Physical Chemistry of Polymers: A Conceptual Introduction

Description

This book introduces the concepts of physical chemistry of polymers. It provides a basis to bridge polymer chemistry, which targets microscopic chain structures, and polymer engineering, which targets macroscopic material properties and functions. Topics covered are single chain statistics, multi-chain interactions, and chain dynamics, both from a viewpoint of structure, properties (mostly mechanical ones), and their interrelation. In all that, the author encourages the reader to think conceptually. Explains complex facts through models, diagrams and illustrations, rather than equations. Accessible to chemists, chemical engineers, and materials scientists. Cover Half Title Also of Interest Physical Chemistry of Polymers : A Conceptual Introduction Copyright Foreword Contents Lesson Literature Basis 1. Introduction to polymer physical chemistry 1.1 Targets of this book 1.2 Definition of terms 1.3 Irregularity of polymers 1.3.1 Nonuniformity of monomer connection in a chain 1.3.2 Polydispersity in an ensemble of chains 1.3.2.1 Derivation of the Schulz–Flory distribution 1.3.2.2 Derivation of the Schulz–Zimm distribution 1.3.2.3 Characteristic averages of the Schulz–Flory and Schulz–Zimm distribution 1.4 Properties of polymers in contrast to low molar mass materials 1.5 Polymers as soft matter 1.6 History of polymer science 2. Ideal polymer chains 2.1 Coil conformation 2.1.1 Micro- and macroconformations of a polymer chain 2.1.2 Measures of size of a polymer coil 2.2 Simple chain models 2.2.1 The random chain (phantom chain, freely jointed chain) 2.2.2 The freely rotating chain 2.2.3 The chain with hindered rotation 2.2.4 The Kuhn model 2.2.5 The rotational isomeric states model 2.2.6 Energetic versus entropic influence on the shape of a polymer 2.2.7 The persistence length 2.2.8 Summary 2.3 The Gaussian coil 2.4 The distribution of end-to-end distances 2.4.1 Random-walk statistics 2.5 The free energy of ideal chains 2.6 Deformation of ideal chains 2.6.1 Entropy elasticity 2.6.2 A scaling argument for the deformation of ideal chains 2.7 Self-similarity and fractal nature of polymers 3. Real polymer chains 3.1 Interaction potentials and excluded volume 3.2 Classification of solvents 3.3 Omnipresence of the Θ-state in polymer melts 3.4 The conformation of real chains 3.4.1 Coil expansion 3.4.2 Flory theory of a polymer in a good solvent 3.5 Deformation of real chains 3.6 Chain dynamics 3.6.1 Brownian motion and diffusion 3.6.2 The Rouse model 3.6.3 The Zimm model 3.6.4 Relaxation modes 3.6.5 Subdiffusion 3.6.6 Validity of the models 4. Polymer thermodynamics 4.1 The Flory–Huggins mean-field theory 4.1.1 The entropy of mixing 4.1.2 The enthalpy of mixing 4.1.3 The Flory–Huggins parameter as a function 4.1.4 Microscopic demixing 4.1.5 Solubility parameters 4.2 Phase diagrams 4.2.1 Equilibrium and stability 4.2.2 Construction of the phase diagram 4.2.3 Mechanisms of phase transitions 4.2.3.1 Spinodal decomposition 4.2.3.2 Nucleation and growth 4.3 Osmotic pressure 4.3.1 Connection of the second virial coefficient, A2, to the Flory–Huggins parameter, χ, and the excluded volume, ve 5. Mechanics and rheology of polymer systems 5.1 Fundamentals of rheology 5.1.1 Elementary cases of mechanical response 5.1.2 Different types of deformation in rheology 5.1.3 The tensor form of Hooke’s law 5.2 Viscoelasticity 5.2.1 Elementary types of rheological experiments 5.2.1.1 The relaxation experiment 5.2.1.2 The creep test 5.2.1.3 The dynamic experiment 5.3 Complex moduli 5.4 Viscous flow 5.5 Methodology in rheology 5.5.1 Oscillatory shear rheology 5.5.2 Microrheology 5.5.2.1 Active microrheology 5.5.2.2 Passive microrheology 5.6 Principles of viscoelasticity 5.6.1 Viscoelastic fluids: the Maxwell model 5.6.2 Viscoelastic solids: the Kelvin–Voigt model 5.6.3 More complex approaches 5.7 Superposition principles 5.7.1 The Boltzmann superposition principle 5.7.2 The thermal activation of relaxation processes 5.7.3 Time–temperature superposition 5.8 Viscoelastic states of a polymer system 5.8.1 Qualitative discussion of the mechanical spectra 5.8.2 Quantitative discussion of the mechanical spectra 5.9 Rubber elasticity 5.9.1 Chemical thermodynamics of rubber elasticity 5.9.2 Statistical thermodynamics of rubber elasticity 5.9.3 Swelling of rubber networks 5.10 Terminal flow and reptation 5.10.1 The tube concept 5.10.2 Rouse relaxation and reptation 5.10.3 Reptation and diffusion 5.10.4 Constraint release 6. Scattering analysis of polymer systems 6.1 Basics of scattering 6.2 Scattering regimes 6.3 Structure and form factor 6.4 Light scattering 6.4.1 Static light scattering 6.4.2 Dynamic light scattering 7. Closing remarks Index