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Preface xv Acknowledgment xvii 1 INTRODUCTION 1 1 1 Expectations from fillers 1 1 2 Typical filler properties 7 1 3 Definitions 8 1 4 Classification 11 1 5 Markets and trends 12 References 13 2 SOURCE[.]
Table of Contents iii Table of Contents Preface Acknowledgment xv xvii INTRODUCTION 1.1 Expectations from fillers 1.2 Typical filler properties 1.3 Definitions 1.4 Classification 1.5 Markets and trends References 1 11 12 13 SOURCES OF FILLERS, THEIR CHEMICAL COMPOSITION, PROPERTIES, AND MORPHOLOGY 2.1 Particulate fillers 2.1.1 Aluminum flakes and powder 2.1.2 Aluminum borate whiskers 2.1.3 Aluminum oxide 2.1.4 Aluminum trihydroxide 2.1.5 Anthracite 2.1.6 Antimony of sodium 2.1.7 Antimony pentoxide 2.1.8 Antimony trioxide 2.1.9 Apatite 2.1.10 Ash, fly 2.1.11 Attapulgite 2.1.12 Barium metaborate 2.1.13 Barium sulfate 2.1.14 Barium & strontium sulfates 2.1.15 Barium titanate 2.1.16 Bentonite 2.1.17 Beryllium oxide 2.1.18 Boron nitride 2.1.19 Calcium carbonate 2.1.20 Calcium hydroxide 2.1.21 Calcium sulfate 2.1.22 Carbon black 2.1.23 Ceramic beads 15 16 16 19 20 22 25 26 27 29 31 32 33 35 36 41 42 43 45 46 48 58 60 62 72 iv 2.1.24 2.1.25 2.1.26 2.1.27 2.1.28 2.1.29 2.1.30 2.1.31 2.1.32 2.1.33 2.1.34 2.1.35 2.1.36 2.1.37 2.1.38 2.1.39 2.1.40 2.1.41 2.1.42 2.1.43 2.1.44 2.1.45 2.1.46 2.1.47 2.1.48 2.1.49 2.1.50 2.1.51 2.1.51.1 2.1.51.2 2.1.51.3 2.1.51.4 2.1.51.5 2.1.51.6 2.1.52 2.1.53 2.1.54 2.1.55 2.1.56 2.1.57 2.1.58 2.1.59 Table of Contents Clay Copper Cristobalite Diatomaceous earth Dolomite Ferrites Feldspar Glass beads Gold Graphite Hydrous calcium silicate Iron oxide Kaolin Lithopone Magnesium oxide Magnesium hydroxide Metal-containing conductive materials Mica Molybdenum Molybdenum disulfide Nickel Perlite Polymeric fillers Pumice Pyrophyllite Rubber particles Sepiolite Silica Fumed silica Fused silica Precipitated silica Quartz (tripoli) Sand Silica gel Silver powder and flakes Slate flour Talc Titanium dioxide Tungsten Vermiculite Wood flour and similar materials Wollastonite 75 77 78 80 84 85 86 87 91 92 96 97 99 104 105 106 107 112 116 117 118 120 122 127 128 129 130 131 132 138 139 142 144 146 147 149 150 154 164 165 166 167 Table of Contents 2.1.60 Zeolites 2.1.61 Zinc borate 2.1.62 Zinc oxide 2.1.63 Zinc stannate 2.1.64 Zinc sulfide 2.2 Fibers 2.2.1 Aramid fibers 2.2.2 Carbon fibers 2.2.3 Cellulose fibers 2.2.4 Glass fibers 2.2.5 Other fibers References v 170 171 172 175 176 178 178 180 184 187 188 189 TRANSPORTATION, STORAGE, AND PROCESSING OF FILLERS 3.1 Filler packaging 3.2 External transportation 3.3 Filler receiving 3.4 Storage 3.5 In-plant conveying 3.6 Semi-bulk unloading systems 3.7 Bag handling equipment 3.8 Blending 3.9 Feeding 3.10 Drying 3.11 Dispersion References 203 203 205 206 208 210 215 216 217 218 220 222 227 QUALITY CONTROL OF FILLERS 4.1 Absorption coefficient 4.2 Acidity or alkalinity of water extract 4.3 Ash content 4.4 Brightness 4.5 Coarse particles 4.6 Color 4.7 CTAB surface area 4.8 DBP absorption number 4.9 Density 4.10 Electrical properties 4.11 Extractables 4.12 Fines content 231 231 231 231 232 232 232 232 233 233 233 234 234 vi 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 4.24 4.25 4.26 4.27 4.28 4.29 4.30 4.31 4.32 4.33 4.34 4.35 Table of Contents Heating loss Heat stability Hegman fineness Hiding power Iodine absorption number Lightening power of white pigments Loss on ignition Mechanical and related properties Oil absorption Particle size Pellet strength pH Resistance to light Resistivity of aqueous extract Sieve residue Soluble matter Specific surface area Sulfur content Tamped volume Tinting strength Volatile matter Water content Water-soluble sulfates, chlorides and nitrates References PHYSICAL PROPERTIES OF FILLERS AND FILLED MATERIALS 5.1 Density 5.2 Particle size 5.3 Particle size distribution 5.4 Particle shape 5.5 Particle surface morphology and roughness 5.6 Specific surface area 5.7 Porosity 5.8 Particle-particle interaction and spacing 5.9 Agglomerates 5.10 Aggregates and structure 5.11 Flocculation and sedimentation 5.12 Aspect ratio 5.13 Packing volume 5.14 pH 5.15 ζ-potential 234 234 234 234 235 235 235 235 235 236 236 236 236 236 237 237 237 237 237 238 238 238 238 239 241 241 245 246 251 251 253 254 255 257 259 261 263 264 269 270 Table of Contents 5.16 5.17 5.18 5.19 5.20 5.21 5.22 5.23 5.24 5.25 5.26 5.27 5.28 5.29 5.30 5.31 Surface energy Moisture Absorption of liquids and swelling Permeability and barrier properties Oil absorption Hydrophilic/hydrophobic properties Optical properties Refractive index Friction properties Hardness Intumescent properties Thermal conductivity Thermal expansion coefficient Melting temperature Electrical properties Magnetic properties References CHEMICAL PROPERTIES OF FILLERS AND FILLED MATERIALS 6.1 Reactivity 6.2 Chemical groups on the filler surface 6.3 Filler surface modification 6.4 Effect of filler modification on material properties 6.5 Resistance to various chemical materials 6.6 Cure in filler's presence 6.7 Polymerization in filler's presence 6.8 Grafting 6.9 Crosslink density 6.10 Reaction kinetics 6.11 Molecular mobility References vii 271 275 278 280 280 281 284 285 286 287 288 289 290 291 291 295 297 7.1 7.2 7.3 7.4 7.5 7.6 7.7 ORGANIZATION OF INTERFACE AND MATRIX CONTAINING FILLERS Particle distribution in matrix Orientation of filler particle in a matrix Voids Matrix-filler interaction Chemical interactions Other interactions Interphase organization 305 305 308 312 324 330 331 336 337 338 339 341 343 347 347 351 356 358 359 363 367 viii 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15 Table of Contents Interfacial adhesion Interphase thickness Filler-chain links Chain dynamics Bound rubber Debonding Mechanisms of reinforcement Benefits of organization on molecular level References THE EFFECT OF FILLERS ON THE MECHANICAL PROPERTIES OF FILLED MATERIALS 8.1 Tensile strength and elongation 8.2 Tensile yield stress 8.3 Elastic 8.4 Flexural strength and modulus 8.5 Impact resistance 8.6 Hardness 8.7 Tear strength 8.8 Compressive strength 8.9 Fracture resistance 8.10 Wear 8.11 Friction 8.12 Abrasion 8.13 Scratch resistance 8.14 Fatigue 8.15 Failure 8.16 Adhesion 8.17 Thermal deformation 8.18 Shrinkage 8.19 Warpage 8.20 Compression set 8.21 Load transfer 8.22 Residual stress 8.23 Creep References 369 370 372 373 374 380 384 389 392 THE EFFECT OF FILLERS ON RHEOLOGICAL PROPERTIES OF FILLED MATERIALS 9.1 Viscosity 9.2 Flow 9.3 Flow induced filler orientation 395 395 402 407 410 412 414 417 418 419 426 429 430 432 433 440 442 444 444 448 449 451 453 454 455 461 461 465 468 Table of Contents 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 Torque Viscoelasticity Dynamic mechanical behavior Complex viscosity Shear viscosity Elongational viscosity Melt rheology Yield value References ix 470 471 472 474 478 478 481 481 483 10 MORPHOLOGY OF FILLED SYSTEMS 10.1 Crystallinity 10.2 Crystallization behavior 10.3 Nucleation 10.4 Crystal size 10.5 Spherulites 10.6 Transcrystallinity 10.7 Orientation References 485 485 487 490 492 493 495 497 498 11 EFFECT OF FILLERS ON DEGRADATIVE PROCESSES 11.1 Irradiation 11.2 UV radiation 11.3 Temperature 11.4 Liquids and vapors 11.5 Stabilization 11.6 Degradable materials References 501 501 505 510 512 516 517 518 12 ENVIRONMENTAL IMPACT OF FILLERS 12.1 Definitions 12.2 Limiting oxygen index 12.3 Ignition and flame spread rate 12.4 Heat transmission rate 12.5 Decomposition and combustion 12.6 Emission of gaseous components and heavy metals 12.7 Smoke 12.8 Char 12.9 Recycling References 521 521 522 523 527 527 530 531 531 531 536 x Table of Contents 13 INFLUENCE OF FILLERS ON PERFORMANCE OF OTHER ADDITIVES AND VICE VERSA 13.1 Adhesion promoters 13.2 Antistatics 13.3 Blowing agents 13.4 Catalysts 13.5 Compatibilizers 13.6 Coupling agents 13.7 Dispersing agents and surface active agents 13.8 Flame retardants 13.9 Impact modifiers 13.10 UV stabilizers 13.11 Other additives References 539 539 541 541 543 544 545 547 549 551 552 554 555 14 TESTING METHODS IN FILLED SYSTEMS 14.1 Physical methods 14.1.1 Atomic force microscopy 14.1.2 Autoignition test 14.1.3 Bound rubber 14.1.4 Char formation 14.1.5 Cone calorimetry 14.1.6 Contact angle 14.1.7 Dispersing agent requirement 14.1.8 Dispersion tests 14.1.9 Dripping test 14.1.10 Dynamic mechanical analysis 14.1.11 Electrical constants determination 14.1.12 Electron microscopy 14.1.13 Fiber orientation 14.1.14 Flame propagation test 14.1.15 Glow wire test 14.1.16 Image analysis 14.1.17 Limiting oxygen index 14.1.18 Magnetic properties 14.1.19 Optical microscopy 14.1.20 Particle size analysis 14.1.21 Radiant panel test 14.1.22 Rate of combustion 14.1.23 Scanning acoustic microscopy 14.1.24 Smoke chamber 14.1.25 Sonic methods 559 559 559 560 560 561 562 563 565 566 567 568 568 571 572 572 574 574 577 578 579 580 580 580 581 581 582 Table of Contents xi 14.1.26 Specific surface area 14.1.27 Thermal analysis 14.2 Chemical and instrumental analysis 14.2.1 Electron spin resonance 14.2.2 Electron spectroscopy for chemical analysis 14.2.3 Inverse gas chromatography 14.2.4 Gas chromatography 14.2.5 Gel content 14.2.6 Infrared and Raman spectroscopy 14.2.7 Nuclear magnetic resonance spectroscopy 14.2.8 UV and visible spectrophotometry 14.2.9 X-ray analysis 14.2.10 X-ray photoelectron Spectroscopy References 584 585 586 586 587 588 592 592 593 594 597 598 598 599 15 FILLERS IN COMMERCIAL POLYMERS 15.1 Acrylics 15.2 Acrylonitrile-butadiene-styrene copolymer 15.3 Acrylonitrile-styrene-acrylate 15.4 Aliphatic polyketone 15.5 Alkyd resins 15.6 Elastomers 15.7 Epoxy resins 15.8 Ethylene vinyl acetate copolymers 15.9 Ethylene ethyl acetate copolymer 15.10 Ethylene propylene copolymers 15.11 Ionomers 15.12 Liquid crystalline polymers 15.13 Perfluoroalkoxy resin 15.14 Phenolic resins 15.15 Poly(acrylic acid) 15.16 Polyamides 15.17 Polyamide imide 15.18 Polyamines 15.19 Polyaniline 15.20 Polyarylether ketone 15.21 Poly(butylene terephthalate) 15.22 Polycarbonate 15.23 Polyetheretherketone 15.24 Polyetherimide 15.25 Polyether sulfone 15.26 Polyethylene 605 606 608 610 611 612 613 614 619 620 621 622 623 624 625 628 629 633 634 635 636 638 639 642 644 645 646 xii Table of Contents 15.27 Polyethylene, chlorinated 15.28 Polyethylene, chlorosulfonated 15.29 Poly(ethylene oxide) 15.30 Poly(ethylene terephthalate) 15.31 Polyimide 15.32 Polymethylmethacrylate 15.33 Polyoxymethylene 15.34 Poly(phenylene ether) 15.35 Poly(phenylene sulfide) 15.36 Polypropylene 15.37 Polypyrrole 15.38 Polystyrene & high impact 15.39 Polysulfides 15.40 Polysulfone 15.41 Polytetrafluoroethylene 15.42 Polyurethanes 15.43 Poly(vinyl acetate) 15.44 Poly(vinyl alcohol) 15.45 Poly(vinyl butyral) 15.46 Poly(vinyl chloride) 15.47 Rubbers 15.47.1 Natural rubber 15.47.2 Nitrile rubber 15.47.3 Polybutadiene rubber 15.47.4 Polybutyl rubber 15.47.5 Polychloroprene 15.47.6 Polyisobutylene 15.47.7 Polyisoprene 15.47.8 Styrene-butadiene rubber 15.48 Silicones 15.49 Styrene acrylonitrile copolymer 15.50 Tetrafluoroethylene-perfluoropropylene 15.51 Unsaturated polyesters 15.52 Vinylidene-fluoride terpolymers References 651 652 653 655 656 658 660 661 662 663 668 669 672 673 674 676 679 680 681 682 684 685 687 690 691 692 694 695 696 698 700 701 702 704 705 16 FILLER IN MATERIALS COMBINATIONS 16.1 Blends, alloys and interpenetrating networks 16.2 Composites 16.3 Nanocomposites 16.4 Laminates References 717 717 726 730 736 737 Table of Contents xiii 17 FORMULATION WITH FILLERS References 741 746 18 FILLERS IN DIFFERENT PROCESSING METHODS 18.1 Blow molding 18.2 Calendering and hot-melt coating 18.3 Compression molding 18.4 Dip coating 18.5 Dispersion 18.6 Extrusion 18.7 Foaming 18.8 Injection molding 18.9 Knife coating 18.10 Mixing 18.11 Pultrusion 18.12 Reaction injection molding 18.13 Rotational molding 18.14 Sheet molding 18.15 Thermoforming 18.16 Welding and machining References 749 749 751 752 754 755 757 760 761 763 764 769 769 771 772 773 773 774 19 FILLERS IN DIFFERENT PRODUCTS 19.1 Adhesives 19.2 Agriculture 19.3 Aerospace 19.4 Appliances 19.5 Automotive materials 19.6 Bottles and containers 19.7 Building components 19.8 Business machines 19.9 Cables and wires 19.10 Coated fabrics 19.11 Coatings and paints 19.12 Cosmetics and pharmaceutical products 19.13 Dental restorative composites 19.14 Electrical and electronic materials 19.15 Electromagnetic interference shielding 19.16 Fibers 19.17 Film 19.18 Foam 19.19 Food and feed 779 779 782 782 783 784 785 786 786 787 788 788 793 795 796 797 799 799 802 802 xiv Table of Contents 19.20 19.21 19.22 19.23 19.24 19.25 19.26 19.27 19.28 19.29 19.30 19.31 19.32 19.33 19.34 19.35 19.36 19.37 19.38 Friction materials Geosynthetics Hoses and pipes Magnetic devices Medical applications Membranes Noise damping Optical devices Paper Radiation shields Rail transportation Roofing Telecommunication Tires Sealants Siding Sports equipment Waterproofing Windows References 20 HAZARDS IN FILLER USE References 803 803 803 804 804 807 807 807 809 812 813 814 814 815 817 818 819 819 820 821 825 831 INDEX OF ABBREVIATIONS 833 DIRECTORY OF FILLER MANUFACTURERS AND DISTRIBUTORS 837 DIRECTORY OF EQUIPMENT MANUFACTURERS 877 INDEX 881