Micelles, Membranes, Microemulsions, and Monolayers

1 Statistical Thermodynamics of Amphiphile Self-Assembly: Structure and Phase Transitions in Micellar Solutions.- 1.1 Introduction.- 1.2 Amphiphile Self-Assembly in Dilute Solutions.- 1.2.1 Underlying Statistical Thermodynamics.- 1.2.2 The Equilibrium Size Distribution.- 1.2.3 From Monomers to Aggregates—the CMC.- 1.2.4 Micellar Growth.- 1.2.5 Other Aggregates.- 1.2.6 The Aggregate’s Partition Function: Rotation-Translation Contributions.- 1.3 Molecular Organization of Aggregates.- 1.3.1 Separation of Head and Tail Contributions.- 1.3.2 Hydrocarbon Droplet Models.- 1.3.3 Chain Packing Statistics.- 1.3.4 Elastic Properties.- 1.4 Interaction Effects in Dilute Solution and Beyond.- 1.4.1 Isotropic Solution Effects.- 1.4.2 Isotropic-to-Nematic Transition.- 1.4.3 Nematic-to-Hexagonal Transition.- 1.4.4 Interaction-induced Suppression of Curvature in Lamellar Phases.- 1.5 Concluding Discussion.- 2 Micellar Growth, Flexibility and Polymorphism in Dilute Solutions.- 2.1 Introduction.- 2.2 Globule to Rod Transformation.- 2.2.1 Scattering Probes and Concentration Effects.- 2.2.2 Local Structure.- 2.2.3 Thermodynamics of the Growth.- 2.3 Polymerlike Behavior.- 2.3.1 Flexibility.- 2.3.2 The Semi Dilute Regime.- 2.4 Bidimensional Aggregation.- 2.4.1 The Swollen Lamellar Phase (L?).- 2.4.2 The Anomalous Isotropic Phase (L3).- 2.5 The Physical Basis of Micellar Polymorphism.- 2.6 Connection with Microemulsions.- 3 Micellar Liquid Crystals.- 3.1 Introduction.- 3.2 Nomenclature.- 3.3 Preparation of Stable Nematic Phases.- 3.4 Factors Governing Size and Shape of Micelles in Concentrated Solutions.- 3.5 Experimental Characterization of Nematic Phases.- 3.5.1 Polarizing Optical Microscopy.- 3.5.2 NMR Spectroscopy.- 3.5.3 X-ray Diffraction.- 3.6 Phase Transitions in Micellar Solutions.- 3.6.1 I-to-ND+ Transition in the CsPFO/Water System.- 3.6.2 ND+-to-LD Transition in the CsPFO/Water System.- 3.6.3 ND--to-NB-to-NC+ Transitions in the Potassium Laurate/Decanol Water System.- 3.6.4 Nematic-to-Cholesteric Transitions Induced by Chiral Solutes.- 3.7 Conclusions.- 4 Geometrical Foundation of Mesomorphic Polymorphism.- 4.1 Introduction.- 4.2 Mesophases as Structures of Films.- 4.3 Frustration, Curved Spaces and Disclinations.- 4.3.1 Principle of the Method.- 4.3.2 A Simple 2-D Example.- 4.3.3 Concluding Remark.- 4.4 The Periodic System of Parallel Films.- 4.4.1 Topologies.- 4.4.2 Sequence.- 4.4.3 Ordered Organizations.- 4.5 Comments.- 4.6 Conclusion.- 4.7 Appendix.- 4.7.1 S3 in Toroidal Coordinates.- 4.7.2 S3 in Spherical Coordinates.- 5 Contents Lamellar Phases: Effect of Fluctuations (Theory).- 5.1 Introduction.- 5.2 Model of Isolated Membranes.- 5.2.1 The Deformation Energy of Two-dimensional Membranes.- 5.2.2 The Harmonic Approximation for the Computation of Fluctuation Amplitudes.- 5.2.3 The Persistence Length.- 5.2.4 Renormalization of Bending Rigidity k by Fluctuations.- 5.3 Membranes in Interaction.- 5.3.1 Statement of the Problem and Analogy with Wetting and Incommensurate-Commensurate Transitions.- 5.3.2 Review of Microscopic Interactions between Membranes (in Absence of Fluctuations).- 5.3.3 The Steric Interaction as the Ideal Gas Limit for Lamellar Phases.- 5.3.4 Lamellar Phases: The Smectic Liquid Crystal Analogy for the Steric Interaction.- 5.3.5 Universality of the z-2 Power Law and Numerical Value of the Coefficient ? of the Steric Interaction between Membranes.- 5.3.6 Entropic Undulation Interaction between Membranes or Interfaces with Non-zero Surface Tension ?.- 5.3.7 Thermal Undulations of Membranes: Extensions.- 5.4 Conclusion.- 5.5 Appendix.- 5.5.1 Heuristic Derivation of the Renormalization of k.- 5.5.2 Steric Interaction between Cylinders in a Hexagonal Phase.- 5.5.3 Short Range Non-universal Behavior.- 5.5.4 Steric Interaction in Two Dimensions: Exact Results.- 6 Lyotropic Lamellar L? Phases.- 6.1 Introduction.- 6.2 Phase Diagrams.- 6.2.1 Binary Systems.- 6.2.2 Multicomponent Systems.- 6.3 Membranes and Smectic Properties.- 6.3.1 Membrane Elasticity and Interactions.- 6.3.2 Elasticity and Hydrodynamics of the Two-component Smectic A.- 6.3.3 Microscopic Models for the Lyotropic Smectic A Phase.- 6.4 Static Scattering Studies of Lyotropic Lamellar Phases...- 6.4.1 Peak Position Analysis.- 6.4.2 Small Angle Scattering.- 6.4.3 Line Shape Analysis.- 6.5 Dynamic Light Scattering.- 6.5.1 Undulation Mode.- 6.5.2 Baroclinic Mode.- 6.6 Conclusion.- 7 The Structure of Microemulsions: Experiments.- 7.1 Introduction.- 7.2 The Interfacial Film of Surfactant.- 7.2.1 Composition.- 7.2.2 Density.- 7.2.3 Local State of the Film.- 7.3 Dilute Microemulsions.- 7.3.1 Polydispersity and Shape Fluctuations.- 7.3.2 Interactions between Droplets.- 7.4 Structure of Concentrated Microemulsions.- 7.4.1 Different Types of Structure.- 7.4.2 Dynamical Characterization of the Different Structures.- 7.4.3 Scattering Studies of Concentrated Droplet Microemulsions.- 7.4.4 Structure of Random Microemulsions with a Flexible Interfacial Film.- 7.5 Conclusions.- 7.6 Appendix: X-ray and Neutron Scattering.- 8 Lattice Theories of Microemulsions.- 8.1 Introduction: Aims of a Lattice Theory of Microemulsions.- 8.1.1 Phase Behavior.- 8.1.2 Low Surface Tensions.- 8.1.3 Structure.- 8.1.4 Efficient Solubilization of Oil and Water.- 8.1.5 Relation to Lyotropic Phases.- 8.2 The Lattice Formulation.- 8.2.1 The Widom-Wheeler Model.- 8.2.2 The Three Component Model.- 8.2.3 The Alexander Model.- 8.2.4 Other Lattice Models.- 8.3 Some Results of the Three Component Model.- 8.3.1 Phase Behavior.- 8.3.2 Microemulsion Structure.- 8.3.3 Surface Tension.- 8.3.4 Wetting.- 8.3.5 Solubilization of Oil and Water.- 8.3.6 Surfactants vs. Amphiphiles.- 8.4 Some Results of Other Lattice Models.- 8.4.1 The Widom-Wheeler Model.- 8.4.2 The Alexander Model.- 8.5 Comparison with Phenomenological Models.- 9 Fluctuating Interfaces and the Structure of Microemulsions.- 9.1 Introduction.- 9.2 Experimental Observations and Theoretical Models.- 9.2.1 Experimental Observations.- 9.2.2 Theoretical Models.- 9.2.3 Interfacial Model.- 9.3 Fluctuation of Microemulsions.- 9.3.1 Spherical Droplets.- 9.3.2 Cylindrical Globules.- 9.4 Lamellar and Random/Bicontinuous Systems.- 9.4.1 Fluctuations of Lamellar Systems.- 9.4.2 Film Fluctuations and Thermodynamics of Random Microemulsions.- 9.4.3 Scattering from Random Microemulsions.- 9.4.4 Sponge-like L3 Phases in Two-component Systems.- 9.5 Outstanding Problems.- 10 Interfacial Tension: Theory and Experiment.- 10.1 Introduction.- 10.1.1 Monolayer Adsorption.- 10.1.2 Soluble Monolayers.- 10.2 Experimental Techniques and Data Analysis.- 10.2.1 Ellipsometry and Reflectivity.- 10.2.2 Measurement of Thermal Roughness.- 10.2.3 Dynamic Surface Light Scattering Measurement of Low Surface Tensions.- 10.3 The Bending Elasticity of Monolayers: Experimental Results.- 10.3.1 Monolayers at the Free Surface of Water.- 10.3.2 Monolayers at the Oil-Water Interface.- 10.4 Experimental Study of Low Surface Tensions in Winsor Equilibrium.- 10.5 Structure of the Oil Microemulsion and the Water Microemulsion Interfaces in Winsor Equilibria.- 11 Critical Behavior of Surfactant Solutions.- 11.1 Introduction.- 11.2 Structure and Interactions.- 11.2.1 Micellar Solutions.- 11.2.2 Microemulsions.- 11.3 Critical Phenomena.- 11.3.1 General Considerations.- 11.3.2 Critical Behavior in Fluids and Multicomponent Mixtures.- 11.3.3 Experimental Results on Critical Behavior of Micellar and Microemulsion Systems.- 11.4 Conclusion.- 12 Structures and Phase Transitions in Langmuir Monolayers.- 12.1 Introduction.- 12.2 The Experimental Situation.- 12.2.1 Classical Studies.- 12.2.2 New Experimental Methods.- 12.2.3 The Current Situation.- 12.3 Equilibrium Theories of Monolayers.- 12.3.1 Fluid-Fluid Phase Transitions and Chain Statistics.- 12.3.2 Pattern Formation and Domain Shapes.- 12.3.3 Dipolar and Charged Langmuir Monolayers.- 12.4 Dynamical Properties of Amphiphilic Monolayers.- 12.4.1 Lateral Diffusion in Monolayers.- 12.4.2 Dynamics of Phase Separation in Monolayers.- 12.5 Conclusions and Future Prospects.