Surfactant Science and Technology

TLDR: This chapter discusses the chemistry of Surfactants in Solution: Micellization and Related Association Phenomena, as well as their applications in solubilization, microemulsions, and micellar Catalysis.

Abstract: Preface to the Third Edition. Chapter 1. An Overview of Surfactant Science and Technology. 1.1. A Brief History of Surfactant Science and Technology. 1.2. The Economic Importance of Surfactants. 1.3. Some Traditional and Non-Traditional Applications of Surfactants. 1.3.1. Detergents and Cleaners. 1.3.2. Cosmetics and Personal Care Products. 1.3.3. Textiles and fibers. 1.3.4. Leather and furs. 1.3.5. Paints, Lacquers and Other Coating Products. 1.3.6. Paper and Cellulose Products. 1.3.7. Mining and Ore Flotation. 1.3.8. Metal Processing Industries. 1.3.9. Plant Protection and Pest Control. 1.3.10. Foods and Food Packaging. 1.3.11. The Chemical Industry. 1.3.12. Oilfields Chemicals and Petroleum Production. 1.3.13. Plastics and Composite Materials. 1.3.14. Pharmaceuticals. 1.3.15. Medicine and Biochemical Research. 1.3.16. Other "Hi-Tech" Areas. 1.4. Surfactant Consumption. 1.5. The Economic and Technological Future. 1.6. Surfactants In the Environment. 1.7. Petrochemical vs. "Renewable" Oleochemical-based Surfactants. 1.8. A Surfactant Glossary. Chapter 2. The Organic Chemistry of Surfactants. 2.1. Basic Surfactant Building Blocks. 2.1.1. Basic Surfactant Classifications. 2.1.2. Making A Choice. 2.2. The Generic Anatomy of Surfactants. 2.2.1. The Many Faces of Dodecane. 2.2.2. Surfactant Solubilizing Groups. 2.2.3. Common Surfactant Hydrophobic Groups. 2.2.3.1. The Natural Fatty Acids. 2.2.3.2. Saturated Hydrocarbons or Paraffins. 2.2.3.3. Olefins. 2.2.3.4. Alkyl benzenes. 2.2.3.5. Alcohols. 2.2.3.6. Alkyl phenols. 2.2.3.7. Polyoxypropylenes. 2.2.3.8. Fluorocarbons. 2.2.3.9. Silicone Surfactants. 2.2.3.10. Miscellaneous Biological Structures. 2.3. The Systematic Classification of Surfactants. 2.4. Anionic Surfactants. 2.4.1. Sulfate Esters. 2.4.1.1. Fatty Alcohol Sulfates. 2.4.1.2. Sulfated Fatty Acid Condensation Products. 2.4.1.3. Sulfated Ethers. 2.4.1.4. Sulfated Fats and Oils. 2.4.2. Sulfonic Acid Salts. 2.4.2.1. Aliphatic Sulfonates. 2.4.2.2. Alkylaryl Sulfonates. 2.4.2.3. a-Sulfocarboxylic Acids and Their Derivatives. 2.4.2.4. Miscellaneous Sulfo-Ester and Amide Surfactants. 2.4.2.5. Alkyl Glyceryl Ether Sulfonates. 2.4.2.6. Lignin sulfonates. 2.4.3. Carboxylate Soaps and Detergents. 2.4.4. Phosphoric Acid Esters and Related Surfactants. 2.5. Cationic Surfactants. 2.6. Nonionic Surfactants. 2.6.1. Polyoxyethylene-Based Surfactants. 2.6.2. Derivatives of Polyglycerols and Other Polyols. 2.6.3. Block Copolymer Nonionic Surfactants. 2.6.4. Miscellaneous Nonionic Surfactants. 2.7. Amphoteric Surfactants. 2.7.1. Imidazoline Derivatives. 2.7.2. Surface Active Betaines and Sulfobetaines. 2.7.3. Phosphatides and Related Amphoteric Surfactants. Problems. Chapter 3. Fluid Surfaces and Interfaces. 3.1. Molecules At Interfaces. 3.2. Interfaces and Adsorption Phenomena. 3.2.1. A Thermodynamic Picture of Adsorption. 3.2.2. Surface and Interfacial Tensions. 3.2.3. The Effect of Surface Curvature. 3.3. The Surface Tension of Solutions. 3.3.1. Surfactants and the Reduction of Surface Tension. 3.3.2. Efficiency, Effectiveness, and Surfactant Structure. Problems. Chapter 4. Surfactants in Solution: Monolayers and Micelles. 4.1. Surfactant Solubility. 4.2. The Phase Spectrum of Surfactants In Solution. 4.3. The History and Development of Micellar Theory. 4.3.1. Manifestations of Micelle Formations. 4.3.2. Thermodynamics of Dilute Surfactant Solutions. 4.3.3. Classical Theories of Micelle Formation. 4.3.4. Free Energy of Micellization. 4.4. Molecular Geometry and the Formation of Association Colloids. 4.5. Experimental Observations of Micellar Systems. 4.5.1. Micellar Aggregation Numbers. 4.5.2. The Critical Micelle Concentration. 4.5.3. The Hydrophobic Group. 4.5.4. The Hydrophilic Group. 4.5.5. Counter-ion Effects on Micellization. 4.5.6. The Effects of Additives On the Micellization Process. 4.5.6.1. Electrolyte Effects on Micelle Formation. 4.5.6.2. The Effect of pH. 4.5.6.3. The Effects of Added Organic Materials. 4.5.7. The Effect of Temperature On Micellization. 4.6. Micelle Formation In Mixed Surfactant Systems. 4.7. Micelle Formation In Nonaqueous Media. 4.7.1. Aggregation in Polar Organic Solvents. 4.7.2. Micelles in Nonpolar Solvents. Problems. Chapter 5. Higher Level Surfactant Aggregate Structures: Liquid Crystals, Continuous Bi-phases, and Microemulsions. 5.1. The Importance of Surfactant Phase Information. 5.2. Amphiphilic Fluids. 5.2.1. Liquid Crystalline, Bicontinuous, and Microemulsion Structures. 5.2.2. "Classical" Liquid Crystals. 5.2.3. Liquid Crystalline Phases in Simple Binary Systems. 5.3. Temperature and Additive Effects on Phase Behavior. 5.4. Some Current Theoretical Analyses of Novel Mesophases. 5.5. Vesicles and Bilayer Membranes. 5.5.1. Vesicles. 5.5.2. Polymerized Vesicles. 5.6. Biological Membranes. 5.6.1. Some Biological Implications of Mesophases. 5.6.2. Membrane Surfactants and Lipids. 5.7. Microemulsions. 5.7.1. Surfactants, Co-surfactants, and Microemulsion Formation. 5.7.1.1. Ionic Surfactant Systems. 5.7.1.2. Nonionic Surfactant Systems. 5.7.2. Applications. Problems. Chapter 6. Solubilization and Micellar and Phase Transfer Catalysis. 6.1. Solubilization In Surfactants Micelles. 6.1.1. The "Geography" of Solubilization in Micelles. 6.1.2. Surfactant Structure and the Solubilization Process. 6.1.3. Solubilization and the Nature of the Additive. 6.1.4. The Effect of Temperature on Solubilization Phenomena. 6.1.5. The Effects of Non-electrolyte Solutes. 6.1.6. The Effects of Added Electrolyte. 6.1.7. Miscellaneous Factors Affecting Solubilization. 6.2. Micellar Catalysis. 6.2.1. Micellar Catalysis in Aqueous Solution. 6.2.2. Micellar Catalysis in Nonaqueous Solvents. 6.3. Phase Transfer Catalysis. 6.3.1. Cross-phase Reactions. 6.3.2. Some Examples of PTC Applications. 6.3.2.1. Alkylnitrile Synthesis. 6.3.2.2. Dihalocyclopropanes. 6.3.3. Some Notes on the Use of PTC. 6.3.4. Some Requirements for a Successful PTC Reaction. Problems. Chapter 7. Polymeric Surfactants and Surfactant-Polymer Interactions. 7.1. Polymeric Surfactants and Amphiphiles. 7.2. Some Basic Chemistry of Polymeric Surfactant Synthesis. 7.2.1. The Modification of Natural Cellulosics, Gums, and Proteins. 7.2.2. Synthetic Polymeric Surfactants. 7.3. Polymeric Surfactants at Interfaces: Structure & Methodology. 7.4. The Interactions of "Normal" Surfactants with Polymers. 7.4.1. Surfactant-Polymer Complex Formation. 7.4.2. Nonionic Polymers. 7.4.3. Ionic Polymers and Proteins. 7.5. Polymers, Surfactants, and Solubilization. 7.6. Surfactant-Polymer Interactions in Emulsion Polymerization. Problems. Chapter 8. Foams and Liquid Aerosols. 8.1. The Physical Basis for Foam Formation. 8.2. The Role of Surfactant in Foams. 8.2.1. Foam Formation and Surfactant Structure. 8.2.2. Amphiphilic Mesophases and Foam Stability. 8.2.3. The Effects of Additives on Surfactant Foaming Properties. 8.3. Foam Inhibition. 8.4. Chemical Structures of Antifoaming Agents. 8.5. A Summary of the Foaming and Antifoaming Activity of Additives. 8.6. The Spreading Coefficient. 8.7. Liquid Aerosols. 8.7.1. The Formation of Liquid Aerosols. 8.7.1.1. Spraying and Related Mechanisms of Mist and Fog Formation. 8.7.1.2. Nozzle Atomization. 8.7.1.3. Rotary Atomization. 8.7.2. Aerosol Formation by Condensation. 8.7.3. Colloidal Properties of Aerosols. 8.7.3.1. The Dynamics of Aerosol Movement. 8.7.3.2.Colloidal Interactions in Aerosols. Problems. Chapter 9. Emulsions. 9.1. The Liquid/Liquid Interface. 9.2. General Considerations of Emulsion Stability. 9.2.1. The Lifetimes of Typical Emulsions. 9.2.2. Theories of Emulsion Stability. 9.3. Emulsion Type and the Nature of the Surfactant. 9.4. Surface Activity and Emulsion Stability. 9.5. Mixed Surfactant Systems and Interfacial Complexes. 9.6. Amphiphile Mesophases and Emulsion Stability. 9.7. Surfactant Structure and Emulsion Stability. 9.7.1. The Hydrophile-Lipophile Balance (HLB). 9.7.2. Phase Inversion Temperature (PIT). 9.7.3. Application of HLB and PIT in Emulsion Formulation. 9.7.4. The Effects of Additives on the "Effective" HLB of Surfactants. 9.8. Multiple Emulsions. 9.8.1. Nomenclature for Multiple Emulsions. 9.8.2. Preparation and Stability of Multiple Emulsions. 9.8.3. Pathways for Primary Emulsion Breakdown. 9.8.4. The Surfactants and Phase Components. Problems. Chapter 10. Solid Surfaces and Dispersions. 10.1. The Nature of Solid Surfaces. 10.2. Liquid versus Solid Surfaces. 10.3. Adsorption At the Solid/Liquid Interface. 10.3.1. Adsorption Isotherms. 10.3.2. Mechanisms of Surfactant Adsorption. 10.3.2.1. Dispersion Forces. 10.3.2.2. Polarization and Dipolar Interactions. 10.3.2.3. Electrostatic Interactions. 10.3. The Electrical Double Layer. 10.4. The Mechanics of Surfactant Adsorption. 10.4.1. Adsorption and the Nature of the Adsorbent Surface. 10.4.2. Nonpolar, Hydrophobic Surfaces. 10.4.3. Polar, Uncharged Surfaces. 10.4.4. Surfaces Having Discrete Electrical Charges. 10.5. Surfactant Structure and Adsorption from Solution. 10.5.1. Surfaces Possessing Strong Charge Sites. 10.5.2. Adsorption by Uncharged, Polar Surfaces. 10.5.3. Surfactants at Nonpolar, Hydrophobic Surfaces. 10.6. Surfactant Adsorption and the Character of Solid Surfaces. 10.7. Wetting and Related Phenomena. 10.7.1. Surfactant Manipulation of the Wetting Process. 10.7.2. Some Practical Examples of Wetting Control By Surfactants. 10.7.3. Detergency and Soil Removal. 10.7.4. The Cleaning Process. 10.7.5. Soil Types. 10.7.6. Solid Soil Removal. 10.7.7. Liquid Soil Removal. 10.7.8. Soil Re-deposition. 10.7.9. Correlations of Surfactant Structure and Detergency. 10.7.10. Nonaqueous Cleaning Solutions. 10.8. Enhanced Oil Recovery. 10.9. Suspensions and Dispersions. Problems. Bibliography. Index.