Micelles, Membranes, Microemulsions, and Monolayers: (Partially Ordered Systems)

Over the last decades, the study of surfactants (detergents, for example) has been profoundly changed by ideas and techniques from physics, chemistry, and materials science. Among these are: self assembly; critical phenomena, scaling, and renormalization; high-resolution scattering, and magnetic resonance spectroscopy. This book represents the first systematic account of these new developments, providing both a general introduction to the subject as well as a review of recent developments. The book will be a very useful tool for the biophysist, biochemist or physical chemist working in the field of surfactants.

Table of Contents:
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.