Rubber Reinforcement with Particulate Fillers(�������ό����z���a(b��)��(qi��ng))

Preface ��

About the Authors ��

1. Manufacture of Fillers 1
1.1 Manufacture of Carbon Black 3
1.1.1 Mechanisms of Carbon Black Formation 3
1.1.2 Manufacturing Process of Carbon Black 6
1.1.2.1 Oil-Furnace Process 6
1.1.2.2 The Thermal Black Process 10
1.1.2.3 Acetylene Black Process 11
1.1.2.4 Lampblack Process 11
1.1.2.5 Impingement (Channel, Roller) Black Process 12
1.1.2.6 Recycle Blacks 12
1.1.2.7 Surface Modification of Carbon Blacks 13
1.1.2.7.1 Attachments of the Aromatic Ring Nucleus to Carbon Black 13
1.1.2.7.2 Attachments to the Aromatic Ring Structure through Oxidized Groups 13
1.1.2.7.3 Metal Oxide Treatment 14
1.2 Manufacture of Silica 14
1.2.1 Mechanisms of Precipitated Silica Formation 15
1.2.2 Manufacturing Process of Precipitated Silica 16
1.2.3 Mechanisms of Fumed Silica Formation 18
1.2.4 Manufacture Process of Fumed Silica 18
References 19

2. Characterization of Fillers 22
2.1 Chemical Composition 23
2.1.1 Carbon Black 23
2.1.2 Silica 25
2.2 Micro-Structure of Fillers 27
2.2.1 Carbon Black 27
2.2.2 Silica 29
2.3 Filler Morphologies 29
2.3.1 Primary Particles-Surface Area 29
2.3.1.1 Transmission Electron Microscope (TEM) 30
2.3.1.2 Gas Phase Adsorptions 34
2.3.1.2.1 Total Surface Area Measured by Nitrogen Adsorption-BET/NSA 35
2.3.1.2.2 External Surface Area Measured by Nitrogen Adsorption-STSA 41
2.3.1.2.3 Micro-Pore Size Distribution Measured by Nitrogen Adsorption 46
2.3.1.3 Liquid Phase Adsorptions 51
2.3.1.3.1 Iodine Adsorptions 52
2.3.1.3.2 Adsorption of Large Molecules 56
2.3.2 Structure-Aggregate Size and Shape 61
2.3.2.1 Transmission Electron Microscopy 62
2.3.2.2 Disc Centrifuge Photosedimentometer 66
2.3.2.3 Void Volume Measurement 68
2.3.2.3.1 Oil Absorption 69
2.3.2.3.2 Compressed Volume 75
2.3.2.3.3 Mercury Porosimetry 80
2.3.3 Tinting Strength 83
2.4 Filler Surface Characteristics 92
2.4.1 Characterization of Surface Chemistry of Filler-Surface Groups 92
2.4.2 Characterization of Physical Chemistry of Filler Surface-Surface Energy 93
2.4.2.1 Contact Angle 98
2.4.2.1.1 Single Liquid Phase 98
2.4.2.1.2 Dual Liquid Phases 102
2.4.2.2 Heat of Immersion 106
2.4.2.3 Inverse Gas Chromatograph 111
2.4.2.3.1 Principle of Measuring Filler Surface Energy with IGC 111
2.4.2.3.2 Adsorption at Infinite Dilution 112
2.4.2.3.3 Adsorption at Finite Concentration 118
2.4.2.3.4 Surface Energy of the Fillers 123
2.4.2.3.5 Estimation of Rubber-Filler Interaction from Adsorption Energy of Elastomer Analogs 139
2.4.2.4 Bound Rubber Measurement 142
References 143

3. Effect of Fillers in Rubber 153
3.1 Hydrodynamic Effect ? Strain Amplification 153
3.2 Interfacial Interaction between Filler and Polymer 155
3.2.1 Bound Rubber 155
3.2.2 Rubber Shell 159
3.3 Occlusion of Rubber 161
3.4 Filler Agglomeration 163
3.4.1 Observations of Filler Agglomeration 163
3.4.2 Modes of Filler Agglomeration 164
3.4.3 Thermodynamics of Filler Agglomeration 167
3.4.4 Kinetics of Filler Agglomeration 170
References 173

4. Filler Dispersion 177
4.1 Basic Concept of Filler Dispersion 177
4.2 Parameters Influencing Filler Dispersion 179
4.3 Liquid Phase Mixing 187
References 191

5. Effect of Fillers on the Properties of Uncured Compounds 193
5.1 Bound Rubber 193
5.1.1 Significance of Bound Rubber 194
5.1.2 Measurement of Bound Rubber 195
5.1.3 Nature of Bound Rubber Attachment 197
5.1.4 Polymer Mobility in Bound Rubber 202
5.1.5 Polymer Effects on Bound Rubber 203
5.1.5.1 Molecular Weight Effects 203
5.1.5.2 Polymer Chemistry Effects 203
5.1.6 Effect of Filler on Bound Rubber 204
5.1.6.1 Surface Area and Structure 204
5.1.6.2 Specific Surface Activity of Carbon Blacks 206
5.1.6.3 Effect of Surface Characteristics on Bound Rubber 210
5.1.6.4 Carbon Black Surface Modification 211
5.1.6.5 Silica Surface Modification 215
5.1.7 Effect of Mixing Conditions on Bound Rubber 215
5.1.7.1 Temperature and Time of Mixing 216
5.1.7.2 Mixing Sequence Effect of Rubber Ingredients 218
5.1.7.2.1 Mixing Sequence of Oil and Other Additives 219
5.1.7.2.2 Mixing Sequence of Sulfur, Sulfur Donor, and Other Crosslinkers 221
5.1.7.2.3 Bound Rubber of Silica Compounds 222
5.1.7.3 Bound Rubber in Wet Masterbatches 223
5.1.7.4 Bound Rubber of Fumed Silica-Filled Silicone Rubber 225
5.2 Viscosity of Filled Compounds 227
5.2.1 Factors Influencing Viscosity of the Carbon Black-Filled Compounds 227
5.2.2 Master Curve of Viscosity vs. Effective Volume of Carbon Blacks 230
5.2.3 Viscosity of Silica Compounds 233
5.2.4 Viscosity Growth ? Storage Hardening 238
5.3 Die Swell and Surface Appearance of the Extrudate 241
5.3.1 Die Swell of Carbon Black Compounds 241
5.3.2 Die Swell of Silica Compounds 246
5.3.3 Extrudate Appearance 247
5.4 Green Strength 249
5.4.1 Effect of Polymers 249
5.4.2 Effect of Filler Properties 252
References 255