Emulsion formation and stability / edited by Tharwat F. Tadros.
–
Weinheim, cop. 2013
Spis treści
Preface XI
List of Contributors XIII
1 Emulsion Formation, Stability, and Rheology 1
Thanvat F. Tadros
1.1 Introduction 1
1.1.1 Nature of the Emulsifier 1
1.1.2 Structure of the System 2
1.1.3 Breakdown Processes in Emulsions 3
1.1.4 Creaming and Sedimentation 3
1.1.5 Flocculation 4
1.1.6 Ostwald Ripening (Disproportionation) 4
1.1.7 Coalescence 4
1.1.8 Phase Inversion 4
1.2 Industrial Applications of Emulsions 4
1.3 Physical Chemistry of Emulsion Systems 5
1.3.1 The Interface (Gibbs Dividing Line) 5
1.4 Thermodynamics of Emulsion Formation and Breakdown 6
1.5 Interaction Energies (Forces) between Emulsion Droplets and Their
Combinations 8
1.5.1 van der Waals Attraction 8
1.5.2 Electrostatic Repulsion 9
1.5.3 Steric Repulsion 12
1.6 Adsorption of Surfactants at the Liquid/Liquid Interface 14
1.6.1 The Gibbs Adsorption Isotherm 14
1.6.2 Mechanism of Emulsification 17
1.6.3 Methods of Emulsification 19
1.6.4 Role of Surfactants in Emulsion Formation 21
1.6.5 Role of Surfactants in Droplet Deformation 22
1.7 Selection of Emulsifiers 26
1.7.1 The Hydrophilic-Lipophilic Balance (HLB) Concept 26
1.7.2 The Phase Inversion Temperature (PIT) Concept 29
1.7.3 The Cohesive Energy Ratio (CER) Concept 31
1.7.4 The Critical Packing Parameter (CPP) for Emulsion Selection 32
1.8 Creaming or Sedimentation of Emulsions 35
1.8.1 Creaming or Sedimentation Rates 36
1.8.2 Prevention of Creaming or Sedimentation 37
1.9 Flocculation of Emulsions 40
1.9.1 Mechanism of Emulsion Flocculation 40
[Link] Flocculation of Electrostatically Stabilized Emulsions 41
[Link] Flocculation of Sterically Stabilized Emulsions 42
1.9.2 General Rules for Reducing (Eliminating) Flocculation 43
1.10 Ostwald Ripening 44
1.11 Emulsion Coalescence 45
1.11.1 Rate of Coalescence 46
1.11.2 Phase Inversion 47
1.12 Rheology of Emulsions 48
1.12.1 Interfacial Rheology 48
[Link] Interfacial Tension and Surface Pressure 48
[Link] Interfacial Shear Viscosity 49
1.12.2 Measurement of Interfacial Viscosity 49
1.12.3 Interfacial Dilational Elasticity 50
1.12.4 Interfacial Dilational Viscosity 51
1.12.5 Non-Newtonian Effects 51
1.12.6 Correlation of Emulsion Stability with Interfacial Rheology 51
[Link] Mixed Surfactant Films 51
[Link] Protein Films 51
1.13 Bulk Rheology of Emulsions 53
1.13.1 Analysis of the Rheological Behavior of Concentrated Emulsions 54
1.14 Experimental ηr - φ Curves 57
1.14.1 Experimental ηr - φ Curves 58
1.14.2 Influence of Droplet Deformability 58
1.15 Viscoelastic Properties of Concentrated Emulsions 59
1.15.1 High Internal Phase Emulsions (HIPEs) 61
1.15.2 Deformation and Breakup of Droplets in Emulsions during Flow 66
References 73
2 Emulsion Formation in Membrane and Microfluidic Devices 77
Goran T. Vladisavljević, Isao Kobayashi, and Mitsutoshi Nakajima
2.1 Introduction 77
2.2 Membrane Emulsification (ME) 78
2.2.1 Direct Membrane Emulsification 78
2.2.2 Premix Membrane Emulsification 79
2.2.3 Operating Parameters in Membrane Emulsification 80
2.2.4 Membrane Type 80
[Link] Surfactant Type 80
[Link] Transmembrane Pressure and Wall Shear Stress 81
2.3 Microfluidic junctions and Flow-Focusing Devices 82
2.3.1 Microfluidic Junctions 82
2.3.2 Microfluidic Flow-Focusing Devices (MFFD) 83
2.4 Microfluidic Devices with Parallel Microchannel Arrays 85
2.4.1 Grooved-Type Microchannel Arrays 86
2.4.2 Straight-through Microchannel Arrays 88
2.5 Glass Capillary Microfluidic Devices 89
2.6 Application of Droplets Formed in Membrane and Microfluidic Devices 93
2.7 Conclusions 93
Acknowledgments 94
References 94
3 Adsorption Characteristics of Ionic Surfactants at Water/
Hexane Interface Obtained by PAT and ODBA 99
Nenad Mucic, Vincent Pradines, Aliyar Javadi, Altynay Sharipova,
Jürgen Krägel, Martin E. Leser, Eugene V. Aksenenko,
Valentin B. Fainerman, and Reinhard Miller
3.1 Introduction 99
3.2 Experimental Tools 99
3.3 Theory 101
3.4 Results 102
3.5 Summary 107
Acknowledgments 107
References 107
4 Measurement Techniques Applicable to the Investigation
of Emulsion Formation during Processing 109
Nima Niknafs, Robin D. Hancocks, and Ian T. Norton
4.1 Introduction 109
4.2 Online Droplet Size Measurement Techniques 112
4.2.1 Laser Systems 112
4.2.2 Sound Systems 115
4.2.3 Direct Imaging 115
4.2.4 Other Techniques 118
4.3 Techniques Investigating Droplet Coalescence 121
4.4 Concluding Remarks 123
References 125
5 Emulsification in Rotor-Stator Mixers 127
Andrzej W. Pacek, Steven Hall, Michael Cooke, and Adam J. Kowalski
5.1 Introduction 127
5.2 Classification and Applications of Rotor-Stator Mixers 128
5.2.1 Colloid Mills 129
5.2.2 In-Line Radial Discharge Mixers 130
5.2.3 Toothed Devices 131
5.2.4 Batch Radial Discharge Mixers 132
5.2.5 Design and Arrangement 133
5.2.6 Operation 136
5.3 Engineering Description of Emulsification/Dispersion Processes 138
5.3.1 Drop Size Distributions and Average Drop Sizes 138
5.3.2 Drop Size in Liquid-Liquid Two-Phase Systems - Theory 140
5.3.3 Maximum Stable Drop Size in Laminar Flow 141
5.3.4 Maximum Stable Drop Size in Turbulent Flow 142
5.3.5 Characterization of Flow in Rotor-Stator Mixers 143
[Link] Shear Stress 143
[Link] Average Energy Dissipation Rate 144
[Link] Power Draw 144
5.3.6 Average Drop Size in Liquid-Liquid Systems 145
5.3.7 Scaling-up of Rotor-Stator Mixers 147
5.4 Advanced Analysis of Emulsification/Dispersion Processes
in Rotor-Stator Mixers 152
5.4.1 Velocity and Energy Dissipation Rate in Rotor-Stator Mixers 153
[Link] Batch Rotor-Stator Mixers 154
[Link] In-Line Rotor-Stator Mixers 157
5.4.2 Prediction of Drop Size Distributions during Emulsification 160
5.5 Conclusion 163
Nomenclature 163
References 165
6 Formulation, Characterization, and Property Control
of Paraffin Emulsions 169
Jordi Esquena and Jon Vilasau
6.1 Introduction 169
6.1.1 Industrial Applications of Paraffin Emulsions 170
6.1.2 Properties of Paraffin 170
6.1.3 Preparation of Paraffin Emulsions 172
6.2 Surfactant Systems Used in Formulation of Paraffin Emulsions 174
6.2.1 Phase Behavior 175
6.3 Formation and Characterization of Paraffin Emulsions 178
6.4 Control of Particle Size 181
6.5 Stability of Paraffin Emulsions 185
6.5.1 Stability as a Function of Time under Shear (Orthokinetic Stability) 185
6.5.2 Stability as a Function of Freeze-Thaw Cycles 186
6.5.3 Stability as a Function of Electrolytes 189
6.6 Conclusions 195
Acknowledgments 196
References 196
7 Polymeric O/W Nano-emulsions Obtained by the Phase
Inversion Composition (PIC) Method for Biomedical
Nanoparticle Preparation 199
Gabriela Calderó and Conxita Solans
7.1 Introduction 199
7.2 Phase Inversion Emulsification Methods 200
7.3 Aspects on the Choice of the Components 201
7.4 Ethylcellulose Nano-Emulsions for Nanoparticle Preparation 202
7.5 Final Remarks 204
Acknowledgments 205
References 205
8 Rheology and Stability of Sterically Stabilized Emulsions 209
Tharwat F. Tadros
8.1 Introduction 209
8.2 General Classification of Polymeric Surfactants 210
8.3 Interaction between Droplets Containing Adsorbed Polymeric
Surfactant Layers: Steric Stabilization 212
8.3.1 Mixing Interaction Gmix 213
8.3.2 Elastic Interaction Gel 214
8.4 Emulsions Stabilized by Polymeric Surfactants 216
8.4.1 W/O Emulsions Stabilized with PHS-PEO-PHS Block Copolymer 219
8.5 Principles of Rheological Techniques 220
8.5.1 Steady State Measurements 220
[Link] Bingham Plastic Systems 221
[Link] Pseudoplastic (Shear Thinning) System 221
[Link] Herschel-Bulkley General Model 222
8.5.2 Constant Stress (Creep) Measurements 222
8.5.3 Dynamic (Oscillatory) Measurements 223
8.6 Rheology of Oil-in-Water (O/W) Emulsions Stabilized with
Poly(Vinyl Alcohol) 226
8.6.1 Effect of Oil Volume Fraction on the Rheology of the Emulsions 226
8.6.2 Stability of PVA-Stabilized Emulsions 229
8.6.3 Emulsions Stabilized with an A-B-A Block Copolymer 236
8.6.4 Water-in-Oil Emulsions Stabilized with A-B-A Block Copolymer 240
References 245
Index 247
oprac. BPK