Science and Industrial Applications

Filled Polymers Science and Industrial Applications Filled Polymers Science and Industrial Applications Jean L Leblanc Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2010 by Taylor and Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Printed in the United States of America on acid-free paper 10 International Standard Book Number: 978-1-4398-0042-3 (Hardback) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this 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CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface .xi Author Bio .xv   Introduction 1.1 Scope of the Book 1.2 Filled Polymers vs Polymer Nanocomposites References   Types of Fillers 11   Concept of Reinforcement 15 Reference 19   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 v vi Contents Appendix 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   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 Contents vii 5.2.3 Effect of Carbon Black on Electrical Conductivity of Thermoplastics 175 References 179 Appendix 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 viii Contents 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   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 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 Contents ix 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   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 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 Index Maier and Göritz model, 227–232 percolation theory, 153 Dynamic stress softening (DSS), 141 effect of mixing duration on magnitude, 148 as filler network effect, 152 as filler–polymer network effect, 168 nonlinear viscoelastic properties, 151 origins of, 151–152 Payne effect, 151 stress/strain proportionality, 151 E Effective fiber length effect fiber-to-matrix modulus ratio, 391 matrix modulus, 390–391 volume fraction, 389–390 Elasticity dissipation structure, 114 Elastic modulus, 166, 212, 223, 230 effect of carbon black specific area on, 144 temperature effect, 143 Elastomers carbon black filled SBR compound, mechanical properties, 381 cellulose fibers and chopped aramid fibers industrial importance, 380–381 extrusion moving die technology, 380 fiber orientation, 382–383 glass fibers exhibit, 381–382 hexa(methoxymethyl)melamine (HMMM), 377 inter-aggregates distances face-centered cubic lattice model, 93–94 for optimal reinforcement, 94 natural fiber filled rubber composites, selected published works, 378 optimum dispersion, 92–93 properties of, 91 reinforcing elastomers, 375–376 resorcinol-HEXA system, 379 rubber-fiber bonding, 376 415 rubber matrix, 375–376 short fiber reinforced rubber composites, 379–380 in extruded rubber hoses, controlling, 381 special fiber–elastomer composites, 378–379 specific gravity, 92 Stokes diameter, 93 strain amplification in, 130 styrene butadiene copolymer (SBR), 376–377 and talc fractured surfaces, 260 ground talc, 260 technical constraints, 382 thermoplastic systems micromechanic models for (synthetic) fiber, 382 volume fraction of, 92 Elastomers and white fillers, 235 elastomers and clays, 257–260 elastomers and silica, 235 diene elastomers carbon black, comparison, 237–239 polydimethylsiloxane, 246–257 silanisation, reinforcement diene, 239–245 surface chemistry of, 235–237 elastomers and talc, 260–266 Engineering plastics, 301 ENR, see Epoxidized natural rubber (ENR) EPDM, see Ethylene-Propylene-Diene Monomer rubber (EPDM) compounds Epoxidized natural rubber (ENR), 45 EPR, see Ethylene-Propylene rubber (EPR) Equivalent circuit model, 172 Eshelby’s tensor, 399–400, 406 transformation tensor, 351–352 Ethylene-Propylene-Diene Monomer rubber (EPDM) compounds, 38 Ethylene-Propylene rubber (EPR), 45 Evonik, see Degussa Experimental results calculated data, comparison, 191–192 416 Extraction kinetic method for bound rubber assessment, 116 Extrudate swell, see Postextrusion swelling F Fabrication processes for carbon black (CB) aggregates, 21 for furnace black, 22 lamp black, manufacturing process, 23 methods, 22 smoke, 23–24 thermal black process, 24 thermo-oxidative processes, 21 Face-centered cubic lattice model, 93 FE, see Finite element (FE) calculations Fiber-polymer systems, 341 Fiber-reinforced composites shear-lag analysis, 389 Fiber-to-matrix modulus ratio, effect of, 391 Fibrous fillers, 343 Filled/composite polymer systems classification, Filled compounds with carbon black (CB) extraction kinetic data on N330, 117 morphology and nonlinear flow properties, 113 stress overshoot experiments on, 106 tridimensional representation of morphology of, 111 Filled polymers, fitting experimental data, 322–324, 326 observations, 323 and polymer nanocomposites, preparing and using, shear viscosity function, model, 319–321 filler fraction, effect of, 320 Filled rubber compounds, flow anisotropy effects in, 115 Filler–filler network considerations, 171 Filler network effect, 152; see also Dynamic stress softening (DSS) Index Fillers classification based on fabrication process and reinforcing activity, 12 particle sizes, 14 effect of viscosity, 123–124, 333 Yasuda parameter, 334 yield stress, 333 fraction effect, 320 incorporation effect, 125 loading and vulcanization, expected variation of modulus function during, 126 and pigment, distinguishing between, 13 refractive indices, 12 shapes, 11–12 shear viscosity of, 95 structures, 12 types, 11 use as color modifier, 12 Filler–thermoplastic systems, 267 Filler volume fraction modulus, function, 220–221 Finite element (FE) calculations, 353 Fitting data for filled polymer systems, 322–323 filled polystyrene (PS) shear viscosity, 326 on PDMS/silica compound, 309–310 silica weight fraction compound, 311–312 virgin polystyrene (PS) data with Carreau–Yasuda model, 324 FKM, see Fluoroelastomers (FKM) Flexural modulus, 404–405 Floc simulation, 137 approach, 38–39 Flow anisotropy effects, 114 in filled rubber compounds, 115 Flow properties, 263 Flow zone, 125 Fluoroelastomers (FKM), 52 Fluorohydric acid (HF), 56 Fractal geometry solid volume fraction, 41 Fractal scaling law, 33 Fractional linear solid model, 222–223 417 Index Fumed silica combustion process, 58 density, 58 pyrolitic process, 56 G Gas black process, 23 Gaussian peaks, 47 Gaussian statistics, 251 GCC, see Ground calcium carbonate (GCC) General purpose (GP) resins, GenFit function, 324 Glass fibers, 69 types of, 71 Glass fibers reinforced polyesters, Grain effect, 114 Green tire, 235 Ground calcium carbonate (GCC), 55 Ground talc, 260 Guth, Gold, and Simha equation, 122 Guth and Gold approach, 138 H HAF, see High abrasion furnace (HAF) Halpin–Tsai equations curves calculations, 347 fiber aspect ratio, 350–351 fiber orientation distribution, 348 filler particle’s geometry, ζ parameter expressions for, 346 fitting experimental data with, 348 glass fibers, 348–349 mechanical properties, 346 Nielsen modification of Halpin, 396 longitudinal (tensile) modulus, 398 maximum packing functions, 397 transverse (tensile) modulus and shear modulus, 398–399 PBT and PA/PAT composites with short glass fibers, 349 short fibers filled systems, 347, 391–392 average orientation parameters from, 394–396 longitudinal (tensile) modulus, 392 random fiber orientation, modulus and adjustable parameter, 394 transversal (tensile) and shear modulus, 393 Halpin–Tsai model, 361 commercial SGF-filled polyamide and 66 composites, flexural and tensile moduli of, 362 commercial SGF-filled polyamide 11 composites, flexural and tensile moduli of, 363 Hard clay, 257 Hard fibers, 72 Henry’s law, 46 Herschel–Bulkley equation, 270 Herschel–Bulkley model for yield stress fluids, 100–101 HEXA, see Hexamethylenetetramine (HEXA) Hexa(methoxymethyl)melamine (HMMM), 377 Hexamethylenetetramine (HEXA), 377 HF, see Fluorohydric acid (HF) High abrasion furnace (HAF), 28–29 grade, 40 High structure silica, 61 HMMM, see Hexa(methoxymethyl) melamine (HMMM) Hydrophilic fillers, 263 Hydrophilic polymers, Hydrous kaolin, 49 I IGC, see Inverse gas chromatography (IGC) Injection molded fatigue test samples (ASTM D1708), 395 in situ polimerization, Inter-aggregates distances face-centered cubic lattice model, 93–94 for optimal reinforcement, 94 Intermediate super abrasion furnace carbon black (ISAF), 45 418 International Organization for Standardization (ISO), 27 Intrinsic viscosity, 272, 335 Inverse gas chromatography (IGC), 46 ISAF, see Intermediate super abrasion furnace carbon black (ISAF) ISO, see International Organization for Standardization (ISO) Isolator–conductor transition, 172 J Junction gap width, 189 in CB, 136 Junction rubber, 133 K Kaolin, 257 grades, 245, 258–259 Kaolins, see Clay(s) Kraus deagglomeration– reagglomeration model dynamic strain softening (DSS), 196–202, 209 complex modulus, 202 modeling, 197–200 soft spheres interactions, 196 Kraus model deagglomeration–reagglomeration of filler aggregates, 155 G′ and G″ data, 157 mathematical aspects, 204–205 rate equilibrium between dislocated and flocculated aggregates, 163 SBR/carbon black compounds, 158 Ulmer modification, dynamic strain softening (DSS), 212–215 modeling G′, strain, 213–215 Kraus–Ulmer equations, 253, 255 Krieger–Dougherty equation, 272, 274–275 polynomial, relative viscosity variations, 276 Krieger–Dougherty relationship expansion, 335 numerical illustration, 336 Kuhn length, 246 Index L Ladouce–Stelandre model, 171 Lamp black process, 23 Langmuir’s theory, 168 Lattice gas model, 172 Layered silicates, 3, Lennard-Jones potential, 154 Liege, 12 Lignin, 75, 77 Lion model dynamic strain softening (DSS), 223–225 Local drag flow mechanisms of rubber–aggregate flow units, 114 Longitudinal (tensile) modulus, 392, 395, 398, 409 calculation, 402 Low strain amplitude dynamic properties silica reinforcement, 238 M Magnesium hydroxide, 263 Magnesium oxide fluorohydric acid (HF), 56 Maier and Göritz model, 170, 227 development, 227–228 experimental data, fitting, 230 mathematical aspects, 229 modeling G′, strain, 231 modeling G″, strain, 232–233 Mass fractal dimension of carbon black (CB), 30, 33 aggregate, volume of particle, 39 and aggregates, 33 connectivity exponent, 36 critical filler level, 43–44 DPBA, 39–40 ethylene-propylene-diene monomer rubber (EPDM) compounds, 38 fractal geometry, 36–37, 41 fractal nature, 43 geometry description of aggregates, 34 HAF grade, 40 Index Medalia, floc simulation approach, 38–39 Medalia aggregates, concept of, 37–38 Medalia occluded rubber, 42–43 pellets and agglomerates, 42 pellets mixing operations, 43 TEM/AIA study, 37 void ratio, 39 volume fraction, 41–42 well dispersed state, 43 X-ray scattering experiments, 35 Mastics, 247 Matrix modulus, effect of, 390–391 Maximum packing fraction, 315 effect of, 317, 337 Medalia’s aggregate morphology approach, 86 void ratio and DPB absorption, relationship, 87–88 Medalia’s floc simulation, 193 data, 85 Mesophase concept, 150 Mesophase-pitch-precursor (MPPfibers), 71 Metamorphic rocks, 54 Methoxy group, 243 Mica filled PP compounds, application, 298 and thermoplastics, 297 volume fraction, effect of, 300 Michelin formulation, 246 Mineral fillers cost of, industrial use, 264 Model equation, 326 Modeling G′, strain, 213–215, 231–232 Modeling G″, strain, 215–218, 232–233 Modeling, polymer systems shear viscosity function, 312–315 Modeling tan δ, γ0, 200–202 Models aggregates flocculation/ entanglement model, 218–221 aggregate, solid fraction of, 219–220 filler volume fraction, modulus, 220–221 strain dependence, modulus, 221–222 419 Carreau–Yasuda model, 268–269, 278 Casson model, 101 for yield stress fluids, 102 cluster-cluster-aggregation (CCA) model, 158, 218–221 aggregate, solid fraction of, 219–220 filler volume fraction, modulus, 220–221 strain dependence, modulus, 221–222 Cohen–Addad percolation model maximum adsorbed polymer at saturation, 251 for silica-PDMS, 120 comparison sharp variation, 317 smooth variation, 317 equivalent circuit model, 172 face-centered cubic lattice model, 93–94 fractional linear solid model, 222–223 Halpin–Tsai model, 361 commercial SGF-filled polyamide and 66 composites, flexural and tensile moduli of, 362 commercial SGF-filled polyamide 11 composites, flexural and tensile moduli of, 363 Herschel–Bulkley model for yield stress fluids, 100–101 Kraus deagglomeration– reagglomeration model dynamic strain softening (DSS), 196–202, 209 Kraus model deagglomeration– reagglomeration of filler aggregates, 155 G′ and G″ data, 157 mathematical aspects, 204–205 rate equilibrium between dislocated and flocculated aggregates, 163 SBR/carbon black compounds, 158 Ulmer modification, dynamic strain softening (DSS), 212–215 420 Ladouce–Stelandre model, 171 lattice gas model, 172 Lion model dynamic strain softening (DSS), 223–225 Maier and Göritz model, 170, 227–232 development, 227–228 experimental data, fitting, 230 mathematical aspects, 229 modeling G′, strain, 231 modeling G″, strain, 232–233 Mori–Tanaka’s averaging hypothesis and derived models average strain approach, 352 fiber aspect ratio, 352–353 finite element (FE) calculations, 353 liquid fillers, 353 Poisson’s ratio, 352 thermoplastic polymer systems, flexural and tensile moduli comparison, 353–354 network junction (NJ) model, 134 shear lag models, 353, 355 efficiency factor, 355 fiber aspect ratio, 357 fiber lengths, distribution of, 358 packing ratio, 356 shear viscosity function model, 319–321 Toom model, 48 Vand cubic model, 122 van de Walle, Tricot and Gerspacher (VTG) model, 165 White–Wang model, 101 for carbon black filled compounds, 103 CB filled rubber compounds, 102 Mohs hardness, 265 gypsum, 265 scale, 266 soft minerals, 265 wollastonite, 265 Molten polymer, Monte Carlo method, 167 Montmorillonite, 50 Mooney and Rivlin equation, 130–131 Mooney functional analysis, 272 Index Mooney viscometer, 98 Mori–Tanaka’s average stress concept Eshelby’s tensor, 399–400 experimental data, comparison, 404–405 longitudinal (tensile) modulus calculation, 402 materials and volume fraction depending constants, 401 materials constants, 400–401 shear modulus calculation, 403–404 transversal (tensile) modulus calculation, 402–403 Mori–Tanaka’s averaging hypothesis and derived models average strain approach, 352 fiber aspect ratio, 352–353 finite element (FE) calculations, 353 liquid fillers, 353 Poisson’s ratio, 352 thermoplastic polymer systems, flexural and tensile moduli comparison, 353–354 Mullins effect, 127–128 N Nanocomposites commercial demand, fundamental research on, Hamed’s proposal, 6–7 Nanometer-size materials, 4–5 Natural fiber filled rubber composites selected published works, 378 Natural fibers cellulose structure, 74, 77 composition, 72 lignin, 75, 77 polymers matrix interactions, chemical approaches, 78 potential fillers for, 76 SEM microphotographs, 78 synthetic fibers, properties of, 72–73 Natural rubber (NR), 45, 382 pseudo-Newtonian plateau, 95 421 Index Natural rubber (RSS1) compounds, 237 Natural silica neuburg silica, 52 quartz, 52 siliceous fillers, 53 diatomaceous earths, 53 white calcium silicate (CaSiO3), 52–53 Network junction (NJ) model, 134, 187 junction gap width, 189 theory, strain amplification factor, 190–194 typical calculations, 188 strain amplification factor experimental data, comparison, 194–196 Network junction (NJ) theory, 133 model development, 185–189 absorbed DBP, 185 NJ model, 185–187 strain amplification factor and, 139 Neuburg silica, 52 Newtonian plateau, 267 Nielsen modification of Halpin, 396 longitudinal (tensile) modulus, 398 maximum packing functions, 397 transverse (tensile) modulus and shear modulus, 398–399 Nonlinear fitting algorithm, 309, 311 NR, see Natural Rubber (NR); Natural rubber (NR) N330 SBR compound, 93 Nuclear magnetic resonance (NMR), 248 O OESBR/BR tread compound, 261 Organic ammonium salts, Organic fillers chemical synthesis by, 12–13 of natural origin, 12 Organo-clays, 50–51 Organophilic clays, Organophilicity, degree of, 237 Organo-silanes, 236, 243, 261 Bis(3-triethoxysilylpropyl) tetrasulfane (TESPT), 240 silanization efficiency alkoxy groups, effect of, 243 3-thiocyanatopropyl-triethoxy silane (TCPTS), 240 Orientation parameter, 396 P Packing fraction, 337 Packing of objects, 270 Parallelepiped samples, 348 Particle/matrix adhesion, 284 Payne effect, 141 PBT, see Polybutylene therephtalate (PBT) PCC, Precipitated Calcium Carbonate (PCC) PDMS, see Polydimethylsiloxane (PDMS) Percolation level, 46 Percolation theory, 153; see also Dynamic stress softening (DSS) Phyllosilicate, Plan-plan rheometer, 96 Plastics organoclay additives, Platy fillers, oriented, 260 Polyacrylonitrile (PAN-fibers), 71 Polyamides, 4, 360 Polybutylene therephtalate (PBT), 348 Polydimethylsiloxane (PDMS), 237, 246–247 adsorption kinetics of, 250 chains, 248 chlorosilanes, hydrolysis of, 247 gel, 252 Polyethylene, 17–18 Polymers adsorption kinetics, model, 308 cost of, molecular weight, effect of, 308–310 PDMS/silica compound, fitting data, 309 natural fibers matrix interactions, chemical approaches, 78 potential fillers for, 76 polymer–glass fiber systems, 150 422 polymer-short fiber systems for industrial applications, 341 and short fibers elastomers tensile properties difference, 339 fiber-polymer systems, 341 fibers-to-matrix adhesion role, 341 fibrous fillers, 343 harmonic mixing rule, 340–341 upper and lower bound moduli curves, 340 Voigt average, 339–340 silicone polymer molecular weight, 308–310 silica adsorption kinetics of, 308–312 silica weight fraction, 310–312 and short fibers filler, 341 Polynomial equation, 275 Polyolefins, Polyorganosiloxanes, 246 Polypropylene (PP), 287, 298 filler compounds, effect of talc volume fraction, 295–296 Polyvinyl chloride (PVC), 2, 18 Postextrusion swelling, 106 and entrance pressure drop in CB, 108 PP–CaCO3 composites, 281–282, 286–287 mechanical properties, 284, 289 Precipitated calcium carbonate (PCC), 55 Precipitated silica, 58 amorphous, grades of, 58 dispersion of, 61 high structure silica, 61 manufacturing process of, 58–60 properties of, 60 synthetic, types of, 62 Probe, 46 PVC, see Polyvinyl chloride (PVC) Q Quartz BET, specific surface area, 52 Index R Reduced segmental mobility of rigid body with interactions, 150 Reinforcement fillers, 15 structure of, 17 polyethylene or polypropylene, 18 promoters, 240 relative variation of rubber compound properties, 15–16 thermoplastics, 17–18 Reinforcing elastomers, 375–376 Relative viscosity of suspensions comparing model equations, 273 Relaxation modulus function, 125 Rheology of suspensions of rigid particles, 315 Rigid particles suspensions rheology, models, 315–319 criteria, 315–316 Rigid PVC CaCO3 particle size effect, 290 Rigid spherical particles models, 125 Rubber, dynamic properties as tire technology requirements, 140 elastic behavior of modeling, 190–191 matrix CB aggregates, 186 well dispersed state, 43 reinforcement, 24–25 silica silanisation reaction, type on, 244 technology, 91 Rubber–carbon black interaction chemical reticulation, 169 hard and soft regions, 129 stress–strain behavior, 131 as topological constraints effect, 120 Rubbery plateau, 125 S SAXS, see Small-angle X-ray scattering (SAXS) SBR, see Styrene-butadiene rubber (SBR) Index Scanning tunneling microscopy (STM), 35 Sealants, 247 Sedimentary rocks, 54 SEM microphotographs, 78 SGF, see Short glass fibers (SGF) Shape factor, 271 Shear lag analysis, 389 models, 171, 409 analysis, 344–345 efficiency factor, 355 fiber aspect ratio, 357 fiber lengths, distribution of, 358 longitudinal (tensile) modulus E11, 409 packing ratio, 356 Shear modulus, 393, 398–399 calculation, 403–404, 408–409 Shear viscosity complex cosmetic material, 98–99 filled BR compound, 98 function, effect on, 95 Herschel–Bulkley equation, 100 plots and level, 97 power law model with yield stress, 99–100 Shear viscosity function capabilities, model filled polymers, 319–321 critical shear rate and viscosity, 314 effect on carbon black (CB), 95 modeling, polymer systems, 312–315 mathematical aspects, 313 Short E-glass fiber in different thermoplastics, effects of, 342 on heat distortion temperature of various thermoplastics, effects of, 343 on impact resistance of various thermoplastics, effects of, 343 Short fibers carbon black filled SBR compound, mechanical properties, 381 cellulose fibers and chopped aramid fibers industrial importance, 380–381 423 extrusion moving die technology, 380 fiber orientation, 382–383 glass fibers exhibit, 381–382 hexa(methoxymethyl)melamine (HMMM), 377 natural fiber filled rubber composites, selected published works, 378 natural origin commercial fibers-filled polypropylene composites, 371 wood flour and high stiffness of, 371 wood–polymer composites (WPC), 371–374 and polymers elastomers tensile properties difference, 339 fiber-polymer systems, 341 fibers-to-matrix adhesion role, 341 fibrous fillers, 343 filler, 341 harmonic mixing rule, 340–341 upper and lower bound moduli curves, 340 Voigt average, 339–340 reinforcing elastomers, 375–376 resorcinol-HEXA system, 379 rubber-fiber bonding, 376 rubber matrix, 375–376 short fiber reinforced rubber composites, 379–380 in extruded rubber hoses, controlling, 381 special fiber–elastomer composites, 378–379 styrene butadiene copolymer (SBR), 376–377 technical constraints, 382 thermoplastic systems micromechanic models for (synthetic) fiber, 382 Short fibers-filled polymer composites, micromechanic models Halpin–Tsai equations, 345 curves calculations, 347 fiber aspect ratio, 350–351 424 fiber orientation distribution, 348 filler particle’s geometry, ξ parameter expressions for, 346 fitting experimental data with, 348 glass fibers, 348–349 mechanical properties, 346 PBT and PA/PAT composites with short glass fibers, 349 short fibers-filled systems, 347 minimum fiber length homogeneous matrix, 344 load transfer, 344–345 shear-lag analysis, 345 Mori–Tanaka’s averaging hypothesis and derived models average strain approach, 352 average stress/strain concept, 351 Eshelby’s transformation tensor, 351–352 fiber aspect ratio, 352–353 finite element (FE) calculations, 353 liquid fillers, 353 moduli composite model, explicit relationships, 351 Poisson’s ratio, 352 shear lag models, 353, 355 efficiency factor, 355 fiber aspect ratio, 357 fiber lengths, distribution of, 358 packing ratio, 356 Short fibers-filled systems, 347, 391–392, 394–396 average orientation parameters longitudinal (tensile) modulus, 392, 395 orientation parameter, 396 transversal (tensile) modulus, 393, 396 random fiber orientation, modulus and adjustable parameter, 394 Short glass fibers (SGF), 341 aliphatic polyamides, filling, 360 commercial composites flexural and tensile moduli data for, 361 PA6, average suppliers’ data, 364–365 Index PA11, average suppliers’ data, 367 PA66, average suppliers’ data, 366 polyamide and 66 composites, flexural and tensile moduli of, 362 polyamide 11 composites, flexural and tensile moduli of, 362 residual stresses, 363, 368 commercial polypropylene, mechanical properties of, 360 E-glass fibers, 358, 360 filling polyamides with, 363–364 impact resistance, 361 thermoplastic polymers Bagley plots in capillary rheometry, 368 high fiber alignment, converging flow results in, 369–370 injection molding, 368–369 slit extrusion of, 369 Short synthetic fibers carbon fibers aramid fibers, 71–72 PAN-fibers and MPP-fibers, 71 glass fibers, 69 types of, 71 Silanes as coagents, benefits, 240 Silanisation, 262 efficiency, organo-silanes alkoxy groups, 243 reinforcing properties, effect of NR compounds, 244 silica, 239 silica, reaction rubber type, effect, 244 in situ, 241, 243, 245 ethanol formation, 243 problems, 241 steps silane condensation reaction, 242 silanol, alkoxy reaction, 242 Silanols, 245 Silica carbon black comparable series, 237 tensile properties, 238 Index carbon black, effect of low strain dynamic properties, 239 fabrication processes fumed silica, 56, 58 precipitated silica, 58–62 modification, bi-functional organosilane, 241–242 network, 238 peculiar dynamic properties, 235 reinforcement low strain amplitude dynamic properties, 238 silanisation, 239–240, 243, 246 silanes, as coagents, 240 silica/PDMS systems, 247–249 adsorption, kinetics properties, 247 dynamic strain softening effect, modeling, 254–255 low strain dynamic properties, variation of, 256 silica/polysiloxane system, 253 surface chemistry of, 235–237, 249 carbon black, comparison, 236 surface energy aspects chemistry of, 68–69 components for, 70 dispersive and polar components, 69 particles, 69 weight fraction, effect of, 310–312 fitting data, 311–312 Silicates calcined clays calcination steps, 51 clay and chemical grafting of, 50–51 China clay, 49–50 hard and soft clays, distinction of, 49 montmorillonite, 50 one-step and two-step grafting technique, mechanism for, 51 physical adsorption of functional polymers, 50 polymer nanocomposites, 50 mica color, 52 muscovite, 51–52 425 talc lamellar surface, 51 Silicone polymers silica, adsorption kinetics of, 308–312 polymer molecular weight, 308–310 silica weight fraction, 310–312 Siloxane group, 236 chains, adsorption empirical model, 248 Simulation algorithms, 277 Small-angle x-ray scattering (SAXS), 35 Soft clays, 257 Soft spheres interactions, 196 Spring-and-dashpot system, 164 S-SBR, see Styrene butadiene copolymer (S-SBR) Stiffness (elasticity modulus), 292 STM, see Scanning tunneling microscopy (STM) Stokes diameter, 93 Storage effects, 118 Storage modulus strain dependence, 221–222 Strain amplification concept of Mullins and Tobin, 132 Strain amplification factor, 193–194 NJ theory, 190–194 elastic behavior of a rubber, modeling, 190–191 Strain crystallization effect of NR, 127 Strain sweep experiments, 213, 230 on SSBR compounds, 141 Strain sweep tests, 178 Stress overshoot experiments on carbon black filled compounds, 106 stress overshoot effect, 105 Structural aspects and characterization of CB aggregates, 25–26 ASTM classification of, 29–30 Brunauer, Emmet, Teller (BET) method, 28 cetyltrimethylammonium bromide CTAB adsorption methods, 27–28 dibutylphthalate (DBP) method, 28 DPA absorption method, 28 426 elementary analysis, 26 elementary particles and structure of aggregates, size, 28–29 rubber reinforcement, 24–25 shapes of, 25 standard characterization methods, 27 tread and carcass tire applications, 30 Styrene-butadience rubber (SBR), 45 Styrene butadiene copolymer (S-SBR) anionic polymerization, production, 246 Styrene-butadiene rubber (SBR) formulation, 91 Surface energy aspects of carbon black (CB) energetic sites, 47–48 esterification of, 48 lamp and gas, chemical functions detection, 44 new equilibrium gas adsorption techniques, 46–47 percolation level, 46 probe, 46 rubber–filler interactions, 45 rubber grade, 44 surface activity, 44 ToF-SIMS and XPS, 45 Toom model, 48 Surface properties, 263 Swollen rubber–filler gel, 118 Synthetic resins, 13 Synthetic silica, 53 ASTM classification, 64 characterization and structural aspects of, 62–63 IGC techniques, 64 precipitated silicic acids (silica) and active silicates, properties of, 54 property ranges for, 63 silicates, 64 suppliers data, 65–67 usage in, 54 T Talc, 260, 291 chemical modification, 261 Index coarse grades, 262 and elastomers fractured surfaces, 260 ground talc, 260 magnesium silicate, crystalline form, 291 minerals, 11 myriad products, 292 platelets, basal surfaces, 261 PP Composites, data, 292–294 properties, 292 thermoplastics, application, 297 volume fraction, effect of, 295–296 Tandon–Weng expressions for randomly distributed spherical particles Eshelby’s tensor, 406 materials and volume fraction depending constants, 407 materials constants, 406–407 shear modulus, calculation, 408–409 tensile modulus, calculation, 408 Tan δ variation, with strain amplitude and temperature, 142 TCPTS, see 3-Thiocyanatopropyltriethoxy silane (TCPTS) TEM/AIA, see Transmission electronmicroscopy/automatedimage-analysis (TEM/ AIA) study Tensile measurements (ASTMD638), 395 Tensile modulus, 126 Tensile modulus calculation, 408 Tensile stress softening (TSS), 127–128 TESPT, see Bis(triethoxysilylpropyl) tetrasulfane (TESPT) Tetra organic phosphonium solutions, 4 Theoretical model approximate fitted equation, comparison, 192 Thermal black process, 24 Thermo-activated reactions, 243 Thermo-oxidative processes, 21 427 Index Thermoplastics, 172 effect of CB on electrical conductivity, 175–177 rheological properties of, 173–175 materials polyamides, 360 processors, 358–359 natural origin commercial fibers-filled polypropylene composites, 371 lignocellulosic fibers, polymer composites preparation, 370 moisture diffusion, 370 wood flour and high stiffness of, 371 wood–polymer composites (WPC), 371–374 thermoplastic polymer systems flexural and tensile moduli, comparison, 353–354 Thermoplastics and white fillers, 262 and calcium carbonates, 280 and clay(s), 300–301 and mica, 297–300 talc, 291 application, 297 properties, 292 3-Thiocyanatopropyl-triethoxy silane (TCPTS), 240 Tightly BdR, 112 Time-of-flight secondary ion mass spectrometry (ToF-SIMS), 45 Tire technology requirements for rubber dynamic properties, 140 Titanium dioxide, 288 ToF-SIMS, see Time-of-flight secondary ion mass spectrometry (ToF-SIMS) Toom model, 48 Transmission electron-microscopy/ automated-image-analysis (TEM/AIA) study, 37 Transversal (tensile) modulus, 393, 396 calculation, 402–403 Transverse (tensile) modulus, 398–399 Tread tire applications, 30 TSS, see Tensile stress softening (TSS) Tunnel effects, 173 Two-roll laboratory mill, 260 U Unbound rubber, 112 Upper and lower bound moduli curves, 340 V Vand cubic model, 122 Van der Waals forces, 152 van de Walle, Tricot and Gerspacher (VTG) model, 165 Vapor-grown carbon fibers (VGCF), 176–177 Vegetal fibers, 12 VGCF, see Vapor-grown carbon fibers (VGCF) Vicinal silanols, 236, 243 condensation, 236 Vinyl-based polymer, Viscous modulus, 166, 207, 212, 224, 230 Void ratio, 39 Medalia classification and assumption, 43 Volume Packing Fraction, 277 VTG, see van de Walle, Tricot and Gerspacher (VTG) model Vulcanizable elastomers, 247 Vulcanization, 56 silica–rubber bonding, 241–242 system, 240 Vulcanized PDMS/silica systems dynamic properties, 253 W Western Europe consumption of rubbers, White fillers carbonates dolomite, 56 GCC and PCC, 55 grades, PCC, 55 concept of maximum volume fraction, 266–268 428 and elastomers, 235 mineral fillers barium sulfate, 56 calcium oxide, 56–57 zinc and magnesium oxide, 56 natural silica neuburg silica, 52 quartz, 52 siliceous fillers, 53 white calcium silicate (CaSiO3), 52–53 silica, surface energy aspects chemistry of, 68–69 components for, 70 dispersive and polar components, 69 particles, 69 silica fabrication processes fumed silica, 56, 58 precipitated silica, 58–62 silicates calcined clays and talc, 51 clays, 49–51 mica, 51–52 synthetic silica, 53 characterization and structural aspects of, 62–67 precipitated silicic acids (silica) and active silicates, properties of, 54 usage in, 54 thermoplastics properties, affect, 263 White–Wang model, 101 for carbon black filled compounds, 103 CB filled rubber compounds, 102 Wollastonite filled compounds, 53 fluoroelastomers (FKM), 52 grades, 52 Index Wood flour, 12 Wood–polymer composites (WPC), 371 flexural properties, 373–374 formulation, 374 injection molding and compression molding, 372–373 maleic anhydride-grafted, 375 market amounts in North America, 11 PP based composites, (pine) wood flour effect of, 374 production and processing, problems, 373 wood-filled thermoplastic composites, 372 WPC, see Wood-polymer composites (WPC) X XNBR, see Carboxylated nitrile rubber (XNBR) XPS, see X-ray photoelectron spectroscopy (XPS) X-ray photoelectron spectroscopy (XPS), 45 Y Yield stress data for filled rubber compounds, 104 Z Zero-shear viscosity, 278 Zinc oxide, 56 as weight predispersion in EVA, 92 [...]... are similar in certain aspects and different in others Understanding why is likely to be the source of promising scientific and engineering developments The possibilities offered by combining one (or several) polymer(s) with one (or several) foreign stiffer component(s) are infinite and the just emerging nanocomposites science is an expected development of the science and technology of filled polymers,... writing a science book on an active field is (by essence) a never ending task since new interesting contributions are published every day But working with an editor forces the scientistwriter to accept a deadline, in other words to make choices, to develop more certain subjects and drop other ones, and eventually to bring an end point, not final but temporary as always in science and industrial applications. .. processing and reduce component weight, and in addition, certain value added properties not normally possible with traditional fillers are also observed, such as higher stiffness, reduced permeability, optical clarity, and electrical conductivity But the chemical and processing operations to disrupt the low-dimensional crystallites and to achieve uniform distribution of the nanoelement (layered silicate and. .. tons/year, essentially for building and garden applications, particularly decking and associated products. Estimated over $600 Mio in 2002, the USA and Canada segment is nowadays worth over $2 billion and worldwide estimates are in the $3 billion range Market growth is slower in West Europe with a consumption of around 140,000 tons in 2002, over 200,000 tons in 2005 and estimated to reach some 270,000... preparation, the development and the applications of filled polymers, not all yet fully understood, despite considerable progresses over the last 50 years As usual, scientific investigations on filled polymer systems started later than empirical engineering (trial -and- error) Introduction 3 and it is only the recent development of advanced investigation means that really boosted research and development work... years to master and doctorate students in polymer science and engineering at the Université Pierre et Marie Curie (Paris, France) It is also based on around 30 years of interest, research and engineering activities in the fascinating field of so-called complex polymer systems, i.e., heterogeneous polymer based materials with strong interactions between phases Obviously, rubber compounds and filled thermoplastics... savings But such favorable cases are rare and restricted to very specific applications A recent study by a market research company claims that, by 2010, nanocomposites demand will grow to nearly 150,000 tons, and will rise to over 3 million tons with a value approaching $15 billion by 2020.3 So far however the market for these new materials has not developed as expected and if, indeed, exfoliated (or surface... seem restricted to very specific cases Packaging and parts for motor vehicles are nevertheless expected to be key markets for nanoclay and nanotube composites With respect to the improved barrier, strength and conductive properties that they can offer, polymer nanocomposites should somewhat penetrate certain food, beverage, and pharmaceutical packaging applications, as well as specific parts for electronics... fabricated Minerals such as talc and clays (Al2O3, 2SiO2, 2H2O) are extracted, grinded, and possibly treated and therefore belong to the first class Calcite (CaCO3) belongs to both classes, as it can be either extracted and grinded or obtained through a chemical process that involves precipitation Carbon blacks result from the incomplete combustion of hydrocarbon feedstock, and are consequently fabricated... the Plastics and Rubber Institute (U.K.) and in 1993 he qualified as European Chemist (EurChem) In 1993, he was elected Professeur des Universités in France and joined the Université Pierre et Marie Curie (Paris, France), as head of the then newly developed polymer rheology and processing laboratory, in collaboration with the French Rubber Institute He is still in this position today and, since 1997,