Contents. Preface XIII. 1 General Introduction 1 References 6
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1 VII Contents Preface XIII 1 General Introduction 1 References 6 2 Interparticle Interactions and Their Combination Hard-Sphere Interaction Soft or Electrostatic Interaction Steric Interaction van der Waals Attractions Combination of Interaction Forces Flocculation of Dispersions, and Its Prevention Mechanism of Flocculation Flocculation of Electrostatically Stabilized Suspensions Flocculation of Sterically Stabilized Dispersions Bridging or Charge Neutralization by Polymers General Rules for Reducing (Eliminating) Flocculation Distinction between Dilute, Concentrated, and Solid Dispersions States of Suspension on Standing States of the Emulsion on Standing Creaming and Sedimentation Flocculation Ostwald Ripening (Disproportionation) Emulsion Coalescence Phase Inversion 35 References 36 3 Principles of Steady-State Measurements Strain Rate or Shear Rate Types of Rheological Behavior in Simple Shear Models for Flow Behavior 39 Rheology of Dispersions: Principles and Applications. Tharwat F. Tadros 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN:
2 VIII Contents Law of Elasticity (Hooke s Model) Newton s Law of Viscosity The Kinematic Viscosity ν Non-Newtonian Flow Rheological Models for the Analysis of Flow Curves Newtonian Systems Bingham Plastic Systems Pseudoplastic (Shear Thinning) System Dilatant (Shear Thickening) System The Herschel Bulkley General Model The Casson Model The Cross Equation Time Effects During Flow: Thixotropy and Negative (or Anti-) Thixotropy Rheopexy Turbulent Flow Effect of Temperature Measurement of Viscosity as a Function of Shear Rate: The Steady- State Regime Capillary Viscometers Measurement of Intrinsic Viscosity of Polymers Capillary Rheometry for Non-Newtonians Rotational Viscometers Concentric Cylinder Viscometer Non-Newtonians Shear Thinning or Pseudoplastic Bingham Plastic Major Precautions with Concentric Cylinder Viscometers Shear Rate Calculations Wall Slip and Sample Evaporation During Measurement The Vane Rheometer Cone and Plate Rheometer Parallel Plates (Discs) The Brookfield Viscometer 62 References 64 4 Principles of Viscoelastic Behavior Introduction The Deborah Number Strain Relaxation after the Sudden Application of Stress (Creep) Analysis of Creep Curves Viscous Fluid Elastic Solid Viscoelastic Response Viscoelastic Liquid Viscoelastic Solid 69
3 Contents IX 4.5 The Berger Model (Maxwell + Kelvin) Creep Procedure Stress Relaxation after Sudden Application of Strain Dynamic (Oscillatory) Techniques Analysis of Oscillatory Response for a Viscoelastic System Vector Analysis of the Complex Modulus The Cohesive Energy Density E c The Weissenberg Effect and Normal Forces Viscoelastic Measurements Constant Stress (Creep) Measurements Dynamic (Oscillatory) Measurements Shear Modulus (Rigidity) Measurement 83 References 84 5 Rheology of Suspensions Introduction The Einstein Equation The Bachelor Equation Rheology of Concentrated Suspensions Rheology of Hard-Sphere Suspensions Analysis of the Viscosity Volume Fraction Curve Rheology of Systems with Soft or Electrostatic Interaction Viscoelastic Behavior of Electrostatically Stabilized Suspensions Elastic Modulus (G ) Distance (h) Relation Scaling Laws for Dependence of G on φ Control of Rheology of Electrostatically Stabilized Suspensions Rheology of Sterically Stabilized Dispersions Viscoelastic Properties of Sterically Stabilized Suspensions Correlation of the Viscoelastic Properties of Sterically Stabilized Suspensions with Their Interparticle Interactions The High-Frequency Modulus Volume Fraction Results Rheology of Flocculated Suspensions Weakly Flocculated Suspensions Strongly Flocculated (Coagulated) Suspensions Analysis of the Flow Curve Fractal Concept for Flocculation Examples of Strongly Flocculated (Coagulated) Suspensions Strongly Flocculated, Sterically Stabilized Systems Models for the Interpretation of Rheological Results Doublet Floc Structure Model Elastic Floc Model 117 References Rheology of Emulsions Introduction Interfacial Rheology 121
4 X Contents Interfacial Tension and Surface Pressure Interfacial Shear Viscosity Measurement of Interfacial Viscosity Interfacial Dilational Elasticity Interfacial Dilational Viscosity Non-Newtonian Effects Correlation of Emulsion Stability with Interfacial Rheology Mixed-Surfactant Films Protein Films Bulk Rheology of Emulsions Analysis of the Rheological Behavior of Concentrated Emulsions Experimental η r φ Curves Influence of Droplet Deformability Viscoelastic Properties of Concentrated Emulsions High-Internal Phase Emulsions (HIPES) Deformation and Break-Up of Droplets in Emulsions During Flow 138 References Rheology Modifiers, Thickeners, and Gels Introduction Classification of Thickeners and Gels Definition of a Gel Rheological Behavior of a Gel Stress Relaxation (after Sudden Application of Strain) Constant Stress (Creep) Measurements Dynamic (Oscillatory) Measurements Classification of Gels Polymer Gels Physical Gels Obtained by Chain Overlap Gels Produced by Associative Thickeners Crosslinked Gels (Chemical Gels) Particulate Gels Aqueous Clay Gels Organo-Clays (Bentones) Oxide Gels Gels Produced using Particulate Solids and High-Molecular-Weight Polymers Rheology Modifiers Based on Surfactant Systems 164 References Use of Rheological Measurements for Assessment and Prediction of the Long-Term Physical Stability of Formulations (Creaming and Sedimentation) Introduction Sedimentation of Suspensions 169
5 Contents XI Accelerated Tests and Their Limitations Application of a High-Gravity (g) Force Rheological Techniques for the Prediction of Sedimentation or Creaming Separation of Formulation: Syneresis Examples of Correlation of Sedimentation or Creaming with Residual (Zero-Shear) Viscosity Model Suspensions of Aqueous Polystyrene Latex Sedimentation in Non-Newtonian Liquids Role of Thickeners Prediction of Emulsion Creaming Creep Measurements for Prediction of Creaming Oscillatory Measurements for Prediction of Creaming Assessment and Prediction of Flocculation Using Rheological Techniques Introduction Wall Slip Steady-State Shear Stress Shear Rate Measurements Influence of Ostwald Ripening and Coalescence Constant-Stress (Creep) Experiments Dynamic (Oscillatory) Measurements Strain Sweep Measurements Oscillatory Sweep Measurements Examples of Application of Rheology for Assessment and Prediction of Flocculation Flocculation and Restabilization of Clays Using Cationic Surfactants Flocculation of Sterically Stabilized Dispersions Flocculation of Sterically Stabilized Emulsions Assessment and Prediction of Emulsion Coalescence Using Rheological Techniques Introduction Rate of Coalescence Rheological Techniques Viscosity Measurements Measurement of Yield Value as a Function of Time Measurement of Storage Modulus G as a Function of Time Correlation between Elastic Modulus and Coalescence Cohesive Energy E c 191 References 191 Index 193
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Contents. Preface XIII
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