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分享——填充的高分子：科学与工业应用（英文版）
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Filled Polymers: Science and Industrial Applications CRC | 2009 | ISBN: 1439800421 | 444 pages | PDF | 8,6 MB Based on the author’s 30 years of research and engineering activities in the field of complex polymer systems, this volume is a comprehensive survey of the many aspects of rubber and thermoplastic filled polymers.  CRC | 2009 | ISBN: 1439800421 | 444 pages | PDF | 8,6 MB |
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Contents Preface.......................................................................................................................xi Author Bio...............................................................................................................xv 1. Introduction....................................................................................................1 1.1. Scope of the Book...................................................................................1 1.2. Filled Polymers vs. Polymer Nanocomposites...................................3 References........................................................................................................8 2. Types of Fillers............................................................................................ 11 3. Concept of Reinforcement......................................................................... 15 Reference........................................................................................................ 19 4. Typical Fillers for Polymers...................................................................... 21 4.1 Carbon Black......................................................................................... 21 4.1.1 Usages of Carbon Blacks.......................................................... 21 4.1.2 Carbon Black Fabrication Processes....................................... 21 4.1.3 Structural Aspects and Characterization of Carbon Blacks....................................................................... 24 4.1.4 Carbon Black Aggregates as Mass Fractal Objects..............30 4.1.5 Surface Energy Aspects of Carbon Black..............................44 4.2 White Fillers..........................................................................................49 4.2.1 A Few Typical White Fillers....................................................49 4.2.1.1 Silicates.........................................................................49 4.2.1.2 Natural Silica............................................................... 52 4.2.1.3 Synthetic Silica............................................................53 4.2.1.4 Carbonates...................................................................54 4.2.1.5 Miscellaneous Mineral Fillers...................................56 4.2.2. Silica Fabrication Processes.....................................................56 4.2.2.1 Fumed Silica................................................................56 4.2.2.2 Precipitated Silica.......................................................58 4.2.3 Characterization and Structural Aspects of Synthetic Silica.......................................................................... 62 4.2.4 Surface Energy Aspects of Silica............................................68 4.3 Short Synthetic Fibers..........................................................................69 4.4 Short Fibers of Natural Origin...........................................................72 References......................................................................................................79 Appendix 4....................................................................................................82 A4.1 Carbon Black Data............................................................................82 A4.1.1 Source of Data for Table 4.5...............................................82 A4.1.2 Relationships between Carbon Black Characterization Data........................................................84 A4.2 Medalia’s Floc Simulation for Carbon Black Aggregate.............85 A4.3 Medalia’s Aggregate Morphology Approach...............................86 A4.4 Carbon Black: Number of Particles/Aggregate............................89 5. Polymers and Carbon Black...................................................................... 91 5.1 Elastomers and Carbon Black (CB).................................................... 91 5.1.1 Generalities................................................................................ 91 5.1.2 Effects of Carbon Black on Rheological Properties.............95 5.1.3 Concept of Bound Rubber (BdR).......................................... 108 5.1.4 Bound Rubber at the Origin of Singular Flow Properties of Rubber Compounds.......................... ............... 112 5.1.5 Factors Affecting Bound Rubber.......................................... 114 5.1.6 Viscosity and Carbon Black Level........................................ 121 5.1.7 Effect of Carbon Black on Mechanical Properties.............. 125 5.1.8 Effect of Carbon Black on Dynamic Properties.................. 140 5.1.8.1 Variation of Dynamic Moduli with Strain Amplitude (at Constant Frequency and Temperature)............................................................. 141 5.1.8.2 Variation of tan δ with Strain Amplitude and Temperature (at Constant Frequency)...................142 5.1.8.3 Variation of Dynamic Moduli with Temperature (at Constant Frequency and Strain Amplitude)..................................................... 142 5.1.8.4 Effect of Carbon Black Type on G′ and tan δ.................................................................... 144 5.1.8.5 Effect of Carbon Black Dispersion on Dynamic Properties................................................. 146 5.1.9 Origin of Rubber Reinforcement by Carbon Black............................................................................ 148 5.1.10 Dynamic Stress Softening Effect.......................................... 151 5.1.10.1 Physical Considerations........................................... 151 5.1.10.2 Modeling Dynamic Stress Softening as a “Filler Network” Effect............................................ 152 5.1.10.3 Modeling Dynamic Stress Softening as a “Filler–Polymer Network” Effect........................... 168 5.2 Thermoplastics and Carbon Black................................................... 172 5.2.1 Generalities.............................................................................. 172 5.2.2 Effect of Carbon Black on Rheological Properties of Thermoplastics........................................................................ 173 5.2.3 Effect of Carbon Black on Electrical Conductivity of Thermoplastics........................................................................ 175 References.................................................................................................... 179 Appendix 5.................................................................................................. 185 A5.1 Network Junction Theory.............................................................. 185 A5.1.1 Developing the Model...................................................... 185 A5.1.2 Typical Calculations with the Network Junction Model.................................................................. 188 A5.1.3 Strain Amplification Factor from the Network Junction Theory................................................................. 190 A5.1.3.1 Modeling the Elastic Behavior of a Rubber Layer between Two Rigid Spheres................................................... 190 A5.1.3.2 Experimental Results vs. Calculated Data................................................ 191 A5.1.3.3 Comparing the Theoretical Model with the Approximate Fitted Equation.... ............ 192 A5.1.3.4 Strain Amplification Factor............................ 193 A5.1.4 Comparing the Network Junction Strain Amplification Factor with Experimental Data............. 194 A5.2 Kraus Deagglomeration–Reagglomeration Model for Dynamic Strain Softening............................................................. 196 A5.2.1 Soft Spheres Interactions................................................. 196 A5.2.2 Modeling G′ vs. γ0............................................................. 197 A5.2.3 Modeling G″ vs. γ0............................................................. 198 A5.2.4 Modeling tan δ vs. γ0.........................................................200 A5.2.5 Complex Modulus G* vs. γ0............................................. 202 A5.2.6 A Few Mathematical Aspects of the Kraus Model......................................................................204 A5.2.7 Fitting Model to Experimental Data..............................206 A5.2.7.1 Modeling G′ vs. Strain.................................... 207 A5.2.7.2 Modeling G″ vs. Strain....................................209 A5.3 Ulmer Modification of the Kraus Model for Dynamic Strain Softening: Fitting the Model.............................................. 212 A5.3.1 Modeling G′ vs. Strain (same as Kraus)......................... 213 A5.3.2 Modeling G′′ vs. Strain..................................................... 215 A5.4 Aggregates Flocculation/Entanglement Model (Cluster–Cluster Aggregation Model, Klüppel et al.)............... 218 A5.4.1 Mechanically Effective Solid Fraction of Aggregate...................................................................... 219 A5.4.2 Modulus as Function of Filler Volume Fraction...........220 A5.4.3 Strain Dependence of Storage Modulus........................ 221 A5.5 Lion et al. Model for Dynamic Strain Softening........................222 A5.5.1 Fractional Linear Solid Model.........................................222 A5.5.2 Modeling the Dynamic Strain Softening Effect...........223 A5.5.3 A Few Mathematical Aspects of the Model..................226 A5.6 Maier and Göritz Model for Dynamic Strain Softening...........227 A5.6.1 Developing the Model......................................................227 A5.6.2 A Few Mathematical Aspects of the Model..................229 A5.6.3 Fitting the Model to Experimental Data........................230 A5.6.3.1 Modeling G′ vs. Strain.................................... 231 A5.6.3.2 Modeling G″ vs. Strain.................................... 232 6. Polymers and White Fillers.....................................................................235 6.1 Elastomers and White Fillers...........................................................235 6.1.1 Elastomers and Silica..............................................................235 6.1.1.1 Generalities................................................................235 6.1.1.2 Surface Chemistry of Silica.....................................236 6.1.1.3 Comparing Carbon Black and (Untreated) Silica in Diene Elastomers....................................... 237 6.1.1.4 Silanisation of Silica and Reinforcement of Diene Elastomers...................................................... 239 6.1.1.5 Silica and Polydimethylsiloxane............................. 246 6.1.2 Elastomers and Clays (Kaolins)............................................ 257 6.1.3 Elastomers and Talc................................................................ 260 6.2 Thermoplastics and White Fillers.................................................... 262 6.2.1 Generalities.............................................................................. 262 6.2.2 Typical White Filler Effects and the Concept of Maximum Volume Fraction.................................................. 266 6.2.3 Thermoplastics and Calcium Carbonates...........................280 6.2.4 Thermoplastics and Talc........................................................ 291 6.2.5 Thermoplastics and Mica...................................................... 297 6.2.6 Thermoplastics and Clay(s)...................................................300 References....................................................................................................302 Appendix 6..................................................................................................308 A6.1 Adsorption Kinetics of Silica on Silicone Polymers...................308 A6.1.1 Effect of Polymer Molecular Weight..............................308 A6.1.2 Effect of Silica Weight Fraction....................................... 310 A6.2 Modeling the Shear Viscosity Function of Filled Polymer Systems............................................................................. 312 A6.3 Models for the Rheology of Suspensions of Rigid Particles, Involving the Maximum Packing Fraction Φm........................... 315 A6.4 Assessing the Capabilities of Model for the Shear Viscosity Function of Filled Polymers......................................... 319 A6.4.1 Effect of Filler Fraction..................................................... 320 A6.4.2 Effect of Characteristic Time λ0...................................... 320 A6.4.3 Effect of Yasuda Exponent a............................................ 321 A6.4.4 Effect of Yield Stress σc................................................... 321 A6.4.5 Fitting Experimental Data for Filled Polymer Systems.............................................................. 322 A6.4.6 Observations on Experimental Data............................ 323 A6.4.7 Extracting and Arranging Shear Viscosity Data.................................................................. 324 A6.4.8 Fitting the Virgin Polystyrene Data with the Carreau–Yasuda Model.................................................. 324 A6.4.9 Fitting the Filled Polystyrene Shear Viscosity Data................................................................................... 326 A6.4.10 Assembling and Analyzing all Results........................ 332 A6.5 Expanding the Krieger–Dougherty Relationship......................335 7. Polymers and Short Fibers...................................................................... 339 7.1 Generalities......................................................................................... 339 7.2 Micromechanic Models for Short Fibers-Filled Polymer Composites..........................................................................................344 7.2.1 Minimum Fiber Length.........................................................344 7.2.2 Halpin–Tsai Equations...........................................................345 7.2.3 Mori–Tanaka’s Averaging Hypothesis and Derived Models...................................................................................... 351 7.2.4 Shear Lag Models....................................................................353 7.3 Thermoplastics and Short Glass Fibers...........................................358 7.4 Typical Rheological Aspect of Short Fiber-Filled Thermoplastic Melts..........................................................................368 7.5 Thermoplastics and Short Fibers of Natural Origin..................... 370 7.6 Elastomers and Short Fibers............................................................. 375 References....................................................................................................383 Appendix 7.................................................................................................. 389 A7.1 Short Fiber-Reinforced Composites: Minimum Fiber Aspect Ratio..................................................................................... 389 A7.1.1 Effect of Volume Fraction on Effective Fiber Length...................................................................... 389 A7.1.2 Effect of Matrix Modulus on Effective Fiber Length...................................................................... 390 A7.1.3 Effect of Fiber-to-Matrix Modulus Ratio on Effective Fiber Length/Diameter Ratio......................... 391 A7.2 Halpin–Tsai Equations for Short Fibers Filled Systems: Numerical Illustration.................................................................... 391 A7.2.1 Longitudinal (Tensile) Modulus E11............................... 392 A7.2.2 Transversal (Tensile) Modulus E22.................................. 393 A7.2.3 Shear Modulus G12............................................................ 393 A7.2.4 Modulus for Random Fiber Orientation........................ 394 A7.2.5 Fiber Orientation as an Adjustable Parameter. ......................................................................................394 A7.2.6 Average Orientation Parameters from Halpin–Tsai Equations for Short Fibers Filled Systems.................................................................... 394 A7.2.6.1 Longitudinal (Tensile) Modulus E11.............. 395 A7.2.6.2 Transversal (Tensile) Modulus E22................. 396 A7.2.6.3 Orientation Parameter X................................. 396 A7.3 Nielsen Modification of Halpin–Tsai Equations with Respect to the Maximum Packing Fraction: Numerical Illustration........................................................................................ 396 A7.3.1 Maximum Packing Functions......................................... 397 A7.3.2 Longitudinal (Tensile) Modulus E11............................... 398 A7.3.3 Transverse (Tensile) Modulus Ey.................................... 398 A7.3.4 Shear Modulus G.............................................................. 398 A7.4 Mori–Tanaka’s Average Stress Concept: Tandon–Weng Expressions for Randomly Distributed Ellipsoidal (Fiber-Like) Particles: Numerical Illustration............................. 399 A7.4.1 Eshelby’s Tensor (Depending on Matrix Poisson’s Ratio and Fibers Aspect Ratio Only).............................. 399 A7.4.2 Materials’ Constants (i.e., Not Depending on Fiber Volume Fraction)...............................................................400 A7.4.3 Materials and Volume Fraction Depending Constants............................................................................ 401 A7.4.4 Calculating the Longitudinal (Tensile) Modulus E11........................................................402 A7.4.5 Calculating the Transverse (Tensile) Modulus E22.......402 A7.4.6 Calculating the (In-Plane) Shear Modulus G12.............403 A7.4.7 Calculating the (Out-Plane) Shear Modulus G23...........404 A7.4.8 Comparing with Experimental Data.............................404 A7.4.9 Tandon–Weng Expressions for Randomly Distributed Spherical Particles: Numerical illustration...................................................... 406 A7.4.9.1 Eshelby’s Tensor (Depending on Matrix Poisson’s Ratio Only).......................................406 A7.4.9.2 Materials’ Constants (i.e., Not Depending on Filler Volume Fraction).........406 A7.4.9.3 Materials and Volume Fraction Depending Constants.....................................407 A7.4.9.4 Calculating the Tensile Modulus E...............408 A7.4.9.5 Calculating the Shear Modulus G.................408 A7.5 Shear Lag Model: Numerical illustration....................................409 Index........................................................................................................... 411 |
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