| Preface |
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xv | |
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1 | (10) |
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1.1 The Disperse Particles |
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2 | (3) |
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1.2 The Dispersion Medium and Film Formers |
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5 | (3) |
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1.3 Deposition of Particles and Their Adhesion to the Substrate |
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8 | (1) |
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1.4 Flow Characteristics (Rheology) of Paints |
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8 | (3) |
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9 | (2) |
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2 Emulsion, Dispersion and Suspension Polymerization: Preparation of Polymer Colloids and Their Stabilization |
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11 | (22) |
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2.1 Emulsion Polymerization |
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11 | (12) |
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2.1.1 Mechanism of Emulsion Polymerization |
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14 | (1) |
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2.1.2 Block Copolymers as Stabilizers in Emulsion Polymerization |
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15 | (3) |
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2.1.3 Graft Copolymers as Stabilizers in Emulsion Polymerization |
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18 | (5) |
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2.2 Polymeric Surfactants for Stabilization of Preformed Latex Dispersions |
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23 | (4) |
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2.3 Dispersion Polymerization |
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27 | (6) |
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2.3.1 Mechanism of Dispersion Polymerization |
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29 | (1) |
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2.3.2 Influence of Polymeric Surfactant Concentration and Molecular Weight on Particle Formation |
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30 | (1) |
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2.3.3 Effect of Monomer Solubility and Concentration in the Continuous Phase |
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30 | (1) |
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2.3.4 Stability/Instability of the Resulting Latex |
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31 | (1) |
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2.3.5 Particle Formation in Polar Media |
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31 | (1) |
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32 | (1) |
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33 | (38) |
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33 | (23) |
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3.1.1 Wetting of Substrates |
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33 | (3) |
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36 | (1) |
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3.1.3 Work of Adhesion, Wa |
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36 | (1) |
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3.1.4 The Work of Cohesion |
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37 | (1) |
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3.1.5 Spreading Coefficient, S |
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37 | (1) |
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3.1.6 Contact Angle Hysteresis |
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38 | (1) |
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3.1.7 Reasons for Hysteresis |
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38 | (1) |
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39 | (1) |
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3.1.9 Surface Heterogeneity |
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39 | (1) |
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3.1.10 Critical Surface Tension of Wetting |
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40 | (1) |
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3.1.11 Effect of Surfactant Adsorption |
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41 | (1) |
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3.1.12 Wetting of Powders by Liquids |
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42 | (2) |
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3.1.13 Rate of Penetration of Liquids. The Rideal-Washburn Equation |
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44 | (1) |
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3.1.14 Measurement of Wettability of Powders |
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44 | (1) |
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3.1.14.1 Submersion Test - Sinking Time or Immersion Time |
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44 | (1) |
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3.1.14.2 Measurement of Contact Angles of Liquids and Surfactant Solutions on Powders |
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45 | (1) |
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3.1.15 Wetting Agents for Hydrophobic Pigments |
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46 | (2) |
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3.1.16 Adsorption and Wetting Dynamics |
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48 | (1) |
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3.1.17 General Theory of Adsorption Kinetics |
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48 | (3) |
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3.1.17.1 Adsorption Kinetics from Micellar Solutions |
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51 | (1) |
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3.1.17.2 Experimental Techniques for Studying Adsorption Kinetics |
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52 | (4) |
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3.2 Breaking of Aggregates and Agglomerates (Deagglomeration) |
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56 | (11) |
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3.2.1 Classification of Dispersants |
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57 | (3) |
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3.2.2 Assessment and Selection of Dispersants |
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60 | (1) |
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3.2.2.1 Adsorption Isotherms |
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60 | (2) |
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3.2.3 Measurement of Dispersion and Particle Size Distribution |
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62 | (1) |
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3.2.3.1 Optical Microscopy |
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62 | (1) |
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3.2.3.2 Electron Microscopy |
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63 | (1) |
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3.2.3.3 Confocal Scanning Laser Microscopy (CLSM) |
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64 | (1) |
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3.2.3.4 Scattering Techniques |
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64 | (3) |
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3.3 Wet Milling (Comminution) |
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67 | (4) |
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69 | (1) |
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3.3.2 Principle of Operation of Bead Mills |
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69 | (1) |
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70 | (1) |
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4 Colloid Stabilization of Paint Dispersions |
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71 | (38) |
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4.1 Electrostatic Double Layer Repulsion |
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71 | (7) |
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4.1.1 Structure of the Solid/Liquid Interface - Origin of Charges on Surfaces |
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71 | (2) |
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4.1.2 Structure of the Electrical Double Layer |
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73 | (1) |
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4.1.2.1 Diffuse Double layer (Gouy and Chapman) |
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73 | (1) |
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4.1.2.2 Stern-Grahame Model of the Double Layer |
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74 | (1) |
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4.1.3 Electrical Double Layer Repulsion |
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75 | (1) |
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4.1.4 Van der Waals Attraction |
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76 | (2) |
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4.2 Total Energy of Interaction |
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78 | (9) |
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4.2.1 Deryaguin-Landau-Verwey-Overbeek (DLVO) Theory |
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78 | (2) |
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4.2.2 Flocculation of Electrostatically Stabilized Suspensions |
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80 | (2) |
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4.2.3 Criteria for Stabilization of Dispersions with Double Layer Interaction |
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82 | (1) |
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4.2.4 Electrokinetic Phenomena and Zeta Potential |
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82 | (2) |
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4.2.5 Calculation of Zeta Potential |
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84 | (1) |
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4.2.5.1 Von Smoluchowski (Classical) Treatment |
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84 | (1) |
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4.2.5.2 The Huckel Equation |
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85 | (1) |
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4.2.5.3 Henry's Treatment |
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85 | (1) |
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4.2.6 Measurement of Electrophoretic Mobility |
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86 | (1) |
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4.2.6.1 Ultramicroscopic Technique (Microelectrophoresis) |
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86 | (1) |
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4.2.6.2 Laser Velocimetry Technique |
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86 | (1) |
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4.3 Adsorption and Conformation of Polymeric Surfactants at Interfaces |
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87 | (14) |
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4.3.1 Theories of Polymer Adsorption |
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90 | (3) |
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4.3.2 Experimental Techniques for Studying Polymeric Surfactant Adsorption |
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93 | (1) |
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4.3.2.1 Measurement of the Adsorption Isotherm |
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93 | (1) |
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4.3.2.2 Measurement of the Fraction of Segments p |
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94 | (1) |
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4.3.2.3 Determination of the Segment Density Distribution p(z) and Adsorbed Layer Thickness γh |
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94 | (2) |
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4.3.3 Examples of the Adsorption Isotherms of Nonionic Polymeric Surfactants |
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96 | (5) |
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4.4 Interaction Between Particles Containing Adsorbed Polymeric Surfactant Layers |
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101 | (8) |
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4.4.1 Steric Stabilization |
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101 | (1) |
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4.4.2 Mixing Interaction Gmix |
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102 | (1) |
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4.4.3 Elastic Interaction Ge |
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103 | (2) |
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4.4.4 Criteria for Effective Steric Stabilization |
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105 | (1) |
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4.4.5 Flocculation of Sterically Stabilized Dispersions |
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105 | (2) |
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107 | (2) |
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5 Particle Deposition and Adhesion |
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109 | (14) |
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5.1 Deposition of Particles on Surfaces |
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109 | (8) |
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5.1.1 Van der Waals Attraction |
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109 | (1) |
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5.1.2 Electrostatic Repulsion |
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110 | (4) |
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5.1.3 Effect of Polymers and Polyelectrolytes on Particle Deposition |
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114 | (1) |
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5.1.4 Effect of Nonionic Polymers on Particle Deposition |
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115 | (1) |
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5.1.5 Effect of Anionic Polymers on Particle Deposition |
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116 | (1) |
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5.1.6 Effect of Cationic Polymers on Particle Deposition |
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117 | (1) |
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5.2 Particle-Surface Adhesion |
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117 | (6) |
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5.2.1 Surface Energy Approach to Adhesion |
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118 | (1) |
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5.2.1.1 Fox and Zisman Critical Surface Tension Approach |
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119 | (1) |
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5.2.1.2 Neuman's Equation of State Approach |
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119 | (1) |
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5.2.2 Experimental Methods for Measurement of Particle-Surface Adhesion |
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120 | (1) |
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5.2.2.1 Centrifugal Method (Krupp, 1967) |
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120 | (1) |
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5.2.2.2 Hydrodynamic Method (Visser, 1970) |
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120 | (1) |
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121 | (2) |
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6 Basic Principles of Rheology |
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123 | (42) |
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6.1 Principles of Steady-state Measurements |
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123 | (20) |
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6.1.1 Strain Rate or Shear Rate |
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124 | (1) |
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6.1.2 Types of Rheological Behavior in Simple Shear |
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125 | (1) |
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6.1.3 Models for Flow Behavior |
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125 | (1) |
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6.1.3.1 Law of Elasticity (Hooke's Model) |
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125 | (1) |
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6.1.3.2 Newton's Law of Viscosity |
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125 | (1) |
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6.1.3.3 Non-Newtonian Flow |
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126 | (1) |
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6.1.4 Rheological Models for Analysis of Flow Curves |
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127 | (1) |
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6.1.4.1 Newtonian Systems |
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127 | (1) |
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6.1.4.2 Bingham Plastic Systems |
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128 | (1) |
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6.1.4.3 Pseudoplastic (Shear Thinning) System |
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128 | (1) |
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6.1.4.4 Dilatant (Shear Thickening) System |
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128 | (1) |
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6.1.4.5 Herschel-Bulkley General Model |
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128 | (1) |
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6.1.4.6 The Casson Equation |
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129 | (1) |
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6.1.4.7 The Cross Equation |
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129 | (1) |
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6.1.5 Time Effects During Flow - Thixotropy and Negative (or Anti-) Thixotropy |
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130 | (2) |
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132 | (1) |
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6.1.7 Measurement of Viscosity as a Function of Shear Rate - Steady-state Regime |
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132 | (1) |
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6.1.8 Capillary Viscometers |
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133 | (1) |
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6.1.9 Measurement of Intrinsic Viscosity of Polymers |
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134 | (1) |
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6.1.10 Capillary Rheometry for Non-Newtonians |
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135 | (1) |
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6.1.11 Rotational Viscometers |
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136 | (1) |
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6.1.12 Concentric Cylinder Viscometer |
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136 | (1) |
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137 | (1) |
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6.1.13.1 Shear Thinning or Pseudoplastic |
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137 | (1) |
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138 | (1) |
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6.1.14 Major Precautions with Concentric Cylinder Viscometers |
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138 | (1) |
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6.1.14.1 Shear Rate Calculations |
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138 | (1) |
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6.1.14.2 Wall Slip and Sample Evaporation During Measurement |
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139 | (1) |
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6.1.14.3 The Vane Rheometer |
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139 | (1) |
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6.1.14.4 Cone and Plate Rheometer |
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140 | (1) |
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6.1.14.5 Parallel Plates (Disks) |
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141 | (1) |
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6.1.14.6 The Brookfield Viscometer |
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141 | (2) |
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6.2 Principles of Viscoelastic Behavior |
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143 | (22) |
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143 | (1) |
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6.2.1.1 The Deborah Number |
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144 | (1) |
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6.2.2 Strain Relaxation After Sudden Application of Stress (Creep) |
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144 | (1) |
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6.2.3 Analysis of Creep Curves |
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145 | (1) |
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145 | (1) |
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146 | (1) |
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6.2.4 Viscoelastic Response |
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146 | (1) |
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6.2.4.1 Viscoelastic Liquid |
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146 | (1) |
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6.2.4.2 Viscoelastic Solid |
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147 | (1) |
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6.2.5 The Berger Model (Maxwell + Kelvin) |
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148 | (1) |
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149 | (1) |
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6.2.7 Stress Relaxation After Sudden Application of Strain |
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150 | (3) |
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6.2.8 Dynamic (Oscillatory) Techniques |
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153 | (1) |
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6.2.8.1 Analysis of Oscillatory Response for a Viscoelastic System |
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154 | (1) |
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6.2.8.2 Vector Analysis of the Complex Modulus |
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155 | (1) |
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156 | (1) |
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156 | (2) |
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6.2.11 The Cohesive Energy Density, Ec |
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158 | (1) |
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6.2.12 Viscoelastic Measurements |
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158 | (1) |
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6.2.12.1 Constant Stress (Creep) Measurements |
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158 | (2) |
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6.2.12.2 Stress Relaxation (After Application of Constant Strain) |
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160 | (1) |
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6.2.12.3 Dynamic (Oscillatory) Measurements |
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161 | (1) |
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6.2.12.4 Shear Modulus (Rigidity) Measurement |
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162 | (1) |
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163 | (2) |
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7 Rheology of Suspensions, Emulsions and Their Mixtures (Suspoemulsions) |
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165 | (28) |
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7.1 Rheology of Suspensions |
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165 | (11) |
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165 | (1) |
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7.1.2 The Einstein Equation |
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165 | (1) |
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7.1.3 The Batchelor Equation |
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166 | (1) |
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7.1.4 Rheology of Concentrated Suspensions |
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166 | (1) |
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7.1.5 Rheology of Hard-Sphere Suspensions |
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167 | (2) |
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7.1.6 Analysis of the Viscosity-Volume Fraction Curve |
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169 | (1) |
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7.1.7 Rheology of Systems with `Soft' or Electrostatic Interaction |
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169 | (1) |
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7.1.8 Viscoelastic Behavior of Electrostatically Stabilized Suspensions |
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170 | (1) |
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7.1.9 Rheology of Sterically Stabilized Dispersions |
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171 | (1) |
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7.1.10 Rheology of Flocculated Suspensions |
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171 | (1) |
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7.1.10.1 Weakly Flocculated Suspensions |
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172 | (1) |
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7.1.10.2 Strongly Flocculated (Coagulated) Suspensions |
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173 | (1) |
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7.1.11 Analysis of the Flow Curve |
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174 | (1) |
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7.1.11.1 Impulse Theory: Goodeve and Gillespie |
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174 | (1) |
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7.1.11.2 Elastic Floc Model: Hunter and Co-workers |
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174 | (1) |
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7.1.12 Fractal Concept of Flocculation |
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175 | (1) |
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7.2 Rheology of Emulsions |
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176 | (10) |
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176 | (1) |
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7.2.2 Interfacial Rheology |
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176 | (1) |
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7.2.2.1 Interfacial Tension and Surface Pressure |
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176 | (1) |
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7.2.2.2 Interfacial Shear Viscosity |
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177 | (1) |
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7.2.2.3 Measurement of Interfacial Viscosity |
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177 | (1) |
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7.2.3 Interfacial Dilational Elasticity |
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178 | (1) |
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7.2.4 Interfacial Dilational Viscosity |
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179 | (1) |
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7.2.5 Non-Newtonian Effects |
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179 | (1) |
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7.2.6 Correlation of Emulsion Stability with Interfacial Rheology |
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179 | (1) |
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7.2.6.1 Mixed Surfactant Films |
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179 | (1) |
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180 | (1) |
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7.2.7 Bulk Rheology of Emulsions |
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181 | (2) |
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7.2.8 Experimental ni-ø Curves |
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183 | (1) |
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7.2.8.1 Influence of Droplet Deformability |
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184 | (1) |
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7.2.9 Viscoelastic Properties of Concentrated Emulsions |
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184 | (2) |
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7.3 Rheology of Suspoemulsions of Polystyrene Latex and Isoparaffinic Oil Stabilized with Synperonic PE (PEO-PPO-PEO A-B-A Block Copolymer) |
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186 | (7) |
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7.3.1 Model Systems of Polystyrene Latex with Grafted PEO Chains and Hexadecane Emulsions |
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188 | (2) |
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190 | (3) |
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8 Rheology Modifiers, Thickeners and Gels |
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193 | (18) |
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193 | (1) |
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8.2 Classification of Thickeners and Gels |
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193 | (1) |
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8.3 Definition of a `Gel' |
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193 | (1) |
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8.4 Rheological Behavior of a `Gel' |
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194 | (3) |
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8.4.1 Stress Relaxation (After Sudden Application of Strain) |
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194 | (2) |
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8.4.2 Constant Stress (Creep) Measurements |
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196 | (1) |
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8.4.3 Dynamic (Oscillatory) Measurements |
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196 | (1) |
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8.5 Classification of Gels |
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197 | (1) |
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198 | (7) |
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8.6.1 Physical Gels Obtained by Chain Overlap |
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198 | (1) |
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8.6.2 Gels Produced by Associative Thickeners |
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199 | (5) |
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8.6.3 Cross-linked Gels (Chemical Gels) |
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204 | (1) |
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205 | (6) |
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205 | (2) |
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8.7.2 Organo-clays (Bentones) |
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207 | (1) |
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207 | (1) |
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8.7.4 Gels Produced Using Particulate Solids and High Molecular Weight Polymers |
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208 | (1) |
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209 | (2) |
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211 | (32) |
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211 | (3) |
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9.2 Experimental Techniques for Studying Paint Rheology |
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214 | (14) |
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9.2.1 Experimental Methods for Quality Control |
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214 | (1) |
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9.2.2 Measurement of Film Flow-out (Leveling and Sagging) |
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215 | (1) |
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9.2.2.1 Impact Method (Bouncing Ball) |
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215 | (1) |
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9.2.2.2 Impedance Method at High Frequency |
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216 | (1) |
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9.2.3 Rheological Techniques for Research and Development of a Paint System |
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217 | (1) |
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9.2.4 Steady-state Shear Stress-Shear Rate Measurements |
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217 | (1) |
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9.2.4.1 Power Law Fluid Model |
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218 | (1) |
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9.2.4.2 Herschel-Bulkley General Model |
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218 | (1) |
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219 | (1) |
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219 | (1) |
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220 | (2) |
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9.2.5.1 Transient Methods for Studying Paint Rheology |
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222 | (1) |
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9.2.6 Analysis of Creep Curves |
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223 | (1) |
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9.2.6.1 Viscoelastic Liquid |
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223 | (1) |
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9.2.6.2 Viscoelastic Solid |
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223 | (1) |
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9.2.6.3 Berger Model (Maxwell + Kelvin) |
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223 | (1) |
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223 | (2) |
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9.2.7 Dynamic (Oscillatory) Techniques |
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225 | (1) |
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9.2.7.1 Analysis of Oscillatory Response for a Viscoelastic System |
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225 | (1) |
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226 | (1) |
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9.2.7.3 Oscillatory Sweep |
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227 | (1) |
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9.2.7.4 Cohesive Energy Density, Ec |
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227 | (1) |
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227 | (1) |
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9.2.9 Extensional (Elongational) Viscosity |
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228 | (1) |
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9.3 Application of Rheological Techniques to Paint Formulations |
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228 | (6) |
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229 | (1) |
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230 | (1) |
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9.3.3 Dispersion and Ingredients |
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230 | (2) |
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9.3.4 Effect of Surface-active Agents and Dispersants |
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232 | (1) |
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9.3.5 Grinding and Mixing |
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233 | (1) |
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9.4 Application of Rheology for Paint Evaluation |
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234 | (4) |
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236 | (2) |
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9.5 Examples of the Flow Properties of Some Commercial Paints |
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238 | (5) |
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241 | (2) |
| Index |
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243 | |