Rheology for Chemists

Contents: Chapter 1: Introduction;

1.1 Definitions;

1.1.1 Stress and Strain;

1.1.2 Rate of Strain and Flow;

1.2 Simple Constitutive Equations;

1.2.1 Linear and Non-linear Behaviour;

1.2.2 Using Constitutive Equations;

1.3 Dimensionless Groups;

1.3.1 The Deborah Number;

1.3.2 The PUclet Number;

1.3.3 The Reduced Stress;

1.3.4 The Taylor Number, NTa;

1.3.5 The Reynolds Number, NRe;

1.4 Macromolecular and Colloidal Systems;

1.5 References;

Chapter 2: Elasticity: High Deborah Number Measurements;

2.1 Introduction;

2.2 The Liquid-Solid Transition;

2.2.1 Bulk Elasticity;

2.2.2 Wave Propagation;

2.3 Crystalline Solids At Large Strains;

2.3.1 Lattice Defects;

2.4 Macromolecular Solids;

2.4.1 Polymers - An Introduction;

2.4.2 Chain Conformation;

2.4.3 Polymer Crystallinity;

2.4.4 Crosslinked Elastomers;

2.4.5 Self-associating Polymers;

2.4.6 Non-interactive Fillers;

2.4.7 Interactive Fillers;

2.4.8 Summary of Polymeric Systems;

2.5 Colloidal Gels;

2.5.1 Interactions Between Colloidal Particles;

2.5.2 London - van der Waals' Interactions;

2.5.3 Depletion Interactions;

2.5.4 Electrostatic Repulsion;

2.5.5 Steric Repulsion;

2.5.6 Electrosteric Interactions;

2.6 References;

Chapter 3: Viscosity: Low Deborah Number Measurements;

3.1 Initial Considerations;

3.2 Viscometric Measurement;

3.2.1 The Cone and Plate;

3.2.2 The Couette or Concentric Cylinder;

3.3 The Molecular Origins on Viscosity;

3.3.1 The Flow of Gases;

3.3.2 The Flow of Liquids;

3.3.3 Density and Phase Changes;

3.3.4 Free Volume Model of Liquid Flow;

3.3.5 Activation energy Models;

3.4 Superfluids;

3.5 Macromolecular Fluids;

3.5.1 Colloidal Dispersions;

3.5.2 Dilute Dispersions of Spheres;

3.5.3 Concentrated Dispersions of Spheres;

3.5.4 Shear Thickening Behaviour in Dense Suspensions;

3.5.5 Charge Stabilised Dispersions;

3.5.6 Dilute Polymer Solutions;

3.5.7 Surfactant Solutions;

3.6 References;

Chapter 4: Linear Viscoelasticity I Phenomenological Approach;

4.1 Viscoelasticity;

4.2 Length and Timescales;

4.3 Mechanical Spectroscopy;

4.4 Linear Viscoelasticity;

4.4.1 Mechanical Analogues;

4.4.2 Relaxation Derived as an Analogue to 1 st Order Chemical Kinetics;

4.4.1 Oscillation Response;

4.4.2 Multiple Processes;

4.4.3 A Spectral Approach To Linear Viscoelastic Theory;

4.5 Linear Viscoelastic Experiments;

4.4.1 Relaxation;

4.4.2 Stress Growth;

4.4.3 Antthixotropic Response;

4.4.4 Creep and Recovery;

4.4.5 Strain Oscillation;

4.4.6 Stress Oscillation;

4.6 Interrelationships Between the Measurements and the Spectra;

4.6.1 The Relationship Between Compliance and Modulus;

4.6.1 Retardation and Relaxation Spectrum;

4.6.2 The Relaxation Function and the Storage and Loss Moduli;

4.6.3 Creep and Relaxation Interrelations;

4.7 Applications to the Models;

4.8 Microstructural Influences on the Kernel;

4.8.1 The Extended Exponential;

4.8.2 Power law or the Gel Equation;

4.8.3 Exact Inversions from the Relaxation or Retardation Spectrum;

4.9 Non-shearing Fields and Extension;

4.10 References;

Chapter 5: Linear Viscoelasticity II. Microstructural Approach;

5.1 Intermediate Deborah Numbers;

5.2 Hard Spheres and Atomic Fluids;

5.3 Quasi-hard Spheres;

5.3.1 Quasi-hard Sphere Phase Diagrams;

5.3.2 Quasi-hard Sphere Viscoelasticity and Viscosity;

5.4 Weakly Attractive Systems;

5.5 Charge Repulsion Systems;

5.6 Simple Homopolymer systems;

5.6.1 Phase Behaviour and the Chain Overlap in Good Solvents;

5.6.2 Dilute Solution Polymers;

5.6.3 Undiluted and Concentrated Non-entangled Polymers;

5.6.4 Entanglement coupling;

5.6.5 Reptation and Linear Viscoelasticity;

5.7 Polymer Network Structure;

5.7.1 The Formation of Gels;

5.7.2 Chemical Networks;

5.7.3 Physical Networks;

5.8 References;

Chapter 6: Non-Linear Responses;

6.1 Introduction;

6.2 The Phenomenological Approach;

6.2.1 Flow Curve4s;

Definitions and Equations;

6.2.2 Time Dependence in Flow and The Boltzmann Superposition Principle;

6.2.3 Yield Stress Sedimentation and Linearity;

6.3 The Microstructural Approach - Particles;

6.2.1 Flow in Hard Sphere Systems;

6.2.2 The Addition of a Surface Layer;

6.2.3 Aggregation and Dispersion in Shear;

6.2.4 Weakly Flocculated Dispersions;

6.2.5 Strongly Aggregated and Coagulated Systems;

6.2.6 Long Range Repulsive Systems;

6.2.7 Rod-like Particles;

6.4 The Microstructural Approach - Polymers;

6.4.1 The Role of Entanglements in Non-linear Viscoelasticity;

6.4.2 Entanglements of Solution Homopolymers;

6.4.3 The Reptation Approach;

6.5 Novel Applications;

6.5.1 Extension and Complex Flows;

6.5.2 Uniaxial Compression Modulus;

6.5.3 Deformable Particles;

6.5 References;

Subject Index;