John S. Dick
Rubber Technology
Compounding and Testing for Performance
Preface
6
Contents
8
Contributers
22
1 Rubber Compounding: Introduction, Definitions, and Available Resources
26
1.1 Introduction
26
1.2 The Recipe
27
1.3. Classification of Rubber Compounding Ingredients
28
1.4 Standard Abbreveiations for Compounding Ingredients
29
1.5 The Diversity of Rubber Recipes
29
1.6 Compatibility of Compounding Ingredients
30
1.7 Rubber Compounding Ingredients' Specifications
32
1.8 Raw Material Source Books
32
1.9 Key Source References for Formulations
34
1.10 Technical Organizations
35
1.11 Key Technical Journals and Trade Magazines
36
1.12 Regurarly Scheduled Technical Conferences
38
1.12.1 Regurarly Scheduled Courses
38
1.13 Web Sites Available
39
2. Compound Processing Characteristics and Testing
42
2.1 Introduction
42
2.2 Manufacturing Process
42
2.2.1 Two Roll Mill
42
2.2.2 Internal Mixers
42
2.2.3 Further Downstream Processing
44
2.2.4 Curing Process
45
2.2.5 Factory Problems
45
2.3 Processability Characteristics and Measurements
46
2.3.1 Viscosity
47
2.3.2 Shear Thinning
52
2.3.3 Elasticity
54
2.3.4 Time to Scorch
58
2.3.5 Cure Rate
61
2.3.6 Ultimate State of Cure
64
2.3.7 Reversion Resistance
65
2.3.8 Green Strength
66
2.3.9 Tackiness
67
2.3.10 Stickiness
67
2.3.11 Dispersion
67
2.3.12 Stock Storage Stability
68
2.3.13 Mis-Compounding
68
2.3.14 Cellular Rubber Blow Reaction
68
3 Vulcanizate Physical Properties, Performance Charecteristics, and Testing
71
3.1 Introduction
71
3.2 Density
71
3.3. Hardness
72
3.4 Tensile Stress-Strain
73
3.5 Stress-Strain Properties under Compression
74
3.6 Stress Strain Properties under Shear
75
3.7 Dynamic Properties
75
3.8 Low Temperature Properties
78
3.8.1 Brittle Point
79
3.8.2 Gehman Test
79
3.9 Stress Relevation, Creep, and Set
80
3.10 Permeability (Transmission)
82
3.11 Cured Adhesion
82
3.12 Tear Resistance
83
3.13 Degredation Properties
85
3.13.1 Flex Fatigue Resistance
85
3.13.2 Heat Resistance
87
3.13.3 Ozone Resistance
89
3.13.4 Weathering Resistance
90
3.13.5 Resitance of Liquids
90
3.13.6 Abrasion and Wear Resistance
91
4 Rubber Compound Economics
94
4.1. Introduction
94
4.2. Compound Cost Calculations
94
4.2.1 Specific Gravity
94
4.2.2 Cost/lb
95
4.2.3 Lb-Volume Cost
95
4.2.4 Part Cost
95
4.2.5 Conversion Factors for Calculating Part Cost
95
4.3 Measuring Specific Gravity (Density)
97
4.4 Cost Calculations
97
4.4.1 Base Compound
97
4.4.2 Same Ingredient Volume and Equal Cost
98
4.4.3 Low Cost/lb
98
4.4.4 High Specific Gravity
99
4.5 Compound Design and Cost
100
4.6 Reducing Compound Cost
100
4.6.1 High-Structure Carbon Blacks
101
4.6.2 White Compounds
101
4.6.3 Antioxidants/Antiozonants
101
4.6.4 Polymer Substitutions
102
5 The Technical Project Approach to Experimental Design and Compound Development
111
5.1 Introduction
111
5.2 Part 1: Steps in a Technical Project
113
5.2.1 Initial Action Required
113
5.2.2 Experimental Design
113
5.2.3 Conduct Measurements
120
5.2.4 Conduct Analysis and Evaluate Preliminary Modell
121
5.2.5 Prepare Report
121
5.3 Part 2: Using Experimental Designs
121
5.3.1 Screening Designs - Simple Treatment Comparisons
121
5.3.2 Screening Designs - Multifactor Experiments
124
5.3.3 Exploratory Designs - Multifactor Experiments
128
5.3.4 Evaluating the Statistical Significance of Effect Coefficients
129
6 Elastomer Selection
150
6.1 Overview
150
6.1.1 Commodity and General Purpose Elastomers
150
6.1.2 High Volume Specialty Elastomers
155
6.1.3 Low Volume Specialty Elastomers
160
6.1.4 Thermoplastic Elastomers
164
7 General Purpose Elastomers and Blends
166
7.1 Introduction
166
7.2 Natural Rubber and Polyisoprene
166
7.3 Polybutadiene
169
7.4 Copolymers and Terpolymers of Styrene, Butadiene, and Isoprene
172
7.5 Compounding with General Purpose Polymers
175
7.5.1 Polymer Characterization
176
7.5.2 Polymer Effect on Cure Rate
178
7.5.3 Polymer Effect on Stress-Strain
181
7.5.4 Hysteresis
182
7.5.5 Compability with SIR 10
190
7.5.6 Fatigue Properties
194
7.5.7 Compression Set
195
7.6 Conclusion
196
8 Specialty Elastomers
198
8.1 Introduction
198
8.2 Butyl Rubber
198
8.2.1 Introduction
198
8.2.2 Butyl Rubber Physical Properties
199
8.2.3 Butyl Rubber Properties, Vulcanization, and Applications
199
8.2.4 Gas Permeabiltity
200
8.2.5 Ozone and Weathering Resistance
201
8.2.6 Butyl Rubber Vulcanization
201
8.3 Halogenated Butyl Rubber
203
8.3.1 Introduction
203
8.3.2 Compounding Halobutyl and Star-Branched Halobutyl Rubbers
204
8.3.3 Processing Halobutyl Rubber
206
8.3.4 Halobutyl Rubber Vulcanization and Applications
207
8.3.5 Halobutyl Rubber General Applications
210
8.3.6 Cured Properties
211
8.3.7 Flex Resistance/Dynamic Properties
211
8.3.8 Compatibility with Other Elastomers
212
8.3.9. Halobutyl Rubber Compound Applications
212
8.4 EPM/EPDM
215
8.4.1 Introduction
215
8.4.2 Ethylene/Propylene Content
215
8.4.3 Diene Content
216
8.4.4 Rheology
217
8.5 Acrylonitrile-Butadiene Rubber
218
8.5.1 Introduction
218
8.5.2 Chemical and Physical Properties - Relating to Application
218
8.5.3 Polymer (Elastomer) Microstructure
221
8.5.4 Polymer (Elastomer) Macrostructure
221
8.5.5 Gel
221
8.5.6 Molecular Weight
222
8.5.7 Hot NBR
222
8.5.8 Crosslinked Hot NBR
223
8.5.9 Cold NBR
223
8.5.10 Carboxylated Nitrile (XNBR)
223
8.5.11 Bound Antioxidant NBR
224
8.6 Hydrogenated Nitrile Butadiene Elastomers
226
8.6.1 Introduction
226
8.6.2 Applications
227
8.6.3 Properties
227
8.6.4 Formulating
227
8.6.5 Processing
228
8.7 Polyacrylate Elastomers
228
8.7.1 Polymer Composition
228
8.7.2 Basic Compounding of Polyacrylate Polymers
230
8.7.3 Processing Guidelines
231
8.8 Polychloroprene (Neoprene)
232
8.8.1 Introduction
232
8.8.2 Basic Characteristics of Polychloroprene
233
8.8.3 Families of Neoprene
233
8.8.4 Neoprene 'G' Family
233
8.8.5 Neoprene 'W' Family
235
8.8.6 Neoprene 'T' Family
236
8.9 Chlorinated Polyethylene (CM)
236
8.9.1 Introduction
236
8.9.2 General Characteristics
237
8.10 Chlorosulfonated Polyethylene (CSM)
238
8.10.1 Introduction
238
8.10.2 General Purpose Types of Hypalon
240
8.10.3 Speciality Types of Hypalon
240
8.10.4 Unvulcanized Applications
241
8.11 Polyepichlorohydrin Elastomer
241
8.11.1 Introduction
241
8.11.2 Properties
241
8.11.3 Formulating
242
8.11.4 Nonlead Cure System
243
8.11.5 Adjustments
243
8.11.6 Processing
243
8.11.7 Internal Mixer - Procedure
244
8.11.8 Extrusion
244
8.11.9 Molding
244
8.12 Ethylene-Acrylic Elastomers
246
8.12.1 Introduction
246
8.12.2 Polymer Composition and Effect on Properties
247
8.12.3 Polymer Selection
248
8.13 Polynorbornene
249
8.13.1 Introduction
249
8.13.2 Applications
249
8.13.3 Compounding
250
8.13.4 Fillers
250
8.13.5 Oils/Plastizers
250
8.13.6 Cure System
250
8.13.7 Rebound/Resilience
251
8.13.8 Vibration Damping
251
8.13.9 Blends
251
8.13.10 Mixing and Processing
251
8.13.11 Calendaring
252
8.13.12 Extrusion
252
8.13.13 Molding
254
8.13.14 Summary
254
8.14 Fluoroelastometer
254
8.14.1 Introduction
254
8.14.2 Background
254
8.14.3 Applications
256
8.14.4 Viton Types
256
8.15 Silicone Elastomers
260
8.15.1 Introduction
260
8.15.2 Selection
260
8.15.3 Fillers
260
8.15.4 Antistructuring Agents
261
8.15.5 Heat Stabilizers
261
8.15.6 Peroxide Cures
261
8.15.7 Platinum Cures
262
8.15.8 RTV Cures
262
9 Polyurethane Elastomers
263
9.1 Introduction
263
9.2 Polyurethane Chemistry ans Morphology
263
9.3 Polyurethane Products
266
9.4 Cast Polyurethane Processing Overview
267
9.5. Molding Methods
269
9.5.1 Open Casting
269
9.5.2 Centrifugal Molding
270
9.5.3 Vacuum Casting
270
9.5.4 Compression Molding
270
9.5.5 Transfer Molding
270
9.5.6 Liquid Injection Molding (LIM)
271
9.5.7 Spraying
271
9.5.8 Moldless Rotational Casting
271
9.6. How to select a Polyurethane Elastomer
271
9.6.1 Types of Prepolymers
272
9.6.2 Types of Curatives
274
9.6.3 Processing Conditions
275
9.6.4 Additives
277
9.7 Comparison of Polyuethanes with Other Elastomers
278
9.7.1 Limitations of Polyuerthane Elastomers
280
9.8 Polyuerthane Selection Guidelines
282
9.8.1 Selecting a Polyuerthane Elastomer for a New Application
285
9.9 Millable Gums
286
9.10 Thermoplastic Polyuethanes
287
10 Thermoplastic Elastomers
289
10.1 Introduction
289
10.2 Position in Spectrum of Polymeric Materials
289
10.3 Classification of TPEs
290
10.3.1 Chemistry and Morphology
290
10.3.2 Styrenic Block Copolymers
293
10.3.3 Copolysters
295
10.3.4 Thermoplastic Polyurethanes
296
10.3.5 Polyamides
297
10.3.6 Thermoplastic Elastomeric Olefins
298
10.3.7 Thermoplastic Vulcanizates
299
10.4 TPEs and Thermoset Rubbers
301
10.5 Fabrication of TPEs
303
10.5.1 Economy of Thermoplastics Processing
303
10.5.2 Injection Molding
303
10.5.3 Extrusion
303
10.5.4 Blow Molding
305
10.5.5 Other Processing Methods
306
10.6 Acknowledgments
306
11 Recycled Rubber
309
11.1 Introduction
11.1 Introduction
11.1.1 Tire Derived Fuel
11.1.1 Tire Derived Fuel
11.1.2 Automotive Industry's Recycling Efforts
11.1.2 Automotive Industry's Recycling Efforts
11.2 Recycling Methods
311
11.2.1 Reclaiming
311
11.2.2 Ambient Ground Rubber
312
11.2.3 Cyrogenic Ground Rubber
313
11.2.4 Wet Ground Rubber
317
11.2.5 Surface Treatment and Additives for Producing Recycled Rubber
317
11.3 Testing, Storage, and Characterization
317
11.3.1 Testing STandards
317
11.3.2 Material Storage
318
11.3.3 Moisture Content
318
11.3.4 Bulk Density
318
11.3.5 Chemical Analysis and Material Specifications
318
11.3.6 Particle Size and Distribution
319
12 Compounding with Carbon Black and Oil
322
12.1 Introduction: Carbon Black Affects Everything
322
12.2 Characterization of Carbon Black
322
12.2.1 The Particle, the Aggregate, and the Agglomerate
323
12.2.2 Surface Area, Structure, and Surface Acticity
323
12.2.3 Continents Other than Carbon (Impurities)
325
12.2.4 Pellets
326
12.2.5 ASTM Nomenclature
326
12.3 Handling Carbon Black
328
12.4 Mixing Carbon Black
328
12.4.1 Pellet Properties and Analyticals
328
12.4.2. Effect of Analytics on Dispersion
328
12.4.3 The Mixing Process
329
12.5 Subsequent Processability of the Company
331
12.6 Compounding Carbon Black
331
12.6.1 Optimum Loading
331
12.6.2 Importance of Dispersion
334
12.6.3 Carbon Black Compounding Tips
335
12.6.4 The Tire Industry's Tradeoffs
339
12.7 Hysteresis Reducing Tips
341
12.7.1 Radical Compounding
341
12.7.2 Lower Loadings of High Structure
342
12.7.3 Carbon-Silica Dual Phase Fillers
343
12.8 Practical Applications: Tire Examples
343
12.8.1. OE Passenger
343
12.8.2 Replacement Passenger-Tire
343
12.8.3 HP Passenger-Tire Treads
344
12.8.4 Medium Radial Truck Treads
344
12.8.5 Wire Coat or Skim Stocks
344
12.8.6 Innerliner Compounding
344
12.9 Major Tradcoffs for Industrial Rubber Products
345
12.9.1 Loading/Reinforcement/Cost
345
12.10 Compounding Tips: Industrial Rubber Products
345
12.10.1 Extrusion Profiles and Products
345
12.10.2 Molded Products
346
12.10.3 Hose Applications
346
12.11 Basics of Carbon Black Manufacture
347
12.11.1 History
347
12.11.2 The Oil-Furnace Process
347
13 Precipated Silicia and Non-Black Fillers
350
13.1 Introduction
350
13.2 Mineral Fillers
350
13.2.1 Calcium Carbonate
351
13.2.2 Baryte
351
13.2.3 Ground Crystalline SIlica
351
13.2.4 Biogenic Silica
352
13.2.5 Kaolin Clay
352
13.2.6 Talc
13.2.6 Talc
13.2.7 Alumina Trihydrate
353
13.3 Synthetic Fillers
353
13.3.1 Precipated Calcium Carbonate
354
13.3.2 Metal Oxides
354
13.3.3. Precipated Silica
354
13.3.4 Silicates
356
13.4 Surface Treatment
356
13.5 Compound Applications
357
13.5.1 General Compounding Principles
358
13.5.2 White Sidewall
359
13.5.3 Black Sidewall
361
13.5.4 Wire Coat
361
13.5.5 Innerliner
364
13.5.6 Tread
365
13.5.7 Specialty Applications
366
14 Ester Plasticizers and Processing Additives
369
14.1 Ester Plasticizers for Elastomers
369
14.1.1 Derivation
369
14.1.2 Philosophical
372
14.1.3 Applications
373
14.1.4 Applicatum Trends
385
14.2 Process Additives
388
14.2.1 Control of Viscosity
389
14.2.2 Mode of Action of Process Additives
394
14.2.3 Application of Process Additives
398
15 Sulfur Cure System
405
15.1 Introduction and Historical Background
405
15.2 Vulcanizing Agents
406
15.3. Activators
407
15.4. Accelerators
408
15.5 Conventional, Semi-Efficient
411
15.6 Retarders and Inhibitors
412
15.7 Recent Developments
414
16 Cures for Specialty Elastomers
420
16.1 Introduction
420
16.2 Cure System for EPDM
420
16.3 Cure Systems for Nitrile
422
16.4 Cure Systems for Polychloroprene
425
16.5 Cure Systems for Butyl and Halobutyl Rubber
427
17 Peroxide Cure Systems
436
17.1 Introduction
436
17.1.1 What is an Organic Peroxide?
17.1.1 What is an Organic Peroxide?
17.1.2 Classes of Organic Peroxides
17.1.2 Classes of Organic Peroxides
17.1.3 General Peroxide Selection Guidelines
17.1.3 General Peroxide Selection Guidelines
17.2 Peroxide Used in Crosslinking
445
17.2.1 Diacyl Peroxides
17.2.1 Diacyl Peroxides
17.2.2 Peroxyester and Monoperoxycarbonate Peroxides
17.2.2 Peroxyester and Monoperoxycarbonate Peroxides
17.2.3 Peroxyketal and Dialkyl Type Peroxides
17.2.3 Peroxyketal and Dialkyl Type Peroxides
17.2.4 Performance Characteristics of Type Peroxides
17.2.4 Performance Characteristics of Type Peroxides
17.2.5 t-Amyl and t-Butyl Type Peroxides
17.2.5 t-Amyl and t-Butyl Type Peroxides
17.2.6 Effect of Additives When Crosslinking with Peroxides
17.2.6 Effect of Additives When Crosslinking with Peroxides
17.3 Role of Monomeric Coagnets in Peroxide Crosslinking
455
17.3.1 Crosslinking PE with Coagentsand Peroxides
457
17.3.2 Crosslinking EPDM with Coagents and Peroxides
17.3.2 Crosslinking EPDM with Coagents and Peroxides
17.3.3 Crosslinking HNBR with Coagents and Peroxides
17.3.3 Crosslinking HNBR with Coagents and Peroxides
17.4 Advantages and Disadvantages of Peroxide Crosslinking versus Sulfur Vulcanization
459
18 Tackifiying, Curing, and Reinforcing Resins
463
18.1 Introduction
463
18.2 Phenol-Formaldehyde Resins
463
18.2.1 Types of Phenol-Formaldehyde Resins
18.2.1 Types of Phenol-Formaldehyde Resins
18.3 Methylene Donor Resins
470
18.4 Resorcinol-Based Resins
471
18.5 High Styrene Resins
471
18.6 Petroleum-Derived Resins
471
18.7 Wood-Derived Resins
471
19 Antidegredants
473
19.1 Introduction
473
19.2 Properties of Antidegredants
474
19.2.1 Discoloration and Staining
474
19.2.2 Volatility
474
19.2.3 Solubility and Migration
474
19.2.4 Chemical Stability
475
19.2.5 Physical Form
476
19.2.6 Antidegradant Concentration
476
19.3 Antidegradant Types
476
19.3.1 Non Staining, Non Discoloring Antioxidants
477
19.3.2 STaining/DIscoloring Antioxidants
479
19.3.3 Antioxidants
481
19.4 Examples of Antidegradant Activity
483
19.4.1 Oxidation Resistance
483
19.4.2 Effect of Antidegradants on Fatigue Life
483
19.4.3 Combinations of Antiozonants and Antioxidants
485
19.4.4 Resistance to Metal Poisoning
486
20 Compounding for Brass WIre Adhesion
489
20.1 Introduction
489
20.2 WIre Bonding Sytems
489
20.2.1 Cobalt
490
20.2.2 RF Resin Cobalt
490
20.3 The Adhesion Mechanism
491
20.4 Compound Ingredient Effects
491
20.4.1 Mixing
492
20.4.2 Testing
492
20.4.3 Regression Plots
493
20.5 Model NR Ply Compounds
498
20.5.1 Black Control Compound
498
20.5.2 Black/Cobalt Compund
498
20.5.3 Black/Cobalt/RF Resin
499
20.5.4 Black/Silica/Cobalt/RF Resin
499
20.6 Summary
499
21 Chemical Blowing Agents
501
21.1 Introduction
501
21.2 Terminology
501
21.2.1 Open Cell Structure
502
21.2.2 Closed Cell Structure
502
21.3 Inorganic Blowing Agents
503
21.4 Organic Blowing Agents
503
21.4.1 Azodicarbonamide
504
21.4.2 Sulfonyl Hydrazides
509
21.4.3 Dinitrosopentamethylenetetramine
509
21.5 Methods of Expansion
511
21.5.1 Low Pressure Molding Process
511
21.5.2 High Pressure Molding Process
511
21.5.3 Continuous Vulcanization
512
22 Flame Retardants
514
22.1 Introduction
514
22.2 Fire Standards, Testing, and Application
514
22.3 Commonly Used Flame Retardants in Elastomers
516
22.3.1 Aliphatic and Alicyclic Halogen Sources
516
22.3.2 Aromatic Halogen Sources
516
22.3.3 Synergists of Halogen Sources
516
22.4 Compounding and Dispersion Considerations
518
22.4.1 Polychloroprene
519
22.4.2 Chlorinated Polyethylene (CM)
520
22.4.3 Chlorosulfonated Polyethylene (CSM)
521
22.4.4 Ethylene-Propylene-Diene-Monomer (EPDM)
521
22.4.5 Styrene-Butadiene (SBR)
524
22.4.6 Nitrile-Butadiene Rubber (NBR) and Hydrogenated-Nitrile-Butadiene Rubber (HNBR)
524
22.4.7 Silicone Elastomer
525
22.4.8 Ethylene-Vinyl Acetate (EVM)
526
22.4.9 Ethylene-Propylene Elastomer (EPR)
527
22.4.10 Thermoplastic Elastomers (TPE)
527
23 Rubber Mixing
529
23.1 Introduction
529
23.2 History
529
23.3 Equipment
530
23.3.1 Mills
530
23.3.2 Internal Mixers
530
23.4 Mixing
535
23.4.1 Mill Mixing
535
23.4.2 Internal Mixer
536
23.5 Mixing Methods
539
23.5.1 Natural Rubber Mastication
539
23.5.2 Masterbatch
540
23.5.3 Phase Mixing
540
23.5.4 Single-Stage Mix
542
23.5.5 Single-Cycle Mix
542
23.5.6 Two-Stage Mix
542
23.5.7 Tandem Mix
542
23.5.8 Three-Stage Mix
543
23.5.9 Upside Down Mix
543
23.5.10 Variable Speed Mixing
543
23.5.11 Final Mix
544
23.5.12 Conntinous Mixing
545
23.5.13 E-SBR Carbon Black Masterbatch
545
23.5.14 Energy Mixing
546
Index
548
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