Emulsions, Microemulsions and Foams

Preface
Acknowledgements
Contents
Acronyms
Chapter 1: Interfaces Between Two Fluids
1.1 Interfaces Between Pure Fluids
1.1.1 Surface Tension, Contact Angle, Wetting
1.1.2 Gibbs Description of the Surface Region
1.1.3 Thermal Fluctuations
1.2 Insoluble Surface Layers
1.2.1 Surface Pressure
1.2.2 Surface Rheology (Compression, Shear and Bending, Viscoelasticity)
1.2.2.1 Linear Viscoelasticity; Planar Surfaces
1.2.2.2 Solid Monolayers
1.2.2.3 Surface Viscosity
1.2.2.4 Non-planar Surfaces
1.2.2.5 Curvature Elasticity
1.2.3 Monolayers of Small Molecules
1.2.4 Polymer Monolayers
1.2.5 Soluble Protein Monolayers
1.2.6 Asphaltene Monolayers
1.2.7 Particle Monolayers
1.3 Soluble Surface Layers: Case of Surfactants
1.3.1 Gibbs Description of the Interfacial Region
1.3.2 Area per Surfactant Molecule
1.3.3 Aqueous Solutions of Salts
1.3.4 Equations of State, Energy Sorption Barriers
1.3.5 Solid Surfactant Monolayers
1.3.6 Non-equilibrium Systems: Sorption and Transfer Kinetics, ``Dynamic´´ Tension
1.3.6.1 Diffusion-Controlled Adsorption
1.3.6.2 Adsorption Barriers
1.3.6.3 Micellar Solutions
1.3.7 Surface Rheology: Resistance to Compression and Shear, Viscoelasticity
1.4 Monolayers of Other Surface-Active Species
1.4.1 Polymer and Protein Monolayers
1.4.2 Asphaltenes and Particle Layers
1.4.3 Mixed Layers
1.5 Measurement Methods
1.5.1 Surface Tension
1.5.2 Adsorption and Desorption Kinetics
1.5.3 Measurement of Other Equilibrium Properties
1.5.4 Surface Shear Rheology
1.5.5 Surface Compression Rheology
1.5.6 Solid Monolayers
1.5.7 Curvature Elasticity
1.6 Summary
Chapter 2: Thin Liquid Films
2.1 Film Formation
2.2 Film Elasticity
2.3 Film Thinning
2.3.1 Vertical Films
2.3.2 Curved Films
2.3.3 Horizontal Films
2.3.3.1 Surfactant-Free Films
2.3.3.2 Surfactant-Stabilized Films
2.4 Interaction Between Surfaces (van der Waals, Electrostatic, and Short Range), Disjoining Pressure
2.4.1 Definition of the Disjoining Pressure
2.4.2 Contributions to the Disjoining Pressure
2.4.2.1 Electrostatic Contributions
2.4.2.2 Van der Waals Contributions
2.4.2.3 Short-Range Forces
2.4.2.4 Other Types of Forces
2.4.2.5 Experimental Investigations
2.5 Oscillatory Forces, Film Stratification
2.5.1 Surfactant-Stabilized Films
2.5.2 Films Made from Amphiphilic Polymer Solutions
2.5.3 Films Made from Mixed Polymer-Surfactant Solutions
2.6 Film Rupture
2.6.1 Films Made of Pure Liquids
2.6.2 Films Made of Dilute Surfactant Solutions. Models
2.6.3 Films Made of Concentrated Surfactant Solutions. Rupture During Thinning
2.6.4 Rupture of Equilibrium Films Made of Concentrated Surfactant Solutions. Models
2.6.5 Films Made of Surfactant Solutions. Experiments
2.6.6 Films Made with Surfactants and Polymers, Proteins, or Particles
2.6.7 Oil Films
2.6.8 Opening of Holes
2.7 Measurement Methods
2.7.1 Vertical Films
2.7.2 Curved Films
2.7.3 Horizontal Films
2.8 Summary
Chapter 3: Self-Assembly in Bulk
3.1 Surfactant Self-Assembly
3.1.1 Spherical Surfactant Micelles
3.1.1.1 Critical Micellar Concentration: Micelle Aggregation Number and Polydispersity
3.1.1.2 Exchanges with Bulk
3.1.2 Other Surfactant Aggregates: Dilute Solutions
3.1.2.1 Surfactant Packing Parameter
3.1.2.2 Spontaneous Curvature and Curvature Elastic Constants
3.1.3 Bilayers and Vesicles
3.1.4 Micelles in Non-aqueous Solvents
3.1.5 Bulk Aggregates: Concentrated Solutions
3.2 Mixed Solutions
3.2.1 Polymer Solutions
3.2.1.1 Neutral Polymers
3.2.1.2 Polyelectrolytes
3.2.1.3 Scattering by Semi-dilute Polymer Solutions and Osmotic Pressure
3.2.2 Surfactant-Polymer Mixed Solutions
3.2.2.1 Cooperative Binding
3.2.2.2 Polyelectrolyte Chain Collapse
3.2.2.3 Formation of Multi-chain Aggregates
3.2.2.4 Precipitation Regime
3.2.3 Surfactant-Particle Mixed Dispersions
3.3 Microemulsions
3.3.1 Microemulsion Types, Spontaneous Curvature of the Surfactant Monolayer
3.3.2 Microemulsion Stability
3.3.3 Droplet Microemulsions: Emulsification Failure and Other Solubility Limits
3.3.4 Bicontinuous Microemulsions
3.3.5 Phase Diagrams
3.3.6 Dynamic Properties of Droplet Microemulsions: Percolation, Exchange, and Shape Fluctuations
3.3.7 Ultralow Interfacial Tensions and Their Origin
3.3.8 Microemulsion Applications
3.4 Summary
Chapter 4: Emulsions and Foams
4.1 Emulsion and Foam Structure
4.2 Foaming and Emulsification
4.2.1 Emulsion Type
4.2.1.1 Bancroft Rule
4.2.1.2 Emulsion Inversion
4.2.2 Emulsification and Foaming Devices
4.2.2.1 Injection of a Fluid into a Stationary Second Fluid
4.2.2.2 Co-injection of Fluids. Microfluidics
4.2.2.3 Breakup of Drops/Bubbles Under Shear
4.2.2.4 Phase Transitions
4.2.2.5 Spontaneous Emulsification
4.2.3 Physicochemical Factors Controlling Drop/Bubble Size
4.2.3.1 Adsorption Kinetics
4.2.3.2 Surface Coverage
4.2.3.3 Surface Rheology
4.3 Foam and Emulsion Properties
4.3.1 Electrical Conductivity
4.3.2 Osmotic Pressure
4.3.3 Rheology
4.3.3.1 Dilute Dispersions
4.3.3.2 Concentrated Dispersions. Linear Regime (Quasi-static)
4.3.3.3 Linear Regime. Vicinity of Jamming
4.3.3.4 Linear Regime. Dissipation
4.3.3.5 Non-linear Plastic Regime and Yield
4.3.3.6 Flow Regime
4.3.3.7 Flow in Smaller Dimensions. Case of Monodisperse Foams
4.4 Foam and Emulsion Stability
4.4.1 Sedimentation/Creaming of Emulsions. Foam Drainage
4.4.1.1 Fluid Dispersions
4.4.1.2 Foam Drainage
4.4.2 Ripening
4.4.2.1 Ostwald Ripening: Influence of the Surface-Active Agent
4.4.2.2 Coarsening of Concentrated Dispersions. Case of 2D Foams
4.4.2.3 Coarsening of 3D Foams, Theory
4.4.2.4 Coarsening of 3D Foams; Experiments
4.4.2.5 T1 Rearrangements
4.4.3 Coalescence of Bubbles/Drops
4.4.3.1 Unstable Emulsions and Foams
4.4.3.2 Long-Lived Emulsion and Foams. Coalescence at Rest
4.4.3.3 Limited Coalescence
4.4.3.4 Forced Coalescence
4.4.4 How to Obtain Very Stable Emulsions and Foams
4.4.4.1 Arrest of Sedimentation, Creaming, or Drainage
4.4.4.2 Arrest of Ripening
4.4.4.3 Arrest of Coalescence
4.4.5 Antifoams, Defoamers, Demulsifiers
4.4.5.1 Antifoams for Aqueous Foams
4.4.5.2 Antifoams for Non-aqueous Foams
4.4.5.3 Demulsifiers
4.5 Why Are Bubbles Larger than Drops; Why Are Emulsions Longer Lived than Foams?
4.6 Practical Applications
4.6.1 Emulsion Applications
4.6.2 Foam Applications
4.7 Summary
Appendices
A1 Calculation of the Surface Tension by van der Waals
A2 Capillary Length
A3 Adsorption Kinetics and Equation of State of Reversibly Adsorbed Surfactant Monolayers
A3.1 Diffusion-Limited Adsorption
A3.2 Kinetic-Limited Adsorption
A3.3 Ionic Surfactants and Electrostatic Barriers
A4 Levich-Lucassen-van den Tempel Model for the Frequency Variation of the Surface Compression Elastic Moduli
A5 Waves on Surfaces and on Films
A5.1 Capillary Waves at the Surface of Pure Fluids
A5.2 Case of the Surface of a Fluid Covered by a Monolayer
A5.3 Waves on Thin Films
A5.5.1 Undulation Mode
A5.3.2 Peristaltic Mode
A6 Vertical Liquid Films Held in Rectangular Frames
A6.1 Frankel Law
A6.2 Film Thinning, Rigid Surfaces
A7 Thinning of Horizontal Liquid Films
A7.1 Films with Rigid Surfaces
A7.2. Flat Films with Rigid Surfaces
A7.3. Flat Films with Mobile Surfaces
A8 Vrij´s Model for Film Rupture
A9 Elasticity of 2D Dry Foams: Princen calculation
A10 Coarsening of 2D Dry Foams (Bubbles Confined Between Two Plates): Von Neumann´s Law
A11 Coagulation in Dispersions: Von Smoluchowski Model
Glossary
References
Index