rock itself at the top, start moving some miliseconds before detonation of the lower part of the explosive. The fall of the presure of the gases is greater in long explosive columns with low

142

Drilling and blasting of rocks

RESULTANT STRAIN PULSE AT POINT P

STRAIN PULSES

's.

-

0 INITIATION POINT

detonation velocity and insufficient sternming, or small burden size. When the detonation reaches bench floor level, the pressure of the gases falls rapidly from its highest value, due to their escape towards lower pressure zones. This phenomenon gives poor fragmentation in the bottom of the blasthole and especially a reduced displacement of the lower rock.

TIME

/\

RES~LTANT

14.6.3 Multi-pointpriming If various primers are used, they should be located in positions such as to produce collision of the detonation

OIN(TIATIMI PciNT

TIME

Fig. 14.14. Strain pulses on burden alongside stemming column for charges primed at and somewhat below their uppermost point.

(Starfield, 1966). When the charges do not offer loss of velocity, fragmentation is improved in multi-point prirning through strain energy reinforcement. 14.6.4 Continuous side iniriation When the explosive columns are continuously side initiated by a detonating cord (downline), the detonation velocities are relatively lower than the regime. Thus, side initiation is more effective in highly fissurized soft rock

il

a) ELECTRIC

. .

+ig~l4-l-5;Applieationssoffmu1

p-it-

b) ELECTRIC

.. I . L-,

.. . . . ....... ... ... . .... .... . .. ..

.

.

C) WlTH DETONATING CORD

CORRECT

INCORRECT

Fig. 14.16. Cartridge priming with an electnc detonator.

Fig. 14.17. Priming cartridges and blastholes.

P P

Initiation andpriming Systems

143

formations where more bubble energy is preferible. The theory that continuous side initiation significantly increases the VOD of ANFO cannot be maintained, as has been demonstrated in practice.

C) Detonating cord. Contour blasthole or in soft rock, with decking to lower the total charge along the length of the column.

14.7 PRIMING CONVENTIONAL CARTRIDGED EXPLOSIVES

REFERENCES

The priming of cartridges consists of inserting a detonator or the end of a detonating cord in the cartridge to activate or initiate the detonation of the main charge in the blasthole. To maximize the use of the shock effect produced by

Anonymous: Puuled about primers for large-diameter ANFO charges? Here's some help to end the mystery. Coal Age. August, 1976. Anonymous:Safe und eficient initiation of explosives. Downline, ICI, NO.7, 10, 1988- 1990. Condon, J. L. & J. J. Snodgmss: Effects of primer type und borehole diamerer on ANFO deronation velociries. Min. Cong. J. June,

t h ~

r

cartridge and to the axis of the explosive column, Fig. 14.16. Any primer is an activated explosive ready to detonate under different stimulations, fire, strikes, etc., which means that they must be handled with extreme care, in transportation as well as when being placed in the blastholes. They should never be directly tamped. For priming cartridges and blastholes with electric detonators and detonating cords, the Patterns given in Fig. 14.17 should be followed. The procedures for priming blastholes are as follows: a) With instantaneous electric detonators. For isolated or simultaneous blastholes in rock of low to medium strength. Wet blastholes. b) With electric delay detonator. Bottom priming for simultaneous blastholes or without a face, without water and in medium to hard type rock. With this System fragmentation is improved.

1 Y14.

_

G ~ . ~ r n o ~ ~ ~ l ~ n sifenvrac. Annales des Mines de Belgique, September, 1977. Hagan, T. N. & C. Rashleigh: Initiating systems for underground mass Jiring using large diameter blastholes. The Aus. IMM. 1978. Hagan, T.N.: Optimum priming systems for ammonium nitrate fuel-oil type explosives. The Aus. IMM.July, 1974. Hagan, T.N.: Optimum initiating, priming und boostering Systems. AME 1985. Junk, N.M.: Overburden blasting takes on new dimensions. Coal Age, January, 1972. Konya, C.J.: Initiierungstechnick für Lange Bohrlochladungen. 1974. Konya, C.J. & E.J. Walter: Surface Blast Design. Prentice Hall, 1990. Neil, I.A. & A.C. Torrance: The injuence of primer size on explosive perfonnance. Explosives in Mining Workshop. The Australasian Institute of Mining and Metallurgy. 1988. Smith, N.S.: An investigation of the effects of explosive primer location on rock fragmentation und ground vibration. University of Missoun-Rolla. 1980. Thiard, R. & A. Blanchier: Evolution des systemes d'Amorcage. Industrie Minerale Les Techniques. Fevner, 1984

u

e

~

CHAPTER 15

Mechanized systems for charging and dewatering blastholes

15.1 INTRODUCTION

man team, oscillates between 500 and 1.000 kilos per shift, depending upon the cartridge sizes. ' AlOng witn tne aeveiopment of 11 Tat>te 15.1, Par~ e w a t e - ~ ~ W h 0 ~ ~ ~ ~ ~ ~ j e c t e d - t 0~ rim d gee c d ahs eaf na rid izf f~e r e n t blasthole diameters are tion, driven by the numerous advantagesthat this offers to indicated. blasting as described below: The chargers, Fig. 15.1, consist of a tubular chamber - Better use of the volume drilled in rock by being with a flip valve at each end, a charging funnel through able to fill the entire blasthole with the explosive and put which the cartrigdes are introduced, a plastic loading it into contact with the blasthole walls. hose and an ensemble of pressure-release pneumatic - Increase in charge density inside the blastholes. valves. - The possibility of forming selective charges by The pressurized air reaches the charger at a maximum varying densities and specific energies along the column pressure of around 1 MPa and with a senes of regulators, length. it is reduced to 0.3 MPa. There is also a safety valve. - The use of bulk or loose-poured explosives which The loading hoses are made of black anti-static plastic, are less costly than cartridged. although in certain special operations metal tubes can be - Less charging time. used. The diameters of these hoses is in function with the - Less personnel required for the chargng operation. cartridge sizes, and its length should not exceed 50 m. At - The possibility of using ANFO, of lower cost than the end of the hose where the explosive emerges there are watergels and emulsions, after dewatering the blast-oles. Cutter blades which slit the cartridges Open, and the force - Better control over explosives and their supply. of ejection drives them to the bottom of the blasthole, All these advantages lower drilling and blasting costs compacting and completely filling it. as the dnlling Patterns can be more Open and the charging The tamping of these units is done manually, unless a tirnes reduced. Robot, which can be attached to the charger, is used, Photo 15.1, which substitutes the Operator in this tedious and tiring work, especially in long blastholes, and allows 15.2 MECHANIZED BLASTHOLE CHARGING a more regular and unitorm charging. SYSTEMS This complement consists of a double-action pneumatic cylinder with a piston that is joined to a pneumatic The mechanized charging systems are classified in two pusher, a front spacer tube and a support that holds the large groups, depending upon whether they are merely aparatus in place against the blasthole. The cylinder has charging instruments or integral systems of manufacture an oscillating movement hat is transmitted by the pusher and charge. to the loading hose which, upon return, allows another In the following, the present day methods for the most cartridge to emerge. The degrees of stemming achieved important types of explosives are described: with the forward movements of the hoses vary between Gartridged slurriesandgelatindynamites--1.4aCcl16. - ANFO and its derivatives (ALANFO and Heavy The use of these chargers is especially interesting ANFO). when the rounds are made up of horizontal blastholes or - Bulk slurries and emulsions. long, inclined upholes. The only limitations are based upon the sensitivity to impact or friction of the cartridges, thus in some instances the velocity has to be drastically 15.2.1 Cartridged explosives reduced. Owing to the recent tendency towards using large Pneumatic cartridge charging equipment was developed diameter blastholes. above 100 mm in underground rnin-in Sweden during the decade of the fifties. These units ing the conventional chargers have become useless. allow the charging of blastholes with diameters between However, the largest chargers on the market with hose 35 and 100 mm, obtaining a 15 to 20% increase in centralizers have been used. This way, the cartridges of packing densities when compared to manual tamping, or emulsion or slurry make impact in the center of the even up to 30% if a robot is used. column, reducing the risk of dislodging or falling back of The charging capacities for these Systems, with a twoT

-

\

P -

Mechanized systemsfor churging und dewatering blastholes

k WHEEL

SWITCHER VALVE

TRIP00 MOUNT

FLAP VALVE

Fig. 15.1. Pneumatic charger.

Photo 15.1. Robot charger.

Fig. 15.2. The Half-Pusher technique (Nitro-Nobel).

Table 15.1. Drill bit diameter minlmax (mm) 38-45 40-5 1 [email protected]=

5 1 -76 64- 102

Cartridge diameter (mm)

Hose dimensions (mm) Inside diam. Outside diam.

22 25 29 32 38-40

23.2 27 30 33.5 41

30 34 38 41.5 51

the explosive in upholes. It has also been demonstrated, in experimental tests, that a standoff distance must be maintained between the end of the loading hose and the explosive column. The optimum is 45 cm for 165 mm blastholes, and 60 cm for those of 100 mrn diameter. In order to reduce friction of the cartridges against the inside walls of the hose, reaching high impact energy, water lubrication is recommended.

At present, Nitro-Nobel A. B is developing new equipment for charging upholes with diameters of up to 165 mrn. Of the two systems that are in experimental phase, Charge-Pusher and Half-Pusher, Fig. 15.2 shows the working principle of the latter. W i t h o u t going into detail, this device has a cfimbing mechanism with which, by upward movements, it pushes the charge ahead to the desired position. In each pushing movement an expansion element presses against the walls of the blasthole, retaining the climber in place while the piston rod forces the cartridge upwards which is held in place by a spider-like piece. 15.2.2 ANFO type explosives Charging systems Depending upon the capacities of the containers, the charging systems are classified as follows: - Pneumatic chargers - Charging trucks (Mix-Load and Mix-Pump) The first System is mainly used in underground operations and small surface mines, whereas the second is exclusively for large mines and surface operations. Pneumatic churgers. In these chargers, Fig. 15.3, the explosive is propelled through an antistatic, semiconductive hose by air pressure contained in a metal vessel or pot that is hermetically closed. The design

146

Drilling and blasting of rocks

Fig. 15.3. Pneumatic charger.

SEMl'33tJWIiVC ANFO PRESSVRE VESSEL

AIR HOSE

SEMlCONDUCTlVE PATH T 0 GROVHD

Fig. 15.4. Control of static energy in pneumatic loading.

consists in a funnel-shaped bottom, a cylinder-shaped body and another cone-like shaped of stainless steel that is corrosion resistant. The capacity of these chargers varies from 100 to 750 liters, and when transported they are mounted individually on wheels or upon a vehicle, Photo 15.2. For the latter, the air is pressurized by compressor activated by the motor of the vehicle, which also has recipients of the explosive for the automatic recharging of the vessels, or a prepared space for ANFO sack Storage when the refilling is done by hand. When upholes are loaded in underground operations, the pressure of the vessel must be combined with the Venturi effect created by blowing pressurized air through i I L t h e 4 . ~ ü o ~ n o f t hblasthole e so that they will stick and not fall out. The working pressures go from 0.15 to 0.3 MPa in the vessels, and from 0.2 to 0.35 MPa in the injectors. This type of charging equipment is recommended for blastholes with diameters between 26 and 150 mm, unless they are upholes, where the diameters are limited to 100 mm. The yield of the chargers depends upon the interior diameters of the hoses and their length, which should never be over 50 m, and the inclination of the boreholes. The maximum charging capacity oscillates between 2 and 4 tons. Apart from the equipment already described, there are lighter models on the market which can be transported by the Operator himself, with a capacity of from 25 to 40 kg of ANFO. These are used in underground operations to charge blastholes of 28 to 65 mm in diameter and basically consist of small vessels of polyethylene plastic with Straps for their transport. They work with air pressures that go from 0.4 to 0.8 MPa and the charging capacity reaches 7 kglmin. A very importantaSpect,from a the elimination of the large amount of static electricity that is produced. In order to do this, it is necessary to properly connect the loading hose, made of semiconductive material, and properly ground the whole equipment, Fig. 15.4. In the particular case of large diameter upholes, the traditional method of pneumatic loading, consisting of a lower closing plug and a charging tube has been progressi v e l y s y b s t i h t e d by the direct method repre=ed in Fig. 15.5, where the pressure given to the A G ~which , varies between 0.14 and 0.2 MPa, is sufficient to make the ANFO prills stick to the bottom of the holes giving charge densities of 0.95 to 1 g/cm3. It is of vital importance in this System to have a correct design of the centralizer in the charging tube. If there is water present in the blastholes, the loading can be done after placing a plastic liner. The primers that are connected to downlines or to the detonator are usually placed in the bottom of the blastholes by means of a retainer with help of the loading hose itself. P

Fig. 15.5.Pneumatic loading of ANFO in upholes. P

Photo 15.2.ANFO loader on vehicle.

~~~~~~~~~~~~--

Mechanized systemsfor charging und dewatering blastholes

147

STER/DETONATOR

CENTRALIZER

CONWCTIVE HOSE

"270-340

Fig. 15.7. Types of bulk loading tmcks, (a) pneumatic delivery, (b, C, and d) auger delivery.

KPa AR

Fig. 15.6. Placing the primer in the bottom o f a large diameter uphole -hreI-m&mg.

Photo 15.3. Bulk loading truck with helicodial auger (Courtesy of Amennd-MacKissic, Inc). -

-

Bulk loading trucks. The types of tank irucks used for charging granular ANFO-type explosives are: - Pneumatic delivery System - Auger delivery, Fig. 15.7. The first type of iruck is the most used in Spain at the moment, and it consists of a closed aluminum deposit (AN hopper) with top and bottom V-shaped charge openings to aid in the descent of the explosive towards the conveyer or feed auger which conveys the ANFO for mixing and should be protected by an inverted V-trough which keeps the conveyer from holding the whole weight of the charge.

On the outside part of the deposit is a mechanism which regulates the height of the explosive on the feed auger, as well as a tachometer for the roller motor permittimg variations in the speed, dosifying the supply of the rotary air-lock feeder which discharges the explosive by air pressure through an antistatic hose to the inside of the blasthole. The rotary air-lock feeder is composed of a drum wheel with plastic blades which also keeps the pressured air out of the ANFO bin. The engine of the vehicle is connected to the hydraulic pumps that activate the feed auger and the rotary air-lock

148

Drilling and blasting of rocks

feeder, as well as the air compressor. The loading hose is located in the back of the truck and is about 10 m in length which permits the charging of 3 or 4 blastholes from the Same position when the truck is driven between two rows. The problems with this System are the segregation of the aluminum when ALANFO is used, and the impossibility of loading Heavy ANFO. The second model of truck has, at the bottom of the deposit and lengthwise, a helicoid auger that is also protected by deflecting plates. This auger feeds another vertical one which then delivers the product to a third subhorizontal, pivoting boom auger. This last auger has a length of between 5 and 6 b l a s t h o l e s g h a flexible hose that are 6 or 7 m from the back part of the truck, Photo 15.3. When the truck is between two rows of large-diarneter blastholes, the number of these that can be loaded from one position is limited to one or two. The loading flow of these tmcks varies between 150 and 750 kglmin. A more simple version of this truck is one called Side Auger Discharge System. In the back of the vehicle there is an inclined discharge auger that delivers the explosive to another swiveling boom auger of approximately 3 m in

FUEL OIL TANK

ALUMINUM TANK

AN HOPPER

Fig. 15.8. Deposits on a rnix-load tmck.

- r o t a t i o n ~ w e l l M e Y a t i o nnr Inwenng.gkpxu2meansoL small hand winch. During transit the auger rests in a cradle along the lower left side of the body. During the last few years, there has been a progressive tendency towards trucks having an auger delivery system, owing to the following advantages: - The possibility of charging Heavy ANFO as well as ANFO and ALANFO. - Greater discharge rates, and - Lower loss of ammonium nitrate and distillate vapor around the collars of blastholes.

Photo 15.4. Bowl-type rnix-load tmck.

Mix and load systems Conventional Mix-Load truck. These have a hopper of ammonium nitrate and a tank of fuel oil. If ALANFO or Heavy ANFO is required, there is also a third tank with the emulsion blasting agent or aluminum powder, Fig. 15.8. Moments before loading the blastholes, the two or three components are mixed in the truck, in the desired proportions, and the resulting explosive is then delivered by either of the two systems described previously. The hopper of ammonium-s simi-i already mentioned. In the pneumatic discharge units the fuel is added with the air whereas in those of auger delivery, the fuel oil and other additives are delivered through the vertical auger.

Photo 15.5. ANFO cartridges (Arnerind Mackissic, Inc.).

Bowl-Qpe Mix-Load truck. These trucks are similar to concrete trucks with slight modifications to make them safe for mixing and charging bulk blasting agents. The ~=ompomenLs~ae~p~kced~in_the bowl in adequate provortions and are Gxed accordingly before being discharged. The explosive obtained with these units is characterized by: - Smaller errors in the overall chemical composition - More uniform blending and, therefore, - The energy outputs closely resembles those achieved in laboratories. When compared with conventional mix-load trucks, bowl-type trucks offer the following advantages: - Lower capital cost (about 30%). - Hinher discharge rates, close to 2.000 kglmin. (this is 2.5 to-4 times those obtained by conventionil trucks).

Mechanized systems for charging and dewatering blastholes

-

149

On the other hand, bowl-type tmcks have the following disadvantages: - The truck must be positioned very close to the blasthole for loading, losing time in changing posi-ions. - Only one type of explosive can be charged each time, eliminating the possibility of selective charg-ng. - The quantity of explosive mixed must be exactly the arnount required in order to avoid excess, which must be removed. - The capacity of these tmcks (approxirnately 1 1.5 t) is 25% less than conventional trucks.

which the products are continuously rnixed and are pumped directly into the blastholes through a Aexible hose. This system is quite versatil, as it allows variation in the cornpositions before charging begins. The vehicles have a capacity of between 5 and 15 t and are designed to produce at least two types of explosives, one for bottom charging and one for the column charge. These mobile plants are very safe as the ingredients they carry are not explosive alone and they are mixed only instants before charging. On the other hand, quality control is more difficult than with pump trucks.

Cartridged ANFO When drilling 76 to 190 mm diarneter blastholes and

a) Slurry mix-pump truck These trucks transport the following ingredients: A A oxidizers such as sodiurn nitrate. calciurn nitrate. etc., thickened by gurns. This solution is prepared at a static plant near the minesite. - Ammonium nitrate in pourous prill form (optional). - Liquid fuel-oil or a mixture of solid fuels that are called pre-mixes, with a percentage of aluminum as high as the required weight strength of the watergel. - A cross-linking solution and a gassing agent. The ingredients are put into the tmck's mixing funnel from which they pumped into the blasthole through a flexible hose. The charging rates vary between 80 and 350 kglmin. Thickening and cross-linking starts as soon as the products are mixed so that the watergel is highly viscous by the time it enters the blasthole. The gelling can be controlled by adjusting the crosslinking solution. When the gelling ocurrs too rapidly, purnping difficulties appear, whereas if the gelling time is too long the s1un-y can become diluted or even dissolved before its viscosity permits it to resist the effect of the water present in the blastholes. The loading hose Operator should be certain that there 1s a mnimum agitation oI the explosive

-edr.t-t The packaging of ANFO is done with simple equiprnent consisting in a hopper, a one meter long tube, a feed auger and a piston system that works with pressurized air to achieve the required charge density that can reach 1.1 g/cm3. The yield is around 3 cartridges per minute. 15.2.3 Slurry and emulsion-type explosives Pump trucksfor slurries and emulsions. These tmcks are used for pumping explosives such as slumes and emulsions, and mixtures of emulsions with ANFO, whenever the solid phase of these mixtures is not rnore than 35%, because then the product would no longer be purnpable. The physical consistency of these blasting agents is so high that for their pumping the injection of a liquid lubricant along the inside wall of the loading hose is usually necessary to reduce friction and facilitate easy, rapid purnping. It is important to use the lowest feasible arnount of lubricant, and that it contribute to enhancing the effective explosion energy whenever possible.

M i x - p u m p t r u c E A mix-pump truck is a mobilF$plantin

Photo 15.6. Static plant and pump tmck (Nitro Nobel).

Drilling und blasting of rocks HOPPER THERMIC

DELIVERY AUGER THAT CAN BE REGVLATED

CONTROL PANNEL

ALWINUM FEEDER MlXlNG HOPPER

Fig. 15.9.Mix-pump tmck (Ireco Inc.).

when it enters into contact with the water. The proportion of gassing agent should be adjusted to give the sluny the required sensitivity and bulk strength. If the gassing is insufficient, a density in the botton of the column will be produced, reducing the optimum yield of the explosive. On the other hand, excessive gassing can reduce the density of the explosive making it float in the water. The flow of gassing solution can be controlled and can give slumes with a wide range of densities. This possibility is the basis of the technique called Powerdecking. b) MLx-pump trucksfor charging emulsions und mixtures of emulsion/dty phase Inlhis type of trucks, a continuous mixture of a saturated solution of oxidizers is proquced, with an oil phase and some other ingredients in smail amounts. The resulting product is pumped into the blasthole. If a dry phase such as ANFO or ammonium nitrate prills are added to the mixture, it is important to ensure that the emulsion produced does not lose its pumpable qualities.

Drift driving. The motor-pump system used is customarily mounted on a small size vehicle that sometimes has a hydraulically powered man basket enabling the blaster to have access to the back holes, operating the pump with remote control. The most popular types of pumps are those of diaphragm and those with auger which aspirates the explosive from the tanks which have a capacity of up to 500 kg and load it with a pressure of about 0.5 MPa, Photo 15.7. The loading hoses Ge semi-conductive to eliminate static electricity and are introduced into the blastholes up to about 20 cm from the bottom, then pumping the explosive which gradually pushes the hose out of the hole until the desired charge height is reached. Initiation is usuaily achieved with a primer cartridge and an electric blasting cap, previously placed in the bottom of the hole. The flow rates are comparable to those obtained with' ANFO pneumatic chargers. Depending upon the pump speed, a 3 meter long blasthole with 41 rnm in diameter can be charged in 6 to 10 seconds.

Pump trucks. When pump trucks are~sed~tbe41asring agent is previously manufactured in a static plant near or on the minesite. The advantages of this system are: - The static plant can be located in the Center of the various points of consumption,supplying the sluny or the emulsion in severai trucks, and - The product is of higher quaiity than that produced in the rnix truck. Underground charging of slurried und emulsions Loading blastholes in underground operations has different methods, depending upon the type of work at hand: Photo 15.7. Charging equipment for development headings.

Mechanized systemsfor charging and dewatering blastholes

151

Shaft sinking. Pressurized vessels are used, similar to those used with buk ANFO. The discharge of the explosive through a main hose of 45 mm,reaches a flow rate of 77 kglmin, that is at the Same time divided into 5 flexible hoses of 17 rnm diameter which permits the loading of blastholes in a very short time, Fig. 15.10. Production blasts. In production blasts with large diameter blastholes, more than 125 mrn, there are two different charging situations: upholes and downholes. a) Downholes. They are used in the operational methods of inverted craters and in levelling with long blastholes. Charging is camied out very easily because the explosive is pumped and descends by gravity to the

- & ~ s i ~ - l ~ ) x p r ~ i l i t ~ h e i r a r n p f explosive from the surface as well as in the mines. The exchangeable tanks of explosive are made of stainless steel with capacities of close to 2.000 kg. The pump, hose and the inclination hinge of the tank are hydraulically powered. b) Upholes. The charging of upholes with blasting agents such a slumes and emulsions is even more difficult than with ANFO, as it is first necessary to apply a borehole plug to keep the explosive from falling out and, secondly, the product must have an adequate consistency for pumping. The latter seems to have been solved for emulsions by cooling. As to plugs, there are various systems used. The first ones used a wooden plug with an interior tube that had a check valve with a brass anti-retum ball, Fig. 15.11. Plastic tubes have also been used to make up the explosive columns, and wooden plugs with holes that

photo 15.8. Pneumatic pump (Bill Lane Inc.):

V ALVES

017rrm HOSE

BROKEN MUCKPILE

ing.

DETONATHG CORD

L O A W G PiPE

DELAY LEADS CHECK VALVE

Fig. 15.11. Wooden plug with anti-return check valve.

Fig. 15.12. Tubed charging with wooden plug.

Drilling and blasting of rocks

152

inflatable lances have been tned with success. These devices have two inches of flexible hose with a rigid tube on one end, upon which an inflatable rubber bladder is mounted and inflated by pressurized air, Fig. 15.14. The advantages of this System are its simplicity and low cost. It is quick and efficient, having been successfully tned in blastholes of up to 115 mm in diameter.

LIOMD FOAM CONTAHER

15.3 BLASTHOLE DEWATERING SYSTEMS stholes widens th

- Air operated pumps and, - Submergible impellent pumps. The first are applied to small and medium diameter (63 to 172 rnm) blastholes with a maximum bench height of about 15 meters. Pressunzed air supplied by compressors of the dnlling rigs is used, which is introduced into the blastholes through a flexible plastic hose. In some equipment, Fig. 15.15, the pushing effect is achieved when the obturator'or plastic closing sleeve expands when the air pass through. The pumping rates are approximately 50 to 80llmin. The second dewatenng System has a submergible impellent pump and a reel for the hose. The unit can be installed on a jeep-type vehicle or on the back of an ANFO charge truck. The reel and pump are hydraulically driven and the hydraulic fluid tubes of the latter arejoined inside the water hose, enabling the whole ensemble to be lowered into the blasthole at of approximately m/s. To avoid stoppageproduced by coarse waste material, the pump should by placed at a few centimeters from the bottom. -, Once the dewatenng of the blastholes is finished, the mechanism of the drum wheel reverses to clean it of sand and waste that might have entered. These units can dewater blastholes in a few seconds,

Fig. 15.13. Polyurethane foam uphole plug.

-R,MT

N F L A T A B ~ ~B L A D ~ P

EUULS~~~ HOPPER

Fig. 15.14. Charging of a rcpumpablc emulrion in an uphole with an inflatable lance. WATER DISCHARGES FROM HOSE

AIR SUPPLY

SLEEVE

Photo. 15.9. Hydraulic dewatenng pump (Swanson Eng. Inc.)

W

Fig. 15.15. Pneumatic pump.

SLEEVE W L A l

Mechanized systernsfor charging and dewatering blastholes

153

Table 15.2. Flow (Ilmin)

Total elevation height (m)

a Ipm, I I MPa

Table 15.3. Blasthole diameters Imm)

Ipm, 13 MPa

Ipm, 13 MPa

Nominal diameter of plastic liner Imm)

owing to the strong pumping rates, Table 15.2, permitting use of the plastic sieeves and charging before the Water enters again. The type of plastic used should be flexible and resistant so that it will not tear when in contact with the rock, recommending h a t it be of 600 to 1.000 gage, depending upon each case. The liners Or plastic sleeves, which the bulk explosive, should have a diameter that is slightly more than that of the holes, Table 15.3, so that the volume of rock drilled can be used to maximum advantage and achieve a good adaptation of the charge.

Amerind-Mackissic, Inc.: Technical fnformation 1986 Bauer, A.: Trends in Explosives, Drilling und Blasting. CIM Bulletin, February, 1974. Bauer, A. et al.: Drilling und Blasting in Open Pits und Quarries. 1980. Bill Lane, INC.: Lane Pump. 1986. Champion, M.M.: Explosives Loading Equipment. Underground Mining Methods Handbook. AIME, 1982. Dannenberg, J.: Contemporary history of industrial explosives in America. Day, F!R. & D. K. Joyce: Lwding explosives in large diameter upholes. SEE. 1988. Giorgio, C.: Evolucibn de los Explosivos en los Treinta UltimosAEos. Rocas y Minerales.

Photo 15.10. Preparation of the primer charge in a plastic sleeve.

Gustafsson, R.:Swedish Blasting Technique. SPI, 1973. Hagan, T.N.: Charging and Dewatering Equipment. AMF. 1985. Irvine, J.C.: Pillar recovery at the Pea Ridge Mine. Mining Engineering. September, 1976. Jerberyd, L.: Half-pusher - A method to charge large diameter upholes. Swedish Mining Research Foundation, 1985. Legorburu, V.: Sistemas Mecanizadas de Carga de Explosives en Proyectos Subterrhneos. I Seminario de Ingenieria de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundaci6n G6mez-Pardo, 1986. Lopez Jimeno, C.: Desagüe y Drenaje de Explotaciones a Cielo Abierto. IV Curso sobre Mantenimiento y Servicios en Mineria a Cielo Abierto. Fundaci6n G6mez-Pardo. 1984. _ M a i r s , ~ B B T ~ + ~ u & i ~ ~ - e x p W n underground. CIM Meeting, 1985. Michaud, F! & A. Laveault: Essai d'un Systeme de chargement en vrac pouremulsions aux Mines d'Amiente Bell. SEEQ, 1984. Nitro-Nobel: ANFO Mixing and Charging Equipment. 1986. Swedish Methodsfor Mechanized Blasthole Charging. Puntous, R.: Mkthodes Modernes de Chargementdes Explosifs. Industrie Minerale - Les Techniques. Fevrier, 1984. Sharpe, K. R.: Plugging and loading upholes at La Mine Bosquet. CIL Inc. 1986. Swanson Engineering Inc.: Blasthole dewatering - Cuts costs. Union Espaiiola De Explosivos: Tendencias Actuales en el Almacenamiento.Traßspo~e~arga-Meeaninida-deExptmivos-en~aMineria a Cielo Abierto. Jornadas Tecnicas, UEE. VME-Nitro Consult, Inc.: Pneumatic Cartridge Charging. Yetter, A. & R. Malo: The evolution of loading 4.5 inch diameter upholes at Kidd Creek No. 1 Mine. SEE. 1984.

CHAPTER 16

Mechanisms of rock breakage

16.1 INTRODUCTION

increase the surface area by crushing, it has a slower rate of stress decay than (A).

theconditionspresencharactenzedbytm-phaes2onsumes of action: Ist. phase. A strong impact is produced by the shock wave linked to the Strain Energy, during a short period of time. 2nd. phase. The gases produced behind the detonation front come into action, at high temperature and pressure, carrying the Thermodynamicor Bubble Energy. Since the decade of the fifties, many theories have been developed to explain the behavior of rocks under the effect of an explosion; even nowadays it still remains a problem to be solved and defined in the technology of application of explosives to breakage. Without entering into detail, the different mechanisms of rock breakage that have been identified in blasting up to now are exposed in the following paragraphs. 16.2 ROCK BREAKAGE MECHANISMS In the fragmentation of rocks with explosives at least eight breakage mechanisms are involved, with more or less responsabiXty, but they an exert influence upon the -, results of the blastings. 16.2.1 Crushing of rock In the first instants of detonation, the pressure in front of the strain wave, which expands in cylindrical form, reaches values that well exceed the dynamic compressive strength of the rock, provoking the destruction of its intercrystalline and internranular structure. The thickness of the so cailed crushed zone increases with detonation pressure of the explosive and with the coupling between the charge and the blasthole wall. According to Duvall and Atchison (1957), with high strength explosives in porous rocks it might reach a radius of up to 8 D, but it is normally between 2 and 4 D. In Fig. 16.1. the variations in compressive stresses generated by two fully-coupled charges are shown. The crushing of the rock is produced at a pressure of 4 GPa, so the curve of the explosive (A) which produces a tension of 7 GPa on the blasthole wall has a very sharp decrease in peak stress due to the large increase in surface area during the pulverization of the rock. As explosive (B) does not

almost 30% of the energy transported by the strain wave, only contributing a very small volume to the actual rock fragmentation, around 0.1% of the total volume corresponding to the normal breakage per blasthole. Therefore, there is no incentive to use high explosives that generate high stresses on the blasthole walls: which would even make it advisable to decouple the charges and increase EB in detriment of ET. 16.2.2 Radial fracturing

During propagation of the strain wave, the rock surrounding the blasthole is subjected to an intense radial compression which induces tensile components in the tangential planes of the wave front. When the tangential strains exceed the dynamic tensile strength of the rock, the formation of a dense area of radial cracks around the crushed Zone that surrounds the blasthole is initiated, Fig. 16.2. The number and length of these radial cracks increase with: 1. The intensity of the strain wave on the blasthole wall or on the extenor Iimit ot the crushed z m d 2. The decrease in dynamic tensile strength of the rock and the attenuation of the Strain Energy. Beyond this inner Zone of intense fractunng, some of the cracks extend noticeably and are symmetrically distributed around the blasthole. The propagation velocity of the cracks is from 0.15 to 0.40 times that of the strain wave, although the first microcracks are developed in a very short time, around 2 ms. When the rock has natural fractures, the extension of the cracks is closely related to these. If the explosive columns are intersected lengthwise by a pre-existing crack, these will Open with the effect of the strain wave and the development of radial cracks in other directions will be limited. The natural fractures that are parallel to the blastholes, but at some distance from them, will interrupt the propagation of the radial cracks, Fig. 16.3. 16.2.3 Rejlection breakage or spalling When the strain wave reaches a free surface two waves are generated, a tensile wave and a shear wave. This occurs when the radial cracks have not propagated farther

Mechanisms of rock breakage

Fig. 16.4. Reflection of a wave upon a cylindncal cavity.

Fig. 16.1. Variation of peak compressive stress with distance from OmsihotewatUHaga~~).

UD COMPRESSION TENSION

Fig. 16.2. Radial fracturing.

FRACTURES CAUSED B Y INTERNAL SPALLIN

X)(NT PLANE

ZONE OF- DENSE RADIAL CRACKlNG

-

-

WATER FILLED JOINT PLANE

/ RADIAL CRACKS A R R E S T E D ~ PREMATURELY AT JOlNT

Fig. 16.3. Radial fracturing and breakage through reflection of the strain wave.

than one third the distance between the charge and the free face. Although the relative magnitud of the energies associated with the two waves depends upon the incident angle of the compressive strain wave, the fracturing is usually caused by the reflected tensile wave. If the tensile wave is strong enough to exceed the dynamic strength of the rock, the phenomenon known as spalling will corne about, back towards the interior of the rock. The tensile

strengths of the rock reach values that are between 5 and 15% of the compressive strengths. The front of the reflected wave is more convex than that of the incident wave, which means that the dispersion index of the tensile wave energy is much larger when the surface is cylindncal, such as that of the central blasthole of a cut instead of when there is a plane as in bench blasting, Fig. 16.4. This mechanism does not contribute much to the global fragmentation process, estimating that eight times more explosive charge would be necessary if rock were to be fragmented solely by reflected waves. However, in the inner discontinuities of the rock mass which are close to the charge, less than 15 D, and are not infilled with rneteorized material, the effect of the reflected waves is more important due to the difference in impedances. When excavating inclined ramps or shafts by blasting, it must be checked that the empty blastholes are not be filled with water in order to achieve the benefits of this mechanism of breakage.

After the strain wave passes, the pressure of the gases cause a quasi-static stress field around the blasthole. During or after the formation of radial cracks by the tangential tensile component of the wave, the gases start to expand and penetrate into the fractures. The radial cracks are prolonged under the influence of the stress concentrations at their tips. The number and length of the opened and developed cracks strongly depend upon the pressure of the gases, and a premature escape of these due to insufficient stemming or by the presence of a plane of weakness in the free face could lead to a lower performance of the explosive energy. 16.2.5 Fracturing by release-of-load Before the strain wave reaches the free face, the total energy transferred to the rock by initial cornpression varies between 60 and 70% of the blast energy (Cook et al. 1966). After the compressive wave has passed, a state of quasi-static equilibrium is produced, followed by a subsequent fall of pressure in the blasthole as the gases escape through the stemming, through the radial cracks

Drilling und blasting of rocks

156

t:Xmr

I=O

and with rock displacement. The stored Stress Energy is rapidly released, generating an initiation of tensile and shear fractures in the rock mass. This affects a large volume of rock, not only in front of the blastholes but behind the line of the blast cut as well, having registered damages in up to dozens of meters away, Fig. 16.5. 16.2.6 Fracturing along boundaries ojmodülus contrast of shearfracturing In sedimentary rock formations when the bedding planes, joints etc., have different elasticity modulus or geomechanic Parameters, breakage is produced in the separation planes when the strain wave passes through because of the strain differential in these points, Fig. 16.6.

Fig. 16.5. Separation of layers of compressible medium by release-of-load.

t=~xrnr

where n, is the relationship between the impedance of the explosive and that of the rock:

t h r o u L rock mass (m/s), D. = Rock density (g/cm3). This means that the explosive wave is better transmitted to the rock when the impedance of the explosive is close to that of the rock, given that n, will tend towards 1, while PT will simultaneously tend towards PD. The pressure of the wave inside the rock decreases with the law of exponentials, so the radial stress generated at a determined distance will be:

16.2.7 Breakage byflexion During and after the mechanisms of radial fracturing and spalling, the pressure applied by the explosion gases upon the material in front of the explosive column makes the rock act like a k a m embedded in the bottom of the blasthole G d in the stemming area, producing the deformation and fracturing of the Same buy the phenomena of flexion, Fig. 16.7. 16.2.8 Fracture by in-flight collisions The rock fragments created by the previous mechanisms and acceleratedby the gases are projected towards the free face, colliding with eachother and thereby producing additional fragmentation which has been demonstrated by ultra-speed photographs (Hino, 1959;Petkof, 1969). 16.3 TRANSMISSION OF THE STRAIN WAVE THROUGH THE ROCK MASS

-Asshown-befo~ehand&theDetonationessure can be expressed by the following simplified equation:

where: o = Radial compressive stress, PB = Pressure on the blasthole wall, r, = Radius of the blasthole, DS = Distance from the Center of the blasthole to the point in study, X = Exponent of the law of absorption which, for cylindrical charges is near 2. If the wave encounters diverse material in its path, with different impedances and in correspondance with separating surfaces that can be in contact or separated by air or water, the transmission of the strain wave will be govemed by the ratios of the acoustic impedances of the -dlPf=es-of rmercparmf-transferred in the material and at the Same time some is reflected back, as a function of the ratio. When the impedances of the mediums are equal (pr2 X VC2 = pri X VC,), a large part of the energy will be transmitted and the rest will be reflected, arriving at the lirnit when (pr2 X VC2
.--_

P -

#

where: PD = Detonation pressure (kPa), p, = Explosive density (g/cm3),VD = Detonation velocity (mls). The maximum Pressure Transmitted to the rock is the equivalent of: PT,,, =

L

-PD 1 + n,

n, =

Pri

X

'CI

Pr2 X 2" the following will be obtained:

Mechanisms of rock breakage I BED X

EXPLOSIVE CHARGE

I

Fig. 16.6.Shear Fracturing (Hagan).

MSCONTINUITY

where: PI = Pressure of the incident wave, PT= Pressure of the transmitted wave, PR = Pressure of the reflected wave.

16.4 ENERGETIC YIELD OF THE BLASTINGS Itaneously in a few miliseconds, associated with the effects of the strain wave which transports the Stress Energy, and with the effects of the explosion gases or Bubble Energy, Fig. 16.8. The total energy developed by the explosive and measured by the method proposed by Cole can thus be expressed as the sum of these two components.

fare.ag.roupofelementalmmwh&pe

ETD = ET Fig. 16.7.Mechanism of breakage by flexion.

+ EB

where:

The estimates canied out by Hagan (1977) have demonstrated that only a 15%of the total energy generated in the blasting is used as a working tool in the mechanisms of rock fragmentation and displacement. R a s c h e f f a n d G v 7 7 F h a v e esta6IiSEd a model that theoretically distributes the energy, as represented in Fig. 16.9, from tests made upon cubic blocks of rock placed underwater in swimrning pools. These investigators assure that approximately 53%of the explosive energy is associated with the strain wave. This value depends upon the conditions of the experiment and very different results can be found that go from 5 to 50%of the total energy, depending upon the various types of rock that are to be fra~mentedand the explosives used. Therefore, in hard rock the Strain Energy of a breaking explosive is more important in fragmentation than the Bubble Energy, and the contrary is true for soft, porous or fissured rocks and in low density explosives. From the tests canied out by Rascheff and Geomans, Table 16.1 s u k a r i z e s the energy distribution of the strain wave. It can be observed that in conventional bench blastings a large part of the strain wave energy is transformed into seismic energy which causes ground vibrations to which some of the gas energy must be added. The data exposed are quite in accordance with that Photo 16.1. Rock breakage by flexion.

Drilling und blasting of rocks PHASE

I

FREE FACE ORIGiNAL

Fig. 16.8. Summary of the breakage mechanisms.

PO R

-

U . -

- ~slll

nm

p i e p e s l v . m bhmlho* w i l

p e s ~ of a expindhp p i s s i rpon hipmonled r a *

-snmgm

01

aiifui w a t w wu

Fig. 16.9. Distribution model of the explosive energy in ablast.

W '

a

3

V)

VOLUME

Fig. 16.10. Pressurelvolumediagram of explosion product gases showing partition of energy in blasting.

1

I

Mechanisms of rock breakage Table 16.1. Distribution of shock wave energy. Granite block Conventional with infinite bench blastconfinernent ing of granite Pulverization 15% 15% Primary radial cracking 3% 3% 0% 16% Crack extension Energy transrnitted 82% 34%

Granite block submerged in water 15% 2% 39% 22%

Useful energy

56%

18%

34%

Table 16.2 Zone

1 + 2 + 3 +4 + 5

159 Energv Kinetic component of shock energy Strain component of shock energy Brissance energy Energy released during crack propagation Fragmentationenergy Strain energy in burden at time gases escape Blast energy Heave energy Total available energy or absolute strength value

pressed by the gas in ihe cracks with a strain energy obtained by other investigators such as Mancini and stored in ihe rock (Zone 4). This energy has little Occella. Ic snouia no-~gorrerrnizittcter co o m n from Zones 2 and 3 is the most useful in - c ~ r i r ~ ~ e b ~ ~ t - i s R o ~ ~ n e c eThes energy s n ~ rock blasting and is called Fragmentation Energy. to fragment the rock but also to cause swelling and At ihe time of escape, some of the energy in the gases displace it a dete&ned distance. For ihis reason, in ihe (Zone 5) moves ihe burden and represents heave energy. latter stages the gases also play a decisive role. The rest of this energy is lost as heat and noise in the Lowends' used a simplified model of explosivelrock escaping gases. interaction to describe the partition of explosive energy in Alihough this model of energy partition overthe process of rock blasting. The energy is partitioned simplifies the blasting process, it gives valuable insight into different zones h a t are related to the pressurel into where ihe energy goes during the various phases of volume expansion of ihe gases during ihe different the process. It also provides approximate comparisons of phases of blasting. An illustration of ihis partition of ihe magnitude of ihe energy fractions used in the various energy is given in Fig. 16.10. phases of the blasting process as the explosive gases The energies associated wiih the different zones given expand from the initial pressure in the blasthole to atrnosin the figure are, as follows: pheric pressure. Not all of ihe availableenergy is useful in When ihe explosive detonates in the blasthole, the high fragmentation and heave. It may be possible to improve pressure gases at the initial or explosion state P3 send a the efficiency of the blasting process by using explosives, shock wave into the rock. The strains from this shock wheiher ideal or not, ihat are designed to keep energy near the blasthole are greater than the dynamic compresslosses at a minimum. ive and shear strength of the rock. They cause v q i n g amounts of rock compression and crushing in ihe sur: rounding area of the blasthole depending upon ihe REFERENCES strength and stiffness of the rock. With rock compression and crushing ihe volume of the blasihole increases and Ash. R.L.: The Mechanics qf-e. Pit and Q u a q no. 56. ihe pressure decreases until ihe strain in ihe rock balances 1963. Duvall, W. I. & T.C. Atchison: Rock Breakage by Explosives. U.S. B.M. the pressure. This is shown as74 on ihe pressurelvolume RI 5356,1957. curve of Figure 16.10, and is called blasihole equilibrium Hagan, T.N.: Rock Breakage by Explosives. Proc. National Syrnpostate. During the expansion, the work being done by ihe sium on Rock Fragrnentation. Australian Geornechanics Society. explosive is called bnssance energy and consists of the . Adelaide, Feb. 1973. Hagan, T.N. & G.D. Just: Rock Breakage by Explosives. T h e o q strain energy stored in the rock (Zone 2) and ihe kinetic Practice und Optimization. Proc. Congress International Society of energy of the shock wave (Zone 1). The kinetic shock Rock Mechanics. Vol. 11, 1974 energy is essentially lost as useful work during ihe blastHagan, T.N.: Rock Breakage by Explosives. 6th Symposium on Gas ing process and appears as crushed rock surrounding ihe Dynarnics of Explosives and Reactive Systems. Stockhlom, 1977, b l a s t h n l e a n d aq s e i s m i c p a p a g a i e d h LL ~a n d J A L L R & E w r e a & a d e m a p p r a a I n p e a p i h l n ~ r design und anulysis. CIM Bulletin. June, 1972. ground. Lopez Jirneno, C.: Los Mecanismos de Fragmentacibn con Explosivos The strains in the rock coming from ihe residual blasty la Injluencia de las Propiedades de las Rocns en los Resultados hole pressure P4 cause fracture. The explosion product de las Voladuras. I Serninario de Ingenieria de Arranque de Rocas gases enter at least the cracks existing between the hole con Explosivos en Proyectos Subterriineos. Fundation GornezPardo, 1986. and the free face, resulting in fragmentation and possibly Rascheef, N. & I? Goernans: Contribution 6 l'etude quantitative de contributing to the heave. When ihe gases reach the free l'energie consommie dans la fragmentation pur explosif. 0ct.face through the burden, the process ends more or less Dec., 1977. abruptly. The pressure of the gases at escape is shown at Thurn, W.: Quantite d'energie requisepour L'extraction et lafragmentation des roches au moyen d'explosives. Explosifs, 1972. P5 in Figure 16.10. During escape, the burden is comP

CHAPTER 17

Rock and rock mass properties and their influence on the results of blasting

17.1 INTRODUCTION ,

-

The matenals of which rock masses are maae possess ~ ~ ~ ~ ~ ~ h a t origin and of the posterior geological processes which have affected them. The whole of these phenomena make up a certain environment, a particular lithology with heterogeneities caused by the added polycrystalline minerals and by the discontinuities of the rock matrix (pores and fissures): and by a geological structure in a characteristic state of Stress, with a large number of structural discontinuities such as bedding planes, fractures, diabases, joints, etc. 17.2 ROCK PROPERTIES

Persson et al., 1970) arriving at values that are between 5 and 13 times more than the static. . . W nen me ~ y ~ t w mn m &n r ip 9 ec i ~v p 't r r ~ n g t ~ 4 surrounding the blasthole wall is produced by collapse of the intercrystalline structure. However, this excessive crushing does little to aid in fragmentation and gravely reduces the strain wave energy. Therefore the following is recommended: - Explosives that develop blasthole wall strain energy that is lower than or equal to RC must be chosen. - Provoke a variation in the Pressure-Time curve (P t) by decoupling the charge in the blasthole. These points are of maximum importance in perimeter or contour blastings. The powder factors required in bench blastings can be correlated with the compressive strength, as indicated in Table 17.1 (Kutuzov, 1979). m

m -

The densities and strengths of rocks are normally quite well correlated. In general, low density rocks are deThere are two types of porosity: intergranular or formaformed and broken quite easily, requiring relatively low energy factors, whereas dense rocks need a higher quanttional, and that of disolution or post-formation. ity of energy to achieve a satisfactory fragmentation, as The first, which has a uniform distribution in the rock mass, provokes two effects: d and swelling. well as a ~ o o disdacement In high density rocks, the following measures should - Attenuation of the strain wave energy. be taken to ensure adequate hegvy energy: - Reduction of the dynarnic compressive strength and, - Increase the drilling diameter in order to elevate the consequently, an increase in crushing and percentage of where VD is the detoblasthole pressure, PB = k X VD2, fines. nating velocity of the explosive. The fragmentation of very porous rocks is carried out, - Reduce the Pattern and modifj the initiation sealmost exclusively, by bubble energy, so the following quence. recommendations should be observed: - Improve the effectivity of the stemming to increase - Use explosives with a high EBIET ratio, such as the time of gas performance and make certain that they ANFO. eseapeheugkchefr e e f a ~ ~ ~ s t e a B O ~ u g U -~ I kn cmr e~a s e _ E B a t t h e o o f E T y decoupling the charges and the initiation Systems. ming. - Use explosives with high bubble energy EB. - Maintain the explosion gases at high pressure with an adequate stemming height and type. - Maintain the burden equal for each hole by using 17.2.2 The dynarnic strengths of the rocks various free faces. The static compressive RC and tensile RT strengths are The post-fomation porosity is caused by spaces and initially used as indicative parameters of the suitability of cavities that result from the disolving of the rock material the rock for blasting. The Index of Blastability was by underground water (karstification).The empty spaces defined (Hino, 1959) as the relationship 'RC/RT1, the are much larger and their distribution is much less unilarger the value, the easier the fragmentation. form than in the intergranular porosity. The rational treatment of the existing problems require In rock of volcanic origin it is also frequent to find a taking into consideration the dynamic strengths, as these large number of cavities formed during its consolidation. increase with the index of the charge (Rinehart, 1958: The cavities that are intersected by blastholes not only

161

Rock and rock muss properties Table 17.1. Rock classificationaccording to their facility of fragmentatiin by explosives in Open pit mines. Powder factor Mean distance between natural Uniaxial compressive rock strength (MPa) Class limit (kglm') Average value (kglm') fractures in rock mass (m)

r

aI .-encqnnfiheblasr,eqecid&if

loosepacked or pumpable explosives are used, Fig. 17.1. If the boreholes do not intersect the cavities, the yield of the blast also descends because: - The propagation of radial cracks is intermpted by the cavities. - The rapid fall in pressure of the gases as the blastholes intercommunicate with the cavities, halting the opening of the radial cracks, while the gases escape towards the empty spaces.

As the rocks do not form an elastic media, part of the strain wave energy that propagates through them is converted to heat by diverse mechanisms. These mechanisms are known as intemal friction or specijic darnping c a p a c i ~SDC, which measure the ability of the rock to attenuate sirain waves generated by the detonation of the explosive. SDC varies considerably with the type of rock from values of 0.02-0.06 for granites (Windes, 1950; Blair, 1956) up to 0.07-0.33 for sandstones. SDC increases with porosity, permeabillity, joints and water content of the rock. It also increqses considerably with the meteorized levels in function with their thickness and weathering. The intensity of the fracturation by the strain wave increases as the SDC decreases. Therefore, watergel type explosives are more effective in hard and crystalline formations than in soft and decomposed materials (Cook, 1961;Lang, 1966). On the other hand, in the latter, ANFO

Rock density (tlm3)

.

iated ana protectea. l t 1s recommende -~e&o~~beuse& The failure of one of the detonators could considerably affect the results of the blast. 17.2.6 The cornposition of the rock and the secondary dust explosions The secondary dust explosions usually occur in coal mines and in highly pyritic areas such as underground meta1 mines, and are more frequent each day due to the use of large diameter blastholes. The first charges'fired create, on one hand, a high quantity of fines which are thrown into the atmosphere and, on the other, agitate the dust deposited on the sidewalls and roof of the excavation with the airblast and vibrations. If the energy of the gases from the last charges is sufficiently high, it could ignite the concenirated dust causing secondary explosions with devastating effects upon the ventilation installations, doors, mobile equipment, etc. The probability of secondary explosions can be reduced by taking some of the following steps: - Eliminate the use of aluminized explosives since the particles of A1203at high temperatures in the detonation products are potential ignition centers. - Select an explosive and blasthole gqmetry for bum cuts which produce coarse material. - Stem all blastholes with sand, clay plugs or water. - Create a cloud of limestone or another inhibitor in front of the face by exploding a bag of said material with a detonator fired some miliseconds before the blast.

isb~sade~eventhoughitsstrainenergyis-

-

Waskth~~md-Boo~eex~a~tior

lower.

quently to remove the deposited dust. - Fire the blasts after evacuating all personnel from the mine.

The leakageor shunting of electrical current can occur when the detonators are placed in blastholes that are in rock of certain conductivity, such as complex sulfides, magnetites, etc., especially when the rocks are abrasive and water is present near the round. The measures that should be taken to avoid these problems are: - Check that the cables of the detonators are well enclosed in plastic and, - That all the connections of the circuit are well insu-

17.3 PROPERTIES OF THE ROCK MASS 17.3.1 Lithology The blasts in zones where an abrupt lithological change is produced, for example in waste and ore and, in consequence, a variation in the strength of the rocks, the design must be reconsidered. One of the two following methods could be used:

Drilling and blasting of rocks

162

Fig. 17.1. Correct use of a bulk explosive charge in ground with large cavities.

RELAY

SOFT ROCK

DETONATING CORD

---+-

-

Fig. 17.2. Recommended change in blasthole pattem of V type blast at contact between waste and ore. Photo 17.1. Blocks with columnar geometry in basaltic formations. STRONG UNFISSURED BOULDERS O F LIMESTONE

SOFT. PLASTIC ACTING MATERIAL (SOIL. GRAVEL. CLAY)

Photo 17.2. Intenselyjointed limestone rock mass.

-a+Eq&a1~m**fOfre-~

Fig. 17.3. Typical cases of lithological changes with contact between competent rocks and plastic matenals (Hagan).

. .

in the unitary charges. b) Different Patterns with equal charges per hole. This placement is usually adopted maintaining equal burden, Fig. 17.2, as the introduction of a different S X B pattern for each Zone would entail a more complex dnlling and the newly created face may be stepped. The serni-horizontal stratiform beds presented by some very resistant layers may lead to a peculiar type of blastings in which the charges are placed in the blastholes and completely confined at these levels. It is also recommended that the pnmers of the explosive columns coincide with the strongest levels in order to obtain maximum effect from the strain energy.

Rock and rock muss properties Table 17.2. Absorption of strain wave energy by joints 1. Small(< 20%) 2. Slight (20-40%) 3. Medium (40-80%) 4. Large (> 80%)

163

Joint width (mm)

Natureof joints

('4) 0 (B) 0-4.0 (A) Up to 0.5 (B) Up to 4.0 0.5-1 .O (A)O.l-1.0 (B) 1.0

(A) Tightly stacked (B) Cemented with material of acoustic impedance close to that of the main rock (A) Open joints filled with air or water (B) Cemented with material of acoustic impedance 1.5-2 times less than that of main rock Open joints filled with air or water (A) Joints filled with loose and porous material (B) Open joints filled with loose, porous material, air and water

When two matenals of very different strengths come Table 17.3. Possible combinations of spacing between blastholes (S), joints (J), and maximum adrnissable block size (M). into contact as, for example, a competent limestone with Case Js:S Js:M S:M Fragmentation % of very plastic clays and, if the blastholes pass through these sensitive to Iormations, a great 105s of energy associated with a drop specific charge ~ p r e ~ s e ; t p e o f g m w i t t a ap ~ ~ g Yes Medium S>M Js>M I J,>S rapid deformation of soft material and, as a consequence, Yes Low S<M Js>M Js>S 2 poor fragmentation, Fig. 17.3. Yes Low S<M Js<M 3 J,>S In order to increase the yield of the blasts in these No High S>M Js>M 4 J,<S No Low S<M Js<M J,<S 5 cases, the following is recomrnended: No Low S > M J < M 6 J , < S - Stem with adequate material the zones of the blastholes that are in contact with or near plastic material. - Use explosive charges that are totally coupled to the competent rock with a high detonation velocity and ET/ OVERBREAK ZONE b BACK-ROW BLASTHOLE EB relationship. JOINT OF PREVIOUS BLAST PLANES NEXT FACE - Place the primers in the rniddle of the hard rock to \ increase the resulting strain wave that acts upon both sides. - Avoid premature escape of gases to the atrnosphere insuring that both the sternming height (at least 20 D) and the size of the burden are correct at the top of the blastholes. 17.3.2 Pre-existingfractures

~

Fig. 17.4. Excessive toe burden caused bv stmcturally . - controlled backbreak Zone and face angle. All rocks in nature have some type of discontinuity, microfissusandmacrofissiares, which deckkelyY influence the physical and mechanical properties of the that might arise are indicated, taking into account the rocks and, consequently, the bbting results, Photos 17.1 inclination of the discontinuititesand the relative angle of and 17.2. the strike and dip. The areas of discontinuity can be varied: bedding Special precautions should be taken when the discontiplanes, planes of lamination and primary foliation, planes nuities are subvertical and the direction of the shot is of schistose and slate, fractures and joints. normal (parallel) to theirs, because overbreak is frequent The discontinuities can be tight, Open or filled and, for behind the last row of blastholes and inclined dnlling this reason, can exhibit different degrees of explosive becomes necessary to maintain the burden dimension in energy transmission. Table 17.2. The walls of these disthe first row of the round. Fig. 17.4 and Photo 17.3. ~ ~ i e ~ - ~ v e f t ~ w f a e s +entkie&&ni-m7he t t p e ~ t h ~ jöinrsystem~a-an-xnsie n waves may be reflected, suffering attenuation and dispersmaller than 30°, it is recommended that the blastholes be sion. normal to said planes in order to increase the yield of the The fragmentation is influenced by the spacing beblasts. tween blastholes S, the separation between joints J and In tunnel excavations, the structural characteristics the maximum admissible block size M. In Table 17.3, largely condition the geometry of their profile, almost various possible combinations are indicated, as well as rectangular if the rocks are massive and with a curved their repercussion upon the percentage of forseen arch if the rock is more unstable. When the discontinuiboulders. ties are normal to the tumel's axis, the blasts usually have Another aspect of the design of the blastings is referred good results. Fig. 17.5a. If the bedding or the discontinuito as geostructural control of the rock mass, which refers ties are parallel to the axes of the tunnels, Fig. 17.5b, to the relative orientation of the face and break direction frequently the advances are not satisfactory and the faces of the round with respect to the strike and dip of the Strata. are uneven. When the bedding has an oblique direction In Table 17.4, the forseen results for the different cases with respect to the axis of the tunnel, there will be one "

164

Drilling and blasting oj'rocks

Photo 17.3. Face of a blast that coincides with a bedding plane.

side on which it is easier to blast, such as in the case of Fig. 17.5c, the left side. On the other hand, very laminated rocks with high schistosity and fissurization rese-a-4 deep pulls of up to 6 m are possible with this type of cut. When V cuts are used in sinki~grectangular shafts, the best results are obtained when the discontinuities are parallel to the line joining the bottom of the V cut, Fig. 17.6.

When the stress fields, either tectonic andlor gravita~nnai-(non-hydrostatic)-ac~e-fracture-pattem-gen~ rated around the blastholes can be influenced by the non-uniform stress concentrationsaround the same. In hornogeneous massive rock, the cracks which Start to propagate radially frorn the blastholes tend to follow the direction of the principai stresses. Therefore, when driving shafts in rock masses with a high concentration of residual stresses, as in the case of Fig. 17.7, the firing sequence in the blastholes of the cut should be adapted to this situation. If in the presplitting planes of the planned excavation the influencing stresses are normal to the same, the obtained results will not be satisfactory unless the spacing is considerably reduced or a pilot excavation is carried out

Fig. 17.5. Relative directions of the beds with regard to the axes of the tunnels.

to relax the mass and free the stresses, and presplitting is substituted for smooth blasting. 17.3.4 Water content Porous and intensely fissured rock, when saturated with water, usually Pose certain problems:

Rock und rock muss properties Table 17.4. Design of the blasts with attention to geostmctural control.

Inclination of the strata a =0°

Angle between the direction of the Strata and the blast break Indifferentbreak direction

3 = 45" = 135" = 225' = 315" ß = 90" = 270"

face Variable fngmentation. sawtooth face Most favorable direction

Good Unfavorable Not very favorable Acceptable Very favorable

(Sirnilar to the previous case hardness is determining factor)

45" < a < 90"

MAJOR. PHYSICAL DlSCONTlNUlTlES

SHAFT PERIMETER

ß =22S0 =31S0 = 2700

Good Unfavorable Not very favorable Acceptable Very favorable

ß = 90"

Not very favorable ß = 270" Favorable (Depending upon the value of a and upon the rock competence, the results will be closer a a = 45" 6 a = 90")

3 --

-/ L

.

NITIATION SEOUENCE

\

3

BLASTHOLE 4 DlRECTlON OF MAL~MuM PRINCIPAL STRESS

-

-7/

Fig. 17.7. Initiation sequence for burn cut in high horizontal Stress field: (a) tobe avoided, (b) satisfactory.(Hagan, 1983).

Fig. 17.6. Rectangular sinking shaft with V cut. (Hagan, 1983)

166

Drilling und blasting of roch

- Only explosives that are unaltered by water can be used. - Blastholes are lost due to caving, and - Inclined drilling is difficult. On the other hand, water affects the rock and the rock masses by the following: - Increase in propagation velocity of the elastic waves in porous and fissured ground. - Reduction of the compressive and tensile strength of the rocks (Obert and Duvall, 1967) as the friction between particles is lower. - Reduction of the Stress wave attenuation and, because of this, the breakage effects are intensified by ET (Ash, 1968).

which it is in contact and, because of this, great attention must be paid to this phenomenon. A general recommendation when these problems are present is to limit the number of blastholes per blast, in order to lower the time that passes between the charging and the firing.

REFERENCES Ash, R.I.: The design of blasting roundi. Ch. 7.3. Surface Mining, Ed. E. F? Pfleider, AIME, 1968. Atchison, TC.: Fragmentation principles. Ch. 7.2. Surface Mining, Ed. E.F?Pfleider, AIME, 1968. Belland, J.M.: Structure as a control in rock fragmentation. Carol - i%b. LaKe rron ore deposrts. L ~ u i i e r i nMarch , Bhandari, S.: Blastinn in non-homogeneous rocks. Australian Mining, i e r ~ i ~ May, 1974. Blair, B.E.: Physical properties of mine rock. Part 111. USBM RI No. 5 130, 1955: Part IV USBM-RI, No. 5244,1956. Grant, C. H.: How to muke explosives domore work. Mining- Magazine, August, 1970. Hagan, T.N.: The effects of some structural properties of rock on the design und results of blasting. ICI Australia Operations PTY.Ltd. Melboume, 1979. Hagan, T. N.: 'The influence of rock properties of blasts in underground construction. Proc. Int. Symp. on Engineering Geology and Underground Construction. Lisboa, Portugal, 1983. Hanies, G.: Breakage of rock by explosives. Aus. I.M.M., London, 1978. Kutuzov, B.N. et al.: Classification des roches d'apres leur explosibi1it.i pour les decouvertes. Gomyl, Zumal, Moscow, 1979. Lopez Jimeno, E.: Inpuencia de Iaspropiedades de las rocas y Macizos Rocosos en el diseiio y resultado de las voladuras. Tecniterrae, 1982. Memt, A. H.: Geological predictions for underground excavations. North American RETC Conference. Polak, E.J.: Seismic attenuation in engineering site investigations. Proc. Ist. Aust. N.Z. Conf. Geomechanics, Melboume, 1971. Rinehart, J.S.: Fractures und strain generated in joints and layered rock masses by explosions. Proc. Symp. Mechanism of Rock Failure by Explosions. Fontainebleau, October. 1970. Sassa, K. & I. Ito: On the relation berween the strength of a rock und the panern of breakage by blasting. Proc. 3rd. Congress Intemational Society of Rock Mechanics. Denver, 1974. Sjogren, B. et al.: Seismic classification of rock muss qualities. Geophysical Prospecting, No, 27,1979. Wild, H.W.: Geology und blasting in openpits. Erzmetall, 1976. U

w i t h n i i t i n t P . m ~ i n ~ R i i t e ~ e m a s s _ e n tension, the water is mobilized, forming a wedge which could provoke a great overbreak.

17.3.5 Temperature of the rock muss The orebeds that contain pyrites usually have high rock temperature problems because of the effect of slow oxidation of this mineral, causing the explosive agents such as ANFO to react exothermically with the pyrite, with stimulation from 120°C f 10°C. The latest investigations point to a first reaction between ANFO and hydrated ferrous sulphate, and even more so between the latter and amrnonic nitrate, initiating an exothermic reaction that is self-maintaining from 80°C On. This ferrous sulphate is one of the products of decomposition of the pyrites, apart from the femc sulphate and the sulfuric acid. To avoid this problem, which has caused severe accidents on several occasions, diverse substances which inhibit ANFO have been added, such as urea, potassic oxalate, etc., arriving at the conclusion that by adding to ANFO a 5% in weight of urea, the exothermic reaction of the ternary mixture is avoided up to a temperature of 180°C (Miron et al., 1979). The sensitivity of the water gel type explosives also depends highly upon the temperature of the rock with

.

%

*

CHAFIER 18

Characterization of the rock masses for blast designing

18.1 INTRODUCTION The properties ot rock masses that most infiuence blast

- Dynamic strengths of the rocks. - Spacing and orientation of the planes of weakness. - Lithology and thickness of the sedimentary bedding planes. - Velocity of wave propagation. - Elastic properties of the rocks. - Types of infilling material and tightness of the joints. - Indexes of anisotropy and heterogeneity of the rock masses, etc. The determination of these parameters by direct or laboratory methods is very costly and difficult, as the samples tested do not usually include discontinuities and the lithologicalchanges of the rock mass from where they were taken. In order to obtain a representative sample, it would be necessary for it to have a size ten times larger than the mean spacing between joints. However, these methods do complement the characterization of the rock masses to be blasted. At the moment, the most common geomechanic techniques for monitoring are: - Diamond drilling with core recovery and geomechanic testing. -, - Structural studies of the joint System. - Seismic survey profiles. - Geophysical logs of investigation drill holes. - Geophysical logs of production blastholes. - Logging and individual treatment during drilling of production blastholes.

RC (MPa) = 24 . 1, (50) (MPa) the Pierce equation, for the calculation of the Burdm from the RQD index, corrected by a Coefficient of Alteration which takes into account the Joint Strength as a function of their tightness and the type of infilling, Fig. 18.1 and Table 18.2. The company Steffen, Robertson and Kirsten, Ltd. (1985), used various geomechanic Parameters to calculate the powder factors in bench blasting, among which RQD, the Uniaxial Compressive Strength (MPa), the Interna1 Friction Angles and Abrasiveness of the joints and the Density are found (t/m3),Fig, 18.2. This procedure is one of the few that take into account the effect of blasthole diameter (mm) or spacial distribution of the explosives upon the powder factor of the blast. 18.3 CHARACTERISTICS OF THE JOINT SYSTEMS There are various properties of the joints that can be measured in a characterization study, but the most important from a breakage point of view are spacing and onentation. An index obtained frequently is that known as the Volumetric Joint Count, J, which is defined by the total number of joints per cubic meter, obtained from the summing of the joints present per meter for each one of the existing families. The relationship between the index J, and the RQD is, according to Pallsmtrom (1974), the following: RQD = 115 - 3.3 J,For J, < 4.5, RQD = 100

18.2 DIAMOND DRILLING WITH CORE RECOVERY AND GEOMECHANIC TESTING With core recovery by diamond drilling, one of the most extensive rock mass clasifications known can be applied, called RQD (Rock Quality Designation, Deere 1968) which is defined as the percentage of the core length recovered in pieces larger than 10 cm with respect to the length of the core run, Table 18.1. Apart from this, the geomechanic testing of Point Load Strength I, can be canied out either in the diametral or axial position, to be able to estimate the Uniaxial Compressive Strength RC.

According to the orientation of the joints, the in-situ blocks will show different geometries that doubly affect the fragmentation of the blast and the most useful break direction of the round. In Fig. 18.3, the approximate volume of the blocks taken from J, and the relationship of the three characteristic intersections of the Same can be estimated. An attempt to take into consideration the structural discontinuities when designing the rounds is owed to Ashby (1977), which relates the fracture frequency and their shear strength to the powder factors of the explosive, Fig. 18.4. Lilly (1986) defined a Blastability Index BI that is

168

Drilling und blasting of rocks

Table 18.1. RQD 0-25 25-50 50-75 75-90 90-100

Rock quality Very poor Poor Fair GOO~ Excellent

Table 18.2. Joint strength Strong Medium weak Very weak

Y = a + b l n X

m

Correction factor 1O . 0.9 0.8 0.7

0.9

-

0.8

-

0.7

-

3.6

Table 18.3. J

>I 1-3 3-10 10-30 > 30

Characteristicsof the mass Massive blocks Large blocks Medium size blocks Small blocks Very small%locks

0.3

1

"'1

0.1

0.0

DESCRlPTlON OF ROCK OUALITY

1

VERY POOR

POOR

I

I

0

10

20

I

FAIR

GO09

I

I

:

I

I

i

I

30

I

I

I

I

I

40

50

60

70

I

1

80

p-~ I 90

100

EOUIVALENT ROCK QUALITY DESIGNATION (%) €ROD = ROD X ALTERATION FACTOR

Table 18.4. Geomechanic ~arameters 1. Rock mass description (RMD) I. I Powderylfriable 1.2 Blocky 1.3 Totally massive

Ratine

Fig. 18.1. Blastability factor k vs equivalent rock quality designation, RQDE.

10 20 50

2. Joint Plane Spacing (JPS) 2.1 Close (< 0.1 m) 2.2 Intermediate (0. I to 1 m) 2.3 Wide (> 1 m)

10 20 50

-

3. Joint Plane Onentation (JPO) 3.1 Horizontal 3.2 Dip out of face 3.3 Strike normal to face 3.4 Dip into face

10 20 30

4. Specific Gravity Influence (SGI) SGI = 25 SG - 50 (where SG is In Tonslcu metre) 5. Hardness (H)

1-10

obtained by summing the representative values of five geomechanics parameters. Rl= Q 5 ( R M 1 3 t l m - u D L

In Table 18.4, the ratings for Blastability Index parameters are described. The Powder Factors CE or the Energy Factors FE are : or the equations calculated with ~ i g18.5, CE (Kg ANFO/t) = 0.004

X

BI, or

FE (MJ/t) = 0.015 X BI

From the numerous experiences canied out in Australia, it has been concluded that the Rock Factor of the Model Kuz-Ram of Cunningham (1983) can be obtained by multiplying BI by 0.12.

Fig. 18.2. Calculation of the Powder Factor as a function of the different geomechanicparameters of the rock mass.

Example: Consider a highly laminated, soft ferruginous shale which has horizontal to sub-horizontal bedding to which the-fofIowing~due~me~ri.

RMD = 15 P S = 10 JPO = 10 SGI = 10 H=l The total sum is 46 and the Blastability Index is BI = 23. From Fig. 18.4, a powder factor of 0.1 kg/t is obtained. Ghose (1988) also proposes a geomechanic classification System of the rock masses in coal mines for predicting powder factors in surface blastings. The four parametersmeasured are indicated in Table 18.5.

Characterization of the rock masses for blast designing

Fig. 18.3. Estimation of the volume of the in-situ blocks.

Parameters 1. Density Ratio 2. Spacing of discontinuities (m) Ratio 3. Point load strength Index (MPa) Ratio 4. Joint plane onentation Ratio

Range of values 1.3-1.6 20 < 0.2 35
1.6-2.0 15 0.2-0.4 25 1-2 20 Strike at an acute angle to face 15

20

Table 18.6. Adjustment factors I. Degree of confinement Highly confined Reasonably free

-5 0

2. Bench stiffness Hole depthlburden > 2 Hole depthlburden C 1.5 Hole depthlburden 1.5-2

0 -5 -2

Values

2.0-2.3 12 0.4-0.6 20 2-4 15 Strike normal to face

2.3-2.5 6 0.6-2.0 12 46 8 Dip out of face

> 2.5

12

10

6

Table 18.7. Blastability index 80-85 60-70 5MO 40-50 30-40

4

> 2.0 8 >6 5 Horizontal

Powder factor (kg/m3) 0.2-0.3 0.3-0.5 0.5-0.6 O.M.7 0.7-0.8

170

Drilling and bhsting of rocks

POWDEA FACTOR

'

BLASTING

-

POWDEA FACTOR ,KO A N F O ~ ~ J

'

lag

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-Handbook of Solvents

Citation preview

HANDBOOK OF

SOLVENTS George Wypych, Editor

ChemTec Publishing

Toronto − New York 2001

Published by ChemTec Publishing 38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada Co-published by William Andrew Inc. 13 Eaton Avenue, Norwich, N Y 13815, USA © Chem Tec Publishing, 2001 ISBN 1-895198-24-0 All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibility is assumed by the Author and the Publisher for any injury or/and damage to persons or properties as a matter of products liability, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.

Canadian Cataloguing in Publication Data Handbook of Solvents Includes bibliographical references and index ISBN 1-895198-24-0 (ChemTec Publishing) ISBN 0-8155-1458-1 (William Andrew Inc.) Library of Congress Catalog Card Number: 00-106798 1. Solvents--Handbooks, manuals, etc. I. Wypych, George TP247.5.H35 2000

661’.807

C00-900997-3

Printed in Canada by Transcontinental Printing Inc., 505 Consumers Rd. Toronto, Ontario M2J 4V8

Table of Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxvii GEORGE WYPYCH

1

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 2.1

FUNDAMENTAL PRINCIPLES GOVERNING SOLVENTS USE . . . . 7 Solvent effects on chemical systems . . . . . . . . . . . . . . . . . . . . . . . 7

2.1.1 2.1.2 2.1.2.1 2.1.2.2 2.1.2.3 2.1.2.4 2.1.2.5 2.1.2.6 2.1.3 2.1.3.1 2.1.3.2 2.1.3.3 2.1.3.4 2.1.3.5 2.1.4 2.1.4.1 2.1.4.2 2.1.4.3 2.1.5 2.2

Historical outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Classification of solute-solvent interactions . . . . . . . . . . . . . . . . . . Electrostatic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Repulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Specific interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hydrophobic interactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . Modelling of solvent effects . . . . . . . . . . . . . . . . . . . . . . . . . . Computer simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Continuum models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cavity surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Supermolecule models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Application example: glycine in solution . . . . . . . . . . . . . . . . . . . Thermodynamic and kinetic characteristics of chemical reactions in solution Solvent effects on chemical equilibria . . . . . . . . . . . . . . . . . . . . . Solvent effects on the rate of chemical reactions. . . . . . . . . . . . . . . . Example of application: addition of azide anion to tetrafuranosides. . . . . . Solvent catalytic effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular design of solvents . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . .

7 10 11 12 13 14 15 16 17 18 20 21 22 23 27 27 28 30 32 36

2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.3

Molecular design and molecular ensemble design . . . . . . . . . . . . . . . From prediction to design . . . . . . . . . . . . . . . . . . . . . . . . . . . Improvement in prediction method. . . . . . . . . . . . . . . . . . . . . . . Role of molecular simulation. . . . . . . . . . . . . . . . . . . . . . . . . . Model system and paradigm for design . . . . . . . . . . . . . . . . . . . . Appendix. Predictive equation for the diffusion coefficient in dilute solution Basic physical and chemical properties of solvents . . . . . . . . . . . . . .

. . . . . . .

36 37 38 39 40 41 42

2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 2.3.6 2.3.7 2.3.8 2.3.9 2.3.10 2.3.11 2.3.12 2.3.13 2.3.14 2.3.15

Molecular weight and molar volume . . . . . . . Boiling and freezing points. . . . . . . . . . . . Specific gravity . . . . . . . . . . . . . . . . . . Refractive index . . . . . . . . . . . . . . . . . Vapor density and pressure. . . . . . . . . . . . Solvent volatility . . . . . . . . . . . . . . . . . Flash point . . . . . . . . . . . . . . . . . . . . Flammability limits. . . . . . . . . . . . . . . . Sources of ignition and autoignition temperature Heat of combustion (calorific value) . . . . . . . Heat of fusion. . . . . . . . . . . . . . . . . . . Electric conductivity . . . . . . . . . . . . . . . Dielectric constant (relative permittivity) . . . . Occupational exposure indicators . . . . . . . . Odor threshold . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

43 44 46 47 48 49 50 51 52 54 54 54 54 56 56

CHRISTIAN REICHARDT

ESTANISLAO SILLA, ARTURO ARNAU, IÑAKI TUÑÓN

KOICHIRO NAKANISHI

GEORGE WYPYCH

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

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. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

ii 2.3.16 2.3.17 2.3.18 2.3.19 2.3.20 3

Handbook of Solvents

3.1

Toxicity indicators . . . . . . . . . . . . . . . . Ozone-depletion and creation potential . . . . . Oxygen demand . . . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . . Other typical solvent properties and indicators . PRODUCTION METHODS, PROPERTIES, AND MAIN APPLICATIONS . . . . . . . . . Definitions and solvent classification . . . . . .

3.2

Overview of methods of solvent manufacture . . . . . . . . . . . . . . . . . . 69

3.3

Solvent properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

3.3.1 3.3.1.1 3.3.1.2 3.3.2 3.3.3 3.3.4 3.3.5 3.3.6 3.3.7 3.3.8 3.3.9 3.3.10 3.3.11 3.3.11 3.3.12 3.3.13 3.3.14 3.4

Hydrocarbons. . . . . . . . . . . . . . . . . . . . Aliphatic hydrocarbons. . . . . . . . . . . . . . . Aromatic hydrocarbons. . . . . . . . . . . . . . . Halogenated hydrocarbons . . . . . . . . . . . . . Nitrogen-containing compounds (nitrates, nitriles) Organic sulfur compounds . . . . . . . . . . . . . Monohydric alcohols . . . . . . . . . . . . . . . . Polyhydric alcohols. . . . . . . . . . . . . . . . . Phenols . . . . . . . . . . . . . . . . . . . . . . . Aldehydes . . . . . . . . . . . . . . . . . . . . . Ethers . . . . . . . . . . . . . . . . . . . . . . . . Glycol ethers . . . . . . . . . . . . . . . . . . . . Ketones . . . . . . . . . . . . . . . . . . . . . . . Acids . . . . . . . . . . . . . . . . . . . . . . . . Amines . . . . . . . . . . . . . . . . . . . . . . . Esters . . . . . . . . . . . . . . . . . . . . . . . . Comparative analysis of all solvents . . . . . . . . Terpenes . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . .

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75 75 76 78 79 80 81 83 84 85 86 87 88 90 91 92 94 96

3.4.1 3.4.2 3.4.3 3.4.4 3.4.5 4

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96 96 96 97 97

4.1

Definitions and nomenclature . . . . . . . . . . . . . . . . . . Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . Threshold limit values . . . . . . . . . . . . . . . . . . . . . . GENERAL PRINCIPLES GOVERNING DISSOLUTION OF MATERIALS IN SOLVENTS . . . . . . . . . . . . . . . Simple solvent characteristics . . . . . . . . . . . . . . . . . .

4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 4.1.6 4.1.7 4.2

Solvent power . . . . . . . . . . . . . . . . . . One-dimensional solubility parameter approach . Multi-dimensional approaches . . . . . . . . . . Hansen’s solubility . . . . . . . . . . . . . . . . Three-dimensional dualistic model. . . . . . . . Solubility criterion . . . . . . . . . . . . . . . . Solvent system design . . . . . . . . . . . . . . Effect of system variables on solubility . . . . .

. . . . . . . .

. . . . . . . .

. . . . . . . .

. . . . . . . .

. . . . . . . .

101 103 110 112 116 119 120 124

4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6

General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Flexibility of a polymer chain . . . . . . . . . . . . . . . . . . . . . . . Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Temperature and pressure . . . . . . . . . . . . . . . . . . . . . . . . . Methods of calculation of solubility based on thermodynamic principles .

. . . . . .

. . . . . .

. . . . . .

124 126 127 128 128 130

GEORGE WYPYCH

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57 58 58 58 60

. . . . . . . . . . . . . . . . 65 . . . . . . . . . . . . . . . . 65

GEORGE WYPYCH GEORGE WYPYCH

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

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. . . . . . . . 101 . . . . . . . . 101 . . . . . . . .

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Table of contents

iii

4.3

Polar solvation dynamics: Theory and simulations . . . . . . . . . . . . . . . 132

4.3.1 4.3.2 4.3.3 4.3.4

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Continuum dielectric theory of solvation dynamics . . . . . . . . . . . Linear response theory of solvation dynamics . . . . . . . . . . . . . . Numerical simulations of solvation in simple polar solvents: The simulation model . . . . . . . . . . . . . . . . . . . . . . . . . . Numerical simulations of solvation in simple polar solvents: Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . Solvation in complex solvents . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods for the measurement of solvent activity of polymer solutions .

. . . . 132 . . . . 133 . . . . 136

. . . .

. . . .

. . . .

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140 144 145 146

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Necessary thermodynamic equations. . . . . . . . . . . . . . . . . Experimental methods, equipment and data reduction . . . . . . . . Vapor-liquid equilibrium (VLE) measurements . . . . . . . . . . . Experimental equipment and procedures for VLE-measurements . . Primary data reduction . . . . . . . . . . . . . . . . . . . . . . . . Comparison of experimental VLE-methods . . . . . . . . . . . . . Other measurement methods . . . . . . . . . . . . . . . . . . . . . Membrane osmometry . . . . . . . . . . . . . . . . . . . . . . . . Light scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . X-ray scattering. . . . . . . . . . . . . . . . . . . . . . . . . . . . Neutron scattering . . . . . . . . . . . . . . . . . . . . . . . . . . Ultracentrifuge . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cryoscopy (freezing point depression of the solvent) . . . . . . . . Liquid-liquid equilibrium (LLE) . . . . . . . . . . . . . . . . . . . Swelling equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . Thermodynamic models for the calculation of solvent activities of polymer solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . Models for residual chemical potential and activity coefficient in the liquid phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fugacity coefficients from equations of state . . . . . . . . . . . . Comparison and conclusions . . . . . . . . . . . . . . . . . . . . . Appendix 4.4A . . . . . . . . . . . . . . . . . . . . . . . . . . . . SOLUBILITY OF SELECTED SYSTEMS AND INFLUENCE OF SOLUTES . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental methods of evaluation and calculation of solubility parameters of polymers and solvents. Solubility parameters data . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

146 149 154 154 155 170 175 178 178 181 184 185 186 188 189 193

4.3.5 4.3.6 4.3.7 4.4 4.4.1 4.4.2 4.4.3 4.4.3.1 4.4.3.1.1 4.4.3.1.2 4.4.3.1.3 4.4.3.2 4.4.3.2.1 4.4.3.2.2 4.4.3.2.3 4.4.3.2.4 4.4.3.2.5 4.4.3.2.6 4.4.3.2.7 4.4.3.2.8 4.4.4 4.4.4.1 4.4.4.2 4.4.4.3 5 5.1 5.1.1 5.1.1.1 5.1.1.2 5.1.1.3 5.1.1.4 5.1.2

ABRAHAM NITZAN

CHRISTIAN WOHLFARTH

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

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. . . . . . 195 . . . .

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. . . .

196 207 214 223

. . . . . . 243

5.2 5.2.1 5.2.2 5.2.2.1 5.2.2.2 5.2.3 5.3

Solubility parameter of polymers . . . . . . . . . . . . . . . . . . . . . Glass transition in polymers . . . . . . . . . . . . . . . . . . . . . . . . Glass transition enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . Cp jump at the glass transition . . . . . . . . . . . . . . . . . . . . . . . Prediction from thermal transition enthalpies . . . . . . . . . . . . . . . Methods of calculation of solubility parameters of solvents and polymers VALERY YU. SENICHEV, VASILIY V. TERESHATOV

. . . .

. . . . . . 243

Experimental evaluation of solubility parameters of liquids . . . . Direct methods of evaluation of the evaporation enthalpy . . . . Indirect methods of evaluation of evaporation enthalpy . . . . . . Static and quasi-static methods of evaluation of pair pressure . . . Kinetic methods . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of experimental evaluation and calculation of solubility parameters of polymers. . . . . . . . . . . . . . . . . . . . . . . Prediction of solubility parameter . . . . . . . . . . . . . . . . . NOBUYUKI TANAKA

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. . . . 138

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243 243 244 245 245

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253 254 254 256 258 261

iv

Handbook of Solvents

5.4

Mixed solvents, a way to change the polymer solubility. . . . . . . . . . . . . 267

5.4.1 5.4.2 5.4.3 5.4.4

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solubility-cosolvency phenomenon . . . . . . . . . . . . . . . . . . . . . . . New cosolvents effects. Solubility behavior . . . . . . . . . . . . . . . . . . . Thermodynamical description of ternary systems. Association equilibria theory of preferential adsorption . . . . . . . . . . . . . . . . . . . . . . . . . Polymer structure of the polymer dependence of preferential adsorption. Polymer molecular weight and tacticity dependence of preferential adsorption. The phenomenological theory of solvent effects in mixed solvent systems . . .

267 268 273

6 6.1

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The intersolute effect: solute-solute interactions . . . . . . . . . . . . . . . The solvation effect: solute-solvent interaction . . . . . . . . . . . . . . . The general medium effect: solvent-solvent interactions . . . . . . . . . . The total solvent effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Surface tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electronic absorption spectra. . . . . . . . . . . . . . . . . . . . . . . . . Complex formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Liquid chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . Interpretations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ambiguities and anomalies. . . . . . . . . . . . . . . . . . . . . . . . . . A modified derivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . Interpretation of parameter estimates. . . . . . . . . . . . . . . . . . . . . Confounding effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solute-solute interactions. . . . . . . . . . . . . . . . . . . . . . . . . . . Coupling of general medium and solvation effects . . . . . . . . . . . . . The cavity surface area . . . . . . . . . . . . . . . . . . . . . . . . . . . . The role of interfacial tension . . . . . . . . . . . . . . . . . . . . . . . . SWELLING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Modern views on kinetics of swelling of crosslinked elastomers in solvents

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281 281 281 282 283 284 285 285 285 288 290 291 295 298 298 298 299 300 301 301 301 301 302 305 305

6.1.1 6.1.2 6.1.3 6.1.4 6.1.5 6.2

Introduction. . . . . . . . . . . . . . . . . . . . . . Formulation of swelling for a plane elastomer layer . Diffusion kinetics of plane layer swelling . . . . . . Experimental study of elastomer swelling kinetics . Conclusions. . . . . . . . . . . . . . . . . . . . . . Equilibrium swelling in binary solvents . . . . . . .

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305 306 310 314 317 318

6.3

Swelling data on crosslinked polymers in solvents . . . . . . . . . . . . . . . 327

6.4

Influence of structure on equilibrium swelling. . . . . . . . . . . . . . . . . . 331

7 7.1

SOLVENT TRANSPORT PHENOMENA . . . . . . . . . . . . . . . . . . 339 Introduction to diffusion, swelling, and drying . . . . . . . . . . . . . . . . . 339

7.1.1 7.1.2 7.1.3 7.2

Diffusion . . . . . . . . . . . . . . . . . . . . . . . . Swelling . . . . . . . . . . . . . . . . . . . . . . . . Drying . . . . . . . . . . . . . . . . . . . . . . . . . Bubbles dynamics and boiling of polymeric solutions .

7.2.1

Rheology of polymeric solutions and bubble dynamics . . . . . . . . . . . . . 356

5.4.5 5.5 5.5.1 5.5.2 5.5.2.1 5.5.2.2 5.5.2.3 5.5.2.4 5.5.2.5 5.5.3 5.5.3.1 5.5.3.2 5.5.3.3 5.5.3.4 5.5.3.5 5.5.3.6 5.5.4 5.5.4.1 5.5.4.2 5.5.4.3 5.5.4.4

LIGIA GARGALLO AND DEODATO RADIC

KENNETH A. CONNORS

E. YA. DENISYUK, V. V. TERESHATOV

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

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274 277 281

VASILIY V. TERESHATOV, VALERY YU. SENICHEV VASILIY V. TERESHATOV, VALERY YU. SENICHEV

GEORGE WYPYCH

SEMYON LEVITSKY, ZINOVIY SHULMAN

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339 344 348 356

Table of contents

v

7.2.1.1 7.2.1.2 7.2.2 7.2.3 7.3

Rheological characterization of solutions of polymers. . . . . . . Dynamic interaction of bubbles with polymeric liquid . . . . . . Thermal growth of bubbles in superheated solutions of polymers Boiling of macromolecular liquids . . . . . . . . . . . . . . . . . Drying of coated film. . . . . . . . . . . . . . . . . . . . . . . .

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356 363 372 377 386

7.3.1 7.3.2 7.3.2.1 7.3.2.2 7.3.2.3 7.3.2.4 7.3.2.5

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Theory for the drying . . . . . . . . . . . . . . . . . . . . . . . . . . . Simultaneous heat and mass transfer . . . . . . . . . . . . . . . . . . . Liquid-vapor equilibrium. . . . . . . . . . . . . . . . . . . . . . . . . Heat and mass transfer coefficient . . . . . . . . . . . . . . . . . . . . Prediction of drying rate of coating . . . . . . . . . . . . . . . . . . . Drying regimes: constant drying rate period (CDRP) and falling drying rate period (FDRP) . . . . . . . . . . . . . . . . . . . . . . . . Measurement of the drying rate of coated film. . . . . . . . . . . . . . Thermo-gravimetric analysis . . . . . . . . . . . . . . . . . . . . . . . Rapid scanning FT-IR spectrometer analysis . . . . . . . . . . . . . . High-airflow drying experiment using flame ionization detector (FID) total hydrocarbon analyzer . . . . . . . . . . . . . . . . . . . . . . . . Measurement of drying rate in the production scale dryer . . . . . . . . Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Drying of coated film with phase separation . . . . . . . . . . . . . . . Drying defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Internal stress induced defects . . . . . . . . . . . . . . . . . . . . . . Surface tension driven defects . . . . . . . . . . . . . . . . . . . . . . Defects caused by air motion and others . . . . . . . . . . . . . . . . . Control of lower explosive level (LEL) in a multiple zone dryer . . . . INTERACTIONS IN SOLVENTS AND SOLUTIONS . . . . . . .

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386 388 388 389 390 392

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394 396 396 399

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401 404 407 407 409 409 412 414 414 419

Solvents and solutions as assemblies of interacting molecules . . . . . . Basic simplifications of the quantum model . . . . . . . . . . . . . . . . Cluster expansion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Two-body interaction energy: the dimer . . . . . . . . . . . . . . . . . . Decomposition of the interaction energy of a dimer: variational approach The electrostatic term. . . . . . . . . . . . . . . . . . . . . . . . . . . . The induction term . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The exchange term . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The charge transfer term . . . . . . . . . . . . . . . . . . . . . . . . . . The dispersion term . . . . . . . . . . . . . . . . . . . . . . . . . . . . The decomposition of the interaction energy through a variational approach: a summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . Basis set superposition error and counterpoise corrections . . . . . . . . Perturbation theory approach. . . . . . . . . . . . . . . . . . . . . . . . Modeling of the separate components of ∆E . . . . . . . . . . . . . . . . The electrostatic term. . . . . . . . . . . . . . . . . . . . . . . . . . . . The induction term . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The dispersion term . . . . . . . . . . . . . . . . . . . . . . . . . . . . The exchange (or repulsion) term . . . . . . . . . . . . . . . . . . . . . The other terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A conclusive view . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The relaxation of the rigid monomer constraint . . . . . . . . . . . . . . Three- and many-body interactions . . . . . . . . . . . . . . . . . . . . Screening many-body effects. . . . . . . . . . . . . . . . . . . . . . . . Effective interaction potentials . . . . . . . . . . . . . . . . . . . . . . . The variety of interaction potentials . . . . . . . . . . . . . . . . . . . . Theoretical and computing modeling of pure liquids and solutions . . . . Physical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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419 420 424 424 426 426 428 428 429 430

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432 433 436 441 441 445 446 447 448 448 449 451 453 454 456 461 461

7.3.3 7.3.3.1 7.3.3.2 7.3.3.3 7.3.3.4 7.3.4 7.3.4.1 7.3.4.2 7.3.4.2.1 7.3.4.2.2 7.3.4.2.3 7.3.4.3 8 8.1 8.2 8.3 8.4 8.4.1

8.4.2 8.4.3 8.4.4

8.4.5 8.5 8.6 8.7 8.7.1

SEUNG SU KIM AND JAE CHUN HYUN

JACOPO TOMASI, BENEDETTA MENNUCCI, CHIARA CAPPELLI

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vi 8.7.1.1 8.7.1.2 8.7.2 8.7.2.1 8.7.2.2

8.7.3 8.7.3.1 8.8

8.9 8.9.1 8.9.2 8.9.3 9 9.1 9.2 9.2.1 9.2.2 9.2.3 9.2.4 9.2.5 9.2.6 9.2.7 9.2.8 9.2.8.1 9.2.8.2 9.2.8.3 9.2.8.4 9.3 9.3.1 9.3.1.1 9.3.1.2 9.3.1.3 9.3.1.4 9.3.2 9.3.2.1 9.3.2.2 9.3.2.3 9.3.2.4 9.3.3 9.3.3.1 9.3.3.2 9.3.3.3 9.4 9.4.1 9.4.2 9.4.3

Handbook of Solvents Integral equation methods . . . . . . . . . . . . Perturbation theories . . . . . . . . . . . . . . . Computer simulations . . . . . . . . . . . . . . Car-Parrinello direct QM simulation . . . . . . . Semi-classical simulations . . . . . . . . . . . . Molecular dynamics . . . . . . . . . . . . . . . Monte Carlo . . . . . . . . . . . . . . . . . . . QM/MM . . . . . . . . . . . . . . . . . . . . . Continuum models . . . . . . . . . . . . . . . . QM-BE methods: the effective Hamiltonian . . . Practical applications of modeling . . . . . . . . Dielectric constant . . . . . . . . . . . . . . . . Thermodynamical properties . . . . . . . . . . . Compressibilities . . . . . . . . . . . . . . . . . Relaxation times and diffusion coefficients . . . Shear viscosity . . . . . . . . . . . . . . . . . . Liquid surfaces . . . . . . . . . . . . . . . . . . The basic types of liquid surfaces . . . . . . . . Systems with a large surface/bulk ratio . . . . . Studies on interfaces using interaction potentials MIXED SOLVENTS . . . . . . . . . . . . . .

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465 467 468 470 472 472 473 478 479 482 487 487 490 490 491 492 492 493 495 497 505

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical interaction between components in mixed solvents . . . . . . Processes of homomolecular association. . . . . . . . . . . . . . . . . Conformic and tautomeric equilibrium. Reactions of isomerization. . . Heteromolecular association . . . . . . . . . . . . . . . . . . . . . . . Heteromolecular associate ionization . . . . . . . . . . . . . . . . . . Electrolytic dissociation (ionic association) . . . . . . . . . . . . . . . Reactions of composition. . . . . . . . . . . . . . . . . . . . . . . . . Exchange interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . Amphoterism of mixed solvent components . . . . . . . . . . . . . . . Amphoterism of hydrogen acids . . . . . . . . . . . . . . . . . . . . . Amphoterism of L-acids . . . . . . . . . . . . . . . . . . . . . . . . . Amphoterism in systems H-acid-L-acid . . . . . . . . . . . . . . . . . Amphoterism in binary solutions amine-amine . . . . . . . . . . . . . Physical properties of mixed solvents . . . . . . . . . . . . . . . . . . The methods of expression of mixed solvent compositions . . . . . . . Permittivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Density, molar volume . . . . . . . . . . . . . . . . . . . . . . . . . . Electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . Physical characteristics of the mixed solvents with chemical interaction between components . . . . . . . . . . . . . . . . . . . . . . . . . . . Permittivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Density, molar volume . . . . . . . . . . . . . . . . . . . . . . . . . . Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical properties of mixed solvents. . . . . . . . . . . . . . . . . . Autoprotolysis constants . . . . . . . . . . . . . . . . . . . . . . . . . Solvating ability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Donor-acceptor properties . . . . . . . . . . . . . . . . . . . . . . . . Mixed solvent influence on the chemical equilibrium . . . . . . . . . . General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . Mixed solvent effect on the position of equilibrium of homomolecular association process . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mixed solvent influence on the conformer equilibrium . . . . . . . . .

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505 505 505 506 507 507 508 508 509 509 509 509 510 510 511 511 513 515 516 516

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517 518 519 521 522 524 524 526 527 527 527

Y. Y. FIALKOV, V. L. CHUMAK

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Table of contents 9.4.4 9.4.4.1 9.4.5 9.4.6

9.4.7 9.5 10 10.1

Solvent effect on the process of heteromolecular association . . . . . . Selective solvation. Resolvation . . . . . . . . . . . . . . . . . . . . . Mixed solvent effect on the ion association process . . . . . . . . . . . Solvent effect on exchange interaction processes . . . . . . . . . . . . Systems with non-associated reagents . . . . . . . . . . . . . . . . . . Systems with one associated participant of equilibrium . . . . . . . . . Systems with two associated participants of equilibrium . . . . . . . . Mixed solvent effect on processes of complex formation . . . . . . . . The mixed solvent effect on the chemical equilibrium thermodynamics ACID-BASE INTERACTIONS . . . . . . . . . . . . . . . . . . . . General concept of acid-base interactions . . . . . . . . . . . . . . . . GEORGE WYPYCH

vii . . . . . . . . . . .

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532 538 546 552 552 553 553 556 557 565 565

10.2

Effect of polymer/solvent acid-base interactions: relevance to the aggregation of PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570

10.2.1 10.2.1.1 10.2.1.1.1 10.2.1.1.2 10.2.1.1.3 10.2.1.2 10.2.1.2.1 10.2.1.2.2 10.2.1.2.3 10.2.1.2.4 10.2.1.2.5 10.2.1.2.6 10.2.2 10.2.2.1 10.2.2.2

Recent concepts in acid-base interactions . . . . . . . . . . . . . . . . . . . . The nature of acid-base molecular interactions . . . . . . . . . . . . . . . . . The original Lewis definitions . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular Orbital (MO) approach to acid-base reactions . . . . . . . . . . . . The case of hydrogen bonding . . . . . . . . . . . . . . . . . . . . . . . . . . Quantitative determination of acid-base interaction strength . . . . . . . . . . Perturbation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hard-Soft Acid-Base (HSAB) principle . . . . . . . . . . . . . . . . . . . . . Density functional theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effect of ionocity and covalency: Drago’s concept . . . . . . . . . . . . . . . Effect of amphotericity of acid-base interaction: Gutmann’s numbers . . . . . Spectroscopic measurements: Fowkes’ approach . . . . . . . . . . . . . . . . Effect of polymer/solvent interactions on aggregation of stereoregular PMMA Aggregation of stereoregular PMMA . . . . . . . . . . . . . . . . . . . . . . Relation between the complexing power of solvents and their acid-base properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Influence of the nature of the solvent on the α and β-relaxations of conventional PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dielectric spectroscopy results . . . . . . . . . . . . . . . . . . . . . . . . . . Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent effects based on pure solvent scales . . . . . . . . . . . . . . . . . . .

10.2.3 10.2.3.1 10.2.3.2 10.2.4 10.3 10.3.1 10.3.2 10.3.3 10.3.3.1 10.3.3.2 10.3.3.3 10.3.3.4 10.3.3.5 10.3.3.6 10.3.3.7 10.3.3.8 10.3.4 10.3.5 10.3.6 10.3.7 10.3.7.1 10.3.7.2

S. BISTAC, M. BROGLY

JAVIER CATALÁN

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The solvent effect and its dissection into general and specific contributions . Characterization of a molecular environment with the aid of the probe/homomorph model. . . . . . . . . . . . . . . . . . . . . . . . . . . . Single-parameter solvent scales: the Y, G, ET(30), Py , Z, χR, Φ, and S' scales. The solvent ionizing power scale or Y scale . . . . . . . . . . . . . . . . . . The G values of Allerhand and Schleyer . . . . . . . . . . . . . . . . . . . . The ET(30) scale of Dimroth and Reichardt . . . . . . . . . . . . . . . . . . The Py scale of Dong and Winnick . . . . . . . . . . . . . . . . . . . . . . . The Z scale of Kosower . . . . . . . . . . . . . . . . . . . . . . . . . . . . The χR scale of Brooker . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Φ scale of Dubois and Bienvenüe . . . . . . . . . . . . . . . . . . . . . The S' scale of Drago . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent polarity: the SPP scale . . . . . . . . . . . . . . . . . . . . . . . . . Solvent basicity: the SB scale . . . . . . . . . . . . . . . . . . . . . . . . . Solvent acidity: the SA scale . . . . . . . . . . . . . . . . . . . . . . . . . . Applications of the pure SPP, SA and SB scales. . . . . . . . . . . . . . . . Other reported solvents scales . . . . . . . . . . . . . . . . . . . . . . . . . Treatment of the solvent effect in: . . . . . . . . . . . . . . . . . . . . . . .

570 571 571 571 573 574 574 574 575 576 577 578 578 578 579 581 581 581 582 583

. 583 . 584 . . . . . . . . . . . . . . . .

585 587 587 588 588 589 589 590 590 591 591 600 601 605 605 608

viii

Handbook of Solvents

10.3.7.2.1 10.3.7.2.2 10.3.7.2.3 10.3.7.2.4 10.3.7.3 10.4

Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mixtures of solvents. Understanding the preferential solvation model Acid-base equilibria in ionic solvents (ionic melts) . . . . . . . . . .

10.4.1

Acid-base definitions used for the description of donor-acceptor interactions in ionic media . . . . . . . . . . . . . . . . . . . . . . . . The Lewis definition . . . . . . . . . . . . . . . . . . . . . . . . . . . The Lux-Flood definition. . . . . . . . . . . . . . . . . . . . . . . . . The features of ionic melts as media for acid-base interactions . . . . . Oxygen-less media . . . . . . . . . . . . . . . . . . . . . . . . . . . . Oxygen-containing melts . . . . . . . . . . . . . . . . . . . . . . . . . The effect of the ionic solvent composition on acid-base equilibria . . . Methods for estimations of acidities of solutions based on ionic melts . On studies of the homogeneous acid-base reactions in ionic melts . . . Nitrate melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sulphate melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Silicate melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The equimolar mixture KCl-NaCl . . . . . . . . . . . . . . . . . . . . Other alkaline halide melts . . . . . . . . . . . . . . . . . . . . . . . . Reactions of melts with gaseous acids and bases . . . . . . . . . . . . High-temperature hydrolysis of molten halides . . . . . . . . . . . . . The processes of removal of oxide admixtures from melts . . . . . . . ELECTRONIC AND ELECTRICAL EFFECTS OF SOLVENTS . Theoretical treatment of solvent effects on electronic and vibrational spectra of compounds in condensed media. . . . . . . . . . . . . . . .

10.4.1.1 10.4.1.2 10.4.2 10.4.2.1 10.4.2.2 10.4.2.3 10.4.3 10.4.4 10.4.4.1 10.4.4.2 10.4.4.3 10.4.4.4 10.4.4.5 10.4.5 10.4.5.1 10.4.5.2 11 11.1 11.1.1 11.1.2 11.1.3 11.1.4 11.1.5 11.2 11.2.1 11.2.2 11.2.3 12

VICTOR CHERGINETS

. . . . . .

MATI KARELSON

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. . . . . .

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. . . . . .

608 611 612 612 612 616

. . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . .

617 617 618 618 619 619 620 623 625 625 627 628 629 631 632 632 633 639

. . . . 639

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Theoretical treatment of solvent cavity effects on electronic-vibrational spectra of molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Theoretical treatment of solvent electrostatic polarization on electronic-vibrational spectra of molecules . . . . . . . . . . . . . . . . . . . Theoretical treatment of solvent dispersion effects on electronic-vibrational spectra of molecules . . . . . . . . . . . . . . . . . . . Supermolecule approach to the intermolecular interactions in condensed media Dielectric solvent effects on the intensity of light absorption and the radiative rate constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . TAI-ICHI SHIBUYA

639 647 649 671 674 680

The Chako formula or the Lorentz-Lorenz correction . . . . . . . . . . The generalized local-field factor for the ellipsoidal cavity . . . . . . . Dielectric solvent effect on the radiative rate constant. . . . . . . . . . OTHER PROPERTIES OF SOLVENTS, SOLUTIONS, AND PRODUCTS OBTAINED FROM SOLUTIONS . . . . . . . . Rheological properties, aggregation, permeability, molecular structure, crystallinity, and other properties affected by solvents . . . . . . . . .

. . . . 680 . . . . 680 . . . . 682

12.1.1 12.1.2 12.1.3 12.1.4 12.1.5 12.2

Rheological properties . . . . . . . . . . . . . . . . . . . . . Aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . Permeability . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular structure and crystallinity . . . . . . . . . . . . . . Other properties affected by solvents . . . . . . . . . . . . . Chain conformations of polysaccharides in different solvents .

. . . . . .

12.2.1 12.2.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706 Structure and conformation of polysaccharides in solution . . . . . . . . . . . 707

12.1

GEORGE WYPYCH

RANIERI URBANI AND ATTILIO CESÀRO

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . 683 . . . . 683 . . . . . .

. . . . . .

. . . . . .

683 689 693 697 700 706

Table of contents 12.2.2.1 12.2.2.2 12.2.3 12.2.4 12.2.4.1 12.2.4.2 12.2.5 12.2.6 12.2.6.1 12.2.6.2 12.2.6.3 12.2.6.4 12.2.7 13 13.1 13.1.1 13.1.2 13.1.3 13.1.4 13.1.5 13.1.6 13.1.7

ix

Chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solution chain conformation . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental evidence of solvent effect on oligosaccharide conformational equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Theoretical evaluation of solvent effect on conformational equilibria of sugars Classical molecular mechanics methods . . . . . . . . . . . . . . . . . . . . . Molecular dynamic methods . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent effect on chain dimensions and conformations of polysaccharides . . . Solvent effect on charged polysaccharides and the polyelectrolyte model . . . Experimental behavior of polysaccharides polyelectrolytes . . . . . . . . . . . The Haug and Smidsrød parameter: description of the salt effect on the chain dimension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The statistical thermodynamic counterion-condensation theory of Manning . . Conformational calculations of charged polysaccharides . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . EFFECT OF SOLVENT ON CHEMICAL REACTIONS AND REACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent effects on chemical reactivity . . . . . . . . . . . . . . . . . . . . . . ROLAND SCHMID

707 707 711 715 715 720 722 726 726 727 729 731 733 737 737

13.1.8 13.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . The dielectric approach. . . . . . . . . . . . . . . . . . The chemical approach . . . . . . . . . . . . . . . . . . Dielectric vs. chemical approach . . . . . . . . . . . . . Conceptual problems with empirical solvent parameters The physical approach . . . . . . . . . . . . . . . . . . Some highlights of recent investigations . . . . . . . . . The like dissolves like rule . . . . . . . . . . . . . . . . Water’s anomalies . . . . . . . . . . . . . . . . . . . . The hydrophobic effect . . . . . . . . . . . . . . . . . . The structure of liquids . . . . . . . . . . . . . . . . . . Solvent reorganization energy in ET . . . . . . . . . . . The solution ionic radius . . . . . . . . . . . . . . . . . The future of the phenomenological approach . . . . . . Solvent effects on free radical polymerization . . . . . .

. . . . . . . . . . . . . . .

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. . . . . . . . . . . . . . .

737 737 738 742 744 746 753 753 755 758 762 765 768 772 777

13.2.1 13.2.2 13.2.2.1 13.2.2.2 13.2.2.3 13.2.2.4 13.2.3 13.2.3.1 13.2.3.1.1 13.2.3.1.2 13.2.3.1.3 13.2.3.2 13.2.3.2.1 13.2.3.2.2 13.2.3.2.3 13.2.3.3 13.2.3.3.1 13.2.3.3.2 13.2.3.3.3 13.2.3.3.4 13.2.3.4 13.2.3.4.1

Introduction. . . . . . . . . . . . . . . . . . . . . . . Homopolymerization . . . . . . . . . . . . . . . . . . Initiation . . . . . . . . . . . . . . . . . . . . . . . . Propagation . . . . . . . . . . . . . . . . . . . . . . . Transfer . . . . . . . . . . . . . . . . . . . . . . . . . Termination. . . . . . . . . . . . . . . . . . . . . . . Copolymerization. . . . . . . . . . . . . . . . . . . . Polarity effect. . . . . . . . . . . . . . . . . . . . . . Basic mechanism . . . . . . . . . . . . . . . . . . . . Copolymerization model . . . . . . . . . . . . . . . . Evidence for polarity effects in propagation reactions . Radical-solvent complexes . . . . . . . . . . . . . . . Basic mechanism . . . . . . . . . . . . . . . . . . . . Copolymerization model . . . . . . . . . . . . . . . . Experimental evidence . . . . . . . . . . . . . . . . . Monomer-solvent complexes. . . . . . . . . . . . . . Introduction. . . . . . . . . . . . . . . . . . . . . . . Monomer-monomer complex participation model . . . Monomer-monomer complex dissociation model . . . Specific solvent effects . . . . . . . . . . . . . . . . . Bootstrap model . . . . . . . . . . . . . . . . . . . . Basic mechanism . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . . . . . . . . . . . . . . . .

777 777 777 778 779 779 779 780 780 781 781 782 782 782 783 785 785 785 790 791 791 791

MICHELLE L. COOTE AND THOMAS P. DAVIS

. . . . . . . . . . . . . . . . . . . . . .

x

Handbook of Solvents

13.2.3.4.2 13.2.3.4.3 13.2.4 13.3

Copolymerization model . . . . . . . . . . . . . . . . Experimental evidence . . . . . . . . . . . . . . . . . Concluding remarks . . . . . . . . . . . . . . . . . . Effects of organic solvents on phase-transfer catalysis

. . . .

. . . .

791 793 795 798

13.3.1 13.3.1.1 13.3.1.2 13.3.1.3 13.3.1.4

Two-phase phase-transfer catalytic reactions . . . . . . . . . . . . . . . . . Theoretical analysis of the polarity of the organic solvents and the reactions . Effect of organic solvent on the reaction in various reaction systems . . . . . Effects of the organic solvents on the reactions in other catalysts . . . . . . . Effect of the volume of organic solvent and water on the reactions in various reaction systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effects of organic solvents on other phase-transfer catalytic reactions . . . . Other effects on the phase-transfer catalytic reactions . . . . . . . . . . . . . Three-phase reactions (triphase catalysis) . . . . . . . . . . . . . . . . . . . The interaction between solid polymer (hydrophilicity) and the organic solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effect of solvents on the reaction in triphase catalysis . . . . . . . . . . . . . Effect of volume of organic solvent and water on the reactions in triphase catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effect of polymerization solvent on the chemical structure and curing of aromatic poly(amideimide). . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . .

801 801 805 811

. . . .

822 825 828 830

13.3.1.5 13.3.1.6 13.3.2 13.3.2.1 13.3.2.2 13.3.2.3 13.4

MAW-LING WANG

NORIO TSUBOKAWA

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. . . .

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. . . . . . . . . .

. 830 . 833 . 836 . 841

13.4.1 13.4.2 13.4.2.1 13.4.2.2 13.4.3 13.4.3.1 13.4.3.2 13.4.4 14 14.1

Introduction. . . . . . . . . . . . . . . . . . . . . . . . Effect of solvent on the chemical structure of PAI. . . . Imide and amide bond content of PAI . . . . . . . . . . Intrinsic viscosity and carboxyl group content . . . . . . Effect of solvent on the curing of PAI by heat treatment Chemical structure of PAI after heat treatment . . . . . Curing PAI by post-heating . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . SOLVENT USE IN VARIOUS INDUSTRIES . . . . Adhesives and sealants . . . . . . . . . . . . . . . . . .

14.2

Aerospace. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852

14.3

Asphalt compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855

14.4 14.4.1

Biotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856 Organic solvents in microbial production processes . . . . . . . . . . . . . . . 856

14.4.1.1 14.4.1.2 14.4.1.3 14.4.1.4 14.4.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . Toxicity of organic solvents . . . . . . . . . . . . . . . . Solvent-tolerant bacteria . . . . . . . . . . . . . . . . . . Biotransformation using solvent-tolerant microorganisms. Solvent-resistant microorganisms . . . . . . . . . . . . .

. . . . .

. . . . .

. . . . .

856 859 862 863 865

14.4.2.1 14.4.2.2 14.4.2.2.1 14.4.2.2.2 14.4.2.3 14.4.2.3.1 14.4.2.3.2 14.4.2.4 14.4.2.4.1 14.4.3

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Toxicity of solvents for microorganisms . . . . . . . . . . . . . . . . . . . Spectrum of microorganisms and solvents . . . . . . . . . . . . . . . . . . Mechanisms of solvent toxicity for microorganisms. . . . . . . . . . . . . Adaption of microorganisms to solvents - solvent-resistant microorganisms Spectrum of solvent-resistant microorganisms. . . . . . . . . . . . . . . . Adaption mechanisms of microorganisms to solvents . . . . . . . . . . . . Solvents and microorganisms in the environment and industry - examples . Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Choice of solvent for enzymatic reaction in organic solvent. . . . . . . . .

. . . . . . . . . .

. . . . . . . . . .

865 865 865 866 867 867 868 869 869 872

GEORGE WYPYCH

. . . . . . . . . .

. . . .

. . . . . . . . . .

841 842 842 844 844 844 845 846 847 847

GEORGE WYPYCH GEORGE WYPYCH

MICHIAKI MATSUMOTO, SONJA ISKEN, JAN A. M. DE BONT

TILMAN HAHN, KONRAD BOTZENHART

TSUNEO YAMANE

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. . . . .

. . . . .

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. . . . .

. . . . .

. . . . .

. . . . .

Table of contents 14.4.3.1 14.4.3.2 14.4.3.3

xi

14.4.3.4 14.4.3.5 14.5

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Classification of organic solvents . . . . . . . . . . . . . . . . . . Influence of solvent parameters on nature of enzymatic reactions in organic media. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Properties of enzymes affected by organic solvents . . . . . . . . . Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . Coil coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

14.6

Cosmetics and personal care products . . . . . . . . . . . . . . . . . . . . . . 881

14.7

Dry cleaning - treatment of textiles in solvents . . . . . . . . . . . . . . . . . 883

14.7.1 14.7.1.1 14.7.1.2 14.7.1.3 14.7.1.4 14.7.1.5 14.7.1.6 14.7.1.7 14.7.2 14.7.2.1 14.7.2.2 14.7.2.3 14.7.3 14.7.3.1 14.7.3.2 14.7.3.3 14.8

Dry cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . History of dry cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Basis of dry cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Behavior of textiles in solvents and water . . . . . . . . . . . . . . . . . . . . Removal of soiling in dry cleaning. . . . . . . . . . . . . . . . . . . . . . . . Activity of detergents in dry cleaning . . . . . . . . . . . . . . . . . . . . . . Dry cleaning processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Recycling of solvents in dry cleaning . . . . . . . . . . . . . . . . . . . . . . Spotting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Spotting in dry cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Spotting agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Spotting procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Textile finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Waterproofing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Antistatic finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electronic industry - CFC-free alternatives for cleaning in electronic industry.

883 883 884 885 886 887 888 890 891 891 891 892 893 893 893 893 894

14.8.1 14.8.2 14.8.2.1 14.8.2.1.1 14.8.2.1.2 14.8.2.1.3 14.8.2.1.4

Cleaning requirements in the electronic industry . . . . . . . . . . . . . . . . Available alternatives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Water based systems; advantages and disadvantages . . . . . . . . . . . . . . Cleaning with DI - water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cleaning with alkaline water-based media . . . . . . . . . . . . . . . . . . . . Aqueous-based cleaning agents containing water soluble organic components . Water-based cleaning agents based on MPC® Technology (MPC = Micro Phase Cleaning) . . . . . . . . . . . . . . . . . . . . . . . . . Advantages and disadvantages of aqueous cleaning media . . . . . . . . . . . Semi-aqueous cleaners based on halogen-free solvents, advantages and disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Water insoluble cleaning fluids . . . . . . . . . . . . . . . . . . . . . . . . . Water-soluble, water-based cleaning agents . . . . . . . . . . . . . . . . . . . Comparison of the advantages (+) and disadvantages (-) of semi-aqueous cleaning fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other solvent based cleaning systems . . . . . . . . . . . . . . . . . . . . . . Cleaning of tools and auxiliaries . . . . . . . . . . . . . . . . . . . . . . . . . Cleaning substrates and contamination. . . . . . . . . . . . . . . . . . . . . . Compatibility of stencil and cleaning agent . . . . . . . . . . . . . . . . . . . Different cleaning media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Comparison of manual cleaning vs. automated cleaning. . . . . . . . . . . . . Cleaning equipment for stencil cleaning applications . . . . . . . . . . . . . . Stencil cleaning in screen printing machines. . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cleaning agents and process technology available for cleaning PCB . . . . . . Flux remove and aqueous process . . . . . . . . . . . . . . . . . . . . . . . . The limits of a no-clean process . . . . . . . . . . . . . . . . . . . . . . . . .

894 896 897 897 898 898

14.8.2.1.5 14.8.2.2 14.8.2.2.1 14.8.2.2.2 14.8.2.2.3 14.8.2.3 14.8.3 14.8.3.1 14.8.3.2 14.8.3.3 14.8.3.4 14.8.3.5 14.8.3.6 14.8.3.7 14.8.4 14.8.4.1 14.8.4.1.1

GEORGE WYPYCH

. . . . . . 872 . . . . . . 872 . . . .

. . . .

. . . .

. . . .

. . . .

. . . .

873 875 879 880

GEORGE WYPYCH

KASPAR D. HASENCLEVER

MARTIN HANEK, NORBERT LÖW, ANDREAS MÜHLBAUER

899 899 900 901 901 901 902 904 904 905 906 908 909 911 911 911 911 911

xii

Handbook of Solvents

14.8.4.1.2 14.8.4.1.3 14.8.4.1.4 14.8.4.2 14.8.4.2.1

Different cleaning media and cleaning processes . . . . . . . . . . . . . . . . Semi-aqueous cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Aqueous cleaning in spray in air cleaning equipment . . . . . . . . . . . . . . Flux removal from printed circuit boards - water-free cleaning processes . . . Water-free cleaning processes using HFE (hydrofluoroethers) in combination with a cosolvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.8.4.2.2 Water-free cleaning processes in closed, one-chamber vapor defluxing systems 14.8.5 Criteria for assessment and evaluation of cleaning results . . . . . . . . . . . . 14.8.6 Cost comparison of different cleaning processes. . . . . . . . . . . . . . . . . 14.9 Fabricated metal products . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10 14.10.1 14.10.2 14.10.2.1 14.10.2.1.1 14.10.2.1.2 14.10.2.1.3 14.10.2.2 14.10.2.2.1 14.10.2.2.2 14.10.2.2.3 14.10.2.2.4

GEORGE WYPYCH

912 913 913 914 915 916 917 919 920

Food industry - solvents for extracting vegetable oils . . . . . . . . . . . . . . 923 PHILLIP J. WAKELYN, PETER J. WAN

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Regulatory concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Workplace regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Air Contaminants Standard (29 CFR 1910.1000) . . . . . . . . . . . . . . . . Hazard Communication Standard (HCS) (29 CFR 1910.1200) . . . . . . . . . Process Safety Management (PSM) Standard (29 CFR 1910.119) . . . . . . . Environmental regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . Clean Air Act (CAA; 42 U.S. Code 7401 et seq.) . . . . . . . . . . . . . . . . Clean Water Act (CWA; 33 U.S. Code 1251 et seq.) . . . . . . . . . . . . . . Resource Conservation and Recovery Act (RCRA; 42 U.S.Code 6901 et seq.) . Emergency Planning and Community Right-to-Know Act (EPCRA; 42 U.S. Code 11001 et seq.) . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.2.2.5 Toxic Substances Control Act (TSCA; 15 U.S. Code 2601 et seq.) . . . . . . . 14.10.2.3 Food safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.3 The solvent extraction process . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.3.1 Preparation for extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.3.2 Oil extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.3.3 Processing crude oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.4 Review of solvents studied for extraction efficiency. . . . . . . . . . . . . . . 14.10.4.1 Hydrocarbon solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.10.4.1.1 Nomenclature, structure, composition and properties of hydrocarbons . . . . . 14.10.4.1.2 Performance of selected hydrocarbon solvents. . . . . . . . . . . . . . . . . . 14.10.5 Future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.11 Ground transportation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . GEORGE WYPYCH

923 924 925 925 926 927 927 929 932 932 933 933 934 935 936 938 938 940 941 942 942 946 950

14.12

Inorganic chemical industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 950

14.13

Iron and steel industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951

14.14

Lumber and wood products - Wood preservation treatment: significance of solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953

14.14.1 14.14.2 14.14.2.1 14.14.2.2 14.15

General aspects . . . . . . . . . . . . Role of solvents . . . . . . . . . . . Occurrence . . . . . . . . . . . . . . Technical and environmental aspects Medical applications . . . . . . . . .

14.16

Metal casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957

14.17

Motor vehicle assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958

14.18

Organic chemical industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962

GEORGE WYPYCH GEORGE WYPYCH

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

GEORGE WYPYCH

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953 954 954 955 955

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

Table of contents

xiii

14.19 14.19.1

Paints and coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963 Architectural surface coatings and solvents . . . . . . . . . . . . . . . . . . . 963

14.19.1.1 14.19.1.2 14.19.2

General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963 Technical aspects and properties of coating materials . . . . . . . . . . . . . . 963 Recent advances in coalescing solvents for waterborne coatings . . . . . . . . 969

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

DAVID RANDALL

14.19.2.1 Introduction. . . . . . . . . . . . . . . . . . . . 14.19.2.2 Water based coatings . . . . . . . . . . . . . . . 14.19.2.3 Emulsion polymers . . . . . . . . . . . . . . . . 14.19.2.4 Role of a coalescing solvent . . . . . . . . . . . 14.19.2.5 Properties of coalescing agents. . . . . . . . . . 14.19.2.5.1 Hydrolytic stability . . . . . . . . . . . . . . . . 14.19.2.5.2 Water solubility. . . . . . . . . . . . . . . . . . 14.19.2.5.3 Freezing point . . . . . . . . . . . . . . . . . . 14.19.2.5.4 Evaporation rate . . . . . . . . . . . . . . . . . 14.19.2.5.5 Odor . . . . . . . . . . . . . . . . . . . . . . . 14.19.2.5.6 Color . . . . . . . . . . . . . . . . . . . . . . . 14.19.2.5.7 Coalescing efficiency. . . . . . . . . . . . . . . 14.19.2.5.8 Incorporation . . . . . . . . . . . . . . . . . . . 14.19.2.5.9 Improvement of physical properties . . . . . . . 14.19.2.5.10 Biodegradability. . . . . . . . . . . . . . . . . 14.19.2.5.11 Safety . . . . . . . . . . . . . . . . . . . . . . 14.19.2.6 Comparison of coalescing solvents. . . . . . . . 14.19.2.7 Recent advances in diester coalescing solvents . 14.19.2.8 Appendix - Classification of coalescing solvents 14.20 Petroleum refining industry . . . . . . . . . . . 14.21 14.21.1 14.21.1.1 14.21.1.2 14.21.1.2.1 14.21.1.2.2 14.21.1.3

GEORGE WYPYCH

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969 970 970 971 972 972 972 972 972 972 973 973 973 973 973 973 973 974 975 975

Pharmaceutical industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977 Use of solvents in the manufacture of drug substances (DS) and drug products (DP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977 MICHEL BAUER, CHRISTINE BARTHÉLÉMY

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Where are solvents used in the manufacture of pharmaceutical drugs? . . . Intermediates of synthesis, DS and excipients . . . . . . . . . . . . . . . . Drug products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Impacts of the nature of solvents and their quality on the physicochemical characteristics of raw materials and DP . . . . . . . . . . . . . . . . . . . 14.21.1.3.1 Raw materials (intermediates, DS, excipients) . . . . . . . . . . . . . . . . 14.21.1.3.2 Drug product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.21.1.3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.21.1.4 Setting specifications for solvents . . . . . . . . . . . . . . . . . . . . . . 14.21.1.4.1 Solvents used for the raw material manufacture . . . . . . . . . . . . . . . 14.21.1.4.2 Solvents used for the DP manufacture . . . . . . . . . . . . . . . . . . . . 14.21.1.5 Quality of solvents and analysis . . . . . . . . . . . . . . . . . . . . . . . 14.21.1.5.1 Quality of solvents used in spectroscopy. . . . . . . . . . . . . . . . . . . 14.21.1.5.2 Quality of solvents used in chromatography . . . . . . . . . . . . . . . . . 14.21.1.5.3 Quality of solvents used in titrimetry . . . . . . . . . . . . . . . . . . . . 14.21.1.6 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.21.2 Predicting cosolvency for pharmaceutical and environmental applications .

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977 979 979 984

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985 985 988 989 990 990 991 991 991 993 996 996 997

14.21.2.1 14.21.2.2 14.21.2.3 14.21.2.4 14.21.2.5 14.21.2.6

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997 998 1000 1001 1003 1007

AN LI

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Applications of cosolvency in pharmaceutical sciences and industry . . Applications of cosolvency in environmental sciences and engineering. Experimental observations . . . . . . . . . . . . . . . . . . . . . . . . Predicting cosolvency in homogeneous liquid systems . . . . . . . . . Predicting cosolvency in non-ideal liquid mixtures . . . . . . . . . . .

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xiv

Handbook of Solvents

14.21.2.7 14.22

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013 Polymers and man-made fibers. . . . . . . . . . . . . . . . . . . . . . . . . . 1016

14.23

Printing industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1020

14.24

Pulp and paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023

14.25

Rubber and plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1025

14.26

Use of solvents in the shipbuilding and ship repair industry . . . . . . . . . . . 1026

14.26.1 14.26.2 14.26.3 14.26.4 14.26.4.1 14.26.4.2 14.26.4.3 14.26.5 14.26.6 14.26.7 14.26.8 14.26.9 14.26.10 14.27

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . Shipbuilding and ship repair operations . . . . . . . . . . . Coating operations . . . . . . . . . . . . . . . . . . . . . . Cleaning operations using organic solvents . . . . . . . . . Surface preparation and initial corrosion protection . . . . . Cleaning operations after coatings are applied . . . . . . . . Maintenance cleaning of equipment items and components . Marine coatings. . . . . . . . . . . . . . . . . . . . . . . . Thinning of marine coatings . . . . . . . . . . . . . . . . . Solvent emissions . . . . . . . . . . . . . . . . . . . . . . Solvent waste . . . . . . . . . . . . . . . . . . . . . . . . . Reducing solvent usage, emissions, and waste. . . . . . . . Regulations and guidelines for cleaning solvents . . . . . . Stone, clay, glass, and concrete . . . . . . . . . . . . . . .

14.28

Textile industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1041

14.29

Transportation equipment cleaning. . . . . . . . . . . . . . . . . . . . . . . . 1042

14.30

Water transportation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1042

14.31

Wood furniture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1043

14.32 15 15.1

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045 METHODS OF SOLVENT DETECTION AND TESTING . . . . . . . . . 1053 Standard methods of solvent analysis . . . . . . . . . . . . . . . . . . . . . . 1053

15.1.1 15.1.2 15.1.3 15.1.4 15.1.5 15.1.6 15.1.7 15.1.8 15.1.9 15.1.10 15.1.11 15.1.12 15.1.13 15.1.14 15.1.15 15.1.16 15.1.17 15.1.18 15.1.19

Alkalinity and acidity. . . . . . . . . . Autoignition temperature . . . . . . . . Biodegradation potential . . . . . . . . Boiling point . . . . . . . . . . . . . . Bromine index . . . . . . . . . . . . . Calorific value . . . . . . . . . . . . . Cleaning solvents . . . . . . . . . . . . Color . . . . . . . . . . . . . . . . . . Corrosion (effect of solvents) . . . . . Density . . . . . . . . . . . . . . . . . Dilution ratio . . . . . . . . . . . . . . Dissolving and extraction . . . . . . . Electric properties . . . . . . . . . . . Environmental stress crazing . . . . . . Evaporation rate . . . . . . . . . . . . Flammability limits. . . . . . . . . . . Flash point . . . . . . . . . . . . . . . Freezing point . . . . . . . . . . . . . Free halogens in halogenated solvents .

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

MOHAMED SERAGELDIN, DAVE REEVES

GEORGE WYPYCH

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1026 1026 1026 1027 1027 1028 1031 1031 1032 1033 1035 1036 1037 1039

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

GEORGE WYPYCH

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1053 1054 1054 1055 1055 1056 1056 1056 1057 1057 1057 1058 1058 1059 1059 1059 1060 1061 1061

Table of contents

xv

15.1.20 15.1.21 15.1.22 15.1.23 15.1.24 15.1.25 15.1.26 15.1.27 15.1.28 15.1.29 15.1.30 15.1.31 15.1.32 15.1.33 15.1.34 15.1.35 15.2 15.2.1

Gas chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Odor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Paints standards related to solvents . . . . . . . . . . . . . . . . . . . . pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Purity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Refractive index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Residual solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent partitioning in soils . . . . . . . . . . . . . . . . . . . . . . . . Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Specifications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sustained burning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vapor pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatile organic compound content, VOC . . . . . . . . . . . . . . . . . Special methods of solvent analysis . . . . . . . . . . . . . . . . . . . . Use of breath monitoring to assess exposures to volatile organic solvents

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1061 1062 1062 1063 1063 1063 1066 1066 1066 1066 1067 1067 1067 1068 1068 1069 1078 1078

15.2.1.1 15.2.1.2 15.2.1.3 15.2.1.3.1 15.2.1.3.2 15.2.1.3.3 15.2.1.4 15.2.1.5 15.2.1.6 15.2.1.7 15.2.2

Principles of breath monitoring . . . . . . . . . Types of samples used for biological monitoring Fundamentals of respiratory physiology . . . . . Ventilation . . . . . . . . . . . . . . . . . . . . Partition coefficients . . . . . . . . . . . . . . . Gas exchange . . . . . . . . . . . . . . . . . . . Types of exhaled air samples. . . . . . . . . . . Breath sampling methodology . . . . . . . . . . When is breath monitoring appropriate? . . . . . Examples of breath monitoring. . . . . . . . . . A simple test to determine toxicity using bacteria

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1078 1080 1080 1081 1081 1082 1083 1084 1087 1088 1095

15.2.2.1 15.2.2.2 15.2.2.3 15.2.2.4 15.2.2.5 15.2.2.6 15.2.2.7 15.2.2.8 15.2.2.9 15.2.2.10 15.2.3

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Toxicity defined . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . An alternative. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemicals tested . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Comparisons with other tests . . . . . . . . . . . . . . . . . . . . . . . . . Toxic herbicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Toxicity of divalent cations . . . . . . . . . . . . . . . . . . . . . . . . . Toxicity of organics in the presence of EDTA . . . . . . . . . . . . . . . . Mechanism for reduction of the dye . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Description of an innovative GC method to assess the influence of crystal texture and drying conditions on residual solvent content in pharmaceutical products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1095 1095 1097 1099 1103 1107 1108 1108 1110 1111

MYRTO PETREAS

JAMES L. BOTSFORD

CHRISTINE BARTHÉLÉMY, MICHEL BAUER

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15.2.3.1 15.2.3.2 15.2.3.2.1 15.2.3.2.2 15.2.3.2.3 16 16.1

Description of the RS determination method . . . . . . . . . . . . . . . . . Application: Influence of crystal texture and drying conditions on RS content First example: monocrystalline particles of paracetamol . . . . . . . . . . . Second example: polycrystalline particles of meprobamate and ibuprofen . . Third example: polycrystalline particles of paracetamol. . . . . . . . . . . . RESIDUAL SOLVENTS IN PRODUCTS . . . . . . . . . . . . . . . . . Residual solvents in various products . . . . . . . . . . . . . . . . . . . . .

16.2

Residual solvents in pharmaceutical substances . . . . . . . . . . . . . . . . . 1129

16.2.1 16.2.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129 Why should we look for RS? . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129

GEORGE WYPYCH

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

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1113 1114 1116 1119 1122 1125 1125

xvi 16.2.2.1 16.2.2.2

Handbook of Solvents Modifying the acceptability of the drug product . . . . . . . . . . . . . . . Modifying the physico-chemical properties of drug substances (DS) and drug products (DP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Implications of possible drug/container interactions . . . . . . . . . . . . . As a tool for forensic applications . . . . . . . . . . . . . . . . . . . . . . As a source of toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . General points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Brief overview of the toxicology of solvents. . . . . . . . . . . . . . . . . How to identify and control RS in pharmaceutical substances?. . . . . . . Loss of weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Miscellaneous methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . Gas chromatography (GC) . . . . . . . . . . . . . . . . . . . . . . . . . . General points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Review of methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Official GC methods for RS determination . . . . . . . . . . . . . . . . . How to set specifications? Examination of the ICH guidelines for residual solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Classification of residual solvents by risk assessment . . . . . . . . . . . . Definition of PDE. Method for establishing exposure limits . . . . . . . . Limits for residual solvents. . . . . . . . . . . . . . . . . . . . . . . . . . Analytical procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions regarding the ICH guideline . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ENVIRONMENTAL IMPACT OF SOLVENTS . . . . . . . . . . . . . The environmental fate and movement of organic solvents in water, soil, and air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . 1149

17.1.1 17.1.2 17.1.2.1 17.1.2.2 17.1.2.3 17.1.2.4 17.1.3 17.1.3.1 17.1.3.2 17.1.3.3 17.1.4 17.1.4.1 17.1.4.2 17.1.5 17.1.5.1 17.1.5.2 17.1.5.3 17.1.6 17.1.6.1 17.1.6.2 17.1.6.3 17.1.7 17.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatilization . . . . . . . . . . . . . . . . . . . . . . . . . . Degradation. . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatilization . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . Degradation. . . . . . . . . . . . . . . . . . . . . . . . . . . Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Degradation. . . . . . . . . . . . . . . . . . . . . . . . . . . Atmospheric residence time . . . . . . . . . . . . . . . . . . The 31 solvents in water . . . . . . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatilization from water. . . . . . . . . . . . . . . . . . . . Degradation in water . . . . . . . . . . . . . . . . . . . . . . Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatilization . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . Degradation. . . . . . . . . . . . . . . . . . . . . . . . . . . Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fate-based management of organic solvent-containing wastes

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1149 1150 1150 1150 1151 1151 1151 1151 1152 1153 1153 1153 1154 1154 1154 1155 1155 1157 1157 1159 1160 1161 1162

17.2.1 17.2.1.1 17.2.1.2 17.2.1.3 17.2.1.4

Introduction. . . . . . . . . . . . . . . . . . . . . . . The waste disposal site . . . . . . . . . . . . . . . . . The advection-dispersion model and the required input Maximum permissible concentrations . . . . . . . . . Distribution of organic compounds in leachate . . . .

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1162 1163 1164 1164 1164

16.2.2.3 16.2.2.4 16.2.2.5 16.2.2.5.1 16.2.2.5.2 16.2.3 16.2.3.1 16.2.3.2 16.2.3.3 16.2.3.3.1 16.2.3.3.2 16.2.3.3.3 16.2.4 16.2.4.1 16.2.4.2 16.2.4.3 16.2.4.4 16.2.4.5 16.2.4.6 16.2.5 17 17.1

WILLIAM R. ROY

WILLIAM R. ROY

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. . 1129 . . . . . . . . . . . . .

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1130 1131 1131 1131 1131 1132 1133 1133 1133 1134 1134 1135 1139

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1140 1143 1143 1143 1143 1145 1145 1146 1149

Table of contents

xvii

17.2.2 17.2.3 17.3

Movement of solvents in groundwater . . . . . . . . . . . . . . . . . . . . . . 1166 Mass limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167 Environmental fate and ecotoxicological effects of glycol ethers . . . . . . . . 1169

17.3.1 17.3.2 17.3.3 17.3.4 17.3.4.1 17.3.4.2 17.3.5 17.4

Introduction. . . . . . . . . . . . . . . . . . . . . . . Occurrence . . . . . . . . . . . . . . . . . . . . . . . Environmental behavior . . . . . . . . . . . . . . . . Ecotoxicity . . . . . . . . . . . . . . . . . . . . . . . Survival and growth . . . . . . . . . . . . . . . . . . Reproduction and development . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . Organic solvent impacts on tropospheric air pollution .

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1169 1170 1171 1175 1175 1185 1187 1188

17.4.1 17.4.2 17.4.2.1 17.4.2.2 17.4.2.3 17.4.2.3.1 17.4.2.3.2 17.4.2.3 17.4.2.4 17.4.3 17.4.3.1 17.4.3.2 17.4.3.3 17.4.3.3.1 17.4.4 17.4.5 18

Sources and impacts of volatile solvents . . . . . . . . . . . . . . . . . . Modes and scales of impact . . . . . . . . . . . . . . . . . . . . . . . . Direct exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Formation of secondary compounds . . . . . . . . . . . . . . . . . . . . Spatial scales of secondary effects . . . . . . . . . . . . . . . . . . . . . Global impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Stratospheric ozone depletion . . . . . . . . . . . . . . . . . . . . . . . Global climate forcing . . . . . . . . . . . . . . . . . . . . . . . . . . . Urban and regional scales . . . . . . . . . . . . . . . . . . . . . . . . . Tropospheric ozone. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tropospheric photochemistry and ozone formation . . . . . . . . . . . . Assessing solvent impacts on ozone and VOC reactivity . . . . . . . . . Quantification of solvent emissions on ozone formation . . . . . . . . . Regulatory approaches to ozone control and solvents . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CONCENTRATION OF SOLVENTS IN VARIOUS INDUSTRIAL ENVIRONMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . Measurement and estimation of solvents emission and odor. . . . . . . .

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1188 1189 1189 1190 1190 1190 1191 1191 1192 1192 1192 1193 1195 1196 1198 1299

Definition “solvent” and “volatile organic compounds” (VOC) . . . . . . Review of sources of solvent emissions . . . . . . . . . . . . . . . . . . Causes for emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . Emissions of VOCs from varnishes and paints . . . . . . . . . . . . . . VOC emissions from emulsion paints . . . . . . . . . . . . . . . . . . . Measuring of VOC-content in paints and varnishes . . . . . . . . . . . . Definition of low-emissive coating materials . . . . . . . . . . . . . . . Determination of the VOC content according to ASTM D 3960-1 . . . . Determination of the VOC content according to ISO/DIS 11 890/1 and 2 VOC content > 15% . . . . . . . . . . . . . . . . . . . . . . . . . . . . VOC content > 0.1 and < 15 %. . . . . . . . . . . . . . . . . . . . . . . Determination of VOC-content in water-thinnable emulsion paints (in-can VOC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Measurement of solvent emissions in industrial plants . . . . . . . . . . Plant requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The determination of the total carbon content in mg C/Nm³. . . . . . . . Flame ionization detector (FID) . . . . . . . . . . . . . . . . . . . . . . Silica gel approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Qualitative and quantitative assessment of individual components in the exhaust-gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Indicator tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Quantitative solvent determination in exhaust gas of plants by means of gas-chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . “Odor” definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1201 1203 1203 1203 1205 1205 1205 1205 1206 1206 1208

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1208 1209 1209 1214 1214 1214

18.1 18.1.1 18.1.2 18.1.2.1 18.1.2.2 18.1.2.3 18.1.3 18.1.3.1 18.1.3.2 18.1.3.3 18.1.3.3.1 18.1.3.3.2 18.1.3.4 18.1.4 18.1.4.1 18.1.4.2 18.1.4.2.1 18.1.4.2.2 18.1.4.3 18.1.4.3.1 18.1.4.3.2 18.1.5

JAMES DEVILLERS, AURÉLIE CHEZEAU, ANDRÉ CICOLELLA, ERIC THYBAUD

MICHELLE BERGIN, ARMISTEAD RUSSELL

MARGOT SCHEITHAUER

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. . . 1201 . . . 1201

. . . 1215 . . . 1215 . . . 1215 . . . 1219

xviii 18.1.6 18.1.6.1 18.1.6.2 18.1.6.3 18.1.6.4

Handbook of Solvents . . . .

18.2

Measurement of odor in materials and industrial plants . . . . . . . . . . Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Odor determination by means of the “electronic nose” . . . . . . . . . . Odor determination by means of the olfactometer . . . . . . . . . . . . . Example for odor determination for selected materials: Determination of odorant concentration in varnished furniture surfaces . . . . . . . . . . . Example of odor determination in industrial plants: Odor measurement in an industrial varnishing plant. . . . . . . . . . . . . . . . . . . . . . . . Prediction of organic solvents emission during technological processes .

18.2.1 18.2.2 18.2.3 18.2.4 18.2.5 18.2.6 18.2.7 18.2.7.1 18.2.7.2 18.2.7.3 18.2.7.4 18.2.8 18.2.9 18.3

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of degreasing . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Identification of the emitted compounds . . . . . . . . . . . . . . . . . . Emission of organic solvents during technological processes . . . . . . . Verification of the method . . . . . . . . . . . . . . . . . . . . . . . . . Relationships between emission and technological parameters . . . . . . Laboratory test stand . . . . . . . . . . . . . . . . . . . . . . . . . . . . The influence of temperature on emission . . . . . . . . . . . . . . . . . The influence of air velocity on emission . . . . . . . . . . . . . . . . . The relationship between the mass of solvent on wet parts and emissions Emission of solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . Verification in industrial conditions . . . . . . . . . . . . . . . . . . . . Indoor air pollution by solvents contained in paints and varnishes . . . .

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1227 1227 1228 1228 1228 1230 1231 1231 1231 1232 1232 1232 1232 1234

18.3.1 18.3.2 18.3.2.1 18.3.2.2 18.3.3 18.3.3.1 18.3.3.2 18.3.4 18.3.4.1 18.3.4.2 18.3.4.2.1 18.3.4.2.2 18.3.4.2.3 18.3.4.2.4 18.3.4.2.5 18.3.4.2.6 18.3.4.2.7 18.3.5 18.3.5.1 18.3.5.1.1 18.3.5.1.2 18.3.5.2 18.3.5.2.1 18.3.5.2.2 18.4

Composition - solvents in paints and varnishes. Theoretical aspects Occurrence of solvents in paints and varnishes . . . . . . . . . . . Solvents in products . . . . . . . . . . . . . . . . . . . . . . . . . Paints and varnishes . . . . . . . . . . . . . . . . . . . . . . . . . Emission of solvents . . . . . . . . . . . . . . . . . . . . . . . . . Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Immission. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effects on health of solvents from paints and varnishes . . . . . . . Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Health effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Toxic responses of skin and mucose membranes . . . . . . . . . . Neurological disorders . . . . . . . . . . . . . . . . . . . . . . . . Carcinogenic effects . . . . . . . . . . . . . . . . . . . . . . . . . Respiratory effects . . . . . . . . . . . . . . . . . . . . . . . . . . Toxic responses of blood . . . . . . . . . . . . . . . . . . . . . . . Toxic responses of the reproductive system . . . . . . . . . . . . . Toxic responses of other organ systems . . . . . . . . . . . . . . . Methods for the examination of solvents in paints and varnishes . . Environmental monitoring . . . . . . . . . . . . . . . . . . . . . . Solvents in products . . . . . . . . . . . . . . . . . . . . . . . . . Emission of solvents . . . . . . . . . . . . . . . . . . . . . . . . . Biological monitoring of solvents in human body fluids . . . . . . Solvents and metabolites in human body fluids and tissues . . . . . Biomarkers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent uses with exposure risks . . . . . . . . . . . . . . . . . . .

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1234 1235 1235 1237 1240 1240 1242 1243 1243 1243 1243 1244 1245 1246 1247 1247 1247 1248 1248 1248 1248 1248 1248 1248 1251

18.4.1 18.4.2 18.4.3 18.4.4 18.4.5 18.4.6

Introduction. . . . . . . . . . . . . . . . . . . Exposure assessment . . . . . . . . . . . . . . Production of paints and printing inks . . . . . Painting . . . . . . . . . . . . . . . . . . . . . Printing . . . . . . . . . . . . . . . . . . . . . Degreasing, press cleaning and paint removal .

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1251 1252 1255 1256 1257 1258

18.1.6.5

KRZYSZTOF M. BENCZEK, JOANNA KURPIEWSKA

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

pentti kalliokoski, kai savolinen

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1222 1222 1222 1223

. . . 1223 . . . 1225 . . . 1227

Table of contents

xix

18.4.7 18.4.8 18.4.9 18.4.10 18.4.11 19

Dry cleaning . . . . . . . . Reinforced plastics industry Gluing . . . . . . . . . . . Other . . . . . . . . . . . . Summary . . . . . . . . . . REGULATIONS . . . . .

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1260 1261 1262 1262 1263 1267

19.1 19.2 19.2.1 19.2.1.1 19.2.1.2

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1267 1282 1282 1282

19.2.1.3 19.2.1.4 19.2.1.5 19.3 19.3.1 19.3.1.1 19.3.1.2 19.3.1.3 19.3.2 19.3.2.1 19.3.2.2 19.4 19.4.1 19.4.1.1 19.4.1.2 19.5 19.5.1 19.5.1.1 19.5.1.2 19.5.2 19.5.2.1 19.5.2.2 19.6 19.6.1 19.6.1.1 19.6.1.2 19.6.1.3 19.7 19.7.1 19.7.2 19.8 19.9 19.10

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Air laws and regulations . . . . . . . . . . . . . . . . . . . . . . . . . . Clean Air Act Amendments of 1990 . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Title I - Provisions for Attainment and Maintenance of National Ambient Air Quality Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . Title III - Hazardous Air Pollutants . . . . . . . . . . . . . . . . . . . . Title V - Permits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Title VI - Stratospheric Ozone Protection . . . . . . . . . . . . . . . . . Water laws and regulations. . . . . . . . . . . . . . . . . . . . . . . . . Clean Water Act . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Effluent Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . Permit Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Safe Drinking Water Act . . . . . . . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . National Primary Drinking Water Regulations. . . . . . . . . . . . . . . Land laws & regulations . . . . . . . . . . . . . . . . . . . . . . . . . . Resource Conservation and Recovery Act (RCRA) . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . RCRA, Subtitle C - Hazardous Waste . . . . . . . . . . . . . . . . . . . Multimedia laws and regulations . . . . . . . . . . . . . . . . . . . . . . Pollution Prevention Act of 1990 . . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Source Reduction Provisions . . . . . . . . . . . . . . . . . . . . . . . . Toxic Substances Control Act . . . . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Controlling toxic substances . . . . . . . . . . . . . . . . . . . . . . . . Occupational laws and regulations . . . . . . . . . . . . . . . . . . . . . Occupational Safety and Health Act . . . . . . . . . . . . . . . . . . . . Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Air contaminants exposure limits . . . . . . . . . . . . . . . . . . . . . Hazard Communication Standard . . . . . . . . . . . . . . . . . . . . . International perspective . . . . . . . . . . . . . . . . . . . . . . . . . . Canada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . European Union . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tools and resources for solvents . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Regulations in Europe . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1284 1288 1292 1292 1293 1293 1293 1293 1294 1294 1294 1295 1295 1295 1295 1296 1297 1297 1297 1298 1300 1300 1300 1301 1301 1301 1301 1302 1302 1303 1303 1304 1306 1311

19.10.1 19.10.2 20 20.1

EEC regulations . . . . . . . . . . . . . . . . . . German regulations. . . . . . . . . . . . . . . . . TOXIC EFFECTS OF SOLVENT EXPOSURE Toxicokinetics, toxicodynamics, and toxicology .

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1311 1312 1315 1315

20.1.1 20.1.1.1 20.1.1.2 20.1.1.2.1 20.1.1.2.2

Toxicokinetics and toxicodynamics Exposure . . . . . . . . . . . . . . Uptake . . . . . . . . . . . . . . . Inhalation . . . . . . . . . . . . . . Dermal uptake . . . . . . . . . . .

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1315 1315 1315 1316 1316

CARLOS M. NU~ NEZ

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TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

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xx 20.1.1.2 20.1.1.3 20.1.2 20.1.2.1 20.1.2.2 20.1.2.3 20.1.2.4 20.1.2.5 20.1.2.6 20.1.3 20.2

Handbook of Solvents Metabolism, distribution, excretion . . . . . . . . . . . . . . . . . . Modeling of toxicokinetics and modifying factors. . . . . . . . . . . Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . General effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Specific non-immunological effects . . . . . . . . . . . . . . . . . . Immunological effects . . . . . . . . . . . . . . . . . . . . . . . . . Toxic effects of solvents on other organisms . . . . . . . . . . . . . Carcinogenicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Risk assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cognitive and psychosocial outcome of chronic occupational solvent neurotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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20.2.1 20.2.2 20.2.3 20.2.4 20.2.5 20.2.6 20.2.7 20.3

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acute symptoms of solvent neurotoxicity . . . . . . . . . . . . . Categorization of OSN . . . . . . . . . . . . . . . . . . . . . . . Assessment of OSN . . . . . . . . . . . . . . . . . . . . . . . . Do the symptoms of Type 2 OSN resolve? . . . . . . . . . . . . Individual differences in susceptibility to OSN . . . . . . . . . . Psychosocial consequences of OSN, and rehabilitation . . . . . . Pregnancy outcome following maternal organic solvent exposure

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20.3.1 20.3.2 20.3.3

20.3.6

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Animal studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pregnancy outcome following maternal organic solvent exposure: a meta-analysis of epidemiologic studies . . . . . . . . . . . . . . . . Pregnancy outcome following gestational exposure to organic solvents: a prospective controlled study . . . . . . . . . . . . . . . . . . . . . . A proactive approach for the evaluation of fetal safety in chemical industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Overall conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . .

20.4

Industrial solvents and kidney disease . . . . . . . . . . . . . . . . . . . . . . 1355

20.4.1 20.4.2 20.4.3 20.4.4 20.4.5 20.4.6 20.5

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental animal studies . . . . . . . . . . . . . . . . . . . . . . . Case reports. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Case control studies . . . . . . . . . . . . . . . . . . . . . . . . . . . Epidemiological assessment . . . . . . . . . . . . . . . . . . . . . . . Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lymphohematopoietic study of workers exposed to benzene including multiple myeloma, lymphoma and chronic lymphatic leukemia. . . . .

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20.5.1 20.5.2 20.5.3 20.5.4 20.5.5 20.5.6 20.5.7 20.5.8 20.5.9 20.5.10 20.6

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . Routes of exposure . . . . . . . . . . . . . . . . . . . . . . Hematopoietic effects of benzene . . . . . . . . . . . . . . Carcinogenic effects of benzene . . . . . . . . . . . . . . . Risk assessment estimates . . . . . . . . . . . . . . . . . . Levels of exposure . . . . . . . . . . . . . . . . . . . . . . Cell types: hematolymphoproliferative effects of benzene . Epidemiological studies . . . . . . . . . . . . . . . . . . . Solvents and benzene. . . . . . . . . . . . . . . . . . . . . Genetic fingerprint theory . . . . . . . . . . . . . . . . . . Chromosomal aberrations and sister chromatoid exchanges .

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20.7

Hepatotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379

20.3.4 20.3.5

JENNI A OGDEN

KRISTEN I. MCMARTIN, GIDEON KOREN

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NACHMAN BRAUTBAR

NACHMAN BRAUTBAR

NACHMAN BRAUTBAR NACHMAN BRAUTBAR

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1317 1317 1318 1318 1318 1319 1320 1320 1323 1323

1326 1327 1327 1328 1330 1331 1331 1333

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1355 1356 1356 1357 1360 1361

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1363 1363 1365 1365 1367 1367 1369 1369 1370 1372 1375

Table of contents

xxi

20.7.1 20.7.2 20.7.3 20.7.4 20.7.5 20.7.6 20.7.7 20.7.8 20.7.9 20.7.10 20.7.11 20.8

Introduction. . . . . . . . . . . . . . . . . . . . . . Individual variability and hepatotoxicity of solvents Non-halogenated solvents . . . . . . . . . . . . . . Solvent mixtures . . . . . . . . . . . . . . . . . . . Trichloroethylene. . . . . . . . . . . . . . . . . . . Tetrachloroethylene . . . . . . . . . . . . . . . . . Toluene . . . . . . . . . . . . . . . . . . . . . . . . Dichloromethane . . . . . . . . . . . . . . . . . . . Stoddard solvent . . . . . . . . . . . . . . . . . . . 1,1,1-Trichloroethane. . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . Solvents and the liver. . . . . . . . . . . . . . . . .

20.8.1 20.8.1.1 20.8.1.2

Normal anatomic and physiologic function of the liver . . . . . . . . Factors influencing solvent hepatotoxicity . . . . . . . . . . . . . . . Microscopic, biochemical and clinical findings associated with liver injury due to solvents . . . . . . . . . . . . . . . . . . . . . . . . . . Hepatotoxicity associated with specific solvents. . . . . . . . . . . . Haloalkanes and haloalkenes . . . . . . . . . . . . . . . . . . . . . . Carbon tetrachloride . . . . . . . . . . . . . . . . . . . . . . . . . . Chloroform . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dichloromethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trichloroethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1,1,2,2-Tetrachloroethane . . . . . . . . . . . . . . . . . . . . . . . Tetrachloroethylene and trichloroethylene . . . . . . . . . . . . . . . Other halogenated hydrocarbons . . . . . . . . . . . . . . . . . . . . Styrene and aromatic hydrocarbons . . . . . . . . . . . . . . . . . . N-substituted amides . . . . . . . . . . . . . . . . . . . . . . . . . . Nitroparaffins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other solvents and mixed solvents . . . . . . . . . . . . . . . . . . . Toxicity of environmental solvent exposure for brain, lung and heart.

20.8.2 20.8.2.1 20.8.2.2 20.8.2.3 20.8.2.4 20.8.2.5 20.8.2.6 20.8.2.7 20.8.2.8 20.8.2.9 20.8.2.10 20.8.2.11 20.8.2.12 20.9 21

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DAVID K. BONAUTO, C. ANDREW BRODKIN, WILLIAM O. ROBERTSON

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KAYE H. KILBURN

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1379 1384 1385 1386 1387 1388 1388 1389 1389 1389 1390 1393

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1394 1395 1396 1396 1397 1398 1398 1398 1399 1399 1399 1400 1400 1401 1404

21.1

SUBSTITUTION OF SOLVENTS BY SAFER PRODUCTS AND PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1419 Supercritical solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1419

21.1.1 21.1.1.1 21.1.1.2 21.1.1.3 21.1.2 21.1.2.1 21.1.2.1.1 21.1.2.1.2 21.1.2.1.3 21.1.2.2 21.1.2.2.1 21.1.2.2.2 21.1.2.2.3 21.1.2.2.4 21.1.2.3 21.1.2.4 21.1.2.5 21.1.2.6 21.1.2.7 21.1.3 21.1.3.1

Introduction. . . . . . . . . . . . . . . . . . . . . . . A promising path to green chemistry. . . . . . . . . . Unique and tunable physico-chemical properties . . . Sustainable applications in many different areas. . . . Fundamentals . . . . . . . . . . . . . . . . . . . . . . Phase behavior with supercritical solvents . . . . . . . Experimental methods . . . . . . . . . . . . . . . . . Computational aspects . . . . . . . . . . . . . . . . . Modeling . . . . . . . . . . . . . . . . . . . . . . . . Transport properties of supercritical solvents . . . . . Viscosity . . . . . . . . . . . . . . . . . . . . . . . . Diffusivity . . . . . . . . . . . . . . . . . . . . . . . Thermal conductivity . . . . . . . . . . . . . . . . . . Surface tension . . . . . . . . . . . . . . . . . . . . . Entrainer (co-solvent effects) of supercritical solvents Reaction rate implication in supercritical solvents . . . Sorption behavior of supercritical solvents. . . . . . . Swelling with supercritical solvents . . . . . . . . . . Surfactants and micro-emulsions. . . . . . . . . . . . Separation with supercritical solvents . . . . . . . . . Leaching - generic application . . . . . . . . . . . . .

AYDIN K. SUNOL, SERMIN G. SUNOL

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1419 1422 1422 1422 1423 1423 1426 1428 1429 1431 1431 1432 1433 1435 1435 1436 1437 1437 1438 1438 1441

xxii

Handbook of Solvents

21.1.3.2 21.1.3.3 21.1.3.4 21.1.4 21.1.4.1 21.1.4.1.1 21.1.4.1.2 21.1.4.1.3 21.1.4.2 21.1.4.2.1 21.1.4.2.2 21.1.4.3 21.1.4.4 21.1.4.5 21.1.4.6 21.1.4.7 21.1.4.8 21.1.4.9 21.1.4.10 21.1.4.11 21.1.4.12 21.2

Extraction - generic applications . . . . . . . . . . . . . . . . . . Crystallization - generic applications. . . . . . . . . . . . . . . . Sorption - generic applications . . . . . . . . . . . . . . . . . . . Reactions in supercritical solvents . . . . . . . . . . . . . . . . . Homogenous reactions in supercritical solvents - examples . . . . Homogeneous reactions catalyzed by organometallic compounds Homogeneous reactions of supercritical water . . . . . . . . . . . Homogeneous non-catalytic reactions in supercritical solvents . . Heterogeneous reactions in supercritical solvents - examples . . . Heterogeneous catalytic reactions in supercritical solvents . . . . Heterogeneous non-catalytic reactions in supercritical solvents . . Biochemical reactions - examples . . . . . . . . . . . . . . . . . Polymerization reactions - examples . . . . . . . . . . . . . . . . Materials processing with supercritical solvents . . . . . . . . . . Particle synthesis - generic application. . . . . . . . . . . . . . . Encapsulation - generic application . . . . . . . . . . . . . . . . Spraying and coating - generic application. . . . . . . . . . . . . Extrusion - generic application . . . . . . . . . . . . . . . . . . . Perfusion (impregnation) - generic application . . . . . . . . . . Parts cleaning - generic application . . . . . . . . . . . . . . . . Drying - generic application . . . . . . . . . . . . . . . . . . . . Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1442 1443 1443 1444 1445 1446 1447 1448 1448 1449 1450 1451 1451 1452 1453 1454 1454 1454 1454 1455 1455 1459

21.2.1 21.2.2 21.2.2.1 21.2.2.2 21.2.3 21.2.3.1 21.2.3.2 21.2.4 21.2.4.1 21.2.5 21.2.5.1 21.2.5.2 21.2.6 21.3

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fundamental principles of the formation of room temperature ionic liquids Development of ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . Binary ionic liquid systems. . . . . . . . . . . . . . . . . . . . . . . . . . Catalysis in ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . Reactions involving first generation chloroaluminate(III) ionic liquids . . . Reactions in neutral or second generation ionic liquids . . . . . . . . . . . Electrochemical applications . . . . . . . . . . . . . . . . . . . . . . . . . Electrosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Physical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Oxide solubilities in ionic melts . . . . . . . . . . . . . . . . . . . . . . .

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1459 1461 1461 1465 1466 1467 1469 1472 1473 1473 1473 1478 1480 1484

21.3.1 21.3.1.1 21.3.1.2 21.3.2 21.3.3 21.3.3.1 21.3.3.2 21.3.3.3 21.3.3.4 21.3.4 21.3.4.1 21.3.4.2 21.3.4.3 21.3.5 21.4

Methods used for solubility estimations in ionic melts . . . . . . . . . . . . Isothermal saturation method. . . . . . . . . . . . . . . . . . . . . . . . . . Potentiometric titration method . . . . . . . . . . . . . . . . . . . . . . . . Oxygen-containing melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . Halide melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The eutectic mixture KCl-LiCl (0.41:0.59) . . . . . . . . . . . . . . . . . . Molten KCl-NaCl (0.50:0.50) . . . . . . . . . . . . . . . . . . . . . . . . . Other chloride-based melts . . . . . . . . . . . . . . . . . . . . . . . . . . . Other alkaline halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . On the possibility to predict oxide solubilities on the base of the existing data The estimation of effect of anion . . . . . . . . . . . . . . . . . . . . . . . . The estimation of effect of melt acidity . . . . . . . . . . . . . . . . . . . . The estimation of effect of temperature . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Alternative cleaning technologies/drycleaning installations . . . . . . . . . .

. . . . . . . . . . . . . . .

1484 1485 1486 1487 1487 1487 1488 1491 1493 1494 1494 1494 1495 1495 1497

21.4.1 21.4.1.1 21.4.1.2

Drycleaning with liquid carbon dioxide (LCD) . . . . . . . . . . . . . . . . . 1497 Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1497 State of the art . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1498

D.W. ROONEY, K.R. SEDDON

VICTOR CHERGINETS

KASPAR D. HASENCLEVER

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Table of contents

xxiii

21.4.1.3 21.4.1.4 21.4.1.5 21.4.2 21.4.2.1 21.4.2.2 21.4.2.3 21.4.2.4 21.4.3 22 22.1

Process technology . . . . . . . . . . . . . . . . . . . . . . . . . . . Risks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Competition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Wet cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kreussler textile cleaning system. . . . . . . . . . . . . . . . . . . . Possibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adapting to working practices . . . . . . . . . . . . . . . . . . . . . Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . SOLVENT RECYCLING, REMOVAL, AND DEGRADATION . Absorptive solvent recovery . . . . . . . . . . . . . . . . . . . . . .

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1498 1499 1500 1501 1501 1503 1504 1504 1505 1507 1507

22.1.1 22.1.2 22.1.2.1 22.1.2.2 22.1.2.3 22.1.2.4 22.1.3 22.1.3.1 22.1.3.2 22.1.3.3 22.1.4 22.1.4.1 22.1.4.2 22.1.4.2.1 22.1.4.2.2 22.1.4.2.3 22.1.4.2.4 22.1.4.3 22.1.4.3.1 22.1.4.3.2 22.1.4.3.3 22.1.4.3.4 22.1.4.3.5 22.1.4.3.6 22.1.5 22.1.5.1 22.1.5.2 22.1.5.2.1 22.1.5.2.2 22.1.5.3 22.1.5.4 22.1.5.5 22.1.5.6 22.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Basic principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fundamentals of adsorption . . . . . . . . . . . . . . . . . . . . . . . . Adsorption capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dynamic adsorption in adsorber beds . . . . . . . . . . . . . . . . . . . Regeneration of the loaded adsorbents . . . . . . . . . . . . . . . . . . . Commercially available adsorbents . . . . . . . . . . . . . . . . . . . . Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular sieve zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . Polymeric adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorptive solvent recovery systems. . . . . . . . . . . . . . . . . . . . Basic arrangement of adsorptive solvent recovery with steam desorption. Designing solvent recovery systems . . . . . . . . . . . . . . . . . . . . Design basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorber types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Safety requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . Special process conditions . . . . . . . . . . . . . . . . . . . . . . . . . Selection of the adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . Air velocity and pressure drop . . . . . . . . . . . . . . . . . . . . . . . Effects of solvent-concentration, adsorption temperature and pressure . . Influence of humidity. . . . . . . . . . . . . . . . . . . . . . . . . . . . Interactions between solvents and activated carbon . . . . . . . . . . . . Activated carbon service life . . . . . . . . . . . . . . . . . . . . . . . . Examples from different industries. . . . . . . . . . . . . . . . . . . . . Rotogravure printing shops. . . . . . . . . . . . . . . . . . . . . . . . . Packaging printing industry . . . . . . . . . . . . . . . . . . . . . . . . Fixed bed adsorption with circulating hot gas desorption . . . . . . . . . Solvent recovery with adsorption wheels . . . . . . . . . . . . . . . . . Viscose industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Refrigerator recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . Petrochemical industry and tank farms. . . . . . . . . . . . . . . . . . . Chemical industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1507 1509 1509 1510 1511 1512 1513 1513 1514 1515 1515 1515 1518 1518 1519 1521 1522 1523 1523 1526 1526 1528 1529 1531 1531 1531 1532 1533 1535 1535 1539 1539 1541 1543

22.2.1 22.2.2 22.2.3

Activated carbon in fluidized bed adsorption method . . . . . . . . Application of molecular sieves . . . . . . . . . . . . . . . . . . . Continuous process for air cleaning using macroporous particles as adsorption agents . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent recovery from hazardous wastes. . . . . . . . . . . . . . . Halogenated solvent recovery . . . . . . . . . . . . . . . . . . . . Coating process. . . . . . . . . . . . . . . . . . . . . . . . . . . . Tableting process of pharmaceutical products . . . . . . . . . . . . Energy recovery from waste solvent . . . . . . . . . . . . . . . . . Solvent treatment in a paints and coating plant . . . . . . . . . . .

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22.2.4 22.2.5 22.2.5.1 22.2.5.2 22.2.6 22.3

KLAUS-DIRK HENNING

ISAO KIMURA

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. . . . . . 1543 . . . . . . 1544 . . . . . . .

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1546 1548 1549 1549 1552 1553 1555

xxiv

Handbook of Solvents DENIS KARGOL

22.4

Application of solar photocatalytic oxidation to VOC-containing airstreams . . 1559

22.4.1 22.4.2 22.4.2.1 22.4.2.2 22.4.3 22.4.3.1 22.4.3.2 22.4.4 23

Solvent degradation by photocatalytic oxidation. . . . . . . . . . . . . . . PCO pilot scale systems . . . . . . . . . . . . . . . . . . . . . . . . . . . Air stripper application . . . . . . . . . . . . . . . . . . . . . . . . . . . . Paint booth application . . . . . . . . . . . . . . . . . . . . . . . . . . . . Field test results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Air stripper application . . . . . . . . . . . . . . . . . . . . . . . . . . . . Paint booth application . . . . . . . . . . . . . . . . . . . . . . . . . . . . Comparison with other treatment systems . . . . . . . . . . . . . . . . . . CONTAMINATION CLEANUP: NATURAL ATTENUATION AND ADVANCED REMEDIATION TECHNOLOGIES . . . . . . . . . . . Natural attenuation of chlorinated solvents in ground water . . . . . . . . .

23.1 23.1.1 23.1.2 23.1.2.1 23.1.2.2 23.1.2.3 23.1.2.4 23.1.2.5 23.1.2.6 23.1.2.7 23.1.2.8 23.1.3 23.1.3.1 23.1.3.1.1 23.1.3.1.2 23.1.3.2 23.1.3.2.1 23.1.3.2.2 23.1.3.2.3 23.1.4 23.1.4.1 23.1.4.2 23.1.4.3 23.1.5 23.1.5.1 23.1.5.2 23.1.5.2.1 23.1.5.2.2 23.1.5.2.3 23.1.5.2.4 23.1.6 23.1.6.1 23.1.6.2 23.1.6.2.1 23.1.6.3 23.1.6.4 23.2 23.2.1 23.2.1.1 23.2.1.2

K. A. MAGRINI, A. S. WATT, L. C. BOYD, E. J. WOLFRUM, S. A. LARSON, C. ROTH

G. C. Glatzmaier

HANADI S. RIFAI, CHARLES J. NEWELL, TODD H. WIEDEMEIER

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1559 1560 1560 1562 1564 1564 1566 1568

. . 1571 . . 1571

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Natural attenuation processes affecting chlorinated solvent plumes . . . . . . Advection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . One-dimensional advection-dispersion equation with retardation . . . . . . . Dilution (recharge) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Volatilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hydrolysis and dehydrohalogenation . . . . . . . . . . . . . . . . . . . . . Reduction reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Biodegradation of chlorinated solvents . . . . . . . . . . . . . . . . . . . . Halorespiration or reductive dechlorination using hydrogen. . . . . . . . . . Stoichiometry of reductive dechlorination . . . . . . . . . . . . . . . . . . . Chlorinated solvents that are amenable to halorespiration . . . . . . . . . . . Oxidation of chlorinated solvents . . . . . . . . . . . . . . . . . . . . . . . Direct aerobic oxidation of chlorinated compounds . . . . . . . . . . . . . . Aerobic cometabolism of chlorinated compounds . . . . . . . . . . . . . . . Anaerobic oxidation of chlorinated compounds . . . . . . . . . . . . . . . . Biodegradation rates for chlorinated solvents . . . . . . . . . . . . . . . . . Michaelis-Menten rates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Zero-order rates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . First-order rate constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . Geochemical evidence of natural bioremediation at chlorinated solvent sites . Assessing reductive dechlorination at field sites . . . . . . . . . . . . . . . . Plume classification schemes. . . . . . . . . . . . . . . . . . . . . . . . . . Type 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Type 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Type 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mixed environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chlorinated solvent plumes - case studies of natural attenuation . . . . . . . Plume databases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Modeling chlorinated solvent plumes . . . . . . . . . . . . . . . . . . . . . BIOCHLOR natural attenuation model . . . . . . . . . . . . . . . . . . . . RT3D numerical model . . . . . . . . . . . . . . . . . . . . . . . . . . . . CS case study - The Plattsburgh Air Force Base . . . . . . . . . . . . . . . . Remediation technologies and approaches for managing sites impacted by hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . BARRY J. SPARGO, JAMES G. MUELLER

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1571 1572 1572 1573 1574 1577 1577 1578 1579 1581 1581 1582 1585 1585 1586 1586 1587 1587 1588 1588 1590 1591 1599 1599 1599 1599 1600 1601 1601 1602 1602 1605 1605 1609 1611

. 1617

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617 Understanding HC and CHC in the environment . . . . . . . . . . . . . . . . 1617 Sources of HC in the environment . . . . . . . . . . . . . . . . . . . . . . . . 1617

Table of contents 23.2.1.3 23.2.2 23.2.2.1 23.2.2.1.1 23.2.2.2 23.2.2.2.1

xxv

23.2.4 24

Sources of CHC in the environment . . . . . . . . . . . . . . . . . . . . . . In situ biotreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Microbial-enhanced natural attenuation/bioremediation . . . . . . . . . . . . Case study - Cooper River Watershed, Charleston, SC, USA . . . . . . . . . Phytoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Case study - phytoremediation for CHCs in groundwater at a chemical plant in Louisiana. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . In situ treatment technologies . . . . . . . . . . . . . . . . . . . . . . . . . Product recovery via GCW technology . . . . . . . . . . . . . . . . . . . . Case study - GCW recovery of creosote, Cabot/Kopper’s Superfund Site, Gainesville, FL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Surfactant enhanced product recovery . . . . . . . . . . . . . . . . . . . . . Case study - Surfactant-aided chlorinated HC DNAPL recovery, Hill Air Force Base, Ogden, Utah . . . . . . . . . . . . . . . . . . . . . . . Foam-enhanced product recovery . . . . . . . . . . . . . . . . . . . . . . . Thermal desorption - Six Phase Heating . . . . . . . . . . . . . . . . . . . . Case study - Six-Phase Heating removal of CHC at a manufacturing facility near Chicago, IL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . In situ steam enhanced extraction (Dynamic Underground Stripping) . . . . In situ permeable reactive barriers (funnel and gate). . . . . . . . . . . . . . Case study - CHC remediation using an in situ permeable reactive barrier at Naval Air Station Moffett Field, CA . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . PROTECTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. 1628 . 1629 . 1631

24.1 24.2 24.3 25

Gloves . . . . . . . . . . . . . . . . . . . . . . . . . . . Suit materials . . . . . . . . . . . . . . . . . . . . . . . . Respiratory protection . . . . . . . . . . . . . . . . . . . NEW TRENDS BASED ON PATENT LITERATURE

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1631 1633 1633 1637

25.1 25.2 25.3 25.4 25.5 25.6 25.7 25.8 25.9 25.10 25.11 25.12 25.13 25.14 25.15 25.16 25.17

New solvents . . . . . . . . . Adhesives. . . . . . . . . . . Aerospace. . . . . . . . . . . Agriculture . . . . . . . . . . Asphalt . . . . . . . . . . . . Automotive applications . . . Coil coating. . . . . . . . . . Composites and laminates . . Cosmetics. . . . . . . . . . . Cleaning . . . . . . . . . . . Fibers . . . . . . . . . . . . . Furniture and wood coatings . Paper . . . . . . . . . . . . . Printing . . . . . . . . . . . . Stone and concrete . . . . . . Wax . . . . . . . . . . . . . . Summary . . . . . . . . . . . ACKNOWLEDGMENTS . INDEX . . . . . . . . . . . .

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1637 1638 1640 1640 1640 1641 1641 1642 1643 1644 1645 1646 1647 1647 1648 1648 1649 1653 1657

23.2.3 23.2.3.1 23.2.3.1.1 23.2.3.2 23.2.3.2.1 23.2.3.3 23.2.3.4 23.2.3.4.1 23.2.3.5 23.2.3.6 23.2.3.6.1

GEORGE WYPYCH

GEORGE WYPYCH

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1618 1618 1618 1620 1622

. 1622 . 1623 . 1623 . 1624 . 1625 . 1625 . 1626 . 1626 . 1627 . 1628 . 1628

Preface Although the chemical industry can trace its roots into antiquity, it was during the industrial revolution that it started to become an actual industry and began to use the increased knowledge of chemistry as a science and technology to produce products that were needed by companion industries and consumers. These commercial efforts resulted in the synthesis of many new chemicals. Quite quickly, in these early days, previously unknown materials or materials that had been present only in low concentrations, were now in contact with people in highly concentrated forms and in large quantities. The people had little or no knowledge of the effects of these materials on their bodies and the natural biological and physical processes in the rivers and oceans, the atmosphere, and in the ground. Until the end of the nineteenth century these problems were not addressed by the chemical industry and it is only recently that the industry began to respond to public criticism and political efforts. Legal restrictions aimed at preserving the quality of life have been directed at health, safety and longevity issues and the environment. Solvents have always been mainstays of the chemical industry and because of their widespread use and their high volume of production they have been specifically targeted by legislators throughout the world. The restrictions range from total prohibition of production and use, to limits placed on vapor concentrations in the air. As with any arbitrary measures some solvents have been damned unfairly. However, there is no question that it is best to err on the side of safety if the risks are not fully understood. It is also true that solvents should be differentiated based on their individual properties. This book is intended to provide a better understanding of the principles involved in solvent selection and use. It strives to provide information that will help to identify the risks and benefits associated with specific solvents and classes of solvents. The book is intended to help the formulator select the ideal solvent, the safety coordinator to safeguard his or her coworkers, the legislator to impose appropriate and technically correct restrictions and the student to appreciate the amazing variety of properties, applications and risks associated with the more than one thousand solvents that are available today. By their very nature, handbooks are intended to provide exhaustive information on the subject. While we agree that this is the goal here, we have attempted to temper the impact of information, which may be too narrow to make decision. Many excellent books on solvents have been published in the past and most of these are referenced in this book. But of all these books none has given a comprehensive overview of all aspects of solvent use. Access to comprehensive data is an essential part of solvent evaluation and it has been a hallmark of such books to provide tables filled with data to the point at which 50 to 95% of the book is data. This approach seems to neglect a fundamental requirement of a handbook - to provide the background, explanations and clarifications that are needed to convert data to information and assist the reader in gaining the knowledge to make a decision on selecting a process or a solvent. Unfortunately, to meet the goal of providing both the data and the fundamental explanations that are needed, a book of 4,000 to 5,000 pages might be required. Even if this was possible, much of the data would fall out of date quite quickly. For example, a factor that defines solvent safety such as threshold limit

xxviii

Preface

values (TLVs) for worker exposure or some single toxicity determinants may change frequently. This book would be huge and it would have to be updated frequently to continue to claim that it is current. What we have attempted to do here is to give you a book with a comprehensive and extensive analysis of all current information on solvents then use other media to present the supporting data on individual solvents. These data are provided on a CD-ROM as a searchable database. Data are provided on more than 1140 solvents in 110 fields of data. The medium permits frequent updates. If the same data were presented in book form, more than 2,000 pages would be needed which exceeds the size of any data in handbook form offered to date. The best approach in presenting an authoritative text for such a book is to have it written by experts in their fields. This book attracted well-known experts who have written jointly 47 books and authored or coauthored hundreds of papers on their areas of expertise. The authors have made their contributions to this book in late 1999 and early 2000 providing the most current picture of the technology. Their extreme familiarity with their subjects enables them to present information in depth and detail, which is essential to the reader’s full understanding of the subject. The authors were aware of the diversity of potential readers at the outset and one of their objectives was to provide information to various disciplines expressed in a way that all would understand and which would deal with all aspects of solvent applications. We expect professionals and students from a wide range of businesses, all levels of governments and academe to be interested readers. The list includes solvent manufacturers, formulators of solvent containing products, industrial engineers, analytical chemists, government legislators and their staffs, medical professionals involved in assessing the impact on health of solvents, biologists who are evaluating the interactions of solvents with soil and water, environmental engineers, industrial hygienists who are determining protective measures against solvent exposure, civil engineers who design waste disposal sites and remediation measures, people in industries where there are processes which use solvents and require their recovery and, perhaps most important, because understanding brings improvements, those who teach and learn in our universities, colleges and schools. A growing spirit of cooperation is evident between these groups and this can be fostered by providing avenues of understanding based on sharing data and information on common problems. We hope to provide one such avenue with this book. We have tried to present a balanced picture of solvent performance by dealing not only with product performance and ease of processing but also by giving environmental and health issues full consideration. Data and information on known products and processes should be cornerstones of the understanding of a technology but there is another aspect of technology, which can lead to advances and improvements in utility, safety and in safeguarding the environment. This must come from you, the reader. It is your ideas and creative thinking that will bring these improvements. The authors have crammed their ideas into the book and we hope these will stimulate responsible and effective applications of solvents. Francis Bacon wrote, “The end of our foundation is the knowledge of causes, and the secret motion of things, and the enlarging of the bound of human Empire, to the effecting of all things possible.” Today there are few technical activities that do not employ solvents. Almost all industries, almost all consumer products, almost everything we use can, if analyzed, be shown to

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xxix

contain or to have used in its processing, a solvent. Solvent elimination need never be a technical objective. Rather, we need to use our increasing understanding and knowledge to find the safest and the most effective means of meeting our goals. I would like to thank the authors for their relentless efforts to explain the difficult in an interesting way. In advance, I would like to thank the reader for choosing this book and encourage her or him to apply the knowledge to make our world a better, more livable place. George Wypych Toronto, August 3, 2000

1

Introduction Christian Reichardt

Department of Chemistry, Philipps University, Marburg, Germany

Chemical transformations can be performed in a gas, liquid, or solid phase, but, with good reasons, the majority of such reactions is carried out in the liquid phase in solution. At the macroscopic level, a liquid is the ideal medium to transport heat to and from exo- and endothermic reactions. From the molecular-microscopic point of view, solvents break the crystal lattice of solid reactants, dissolve gaseous or liquid reactants, and they may exert a considerable influence over reaction rates and the positions of chemical equilibria. Because of nonspecific and specific intermolecular forces acting between the ions or molecules of dissolved reactants, activated complexes as well as products and solvent molecules (leading to differential solvation of all solutes), the rates, equilibria, and the selectivity of chemical reactions can be strongly influenced by the solvent. Other than the fact that the liquid medium should dissolve the reactants and should be easily separated from the reaction products afterwards, the solvent can have a decisive influence on the outcome (i.e., yield and product distribution) of the chemical reaction under study. Therefore, whenever a chemist wishes to perform a certain chemical reaction, she/he has to take into account not only suitable reaction partners and their concentrations, the proper reaction vessel, the appropriate reaction temperature, and, if necessary, the selection of the right reaction catalyst but also, if the planned reaction is to be successful, the selection of an appropriate solvent or solvent mixture. Solvent effects on chemical reactivity have been studied for more than a century, beginning with the pioneering work of Berthelot and Saint Gilles1 in Paris in 1862 on esterification reactions and with that of Menschutkin2 in St. Petersburg in 1880 on the quaternization of tertiary amines by haloalkanes. At this time Menschutkin remarked that “a reaction cannot be separated from the medium in which it is performed... Experience shows that solvents exert considerable influence on reaction rates.” Today, we can suggest a striking example to reinforce his remark, the rate of the unimolecular heterolysis of 2-chloro-2-methylpropane observed in water and benzene increases by a factor of approximately1011 when the nonpolar benzene is replaced by water.3,4 The influence of solvents on the position of chemical equilibria was discovered in 1896 by Claisen5 in Aachen, Knorr6 in Jena, Wislicenus7 in Wòrzburg, and Hantzsch8 in Wòrzburg. They investigated almost simultaneous but independent of one another the keto-enol tautomerism of 1,3-dicarbonyl compounds and the nitro-isonitro tautomerism of primary and secondary

2

Christian Reichardt

aliphatic nitro compounds. With this example, the enol content of acetylacetone increases from 62 to 95 % when acetonitrile is substituted with n-hexane.3,9 The proper solvent and solvent mixture selection is not only important for chemical but also for physical processes such as recrystallization, all extraction processes, partitioning, chromatographic separations, phase-transfer catalytic reactions, etc. Of particular interest in this context is the influence of solvents on all types of light absorption processes, e.g., on UV/Vis, IR, ESR, and NMR spectra, caused by differential solvation of the ground and excited states of the absorbing species.3,12 In 1878, Kundt10 in Zòrich proposed the rule that increasing dispersion interactions between the absorbing solute and the solvent lead in general to a bathochromic shift of an UV/Vis absorption band. Later, in 1922, Hantzsch11 termed the solvent-dependence of UV/Vis absorption spectra “solvatochromism”. UV/Vis absorption of solute molecules can be influenced not only by the surrounding solvent sphere, but also by other entities in the surroundings such as solids, polymers, glasses, and surfaces. In order to emphasize this influence, the use of the more general term “perichromism” (from Greek peri = around) has been recommended.12,13 A typical, more recent, example of extraordinary solvatochromism is the intramolecular charge-transfer Vis-absorption of 2,6-diphenyl-4-(2,4,6-triphenyl-l-pyridinio)phenolate, a zwitterionic betaine dye: its corresponding absorption band is shifted from λmax = 810 nm to λmax = 453 nm (∆λ = 357 nm) when diphenyl ether is replaced by water as solvent.3,12 Such solvatochromic dyes can be used as empirical solvent polarity indicators.12 The number of solvents generally available to chemists working in research and industrial laboratories is between 250 and 3003,14 (there is an infinite number of solvent mixtures), and this number is increasing. More recently and for obvious reasons, the search for new solvents has been intensified: peroxide-forming solvents are being substituted by solvents which are more stable against oxidation (e.g., diethyl ether by t-butyl methyl ether or by formaldehyde dialkyl acetals), toxic solvents are being replaced by nontoxic ones (e.g., the cancerogenic hexamethylphosphoric triamide, HMPT, by N,N'-dimethylpropyleneurea, DMPU15) and environmentally dangerous solvents by benign ones (e.g., tetrachloromethane by perfluorohexane16). The development of modern solvents for organic syntheses is the subject of much current research.17 Amongst these modern solvents, also called “neoteric solvents” (neoteric = recent, new, modern) in contrast to the classical ones, are ionic liquids (i.e., room-temperature liquid salts such as 1-ethyl-3-methylimidazolium tetra-chloroaluminates18,19), supercritical-fluid solvents, SCF, (such as SCF carbon dioxide20,21), and perfluorinated solvents (e.g., partially or perfluorinated hydrocarbons as used in so-called “fluorous biphase catalysis reactions”, making possible mono-phase reactions and a two-phase separation of catalyst and reaction products22-24). Even plain water has found a magnificent renaissance as a solvent for organic reactions.25,26 These efforts have also recently strengthened the search for completely solvent-free reactions, thus avoiding the use of expensive, toxic, and environmentally problematic solvents.27,28 With respect to the large and still increasing number of valuable solvents useful for organic syntheses, a chemist needs, in addition to his experience and intuition, to have general rules, objective criteria, and the latest information about the solvents' physical, chemical, and toxicological properties for the selection of the proper solvent or solvent mixture for a planned reaction or a technological process. To make this often cumbersome and time-consuming task easier, this “Handbook of Solvents” with its twenty-five chapters is designed to provide a comprehensive source of information on solvents over a broad range

1 Introduction

3

of applications. It is directed not only to chemists working in research laboratories, but also to all industries using solvents for various purposes. A particular advantage is that the printed handbook is accompanied by a compact-disc (CD-ROM) containing additional solvent databases with hundred ten fields for over eleven hundred solvents. This makes large data sets easily available for quick search and retrieval and frees the book text from bulky tables, thus giving more room for a thorough description of the underlying theoretical and practical fundamental subjects. Fundamental principles governing the use of solvents (i.e., chemical structure, molecular design as well as physical and chemical properties of solvents) are given in Chapter 2. Solvent classification, methods of solvent manufacture together with properties and typical applications of various solvents are provided in Chapter 3. Chapters 4, 5 and 6 deal with all aspects of the dissolution of materials in solvents as well as with the solubility of selected systems (e.g., polymers and elastomers) and the influence of the solute's molecular structure on its solubility behavior. In particular, the valuable solubility-parameter concept is extensively treated in these chapters. All aspects of solvent transport within polymeric system and the drying of such polymeric systems, including coated films, are described in Chapter 7. The fundamentals of the interaction forces acting between ions or molecules of the solvents themselves and between solutes and solvents in solutions are presented in Chapter 8. Chapter 9 deals with the corresponding properties of solvent mixtures. Specific solute/solvent interactions, particularly Lewis acid/base interactions between electron-pair donors (EPD) and electron-pair acceptors (EPA), are reviewed in Chapter 10, together with the development of empirical scales of solvent polarity and Lewis acidity/basicity, based on suitable solvent-dependent reference processes, and their application for the treatment of solvent effects. The theory for solvent effects on electronic properties is provided in Chapter 11 and extended to solvent-dependent properties of solutes such as fluorescence spectra, ORD and CD spectra. Aggregation, swelling of polymers, their conformations, the viscosity of solutions and other solvent-related properties are treated in Chapter 12. A review concerning solvent effects on various types of chemical reactivity is given in Chapter 13, along with a discussion of the effects of solvent on free-radical polymerization and phase-transfer catalysis reactions. The second part of this handbook (Chapters 14-25) is devoted more to the industrial use of solvents. Formulating with solvents applied in a broad range of industrial areas such as biotechnology, dry cleaning, electronic industry, food industry, paints and coatings, petroleum refining industry, pharmaceutical industry, textile industry, to mention only a few, is extensively described in Chapter 14. Standard and special methods of solvent detection and solvent analysis as well as the problem of residual solvents in various products, particularly in pharmaceutical ones, are the topics of Chapters 15 and 16. At present, large-scale chemical manufacturing is facing serious solvent problems with respect to environmental concerns. National and international regulations for the proper use of hazardous solvents are becoming increasingly stringent and this requires the use of environmentally more benign but nevertheless economical liquid reaction media. This has enormously stimulated the search for such new solvent systems within the framework of so-called green chemistry. Supercritical fluids, SCF,20,21 and ionic liquids (room temperature liquid salts)18,19 have been known and have been the subject of scientific interest for a long time. It is only recently, however, that the potential benefits of these materials in solvent applications have been realized.17 This handbook includes in Chapters 17-25 all

4

Christian Reichardt

the knowledge necessary for a safe handling of solvents in research laboratories and in large-scale manufacturing, beginning with the environmental impact of solvents on water, soil, and air in Chapter 17, followed by considerations about safe solvent concentrations and the risks of solvent exposure in various industrial environments in Chapter 18. Chapter 19 summarizes the corresponding legal regulations, valid for North America and Europe, and Chapter 20 describes in detail the toxic effects of solvent exposure to human beings. Authors specializing in different fields of solvent toxicity give the most current information on the effect of solvent exposure from the point of view of neurotoxicity, reproductive and maternal effects, nephrotoxicity, cancerogenicity, hepatotoxicity, chromosomal aberrations, and toxicity to brain, lungs, and heart. This information brings both the results of documented studies and an evaluation of risk in different industrial environments in a comprehensive but easy to understand form to engineers and decision-makers in industry. Chapter 21 is focused on the substitution of harmful solvents by safer ones and on the development of corresponding new technological processes. Chapter 22 describes modern methods of solvent recovery, solvent recycling. When recycling is not possible, then solvents have to be destroyed by incineration or other methods of oxidation, as outlined in Chapter 22. Chapter 23 describes natural attenuation of solvents in groundwater and advanced remediation technologies as well as management strategies for sites impacted by solvent contamination. Protection from contact with solvents and their vapors is discussed in Chapter 24. Finally, new trends in solvent chemistry and applications based on the recent patent literature are discussed in Chapter 25. In most cases, the intelligent choice of the proper solvent or solvent mixture is essential for the realization of certain chemical transformations and physical processes. This handbook tries to cover all theoretical and practical information necessary for this often difficult task for both academic and industrial applications. It should be used not only by chemists, but also by physicists, chemical engineers, and technologists as well as environmental scientists in academic and industrial institutions. It is to be hoped that the present compilation of all relevant aspects connected with the use of solvents will also stimulate further basic and applied research in the still topical field of the physics and chemistry of liquid media.

REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

M Berthelot, L P¾an de Saint Gilles, Ann. Chim. Phys., 3. S¾r., 65, 385 (1862); ibid. 66, 5 (1862); ibid. 68, 255 (1863). N Menschutkin, Z. Phys. Chem., 5, 589 (1890); ibid. 6, 41 (1890); ibid. 34, 157 (1900). C Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed., VCH, Weinheim, 1988. (a) G F Dvorko, E A Ponomareva, Usp. Khim., 53, 948 (1984); Russ. Chem. Rev., 53, 547 (1984); (b) M H Abraham, Pure Appl. Chem., 57, 1055 (1985); and references cited therein. L Claisen, Justus Liebigs Ann. Chem., 291, 25 (1896). L Knorr, Justus Liebigs Ann. Chem., 293, 70 (1896). W Wislicenus, Justus Liebigs Ann. Chem., 291, 147 (1896). A Hantzsch, O W Schultze, Ber. Dtsch. Chem. Ges., 29, 2251 (1896). M T Rogers, J L Burdett, Can. J Chem., 43, 1516 (1965). A Kundt, Poggendorfs Ann. Phys. Chem. N. F., 4, 34 (1878); Chem. Zentralbl., 498 (1878). A Hantzsch, Ber. Dtsch. Chem. Ges., 55, 953 (1922). C Reichardt, Chem. Rev., 94, 2319 (1994). Prof. E M Kosower, Tel Aviv, private communication to C.R. Y Marcus, The Properties of Solvents, Wiley, Chichester, 1998. (a) Editorial, Chimia, 39, 147 (1985); (b) D Seebach, Chemistry in Britain, 21, 632 (1985). S M Pereira, G P Sauvage, G. W. Simpson, Synth. Commun., 25, 1023 (1995).

Introduction 17 18 19 20 21 22 23 24 25 26 27 28

5

P Knochel (Ed.), Modern Solvents in Organic Synthesis, Topics in Current Chemistry, Vol. 206, Springer, Berlin, 1999. Y Chauvin, H Olivier-Bourbigou, CHEMTECH, 25(9), 26 (1995). (a) K R Seddon, Kinetika i Kataliz, 37, 743 (1996); Kinetics and Catalysis, 37, 693 (1996); Chem. Abstr., 125, 285927s (1996); (b) K R Seddon, J. Chem. Technol. Biotechnol., 68, 351 (1997); Chem. Abstr., 126, 306898w (1997). R Noyori (Ed.), Supercritical Fluids, Chem. Rev., 99, 353-633 (1999). W Leitner, Top. Curr. Chem., 206, 107 (1999). B Cornils, Angew. Chem., 109, 2147 (1997); Angew. Chem., Int. Ed. Engl., 36, 2057 (1997). B Betzemeier, P Knochel, Top. Curr. Chem., 206, 61 (1999). J J Maul, P J Ostrowski, G A Ublacker, B Linclau, D P Curran, Top. Curr. Chem., 206, 79 (1999). P A Grieco, Organic Synthesis in Water, Blackie Academic and Professional, Hampshire, 1998. A Lubineau and J. Aug¾, Top. Curr. Chem., 206, 1 (1999). J O Metzger, Angew, Chem., 110, 3145 (1998); Angew. Chem., Int. Ed. Engl., 37, 2975 (1998). A Loupy, Top. Curr. Chem., 206, 153 (1999).

2

Fundamental Principles Governing Solvents Use 2.1 SOLVENT EFFECTS ON CHEMICAL SYSTEMS Estanislao Silla, Arturo Arnau and Iñaki TuñóN Department of Physical Chemistry, University of Valencia, Burjassot (Valencia), Spain

2.1.1 HISTORICAL OUTLINE According to a story, a little fish asked a big fish about the ocean, since he had heard it being talked about but did not know where it was. Whilst the little fish’s eyes turned bright and shiny full of surprise, the old fish told him that all that surrounded him was the ocean. This story illustrates in an eloquent way how difficult it is to get away from every day life, something of which the chemistry of solvents is not unaware. The chemistry of living beings and that which we practice in laboratories and factories is generally a chemistry in solution, a solution which is generally aqueous. A daily routine such as this explains the difficulty which, throughout the history of chemistry, has been encountered in getting to know the effects of the solvent in chemical transformations, something which was not achieved in a precise way until well into the XX century. It was necessary to wait for the development of experimental techniques in vacuo to be able to separate the solvent and to compare the chemical processes in the presence and in the absence of this, with the purpose of getting to know its role in the chemical transformations which occur in its midst. But we ought to start from the beginning. Although essential for the later cultural development, Greek philosophy was basically a work of the imagination, removed from experimentation, and something more than meditation is needed to reach an approach on what happens in a process of dissolution. However, in those remote times, any chemically active liquid was included under the name of “divine water”, bearing in mind that the term “water” was used to refer to anything liquid or dissolved.1 Parallel with the fanciful search for the philosopher’s stone, the alchemists toiled away on another impossible search, that of a universal solvent which some called “alkahest” and others referred to as “menstruum universale”, which term was used by the very Paracelsus (1493-1541), which gives an idea of the importance given to solvents during that dark and obscurantist period. Even though the “menstruum universale” proved just as elusive as the philosopher’s stone, all the work carried out by the alchemists in search of these

8

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

illusionary materials opened the way to improving the work in the laboratory, the development of new methods, the discovery of compounds and the utilization of novel solvents. One of the tangible results of all that alchemistry work was the discovery of one of the first experimental rules of chemistry: “similia similibus solvuntor”, which reminds us of the compatibility in solution of those substances of similar nature. Even so, the alchemistry only touched lightly on the subject of the role played by the solvent, with so many conceptual gulfs in those pre-scientific times in which the terms dissolution and solution referred to any process which led to a liquid product, without making any distinction between the fusion of a substance - such as the transformation of ice into liquid water -, mere physical dissolution - such as that of a sweetener in water - or the dissolution which takes place with a chemical transformation - such as could be the dissolution of a metal in an acid. This misdirected vision of the dissolution process led the alchemists down equally erroneous collateral paths which were prolonged in time. Some examples are worth quoting: Hermann Boerhaave (1688-1738) thought that dissolution and chemical reaction constituted the same reality; the solvent, (menstruum), habitually a liquid, he considered to be formed by diminutive particles moving around amongst those of the solute, leaving the interactions of these particles dependent on the mutual affinities of both substances.2 This paved the way for Boerhaave to introduce the term affinity in a such a way as was conserved throughout the whole of the following century.3 This approach also enabled Boerhaave to conclude that combustion was accompanied by an increase of weight due to the capturing of “particles” of fire, which he considered to be provided with weight by the substance which was burned. This explanation, supported by the well known Boyle, eased the way to considering that fire, heat and light were material substances until when, in the XIX century, the modern concept of energy put things in their place.4 Even Bertollet (1748-1822) saw no difference between a dissolution and a chemical reaction, which prevented him from reaching the law of definite proportions. It was Proust, an experimenter who was more exacting and capable of differentiating between chemical reaction and dissolution, who made his opinion prevail:

“The dissolution of ammonia in water is not the same as that of hydrogen in azote (nitrogen), which gives rise to ammonia”5 There were also alchemists who defended the idea that the substances lost their nature when dissolved. Van Helmont (1577-1644) was one of the first to oppose this mistaken idea by defending that the substance dissolved remains in the solution in aqueous form, it being possible to recover it later. Later, the theories of osmotic pressure of van´t Hoff (1852-1911) and that of electrolytic dissociation of Arrhenius (1859-1927) took this approach even further. Until almost the end of the XIX century the effects of the solvent on the different chemical processes did not become the object of systematic study by the experimenters. The effect of the solvent was assumed, without reaching the point of awakening the interest of the chemists. However, some chemists of the XIX century were soon capable of unraveling the role played by some solvents by carrying out experiments on different solvents, classified according to their physical properties; in this way the influence of the solvent both on chemical equilibrium and on the rate of reaction was brought to light. Thus, in 1862, Berthelot and Saint-Gilles, in their studies on the esterification of acetic acid with ethanol,

2.1 Solvent effects on chemical systems

9

discovered that some solvents, which do not participate in the chemical reaction, are capable of slowing down the process.6 In 1890, Menschutkin, in a now classical study on the reaction of the trialkylamines with haloalcans in 23 solvents, made it clear how the choice of one or the other could substantially affect the reaction rate.7 It was also Menschutkin who discovered that, in reactions between liquids, one of the reactants could constitute a solvent inadvisable for that reaction. Thus, in the reaction between aniline and acetic acid to produce acetanilide, it is better to use an excess of acetic acid than an excess of aniline, since the latter is a solvent which is not very favorable to this reaction. The fruits of these experiments with series of solvents were the first rules regarding the participation of the solvent, such as those discovered by Hughes and Ingold for the rate of the nucleophilic reactions.8 Utilizing a simple electrostatic model of the solute - solvent interactions, Hughes and Ingold concluded that the state of transition is more polar than the initial state, that an increase of the polarity of the solvent will stabilize the state of transition with respect to the initial state, thus leading to an increase in the reaction rate. If, on the contrary, the state of transition is less polar, then the increase of the polarity of the solvent will lead to a decrease of the velocity of the process. The rules of Hughes-Ingold for the nucleophilic aliphatic reactions are summarized in Table 2.1.1. Table 2.1.1. Rules of Hughes-Ingold on the effect of the increase of the polarity of the solvent on the rate of nucleophilic aliphatic reactions Mechanism

Initial state -

S N2

-

Effect on the reaction rate

Y + RX

[Y--R--X]

slight decrease

Y + RX

[Y--R--X]

large increase

-

+

Y + RX

+

S N1

State of transition

[Y--R--X] +

large decrease

Y + RX

[Y--R--X]

slight decrease

RX

[R--X]

large increase

+

RX

[R--X]

+

slight decrease

In 1896 the first results about the role of the solvent on chemical equilibria were obtained, coinciding with the discovery of the keto-enolic tautomerism.9 Claisen identified the medium as one of the factors which, together with the temperature and the substituents, proved to be decisive in this equilibrium. Soon systematic studies began to be done on the effect of the solvent in the tautomeric equilibria. Wislicenus studied the keto-enolic equilibrium of ethylformylphenylacetate in eight solvents, concluding that the final proportion between the keto form and the enol form depended on the polarity of the solvent.10 This effect of the solvent also revealed itself in other types of equilibria: acid-base, conformational, those of isomerization and of electronic transfer. The acid-base equilibrium is of particular interest. The relative scales of basicity and acidity of different organic compounds and homologous families were established on the basis of measurements carried out in solution, fundamentally aqueous. These scales permitted establishing hypotheses regarding the effect of the substituents on the acidic and basic centers, but without being capable of separating this from the effect of the solvent. Thus, the scale obtained in solution for the acidity of

10

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

the α-substituted methyl alcohols [(CH3)3COH > (CH3)2CHOH > CH3CH2OH > CH3OH]11 came into conflict with the conclusions extracted from the measurements of movements by NMR.12 The irregular order in the basicity of the methyl amines in aqueous solution also proved to be confusing [NH3 < CH3NH2 < (CH3)2NH > (CH3)3N],13 since it did not match any of the existing models on the effects of the substituents. These conflicts were only resolved when the scales of acidity-basicity were established in the gas phase. On carrying out the abstraction of the solvent an exact understanding began to be had of the real role it played. The great technological development which arrived with the XIX century has brought us a set of techniques capable of giving accurate values in the study of chemical processes in the gas phase. The methods most widely used for these studies are: • The High Pressure Mass Spectrometry, which uses a beam of electron pulses14 • The Ion Cyclotron Resonance and its corresponding Fourier Transform (FT-ICR)15 • The Chemical Ionization Mass Spectrometry, in which the analysis is made of the kinetic energy of the ions, after generating them by collisions16 • The techniques of Flowing Afterglow, where the flow of gases is submitted to ionization by electron bombardment17-19 All of these techniques give absolute values with an accuracy of ±(2-4) Kcal/mol and of ±0.2 Kcal/mol for the relative values.20 During the last decades of XX century the importance has also been made clear of the effects of the solvent in the behavior of the biomacromolecules. To give an example, the influence of the solvent over the proteins is made evident not only by its effects on the structure and the thermodynamics, but also on the dynamics of these, both at local as well as at global level.21 In the same way, the effect of the medium proves to be indispensable in explaining a large variety of biological processes, such us the rate of interchange of oxygen in myoglobin.22 Therefore, the actual state of development of chemistry, as much in its experimental aspect as in its theoretical one, allows us to identify and analyze the influence of the solvent on processes increasingly more complex, leaving the subject open for new challenges and investigating the scientific necessity of creating models with which to interpret such a wide range of phenomena as this. The little fish became aware of the ocean and began explorations. 2.1.2 CLASSIFICATION OF SOLUTE-SOLVENT INTERACTIONS Fixing the limits of the different interactions between the solute and the solvent which envelopes it is not a trivial task. In the first place, the liquid state, which is predominant in the majority of the solutions in use, is more difficult to comprehend than the solid state (which has its constitutive particles, atoms, molecules or ions, in fixed positions) or the gaseous state (in which the interactions between the constitutive particles are not so intense). Moreover, the solute-solvent interactions, which, as has already been pointed out, generally happen in the liquid phase, are half way between the predominant interactions in the solid phase and those which happen in the gas phase, too weak to be likened with the physics of the solid state but too strong to fit in with the kinetic theory of gases. In the second place, dissecting the solute-solvent interaction into different sub-interactions only serves to give us an approximate idea of the reality and we should not forget that, in the solute-solvent interaction, the all is not the sum of the parts. In the third place, the world of the solvents is very varied from those which have a very severe internal structure, as in the case of water, to those

2.1 Solvent effects on chemical systems

11

whose molecules interact superficially, as in the case of the hydrocarbons. At all events, there is no alternative to meeting the challenge face to face. If we mix a solute and a solvent, both being constituted by chemically saturated molecules, their molecules attract one another as they approach one another. This interaction can only be electrical in its nature, given that other known interactions are much more intense and of much shorter range of action (such as those which can be explained by means of nuclear forces) or much lighter and of longer range of action (such as the gravitational force). These intermolecular forces usually also receive the name of van der Waals forces, from the fact that it was this Dutch physicist, Johannes D. van der Waals (1837-1923), who recognized them as being the cause of the non-perfect behavior of the real gases, in a period in which the modern concept of the molecule still had to be consolidated. The intermolecular forces not only permit the interactions between solutes and solvents to be explained but also determine the properties of gases, liquids and solids; they are essential in the chemical transformations and are responsible for organizing the structure of biological molecules. The analysis of solute-solvent interactions is usually based on the following partition scheme: ∆E = ∆E i + ∆E ij + ∆E jj

[2.1.1]

where i stands for the solute and j for the solvent.This approach can be maintained while the identities of the solute and solvent molecules are preserved. In some special cases (see below in specific interactions) it will be necessary to include some solvent molecules in the solute definition. The first term in the above expression is the energy change of the solute due to the electronic and nuclear distortion induced by the solvent molecule and is usually given the name solute polarization. ∆Eij is the interaction energy between the solute and solvent molecules. The last term is the energy difference between the solvent after and before the introduction of the solute. This term reflects the changes induced by the solute on the solvent structure. It is usually called cavitation energy in the framework of continuum solvent models and hydrophobic interaction when analyzing the solvation of nonpolar molecules. The calculation of the three energy terms needs analytical expressions for the different energy contributions but also requires knowledge of solvent molecules distribution around the solute which in turn depends on the balance between the potential and the kinetic energy of the molecules. This distribution can be obtained from diffraction experiments or more usually is calculated by means of different solvent modelling. In this section we will comment on the expression for evaluating the energy contributions. The first two terms in equation [2.1.1] can be considered together by means of the following energy partition : ∆E i + ∆E ij = ∆E el + ∆E pol + ∆E d − r

[2.1.2]

Analytical expressions for the three terms (electrostatic, polarization and dispersion-repulsion energies) are obtained from the intermolecular interactions theory. 2.1.2.1 Electrostatic The electrostatic contribution arises from the interaction of the unpolarized charge distribution of the molecules. This interaction can be analyzed using a multipolar expansion of the charge distribution of the interacting subsystems which usually is cut off in the first term

12

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

which is different from zero. If both the solute and the solvent are considered to be formed by neutral polar molecules (with a permanent dipolar moment different from zero), due to an asymmetric distribution of its charges, the electric interaction of the type dipole-dipole will normally be the most important term in the electrostatic interaction. The intensity of this interaction will depend on the relative orientation of the dipoles. If the molecular rotation is not restricted, we must consider the weighted average over different orientations E d −d = − where:

µ i, µ j k ε T r

2 µ 12µ 22 3 (4πε) 2 kTr 6

[2.1.3]

dipole moments Boltzmann constant dielectric constant absolute temperature intermolecular distance

The most stable orientation is the antiparallel, except in the case that the molecules in play are very voluminous. Two dipoles in rapid thermal movement will be orientated sometimes in a way such that they are attracted and at other times in a way that they are repelled. On the average, the net energy turns out to be attractive. It also has to be borne in mind that the thermal energy of the molecules is a serious obstacle for the dipoles to be oriented in an optimum manner. The average potential energy of the diFigure 2.1.1. The dipoles of two molecules can approach one another under an infinite variety of attractive orienta- pole-dipole interaction, or of orientation, is, tions, among which these two extreme orientations stand therefore, very dependent on the temperaout. ture. In the event that one of the species involved were not neutral (for example an anionic or cationic solute) the predominant term in the series which gives the electrostatic interaction will be the ion-dipole which is given by the expression: E i −d = −

q i2 µ 2j 6( 4πε) 2 kTr 4

[2.1.4]

2.1.2.2 Polarization If we dissolve a polar substance in a nonpolar solvent, the molecular dipoles of the solute are capable of distorting the electronic clouds of the solvent molecules inducing the appearance in these of new dipoles. The dipoles of solute and those induced will line up and will be attracted and the energy of this interaction (also called interaction of polarization or induction) is:

2.1 Solvent effects on chemical systems

E d − id = − where:

µi αj r

α j µ i2

13

[2.1.5]

( 4πε) 2 r 6 dipole moment polarizability intermolecular distance

In a similar way, the dissolution of an ionic substance in a nonpolar solvent also will occur with the induction of the dipoles in the molecules of the solvent by the solute ions. These equations make reference to the interactions between two molecules. Because the polarization energy (of the solute or of the solvent) is not pairwise additive magnitude, the consideration of a third molecule should be carried out simultaneously, it being impossible to decompose the interaction of the three bodies in a sum of the interactions of two bodies. The interactions between molecules in solution are different from those which take place between isolated molecules. For this reason, the dipolar moment of a molecule may vary considerably from the gas phase to the solution, and will depend in a complicated fashion on the interactions which may take place between the molecule of solute and its specific surroundings of molecules of solvent. 2.1.2.3 Dispersion Even when solvent and solute are constituted by nonpolar molecules, there is interaction between them. It was F. London who was first to face up to this problem, for which reason these forces are known as London’s forces, but also as dispersion forces, charge-fluctuations forces or electrodynamic forces. Their origin is as follows: when we say that a substance is nonpolar we are indicating that the distribution of the charges of its molecules is symmetrical throughout a wide average time span. But, without doubt, in an interval of time sufficiently restricted the molecular movements generate displacements of their charges which break that symmetry giving birth to instantaneous dipoles. Since the orientation of the dipolar moment vector is varying constantly due to the molecular movement, the average dipolar moment is zero, which does not prevent the existence of these interactions between momentary dipoles. Starting with two instantaneous dipoles, these will be oriented to reach a disposition which will favor them energetically. The energy of this dispersion interaction can be given, to a first approximation, by: E disp = − where:

Ii, Ij αi, αj r

3I i I j

αi α j

2( 4πε) (I i + I j ) r 6 2

ionization potentials polarizabilities intermolecular distance

[2.1.6]

From equation [2.1.6] it becomes evident that dispersion is an interaction which is more noticeable the greater the volume of molecules involved. The dispersion forces are often more intense than the electrostatic forces and, in any case, are universal for all the atoms and molecules, given that they are not seen to be subjected to the requirement that permanent dipoles should exist beforehand. These forces are responsible for the aggregation of the substances which possess neither free charges nor permanent dipoles, and are also the

14

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

Источник: https://pdfcoffee.com/-handbook-of-solvents-pdf-free.html

Handbook of Solvents - George Wypych - ChemTech - Ventech!

HANDBOOK OF

SOLVENTS

GeorgeWypych, Editor

ChemTec Publishing

Toronto − New York 2001


Published by ChemTec Publishing

38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada

Co-published by William Andrew Inc.

13 Eaton Avenue, Norwich, NY 13815, USA

© Chem Tec Publishing, 2001

ISBN 1-895198-24-0

All rights reserved. No part of this publication may be reproduced, stored or

transmitted in any form or by any means without written permission of copyright

owner. No responsibility is assumed by the Author and the Publisher for any injury

or/and damage to persons or properties as a matter of products liability, negligence,

use, or operation of any methods, product ideas, or instructions published or

suggested in this book.

Canadian Cataloguing in Publication Data

HandbookofSolvents

Includes bibliographical references and index

ISBN 1-895198-24-0 (ChemTec Publishing)

ISBN 0-8155-1458-1 (William Andrew Inc.)

Library of Congress Catalog Card Number: 00-106798

1. Solvents--Handbooks, manuals, etc. I. Wypych, George

TP247.5.H35 2000 661’.807 C00-900997-3

Printed in Canada by Transcontinental Printing Inc., 505 Consumers Rd.

Toronto, Ontario M2J 4V8


Preface

Although the chemical industry can trace its roots into antiquity, it was during the industrial

revolution that it started to become an actual industry and began to use the increased knowledge

of chemistry as a science and technology to produce products that were needed by

companion industries and consumers. These commercial efforts resulted in the synthesis of

many new chemicals. Quite quickly, in these early days, previously unknown materials or

materials that had been present only in low concentrations, were now in contact with people

in highly concentrated forms and in large quantities. The people had little or no knowledge

of the effects of these materials on their bodies and the natural biological and physical

processes in the rivers and oceans, the atmosphere, and in the ground.

Until the end of the nineteenth century these problems were not addressed by the

chemical industry and it is only recently that the industry began to respond to public criticism

and political efforts. Legal restrictions aimed at preserving the quality of life have been

directed at health, safety and longevity issues and the environment. Solvents have always

been mainstays of the chemical industry and because of their widespread use and their high

volume of production they have been specifically targeted by legislators throughout the

world. The restrictions range from total prohibition of production and use, to limits placed

on vapor concentrations in the air. As with any arbitrary measures some solvents have been

damned unfairly. However, there is no question that it is best to err on the side of safety if the

risks are not fully understood. It is also true that solvents should be differentiated based on

their individual properties.

This book is intended to provide a better understanding of the principles involved in

solvent selection and use. It strives to provide information that will help to identify the risks

and benefits associated with specific solvents and classes of solvents. The book is intended

to help the formulator select the ideal solvent, the safety coordinator to safeguard his or her

coworkers, the legislator to impose appropriate and technically correct restrictions and the

student to appreciate the amazing variety of properties, applications and risks associated

with the more than one thousand solvents that are available today.

By their very nature, handbooks are intended to provide exhaustive information on the

subject. While we agree that this is the goal here, we have attempted to temper the impact of

information, which may be too narrow to make decision.

Many excellent books on solvents have been published in the past and most of these

are referenced in this book. But of all these books none has given a comprehensive overview

of all aspects of solvent use. Access to comprehensive data is an essential part of solvent

evaluation and it has been a hallmark of such books to provide tables filled with data to the

point at which 50 to 95% of the book is data. This approach seems to neglect a fundamental

requirement of a handbook - to provide the background, explanations and clarifications that

are needed to convert data to information and assist the reader in gaining the knowledge to

make a decision on selecting a process or a solvent. Unfortunately, to meet the goal of providing

both the data and the fundamental explanations that are needed, a book of 4,000 to

5,000 pages might be required. Even if this was possible, much of the data would fall out of

date quite quickly. For example, a factor that defines solvent safety such as threshold limit


xxviii Preface

values (TLVs) for worker exposure or some single toxicity determinants may change

frequently. This book would be huge and it would have to be updated frequently to continue

to claim that it is current.

What we have attempted to do here is to give you a book with a comprehensive and extensive

analysis of all current information on solvents then use other media to present the

supporting data on individual solvents. These data are provided on a CD-ROM as a

searchable database. Data are provided on more than 1140 solvents in 110 fields of data.

The medium permits frequent updates. If the same data were presented in book form, more

than 2,000 pages would be needed which exceeds the size of any data in handbook form

offered to date.

The best approach in presenting an authoritative text for such a book is to have it written

by experts in their fields. This book attracted well-known experts who have written

jointly 47 books and authored or coauthored hundreds of papers on their areas of expertise.

The authors have made their contributions to this book in late 1999 and early 2000

providing the most current picture of the technology. Their extreme familiarity with their

subjects enables them to present information in depth and detail, which is essential to the

reader’s full understanding of the subject.

The authors were aware of the diversity of potential readers at the outset and one of

their objectives was to provide information to various disciplines expressed in a way that all

would understand and which would deal with all aspects of solvent applications. We expect

professionals and students from a wide range of businesses, all levels of governments and

academe to be interested readers. The list includes solvent manufacturers, formulators of

solvent containing products, industrial engineers, analytical chemists, government legislators

and their staffs, medical professionals involved in assessing the impact on health of solvents,

biologists who are evaluating the interactions of solvents with soil and water,

environmental engineers, industrial hygienists who are determining protective measures

against solvent exposure, civil engineers who design waste disposal sites and remediation

measures, people in industries where there are processes which use solvents and require

their recovery and, perhaps most important, because understanding brings improvements,

those who teach and learn in our universities, colleges and schools.

A growing spirit of cooperation is evident between these groups and this can be fostered

by providing avenues of understanding based on sharing data and information on common

problems. We hope to provide one such avenue with this book. We have tried to

present a balanced picture of solvent performance by dealing not only with product performance

and ease of processing but also by giving environmental and health issues full consideration.

Data and information on known products and processes should be cornerstones of the

understanding of a technology but there is another aspect of technology, which can lead to

advances and improvements in utility, safety and in safeguarding the environment. This

must come from you, the reader. It is your ideas and creative thinking that will bring these

improvements. The authors have crammed their ideas into the book and we hope these will

stimulate responsible and effective applications of solvents. Francis Bacon wrote, “The end

of our foundation is the knowledge of causes, and the secret motion of things, and the enlarging

of the bound of human Empire, to the effecting of all things possible.”

Today there are few technical activities that do not employ solvents. Almost all industries,

almost all consumer products, almost everything we use can, if analyzed, be shown to


Preface xxix

contain or to have used in its processing, a solvent. Solvent elimination need never be a

technical objective. Rather, we need to use our increasing understanding and knowledge to

find the safest and the most effective means of meeting our goals.

I would like to thank the authors for their relentless efforts to explain the difficult in an

interesting way. In advance, I would like to thank the reader for choosing this book and encourage

her or him to apply the knowledge to make our world a better, more livable place.

GeorgeWypych

Toronto, August 3, 2000


Acknowledgments 1653

ACKNOWLEDGMENTS

This following section contains acknowledgments included in the various sections of the

book which were combined to form one section. For better identification, individual acknowledgments

follow the reference to the title and authors of the book section.

Preface

GeorgeWypych, ChemTec Laboratories, Inc., Toronto, Canada

I would like to thank Dr. Robert Fox and John Paterson who made all efforts that the

language used in this book is simple to understand and the book is read with pleasure.

4.2 Polar solvation dynamics: Theory and simulations

Abraham Nitzan, School of Chemistry, the Sackler Faculty of Sciences, Tel Aviv University,

Tel Aviv, 69978, Israel

This work was supported by Israel Science Foundation. I thank my E. Neria, R.

Olender and P. Graf who collaborated with me on some of the works described in this report.

4.4 Methods for the measurement of solvent activity of polymer solutions

Christian Wohlfarth, Martin-Luther-University Halle-Wittenberg, Institute of Physical

Chemistry, Geusaer Straße, D-06217 Merseburg, Germany

Thanks are given to G. Sadowski (TU Berlin) for providing Figure 4.4-7(b), B. A Wolf

(Univ. Mainz) for providing Figure 4.4-13, and G. Maurer (Univ. Kaiserslautern) for providing

Figure 4.4-6. Furthermore, I wish to thank M. D. Lechner (Univ. Osnabrück) and G.

Sadowski for many helpful comments and discussions about this manuscript.

5.4 Mixed solvents, a way to change the polymer solubility

Ligia Gargallo and Deodato Radic, Facultad de Quimica, Pontificia Universidad Catolica

de Chile, Casilla 306, Santiago 22, Chile

The authors wish to express their appreciation to Mrs. Viviana Ulloa for her technical

assistance in this work and to publishers and authors for permission to reproduce figures

and tables from their publications as indicated specifically in the legends of the figures and

tables.

6.1 Modern views on kinetics of swelling of crosslinked elastomers in solvents

E. Ya. Denisyuk, Institute of Continuous Media Mechanics; V. V. Tereshatov, Institute of

Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia

This work was supported by a grant from Russian Fund of Fundamental Research

(grant No 98-03-33333).


1654 Acknowledgments

10.3 Solvent effects based on pure solvent scales

Javier Catalán, Departamento de Química Fisíca Aplicada, Universidad Autónoma de Madrid,

Cantoblanco, E-28049, Madrid, Spain

The author wishes to thank all those who contributed to the development of our solvent

scales (C. Díaz, P. Pérez, V. López, J.L. G de Paz, R. Martín-Villamil, J.G. González ,

J. Palomar, and F. García-Blanco) and also Spain’s DGICyT (Project PB98-0063) for funding

this work.

12.2 Chain conformations of polysaccharides in different solvents

Ranieri Urbani and Attilio Cesàro, Department of Biochemistry, Biophysics and

Macromolecular Chemistry, University of Trieste, Italy

The paper has been prepared with financial support of University of Trieste and of

Progetto Coordinato “Proprietà dinamiche di oligo e polisaccaridi”, Grant CT97-02765.03

of the National Research Council of Italy (Rome). The authors wish also to thank dr. Paola

Sist for patient technical assistance.

13.2 Solvent Effects on Free Radical Polymerization

Michelle L. Coote and Thomas P. Davis, Centre for Advanced Macromolecular Design,

School of Chemical Engineering & Industrial Chemistry, The University of New South

Wales, Sydney, Australia

We acknowledge the publishers Marcel Dekker for allowing us to reproduce sections

of an earlier review, “A Mechanistic Perspective on Solvent Effects in Free Radical Polymerization”.

128 MLC acknowledges the receipt of an Australian Postgraduate Award.

14.19.2 Recent advances in coalescing solvents for waterborne coatings

David Randall, Chemoxy International pcl, Cleveland, United Kingdom

I would like to acknowledge with much gratitude the help given by Mr R J Foster of

Harco for his help in assembling the MFFT data for the presentation. I must also thank my

colleagues at Chemoxy, Ms Carol White, who assembled much of the data used in this paper,

and Miss Tracy McGough, who helped me produce the OHPs. Finally, I must acknowledge

the assistance given by MrTJPThomas, who has acted as a consultant to Chemoxy

International in this whole area.

I am indebted to Bob Foster at Harco, who kindly carried out some comparative formulations

using Coasol, Di-isopropyl AGS and Di-isopropyl Adipate in comparison with a

Monoester of Pentane Diol.

14.21.1 Use of solvents in the manufacture of drug substances (DS) and drug products (DP)

16.2 Residual solvents in pharmaceutical substances

Michel Bauer, International Analytical Department, Sanofi-Synthélabo, Toulouse, France;

Christine Barthélémy, Laboratoire de Pharmacie Galénique et Biopharmacie, Faculté des

Sciences Pharmaceutiques et Biologiques, Université de Lille 2, Lille, France

The authors thank Nick Anderson, Steve Byard, Juliette de Miras and Susan Richardson

for their participation in the elaboration of this document.


Acknowledgments 1655

15.2.2 A simple test to determine toxicity using bacteria

James L. Botsford, Department of Biology, New Mexico State University, Las Cruces, NM,

USA

This work has been supported by the principal investigator’s participation in several

programs to assist ethnic minorities in the sciences. Many students have helped with this

work.

20.3 Pregnancy outcome following maternal organic solvent exposure

Kristen I. McMartin and Gideon Koren, The Motherisk Program, Division of Clinical Pharmacology

and Toxicology, Hospital for Sick Children, Toronto, Canada

Supported by grants from Imperial Oil Limited, Physician Services Incorporated, The

Medical Research Council of Canada, and the CIBC Global Market Children’s Miracle

Foundation Chair in Child Health Research, The University of Toronto.

20.4 Industrial solvents and kidney disease

20.6 Chromosomal aberrations and sister chromatoid exchanges

20.7 Hepatotoxicity

Nachman Brautbar, University of Southern California, School of Medicine, Department of

Medicine, Los Angeles, CA, USA

The author wishes to thank Ms. S. Loomis for her tireless work in transcribing this

manuscript.

21.1 Supercritical solvents

Aydin K. Sunol and Sermin G. Sunol, Department of Chemical Engineering, University of

South Florida, Tampa, FL, USA

Assistance of both Dr. John P. Kosky of MEI Corporation and Irmak E. Serifoglu with

editing and typesetting are appreciated.


Table of Contents

Preface ......................................xxvii

GEORGE WYPYCH

1 INTRODUCTION ...............................1

CHRISTIAN REICHARDT

2 FUNDAMENTAL PRINCIPLES GOVERNING SOLVENTS USE ....7

2.1 Solvent effects on chemical systems .......................7

ESTANISLAO SILLA, ARTURO ARNAU, IÑAKI TUÑÓN

2.1.1 Historical outline .................................7

2.1.2 Classification of solute-solvent interactions ...................10

2.1.2.1 Electrostatic ...................................11

2.1.2.2 Polarization ...................................12

2.1.2.3 Dispersion ....................................13

2.1.2.4 Repulsion .....................................14

2.1.2.5 Specific interactions ...............................15

2.1.2.6 Hydrophobic interactions. ............................16

2.1.3 Modelling of solvent effects ...........................17

2.1.3.1 Computer simulations ..............................18

2.1.3.2 Continuum models ................................20

2.1.3.3 Cavity surfaces ..................................21

2.1.3.4 Supermolecule models ..............................22

2.1.3.5 Application example: glycine in solution ....................23

2.1.4 Thermodynamic and kinetic characteristics of chemical reactions in solution . 27

2.1.4.1 Solvent effects on chemical equilibria ......................27

2.1.4.2 Solvent effects on the rate of chemical reactions. ................28

2.1.4.3 Example of application: addition of azide anion to tetrafuranosides. ......30

2.1.5 Solvent catalytic effects .............................32

2.2 Molecular design of solvents ...........................36

KOICHIRO NAKANISHI

2.2.1 Molecular design and molecular ensemble design ................36

2.2.2 From prediction to design ............................37

2.2.3 Improvement in prediction method. .......................38

2.2.4 Role of molecular simulation. ..........................39

2.2.5 Model system and paradigm for design .....................40

Appendix. Predictive equation for the diffusion coefficient in dilute solution . 41

2.3 Basic physical and chemical properties of solvents ...............42

GEORGE WYPYCH

2.3.1 Molecular weight and molar volume .......................43

2.3.2 Boiling and freezing points. ...........................44

2.3.3 Specific gravity ..................................46

2.3.4 Refractive index .................................47

2.3.5 Vapor density and pressure. ...........................48

2.3.6 Solvent volatility .................................49

2.3.7 Flash point ....................................50

2.3.8 Flammability limits. ...............................51

2.3.9 Sources of ignition and autoignition temperature ................52

2.3.10 Heat of combustion (calorific value) .......................54

2.3.11 Heat of fusion. ..................................54

2.3.12 Electric conductivity ...............................54

2.3.13 Dielectric constant (relative permittivity) ....................54

2.3.14 Occupational exposure indicators ........................56

2.3.15 Odor threshold ..................................56


ii HandbookofSolvents

2.3.16 Toxicity indicators ................................57

2.3.17 Ozone-depletion and creation potential .....................58

2.3.18 Oxygen demand .................................58

2.3.19 Solubility .....................................58

2.3.20 Other typical solvent properties and indicators .................60

3 PRODUCTION METHODS, PROPERTIES,

AND MAIN APPLICATIONS .........................65

3.1 Definitions and solvent classification ......................65

GEORGE WYPYCH

3.2 Overview of methods of solvent manufacture ..................69

GEORGE WYPYCH

3.3 Solvent properties ................................74

GEORGE WYPYCH

3.3.1 Hydrocarbons. ..................................75

3.3.1.1 Aliphatic hydrocarbons. .............................75

3.3.1.2 Aromatic hydrocarbons. .............................76

3.3.2 Halogenated hydrocarbons ............................78

3.3.3 Nitrogen-containing compounds (nitrates, nitriles) ...............79

3.3.4 Organic sulfur compounds ............................80

3.3.5 Monohydric alcohols ...............................81

3.3.6 Polyhydric alcohols. ...............................83

3.3.7 Phenols ......................................84

3.3.8 Aldehydes ....................................85

3.3.9 Ethers .......................................86

3.3.10 Glycol ethers ...................................87

3.3.11 Ketones ......................................88

3.3.11 Acids .......................................90

3.3.12 Amines ......................................91

3.3.13 Esters .......................................92

3.3.14 Comparative analysis of all solvents .......................94

3.4 Terpenes .....................................96

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

3.4.1 Definitions and nomenclature ..........................96

3.4.2 Occurrence ....................................96

3.4.3 General ......................................96

3.4.4 Toxicology ....................................97

3.4.5 Threshold limit values ..............................97

4 GENERAL PRINCIPLES GOVERNING DISSOLUTION

OF MATERIALS IN SOLVENTS. ......................101

4.1 Simple solvent characteristics ..........................101

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

4.1.1 Solvent power ..................................101

4.1.2 One-dimensional solubility parameter approach .................103

4.1.3 Multi-dimensional approaches ..........................110

4.1.4 Hansen’s solubility ................................112

4.1.5 Three-dimensional dualistic model. .......................116

4.1.6 Solubility criterion ................................119

4.1.7 Solvent system design ..............................120

4.2 Effect of system variables on solubility .....................124

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

4.2.1 General considerations ..............................124

4.2.2 Chemical structure ................................126

4.2.3 Flexibility of a polymer chain ..........................127

4.2.4 Crosslinking ...................................128

4.2.5 Temperature and pressure ............................128

4.2.6 Methods of calculation of solubility based on thermodynamic principles ....130


Table of contents iii

4.3 Polar solvation dynamics: Theory and simulations ...............132

ABRAHAM NITZAN

4.3.1 Introduction. ...................................132

4.3.2 Continuum dielectric theory of solvation dynamics ...............133

4.3.3 Linear response theory of solvation dynamics ..................136

4.3.4 Numerical simulations of solvation in simple polar solvents:

The simulation model ..............................138

4.3.5 Numerical simulations of solvation in simple polar solvents:

Results and discussion ..............................140

4.3.6 Solvation in complex solvents ..........................144

4.3.7 Conclusions. ...................................145

4.4 Methods for the measurement of solvent activity of polymer solutions .....146

CHRISTIAN WOHLFARTH

4.4.1 Introduction. ...................................146

4.4.2 Necessary thermodynamic equations. ......................149

4.4.3 Experimental methods, equipment and data reduction. .............154

4.4.3.1 Vapor-liquid equilibrium (VLE) measurements .................154

4.4.3.1.1 Experimental equipment and procedures for VLE-measurements ........155

4.4.3.1.2 Primary data reduction ..............................170

4.4.3.1.3 Comparison of experimental VLE-methods ...................175

4.4.3.2 Other measurement methods ...........................178

4.4.3.2.1 Membrane osmometry ..............................178

4.4.3.2.2 Light scattering ..................................181

4.4.3.2.3 X-ray scattering. .................................184

4.4.3.2.4 Neutron scattering ................................185

4.4.3.2.5 Ultracentrifuge ..................................186

4.4.3.2.6 Cryoscopy (freezing point depression of the solvent) ..............188

4.4.3.2.7 Liquid-liquid equilibrium (LLE) .........................189

4.4.3.2.8 Swelling equilibrium ...............................193

4.4.4 Thermodynamic models for the calculation of solvent activities of

polymer solutions. ................................195

4.4.4.1 Models for residual chemical potential and activity coefficient in

the liquid phase ..................................196

4.4.4.2 Fugacity coefficients from equations of state ..................207

4.4.4.3 Comparison and conclusions ...........................214

Appendix 4.4A ..................................223

5 SOLUBILITY OF SELECTED SYSTEMS AND INFLUENCE

OF SOLUTES ..................................243

5.1 Experimental methods of evaluation and calculation of solubility

parameters of polymers and solvents. Solubility parameters data ........243

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

5.1.1 Experimental evaluation of solubility parameters of liquids ...........243

5.1.1.1 Direct methods of evaluation of the evaporation enthalpy ...........243

5.1.1.2 Indirect methods of evaluation of evaporation enthalpy .............244

5.1.1.3 Static and quasi-static methods of evaluation of pair pressure. .........245

5.1.1.4 Kinetic methods .................................245

5.1.2 Methods of experimental evaluation and calculation of solubility

parameters of polymers. .............................246

5.2 Prediction of solubility parameter ........................253

NOBUYUKI TANAKA

5.2.1 Solubility parameter of polymers ........................253

5.2.2 Glass transition in polymers ...........................254

5.2.2.1 Glass transition enthalpy .............................254

5.2.2.2 Cp jump at the glass transition ..........................256

5.2.3 Prediction from thermal transition enthalpies ..................258

5.3 Methods of calculation of solubility parameters of solvents and polymers ...261

VALERY YU. SENICHEV, VASILIY V. TERESHATOV


iv HandbookofSolvents

5.4 Mixed solvents, a way to change the polymer solubility. ............267

LIGIA GARGALLO AND DEODATO RADIC

5.4.1 Introduction. ...................................267

5.4.2 Solubility-cosolvency phenomenon .......................268

5.4.3 New cosolvents effects. Solubility behavior ...................273

5.4.4 Thermodynamical description of ternary systems. Association equilibria

theory of preferential adsorption .........................274

5.4.5 Polymer structure of the polymer dependence of preferential adsorption.

Polymer molecular weight and tacticity dependence of preferential adsorption. 277

5.5 The phenomenological theory of solvent effects in mixed solvent systems ...281

KENNETH A. CONNORS

5.5.1 Introduction. ...................................281

5.5.2 Theory ......................................281

5.5.2.1 Principle .....................................281

5.5.2.2 The intersolute effect: solute-solute interactions .................282

5.5.2.3 The solvation effect: solute-solvent interaction .................283

5.5.2.4 The general medium effect: solvent-solvent interactions ............284

5.5.2.5 The total solvent effect ..............................285

5.5.3 Applications ...................................285

5.5.3.1 Solubility .....................................285

5.5.3.2 Surface tension ..................................288

5.5.3.3 Electronic absorption spectra. ..........................290

5.5.3.4 Complex formation ................................291

5.5.3.5 Chemical kinetics. ................................295

5.5.3.6 Liquid chromatography. .............................298

5.5.4 Interpretations ..................................298

5.5.4.1 Ambiguities and anomalies. ...........................298

5.5.4.2 A modified derivation ..............................299

5.5.4.3 Interpretation of parameter estimates. ......................300

5.5.4.4 Confounding effects ...............................301

Solute-solute interactions. ............................301

Coupling of general medium and solvation effects ...............301

The cavity surface area ..............................301

The role of interfacial tension ..........................302

6 SWELLING ...................................305

6.1 Modern views on kinetics of swelling of crosslinked elastomers in solvents . . 305

E. YA. DENISYUK, V. V. TERESHATOV

6.1.1 Introduction. ...................................305

6.1.2 Formulation of swelling for a plane elastomer layer ...............306

6.1.3 Diffusion kinetics of plane layer swelling ....................310

6.1.4 Experimental study of elastomer swelling kinetics ...............314

6.1.5 Conclusions. ...................................317

6.2 Equilibrium swelling in binary solvents .....................318

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

6.3 Swelling data on crosslinked polymers in solvents ...............327

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

6.4 Influence of structure on equilibrium swelling. .................331

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

7 SOLVENT TRANSPORT PHENOMENA ..................339

7.1 Introduction to diffusion, swelling, and drying .................339

GEORGE WYPYCH

7.1.1 Diffusion .....................................339

7.1.2 Swelling .....................................344

7.1.3 Drying ......................................348

7.2 Bubbles dynamics and boiling of polymeric solutions. .............356

SEMYON LEVITSKY, ZINOVIY SHULMAN

7.2.1 Rheology of polymeric solutions and bubble dynamics .............356


Table of contents v

7.2.1.1 Rheological characterization of solutions of polymers. .............356

7.2.1.2 Dynamic interaction of bubbles with polymeric liquid .............363

7.2.2 Thermal growth of bubbles in superheated solutions of polymers .......372

7.2.3 Boiling of macromolecular liquids ........................377

7.3 Drying of coated film. ..............................386

SEUNG SU KIM AND JAE CHUN HYUN

7.3.1 Introduction. ...................................386

7.3.2 Theory for the drying. ..............................388

7.3.2.1 Simultaneous heat and mass transfer .......................388

7.3.2.2 Liquid-vapor equilibrium. ............................389

7.3.2.3 Heat and mass transfer coefficient ........................390

7.3.2.4 Prediction of drying rate of coating .......................392

7.3.2.5 Drying regimes: constant drying rate period (CDRP) and falling

drying rate period (FDRP) ............................394

7.3.3 Measurement of the drying rate of coated film. .................396

7.3.3.1 Thermo-gravimetric analysis ...........................396

7.3.3.2 Rapid scanning FT-IR spectrometer analysis ..................399

7.3.3.3 High-airflow drying experiment using flame ionization detector (FID)

total hydrocarbon analyzer ............................401

7.3.3.4 Measurement of drying rate in the production scale dryer ............404

7.3.4 Miscellaneous ..................................407

7.3.4.1 Drying of coated film with phase separation ...................407

7.3.4.2 Drying defects ..................................409

7.3.4.2.1 Internal stress induced defects ..........................409

7.3.4.2.2 Surface tension driven defects ..........................412

7.3.4.2.3 Defects caused by air motion and others .....................414

7.3.4.3 Control of lower explosive level (LEL) in a multiple zone dryer ........414

8 INTERACTIONS IN SOLVENTS AND SOLUTIONS ...........419

JACOPO TOMASI, BENEDETTA MENNUCCI, CHIARA CAPPELLI

8.1 Solvents and solutions as assemblies of interacting molecules .........419

8.2 Basic simplifications of the quantum model ...................420

8.3 Cluster expansion. ................................424

8.4 Two-body interaction energy: the dimer .....................424

8.4.1 Decomposition of the interaction energy of a dimer: variational approach ...426

The electrostatic term. ..............................426

The induction term ................................428

The exchange term ................................428

The charge transfer term .............................429

The dispersion term ...............................430

The decomposition of the interaction energy through a variational

approach: a summary ...............................432

8.4.2 Basis set superposition error and counterpoise corrections ...........433

8.4.3 Perturbation theory approach. ..........................436

8.4.4 Modeling of the separate components of ΔE...................441

The electrostatic term. ..............................441

The induction term ................................445

The dispersion term ...............................446

The exchange (or repulsion) term ........................447

The other terms ..................................448

A conclusive view ................................448

8.4.5 The relaxation of the rigid monomer constraint .................449

8.5 Three- and many-body interactions .......................451

Screening many-body effects. ..........................453

Effective interaction potentials ..........................454

8.6 The variety of interaction potentials .......................456

8.7 Theoretical and computing modeling of pure liquids and solutions .......461

8.7.1 Physical models .................................461


vi HandbookofSolvents

8.7.1.1 Integral equation methods ............................465

8.7.1.2 Perturbation theories ...............................467

8.7.2 Computer simulations ..............................468

8.7.2.1 Car-Parrinello direct QM simulation .......................470

8.7.2.2 Semi-classical simulations ............................472

Molecular dynamics ...............................472

Monte Carlo ...................................473

QM/MM .....................................478

8.7.3 Continuum models ................................479

8.7.3.1 QM-BE methods: the effective Hamiltonian ...................482

8.8 Practical applications of modeling ........................487

Dielectric constant ................................487

Thermodynamical properties ...........................490

Compressibilities .................................490

Relaxation times and diffusion coefficients ...................491

Shear viscosity ..................................492

8.9 Liquid surfaces ..................................492

8.9.1 The basic types of liquid surfaces ........................493

8.9.2 Systems with a large surface/bulk ratio .....................495

8.9.3 Studies on interfaces using interaction potentials ................497

9 MIXED SOLVENTS ..............................505

Y. Y. FIALKOV, V. L. CHUMAK

9.1 Introduction. ...................................505

9.2 Chemical interaction between components in mixed solvents ..........505

9.2.1 Processes of homomolecular association. ....................505

9.2.2 Conformic and tautomeric equilibrium. Reactions of isomerization. ......506

9.2.3 Heteromolecular association ...........................507

9.2.4 Heteromolecular associate ionization ......................507

9.2.5 Electrolytic dissociation (ionic association) ...................508

9.2.6 Reactions of composition. ............................508

9.2.7 Exchange interaction ...............................509

9.2.8 Amphoterism of mixed solvent components ...................509

9.2.8.1 Amphoterism of hydrogen acids .........................509

9.2.8.2 Amphoterism of L-acids .............................509

9.2.8.3 Amphoterism in systems H-acid-L-acid .....................510

9.2.8.4 Amphoterism in binary solutions amine-amine .................510

9.3 Physical properties of mixed solvents ......................511

9.3.1 The methods of expression of mixed solvent compositions ...........511

9.3.1.1 Permittivity ....................................513

9.3.1.2 Viscosity .....................................515

9.3.1.3 Density, molar volume ..............................516

9.3.1.4 Electrical conductivity ..............................516

9.3.2 Physical characteristics of the mixed solvents with chemical interaction

between components ...............................517

9.3.2.1 Permittivity ....................................518

9.3.2.2 Viscosity .....................................519

9.3.2.3 Density, molar volume ..............................521

9.3.2.4 Conductivity ...................................522

9.3.3 Chemical properties of mixed solvents. .....................524

9.3.3.1 Autoprotolysis constants .............................524

9.3.3.2 Solvating ability .................................526

9.3.3.3 Donor-acceptor properties ............................527

9.4 Mixed solvent influence on the chemical equilibrium ..............527

9.4.1 General considerations ..............................527

9.4.2 Mixed solvent effect on the position of equilibrium of homomolecular

association process ................................529

9.4.3 Mixed solvent influence on the conformer equilibrium .............530


Table of contents vii

9.4.4 Solvent effect on the process of heteromolecular association ..........532

9.4.4.1 Selective solvation. Resolvation .........................538

9.4.5 Mixed solvent effect on the ion association process ...............546

9.4.6 Solvent effect on exchange interaction processes ................552

Systems with non-associated reagents ......................552

Systems with one associated participant of equilibrium .............553

Systems with two associated participants of equilibrium ............553

9.4.7 Mixed solvent effect on processes of complex formation ............556

9.5 The mixed solvent effect on the chemical equilibrium thermodynamics ....557

10 ACID-BASE INTERACTIONS ........................565

10.1 General concept of acid-base interactions ....................565

GEORGE WYPYCH

10.2 Effect of polymer/solvent acid-base interactions: relevance to

the aggregation of PMMA ............................570

S. BISTAC, M. BROGLY

10.2.1 Recent concepts in acid-base interactions ....................570

10.2.1.1 The nature of acid-base molecular interactions .................571

10.2.1.1.1 The original Lewis definitions ..........................571

10.2.1.1.2 Molecular Orbital (MO) approach to acid-base reactions ............571

10.2.1.1.3 The case of hydrogen bonding ..........................573

10.2.1.2 Quantitative determination of acid-base interaction strength ..........574

10.2.1.2.1 Perturbation theory ................................574

10.2.1.2.2 Hard-Soft Acid-Base (HSAB) principle .....................574

10.2.1.2.3 Density functional theory. ............................575

10.2.1.2.4 Effect of ionocity and covalency: Drago’s concept ...............576

10.2.1.2.5 Effect of amphotericity of acid-base interaction: Gutmann’s numbers .....577

10.2.1.2.6 Spectroscopic measurements: Fowkes’ approach ................578

10.2.2 Effect of polymer/solvent interactions on aggregation of stereoregular PMMA 578

10.2.2.1 Aggregation of stereoregular PMMA ......................578

10.2.2.2 Relation between the complexing power of solvents and their

acid-base properties ...............................579

10.2.3 Influence of the nature of the solvent on the α and β-relaxations of

conventional PMMA ...............................581

10.2.3.1 Introduction. ...................................581

10.2.3.2 Dielectric spectroscopy results ..........................581

10.2.4 Concluding remarks ...............................582

10.3 Solvent effects based on pure solvent scales ...................583

JAVIER CATALÁN

Introduction. ...................................583

10.3.1 The solvent effect and its dissection into general and specific contributions . . 584

10.3.2 Characterization of a molecular environment with the aid of the

probe/homomorph model. ............................585

10.3.3 Single-parameter solvent scales: the Y, G, ET(30), P y ,Z,χR,Φ, and S� scales. . 587

10.3.3.1 The solvent ionizing power scale or Y scale ...................587

10.3.3.2 The G values of Allerhand and Schleyer .....................588

10.3.3.3 The ET(30) scale of Dimroth and Reichardt ...................588

10.3.3.4 The Py scale of Dong and Winnick. .......................589

10.3.3.5 The Z scale of Kosower .............................589

10.3.3.6 The χR scale of Brooker .............................590

10.3.3.7 The Φ scale of Dubois and Bienvenüe ......................590

10.3.3.8 The S� scale of Drago ...............................591

10.3.4 Solvent polarity: the SPP scale ..........................591

10.3.5 Solvent basicity: the SB scale ..........................600

10.3.6 Solvent acidity: the SA scale ...........................601

10.3.7 Applications of the pure SPP, SA and SB scales. ................605

10.3.7.1 Other reported solvents scales ..........................605

10.3.7.2 Treatment of the solvent effect in: ........................608


viii HandbookofSolvents

10.3.7.2.1 Spectroscopy ...................................608

10.3.7.2.2 Kinetics ......................................611

10.3.7.2.3 Electrochemistry .................................612

10.3.7.2.4 Thermodynamics .................................612

10.3.7.3 Mixtures of solvents. Understanding the preferential solvation model .....612

10.4 Acid-base equilibria in ionic solvents (ionic melts) ...............616

VICTOR CHERGINETS

10.4.1 Acid-base definitions used for the description of donor-acceptor

interactions in ionic media ............................617

10.4.1.1 The Lewis definition ...............................617

10.4.1.2 The Lux-Flood definition. ............................618

10.4.2 The features of ionic melts as media for acid-base interactions .........618

10.4.2.1 Oxygen-less media ................................619

10.4.2.2 Oxygen-containing melts. ............................619

10.4.2.3 The effect of the ionic solvent composition on acid-base equilibria .......620

10.4.3 Methods for estimations of acidities of solutions based on ionic melts .....623

10.4.4 On studies of the homogeneous acid-base reactions in ionic melts .......625

10.4.4.1 Nitrate melts ...................................625

10.4.4.2 Sulphate melts ..................................627

10.4.4.3 Silicate melts ...................................628

10.4.4.4 The equimolar mixture KCl-NaCl ........................629

10.4.4.5 Other alkaline halide melts ............................631

10.4.5 Reactions of melts with gaseous acids and bases ................632

10.4.5.1 High-temperature hydrolysis of molten halides .................632

10.4.5.2 The processes of removal of oxide admixtures from melts ...........633

11 ELECTRONIC AND ELECTRICAL EFFECTS OF SOLVENTS .....639

11.1 Theoretical treatment of solvent effects on electronic and vibrational

spectra of compounds in condensed media. ...................639

MATI KARELSON

11.1.1 Introduction. ...................................639

11.1.2 Theoretical treatment of solvent cavity effects on electronic-vibrational

spectra of molecules ...............................647

11.1.3 Theoretical treatment of solvent electrostatic polarization on

electronic-vibrational spectra of molecules ...................649

11.1.4 Theoretical treatment of solvent dispersion effects on

electronic-vibrational spectra of molecules ...................671

11.1.5 Supermolecule approach to the intermolecular interactions in condensed media 674

11.2 Dielectric solvent effects on the intensity of light absorption and

the radiative rate constant ............................680

TAI-ICHI SHIBUYA

11.2.1 The Chako formula or the Lorentz-Lorenz correction ..............680

11.2.2 The generalized local-field factor for the ellipsoidal cavity ...........680

11.2.3 Dielectric solvent effect on the radiative rate constant. .............682

12 OTHER PROPERTIES OF SOLVENTS, SOLUTIONS,

AND PRODUCTS OBTAINED FROM SOLUTIONS. ...........683

12.1 Rheological properties, aggregation, permeability, molecular structure,

crystallinity, and other properties affected by solvents .............683

GEORGE WYPYCH

12.1.1 Rheological properties ..............................683

12.1.2 Aggregation ...................................689

12.1.3 Permeability ...................................693

12.1.4 Molecular structure and crystallinity .......................697

12.1.5 Other properties affected by solvents ......................700

12.2 Chain conformations of polysaccharides in different solvents. .........706

RANIERI URBANI AND ATTILIO CESÀRO

12.2.1 Introduction. ...................................706

12.2.2 Structure and conformation of polysaccharides in solution ...........707


Table of contents ix

12.2.2.1 Chemical structure ................................707

12.2.2.2 Solution chain conformation ...........................707

12.2.3 Experimental evidence of solvent effect on oligosaccharide conformational

equilibria .....................................711

12.2.4 Theoretical evaluation of solvent effect on conformational equilibria of sugars 715

12.2.4.1 Classical molecular mechanics methods .....................715

12.2.4.2 Molecular dynamic methods ...........................720

12.2.5 Solvent effect on chain dimensions and conformations of polysaccharides ...722

12.2.6 Solvent effect on charged polysaccharides and the polyelectrolyte model ...726

12.2.6.1 Experimental behavior of polysaccharides polyelectrolytes ...........726

12.2.6.2 The Haug and Smidsrød parameter: description of the salt effect on the chain

dimension. ....................................727

12.2.6.3 The statistical thermodynamic counterion-condensation theory of Manning . . 729

12.2.6.4 Conformational calculations of charged polysaccharides ............731

12.2.7 Conclusions. ...................................733

13 EFFECT OF SOLVENT ON CHEMICAL REACTIONS AND

REACTIVITY. .................................737

13.1 Solvent effects on chemical reactivity ......................737

ROLAND SCHMID

13.1.1 Introduction. ...................................737

13.1.2 The dielectric approach. .............................737

13.1.3 The chemical approach ..............................738

13.1.4 Dielectric vs. chemical approach .........................742

13.1.5 Conceptual problems with empirical solvent parameters ............744

13.1.6 The physical approach ..............................746

13.1.7 Some highlights of recent investigations .....................753

The like dissolves like rule ............................753

Water’s anomalies ................................755

The hydrophobic effect. .............................758

The structure of liquids ..............................762

Solvent reorganization energy in ET .......................765

The solution ionic radius .............................768

13.1.8 The future of the phenomenological approach ..................772

13.2 Solvent effects on free radical polymerization ..................777

MICHELLE L. COOTE AND THOMAS P. DAVIS

13.2.1 Introduction. ...................................777

13.2.2 Homopolymerization ...............................777

13.2.2.1 Initiation .....................................777

13.2.2.2 Propagation ....................................778

13.2.2.3 Transfer. .....................................779

13.2.2.4 Termination. ...................................779

13.2.3 Copolymerization. ................................779

13.2.3.1 Polarity effect. ..................................780

13.2.3.1.1 Basic mechanism .................................780

13.2.3.1.2 Copolymerization model .............................781

13.2.3.1.3 Evidence for polarity effects in propagation reactions ..............781

13.2.3.2 Radical-solvent complexes ............................782

13.2.3.2.1 Basic mechanism .................................782

13.2.3.2.2 Copolymerization model .............................782

13.2.3.2.3 Experimental evidence ..............................783

13.2.3.3 Monomer-solvent complexes. ..........................785

13.2.3.3.1 Introduction. ...................................785

13.2.3.3.2 Monomer-monomer complex participation model ................785

13.2.3.3.3 Monomer-monomer complex dissociation model ................790

13.2.3.3.4 Specific solvent effects ..............................791

13.2.3.4 Bootstrap model .................................791

13.2.3.4.1 Basic mechanism .................................791


x HandbookofSolvents

13.2.3.4.2 Copolymerization model .............................791

13.2.3.4.3 Experimental evidence ..............................793

13.2.4 Concluding remarks ...............................795

13.3 Effects of organic solvents on phase-transfer catalysis .............798

MAW-LING WANG

13.3.1 Two-phase phase-transfer catalytic reactions ..................801

13.3.1.1 Theoretical analysis of the polarity of the organic solvents and the reactions . . 801

13.3.1.2 Effect of organic solvent on the reaction in various reaction systems ......805

13.3.1.3 Effects of the organic solvents on the reactions in other catalysts ........811

13.3.1.4 Effect of the volume of organic solvent and water on the reactions in

various reaction systems .............................822

13.3.1.5 Effects of organic solvents on other phase-transfer catalytic reactions .....825

13.3.1.6 Other effects on the phase-transfer catalytic reactions ..............828

13.3.2 Three-phase reactions (triphase catalysis) ....................830

13.3.2.1 The interaction between solid polymer (hydrophilicity) and the organic

solvents ......................................830

13.3.2.2 Effect of solvents on the reaction in triphase catalysis. .............833

13.3.2.3 Effect of volume of organic solvent and water on the reactions in

triphase catalysis .................................836

13.4 Effect of polymerization solvent on the chemical structure and curing of

aromatic poly(amideimide). ...........................841

NORIO TSUBOKAWA

13.4.1 Introduction. ...................................841

13.4.2 Effect of solvent on the chemical structure of PAI. ...............842

13.4.2.1 Imide and amide bond content of PAI ......................842

13.4.2.2 Intrinsic viscosity and carboxyl group content ..................844

13.4.3 Effect of solvent on the curing of PAI by heat treatment ............844

13.4.3.1 Chemical structure of PAI after heat treatment .................844

13.4.3.2 Curing PAI by post-heating ...........................845

13.4.4 Conclusions. ...................................846

14 SOLVENT USE IN VARIOUS INDUSTRIES ................847

14.1 Adhesives and sealants ..............................847

GEORGE WYPYCH

14.2 Aerospace. ....................................852

GEORGE WYPYCH

14.3 Asphalt compounding ..............................855

GEORGE WYPYCH

14.4 Biotechnology ..................................856

14.4.1 Organic solvents in microbial production processes ...............856

MICHIAKI MATSUMOTO, SONJA ISKEN, JAN A. M. DE BONT

14.4.1.1 Introduction. ...................................856

14.4.1.2 Toxicity of organic solvents ...........................859

14.4.1.3 Solvent-tolerant bacteria .............................862

14.4.1.4 Biotransformation using solvent-tolerant microorganisms. ...........863

14.4.2 Solvent-resistant microorganisms ........................865

TILMAN HAHN, KONRAD BOTZENHART

14.4.2.1 Introduction. ...................................865

14.4.2.2 Toxicity of solvents for microorganisms .....................865

14.4.2.2.1 Spectrum of microorganisms and solvents ....................865

14.4.2.2.2 Mechanisms of solvent toxicity for microorganisms. ..............866

14.4.2.3 Adaption of microorganisms to solvents - solvent-resistant microorganisms . . 867

14.4.2.3.1 Spectrum of solvent-resistant microorganisms. .................867

14.4.2.3.2 Adaption mechanisms of microorganisms to solvents ..............868

14.4.2.4 Solvents and microorganisms in the environment and industry - examples ...869

14.4.2.4.1 Examples .....................................869

14.4.3 Choice of solvent for enzymatic reaction in organic solvent. ..........872

TSUNEO YAMANE


Table of contents xi

14.4.3.1 Introduction. ...................................872

14.4.3.2 Classification of organic solvents ........................872

14.4.3.3 Influence of solvent parameters on nature of enzymatic reactions in

organic media. ..................................873

14.4.3.4 Properties of enzymes affected by organic solvents ...............875

14.4.3.5 Concluding remarks ...............................879

14.5 Coil coating. ...................................880

GEORGE WYPYCH

14.6 Cosmetics and personal care products ......................881

GEORGE WYPYCH

14.7 Dry cleaning - treatment of textiles in solvents .................883

KASPAR D. HASENCLEVER

14.7.1 Dry cleaning ...................................883

14.7.1.1 History of dry cleaning ..............................883

14.7.1.2 Basis of dry cleaning ...............................884

14.7.1.3 Behavior of textiles in solvents and water ....................885

14.7.1.4 Removal of soiling in dry cleaning. .......................886

14.7.1.5 Activity of detergents in dry cleaning ......................887

14.7.1.6 Dry cleaning processes ..............................888

14.7.1.7 Recycling of solvents in dry cleaning ......................890

14.7.2 Spotting. .....................................891

14.7.2.1 Spotting in dry cleaning .............................891

14.7.2.2 Spotting agents ..................................891

14.7.2.3 Spotting procedure ................................892

14.7.3 Textile finishing .................................893

14.7.3.1 Waterproofing ..................................893

14.7.3.2 Milling ......................................893

14.7.3.3 Antistatic finishing ................................893

14.8 Electronic industry - CFC-free alternatives for cleaning in electronic industry. 894

MARTIN HANEK, NORBERT LÖW, ANDREAS MÜHLBAUER

14.8.1 Cleaning requirements in the electronic industry ................894

14.8.2 Available alternatives. ..............................896

14.8.2.1 Water based systems; advantages and disadvantages ..............897

14.8.2.1.1 Cleaning with DI - water .............................897

14.8.2.1.2 Cleaning with alkaline water-based media ....................898

14.8.2.1.3 Aqueous-based cleaning agents containing water soluble organic components . 898

14.8.2.1.4 Water-based cleaning agents based on MPC® Technology

(MPC = Micro Phase Cleaning) .........................899

14.8.2.1.5 Advantages and disadvantages of aqueous cleaning media ...........899

14.8.2.2 Semi-aqueous cleaners based on halogen-free solvents, advantages and

disadvantages ...................................900

14.8.2.2.1 Water insoluble cleaning fluids .........................901

14.8.2.2.2 Water-soluble, water-based cleaning agents ...................901

14.8.2.2.3 Comparison of the advantages (+) and disadvantages (-) of semi-aqueous

cleaning fluids ..................................901

14.8.2.3 Other solvent based cleaning systems ......................902

14.8.3 Cleaning of tools and auxiliaries .........................904

14.8.3.1 Cleaning substrates and contamination. .....................904

14.8.3.2 Compatibility of stencil and cleaning agent ...................905

14.8.3.3 Different cleaning media .............................906

14.8.3.4 Comparison of manual cleaning vs. automated cleaning. ............908

14.8.3.5 Cleaning equipment for stencil cleaning applications ..............909

14.8.3.6 Stencil cleaning in screen printing machines. ..................911

14.8.3.7 Summary .....................................911

14.8.4 Cleaning agents and process technology available for cleaning PCB ......911

14.8.4.1 Flux remove and aqueous process ........................911

14.8.4.1.1 The limits of a no-clean process .........................911


xii HandbookofSolvents

14.8.4.1.2 Different cleaning media and cleaning processes ................912

14.8.4.1.3 Semi-aqueous cleaning ..............................913

14.8.4.1.4 Aqueous cleaning in spray in air cleaning equipment ..............913

14.8.4.2 Flux removal from printed circuit boards - water-free cleaning processes ...914

14.8.4.2.1 Water-free cleaning processes using HFE (hydrofluoroethers) in combination

with a cosolvent .................................915

14.8.4.2.2 Water-free cleaning processes in closed, one-chamber vapor defluxing systems 916

14.8.5 Criteria for assessment and evaluation of cleaning results ............917

14.8.6 Cost comparison of different cleaning processes. ................919

14.9 Fabricated metal products ............................920

GEORGE WYPYCH

14.10 Food industry - solvents for extracting vegetable oils ..............923

PHILLIP J. WAKELYN, PETER J. WAN

14.10.1 Introduction. ...................................923

14.10.2 Regulatory concerns ...............................924

14.10.2.1 Workplace regulations ..............................925

14.10.2.1.1 Air Contaminants Standard (29 CFR 1910.1000) ................925

14.10.2.1.2 Hazard Communication Standard (HCS) (29 CFR 1910.1200) .........926

14.10.2.1.3 Process Safety Management (PSM) Standard (29 CFR 1910.119) .......927

14.10.2.2 Environmental regulations ............................927

14.10.2.2.1 Clean Air Act (CAA; 42 U.S. Code 7401 et seq.) ................929

14.10.2.2.2 Clean Water Act (CWA; 33 U.S. Code 1251 et seq.) ..............932

14.10.2.2.3 Resource Conservation and Recovery Act (RCRA; 42 U.S.Code 6901 et seq.). 932

14.10.2.2.4 Emergency Planning and Community Right-to-Know Act (EPCRA;

42 U.S. Code 11001 et seq.) ...........................933

14.10.2.2.5 Toxic Substances Control Act (TSCA; 15 U.S. Code 2601 et seq.) .......933

14.10.2.3 Food safety ....................................934

14.10.3 The solvent extraction process ..........................935

14.10.3.1 Preparation for extraction ............................936

14.10.3.2 Oil extraction ...................................938

14.10.3.3 Processing crude oil ...............................938

14.10.4 Review of solvents studied for extraction efficiency. ..............940

14.10.4.1 Hydrocarbon solvents ..............................941

14.10.4.1.1 Nomenclature, structure, composition and properties of hydrocarbons .....942

14.10.4.1.2 Performance of selected hydrocarbon solvents. .................942

14.10.5 Future trends ...................................946

14.11 Ground transportation ..............................950

GEORGE WYPYCH

14.12 Inorganic chemical industry ...........................950

GEORGE WYPYCH

14.13 Iron and steel industry ..............................951

GEORGE WYPYCH

14.14 Lumber and wood products - Wood preservation treatment:

significance of solvents. .............................953

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

14.14.1 General aspects ..................................953

14.14.2 Role of solvents .................................954

14.14.2.1 Occurrence ....................................954

14.14.2.2 Technical and environmental aspects ......................955

14.15 Medical applications ...............................955

GEORGE WYPYCH

14.16 Metal casting ...................................957

GEORGE WYPYCH

14.17 Motor vehicle assembly .............................958

GEORGE WYPYCH

14.18 Organic chemical industry ............................962

GEORGE WYPYCH


Table of contents xiii

14.19 Paints and coatings ................................963

14.19.1 Architectural surface coatings and solvents ...................963

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

14.19.1.1 General aspects ..................................963

14.19.1.2 Technical aspects and properties of coating materials ..............963

14.19.2 Recent advances in coalescing solvents for waterborne coatings ........969

DAVID RANDALL

14.19.2.1 Introduction. ...................................969

14.19.2.2 Water based coatings ...............................970

14.19.2.3 Emulsion polymers ................................970

14.19.2.4 Role of a coalescing solvent ...........................971

14.19.2.5 Properties of coalescing agents. .........................972

14.19.2.5.1 Hydrolytic stability ................................972

14.19.2.5.2 Water solubility. .................................972

14.19.2.5.3 Freezing point ..................................972

14.19.2.5.4 Evaporation rate .................................972

14.19.2.5.5 Odor .......................................972

14.19.2.5.6 Color .......................................973

14.19.2.5.7 Coalescing efficiency. ..............................973

14.19.2.5.8 Incorporation ...................................973

14.19.2.5.9 Improvement of physical properties .......................973

14.19.2.5.10 Biodegradability. ................................973

14.19.2.5.11 Safety ......................................973

14.19.2.6 Comparison of coalescing solvents. .......................973

14.19.2.7 Recent advances in diester coalescing solvents .................974

14.19.2.8 Appendix - Classification of coalescing solvents ................975

14.20 Petroleum refining industry ...........................975

GEORGE WYPYCH

14.21 Pharmaceutical industry .............................977

14.21.1 Use of solvents in the manufacture of drug substances (DS) and drug

products (DP). ..................................977

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

14.21.1.1 Introduction. ...................................977

14.21.1.2 Where are solvents used in the manufacture of pharmaceutical drugs? .....979

14.21.1.2.1 Intermediates of synthesis, DS and excipients ..................979

14.21.1.2.2 Drug products ..................................984

14.21.1.3 Impacts of the nature of solvents and their quality on the physicochemical

characteristics of raw materials and DP .....................985

14.21.1.3.1 Raw materials (intermediates, DS, excipients). .................985

14.21.1.3.2 Drug product ...................................988

14.21.1.3.3 Conclusions. ...................................989

14.21.1.4 Setting specifications for solvents ........................990

14.21.1.4.1 Solvents used for the raw material manufacture .................990

14.21.1.4.2 Solvents used for the DP manufacture ......................991

14.21.1.5 Quality of solvents and analysis .........................991

14.21.1.5.1 Quality of solvents used in spectroscopy. ....................991

14.21.1.5.2 Quality of solvents used in chromatography ...................993

14.21.1.5.3 Quality of solvents used in titrimetry ......................996

14.21.1.6 Conclusions. ...................................996

14.21.2 Predicting cosolvency for pharmaceutical and environmental applications ...997

AN LI

14.21.2.1 Introduction. ...................................997

14.21.2.2 Applications of cosolvency in pharmaceutical sciences and industry ......998

14.21.2.3 Applications of cosolvency in environmental sciences and engineering. ....1000

14.21.2.4 Experimental observations ............................1001

14.21.2.5 Predicting cosolvency in homogeneous liquid systems .............1003

14.21.2.6 Predicting cosolvency in non-ideal liquid mixtures ...............1007


xiv HandbookofSolvents

14.21.2.7 Summary .....................................1013

14.22 Polymers and man-made fibers. .........................1016

GEORGE WYPYCH

14.23 Printing industry .................................1020

GEORGE WYPYCH

14.24 Pulp and paper ..................................1023

GEORGE WYPYCH

14.25 Rubber and plastics. ...............................1025

GEORGE WYPYCH

14.26 Use of solvents in the shipbuilding and ship repair industry. ..........1026

MOHAMED SERAGELDIN, DAVE REEVES

14.26.1 Introduction. ...................................1026

14.26.2 Shipbuilding and ship repair operations .....................1026

14.26.3 Coating operations ................................1026

14.26.4 Cleaning operations using organic solvents ...................1027

14.26.4.1 Surface preparation and initial corrosion protection ...............1027

14.26.4.2 Cleaning operations after coatings are applied ..................1028

14.26.4.3 Maintenance cleaning of equipment items and components ...........1031

14.26.5 Marine coatings. .................................1031

14.26.6 Thinning of marine coatings ...........................1032

14.26.7 Solvent emissions ................................1033

14.26.8 Solvent waste ...................................1035

14.26.9 Reducing solvent usage, emissions, and waste. .................1036

14.26.10 Regulations and guidelines for cleaning solvents ................1037

14.27 Stone, clay, glass, and concrete .........................1039

GEORGE WYPYCH

14.28 Textile industry ..................................1041

GEORGE WYPYCH

14.29 Transportation equipment cleaning. .......................1042

GEORGE WYPYCH

14.30 Water transportation ...............................1042

GEORGE WYPYCH

14.31 Wood furniture ..................................1043

GEORGE WYPYCH

14.32 Summary .....................................1045

15 METHODS OF SOLVENT DETECTION AND TESTING. ........1053

15.1 Standard methods of solvent analysis ......................1053

GEORGE WYPYCH

15.1.1 Alkalinity and acidity. ..............................1053

15.1.2 Autoignition temperature. ............................1054

15.1.3 Biodegradation potential .............................1054

15.1.4 Boiling point ...................................1055

15.1.5 Bromine index ..................................1055

15.1.6 Calorific value ..................................1056

15.1.7 Cleaning solvents. ................................1056

15.1.8 Color .......................................1056

15.1.9 Corrosion (effect of solvents) ..........................1057

15.1.10 Density ......................................1057

15.1.11 Dilution ratio ...................................1057

15.1.12 Dissolving and extraction ............................1058

15.1.13 Electric properties ................................1058

15.1.14 Environmental stress crazing ...........................1059

15.1.15 Evaporation rate .................................1059

15.1.16 Flammability limits. ...............................1059

15.1.17 Flash point ....................................1060

15.1.18 Freezing point ..................................1061

15.1.19 Free halogens in halogenated solvents ......................1061


Table of contents xv

15.1.20 Gas chromatography ...............................1061

15.1.21 Labeling .....................................1062

15.1.22 Odor .......................................1062

15.1.23 Paints standards related to solvents .......................1063

15.1.24 pH. ........................................1063

15.1.25 Purity .......................................1063

15.1.26 Refractive index .................................1066

15.1.27 Residual solvents .................................1066

15.1.28 Solubility .....................................1066

15.1.29 Solvent partitioning in soils ...........................1066

15.1.30 Solvent extraction ................................1067

15.1.31 Specifications. ..................................1067

15.1.32 Sustained burning ................................1067

15.1.33 Vapor pressure ..................................1068

15.1.34 Viscosity .....................................1068

15.1.35 Volatile organic compound content, VOC ....................1069

15.2 Special methods of solvent analysis .......................1078

15.2.1 Use of breath monitoring to assess exposures to volatile organic solvents . . . 1078

MYRTO PETREAS

15.2.1.1 Principles of breath monitoring .........................1078

15.2.1.2 Types of samples used for biological monitoring ................1080

15.2.1.3 Fundamentals of respiratory physiology .....................1080

15.2.1.3.1 Ventilation ....................................1081

15.2.1.3.2 Partition coefficients ...............................1081

15.2.1.3.3 Gas exchange ...................................1082

15.2.1.4 Types of exhaled air samples. ..........................1083

15.2.1.5 Breath sampling methodology ..........................1084

15.2.1.6 When is breath monitoring appropriate? .....................1087

15.2.1.7 Examples of breath monitoring. .........................1088

15.2.2 A simple test to determine toxicity using bacteria ................1095

JAMES L. BOTSFORD

15.2.2.1 Introduction. ...................................1095

15.2.2.2 Toxicity defined .................................1095

15.2.2.3 An alternative. ..................................1097

15.2.2.4 Chemicals tested .................................1099

15.2.2.5 Comparisons with other tests. ..........................1103

15.2.2.6 Toxic herbicides .................................1107

15.2.2.7 Toxicity of divalent cations ...........................1108

15.2.2.8 Toxicity of organics in the presence of EDTA ..................1108

15.2.2.9 Mechanism for reduction of the dye .......................1110

15.2.2.10 Summary .....................................1111

15.2.3 Description of an innovative GC method to assess the influence of crystal

texture and drying conditions on residual solvent content in pharmaceutical

products. .....................................1113

CHRISTINE BARTHÉLÉMY, MICHEL BAUER

15.2.3.1 Description of the RS determination method ..................1113

15.2.3.2 Application: Influence of crystal texture and drying conditions on RS content . 1114

15.2.3.2.1 First example: monocrystalline particles of paracetamol ............1116

15.2.3.2.2 Second example: polycrystalline particles of meprobamate and ibuprofen . . . 1119

15.2.3.2.3 Third example: polycrystalline particles of paracetamol. ............1122

16 RESIDUAL SOLVENTS IN PRODUCTS ..................1125

16.1 Residual solvents in various products ......................1125

GEORGE WYPYCH

16.2 Residual solvents in pharmaceutical substances .................1129

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

16.2.1 Introduction. ...................................1129

16.2.2 Why should we look for RS?. ..........................1129


xvi HandbookofSolvents

16.2.2.1 Modifying the acceptability of the drug product .................1129

16.2.2.2 Modifying the physico-chemical properties of drug substances (DS) and

drug products (DP) ................................1130

16.2.2.3 Implications of possible drug/container interactions ...............1131

16.2.2.4 As a tool for forensic applications ........................1131

16.2.2.5 As a source of toxicity ..............................1131

16.2.2.5.1 General points ..................................1131

16.2.2.5.2 Brief overview of the toxicology of solvents. ..................1132

16.2.3 How to identify and control RS in pharmaceutical substances?. ........1133

16.2.3.1 Loss of weight ..................................1133

16.2.3.2 Miscellaneous methods. .............................1133

16.2.3.3 Gas chromatography (GC) ............................1134

16.2.3.3.1 General points ..................................1134

16.2.3.3.2 Review of methods ................................1135

16.2.3.3.3 Official GC methods for RS determination ...................1139

16.2.4 How to set specifications? Examination of the ICH guidelines for residual

solvents ......................................1140

16.2.4.1 Introduction. ...................................1143

16.2.4.2 Classification of residual solvents by risk assessment ..............1143

16.2.4.3 Definition of PDE. Method for establishing exposure limits ..........1143

16.2.4.4 Limits for residual solvents. ...........................1143

16.2.4.5 Analytical procedures ..............................1145

16.2.4.6 Conclusions regarding the ICH guideline ....................1145

16.2.5 Conclusions. ...................................1146

17 ENVIRONMENTAL IMPACT OF SOLVENTS. ..............1149

17.1 The environmental fate and movement of organic solvents in water, soil,

andair ......................................1149

WILLIAM R. ROY

17.1.1 Introduction. ...................................1149

17.1.2 Water .......................................1150

17.1.2.1 Solubility .....................................1150

17.1.2.2 Volatilization ...................................1150

17.1.2.3 Degradation. ...................................1151

17.1.2.4 Adsorption ....................................1151

17.1.3 Soil ........................................1151

17.1.3.1 Volatilization ...................................1151

17.1.3.2 Adsorption ....................................1152

17.1.3.3 Degradation. ...................................1153

17.1.4 Air ........................................1153

17.1.4.1 Degradation. ...................................1153

17.1.4.2 Atmospheric residence time ...........................1154

17.1.5 The 31 solvents in water .............................1154

17.1.5.1 Solubility .....................................1154

17.1.5.2 Volatilization from water. ............................1155

17.1.5.3 Degradation in water ...............................1155

17.1.6 Soil ........................................1157

17.1.6.1 Volatilization ...................................1157

17.1.6.2 Adsorption ....................................1159

17.1.6.3 Degradation. ...................................1160

17.1.7 Air ........................................1161

17.2 Fate-based management of organic solvent-containing wastes .........1162

WILLIAM R. ROY

17.2.1 Introduction. ...................................1162

17.2.1.1 The waste disposal site ..............................1163

17.2.1.2 The advection-dispersion model and the required input .............1164

17.2.1.3 Maximum permissible concentrations ......................1164

17.2.1.4 Distribution of organic compounds in leachate .................1164


Table of contents xvii

17.2.2 Movement of solvents in groundwater ......................1166

17.2.3 Mass limitations .................................1167

17.3 Environmental fate and ecotoxicological effects of glycol ethers ........1169

JAMES DEVILLERS, AURÉLIE CHEZEAU, ANDRÉ CICOLELLA, ERIC THYBAUD

17.3.1 Introduction. ...................................1169

17.3.2 Occurrence ....................................1170

17.3.3 Environmental behavior .............................1171

17.3.4 Ecotoxicity ....................................1175

17.3.4.1 Survival and growth ...............................1175

17.3.4.2 Reproduction and development .........................1185

17.3.5 Conclusion ....................................1187

17.4 Organic solvent impacts on tropospheric air pollution. .............1188

MICHELLE BERGIN, ARMISTEAD RUSSELL

17.4.1 Sources and impacts of volatile solvents .....................1188

17.4.2 Modes and scales of impact ...........................1189

17.4.2.1 Direct exposure ..................................1189

17.4.2.2 Formation of secondary compounds .......................1190

17.4.2.3 Spatial scales of secondary effects ........................1190

17.4.2.3.1 Global impacts ..................................1190

17.4.2.3.2 Stratospheric ozone depletion ..........................1191

17.4.2.3 Global climate forcing ..............................1191

17.4.2.4 Urban and regional scales ............................1192

17.4.3 Tropospheric ozone. ...............................1192

17.4.3.1 Effects ......................................1192

17.4.3.2 Tropospheric photochemistry and ozone formation ...............1193

17.4.3.3 Assessing solvent impacts on ozone and VOC reactivity ............1195

17.4.3.3.1 Quantification of solvent emissions on ozone formation ............1196

17.4.4 Regulatory approaches to ozone control and solvents ..............1198

17.4.5 Summary .....................................1299

18 CONCENTRATION OF SOLVENTS IN VARIOUS INDUSTRIAL

ENVIRONMENTS ...............................1201

18.1 Measurement and estimation of solvents emission and odor. ..........1201

MARGOT SCHEITHAUER

18.1.1 Definition “solvent” and “volatile organic compounds” (VOC) .........1201

18.1.2 Review of sources of solvent emissions .....................1203

18.1.2.1 Causes for emissions ...............................1203

18.1.2.2 Emissions of VOCs from varnishes and paints .................1203

18.1.2.3 VOC emissions from emulsion paints ......................1205

18.1.3 Measuring of VOC-content in paints and varnishes. ..............1205

18.1.3.1 Definition of low-emissive coating materials ..................1205

18.1.3.2 Determination of the VOC content according to ASTM D 3960-1 .......1205

18.1.3.3 Determination of the VOC content according to ISO/DIS 11 890/1 and 2 . . . 1206

18.1.3.3.1 VOC content > 15% ...............................1206

18.1.3.3.2 VOC content > 0.1 and < 15 %. .........................1208

18.1.3.4 Determination of VOC-content in water-thinnable emulsion paints

(in-can VOC) ...................................1208

18.1.4 Measurement of solvent emissions in industrial plants .............1209

18.1.4.1 Plant requirements ................................1209

18.1.4.2 The determination of the total carbon content in mg C/Nm³. ..........1214

18.1.4.2.1 Flame ionization detector (FID) .........................1214

18.1.4.2.2 Silica gel approach ................................1214

18.1.4.3 Qualitative and quantitative assessment of individual components in the

exhaust-gas ....................................1215

18.1.4.3.1 Indicator tubes ..................................1215

18.1.4.3.2 Quantitative solvent determination in exhaust gas of plants by means of

gas-chromatography ...............................1215

18.1.5 “Odor” definition .................................1219


xviii HandbookofSolvents

18.1.6 Measurement of odor in materials and industrial plants .............1222

18.1.6.1 Introduction. ...................................1222

18.1.6.2 Odor determination by means of the “electronic nose” .............1222

18.1.6.3 Odor determination by means of the olfactometer ................1223

18.1.6.4 Example for odor determination for selected materials: Determination of

odorant concentration in varnished furniture surfaces ..............1223

18.1.6.5 Example of odor determination in industrial plants: Odor measurement in

an industrial varnishing plant. ..........................1225

18.2 Prediction of organic solvents emission during technological processes ....1227

KRZYSZTOF M. BENCZEK, JOANNA KURPIEWSKA

18.2.1 Introduction. ...................................1227

18.2.2 Methods of degreasing ..............................1227

18.2.3 Solvents. .....................................1228

18.2.4 Identification of the emitted compounds .....................1228

18.2.5 Emission of organic solvents during technological processes ..........1228

18.2.6 Verification of the method ............................1230

18.2.7 Relationships between emission and technological parameters .........1231

18.2.7.1 Laboratory test stand ...............................1231

18.2.7.2 The influence of temperature on emission ....................1231

18.2.7.3 The influence of air velocity on emission ....................1232

18.2.7.4 The relationship between the mass of solvent on wet parts and emissions . . . 1232

18.2.8 Emission of solvents ...............................1232

18.2.9 Verification in industrial conditions .......................1232

18.3 Indoor air pollution by solvents contained in paints and varnishes .......1234

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

18.3.1 Composition - solvents in paints and varnishes. Theoretical aspects ......1234

18.3.2 Occurrence of solvents in paints and varnishes .................1235

18.3.2.1 Solvents in products ...............................1235

18.3.2.2 Paints and varnishes ...............................1237

18.3.3 Emission of solvents ...............................1240

18.3.3.1 Emission .....................................1240

18.3.3.2 Immission. ....................................1242

18.3.4 Effects on health of solvents from paints and varnishes .............1243

18.3.4.1 Exposure .....................................1243

18.3.4.2 Health effects ...................................1243

18.3.4.2.1 Toxic responses of skin and mucose membranes ................1243

18.3.4.2.2 Neurological disorders ..............................1244

18.3.4.2.3 Carcinogenic effects ...............................1245

18.3.4.2.4 Respiratory effects ................................1246

18.3.4.2.5 Toxic responses of blood .............................1247

18.3.4.2.6 Toxic responses of the reproductive system ...................1247

18.3.4.2.7 Toxic responses of other organ systems .....................1247

18.3.5 Methods for the examination of solvents in paints and varnishes ........1248

18.3.5.1 Environmental monitoring ............................1248

18.3.5.1.1 Solvents in products ...............................1248

18.3.5.1.2 Emission of solvents ...............................1248

18.3.5.2 Biological monitoring of solvents in human body fluids ............1248

18.3.5.2.1 Solvents and metabolites in human body fluids and tissues ...........1248

18.3.5.2.2 Biomarkers ....................................1248

18.4 Solvent uses with exposure risks .........................1251

pentti kalliokoski, kai savolinen

18.4.1 Introduction. ...................................1251

18.4.2 Exposure assessment ...............................1252

18.4.3 Production of paints and printing inks ......................1255

18.4.4 Painting ......................................1256

18.4.5 Printing ......................................1257

18.4.6 Degreasing, press cleaning and paint removal ..................1258


Table of contents xix

18.4.7 Dry cleaning ...................................1260

18.4.8 Reinforced plastics industry ...........................1261

18.4.9 Gluing ......................................1262

18.4.10 Other .......................................1262

18.4.11 Summary .....................................1263

19 REGULATIONS ................................1267

CARLOS M. NU ~ NEZ

19.1 Introduction. ...................................1267

19.2 Air laws and regulations .............................1282

19.2.1 Clean Air Act Amendments of 1990 .......................1282

19.2.1.1 Background. ...................................1282

19.2.1.2 Title I - Provisions for Attainment and Maintenance of National Ambient

Air Quality Standards ..............................1284

19.2.1.3 Title III - Hazardous Air Pollutants .......................1288

19.2.1.4 Title V - Permits .................................1292

19.2.1.5 Title VI - Stratospheric Ozone Protection ....................1292

19.3 Water laws and regulations. ...........................1293

19.3.1 Clean Water Act .................................1293

19.3.1.1 Background. ...................................1293

19.3.1.2 Effluent Limitations ...............................1293

19.3.1.3 Permit Program ..................................1294

19.3.2 Safe Drinking Water Act .............................1294

19.3.2.1 Background. ...................................1294

19.3.2.2 National Primary Drinking Water Regulations. .................1295

19.4 Land laws & regulations .............................1295

19.4.1 Resource Conservation and Recovery Act (RCRA) ...............1295

19.4.1.1 Background. ...................................1295

19.4.1.2 RCRA, Subtitle C - Hazardous Waste ......................1296

19.5 Multimedia laws and regulations. ........................1297

19.5.1 Pollution Prevention Act of 1990 ........................1297

19.5.1.1 Background. ...................................1297

19.5.1.2 Source Reduction Provisions ...........................1298

19.5.2 Toxic Substances Control Act ..........................1300

19.5.2.1 Background. ...................................1300

19.5.2.2 Controlling toxic substances ...........................1300

19.6 Occupational laws and regulations ........................1301

19.6.1 Occupational Safety and Health Act .......................1301

19.6.1.1 Background. ...................................1301

19.6.1.2 Air contaminants exposure limits ........................1301

Источник: https://www.yumpu.com/en/document/view/10607080/handbook-of-solvents-george-wypych-chemtech-ventech
308 pages ISBN: 1785887513

-Handbook of Solvents

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HANDBOOK OF

SOLVENTS George Wypych, Editor

ChemTec Publishing

Toronto − New York 2001

Published by ChemTec Publishing 38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada Co-published by William Andrew Inc. 13 Eaton Avenue, Norwich, N Y 13815, USA © Chem Tec Publishing, 2001 ISBN 1-895198-24-0 All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibility is assumed by the Author and the Publisher for any injury or/and damage to persons or properties as a matter of products liability, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.

Canadian Cataloguing in Publication Data Handbook of Solvents Includes bibliographical references and index ISBN 1-895198-24-0 (ChemTec Publishing) ISBN 0-8155-1458-1 AVS Video Editor 9.4.4.375 Crack Activation key Free Andrew Inc.) Library of Congress Catalog Card Number: 00-106798 1. Solvents--Handbooks, manuals, etc. I. Wypych, George TP247.5.H35 2000

661’.807

C00-900997-3

Printed in Canada by Transcontinental Printing Inc., 505 Consumers Rd. Toronto, Ontario M2J 4V8

Table of Contents Preface. . xxvii GEORGE WYPYCH

1

INTRODUCTION. . 1

2 2.1

FUNDAMENTAL PRINCIPLES GOVERNING SOLVENTS USE. 7 Solvent effects on chemical systems. . 7

2.1.1 2.1.2 2.1.2.1 2.1.2.2 2.1.2.3 2.1.2.4 2.1.2.5 2.1.2.6 2.1.3 2.1.3.1 2.1.3.2 2.1.3.3 2.1.3.4 2.1.3.5 2.1.4 2.1.4.1 2.1.4.2 2.1.4.3 2.1.5 2.2

Historical outline. Classification of solute-solvent interactions. . Electrostatic. . Polarization. . Dispersion. . Repulsion. Specific interactions. . Hydrophobic interactions. . Modelling of solvent effects. . Computer simulations. Continuum models. . Cavity surfaces. adobe acrobat 9 pro crack - Crack Key For U.. Supermolecule models. Application example: glycine in solution. . Thermodynamic and kinetic characteristics of chemical reactions in solution Solvent effects on chemical equilibria. Solvent effects on the rate of chemical reactions. . Example of application: addition of azide anion to tetrafuranosides. Solvent catalytic effects. Molecular design of solvents. .

. . .

7 10 11 12 13 14 15 16 17 18 20 21 22 23 27 27 28 30 32 36

2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.3

Molecular design and molecular ensemble design. . From prediction to design. . Improvement in prediction method. . Role of molecular simulation. Model system and paradigm for design. Appendix. Predictive equation for the diffusion coefficient in dilute solution Basic physical and chemical properties of solvents. .

. . .

36 37 38 39 40 41 42

2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 2.3.6 2.3.7 2.3.8 2.3.9 2.3.10 2.3.11 2.3.12 2.3.13 2.3.14 2.3.15

Molecular weight and molar volume. . Boiling and freezing points. . Specific gravity. . Refractive index. Vapor density and pressure. . Solvent volatility. Flash point. Flammability limits. . Sources of ignition and autoignition temperature Heat of combustion (calorific value). . Heat of fusion. . Electric conductivity. . Dielectric constant (relative permittivity). Occupational exposure indicators. Odor threshold. .

. . .

43 44 46 47 48 49 50 51 52 54 54 54 54 56 56

CHRISTIAN REICHARDT

ESTANISLAO SILLA, ARTURO ARNAU, IÑAKI TUÑÓN

KOICHIRO NAKANISHI

GEORGE WYPYCH

. . .

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ii 2.3.16 2.3.17 2.3.18 2.3.19 2.3.20 3

Handbook of Solvents

3.1

Toxicity indicators. Ozone-depletion and creation potential. Oxygen demand. Solubility. Other typical solvent properties and indicators. PRODUCTION METHODS, PROPERTIES, AND MAIN APPLICATIONS. Definitions and solvent classification. .

3.2

Overview of methods of solvent manufacture. . 69

3.3

Solvent properties. 74

3.3.1 3.3.1.1 3.3.1.2 3.3.2 3.3.3 3.3.4 3.3.5 3.3.6 3.3.7 3.3.8 3.3.9 3.3.10 3.3.11 3.3.11 3.3.12 3.3.13 3.3.14 3.4

Hydrocarbons. . Aliphatic hydrocarbons. . Aromatic hydrocarbons. . Halogenated hydrocarbons. Nitrogen-containing compounds (nitrates, nitriles) Organic sulfur compounds. Monohydric alcohols. Polyhydric alcohols. Phenols. . Aldehydes. Ethers. Glycol ethers. Ketones. . Acids. Amines. . Esters. Comparative analysis of all solvents. Terpenes. .

. .

. .

. .

. .

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. .

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. .

75 75 76 78 79 80 81 83 84 85 86 87 88 90 91 92 94 96

3.4.1 3.4.2 3.4.3 3.4.4 3.4.5 4

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. .

. .

. .

. .

. .

. .

. .

96 96 96 97 97

4.1

Definitions and nomenclature. . Occurrence. General. . Toxicology. Threshold limit values. . GENERAL PRINCIPLES GOVERNING DISSOLUTION OF MATERIALS IN SOLVENTS. . Simple solvent characteristics. .

4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 4.1.6 4.1.7 4.2

Solvent power. . One-dimensional solubility parameter approach. Multi-dimensional approaches. . Hansen’s solubility. Three-dimensional dualistic model. . Solubility criterion. Solvent system design. . Effect of system variables on solubility. .

. . .

. . .

. . .

. . .

. . .

101 103 110 112 116 119 120 124

4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6

General considerations. . Chemical structure. Flexibility of a polymer chain. . Crosslinking. Temperature and pressure. Methods of calculation of solubility based on thermodynamic principles .

. .

. .

. .

124 126 127 128 128 130

GEORGE WYPYCH

. .

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57 58 58 58 60

. 65. 65

GEORGE WYPYCH GEORGE WYPYCH

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

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. 101. 101. . .

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. . .

Table of contents

iii

4.3

Polar solvation dynamics: Theory and simulations. . 132

4.3.1 4.3.2 4.3.3 4.3.4

Introduction. . Continuum dielectric theory of solvation dynamics. . Linear response theory of solvation dynamics. Secure-cleaning - Activators Patch.. Numerical simulations of solvation in simple polar solvents: The simulation model. . Numerical simulations of solvation in simple polar solvents: Results and discussion. . Solvation in complex solvents. . Conclusions. . Methods for the measurement of solvent activity of polymer solutions .

. 132. 133. 136

. . .

. . .

. . .

. . .

140 144 145 146

Introduction. Necessary thermodynamic equations. Experimental methods, equipment and data reduction. Vapor-liquid equilibrium (VLE) measurements. . Experimental equipment and procedures for VLE-measurements. . Primary data reduction. Comparison of experimental VLE-methods. Other measurement methods. Membrane osmometry. Light scattering. X-ray scattering. . Neutron scattering. . Ultracentrifuge. Cryoscopy (freezing point depression of the solvent). Liquid-liquid equilibrium (LLE). . Swelling equilibrium. Thermodynamic models for the calculation of solvent activities of polymer solutions. . Models for residual chemical potential and activity coefficient in the liquid phase. Fugacity coefficients from equations of state. Comparison and conclusions. Appendix 4.4A. SOLUBILITY OF SELECTED SYSTEMS AND INFLUENCE OF SOLUTES. Experimental methods of evaluation and calculation of solubility parameters of polymers and solvents. Solubility parameters data. .

. . .

. . .

. . .

. . .

146 149 154 154 155 170 175 178 178 181 184 185 186 188 189 193

4.3.5 4.3.6 4.3.7 4.4 4.4.1 4.4.2 4.4.3 4.4.3.1 4.4.3.1.1 4.4.3.1.2 4.4.3.1.3 4.4.3.2 4.4.3.2.1 4.4.3.2.2 4.4.3.2.3 4.4.3.2.4 4.4.3.2.5 4.4.3.2.6 4.4.3.2.7 4.4.3.2.8 4.4.4 4.4.4.1 4.4.4.2 4.4.4.3 5 5.1 5.1.1 5.1.1.1 5.1.1.2 5.1.1.3 5.1.1.4 5.1.2

ABRAHAM NITZAN

CHRISTIAN WOHLFARTH

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

. . .

. . 195. . .

. . .

. . .

. . .

. . .

196 207 214 223

. . 243

5.2 5.2.1 5.2.2 5.2.2.1 5.2.2.2 5.2.3 5.3

Solubility parameter of polymers. Glass transition in polymers. Glass transition enthalpy. . Cp jump at the glass transition. . Prediction from thermal transition enthalpies. . Methods of calculation of solubility parameters of solvents and polymers VALERY YU. SENICHEV, VASILIY V. TERESHATOV

. . .

. . 243

Experimental evaluation of solubility parameters of liquids. Direct methods of evaluation of the evaporation enthalpy. Indirect methods of evaluation of evaporation enthalpy. . Static and quasi-static methods of evaluation of pair pressure. . Kinetic methods. . Methods of experimental evaluation and calculation of solubility parameters of polymers. . Prediction of solubility parameter. NOBUYUKI TANAKA

. .

. . .

. 138

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243 243 244 245 245

. . 246. . 253. .

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. .

253 254 254 256 258 261

iv

Handbook of Solvents

5.4

Mixed solvents, a way to change the polymer solubility. 267

5.4.1 5.4.2 5.4.3 5.4.4

Introduction. . Solubility-cosolvency phenomenon. . New cosolvents effects. Solubility behavior. . Thermodynamical description of ternary systems. Association equilibria theory of preferential adsorption. Polymer structure of the polymer dependence of preferential adsorption. Polymer molecular weight and tacticity dependence of preferential adsorption. The phenomenological theory of solvent effects in mixed solvent systems. . .

267 268 273

6 6.1

Introduction. Theory. Principle. . The intersolute effect: solute-solute interactions. . The solvation effect: solute-solvent interaction. . The general medium effect: solvent-solvent interactions. . The total solvent effect. Applications. Solubility. . Surface tension. Electronic absorption spectra. Complex formation. . Chemical kinetics. . Liquid chromatography. . Interpretations. Ambiguities and anomalies. A modified derivation. Interpretation of parameter estimates. Confounding effects. Solute-solute interactions. . Coupling of general medium and solvation effects. The cavity surface area. The role of interfacial tension. SWELLING. Modern views on kinetics of swelling of crosslinked elastomers in solvents

. .

. .

281 281 281 282 283 284 285 285 285 288 290 291 295 298 298 298 299 300 301 301 301 301 302 305 305

6.1.1 6.1.2 6.1.3 6.1.4 6.1.5 6.2

Introduction. Formulation of swelling for a plane elastomer layer. Diffusion kinetics of plane layer swelling. . Experimental study of elastomer swelling kinetics. Conclusions. Equilibrium swelling in binary solvents. . .

. .

. .

305 306 310 314 317 318

6.3

Swelling data on crosslinked polymers in solvents. . 327

6.4

Influence of structure on equilibrium swelling. 331

7 7.1

SOLVENT TRANSPORT PHENOMENA. . 339 Introduction to diffusion, swelling, and drying. 339

7.1.1 7.1.2 7.1.3 7.2

Diffusion. Swelling. Drying. Bubbles dynamics and boiling of polymeric solutions .

7.2.1

Rheology of polymeric solutions and bubble dynamics. 356

5.4.5 5.5 5.5.1 5.5.2 5.5.2.1 5.5.2.2 5.5.2.3 5.5.2.4 5.5.2.5 5.5.3 5.5.3.1 5.5.3.2 5.5.3.3 5.5.3.4 5.5.3.5 5.5.3.6 5.5.4 5.5.4.1 5.5.4.2 5.5.4.3 5.5.4.4

LIGIA GARGALLO AND DEODATO RADIC

KENNETH A. CONNORS

E. YA. DENISYUK, V. V. TERESHATOV

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

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. .

. .

. .

. .

. .

. .

. .

. .

. .

. .

. .

274 277 281

VASILIY V. TERESHATOV, VALERY YU. SENICHEV VASILIY V. TERESHATOV, VALERY YU. SENICHEV

GEORGE WYPYCH

SEMYON LEVITSKY, ZINOVIY SHULMAN

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. . .

339 344 348 356

Table of contents

v

7.2.1.1 7.2.1.2 7.2.2 7.2.3 7.3

Rheological characterization of solutions of polymers. . Dynamic interaction of bubbles with polymeric liquid. . Thermal growth of bubbles in superheated solutions of polymers Boiling of macromolecular liquids. Drying of coated film. . .

. .

. .

. .

. .

. .

356 363 372 377 386

7.3.1 7.3.2 7.3.2.1 7.3.2.2 7.3.2.3 7.3.2.4 7.3.2.5

Introduction. . Theory for the drying. . Simultaneous heat and mass transfer. . Liquid-vapor equilibrium. Heat and mass transfer coefficient. Prediction of drying rate of coating. . Drying regimes: constant drying rate period (CDRP) and falling drying rate period (FDRP). Measurement of the drying rate of coated film. Thermo-gravimetric analysis. . Rapid scanning FT-IR spectrometer analysis. . High-airflow drying experiment using flame ionization detector (FID) total hydrocarbon analyzer. Measurement of drying rate in the production scale dryer. Miscellaneous. . Drying of coated film with phase separation. . Drying defects. . Internal stress induced defects. . Surface tension driven defects. . Defects caused by air motion and others. Control of lower explosive level (LEL) in a multiple zone dryer. INTERACTIONS IN SOLVENTS AND SOLUTIONS. . .

. .

. .

. .

. .

386 388 388 389 390 392

. . .

. . .

. . .

. . .

394 396 396 399

. .

. .

. .

. .

401 404 407 407 409 409 412 414 414 419

Solvents and solutions as assemblies of interacting molecules. . Basic simplifications of the quantum model. Cluster expansion. Two-body interaction energy: the dimer. . Decomposition of the interaction energy of a dimer: variational approach The electrostatic term. . The induction term. avast premier license file till 2050 - Activators Patch.. . The exchange term. The charge transfer term. . The dispersion term. The decomposition Altium Designer 20.2.6 Build 244 Crack the interaction energy through a variational approach: a summary. Basis set superposition error and counterpoise corrections. Perturbation theory approach. . Modeling of the separate components of ∆E. The electrostatic term. . The induction term. The dispersion term. The exchange (or repulsion) term. The other terms. . A conclusive view. The relaxation of the rigid monomer constraint. . Three- and many-body interactions. Screening many-body effects. . Effective interaction potentials. . The variety of interaction potentials. Theoretical and computing modeling of pure liquids and solutions. Physical models. .

. .

. .

. .

419 420 424 424 426 426 428 428 429 430

. . SecuritySpy 5.3.2 Crack+ Keygen Code 2021 - Free Activators.. .

. .

. .

432 433 436 441 441 445 446 447 448 448 449 451 453 454 456 461 461

7.3.3 7.3.3.1 7.3.3.2 7.3.3.3 7.3.3.4 7.3.4 7.3.4.1 7.3.4.2 7.3.4.2.1 7.3.4.2.2 7.3.4.2.3 7.3.4.3 8 8.1 8.2 8.3 8.4 8.4.1

8.4.2 8.4.3 8.4.4

8.4.5 8.5 8.6 8.7 8.7.1

SEUNG SU KIM AND JAE CHUN HYUN

JACOPO TOMASI, BENEDETTA MENNUCCI, CHIARA CAPPELLI

. .

. .

vi 8.7.1.1 8.7.1.2 8.7.2 8.7.2.1 8.7.2.2

8.7.3 8.7.3.1 8.8

8.9 8.9.1 8.9.2 8.9.3 9 9.1 9.2 9.2.1 9.2.2 9.2.3 9.2.4 9.2.5 9.2.6 9.2.7 9.2.8 9.2.8.1 9.2.8.2 9.2.8.3 9.2.8.4 9.3 9.3.1 9.3.1.1 9.3.1.2 9.3.1.3 9.3.1.4 9.3.2 9.3.2.1 9.3.2.2 9.3.2.3 9.3.2.4 9.3.3 9.3.3.1 9.3.3.2 9.3.3.3 9.4 9.4.1 9.4.2 9.4.3

Handbook of Solvents Integral equation methods. Perturbation theories. . Computer simulations. . Car-Parrinello direct QM simulation. . Semi-classical simulations. Molecular dynamics. . Monte Carlo. . QM/MM. Continuum models. QM-BE methods: the effective Hamiltonian. . Practical applications of modeling. Dielectric constant. Thermodynamical properties. . Compressibilities. Relaxation times and diffusion coefficients. . Shear viscosity. . Liquid surfaces. . The basic types of liquid surfaces. Systems with a large surface/bulk ratio. Studies on interfaces using interaction potentials MIXED SOLVENTS. .

. .

. .

. .

. .

. .

465 467 468 470 472 472 473 478 479 482 487 487 490 490 491 492 492 493 495 497 505

Introduction. . Chemical interaction between components in mixed solvents. . Processes of homomolecular association. Conformic and tautomeric equilibrium. Reactions of isomerization. . Heteromolecular association. . Heteromolecular associate ionization. . Electrolytic dissociation (ionic association). . Reactions of composition. Exchange interaction. . Amphoterism of mixed solvent components. . Amphoterism of hydrogen acids. Amphoterism of L-acids. Amphoterism in systems H-acid-L-acid. Amphoterism in binary solutions amine-amine. Physical properties of mixed solvents. . The methods of expression of mixed solvent compositions. . Permittivity. Viscosity. Density, molar volume. . Electrical conductivity. . Physical characteristics of the mixed solvents with chemical interaction between components. . Permittivity. Viscosity. Density, molar volume. . Conductivity. . Chemical properties of mixed solvents. Autoprotolysis constants. Solvating ability. Donor-acceptor properties. Mixed solvent influence on the chemical equilibrium. . General considerations. . Mixed solvent effect on the position of equilibrium of homomolecular association process. Mixed solvent influence on the conformer equilibrium. .

. . .

. . .

. . .

. . .

505 505 505 506 507 507 508 508 509 509 509 509 510 510 511 511 513 515 516 516

. . .

. . .

. . .

. . .

517 518 519 521 522 524 524 526 527 527 527

Y. Y. FIALKOV, V. L. CHUMAK

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. .

. . Altium Designer 20.2.6 Build 244 Crack. .

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. 529. 530

Table of contents 9.4.4 9.4.4.1 9.4.5 9.4.6

9.4.7 9.5 10 10.1

Solvent effect on the process of heteromolecular association. . Selective solvation. Resolvation. Mixed solvent effect on the ion association process. . Solvent effect on exchange interaction processes. Systems with non-associated reagents. . Systems with one associated participant of equilibrium. Systems with two associated participants of equilibrium. Mixed solvent effect on processes of complex formation. The mixed solvent effect on the chemical equilibrium thermodynamics ACID-BASE INTERACTIONS. General concept of acid-base interactions. GEORGE WYPYCH

vii. . .

. . .

. . .

. . .

532 538 546 552 552 553 553 556 557 565 565

10.2

Effect of polymer/solvent acid-base interactions: relevance to the aggregation of PMMA. 570

10.2.1 10.2.1.1 10.2.1.1.1 10.2.1.1.2 10.2.1.1.3 10.2.1.2 10.2.1.2.1 10.2.1.2.2 10.2.1.2.3 10.2.1.2.4 10.2.1.2.5 10.2.1.2.6 10.2.2 10.2.2.1 10.2.2.2

Recent concepts in acid-base interactions. The nature of acid-base molecular interactions. The original Lewis definitions. . Molecular Orbital (MO) approach to acid-base reactions. The case of hydrogen bonding. . Quantitative determination of acid-base interaction strength. . Perturbation theory. Hard-Soft Acid-Base (HSAB) principle. Density functional theory. Effect of ionocity and covalency: Drago’s concept. . Effect of amphotericity of acid-base interaction: Gutmann’s numbers. Spectroscopic measurements: Fowkes’ approach. Effect of polymer/solvent interactions on aggregation of stereoregular PMMA Aggregation of stereoregular PMMA. . Relation between the complexing power of solvents and their acid-base properties. . Influence of the nature of the solvent on the α and β-relaxations of conventional PMMA. . Introduction. . Dielectric spectroscopy results. . Concluding remarks. . Solvent effects based on pure solvent scales. . .

10.2.3 10.2.3.1 10.2.3.2 10.2.4 10.3 10.3.1 10.3.2 10.3.3 10.3.3.1 10.3.3.2 10.3.3.3 10.3.3.4 10.3.3.5 10.3.3.6 10.3.3.7 10.3.3.8 10.3.4 10.3.5 10.3.6 10.3.7 10.3.7.1 10.3.7.2

S. BISTAC, M. BROGLY

JAVIER CATALÁN

Introduction. . The solvent effect and its dissection into general and specific contributions. Characterization of a molecular environment with the aid of the probe/homomorph model. . Single-parameter solvent scales: the Y, G, ET(30), PyZ, χR, Φ, and S' scales. The solvent ionizing power scale or Y scale. . The G values of Allerhand and Schleyer. The ET(30) scale of Dimroth and Reichardt. . The Py scale of Dong and Winnick. . The Z scale of Kosower. The χR scale of Brooker. The Φ scale of Dubois and Bienvenüe. The S' scale of Drago. . Solvent polarity: the SPP scale. Solvent basicity: the SB scale. Solvent acidity: the SA scale. . Applications of the pure SPP, SA and SB scales. . Other reported solvents scales. Treatment of the solvent effect in:. . .

570 571 571 571 573 574 574 574 575 576 577 578 578 578 579 581 581 581 582 583

. 583. 584. . .

585 587 587 588 588 589 589 590 590 591 591 600 601 605 605 608

viii

Handbook of Solvents

10.3.7.2.1 10.3.7.2.2 10.3.7.2.3 10.3.7.2.4 10.3.7.3 10.4

Spectroscopy. . Kinetics. Electrochemistry. Thermodynamics. Mixtures of solvents. Understanding the preferential solvation model Acid-base equilibria in ionic solvents (ionic melts). .

10.4.1

Acid-base definitions used for the description of donor-acceptor interactions in ionic media. The Lewis definition. . The Lux-Flood definition. The features of ionic melts as media for acid-base interactions. Oxygen-less media. Altium Designer 20.2.6 Build 244 Crack.. . Oxygen-containing melts. The effect of the ionic solvent composition on acid-base equilibria. . Methods for estimations of acidities of solutions based on ionic melts. On studies of the homogeneous acid-base reactions in ionic melts. . Nitrate melts. . Sulphate melts. . Silicate melts. . The equimolar mixture KCl-NaCl. Other alkaline halide melts. Reactions of melts with gaseous acids and bases. High-temperature hydrolysis of molten halides. The processes of removal of oxide admixtures from melts. . ELECTRONIC AND ELECTRICAL EFFECTS OF SOLVENTS. Theoretical treatment of solvent effects on electronic and vibrational spectra of compounds in condensed media. . .

10.4.1.1 10.4.1.2 10.4.2 10.4.2.1 10.4.2.2 10.4.2.3 10.4.3 10.4.4 10.4.4.1 10.4.4.2 10.4.4.3 10.4.4.4 10.4.4.5 10.4.5 10.4.5.1 10.4.5.2 11 11.1 11.1.1 11.1.2 11.1.3 11.1.4 11.1.5 11.2 11.2.1 11.2.2 11.2.3 12

VICTOR CHERGINETS

. .

MATI KARELSON

. .

. .

. .

. .

608 611 612 612 612 616

. .

. .

. .

. .

617 617 618 618 619 619 620 623 625 625 627 628 629 631 632 632 633 639

. 639

Introduction. . Theoretical treatment of solvent cavity effects on electronic-vibrational spectra of molecules. . Theoretical treatment of solvent electrostatic polarization on electronic-vibrational spectra of molecules. . Altium Designer 20.2.6 Build 244 Crack.. Theoretical treatment of solvent dispersion effects on electronic-vibrational spectra of molecules. . Supermolecule approach to the intermolecular interactions in condensed media Dielectric solvent effects on the intensity of light absorption and the radiative rate constant. TAI-ICHI SHIBUYA

639 647 649 671 674 680

The Chako formula or the Lorentz-Lorenz correction. . The generalized local-field factor for the ellipsoidal cavity. . Dielectric solvent effect on the radiative rate constant. OTHER PROPERTIES OF SOLVENTS, SOLUTIONS, AND PRODUCTS OBTAINED FROM SOLUTIONS. Rheological properties, aggregation, permeability, molecular structure, crystallinity, and other properties affected by solvents. .

. 680. 680. 682

12.1.1 12.1.2 12.1.3 12.1.4 12.1.5 12.2

Rheological properties. Aggregation. . Permeability. . Molecular structure and crystallinity. . Other properties affected by solvents. Chain conformations of polysaccharides in different solvents .

. .

12.2.1 12.2.2

Introduction. . parallels desktop 15.1.2 activation key.. 706 Structure and conformation of polysaccharides in solution. . 707

12.1

GEORGE WYPYCH

RANIERI URBANI AND ATTILIO CESÀRO

. .

. .

. .

. .

. .

. 683. 683. .

. .

. .

683 689 693 697 700 706

Table of contents 12.2.2.1 12.2.2.2 12.2.3 12.2.4 12.2.4.1 12.2.4.2 12.2.5 12.2.6 12.2.6.1 12.2.6.2 12.2.6.3 12.2.6.4 12.2.7 13 13.1 13.1.1 13.1.2 13.1.3 13.1.4 13.1.5 13.1.6 13.1.7

ix

Chemical structure. Solution chain conformation. . Experimental evidence of solvent effect on oligosaccharide conformational equilibria. Theoretical evaluation of solvent effect on conformational equilibria of sugars Classical molecular mechanics methods. Molecular dynamic methods. . Solvent effect on chain dimensions and conformations of polysaccharides. . Solvent effect on charged polysaccharides and the polyelectrolyte model. . Experimental behavior of polysaccharides polyelectrolytes. . The Haug and Smidsrød parameter: description of the salt effect on the chain dimension. The statistical thermodynamic counterion-condensation theory of Manning. . Altium Designer 20.2.6 Build 244 Crack calculations of charged polysaccharides. Conclusions. . EFFECT OF SOLVENT ON CHEMICAL REACTIONS AND REACTIVITY. . Solvent effects on chemical reactivity. . ROLAND SCHMID

707 707 711 715 715 720 722 726 726 727 729 731 733 737 737

13.1.8 13.2

Introduction. . The dielectric approach. The chemical approach. . Dielectric vs. chemical approach. Conceptual problems with empirical solvent parameters The physical approach. . Some highlights of recent investigations. The like dissolves like rule. Water’s anomalies. The hydrophobic effect. . The structure of liquids. . Solvent reorganization energy in ET. . The solution ionic radius. The future of the phenomenological approach. . Solvent effects on free radical polymerization. .

. . .

. . .

. . .

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737 737 738 742 744 746 753 753 755 758 762 765 768 772 777

13.2.1 13.2.2 13.2.2.1 13.2.2.2 13.2.2.3 13.2.2.4 13.2.3 13.2.3.1 13.2.3.1.1 13.2.3.1.2 13.2.3.1.3 13.2.3.2 13.2.3.2.1 13.2.3.2.2 13.2.3.2.3 13.2.3.3 13.2.3.3.1 13.2.3.3.2 13.2.3.3.3 13.2.3.3.4 13.2.3.4 13.2.3.4.1

Introduction. . Homopolymerization. . Initiation. Propagation. . Transfer. Termination. . Copolymerization. . Polarity effect. Basic mechanism. Copolymerization model. Evidence for polarity effects in propagation reactions. Radical-solvent complexes. . Basic mechanism. Copolymerization model. Experimental evidence. Monomer-solvent complexes. Introduction. . Monomer-monomer complex participation model. . Monomer-monomer complex dissociation model. . Specific solvent effects. Bootstrap model. Basic mechanism. . .

. .

. .

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777 777 777 778 779 779 779 780 780 781 781 782 782 782 783 785 785 785 790 791 791 791

MICHELLE L. COOTE AND THOMAS P. DAVIS

. .

x

Handbook of Solvents

13.2.3.4.2 13.2.3.4.3 13.2.4 13.3

Copolymerization model. Experimental evidence. Concluding remarks. . Effects of organic solvents on phase-transfer catalysis

. . .

. . .

791 793 795 798

13.3.1 13.3.1.1 13.3.1.2 13.3.1.3 13.3.1.4

Two-phase phase-transfer catalytic reactions. Theoretical analysis of the polarity of the organic solvents and the reactions. Effect of organic solvent on the reaction in various reaction systems. Effects of the organic solvents on the reactions in other catalysts. . Effect of the volume of organic solvent and water on the reactions in various reaction systems. Effects of organic solvents on other phase-transfer catalytic reactions. Other effects on the phase-transfer catalytic reactions. Three-phase reactions (triphase catalysis). . The interaction between solid polymer (hydrophilicity) and the organic solvents. Effect of solvents on the reaction in triphase catalysis. Effect of volume of organic solvent and water on the reactions in triphase catalysis. Effect of polymerization solvent on the chemical structure and curing of aromatic poly(amideimide). .

. . .

801 801 805 811

. . .

822 825 828 830

13.3.1.5 13.3.1.6 13.3.2 13.3.2.1 13.3.2.2 13.3.2.3 13.4

MAW-LING WANG

NORIO TSUBOKAWA

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. 830. 833. 836. 841

13.4.1 13.4.2 13.4.2.1 13.4.2.2 13.4.3 13.4.3.1 13.4.3.2 3D Coat v4.9.05 Crack Full Version 2019 Free Download [Fixed] 14 14.1

Introduction. . Effect of solvent on the chemical structure of PAI. . Imide and amide bond content of PAI. . Intrinsic viscosity and carboxyl group content. . Effect of solvent on the curing of PAI by heat treatment Chemical structure of PAI after heat treatment. Curing PAI by post-heating. . Conclusions. . SOLVENT USE IN VARIOUS INDUSTRIES. Adhesives and sealants. .

14.2

Aerospace. 852

14.3

Asphalt compounding. . 855

14.4 14.4.1

Biotechnology. . 856 Organic solvents in microbial production processes. . 856

14.4.1.1 14.4.1.2 14.4.1.3 14.4.1.4 14.4.2

Introduction. Toxicity of organic solvents. Solvent-tolerant bacteria. . Biotransformation using solvent-tolerant microorganisms. Solvent-resistant microorganisms. .

. .

. .

. .

856 859 862 863 865

14.4.2.1 14.4.2.2 14.4.2.2.1 14.4.2.2.2 14.4.2.3 14.4.2.3.1 14.4.2.3.2 14.4.2.4 14.4.2.4.1 14.4.3

Introduction. avast internet security free - Crack Key For U.. Toxicity of solvents for microorganisms. . Spectrum of microorganisms and solvents. . Mechanisms of solvent toxicity for microorganisms. Adaption of microorganisms to solvents - solvent-resistant microorganisms Spectrum of solvent-resistant microorganisms. . Adaption mechanisms of microorganisms to solvents. Solvents and microorganisms in the environment and industry - examples. Examples. . Choice of solvent for enzymatic reaction in organic solvent. . .

. .

. .

865 865 865 866 867 867 868 869 869 872

GEORGE WYPYCH

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. . .

. .

841 842 842 844 844 844 845 846 847 847

GEORGE WYPYCH GEORGE WYPYCH

MICHIAKI MATSUMOTO, SONJA ISKEN, JAN A. M. DE BONT

TILMAN HAHN, KONRAD BOTZENHART

TSUNEO YAMANE

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Table of contents 14.4.3.1 14.4.3.2 14.4.3.3

xi

14.4.3.4 14.4.3.5 14.5

Introduction. Classification of organic solvents. . Influence of solvent parameters on nature of enzymatic reactions in organic media. Properties of enzymes affected by organic solvents. Concluding remarks. Coil coating. .

14.6

Cosmetics and personal care products. . 881

14.7

Dry cleaning - treatment of textiles in solvents. 883

14.7.1 14.7.1.1 14.7.1.2 14.7.1.3 14.7.1.4 14.7.1.5 14.7.1.6 14.7.1.7 14.7.2 14.7.2.1 14.7.2.2 14.7.2.3 14.7.3 14.7.3.1 14.7.3.2 14.7.3.3 14.8

Dry cleaning. . History of dry cleaning. . Basis of dry cleaning. . Behavior of textiles in solvents and water. Removal of soiling in dry cleaning. . Activity of detergents in dry cleaning. . Dry cleaning processes. . Recycling of solvents in dry cleaning. . Spotting. . Spotting in dry cleaning. Spotting agents. . Spotting procedure. Textile finishing. Waterproofing. . Milling. . Antistatic finishing. Electronic industry - CFC-free alternatives for cleaning in electronic industry.

883 883 884 885 886 887 888 890 891 891 891 892 893 893 893 893 894

14.8.1 14.8.2 14.8.2.1 14.8.2.1.1 14.8.2.1.2 14.8.2.1.3 14.8.2.1.4

Cleaning requirements in the electronic industry. Available alternatives. . Water based systems; advantages and disadvantages. . Cleaning with DI - water. Cleaning with alkaline water-based media. Aqueous-based cleaning agents containing water soluble organic components. Water-based cleaning agents based on MPC® Technology (MPC = Micro Phase Cleaning). take command linux.. Advantages and disadvantages of aqueous cleaning media. . Semi-aqueous cleaners based on halogen-free solvents, advantages and disadvantages. . Water insoluble cleaning fluids. Water-soluble, water-based cleaning agents. . Comparison of the advantages (+) and disadvantages (-) of semi-aqueous cleaning fluids. . Other solvent based cleaning systems. . Cleaning of tools and auxiliaries. Cleaning substrates and contamination. Compatibility of stencil and cleaning agent. . Different cleaning media. Comparison of manual cleaning vs. automated cleaning. Cleaning equipment for stencil cleaning applications. . Stencil cleaning in screen printing machines. . Summary. Cleaning agents and process technology available for cleaning PCB. . Flux remove and aqueous process. The limits of a no-clean process. .

894 896 897 897 898 898

14.8.2.1.5 14.8.2.2 14.8.2.2.1 14.8.2.2.2 14.8.2.2.3 14.8.2.3 14.8.3 14.8.3.1 14.8.3.2 14.8.3.3 14.8.3.4 14.8.3.5 14.8.3.6 14.8.3.7 14.8.4 14.8.4.1 14.8.4.1.1

GEORGE WYPYCH

. . 872. . 872. . .

. . .

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. . .

873 875 879 880

GEORGE WYPYCH

KASPAR D. HASENCLEVER

MARTIN HANEK, NORBERT LÖW, ANDREAS MÜHLBAUER

899 899 900 901 901 901 902 904 904 905 906 908 909 911 911 911 911 911

xii

Handbook of Solvents

14.8.4.1.2 14.8.4.1.3 14.8.4.1.4 14.8.4.2 14.8.4.2.1

Different cleaning media and cleaning processes. Semi-aqueous cleaning. . Aqueous cleaning in spray in air cleaning equipment. . Flux removal from printed circuit boards - water-free cleaning processes. . Water-free cleaning processes using HFE (hydrofluoroethers) in combination with a cosolvent. 14.8.4.2.2 Water-free cleaning processes in closed, one-chamber vapor defluxing systems 14.8.5 Criteria for assessment and evaluation of cleaning results. 14.8.6 Cost comparison of different cleaning processes. 14.9 Fabricated metal products. 14.10 14.10.1 14.10.2 14.10.2.1 14.10.2.1.1 14.10.2.1.2 14.10.2.1.3 14.10.2.2 14.10.2.2.1 14.10.2.2.2 14.10.2.2.3 14.10.2.2.4

GEORGE WYPYCH

912 913 913 914 915 916 917 919 920

Food industry - solvents for extracting vegetable oils. . 923 PHILLIP J. WAKELYN, PETER J. WAN

Introduction. . Regulatory concerns. . Workplace regulations. . Air Contaminants Standard (29 CFR 1910.1000). Hazard Communication Standard (HCS) (29 CFR 1910.1200). Process Safety Management (PSM) Standard (29 CFR 1910.119). . Environmental regulations. Clean Air Act (CAA; 42 U.S. Code 7401 et seq.). Clean Water Act (CWA; 33 U.S. Code 1251 et seq.). . Resource Conservation and Recovery Act (RCRA; 42 U.S.Code 6901 et seq.). Emergency Planning and Community Right-to-Know Act (EPCRA; 42 U.S. Code 11001 et seq.). . 14.10.2.2.5 Toxic Substances Control Act (TSCA; 15 U.S. Code 2601 et seq.). . 14.10.2.3 Food safety. 14.10.3 The solvent extraction process. . 14.10.3.1 Preparation for extraction. 14.10.3.2 Oil extraction. . 14.10.3.3 Processing crude oil. . 14.10.4 Review of solvents studied for extraction efficiency. . 14.10.4.1 Hydrocarbon solvents. . 14.10.4.1.1 Nomenclature, structure, composition and properties of hydrocarbons. 14.10.4.1.2 Performance of selected hydrocarbon solvents. 14.10.5 Future trends. Express VPN 10.9.3 Crack+ Keygen With Activation Code [2021].. 14.11 Ground transportation. Altium Designer 20.2.6 Build 244 Crack.. GEORGE WYPYCH

923 924 925 925 926 927 927 929 932 932 933 933 934 935 936 938 938 940 941 942 942 946 950

14.12

Inorganic chemical industry. . 950

14.13

Iron and steel industry. . 951

14.14

Lumber and wood products - Wood preservation treatment: significance of solvents. 953

14.14.1 14.14.2 14.14.2.1 14.14.2.2 14.15

General aspects. Role of solvents. . Occurrence. . Technical and environmental aspects Medical applications. .

14.16

Metal casting. . 957

14.17

Motor vehicle assembly. 958

14.18

Organic chemical industry. 962

GEORGE WYPYCH GEORGE WYPYCH

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

GEORGE WYPYCH

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953 954 954 955 955

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

Table of contents

xiii

14.19 14.19.1

Paints and coatings. 963 Architectural surface coatings and solvents. . 963

14.19.1.1 14.19.1.2 14.19.2

General aspects. . 963 Technical aspects and properties of coating materials. . 963 Recent advances in coalescing solvents for waterborne coatings. 969

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

DAVID RANDALL

14.19.2.1 Introduction. . 14.19.2.2 Water based coatings. . 14.19.2.3 Emulsion polymers. 14.19.2.4 Role of a coalescing solvent. . 14.19.2.5 Properties of coalescing agents. 14.19.2.5.1 Hydrolytic stability. 14.19.2.5.2 Water solubility. 14.19.2.5.3 Freezing point. . 14.19.2.5.4 Evaporation rate. 14.19.2.5.5 Odor. . 14.19.2.5.6 Color. . 14.19.2.5.7 Coalescing efficiency. . 14.19.2.5.8 Incorporation. . 14.19.2.5.9 Improvement of physical properties. . 14.19.2.5.10 Biodegradability. 14.19.2.5.11 Safety. . 14.19.2.6 Comparison of coalescing solvents. . 14.19.2.7 Recent advances in diester coalescing solvents. 14.19.2.8 Appendix - Classification of coalescing solvents 14.20 Petroleum refining industry. . 14.21 14.21.1 14.21.1.1 14.21.1.2 14.21.1.2.1 14.21.1.2.2 14.21.1.3

GEORGE WYPYCH

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969 970 970 971 972 972 972 972 972 972 973 973 973 973 973 973 973 974 975 975

Pharmaceutical industry. 977 Use of solvents in the manufacture of drug substances (DS) and drug products (DP). . 977 MICHEL BAUER, CHRISTINE BARTHÉLÉMY

Introduction. Where are solvents used in the manufacture of pharmaceutical drugs?. . Intermediates of synthesis, DS and excipients. Drug products. Impacts of the nature of solvents and their quality on the physicochemical characteristics of raw materials and DP. . 14.21.1.3.1 Raw materials (intermediates, DS, excipients). 14.21.1.3.2 Drug product. 14.21.1.3.3 Conclusions. . 14.21.1.4 Setting specifications for solvents. . 14.21.1.4.1 Solvents used for the raw material manufacture. . 14.21.1.4.2 Solvents used for the DP manufacture. 14.21.1.5 Quality of solvents and analysis. . 14.21.1.5.1 Quality of solvents used in spectroscopy. . 14.21.1.5.2 Quality of solvents used in chromatography. 14.21.1.5.3 Quality of solvents used in titrimetry. 14.21.1.6 Conclusions. 14.21.2 Predicting cosolvency for pharmaceutical and environmental applications .

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. . .

977 979 979 984

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. .

985 985 988 989 990 990 991 991 991 993 996 996 997

14.21.2.1 14.21.2.2 14.21.2.3 14.21.2.4 14.21.2.5 14.21.2.6

. .

. .

997 998 1000 1001 1003 1007

AN LI

Introduction. . Applications of cosolvency in pharmaceutical sciences and industry. . Applications of cosolvency in environmental sciences and engineering. Experimental observations. Predicting cosolvency in homogeneous liquid systems. Predicting cosolvency in non-ideal liquid mixtures. . .

. .

. .

xiv

Handbook of Solvents

14.21.2.7 14.22

Summary. 1013 Polymers and man-made fibers. 1016

14.23

Printing industry. 1020

14.24

Pulp and paper. . 1023

14.25

Rubber and plastics. 1025

14.26

Use of solvents in the shipbuilding and ship repair industry. . 1026

14.26.1 14.26.2 14.26.3 14.26.4 14.26.4.1 14.26.4.2 14.26.4.3 14.26.5 14.26.6 14.26.7 14.26.8 14.26.9 14.26.10 14.27

Introduction. Shipbuilding and ship repair operations. . Coating operations. . Cleaning operations using organic solvents. Surface preparation and initial corrosion protection. Cleaning operations after coatings are applied. Maintenance cleaning of equipment items and components. Marine coatings. . Thinning of marine coatings. Solvent emissions. . Solvent waste. Reducing solvent usage, emissions, and waste. . Regulations and guidelines for cleaning solvents. . Stone, clay, glass, and concrete. . .

14.28

Textile industry. . 1041

14.29

Transportation equipment cleaning. . 1042

14.30

Water transportation. . 1042

14.31

Wood furniture. . 1043

14.32 15 15.1

Summary. 1045 METHODS OF SOLVENT DETECTION AND TESTING. 1053 Standard methods of solvent analysis. . 1053

15.1.1 15.1.2 15.1.3 15.1.4 15.1.5 15.1.6 15.1.7 15.1.8 15.1.9 15.1.10 15.1.11 15.1.12 15.1.13 15.1.14 15.1.15 15.1.16 15.1.17 15.1.18 15.1.19

Alkalinity and acidity. Autoignition temperature. Biodegradation potential. Boiling point. . Bromine index. Calorific value. Cleaning solvents. Color. . Corrosion (effect of solvents). Density. Dilution ratio. . Dissolving and extraction. . Electric properties. . Environmental stress crazing. . Evaporation rate. Flammability limits. . Flash point. . Freezing point. Free halogens in halogenated solvents .

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

MOHAMED SERAGELDIN, DAVE REEVES

GEORGE WYPYCH

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1026 1026 1026 1027 1027 1028 1031 1031 1032 1033 1035 1036 1037 1039

GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH GEORGE WYPYCH

GEORGE WYPYCH

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1053 1054 1054 1055 1055 1056 1056 1056 1057 1057 1057 1058 1058 1059 1059 1059 1060 1061 1061

Table of contents

xv

15.1.20 15.1.21 15.1.22 15.1.23 15.1.24 15.1.25 15.1.26 15.1.27 15.1.28 15.1.29 15.1.30 15.1.31 15.1.32 15.1.33 15.1.34 15.1.35 15.2 15.2.1

Gas chromatography. Labeling. . Odor. Paints standards related to solvents. pH. Purity. Refractive index. . Residual solvents. . Solubility. . Solvent partitioning in soils. Solvent extraction. Specifications. . Sustained burning. Vapor pressure. . Viscosity. . Volatile organic compound content, VOC. Special methods of solvent analysis. Use of breath monitoring to assess exposures to volatile organic solvents

. .

. .

. .

1061 1062 1062 1063 1063 1063 1066 1066 1066 1066 1067 1067 1067 1068 1068 1069 1078 1078

15.2.1.1 15.2.1.2 15.2.1.3 15.2.1.3.1 15.2.1.3.2 15.2.1.3.3 15.2.1.4 15.2.1.5 15.2.1.6 15.2.1.7 15.2.2

Principles of breath monitoring. Types of samples used for biological monitoring Fundamentals of respiratory physiology. Ventilation. Partition coefficients. . Gas exchange. . Types of exhaled air samples. . Breath sampling methodology. . When is breath monitoring appropriate?. Examples of breath monitoring. A simple test to determine toxicity using bacteria

. . .

. . .

. . .

1078 1080 1080 1081 1081 1082 1083 1084 1087 1088 1095

15.2.2.1 15.2.2.2 15.2.2.3 15.2.2.4 15.2.2.5 15.2.2.6 15.2.2.7 15.2.2.8 15.2.2.9 15.2.2.10 15.2.3

Introduction. Toxicity defined. . An alternative. Chemicals tested. . Comparisons with other tests. Toxic herbicides. . Toxicity of divalent cations. Toxicity of organics in the presence of EDTA. Mechanism for reduction of the dye. Summary. . Description of an innovative GC method to assess the influence of crystal texture and drying conditions on residual solvent content in pharmaceutical products. . .

. .

. .

1095 1095 1097 1099 1103 1107 1108 1108 1110 1111

MYRTO PETREAS

JAMES L. BOTSFORD

CHRISTINE BARTHÉLÉMY, MICHEL BAUER

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. . 1113

15.2.3.1 15.2.3.2 15.2.3.2.1 15.2.3.2.2 15.2.3.2.3 16 16.1

Description of the RS determination method. Application: Influence of crystal texture and drying conditions on RS content First example: monocrystalline particles of paracetamol. . Second example: polycrystalline particles of meprobamate and ibuprofen. . Third example: polycrystalline particles of paracetamol. . RESIDUAL SOLVENTS IN PRODUCTS. Residual solvents in various products. .

16.2

Residual solvents in pharmaceutical substances. 1129

16.2.1 16.2.2

Introduction. . 1129 Why should we look for RS?. . 1129

GEORGE WYPYCH

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

. . .

1113 1114 1116 1119 1122 1125 1125

xvi 16.2.2.1 16.2.2.2

Handbook of Solvents Modifying the acceptability of the drug product. . Modifying the physico-chemical properties of drug substances (DS) and drug products (DP). . Implications of possible drug/container interactions. As a tool for forensic applications. . As a source of toxicity. General points. Brief overview of the toxicology of solvents. How to identify and control RS in pharmaceutical substances?. . Loss of weight. Miscellaneous methods. . Gas chromatography (GC). . General points. Review of methods. . Official GC methods for RS determination. How to set specifications? Examination of the ICH guidelines for residual solvents. Introduction. Classification of residual solvents by risk assessment. Definition of PDE. Method for establishing exposure limits. Limits for residual solvents. Analytical procedures. Conclusions regarding the ICH guideline. . Conclusions. ENVIRONMENTAL IMPACT OF SOLVENTS. The environmental fate and movement of organic solvents in water, soil, and air. . .

. . 1149

17.1.1 17.1.2 17.1.2.1 17.1.2.2 17.1.2.3 17.1.2.4 17.1.3 17.1.3.1 17.1.3.2 17.1.3.3 17.1.4 17.1.4.1 17.1.4.2 17.1.5 17.1.5.1 17.1.5.2 17.1.5.3 17.1.6 17.1.6.1 17.1.6.2 17.1.6.3 17.1.7 17.2

Introduction. . Water. . Solubility. Volatilization. . Degradation. . Adsorption. . Soil. . Volatilization. . Adsorption. . Degradation. . Air. . Degradation. . Atmospheric residence time. . The 31 solvents in water. Solubility. Volatilization from water. . Degradation in water. . Soil. . Volatilization. . Adsorption. . Degradation. . Air. . Fate-based management of organic solvent-containing wastes

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1149 1150 1150 1150 1151 1151 1151 1151 1152 1153 1153 1153 1154 1154 1154 1155 1155 1157 1157 1159 1160 1161 1162

17.2.1 17.2.1.1 17.2.1.2 17.2.1.3 17.2.1.4

Introduction. . The waste disposal site. The advection-dispersion model and the required input Maximum permissible concentrations. Distribution of organic compounds in leachate. . .

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1162 1163 1164 1164 1164

16.2.2.3 16.2.2.4 16.2.2.5 16.2.2.5.1 16.2.2.5.2 16.2.3 16.2.3.1 16.2.3.2 16.2.3.3 16.2.3.3.1 16.2.3.3.2 16.2.3.3.3 16.2.4 16.2.4.1 16.2.4.2 16.2.4.3 16.2.4.4 16.2.4.5 16.2.4.6 16.2.5 17 17.1

WILLIAM R. ROY

WILLIAM R. ROY

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. . 1129. .

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1130 1131 1131 1131 1131 1132 1133 1133 1133 1134 1134 1135 1139

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1140 1143 1143 1143 1143 1145 1145 1146 1149

Table of contents

xvii

17.2.2 17.2.3 17.3

Movement of solvents in groundwater. . 1166 Mass limitations. 1167 Environmental fate and ecotoxicological effects of glycol ethers. 1169

17.3.1 17.3.2 17.3.3 17.3.4 17.3.4.1 17.3.4.2 17.3.5 17.4

Introduction. . Occurrence. . Environmental behavior. Ecotoxicity. . Survival and growth. . Reproduction and development. Conclusion. . Organic solvent impacts on tropospheric air pollution .

. . .

. . .

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. . .

1169 1170 1171 1175 1175 1185 1187 1188

17.4.1 17.4.2 17.4.2.1 17.4.2.2 17.4.2.3 17.4.2.3.1 17.4.2.3.2 17.4.2.3 17.4.2.4 17.4.3 17.4.3.1 17.4.3.2 17.4.3.3 17.4.3.3.1 17.4.4 17.4.5 18

Sources and impacts of volatile solvents. . Modes and scales of impact. Direct exposure. . Formation of secondary compounds. Spatial scales of secondary effects. Global impacts. . Stratospheric ozone depletion. . Global climate forcing. . Urban and regional scales. Tropospheric ozone. Effects. . Tropospheric photochemistry and ozone formation. Assessing solvent impacts on ozone and VOC reactivity. Quantification of solvent emissions on ozone formation. Regulatory approaches to ozone control and solvents. . Summary. . CONCENTRATION OF SOLVENTS IN VARIOUS INDUSTRIAL ENVIRONMENTS. Measurement and estimation of solvents emission and odor. . .

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. . .

. . .

1188 1189 1189 1190 1190 1190 1191 1191 1192 1192 1192 1193 1195 1196 1198 1299

Definition “solvent” and “volatile organic compounds” (VOC). . Review of sources of solvent emissions. . Causes for emissions. Emissions of VOCs from varnishes and paints. . VOC emissions from emulsion paints. . Measuring of VOC-content in paints and varnishes. Definition of low-emissive coating materials. . Determination of the VOC content according to ASTM D 3960-1. Determination of the VOC content according to ISO/DIS 11 890/1 and 2 VOC content > 15%. VOC content > 0.1 and < 15 %. . Determination of VOC-content in water-thinnable emulsion paints (in-can VOC). Measurement of solvent emissions in industrial plants. . Plant requirements. The determination of the total carbon content in mg C/Nm³. . Flame ionization detector (FID). . Silica gel approach. Qualitative and quantitative assessment of individual components in the exhaust-gas. Indicator tubes. . Quantitative solvent determination in exhaust gas of plants by means of gas-chromatography. “Odor” definition. .

. . .

. . .

. . .

1201 1203 1203 1203 1205 1205 1205 1205 1206 1206 1208

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. .

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1208 1209 1209 1214 1214 1214

18.1 18.1.1 18.1.2 18.1.2.1 18.1.2.2 18.1.2.3 18.1.3 18.1.3.1 18.1.3.2 18.1.3.3 18.1.3.3.1 18.1.3.3.2 18.1.3.4 18.1.4 18.1.4.1 18.1.4.2 18.1.4.2.1 18.1.4.2.2 18.1.4.3 18.1.4.3.1 18.1.4.3.2 18.1.5

JAMES DEVILLERS, AURÉLIE CHEZEAU, ANDRÉ CICOLELLA, ERIC THYBAUD

MICHELLE BERGIN, ARMISTEAD RUSSELL

MARGOT SCHEITHAUER

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. . 1215. . 1215. . 1215. . 1219

xviii 18.1.6 18.1.6.1 18.1.6.2 18.1.6.3 18.1.6.4

Handbook of Solvents. . .

18.2

Measurement of odor in materials and industrial plants. . Introduction. Odor determination by means of the “electronic nose”. . Odor determination by means of the olfactometer. Example for odor determination for selected materials: Determination of odorant concentration in varnished furniture surfaces. . Example of odor determination in industrial plants: Odor measurement in an industrial varnishing plant. . Prediction of organic solvents emission during technological processes .

18.2.1 18.2.2 18.2.3 18.2.4 18.2.5 18.2.6 18.2.7 18.2.7.1 18.2.7.2 18.2.7.3 18.2.7.4 18.2.8 18.2.9 18.3

Introduction. Methods of degreasing. . Solvents. . Identification of the emitted compounds. . Emission of organic solvents during technological processes. . Verification of the method. Relationships between emission and technological parameters. . Laboratory test stand. The influence of temperature on emission. The influence of air velocity on emission. The relationship between the mass of solvent on wet parts and emissions Emission of solvents. Verification in industrial conditions. Indoor air pollution by solvents contained in paints and varnishes. . .

. .

. .

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1227 1227 1228 1228 1228 1230 1231 1231 1231 1232 1232 1232 1232 1234

18.3.1 18.3.2 18.3.2.1 18.3.2.2 18.3.3 18.3.3.1 18.3.3.2 18.3.4 18.3.4.1 18.3.4.2 18.3.4.2.1 18.3.4.2.2 18.3.4.2.3 18.3.4.2.4 18.3.4.2.5 18.3.4.2.6 18.3.4.2.7 18.3.5 18.3.5.1 18.3.5.1.1 18.3.5.1.2 18.3.5.2 18.3.5.2.1 18.3.5.2.2 18.4

Composition - solvents in paints and varnishes. Theoretical aspects Occurrence of solvents in paints and varnishes. . Solvents in products. Paints and varnishes. Emission of solvents. Emission. . Immission. . Effects on health of solvents from paints and varnishes. . Exposure. . Health effects. Toxic responses of skin and mucose membranes. . Neurological disorders. Carcinogenic effects. Respiratory effects. . Toxic responses of blood. . Toxic responses of the reproductive system. Toxic responses of other organ systems. . Methods for the examination of solvents in paints and varnishes. . Environmental monitoring. . Solvents in products. Emission of solvents. Biological monitoring of solvents in human body fluids. . Solvents and metabolites in human body fluids and tissues. Biomarkers. . Solvent uses with exposure risks. . .

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1234 1235 1235 1237 1240 1240 1242 1243 1243 1243 1243 1244 1245 1246 1247 1247 1247 1248 1248 1248 1248 1248 1248 1248 1251

18.4.1 18.4.2 18.4.3 18.4.4 18.4.5 18.4.6

Introduction. . Exposure assessment. . Production of paints and printing inks. Painting. Printing. Degreasing, press cleaning and paint removal .

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1251 1252 1255 1256 1257 1258

18.1.6.5

KRZYSZTOF M. BENCZEK, JOANNA KURPIEWSKA

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

pentti kalliokoski, kai savolinen

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1222 1222 1222 1223

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Table of contents

xix

18.4.7 18.4.8 18.4.9 18.4.10 18.4.11 19

Dry cleaning. Reinforced plastics industry Gluing. . Other. Summary. . REGULATIONS. .

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1260 1261 1262 1262 1263 1267

19.1 19.2 19.2.1 19.2.1.1 19.2.1.2

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1267 1282 1282 1282

19.2.1.3 19.2.1.4 19.2.1.5 19.3 19.3.1 19.3.1.1 19.3.1.2 19.3.1.3 19.3.2 19.3.2.1 19.3.2.2 19.4 19.4.1 19.4.1.1 19.4.1.2 19.5 19.5.1 19.5.1.1 19.5.1.2 19.5.2 19.5.2.1 19.5.2.2 19.6 19.6.1 19.6.1.1 19.6.1.2 19.6.1.3 19.7 19.7.1 19.7.2 19.8 19.9 19.10

Introduction. Air laws and regulations. . Clean Air Act Amendments of 1990. Background. Title I - Provisions for Attainment and Maintenance of National Ambient Air Quality Standards. . Title III - Hazardous Air Pollutants. Title V - Permits. . Title VI - Stratospheric Ozone Protection. Altium Designer 20.2.6 Build 244 Crack.. Water laws and regulations. Clean Water Act. . Background. Effluent Limitations. Permit Program. . Safe Drinking Water Act. . Background. National Primary Drinking Water Regulations. . Land laws & regulations. . Resource Conservation and Recovery Act (RCRA) filmora 9 activation lifetime - Free Activators.. . Background. RCRA, Subtitle C - Hazardous Waste. . Multimedia laws and regulations. . Pollution Prevention Act of 1990. Background. Source Reduction Provisions. Toxic Substances Control Act. . Background. Controlling toxic substances. Occupational laws and regulations. Occupational Safety and Health Act. Background. Air contaminants exposure limits. Hazard Communication Standard. International perspective. . Canada. . European Union. . Tools and resources for solvents. . Summary. . Regulations in Europe. . .

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1284 1288 1292 1292 1293 1293 1293 1293 1294 1294 1294 1295 1295 1295 1295 1296 1297 1297 1297 1298 1300 1300 1300 1301 1301 1301 1301 1302 1302 1303 1303 1304 1306 1311

19.10.1 19.10.2 20 20.1

EEC regulations. . German regulations. TOXIC EFFECTS OF SOLVENT EXPOSURE Toxicokinetics, toxicodynamics, and toxicology .

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1311 1312 1315 1315

20.1.1 20.1.1.1 20.1.1.2 20.1.1.2.1 20.1.1.2.2

Toxicokinetics and toxicodynamics Exposure. . Uptake. . Inhalation. . Dermal uptake. . .

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1315 1315 1315 1316 1316

CARLOS M. NU~ NEZ

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TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

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xx 20.1.1.2 20.1.1.3 20.1.2 20.1.2.1 20.1.2.2 20.1.2.3 20.1.2.4 20.1.2.5 20.1.2.6 20.1.3 20.2

Handbook of Solvents Metabolism, distribution, excretion. . Modeling of toxicokinetics and modifying factors. . Toxicology. proshow producer 2020 full crack.. General effects. Specific non-immunological effects. . Immunological effects. Toxic effects of solvents on other organisms. Carcinogenicity. Risk assessment. Conclusions. . Cognitive and psychosocial outcome of chronic occupational solvent neurotoxicity. .

. 1326

20.2.1 20.2.2 20.2.3 20.2.4 20.2.5 20.2.6 20.2.7 20.3

Introduction. Acute symptoms of solvent neurotoxicity. Categorization of OSN. . Assessment of OSN. Do the symptoms of Type 2 OSN resolve?. Individual differences in susceptibility to OSN. . Psychosocial consequences of OSN, and rehabilitation. . Pregnancy outcome following maternal organic solvent exposure

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20.3.1 20.3.2 20.3.3

20.3.6

Introduction. . Animal studies. . Pregnancy outcome following maternal organic solvent exposure: a meta-analysis of epidemiologic studies. Pregnancy outcome following gestational exposure to organic solvents: a prospective controlled study. . A proactive approach for the evaluation of fetal safety in chemical industries. Overall conclusion. . .

20.4

Industrial solvents and kidney disease. . VSO Downloader Ultimate Crack.. . 1355

20.4.1 20.4.2 20.4.3 20.4.4 20.4.5 20.4.6 20.5

Introduction. . Experimental animal studies. . Case reports. . Case control studies. . Epidemiological assessment. . Mechanism. Lymphohematopoietic study of workers exposed to benzene including multiple myeloma, lymphoma and chronic lymphatic leukemia. . .

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20.5.1 20.5.2 20.5.3 20.5.4 20.5.5 20.5.6 20.5.7 20.5.8 20.5.9 20.5.10 20.6

Introduction. Routes of exposure. . Hematopoietic effects of benzene. . Carcinogenic effects of benzene. . Risk assessment estimates. . Levels of exposure. . Cell types: hematolymphoproliferative effects of benzene. Epidemiological studies. Malware Hunter 1.77.0.663 keygen - Crack Key For U.. . Solvents and benzene. Genetic fingerprint theory. . Chromosomal aberrations and sister chromatoid exchanges .

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20.7

Hepatotoxicity. . 1379

20.3.4 20.3.5

JENNI A OGDEN

KRISTEN I. MCMARTIN, GIDEON KOREN

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NACHMAN BRAUTBAR

NACHMAN BRAUTBAR

NACHMAN BRAUTBAR NACHMAN BRAUTBAR

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1317 1317 1318 1318 1318 1319 1320 1320 1323 1323

1326 1327 1327 1328 1330 1331 1331 1333

. 1333. 1334. 1338. 1345. 1347. 1353

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1355 1356 1356 1357 1360 1361

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1363 1363 1365 1365 1367 1367 1369 1369 1370 1372 1375

Table of contents

xxi

20.7.1 20.7.2 20.7.3 20.7.4 20.7.5 20.7.6 20.7.7 20.7.8 20.7.9 20.7.10 20.7.11 20.8

Introduction. Individual variability and hepatotoxicity of solvents Non-halogenated solvents. . Solvent mixtures. . Trichloroethylene. . Tetrachloroethylene. Toluene. Dichloromethane. . Stoddard solvent. . 1,1,1-Trichloroethane. Summary. . Solvents and the liver. . .

20.8.1 20.8.1.1 20.8.1.2

Normal anatomic and physiologic function of the liver. Factors influencing solvent hepatotoxicity. . Microscopic, biochemical and clinical findings associated with liver injury due to solvents. . Hepatotoxicity associated with specific solvents. . Haloalkanes and haloalkenes. . Carbon tetrachloride. . Chloroform. . Dichloromethane. Trichloroethanes. 1,1,2,2-Tetrachloroethane. . Tetrachloroethylene and trichloroethylene. . Other halogenated hydrocarbons. Styrene and aromatic hydrocarbons. . N-substituted amides. . Nitroparaffins. gom player review - Crack Key For U.. . Other solvents and mixed solvents. . Toxicity of environmental solvent exposure for brain, lung and heart.

20.8.2 20.8.2.1 20.8.2.2 20.8.2.3 20.8.2.4 20.8.2.5 20.8.2.6 20.8.2.7 20.8.2.8 20.8.2.9 20.8.2.10 20.8.2.11 20.8.2.12 20.9 21

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DAVID K. BONAUTO, C. ANDREW BRODKIN, WILLIAM O. ROBERTSON

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KAYE H. KILBURN

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1379 1384 1385 1386 1387 1388 1388 1389 1389 1389 1390 1393

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1394 1395 1396 1396 1397 1398 1398 1398 1399 1399 1399 1400 1400 1401 1404

21.1

SUBSTITUTION OF SOLVENTS BY SAFER PRODUCTS AND PROCESSES. . 1419 Supercritical solvents. . 1419

21.1.1 21.1.1.1 21.1.1.2 21.1.1.3 21.1.2 21.1.2.1 21.1.2.1.1 21.1.2.1.2 21.1.2.1.3 21.1.2.2 21.1.2.2.1 21.1.2.2.2 21.1.2.2.3 21.1.2.2.4 21.1.2.3 21.1.2.4 21.1.2.5 21.1.2.6 21.1.2.7 21.1.3 21.1.3.1

Introduction. . A promising path to green chemistry. Unique and tunable physico-chemical properties. . Sustainable applications in many different areas. . Fundamentals. . Phase behavior with supercritical solvents. . Experimental methods. Computational aspects. Modeling. Transport properties of supercritical solvents. Viscosity. Diffusivity. . Thermal conductivity. . Surface tension. Entrainer (co-solvent effects) of supercritical solvents Reaction rate implication in supercritical solvents. . Sorption behavior of supercritical solvents. . Swelling with supercritical solvents. . Surfactants and micro-emulsions. . Separation with supercritical solvents. Leaching - generic application. .

AYDIN K. SUNOL, SERMIN G. SUNOL

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1419 1422 1422 1422 1423 1423 1426 1428 1429 1431 1431 1432 1433 1435 1435 1436 1437 1437 1438 1438 1441

xxii

Handbook of Solvents

21.1.3.2 21.1.3.3 21.1.3.4 21.1.4 21.1.4.1 21.1.4.1.1 21.1.4.1.2 21.1.4.1.3 21.1.4.2 21.1.4.2.1 21.1.4.2.2 21.1.4.3 21.1.4.4 21.1.4.5 21.1.4.6 21.1.4.7 21.1.4.8 21.1.4.9 21.1.4.10 21.1.4.11 21.1.4.12 21.2

Extraction - generic applications. . Crystallization - generic applications. . Sorption - generic applications. . Reactions in supercritical solvents. Homogenous reactions in supercritical solvents - examples. Homogeneous reactions catalyzed by organometallic compounds Homogeneous reactions of supercritical water. . Homogeneous non-catalytic reactions in supercritical solvents. . Heterogeneous reactions in supercritical solvents - examples. . Heterogeneous catalytic reactions in supercritical solvents. Heterogeneous non-catalytic reactions in supercritical solvents. . Biochemical reactions - examples. Polymerization reactions - examples. Materials processing with supercritical solvents. . Particle synthesis - generic application. . Encapsulation - generic application. Spraying and coating - generic application. Extrusion - generic application. . Perfusion (impregnation) - generic application. . Parts cleaning - generic application. Drying - generic application. Ionic liquids. . .

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1442 1443 1443 1444 1445 1446 1447 1448 1448 1449 1450 1451 1451 1452 1453 1454 1454 1454 1454 1455 1455 1459

21.2.1 21.2.2 21.2.2.1 21.2.2.2 21.2.3 21.2.3.1 21.2.3.2 21.2.4 21.2.4.1 21.2.5 21.2.5.1 21.2.5.2 21.2.6 21.3

Introduction. Fundamental principles of the formation of room temperature ionic liquids Development of ionic liquids. Binary ionic liquid systems. Catalysis in ionic liquids. . Reactions involving first generation chloroaluminate(III) ionic liquids. . Reactions in neutral or second generation ionic liquids. . Electrochemical applications. Electrosynthesis. . Physical characterization. . Viscosity. . Density. Summary. . Oxide solubilities in ionic melts. . .

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1459 1461 1461 1465 1466 1467 1469 1472 1473 1473 1473 1478 1480 1484

21.3.1 21.3.1.1 21.3.1.2 21.3.2 21.3.3 21.3.3.1 21.3.3.2 21.3.3.3 21.3.3.4 21.3.4 21.3.4.1 21.3.4.2 21.3.4.3 21.3.5 21.4

Methods used for solubility estimations in ionic melts. Isothermal saturation method. Potentiometric titration method. Oxygen-containing melts. Halide melts. . The eutectic mixture KCl-LiCl (0.41:0.59). . Molten KCl-NaCl (0.50:0.50). Other chloride-based melts. . Other alkaline halides. On the possibility to predict oxide solubilities on the base of the existing data The estimation of effect of anion. The estimation of effect of melt acidity. The estimation of effect of temperature. Conclusions. . Alternative cleaning technologies/drycleaning installations. .

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1484 1485 1486 1487 1487 1487 1488 1491 1493 1494 1494 1494 1495 1495 1497

21.4.1 21.4.1.1 21.4.1.2

Drycleaning with liquid carbon dioxide (LCD). 1497 Basics. . 1497 State of the art. . 1498

D.W. ROONEY, K.R. SEDDON

VICTOR CHERGINETS

KASPAR D. HASENCLEVER

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Table of contents

xxiii

21.4.1.3 21.4.1.4 21.4.1.5 21.4.2 21.4.2.1 21.4.2.2 21.4.2.3 21.4.2.4 21.4.3 22 22.1

Process technology. . Risks. . Competition. . Wet cleaning. . Kreussler textile cleaning system. . Possibilities. . Limitations. . Adapting to working practices. Future. . SOLVENT RECYCLING, REMOVAL, AND DEGRADATION. Absorptive solvent recovery. .

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1498 1499 1500 1501 1501 1503 1504 1504 1505 1507 1507

22.1.1 22.1.2 22.1.2.1 22.1.2.2 22.1.2.3 22.1.2.4 22.1.3 22.1.3.1 22.1.3.2 22.1.3.3 22.1.4 22.1.4.1 22.1.4.2 22.1.4.2.1 22.1.4.2.2 22.1.4.2.3 22.1.4.2.4 22.1.4.3 22.1.4.3.1 22.1.4.3.2 22.1.4.3.3 22.1.4.3.4 22.1.4.3.5 22.1.4.3.6 22.1.5 22.1.5.1 22.1.5.2 22.1.5.2.1 22.1.5.2.2 22.1.5.3 22.1.5.4 22.1.5.5 22.1.5.6 22.2

Introduction. Basic principles. . Fundamentals of adsorption. Adsorption capacity. Dynamic adsorption in adsorber beds. . Regeneration of the loaded adsorbents. . Commercially available adsorbents. Activated carbon. . Molecular sieve zeolites. . Polymeric adsorbents. Adsorptive solvent recovery systems. . Basic arrangement of adsorptive solvent recovery with steam desorption. Designing solvent recovery systems. Design basis. Adsorber types. . Regeneration. Safety requirements. Special process conditions. Selection of the adsorbent. Air velocity and pressure drop. . Effects of solvent-concentration, adsorption temperature and pressure. . Influence of humidity. . Interactions between solvents and activated carbon. Activated carbon service life. Examples from different industries. Rotogravure printing shops. Packaging printing industry. Fixed bed adsorption with circulating hot gas desorption. Solvent recovery with adsorption wheels. Viscose industry. . Refrigerator recycling. . Petrochemical industry and tank farms. . Chemical industry. Solvent recovery. .

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1507 1509 1509 1510 1511 1512 1513 1513 1514 1515 1515 1515 1518 1518 1519 1521 1522 hd video converter factory pro review - Free Activators 1523 1526 1526 1528 1529 1531 1531 1531 1532 1533 1535 1535 1539 1539 1541 1543

22.2.1 22.2.2 22.2.3

Activated carbon in fluidized bed adsorption method. Application of molecular sieves. . Continuous process for air cleaning using macroporous particles as adsorption agents. . Solvent recovery from hazardous wastes. . Halogenated solvent recovery. Coating process. . Tableting process of pharmaceutical products. Energy recovery from waste solvent. Solvent treatment in a paints and coating plant. . .

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22.2.4 22.2.5 22.2.5.1 22.2.5.2 22.2.6 22.3

KLAUS-DIRK HENNING

ISAO KIMURA

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1546 1548 1549 1549 1552 1553 1555

xxiv

Handbook of Solvents DENIS KARGOL

22.4

Application of solar photocatalytic oxidation to VOC-containing airstreams. . 1559

22.4.1 22.4.2 22.4.2.1 22.4.2.2 22.4.3 22.4.3.1 22.4.3.2 22.4.4 23

Solvent degradation by photocatalytic oxidation. . PCO pilot scale systems. . Air stripper application. Paint booth application. how to convert pdf to jpg offline - Crack Key For U.. . Field test results. . Air stripper application. Paint booth application. Comparison with other treatment systems. . CONTAMINATION CLEANUP: NATURAL ATTENUATION AND ADVANCED REMEDIATION TECHNOLOGIES. . Natural attenuation of chlorinated solvents in ground water. .

23.1 23.1.1 23.1.2 23.1.2.1 23.1.2.2 23.1.2.3 23.1.2.4 23.1.2.5 23.1.2.6 23.1.2.7 23.1.2.8 23.1.3 23.1.3.1 23.1.3.1.1 23.1.3.1.2 23.1.3.2 23.1.3.2.1 23.1.3.2.2 23.1.3.2.3 23.1.4 23.1.4.1 23.1.4.2 23.1.4.3 23.1.5 23.1.5.1 23.1.5.2 23.1.5.2.1 23.1.5.2.2 23.1.5.2.3 23.1.5.2.4 23.1.6 23.1.6.1 23.1.6.2 23.1.6.2.1 23.1.6.3 23.1.6.4 23.2 23.2.1 23.2.1.1 23.2.1.2

K. A. MAGRINI, A. S. WATT, L. C. BOYD, E. J. WOLFRUM, S. A. LARSON, C. ROTH

G. C. Glatzmaier

HANADI S. RIFAI, CHARLES J. NEWELL, TODD H. WIEDEMEIER

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1559 1560 1560 1562 1564 1564 1566 1568

. . 1571. . 1571

Introduction. . Natural attenuation processes affecting chlorinated solvent plumes. . Advection. . Dispersion. . Sorption. One-dimensional advection-dispersion equation with retardation. . Dilution (recharge). . Volatilization. . Hydrolysis and dehydrohalogenation. Reduction reactions. . Biodegradation of chlorinated solvents. Halorespiration or reductive dechlorination using hydrogen. Stoichiometry of reductive dechlorination. . Chlorinated solvents that are amenable to halorespiration. . Oxidation of chlorinated solvents. Adobe Dreamweaver CC 2021 Crack With Activator Key Free Download.. . Direct aerobic oxidation of chlorinated compounds. . Aerobic cometabolism of chlorinated compounds. . Anaerobic oxidation of chlorinated compounds. Biodegradation rates for chlorinated solvents. Michaelis-Menten rates. . Altium Designer 20.2.6 Build 244 Crack. Zero-order rates. First-order rate constants. Geochemical evidence of natural bioremediation at chlorinated solvent sites. Assessing reductive dechlorination at field sites. Plume classification schemes. Type 1. Type 2. Type 3. Mixed environments. . Chlorinated solvent plumes - case studies of natural attenuation. . Plume databases. Modeling chlorinated solvent plumes. BIOCHLOR natural attenuation model. RT3D numerical model. CS case study - The Plattsburgh Air Force Base. Remediation technologies and approaches for managing sites PC HelpSoft Driver Updater 5.1.389 License key Crack Free by hydrocarbons. . BARRY J. SPARGO, JAMES G. MUELLER

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1571 1572 1572 1573 1574 1577 1577 1578 1579 1581 1581 1582 1585 1585 1586 1586 1587 1587 1588 1588 1590 1591 1599 1599 1599 1599 1600 1601 1601 1602 1602 1605 1605 1609 1611

. 1617

Introduction. . 1617 Understanding HC and CHC in the environment. 1617 Sources of HC in the environment. 1617

Table of contents 23.2.1.3 23.2.2 23.2.2.1 23.2.2.1.1 23.2.2.2 23.2.2.2.1

xxv

23.2.4 24

Sources of CHC in the environment. . In situ biotreatment. . Microbial-enhanced natural attenuation/bioremediation. Case study - Cooper River Watershed, Charleston, SC, USA. Phytoremediation. Case study - phytoremediation for CHCs in groundwater at a chemical plant in Louisiana. . In situ treatment technologies. Product recovery via GCW technology. Case study - GCW recovery of creosote, Cabot/Kopper’s Superfund Site, Gainesville, FL. Surfactant enhanced product recovery. Case study - Surfactant-aided chlorinated HC DNAPL recovery, Hill Air Force Base, Ogden, Utah. . Foam-enhanced product recovery. . Thermal desorption - Six Phase Heating. Case study - Six-Phase Heating removal of CHC at a manufacturing facility near Chicago, IL. In situ steam enhanced extraction (Dynamic Underground Stripping). In situ permeable reactive barriers (funnel and gate). Case study - CHC remediation using an in situ permeable reactive barrier at Naval Air Station Moffett Field, CA. Conclusions. . PROTECTION. . .

. 1628. 1629. 1631

24.1 24.2 24.3 25

Gloves. . Suit materials. Respiratory protection. . NEW TRENDS BASED ON PATENT LITERATURE

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1631 1633 1633 1637

25.1 25.2 25.3 25.4 25.5 25.6 25.7 25.8 25.9 25.10 25.11 25.12 25.13 25.14 25.15 25.16 25.17

New solvents. Adhesives. . Aerospace. . Agriculture. . Asphalt. Automotive applications. . Coil coating. Composites and laminates. . Cosmetics. . Cleaning. . Fibers. Furniture and wood coatings. Paper. Printing. Stone and concrete. . Wax. . Summary. . ACKNOWLEDGMENTS. INDEX. . .

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1637 1638 1640 1640 1640 1641 1641 1642 1643 1644 1645 1646 1647 1647 1648 1648 1649 1653 1657

23.2.3 23.2.3.1 23.2.3.1.1 23.2.3.2 23.2.3.2.1 23.2.3.3 23.2.3.4 23.2.3.4.1 23.2.3.5 23.2.3.6 23.2.3.6.1

GEORGE WYPYCH

GEORGE WYPYCH

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1618 1618 1618 1620 1622

. 1622. 1623. 1623. 1624. 1625. 1625. 1626. 1626. 1627. 1628. 1628

Preface Although the chemical industry can trace its roots into antiquity, it was during the industrial revolution that it started to become an actual industry and began to use the increased knowledge of chemistry as a science and technology to produce products that were needed by companion industries and consumers. These commercial efforts resulted in the synthesis of many new chemicals. Quite quickly, in these early days, previously unknown materials or materials that had been present only in low concentrations, were now in contact with people in highly concentrated forms and in large quantities. The people had little or no knowledge of the effects of these materials on their bodies and the natural biological and physical processes in the rivers and oceans, the atmosphere, and in the ground. Until the end of the nineteenth century these problems were not addressed by the chemical industry and it is only recently that the industry began to respond to public criticism and political efforts. Legal restrictions aimed at preserving the quality of life have been directed at health, safety and longevity issues and the environment. Solvents have always been mainstays of the chemical industry and because of their widespread use and their high volume of production they have been specifically targeted by legislators throughout the world. The restrictions range from total prohibition of production and use, to limits placed on vapor concentrations in the air. As with any arbitrary measures some solvents have been damned unfairly. However, there is no question that it is best to err on the side of safety if the risks are not fully understood. It is also true that solvents should be differentiated based on their individual properties. This book is intended to provide a better understanding of the principles involved in solvent selection and use. It strives to provide information that will help to identify the risks and benefits associated with specific solvents and classes of solvents. The book is intended to help the formulator select the ideal solvent, the safety coordinator to safeguard his or her coworkers, the legislator to impose appropriate and technically correct restrictions and the student to appreciate the amazing variety of properties, applications and risks associated with the more than one thousand solvents that are available today. By their very nature, handbooks are intended to provide exhaustive information on the subject. While we agree that this is the goal here, we have attempted to temper the impact of information, which may be too narrow to make decision. Many excellent books on solvents have been published in the past and most of these are referenced in this book. But of all these books none has given a comprehensive overview of all aspects of solvent use. Access to comprehensive data is an essential part of solvent evaluation and it has been a hallmark of such books to provide tables filled with data to the point at which 50 to 95% of the book is data. This approach seems to neglect a fundamental requirement of a handbook - to provide the background, explanations and clarifications that are needed to convert data to information and assist the reader in gaining the knowledge to make a decision on selecting a process or a solvent. Unfortunately, to meet the goal of providing both the data and the fundamental explanations that are needed, a book of 4,000 to 5,000 pages might be required. Even if this was possible, much of the data would fall out of date quite quickly. For example, a factor that defines solvent safety such as threshold limit

xxviii

Preface

values (TLVs) for worker exposure or some single toxicity determinants may change frequently. This book would be huge and it would have to be updated frequently to continue to claim that it is current. What we have attempted to do here is to give you a book with a comprehensive and extensive analysis of all current information on solvents then use other media to present the supporting data on individual solvents. These data are provided on a CD-ROM as a searchable database. Data are provided on more than 1140 solvents in 110 fields of data. The medium permits frequent updates. If the same data were presented in book form, more than 2,000 pages would be needed which exceeds the size of any data in handbook form offered to date. The best approach in presenting an authoritative text for such a book is to have it written by experts in their fields. This book attracted well-known experts who have written jointly 47 books and authored or coauthored hundreds of papers on their areas of expertise. The authors have made their contributions to this book in late 1999 and early 2000 providing the most current picture of the technology. Their extreme familiarity with their subjects enables them to present information in depth and detail, which is essential to the reader’s full understanding of the subject. The authors were aware of the diversity of potential readers at the outset and one of their objectives was to provide information to various disciplines expressed in a way that all would understand and which would deal with all aspects of solvent applications. We expect professionals and students from a wide range of businesses, all levels of governments and academe to be interested readers. The list includes solvent manufacturers, formulators of solvent containing products, industrial engineers, analytical chemists, government legislators and their staffs, medical professionals involved in assessing the impact on health of solvents, biologists who are evaluating the interactions of solvents with soil and water, environmental engineers, industrial hygienists who are determining protective measures against solvent exposure, civil engineers who design waste disposal sites and remediation measures, people in industries where there are processes which use solvents and require their recovery and, perhaps most important, because understanding brings improvements, those who teach and learn in our universities, colleges and schools. A growing spirit of cooperation is evident between these groups and this can be fostered by providing avenues of understanding based on sharing data and information on common problems. We hope to provide one such avenue with this book. We have tried to present a balanced picture of solvent performance by dealing not only with product performance and ease of processing but also by giving environmental and health issues full consideration. Data and information on known products and processes should be cornerstones of the understanding of a technology but there is another aspect of technology, which can lead to advances and improvements in utility, safety and in safeguarding the environment. This must come from you, the reader. It is your ideas and creative thinking that will bring these improvements. The authors have crammed their ideas into the book and we hope these will stimulate responsible and effective applications of solvents. Francis Bacon wrote, “The end of our foundation is the knowledge of causes, and the secret motion of things, and the enlarging of the bound of human Empire, to the effecting of all things possible.” Today there are few technical activities that do not employ solvents. Almost all industries, almost all consumer products, almost everything we use can, if analyzed, be shown to

Preface

xxix

contain or to have used in its processing, a solvent. Solvent elimination need never be a technical objective. Rather, we need to use our increasing understanding and knowledge to find the safest and the most effective means of meeting our goals. I would like to thank the authors for their relentless efforts to explain the difficult in an interesting way. In advance, I would like to thank the reader for choosing this book and encourage her or him to apply the knowledge to make our world a better, more livable place. George Wypych Toronto, August 3, 2000

1

Introduction Christian Reichardt

Department of Chemistry, Philipps University, Marburg, Germany

Chemical transformations can be performed in a gas, liquid, or solid phase, but, with good reasons, the majority of such reactions is carried out in the liquid phase in solution. At the macroscopic level, a liquid is the ideal medium to transport heat to and from exo- and endothermic reactions. From the molecular-microscopic point of view, solvents break the crystal lattice of solid reactants, dissolve gaseous or liquid reactants, and they may exert a considerable influence over reaction rates and the positions of chemical equilibria. Because of nonspecific and specific intermolecular forces acting between the ions or molecules of dissolved reactants, activated complexes as well as products and solvent molecules (leading to differential solvation of all solutes), the rates, equilibria, and the selectivity of chemical reactions can be strongly influenced by the solvent. Other than the fact that the liquid medium should dissolve the reactants and should be easily separated from the reaction products afterwards, the solvent can have a decisive influence on the outcome (i.e., yield and product distribution) of the chemical reaction under study. Therefore, whenever a chemist wishes to perform a certain chemical reaction, she/he has to take into account not only suitable reaction partners and their concentrations, the proper reaction vessel, the appropriate reaction temperature, and, if necessary, the selection of the right reaction catalyst but also, if the planned reaction is to be successful, the selection of an appropriate solvent or solvent mixture. Solvent effects on chemical reactivity have been studied for more than a century, beginning with the pioneering work of Berthelot and Saint Gilles1 in Paris in 1862 on esterification reactions and with that of Menschutkin2 in St. Petersburg in 1880 on the quaternization of tertiary amines by haloalkanes. At this time Menschutkin remarked that “a reaction cannot be separated from the medium in which it is performed. Experience shows that solvents exert considerable influence on reaction rates.” Today, we can suggest a striking example to reinforce his remark, the rate of the unimolecular heterolysis of 2-chloro-2-methylpropane observed in water and benzene increases by a factor of approximately1011 when the nonpolar benzene is replaced by water.3,4 The influence of solvents on the position of chemical equilibria was discovered in 1896 by Claisen5 in Aachen, Knorr6 in Jena, Wislicenus7 in Wòrzburg, and Hantzsch8 in Wòrzburg. They investigated almost simultaneous but independent of one another the keto-enol tautomerism of 1,3-dicarbonyl compounds and the nitro-isonitro tautomerism of primary and secondary

2

Christian Reichardt

aliphatic nitro compounds. With this example, the enol content of acetylacetone increases from 62 to 95 % when acetonitrile is substituted with n-hexane.3,9 The proper solvent and solvent mixture selection is not only important for chemical but also for physical processes such as recrystallization, all extraction processes, partitioning, chromatographic separations, phase-transfer catalytic reactions, etc. Of particular interest in this context is the influence of solvents on all types of light absorption processes, e.g., on UV/Vis, IR, ESR, and NMR spectra, caused by differential solvation of the ground and excited states of the absorbing species.3,12 In 1878, Kundt10 in Zòrich proposed the rule that increasing dispersion interactions between the absorbing solute and the solvent lead in general to a bathochromic shift of an UV/Vis absorption band. Later, in 1922, Hantzsch11 termed the solvent-dependence of UV/Vis absorption spectra “solvatochromism”. UV/Vis absorption of solute molecules can be influenced not only by the surrounding solvent sphere, but also by other entities in the surroundings such as solids, polymers, glasses, and surfaces. In order to emphasize this influence, the use of the more general term “perichromism” (from Greek peri = around) has been recommended.12,13 A typical, more recent, example of extraordinary solvatochromism is the intramolecular charge-transfer Vis-absorption of 2,6-diphenyl-4-(2,4,6-triphenyl-l-pyridinio)phenolate, a zwitterionic betaine dye: its corresponding absorption band is shifted from λmax = 810 nm to λmax = 453 nm (∆λ = 357 nm) when diphenyl ether is replaced by water as solvent.3,12 Such solvatochromic dyes can be used as empirical solvent polarity indicators.12 The number of solvents generally available to chemists working in research and industrial laboratories is between 250 and 3003,14 (there is an infinite number of solvent mixtures), and this number is increasing. More recently and for obvious reasons, the search for new solvents has been intensified: peroxide-forming solvents are being substituted by solvents which are more stable against oxidation (e.g., diethyl ether by t-butyl methyl ether or by formaldehyde dialkyl acetals), toxic solvents are being replaced by nontoxic ones (e.g., the cancerogenic hexamethylphosphoric triamide, HMPT, by N,N'-dimethylpropyleneurea, DMPU15) and environmentally Atlantis Word Processor 4.1.3.6 + Crack [Latest Version] Free solvents by benign ones (e.g., tetrachloromethane by perfluorohexane16). The development of modern solvents for organic syntheses is the subject of much current research.17 Amongst these modern solvents, also called “neoteric solvents” (neoteric = recent, new, modern) in contrast to the classical ones, are ionic liquids (i.e., room-temperature liquid salts such as 1-ethyl-3-methylimidazolium tetra-chloroaluminates18,19), supercritical-fluid solvents, SCF, (such as SCF carbon dioxide20,21), and perfluorinated solvents (e.g., partially or perfluorinated hydrocarbons as used in so-called “fluorous biphase catalysis reactions”, making possible mono-phase reactions and a two-phase separation of catalyst and reaction products22-24). Even plain water has found a magnificent renaissance as a solvent for organic reactions.25,26 These efforts have also recently strengthened the search for completely solvent-free reactions, thus avoiding the use of expensive, toxic, and environmentally problematic solvents.27,28 With respect to the large and still increasing number of valuable solvents useful for organic syntheses, a chemist needs, in addition to his experience and intuition, to have general rules, objective criteria, and the latest information about the solvents' physical, chemical, and toxicological properties for the selection of the proper solvent or solvent mixture for a planned reaction or a technological process. To make this often cumbersome and time-consuming task easier, this “Handbook of Solvents” with its twenty-five chapters is designed to provide a comprehensive source of information on solvents over a broad range

1 Introduction

3

of applications. It is directed not only to chemists working in research laboratories, but also to all industries using solvents for various purposes. A particular advantage is that the printed handbook is accompanied by a compact-disc (CD-ROM) containing additional solvent databases with hundred ten fields for over eleven hundred solvents. This makes large data sets easily available for quick search and retrieval and frees the book text from bulky tables, thus giving more room for a thorough description of the underlying theoretical and practical fundamental subjects. Fundamental principles governing the use of solvents (i.e., chemical structure, molecular design as well as physical and chemical properties of solvents) are given in Chapter 2. Solvent classification, methods of solvent manufacture together with properties and typical applications of various solvents are provided in Chapter 3. Chapters 4, 5 and 6 deal with all aspects of the dissolution of materials in solvents as well as with the solubility of selected systems (e.g., polymers and elastomers) and the influence of the solute's molecular structure on its solubility behavior. In particular, the valuable solubility-parameter concept is extensively treated in these chapters. All aspects of solvent transport within polymeric system and the drying of such polymeric systems, including coated films, are described in Chapter 7. The fundamentals of the interaction forces acting between ions or molecules of the solvents themselves and between solutes and solvents in solutions are presented in Chapter 8. Chapter 9 deals with the corresponding properties of solvent mixtures. Specific solute/solvent interactions, particularly Lewis acid/base interactions between electron-pair donors (EPD) and electron-pair acceptors (EPA), are reviewed in Chapter 10, together with the development of empirical scales of solvent polarity and Lewis acidity/basicity, based on suitable solvent-dependent reference processes, and their application for the treatment of solvent effects. The theory for solvent effects on electronic properties is provided in Chapter 11 and extended to solvent-dependent properties of solutes such as fluorescence spectra, ORD and CD spectra. Aggregation, swelling of polymers, their conformations, the viscosity of solutions and other solvent-related properties are treated in Chapter 12. A review concerning solvent effects on various types of chemical reactivity is given in Chapter 13, along with a discussion of the effects of solvent on free-radical polymerization and phase-transfer catalysis reactions. The second part of this handbook (Chapters 14-25) is devoted more to the industrial use of solvents. Formulating with solvents applied in a broad range of industrial areas such as biotechnology, dry cleaning, electronic industry, food industry, paints and coatings, petroleum refining industry, pharmaceutical industry, textile industry, to mention only a few, is extensively described in Chapter 14. Standard and special methods of solvent detection and solvent analysis as well as the problem of residual solvents in various products, particularly in pharmaceutical ones, are the topics of Chapters 15 and 16. At present, large-scale chemical manufacturing is facing serious solvent problems with respect to environmental concerns. National and international regulations for the proper use of hazardous solvents are becoming increasingly stringent and this requires the use of environmentally more benign but nevertheless economical liquid reaction media. This has enormously stimulated the search for such new solvent systems within the framework of so-called green chemistry. Supercritical fluids, SCF,20,21 and ionic liquids (room temperature liquid salts)18,19 have been known and have been the subject of scientific interest for a long time. It is only recently, however, that the potential benefits of these materials in solvent applications have been realized.17 This handbook includes in Chapters 17-25 all

4

Christian Reichardt

the knowledge necessary for a safe handling flashback pro 5 license key 2020 solvents in research laboratories and in large-scale manufacturing, beginning with the environmental impact of solvents on water, soil, and air in Chapter 17, followed by considerations about safe solvent concentrations and the risks of solvent exposure in various industrial environments in Chapter 18. Chapter 19 summarizes the corresponding legal regulations, valid for North America and Europe, and Chapter 20 describes in detail the toxic effects of solvent exposure to human beings. Authors specializing in different fields of solvent toxicity give the most current information on the effect of solvent exposure from the point of view of neurotoxicity, reproductive and maternal effects, nephrotoxicity, cancerogenicity, hepatotoxicity, chromosomal aberrations, and toxicity to brain, lungs, and heart. This information brings both the results of documented studies and an evaluation of risk in different industrial environments in a comprehensive but easy to understand form to engineers and decision-makers in industry. Chapter 21 is focused on the substitution of harmful solvents by safer ones and on the development of corresponding new technological processes. Chapter 22 describes modern methods of solvent recovery, solvent recycling. When recycling is not possible, then solvents have to be destroyed by incineration or other methods of oxidation, as outlined in Chapter 22. Chapter 23 describes natural attenuation of solvents in groundwater and advanced remediation technologies as well as management strategies for sites impacted by solvent contamination. Protection from contact with solvents and their vapors is discussed in Chapter 24. Finally, new trends in solvent chemistry and applications based on the recent patent literature are discussed in Chapter 25. In most cases, the intelligent choice of the proper solvent or solvent mixture is essential for the realization of certain chemical transformations and physical processes. This handbook tries to cover all theoretical and practical information necessary for this often difficult task for both academic and industrial applications. It should be used not only by chemists, but also by physicists, chemical engineers, and technologists as well as environmental scientists in academic and industrial institutions. It is to be hoped that the present compilation of all relevant aspects connected with the use of solvents will also stimulate further basic and applied research in the still topical field of the physics and chemistry of liquid media.

REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

M Berthelot, L P¾an de Saint Gilles, Ann. Chim. Phys., 3. S¾r., 65, 385 (1862); ibid. 66, 5 (1862); ibid. 68, 255 (1863). N Menschutkin, Z. Phys. Chem., 5, 589 (1890); ibid. 6, 41 (1890); ibid. 34, 157 (1900). C Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed., VCH, Weinheim, 1988. (a) G F Dvorko, E A Ponomareva, Usp. Khim., 53, 948 (1984); Russ. Chem. Rev., 53, 547 (1984); (b) M H Abraham, Pure Appl. Chem., 57, 1055 (1985); and references cited therein. L Claisen, Justus Liebigs Ann. Chem., 291, 25 (1896). L Knorr, Justus Liebigs Ann. Chem., 293, 70 (1896). W Wislicenus, Justus Liebigs Ann. Chem., 291, 147 (1896). A Hantzsch, O W Schultze, Ber. Dtsch. Chem. Ges., 29, 2251 (1896). M T Rogers, J L Burdett, Can. J Chem., 43, 1516 (1965). A Kundt, Poggendorfs Ann. Phys. Chem. N. F., 4, 34 (1878); Chem. Zentralbl., 498 (1878). A Hantzsch, Ber. Dtsch. Chem. Ges., 55, 953 (1922). C Reichardt, Chem. Rev., 94, 2319 (1994). Prof. E M Kosower, Tel Aviv, private communication to C.R. Y Marcus, The Properties of Solvents, Wiley, Chichester, 1998. (a) Editorial, Chimia, 39, 147 (1985); (b) D Seebach, Chemistry in Britain, 21, 632 (1985). S M Pereira, G P Sauvage, G. W. Simpson, Synth. Commun., 25, 1023 (1995).

Introduction 17 18 19 20 21 22 23 24 25 26 27 28

5

P Knochel (Ed.), Modern Solvents in Organic Synthesis, Topics in Current Chemistry, Vol. 206, Springer, Berlin, 1999. Y Chauvin, H Olivier-Bourbigou, CHEMTECH, 25(9), 26 (1995). (a) K R Seddon, Kinetika i Kataliz, 37, 743 (1996); Kinetics and Catalysis, 37, 693 (1996); Chem. Abstr., 125, 285927s (1996); (b) K R Seddon, J. Chem. Technol. Biotechnol., 68, 351 (1997); Chem. Abstr., 126, 306898w (1997). R Noyori (Ed.), Supercritical Fluids, Chem. Rev., 99, 353-633 (1999). W Leitner, Top. Curr. Chem., 206, 107 (1999). B Cornils, Angew. Chem., 109, 2147 (1997); Angew. Chem., Int. Ed. Engl., 36, 2057 (1997). B Betzemeier, P Knochel, Top. Curr. Chem., 206, 61 (1999). J J Maul, P J Ostrowski, G A Ublacker, B Linclau, D P Curran, Top. Curr. Chem., 206, 79 (1999). P A Grieco, Organic Synthesis in Water, Blackie Academic and Professional, Hampshire, 1998. A Lubineau and J. Aug¾, Top. Curr. Chem., 206, 1 (1999). J O Metzger, Angew, Chem., 110, 3145 (1998); Angew. Chem., Int. Ed. Engl., 37, 2975 (1998). A Loupy, Top. Curr. Chem., 206, 153 (1999).

2

Fundamental Principles Governing Solvents Use 2.1 SOLVENT EFFECTS ON CHEMICAL SYSTEMS Estanislao Silla, Arturo Arnau and Iñaki TuñóN Department of Physical Chemistry, University of Valencia, Burjassot (Valencia), Spain

2.1.1 HISTORICAL OUTLINE According to a story, a little fish asked a big fish about the ocean, since he had heard it being talked about but did not know where it was. Whilst the little fish’s eyes turned bright and shiny full of surprise, the old fish told him that all that surrounded him was the ocean. This story illustrates in an eloquent way how difficult it is to get away from every day life, something of which the chemistry of solvents is not unaware. The chemistry of living beings and that which we practice in laboratories and factories is generally a chemistry in solution, a solution which is generally aqueous. A daily routine such as this explains the difficulty which, throughout the history of chemistry, has been encountered in getting to know the effects of the solvent in chemical transformations, something which was not achieved in a precise way until well into the XX century. It was necessary to wait for the development of experimental techniques in vacuo to be able to separate the solvent and to compare the chemical processes in the presence and in the absence of this, with the purpose of getting to know its role in the chemical transformations which occur in its midst. But we ought to start from the beginning. Although essential for the later cultural development, Greek philosophy was basically a work of the imagination, removed from experimentation, and something more than meditation is needed to reach an approach on what happens in a process of dissolution. However, in those remote times, any chemically active liquid was included under the name of “divine water”, bearing in mind that the term “water” was used to refer to anything liquid or dissolved.1 Parallel with the fanciful search for the philosopher’s stone, the alchemists toiled away on another impossible search, that of a universal solvent which some called “alkahest” and others referred to as “menstruum universale”, which term was used by the very Paracelsus (1493-1541), which gives an idea of the importance given to solvents during that dark and obscurantist period. Even though the “menstruum universale” proved just as elusive as the philosopher’s stone, all the work carried out by the alchemists in search of these

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Estanislao Silla, Arturo Arnau and Iñaki Tuñón

illusionary materials opened the way to improving the work in the laboratory, the development of new methods, the discovery of compounds and the utilization of novel solvents. One of the tangible results of all that alchemistry work was the discovery of one of the first experimental rules of chemistry: “similia similibus solvuntor”, which reminds us of the compatibility in solution of those substances of similar nature. Even so, the alchemistry only touched lightly on the subject of the role played by the solvent, with so many conceptual gulfs in those pre-scientific times in which the terms dissolution and solution referred to any process which led to a liquid product, without making any distinction between the fusion of a substance - such as the transformation of ice into liquid water - mere physical dissolution - such as that of a sweetener in water - or the dissolution which takes place with a chemical transformation - such as could be the dissolution of a metal in an acid. This misdirected vision of the dissolution process led the alchemists down equally erroneous collateral paths which were prolonged in time. Some examples are worth quoting: Hermann Boerhaave (1688-1738) thought that dissolution and chemical reaction constituted the same reality; the solvent, (menstruum), habitually a liquid, he considered to be formed by diminutive particles moving around amongst those of the solute, leaving the interactions of these particles dependent on the mutual affinities of both substances.2 This paved the way for Boerhaave to introduce the term affinity in a such a way as was conserved throughout the whole of the following century.3 This approach also enabled Boerhaave to conclude that combustion was accompanied by an increase of weight due to the capturing of “particles” of fire, which he considered to be provided with weight by the substance which was burned. This explanation, supported by the well known Boyle, eased the way to considering that fire, heat and light were material substances until when, in the XIX century, the modern concept of energy put things in their place.4 Even Bertollet (1748-1822) saw no difference between a dissolution and a chemical reaction, which prevented him from reaching the law of definite proportions. It was Proust, an experimenter who was more exacting and capable of differentiating between chemical reaction and dissolution, who made his opinion prevail:

“The dissolution of ammonia in water is not the same as that of hydrogen in azote (nitrogen), which gives rise to ammonia”5 There were also alchemists who defended the idea that the substances lost their nature when dissolved. Van Helmont (1577-1644) was one of the first to oppose this mistaken idea by defending that the substance dissolved remains in the solution in aqueous form, it being possible to recover it later. Later, the theories of osmotic pressure of van´t Hoff (1852-1911) and that of electrolytic dissociation of Arrhenius (1859-1927) took this approach even further. Until almost the end of the XIX century the effects of the solvent on the different chemical processes did not become the object of systematic study by the experimenters. The effect of the solvent was assumed, without reaching the point of awakening the interest of the chemists. However, some chemists of the XIX century were soon capable of unraveling the role played by some solvents by carrying out experiments on different solvents, classified according to their physical properties; in this way the influence of the solvent both on chemical equilibrium and on the rate of reaction was brought to light. Thus, in 1862, Berthelot and Saint-Gilles, in their studies on the esterification of acetic acid with ethanol,

2.1 Solvent effects on chemical systems

9

discovered that some solvents, which do not participate in the chemical reaction, are capable of slowing down the process.6 In 1890, Menschutkin, in a now classical study on the reaction of the trialkylamines with haloalcans in 23 solvents, made it clear how the choice of one or the other could substantially affect the reaction rate.7 It was also Menschutkin who discovered that, in reactions between liquids, one of the reactants could constitute a solvent inadvisable for that reaction. Thus, in the reaction between aniline and acetic acid to produce acetanilide, it is better to use an excess of acetic acid than an excess of aniline, since the latter is a solvent which is not very favorable to this reaction. The fruits of these experiments with series of solvents were the first rules regarding the participation of the solvent, such as those discovered by Hughes and Ingold for the rate of the nucleophilic reactions.8 Utilizing a simple electrostatic model of the solute - solvent interactions, Hughes and Ingold concluded that the state of transition is more polar than the initial state, that an increase of the polarity of the solvent will stabilize the state of transition with respect to the initial state, thus leading to an increase in the reaction rate. If, on the contrary, the state of transition is less polar, then the increase of the polarity of the solvent will lead to a decrease of the velocity of the process. The rules of Hughes-Ingold for the nucleophilic aliphatic reactions are summarized in Table 2.1.1. Table 2.1.1. Rules of Hughes-Ingold on the effect of the increase of the polarity of the solvent on the rate of nucleophilic aliphatic reactions Mechanism

Initial state -

S N2

-

Effect on the reaction rate

Y + RX

[Y--R--X]

slight decrease

Y + RX

[Y--R--X]

large increase

-

+

Y + RX

+

S N1

State of transition

[Y--R--X] +

large decrease

Y + RX

[Y--R--X]

slight decrease

RX

[R--X]

large increase

+

RX

[R--X]

+

slight decrease

In 1896 the first results about the role of the solvent on chemical equilibria were obtained, coinciding with the discovery of the keto-enolic tautomerism.9 Claisen identified the medium as one of the factors which, together with the temperature and the substituents, proved to be decisive in this equilibrium. Soon systematic studies began to be done on the effect of the solvent in the tautomeric equilibria. Wislicenus studied the keto-enolic equilibrium of ethylformylphenylacetate in eight solvents, concluding that the final proportion between the keto form and the enol form depended on the polarity of the solvent.10 This effect of the solvent also revealed itself in other types of equilibria: acid-base, conformational, those of isomerization and of electronic transfer. The acid-base equilibrium is of particular interest. The relative scales of basicity and acidity of different organic compounds and homologous families were established on the basis of measurements carried out in solution, fundamentally aqueous. These scales permitted establishing hypotheses regarding the effect of the substituents on the acidic and basic centers, but without being capable of separating this from the effect of the solvent. Thus, the scale obtained in solution for the acidity of

10

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

the α-substituted methyl alcohols [(CH3)3COH > (CH3)2CHOH > CH3CH2OH > CH3OH]11 came into conflict with the conclusions extracted from the measurements of movements by NMR.12 The irregular order in the basicity of the methyl amines in aqueous solution also proved to be confusing [NH3 < CH3NH2 < (CH3)2NH > (CH3)3N],13 since it did not match any of the existing models on the effects of the substituents. These conflicts were only resolved when the scales of acidity-basicity were established in the gas phase. On carrying out the abstraction of the solvent an exact understanding began to be had of the real role it played. The great technological development which arrived with the XIX century has brought us a set of techniques capable of giving accurate values in the study of chemical processes in the gas phase. The methods most widely used for these studies are: • The High Pressure Mass Spectrometry, which uses a beam of electron pulses14 • The Ion Cyclotron Resonance and its corresponding Fourier Transform (FT-ICR)15 • The Chemical Ionization Mass Spectrometry, in which the analysis is made of the kinetic energy of the ions, after generating them by collisions16 • The techniques of Flowing Afterglow, where the flow of gases is submitted to ionization by electron bombardment17-19 All of these techniques give absolute values with an accuracy of ±(2-4) Kcal/mol and of ±0.2 Kcal/mol for the relative values.20 During the last decades of XX century the importance has also been made clear of the effects of the solvent in the behavior of the biomacromolecules. To give an example, the influence of the solvent over the proteins is made evident not only by its effects on the structure and the thermodynamics, but also on the dynamics of these, both at local as well as at global level.21 In the same way, the effect of the medium proves to be indispensable in explaining a large variety of biological processes, such us the rate of interchange of oxygen in myoglobin.22 Therefore, the actual state of development of chemistry, as much in its experimental aspect as in its theoretical one, allows us to identify and analyze the influence of the solvent on processes increasingly more complex, leaving the subject open for new challenges and investigating the scientific necessity of creating movavi video editor tutorial pdf - Crack Key For U with which to interpret such a wide range of phenomena as this. The little fish became aware of the ocean and began explorations. 2.1.2 CLASSIFICATION OF SOLUTE-SOLVENT INTERACTIONS Fixing the limits of the different interactions between the solute and the solvent which envelopes it is not a trivial task. In the first place, the liquid state, which is predominant in the majority of the solutions in use, is more difficult to comprehend than the solid state (which has its constitutive particles, atoms, molecules or ions, in fixed positions) or the gaseous state (in which the interactions between the constitutive particles are not so intense). Moreover, the solute-solvent interactions, which, as has already been pointed out, generally happen in the liquid phase, are half way between the predominant interactions in the solid phase and those which happen in the gas phase, too weak to be likened with the physics of the solid state but too strong to fit in with the kinetic theory of gases. In the second place, dissecting the solute-solvent interaction into different sub-interactions only serves to give us an approximate idea of the reality and we should not forget that, in the solute-solvent interaction, the all is not the sum of the parts. In the third place, the world of the solvents is very varied from those which have a very severe internal structure, as in the case of water, to those

2.1 Solvent effects on chemical systems

11

whose molecules interact superficially, as in the case of the hydrocarbons. At all events, there is no alternative to meeting the challenge face to face. If we mix a solute and a solvent, both being constituted by chemically saturated molecules, their molecules attract one another as they approach one another. This interaction can only be electrical in its nature, given that other known interactions are much more intense and of much shorter range of action (such as those which can be explained by means of nuclear forces) or much lighter and of longer range of action (such as the gravitational force). These intermolecular forces usually also receive the name of van der Waals forces, from the fact that it was this Dutch physicist, Johannes D. van der Waals (1837-1923), who recognized them as being the cause of the non-perfect behavior of the real gases, in a period in which the modern concept of the molecule still had to be consolidated. The intermolecular forces not only permit the interactions between solutes and solvents to be explained but also determine the properties of gases, liquids and solids; they are essential in the chemical transformations and are responsible for organizing the structure of biological molecules. The analysis of solute-solvent interactions is usually based on the following partition scheme: ∆E = ∆E i + ∆E ij + ∆E jj

[2.1.1]

where i stands for the solute and j for the solvent.This approach can be maintained while the identities of the solute and solvent molecules are preserved. In some special cases (see below in specific interactions) it will be necessary to include some solvent molecules in the solute definition. The first term in the above expression is the energy change of the solute due to the electronic and nuclear distortion induced by the solvent molecule and is usually given the name solute polarization. ∆Eij is the interaction energy between the solute and solvent molecules. The last term is the energy difference between the solvent after and before the introduction of the solute. This term reflects the changes induced by the solute on the solvent structure. It is usually called cavitation energy in the framework of continuum solvent models and hydrophobic interaction when analyzing the solvation of nonpolar molecules. The calculation of the three energy terms needs analytical expressions for the different energy contributions but also requires knowledge of solvent molecules distribution around the solute which in turn depends on the balance between the potential and the kinetic energy of the molecules. This distribution can be obtained from diffraction experiments or more usually is calculated by means of different solvent modelling. In this section we will comment on the expression for evaluating the energy contributions. The first two terms in equation [2.1.1] can be considered together by means of the following energy partition : ∆E i + ∆E ij = ∆E el + ∆E pol + ∆E d − r

[2.1.2]

Analytical expressions for the three terms (electrostatic, polarization and dispersion-repulsion energies) are obtained from the intermolecular interactions theory. 2.1.2.1 Electrostatic The electrostatic contribution arises from the interaction of the unpolarized charge distribution of the molecules. This interaction can be analyzed using a multipolar expansion of the charge distribution of the interacting subsystems which usually is cut off in the first term

12

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

which is different from zero. If both the solute and the solvent are considered to be formed by neutral polar molecules (with a permanent dipolar moment different from zero), due to an asymmetric distribution of its charges, the electric interaction of the type dipole-dipole will normally be the most important term in the electrostatic interaction. The intensity of this interaction will depend on the relative orientation of the dipoles. If the molecular rotation is not restricted, we must consider the weighted average over different orientations E d −d = − where:

µ i, µ j k ε T r

2 µ 12µ 22 3 (4πε) 2 kTr 6

[2.1.3]

dipole moments Boltzmann constant dielectric constant absolute temperature intermolecular distance

The most stable orientation is the antiparallel, except in the case that the molecules in play are very voluminous. Two dipoles in rapid thermal movement will be orientated sometimes in a way such that they are attracted and at other times in a way that they are repelled. On the average, the net energy turns out to be attractive. It also has to be borne in mind that the thermal energy of the molecules is a serious obstacle for the dipoles to be oriented in an optimum manner. The average potential energy of the diFigure 2.1.1. The dipoles of two molecules can approach one another under an infinite variety of attractive orienta- pole-dipole interaction, or of orientation, is, tions, among which these two extreme orientations stand therefore, very dependent on the temperaout. ture. In the event that one of the species involved were not neutral (for example an anionic or cationic solute) the predominant term in the series which gives the electrostatic interaction will be the ion-dipole which is given by the expression: E i −d = −

q i2 µ 2j 6( 4πε) 2 kTr 4

[2.1.4]

2.1.2.2 Polarization If we dissolve a polar substance in a nonpolar solvent, the molecular dipoles of the solute are capable of distorting the electronic clouds of the solvent molecules inducing the appearance in these of new dipoles. The dipoles of solute and those induced will line up and will be attracted and the energy of this interaction (also called interaction of polarization or induction) is:

2.1 Solvent effects on chemical systems

E d − id = − where:

µi αj r

α j µ i2

13

[2.1.5]

( 4πε) 2 r 6 dipole moment polarizability intermolecular distance

In a similar way, the dissolution of an ionic substance in a nonpolar solvent also will occur with the induction of the dipoles in the molecules of the solvent by the solute ions. These equations make reference to the interactions between two molecules. Because the polarization energy (of the solute or of the solvent) is not pairwise additive magnitude, the consideration of a third molecule should be carried out simultaneously, it being impossible to decompose the interaction of the three bodies in a sum of the interactions of two bodies. The interactions between molecules in solution are different from those which take place between isolated molecules. For this reason, the dipolar moment of a molecule may vary considerably from the gas phase to the solution, and will depend in a complicated fashion on the interactions which may take place between the molecule of solute and its specific surroundings of molecules of solvent. 2.1.2.3 Dispersion Even when solvent and solute are constituted by nonpolar molecules, there is interaction between them. It was F. London who was first to face up to this problem, for which reason these forces are known as London’s forces, but also as dispersion forces, charge-fluctuations forces or electrodynamic forces. Their origin is as follows: when we say that a substance is nonpolar we are indicating that the distribution of the charges of its molecules is symmetrical throughout a wide average time span. But, without doubt, in an interval of time sufficiently restricted the molecular movements generate displacements of their charges which break that symmetry giving birth to instantaneous dipoles. Since the orientation of the dipolar moment vector is varying constantly due to the molecular movement, the average dipolar moment is zero, which does not prevent the existence of these interactions between momentary dipoles. Starting with two instantaneous dipoles, these will be oriented to reach a disposition which will favor them energetically. The energy of this dispersion interaction can be given, to a first approximation, by: E disp = − where:

Ii, Ij αi, αj r

3I i Adobe Photoshop 22.5.0.384 Crack With Torrent Full Version 2021 j

αi α j

2( 4πε) (I i + I j ) r 6 2

ionization potentials polarizabilities intermolecular distance

[2.1.6]

From equation [2.1.6] it becomes evident that dispersion is an interaction which is more noticeable the greater the volume of molecules involved. The dispersion forces are often more intense than the electrostatic forces and, in any case, are universal for all the atoms and molecules, given that they are not seen to be subjected to the requirement that permanent dipoles should exist beforehand. These forces are responsible for the aggregation of the substances which possess neither free charges nor permanent dipoles, and are also the

14

Estanislao Silla, Arturo Arnau and Iñaki Tuñón

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Handbook of Solvents - George Wypych - ChemTech - Ventech!

HANDBOOK OF

SOLVENTS

GeorgeWypych, Editor

ChemTec Publishing

Toronto − New York 2001


Published by ChemTec Publishing

38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada

Co-published by William Andrew Inc.

13 Eaton Avenue, Norwich, NY 13815, USA

© Chem Tec Publishing, 2001

ISBN 1-895198-24-0

All rights reserved. No part of this publication may be reproduced, stored or

transmitted in any form or by any means without written permission of copyright

owner. No responsibility is assumed by the Author and the Publisher for any injury

or/and damage to persons or properties as a matter of products liability, negligence,

use, or operation of any methods, product ideas, or instructions published or

suggested in this book.

Canadian Cataloguing in Publication Data

HandbookofSolvents

Includes bibliographical references and index

ISBN 1-895198-24-0 (ChemTec Publishing)

ISBN 0-8155-1458-1 (William Andrew Inc.)

Library of Congress Catalog Card Number: 00-106798

1. Solvents--Handbooks, manuals, etc. I. Wypych, George

TP247.5.H35 2000 661’.807 C00-900997-3

Printed in Canada by Transcontinental Printing Inc., 505 Consumers Rd.

Toronto, Ontario M2J 4V8


Preface

Although the chemical industry can trace its roots into antiquity, it was during the industrial

revolution that it started to become an actual industry and began to use the increased knowledge

of chemistry as a science and technology to produce products that were needed by

companion industries and consumers. These commercial efforts resulted in the synthesis of

many new chemicals. Quite quickly, in these early days, previously unknown materials or

materials that had been present only in low concentrations, were now in contact with people

in highly concentrated forms and in large quantities. The people had little or no knowledge

of the effects of these materials on their bodies and the natural biological and physical

processes in the rivers and oceans, the mixcraft 9 crack - Activators Patch, and in the ground.

Until the end of the nineteenth century these problems were not addressed by the

chemical industry and it is only recently that the industry began to respond to public criticism

and political efforts. Legal restrictions aimed at preserving the quality of life have been

directed at health, safety and longevity issues and the environment. Solvents have always

been mainstays of the chemical industry and because of their widespread use and their high

volume of production they have been specifically targeted by legislators throughout the

world. The restrictions range from total prohibition of production and use, to limits placed

on vapor concentrations in the air. As with any arbitrary measures some solvents have been

damned unfairly. However, there is no question that it is best to err on the side of safety if the

risks are not fully understood. It is also true that solvents should be differentiated based on

their individual properties.

This book is intended to provide a better understanding of the principles involved in

solvent selection and use. It strives to provide information that will help to identify the risks

and benefits associated with specific solvents and classes of solvents. The book is intended

to help the formulator select the ideal solvent, the safety coordinator to safeguard his or her

coworkers, the legislator to impose appropriate and technically correct restrictions and the

student to appreciate the amazing variety of properties, applications and risks associated

with the more than one thousand solvents that are available today.

By their very nature, handbooks are intended to provide exhaustive information on the

subject. While we agree that this is the goal here, we have attempted to temper the impact of

information, which may be too narrow to make decision.

Many excellent books on solvents have been published in the past and most of these

are referenced in this book. But of all these books none has given a comprehensive overview

of all aspects of solvent use. Access to comprehensive data is an essential part of solvent

evaluation and it has been a hallmark of such books to provide tables filled with data to the

point at which 50 to 95% of the book Altium Designer 20.2.6 Build 244 Crack data. This approach seems to neglect a fundamental

requirement of a handbook - to provide the background, explanations and clarifications that

are needed to convert data to information and assist the reader in gaining the knowledge to

make a decision on selecting a process or a solvent. Unfortunately, to meet the goal of providing

both the data and the fundamental explanations that are needed, a book of 4,000 to

5,000 pages might be required. Even if this was possible, much of the data would fall out of

date quite quickly. For example, a factor that defines solvent safety such as threshold limit


xxviii Preface

values (TLVs) for worker exposure or some single toxicity determinants may change

frequently. This book would be huge and it would have to be updated frequently to continue

to claim that it is current.

What we have attempted to do here is to give you a book with a comprehensive and extensive

analysis of all current information on solvents then use other media to present the

supporting data on individual solvents. These data are provided on a CD-ROM as a

searchable database. Data are provided on more than 1140 solvents in 110 fields of data.

The medium permits frequent updates. If the same data were presented in book form, more

than 2,000 pages would be needed which exceeds the size of any data in handbook form

offered to date.

The best approach in presenting an authoritative text for such a book is to have it written

by experts in their fields. This book attracted well-known experts who have written

jointly 47 books and authored or coauthored hundreds of papers on their areas of expertise.

The authors have made their contributions to this book in late 1999 and early 2000

providing the most current picture of the technology. Their extreme familiarity with their

subjects enables them to present information in depth and detail, which is essential to the

reader’s full understanding of the subject.

The authors were aware of the diversity of potential readers at the outset and one of

their objectives was to provide information to various disciplines expressed in a way that all

would understand and which would deal with all aspects of solvent applications. We expect

professionals and students from a wide range of businesses, all levels of governments and

academe to be interested readers. The list includes solvent manufacturers, formulators of

solvent containing products, industrial engineers, analytical chemists, government legislators

and their staffs, medical professionals involved in assessing the impact on health of solvents,

biologists who are evaluating the interactions of solvents with soil and water,

environmental engineers, industrial hygienists who are determining protective measures

against solvent exposure, civil engineers who design waste disposal sites and remediation

measures, people in industries where there are processes which use solvents and require

their recovery and, perhaps most important, because understanding brings improvements,

those who teach and learn in our universities, colleges and schools.

A growing spirit of cooperation is evident between these groups and this can be fostered

by providing avenues of understanding based on sharing data and information on common

problems. We hope to provide one such avenue with this book. We have tried to

present a balanced picture of solvent performance by dealing not only with product performance

and ease of processing but also by giving environmental and health issues full consideration.

Data and information on known products and processes should be cornerstones of the

understanding of a technology but there is another aspect of technology, which can lead to

advances and improvements in utility, safety and in safeguarding the environment. This

must come from you, the reader. It is your ideas and creative thinking that will bring these

improvements. The authors have crammed their ideas into the book and we hope these will

stimulate responsible and effective applications of solvents. Francis Bacon wrote, “The end

of our foundation is the knowledge of causes, and the secret motion of things, and the enlarging

of the bound of human Empire, to the effecting of all things possible.”

Today there are few technical activities that do not employ solvents. Almost all industries,

almost all consumer products, almost everything we use can, if analyzed, be shown to


Preface xxix

contain or to have used in its processing, a solvent. Solvent elimination need never be a

technical objective. Rather, we need to use our increasing understanding and knowledge to

find the safest and the most effective means of meeting our goals.

I would like to thank the authors for their relentless efforts to explain the difficult in an

interesting way. In advance, I would like to thank the reader for choosing this book and encourage

her or him to apply the knowledge to make our world a better, more livable place.

GeorgeWypych

Toronto, August 3, 2000


Acknowledgments 1653

ACKNOWLEDGMENTS

This following section contains acknowledgments included in the various sections of the

book which were combined to form one section. For better identification, individual acknowledgments

follow the reference to the title and authors of the book section.

Preface

GeorgeWypych, ChemTec Laboratories, Inc., Toronto, Canada

I would like to thank Dr. Robert Fox and John Paterson who made all efforts that the

language used in this book is simple to understand and the book is read with pleasure.

4.2 Polar solvation dynamics: Theory and simulations

Abraham Nitzan, School of Chemistry, the Sackler Faculty of Sciences, Tel Aviv University,

Tel Aviv, 69978, Israel

This work was supported by Israel Science Foundation. I thank my E. Neria, R.

Olender and P. Graf who collaborated with me on some of the works described in this report.

4.4 Methods for the measurement of solvent activity of polymer solutions

Christian Wohlfarth, Martin-Luther-University Halle-Wittenberg, Institute of Physical

Chemistry, Geusaer Straße, D-06217 Merseburg, Germany

Thanks are given to G. Sadowski (TU Berlin) for providing Figure 4.4-7(b), B. A Wolf

(Univ. Mainz) for providing Figure 4.4-13, and G. Maurer (Univ. Kaiserslautern) for providing

Figure 4.4-6. Furthermore, I wish to thank M. D. Lechner (Univ. Osnabrück) and G.

Sadowski for many helpful comments and discussions about this manuscript.

5.4 Mixed solvents, a way to change the polymer solubility

Ligia Gargallo and Deodato Radic, Facultad de Quimica, Pontificia Universidad Catolica

de Chile, Casilla 306, Santiago 22, Chile

The authors wish to express their appreciation to Mrs. Viviana Ulloa for her technical

assistance in this work and to publishers and authors for permission to reproduce figures

and tables from their publications as indicated specifically in the legends of the figures and

tables.

6.1 Modern views on kinetics of swelling of crosslinked elastomers in solvents

E. Ya. Denisyuk, Institute of Continuous Media Mechanics; V. V. Tereshatov, Institute of

Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia

This work was supported by a grant from Russian Fund of Fundamental Research

(grant No 98-03-33333).


1654 Acknowledgments

10.3 Solvent effects based on pure solvent scales

Javier Catalán, Departamento de Química Fisíca Aplicada, Universidad Autónoma de Madrid,

Cantoblanco, E-28049, Madrid, Spain

The author wishes to thank all those who contributed to the development of our solvent

scales (C. Díaz, P. Pérez, V. López, J.L. G de Paz, R. Martín-Villamil, J.G. González ,

J. Palomar, and F. García-Blanco) and also Spain’s DGICyT (Project PB98-0063) for funding

this work.

12.2 Chain conformations of polysaccharides in different solvents

Ranieri Urbani and Attilio Cesàro, Department of Biochemistry, Biophysics and

Macromolecular Chemistry, University of Trieste, Italy

The paper has been prepared with financial support of University of Trieste and of

Progetto Coordinato “Proprietà dinamiche di oligo e polisaccaridi”, Grant CT97-02765.03

of the National Research Council of Italy (Rome). The authors wish also to thank dr. Paola

Sist for patient technical assistance.

13.2 Solvent Effects on Free Radical Polymerization

Michelle L. Coote and Thomas P. Davis, Centre for Advanced Macromolecular Design,

School of Chemical Engineering & Industrial Chemistry, The University of New South

Wales, Sydney, Australia

We acknowledge the publishers Marcel Dekker for allowing us to reproduce sections

of an earlier review, “A Mechanistic Perspective on Solvent Effects in Free Radical Polymerization”.

128 MLC acknowledges the receipt of an Australian Postgraduate Award.

14.19.2 Recent advances in coalescing solvents for waterborne coatings

David Randall, Chemoxy International pcl, Cleveland, United Kingdom

I would like to acknowledge with much gratitude the help given by Mr R J Foster of

Harco for his help in assembling the MFFT data for the presentation. I must also thank my

colleagues at Chemoxy, Ms Carol White, who assembled much of the data used in this paper,

and Miss Tracy McGough, who helped me produce the OHPs. Finally, I must acknowledge

the assistance given by MrTJPThomas, who has acted as a consultant to Chemoxy

International in this whole area.

I am indebted to Bob Foster at Harco, who kindly carried out some comparative formulations

using Coasol, Di-isopropyl AGS and Di-isopropyl Adipate in comparison with a

Monoester of Pentane Diol.

14.21.1 Use of solvents in the manufacture of drug substances (DS) and drug products (DP)

16.2 Residual solvents in pharmaceutical substances

Michel Bauer, International Analytical Department, Sanofi-Synthélabo, Toulouse, France;

Christine Barthélémy, Laboratoire de Pharmacie Galénique et Biopharmacie, Faculté des

Sciences Pharmaceutiques et Biologiques, Université de Lille 2, Lille, France

The authors thank Nick Anderson, Steve Byard, Juliette de Miras and Susan Richardson

for their participation in the elaboration of this document.


Acknowledgments 1655

15.2.2 A simple test to determine toxicity using bacteria

James L. Botsford, Department of Biology, New Mexico State University, Las Cruces, NM,

USA

This work has been supported by the principal investigator’s participation in several

programs to assist ethnic minorities in the sciences. Many students have helped with this

work.

20.3 Pregnancy outcome following maternal organic solvent exposure

Kristen I. McMartin and Gideon Koren, The Motherisk Program, Division of Clinical Pharmacology

and Toxicology, Hospital for Sick Children, Toronto, Canada

Supported by grants from Imperial Oil Limited, Physician Services Incorporated, The

Medical Research Council of Canada, and the CIBC Global Market Children’s Miracle

Foundation Chair in Child Health Research, The University of Toronto.

20.4 Industrial solvents and kidney disease

20.6 Chromosomal aberrations and sister chromatoid exchanges

20.7 Hepatotoxicity

Nachman Brautbar, University of Southern California, School of Medicine, Department of

Medicine, Los Angeles, CA, USA

The author wishes to thank Ms. S. Loomis for her tireless work in transcribing this

manuscript.

21.1 Supercritical solvents

Aydin K. Sunol and Sermin G. Sunol, Department of Chemical Engineering, University of

South Florida, Tampa, FL, USA

Assistance of both Dr. John P. Kosky of MEI Corporation and Irmak E. Serifoglu with

editing and typesetting are appreciated.


Table of Contents

Preface .xxvii

GEORGE WYPYCH

1 INTRODUCTION .1

CHRISTIAN REICHARDT

2 FUNDAMENTAL PRINCIPLES GOVERNING SOLVENTS USE .7

2.1 Solvent effects on chemical systems .7

ESTANISLAO SILLA, ARTURO ARNAU, IÑAKI TUÑÓN

2.1.1 Historical outline .7

2.1.2 Classification of solute-solvent interactions .10

2.1.2.1 Electrostatic .11

2.1.2.2 Polarization .12

2.1.2.3 Dispersion .13

2.1.2.4 Repulsion .14

2.1.2.5 Specific interactions .15

2.1.2.6 Hydrophobic interactions. .16

2.1.3 Modelling of solvent effects .17

2.1.3.1 Computer simulations .18

2.1.3.2 Continuum models .20

2.1.3.3 Cavity surfaces .21

2.1.3.4 Supermolecule models .22

2.1.3.5 Application example: glycine in solution .23

2.1.4 Thermodynamic and kinetic characteristics of chemical reactions in solution. 27

2.1.4.1 Solvent effects on chemical equilibria .27

2.1.4.2 Solvent effects on the rate of chemical reactions. .28

2.1.4.3 Example of application: addition of azide anion to tetrafuranosides. .30

2.1.5 Solvent catalytic effects .32

2.2 Molecular design of solvents .36

KOICHIRO NAKANISHI

2.2.1 Molecular design and molecular ensemble design .36

2.2.2 From prediction to design .37

2.2.3 Improvement in prediction method. .38

2.2.4 Role of molecular simulation. .39

2.2.5 Model system and paradigm for design .40

Appendix. Predictive equation for the diffusion coefficient in dilute solution. 41

2.3 Basic physical and chemical properties of solvents .42

GEORGE WYPYCH

2.3.1 Molecular weight and molar volume .43

2.3.2 Boiling and freezing points. .44

2.3.3 Specific gravity .46

2.3.4 Refractive index .47

2.3.5 Vapor density and pressure. .48

2.3.6 Solvent volatility .49

2.3.7 Flash point .50

2.3.8 Flammability limits. .51

2.3.9 Sources of ignition and autoignition temperature .52

2.3.10 Heat of combustion (calorific value) .54

2.3.11 Heat of fusion. .54

2.3.12 Electric conductivity .54

2.3.13 Dielectric constant (relative permittivity) .54

2.3.14 Occupational exposure indicators .56

2.3.15 Odor threshold .56


ii HandbookofSolvents

2.3.16 Toxicity indicators .57

2.3.17 Ozone-depletion and creation potential .58

2.3.18 Oxygen demand .58

2.3.19 Solubility .58

2.3.20 Other typical solvent properties and indicators .60

3 PRODUCTION METHODS, PROPERTIES,

AND MAIN APPLICATIONS .65

3.1 Definitions and solvent classification .65

GEORGE WYPYCH

3.2 Overview of methods of solvent manufacture .69

GEORGE WYPYCH

3.3 Solvent properties .74

GEORGE WYPYCH

3.3.1 Hydrocarbons. .75

3.3.1.1 Aliphatic hydrocarbons. .75

3.3.1.2 Aromatic hydrocarbons. .76

3.3.2 Halogenated hydrocarbons .78

3.3.3 Nitrogen-containing compounds (nitrates, nitriles) .79

3.3.4 Organic sulfur compounds .80

3.3.5 Monohydric alcohols .81

3.3.6 Polyhydric alcohols. .83

3.3.7 Phenols .84

3.3.8 Aldehydes .85

3.3.9 Ethers .86

3.3.10 Glycol ethers .87

3.3.11 Ketones .88

3.3.11 Acids .90

3.3.12 Amines .91

3.3.13 Esters .92

3.3.14 Comparative analysis of all solvents .94

3.4 Terpenes .96

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG

3.4.1 Definitions and nomenclature .96

3.4.2 Occurrence .96

3.4.3 General .96

3.4.4 Toxicology .97

3.4.5 Threshold limit values .97

4 GENERAL PRINCIPLES GOVERNING DISSOLUTION

OF MATERIALS IN SOLVENTS. .101

4.1 Simple solvent characteristics .101

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

4.1.1 Solvent power .101

4.1.2 One-dimensional solubility parameter approach .103

4.1.3 Multi-dimensional approaches .110

4.1.4 Hansen’s solubility .112

4.1.5 Three-dimensional dualistic model. .116

4.1.6 Solubility criterion .119

4.1.7 Solvent system design .120

4.2 Effect of system variables on solubility .124

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

4.2.1 General considerations .124

4.2.2 Chemical structure .126

4.2.3 Flexibility of a polymer chain .127

4.2.4 Crosslinking .128

4.2.5 Temperature and pressure .128

4.2.6 Methods of calculation of solubility based on thermodynamic principles .130


Table of contents iii

4.3 Polar solvation dynamics: Theory and simulations .132

ABRAHAM NITZAN

4.3.1 Introduction. .132

4.3.2 Continuum dielectric theory of solvation dynamics .133

4.3.3 Linear response theory of solvation dynamics .136

4.3.4 Numerical simulations of solvation in simple polar solvents:

The simulation model .138

4.3.5 Numerical simulations of solvation in simple polar solvents:

Results and discussion .140

4.3.6 Solvation in complex solvents .144

4.3.7 Conclusions. .145

4.4 Methods for the measurement of solvent activity of polymer solutions .146

CHRISTIAN WOHLFARTH

4.4.1 Introduction. .146

4.4.2 Necessary thermodynamic equations. .149

4.4.3 Experimental methods, equipment and data reduction. .154

4.4.3.1 Vapor-liquid equilibrium (VLE) measurements .154

4.4.3.1.1 Experimental equipment and procedures for VLE-measurements .155

4.4.3.1.2 Primary data reduction .170

4.4.3.1.3 Comparison of experimental VLE-methods .175

4.4.3.2 Other measurement methods .178

4.4.3.2.1 Membrane osmometry .178

4.4.3.2.2 Light scattering .181

4.4.3.2.3 X-ray scattering. .184

4.4.3.2.4 Neutron scattering .185

4.4.3.2.5 Ultracentrifuge .186

4.4.3.2.6 Cryoscopy (freezing point depression of the solvent) .188

4.4.3.2.7 Liquid-liquid equilibrium (LLE) .189

4.4.3.2.8 Swelling equilibrium .193

4.4.4 Thermodynamic models for the calculation of solvent activities of

polymer solutions. .195

4.4.4.1 Models for residual chemical potential and activity coefficient in

the liquid phase .196

4.4.4.2 Fugacity coefficients from equations of state .207

4.4.4.3 Comparison and conclusions .214

Appendix 4.4A .223

5 SOLUBILITY OF SELECTED SYSTEMS AND INFLUENCE

OF SOLUTES .243

5.1 Experimental methods of evaluation and calculation of solubility

parameters of polymers and solvents. Solubility parameters data .243

VALERY YU. SENICHEV, VASILIY V. TERESHATOV

5.1.1 Experimental evaluation of solubility parameters of liquids .243

5.1.1.1 Direct methods of evaluation of the evaporation enthalpy .243

5.1.1.2 Indirect methods of evaluation of evaporation enthalpy .244

5.1.1.3 Static and quasi-static methods of evaluation of pair pressure. .245

5.1.1.4 Kinetic methods .245

5.1.2 Methods of experimental evaluation and calculation of solubility

parameters of polymers. .246

5.2 Prediction of solubility parameter .253

NOBUYUKI TANAKA

5.2.1 Solubility parameter of polymers .253

5.2.2 Glass transition in polymers .254

5.2.2.1 Glass transition enthalpy .254

5.2.2.2 Cp jump at the glass transition .256

5.2.3 Prediction from thermal transition enthalpies .258

5.3 Methods of calculation of solubility parameters of solvents and polymers .261

VALERY YU. SENICHEV, VASILIY V. TERESHATOV


iv HandbookofSolvents

5.4 Mixed solvents, a way to change the polymer solubility. .267

LIGIA GARGALLO AND DEODATO RADIC

5.4.1 Introduction. .267

5.4.2 Solubility-cosolvency phenomenon .268

5.4.3 New cosolvents effects. Solubility behavior .273

5.4.4 Thermodynamical description of ternary systems. Association equilibria

theory of preferential adsorption .274

5.4.5 Polymer structure of the polymer dependence of preferential adsorption.

Polymer molecular weight and tacticity dependence of preferential adsorption. 277

5.5 The phenomenological theory of solvent effects in mixed solvent systems .281

KENNETH A. CONNORS

5.5.1 Introduction. .281

5.5.2 Theory .281

5.5.2.1 Principle .281

5.5.2.2 The intersolute effect: solute-solute interactions .282

5.5.2.3 The solvation effect: solute-solvent interaction .283

5.5.2.4 The general medium effect: solvent-solvent interactions .284

5.5.2.5 The total solvent effect .285

5.5.3 Applications .285

5.5.3.1 Solubility .285

5.5.3.2 Surface tension .288

5.5.3.3 Electronic absorption spectra. .290

5.5.3.4 Complex formation .291

5.5.3.5 Chemical kinetics. .295

5.5.3.6 Liquid chromatography. .298

5.5.4 Interpretations .298

5.5.4.1 Ambiguities and anomalies. .298

5.5.4.2 A modified derivation .299

5.5.4.3 Interpretation of parameter estimates. .300

5.5.4.4 Confounding effects .301

Solute-solute interactions. .301

Coupling of general medium and solvation effects .301

The cavity surface area .301

The role of interfacial tension .302

6 SWELLING .305

6.1 Modern views on kinetics of swelling of crosslinked elastomers in solvents. . 305

E. YA. DENISYUK, V. V. TERESHATOV

6.1.1 Introduction. .305

6.1.2 Formulation of swelling for a plane elastomer layer .306

6.1.3 Diffusion kinetics of plane layer swelling .310

6.1.4 Experimental study of elastomer swelling kinetics .314

6.1.5 Conclusions. .317

6.2 Equilibrium swelling in binary solvents .318

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

6.3 Swelling data on crosslinked polymers in solvents .327

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

6.4 Influence of structure on equilibrium swelling. .331

VASILIY V. TERESHATOV, VALERY YU. SENICHEV

7 SOLVENT TRANSPORT PHENOMENA .339

7.1 Introduction to diffusion, swelling, and drying .339

GEORGE WYPYCH

7.1.1 Diffusion .339

7.1.2 Swelling .344

7.1.3 Drying .348

7.2 Bubbles dynamics and boiling of polymeric solutions. .356

SEMYON LEVITSKY, ZINOVIY SHULMAN

7.2.1 Rheology of polymeric solutions and bubble dynamics .356


Table of contents v

7.2.1.1 Rheological characterization of solutions of polymers. .356

7.2.1.2 Dynamic interaction of bubbles with polymeric liquid .363

7.2.2 Thermal growth of bubbles in superheated solutions of polymers .372

7.2.3 Boiling of macromolecular liquids .377

7.3 Drying of coated film. .386

SEUNG SU KIM AND JAE CHUN HYUN

7.3.1 Introduction. .386

7.3.2 Theory for the drying. .388

7.3.2.1 Simultaneous heat and mass transfer .388

7.3.2.2 Liquid-vapor equilibrium. .389

7.3.2.3 Heat and mass transfer coefficient .390

7.3.2.4 Prediction of drying rate of coating .392

7.3.2.5 Drying regimes: constant drying rate period (CDRP) and falling

drying rate period (FDRP) .394

7.3.3 Measurement of the drying rate of coated film. .396

7.3.3.1 Thermo-gravimetric analysis .396

7.3.3.2 Rapid scanning FT-IR spectrometer analysis .399

7.3.3.3 High-airflow drying experiment using flame ionization detector (FID)

total hydrocarbon analyzer .401

7.3.3.4 Measurement of drying rate in the production scale dryer .404

7.3.4 Miscellaneous .407

7.3.4.1 Drying of coated film with phase separation .407

7.3.4.2 Drying defects .409

7.3.4.2.1 Internal stress induced defects .409

7.3.4.2.2 Surface tension driven defects .412

7.3.4.2.3 Defects caused by air motion and others .414

7.3.4.3 Control of lower explosive level (LEL) in a multiple zone dryer .414

8 INTERACTIONS IN SOLVENTS AND SOLUTIONS .419

JACOPO TOMASI, BENEDETTA MENNUCCI, CHIARA CAPPELLI

8.1 Solvents and solutions as assemblies of interacting molecules .419

8.2 Basic simplifications of the quantum model .420

8.3 Cluster expansion. .424

8.4 Two-body interaction energy: the dimer .424

8.4.1 Decomposition of the interaction energy of a dimer: variational approach .426

The electrostatic term. .426

The induction term .428

The exchange term .428

The charge transfer term .429

The dispersion term .430

The decomposition of the interaction energy through a variational

approach: a summary .432

8.4.2 Basis set superposition error and counterpoise corrections .433

8.4.3 Perturbation theory approach. .436

8.4.4 Modeling of the separate components of ΔE.441

The electrostatic term. .441

The induction term .445

The dispersion term .446

The exchange (or repulsion) term .447

The other terms .448

A conclusive view .448

8.4.5 The relaxation of the rigid monomer constraint .449

8.5 Three- and many-body interactions .451

Screening many-body effects. .453

Effective interaction potentials .454

8.6 The variety of interaction potentials .456

8.7 Theoretical and computing modeling of pure liquids and solutions .461

8.7.1 Physical models .461


vi HandbookofSolvents

8.7.1.1 Integral equation methods .465

8.7.1.2 Perturbation theories .467

8.7.2 Computer simulations .468

8.7.2.1 Car-Parrinello direct QM simulation .470

8.7.2.2 Semi-classical simulations .472

Molecular dynamics .472

Monte Carlo .473

QM/MM .478

8.7.3 Continuum models .479

8.7.3.1 QM-BE methods: the effective Hamiltonian .482

8.8 Practical applications of modeling .487

Dielectric constant .487

Thermodynamical properties .490

Compressibilities .490

Relaxation times and diffusion coefficients .491

Shear viscosity .492

8.9 Liquid surfaces .492

8.9.1 The basic types of liquid surfaces .493

8.9.2 Systems with a large surface/bulk ratio .495

8.9.3 Studies on interfaces using interaction potentials .497

9 MIXED SOLVENTS .505

Y. Y. FIALKOV, V. L. CHUMAK

9.1 Introduction. .505

9.2 Chemical interaction between components in mixed solvents .505

9.2.1 Processes of homomolecular association. .505

9.2.2 Conformic and tautomeric equilibrium. Reactions of isomerization. .506

9.2.3 Heteromolecular association .507

9.2.4 Heteromolecular associate ionization .507

9.2.5 Electrolytic dissociation (ionic association) .508

9.2.6 Reactions of composition. .508

9.2.7 Exchange interaction .509

9.2.8 Amphoterism of mixed solvent components .509

9.2.8.1 Amphoterism of hydrogen acids .509

9.2.8.2 Amphoterism of L-acids .509

9.2.8.3 Amphoterism in systems H-acid-L-acid .510

9.2.8.4 Amphoterism in binary solutions amine-amine .510

9.3 Physical properties of mixed solvents .511

9.3.1 The methods of expression of mixed solvent compositions .511

9.3.1.1 Permittivity .513

9.3.1.2 Viscosity .515

9.3.1.3 Density, molar volume .516

9.3.1.4 Electrical conductivity .516

9.3.2 Physical characteristics of the mixed solvents with chemical interaction

between components .517

9.3.2.1 Permittivity .518

9.3.2.2 Viscosity .519

9.3.2.3 Density, molar volume .521

9.3.2.4 Conductivity .522

9.3.3 Chemical properties of mixed solvents. .524

9.3.3.1 Autoprotolysis constants .524

9.3.3.2 Solvating ability .526

9.3.3.3 Donor-acceptor properties .527

9.4 Mixed solvent influence on the chemical equilibrium .527

9.4.1 General considerations .527

9.4.2 Mixed solvent effect on the position of equilibrium of homomolecular

association process .529

9.4.3 Mixed solvent influence on the conformer equilibrium .530


Table of contents vii

9.4.4 Solvent effect on the process of heteromolecular association .532

9.4.4.1 Selective solvation. Resolvation .538

9.4.5 Mixed solvent effect on the ion association process .546

9.4.6 Solvent effect on exchange interaction processes .552

Systems with non-associated reagents .552

Systems with one associated participant of equilibrium .553

Systems with two associated participants of equilibrium .553

9.4.7 Mixed solvent effect on processes of complex formation .556

9.5 The mixed solvent effect on the chemical equilibrium thermodynamics .557

10 ACID-BASE INTERACTIONS .565

10.1 General concept of acid-base interactions .565

GEORGE WYPYCH

10.2 Effect of polymer/solvent acid-base interactions: relevance to

the aggregation of PMMA .570

S. BISTAC, M. BROGLY

10.2.1 Recent concepts in acid-base interactions .570

10.2.1.1 The nature of acid-base molecular interactions .571

10.2.1.1.1 The original Lewis definitions .571

10.2.1.1.2 Molecular Orbital (MO) approach to acid-base reactions .571

10.2.1.1.3 The case of hydrogen bonding .573

10.2.1.2 Quantitative determination of acid-base interaction strength .574

10.2.1.2.1 Perturbation theory .574

10.2.1.2.2 Hard-Soft Acid-Base (HSAB) principle .574

10.2.1.2.3 Density functional theory. .575

10.2.1.2.4 Effect of ionocity and covalency: Drago’s concept .576

10.2.1.2.5 Effect of amphotericity of acid-base interaction: Gutmann’s numbers .577

10.2.1.2.6 Spectroscopic measurements: Fowkes’ approach .578

10.2.2 Effect of polymer/solvent interactions on aggregation of stereoregular PMMA 578

10.2.2.1 Aggregation of stereoregular PMMA .578

10.2.2.2 Relation between the complexing power of solvents and their

acid-base properties .579

10.2.3 Influence of the nature of the solvent on the α and β-relaxations of

conventional PMMA .581

10.2.3.1 Introduction. .581

10.2.3.2 Dielectric spectroscopy results .581

10.2.4 Concluding remarks .582

10.3 Solvent effects based on pure solvent scales .583

JAVIER CATALÁN

Introduction. .583

10.3.1 The solvent effect and its dissection into general and specific contributions. . 584

10.3.2 Characterization of a molecular environment with the aid of the

probe/homomorph model. .585

10.3.3 Single-parameter solvent scales: the Y, G, ET(30), P y ,Z,χR,Φ, and S� scales. 587

10.3.3.1 The solvent ionizing power scale or Y scale .587

10.3.3.2 The G values of Allerhand and Schleyer .588

10.3.3.3 The ET(30) scale of Dimroth and Reichardt .588

10.3.3.4 The Py scale of Dong and Winnick. .589

10.3.3.5 The Z scale of Kosower .589

10.3.3.6 The χR scale of Brooker .590

10.3.3.7 The Φ scale of Dubois and Bienvenüe .590

10.3.3.8 The S� scale of Drago .591

10.3.4 Solvent polarity: the SPP scale .591

10.3.5 Solvent basicity: the SB scale .600

10.3.6 Solvent acidity: the SA scale .601

10.3.7 Applications of the pure SPP, SA and SB scales. .605

10.3.7.1 Other reported solvents scales .605

10.3.7.2 Treatment of the solvent effect in: .608


viii HandbookofSolvents

10.3.7.2.1 Spectroscopy .608

10.3.7.2.2 Kinetics .611

10.3.7.2.3 Electrochemistry .612

10.3.7.2.4 Thermodynamics .612

10.3.7.3 Mixtures of solvents. Understanding the preferential solvation model .612

10.4 Acid-base equilibria in ionic solvents (ionic melts) .616

VICTOR CHERGINETS

10.4.1 Acid-base definitions used for the description of donor-acceptor

interactions in ionic media .617

10.4.1.1 The Lewis definition .617

10.4.1.2 The Lux-Flood definition. .618

10.4.2 The features of ionic melts as media for acid-base interactions .618

10.4.2.1 Oxygen-less media .619

10.4.2.2 Oxygen-containing melts. .619

10.4.2.3 The effect of the ionic solvent composition on acid-base equilibria .620

10.4.3 Methods for estimations of acidities of solutions based on ionic melts .623

10.4.4 On studies of the homogeneous acid-base reactions in ionic melts .625

10.4.4.1 Nitrate melts .625

10.4.4.2 Sulphate melts .627

10.4.4.3 Silicate melts .628

10.4.4.4 The equimolar mixture KCl-NaCl .629

10.4.4.5 Other alkaline halide melts .631

10.4.5 Reactions of melts with gaseous acids and bases .632

10.4.5.1 High-temperature hydrolysis of molten halides .632

10.4.5.2 The processes of removal of oxide admixtures from melts .633

11 ELECTRONIC AND ELECTRICAL EFFECTS OF SOLVENTS .639

11.1 Theoretical treatment of solvent effects on electronic and vibrational

spectra of compounds in condensed media. .639

MATI KARELSON

11.1.1 Introduction. .639

11.1.2 Theoretical treatment of solvent cavity effects on electronic-vibrational

spectra of molecules .647

11.1.3 Theoretical treatment of solvent electrostatic polarization on

electronic-vibrational spectra of molecules .649

11.1.4 Theoretical treatment of solvent dispersion effects on

electronic-vibrational spectra of molecules .671

11.1.5 Supermolecule approach to the intermolecular interactions in condensed media 674

11.2 Dielectric solvent effects on the intensity of light absorption and

the radiative rate constant .680

TAI-ICHI SHIBUYA

11.2.1 The Chako formula or the Lorentz-Lorenz correction .680

11.2.2 The generalized local-field factor for the ellipsoidal cavity .680

11.2.3 Dielectric solvent effect on the radiative rate constant. .682

12 OTHER PROPERTIES OF SOLVENTS, SOLUTIONS,

AND PRODUCTS OBTAINED FROM SOLUTIONS. .683

12.1 Rheological properties, aggregation, permeability, molecular structure,

crystallinity, and other properties affected by solvents .683

GEORGE WYPYCH

12.1.1 Rheological properties .683

12.1.2 Aggregation .689

12.1.3 Permeability .693

12.1.4 Molecular structure and crystallinity .697

12.1.5 Other properties affected by solvents .700

12.2 Chain conformations of polysaccharides in different solvents. .706

RANIERI URBANI AND ATTILIO CESÀRO

12.2.1 Introduction. .706

12.2.2 Structure and conformation of polysaccharides in solution .707


Table of contents ix

12.2.2.1 Chemical structure .707

12.2.2.2 Solution chain conformation .707

12.2.3 Experimental evidence of solvent effect on oligosaccharide conformational

equilibria .711

12.2.4 Theoretical evaluation of solvent effect on conformational equilibria of sugars 715

12.2.4.1 Classical molecular mechanics methods .715

12.2.4.2 Molecular dynamic methods .720

12.2.5 Solvent effect on chain dimensions and conformations of polysaccharides .722

12.2.6 Solvent effect on charged polysaccharides and the polyelectrolyte model .726

12.2.6.1 Experimental behavior of polysaccharides polyelectrolytes .726

12.2.6.2 The Haug and Smidsrød parameter: description of the salt effect on the chain

dimension. .727

12.2.6.3 The statistical thermodynamic counterion-condensation theory of Manning. . 729

12.2.6.4 Conformational calculations of charged polysaccharides .731

12.2.7 Conclusions. .733

13 EFFECT OF SOLVENT ON CHEMICAL REACTIONS AND

REACTIVITY. .737

13.1 Solvent effects on chemical reactivity .737

ROLAND SCHMID

13.1.1 Introduction. .737

13.1.2 The dielectric approach. .737

13.1.3 The chemical approach .738

13.1.4 Dielectric vs. chemical approach .742

13.1.5 Conceptual problems with empirical solvent parameters .744

13.1.6 The physical approach .746

13.1.7 Some highlights of recent investigations .753

The like dissolves like rule .753

Water’s anomalies .755

The hydrophobic effect. .758

The structure of liquids .762

Solvent reorganization energy in ET .765

The solution ionic radius .768

13.1.8 The future of the phenomenological approach .772

13.2 Solvent effects on free radical polymerization .777

MICHELLE L. COOTE AND THOMAS P. DAVIS

13.2.1 Introduction. .777

13.2.2 Homopolymerization .777

13.2.2.1 Initiation .777

13.2.2.2 Propagation .778

13.2.2.3 Transfer. .779

13.2.2.4 Termination. .779

13.2.3 Copolymerization. .779

13.2.3.1 Polarity effect. .780

13.2.3.1.1 Basic mechanism .780

13.2.3.1.2 Copolymerization model .781

13.2.3.1.3 Evidence for polarity effects in propagation reactions .781

13.2.3.2 Radical-solvent complexes .782

13.2.3.2.1 Basic mechanism .782

13.2.3.2.2 Copolymerization model .782

13.2.3.2.3 Experimental evidence .783

13.2.3.3 Monomer-solvent complexes. .785

13.2.3.3.1 Introduction. .785

13.2.3.3.2 Monomer-monomer complex participation model .785

13.2.3.3.3 Monomer-monomer complex dissociation model .790

13.2.3.3.4 Specific solvent effects .791

13.2.3.4 Bootstrap model .791

13.2.3.4.1 Basic mechanism .791


x HandbookofSolvents

13.2.3.4.2 Copolymerization model .791

13.2.3.4.3 Experimental evidence .793

13.2.4 Concluding remarks .795

13.3 Effects of organic solvents on phase-transfer catalysis .798

MAW-LING WANG

13.3.1 Two-phase phase-transfer catalytic reactions .801

13.3.1.1 Theoretical analysis of the polarity of the organic solvents and the reactions. . 801

13.3.1.2 Effect of organic solvent on the reaction in various reaction systems .805

13.3.1.3 Effects of the organic solvents on the reactions in other catalysts .811

13.3.1.4 Effect of the volume of organic solvent and water on the reactions in

various reaction systems .822

13.3.1.5 Effects of organic solvents on other phase-transfer catalytic reactions .825

13.3.1.6 Other effects on the phase-transfer catalytic reactions .828

13.3.2 Three-phase reactions (triphase catalysis) .830

13.3.2.1 The interaction between solid polymer (hydrophilicity) and the organic

solvents .830

13.3.2.2 Effect of solvents on the reaction in triphase catalysis. .833

13.3.2.3 Effect of volume of organic solvent and water on the reactions in

triphase catalysis .836

13.4 Effect of polymerization solvent on the chemical structure and curing of

aromatic poly(amideimide). .841

NORIO TSUBOKAWA

13.4.1 Introduction. .841

13.4.2 Effect of solvent on the chemical structure of PAI. .842

13.4.2.1 Imide and amide bond content of PAI .842

13.4.2.2 Intrinsic viscosity and carboxyl group content .844

13.4.3 Effect of solvent on the curing of PAI by heat treatment .844

13.4.3.1 Chemical structure of PAI after heat treatment .844

13.4.3.2 Curing PAI by post-heating .845

13.4.4 Conclusions. .846

14 SOLVENT USE IN VARIOUS INDUSTRIES .847

14.1 Adhesives and sealants .847

GEORGE WYPYCH

14.2 Aerospace. .852

GEORGE WYPYCH

14.3 Asphalt compounding .855

GEORGE WYPYCH

14.4 Biotechnology .856

14.4.1 Organic solvents in microbial production processes .856

MICHIAKI MATSUMOTO, SONJA ISKEN, JAN A. M. DE BONT

14.4.1.1 Introduction. .856

14.4.1.2 Toxicity of organic solvents .859

14.4.1.3 Solvent-tolerant bacteria .862

14.4.1.4 Biotransformation using solvent-tolerant microorganisms. .863

14.4.2 Solvent-resistant microorganisms .865

TILMAN HAHN, KONRAD BOTZENHART

14.4.2.1 Introduction. .865

14.4.2.2 Toxicity of solvents for microorganisms .865

14.4.2.2.1 Spectrum of microorganisms and solvents .865

14.4.2.2.2 Mechanisms of solvent toxicity for microorganisms. .866

14.4.2.3 Adaption of microorganisms to solvents - solvent-resistant microorganisms. . 867

14.4.2.3.1 Spectrum of solvent-resistant microorganisms. .867

14.4.2.3.2 Adaption mechanisms of microorganisms to solvents .868

14.4.2.4 Solvents and microorganisms in the environment and industry - examples .869

14.4.2.4.1 Examples .869

14.4.3 Choice of solvent for enzymatic reaction in organic solvent. .872

TSUNEO YAMANE


Table of contents xi

14.4.3.1 Introduction. .872

14.4.3.2 Classification of organic solvents .872

14.4.3.3 Influence of solvent parameters on nature of enzymatic reactions in

organic media. .873

14.4.3.4 Properties of enzymes affected by organic solvents .875

14.4.3.5 Concluding remarks .879

14.5 Coil coating. .880

GEORGE WYPYCH

14.6 Cosmetics and personal care products .881

GEORGE WYPYCH

14.7 Dry cleaning - treatment of textiles in solvents .883

KASPAR D. HASENCLEVER

14.7.1 Dry cleaning .883

14.7.1.1 History of dry cleaning .883

14.7.1.2 Basis of dry cleaning .884

14.7.1.3 Behavior of textiles in solvents and water .885

14.7.1.4 Removal Altium Designer 20.2.6 Build 244 Crack soiling in dry cleaning. .886

14.7.1.5 Activity of detergents in dry cleaning .887

14.7.1.6 Dry cleaning processes .888

14.7.1.7 Recycling of solvents in dry cleaning .890

14.7.2 Spotting. .891

14.7.2.1 Spotting in dry cleaning .891

14.7.2.2 Spotting agents .891

14.7.2.3 Spotting procedure .892

14.7.3 Textile finishing .893

14.7.3.1 Waterproofing .893

14.7.3.2 Milling .893

14.7.3.3 Antistatic finishing .893

14.8 Electronic industry - CFC-free alternatives for cleaning in electronic industry. 894

MARTIN HANEK, NORBERT LÖW, ANDREAS MÜHLBAUER

14.8.1 Cleaning requirements in the electronic industry .894

14.8.2 Available alternatives. .896

14.8.2.1 Water based systems; advantages and disadvantages .897

14.8.2.1.1 Cleaning with DI - water .897

14.8.2.1.2 Cleaning with alkaline water-based media .898

14.8.2.1.3 Aqueous-based cleaning agents containing water soluble organic components. 898

14.8.2.1.4 Water-based cleaning agents based on MPC® Technology

(MPC = Micro Phase Cleaning) .899

14.8.2.1.5 Advantages and disadvantages of aqueous cleaning media .899

14.8.2.2 Semi-aqueous cleaners based on halogen-free solvents, advantages and

disadvantages .900

14.8.2.2.1 Water insoluble cleaning fluids .901

14.8.2.2.2 Water-soluble, water-based cleaning agents .901

14.8.2.2.3 Comparison of the advantages (+) and disadvantages (-) of semi-aqueous

cleaning fluids .901

14.8.2.3 Other solvent based cleaning systems .902

14.8.3 Cleaning of tools and auxiliaries .904

14.8.3.1 Cleaning substrates and contamination. .904

14.8.3.2 Compatibility of stencil and cleaning agent .905

14.8.3.3 Different cleaning media .906

14.8.3.4 Comparison of manual cleaning vs. automated cleaning. .908

14.8.3.5 Cleaning equipment for stencil cleaning applications .909

14.8.3.6 Stencil cleaning in screen printing machines. .911

14.8.3.7 Summary .911

14.8.4 Cleaning agents and process technology available for cleaning PCB .911

14.8.4.1 Flux remove and aqueous process .911

14.8.4.1.1 The limits of a no-clean process .911


xii HandbookofSolvents

14.8.4.1.2 Different cleaning media and cleaning processes .912

14.8.4.1.3 Semi-aqueous cleaning .913

14.8.4.1.4 Aqueous cleaning in spray in air cleaning equipment .913

14.8.4.2 Flux removal from printed circuit boards - water-free cleaning processes .914

14.8.4.2.1 Water-free cleaning processes using HFE (hydrofluoroethers) in combination

with a cosolvent .915

14.8.4.2.2 Water-free cleaning processes in closed, one-chamber vapor defluxing systems 916

14.8.5 Criteria for assessment and evaluation of cleaning results .917

14.8.6 Cost comparison of different cleaning processes. .919

14.9 Fabricated metal products .920

GEORGE WYPYCH

14.10 Food industry - solvents for extracting vegetable oils .923

PHILLIP J. WAKELYN, PETER J. WAN

14.10.1 Introduction. .923

14.10.2 Regulatory concerns .924

14.10.2.1 Workplace regulations .925

14.10.2.1.1 Air Contaminants Standard (29 CFR 1910.1000) .925

14.10.2.1.2 Hazard Communication Standard (HCS) (29 CFR 1910.1200) .926

14.10.2.1.3 Process Safety Management (PSM) Standard (29 CFR 1910.119) .927

14.10.2.2 Environmental regulations .927

14.10.2.2.1 Clean Air Act (CAA; 42 U.S. Code 7401 et seq.) .929

14.10.2.2.2 Clean Water Act (CWA; 33 U.S. Code 1251 et seq.) .932

14.10.2.2.3 Resource Conservation and Recovery Act (RCRA; 42 U.S.Code 6901 et seq.). 932

14.10.2.2.4 Emergency Planning and Community Right-to-Know Act (EPCRA;

42 U.S. Code 11001 et seq.) .933

14.10.2.2.5 Toxic Substances Control Act (TSCA; 15 U.S. Code 2601 et seq.) .933

14.10.2.3 Food safety .934

14.10.3 The solvent extraction process .935

14.10.3.1 Preparation for extraction .936

14.10.3.2 Oil extraction .938

14.10.3.3 Processing crude oil .938

14.10.4 Review of solvents studied for extraction efficiency. .940

14.10.4.1 Hydrocarbon solvents .941

14.10.4.1.1 Nomenclature, structure, composition and properties of hydrocarbons .942

14.10.4.1.2 Performance of selected hydrocarbon solvents. .942

14.10.5 Future trends .946

14.11 Ground transportation .950

GEORGE WYPYCH

14.12 Inorganic chemical industry .950

GEORGE WYPYCH

14.13 Iron and steel industry .951

GEORGE WYPYCH

14.14 Lumber and wood products - Wood preservation treatment:

significance of solvents. .953

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

14.14.1 General aspects .953

14.14.2 Role of solvents .954

14.14.2.1 Occurrence .954

14.14.2.2 Technical and environmental aspects .955

14.15 Medical applications .955

GEORGE WYPYCH

14.16 Metal casting .957

GEORGE WYPYCH

14.17 Motor vehicle assembly .958

GEORGE WYPYCH

14.18 Organic chemical industry .962

GEORGE WYPYCH


Table of contents xiii

14.19 Paints and coatings .963

14.19.1 Architectural surface coatings and solvents .963

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

14.19.1.1 General aspects .963

14.19.1.2 Technical aspects and properties of coating materials .963

14.19.2 Recent advances in coalescing solvents for waterborne coatings .969

DAVID RANDALL

14.19.2.1 Introduction. .969

14.19.2.2 Water based coatings .970

14.19.2.3 Emulsion polymers .970

14.19.2.4 Role of a coalescing solvent .971

14.19.2.5 Properties of coalescing agents. .972

14.19.2.5.1 Hydrolytic stability .972

14.19.2.5.2 Water solubility. .972

14.19.2.5.3 Freezing point .972

14.19.2.5.4 Evaporation rate .972

14.19.2.5.5 Odor .972

14.19.2.5.6 Color .973

14.19.2.5.7 Coalescing efficiency. .973

14.19.2.5.8 Incorporation .973

14.19.2.5.9 Improvement of physical properties .973

14.19.2.5.10 Biodegradability. .973

14.19.2.5.11 Safety .973

14.19.2.6 Comparison of coalescing solvents. .973

14.19.2.7 Recent advances in diester coalescing solvents .974

14.19.2.8 Appendix - Classification of coalescing solvents .975

14.20 Petroleum refining industry .975

GEORGE WYPYCH

14.21 Pharmaceutical industry .977

14.21.1 Use of solvents in the manufacture of drug substances (DS) and drug

products (DP). .977

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

14.21.1.1 Introduction. .977

14.21.1.2 Where are solvents used in the manufacture of pharmaceutical drugs? .979

14.21.1.2.1 Intermediates of synthesis, DS and excipients .979

14.21.1.2.2 Drug products .984

14.21.1.3 Impacts of the nature of solvents and their quality on the physicochemical

characteristics of raw materials and DP .985

14.21.1.3.1 Raw materials (intermediates, DS, excipients). .985

14.21.1.3.2 Drug product .988

14.21.1.3.3 Conclusions. .989

14.21.1.4 Setting specifications for solvents .990

14.21.1.4.1 Solvents used for the raw material manufacture .990

14.21.1.4.2 Solvents used for the DP manufacture .991

14.21.1.5 Quality of solvents and analysis .991

14.21.1.5.1 Quality of solvents used in spectroscopy. .991

14.21.1.5.2 Quality of solvents used in chromatography .993

14.21.1.5.3 Quality of solvents used in titrimetry .996

14.21.1.6 Conclusions. .996

14.21.2 Predicting cosolvency for pharmaceutical and environmental applications .997

AN LI

14.21.2.1 Introduction. .997

14.21.2.2 Applications of cosolvency in pharmaceutical sciences and industry .998

14.21.2.3 Applications of cosolvency in environmental sciences and engineering. .1000

14.21.2.4 Experimental observations .1001

14.21.2.5 Predicting cosolvency in homogeneous liquid systems .1003

14.21.2.6 Predicting cosolvency in non-ideal liquid mixtures .1007


xiv HandbookofSolvents

14.21.2.7 Summary .1013

14.22 Polymers and man-made fibers. .1016

GEORGE WYPYCH

14.23 Printing industry .1020

GEORGE WYPYCH

14.24 Pulp and paper .1023

GEORGE WYPYCH

14.25 Rubber and plastics. .1025

GEORGE WYPYCH

14.26 Use of solvents in the shipbuilding and ship repair industry. .1026

MOHAMED SERAGELDIN, DAVE REEVES

14.26.1 Introduction. .1026

14.26.2 Shipbuilding and ship repair operations .1026

14.26.3 Coating operations .1026

14.26.4 Cleaning operations using organic solvents .1027

14.26.4.1 Surface preparation and initial corrosion protection .1027

14.26.4.2 Cleaning operations after coatings are applied Handy Recovery 5.5 Crack + Serial Key Download Free Full Maintenance cleaning of equipment items and components .1031

14.26.5 Marine coatings. .1031

14.26.6 Thinning of marine coatings .1032

14.26.7 Solvent emissions .1033

14.26.8 Solvent waste .1035

14.26.9 Reducing solvent usage, emissions, and waste. .1036

14.26.10 Regulations and guidelines for cleaning solvents .1037

14.27 Stone, clay, glass, and concrete .1039

GEORGE WYPYCH

14.28 Textile industry .1041

GEORGE WYPYCH

14.29 Transportation equipment cleaning. .1042

GEORGE WYPYCH

14.30 Water transportation .1042

GEORGE WYPYCH

14.31 Wood furniture .1043

GEORGE WYPYCH

14.32 Summary .1045

15 METHODS OF SOLVENT DETECTION AND TESTING. .1053

15.1 Standard methods of solvent analysis .1053

GEORGE WYPYCH

15.1.1 Alkalinity and acidity. .1053

15.1.2 Autoignition temperature. .1054

15.1.3 Biodegradation potential .1054

15.1.4 Boiling point .1055

15.1.5 Bromine index .1055

15.1.6 Calorific value .1056

15.1.7 Cleaning solvents. .1056

15.1.8 Color .1056

15.1.9 Corrosion (effect of solvents) .1057

15.1.10 Density .1057

15.1.11 Dilution ratio .1057

15.1.12 Dissolving and extraction .1058

15.1.13 Electric properties .1058

15.1.14 Environmental stress crazing .1059

15.1.15 Evaporation rate .1059

15.1.16 Flammability limits. .1059

15.1.17 Flash point .1060

15.1.18 Freezing point .1061

15.1.19 Free halogens in halogenated solvents .1061


Table of contents xv

15.1.20 Gas chromatography .1061

15.1.21 Labeling .1062

15.1.22 Odor .1062

15.1.23 Paints standards related to solvents .1063

15.1.24 pH. .1063

15.1.25 Purity .1063

15.1.26 Refractive index .1066

15.1.27 Residual solvents .1066

15.1.28 Solubility .1066

15.1.29 Solvent partitioning in soils .1066

15.1.30 Solvent extraction .1067

15.1.31 Specifications. .1067

15.1.32 Sustained burning .1067

15.1.33 Vapor pressure .1068

15.1.34 Viscosity .1068

15.1.35 Volatile organic compound content, VOC .1069

15.2 Special methods of solvent analysis .1078

15.2.1 Use of breath monitoring to assess exposures to volatile organic solvents. . 1078

MYRTO PETREAS

15.2.1.1 Principles of breath monitoring .1078

15.2.1.2 Types of samples used for biological monitoring .1080

15.2.1.3 Fundamentals of respiratory physiology .1080

15.2.1.3.1 Ventilation .1081

15.2.1.3.2 Partition coefficients .1081

15.2.1.3.3 Gas exchange .1082

15.2.1.4 Types of exhaled air samples. .1083

15.2.1.5 Breath sampling methodology .1084

15.2.1.6 When is breath monitoring appropriate? .1087

15.2.1.7 Examples of breath monitoring. .1088

15.2.2 A simple test to determine toxicity using bacteria .1095

JAMES L. BOTSFORD

15.2.2.1 Introduction. .1095

15.2.2.2 Toxicity defined .1095

15.2.2.3 An alternative. .1097

15.2.2.4 Chemicals tested .1099

15.2.2.5 Comparisons with other tests. .1103

15.2.2.6 Toxic herbicides .1107

15.2.2.7 Toxicity of divalent cations .1108

15.2.2.8 Toxicity of organics in the presence of EDTA .1108

15.2.2.9 Mechanism for reduction of the dye .1110

15.2.2.10 Summary .1111

15.2.3 Description of an innovative GC method to assess the influence of crystal

texture and drying conditions on residual solvent content in pharmaceutical

products. .1113

CHRISTINE BARTHÉLÉMY, MICHEL BAUER

15.2.3.1 Description of the RS determination method .1113

15.2.3.2 Application: Influence of crystal texture and drying conditions on RS content. 1114

15.2.3.2.1 First example: monocrystalline particles of paracetamol .1116

15.2.3.2.2 Second example: polycrystalline particles of meprobamate and ibuprofen. . 1119

15.2.3.2.3 Third example: polycrystalline particles of paracetamol. .1122

16 RESIDUAL SOLVENTS IN PRODUCTS .1125

16.1 Residual solvents in various products .1125

GEORGE WYPYCH

16.2 Residual solvents in pharmaceutical substances .1129

MICHEL BAUER, CHRISTINE BARTHÉLÉMY

16.2.1 Introduction. .1129

16.2.2 Why should we look for RS?. .1129


xvi HandbookofSolvents

16.2.2.1 Modifying the acceptability of the drug product .1129

16.2.2.2 Modifying the physico-chemical properties of drug substances (DS) and

drug products (DP) .1130

16.2.2.3 Implications of possible drug/container interactions .1131

16.2.2.4 As a tool for forensic applications .1131

16.2.2.5 As a source of toxicity .1131

16.2.2.5.1 General points .1131

16.2.2.5.2 Brief overview of the toxicology of solvents. .1132

16.2.3 How to identify and control RS in pharmaceutical substances?. .1133

16.2.3.1 Loss of weight .1133

16.2.3.2 Miscellaneous methods. .1133

16.2.3.3 Gas chromatography (GC) .1134

16.2.3.3.1 General points .1134

16.2.3.3.2 Review of methods .1135

16.2.3.3.3 Official GC methods for RS determination .1139

16.2.4 How to set specifications? Examination of the ICH guidelines for residual

solvents .1140

16.2.4.1 Introduction. .1143

16.2.4.2 Classification of residual solvents by risk assessment .1143

16.2.4.3 Definition of PDE. Method for establishing exposure limits .1143

16.2.4.4 Limits for residual solvents. .1143

16.2.4.5 Analytical procedures .1145

16.2.4.6 Conclusions regarding the ICH guideline .1145

16.2.5 Conclusions. .1146

17 ENVIRONMENTAL IMPACT OF SOLVENTS. .1149

17.1 The environmental fate and movement of organic solvents in water, soil,

andair .1149

WILLIAM R. ROY

17.1.1 Introduction. .1149

17.1.2 Water .1150

17.1.2.1 Solubility .1150

17.1.2.2 Volatilization .1150

17.1.2.3 Degradation. .1151

17.1.2.4 Adsorption .1151

17.1.3 Soil .1151

17.1.3.1 Volatilization .1151

17.1.3.2 Adsorption .1152

17.1.3.3 Degradation. .1153

17.1.4 Air .1153

17.1.4.1 Degradation. .1153

17.1.4.2 Atmospheric residence time .1154

17.1.5 The 31 solvents in water .1154

17.1.5.1 Solubility .1154

17.1.5.2 Volatilization from water. .1155

17.1.5.3 Degradation in water .1155

17.1.6 Soil .1157

17.1.6.1 Volatilization .1157

17.1.6.2 Adsorption .1159

17.1.6.3 Degradation. .1160

17.1.7 Air .1161

17.2 Fate-based management of organic solvent-containing wastes .1162

WILLIAM R. ROY

17.2.1 Introduction. .1162

17.2.1.1 The waste disposal site .1163

17.2.1.2 The advection-dispersion model and the required input .1164

17.2.1.3 Maximum permissible concentrations .1164

17.2.1.4 Distribution of organic compounds in leachate .1164


Table of contents xvii

17.2.2 Movement of solvents in groundwater .1166

17.2.3 Mass limitations .1167

17.3 Environmental fate and ecotoxicological effects of glycol ethers .1169

JAMES DEVILLERS, AURÉLIE CHEZEAU, ANDRÉ CICOLELLA, ERIC THYBAUD

17.3.1 Introduction. .1169

17.3.2 Occurrence .1170

17.3.3 Environmental behavior .1171

17.3.4 Ecotoxicity .1175

17.3.4.1 Survival and growth .1175

17.3.4.2 Reproduction and development .1185

17.3.5 Conclusion .1187

17.4 Organic solvent impacts on tropospheric air pollution. .1188

MICHELLE BERGIN, ARMISTEAD RUSSELL

17.4.1 Sources and impacts of volatile solvents .1188

17.4.2 Modes and scales of impact .1189

17.4.2.1 Direct exposure .1189

17.4.2.2 Formation of secondary compounds .1190

17.4.2.3 Spatial scales of secondary effects .1190

17.4.2.3.1 Global impacts .1190

17.4.2.3.2 Stratospheric ozone depletion .1191

17.4.2.3 Global climate forcing .1191

17.4.2.4 Urban and regional scales .1192

17.4.3 Tropospheric ozone. .1192

17.4.3.1 Effects .1192

17.4.3.2 Tropospheric photochemistry and ozone formation .1193

17.4.3.3 Assessing solvent impacts on ozone and VOC reactivity .1195

17.4.3.3.1 Quantification of solvent emissions on ozone formation .1196

17.4.4 Regulatory approaches to ozone control and solvents .1198

17.4.5 Summary .1299

18 CONCENTRATION OF SOLVENTS IN VARIOUS INDUSTRIAL

ENVIRONMENTS .1201

18.1 Measurement and estimation of solvents emission and odor. .1201

MARGOT SCHEITHAUER

18.1.1 Definition “solvent” and “volatile organic compounds” (VOC) .1201

18.1.2 Review of sources of solvent emissions .1203

18.1.2.1 Causes for emissions .1203

18.1.2.2 Emissions of VOCs from varnishes and paints .1203

18.1.2.3 VOC emissions from emulsion paints .1205

18.1.3 Measuring of VOC-content in paints and varnishes. .1205

18.1.3.1 Definition of low-emissive coating materials .1205

18.1.3.2 Determination of the VOC content according to ASTM D 3960-1 .1205

18.1.3.3 Determination of the VOC content according to ISO/DIS 11 890/1 and 2. . 1206

18.1.3.3.1 VOC content > 15% .1206

18.1.3.3.2 VOC content > 0.1 and < 15 %. .1208

18.1.3.4 Determination of VOC-content in water-thinnable emulsion paints

(in-can VOC) .1208

18.1.4 Measurement of solvent emissions in industrial plants .1209

18.1.4.1 Plant requirements .1209

18.1.4.2 The determination of the total carbon content in mg C/Nm³. .1214

18.1.4.2.1 Flame ionization detector (FID) .1214

18.1.4.2.2 Silica gel approach .1214

18.1.4.3 Qualitative and quantitative assessment of individual components in the

exhaust-gas .1215

18.1.4.3.1 Indicator tubes .1215

18.1.4.3.2 Quantitative solvent determination in exhaust gas of plants by means of

gas-chromatography .1215

18.1.5 “Odor” definition .1219


xviii HandbookofSolvents

18.1.6 Measurement of odor in materials and industrial plants .1222

18.1.6.1 Introduction. .1222

18.1.6.2 Odor determination by means of the “electronic nose” .1222

18.1.6.3 Odor determination by means of the olfactometer .1223

18.1.6.4 Example for odor determination for selected materials: Determination of

odorant concentration in varnished furniture surfaces .1223

18.1.6.5 Example of odor determination in industrial plants: Odor measurement in

an industrial varnishing plant. .1225

18.2 Prediction of organic solvents emission during technological processes .1227

KRZYSZTOF M. BENCZEK, JOANNA KURPIEWSKA

18.2.1 Introduction. .1227

18.2.2 Methods of degreasing .1227

18.2.3 Solvents. .1228

18.2.4 Identification of the emitted compounds .1228

18.2.5 Emission of organic solvents during technological processes .1228

18.2.6 Verification of the method .1230

18.2.7 Relationships between emission and technological parameters .1231

18.2.7.1 Laboratory test stand .1231

18.2.7.2 The influence of temperature on emission .1231

18.2.7.3 The influence of air velocity on emission .1232

18.2.7.4 The relationship between the mass of solvent on wet parts and emissions. . 1232

18.2.8 Emission of solvents .1232

18.2.9 Verification in industrial conditions .1232

18.3 Indoor air pollution by solvents contained in paints and varnishes .1234

TILMAN HAHN, KONRAD BOTZENHART, FRITZ SCHWEINSBERG, GERHARD VOLLAND

18.3.1 Composition - solvents in paints and varnishes. Theoretical aspects .1234

18.3.2 Occurrence of solvents in paints and varnishes .1235

18.3.2.1 Solvents in products .1235

18.3.2.2 Paints and varnishes .1237

18.3.3 Emission of solvents .1240

18.3.3.1 Emission .1240

18.3.3.2 Immission. .1242

18.3.4 Effects on health of solvents from paints and varnishes .1243

18.3.4.1 Exposure .1243

18.3.4.2 Health effects .1243

18.3.4.2.1 Toxic responses of skin and mucose membranes .1243

18.3.4.2.2 Neurological disorders .1244

18.3.4.2.3 Carcinogenic effects .1245

18.3.4.2.4 Respiratory effects .1246

18.3.4.2.5 Toxic responses of blood .1247

18.3.4.2.6 Toxic responses of the reproductive system .1247

18.3.4.2.7 Toxic responses of other organ systems .1247

18.3.5 Methods for the examination of solvents in paints and varnishes .1248

18.3.5.1 Environmental monitoring .1248

18.3.5.1.1 Solvents in products .1248

18.3.5.1.2 Emission of solvents .1248

18.3.5.2 Biological monitoring of solvents in human body fluids .1248

18.3.5.2.1 Solvents and metabolites in human body fluids and tissues .1248

18.3.5.2.2 Biomarkers .1248

18.4 Solvent uses with exposure risks .1251

pentti kalliokoski, kai savolinen

18.4.1 Introduction. .1251

18.4.2 Exposure assessment .1252

18.4.3 Production of paints and printing inks .1255

18.4.4 Painting .1256

18.4.5 Printing .1257

18.4.6 Degreasing, press cleaning and paint removal .1258


Table of contents xix

18.4.7 Dry cleaning .1260

18.4.8 Reinforced plastics industry .1261

18.4.9 Gluing .1262

18.4.10 Other .1262

18.4.11 Summary .1263

19 REGULATIONS .1267

CARLOS M. NU ~ NEZ

19.1 Introduction. .1267

19.2 Air laws and regulations .1282

19.2.1 Clean Air Act Amendments of 1990 .1282

19.2.1.1 Background. .1282

19.2.1.2 Title I - Provisions for Attainment and Maintenance of National Ambient

Air Quality Standards .1284

19.2.1.3 Title III - Hazardous Air Pollutants .1288

19.2.1.4 Title V - Permits .1292

19.2.1.5 Title VI - Stratospheric Ozone Protection .1292

19.3 Water laws and regulations. .1293

19.3.1 Clean Water Act .1293

19.3.1.1 Background. .1293

19.3.1.2 Effluent Limitations .1293

19.3.1.3 Permit Program .1294

19.3.2 Safe Drinking Water Act .1294

19.3.2.1 Background. .1294

19.3.2.2 National Primary Drinking Water Regulations. .1295

19.4 Land laws & regulations .1295

19.4.1 Resource Conservation and Recovery Act (RCRA) .1295

19.4.1.1 Background. .1295

19.4.1.2 RCRA, Subtitle C - Hazardous Waste .1296

19.5 Multimedia laws and regulations. .1297

19.5.1 Pollution Prevention Act of 1990 .1297

19.5.1.1 Background. .1297

19.5.1.2 Source Reduction Provisions .1298

19.5.2 Toxic Substances Control Act .1300

19.5.2.1 Background. .1300

19.5.2.2 Controlling toxic substances .1300

19.6 Occupational laws and regulations .1301

19.6.1 Occupational Safety and Health Act .1301

19.6.1.1 Background. .1301

19.6.1.2 Air contaminants exposure limits .1301

Источник: https://www.yumpu.com/en/document/view/10607080/handbook-of-solvents-george-wypych-chemtech-ventech
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Drilling And Blasting Of Rocks Lengkap.pdf

DRILLING ÄND BLASTING OF ROCKS CARLOS LOPEZ JIMENO Project Director for EPM, SA

EMLIO LOPEZ JIMENO FRANCISCO JAVIER AYALA CARCEDO Project Director for ITGE Translated by

YVONNE VISSER DE RAMIRO

A.A. BALKEMA / ROTTERDAM / BROOKFIELD / 1995

This work has been totally financed by the Geornining Technological Institute of Spain under contract with the E.F?M.,S.A. Cornpany (Estudios y Proyectos Mineros, S.A.).

Authorization to photocopy iterns for internal or personal use, or the internal or personal use of specific clients, is granted by A.A.Balkerna, Rotterdarn, provided that the base fee of US$1.50 per copy, plus US$O.lO per Page is paid directly to Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, USA. For those organizations that have been granted a photocopy license by CCC, a separate systern of payrnent has been arranged. The fee code for users of the Transactional Reporting Service is: 90 5410 199 7/95 US$1.50 + US$O. 10. Original text: Manual de perforacion y voladura de rocas O 1987 Instituto Geologico y Minero de Espaila Revised and updated edition in English: O 1995 A.A. Balkerna, PO. Box 1675,3000 BR Rotterdarn, Netherlands (Fax: +3 1.10.4135947)

Distributed in USA & Canada by: A.A. Balkema Publishers, Old Post Road, Brookfield, VT 05036, USA (Fax: 802.276.3837) Printed in the Netherlands

Contents

FOREWORD PREFACE ACKNOWLEDGEMENTS 1 ROCK DRILLING METHODS 1.1 Introduction 1.2 Types of drilling operations used in rock breakage 1.3 Fields of application for the different drilling methods 1.4 Classification of the rocks and their principal physical properties References 2 ROTARY PERCUSSIVE DRILLING 2.1 Introduction 2.2 Fundamentals of rotary percussive drilling 2.3 Top hammer drilling 2.4 Drilling with down the hole harnmer 2.5 Advance systems 2.6 Mounting systems 2.7 Dust collectors 2.8 Inclination instruments 2.9 Penetration rate 2.10 Average penetration rate 2.1 1 Calculation of drilling 'costs References 3 ROTARY PERCUSSIVE DRILLING ACCESSORIES 3.1 Introduction 3.2 Types of threads 3.3 Shank adaptors 3.4 Dnll steel 3.5 Couplings 3.6 Dnll bits 3.7 Calculation of the necessary drilling accessories 3.8 Care and maintenance of the bits 3.9 Care and maintenance of drill steel 3.10 Guide for identifying accessory failure and its causes References

4 ROTARY DRILLING WITH ROLLING TRICONE BITS 4.1 Introduction 4.2 Mounting and propulsion systems 4.3 Power sources 4.4 Rotation systems 4.5 Pulldown/hoisting systems 4.6 Mast and pipe changer 4.7 Control cabin 4.8 System for flushing drill cuttings 4.9 Dnll string 4.10 Auxiliary elements 4.1 1 Operative practice. Drilling parameters 4.12 Penetration rate 4.13 Calculation of drilling costs References 5 ROLLING CONE ROCK BITS 5.1 Rolling cone rock bits 5.2 Major components and design features 5.3 The metallurgy of rolling cone rock bits 5.4 Types of rolling cone bits 5.5 Bit type selection 5.6 Effects of the operating parameters on the rolling cone bits 5.7 Nozzle selection 5.8 Evaluation of du11 rolling cones 5.9 Example of roller iricone bit selection 5.10 IDAC Codes References

6 ROTARY DRILLING WITH CUTTING ACTION 6.1 Introduction 6.2 Fundamentals of drilling with cutting action 6.3 Flushing of drill cuttings 6.4 Cutting tools References 7 SPECIAL DRILLING METHODS AND MOLINTING SYSTEMS 7.1 Introduction 7.2 Drilling through overburden 7.3 Shaft sinking 7.4 Raise driving

Contents

7.5 Jet piercing 7.6 Water-jet drilling 7.7 Drilling ornamental rock References

12.2 Explosive cost 12.3 Charge diameter 12.4 Rock characteristics 12.5 Volume of rock to be blasted 12.6 Atmospheric conditions 12.7 Presence of water 12.8 Environmental problems 12.9 Fumes 12.10 Safety conditions 12.11 Explosive atmospheres 12.12 Supply problems References

8 COMPRESSORS 8.1 Introduction 8.2 Types of compressors 8.3 Drive 8.4 Auxiliary elements 8.5 Calculating pressure drops References 9 THERMOCHEMISTRY OF EXPLOSIVES AND THE DETONATION PROCESS 9.1 Introduction 9.2 Deflagration and detonation 9.3 Detonation process of an explosive 9.4 Thermochemistry of the explosives 9.5 Heat of explosion 9.6 Oxygen balance 9.7 Volume of explosion 9.8 Minimum energy available 9.9 Temperature of the explosion 9.10 Pressure of the explosion References

92 92 92 93 94 94 95 95 96 96 96 97

10 PROPERTIES OF EXPLOSIVES 10.1 Introduction 10.2 Strength and energy 10.3 Detonation velocity 10.4 Density 10.5 Detonation pressure 10.6 Stability 10.7 Water resistance 10.8 Sensitivity 10.9 Detonation transmission 10.10 Desensitization 10.11 Resistance to low temperatures 10.12 Fumes References

98 98 98 101 102 102 102 102 102 103 104 104 104 105

11 INDUSTRIAL EXPLOSIVES 11.1 Introduction 11.2 Dry blasting agents 11.3 Slurries 11.4 Emulsions 11.5 Heavy ANFO 11.6 Gelatin dynamites 11.7 Granular dynamite 11.8 Permissible explosives 11.9 Blackpowders 11.10 Two-component explosives 11.11 Explosives cornmercialized in Spain References

106 106 106 110 111 113 115 115 116 116 117 117 117

12 EXPLOSIVE SELECTION CRITERIA 12.1 Introduction

119 119

13 BLASTING ACCESSORIES 13.1 Introduction 13.2 Nonelectric initiation systems 13.3 Electric initiation systems 13.4 Sources of energy 13.5 Other accessories References

123 123 123 127 130 132 135

14 INITIATION AND PRIMING SYSTEMS 14.1 Introduction 14.2 Priming and boostering bulk ANFO-type blasting agents 14.3 Priming cartridge ANFO type blasting agents 14.4 Priming pumped or poured slurry and emulsion blasting agents 14.5 Priming cartridged watergel and emulsion blasting agents 14.6 Location of primers 14.7 Priming conventional cartridged explosives References

136 136

15 MECHANIZED SYSTEMS FOR CHARGING AND DEWATERING BLASTHOLES 15.1 Introduction 15.2 Mechanized blasthole charging Systems 15.3 Blasthole dewatenng Systems References 16 MECHANISMS OF ROCK BREAKAGE 16.1 Introduction 16.2 Rock breakage mechanisms 16.3 Transmission of the strain wave through the rock mass 16.4 Energetic yield of the blastings References 17 ROCK AND ROCK MASS PROPERTIES AND THEIR INFLLTENCE ON THE RESULTS OF BLASTING 17.1 Introduction 17.2 Rock properties 17.3 Properties of the rock mass References

136 138 139 140 140 143 143 144 144 144 152 153 154 154 154 156 157 159

V11

Contents

18 CHARACTERIZATION OF THE ROCK MASSES FOR BLAST DESIGNING 18.1 Introduction 18.2 Diamond drilling with core recovery and geomechanic testing 18.3. Characteristics of the joint systems 18.4 Seismic survey 18.5 Geophysical techniques to obtain rock mass data 18.6 Logging of production blastholes 18.7 Characterization of the rock mass during blasthole drilling 18.8 The attempt to correlate drilling indexes with the blasting design parameters 18.9 System of drilling data management in actual time References 19 CONTROLLABLE PARAMETERS OF BLASTING 19.1 Introduction 19.2 Blasthole diameter 19.3 Height of bench 19.4 Blasthole inclination 19.5 Sternrning length 19.6 Subdrilling 19.7 Burden and spacing 19.8 Blasthole patterns 19.9 Geometry of the free face 19.10 Sizeandshapeof the blast 19.11 Available expansion volume 19.12 Charge configuration 19.13 Decoupling of the charges 19.14 Explosives 19.15 Distribution of explosives in the blastholes 19.16 Powder factor 19.17 Initiation and priming 19.18 Delay timing and initiation sequences 19.19 Influence of loadiniequipment on the design of the blasts 19.20 Specific dtilling 19.21 Blasthole deviation References

167 167 167 167 170 170 170 171 174 177 178 179 179 179 181 181 182 182 183 183 184 185 186 186 186 187 187 188 188 188 189 189 190 190

20 BENCH BLASTING 20.1 Introduction 20.2 Small diameter bench blasting 20.3 Large diameter blasting 20.4 Bench blasting with horizontal blastholes 20.5 Rip-rap production blasting 20.6 Cast blasting Appendix 1: Formulas to calculate bench blasting patterns References

199 203

21 BLASTING IN OTHER SURFACE OPERATIONS 2 1.1 Introduction 2 1.2 Excavations for highways and railways

205 205 205

191 191 191 193 195 195 196

21.3 Trench blasting 2 1.4 Ramp blasting (sinking cut) 2 1.5 Blasting for ground leveling 21.6 Blastings for foundations 21.7 Mini-hole blasting 2 1.8 Preblastings References

208 210 212 213 2 14 215 216

22 BLASTING FOR TUNNELS AND DRIFTS 22.1 Introduction 22.2 Advance systems 22.3 Blasting Patterns for tunnels 22.4 Types of cuts and calculation of the blasts 22.5 Equipment for marking out dtilling patterns References

217 217 217 218 219

23 SHAFT SINKING AND RAISE DRIVING 23.1 Introduction 23.2 Shaft sinking 23.3 Raise driving References

23 1 23 1 23 1 232 237

230 230

24 UNDERGROUND PRODUCTION BLASTiNG IN MINING AND CIVIL ENGINEERING 239 24.1 Introduction 239 24.2 Crater retreat method 239 24.3 Longhole method 243 24.4 Sublevel stoping with blastholes in fan pattern 245 24.5 Room and pillar mining 248 24.6 Cut and fill mining 248 24.7 Underground chambers in civil engineering projects 249 References 25 1 25 CONTOUR BLASTiNG 25.1 Introduction 25.2 Mechanisms responsable for overbreak 25.3 The theory of contour blasting 25.4 Types of contour blasts 25.5 The parameters that intervene in a contour blasting 25.6 Tendencies in the field of contour blasting 25.7 Evaluation of the results 25.8 Exarnple 25.9 Extraction of ornamental rock with contour blasting References 26 UNDERWATER BLASTiNG 26.1 Introduction 26.2 Methods of execution 26.3 Calculations for charges and drilling patterns 26.4 Charging the blastholes and priming systems 26.5 Types of explosives 26.6 Environmental effects associated with underwater blastings

252 252 252 253 254 256 264 267 268 268 270 272 272 272 247 275 276 276

V11

Contents

18 CHARACTERIZATIONOF THE ROCK MASSES FOR BLAST DESIGNING 18.1 Introduction 18.2 Diamond drilling with core recovery and geomechanic testing 18.3- Characteristics of the joint systems 18.4 Seismic survey 18.5 Geophysical techniques to obtain rock mass data 18.6 Logging of production blastholes 18.7 Characterization of the rock mass during blasthole drilling 18.8 The attempt to correlate drilling indexes with the blasting design parameters 18.9 System of drilling data management in actual time References 19 CONTROLLABLE PARAMETERS OF BLASTING 19.1 Introduction 19.2 Blasthole diameter 19.3 Height of bench 19.4 Blasthole inclination 19.5 Sternming length 19.6 Subdrilling 19.7 Burden and spacing 19.8 Blasthole patterns 19.9 Geometry of the free face 19.10 Size and shape of the blast 19.11 Available expansion volume 19.12 Charge configuration 19.13 Decoupling of the charges 19.14 Explosives 19.15 Distribution of explosives in the blastholes 19.16 Powder factor 19.17 Initiation and prirning 19.18 Delay timing and initiation sequences 19.19 Influence of loadingequipment on the design of the blasts 19.20 Specific drilling 19.21 Blasthole deviation References

167 167 167 167 170 170 170 171 174 177 178 179 179 179 181 181 182 182 183 183 184 185 186 186 186 187 187 188 188 188 189 189 190 190

20 BENCH BLASTING 20.1 Introduction 20.2 Small diameter bench blasting 20.3 Large diameter blasting 20.4 Bench blasting with horizontal blastholes 20.5 Rip-rap production blasting 20.6 Cast blasting Appendix 1: Formulas to calculate bench blasting patterns References

199 203

21 BLASTING IN OTHER SURFACE OPERATIONS 21.1 Introduction 21.2 Excavations for highways and railways

205 205 205

191 191 191 193 195 195 196

21.3 Trench blasting 21.4 Ramp blasting (sinking cut) 21.5 Blasting for ground leveling 21.6 Blastings for foundations 21.7 Mini-hole blasting 2 1.8 Preblastings References

208 210 212 213 214 215 216

22 BLASTING FOR TUNNELS AND DRIFTS 22.1 Introduction 22.2 Advance systems 22.3 Blasting Patterns for tunnels 22.4 Types of cuts and calculation of the blasts 22.5 Equipment for marking out drilling patterns References

217 217 217 218 219 230 230

23 SHAFT SINKING AND M I S E DRIVING 23.1 Introduction 23.2 Shaft sinking 23.3 Raise driving References

23 1 23 1 23 1 232 237

24 UNDERGROUND PRODUCTION BLASTING 239 IN MINING AND CIVIL ENGINEERING 24.1 Introduction 239 24.2 Crater retreat method 239 24.3 Longhole method 243 24.4 Sublevel stoping with blastholes in fan pattern 245 24.5 Room and pillar mining 248 24.6 Cut and fill mining 248 24.7 Underground chambers in civil engineering projects 249 References 25 1 25 CONTOUR BLASTING 25.1 Introduction 25.2 Mechanisms responsable for overbreak 25.3 The theory of contour blasting 25.4 Types of contour blasts 25.5 The parameters that intervene in a contour blasting 25.6 Tendencies in the field of contour blasting 25.7 Evaluation of the results 25.8 Example 25.9 Extraction of ornamental rock with contour blasting References 26 UNDERWATER BLASTING 26.1 Introduction 26.2 Methods of execution 26.3 Calculations for charges and drilling patterns 26.4 Charging the blastholes and priming systems 26.5 Types of explosives 26.6 Environmental effects associated with underwater blastings

252 252 252 253 254 256 264 267 268 268 270 272 272 272 247 275 276 276

V111 26.7 Shaped or concussion charges References 27 INITIATION SEQUENCE AND DELAY TIMING 27.1 Introduction 27.2 Single-row delayed blast 27.3 Multi-row sequenced bench blastings 27.4 Bench blasting sequences for underground stopes 27.5 Delay timings 27.6 Underground blasts in tunnels and drifts References 28 EVALUATION OF BLAST RESULTS 28.1 Introduction 28.2 Fragmentation and swelling of the muckpile 28.3 Geometry of the muckpile, its height and displacement 28.4 Condition of the remaining mass 28.5 Analysis of the bench floor 28.6 Boulders in the muckpile 28.7 Vibrations and airblast 28.8 Profiles of underground excavations 28.9 Conclusions References 29 SECONDARY FRAGMENTATION AND SPECIAL BLASTINGS 29.1 Introduction 29.2 Pop shooting 29.3 Secondary breakage by mechanical means and special methods 29.4 Special blastings References 30 PLANNING THE WORK OF DRILLING \ AND BLASTING 30.1 Introduction 30.2 Factors that have influence on the planning of drillling and blasting 30.3 Planning the Stages of excavation References 31 STRUCTURE AND BUILDING DEMOLITION 3 1.1 Introduction 3 1.2 Drilling diameters and types of explosive 3 1.3 Demolition of structural elements 3 1.4 Demolition of structures 31.5 Demolition of buildings 3 1.6 Demolition of steel structures References

Contents 32 OPTIMIZING COSTS OF FRAGMENTATION WITH DRILLING AND BLASTING 323 32.1 Introduction 323 32.2 Econornical aspects of drilling and blasting 323 32.3 Model for determining cost optimization 325 32.4 Predicting the fragmentation 326 32.5 Probabilistic analysis optimization model 331 References 33 1 33 LAND VIBRATIONS, AIR BLAST AND THEIR CONTROL 33.1 Introduction 33.2 Parameters which affect vibration characteristics 33.3 Characteristics of ground vibrations 33.4 Air blast charactenstics 33.5 Instrumentation for recording and analyzing vibrations and air blast 33.6 Calculators of propogation laws for land and air vibrations 33.7 Studies of vibration and air blast 33.8 Damage prevention critena for buildings 33.9 Effects of vibrations and air blast on people 33.10 Effects of vibrations on rock masses 33.11 Effect of vibrations on freshly poured concrete 33.12 Recommendations for reducing ground vibration and air blast levels References 34 FLYROCKS AND THEIR CONTROL 34.1 Introduction 34.2 Models to calculate the throw of flyrock 34.3 Coverings 34.4 Recommendations for carrying out bench blastings References

333 333 333 337 339 340 342 346 350 357 358 360 36 1 364 366 366 366 368 370 370

35 SAFETY MEASURES FOR DRILLING AND BLASTING OPERATIONS 35.1 Introduction 35.2 Blasthole drilling 35.3 Blastings References

37 1 37 1 37 1 375 38 1

CONVERSION FACTORS

382

GENERAL INFORMATION, WEIGHT OF MATERIALS

383

GLOSSARY

385

SUBJECT INDEX

389

Foreword

During the past two decades, there have been numerous technical contributions which have brought a better understanding of rock fragmentation with explosives, an improvement in drilling equipment and a noticeable evolution in the development of new explosives and blasting accessones. The Geomining Technological Institute of Spain (ITGE), aware of this Progress and of the importance which the breakage process has acquired in mining and civil engineering projects, has considered the publication of a 'Rock Drilling and Blasting Handbook' of great interest. This handbook was conceived with integration in mind, as the Systems and machines of drilling, the types and characteristics of explosives and the methods for calculating the blasts are treated together, without ever forgetting that these breakage operations form part of a

macrosystem and that the results obtained by them influence the production and economy of the whole exploitationor construction process. At the Same time, the objectives and contents of this handbook contribute to improved safety in mining. There are very few similar works in other languages, and certainly none other in Spanish. We sincerely hope that this handbook, which brings together practical and theoretical aspects, will be of use to all engineers who work with drilling and blasting as a rock breakage method. Camilo Caride de Liiian Director of the Geomining Technological Institute of Spain

Preface

'\

Rock breakage with explosives has existed since the XVII century when black powder came into use in mining, rapidly becoming one of the most popular methods. The important historical events which have marked an era were the invention of dynamite by Alfred Nobel in 1867, the use of ANFO starting in 1955, the development of slumes from the late fifties on and, lastly, the preparation of blasting agents such as emulsions, heavy ANFO, etc., which are still in evolution. At the Same time, blasthole drilling progressed with such decisive events as the the use of compressed air as the source of energy in rotary percussive rigs in 1861, the use of large rotary drills and of down-the-hole hammers in the fifties and the development of hydraulic hammers in the late seventies. However, rock blasting was always considered, until recently, as an art bom from the skill and experience of the blasters. Now it has become a technique based on scientific principles derived from knowledge of the action of explosives, the mechanisms of breakage and the geomechanic properties of the rock masses. The purpose of this handbook is to give basic knowledge of the drilling Systems, the types of available explosives and accessaries and the Parameters that intervene in blast designing, whether controllable or not. The handbook is primarily meant for students of the Technical Schools, to be useq as a textbook, and for all professionals who are involved with explosives in mining operations and civil engineenng projects. Carlos and Emilio Lopez Jimeno

This handbook was written by the following engineers: Carlos Lopez Jimeno, Doctor of Mining Engineering, Project Director for EPM., S.A. Emilio Lopez Jimeno, Doctor of Mining Engineering. Francisco Javier Ayala Carcedo, Doctor of Mining Engineering, Project Director for ITGE. Translated by: Yvonne Visser de Ramiro This work has been totally financed by the Geomining Technological Institute of Spain under contract with the EPM, S.A. Company (Estudios y Proyectos Mineros, S.A.).

Acknowledgements

The authors wish to express their most sincere gratitude to the following experts, companies and official organisms for their collaboration and release of technical material as well as permission to reproduce certain data and figures. Amerind-Mackissic,Inc.: G. J. Knotts Amos L. Dolby Co.: J. Petrunyak App1ex:S.O. Olofsson Atlas Copco S.A.E.: E Menendez Atlas Powder Company: VA. Sterner, L. Osen & PM. Miller Atlas Powder International: J. Garcia Milla Bauer, Calder & Workman, Inc.: J.L. Workman & A. Bauer (T) Bill Lane Inc.: W.C. Lane Blasting & Mining Consultants, Inc.: J. Ludwiczak Bucyrys Erie Co.: J.D. Nelmark & G. Rekoske Bendesanstalt für Geowissenschaften und Rohstdffe: R. Lüdeling Canmet: G. Larocque Ci1 Inc.: S. Chung, B. Mohanty, K.C. Joyce, PR. Day, W.K. Webster, D. Dayphinais, I. Huss & K.R. Sharpe Cominco Ltd.: W Russe11 Crowsnest Resources Ltd.: R.A. Reipas David, S. Robertson & Associates Inc.: C. Davenport Dupont Canada: D. Tansey E. I. Du Pont De Nemours & Co.: P D. Porter, B. L. Glenn, J. R. Knudson & A. B. Andrews Entrecanales y Tavora, S.A.: J. Aznar Gardner Denver Mining and konstruction Group Geovanca: R. Ucar Golder Associates: T. N. Hagan, E. Hoek & Guy Le Bell Hullera Vasco Leonesa: E. Castells Hydro-Quebec: F! Lacomte Iberduero, S.A.: J. Fora ICI Australia Operations Pty Ltd.: G. Harries, J. K. Mercer & G.G. Paine Ilmeg: S. Johansson Ingersoll Rand Instituto Tecnologico Geominero de Espaiia: EJ. Ayala & M. Abad Instituto Superior Tecnico de Lisboa: C. Dinis Da Gama Ireco Canada Inc.: L. de Couteur Irish Industrial Explosives, Ltd.: J. P Higgins Julius Kruttschnitt Mineral Research Centre, University of Queensland: C. K. Mckenzie & K. E. Mathews Kaiser Engineers, Inc.: G.V. Borquez

Kemira Oy Kenneth Medearis Associates: K. Medearis Kometa Oy: R. Ikola Kontinitro A.G. L.C. Lang & Associates, Inc.: L.C.Lang Lewis L. Oriard, Inc.: L.L.Oriard LKAB: L. Hermansson Martin Marietta Laboratories: D.A. Anderson & S. R. Winzer McGill University: R.E Favreau, R.R. MacLachlan, W. Comeau & J.C. Leighton Michigan Technological University: F.O. Otuonye New Jersey Institute of Technology: W. Konon Nitro Consult, A.B.: I. Hansson Nitro Nobel AB: B. Larsson, PA. Persson, M. Landberg & G. Lande Nobel's Explosives Company Limited: M. J. Ball The Norwegian Institute of Technology: K. Nielsen The Ohio State University: R.G. Lundquist Oy Forcit Palabora Mining Co.: G. P Fauquier Petromin: \! Cobeiia Precision Blasting Services: C.J. Konya Queen's University: P N. Calder Reed Mining Tools, Inc.: M. Suiirez Richard L. Ash & Associates: R. L. Ash Rietspruit Mining Co.: K. I. Macdonald Societa Esplosivi Industriali S.PA.: G. Calarco & WinRAR 6.02 Crack With Keygen Free Download 2021. Berta Strornrne: A. M. Heltzen Thermex Energy Corporation: R.C. Paddock T Peal, S.A.: J. Alonso & R.Arnaiz Union Espaiiola de Explosivos: R. Blanco University of Missouri Rolla: P N. Worsey, R. R. Rollins & N.S. Smith U.S. Bureau of Mines Twin Cities. Research Center: L. R. Fletcher At the Same time we would also like to acknowledge the drawings and photography done by Jose Maria de Salas and the corrections made by Carlos Ramiro Visser.

CHAPTER 1

Rock drilling methods

1.1 INTRODUCTION Rock drilling, in the field of blasting, is the first operation carried out and its purpose is to Open holes, with the adequate geometry and distribution within the rock masses, where the explosive charges will be placed along with their initiating devices. The systems of rock drilling that have been developed and classified according to their order of present day applicability are: - Mechanical: Percussion, rotary, rotary-percussion. - Themzal: Flame, plasma, hot fluid, Freezing. - Hydraulic: Jet, erosion, cavitation. - Sonic: High frequency vibration. - Chemical: microblast, dissolution. - Electrical: Electric arc, magnetic induction. - Seismic: Laser ray. - Nuclear: Fusion, fission. Even though there is an enormous variety of possible rock drilling systems, in mining and civil engineering drilling is presently canied out, almost exclusively, by mechanical energy. Therefore, in this handbook only the mechanical means will be discussed, reviewing the fundalmentals, tools loaris trojan remover (lifetime license) - Free Activators equipment for each of them. The main components of a drilling system of this type are: the drilling rig which is the source of mechanical energy, the drill steel which is,the means of transmitting that energy, the bit which is the tool that exercises that energy upon the rock, and the flushing air that cleans out and evacuates the drilling cuttings and waste produced. 1.2 TYPES OF DRILLING OPERATIONS USED IN ROCK BREAKAGE Within the large variety of excavations using explosives, numerous machines have been developed which can be classified in two types of drilling procedures: - Manual drilling. This is canied out with light equipment that is hand held by the drillers. It is used in small operations where, due to the size, other machinery cannot be used or its cost is not justified. - Mechanized drilling. The drilling equipment is mounted upon rigs with which the Operator can control all drilling Parameters from a comfortable position. These structures or chasis can themselves be mounted on wheels or tracks and either be self-propelled or towable. On the other hand, the types of work, in surface as well

as in underground operations, can be classified in the following groups: - Bench drilling. This is the best method for rock blasting as a free face is available for the projection of material and it allows work tobe systemized. It is used in surface projects as well as in underground operations, usually with vertical blastholes, although horizontal holes can be drilled on occasion. - Drilling fordrifting and tunnelling. An initial cavity or cut must be opened towards which the rest of the fragmented rock from the other charges is directed. Blasthole drilling can be carried out with hand held drills, but the trend is towards total mechanization, using jumbos with one or various booms. - Production drilling. This term is used in rnining operations, fundamentally underground, to describe the labors of ore extraction. The equipment and methods used v a q with the exploitation systems, having the common factor of little available space in the drifts for blasthole drilling. - Drilling for raises. In many underground and civil engineering projects it is necessary to Open raises. Although there is a tendency to apply the Raise Bonng method, still today the long blasthole method is used as well as other special drilling systems combined with blasting. - Drilling rocks with overburden. The drilling of rock masses which are covered with beds of unconsolidated materials calls for special drilling methods with casing. This method is also used in underwater operations. - Rock supports. In many underground operations and sometimes in surface ones it is necessary to support the rocks by means of bolting or cementing cables, in which drilling is the first phase. 1.3 FiELDS OF APPLICATION FOR THE DIFFERENT DRILLING METHODS The two most used mechanical drilling methods are rotary-percussion and rotary. - Rotary-percussive methods. These are the most frequently used in all types of rocks, the top harnrner as well as the down-the-hole hammer. - Rotary methods. These are subdivided into two groups, depending upon if the penetration is canied out by crushing, with tricones or by cut with drag bits. The first system is used in medium to hard rocks, and the second in soft rocks.

2

Drilling and blasfing of rocks

By taking into account the compressive strength of the rocks and the drilling diameter, the fields of application of the different methods can be defined as refiected in Fig. 1.1. On the other hand, depending upon the type of mining or civil engineenng surface project, the most comrnon equipment and diameters for bench blastings are indicated in Fig. 1.2.

In the Same manner, the most frequently used equipment for the different underground mining methods and the charactenstic drilling data are indicated in Fig. 1.3. Other criteria to be accounted for in the selection of drilling equipment are: cost, mechanical design, maintenance and semice, operative capacity, adaptability to equipment of the exploitation, and the work area conditions (accessability, type of rock, sources of energy, etc.).

DOWN TUE HOLE

I

DIAMETER (Inch)

3"

2"

11/2"

I "

3 1/2"

6"

5"

9,'

12"

15"

"OLE

mOOUCTIOH.-1HO

HUO HEL0 DRLLS

I

N 1mGE SCUE. W A C E W

Fig. 1.1 Fields of application for drilling methods as function of the compressive strength of the mcks and the diameters of the blastholes.

APLlCATlON RANGE L

W BE-

H E A W -B

4

-W

L

METHODS OF BENCH BLASTING

1

1

ROTARY PERCUSSIVE DRILLING

1

DOWN THE HOLE HAMMER

I

I

ROTARY DRILLING CRUSHING

180-200 mm not "."aI)

1

CUTTMG

I

I

(80-200 mm. not "sunll

CONSTRUCTION WORK

SURFACE MlNlNG

I

Fig. 1.2 Drilling methods for surface operations (Atlas Copco).

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Drilling and blasting of rocks

the same sense that igneous rocks are poorer in silica, they are richer in ferromagnesian silicates. The acids are more abrasive and harder than the basic ones, but they are also more dense and resistant to impact.

1.4.1.2 Metamorphic rocks Metamorphic rocks are derived from other pre-existing endogenic or exogenic rocks through important transformations of their mineral components. These marked changes are produced by the necessity of stabilizing their minerals under the new conditions of temperature, pressure and chemism. These rocks are intermediate in physicai and chemical characteristics, between the igneous and the sedimentary, because they have associations of minerais that pertain to the two types. Thus, minerals such as quartz, feldspars, rnicas, amphiboles, and olivines, essential in igneous rocks, are also found in metamorphic rocks; however they do not contain aikali feldspars. As in sedimentary rocks, they can have calcite, dolomite, silica and hematites; but they do not contain evaporites. Minerals comrnon to the two other types also appear such as tourmaline, zircon, magnetite, topaz and corundum; all of which are very stable in any exogenous or endogenous medium. There is a series of minerals that are very specific to metamorphic rocks, which can form part of the grains of detrital rocks, owing to their stability in exogenous medium~,and others are at the same time products of meteoric alteration of the minerals in endogenic rocks. Actually, meteorization is a mineralogical transformation that is both a physical and chemical process, but at low temperature and pressure. 1.4.1.3 Sedimentary rocks Sedimentary rocks are formed by accumulation of broken and decomposed rock material, by chemical precipitation of solubilized minerals or by accumulation of shells or other organic material: animal or vegetable. In the first case, detritic sediments are produced such as gravels, conglomerates or sands in which gravity has played a role in their precipitation. In the second case one

Fig. 1.4. Geological cycle of rocks.

Table 1.1 Classification Very hard Hard Medium hard Medium soft Soft Very soft

Mohs' scale of hardness +7 6-7 4.5-6 3-4.5 2-3 1-2

Compressive strength (MPa) +200 120-200 60- 120 30-60 10-30 -10

can find, as an example, the evaporites or saline rocks precipitated by over-saturationof a brine that is subjected to intense evaporation. The third type are accumulations of shells, skeletons of animals or remains of plants, such as the conchiferous limestones. This last group is subdivided into organogenous biochemistry and mineral biochemistry depending upon whether their components are of organic or inorganic nature. For the first we have coal and petroleum, and for the second the limestones, dolornites and phosphatic rocks. For an initial classification of sedimentary rocks, their formation process is taken into account, later the grain size, the characteristics of their bonding, apart from the types and quantities of their rninerai components. 1.4.2 Rock properties that affect drilling The principal physical rock properties that have influence upon penetration mechanisms and, as a consequence, on choice of the drilling method are: hardness, strength, elasticity, plasticity, abrasiveness, texture, structure, characteristics of breakage. 1.4.2.1 Hardness Hardness is considered to be the resistance of a surface layer to be penetrated by another body of harder consistency. In rock, it is a function of the hardness and composition of its mineral grains, the porosity, degree of humidity, E etc. The hardness of rocks is the principal type of resistance that must be overcome during drilling, because once the bit has penetrated, the rest of the operation is easier. Rocks are classified as to their hardness by using Friedrich von Mohs' Scale of Hardness (1882), in which the concept is that any mineral can scratch anything that has a lower or equai number to it, numbering from 1 to 10. As can be seen from Table 1.1, there is a certain correlation between hardness and compressive strength of the rocks. 1.4.2.2 Strength Mechanical strength of a rock is the property of opposing destruction by an extemal force, either static or dynarnic. The rocks give maximum resistance to compression, normally, as the tensile strength is not more than 10 or 15% of the compressive strength. This is due to the fragility of rocks, to the large quantity of local defects and irregularities that exist and to the small cohesion between the particles of which they are constituted.

Rock drilling rnethods

5

stratification sense or schistosity is larger than in a parallel sense. The quotient that is usually obtained between both strength values varies between 0.3 and 0.8, and it is equal to 1 only for isotropic rocks. In Fig. 1.5, the most frequent compressive strengths for different types of rock are indicated.

The rock strength fundamentally depends on its mineralogical composition. Among the integrating minerals, quartz is the most solid with a strength that goes over 500 MPa, while that of the ferromagnesian silicates and the aluminosilicates vary between 200 and 500 MPa, and that of calcite from 10 to 20 MPa. Therefore, the higher the quartz content, the more the strength increases. The mineral strength depends upon the size of the crystals and diminishes with their increase. This influence is significative when the crystal size is under 0.5 mm. In rocks, the size factor has less influence on strength as the intercrystallinecohesion force also intervenes. For example, the compressive strength of a fine grained arkose sandstone is almost double that of a coarse grained; that of marble composed of 1 rnrn graines is equal to 100 MPa, whereas a fine grained limestone - 3 to 4 mm - has a strength of 200 to 250 MPa. Amongst the sedimentary rocks the ones with highest strength are those that contain silica cement. With the presence of clay cement, the strength is drastically reduced. Porosity in rocks with the Same lithology also reduces strength proportionately, more porosity - less strength; as it simultaneously reduces the number of contacts of the mineral particles and the force of reciprocal action between them. The depth at which rocks were formed arid the degree of metamorphism also have influence upon their strength. Therefore, the strength of clay beddings near the ground surface can be of 2 to 10 MPa, whereas in clay rocks that went through a certain metamorphism the strengths can reach 50 to 100 MPa. On the other hand, the strength of ansiotropic rocks depends upon the sense of action of the force. The compressive strength of rocks in the perpendicular to

1.4.2.3 Elasticity The majonty of rock minerals have an elastic-fragile behavior, which obeys the Law of Hooke, and are destroyed when the strains exceed the limit of elasticity. Depending upon the nature of deformation,as function of the Stresses produced by static charges, three groups of rocks are taken into consideration: 1) The elastic-fragile or those which obey the Law of Hooke, 2) The plasticfragile, that have plastic deformation before destruction, 3) The highly plastic or very porous, in which the elastic deformation is insignificant. The elastic properties of rocks are charactenzed by the elasticity module 'E' and the Poisson coefficient ' V '. The elasticity module is the proportionality factor between the normal Stress in the rock and the relative correspondant deformation, its value in most rocks varies between 0.03 X 104and 1.7 X 1o5 MPa, basically depending upon the mineralogical composition,porosity, type of deformation and magnitud of the applied force. The values of the elasticity modules in the majority of sedimentary rocks are lower than those corresponding to the minerals in their composition.The texture of the rock also has influence on this Parameter, as the elasticity module in the direction of the bedding or schistosity is usually larger than when perpendicular. Poisson's coefficient is the factor of proportionality between the relative longitudinal deformations and the transversal deformations. For most rocks and minerals it is between 0.2 and 0.4, and only in quartz is it abnonnally low, around 0.07.

0

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DEFORMATION (mm x 108) Fig. 1.6. Curves of stress-deformationfor different types of rocks.

6

Drilling und blasting of rocks

1.4.2.4 Plasticity As indicated before, in some rocks the plastic deformation preceeds destruction. This begins when the Stresses exceed the limit of elasticity. In the case of an ideally plastic body, that deformation is developed with an invariable stress. Real rocks are deformed and consolidated at the Same time: in order to increase the plastic deformation it is necessary to increase the effort. The plasticity depends upon the mineral composition of the rocks and diminishes with an increase in quartz content, feldspar and other hard minerals. The humid clays and some homogeneous rocks have plastic properties. The plasticity of the stony rocks (granites, schistoses, crystallines and sandstones) becomes noticeable especially at high temperatures. 1.4.2.5 Abrasiveness Abrasiveness is the capacity of the rocks to wear away the contact surface of another body that is harder, in the rubbing or abrasive process during movement. The factors that enhance abrasive capacities of rocks are the following: - The hardness of the grains of the rock. The rocks that contain quartz grains are highly abrasive. - The shape of the grains. Those that are angular are more abrasive than the round ones. - The size of the grains. - The porosity of the rock. It gives rough contact surfaces with local stress concentrations. - The heterogeneity. Polymineral rocks, although these are equally hard, are more abrasive because they leave rough surfaces with hard grains as, for exarnple, quartz grains in a granite. This property has great influence upon the life of drill steel and bits. In Table 1.2, the mean arnounts of quartz for different types of rock are indicated.

Table 1.2 Rock type Amphibolite Anorthosite Diabase Diorite Gabbro Gneiss Granite Greywacke Limestone Marble Mica gneiss Mica schist Nori te Pegmatite Phyllite Quartzite Sandstone Shale Slate Taconite

Quartz content %

1.4.2.6 Texture The texture of a rock refers to the structure of the grains of minerals that constitute it. The size of the grains are an indication, as well as their shape, porosity etc. All these aspects have significative influence on drilling performance. When the grains have a lenticular shape, as in a schist, drilling is more difficult than when they are round, as in a sandstone. The type of material that makes up the rock matrix and unites the mineral grains also has an important influence. As to porosity, those rocks that have low density and, consequently, are more porous, have low crushing strength and are easier to drill. In Table 1.3 the classification of some types of rocks is shown, with their silica content and grain size.

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Rock drilling methods

7

Table 1.4. Properties of rock types according to origin-based classification. Rock type

Specific gravity (m3)

Grain Swell Compressive size factor strength (mm) (MPa*)

TntruDiorite sive Gabbro INGENOUS Granite Andesite Extrusive Basalt Rhyolite Trachyte

2.65-2.85 2.85-3.2 2.7 2.7 2.8 2.7 2.7

1.5-3 2 0.1-2 0.1 0.1 0.1 0.1

.-

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1.5

170-300

2 0.1-1 1 1-2 1-2 1-2

Gneiss 2.7 2 Marble 2.7 0.1-2 METAMOR- Quartzite 2.7 0.1-1 PHIC Schist 2.7 0.1-L Serpentine 2.6 Slate 2.7 0. L * 1 MPa = 1 MN/^^ = 10 kg/cm2 = 142.2 psi

In Table 1.4, the characteristic properties of different types of rocks are indicated, according to their origin. 1.4.2.7 Structure The stmctural properties of the rock masses, such as schistosity, bedding planes, joints, diabases and faults, as well as their dip and strike affect the allignment of the blastholes, the drilling performance and the stability of the blasthole walls.

SPACING OF JOINTS A) B) C) D)

lOOOcm

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STRONG ROCK MEDIUM ROCK WEAK ROCK VERY WEAK ROCK

Fig. 1.7. Classification of the rock masses.

In Fig. 1.7, the rock masses are classified from the spacing between joints and the strength of the r o c h material. REFERENCES Atlas Copco: Manual atlas copco, 4th edition. 1984. Heinz, W. F.: Diamond drilling handbook. 1989. Hunt, R.E.: Geotechnical engineeßng techniques und pracdces. McGraw Hill. 1986. Sandvik-Coromant: Manual de perforacibn de rocas. Teoria y tkcnica. 1983.

Tamrock: Handbook of surface drilling. 1989.

CHAPTER 2

Rotary percussive diilling

2.1 INTRODUCTION Drilling by rotary percussion is the most classic system for drilling blastholes, and its chronological appearance coincides with the industrial development of the ninteenth century. The first Prototype machines made by Singer (1838) and Couch (1848) were run by steam, but it was when compressed air was used as the source of energy, in the execution of the tunnel of Mont Cenis in 1861, that this system evolved and was put into extensive use. This event, along with the arrival of dynamite, was decisive in the rapid development of rock breakage in mining and civil engineering at the end of the last century. The drilling pnnciple of these rigs is based upon the impact of a steel piece (piston) that hits a utensil which transrnits at the Same time that energy to the bottom of the blasthole by means of the final element called the bit. The rotary percussive rigs are classified in two large groups, depending upon where the hammer is located: - Top hammer. In these drills, two of the basic actions, rotation and percussion, are produced outside the blasthole, and are transmitted by the shank adaptor and the dnll steel to the dnll bit. The hamrners can be driven hydraulically or pneumatically. - Down the hole hammer. The percussion is delivered directly to the drill bit, whereas the rotation is performed outside the hole. The piston is driven pneumatically, while the rotation can be hydraulic or pneumatic. Depending upon the fields of application of these drilling ngs, surface or underground, the most comrnon range of diameters are shown in Table 2.1. The main advantages of rotary percussive dnlling are: - It can be applied to any type of rock, from soft to hard. - Wide range of diameters; - Versatile equipment, it adapts well to different operations and is very Mobile; - Only requires one Operator; - Easy, quick maintenance, and - The capital cost is not high. In view of these advantages and characteristics, the type of operations where it is used are: - Underground civil engineering; tunnels, underground hydraulic plants, residual deposits, etc., and in surface operations; roads, highways, indusirial excavations, etc.

- In underground mines and in small to medium sized surface operations.

2.2 FUNDAMENTALS OF ROTARY PERCUSSIVE DRILLING Rotary percussion drilling is based upon the combination of the following: - Percussion. The impacts produced by repeated blows of the piston generate shock waves that are transmitted to the bit through the drill steel (in top harnmer) or directly upon it (down the hole). - Rotation. With this movement, the bit is turned so that the impacts are produced on the rock in different positions. - Feed, or thrust load. In order to maintain the contact of the dnll bit with the rock, a thrust load or feed force is applied to the drill siring. - Flushing. aushing removes the drill cuttings from the blasthole. The indentation forming process with which penetration is achieved in this drilling system is divided into five times, as indicated in Fig. 2.2. a) Crushing of the rough edges of the rock upon bit contact. b) Radial cracks appear from the points of Stress concentration and a V shaped wedge is formed. C) The rock of the wedge is pulverized. d) The larger fragments are chipped in the zones next to the wedge. e) The drill cuttings are flushed away. This sequence repeats itself with the Same impact rhythrn of the piston upon the system of energy transmission to the bit. The yield of this process increases proportionally with the size of the rock chippings. 2.2.1 Percussion The kinetic energy E, of the piston is transmitted from the hammer to the drill bit, through the dnll steel, in the form of a shock wave. The wave travels at high speed and its shape depends basically on the design of the piston. When the shock wave reaches the drill bit, part of the energy is transformed into work, causing the bit to penetrate, and the rest is reflected and returns through the drill steel. The efficiency of this transmission is difficult to

Rotary percussive drilling Tahle 2.1. Drilling method Top hammer Down the hole

Drilling diameter (mm) Surface Underground 38- 65 50- 127 75-200 100- 165

The percussion mechanism consumes from 80 to 85%of the total power of the equipment.

ROTATION

2.2.2 Rotation

FEED FORCE

Fig. 2.1. Basic actions in rotary percussive drilling.

Fig. 2.2. Sequence of rock failure during Center formation (Hartman, 1959).

evaluate as it depends upon many factors such as: type of rock, shape and size of piston, drill steel characteristics, bit design, etc. Another thing to take into account is that energy is lost through the sleeves of the rod couplings, due to reflection and fricton which is converted into heat and wear on the drill steel threads. In the first coupling the losses oscillate between 8 and 10%of the shock wave energy. In down the hole drilling the piston energy is transrnitted directly to the bit, giving greater performance. In these drilling Systems, percussion force is the parameter that most influences the penetration rate. The energy freed per hammer stroke can be estimated from the following equations:

where: m, = Mass of the piston, V = Maximum piston speed, p, = Pressure of the work ffuid (oil or air) inside the cylinder, A, = Surface area of the piston face, I, = Stroke of the piston. In the majority of hydraulic hammers, the manufacturers indicate the impact energy value, but this is not the case with the pneumatic hammers. Special care should be taken in estimating the p, for these, as it is 30 to 40% lower in the cylinder than in the compressor, owing to charging and expansion losses of air with each stroke of the piston. Thus, the hamrner power is the energy per stroke multiplied by the frequency of strokes n,:

.

.

and taking into account the previous equations, the following can be stated:

Rotation, which tums the dnll bit between consecutive blows, has the function of making the bit stnke upon different points of the rock in the bottom of the blasthole. In each type of rock there is an optimum rotation speed which produces larger sized cuttings taking advantage of the free area of the hole created with each impact. When drilling with insert bits, the most common rotation speeds oscillate between 80 and 150 r.p.m. with angles between indentations of 10 to 20°, Fig. 2.3. For button bits from 51 to 89 mm, the speeds should be lower, between 40 and 60 r.p.m., that bring turning angles between 5 and 7". Bits of larger diameters require even lower speeds.

2.2.3 Thrust load The energy generated by the mechanism of hammer blows should be transfered to the rock, for which it is n e c e s s q to have the dnll bit in permanent contact with the bottom of the hole. This is achieved with the thrust load or pull down, supplied by a pull down motor, which should be adapted to rock type and drill bit. Insufficient thrust load has the following negative effects: lower penetration rates, greater wear of rods and sleeves, loosening of drill steel threads and heating of the Same. On the contrary, if the pull down is excessive the penetration rate is also diminished, there is increased

INSERT BIT

BUTTON BIT

Fig. 2.3. Rotation speed between consecutive blows as a function of penetration rate and bit diameter.

10

Drilling und blasting of rocks FLUSHING FLUID

FEE0

Fig. 2.4. The effect of thmst load upon penetration rate in top hammer dnlling.

rotation resistance, drill steel can become jammed, the wear on the bits increases as well as the rotation rate and equipment vibrations, and the blastholes can be deviated. As occurs with rotation, this Parameter does not have decisive influence on the penetration rates, Fig. 2.4. Pnnciple of fiushing.

2.2.4 Flushing In order to have efficient drilling, the bottoms of the blastholes must be maintained clean by evacuating drill cuttings as soon as they appear. If this is not done, a large quantity of energy will be consumed in regrinding with the consequent wear on drill bits and decrease in penetration, apart from the risk of jamming. Blasthole flushing is carried out with a flow of air, water or foam that is injected by pressure to the bottom through an opening in the Center of the drill steel and flushing holes in the dnll bits. The cuttings are removed up through the space between the rod and the blasthole walls, Fig. 2.5. Fiushing with air is used in surface operations, where the dust produced can be eliminated by means of dust collectors. Water flushing is mostly used in underground drilling, which also keeps dust down, although it reduces performance by about 10 to 20%.Foam is used as a complement to air as it helps bring large particles up to the surface and also acts as a seaier for blasthole walls when drilling through loose material. The velocity of air flow for efficient cleaning with air goes from 15 to 30 mls. The minimum velocities for each case can be calculated from the following equation:

where: V= Velocity of air flow (mls), pr = Rock density (g/cm3),d, = Diameter of the particles (mm). Therefore, the flow that should be supplied by the compressor is:

where: Qa = Fiow (m3/min), D = Blasthole diameter, d = Diameter of the rods (m). When water is used for flushing, the velocity of air

flow should be between 0.4 and 1 m/s. In these cases the pressures are maintained between 0.7 and 1 MPa, to keep the flow from entering into the hammer. When using air with top hammers, it is not common to have a high pressure compressor for flushing alone. Only in down the hole hammer drilling is a high pressure compressor used (1 - 7 MPa) because the percussion power is increased along with the flushing of cuttings. An important factor to remember when estimating the flushing flow is that of charging losses produced due to the narrow conducts through which the fluid must pass (flushing needle, drill steel holes) as well as along the dnll stnng. In Table 2.2, the flushing velocities for top hammer drilling are indicated as function of air compressor flow and drill steel diameter. 2.3 TOP HAMMER DRILLING This drilling System can be qualified as the most conventional or classic, and although its use by pneumatic drive was limited by the down the hole and rotary equipment, the appearance of the hydraulic hammers in the sixties has given a new boost to this method, complementingand widening its field of application. 2.3.1 Pneumatic drilling rigs Hammers driven by compressed air basicaily consist in: - A cylinder with a front Cover that has an axial opening where the rotation chuck goes, as well as a retaining device for the drill rods. - The piston that altemately strikes the dnll steel shank through which the shock wave is transmitted to the rod.

Rotarypercussive drilling - The valve that regulates the passage of compressed air in a pre-set volume and in alternating form to the front and back of the piston. - A rotation mechanism, that can be a spirally fluted nfle bar or of independent rotation. - A flushing System that consists in a tube that allows the passage of air to the inside of the drill steel. These elements are cornrnon to all the types of hammers on the market, with only a few design charactenstics that differ: diameter of the cylinder, length of the piston stroke, distribution valves, etc. The following describes the working pnnciple of a pneumatic harnrner, Figs. 2.6 to 2.12. 1. The piston is at the end of its return stroke and is ready to Start its working stroke. The air, at line pressure, fills the backhead (1) and passes through the back supply port (2) into the cylinder (3). The air pushes the piston fonvard, beginning the working stroke. Meanwhile, the cylinder front end (5) is at atmospheric pressure since the exhaust port (6) is Open. 2. The piston (4) continues to accelerate forward, driven by the line pressure, until the leading edge (7) of the pistons control head shuts off the entrance of compressed air. The air confined in the back end of the cylinder (3) starts to expand and contiunes to drive the piston forward. Note that the piston flange (4) closes the exhaust port (6) and that the front end is still at atmospheric pressure. 3. The air confined at the back of the piston (3) continues to expand until the back edge of the piston flange starts to uncover the exhaust port (6). Remember that the piston control head (7) has already shut off the compressed air entrance, so that no compressed air will be wasted when the exhaust port is opened. Up front, the piston has trapped air that was a atmopheric pressure (5), and has now compressed it to slightly above atmospheric pressure. 4. The piston continues to move forward because of its momentum until it strikes the drill shank steel. Now, the back edge of the piston flange (8) has uncovered the exhaust port (6) and the air in the back end is exhausted into the atmosphere. While this was going On, the back edge (10) of the control head opened the front supply port adrnitting compressed air to the front end (5) driving the piston back on the return stroke. During this Stage there is compressed air pushing against the piston from the front end (5) and also pushing against the back end (10). The front surface area is much larger than the back (10) so the piston moves towards the rear. 5. The piston is accelerated back on the return stroke, until the back edge of the control head (10) Covers up the front air supply port. The air up front then continues to push the piston back. 6. The piston continues to accelerate backwards while the air in the front end (5) expands until the front end of the piston flange (11) uncovers the exhaust port, trapping the air in the back end of the cylinder and compressing it to a pressure slightly more than atmospheric. Note than the front edge of the control head (7) is just about to Open the back supply port.

11

W

Fig. 2.6. Piston at the end of its return stroke.

I Fig. 2.7. The piston accelerates forward.2.

W-

Fig. 2.8. The backedge of the piston flange uncovers the exhaust port.

w-

Fig. 2.9. The piston compresses the air in front of it.

I Fig. 2.10. The piston is accelerated back.

7

Fig. 2.1 1. The front edge of the piston flange uncovers the exhaust port.

Fig. 2.12. Return stroke of the piston finishes.

CHAPTER 6

Rotary drillling with cutting action

6.1 INTRODUCTION Rotary drilling by cutting action was at its peak in the forties, in American coal mines, for blastholes in overburden and in the ore itself. With growing use in surface operations using rotary rigs with rolling tricone rock bits, this method has been limited to soft rocks, usually with small to medium diameters, clearly competing with direct Coolmuster Android Backup Manager Crack 4.10.37 & Serial Code [Latest] Systems. In underground jobs, rotary percussive drilling has taken over most of the work, leaving only low to medium strength rocks that are non-abrasive (potash, coal, etc.) to the rotary rigs. Drilling by cutting action in production blastholes is carried out with bits whose stnictures have elements of tungsten carbide or other materials such as synthetic diamonds or polycrystalines, which vary in shape and angle and can be classified in the following types: a) Two-wing drag bits, with diameters from 36 to 50

mm. b) Three and four-wing drag bits with diameters from 50 to 115 mm. C) Three replaceable blade bit with fluted reamers in diameters that go from 160 to 400 mm.

of cut. This force is divided into two, one tangential N, and another vertical E, Fig. 6.4. The tangential force is the one that overcomes the compressive rock strength when confronted with the bit. The resisting torque T., measured in the axis of the drilling element, is the product of the tangential force multiplied by the radius ApowerEdit Pro Free Download the bit. The resisting torque on the total cutting area, supposing that it is a circularcrown, is given by:

where: T, = Resisting torque, p = Coefficient of friction, E = Thrust on the bit, r, = Outside radius of the bit, r, = Inner radius of the bit. This resisting torque is determined by the rninimum torque of the rock drill that allows the rock to be penetrated. Calling r, the effective radius of the bit, which is equal to

6.2 FUNDAMENTALS OF DRILLING W H CUTTING ACTION

the previous equation is transformed into

The cutting actions of a' rotary drag-bit on rock are, according to Fish, the following: 1. Beginning the cycle immediately after the formation of a large fragment, elastic deformations by stresses owing to the angular deflexion of the bit and to torsional strain in the drill rod. 2. Strain energy is released, with consequent impact of the cutting edge against the rock surface, and comrninution of rock fragments. 3. Build up of stresses at the bit-rock contact area, with further crushing and displacement of rock debris, until the cutting edge is effectively bearing on a step of unbroken rock which subsequently parts to create a large fragment or chip which, once bailed out, allow a new cycle to start, Fig. 6.2. The field tests carried out by Fairhurst (1964) show that the pulldown load and the rotary torque upon the bit undergo great variations owing to the discontinuous nature in chip formation, Fig. 6.3. The cutting force is in function with the geometry of the bit, the compressive strength of the bit and the depth

It is deduced that if p is constant, the torque is proportional to the thrust load on the cutting tool. In reality, the coefficient p is not constant, as it oscillates with the thickness of the cut and with the feed force itself. The index that determines the penetration in the rock is obtained by the relationship between the energy consumed by the drill and the specific rock energy. The total energy consumed by the equipment is 2xNrTr?where Nr is the rotary speed, which gives the following:

where: E, = Specific rock energy, Ar = Area of the blasthole Cross section. From this relationship it can be deduced that the penetration rate for a given rock and for a determined drilling diameter is linearly proportional to the thrust and rotary speed, although this is not completely true in practice, as it has been indicated that the friction coefficient of the rock varies with the Uinist. In Fig. 6.5, it can be obsemed

Rotary drilling with cutting action

73

-THRUST N W 667 -

DARLEY DALE SANDSTONE 229mm/min CUTTING SPEED

---TORQUE

1 150

0 III

2 445-

100

222-

50

a) TWO WlNG DRAG BIT

oL

J

I

o

25

1

I

0

6

o5

12

5

I

I

I

o 75

1 0

I 25

I

I

I

19

25

y)

in

mm

DISTANCE CUT

Fig. 6.3. Drag-bit force - displacement curves (Fairhurst, 1964)

CUTTING EDGE CHIP

I

b) THREE AND FOUR WlNG DRAG BIT

CRACKS

v / / t ; 3

NEW SURFACE

Fig. 6.4. Forces that act upon the cutting tool.

Q

LT

LINEAR PORTION BY CLOGGING AT THE BITS C)

THREE REPLACEABLE BLADE BIT

W

Z

Fig. 6.1. Rotary drag bits.

W

a

DEPARTURE FROM LlNEARlTY DUE T 0 EXCESSlVE WEAR ON BIT

APPLIED THRUST

Fig. 6.5. Basic th~st-penetrationrate curve for rotary drag-bit drilling (Fish and Barker, 1956).

ACCUMULATION TNEw: OF ; R*FINE .!::;CuTTINGs ::::. ?. .:.::.:: :,

s u m E N FRACTURE

.::. .L.

. ::.:.,; :.'.'.::. . .:::. .'.'.'. . .: .'{.'. . .:,:. .:. .:. :::;

'.',>,'., *,'.,;,.

I'.

;

.

U-

--

. '.: ,/,',',!,.,,,, , ,4;&,j2,:,!:;,);:,:,);<;,:, ,;,>.,:.',< . '. '

l.,~,'l',

- -- -I'.

(C)

(,

Fig. 6.2. Drag-bit cutting sequence (Fish and Barker, 1956)

that there is a thrust value under which a theoreticai penetration rate is not achieved, only excessive wear, and a limit vaiue which, if surpassed, will produce clogging of the bit. The rotary speed is limited by the growing frictional wear on the bits as the number of revolutions increases. Apart from the abrasiveness of the rocks, it must be taken into consideration that the wear increases with higher feed loads and the frictional forces between the rock and bit become higher. In Table 6.1, the recornrnended thrusts and rotary speeds are given in function with blasthole diarneter and compressive rock strength.

74

Drilling und blasting of rocks

Table 6.1. Cornpressive rock strenth IMPa)

Unitary thmst (Nimm)

Blasthole diameter (mm)

Rotary speed (rlrnin)

Two practical limits of rotary drilling can be given: compressive rock strength, which should be under 80 MPa, and the siliceous content, which should be less than 8% because, if not, the wear could be uneconomicai. Eimco-Secoma has developed a test for measuring the drillability and abrasiveness of the rocks. It consists of drilling a hole in a rock sample with constant thrust and rotary speed. The bit is of tungsten carbide and the flushing is carried out with water. A penetration-time curve is obtained and, from this, the drillability index or hardness expressed in 1110 mm of advance and, by measuring the wear undergone by the calibrated tool during 30 seconds, the abrasiveness is determined in tenths of mm of bit edge wear. The rocks are clasified in four groups or zones, in function with the two parameters, which define the most adequate drilling methods.

Zone I Zone with soft formation and low abrasiveness. Dry, low-thrust rotary drilling is suggested with low air presSure. Zone II Medium hard formation and low abrasivity. Dry mediumthrust rotary drilling with medium pressure air injection. Zone III Fairly hard rock, low abrasiveness. High-thmst rotary drilling and high pressure water flushing. The thrust can reach 20 kN.

O V)

0.9

Zone IV Very hard formation and high abrasiveness. Use rotary percussive dnlling with air or water flushing. The dnlling parameters for each Zone, for drilling diameters between 30 and 51 rnm are, according to Secoma, the following: Zone I Rotary dnlling with little thrust. - Thrust: From 1 to 8 kN. - Rotary speed: 800 to 1.100 rlmin. - Dry drilling - Types of rock: coai, potash, salt, gypsum and soft phosphate. - Tools: Spiral rods; Two wing drag-bits, 6 = 110125", ß = 75", y = 0-14". - Drilling rates = 3.5 to 5 mlmin. - With humid air the penetration rates are multiplied by 1.5 and 2.

Zone I1 Thrust: 8 to 12 kN. - Rotary speed: 550 to 800 rlrnin. - Drilling with humid air injection. - Types of rock: Limestone and soft bauxites, soft iron ores. - Cutting bits: 6 = 125", ß = 75-80", y = 0-2". - Penetration rate: 2 to 3.5 mlrnin. Zone III Thrust: 12 to 18 kN. - Rotary speed: 300 to 550 rlmin. - Drilling with water injection. - Types of rock: Bauxites and medium limestones, schists without quartzites, hard gypsums and hard phosphates. - Cutting bits: 6 = 125-140°, ß = 80°, y = -2-6" - Penetration rate: 1 to 1.8 mlmin. The rotary power, in HP, necessary to make a drag-bit rotate, is calculated with the following equation:

ROTARY PERCUSSIVE-DRILLING

ROTARY DRILLING

75

Rotary drilling with cutting action

where: D = Diameter (mm), N, = Rotary speed (rlmin), E = Thrust load (W). The necessary rotary torque is deterrnined from the equation:

T, =

HP,

X

7.14

Y

Table 6.2. Type of rock Hard gypsum Limestone, bauxite Soft iron ore Soft gypsum Phosphate, coal, salt, potash

Penetration rate (m/min) 1.5-2 1.5-2.5 1.5-3 3.8-6 3.5-10

Flushing System Water Water Water or dry Humid air or dry Humid air or dry

where: T, = Rotary Torque (kN.m). 6.3 FLUSHING OF DRLLL CUTTINGS Drill cuttings are eliminated with a flushing fluid that can be air, in surface operations, or water or humid air in underground jobs. The advantages that the use of air with water injection brings are the following: - It facilitates upward bailing, thus increasing the advance rate. - It cools the dnll bit, reducing wear. - It avoids blasthole filling. - It eliminates dust which is very important in abrasive formations. According to Eimco-Secoma, in order to inject humid air around 1.000 to 1.500 llmin of air are necessary and, for each rock drill, about 250 cm3/minof water. In very soft rocks, from 30 to 40 MPa, helicoidal dnll steel can be used, with mobaxterm crack reddit - Free Activators pitch as the penetration rate increases for efficient removal of the drill cuttings, Fig. 6.7. In Table 6.2, apart from the typical penetration rates in different types of rocks, the most commonly used flushing systems are indicated. 6.4 CUTTING TOOLS The cutting efficiency of a to?l depends largely upon its

design, according to the type of rock that is to be drilled. Fig. 6.8. The attack angle 6 usually varies between 110" and 140°, becoming increasingly obtuse in harder rock: if not, the hard meta1 would splinter. On occasions bits have been designed with rounded contours. The angle of the cutting wing ß varies between 75 and 80" and that of the cut y between -6 and 14", being positive in soft rocks and negative in hard rocks. Lastly, the backing-off angle or clearance angle is 6 = 90' - ß = Y. During drilling, a point on the cutting bit located at a distance r advances along a helical path. The angle of inclination of this helix is: 0.l

= arc tan

(&)

wherep is the advance of the bit per revolution. Owing to the movement of the bit along the helix, the effective clearance angle is reduced: For points near the center of the bit the effective clearance angle is Zero, as in these zones the tool compresses the rock. For this reason, drag-bits designed with a central gap usually reach higher drilling speeds. At the end of the seventies, General Electric manufactured the first Compact Diamond Polycrystalline-PDC,

CUTTER HEAD ASSEMBLY LEAD ASSEMBLY

-

.

REVERSIBLE LOCKING TYPE

I) HOLLOW STEM AUGER. 1.6m LENGTH 2) HEX DRIVE CAP 3) ROD T 0 DRIVE CAP ADAPTOR 4) LOCKING PIN 6) LOCKING PIN BOLT 6, CENTRE DRILL ROD7) PLUG 8) PLUG BOLT

9) 10) 11) 12) 13) 14) 16)

BIT TYPE CUTTER HEAD BODY CARBIDE INSERT BIT BIT LOCK RING BLADE TYPE CUTTER HEAD CARBIDE INSERT BLADE BLADE BOLT TUNGSTEN CARBIDE PILOT BIT

Fig. 6.7. Helicoidal drill rod and bits with differentconfigurations.

16) PlLOT BIT SHANK

17) 18) 19) 20) 21) 22)

BOLT. PILOT BIT SHANK TUNGSTEN CARBIDE PILOT BIT. LARGE SlZE PILOT BIT, SOFT FORMATION HEX QUICK BREAKOUT ADAPTOR LOCKlNG WEDGE WEDGE PUNCH

Drilling and blasting of rocks

7r

NEGATIVE SIDE RAKE ALL CUTTERS '6

,TER FLUSH HOLES

3- DIAMETER

-E F O R AIR W A T E R FLUSt 7-C2542 STRATAPAX BLANKS

(0)

BIT ROTATION

CORE CRUSHER (TUNGSTEN CARBIDE) SECTION X-X

Fig. 6.10. Drill bit with diarnond cutting elernents. Fig. 6.8. Sorne characteristics of a cutting tool (Fish and Barker, 1956).

RAKE ANGLE ECTIVE DEARANCE W -HELIX ANGLE

"-z

MOVEMENT

BIT AXlS

Fig. 6.9. Direction of a point on the the bit (Fairhurst, 1964).

obtained from a mass of very fine diamond particles that are sinterized under extreme pressure and embedded in tungsten carbide bases that are shaped at high pressures and temperatures. The resulting alloy has exceptional abrasion resistance along with the high resistance of tungsten carbide to impacts. The present day diamonds are thermically stable up to 1200°C in non oxidizing atmospheres and are available in sizes that range from 0.005 to 0.1 8 g (0.025 to 0.9 carats) in triangular prism, parallepiped or cylinder shape. Apart from their use in exploration drilling, diamond bits are used in underground mining for coal, potash, salts and gypsums to drill small diameter blastholes, from 35 to 110 mrn. In many instances, the penetration rates obtained and the Service lives of these bits are quite Superior to their conventional Counterparts.

Atkins, B.C.: Drilling Application Successes Using Stratapax Blank Bits in Mining und Construction. Australian Drilling Association Symposium, 1982. Bemaola, J.: Petforacibn Rotativa. 11 Serninario de Ingeniena de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundacibn Gbrnez-Pardo. 1987. Morales, V.: La Seleccibn y el Funcionamiento de los Triconos. Canteras y Explotaciones. Septiembre, 1984. Roberts, A.: Applied Geotechnology. Pergamon Press, 1981. Rodriguez, L.: Petforacibn Hidrbuiica Rotativa en Proyectos Subterrbneos. I Seminario de Ingenieria de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundacibn Gornez-Pardo, 1986. Tandanand, S.: Principles of Drilling. Mining Engineering Handbook. SME. 1973.

Photo 6.1. Rotaiy drilling equiprnent with heicoidal drill steel in a potash mine.

CHAPTER 7

Special drilling methods and mounting systems

7.1 INTRODUCTION Apart from the standard drilling equipment, there are units and mounting systems on the market for special or very specific applications. Among these jobs, a few can be mentioned such as: drilling rock masses with overburden of a nonconsolidated material andlor sheets of water, drilling rigs for shafts and raises, thermal and water jet drilling, etc. 7.2 DRILLING THROUGH OVERBURDEN These drilling methods were developed to solve problems that appeared spotify - Free Activators drilling in rocky ground, unconsolidated or alterated masses, overburdens, etc., that require continuous casing tubes to maintain blasthole stability. Some of the applications for these systems that are in use at present are: - Drilling for underwater blasting - Drilling for rock rnass blasting with overburden that has not been removed previously. - Anchonng - Foundations - Water wells - Soil and core sampling, etc. The overburdens can be b ~ d sof natural clay, sand, gravel, etc., as well as of fill with compact or noncompact materials, rock fill, etc. Drilling can be canied out, as will be noted later on, with top hammer or down-the-hole hammer, and consists of drilling through the overburden at the Same time that the casing tube is passed down into the hole, to keep loose material from caving in and blocking the hole, so that drilling can proceed into solid rock. One important feature of these techniques is that the flushing, or bailing out, of the debris be very effective. It can be canied out centrally through the shank adaptor or through a separate flushing head, in which case the fluid pressure should be higher. The two methods that have been developed are known as OD and ODEX. 7.2.1 OD (Overburden Drilling) Method In this method, the descent of the casing tube is canied out by percussion and rotation. The equipment consists of an outer casing tube with a tungsten carbide ring bit

mounted on the lower end. The casing tube encloses an inner drill stnng of standard drill steel which is extended by use of coupling sleeves that are independent from those of the casing tube. The casing tubes as well as the drill steel is connected to the hammer by a special shank adaptor, which transmits impact force and rotary force to both, Fig. 7.1. The basic operations for application of the System are: - The casing tubes, with or without the inner drill steel, proceed simultaneously through the overbur-den. - The outer ring bit advances a few centimeters when it reaches the bedrock. - Drilling is carried out with the inner drill steel unless decomposed or sand beds are encountered, in which case the casing tube would descend at the Same time. - The extension rods are drawn up. - The plastic casing tubes are allowed to remain in the hole to serve as channels for charging the explosive, or plastic tubes are inserted for this purpose, and - The casing tubes can be removed. As between the casing tube and the blasthole walls there is friction which increases with depth, the rock drills should be used with high rotary torque. Water is usually the flushing fluid in these cases, or compressed air with or without foam. If the upward bailing of the cuttings is insufficient with central flushing, then lateral flushing can be added. 7.2.2 ODEX Method (Overburden Drilling with Eccentric) In this method, based on the principle of underreaming, the casing tube is driven into place by vibrations from the drill and its own weight. Very little rotation is necessary. The equipment consists of an eccentric reamer bit that drills a hole with a larger diameter than the casing tube which descends as drilling advances. Once the required depth has been reached, the drill string reverses and the reamer bit becomes concentric, loosing diameter, and can then be drawn up through the casing tube. The standard drill steel is then introduced and drilling continues, Fig. 7.3. The rotary percussive rigs can be top or down-the-hole hammers. If top hammers are used, the percussion impacts are transmitted to the casing tube by means of a driving cap and shank adaptor which make the tube rotate slightly and vibrate. The flushingcan be central or lateral, Fig. 7.4.

78

Drilling und blasting of rocks

1 ii L

CHANK ADAPTER

CASING TUBE

Fig. 7.3. The ODEX method (Atlas Copco).

CASlNG TUBE

7.1. The OD Equipment (Atlas Cop-

4

5

6

Fig. 7.2. Operations in the OD System.

Table 7.1. Data

For-down-the-hole-drilis XD X 90 115 Min. inside diameter (mm) 115 90 123 152 Diameter of reamed hole (mm) Normal max hole depth in overburden (m)* 60 100 3"DTH 4"DTH Inner equipment Weld thread Weld thread Casina tube *ODEX 90 at 1.2 MPa, ODEX 115-215 at 1.8 MPa. Source: Atlas Copco.

i5' Fig. 7.4. ODEX top hammer equipment (Atlas Copco).

For top hamrners ODEX OD 140 165 215 127 72 127 72 140 165 215 76 187 212 162 108 278 96 100 40 40 40 100 100 5"DTH 6"DTH 7-8"DTH R38 R38 R38 Weld Weld thread Weld thread Thread Weld Weld X

ODEX 76

Special drilling methods and mounting Systems

Photo 7.1. ODEX drill bit. DTH

Table 7.2.

BIT TUBE

ODEX 90 115 0 X 0 0

GUlDE REAMER

Fig. 7.5. ODEX down-the-hole drilling equiprnent (Atlas Copco).

When down-the-hole hammer is used, the unit has only one wing coupling, as drill tubes are used instead of extension rods. The string of casing tubes is pulled down by means of a specially designed bit tube, and the flushing is carried out through the rotary head, Fig. 7.5. In both methods the cuttings are swept upwards through the annulus that remains between the casing and the drill steel, going out through the headstocks. The flushing fluid can be air up to a depth of 20 m, below which the addition of a foam is recommended to increase the bailing efficiency, wall stability, lower wear and increase penetration rate. This method has numerous advantages, although some important aspects that should be studied are: the sizes of the casing tubes, the flushing and the drilling System. The depth of the blastholes must be taken into account when choosing the equipment. In Table 7.1, a selection guide for both drilling methods is given. On the other hand, as to the applications for these drilling methods, aside from the one described for rock fragmentation blastholes, Table 7.2 indicates other possibilities.

140 165 X X 0 0

76

OD 127 72

Water well drilling Roadembankrnent 0 0 Underwatter drilling O O Blasthole drilling 0 0 X Anchoring X X X Injection X X X O Pros~ectine X X X O X = Suitable, 0 = Cm be used. Source: Atlas Copco.

X X X X X X

7.3 SHAFT SINKING When excavating long, large section shafts or metal structures pneumatic or hydraulic jumbos are used with three or four booms with the Same number of feeds and rock drills. When working, these rigs rest on the bottom of the shaft and are anchored to the walls with horizontal hydraulic cylinders. The central supporting column can turn 360°, and the booms, which are similar to the jumbos used for tunnelling, can vary their inclination withrespect to the vertical and lengthen themselves if they are telescopic. Once each round is drilled and charged, the rig is folded and moved to a safe position, later carrying out the mucking operation with twin valve ladles or hydraulic clam shells, as shown in Fig. 7.6. There are also platforms that have been designed to widen shafts.

80

Drilling und blasting of rocks

1. DRILLING

3. VENTILATION

2. BLASTING

4. SCALING

Fig. 7.7. Work cycle with an Alimak platform.

7.4 RAISE DRIVING 7.4.1 Alimak raise climber This excavation method for raise driving was introduced in 1957 and since then, due to its flexibility, economy and Speed, it is one of the most widely used in the world, especially in cases when there is no other access to the upper level. This equipment consists of a cage, the work platform, the driving motors, the guide rail and auxiliary elements. In Fig. 7.7, a complete work cycle is shown. The platform climbs along a pin rack welded to a guide rail and driven by either compressed air, electric or dieselhydraulic motors. The guide rail is bolted to the wall with Special Alimak design expansion bolts. The air and water pipes, which supply the necessary ventilation and water Spray, are placed on the inside of the guide rail for their protection. During work, the drillers are on a Safe platform, as it is covered and has a protective railing. Men ride up to the face safely in the cage, which is under the platform. In each work shift two drillers can advance from 2.2 to 3 m. Air engines are adequate for lengths under 200 m, the electric for up to 800 rn, and from these distances On, diesel-hydraulicengines are recornrnended. The main benefits of these rigs are: - They can be used for raises of any length and inclination. - Different lengths and geometries of the raises can be achieved by changing the platforms. It is possible to drive cross sections from 3 to 30 m2, Fig. 7.8.

- In the Same operation it is possible to change the direction and inclination of raises by using side-bent (curved) guide rails. - The length or height of the raises is practically unlirnited. Up to the moment, the longest raise driven is 1.040 m long with a 45O inclination. - It can be used as production equipment in some ore beds by applying the Alimak Raise Mining method, Fig. 7.9. - The enlarging of pilot raises for excavation of large cross section shafts can be aided by using horizontal drilling units. - The basic equipment can be used to Open various raises simultaneously. - In poor ground the platforms can be used as supports with bolting, injection, etc. - The investment is lower than with the Raise Borer System. - The labor does not have to be highly specialized. - The initial preparation of the work area is minimum. On the other internet security avast, there are a few disadvantages: - Poor quality work environment. - 'The walls are very rough which is a problem for ventilation raises and an advantage in ore Passage outlets. - The remaining rock mass is left in poorer condition than with the Raise Boring method.

7.4.2 The Jora method This rnachine is manufactured by Atlas Copco and can

Special drilling methods und mounting Systems

Fig. 7.8. Different platforrn configurations.

PILOT HOLE

HORIZONTAL BLAST AND LOADNQ DRILLING

Fig. 7.9. Exploitation method in narrow and inclined beds.

Fig. 7.10. Jora method for vertical and inclined raises (Atlas Copco).

Photo 7.2. Work on Alimak platform.

81

82

Drilling and blasting of rocks

also be used in raising and ore outlets, whether vertical or inclined. The principal difference when compared to the previous equipment is the drilling of a pilot hole with a diameter between 75 and 100 mm through which the cable which holds the lifts is lowered. The main components are the work platform, the lift basket, the hoisting mechanism and, in inclined raises, the guide rail, Fig. 7.10. During drilling, the platform is anchored to the raise walls by a system of telescopic booms. The main inconvenience of this method, against the former, is the pilot hole drilling, as the maximum raise height will depend upon the accuracy of its alignment. Its practical and economical field of application is between 30 and 100 m. For each round it is necessary to remove the cage from the hoisting cable, because, if not, the cable would be damaged during blasting. The central blasthole serves as expansion space for parallel cuts, obtaining advances per round of 3 to 4 m, and also as an entrance for fresh air. 7.4.3 Raise Boring (Full-face)method This method, which has become increasingly popular over the past 20 years, consists of the cutting or reaming of the rock with mechanical equipment. Its main advantages are: - Excellent personnel safety and good work conditions. - Higher productivity than in conventional methods of rock breakage with explosives. - Smooth walls, with minimum losses due to air friction in the ventilation circuits. - Overbreak does not exist. - High advance output. - Possibility of drilling inclined raises although it is better adapted to vertical ones. The most important disadvantages are: - Very high investment. - High excavation costper lineal meter. - Lack of flexibility, as the sizes and shapes of the raises cannot be varied nor the direction changed. - Gives problems in rocks that are in poor condition. - Requires highly specialized personnel and previous preparations of the work area. At the moment there are over 300 rigs in operaton around the world, with the following subsystems of Raise Boring: standard, reversible and blind hole raising. a) Standard raise boring This is the most widely used system and consists of setting up the equipment on the upper of the two levels to be intercomected, or even outside the mine, so that a pilot hole can be drilled down to a previously opened level. Aftenvards, the reamer head is attached to the drill string and the raise is drilled upwards to the rig. b) Reversible raise boring The Same operations are carried out as before, with the difference of placing the equipment on the lower level and inverting the pilot hole and raising execution, which

are ascending and descending, respectively. C) Blind hole raise boring Once the rig has been erected on the lower level, the drilling is done upwards in full section, without the pilot hole, as there is no access to a second level. The basic elements to cany out the work, apart from the rig itself which exerts the rotation and feed force from its point of installation are, for the blasthole, the tricone bit, the roller stabilizers and the drill rods; and for the reaming, the axis, base, Cutters and their sockets, Fig. 7.12. The heads can be integral, segmented or extensible. The first are used for diameters from 1 to 3 m with pilot holes of 200 to 250 mm, the segmented for raise diameters that are between 1.5 and 3 m, and the Same pilot holes as before, and, lastly, the extensible heads are for sections that range from 2 to 6.3 m with pilot holes up to 350 m. The power for the equipment is usually over 600 kW with rotary speed, rotary torque and thrust loads on the rock having values that oscillate between: 15 and 30 r.p.m., 150 and 820 kNm and 4 and 12.5 MN, respectively.

CHAPTER 14

Initiation and priming systems

14.1 INTRODUCTION ries and emulsions in rock breakage has brought about an important development of initiation and priming techniques. This is due to, on one hand, the relative insensitivity of these compounds and, on the other hand, a desire to obtain maximum performance from the energy released by the explosives. The detonation process requires initiation energy so that it can develop and majntain stable conditions. The most frequent tenninology used in initiation is: Primer: High strength, sensitive explosive used to initiate the main column in the blasthole. They are cap and detonating cord sensitive, including ones of low core load. Booster. Powerful explosive charge with no initiation accessory that has two functions: I. Complete the initiation work of the pnmer in the explosive column, and 2. Create zones of high energy release along the length of the column. Since the seventies, various theories have been devel.oped on initiaTion, ~~~~~~~~~~~i~creätIng-sömc confusion amongst operetors. In the following paragraphs present day knowledge is discussed and a series of practical recommendations are given in order to obtain maximum yield from the explosives.

14.2 PRIMING AND BOOSTERING BULK ANFO-TYPE BLASTING AGENTS When blastholes have a length of under 10 in and are kept dry, initiation of ANFO can be carried out safely with only one bottom primer. However, if the bench is very high and the holes pass through zones of different lithological charactenstics and fracture frequency, water can appear and there is the possibility of separation of the explosive column during charging, due to dnll cuttings and loose rock that can fall into the blasthole. In these cases, multiple priming is recommended with an initiator every 4 or 5 m, which, although slightly more costly, would eliminate the risk of incomplete detonation in any of the holes.

14.2.1 Initiation by aprimer In the priming of ANFO, the efficiency of a primer is detined by its detonation pressure, dimensions and -shape. The higher the detonation pressure PD, the greater its initiating ability. The effect of the 'PD' on the detonation velocity VD of ANFO is shown in Fig. 14.1. As can be observed, with detonation pressure that is less than a certain value, a partial reduction in VD is produced, and the contrary is true when PD is Pinnacle Studio 23.1 Crack + License Key Free Download 2020 the mentioned value. Following the Same procedure, the effect of the diarneter of the pnmer has alio been studied, Fig. 14.2. Therefore, the conditions that a primer should comply with in order to eliminate low VD zones in Altium Designer 20.2.6 Build 244 Crack ANFO are: the highest possible detonation pressure and a diameter above 213 that of the charge, - approximately. -The length of the primer is also imkrtant, as the primer itself is initiated by a blasting cap or detonating cord and they have a run-up distance in the VD. For exarnple, for a slurry to reach the detonation velocity regime it usually has a characteristic run-up distance of 3 to 6 times that of the charge. In Table 14.1, the minimum dimensions of pentolite boosters for different blasthole diameters are shown. As to the shape of the primers, the latest investigations have demonstrated that it has a significative effect upon performance, which means that it is a field Open to study. Although it is generally believed that the energy produced by ANFO increases with the transient velocity of the charge, this concept is false because the total energy releasedby an explosive is constant and independent of that velocity. An increase in VD brings about an increase in Strain Energy ET, thus lowering that of the gases EB -butthesum of-both remains constant. The relationship ETIEB is lower in zones of VD reduction and higher when the primer produces a raise in VD. The increase in Strain Energy is only beneficial for fragmentation when hard, fragile and massive rocks are being blasted. In sedimentary bedding planes or highly fissured rocks, the bubble energy should be increased in order to take advantage of the fractures and planes of weakness and obtain adequate rock displacement. Finally, it has been found that the VD steady-state in ANFO is independent of type, weight and shape of the primers (Junk, 1972).

Initiation und priming systems

137

DETONATMG CORD

-

Y

C ~ V E

f

DETONATION PPESSURE OF PRIMER !MP!l

24.000

b 0

$! 7W 4.000-

Fig. 14.3. Conventional primers. STEADY-STATE VOD

3CGU-

P M E R MAMETER- W O MAMETER- 7Omi

2000ASBESTOS TVBE C W N E K N T

K M

200

3m

I

500

400

Fig. 14.4. Primer cartridges with Detaprime primer (Du Pont)

MSTANCE FROM WTlATlON P W T (mm)

Fig. 14.1. Effect of primer's detonation pressure on initial VD of ANFO (Junk, 1972)

14.2.2 Types of primers und boosters

At present time, the most used primers are those made of pentolite as they have numerous advantages, such as: - Insensitivity to impacts and frictions. - High physical strength, therefore dimensionally stable. - They have one or two longitudinal tunnels through which the detonating cord can be threaded and re-ained, or into which a detonator can be inserted, Fig. 14.3. - They are small, compact and easy to handle, and they do not have adverse physiological effects. - They are not alterated by age. ~ e s l u r r i e s a n d e m d s ~ h a ~ e e a ~ ive can be used as primers or primer cartridges, with the advantage that they occupy the entire cross-section of the blasthole and are very efficient. When these explosives require a primer for initiation, they can only be used as boosters (secondary primers) unless special accessories are used such as Detaprime by Du Pont, Fig. 14.4.

STEADY-STATE VOO

M

O

DULIETER- 7

h

ASBESTOS TVBE C O H - N K N T

14.2.3 Initiation by downline P -

iia

k 3 .

350

Sb0

Sb0

MSTANCE FROM MTIATIOW PONT (mnl

Fig. 14.2. Effect of primer's diameter on initial VD of ANFO (Junk, 1972).

Table 14.1 Blasthole diameter (mm) -50 50-1 15 115-160 160-320

Size of pentolite booster (Mass X diameter X length) 3 0 g x 2 3 m m x 52mm 60gx28mmx70mm 150g X 40mm X 79mm 400 e X 80 mm X 59 mm

W e n a d e t o n a t i i ~ i i n s u f f i c i e n core t loadto initiate a charge of ANFO, the detonation of said cord creates a pressure front that expands in cylindrical shape and a chimney of gas inside the ANFO. If the crosssection of the blasthole is small then the lateral pressure can compress and desensitize the explosive. According to Hagan, in blastholes of 75 to 125 mm, a downline with core loads of 10 glm that lies along or near the axes densifies and desensitizes at least some of the ANFO. If the downline is along the blasthole wall, there is very little risk of desensitization with a properly rnixed ANFO, but it is possible in blastholes with water where the explosive is alterated.

138

Drilling und blasting of rocks

1 ANFO DETONATION VELOCITY(VERY LOW)

combustion or deflagration of part of the explosive charge.

3/8 RADNS OF Antivirus - Crack Key For U CHARGE

\

14.2.4 Initiation by primer and detonating Cord REACTION FRONT. C

o

+ Z

BLASTHOLE WALL

W

o

-

1B

I

G -

U

DETONATION V E L ~ ~ lrnlsl l ~ y

I

W t- -

4000

DETONATING CORD

4200

DETONATION PRESSURE (MP4

When the detonating cord does not completely initiate ANFO charges, the following Situations may appear: - In blastholes with diameters larger than 200 rnrn and cords with core loads under 10 g/m, the detonation of the cord has an insignificant effect and the ANFO is only affected by the primer. - When a cord of 10 g/m lies along or near the axis of a 75 to 125 mm blasthole, the detonation of the downline, as indicated before, compresses and desesitized the ANFQ 0. . are not dose to the primer. When this occurs, the fraction of ANFO that detonates decreases as the detonation wave propagates into the ANFO. In practice, above all in angled blastholes, as the downline lies along the blasthole wall and not the charge axis, this situation is not produced. If the downline side-initiates the charges, the primers have little influence on the effect of the ANFO detonation, unless they are very close together.

'"Mo 1300 500

1000

RACMAL DISTANCE (-1

Fig. 14.5. Detonation effect of a downline lying along the axis of a blasthole upon the VD of ANFO.

14.3 PRIMING CARTRIDGE ANFO TYPE BLASTING AGENTS If the covering of an ANFO charge has been damaged, permitting its contents to be alterated by water, the propagation of the detonation can be interrupted unless several primers are placed along the colurnn of cartriged explos-

DOWNLME

0

2

4

6

8

-

X)

gIrn

ALL CARTROGES EXCEPT TWS ONE OETONATE

Fig. 14.6. Energy losses provoked by the downline in ANFO columns (K0nya-&Walter,-1-9-~0>.-

If the downline side-initiates the ANFO, the initial VD is slower and incieases gradually while the detonation wave front passes through the section of the explosive colurnn. With axial initiation an increase in Bubble Energy is produced at expense of the Strain Energy, which can be quite advantageous in soft and highly fissured rocks, and when a controlled trajectory blast is desired with maximum displacement. On the other hand, in Fig. 14.6, the energy losses are shown for ANFO when it suffers damagefrom the downline, owing to the pre~0mpreSSi0nbrought On by the

al I N A o E o U A T E

b) S A T I S F A C T o R Y

Fig. 14.7. Inadequate and satisfactory pnming for cartridged loosepoured ANFO in wet Blastholes (Hagan, 1985).

Initiation und priming Systems ives, Fig. 14.7, and there is certainty that they are in contact. In blastholes with 150 m diameters, pnmers of 125 g weight are recommended, and in larger holes of 500 g. When ANFO has been pressure-packed in cartndges at the factory, the densities reached (1.1 g/cm3) are higher than when the explosive is loose-poured (0.8 g/cm3). Thus, although water is present in the blastholes, it is more probable that the cartridges will come into contact with the pnmers and, apart from this, the wrappings are usually more water and abrasion resistant, requiring less number of primers than in the previous cases. 144 P R T 4 ? Y AND EMULSION BLASTING AGENTS Generally speaking, slumes and emulsions are less sensitive to initiation than ANFO. These blasting agents tend to be more easily compressed and can be desensitized by cord detonation inside the explosive column. Less porosity and the presence of a liquid phase reduce the atenuation of the shock wave produced by the detonating cord and prolong the action of the high pressured gases after the shock wave passes. In order to minimize the risk of cut-offs originated by the detonating cord, in large diarneter blastholes (150 to 381 mm) a multiple pnming system is used. The number of equidistant boosters n, inside a blasthole of D diameter with a column length L is deterrnined, according to Hagan, with the following equation:

Photo 14.1.Placing a booster to initiate a column of poured slurry.

In a 20 m high bench with a diameter of 229 mm, a stemming of 5.70 m and a subdcilling of 1.80 m, the number of cast pnmers required will be:

In order to be certain that the boosters are correctly placed, a weight or heavy rock should be put on the end of the detonating cord to tense the line, and the first boosters should be placed at the calculated depth. When the density of the multiple pnmers is not more -thrthat-of-t~ti~igagentsused-0-that-f-tk mud itself that can exist in the hole, there could be a nsk of inadequate positioning of the pnmers as a consequence of their flotation or being pushed upwards. In these cases it is recomrnended that the downline be prepared for multiple prirning outside the hole, threading twice each of the pnmers, Fig. 14.8.

Fig. 14.8. Recommended priming system for pumped watergel and emulsion changes (Hagan, 1985).

140

Drilling und blasting of rocks

In some place the accessories are lowered with clips in the shape of tweezers that avoid their rising towards the surface. 14.5 PRIMING CARTRIDGED WATERGEL AND EMULSION BLASTING AGENTS Watergels and emulsions have high water resistance, which allows primers to be widely spaced within charges if it were not for the potential problem of desensitization by the downline. The multiple initiation system is recommended, as shown in Fig. 14.9. In blastholes with diameters under 150 mm, the recommended weights of the 13< n

should be increased to 500. As with pourable slurries and emulsions, if two lines of detonating cord are used in the blasthole, only one of these should reach the top of the column to avoid nsk of desensitization.

PACKAGED WATE OR EMULSION

14.6 LOCATION OF PRIMERS 14.6.1 Bottom priming Bottom priming gives maximum use of explosive energy, increasing fragmentation and displacement of the rock with a minimum of flyrock. This is due to the fact that the detonation Progress towards the stemming while the gases of the explosion are entirely confined within the rock mass, until the stemrning material is ejected and allows their escape. This time of confinement is usually around 3 to 4 ms, according to detonation velocity and length of column. The subsequent fall of pressure through escape on bench toe level takes place much later, Fig. 4 4 e ~ a ~as well. e as~a lower vibration level due to shock wave propagation towards the top part of the bench. In bench blasts, as the breakage at floor level is extremely important, the priming should be such as to produce maximum strain at that point. If the priming takes place at floor level and not at the bottom of the blasthole, an increase in peak strain of 37% is obtained (Staxiield, 1966) due to simultaneous detonation of the two parts of the charge that are equidistant from that point, Fig. 14.11. In the Same manner, a 37%greater peak strain can be generated in any strong bed if the primer is placed centrally within the bed. In blastholes without subdrilling, the bottom primer should be located as low as possible but never upon the drill cuttings or in mud, recommending that there be a distance of approximately 4D above the effective base. Apart from the cited advantages, bottom priming has much less chance of cut-offs than top or multiple priming. In Fig. 14.12, two 270 mrn diameter and 20 m long blastholes are shown as an example, where the spacing between explosive columns and sternming height is 7 m. The detonation velocities are 70OCCiKäKand mis in the cord and in the ANFO, respectively, and between both blastholes there is a milisecond delay interval of 25 ms. As blasting failures are produced by cut-off of the cord through ground movement, the larger the difference in

B

W

0

O

T INITIATION

I-

Q W

a

3

V) V)

t'

W

CAST PRIMER

h

(VENTING BEGINS AT COLLAR)

Y1

nN I

I I

VENTlNG REACHES TOE

(RAPID DROP DUE T 0 VENTlNG BEHIND DETONATION WAVE)

\ r

TIME

Fig. 14.9. Priming system for packaged watergel or emulsion blasting agents (Hagan, 1985).

Fig. 14.10. Effect of the position of the pnmer upon the pressure-time profile in the blasthole.

Initiation und priming Systems /: RESULTANT STRAIN r

\PULSE AT POHT P

I

I I

:

RESULTANT STRAIN PULSE AT POINT P

,i

I I

--

TIME

TIME

Fig. 14.11. Strain pulses at point P for charges pnmed (a) at their bases and (b) at bench floor level (Hagan, 1974).

A bottom priming pattern called safety is the one indicated in Fig. 14.13. In this case, if the low core load cord of the detonator N failedfor some reason, at the end of a time equal to the nominal intewal of the series of milisecond delay the top primer would initiate, producing the detonation of the

iai

(b)

Fig. 14.12. The reduced probability of cut-offs where charges arebottom pnmed.

Up until a short time ago, Operators were not interested in bottom priming because the use of detonators inside the blastholes had certain risks, but nowadays nonelectric accessories are available such as low core load downlines and those of very low energy that offer a wide field of possibilities for this initiation System.

14.6.2 Toppriming

Fig. 14.13. Safety Pattern with bottom pnming.

In bench blasts where top priming is used, a high strain wave is propagated towards the subdrilling Zone where, of course, its energy is dissipated and therefore wasted. In blasting overburden for a dragline, this strain energy can be more usefully employed in fragmenting the rock between the bottom of the blasthole and the top of the coal, but not the coal itself, especially if there is a strong bed irnrnediately above the coal andlor a well defined Zone between the waste and the ore. If peak strain is to be maximized along the rock that surrounds the stemming column, the top primer should be atleastl~M-af-the-hurden-be1~~_thetop-af-the~ (Starlield, 1966). If the explosive is initiated with a primer at the highest point, the superposition of the strains generated by adjacent charge elements gives a lower result in any point of the stemming, Fig. 14.14. The elimination of premature escape of the gases into the atmosphere, with adequate stemming height, improves fragmentation and rock displacement by Bubble Energy. For elongated charges, the efficiency of the stemming with top priming is less because the inerte stemming material, as well as the rock itself at the top, start moving some miliseconds before detonation of the lower part of the explosive. The fall of the presure of the gases is greater in long explosive columns with low

142

Drilling and blasting of rocks

RESULTANT STRAIN PULSE AT POINT P

STRAIN PULSES

's.

-

0 INITIATION POINT

detonation velocity and insufficient sternming, or small burden size. When the detonation reaches bench floor level, the pressure of the gases falls rapidly from its highest value, due to their escape towards lower pressure zones. This phenomenon gives poor fragmentation in the bottom of the blasthole and especially a reduced displacement of the lower rock.

TIME

/\

RES~LTANT

14.6.3 Multi-pointpriming If various primers are used, they should be located in positions such as to produce collision of the detonation

OIN(TIATIMI PciNT

TIME

Fig. 14.14. Strain pulses on burden alongside stemming column for charges primed at and somewhat below their uppermost point.

(Starfield, 1966). When the charges do not offer loss of velocity, fragmentation is improved in multi-point prirning through strain energy reinforcement. 14.6.4 Continuous side iniriation When the explosive columns are continuously side initiated by a detonating cord (downline), the detonation velocities are relatively lower than the regime. Thus, side initiation is more effective in highly fissurized soft rock

il

a) ELECTRIC

. .

+ig~l4-l-5;Applieationssoffmu1

p-it-

b) ELECTRIC

. I. L-,

. . .

.

.

C) WlTH DETONATING CORD

CORRECT

INCORRECT

Fig. 14.16. Cartridge priming with an electnc detonator.

Fig. 14.17. Priming cartridges and blastholes.

P P

Initiation andpriming Systems

143

formations where more bubble energy is preferible. The theory that continuous side initiation significantly increases the VOD of ANFO cannot be maintained, as has been demonstrated in practice.

C) Detonating cord. Contour blasthole or in soft rock, with decking to lower the total charge along the length of the column.

14.7 PRIMING CONVENTIONAL CARTRIDGED EXPLOSIVES

REFERENCES

The priming of cartridges consists of inserting a detonator or the end of a detonating cord in the cartridge to activate or initiate the detonation of the main charge in the blasthole. To maximize the use of the shock effect produced by

Anonymous: Puuled about primers for large-diameter ANFO charges? Here's some help to end the mystery. Coal Age. August, 1976. Anonymous:Safe und eficient initiation of explosives. Downline, ICI, NO.7, 10, 1988- 1990. Condon, J. L. & J. J. Snodgmss: Effects of primer type und borehole diamerer on ANFO deronation velociries. Min. Cong. J. June,

t h ~

r

cartridge and to the axis of the explosive column, Fig. 14.16. Any primer is an activated explosive ready to detonate under different stimulations, fire, strikes, etc., which means that they must be handled with extreme care, in transportation as well as when being placed in the blastholes. They should never be directly tamped. For priming cartridges and blastholes with electric detonators and detonating cords, the Patterns given in Fig. 14.17 should be followed. The procedures for priming blastholes are as follows: a) With instantaneous electric detonators. For isolated or simultaneous blastholes in rock of low to medium strength. Wet blastholes. b) With electric delay detonator. Bottom priming for simultaneous blastholes or without a face, without water and in medium to hard type rock. With this System fragmentation is improved.

1 Y14.

_

G ~. ~ r n o ~ ~ ~ l ~ n sifenvrac. Annales des Mines de Belgique, September, 1977. Hagan, T. N. & C. Rashleigh: Initiating systems for underground mass Jiring using large diameter blastholes. The Aus. IMM. 1978. Hagan, T.N.: Optimum priming systems for ammonium nitrate fuel-oil type explosives. The Aus. IMM.July, 1974. Hagan, T.N.: Optimum initiating, priming und boostering Systems. AME 1985. Junk, N.M.: Overburden blasting takes on new dimensions. Coal Age, January, 1972. Konya, C.J.: Initiierungstechnick für Lange Bohrlochladungen. 1974. Konya, C.J. & E.J. Walter: Surface Blast Design. Prentice Hall, 1990. Neil, I.A. & A.C. Torrance: The injuence of primer size on explosive perfonnance. Explosives in Mining Workshop. The Australasian Institute of Mining and Metallurgy. 1988. Smith, N.S.: An investigation of the effects of explosive primer location on rock fragmentation und ground vibration. University of Missoun-Rolla. 1980. Thiard, R. & A. Blanchier: Evolution des systemes d'Amorcage. Industrie Minerale Les Techniques. Fevner, 1984

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CHAPTER 15

Mechanized systems for charging and dewatering blastholes

15.1 INTRODUCTION

man team, oscillates between 500 and 1.000 kilos per shift, depending upon the cartridge sizes. ' AlOng witn tne aeveiopment of 11 Tat>te 15.1, Par~ e w a t e - ~ ~ W h 0 ~ ~ ~ ~ ~ ~ j e c t e d - t 0~ rim d gee c d ahs eaf na rid izf f~e r e n t blasthole diameters are tion, driven by the numerous advantagesthat this offers to indicated. blasting as described below: The chargers, Fig. 15.1, consist of a tubular chamber - Better use of the volume drilled in rock by being with a flip valve at each end, a charging funnel through able to fill the entire blasthole with the explosive and put which the cartrigdes are introduced, a plastic loading it into contact with the blasthole walls. hose and an ensemble of pressure-release pneumatic - Increase in charge density inside the blastholes. valves. - The possibility of forming selective charges by The pressurized air reaches the charger at a maximum varying densities and specific energies along the column pressure of around 1 MPa and with a senes of regulators, length. it is reduced to 0.3 MPa. There is also a safety valve. - The use of bulk or loose-poured explosives which The loading hoses are made of black anti-static plastic, are less costly than cartridged. although in certain special operations metal tubes can be - Less charging time. used. The diameters of these hoses is in function with the - Less personnel required for the chargng operation. cartridge sizes, and its length should not exceed 50 m. At - The possibility of using ANFO, of lower cost than the end of the hose where the explosive emerges there are watergels and emulsions, after dewatering the blast-oles. Cutter blades which slit the cartridges Open, and the force - Better control over explosives and their supply. of ejection drives them to the bottom of the blasthole, All these advantages lower drilling and blasting costs compacting and completely filling it. as the dnlling Patterns can be more Open and the charging The tamping of these units is done manually, unless a tirnes reduced. Robot, which can be attached to the charger, is used, Photo 15.1, which substitutes the Operator in this tedious and tiring work, especially in long blastholes, and allows 15.2 MECHANIZED BLASTHOLE CHARGING a more regular and unitorm charging. SYSTEMS This complement consists of a double-action pneumatic cylinder with a piston that is joined to a pneumatic The mechanized charging systems are classified in two pusher, a front spacer tube and a support that holds the large groups, depending upon whether they are merely aparatus in place against the blasthole. The cylinder has charging instruments or integral systems of manufacture an oscillating movement hat is transmitted by the pusher and charge. to the loading hose which, upon return, allows another In the following, the present day methods for the most cartridge to emerge. The degrees of stemming achieved important types of explosives are described: with the forward movements of the hoses vary between Gartridged slurriesandgelatindynamites--1.4aCcl16. - ANFO and its derivatives (ALANFO and Heavy The use of these chargers is especially interesting ANFO). when the rounds are made up of horizontal blastholes or - Bulk slurries and emulsions. long, inclined upholes. The only limitations are based upon the sensitivity to impact or friction of the cartridges, thus in some instances the velocity has to be drastically 15.2.1 Cartridged explosives reduced. Owing to the recent tendency towards using large Pneumatic cartridge charging equipment was developed diameter blastholes. above 100 mm in underground rnin-in Sweden during the decade of the fifties. These units ing the conventional chargers have become useless. allow the charging of blastholes with diameters between However, the largest chargers on the market with hose 35 and 100 mm, obtaining a 15 to 20% increase in centralizers have been used. This way, the cartridges of packing densities when compared to manual tamping, or emulsion or slurry make impact in the center of the even up to 30% if a robot is used. column, reducing the risk of dislodging or falling back of The charging capacities for these Systems, with a twoT

-

\

P -

Mechanized systemsfor churging und dewatering blastholes

k WHEEL

SWITCHER VALVE

TRIP00 MOUNT

FLAP VALVE

Fig. 15.1. Pneumatic charger.

Photo 15.1. Robot charger.

Fig. 15.2. The Half-Pusher technique (Nitro-Nobel).

Table 15.1. Drill bit diameter minlmax (mm) 38-45 40-5 1 [email protected]=

5 1 -76 64- 102

Cartridge diameter (mm)

Hose dimensions (mm) Inside diam. Outside diam.

22 25 29 32 38-40

23.2 27 30 33.5 41

30 34 38 41.5 51

the explosive in upholes. It has also been demonstrated, in experimental tests, that a standoff distance must be maintained between the end of the loading hose and the explosive column. The optimum is 45 cm for 165 mm blastholes, and 60 cm for those of 100 mrn diameter. In order to reduce friction of the cartridges against the inside walls of the hose, reaching high impact energy, water lubrication is recommended.

At present, Nitro-Nobel A. B is developing new equipment for charging upholes with diameters of up to 165 mrn. Of the two systems that are in experimental phase, Charge-Pusher and Half-Pusher, Fig. 15.2 shows the working principle of the latter. W i t h o u t going into detail, this device has a cfimbing mechanism with which, by upward movements, it pushes the charge ahead to the desired position. In each pushing movement an expansion element presses against the walls of the blasthole, retaining the climber in place while the piston rod forces the cartridge upwards which is held in place by a spider-like piece. 15.2.2 ANFO type explosives Charging systems Depending upon the capacities of the containers, the charging systems are classified as follows: - Pneumatic chargers - Charging trucks (Mix-Load and Mix-Pump) The first System is mainly used in underground operations and small surface mines, whereas the second is exclusively for large mines and surface operations. Pneumatic churgers. In these chargers, Fig. 15.3, the explosive is propelled through an antistatic, semiconductive hose by air pressure contained in a metal vessel or pot that is hermetically closed. The design

146

Drilling and blasting of rocks

Fig. 15.3. Pneumatic charger.

SEMl'33tJWIiVC ANFO PRESSVRE VESSEL

AIR HOSE

SEMlCONDUCTlVE PATH T 0 GROVHD

Fig. 15.4. Control of static energy in pneumatic loading.

consists in a funnel-shaped bottom, a cylinder-shaped body and another cone-like shaped of stainless steel that is corrosion resistant. The capacity of these chargers varies from 100 to 750 liters, and when transported they are mounted individually on wheels or upon a vehicle, Photo 15.2. For the latter, the air is pressurized by compressor activated by the motor of the vehicle, which also has recipients of the explosive for the automatic recharging of the vessels, or a prepared space for ANFO sack Storage when the refilling is done by hand. When upholes are loaded in underground operations, the pressure of the vessel must be combined with the Venturi effect created by blowing pressurized air through i I L t h e 4. ~ ü o ~ n o f t hblasthole e so that they will stick and not fall out. The working pressures go from 0.15 to 0.3 MPa in the vessels, and from 0.2 to 0.35 MPa in the injectors. This type of charging equipment is recommended for blastholes with diameters between 26 and 150 mm, unless they are upholes, where the diameters are limited to 100 mm. The yield of the chargers depends upon the interior diameters of the hoses and their length, which should never be over 50 m, and the inclination of the boreholes. The maximum charging capacity oscillates between 2 and 4 tons. Apart from the equipment already described, there are lighter models on the market which can be transported by the Operator himself, with a capacity of from 25 to 40 kg of ANFO. These are used in underground operations to charge blastholes of 28 to 65 mm in diameter and basically consist of small vessels of polyethylene plastic with Straps for their transport. They work with air pressures that go from 0.4 to 0.8 MPa and the charging capacity reaches 7 kglmin. A very importantaSpect,from a the elimination of the large amount of static electricity that is produced. In order to do this, it is necessary to properly connect the loading hose, made of semiconductive material, and properly ground the whole equipment, Fig. 15.4. In the particular case of large diameter upholes, the traditional method of pneumatic loading, consisting of a lower closing plug and a charging tube has been progressi v e l y s y b s t i h t e d by the direct method repre=ed in Fig. 15.5, where the pressure given to the A G ~whichvaries between 0.14 and 0.2 MPa, is sufficient to make the ANFO prills stick to the bottom of the holes giving charge densities of 0.95 to 1 g/cm3. It is of vital importance in this System to have a correct design of the centralizer in the charging tube. If there is water present in the blastholes, the loading can be done after placing a plastic liner. The primers that are connected to downlines or to the detonator are usually placed in the bottom of the blastholes by means of a retainer with help of the loading hose itself. P

Fig. 15.5.Pneumatic loading of ANFO in upholes. P

Photo 15.2.ANFO loader on vehicle.

~~~~~~~~~~~~--

Mechanized systemsfor charging und dewatering blastholes

147

STER/DETONATOR

CENTRALIZER

CONWCTIVE HOSE

"270-340

Fig. 15.7. Types of bulk loading tmcks, (a) pneumatic delivery, (b, C, and d) auger delivery.

KPa AR

Fig. 15.6. Placing the primer in the bottom o f a large diameter uphole -hreI-m&mg.

Photo 15.3. Bulk loading truck with helicodial auger (Courtesy of Amennd-MacKissic, Inc). -

-

Bulk loading trucks. The types of tank irucks used for charging granular ANFO-type explosives are: - Pneumatic delivery System - Auger delivery, Fig. 15.7. The first type of iruck is the most used in Spain at the moment, and it consists of a closed aluminum deposit (AN hopper) with top and bottom V-shaped charge openings to aid in the descent of the explosive towards the conveyer or feed auger which conveys the ANFO for mixing and should be protected by an inverted V-trough which keeps the conveyer from holding the whole weight of the charge.

On the outside part of the deposit is a mechanism which regulates the height of the explosive on the feed auger, as well as a tachometer for the roller motor permittimg variations in the speed, dosifying the supply of the rotary air-lock feeder which discharges the explosive by air pressure through an antistatic hose to the inside of the blasthole. The rotary air-lock feeder is composed of a drum wheel with plastic blades which also keeps the pressured air out of the ANFO bin. The engine of the vehicle is connected to the hydraulic pumps that activate the feed auger and the rotary air-lock

148

Drilling and blasting of rocks

feeder, as well as the air compressor. The loading hose is located in the back of the truck and is about 10 m in length which permits the charging of 3 or 4 blastholes from the Same position when the truck is driven between two rows. The problems with this System are the segregation of the aluminum when ALANFO is used, and the impossibility of loading Heavy ANFO. The second model of truck has, at the bottom of the deposit and lengthwise, a helicoid auger that is also protected by deflecting plates. This auger feeds another vertical one which then delivers the product to a third subhorizontal, pivoting boom auger. This last auger has a length of between 5 and 6 b l a s t h o l e s g h a flexible hose that are 6 or 7 m from the back part of the truck, Photo 15.3. When the truck is between two rows of large-diarneter blastholes, the number of these that can be loaded from one position is limited to one or two. The loading flow of these tmcks varies between 150 and 750 kglmin. A more simple version of this truck is one called Side Auger Discharge System. In the back of the vehicle there is an inclined discharge auger that delivers the explosive to another swiveling boom auger of approximately 3 m in

FUEL OIL TANK

ALUMINUM TANK

AN HOPPER

Fig. 15.8. Deposits on a rnix-load tmck.

- r o t a t i o n ~ w e l l M e Y a t i o nnr Inwenng.gkpxu2meansoL small hand winch. During transit the auger rests in a cradle along the lower left side of the body. During the last few years, there has been a progressive tendency towards trucks having an auger delivery system, owing to the following advantages: - The possibility of charging Heavy ANFO as well as ANFO and ALANFO. - Greater discharge rates, and - Lower loss of ammonium nitrate and distillate vapor around the collars of blastholes.

Photo 15.4. Bowl-type rnix-load tmck.

Mix and load systems Conventional Mix-Load truck. These have a hopper of ammonium nitrate and a tank of fuel oil. If ALANFO or Heavy ANFO is required, there is also a third tank with the emulsion blasting agent or aluminum powder, Fig. 15.8. Moments before loading the blastholes, the two or three components are mixed in the truck, in the desired proportions, and the resulting explosive is then delivered by either of the two systems described previously. The hopper of ammonium-s simi-i already mentioned. In the pneumatic discharge units the fuel is added with the air whereas in those of auger delivery, the fuel oil and other additives are delivered through the vertical auger.

Photo 15.5. ANFO cartridges (Arnerind Mackissic, Inc.).

Bowl-Qpe Mix-Load truck. These trucks are similar to concrete trucks with slight modifications to make them safe for mixing and charging bulk blasting agents. The ~=ompomenLs~ae~p~kced~in_the bowl in adequate provortions and are Gxed accordingly before being discharged. The explosive obtained with these units is characterized by: - Smaller errors in the overall chemical composition - More uniform blending and, therefore, - The energy outputs closely resembles those achieved in laboratories. When compared with conventional mix-load trucks, bowl-type trucks offer the following advantages: - Lower capital cost (about 30%). - Hinher discharge rates, close to 2.000 kglmin. (this is 2.5 to-4 times those obtained by conventionil trucks).

Mechanized systems for charging and dewatering blastholes

-

149

On the other hand, bowl-type tmcks have the following disadvantages: - The truck must be positioned very close to the blasthole for loading, losing time in changing posi-ions. - Only one type of explosive can be charged each time, eliminating the possibility of selective charg-ng. - The quantity of explosive mixed must be exactly the arnount required in order to avoid excess, which must be removed. - The capacity of these tmcks (approxirnately 1 1.5 t) is 25% less than conventional trucks.

which the products are continuously rnixed and are pumped directly into the blastholes through a Aexible hose. This system is quite versatil, as it allows variation in the cornpositions before charging begins. The vehicles have a capacity of between 5 and 15 t and are designed to produce at least two types of explosives, one for bottom charging and one for the column charge. These mobile plants are very safe as the ingredients they carry are not explosive alone and they are mixed only instants before charging. On the other hand, quality control is more difficult than with pump trucks.

Cartridged ANFO When drilling 76 to 190 mm diarneter blastholes and

a) Slurry mix-pump truck These trucks transport the following ingredients: A A oxidizers such as sodiurn nitrate. calciurn nitrate. etc., thickened by gurns. This solution is prepared at a static plant near the minesite. - Ammonium nitrate in pourous prill form (optional). - Liquid fuel-oil or a mixture of solid fuels that are called pre-mixes, with a percentage of aluminum as high as the required weight strength of the watergel. - A cross-linking solution and a gassing agent. The ingredients are put into the tmck's mixing funnel from which they pumped into the blasthole through a flexible hose. The charging rates vary between 80 and 350 kglmin. Thickening and cross-linking starts as soon as the products are mixed so that the watergel is highly viscous by the time it enters the blasthole. The gelling can be controlled by adjusting the crosslinking solution. When the gelling ocurrs too rapidly, purnping difficulties appear, whereas if the gelling time is too long the s1un-y can become diluted or even dissolved before its viscosity permits it to resist the effect of the water present in the blastholes. The loading hose Operator should be certain that there 1s a mnimum agitation oI the explosive

-edr.t-t The packaging of ANFO is done with simple equiprnent consisting in a hopper, a one meter long tube, a feed auger and a piston system that works with pressurized air to achieve the required charge density that can reach 1.1 g/cm3. The yield is around 3 cartridges per minute. 15.2.3 Slurry and emulsion-type explosives Pump trucksfor slurries and emulsions. These tmcks are used for pumping explosives such as slumes and emulsions, and mixtures of emulsions with ANFO, whenever the solid phase of these mixtures is not rnore than 35%, because then the product would no longer be purnpable. The physical consistency of these blasting agents is so high that for their pumping the injection of a liquid lubricant along the inside wall of the loading hose is usually necessary to reduce friction and facilitate easy, rapid purnping. It is important to use the lowest feasible arnount of lubricant, and that it contribute to enhancing the effective explosion energy whenever possible.

M i x - p u m p t r u c E A mix-pump truck is a mobilF$plantin

Photo 15.6. Static plant and pump tmck (Nitro Nobel).

Drilling und blasting of rocks HOPPER THERMIC

DELIVERY AUGER THAT CAN BE REGVLATED

CONTROL PANNEL

ALWINUM FEEDER MlXlNG HOPPER

Fig. 15.9.Mix-pump tmck (Ireco Inc.).

when it enters into contact with the water. The proportion of gassing agent should be adjusted to give the sluny the required sensitivity and bulk strength. If the gassing is insufficient, a density in the botton of the column will be produced, reducing the optimum yield of the explosive. On the other hand, excessive gassing can reduce the density of the explosive making it float in the water. The flow of gassing solution can be controlled and can give slumes with a wide range of densities. This possibility is the basis of the technique called Powerdecking. b) MLx-pump trucksfor charging emulsions und mixtures of emulsion/dty phase Inlhis type of trucks, a continuous mixture of a saturated solution of oxidizers is proquced, with an oil phase and some other ingredients in smail amounts. The resulting product is pumped into the blasthole. If a dry phase such as ANFO or ammonium nitrate prills are added to the mixture, it is important to ensure that the emulsion produced does not lose its pumpable qualities.

Drift driving. The motor-pump system used is customarily mounted on a small size vehicle norton antivirus 2018 free download full version with key - Crack Key For U sometimes has a hydraulically powered man basket enabling the blaster to have access to the back holes, operating the pump with remote control. The most popular types of pumps are those of diaphragm and those with auger which aspirates the explosive from the tanks which have a capacity of up to 500 kg and load it with a pressure of about 0.5 MPa, Photo 15.7. The loading hoses Ge semi-conductive to eliminate static electricity and are introduced into the blastholes up to about 20 cm from the bottom, then pumping the explosive which gradually pushes the hose out of the hole until the desired charge height is reached. Initiation is usuaily achieved with a primer cartridge and an electric blasting cap, previously placed in the bottom of the hole. The flow rates are comparable to those obtained with' ANFO pneumatic chargers. Depending upon the pump speed, a 3 meter long blasthole with 41 rnm in diameter can be charged in 6 to 10 seconds.

Pump trucks. When pump trucks are~sed~tbe41asring agent is previously manufactured in a static plant near or on the minesite. The advantages of this system are: - The static plant can be located in the Center of the various points of consumption,supplying the sluny or the emulsion in severai trucks, and - The product is of higher quaiity than that produced in the rnix truck. Underground charging of slurried und emulsions Loading blastholes in underground operations has different methods, depending upon the type of work at hand: Photo 15.7. Charging equipment for development headings.

Mechanized systemsfor charging and dewatering blastholes

151

Shaft sinking. Pressurized vessels are used, similar to those used with buk ANFO. The discharge of the explosive through a main hose of 45 mm,reaches a flow rate of 77 kglmin, that is at the Same time divided into 5 flexible hoses of 17 rnm diameter which permits the loading of blastholes in a very short time, Fig. 15.10. Production blasts. In production blasts with large diameter blastholes, more than 125 mrn, there are two different charging situations: upholes and downholes. a) Downholes. They are used in the operational methods of inverted craters and in levelling with long blastholes. Charging is camied out very easily because the explosive is pumped and descends by gravity to the

- & ~ s i ~ - l ~ ) x p r ~ i l i t ~ h e i r a r n p f explosive from the surface as well as in the mines. The exchangeable tanks of explosive are made of stainless steel with capacities of close to 2.000 kg. The pump, hose and the inclination hinge of the tank are hydraulically powered. b) Upholes. The charging of upholes with blasting agents such a slumes and emulsions is even more difficult than with ANFO, as it is first necessary to apply a borehole plug to keep the explosive from falling out and, secondly, the product must have an adequate consistency for pumping. The latter seems to have been solved for emulsions by cooling. As to plugs, there are various systems used. The first ones used a wooden plug with an interior tube that had a check valve with a brass anti-retum ball, Fig. 15.11. Plastic tubes have also been used to make up the explosive columns, and wooden plugs with holes that

photo 15.8. Pneumatic pump (Bill Lane Inc.):

V ALVES

017rrm HOSE

BROKEN MUCKPILE

ing.

DETONATHG CORD

L O A W G PiPE

DELAY LEADS CHECK VALVE

Fig. 15.11. Wooden plug with anti-return check valve.

Fig. 15.12. Tubed charging with wooden plug.

Drilling and blasting of rocks

152

inflatable lances have been tned with success. These devices have two inches of flexible hose with a rigid tube on one end, upon which an inflatable rubber bladder is mounted and inflated by pressurized air, Fig. 15.14. The advantages of this System are its simplicity and low cost. It is quick and efficient, having been successfully tned in blastholes of up to 115 mm in diameter.

LIOMD FOAM CONTAHER

15.3 BLASTHOLE DEWATERING SYSTEMS stholes widens th

- Air operated pumps and, - Submergible impellent pumps. The first are applied to small and medium diameter (63 to 172 rnm) blastholes with a maximum bench height of about 15 meters. Pressunzed air supplied by compressors of the dnlling rigs is used, which is introduced into the blastholes through a flexible plastic hose. In some equipment, Fig. 15.15, the pushing effect is achieved when the obturator'or plastic closing sleeve expands when the air pass through. The pumping rates are approximately 50 to 80llmin. The second dewatenng System has a submergible impellent pump and a reel for the hose. The unit can be installed on a jeep-type vehicle or on the back of an ANFO charge truck. The reel and pump are hydraulically driven and the hydraulic fluid tubes of the latter arejoined inside the water hose, enabling the whole ensemble to be lowered into the blasthole at of approximately m/s. To avoid stoppageproduced by coarse waste material, the pump should by placed at a few centimeters from the bottom. - Once the dewatenng of the blastholes is finished, the mechanism of the drum wheel reverses to clean it of sand and waste that might have entered. These units can dewater blastholes in a few seconds,

Fig. 15.13. Polyurethane foam uphole plug.

-R,MT

N F L A T A B ~ ~B L A D ~ P

EUULS~~~ HOPPER

Fig. 15.14. Charging of a rcpumpablc emulrion in an uphole with an inflatable lance. WATER DISCHARGES FROM HOSE

AIR SUPPLY

SLEEVE

Photo. 15.9. Hydraulic dewatenng pump (Swanson Eng. Inc.)

W

Fig. 15.15. Pneumatic pump.

SLEEVE W L A l

Mechanized systernsfor charging and dewatering blastholes

153

Table 15.2. Flow (Ilmin)

Total elevation height (m)

a Ipm, I I MPa

Table 15.3. Blasthole diameters Imm)

Ipm, 13 MPa

Ipm, 13 MPa

Nominal diameter of plastic liner Imm)

owing to the strong pumping rates, Table 15.2, permitting use of the plastic sieeves and charging before the Water enters again. The type of plastic used should be flexible and resistant so that it will not tear when in contact with the rock, recommending h a t it be of 600 to 1.000 gage, depending upon each case. The liners Or plastic sleeves, which the bulk explosive, should have a diameter that is slightly more than that of the holes, Table 15.3, so that the volume of rock drilled can be used to maximum advantage and achieve a good adaptation of the charge.

Amerind-Mackissic, Inc.: Technical fnformation 1986 Bauer, A.: Trends in Explosives, Drilling und Blasting. CIM Bulletin, February, 1974. Bauer, A. et al.: Drilling und Blasting in Open Pits und Quarries. 1980. Bill Lane, INC.: Lane Pump. 1986. Champion, M.M.: Explosives Loading Equipment. Underground Mining Methods Handbook. AIME, 1982. Dannenberg, J.: Contemporary history of industrial explosives in America. Day, F!R. & D. K. Joyce: Lwding explosives in large diameter upholes. SEE. 1988. Giorgio, C.: Evolucibn de los Explosivos en los Treinta UltimosAEos. Rocas y Minerales.

Photo 15.10. Preparation of the primer charge in a plastic sleeve.

Gustafsson, R.:Swedish Blasting Technique. SPI, 1973. Hagan, T.N.: Charging and Dewatering Equipment. AMF. 1985. Irvine, J.C.: Pillar recovery at the Pea Ridge Mine. Mining Engineering. September, 1976. Jerberyd, L.: Half-pusher - A method to charge large diameter upholes. Swedish Mining Research Foundation, 1985. Legorburu, V.: Sistemas Mecanizadas de Carga de Explosives en Proyectos Subterrhneos. I Seminario de Ingenieria de Arranque de Rocas con Explosivos en Proyectos Subterrineos. Fundaci6n G6mez-Pardo, 1986. Lopez Jimeno, C.: Desagüe y Drenaje de Explotaciones a Cielo Abierto. IV Curso sobre Mantenimiento y Servicios en Mineria a Cielo Abierto. Fundaci6n G6mez-Pardo. 1984. _ M a i r s~ B B T ~ + ~ u & i ~ ~ - e x p W n underground. CIM Meeting, 1985. Michaud, F! & A. Laveault: Essai d'un Systeme de chargement en vrac pouremulsions aux Mines d'Amiente Bell. SEEQ, 1984. Nitro-Nobel: ANFO Mixing and Charging Equipment. 1986. Swedish Methodsfor Mechanized Blasthole Charging. Puntous, R.: Mkthodes Modernes de Chargementdes Explosifs. Industrie Minerale - Les Techniques. Fevrier, 1984. Sharpe, K. R.: Plugging and loading upholes at La Mine Bosquet. CIL Inc. 1986. Swanson Engineering Inc.: Blasthole dewatering - Cuts costs. Union Espaiiola De Explosivos: Tendencias Actuales en el Almacenamiento.Traßspo~e~arga-Meeaninida-deExptmivos-en~aMineria a Cielo Abierto. Jornadas Tecnicas, UEE. VME-Nitro Consult, Inc.: Pneumatic Cartridge Charging. Yetter, A. & R. Malo: The evolution of loading 4.5 inch diameter upholes at Kidd Creek No. 1 Mine. SEE. 1984.

CHAPTER 16

Mechanisms of rock breakage

16.1 INTRODUCTION

increase the surface area by crushing, it has a slower rate of stress decay than (A).

theconditionspresencharactenzedbytm-phaes2onsumes of action: Ist. phase. A strong impact is produced by the shock wave linked to the Strain Energy, during a short period of time. 2nd. phase. The gases produced behind the detonation front come into action, at high temperature and pressure, carrying the Thermodynamicor Bubble Energy. Since the decade of the fifties, many theories have been developed to explain the behavior of rocks under the effect of an explosion; even nowadays it still remains a problem to be solved and defined in the technology of application of explosives to breakage. Without entering into detail, the different mechanisms of rock breakage that have been identified in blasting up to now are exposed in the following paragraphs. 16.2 ROCK BREAKAGE MECHANISMS In the fragmentation of rocks with explosives at least eight breakage mechanisms are involved, with more or less responsabiXty, but they an exert influence upon the - results of the blastings. 16.2.1 Crushing of rock In the first instants of detonation, the pressure in front of the strain wave, which expands in cylindrical form, reaches values that well exceed the dynamic compressive strength of the rock, provoking the destruction of its intercrystalline and internranular structure. The thickness of the so cailed crushed zone increases with detonation pressure of the explosive and with the coupling between the charge and the blasthole wall. According to Duvall and Atchison (1957), with high strength explosives in porous rocks it might reach a radius of up to 8 D, but it is normally between 2 and 4 D. In Fig. 16.1. the variations in compressive stresses generated by two fully-coupled charges are shown. The crushing of the rock is produced at a pressure of 4 GPa, so the curve of the explosive (A) which produces a tension of 7 GPa on the blasthole wall has a very sharp decrease in peak stress due to the large increase in surface area during the pulverization of the rock. As explosive (B) does not

almost 30% of the energy transported by the strain wave, only contributing a very small volume to the actual rock fragmentation, around 0.1% of the total volume corresponding to the normal breakage per blasthole. Therefore, there is no incentive to use high explosives that generate high stresses on the blasthole walls: which would even make it advisable to decouple the charges and increase EB in detriment of ET. 16.2.2 Radial fracturing

During propagation of the strain wave, the rock surrounding the blasthole is subjected to an intense radial compression which induces tensile components in the tangential planes of the wave front. When the tangential strains exceed the dynamic tensile strength of the rock, the formation of a dense area of radial cracks around the crushed Zone that surrounds the blasthole is initiated, Fig. 16.2. The number and length of these radial cracks increase with: 1. The intensity of the strain wave on the blasthole wall or on the extenor Iimit ot the crushed z m d 2. The decrease in dynamic tensile strength of the rock and the attenuation of the Strain Energy. Beyond this inner Zone of intense fractunng, some of the cracks extend noticeably and are symmetrically distributed around the blasthole. The propagation velocity of the cracks is from 0.15 to 0.40 times that of the strain wave, although the first microcracks are developed in a very short time, around 2 ms. When the rock has natural fractures, the extension of the cracks is closely related to these. If the explosive columns are intersected lengthwise by a pre-existing crack, these will Open with the effect of the strain wave and the development of radial cracks in other directions will be limited. The natural fractures that are parallel to the blastholes, but at some distance from them, will interrupt the propagation of the radial cracks, Fig. 16.3. 16.2.3 Rejlection breakage or spalling When the strain wave reaches a free surface two waves are generated, a tensile wave and a shear wave. This occurs when the radial cracks have not propagated farther

Mechanisms of rock breakage

Fig. 16.4. Reflection of a wave upon a cylindncal cavity.

Fig. 16.1. Variation of peak compressive stress with distance from OmsihotewatUHaga~~).

UD COMPRESSION TENSION

Fig. 16.2. Radial fracturing.

FRACTURES CAUSED B Y INTERNAL SPALLIN

X)(NT PLANE

ZONE OF- DENSE RADIAL CRACKlNG

-

-

WATER FILLED JOINT PLANE

/ RADIAL CRACKS A R R E S T E D ~ PREMATURELY AT JOlNT

Fig. 16.3. Radial fracturing and breakage through reflection of the strain wave.

than one third the distance between the charge and the free face. Although the relative magnitud of the energies associated with the two waves depends upon the incident angle of the compressive strain wave, the fracturing is usually caused by the reflected tensile wave. If the tensile wave is strong enough to exceed the dynamic strength of the rock, the phenomenon known as spalling will corne about, back towards the interior of the rock. The tensile

strengths of the rock reach values that are between 5 and 15% of the compressive strengths. The front of the reflected wave is more convex than that of the incident wave, which means that the dispersion index of the tensile wave energy is much larger when the surface is cylindncal, such as that of the central blasthole of a cut instead of when there is a plane as in bench blasting, Fig. 16.4. This mechanism does not contribute much to the global fragmentation process, estimating that eight times more explosive charge would be necessary if rock were to be fragmented solely by reflected waves. However, in the inner discontinuities of the rock mass which are close to the charge, less than 15 D, and are not infilled with rneteorized material, the effect of the reflected waves is more important due to the difference in impedances. When excavating inclined ramps or shafts by blasting, it must be checked that the empty blastholes are not be filled with water in order to achieve the benefits of this mechanism of breakage.

After the strain wave passes, the pressure of the gases cause a quasi-static stress field around the blasthole. During or after the formation of radial cracks by the tangential tensile component of the wave, the gases start to expand and penetrate into the fractures. The radial cracks are prolonged under the influence of the stress concentrations at their tips. The number and length of the opened and developed cracks strongly depend upon the pressure of the gases, and a premature escape of these due to insufficient stemming or by the presence of a plane of weakness in the free face could lead to a lower performance of the explosive energy. 16.2.5 Fracturing by release-of-load Before the strain wave reaches the free face, the total energy transferred to the rock by initial cornpression varies between 60 and 70% of the blast energy (Cook et al. 1966). After the compressive wave has passed, a state of quasi-static equilibrium is produced, followed by a subsequent fall of pressure in the blasthole as the gases escape through the stemming, through the radial cracks

Drilling und blasting of rocks

156

t:Xmr

I=O

and with rock displacement. The stored Stress Energy is rapidly released, generating an initiation of tensile and shear fractures in the rock mass. This affects a large volume of rock, not only in front of the blastholes but behind the line of the blast cut as well, having registered damages in up to dozens of meters away, Fig. 16.5. 16.2.6 Fracturing along boundaries ojmodülus contrast of shearfracturing In sedimentary rock formations when the bedding planes, joints etc., have different elasticity modulus or geomechanic Parameters, breakage is produced in the separation planes when the strain wave passes through because of the strain differential in these points, Fig. 16.6.

Fig. 16.5. Separation of layers of compressible medium by release-of-load.

t=~xrnr

where n, is the relationship between the impedance of the explosive and that of the rock:

t h r o u L rock mass (m/s), D. = Rock density (g/cm3). This means that the explosive wave is better transmitted to the rock when Ghost Browser 2.1.0.6 Keyegn - Crack Key For U impedance of the explosive is close to that of the rock, given that n, will tend towards 1, while PT will simultaneously tend towards PD. The pressure of the wave inside the rock decreases with the law of exponentials, so the radial stress generated at a determined distance will be:

16.2.7 Breakage byflexion During and after the mechanisms of radial fracturing and spalling, the pressure applied by the explosion gases upon the material in front of the explosive column makes the rock act like a k a m embedded in the bottom of the blasthole G d in the stemming area, producing the deformation and fracturing of the Same buy the phenomena of flexion, Fig. 16.7. 16.2.8 Fracture by in-flight collisions The rock fragments created by the previous mechanisms and acceleratedby the gases are projected towards the free face, colliding with eachother and thereby producing additional fragmentation which has been demonstrated by ultra-speed photographs (Hino, 1959;Petkof, 1969). 16.3 TRANSMISSION OF THE STRAIN WAVE THROUGH THE ROCK MASS

-Asshown-befo~ehand&theDetonationessure can be expressed by the following simplified equation:

where: o = Radial compressive stress, PB = Pressure on the blasthole wall, r, = Radius of the blasthole, DS = Distance from the Center of the blasthole to the point in study, X = Exponent of the law of absorption which, for cylindrical charges is near 2. If the wave encounters diverse material in its path, with different impedances and in correspondance with separating surfaces that can be in contact or separated by air or water, the transmission of the strain wave will be govemed by the ratios of the acoustic impedances of the -dlPf=es-of rmercparmf-transferred in the material and at the Same time some is reflected back, as a function of the ratio. When the impedances of the mediums are equal (pr2 X VC2 = pri X VC,), a large part of the NVIDIA GeForce Experience 3.19.0.107 License Key - Crack Key For U will be transmitted and the rest will be reflected, arriving at the lirnit when (pr2 X VC2
.--_

P -

#

where: PD = Detonation pressure (kPa), p, = Explosive density (g/cm3),VD = Detonation velocity (mls). The maximum Pressure Transmitted to the rock is the equivalent of: PT,, =

L

-PD 1 + n,

n, =

Pri

X

'CI

Pr2 X 2" the following will be obtained:

Mechanisms of rock breakage I BED X

EXPLOSIVE CHARGE

I

Fig. 16.6.Shear Fracturing (Hagan).

MSCONTINUITY

where: PI = Pressure of the incident wave, PT= Pressure of the transmitted wave, PR = Pressure of the reflected wave.

16.4 ENERGETIC YIELD OF THE BLASTINGS Itaneously in a few miliseconds, associated with the effects of the strain wave which transports the Stress Energy, and with the effects of the explosion gases or Bubble Energy, Fig. 16.8. The total energy developed by the explosive and measured by the method proposed by Cole can thus be expressed as the sum of these two components.

fare.ag.roupofelementalmmwh&pe

ETD = ET Fig. 16.7.Mechanism of breakage by flexion.

+ EB

where:

The estimates canied out by Hagan (1977) have demonstrated that only a 15%of the total energy generated in the blasting is used as a working tool in the mechanisms of rock fragmentation and displacement. R a s c h e f f a n d G v 7 7 F h a v e esta6IiSEd a model that theoretically distributes the energy, as represented in Fig. 16.9, from tests made upon cubic blocks of rock placed underwater in swimrning pools. These investigators assure that approximately 53%of the explosive energy is associated with the strain wave. This value depends upon the conditions of the experiment and very different results can be found that go from 5 to 50%of the total energy, depending upon the various types of rock that are to be fra~mentedand the explosives used. Therefore, in hard rock the Strain Energy of a breaking explosive is more important in fragmentation than the Bubble Energy, and the contrary is true for soft, porous or fissured rocks and in low density explosives. From the tests canied out by Rascheff and Geomans, Table 16.1 s u k a r i z e s the energy distribution of the strain wave. It can be observed that in conventional bench blastings a large part of the strain wave energy is transformed into seismic energy which causes ground vibrations to which some of the gas energy must be added. The data exposed are quite in accordance with that Photo 16.1. Rock breakage by flexion.

Drilling und blasting of rocks PHASE

I

FREE FACE ORIGiNAL

Fig. 16.8. Summary of the breakage mechanisms.

PO R

-

U. -

- ~slll

nm

p i e p e s l v. m bhmlho* w i l

p e s ~ of a expindhp p i s s i rpon hipmonled r a *

-snmgm

01

aiifui w a t w wu

Fig. 16.9. Distribution model of the explosive energy in ablast.

W '

a

3

V)

VOLUME

Fig. 16.10. Pressurelvolumediagram of explosion product gases showing partition of energy in blasting.

1

I

Mechanisms of rock breakage Table 16.1. Distribution of shock wave energy. Granite block Conventional with infinite bench blastconfinernent ing of granite Pulverization 15% 15% Primary radial cracking 3% 3% 0% 16% Crack extension Energy transrnitted 82% 34%

Granite block submerged in water 15% 2% 39% 22%

Useful energy

56%

18%

34%

Table 16.2 Zone

1 + 2 + 3 +4 + 5

159 Energv Kinetic component of shock energy Strain component of shock energy Brissance energy Energy released during crack propagation Fragmentationenergy Strain energy in burden at time gases escape Blast energy Heave energy Total available energy or absolute strength value

pressed by the gas in ihe cracks with a strain energy obtained by other investigators such as Mancini and stored in ihe rock (Zone 4). This energy has little Occella. Ic snouia no-~gorrerrnizittcter co o m n from Zones 2 and 3 is the most useful in - c ~ r i r ~ ~ e b ~ ~ t - i s R o ~ ~ n e c eThes energy s n ~ rock blasting and is called Fragmentation Energy. to fragment the rock but also to cause swelling and At ihe time of escape, some of the energy in the gases displace it a dete&ned distance. For ihis reason, in ihe (Zone 5) moves ihe burden and represents heave energy. latter stages the gases also play a decisive role. The rest of this energy is lost as heat and noise in the Lowends' used a simplified model of explosivelrock escaping gases. interaction to describe the partition of explosive energy in Alihough this model of energy partition overthe process of rock blasting. The energy is partitioned simplifies the blasting process, it gives valuable insight into different zones h a t are related to the pressurel into where ihe energy goes during the various phases of volume expansion of ihe gases during ihe different the process. It also provides approximate comparisons of phases of blasting. An illustration of ihis partition of ihe magnitude of ihe energy fractions used in the various energy is given in Fig. 16.10. phases of the blasting process as the explosive gases The energies associated wiih the different zones given expand from the initial pressure in the blasthole to atrnosin the figure are, as follows: pheric pressure. Not all of ihe availableenergy is useful in When ihe explosive detonates in the blasthole, the high fragmentation and heave. It may be possible to improve pressure gases at the initial or explosion state P3 send a the efficiency of the blasting process by using explosives, shock wave into the rock. The strains from this shock wheiher ideal or not, ihat are designed to keep energy near the blasthole are greater than the dynamic compresslosses at a minimum. ive and shear strength of the rock. They cause v q i n g amounts of rock compression and crushing in ihe sur: rounding area of the blasthole depending upon ihe REFERENCES strength and stiffness of the rock. With rock compression and crushing ihe volume of the blasihole increases and Ash. R.L.: The Mechanics qf-e. Pit and Q u a q no. 56. ihe pressure decreases until ihe strain in ihe rock balances 1963. Duvall, W. I. & T.C. Atchison: Rock Breakage by Explosives. U.S. B.M. the pressure. This is shown as74 on ihe pressurelvolume RI 5356,1957. curve of Figure 16.10, and is called blasihole equilibrium Hagan, T.N.: Rock Breakage by Explosives. Proc. National Syrnpostate. During the expansion, the work being done by ihe sium on Rock Fragrnentation. Australian Geornechanics Society. explosive is called bnssance energy and consists of the. Adelaide, Feb. 1973. Hagan, T.N. & G.D. Just: Rock Breakage by Explosives. T h e o q strain energy stored in the rock (Zone 2) and ihe kinetic Practice und Optimization. Proc. Congress International Society of energy of the shock wave (Zone 1). The kinetic shock Rock Mechanics. Vol. 11, 1974 energy is essentially lost as useful work during ihe blastHagan, T.N.: Rock Breakage by Explosives. 6th Symposium on Gas ing process and appears as crushed rock surrounding ihe Dynarnics of Explosives and Reactive Systems. Stockhlom, 1977, b l a s t h n l e a n d aq s e i s m i c p a p a g a i e d h LL ~a n d J A L L R & E w r e a & a d e m a p p r a a I n p e a p i h l n ~ r design und anulysis. CIM Bulletin. June, 1972. ground. Lopez Jirneno, C.: Los Mecanismos de Fragmentacibn con Explosivos The strains in the rock coming from ihe residual blasty la Injluencia de las Propiedades de las Rocns en los Resultados hole pressure P4 cause fracture. The explosion product de las Voladuras. I Serninario de Ingenieria de Arranque de Rocas gases enter at least the cracks existing between the hole con Explosivos en Proyectos Subterriineos. Fundation GornezPardo, 1986. and the free face, resulting in fragmentation and possibly Rascheef, N. & I? Goernans: Contribution 6 l'etude quantitative de contributing to the heave. When ihe gases reach the free l'energie consommie dans la fragmentation pur explosif. 0ct.face through the burden, the process ends more or less Dec., 1977. abruptly. The pressure of the gases at escape is shown at Thurn, W.: Quantite d'energie requisepour L'extraction et lafragmentation des roches au moyen d'explosives. Explosifs, 1972. P5 in Figure 16.10. During escape, the burden is comP

CHAPTER 17

Rock and rock mass properties and their influence on the results of blasting

17.1 INTRODUCTION ,

-

The matenals of which rock masses are maae possess ~ ~ ~ ~ ~ ~ h a t origin and of the posterior geological processes which have affected them. The whole of these phenomena make up a certain environment, a particular lithology with heterogeneities caused by the added polycrystalline minerals and by the discontinuities of the rock matrix (pores and fissures): and by a geological structure in a characteristic state of Stress, with a large number of structural discontinuities such as bedding planes, fractures, diabases, joints, etc. 17.2 ROCK PROPERTIES

Persson et al., 1970) arriving at values that are between 5 and 13 times more than the static. . W nen me ~ y ~ t w mn m &n r ip 9 ec i ~v p 't r r ~ n g t ~ 4 surrounding the blasthole wall is produced by collapse of the intercrystalline structure. However, this excessive crushing does little to aid in fragmentation and gravely reduces the strain wave energy. Therefore the following is recommended: - Explosives that develop blasthole wall strain energy that is lower than or equal to RC must be chosen. - Provoke a variation in the Pressure-Time curve (P t) by decoupling the charge in the blasthole. These points are of maximum importance in perimeter or contour blastings. The powder factors required in bench blastings can be correlated with the compressive strength, as indicated in Table 17.1 (Kutuzov, 1979). m

m -

The densities and strengths of rocks are normally quite well correlated. In general, low density rocks are deThere are two types of porosity: intergranular or formaformed and broken quite easily, requiring relatively low energy factors, whereas dense rocks need a higher quanttional, and that of disolution or post-formation. ity of energy to achieve a satisfactory fragmentation, as The first, which has a uniform distribution in the rock mass, provokes two effects: d and swelling. well as a ~ o o disdacement In high density rocks, the following measures should - Attenuation of the strain wave energy. be taken to ensure adequate hegvy energy: - Reduction of the dynarnic compressive strength and, - Increase the drilling diameter in order to elevate the consequently, an increase in crushing and percentage of where VD is the detoblasthole pressure, PB = k X VD2, fines. nating velocity of the explosive. The fragmentation of very porous rocks is carried out, - Reduce the Pattern and modifj the initiation sealmost exclusively, by bubble energy, so the following quence. recommendations should be observed: - Improve the effectivity of the stemming to increase - Use explosives with a high EBIET ratio, such as the time of gas performance and make certain that they ANFO. eseapeheugkchefr e e f a ~ ~ ~ s t e a B O ~ u g U -~ I kn cmr e~a s e _ E B a t t h e o o f E T y decoupling the charges and the initiation Systems. ming. - Use explosives with high bubble energy EB. - Maintain the explosion gases at high pressure with an adequate stemming height and type. - Maintain the burden equal for each hole by using 17.2.2 The dynarnic strengths of the rocks various free faces. The static compressive RC and tensile RT strengths are The post-fomation porosity is caused by spaces and initially used as indicative parameters of the suitability of cavities that result from the disolving of the rock material the rock for blasting. The Index of Blastability was by underground water (karstification).The empty spaces defined (Hino, 1959) as the relationship 'RC/RT1, the are much larger and their distribution is much less unilarger the value, the easier the fragmentation. form than in the intergranular porosity. The rational treatment of the existing problems require In rock of volcanic origin it is also frequent to find a taking into consideration the dynamic strengths, as these large number of cavities formed during its consolidation. increase with the index of the charge (Rinehart, 1958: The cavities that are intersected by blastholes not only

161

Rock and rock muss properties Table 17.1. Rock classificationaccording to their facility of fragmentatiin by explosives in Open pit mines. Powder factor Mean distance between natural Uniaxial compressive rock strength (MPa) Class limit (kglm') Average value (kglm') fractures in rock mass (m)

r

aI .-encqnnfiheblasr,eqecid&if

loosepacked or pumpable explosives are used, Fig. 17.1. If the boreholes do not intersect the cavities, the yield of the blast also descends because: - The propagation of radial cracks is intermpted by the cavities. - The rapid fall in pressure of the gases as the blastholes intercommunicate with the cavities, halting the opening of the radial cracks, while the gases escape towards the empty spaces.

As the rocks do not form an elastic media, part of the strain wave energy that propagates through them is converted to heat by diverse mechanisms. These mechanisms are known as intemal friction or specijic darnping c a p a c i ~SDC, which measure the ability of the rock to attenuate sirain waves generated by the detonation of the explosive. SDC varies considerably with the type of rock from values of 0.02-0.06 for granites (Windes, 1950; Blair, 1956) up to 0.07-0.33 for sandstones. SDC increases with porosity, permeabillity, joints and water content of the rock. It also increqses considerably with the meteorized levels in function with their thickness and weathering. The intensity of the fracturation by the strain wave increases as the SDC decreases. Therefore, watergel type explosives are more effective in hard and crystalline formations than in soft and decomposed materials (Cook, 1961;Lang, 1966). On the other hand, in the latter, ANFO

Rock density (tlm3)

.

iated ana protectea. l t 1s recommende -~e&o~~beuse& The failure of one of the detonators could considerably affect the results of the blast. 17.2.6 The cornposition of the rock and the secondary dust explosions The secondary dust explosions usually occur in coal mines and in highly pyritic areas such as underground meta1 mines, and are more frequent each day due to the use of large diameter blastholes. The first charges'fired create, on one hand, a high quantity of fines which are thrown into the atmosphere and, on the other, agitate the dust deposited on the sidewalls and roof of the excavation with the airblast and vibrations. If the energy of the gases from the last charges is sufficiently high, it could ignite the concenirated dust causing secondary explosions with devastating effects upon the ventilation installations, doors, mobile equipment, etc. The probability of secondary explosions can be reduced by taking some of the following steps: - Eliminate the use of aluminized explosives since the particles of A1203at high temperatures in the detonation products are potential ignition centers. - Select an explosive and blasthole gqmetry for bum cuts which produce coarse material. - Stem all blastholes with sand, clay plugs or water. - Create a cloud of limestone or another inhibitor in front of the face by exploding a bag of said material with a detonator fired some miliseconds before the blast.

isb~sade~eventhoughitsstrainenergyis-

-

Waskth~~md-Boo~eex~a~tior

lower.

quently to remove the deposited dust. - Fire the blasts after evacuating all personnel from the mine.

The leakageor shunting of electrical current can occur when the detonators are placed in blastholes that are in rock of certain conductivity, such as complex sulfides, magnetites, etc., especially when the rocks are abrasive and water is present near the round. The measures that should be taken to avoid these problems are: - Check that the cables of the detonators are well enclosed in plastic and, - That all the connections of the circuit are well insu-

17.3 PROPERTIES OF THE ROCK MASS 17.3.1 Lithology The blasts in zones where an abrupt lithological change is produced, for example in waste and ore and, in consequence, a variation in the strength of the rocks, the design must be reconsidered. One of the two following methods could be used:

Drilling and blasting of rocks

162

Fig. 17.1. Correct use of a bulk explosive charge in ground with large cavities.

RELAY

SOFT ROCK

DETONATING CORD

---+-

-

Fig. 17.2. Recommended change in blasthole pattem of V type blast at contact between waste and ore. Photo 17.1. Blocks with columnar geometry in basaltic formations. STRONG UNFISSURED BOULDERS O F LIMESTONE

SOFT. PLASTIC ACTING MATERIAL (SOIL. GRAVEL. CLAY)

Photo 17.2. Intenselyjointed limestone rock mass.

-a+Eq&a1~m**fOfre-~

Fig. 17.3. Typical cases of lithological changes with contact between competent rocks and plastic matenals (Hagan).

. .

in the unitary charges. b) Different Patterns with equal charges per hole. This placement is usually adopted maintaining equal burden, Fig. 17.2, as the introduction of a different S X B pattern for each Zone would entail a more complex dnlling and the newly created face may be stepped. The serni-horizontal stratiform beds presented by some very resistant layers may lead to a peculiar type of blastings in which the charges are placed in the blastholes and completely confined at these levels. It is also recommended that the pnmers of the explosive columns coincide with the strongest levels in order to obtain maximum effect from the strain energy.

Rock and rock muss properties Table 17.2. Absorption of strain wave energy by joints 1. Small(< 20%) 2. Slight (20-40%) 3. Medium (40-80%) 4. Large (> 80%)

163

Joint width (mm)

Natureof joints

('4) 0 (B) 0-4.0 (A) Up to 0.5 (B) Up to 4.0 0.5-1 .O (A)O.l-1.0 (B) 1.0

(A) Tightly stacked (B) Cemented with material of acoustic impedance close to that of the main rock (A) Open joints filled with air or water (B) Cemented with material of acoustic impedance 1.5-2 times less than that of main rock Open joints filled with air or water (A) Joints filled with loose and porous material (B) Open joints filled with loose, porous material, air and water

When two matenals of very different strengths come Table 17.3. Possible combinations of spacing between blastholes (S), joints (J), and maximum adrnissable block size (M). into contact as, for example, a competent limestone with Case Js:S Js:M S:M Fragmentation % of very plastic clays and, if the blastholes pass through these sensitive to Iormations, a great 105s of energy associated with a drop specific charge ~ p r e ~ s e ; t p e o f g m w i t t a ap ~ ~ g Yes Medium S>M Js>M I J,>S rapid deformation of soft material and, as a consequence, Yes Low S<M Js>M Js>S 2 poor fragmentation, Fig. 17.3. Yes Low S<M Js<M 3 J,>S In order to increase the yield of the blasts in these No High S>M Js>M 4 J,<S No Low S<M Js<M J,<S 5 cases, the following is recomrnended: No Low S > M J < M 6 J< S - Stem with adequate material the zones of the blastholes that are in contact with or near plastic material. - Use explosive charges that are totally coupled to the competent rock with a high detonation velocity and ET/ OVERBREAK ZONE b BACK-ROW BLASTHOLE EB relationship. JOINT OF PREVIOUS BLAST PLANES NEXT FACE - Place the primers in the rniddle of the hard rock to \ increase the resulting strain wave that acts upon both sides. - Avoid premature escape of gases to the atrnosphere insuring that both the sternming height (at least 20 D) and the size of the burden are correct at the top of the blastholes. 17.3.2 Pre-existingfractures

~

Fig. 17.4. Excessive toe burden caused bv stmcturally. - controlled backbreak Zone and face angle. All rocks in nature have some type of discontinuity, microfissusandmacrofissiares, which deckkelyY influence the physical and mechanical properties of the that might arise are indicated, taking into account the rocks and, consequently, the bbting results, Photos 17.1 inclination of the discontinuititesand the relative angle of and 17.2. the strike and dip. The areas of discontinuity can be varied: bedding Special precautions should be taken when the discontiplanes, planes of lamination and primary foliation, planes nuities are subvertical and the direction of the shot is of schistose and slate, fractures and joints. normal (parallel) to theirs, because overbreak is frequent The discontinuities can be tight, Open or filled and, for behind the last row of blastholes and inclined dnlling this reason, can exhibit different degrees of explosive becomes necessary to maintain the burden dimension in energy transmission. Table 17.2. The walls of these disthe first row of the round. Fig. 17.4 and Photo 17.3. ~ ~ i e ~ - ~ v e f t ~ w f a e s +entkie&&ni-m7he t t p e ~ t h ~ jöinrsystem~a-an-xnsie n waves may be reflected, suffering attenuation and dispersmaller than 30°, it is recommended that the blastholes be sion. normal to said planes in order to increase the yield of the The fragmentation is influenced by the spacing beblasts. tween blastholes S, the separation between joints J and In tunnel excavations, the structural characteristics the maximum admissible block size M. In Table 17.3, largely condition the geometry of their profile, almost various possible combinations are indicated, as well as rectangular if the rocks are massive and with a curved their repercussion upon the percentage of forseen arch if the rock is more unstable. When the discontinuiboulders. ties are normal to the tumel's axis, the blasts usually have Another aspect of the design of the blastings is referred good results. Fig. 17.5a. If the bedding or the discontinuito as geostructural control of the rock mass, which refers ties are parallel to the axes of the tunnels, Fig. 17.5b, to the relative orientation of the face and break direction frequently the advances are not satisfactory and the faces of the round with respect to the strike and dip of the Strata. are uneven. When the bedding has an oblique direction In Table 17.4, the forseen results for the different cases with respect to the axis of the tunnel, there will be one "

164

Drilling and blasting oj'rocks

Photo 17.3. Face of photofiltre studio x crack code - Crack Key For U blast that coincides with a bedding plane.

side on which it is easier to blast, such as in the case of Fig. 17.5c, the left side. On the other hand, very laminated rocks with high schistosity and fissurization rese-a-4 deep pulls of up to 6 m are possible with this type of cut. When V cuts are used in sinki~grectangular shafts, the best results are obtained when the discontinuities are parallel to the line joining the bottom of the V cut, Fig. 17.6.

When the stress fields, either tectonic andlor gravita~nnai-(non-hydrostatic)-ac~e-fracture-pattem-gen~ rated around the blastholes can be influenced by the non-uniform stress concentrationsaround the same. In hornogeneous massive rock, the cracks which Start to propagate radially frorn the blastholes tend to follow the direction of the principai stresses. Therefore, when driving shafts in rock masses with a high concentration of residual stresses, as in the case of Fig. 17.7, the firing sequence in the blastholes of the cut should be adapted to this situation. If in the presplitting planes of the planned excavation the influencing stresses are normal to the same, the obtained results will not be satisfactory unless the spacing is considerably reduced or a pilot excavation is carried out

Fig. 17.5. Relative directions of the beds with regard to the axes of the tunnels.

to relax the mass and free the stresses, and presplitting is substituted for smooth blasting. 17.3.4 Water content Porous and intensely fissured rock, when saturated with water, usually Pose certain problems:

Rock und rock muss properties Table 17.4. Design of the blasts with attention to geostmctural control.

Inclination of the strata a =0°

Angle between the direction of the Strata and the blast break Indifferentbreak direction

3 = 45" = 135" = 225' = 315" ß = 90" = 270"

face Variable fngmentation. sawtooth face Most favorable direction

Good Unfavorable Not very favorable Acceptable Very favorable

(Sirnilar to the previous case hardness is determining factor)

45" < a < 90"

MAJOR. PHYSICAL DlSCONTlNUlTlES

SHAFT PERIMETER

ß =22S0 =31S0 = 2700

Good Unfavorable Not very favorable Acceptable Very favorable

ß = 90"

Not very favorable ß = 270" Favorable (Depending upon the value of a and upon the rock competence, the results will be closer a a = 45" 6 a = 90")

3 --

-/ L

.

NITIATION SEOUENCE

\

3

BLASTHOLE 4 DlRECTlON OF MAL~MuM PRINCIPAL STRESS

-

-7/

Fig. 17.7. Initiation sequence for burn cut in high horizontal Stress field: (a) tobe avoided, (b) satisfactory.(Hagan, 1983).

Fig. 17.6. Rectangular sinking shaft with V cut. (Hagan, 1983)

166

Drilling und blasting of roch

- Only explosives that are unaltered by water can be used. - Blastholes are lost due to caving, and - Inclined drilling is difficult. On the other hand, water affects the rock and the rock masses by the following: - Increase in propagation velocity of the elastic waves in porous and fissured ground. - Reduction of the compressive and tensile strength of the rocks (Obert and Duvall, 1967) as the friction between particles is lower. - Reduction of the Stress wave attenuation and, because of this, the breakage effects are intensified by ET (Ash, 1968).

which it is in contact and, because of this, great attention must be paid to this phenomenon. A general recommendation when these problems are present is to limit the number of blastholes per blast, in order to lower the time that passes between the charging and the firing.

REFERENCES Ash, R.I.: The design of blasting roundi. Ch. 7.3. Surface Mining, Ed. E. F? Pfleider, AIME, 1968. Atchison, TC.: Fragmentation principles. Ch. 7.2. Surface Mining, Ed. E.F?Pfleider, AIME, 1968. Belland, J.M.: Structure as a control in rock fragmentation. Carol - i%b. LaKe rron ore deposrts. L ~ u i i e r i nMarchBhandari, S.: Blastinn in non-homogeneous rocks. Australian Mining, i e r ~ i ~ May, 1974. Blair, B.E.: Physical properties of mine rock. Part 111. USBM RI No. 5 130, 1955: Part IV USBM-RI, No. 5244,1956. Grant, C. H.: How to muke explosives domore work. Mining- Magazine, August, 1970. Hagan, T.N.: The effects of some structural properties of rock on the design und results of blasting. ICI Australia Operations PTY.Ltd. Melboume, 1979. Hagan, T. N.: 'The influence of rock properties of blasts in underground construction. Proc. Int. Symp. on Engineering Geology and Underground Construction. Lisboa, Portugal, 1983. Hanies, G.: Breakage of rock by explosives. Aus. I.M.M., London, 1978. Kutuzov, B.N. et al.: Classification des roches d'apres leur explosibi1it.i pour les decouvertes. Gomyl, Zumal, Moscow, 1979. Lopez Jimeno, E.: Inpuencia de Iaspropiedades de las rocas y Macizos Rocosos en el diseiio y resultado de las voladuras. Tecniterrae, 1982. Memt, A. H.: Geological predictions for underground excavations. North American RETC Conference. Polak, E.J.: Seismic attenuation in engineering site investigations. Proc. Ist. Aust. N.Z. Conf. Geomechanics, Melboume, 1971. Rinehart, J.S.: Avg driver updater 2.5 registration key - Free Activators und strain generated in joints and layered rock masses by explosions. Proc. Symp. Mechanism of Rock Failure by Explosions. Fontainebleau, October. 1970. Sassa, K. & I. Ito: On the relation berween the strength of a rock und the panern of breakage by blasting. Proc. 3rd. Congress Intemational Society of Rock Mechanics. Denver, 1974. Sjogren, B. et al.: Seismic classification of rock muss qualities. Geophysical Prospecting, No, 27,1979. Wild, H.W.: Geology und blasting in openpits. Erzmetall, 1976. U

w i t h n i i t i n t P. m ~ i n ~ R i i t e ~ e m a s s _ e n tension, the water is mobilized, forming a wedge which could provoke a great overbreak.

17.3.5 Temperature of the rock muss The orebeds that contain pyrites usually have high rock temperature problems because of the effect of slow oxidation of this mineral, causing the explosive agents such as ANFO to react exothermically with the pyrite, with stimulation from 120°C f 10°C. The latest investigations point to a first reaction between ANFO and hydrated ferrous sulphate, and even more so between the latter and amrnonic nitrate, initiating an exothermic reaction that is self-maintaining from 80°C On. This ferrous sulphate is one of the products of decomposition of the pyrites, apart from the femc sulphate and the sulfuric acid. To avoid this problem, which has caused severe accidents on several occasions, diverse substances which inhibit ANFO have been added, such as urea, potassic oxalate, etc., arriving at the conclusion that by adding to ANFO a 5% in weight of urea, the exothermic reaction of the ternary mixture is avoided up to a temperature of 180°C (Miron et al., 1979). The sensitivity of the water gel type explosives also depends highly upon the temperature of the rock with

.

%

*

CHAFIER 18

Characterization of the rock masses for blast designing

18.1 INTRODUCTION The properties ot rock masses that most infiuence blast

- Dynamic strengths of the rocks. - Spacing and orientation of the planes of weakness. - Lithology and thickness of the sedimentary bedding planes. - Velocity of wave propagation. - Elastic properties of the rocks. - Types of infilling material and tightness of the joints. - Indexes of anisotropy and heterogeneity of the rock masses, etc. The determination of these parameters by direct or laboratory methods is very costly and difficult, as the samples tested do not usually include discontinuities and the lithologicalchanges of the rock mass from where they were taken. In order to obtain a representative sample, it would be necessary for it to have a size ten times larger than the mean spacing between joints. However, these methods do complement the characterization of the rock masses to be blasted. At the moment, the most common geomechanic techniques for monitoring are: - Diamond drilling with core recovery and geomechanic testing. - - Structural studies of the joint System. - Seismic survey profiles. - Geophysical logs of investigation drill holes. - Geophysical logs of production blastholes. - Logging and individual treatment during drilling of production blastholes.

RC (MPa) = 24. 1, (50) (MPa) the Pierce equation, for the calculation of the Burdm from the RQD index, corrected by a Coefficient of Alteration which takes into account the Joint Strength as a function of their tightness and the type of infilling, Fig. 18.1 and Table 18.2. The company Steffen, Robertson and Kirsten, Ltd. (1985), used various geomechanic Parameters to calculate the powder factors in bench blasting, among which RQD, the Uniaxial Compressive Strength (MPa), the Interna1 Friction Angles and Abrasiveness of the joints and the Density are found (t/m3),Fig, 18.2. This procedure is one of the few that take into account the effect of blasthole diameter (mm) or spacial distribution of the explosives upon the powder factor of the blast. 18.3 CHARACTERISTICS OF THE JOINT SYSTEMS There are various properties of the joints that can be measured in a characterization study, but the most important from a breakage point of view are spacing and onentation. An index obtained frequently is that known as the Volumetric Joint Count, J, which is defined by the total number of joints per cubic meter, obtained from the summing of the joints present per meter for each one of the existing families. The relationship between the index J, and the RQD is, according to Pallsmtrom (1974), the following: RQD = 115 - 3.3 J,For J, < 4.5, RQD = 100

18.2 DIAMOND DRILLING WITH CORE RECOVERY AND GEOMECHANIC TESTING With core recovery by diamond drilling, one of the most extensive rock mass clasifications known can be applied, called RQD (Rock Quality Designation, Deere 1968) which is defined as the percentage of the core length recovered in pieces larger than 10 cm with respect to the length of the core run, Table 18.1. Apart from this, the geomechanic testing of Point Load Strength I, can be canied out either in the diametral or axial position, to be able to estimate the Uniaxial Compressive Strength RC.

According to the orientation of the joints, the in-situ blocks will show different geometries that doubly affect the fragmentation of the blast and the most useful break direction of the round. In Fig. 18.3, the approximate volume of the blocks taken from J, and the relationship of the three characteristic intersections of the Same can be estimated. An attempt to take into consideration the structural discontinuities when designing the rounds is owed to Ashby (1977), which relates the fracture frequency and their shear strength to the powder factors of the explosive, Fig. 18.4. Lilly (1986) defined a Blastability Index BI that is

168

Drilling und blasting of rocks

Table 18.1. RQD 0-25 25-50 50-75 75-90 90-100

Rock quality Very poor Poor Fair GOO~ Excellent

Table 18.2. Joint strength Strong Medium weak Very weak

Y = a + b l n X

m

Correction factor 1O. 0.9 0.8 0.7

0.9

-

0.8

-

0.7

-

3.6

Table 18.3. J

>I 1-3 3-10 10-30 > 30

Characteristicsof the mass Massive blocks Large blocks Medium size blocks Small blocks Very small%locks

0.3

1

"'1

0.1

0.0

DESCRlPTlON OF ROCK OUALITY

1

VERY POOR

POOR

I

I

0

10

20

I

FAIR

GO09

I

I

:

I

I

i

I

30

I

I

I

I

I

40

50

60

70

I

1

80

p-~ I 90

100

EOUIVALENT ROCK QUALITY DESIGNATION (%) €ROD = ROD X ALTERATION FACTOR

Table 18.4. Geomechanic ~arameters 1. Rock mass description (RMD) I. I Powderylfriable 1.2 Blocky 1.3 Totally massive

Ratine

Fig. 18.1. Blastability factor k vs equivalent rock quality designation, RQDE.

10 20 50

2. Joint Plane Spacing (JPS) 2.1 Close (< 0.1 m) 2.2 Intermediate (0. I to 1 m) 2.3 Wide (> 1 m)

10 20 50

-

3. Joint Plane Onentation (JPO) 3.1 Horizontal 3.2 Dip out of face 3.3 Strike normal to face 3.4 Dip into face

10 20 30

4. Specific Gravity Influence (SGI) SGI = 25 SG - 50 (where SG is In Tonslcu metre) 5. Hardness (H)

1-10

obtained by summing the representative values of five geomechanics parameters. Rl= Q 5 ( R M 1 3 t l m - u D L

In Table 18.4, the ratings for Blastability Index parameters are described. The Powder Factors CE or the Energy Factors FE are : or the equations calculated with ~ i g18.5, CE (Kg ANFO/t) = 0.004

X

BI, or

FE (MJ/t) = 0.015 X BI

From the numerous experiences canied out in Australia, it has been concluded that the Rock Factor of the Model Kuz-Ram of Cunningham (1983) can be obtained by multiplying BI by 0.12.

Fig. 18.2. Calculation of the Powder Factor as a function of the different geomechanicparameters of the rock mass.

Example: Consider a highly laminated, soft ferruginous shale which has horizontal to sub-horizontal bedding to which the-fofIowing~due~me~ri.

RMD = 15 P S = 10 JPO = 10 SGI = 10 H=l The total sum is 46 and the Debut registration code 2018 - Crack Key For U Index is BI = 23. From Fig. 18.4, a powder factor of 0.1 kg/t is obtained. Ghose (1988) also proposes a geomechanic classification System of the rock masses in coal mines for predicting powder factors in surface blastings. The four parametersmeasured any music mp3 downloader - Crack Key For U indicated in Table 18.5.

Characterization of the rock masses for blast designing

Fig. 18.3. Estimation of the volume of the in-situ blocks.

Parameters 1. Density Ratio 2. Spacing of discontinuities (m) Ratio 3. Point load strength Index (MPa) Ratio 4. Joint plane onentation Ratio

Range of values 1.3-1.6 20 < 0.2 35
1.6-2.0 15 0.2-0.4 25 1-2 20 Strike at an acute angle to face 15

20

Table 18.6. Adjustment factors I. Degree of confinement Highly confined Reasonably free

-5 0

2. Bench stiffness Hole depthlburden > 2 Hole depthlburden C 1.5 Hole depthlburden 1.5-2

0 -5 -2

Values

2.0-2.3 12 0.4-0.6 20 2-4 15 Strike normal to face

2.3-2.5 6 0.6-2.0 12 46 8 Dip out of face

> 2.5

12

10

6

Table 18.7. Blastability index 80-85 60-70 5MO 40-50 30-40

4

> 2.0 8 >6 5 Horizontal

Powder factor (kg/m3) Freemake Video Converter 4.1.11.93 Crack + License Key Free 2020 0.3-0.5 0.5-0.6 O.M.7 0.7-0.8

170

Drilling and bhsting of rocks

POWDEA FACTOR

'

BLASTING

-

POWDEA FACTOR ,KO A N F O ~ ~ J

'

lag

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