Contents

Preface ............................................................................ ix

1. Introduction ............................................................. 1
1.1 Polymers ...................................................................... 1
1.1.1 Thermoplastics, Thermosets and
Elastomers .................................................. 1
1.1.2 Linear, Branched or Network Polymers ....... 2
1.1.3 Crystalline, Semi-Crystalline or
Amorphous Polymers .................................. 5
1.1.4 Homopolymers ............................................ 6
1.1.5 Copolymers and Terpolymers ..................... 7
1.1.6 Liquid Crystalline Polymers ......................... 9
1.2 Fillers ............................................................................ 9
1.2.1 Rigid or Flexible Fillers ................................ 10
1.2.2 Spherical, Ellipsoidal, Platelike or
Fibrous Fillers ............................................. 10
1.2.3 Organic or Inorganic Fillers ......................... 11
1.3 Filled Polymers ............................................................ 11
1.4 Filler-Polymer Interactions ........................................... 16
1.4.1 Filler Geometry ........................................... 18
1.4.2 Volume Fraction .......................................... 19
1.4.3 Filler Surface ............................................... 19
1.4.4 Wettability ................................................... 19
1.4.5 Filler Surface Treatment .............................. 21

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1.5 Rheology ...................................................................... 39

References .......................................................................... 43

2. Basic Rheological Concepts .................................. 54

2.1 Flow Classification ....................................................... 55
2.1.1 Steady Simple Shear Flow .......................... 55
2.1.2 Unsteady Simple Shear Flow ...................... 59
2.1.3 Extensional Flow ......................................... 62
2.2 Non-Newtonian Flow Behavior .................................... 66
2.2.1 Newtonian Fluids ........................................ 66
2.2.2 Non-Newtonian Fluids ................................. 67
2.2.3 Viscoelastic Effects ..................................... 71
2.3 Rheological Models ..................................................... 79
2.3.1 Models for the Steady Shear Viscosity
Function ...................................................... 79
2.3.2 Model for the Normal Stress Difference
Function ...................................................... 84
2.3.3 Model for the Complex Viscosity
Function ...................................................... 86
2.3.4 Model for the Dynamic Modulus
Functions .................................................... 90
2.3.5 Models for the Extensional Viscosity
Function ...................................................... 93
2.4 Other Relationships for Shear Viscosity
Functions ..................................................................... 99
2.4.1 Viscosity-Temperature Relationships .......... 99
2.4.2 Viscosity-Pressure Relationship .................. 103
2.4.3 Viscosity-Molecular Weight
Relationship ................................................ 104
References .......................................................................... 104

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3. Rheometry ............................................................... 112

3.1 Rotational Viscometers ................................................ 113
3.1.1 Cone and Plate Viscometer ......................... 115
3.1.2 Parallel-Disc Viscometer ............................. 117
3.2 Capillary Rheometers .................................................. 118
3.2.1 Constant Plunger Speed Circular Orifice
Capillary Rheometer ................................... 119
3.2.2 Constant Plunger Speed Slit Orifice
Capillary Rheometer ................................... 124
3.2.3 Constant Speed Screw Extrusion Type
Capillary Rheometers .................................. 124
3.2.4 Constant Pressure Circular Orifice
Capillary Rheometer (Melt Flow
Indexer) ....................................................... 126
3.3 Extensional Viscometers ............................................. 128
3.3.1 Filament Stretching Method ........................ 128
3.3.2 Extrusion Method ........................................ 130
References .......................................................................... 131

4. Constitutive Theories and Equations for

Suspensions ........................................................... 136
4.1 Importance of Suspension Rheology .......................... 136
4.2 Shear Viscous Flow ..................................................... 137
4.2.1 Effect of Shape, Concentration and
Dimensions on the Particles ........................ 137
4.2.2 Effect of Size Distribution of the
Particles ...................................................... 147
4.2.3 Effect of the Nature of the Particle
Surface ....................................................... 150
4.2.4 Effect of the Velocity Gradient ..................... 150

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4.2.5 Effect of Flocculation ................................... 151

4.2.6 Effect of the Suspending Medium ................ 153
4.2.7 Effect of Adsorbed Polymers ....................... 154
4.2.8 Effect of Chemical Additives ........................ 160
4.2.9 Effect of Physical and Chemical
Processes ................................................... 160
4.2.10 Effect of an Electrostatic Field ..................... 162
4.3 Extensional Flow .......................................................... 164
References .......................................................................... 167

5. Preparation of Filled Polymer Systems ................ 175

5.1 Goodness of Mixing ..................................................... 175
5.2 Mixing Mechanisms ..................................................... 183
5.3 Compounding Techniques .......................................... 186
5.3.1 Selection Criteria ......................................... 186
5.3.2 Batch Mixers ............................................... 189
5.3.3 Continuous Compounders ........................... 192
5.3.4 Dump Criteria .............................................. 218
5.4 Compounding/Mixing Variables .................................. 221
5.4.1 Mixer Type .................................................. 223
5.4.2 Rotor Geometry .......................................... 224
5.4.3 Mixing Time ................................................. 225
5.4.4 Rotor Speed ................................................ 229
5.4.5 Ram Pressure ............................................. 229
5.4.6 Chamber Loadings ...................................... 231
5.4.7 Mixing Temperature .................................... 232
5.4.8 Order of Ingredient Addition ........................ 236
References .......................................................................... 237

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6. Steady Shear Viscous Properties .......................... 243

6.1 Effect of Filler Type ...................................................... 244
6.2 Effect of Filler Size ....................................................... 246
6.3 Effect of Filler Concentration ....................................... 248
6.4 Effect of Filler Size Distribution .................................... 262
6.5 Effect of Filler Agglomerates ....................................... 272
6.6 Effect of Filler Surface Treatment ................................ 273
6.7 Effect of Polymer Matrix .............................................. 279
6.8 Unification of Steady Shear Viscosity Data ................. 287
References .......................................................................... 303

7. Steady Shear Elastic Properties ............................ 312

7.1 Effect of Filler Type ...................................................... 313
7.2 Effect of Filler Size ....................................................... 315
7.3 Effect of Filler Concentration ....................................... 317
7.4 Effect of Filler Size Distribution .................................... 321
7.5 Effect of Filler Agglomerates ....................................... 321
7.6 Effect of Filler Surface Treatment ................................ 323
7.7 Effect of Polymer Matrix .............................................. 330
References .......................................................................... 332

8. Unsteady Shear Viscoelastic Properties .............. 338

8.1 Effect of Filler Type ...................................................... 344
8.2 Effect of Filler Size ....................................................... 344
8.3 Effect of Filler Concentration ....................................... 345
8.4 Effect of Filler Size Distribution .................................... 350
8.5 Effect of Filler Agglomerates ....................................... 356
8.6 Effect of Filler Surface Treatment ................................ 360
8.7 Effect of Polymer Matrix .............................................. 372

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8.8 Effect of Matrix Additives ............................................. 387

References .......................................................................... 390

9. Extensional Flow Properties .................................. 395

9.1 Effect of Filler Type ...................................................... 396
9.2 Effect of Filler Size ....................................................... 400
9.3 Effect of Filler Concentration ....................................... 402
9.4 Effect of Filler Surface Treatment ................................ 405
References .......................................................................... 409

10. Concluding Remarks .............................................. 416

Appendices .................................................................... 425

Appendix A Glossary .......................................................... 425
Appendix B ASTM Conditions and Specifications for
MFI ............................................................................... 430
Appendix C Data Details and Sources for Master
Rheograms .................................................................. 433
Appendix D Abbreviations .................................................. 439
Appendix E Nomenclature ................................................. 441
Appendix F Greek Symbols ............................................... 449

Author Index .................................................................. 455

Index ............................................................................... 469

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