| Preface |
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xiii | |
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xvii | |
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1 | (70) |
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1 Microgels and Their Synthesis: An Introduction |
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3 | (30) |
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3 | (5) |
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3 | (1) |
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1.1.1.1 The Generic Microgel: Structure and Characterization |
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4 | (2) |
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1.1.2 Microgels Are Special |
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6 | (1) |
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1.1.3 The Microgel Landscape |
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7 | (1) |
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8 | (11) |
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8 | (2) |
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1.2.2 Approach 1: Microgels Formed by Homogeneous Nucleation |
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10 | (1) |
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1.2.2.1 Emulsion Polymerization and Surfactant-Free Emulsion Polymerization |
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11 | (3) |
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1.2.2.2 Homogeneous Nucleation of Microgels from Linear Polymers |
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14 | (1) |
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1.2.2.3 Core-Shell Microgels |
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14 | (1) |
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1.2.3 Approach 2: Microgels from Emulsification |
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15 | (1) |
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1.2.4 Approach 3: Microgels by Polymer Complexation |
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16 | (2) |
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18 | (1) |
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19 | (1) |
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1.3 Particle Derivatization |
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19 | (3) |
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1.3.1 Chemical Coupling to Microgels |
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19 | (1) |
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1.3.2 Microgel Decross-Linking |
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19 | (1) |
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1.3.3 Charged Microgels from Nonionic Precursors |
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20 | (1) |
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1.3.4 Nanoparticle-Filled Gels |
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21 | (1) |
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1.4 Microgel Purification and Storage |
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22 | (3) |
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1.4.1 Microgel Characterization |
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22 | (3) |
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25 | (8) |
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25 | (8) |
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2 Polymerization Kinetics of Microgel Particles |
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33 | (20) |
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33 | (3) |
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2.2 Polymerization Processes |
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36 | (1) |
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2.3 Kinetics of Polymerization Reaction |
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37 | (12) |
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2.3.1 The Influence of Initiators |
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39 | (2) |
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2.3.2 The Effect of the Cross-Linking Agent |
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41 | (1) |
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2.3.3 The Effect of Functional Monomers |
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42 | (3) |
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2.3.4 Kinetic Aspects of Microgel Formation |
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45 | (4) |
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49 | (4) |
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49 | (4) |
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3 New Functional Microgels from Microfluidics |
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53 | (18) |
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53 | (1) |
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3.2 Monodisperse Thermosensitive Microgels Fabricated in a PDMS Microfluidic Chip |
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54 | (3) |
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3.3 Monodisperse Thermosensitive Microgels Fabricated in a Capillary Microfluidic Device |
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57 | (5) |
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3.4 Monodisperse Thermosensitive Microgels with Tunable Volume-Phase Transition Kinetics |
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62 | (1) |
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3.5 Monodisperse Thermosensitive Microgels with Core-Shell Structures Containing Functional Materials |
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63 | (2) |
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3.6 Monodisperse Thermosensitive Microgels with Multiphase Complex Structures |
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65 | (3) |
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68 | (3) |
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68 | (3) |
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Part Two Physical Properties of Microgel Particles |
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71 | (92) |
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4 Swelling Thermodynamics of Microgel Particles |
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73 | (44) |
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Antonio Fernandez-Barbero |
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73 | (3) |
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4.2 Swelling Thermodynamics |
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76 | (18) |
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4.2.1 Polymer/Solvent Mixing |
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76 | (3) |
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79 | (2) |
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81 | (1) |
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4.2.3.1 Ideal Gas Contribution |
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81 | (2) |
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4.2.3.2 Electrostatic Energy of a Homogeneously Charged Microgel |
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83 | (1) |
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4.2.3.3 Contribution from Counterion Correlations |
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84 | (2) |
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4.2.3.4 Effect of a Slightly Inhomogeneous Fixed-Charge Distribution |
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86 | (2) |
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4.2.4 Equilibrium: Equation of State |
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88 | (6) |
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4.3 Theory Versus Experiment |
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94 | (14) |
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4.3.1 Role of Flory Solubility Parameter |
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94 | (3) |
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4.3.2 Influence of Cross-Linking Density |
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97 | (1) |
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4.3.3 Effect of Charge Density |
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98 | (2) |
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100 | (2) |
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4.3.5 Effect of Added Polymer |
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102 | (2) |
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4.3.6 Cononsolvency: Swelling in Solvent Mixtures |
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104 | (2) |
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106 | (2) |
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108 | (2) |
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108 | (1) |
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4.4.2 Brief Remarks on Swelling Kinetics |
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108 | (2) |
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110 | (7) |
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113 | (4) |
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5 Determination of Microgel Structure by Small-Angle Neutron Scattering |
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117 | (16) |
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117 | (1) |
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5.2 Form Factor of Microgels |
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118 | (11) |
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129 | (2) |
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131 | (2) |
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131 | (2) |
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6 Interactions and Colloid Stability of Microgel Particles |
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133 | (30) |
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6.1 Theoretical Background |
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133 | (8) |
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133 | (3) |
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6.1.2 Van der Waals Interactions |
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136 | (1) |
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6.1.3 Electrostatic Interactions |
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137 | (2) |
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6.1.4 Depletion Interactions |
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139 | (1) |
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6.1.5 Criteria for Dispersion Stability |
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140 | (1) |
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141 | (22) |
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6.2.1 Temperature- and Electrolyte-Induced Aggregation |
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141 | (10) |
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6.2.2 Depletion-Induced Aggregation |
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151 | (2) |
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153 | (1) |
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6.2.4 Probing Interactions between Microgel Particles |
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154 | (6) |
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160 | (3) |
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Part Three Phase Behavior and Dynamics of Microgel Suspensions |
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163 | (120) |
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7 Structure and Thermodynamics of Ionic Microgels |
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165 | (30) |
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165 | (2) |
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7.2 Effective Interparticle Potentials |
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167 | (7) |
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7.3 The Fluid Phase of Ionic Microgels |
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174 | (4) |
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7.4 Genetic Algorithms for the Crystal Structures |
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178 | (4) |
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182 | (7) |
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7.6 Summary and Concluding Remarks |
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189 | (6) |
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191 | (4) |
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8 Elasticity of Soft Particles and Colloids Near the Jamming Threshold |
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195 | (12) |
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195 | (1) |
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8.2 Structure and Mechanical Stability |
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196 | (3) |
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199 | (5) |
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8.3.1 Force Balance and Contact Deformation Operators |
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199 | (1) |
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8.3.2 Energy Expansion and Virtual Force Field |
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200 | (2) |
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202 | (2) |
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8.4 Summary and Conclusion |
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204 | (3) |
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205 | (2) |
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9 Crystallization of Microgel Spheres |
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207 | (22) |
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207 | (1) |
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9.2 Synthesis and Characterization of PNIPAM Microgels |
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208 | (2) |
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9.3 Phase Behavior of Dispersions of PNIPAM Microgels at Room Temperature |
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210 | (3) |
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9.3.1 Characterization of Different Phases Using UV--Visible Spectroscopy |
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212 | (1) |
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9.4 Temperature- and Polymer Concentration-Dependent Phases of the PNIPAM Microgel Dispersions |
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213 | (2) |
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9.5 Theoretical Investigation of Phase Behavior |
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215 | (2) |
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9.6 Phase Diagram in Terms of Volume Fraction |
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217 | (2) |
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9.7 The Interparticle Potential |
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219 | (1) |
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9.8 Annealing and Aging Effects |
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220 | (2) |
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9.9 Kinetics of Crystallization |
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222 | (2) |
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9.10 Crystallization Along a Single Direction |
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224 | (1) |
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225 | (4) |
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226 | (3) |
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10 Melting and Geometric Frustration in Temperature-Sensitive Colloids |
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229 | (54) |
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229 | (3) |
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10.2 The Experimental System |
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232 | (10) |
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10.2.1 Synthesis of NIPA Microgel Particles |
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232 | (3) |
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10.2.2 Microscopy and Temperature Control |
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235 | (3) |
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10.2.3 Characterization: Dynamic Light Scattering |
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238 | (2) |
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10.2.4 Characterization: Video Microscopy Measurement of Interparticle Potentials |
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240 | (2) |
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10.3 "First" Melting in Bulk (3D) Colloidal Crystals |
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242 | (12) |
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242 | (2) |
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10.3.2 Sample Preparation and Imaging |
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244 | (2) |
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10.3.3 Positional Fluctuations and the Lindemann Parameter |
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246 | (1) |
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247 | (1) |
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10.3.5 "First" Melting Near Grain Boundaries |
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248 | (2) |
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10.3.6 "First" Melting Near Dislocations |
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250 | (1) |
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10.3.7 Positional and Angular Fluctuations Near Defects |
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251 | (2) |
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253 | (1) |
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10.4 Melting in Two Dimensions: The Hexatic Phase |
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254 | (12) |
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10.4.1 Theoretical Background |
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254 | (3) |
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10.4.2 Experimental Background |
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257 | (1) |
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258 | (1) |
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259 | (5) |
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10.4.5 The Hexatic Phase and Other Features of the Phase Diagram |
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264 | (1) |
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10.4.6 The Order of the Phase Transitions |
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265 | (1) |
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265 | (1) |
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10.5 Geometric Frustration in Colloidal "Antiferromagnets" |
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266 | (7) |
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266 | (3) |
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10.5.2 The Experimental System |
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269 | (1) |
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10.5.3 Antiferromagnetic Order |
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270 | (1) |
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10.5.4 Stripes and the Zigzagging Ground State |
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270 | (1) |
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271 | (2) |
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273 | (1) |
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273 | (10) |
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274 | (9) |
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Part Four Mechanical Properties |
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283 | (72) |
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11 Yielding, Flow, and Slip in Microgel Suspensions: From Microstructure to Macroscopic Rheology |
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285 | (26) |
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285 | (1) |
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11.2 Advanced Techniques for Microgel Rheology |
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286 | (5) |
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11.2.1 Macroscopic Shear Rheology |
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286 | (2) |
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11.2.2 DWS-Based Microrheology |
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288 | (2) |
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11.2.3 Real Space Particle-Tracking Techniques |
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290 | (1) |
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11.3 Near-Equilibrium Properties and Linear Rheology of Microgel Suspensions |
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291 | (6) |
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11.3.1 Dilute Regime and Paste Formation |
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291 | (2) |
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11.3.2 Linear Viscoelasticity of Microgel Pastes |
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293 | (1) |
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11.3.3 Elastic Properties of Concentrated Microgel Pastes |
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294 | (3) |
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11.4 Yielding, Flow, and Aging |
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297 | (6) |
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297 | (2) |
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11.4.2 Flow of Microgel Pastes |
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299 | (2) |
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11.4.3 Slow Dynamics and Aging of Microgel Pastes |
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301 | (2) |
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11.5 Slip and Flow of Microgel Suspensions Near Confining Surfaces |
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303 | (4) |
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303 | (1) |
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11.5.2 Direct Measurements of Slip Velocity |
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304 | (2) |
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11.5.3 Elastohydrodynamic Lubrication as the Origin of Wall Slip |
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306 | (1) |
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307 | (4) |
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307 | (4) |
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12 Mechanics of Single Microgel Particles |
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311 | (16) |
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12.1 Compressive Measurements by Variation of the Osmotic Pressure |
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312 | (3) |
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12.2 Capillary Micromechanics: Full Mechanical Behavior of a Single Microgel Particle |
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315 | (7) |
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12.3 Discussion: Effects of Particle Softness on Suspension Rheology |
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322 | (1) |
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12.4 Microgels as Model Glasses: Soft Particles Make Strong Glasses |
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323 | (1) |
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12.5 Analogy to Emulsions and Foams |
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324 | (3) |
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324 | (3) |
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13 Rheology of Industrially Relevant Microgels |
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327 | (28) |
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327 | (1) |
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328 | (10) |
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13.2.1 Influence of Phase Volume and Concentration |
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329 | (3) |
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13.2.2 Shear Rheology of Concentrated Microgel Suspensions |
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332 | (3) |
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13.2.3 Linear Viscoelasticity of Concentrated Microgel Suspensions |
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335 | (3) |
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13.3 Microgel Suspension Rheology in Applications |
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338 | (12) |
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13.3.1 Coating Formulations |
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339 | (3) |
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13.3.2 Biomedical, Pharmaceutical, Personal Care, and Cosmetic Products |
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342 | (3) |
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13.3.3 Biopolymer Microgels for Food and Other Applications |
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345 | (1) |
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13.3.3.1 Starch Microgels |
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345 | (2) |
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13.3.3.2 Biopolymer Microgels and Particle Anisotropy |
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347 | (3) |
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350 | (5) |
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351 | (4) |
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355 | (96) |
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14 Exploiting the Optical Properties of Microgels and Hydrogels as Microlenses and Photonic Crystals in Sensing Applications |
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357 | (18) |
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357 | (1) |
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14.2 Responsive Microgel and Hydrogel-Based Lenses |
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358 | (4) |
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362 | (6) |
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14.4 Other Responsive Systems |
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368 | (4) |
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372 | (3) |
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372 | (3) |
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15 Microgels in Drug Delivery |
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375 | (32) |
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375 | (1) |
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376 | (2) |
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378 | (15) |
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15.3.1 Temperature Triggering of Microgels |
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380 | (2) |
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15.3.2 Electrostatic Triggering of Microgels |
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382 | (3) |
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15.3.3 Triggering of Microgels by Specific Metabolites |
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385 | (1) |
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15.3.4 Microgel Triggering by External Fields |
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385 | (4) |
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15.3.5 Microgel Triggering by Degradation |
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389 | (4) |
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15.4 Polymer Microcapsules |
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393 | (6) |
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15.4.1 Microcapsule Triggering |
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395 | (4) |
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15.5 Swelling, Loading, and Release Kinetics |
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399 | (3) |
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402 | (5) |
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403 | (4) |
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16 Microgels for Oil Recovery |
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407 | (16) |
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407 | (3) |
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16.2 Microgels Used in Oil Recovery |
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410 | (11) |
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410 | (1) |
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411 | (4) |
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16.2.2 Rheology of Guar Gels and its Relation to Proppant Transport |
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415 | (1) |
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16.2.2.1 Proppant Transport |
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416 | (1) |
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416 | (2) |
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16.2.4 Gels for Gravel Packing |
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418 | (1) |
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16.2.5 Gels for Fluid Loss Control |
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419 | (1) |
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420 | (1) |
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421 | (2) |
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421 | (2) |
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17 Applications of Biopolymer Microgels |
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423 | (28) |
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423 | (2) |
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17.2 Origin, Production, and Molecular Properties of Xanthan Gum |
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425 | (4) |
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17.3 Characterization of Xanthan and CMC Microgels |
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429 | (7) |
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17.4 Rheology of Silica Suspensions in Xanthan Microgel Pastes |
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436 | (6) |
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17.5 Aging of Concentrated Xanthan Suspensions |
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442 | (4) |
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446 | (5) |
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447 | (4) |
| Index |
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451 | |