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Edited by Sadhan K. De and Jim R. White
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom
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First Published 2001 by
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©2001, Rapra Technology Limited
All rights reserved. Except as permitted under current legislation no part
of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
Typeset by Rapra Technology Limited
Printed and bound by Polestar Scientifica, Exeter, UK
Preface
From a materials point of view a rubber product is made from rubber and a host of other
additives, including fillers, vulcanising agents and processing aids along with reinforcing
materials such as textiles. From a manufacturing point of view, a rubber product is made
by following several steps: mixing of additives with the rubber (‘compounding’) when
the rubber is unvulcanised and in the plastic state; shaping the rubber compound and/or
bonding it to a substrate; and finally vulcanising or curing the whole assembly, when
chemical crosslinks are formed between the rubber molecules to give the material its
‘elastic’ recovery behaviour. The final properties of a rubber product depend on the type
of rubber chosen and the additives used and their concentrations. The properties of the
rubber can be further manipulated by varying the processing steps or manufacturing
operations. The cost of a rubber product depends not only on the price of the raw materials
but also on the efficiency of the processing operations. In the last few decades new materials
have emerged and manufacturing has become increasingly automated and more efficient.
This handbook aims to provide a basic foundation in rubber technology and to collate
the most recent developments in the form of chapters, written by experts in their respective
fields. The handbook is intended to serve the needs of those who are already in the
rubber industry and of new entrants who aspire to build a career in rubber and allied
areas. Materials Science students and researchers, designers and engineers should all
find the handbook very helpful.
Fourteen chapters deal with natural rubber, synthetic rubbers, thermoplastic elastomers,
fillers, compounding additives, mixing, engineering design, testing, tyre technology,
automotive applications, footwear, rubbers in construction, durability of rubber products,
and rubber recycling. It is obvious that several important topics could not be
accommodated in the current volume and it is intended that a second volume of the
handbook will be published by RAPRA Technology Ltd in the near future to extend the
coverage. We gratefully acknowledge the cooperation from all of the contributors, without
whom this handbook would not have been a reality. We are especially grateful to the
commissioning editor, Ms Frances Powers, for her unique combination of professionalism
and good humour: her prompt and pointed responses to all of our requests for assistance
were invaluable. We wish to commend all of the staff at RAPRA Technology Ltd who
contributed to the excellent production of the handbook, especially Claire Griffiths and
Sandra Hall.
Rubber Technologist’s Handbook
ii
On a personal note, one of us (JRW) is grateful for being granted leave of absence from
the University of Newcastle upon Tyne for a visit to the Rubber Technology Centre at
the Indian Institute of Technology, Kharagpur in January 2001 during a critical stage of
the preparation of the handbook. Although the purpose of the visit was to conduct
research and teaching in the most stimulating surroundings of the RTC, time was found
for the two editors to renew their friendship, tie up the loose ends of the handbook, and
to lay plans for Volume 2. Finally we are extremely thankful to our wives, Prajna and Li
Tong, for their patience and support during the preparation of the handbook.
S K De and J R White
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Contents
1 Introduction .................................................................................................... 1
1.1 Brief historical review ............................................................................ 1
1.2 The uniqueness of rubber....................................................................... 3
1.3 Survey of the current Handbook ............................................................ 4
1.4 Closing remarks ................................................................................... 10
2 Natural rubber .............................................................................................. 11
2.1 Introduction ......................................................................................... 11
2.2 Source .................................................................................................. 11
2.3 Cultivation ........................................................................................... 13
2.4 Harvesting ........................................................................................... 14
2.5 Biosynthesis of rubber.......................................................................... 15
2.6 Composition of latex ........................................................................... 16
2.7 Crop collection .................................................................................... 17
2.7.1 Pre-processing of latex ............................................................. 18
2.8 Crop processing ................................................................................... 19
2.8.1 Preservation and concentration of latex ................................... 19
2.8.2 Ribbed smoked sheet (RSS)...................................................... 20
2.8.3 Pale latex crepe and sole crepe ................................................. 22
2.8.4 Field coagulum crepe ............................................................... 23
2.8.5 Technically specified rubbers (TSR) ......................................... 23
2.9 Modified forms of NR ......................................................................... 25
2.9.1 Physically modified forms ........................................................ 26
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2.9.2 Chemically modified forms of NR ........................................... 28
2.10 Properties of natural rubber ................................................................. 31
2.10.1 Raw rubber .............................................................................. 31
2.10.2 Vulcanised rubber .................................................................... 33
2.11 Vulcanisation ........................................................................................ 36
2.11.1 Vulcanisation with sulphur ...................................................... 37
2.11.2 Non-sulphur vulcanisation ...................................................... 38
2.12 Applications .......................................................................................... 39
2.12.1 Tyres (see also Chapter 11) ...................................................... 39
2.12.2 Engineering applications .......................................................... 40
2.12.3 Conveyor beltings .................................................................... 41
2.12.4 Linings ..................................................................................... 41
3 Synthetic elastomers ...................................................................................... 47
3.1 Synthetic and natural elastomers ......................................................... 47
3.1.1 Synthesis .................................................................................. 47
3.1.2 Mechanical properties.............................................................. 48
3.1.3 The need for synthetic elastomers ............................................ 49
3.1.4 Compounding and vulcanisation ............................................. 51
3.1.5 Synthetic elastomer polymerisation .......................................... 51
3.1.6 Mechanisms ............................................................................. 53
3.1.7 Polymer synthesis processes ..................................................... 54
3.2 Diene elastomers .................................................................................. 55
3.2.1 Polybutadiene (BR) .................................................................. 56
3.2.2 Polyisoprene (IR) ..................................................................... 58
3.2.3 Styrene-butadiene rubber (SBR) ............................................... 59
3.3 Saturated elastomer ............................................................................. 61
3.3.1 Ethylene-propylene copolymers (EPM) and ethylenepropylene-
diene terpolymers (EPDM)...................................... 61
3.3.2 Butyl and halobutyl rubbers (IIR and BIIR/CIIR) .................... 64
3.3.3 Ethylene-acrylic elastomers (EAM) .......................................... 66
3.4 Solvent resistant elastomers ................................................................. 67
3.4.1 Nitrile rubber (NBR) ............................................................... 68
3.4.2 Polychloroprene (CR) .............................................................. 70
3.4.3 Acrylic elastomers (ACM)........................................................ 72
3.4.4 Chlorosulphonated polyethylene (CSM) .................................. 74
3.5 Temperature resistant elastomers ......................................................... 75
3.5.1 Silicone rubber (Q) .................................................................. 75
3.5.2 Fluorocarbon elastomers (FKM) .............................................. 77
3.6 Specialty elastomers ............................................................................. 79
3.6.1 Phosphazenes (FZ) ................................................................... 79
3.6.2 Polyethers ................................................................................ 80
6.2.3 Structure .................................................................................. 81
3.6.3 Ring opened polymers (TPA, TOR) ......................................... 81
3.7 Thermoplastic elastomers .................................................................... 82
3.7.1 Styrene block copolymers ........................................................ 82
3.7.2 Thermoplastic polyurethanes (TPU) ........................................ 83
4 Thermoplastic elastomers .............................................................................. 87
4.1 Introduction ......................................................................................... 87
4.1.1 Thermoplastic elastomers versus thermoset rubbers ................ 88
4.1.2 Types of thermoplastic elastomers ........................................... 91
4.2 Block copolymers ................................................................................. 94
4.2.1 Polystyrene/elastomer block copolymers .................................. 95
4.2.2 Polyester/elastomer block copolymers .................................... 100
4.2.3 Polyamide/elastomer block copolymers ................................. 101
4.2.4 Polyurethane/elastomer block copolymers ............................. 103
4.3 Dynamically vulcanised rubber/plastic blends .................................... 107
4.3.1 EPDM/polyolefin ................................................................... 108
4.3.2 NBR/polyolefin ...................................................................... 109
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4.3.3 Natural rubber/polyolefin ...................................................... 111
4.3.4 Butyl rubber/polyolefin .......................................................... 111
4.3.5 Melt processable rubber......................................................... 112
4.4 Ionic thermoplastic elastomers ........................................................... 113
4.4.1 Ionic elastomers ..................................................................... 113
4.4.2 Ionomeric polyblends............................................................. 117
5 Fillers ......................................................................................................... 131
5.1 Preface ............................................................................................... 131
5.2 Manufacture of carbon black............................................................. 131
5.3 Surface and particle structure of carbon black ................................... 133
5.4 Carbon black aggregate structure ...................................................... 138
5.5 Classification of carbon black ............................................................ 141
5.6 Mixing of carbon black with rubber and carbon black dispersion ..... 143
5.7 Rheology of carbon black filled rubber .............................................. 146
5.8 Viscoelasticity of carbon black filled rubber ...................................... 148
5.9 Physical properties of carbon black filled rubber ............................... 151
5.10 Non-black fillers and application ....................................................... 155
5.10.1 Calcium carbonate ................................................................. 156
5.10.2 Clay ....................................................................................... 157
5.10.3 Silica ...................................................................................... 158
5.11 Summary............................................................................................ 162
6 Rubber additives - compounding ingredients .............................................. 167
6.1 Vulcanising agents ............................................................................. 167
6.1.1 Sulphur .................................................................................. 167
6.1.2 Sulphur donors ...................................................................... 168
6.1.3 Peroxides ............................................................................... 168
6.1.4 Urethane crosslinking ............................................................ 172
Contents
6.1.5 Metal oxides .......................................................................... 173
6.1.6 Other vulcanising agents ........................................................ 173
6.2 Vulcanisation accelerators .................................................................. 173
6.2.1 Sulphenamides ....................................................................... 174
6.2.2 Thiazoles ............................................................................... 177
6.2.3 Guanidines ............................................................................. 178
6.2.4 Thiurams ............................................................................... 179
6.2.5 Dithiocarbamates ................................................................... 179
6.2.6 Dithiophosphates ................................................................... 180
6.2.7 Miscellaneous ........................................................................ 181
6.2.8 N-Nitrosamines and accelerators ........................................... 181
6.3 Activators of vulcanisation ................................................................ 183
6.4 Retarders and inhibitors of vulcanisation .......................................... 184
6.5 Antidegradants .................................................................................. 185
6.5.1 Antioxidants .......................................................................... 186
6.5.2 Antiozonants ......................................................................... 190
6.6 Antireversion agents .......................................................................... 193
6.6.1 Zinc carboxylates .................................................................. 193
6.6.2 Thiophosphoryl derivatives ................................................... 194
6.6.3 Silane coupling agents ............................................................ 195
6.6.4 Sulphenimide accelerator ....................................................... 195
6.6.5 Hexamethylene-1,6-bis thiosulphate disodium dihydrate
(Duralink HTS)...................................................................... 196
6.6.6 1,3-Bis(citraconimidomethyl)benzene (BCI-MX;
Perkalink 900) ....................................................................... 197
6.7 Plasticisers and softeners .................................................................... 198
6.7.1 Petroleum products ................................................................ 198
6.7.2 Coal tar products ................................................................... 199
6.7.3 Pine products ......................................................................... 199
6.7.4 Synthetic softeners ................................................................. 200
Rubber Technologist’s Handbook
vi
6.7.5 Other products ...................................................................... 200
6.8 Miscellaneous ingredients .................................................................. 200
6.8.1 Peptising agents ..................................................................... 201
6.8.2 Blowing agents ....................................................................... 202
6.8.3 Bonding agents ...................................................................... 202
6.8.4 Pigments ................................................................................ 203
6.9 Concluding remarks ........................................................................... 203
7 Rubber mixing ............................................................................................ 209
7.1 Introduction ....................................................................................... 209
7.2 Mechanisms of mixing ....................................................................... 210
7.2.1 Viscosity reduction ................................................................ 210
7.2.2 Incorporation ......................................................................... 211
7.2.3 Dispersion .............................................................................. 213
7.2.4 Distribution ........................................................................... 213
7.3 Rheology of mixing ........................................................................... 215
7.3.1 Flow behaviour of rubber compounds ................................... 215
7.3.2 Measurement of state-of-mix ................................................. 216
7.3.3 Dependence of flow behaviour on state-of-mix...................... 218
7.3.4 Kinetics of dispersive mixing ................................................. 220
7.3.5 Mixing of blend compounds .................................................. 222
7.4 Heat history ....................................................................................... 222
7.5 Batch mixing methods and systems .................................................... 223
7.5.1 Two-roll mills ........................................................................ 223
7.5.2 Internal mixers – design and performance ............................. 226
7.5.3 Internal mixers – operation .................................................... 231
7.5.4 Mixing sequences ................................................................... 233
7.6 Batch-off extruders and festoon coolers ............................................. 235
7.7 Materials handling ............................................................................. 237
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7.8 Instrumentation and control of mixing
.............................................. 239
.............................................. 239
7.9 Continuous mixing ............................................................................ 242
7.9.1 Continuous mixing versus batch mixing ................................ 242
7.9.2 Powder weighing, blending and handling .............................. 242
7.9.3 Continuous mixing – principles ............................................. 243
7.9.4 Continuous mixers - examples ............................................... 244
7.10 Acknowledgements ............................................................................ 247
8 Durability of engineering products .............................................................. 251
8.1 Introduction ....................................................................................... 251
8.2 Outline design factors of seals, hoses and cables ................................ 253
8.2.1 Seals ....................................................................................... 253
8.2.2 Hoses ..................................................................................... 257
8.2.3 Cables .................................................................................... 259
8.3 Durability aspects .............................................................................. 261
8.3.1 The structural nature of rubbers ............................................ 261
8.3.2 General mechanical properties ............................................... 262
8.3.3 Properties for long-term performance .................................... 262
8.4 Definitions of failure .......................................................................... 268
8.5 Life assessment .................................................................................. 269
8.5.1 Predictions ............................................................................. 270
8.5.2 Permeation/diffusion etc at high pressures/different
temperatures .......................................................................... 273
8.5.3 Factors which can override predictions ................................. 273
8.6 Case studies – components and models.............................................. 273
8.6.1 Predictions by time alone ....................................................... 274
8.6.2 Effects of fluid environments ................................................. 278
8.6.3 Effects of temperature on predictions .................................... 281
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9 Engineering with elastomers ........................................................................ 287
9.1 Introduction ....................................................................................... 287
9.2 Design equations – static force/deflection behaviour .......................... 288
9.2.1 Shear ...................................................................................... 288
9.2.2 Compression .......................................................................... 291
9.2.3 Curved bearings ..................................................................... 292
9.2.4 Non-linearity ......................................................................... 294
9.2.5 Instability ............................................................................... 294
9.3 Design principles-dynamic properties ............................................... 295
9.3.1 Theoretical background ......................................................... 295
9.3.2 Transmissibility ...................................................................... 296
9.3.3 Effect of elastomer type and temperature............................... 296
9.3.4 Effect of non-linearity ............................................................ 298
9.3.5 Effect of fillers and strain amplitude ...................................... 299
9.4 Fatigue of elastomers for engineering components ............................. 299
9.4.1 Material behaviour ................................................................ 300
9.4.2 Calculation of tearing energies for different geometry
components ........................................................................... 300
9.4.3 Finite element analysis ........................................................... 303
9.5 Environmental factors........................................................................ 305
9.5.1 The effect of low temperatures .............................................. 306
9.5.2 Durability .............................................................................. 306
9.5.3 Rubber/metal bonds............................................................... 307
10 Testing......................................................................................................... 311
10.1 Introduction ....................................................................................... 311
10.1.1 General .................................................................................. 311
10.1.2 Test piece preparation ............................................................ 312
10.1.3 Conditioning .......................................................................... 313
10.1.4 Density .................................................................................. 315
10.1.5 Dimensions ............................................................................ 315
10.2 Processability tests ............................................................................. 316
10.2.1 Introduction ........................................................................... 316
10.2.2 Viscoelastic flow behaviour ................................................... 316
10.2.3 Curing characteristics ............................................................ 318
10.2.4 Other tests ............................................................................. 318
10.3 Mechanical properties ........................................................................ 319
10.3.1 Introduction ........................................................................... 319
10.3.2 Hardness ................................................................................ 319
10.3.3 Tensile stress strain properties................................................ 320
10.3.4 Compression stress strain....................................................... 321
10.3.5 Shear stress-strain .................................................................. 322
10.3.6 Tear tests ................................................................................ 323
10.3.7 Dynamic stress strain ............................................................. 325
10.3.8 Creep, stress relaxation and set .............................................. 326
10.3.9 Fatigue ................................................................................... 328
10.3.10 Abrasion ............................................................................... 330
10.4 Other physical properties ................................................................... 331
10.4.1 Introduction ........................................................................... 331
10.4.2 Friction .................................................................................. 332
10.4.3 Electrical properties ............................................................... 332
10.4.4 Thermal properties ................................................................ 333
10.4.5 Permeability ........................................................................... 334
10.4.6 Staining .................................................................................. 335
10.5 Environmental resistance ................................................................... 336
10.5.1 Effect of temperature ............................................................. 336
10.5.2 Effect of liquids ...................................................................... 341
10.5.3 Effect of gases ........................................................................ 342
10.5.4 Weathering............................................................................. 343
10.5.5 Biological attack .................................................................... 343
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10.5.6 Fire resistance ........................................................................ 343
10.5.7 Radiation ............................................................................... 343
11 Trends in tyre technology ............................................................................ 351
11.1 Introduction ....................................................................................... 351
11.1.1 Tyre basics ............................................................................. 351
11.2 New tyre materials ............................................................................. 355
11.2.1 Rubbers ................................................................................. 355
11.2.2 Fillers ..................................................................................... 356
11.2.3 Fabrics and steel wires ........................................................... 357
11.3 Tyre manufacturing technology ......................................................... 358
11.3.1 Process optimisation and design robustness ........................... 358
11.3.2 Design for manufacturability ................................................. 359
11.4 Tyre performance ............................................................................... 365
11.4.1 Rolling resistance ................................................................... 365
11.4.2 Treadwear .............................................................................. 368
11.4.3 Ride and handling.................................................................. 378
11.4.4 Wet/snow/ice traction ............................................................ 380
11.4.5 ‘Run-flat’ safety tyres ............................................................. 382
11.4.6 ‘Intelligent’ or ‘smart’ tyres .................................................... 386
11.5 Advancement of tyre technology with computers .............................. 386
11.5.1 Computer aided engineering .................................................. 386
11.5.2 Computational modelling of tyres ......................................... 388
12 Automotive rubbers .................................................................................... 401
12.1 Rubber selection ................................................................................ 404
12.1.1 Determination of the environmental conditions ..................... 404
12.1.2 Choice of rubber .................................................................... 406
12.1.3 Validation of the choice of rubber ......................................... 406
12.1.4 Example: manifold seals ........................................................ 406
12.2 Identification and characterisation of rubber ..................................... 407
12.2.1 Rubber identification ............................................................. 408
12.2.2 Rubber characterisation ......................................................... 408
12.3 Rubber applications in the car ........................................................... 410
12.3.1 Rubber in the car ................................................................... 411
12.3.2 Applications where rubber is present ..................................... 413
12.3.3 Chemical constraints.............................................................. 416
12.3.4 Appearance of the body seals ................................................. 420
12.4 The future of rubber in the automotive sector ................................... 422
12.4.1 The transport of fluids (water, air, petrol in particular).......... 422
12.4.2 Seals ....................................................................................... 425
12.4.3 Suspensions/damping and fixings ........................................... 427
12.4.4 Mechanical functions of transmissions .................................. 427
12.4.5 Timing belt ............................................................................ 428
12.5 Conclusions ....................................................................................... 428
13 Rubber compounding in footwear .............................................................. 431
13.1 Running shoes ................................................................................... 433
13.1.1 Polymers ................................................................................ 434
13.1.2 Fillers ..................................................................................... 437
13.1.3 Pigments ................................................................................ 440
13.1.4 Cure systems .......................................................................... 441
13.1.5 Plasticisers, processing aids and oils ....................................... 443
13.1.6 Antidegradants ...................................................................... 444
13.1.7 Typical formulas .................................................................... 444
13.1.8 Methods of manufacture........................................................ 445
13.2 Safety shoes ....................................................................................... 445
13.2.1 Nitrile rubber-based compounds............................................ 446
13.2.2 Poly(vinyl chloride)/nitrile blends .......................................... 449
13.2.3 Polychloroprene-based compounds......................................... 450
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xii
13.3 High durability compounds ............................................................... 454
13.3.1 Carboxylated nitrile based compounds .................................. 454
13.3.2 Blends with high styrene resins .............................................. 456
13.3.3 Polybutadiene-based compounds ........................................... 456
13.4 High traction compounds .................................................................. 457
13.4.1 Polyisobutylene-isoprene based compounds........................... 457
13.4.2 Fillers ..................................................................................... 459
13.4.3 Plasticisers, processing aids and oils ....................................... 459
13.4.4 Antidegradants ...................................................................... 459
13.4.5 Cure systems .......................................................................... 459
13.4.6 Typical formulas .................................................................... 460
13.4.7 Mixing ................................................................................... 460
13.5 Blown rubber compounds .................................................................. 462
13.5.1 Classifications of foams ......................................................... 463
13.5.2 Rubber-based compounds ...................................................... 465
13.5.3 Ethylene vinyl acetate rubber-based compounds .................... 465
13.6 Clear compounds ............................................................................... 468
13.6.1 Ethylene propylene diene monomer rubber-based
compounds ............................................................................ 468
13.6.2 Diene rubber blends ............................................................... 468
13.7 Court compounds .............................................................................. 469
13.8 Autoclave shoes ................................................................................. 470
13.8.1 Shoe production ..................................................................... 471
13.9 Thermoplastic elastomers .................................................................. 471
13.9.1 Classes of TPE ....................................................................... 472
13.9.2 Styrenic TPE .......................................................................... 474
13.9.3 Thermoplastic polyurethanes ................................................. 475
13.9.4 Copolyester TPEs ................................................................... 475
13.9.5 Polyether polyamide TPE....................................................... 476
13.9.6 Thermoplastic polyolefins ...................................................... 476
13.9.7 Elastomeric alloys .................................................................. 476
13.10 Polyurethane elastomers ................................................................... 477
13.10.1 Isocyanates ........................................................................... 477
13.10.2 Polyols .................................................................................. 478
13.10.3 Polyurethane elastomers ....................................................... 478
13.10.4 Production methods .............................................................. 478
13.10.5 Millable polyurethane gums ................................................. 479
13.10.6 Cast polyurethane elastomers ............................................... 481
13.11 Poly(vinyl chloride) ........................................................................... 481
13.11.1 PVC compounding................................................................ 482
13.11.2 Production methods .............................................................. 483
13.11.3 Typical formulas ................................................................... 483
13.12 Summary........................................................................................... 485
14 Rubber in construction ............................................................................... 493
14.1 Introduction ....................................................................................... 493
14.2 Vibration control ............................................................................... 494
14.3 Floors................................................................................................. 498
14.4 Walls and windows ............................................................................ 499
14.5 Adhesives and sealants ....................................................................... 501
14.6 Roofing and waterproofing................................................................ 503
14.7 Summary............................................................................................ 508
15 Rubber recycling ......................................................................................... 511
15.1 Introduction ....................................................................................... 511
15.2 Recycling of rubber vulcanisates ........................................................ 512
15.2.1 Pyrolysis and incineration ...................................................... 512
15.2.2 Grinding methods ................................................................... 513
15.2.3 Pulverisation methods ............................................................ 514
15.2.4 Reclaiming processes ............................................................. 516
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15.2.5 Wave methods........................................................................ 519
15.3 The usage of recycled rubber ............................................................. 524
15.3.1 General remarks .................................................................... 524
15.3.2 Rubber/recycled rubber blends .............................................. 526
15.3.3 Thermoplastic/recycled rubber blends.................................... 527
15.3.4 Asphalt modified by tyre rubber ............................................ 533
15.3.5 Cement modified by tyre rubber ............................................ 535
15.4 Summary............................................................................................ 536
Abbreviations and Acronyms............................................................................. 549
Index ................................................................................................................. 559
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Nguồn:
Tuan Van Doan (Ph.D student) Hàn quốc, tặng Cty Cao su Việt
