Surfactants and polymers in aqueous solution.

Format:

Book

Contributor:

Holmberg, Krister, 1946-

Rosengarten Family Fund.

Language:

English

Subjects (All):

Surface active agents.

Polymers.

Solution (Chemistry).

Physical Description:

xvi, 545 pages : illustrations ; 24 cm

Edition:

Second edition / [Krister Holmberg ... [and others].

Place of Publication:

Chichester, West Sussex, England ; Hoboken, NJ : John Wiley & Sons, [2003]

Summary:

Surfactants and Polymers in Aqueous Solution is aimed at those dealing with surface chemistry research at universities and with surfactant formulation in industry.

Contents:

Surfactants Adsorb at Interfaces 1

Surfactants Aggregate in Solution 3

Surfactants are Amphiphilic 3

Surface Active Compounds are Plentiful in Nature 5

Surfactant Raw Materials May be Based on Petrochemicals or Oleochemicals 7

Surfactants are Classified by the Polar Head Group 8

Dermatological Aspects of Surfactants are Vital Issues 24

The Ecological Impact of Surfactants is of Growing Importance 27

The Rate of Biodegradation Depends on Surfactant Structure 30

Environmental Concern is a Strong Driving Force for Surfactant Development 32

2. Surfactant Micellization 39

Different Amphiphile Systems 39

Surfactants Start to Form Micelles at the CMC 39

CMC Depends on Chemical Structure 43

Temperature and Cosolutes Affect the CMC 46

The Solubility of Surfactants may be Strongly Temperature Dependent 49

Driving Forces of Micelle Formation and Thermodynamic Models 52

The Association Process and Counterion Binding can be Monitored by NMR Spectroscopy 55

Hydrophobic Compounds can be Solubilized in Micelles 57

Micelle Size and Structure may Vary 58

A Geometric Consideration of Chain Packing is Useful 60

Kinetics of Micelle Formation 61

Surfactants may Form Aggregates in Solvents other than Water 62

General Comments on Amphiphile Self-Assembly 64

3. Phase Behaviour of Concentrated Surfactant Systems 67

Micelle Type and Size Vary with Concentration 67

Micellar Growth is Different for Different Systems 70

Surfactant Phases are Built Up by Discrete or Infinite Self-Assemblies 74

Micellar Solutions can Reach Saturation 76

Structures of Liquid Crystalline Phases 77

How to Determine Phase Diagrams 80

Binary and Ternary Phase Diagrams are Useful Tools: Two Components 82

Binary and Ternary Phase Diagrams are Useful Tools: Three Components 85

Surfactant Geometry and Packing Determine Aggregate Structure: Packing Parameter and Spontaneous Curvature of the Surfactant Film are Useful Concepts 89

Polar Lipids Show the same Phase Behaviour as other Amphiphiles 93

Liquid Crystalline Phases may Form in Solvents other than Water 94

4. Physicochemical Properties of Surfactants and Polymers Containing Oxyethylene Groups 97

Polyoxyethylene Chains make up the Hydrophilic Part of many Surfactants and Polymers 97

CMC and Micellar Size of Polyoxyethylene-Based Surfactants are Strongly Temperature Dependent 98

Temperature Dependence can be Studied using Phase Diagrams 100

The L[subscript 3] or 'Sponge' Phase 103

Sequence of Self-Assembly Structures as a Function of Temperature 103

The Critical Packing Parameter and the Spontaneous Curvature Concepts are Useful Tools 103

Clouding is a Characteristic Feature of Polyoxyethylene-Based Surfactants and Polymers 109

Physicochemical Properties of Block Copolymers Containing Polyoxethylene Segments Resemble those of Polyoxyethylene-Based Surfactants 111

Temperature Anomalies of Oxyethylene-Based Surfactants and Polymers are Ubiquitous 113

Temperature Anomalies are Present in Solvents other than Water 117

5. Mixed Micelles 119

Systems of Surfactants with Similar Head Groups Require no Net Interaction 119

General Treatment of Surfactants Mixtures Requires a Net Interaction 124

The Concept of Mixed Micelles can also be Applied to Amphiphiles not Forming Micelles 130

Mixed Surfactant Systems at Higher Concentrations Show Interesting Features 131

Mixed Surfactant Systems are used Technically 134

6. Microemulsions 139

Phase Behaviour of Oil-Water-Surfactant Systems can be Illustrated by Phase Diagrams 140

The Choice of Surfactant is Decisive 143

Ternary Phase Diagrams can be Complex 146

How to Approach Microstructure? 146

Molecular Self-Diffusion can be Measured 147

Confinement, Obstruction and Solvation Determine Solvent Self-Diffusion in Microemulsions 148

Self-Diffusion Gives Evidence for a Bicontinuous Structure at Balanced Conditions 151

The Microstructure is Governed by Surfactant Properties 152

7. Intermolecular Interactions 157

Pair Potentials Act between Two Molecules in a Vacuum 157

The Intermolecular Interaction can be Partitioned 159

Effective Pair Potentials Act between Two Molecules in a Medium 167

8. Colloidal Forces 175

Electric Double-Layer Forces are Important for Colloidal Stability 175

Other Types of Forces Exist 181

Colloidal Forces can be Measured Directly 189

9. Polymers in Solution 193

Polymer Properties are Governed by the Choice of Monomers 193

The Molecular Weight is an Important Parameter 195

Dissolving a Polymer can be a Problem 196

Polymers in Solution can be Characterized by Viscosity Measurements 196

Polymer Solutions may Undergo Phase Separation 197

Polymers Containing Oxyethylene Groups Phase-Separate Upon Heating in Aqueous Systems 199

Solvents and Surfactants have Large Effects on Polymer Solutions 199

The Solubility Parameter Concept is a Useful Tool for Finding the Right Solvent for a Polymer 201

The Theta Temperature is of Fundamental Importance 203

There are Various Classes of Water-Soluble Polymers 205

Polyelectrolytes are Charged Polymers 207

Polymer Configurations Depend on Solvent Conditions 207

10. Regular Solution Theory 215

Bragg-Williams Theory Describes Non-ideal Mixtures 215

Flory-Huggins Theory Describes the Phase Behaviour of Polymer Solutions 223

11. Novel Surfactants 227

Gemini Surfactants have an Unusual Structure 227

Cleavable Surfactants are Environmentally Attractive but are of Interest for other Reasons as well 235

Polymerizable Surfactants are of Particular Interest for Coatings Applications 246

Polymeric Surfactants Constitute a Chapter of their Own 258

Special Surfactants Give Extreme Surface Tension Reduction 258

12. Surface Active Polymers 261

Surface Active Polymers can be Designed in Different Ways 261

Polymers may have a Hydrophilic Backbone and Hydrophobic Side Chains 262

Polymers may have a Hydrophobic Backbone and Hydrophilic Side Chains 267

Polymers may Consist of Alternating Hydrophilic and Hydrophobic Blocks 272

Polymeric Surfactants have Attractive Properties 276

13. Surfactant-Polymer Systems 277

Polymers can Induce Surfactant Aggregation 277

Attractive Polymer-Surfactant Interactions Depend on both Polymer and Surfactant 281

Surfactant Association to Surface Active Polymers can be Strong 283

The Interaction between a Surfactant and a Surface Active Polymer is Analogous to Mixed Micelle Formation 285

Phase Behaviour of Polymer-Surfactant Mixtures Resembles that of Mixed Polymer Solutions 288

Phase Behaviour of Polymer-Surfactant Mixtures in Relation to Polymer-Polymer and Surfactant-Surfactant Mixtures 295

Polymers may Change the Phase Behaviour of Infinite Surfactant Self-Assemblies 298

There Are Many Technical Applications of Polymer-Surfactant Mixtures 299

DNA is Compacted by Cationic Surfactants, which gives Applications in Gene Therapy 301

14. Surfactant-Protein Mixtures 305

Proteins are Amphiphilic 305

Surfactant-Protein Interactions have a Broad Relevance 306

Surface Tension and Solubilization give Evidence for Surfactant Binding to Proteins 306

The Binding Isotherms are Complex 308

Protein-Surfactant Solutions may have High Viscosities 310

Protein-Surfactant Solutions may give rise to Phase Separation 311

Surfactants may Induce Denaturation of Proteins 314

15. An Introduction to the Rheology of Polymer and Surfactant Solutions 317

Rheology Deals with how Materials Respond to Deformation 317

The Viscosity Measures how a Simple Fluid Responds to Shear 317

The Presence of Particles Changes the Flow Pattern and the Viscosity 322

The Relationship between Intrinsic Viscosity and Molecular Mass can be Useful 324

The Rheology is often Complex 324

Viscoelasticity 327

The Rheological Behaviour of Surfactant and Polymer Solutions Shows an Enormous Variation: Some Further Examples 329

16. Surface Tension and Adsorption at the Air-Water Interface 337

Surface Tension is due to Asymmetric Cohesive Forces at a Surface 337

Solutes

Affect Surface Tension 339

Dynamic Surface Tension is Important 340

The Surface Tension is Related to Adsorption 342

Surfactant Adsorption at the Liquid-Air Surface is Related to the Critical Packing Parameter 343

Polymer Adsorption can be Misinterpreted 346

Measurement of Surface Tension 347

The Surface and Interfacial Tensions can be Understood in Terms of Molecular Interactions 349

Surface Tension and Adsorption can be Understood in Terms of the Regular Solution Theory 351

17. Adsorption of Surfactants at Solid Surfaces 357

Surfactant Adsorption is Governed both by the Nature of the Surfactant and the Surface 358

Model Surfaces and Methods to Determine Adsorption 359

Analysis of Surfactant Adsorption is Frequently Carried out in Terms of the Langmuir Equation 362

Surfactants Adsorb on Hydrophobic Surfaces 365

Surfactants Adsorb on Hydrophilic Surfaces 372

Competitive Adsorption is a Common Phenomenon 380

18. Wetting and Wetting Agents, Hydrophobization and Hydrophobizing Agents 389

Liquids Spread at Interfaces 389

The Critical Surface Tension of a Solid is a Useful Concept 391

The Critical Surface Tension can be Applied to Coatings 394

Surface Active Agents can Promote or Prevent Wetting and Spreading 395

Measuring Contact Angles 399

19. Interaction of Polymers with surfaces 403

The Adsorbed Amount Depends on Polymer Molecular Weight 404

The Solvent has a Profound Influence on the Adsorption 407

Electrostatic Interactions Affect the Adsorption 408

Polyelectrolyte Adsorption can be Modelled Theoretically 416

Polyelectrolytes Change the Double-Layer Repulsion 419

Polymer Adsorption is Practically Irreversible 427

The Acid-Base Concept can be Applied to Polymer Adsorption 428

Measurement of Polymer Adsorption 431

20. Foaming of Surfactant Solutions 437

There are Transient Foams and Stable Foams 437

Two Conditions must be Fulfilled for a Foam to be Formed 438

There are Four Forces Acting on a Foam 440

The Critical Packing Parameter Concept is a Useful Tool 442

Polymers might Increase or Decrease Foam Stability 446

Particles and Proteins can Stabilize Foams 447

Various Additives are Used to Break Foams 448

21. Emulsions and Emulsifiers 451

Emulsions are Dispersions of One Liquid in Another 451

Emulsions can be Very Concentrated 452

Emulsions can Break Down According to Different Mechanisms 452

The Emulsion Droplets Need a Potential Energy Barrier 453

The DVLO Theory is a Cornerstone in the Understanding of Emulsion Stability 456

Emulsifiers are Surfactants that Assist in Creating an Emulsion 458

The HLB Concept 459

The HLB Method of Selecting an Emulsifier is Crude but Simple 461

The PIT Concept 462

The PIT Method of Selecting an Emulsifier is often Useful 466

Different Types of Non-Ionic Surfactants can be Used as Emulsifiers 466

Bancroft's Rule may be Explained by Adsorption Dynamics of the Surfactant 468

Bancroft's Rule may be Related to the Surfactant Geometry 469

Hydrodynamics may Control what Type of Emulsion will Form 471

22. Microemulsions for Soil and Oil Removal 473

Surfactant-Based Cleaning Formulations may act by in situ Formation of a Microemulsion (Detergency) 473

Microemulsion-Based Cleaning Formulations are Efficient 484

Microemulsions were once Believed to be the Solution to Enhanced Oil Recovery 486

23. Chemical Reactions in Microheterogeneous Systems 493

Microemulsions can be used as Minireactors for Chemical Reactions 493

Surface Active Reagents may be Subject to Micellar Catalysis 494

Microemulsions are Good Solvents for Organic Synthesis 496

Microemulsions are Useful as Media for Enzymatic Reactions 502

Microemulsions can be Used to Prepare Nanosized Lattices 507

Nanosized Inorganic Particles can be Prepared in Microemulsions 511

Mesoporous Materials can be Prepared from Surfactant Liquid Crystals 516.

Notes:

Includes bibliographical references and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Rosengarten Family Fund.

ISBN:

0471498831

OCLC:

49959343