Fundamentals of Polymer Science for Engineers

Stoyko Fakirov is currently visiting professor in the Centre for Advanced Composite Materials at the University of Auckland, New Zealand. He studied chemistry at the University of Sofia, Bulgaria, and received his PhD from the Lomonossov State University in Moscow. Stoyko Fakirov is member of the editorial board of 12 international journals on polymers and advanced materials. He has published more than 300 peer-reviewed papers, edited or co-edited and always contributed to 15 books on polymer science and holds nine US patents.

• Preface xvAcknowledgments xviiPart One Introduction 11 Introduction 31.1 Milestones in the Development of Polymer Science 31.2 Basic Terms and Definitions in Polymer Science 111.2.1 Polymer 111.2.2 Monomer 121.2.3 End Groups 131.2.4 Degree of Polymerization 131.2.5 Copolymers 131.2.6 Average Molecular Weights and Distributions 141.2.7 Molecular Weight and Molar Mass 161.2.8 Polymer Morphology 171.2.9 Thermoplastics 171.2.10 Elastomers 181.2.11 Plastics 191.2.12 Thermosetting Resin 191.2.13 Polymer Blends 191.2.14 Tacticity 201.2.15 Polymerization and Functionality 201.2.16 Polymerization Processes 201.2.17 Addition or Chain Polymerization 211.2.18 Step Polymerization 231.2.19 Molecular Architecture 271.2.20 Phase 271.3 Bonding Opportunities in Chemistry 311.3.1 Primary Bonds 311.3.2 Typical Primary Bond Distances and Energies 321.3.3 Secondary Bond Forces 321.3.3.1 Dipole Forces 331.3.3.2 Hydrogen Bonds 331.3.3.3 Interrelation of Intermolecular Forces 34 General Encyclopedias and Dictionaries 36 References and Literature Recommendations 36Part Two Physical Properties of Polymers 412 Flexibility of Polymer Chains and Its Origin 432.1 Conformational Stereoisomerism of Macromolecules 432.2 Conformational Statistics of Chain Models 492.3 Types of Flexibility and Their Quantitative Treatment 533 Amorphous State of Polymers 593.1 Characterization of State of Matter 593.2 State of Matter and Phase Transitions of Condensed Substances. Glass Transition 613.3 Deformation of Polymers. Three Deformational (Relaxational) States of Polymers 643.4 Relaxation Phenomena 713.4.1 Relaxation Phenomena in Low Molecular Weight Substances 713.4.2 Relaxation Phenomena in High Molecular Weight Substances 723.4.3 Time–Temperature Superposition (WLF Equation) 773.5 Glassy State of Polymers 793.5.1 Dependence of Glass Transition Temperature on Chemical Composition and Structure of the Polymer 793.5.2 Peculiarities of Polymer Glasses 833.6 High Elastic State of Polymers 853.6.1 Molecular Kinetic Interpretation of High Elasticity 863.6.2 Thermodynamic Interpretation of High Elasticity 873.7 Viscous Liquid State of Polymers 883.7.1 Molecular Mechanism of Flow. Rheology of Molten Polymers 883.7.2 Mechanical Glassifying of Polymer Melts. Importance of Viscous Liquid State for Polymer Processing 913.8 Mechanical Models of Linear Polymers 933.9 Structure and Morphology of Amorphous Polymers, Polymer Melts, and Solutions 953.10 Liquid Crystalline Polymers 98References 1014 Crystalline Polymers 1034.1 Peculiarities of Crystalline Polymers. Degree of Crystallinity 1034.2 Prerequisites for Polymer Crystallization 1064.3 Kinetics and Mechanisms of Crystallization 1124.3.1 Thermodynamics of Nuclei Formation 1124.3.2 Nuclei Formation in Polymer Systems 1134.3.3 Dependence of the Rate of Nuclei Formation on Temperature 1144.4 Growth of Nuclei (Crystals) 1164.4.1 Crystal Growth Theories 1164.4.2 Dependence of Crystal Growth Rate on Temperature 1184.5 Total Crystallization Rate 1194.5.1 Mathematical Description of Phase Transition Kinetics 1194.5.2 Basic Factors of the Total Crystallization Rate of Polymers 1214.6 Melting and Recrystallization 1244.6.1 Melting and Partial Melting 1244.6.2 Thermodynamic Description of Melting Process and Melting Interval 1254.6.3 Recrystallization 1264.7 Morphology and Molecular Structure of Crystalline Polymers 1274.7.1 Development of Ideas About the Morphology and Structure of Polymers 1284.7.1.1 Structure of Crystalline Polymers in an Isotropic State 1284.7.1.2 Structure of Crystalline Polymers in an Oriented State 1314.7.2 Polymer Single Crystals 1344.7.3 Spherulites 1364.7.4 Crystalline Fibrils 1385 Mechanics of Polymers 1415.1 Basic Terms and Definitions 1415.2 Nature of Neck Formation 1475.3 Strength of Polymers and Long-term Strength 1495.4 Polymer Failure – Mechanism and Theories 151Reference 1556 Polymer Solutions 1576.1 Development of Ideas Regarding the Nature of Polymer Solutions 1576.2 Thermodynamics of Polymer Solutions 1596.3 Flory–Huggins Theory 1626.4 Concentrated Polymer Solutions. Plasticizing 164References 1657 Polymer Molecular Weights 1677.1 Types of Molecular Weights 1677.1.1 Number-Average Molecular Weight 1677.1.2 Weight-Average Molecular Weight 1687.1.3 z-Average Molecular Weight 1697.2 Polydispersity and Molecular Weight Distribution 1707.3 Methods for Determining the Weight and Sizes of Macromolecules 1727.3.1 Types of Methods for Molecular Weight Determination 1727.3.2 Osmometric Determination of Molecular Weight 1747.3.3 Molecular Weight Determination via Light Scattering 1747.3.4 Diffusion Method for Molecular Weight Determination 1777.3.6 Sedimentation Methods for the Determination of Molecular Weight and its Distribution 1787.3.8 Determination of Molecular Weight and its Distribution via the Method of Gel Permeation Chromatography 182Other Methods for Determining Molecular Weight 1857.4 Methods for Determining the Shape and Size of Macromolecules 1868 Methods for the Characterization and Investigation of Polymers 1898.1 Diffraction Methods 1898.1.1 Wide- and Small-Angle X-Ray Diffraction 1908.1.2 Electron Diffraction 1958.1.3 Light Diffraction 1968.1.4 Neutron Diffraction 1968.2 Microscopic Methods 1978.2.1 Light Microscopy with Common and Polarized Light 1988.2.2 Electron Microscopy (Transmission and Scanning) 1998.2.3 Atomic Force Microscopy 2038.3 Thermal Methods 2058.3.2 Calorimetric Techniques for the Investigation of Polymer Structure and Transitions 205Fast Scanning Calorimeter (Chip Calorimeter) 2098.5 Spectroscopic Techniques for the Investigation of Polymer Structure and Conformational Studies of Macromolecules 210Static and Dynamic-Mechanical Techniques 2128.5.1 Static Techniques 2128.5.2 Dynamic Techniques 2148.5.3 Density Measurements 214References and Sources used for Part Two 217Part Three Synthesis of Polymers 2199 Polycondensation (Condensation Polymerization) 2219.1 Introduction 2219.2 Equilibrium Polycondensation 2259.2.1 Formation of Polymer Chain 2259.2.2 Molecular Weight Distribution in Equilibrium Polycondensation 2259.2.3 Destructive Reactions in Equilibrium Polycondensation 2279.2.4 Termination of Polymer Chain Growth 2299.2.4.1 Chemical Changes in Functional Groups 2309.2.4.2 Stoichiometric Imbalance of Monomers 2319.2.4.3 Equilibrium Establishment Between the Polycondensation and Low Molecular Weight Products 2329.2.5 Kinetics of Equilibrium Polycondensation 2339.2.6 Equilibrium Copolycondensation 2349.3 Non-equilibrium Polycondensation 2359.3.1 General Characteristics of Non-equilibrium Polycondensation 2359.3.2 Ways of Performing Non-equilibrium Polycondensation 2369.3.2.1 Interphase Polycondensation 2379.4 Polycondensation in Three Dimensions 239Reference 24010 Chain Polymerization 24110.1 Introduction 24110.1.1 “Living” Polymerization 24310.2 Radical Polymerization 24410.2.1 Initiation of Radical Polymerization 24410.2.2 Propagation (Chain Growth) 24610.2.2.1 Bonding Types of Monomer Units 24610.2.3 Termination of Chain Growth 24910.2.3.1 Inactivation at a Favorable Meeting of Two Macroradicals 24910.2.3.2 Chain Transfer 24910.2.4 Kinetics of Radical Polymerization 25110.2.4.1 General Kinetic Scheme of Radical Polymerization 25210.2.4.2 Thermodynamics of Polymerization 25410.3 Radical Copolymerization 25510.3.1 Basic Equation of Copolymerization 25610.3.2 Methods for Performing Radical Polymerization 25810.3.2.1 Bulk Polymerization 25910.3.2.2 Polymerization in Solution 25910.3.2.3 Emulsion Polymerization 25910.3.2.4 Suspension (Beads) Polymerization 26010.4 Ionic Polymerization 26110.4.1 Introduction 26110.4.2 Cationic Polymerization 26210.4.2.1 Initiation of Cationic Polymerization 26210.4.2.2 Propagation (Polymer Chain Growth) 26310.4.2.3 Termination of Polymer Chain Growth 26410.4.2.4 Kinetics of Cationic Polymerization 26510.4.3 Anionic Polymerization 26710.4.3.1 Initiation of Anionic Polymerization 26710.4.3.2 Polymer Chain Growth 26810.4.3.3 Termination of Polymer Chain Growth 27010.4.3.4 Kinetics of Anionic Polymerization 27010.4.3.5 Coordination Anionic Polymerization 27210.4.4 Ionic Copolymerization 27410.4.4.1 Peculiarities of Ionic Copolymerization 27410.4.5 Ring-opening Polymerization 275References 2711 Synthesis of Polymers With Special Molecular Arrangements 279 (in bold)11.1 Block and Graft Copolymers 27911.1.1 Block Copolymers 27911.1.1.1 Synthesis of Block Copolymers via Condensation 279 11.1.1.2 Synthesis of Block Copolymers via Radical Polymerization 280 11.1.1.3 Synthesis of Block Copolymers via Anionic Polymerization 281 11.2 Graft Copolymers 28211.3 Stereoregular Polymers 283 11.3.1 Constitutional and Configurational Isomerism 283 11.3.2 Geometrical Isomerism 283 11.3.3 Stereoisomerism 28311.3.4 Energy of Regular Polymer Chain Growth 28511.3.5 Properties of Stereoregular Polymers 286 References 28712 Chemical Reactions with Macromolecules. New Non-traditional Methods for Polymer Synthesis 28912.1 Introduction 28912.2 Polymer-analogous Reactions 289 12.2.1 Solvent Effect 290 12.2.2 Effect of Neighboring Functional Groups 290 12.2.3 Effect of Molecular and Supermolecular Structure 29112.2.4 Examples of Important Polymer-analogous Reactions 29112.3 Polymer Destruction 29312.3.1 Mechanical Destruction 29412.3.2 Radio-chemical Destruction 29412.3.3 Thermal Destruction 29512.4 New Non-traditional Methods for Polymer Synthesis 296 12.4.1 Introduction 29612.4.2 Atom Transfer Radical Polymerization 29712.4.3 Reversible Addition/Fragmentation Chain Transfer 29812.4.4 Polymer Synthesis by Click Chemistry 301 References and Sources used for Part Three 304 Part Four Polymer Materials and Their Processing 30713 Polymer Materials and Their Processing 30913.1 Introduction 30913.2 Environmental Impact Assessment 31213.2.1 Ecological Footprint 31213.2.2 Life Cycle Assessment 31213.2.3 Polymer Processing 31313.3 Fibers 31313.3.1 Melt Spinning 31313.3.2 Gel Spinning 31413.4 Elastomers 31513.4.1 Vulcanized Rubber 31513.4.2 Thermoplastic Elastomers 31613.5 Polymer Blends 32113.6 Films and Sheets 32213.6.1 Solution Casting 32213.6.2 Melt Pressing of Film 32313.6.3 Sinter Fabrication of Film 32413.6.4 Melt Extrusion of Films 32413.6.5 Bubble Blown Films 32413.6.6 Films by Calendaring 32513.7 Polymer Composites 32513.7.1 Types of Composites 32713.7.2 Long Fiber Composites: Some Theoretical Considerations 32813.7.3 Matrices 33013.7.4 Long Fiber Composites: Applications 33213.8 Nanomaterials and Polymer Nanocomposites 33413.9 Basic Problems in Polymer Science and Technology: Environmental Impact, Interfacial Adhesion Quality, Aspect Ratio 33713.10 Polymer–Polymer and Single Polymer Composites: Definitions, Nomenclature, Advantages, and Disadvantages 33813.11 Processing of Fiber-reinforced Composites 34113.12 Fabrication of Shaped Objects from Polymers 34213.12.1 Casting 34213.12.2 Compression Molding 34313.12.3 Injection Molding 34413.12.4 Rotational Molding 34413.12.5 Bag Molding 34413.12.6 Tube Fabrication 345References 34514 Polymers for Special Applications 34714.1 Electrically Conductive Polymers 34714.1.1 Ionic Conduction in Solid Polymers 34814.1.2 Proton Conductors 34914.1.3 Electronically Conducting Polymers 35014.1.4 Optical and Electro-optical Devices 35114.1.5 “Linear” Optical Materials 35114.1.6 Non-linear Optical Polymers 35214.1.7 Photovoltaic Cells 35214.2 High-performance Thermoplastics 35314.3 Polymers for Hydrogen Storage 35514.4 Smart Materials 35714.4.1 Introduction 35714.4.2 Self-healing Polymers 35814.4.3 Shape-memory Polymers 36014.5 Uses of Polymers in Biomedicine 36214.5.1 Cardiovascular Applications 36314.5.2 Stents and Stenting 36514.5.3 Tissue Adhesives and Artificial Skin 36714.5.4 Bones, Joints, and Teeth 36814.5.5 Contact Lenses and Intraocular Lenses 36814.6 Tissue Engineering 36914.7 Controlled Release of Drugs 372References and Sources for Part Four 373Index 375

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