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| Introduction to Chain Molecules | |
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| Introduction | |
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| How Big Is Big? | |
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| Molecular Weight | |
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| Spatial Extent | |
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| Linear and Branched Polymers, Homopolymers, and Copolymers | |
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| Branched Structures | |
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| Copolymers | |
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| Addition, Condensation, and Natural Polymers | |
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| Addition and Condensation Polymers | |
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| Natural Polymers | |
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| Polymer Nomenclature | |
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| Structural Isomerism | |
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| Positional Isomerism | |
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| Stereo Isomerism | |
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| Geometrical Isomerism | |
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| Molecular Weights and Molecular Weight Averages | |
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| Number-, Weight-, and z-Average Molecular Weights | |
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| Polydispersity Index and Standard Deviation | |
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| Examples of Distributions | |
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| Measurement of Molecular Weight | |
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| General Considerations | |
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| End Group Analysis | |
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| MALDI Mass Spectrometry | |
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| Preview of Things to Come | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Step-Growth Polymerization | |
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| Introduction | |
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| Condensation Polymers: One Step at a Time | |
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| Classes of Step-Growth Polymers | |
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| First Look at the Distribution of Products | |
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| A First Look at Reactivity and Reaction Rates | |
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| Kinetics of Step-Growth Polymerization | |
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| Catalyzed Step-Growth Reactions | |
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| How Should Experimental Data Be Compared with Theoretical Rate Laws? | |
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| Uncatalyzed Step-Growth Reactions | |
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| Distribution of Molecular Sizes | |
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| Mole Fractions of Species | |
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| Weight Fractions of Species | |
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| Polyesters | |
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| Polyamides | |
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| Stoichiometric Imbalance | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Chain-Growth Polymerization | |
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| Introduction | |
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| Chain-Growth and Step-Growth Polymerizations: Some Comparisons | |
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| Initiation | |
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| Initiation Reactions | |
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| Fate of Free Radicals | |
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| Kinetics of Initiation | |
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| Photochemical Initiation | |
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| Temperature Dependence of Initiation Rates | |
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| Termination | |
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| Combination and Disproportionation | |
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| Effect of Termination on Conversion to Polymer | |
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| Stationary-State Radical Concentration | |
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| Propagation | |
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| Rate Laws for Propagation | |
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| Temperature Dependence of Propagation Rates | |
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| Kinetic Chain Length | |
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| Radical Lifetime | |
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| Distribution of Molecular Weights | |
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| Distribution of i-mers: Termination by Disproportionation | |
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| Distribution of i-mers: Termination by Combination | |
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| Chain Transfer | |
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| Chain Transfer Reactions | |
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| Evaluation of Chain Transfer Constants | |
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| Chain Transfer to Polymer | |
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| Suppressing Polymerization | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Controlled Polymerization | |
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| Introduction | |
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| Poisson Distribution for an Ideal Living Polymerization | |
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| Kinetic Scheme | |
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| Breadth of the Poisson Distribution | |
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| Anionic Polymerization | |
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| Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization | |
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| Block Copolymers | |
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| End-Functional Polymers | |
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| Regular Branched Architectures | |
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| Cationic Polymerization | |
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| Aspects of Cationic Polymerization | |
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| Living Cationic Polymerization | |
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| Controlled Radical Polymerization | |
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| General Principles of Controlled Radical Polymerization | |
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| Particular Realizations of Controlled Radical Polymerization | |
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| Atom Transfer Radical Polymerization (ATRP) | |
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| Stable Free-Radical Polymerization (SFRP) | |
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| Reversible Addition-Fragmentation Transfer (RAFT) Polymerization | |
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| Polymerization Equilibrium | |
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| Ring-Opening Polymerization (ROP) | |
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| General Aspects | |
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| Specific Examples of Living Ring-Opening Polymerizations | |
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| Poly(ethylene oxide) | |
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| Polylactide | |
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| Poly(dimethylsiloxane) | |
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| Ring-Opening Metathesis Polymerization (ROMP) | |
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| Dendrimers | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Copolymers, Microstructure, and Stereoregularity | |
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| Introduction | |
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| Copolymer Composition | |
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| Rate Laws | |
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| Composition versus Feedstock | |
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| Reactivity Ratios | |
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| Effects of r Values | |
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| Relation of Reactivity Ratios to Chemical Structure | |
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| Resonance and Reactivity | |
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| A Closer Look at Microstructure | |
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| Sequence Distributions | |
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| Terminal and Penultimate Models | |
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| Copolymer Composition and Microstructure: Experimental Aspects | |
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| Evaluating Reactivity Ratios from Composition Data | |
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| Spectroscopic Techniques | |
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| Sequence Distribution: Experimental Determination | |
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| Characterizing Stereoregularity | |
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| A Statistical Description of Stereoregularity | |
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| Assessing Stereoregularity by Nuclear Magnetic Resonance | |
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| Ziegler-Natta Catalysts | |
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| Single-Site Catalysts | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Polymer Conformations | |
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| Conformations, Bond Rotation, and Polymer Size | |
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| Average End-to-End Distance for Model Chains | |
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| The Freely Jointed Chain | |
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| The Freely Rotating Chain | |
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| Hindered Rotation Chain | |
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| Characteristic Ratio and Statistical Segment Length | |
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| Semiflexible Chains and the Persistence Length | |
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| Persistence Length of Flexible Chains | |
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| Worm-Like Chains | |
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| Radius of Gyration | |
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| Spheres, Rods, and Coils | |
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| Distributions for End-to-End Distance and Segment Density | |
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| Distribution of the End-to-End Vector | |
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| Distribution of the End-to-End Distance | |
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| Distribution about the Center of Mass | |
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| Self-Avoiding Chains: A First Look | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Thermodynamics of Polymer Solutions | |
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| Review of Thermodynamic and Statistical Thermodynamic Concepts | |
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| Regular Solution Theory | |
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| Regular Solution Theory: Entropy of Mixing | |
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| Regular Solution Theory: Enthalpy of Mixing | |
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| Flory-Huggins Theory | |
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| Flory-Huggins Theory: Entropy of Mixing by a Quick Route | |
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| Flory-Huggins Theory: Entropy of Mixing by a Longer Route | |
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| Flory-Huggins Theory: Enthalpy of Mixing | |
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| Flory-Huggins Theory: Summary of Assumptions | |
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| Osmotic Pressure | |
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| Osmotic Pressure: General Case | |
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| Number-Average Molecular Weight | |
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| Osmotic Pressure: Flory-Huggins Theory | |
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| Phase Behavior of Polymer Solutions | |
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| Overview of the Phase Diagram | |
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| Finding the Binodal | |
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| Finding the Spinodal | |
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| Finding the Critical Point | |
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| Phase Diagram from Flory-Huggins Theory | |
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| What's in [chi]? | |
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| [chi] from Regular Solution Theory | |
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| [chi] from Experiment | |
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| Further Approaches to [chi] | |
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| Excluded Volume and Chains in a Good Solvent | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Light Scattering by Polymer Solutions | |
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| Introduction: Light Waves | |
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| Basic Concepts of Scattering | |
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| Scattering from Randomly Placed Objects | |
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| Scattering from a Perfect Crystal | |
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| Origins of Incoherent and Coherent Scattering | |
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| Bragg's Law and the Scattering Vector | |
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| Scattering by an Isolated Small Molecule | |
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| Scattering from a Dilute Polymer Solution | |
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| The Form Factor and the Zimm Equation | |
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| Mathematical Expression for the Form Factor | |
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| Form Factor for Isotropic Solutions | |
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| Form Factor as qR[subscript g][Right Arrow]0 | |
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| Zimm Equation | |
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| Zimm Plot | |
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| Scattering Regimes and Particular Form Factors | |
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| Experimental Aspects of Light Scattering | |
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| Instrumentation | |
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| Calibration | |
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| Samples and Solutions | |
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| Refractive Index Increment | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Dynamics of Dilute Polymer Solutions | |
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| Introduction: Friction and Viscosity | |
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| Stokes' Law and Einstein's Law | |
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| Viscous Forces on Rigid Spheres | |
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| Suspension of Spheres | |
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| Intrinsic Viscosity | |
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| General Considerations | |
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| Mark-Houwink Equation | |
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| Measurement of Viscosity | |
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| Poiseuille Equation and Capillary Viscometers | |
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| Concentric Cylinder Viscometers | |
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| Diffusion Coefficient and Friction Factor | |
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| Tracer Diffusion and Hydrodynamic Radius | |
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| Mutual Diffusion and Fick's Laws | |
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| Dynamic Light Scattering | |
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| Hydrodynamic Interactions and Draining | |
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| Size Exclusion Chromatography (SEC) | |
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| Basic Separation Process | |
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| Separation Mechanism | |
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| Two Calibration Strategies | |
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| Limitations of Calibration by Standards | |
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| Universal Calibration | |
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| Size Exclusion Chromatography Detectors | |
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| RI Detector | |
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| UV-Vis Detector | |
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| Light Scattering Detector | |
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| Viscometer | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Networks, Gels, and Rubber Elasticity | |
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| Formation of Networks by Random Cross-Linking | |
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| Definitions | |
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| Gel Point | |
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| Polymerization with Multifunctional Monomers | |
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| Calculation of the Branching Coefficient | |
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| Gel Point | |
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| Molecular-Weight Averages | |
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| Elastic Deformation | |
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| Thermodynamics of Elasticity | |
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| Equation of State | |
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| Ideal Elastomers | |
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| Some Experiments on Real Rubbers | |
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| Statistical Mechanical Theory of Rubber Elasticity: Ideal Case | |
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| Force to Extend a Gaussian Chain | |
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| Network of Gaussian Strands | |
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| Modulus of the Gaussian Network | |
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| Further Developments in Rubber Elasticity | |
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| Non-Gaussian Force Law | |
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| Front Factor | |
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| Network Defects | |
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| Mooney-Rivlin Equation | |
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| Swelling of Gels | |
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| Modulus of a Swollen Rubber | |
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| Swelling Equilibrium | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Linear Viscoelasticity | |
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| Basic Concepts | |
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| Stress and Strain | |
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| Viscosity, Modulus, and Compliance | |
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| Viscous and Elastic Responses | |
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| Response of the Maxwell and Voigt Elements | |
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| Transient Response: Stress Relaxation | |
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| Transient Response: Creep | |
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| Dynamic Response: Loss and Storage Moduli | |
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| Dynamic Response: Complex Modulus and Complex Viscosity | |
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| Boltzmann Superposition Principle | |
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| Bead-Spring Model | |
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| Ingredients of the Bead-Spring Model | |
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| Predictions of the Bead-Spring Model | |
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| Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts | |
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| Phenomenology of Entanglement | |
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| Rubbery Plateau | |
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| Dependence of M[subscript e] on Molecular Structure | |
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| Reptation Model | |
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| Reptation Model: Longest Relaxation Time and Diffusivity | |
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| Reptation Model: Viscoelastic Properties | |
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| Reptation Model: Additional Relaxation Processes | |
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| Aspects of Experimental Rheometry | |
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| Shear Sandwich and Cone and Plate Rheometers | |
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| Further Comments about Rheometry | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Glass Transition | |
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| Introduction | |
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| Definition of a Glass | |
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| Glass and Melting Transitions | |
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| Thermodynamic Aspects of the Glass Transition | |
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| First-Order and Second-Order Phase Transitions | |
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| Kauzmann Temperature | |
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| Theory of Gibbs and DiMarzio | |
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| Locating the Glass Transition Temperature | |
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| Dilatometry | |
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| Calorimetry | |
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| Dynamic Mechanical Analysis | |
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| Free Volume Description of the Glass Transition | |
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| Temperature Dependence of the Free Volume | |
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| Free Volume Changes Inferred from the Viscosity | |
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| Williams-Landel-Ferry Equation | |
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| Time-Temperature Superposition | |
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| Factors that Affect the Glass Transition Temperature | |
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| Dependence on Chemical Structure | |
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| Dependence on Molecular Weight | |
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| Dependence on Composition | |
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| Mechanical Properties of Glassy Polymers | |
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| Basic Concepts | |
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| Crazing, Yielding, and the Brittle-to-Ductile Transition | |
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| Role of Chain Stiffness and Entanglements | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Crystalline Polymers | |
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| Introduction and Overview | |
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| Structure and Characterization of Unit Cells | |
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| Classes of Crystals | |
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| X-Ray Diffraction | |
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| Examples of Unit Cells | |
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| Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structure | |
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| Structure and Melting of Lamellae | |
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| Surface Contributions to Phase Transitions | |
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| Dependence of T[subscript m] on Lamellar Thickness | |
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| Dependence of T[subscript m] on Molecular Weight | |
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| Experimental Characterization of Lamellar Structure | |
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| Kinetics of Nucleation and Growth | |
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| Primary Nucleation | |
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| Crystal Growth | |
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| Morphology of Semicrystalline Polymers | |
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| Spherulites | |
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| Nonspherulitic Morphologies | |
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| Kinetics of Bulk Crystallization | |
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| Avrami Equation | |
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| Kinetics of Crystallization: Experimental Aspects | |
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| Chapter Summary | |
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| Problems | |
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| References | |
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| Further Readings | |
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| Appendix | |
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| Series Expansions | |
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| Summation Formulae | |
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| Transformation to Spherical Coordinates | |
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| Some Integrals of Gaussian Functions | |
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| Complex Numbers | |
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| Index | |