Fundamentals of Polymer Science for Engineers
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Fundamentals of Polymer Science for Engineers

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Filling a gap in the market, this textbook provides a concise, yet thorough introduction to polymer science for advanced engineering students and practitioners, focusing on the chemical, physical and materials science aspects that are most relevant for engineering applications.

After covering polymer synthesis and properties, the major section of the book is devoted to polymeric materials, such as thermoplastics and polymer composites, polymer processing such as injection molding and extrusion, and methods for large-scale polymer characterization. The text concludes with an overview of engineering plastics. The emphasis throughout is on application-relevant topics, and the author focuses on real-life, industry-relevant polymeric materials.
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Product details

  • Hardback | 408 pages
  • 175 x 250 x 24mm | 898g
  • Blackwell Verlag GmbH
  • Berlin, Germany
  • English
  • 3527341315
  • 9783527341313
  • 1,164,537

Table of contents

Preface xv


Acknowledgments xvii


Part One Introduction 1


1 Introduction 3


1.1 Milestones in the Development of Polymer Science 3


1.2 Basic Terms and De nitions in Polymer Science 11


1.2.1 Polymer 11


1.2.2 Monomer 12


1.2.3 End Groups 13


1.2.4 Degree of Polymerization 13


1.2.5 Copolymers 13


1.2.6 Average Molecular Weights and Distributions 14


1.2.7 Molecular Weight and Molar Mass 16


1.2.8 Polymer Morphology 17


1.2.9 Thermoplastics 17


1.2.10 Elastomers 18


1.2.11 Plastics 19


1.2.12 Thermosetting Resin 19


1.2.13 Polymer Blends 19


1.2.14 Tacticity 20


1.2.15 Polymerization and Functionality 20


1.2.16 Polymerization Processes 20


1.2.17 Addition or Chain Polymerization 21


1.2.18 Step Polymerization 23


1.2.19 Molecular Architecture 27


1.2.20 Phase 27


1.3 Bonding Opportunities in Chemistry 31


1.3.1 Primary Bonds 31


1.3.2 Typical Primary Bond Distances and Energies 32


1.3.3 Secondary Bond Forces 32


1.3.3.1 Dipole Forces 33


1.3.3.2 Hydrogen Bonds 33


1.3.3.3 Interrelation of Intermolecular Forces 34 General Encyclopedias and Dictionaries 36 References and Literature Recommendations 36


Part Two Physical Properties of Polymers 41


2 Flexibility of Polymer Chains and Its Origin 43


2.1 Conformational Stereoisomerism of Macromolecules 43


2.2 Conformational Statistics of Chain Models 49


2.3 Types of Flexibility and Their Quantitative Treatment 53


3 Amorphous State of Polymers 59


3.1 Characterization of State of Matter 59


3.2 State of Matter and Phase Transitions of Condensed Substances. Glass Transition 61


3.3 Deformation of Polymers. Three Deformational (Relaxational) States of Polymers 64


3.4 Relaxation Phenomena 71


3.4.1 Relaxation Phenomena in Low Molecular Weight Substances 71


3.4.2 Relaxation Phenomena in High Molecular Weight Substances 72


3.4.3 Time Temperature Superposition (WLF Equation) 77


3.5 Glassy State of Polymers 79


3.5.1 Dependence of Glass Transition Temperature on Chemical Composition and Structure of the Polymer 79


3.5.2 Peculiarities of Polymer Glasses 83


3.6 High Elastic State of Polymers 85


3.6.1 Molecular Kinetic Interpretation of High Elasticity 86


3.6.2 Thermodynamic Interpretation of High Elasticity 87


3.7 Viscous Liquid State of Polymers 88


3.7.1 Molecular Mechanism of Flow. Rheology of Molten Polymers 88


3.7.2 Mechanical Glassifying of Polymer Melts. Importance of Viscous Liquid State for Polymer Processing 91


3.8 Mechanical Models of Linear Polymers 93


3.9 Structure and Morphology of Amorphous Polymers, Polymer Melts, and Solutions 95


3.10 Liquid Crystalline Polymers 98


References 101


4 Crystalline Polymers 103


4.1 Peculiarities of Crystalline Polymers. Degree of Crystallinity 103


4.2 Prerequisites for Polymer Crystallization 106


4.3 Kinetics and Mechanisms of Crystallization 112


4.3.1 Thermodynamics of Nuclei Formation 112


4.3.2 Nuclei Formation in Polymer Systems 113


4.3.3 Dependence of the Rate of Nuclei Formation on Temperature 114


4.4 Growth of Nuclei (Crystals) 116


4.4.1 Crystal Growth Theories 116


4.4.2 Dependence of Crystal Growth Rate on Temperature 118


4.5 Total Crystallization Rate 119


4.5.1 Mathematical Description of Phase Transition Kinetics 119


4.5.2 Basic Factors of the Total Crystallization Rate of Polymers 121


4.6 Melting and Recrystallization 124


4.6.1 Melting and Partial Melting 124


4.6.2 Thermodynamic Description of Melting Process and Melting Interval 125


4.6.3 Recrystallization 126


4.7 Morphology and Molecular Structure of Crystalline Polymers 127


4.7.1 Development of Ideas About the Morphology and Structure of Polymers 128


4.7.1.1 Structure of Crystalline Polymers in an Isotropic State 128


4.7.1.2 Structure of Crystalline Polymers in an Oriented State 131


4.7.2 Polymer Single Crystals 134


4.7.3 Spherulites 136


4.7.4 Crystalline Fibrils 138


5 Mechanics of Polymers 141


5.1 Basic Terms and De nitions 141


5.2 Nature of Neck Formation 147


5.3 Strength of Polymers and Long-term Strength 149


5.4 Polymer Failure Mechanism and Theories 151


Reference 155


6 Polymer Solutions 157


6.1 Development of Ideas Regarding the Nature of Polymer Solutions 157


6.2 Thermodynamics of Polymer Solutions 159


6.3 Flory Huggins Theory 162


6.4 Concentrated Polymer Solutions. Plasticizing 164


References 165


7 Polymer Molecular Weights 167


7.1 Types of Molecular Weights 167


7.1.1 Number-Average Molecular Weight 167


7.1.2 Weight-Average Molecular Weight 168


7.1.3 z-Average Molecular Weight 169


7.2 Polydispersity and Molecular Weight Distribution 170


7.3 Methods for Determining the Weight and Sizes of Macromolecules 172


7.3.1 Types of Methods for Molecular Weight Determination 172


7.3.2 Osmometric Determination of Molecular Weight 174


7.3.3 Molecular Weight Determination via Light Scattering 174


7.3.4 Diffusion Method for Molecular Weight Determination 177


7.3.6 Sedimentation Methods for the Determination of Molecular Weight and its Distribution 178


7.3.8 Determination of Molecular Weight and its Distribution via the Method of Gel Permeation Chromatography 182


Other Methods for Determining Molecular Weight 185


7.4 Methods for Determining the Shape and Size of Macromolecules 186


8 Methods for the Characterization and Investigation of Polymers 189


8.1 Diffraction Methods 189


8.1.1 Wide- and Small-Angle X-Ray Diffraction 190


8.1.2 Electron Diffraction 195


8.1.3 Light Diffraction 196


8.1.4 Neutron Diffraction 196


8.2 Microscopic Methods 197


8.2.1 Light Microscopy with Common and Polarized Light 198


8.2.2 Electron Microscopy (Transmission and Scanning) 199


8.2.3 Atomic Force Microscopy 203


8.3 Thermal Methods 205


8.3.2 Calorimetric Techniques for the Investigation of Polymer Structure and Transitions 205


Fast Scanning Calorimeter (Chip Calorimeter) 209


8.5 Spectroscopic Techniques for the Investigation of Polymer Structure and Conformational Studies of Macromolecules 210


Static and Dynamic-Mechanical Techniques 212


8.5.1 Static Techniques 212


8.5.2 Dynamic Techniques 214


8.5.3 Density Measurements 214


References and Sources used for Part Two 217


Part Three Synthesis of Polymers 219


9 Polycondensation (Condensation Polymerization) 221


9.1 Introduction 221


9.2 Equilibrium Polycondensation 225


9.2.1 Formation of Polymer Chain 225


9.2.2 Molecular Weight Distribution in Equilibrium Polycondensation 225


9.2.3 Destructive Reactions in Equilibrium Polycondensation 227


9.2.4 Termination of Polymer Chain Growth 229


9.2.4.1 Chemical Changes in Functional Groups 230


9.2.4.2 Stoichiometric Imbalance of Monomers 231


9.2.4.3 Equilibrium Establishment Between the Polycondensation and Low Molecular Weight Products 232


9.2.5 Kinetics of Equilibrium Polycondensation 233


9.2.6 Equilibrium Copolycondensation 234


9.3 Non-equilibrium Polycondensation 235


9.3.1 General Characteristics of Non-equilibrium Polycondensation 235


9.3.2 Ways of Performing Non-equilibrium Polycondensation 236


9.3.2.1 Interphase Polycondensation 237


9.4 Polycondensation in Three Dimensions 239


Reference 240


10 Chain Polymerization 241


10.1 Introduction 241


10.1.1 Living Polymerization 243


10.2 Radical Polymerization 244


10.2.1 Initiation of Radical Polymerization 244


10.2.2 Propagation (Chain Growth) 246


10.2.2.1 Bonding Types of Monomer Units 246


10.2.3 Termination of Chain Growth 249


10.2.3.1 Inactivation at a Favorable Meeting of Two Macroradicals 249


10.2.3.2 Chain Transfer 249


10.2.4 Kinetics of Radical Polymerization 251


10.2.4.1 General Kinetic Scheme of Radical Polymerization 252


10.2.4.2 Thermodynamics of Polymerization 254


10.3 Radical Copolymerization 255


10.3.1 Basic Equation of Copolymerization 256


10.3.2 Methods for Performing Radical Polymerization 258


10.3.2.1 Bulk Polymerization 259


10.3.2.2 Polymerization in Solution 259


10.3.2.3 Emulsion Polymerization 259


10.3.2.4 Suspension (Beads) Polymerization 260


10.4 Ionic Polymerization 261


10.4.1 Introduction 261


10.4.2 Cationic Polymerization 262


10.4.2.1 Initiation of Cationic Polymerization 262


10.4.2.2 Propagation (Polymer Chain Growth) 263


10.4.2.3 Termination of Polymer Chain Growth 264


10.4.2.4 Kinetics of Cationic Polymerization 265


10.4.3 Anionic Polymerization 267


10.4.3.1 Initiation of Anionic Polymerization 267


10.4.3.2 Polymer Chain Growth 268


10.4.3.3 Termination of Polymer Chain Growth 270


10.4.3.4 Kinetics of Anionic Polymerization 270


10.4.3.5 Coordination Anionic Polymerization 272


10.4.4 Ionic Copolymerization 274


10.4.4.1 Peculiarities of Ionic Copolymerization 274


10.4.5 Ring-opening Polymerization 275


References 27


11 Synthesis of Polymers With Special Molecular Arrangements 279 (in bold)


11.1 Block and Graft Copolymers 279


11.1.1 Block Copolymers 279


11.1.1.1 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 282


11.3 Stereoregular Polymers 283


11.3.1 Constitutional and Con gurational Isomerism 283


11.3.2 Geometrical Isomerism 283


11.3.3 Stereoisomerism 283


11.3.4 Energy of Regular Polymer Chain Growth 285


11.3.5 Properties of Stereoregular Polymers 286


References 287


12 Chemical Reactions with Macromolecules. New Non-traditional Methods for Polymer Synthesis 289


12.1 Introduction 289


12.2 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 291


12.2.4 Examples of Important Polymer-analogous Reactions 291


12.3 Polymer Destruction 293


12.3.1 Mechanical Destruction 294


12.3.2 Radio-chemical Destruction 294


12.3.3 Thermal Destruction 295


12.4 New Non-traditional Methods for Polymer Synthesis 296


12.4.1 Introduction 296


12.4.2 Atom Transfer Radical Polymerization 297


12.4.3 Reversible Addition/Fragmentation Chain Transfer 298


12.4.4 Polymer Synthesis by Click Chemistry 301


References and Sources used for Part Three 304


Part Four Polymer Materials and Their Processing 307


13 Polymer Materials and Their Processing 309


13.1 Introduction 309


13.2 Environmental Impact Assessment 312


13.2.1 Ecological Footprint 312


13.2.2 Life Cycle Assessment 312


13.2.3 Polymer Processing 313


13.3 Fibers 313


13.3.1 Melt Spinning 313


13.3.2 Gel Spinning 314


13.4 Elastomers 315


13.4.1 Vulcanized Rubber 315


13.4.2 Thermoplastic Elastomers 316


13.5 Polymer Blends 321


13.6 Films and Sheets 322


13.6.1 Solution Casting 322


13.6.2 Melt Pressing of Film 323


13.6.3 Sinter Fabrication of Film 324


13.6.4 Melt Extrusion of Films 324


13.6.5 Bubble Blown Films 324


13.6.6 Films by Calendaring 325


13.7 Polymer Composites 325


13.7.1 Types of Composites 327


13.7.2 Long Fiber Composites: Some Theoretical Considerations 328


13.7.3 Matrices 330


13.7.4 Long Fiber Composites: Applications 332


13.8 Nanomaterials and Polymer Nanocomposites 334


13.9 Basic Problems in Polymer Science and Technology: Environmental Impact, Interfacial Adhesion Quality, Aspect Ratio 337


13.10 Polymer Polymer and Single Polymer Composites: De nitions, Nomenclature, Advantages, and Disadvantages 338


13.11 Processing of Fiber-reinforced Composites 341


13.12 Fabrication of Shaped Objects from Polymers 342


13.12.1 Casting 342


13.12.2 Compression Molding 343


13.12.3 Injection Molding 344


13.12.4 Rotational Molding 344


13.12.5 Bag Molding 344


13.12.6 Tube Fabrication 345


References 345


14 Polymers for Special Applications 347


14.1 Electrically Conductive Polymers 347


14.1.1 Ionic Conduction in Solid Polymers 348


14.1.2 Proton Conductors 349


14.1.3 Electronically Conducting Polymers 350


14.1.4 Optical and Electro-optical Devices 351


14.1.5 Linear Optical Materials 351


14.1.6 Non-linear Optical Polymers 352


14.1.7 Photovoltaic Cells 352


14.2 High-performance Thermoplastics 353


14.3 Polymers for Hydrogen Storage 355


14.4 Smart Materials 357


14.4.1 Introduction 357


14.4.2 Self-healing Polymers 358


14.4.3 Shape-memory Polymers 360


14.5 Uses of Polymers in Biomedicine 362


14.5.1 Cardiovascular Applications 363


14.5.2 Stents and Stenting 365


14.5.3 Tissue Adhesives and Arti cial Skin 367


14.5.4 Bones, Joints, and Teeth 368


14.5.5 Contact Lenses and Intraocular Lenses 368


14.6 Tissue Engineering 369


14.7 Controlled Release of Drugs 372


References and Sources for Part Four 373


Index 375
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About Stoyko Fakirov

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.
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