Nonionic Surfactants

Contents

Foreword iii Preface vii Contributors xi 1.

SURFACE MONOLAYERS 1 Hermann Lange and Peter Jeschke

2.

ADSORPTION AND WETTING 4 5 Wolfgang von Rybinski and Milan J. Schwuger

3.

MICELLE FORMATION IN AQUEOUS MEDIA 1 0 9 Kenjiro Meguro, Minoru Ueno, and Kunio Esumi

4.

MICELLE FORMATION AND CATALYSIS IN NONAQUEOUS MEDIA 1 85 Kijiro Kon-no, Ayao Kitahara, and Omar A. El Seoud

5.

THERMODYNAMICS OF MICELLE FORMATION Denver G. Hall

6.

SOLUBILIZATION 2 9 7 Raymond A. Mackay

233

xiil

CONTENTS

7. PHASE EQUILIBRIA OF NONIONIC SURFACTANTS AND THE FORMATION OF MICROEMULSIONS 369 Johan Sjoblom, Per Stenius, and Ingvar Danielsson 8.

MACROEMULSIONS 4 3 5 Paul Becher and Martin J. Schick

9. HLB OF NONIONIC SURFACTANTS: PIT AND ElP METHODS 493 Leszek Marszall 10. W/O/W-TYPE MULTIPLE EMULSIONS Sachio Matsumoto 11.

549

EFFECT OF NONIONIC SURFACTANTS ON THE STABILITY OF DISPERSIONS 601 David B. Hough and Laurence Thompson

12. STRUCTURE AND DYNAMICS BY SMALL-ANGLE NEUTRON SCATTERING 677 Linda J. Magid 13.

DETERGENCY 7 5 3 Martin J. Schick

14. FOAMING 835 Martin J. Schick and Irving R. Schmolka 15. POLYMER-SURFACTANT INTERACTIONS Shuji Saito

881

16. CONFIGURATION AND HYDRODYNAMIC PROPERTIES OF THE POLYOXYETHYLENE CHAIN IN SOLUTION 927 Frederick E. Bailey, Jr. and Joseph V. Koleske

CONTENTS

xv

1 7. STRUCTURE AND DYNAMICS BY NMR AND OTHER METHODS 971 Anthony A. Ribeiro and Edward A. Dennis 18. STABILITY OF THE POLYOXYETHYLENE CHAIN Max Donbrow Author Index Subject Index

1073 1123

1011

1 Surface Monolayers Hermann Lange and Peter Jeschke Department of Physical Chemistry Henkel KGaA Diisseldorf, West Germany

I. INTRODUCTION 2 A. Significance of the Monolayer State 2 B. General Properties of Monolayers 2 C. Determination of the Surface Pressure-Area Relation 3 D. Interaction Forces in Monolayers 4 H. SPREAD MONOLAYERS 6 A. General Results on the State of Spread Monolayers of Nonionic Surfactants 6 B. Effect of Structure 7 C. Effect of Electrolytes in the Subphase 13 D. Effect of Monolayers on Water Evaporation 15 m . ADSORBED MONOLAYERS 15 A. Results Derived from Static Surface Tension Measurements 15 B. Surface Potential of Monolayers 31 C. Kinetics of Monolayer Formation by Adsorption, Surface Rheology 34 IV. CORRELATION BETWEEN SPREAD AND ADSORBED MONOLAYERS 37 List of Symbols 40 References 40

1

2 Adsorption and Wetting Wolfgang von Rybinski and Milan J. Schwuger Department of Physical Chemistry Henkel KGaA Dusseldorf, West Germany

I. INTRODUCTION 45 H. FUNDAMENTALS OF ADSORPTION AND WETTING 46 A. Mechanism of Adsorption 46 B. Adsorption Isotherms 48 C. Fundamentals of Wetting 51 £ HI. ADSORPTION FROM AQUEOUS SOLUTIONS 52 A. General 52 B. Polyoxy ethylene Alkylphenols 53 C. Polyoxyethylene Alcohols 71 D. Miscellaneous Nonionic Surfactants 86 E. Mixtures of Nonionic Surfactants with Various Adsorbates 87 IV. ADSORPTION FROM NONAQUEOUS SOLVENTS 96 V. APPLICATIONS 99 A. Detergency 99 B. Dispersions 100 C. Flotation 100 D. Tertiary Oil Recovery 101 E. Miscellaneous Applications 101 References 102 I. INTRODUCTION The adsorption of nonionic surfactants on solid surfaces is the basis for many technical applications of these substances. Important areas of application of nonionic surfactants, where adsorption and wetting play a 45

3 Micelle Formation in Aqueous Media Kenjiro Meguro, Minoru Ueno, and Kunio Esumi Department of Chemistry Science University of Tokyo and Institute of Colloid and Interface Science Tokyo, Japan

I. INTRODUCTION 110 H. HOMOGENEOUS SURFACTANTS 110 m . PROPERTIES OF HOMOGENEOUS SURFACTANT SOLUTIONS 112 A. Determination of cmc 112 B. cmc Data of Nonionic Surfactants 124 IV. FACTORS AFFECTING THE CMC OF NONIONIC SURFACTANTS 124 A. Alkyl Chain Length 124 B. Temperature 133 C. Connecting Group in Structure 139 D. Pressure 144 E. Salts and Solvents 150 V. MIXED-SURFACTANT SYSTEMS 157 A. Mixtures of Homogeneous Nonionic Surfactants 158 B. Mixtures of Anionic and Nonionic Surfactants 159 C. Mixtures of Cationic and Nonionic Surfactants 175 VI. SIZE AND SHAPE OF MICELLES OF NONIONIC SURFACTANTS 176 VH. SUMMARY 178 References 178 109

4 Micelle Formation and Catalysis in Nonaqueous Media Kijiro Kon-no and Ayao Kitahara Department of Industrial Chemistry Science University of Tokyo Tokyo, Japan Omar A. El Seoud Institute de Quimica Universidade de Sao Paula Sao Paulo, Brazil

I. INTRODUCTION 186 n . SOLUBILITY BEHAVIOR 186 A. Effect of Solvent Properties 186 B. Effect of Temperature 188 HI. MICELLE FORMATION 192 A. Critical Micelle Concentration 192 B. Distribution of the Micellar Size 194 C. Aggregate Size 196 IV. SOLUBILIZATION 209 A. Water-Induced Aggregate Formation 209 B. Solubility Behavior of Water 210 C. Mechanism of Water-Surfactant Interaction 213 D. Mechanism of Other Polar Substances-Surfactant Interaction 217 E. Acid-Base Indicator Equilibria 218 F. Formation of W/O Microemulsions 218 V. CATALYSIS 219 References 226

5 Thermodynamics of Micelle Formation Denver G. Hall Unilever Research, Port Sunlight Laboratory, Bebington, Merseyside, England and Department of Chemistry Salford University Manchester, England I. INTRODUCTION 234 H. GENERAL THERMODYNAMICS OF MICELLAR SOLUTIONS 236 m . NONINTERACTING MICELLES 241 IV. SOLUTIONS IN COMPLETE EQUILIBRIUM 243 A. General Expressions for Multicomponent Micelles 243 B. The Phase Approximation 246 C. Single-Component Micelles 247 D. Single-Component Micelles in Mixed Solvents 249 V. BEHAVIOR OF THE MICELLE POPULATION 251 A. General Considerations 251 B. Single-Component Micelles 252 C. Two-Component Micelles 258 VI. INTERMICELLAR INTERACTIONS 261 VH. THERMODYNAMICS IN THE TREATMENT OF RATE PROCESSES IN MICELLAR SYSTEMS 263 A. Diffusion in Micellar Systems 264 B. Kinetics of Micellization 266 Vm. A SIMPLE KINETIC MODEL FOR THE MICELLE POPULATION 273

234

HALL

DC. EXPERIMENTAL WORK AND ITS INTERPRETATION 276 A. Colligative Properties and Light Scattering 276 B. Critical Behavior and Cloud Points 281 C. Thermodynamic Parameters of Micellization 284 D. Mixed Micelles 287 X. GLOSSARY OF NOTATION 288 References 290 A general thermodynamic treatment of surfactant solutions containing uncharged micellar aggregates is outlined together with the simplifications which result when interactions between micelles are negligible. The equations which result are applied to multicomponent micelles. For these a variety of expressions are derived which show how the thermodynamic behavior of the solution deviates from that which would apply if the micelles were a separate phase. In addition, the effects of cosolvents on the cmc and aggregation number of single-component micelles are discussed. Recent developments in understanding the form of the micelle population both for single and multicomponent micelles are reviewed with attention given to the underlying thermodynamic framework. The effects of second virial interactions on the micelle population are discussed briefly. The role of thermodynamics in the interpretation of dynamic processes in micellar solutions is illustrated by reference to diffusion and to the kinetics of micelle formation and breakdown. A simple kinetic model of the micelle population is forwarded which illustrates some of the general principles developed in the previous section. Recent developments in experimental thermodynamic studies of nonionic micellar solutions and the interpretation of data are reviewed. Included are brief accounts of upper and lower consolute behavior and of mixed micelles. I. INTRODUCTION

It has been known for many years that surfactant molecules in solution aggregate at low concentrations to form micelles. This leads to marked deviations from thermodynamically ideal behavior. Formally these deviations can be described entirely in phenomenological terms without taking any explicit account of the aggregation process and an approach of this kind has been used to provide a general description of the micelle point

6 Solubilization Raymond A. Mackay

Chemical Research Development and Engineering Center Aberdeen Proving Ground Aberdeen, Maryland

I.

INTRODUCTION 298 A. Solubilization 298 B. Surfactant-Water Systems 299 C. Binary Phase Diagrams 302 D. Effect of Salts on the Cloud Point 306 H. SOLUBILIZATION IN DILUTE AQUEOUS SOLUTIONS 308 A. Locus of Solubilization 308 B. Measurement of Solubilization and the CMC 314 C. Effect of Solubilizate on Micellar Size 318 D. Dependence of Solubilization on Temperature and Cloud Point 320 E. Theory of Solubilization 325 F. Dependence of Saturation SolubUization on Surfactant and Solubilizate Structure 330 m. SOLUBILIZATION OF OIL AND WATER IN CONCENTRATED SOLUTION 341 A. Ternary Structures 341 B. Ternary Phase Diagrams 346 C. Pseudo-Binary Phase Diagrams, Phase Inversion, and HLB Temperatures 349 D. Effect of Salt 353 IV. OTHER ASPECTS OF SOLUBILIZATION 355 A. Cosurfactants 355 B. Mixed Surfactants 356

297

MACKAY

298

C. Other Systems 359 D. Rate of Solubilization References 363

361

I. INTRODUCTION A. Solubilization The term solubilization has been given by McBain and Hutchinson [1] to a particular mode of dissolving substances that are insoluble in a given medium. While this definition has the virtue of not being restricted to the solubilization of insoluble or sparingly soluble organic substances in water by the addition of suitable surfactants, it involves the previous presence of a colloidal solution whose aggregates or particles take up and incorporate within or upon themselves the otherwise insoluble material (the solubilizate). Attwood and Florence [2] suggested as a more general definition "the preparation of a thermodynamically stable isotropic solution of a substance normally insoluble or very slightly soluble in a given solvent by the introduction of an additional amphiphilic compound or component." As will be seen below, this is a preferable definition, particularly in more concentrated solution where the actual mechanism of incorporation may be hydrotropy or comicellization rather than micellization. As will be mentioned in this chapter and discussed in more detail in Chap. 7, liquid crystalline regions such as neat (lamellar) and middle (hexagonal) phases can form in more concentrated surfactant solutions. These phases are capable of incorporating solubilizates and in fact may form at lower surfactant concentration due to the presence of the solubilizate. However, since these ternary systems are anisotropic (and generally very viscous), only isotropic solutions will be considered as "solubilization" in the context of this chapter. Early work in the area of solubilization has been reviewed by McBain and Hutchinson [1] and Klevens [3], and solubilization in nonionic surfactants has been reviewed by Nakagawa [4]. The thrust of this chapter will be to highlight the advances in the understanding of the solubilization process since 1967. Selected references will be used to illustrate the ideas presented. No attempt has been made to provide a comprehensive compendium of solubilization data. However, the journals, articles, and books cited in this chapter as well as the references contained therein should provide extensive coverage of the available information on solubilization by nonionic surfactants.

7 Phase Equilibria of Nonionic Surfactants and the Formation of Microemulsions Johan SjOblom and Per Stenius Institute for Surface Chemistry Stockholm, Sweden Ingvar Danielsson

Department of Physical Chemistry Abo Akademi Abo, Finland

I. INTRODUCTION 370 H. PHASE EQUILIBRIA IN WATER/SURFACTANT SYSTEMS 379 A. Introductory Remarks 379 B. Polyoxyethylene Alcohols 380 C. Polyoxyethylene Alkylphenols 387 D. Alkyl Phosphine Oxides, Alkylphosphates, and Alkylphosphonates 388 E. Alkyl Sulfoxides, Alkylsulfoximine, Alkylsulfone Diimine 390 F. Alkylamine, Alkylamide, and Alkylamine Oxide 394 G. Alkyl Arsine Oxide 399 H. Monoglycerides and Alkylglycerols 400 I. Summarizing Remarks 403 m. THEORIES OF MACROSCOPIC PHASE BEHAVIOR IN BINARY SYSTEMS 404 A. Aggregate and Mesophase Formation 404 B. Surfactant Association in Aqueous Solution 405 C. Interaction Between Nonionic End Groups and the Occurrence of a Lower Critical Temperature 406 369

SJ0BLOM, STENIUS, AND DANIELSSON

370

D. Sequence of Liquid Crystalline Phases 410 IV. PHASE EQUILIBRIA IN THREE- AND MULTICOMPONENT SYSTEMS 412 A. Thermodynamic Conditions for the Occurrence of Multiphase Equilibria and the Formation of Microemulsions 412 B. Phase Equilibria in Ternary Systems at Constant Surfactant Concentration 418 References 431 I.

INTRODUCTION

When a nonionic surfactant is mixed with water several different types of behavior may be observed; to illustrate this we refer to the two typical phase diagrams in Figs. 1 and 2 [1,2]: • The surfactant may be nearly insoluble in water and remain crystalline without swelling appreciably with water. This will usually be the case well below the melting point of the surfactant.

/ !

/

/

/

W + L2

60 r L2

o e 3

I

JU r

'

1

L

1

;

w + u

I i

a

i i i i

25

•

50

75

w

100

Composition (wvt % C.-EO,)

Fig. 1 Phase diagram of the CyE^ system. 1^, = lamellar phase, 1^ = liquid surfactant containing dissolved water, S = solid surfactant [1]. (Reproduced by permission of the Royal Society of Chemistry.)

8 Macroemulsions Paul Becher

Paul Becher Associates Ltd. Wilmington, Delaware Martin J. Schick Consultant New York, New York

I. INTRODUCTION 436 A. Definitions 436 B. Uses of Emulsions 437 C. Advantages of Nonionic Emulsifiers 437 H. PREPARATION OF EMULSIONS 438 A. Methods of Preparation 439 B. Selection of Emulsifier/HLB 439 C. Determination of HLB: Experimental and Theoretical Aspects 442 m . TESTING OF EMULSIONS 456 IV. APPLICATIONS OF NONIONIC EMULSIFIERS 461 V. EMULSION STABILITY 462 A. Effect of Nonionic Surfactant Concentration on Stability of O/W Emulsions 463 B. Effect of Electrical and Steric Contributions to the Stability of Emulsions Stabilized by Nonionic Surfactants 466 C. Surfactant Association and Enhanced Stability 470 D. Phase Inversion 476

435

(

436

BECHER AND SCHICK

VI. INTERFACIAL PROPERTIES OF NONIONIC SURFACTANTS 476 A. General 476 B. Interfacial Tension of Single Species and Normal Distribution Emulsifiers 478 C. Ultralow Interfacial Tensions 483 References 483 I. INTRODUCTION The entire scope of emulsification has been surveyed in great detail by Clayton [1], Becher [2-4], Lissant [5,6], Griffin [7], Sherman [8], Smith [9], Friberg [10], and Johnson [11]. In recent years the study of emulsification has increased in depth and become more fundamental without losing touch with the numerous practical and theoretical applications, as demonstrated among the references cited in the treatment of emulsion science and technology by Becher [3], Sherman [8], and Smith [9]. In view of these existing and thorough treatments of emulsion theory and practice, a detailed discussion would be repetitious. Hence, this chapter is limited to those aspects of em unification relevant to nonionic emulsifying agents. A. Definitions A macroemulsion is a heterogeneous system, consisting of at least one immiscible liquid dispersed in another in the form of droplets, whose diameters generally exceed 0.1 jim (although recent work suggests that a lower limit could be set). Such systems possess a mimimal stability, which must be accentuated by additives such as emulsifiers, finely divided solids, etc. Macroemulsions are turbid since they constitute twophase systems, in which the dispersed phase droplets are larger than the wavelength of visible light. On the other hand, microemulsions (cf. Chap. 7) form spontaneously at contact between two or more components, and are transparent to the naked eye, of low viscosity, and are frequently thermodynamically stable. A few additional terms may usefully be defined. The discontinuous phase is referred to variously as the disperse or internal phase, whereas the phase in which the dispersion occurs is referred to as the continuous or external phase. In the remainder of this chapter, the use of the prefix macro- (used to distinguish the present systems from microemulsions) will be dispensed with. The standard components of an emulsions are an oily and an aqueous phase. When water is the continuous phase, the emulsion is referred to as

9 HLB of Nonionic Surfactants: PIT and EIP Methods Leszek Marszall Pharmacy No 09068 Nowe, Poland

I. INTRODUCTION 494 H. PRINCIPLES OF THE PIT (HLB TEMPERATURE) METHOD 494 A. General Observations 494 B. Dissolution State of Nonionic Surfactants and Type of Dispersion 496 C. PIT and Ultralow Interfacial Tension 500 HI. PRINCIPLES OF THE EIP METHOD 502 IV. CORRELATION BETWEEN PIT AND EIP IN EMULSION AND CLOUD POINT AND PHENOL INDEX IN SOLUTION OF NONIONIC SURFACTANTS 505 V. DETECTION METHODS OF PIT AND EIP 507 VI. PIT AND EIP VS. EMULSION STABILITY 508 VH. EMULSIFICATION BY THE PIT AND EIP METHODS 510 Vm. FACTORS AFFECTING THE HLB OF NONIONIC SURFACTANTS AS MEASURED BY PIT, EIP, AND OTHER METHODS 514 A. Oil Phase 514 B. Surfactant 519 C. Temperature 525 D. Additives 528 E. Preparative Methods 534 DC. EVALUATION OF SURFACTANT BLENDING 535 References 539

493

10 W/O/W-iype Multiple Emulsions Sachio Matsumoto

Department of Agricultural Chemistry College of Agriculture The University of Osaka Prefecture Osaka, Japan I. INTRODUCTION 549 H. STATIC ASPECTS OF MULTIPLE-EMULSION STRUCTURE 550 HI. DEVELOPMENT OF W/O/W-TYPE DISPERSION 554 A. Mechanical Agitation 554 B. Phase Inversion 557 C. Two Separated Steps of Emulsification 560 IV. SOME TRIALS IN PREPARING MULTIPLE EMULSIONS 565 A. Lipid Vesicle Suspensions 565 B. W/O/W Emulsions in an Edible Form 568 C. Multiple Emulsions Stabilized with Microbial Surfactants 570 D. W/O/W-Microemulsion Emulsions 571 V. DYNAMIC ASPECTS OF OIL LAYER IN W/O/W EMULSIONS 573 A. Thinning of Oil Layer 573 B. Water Permeability of Oil Layer 577 C. Estimation of Extent of Oil Layer 586 VI. STABILITY OF W/O/W EMULSIONS 588 References 597 I. INTRODUCTION

The term multiple emulsion describes a series of complex two-phase systems, i.e., the two liquid phases being separated by another immiscible 549

11 Effect of Nonionic Surfactants on the Stability of Dispersions David B. Hough and Laurence Thompson Unilever Research Port Sunlight Laboratory Bebington, Merseyside, England

I. INTRODUCTION 602 H. SURFACTANTS AT INTERFACES 603 A. Surfactant Adsorption 603 B. Effects on the Electrical Double Layer 616 m . PARTICLE INTERACTIONS 624 A. Electrical Double-Layer Interactions 626 B. Dispersion Forces 628 C. Steric Interactions 632 D. Solvation Forces 635 E. Dispersion Stability and Its Relationship to Particle Interactions 637 IV. EXPERIMENTAL STUDIES OF COLLOID STABILITY 642 A. Electrical Double-Layer Effects 642 B. Surfactant Concentration and Type 644 C. Particle Size Effects 649 D. Temperature Effects 651 E. Effects of Additives 658 V. CONCLUDING REMARKS 665 References 667

601

12 Structure and Dynamics by Small-Angle Neutron Scattering Linda J. Mag id Department of Chemistry University of Tennessee Knoxville, Tennessee

I. INTRODUCTION 678 n . NEUTRON-SCATTERING THEORY 681 A. Single-Particle Form Factors 686 B. Form Factors for Polydisperse Spheres, Ellipsoids, and Cylinders 691 C. External and Internal Contrast Variation 693 D. Interparticle Interference 696 E. Experimental Considerations in Static SANS 703 F. Dynamic SANS 708 m . ELUCIDATION OF THE STRUCTURE OF AND INTERACTION BETWEEN MICELLES OF NONIONIC SURFACTANTS USING SANS 710 A. SANS Data for C„Em Surfactants in Water: Introduction 710 B. Static SANS Data for Dilute Solutions 712 C. Dynamic SANS Data for Dilute Solutions 724 D. Static and Dynamic SANS Data for Concentrated Solutions 727 E. Use of External Contrast Variation for Micellar Solutions of C1ZE8 729 F. Apparent Growth of C„Em Micelles: Scattering vs. Nonscattering Techniques 732 G. Attractive Interactions Between Nonionic Micelles 737 H. Surfactant-Dependent Critical Exponents for C„Ems 743 IV. CONCLUSIONS 745 References 746 677

13 Detergency Martin J. Schick Consultant New York, New York I. INTRODUCTION 754 H. TEST METHODS 755 m . MECHANISM OF SOIL REMOVAL 756 A. Theory 756 B. Kinetics 760 IV. CORRELATION BETWEEN DETERGENCY OF NONIONIC SURFACTANTS AND OTHER FACTORS 761 A. Oily Soil Removal from a Synthetic Substrate 761 B. Effect of Substrate on Soil Removal 780 C. Deposition and Transfer of Oily Soil 785 D. Kinetics of Fabric Detergency 788 E. Interaction in the System: Clay-Detergent-Cellulose 792 V. DETERGENCY VALUES OF NONIONIC SURFACTANTS 795 A. Polyoxyethylene Esters of Fatty Acids 795 B. Polyoxyethylene Alcohols 795 C. Polyoxyethylene Alkylphenols 800 D. Polyalkylene Oxide Block Copolymers 802 E. Sugar-Based and Other Surfactants 802 F. Builder Effects 805 G. Combination of Nonionic with Anionic Surfactants 807 H. Combination of Nonionic with Cationic Surfactants 810 I. Alkyl Ether Sulfates 811 VI. DETERGENCY OF NONIONIC SURFACTANTS IN COMPOSITIONS 813 A. Heavy-Duty Laundry Detergents 814 B. Light-Duty Dishwashing Liquids 821 C. Machine Dishwashing Powders 821 D. Rinse Aids 822

753

754

E. Cold Water Detergency 822 F. Hard-Surface Cleaners 823 References 824

I. INTRODUCTION The scope of detergency has been reviewed in great detail in treatises by Cutler and Davis [1-3], Cutler and Kissa [4], and in articles by Schwuger [5], Schwartz [6], Patterson and Grindstaff [7], Kissa [8], and Harris [9]. In recent years the study.pf detegency has progressed more in depth and become more basic without losing touch with the practical applications as demonstrated in the references cited above. In view of these existing thorough coverages of detergency theory and practice, a detailed discussion of detergency would be repetitious; therefore, this chapter emphasizes those aspects of detergency which are relevant to nonionic surfactants. Only a brief section on test methods precedes the main body of the chapter dealing with the mechanism of soil removal, correlation between detergency of nonionic surfactants and other factors, and detergency values of nonionic surfactants. The chapter concludes with a review of the role of nonionic surfactants in commercial compositions. Nonionic surfactants are increasing in importance because of their capacity to remove oily soil from synthetic fabrics. They exhibit good water solubility, are low foamers, and are less sensitive to water hardness than anionic surfactants. One important characteristic of nonionic surfactants is that the amounts necessary in a composition are relatively low as compared with anionic surfactants. According to Scott [10], this effectiveness is the result of their low cmc values, which simply explains that their maximum effect occurs at very low solution concentrations. Shinoda [11] showed that nonionic surfactants are much better solubilizing agents for hydrocarbon soils than anionic surfactants. Several authors [12,13] have demonstrated that nonionic surfactants tend to perform best on hydrophobic substrates with nonpolar soils. Good biodegradability can be achieved by proper choice of the hydrophobic moiety [14]. On the other hand, nonionic surfactants are difficult to incorporate into powdered compositions because of their liquid or semiliquid state and their oxidative sensitivity to the heat and large volumes of air used in the spraydrying process. Many types of nonionic surfactants exist [15], but the greatest volume used presently in household detergents are oxyethylene (EO) adducts. Here the hydrophile-hydrophobe balance (HLB) controls the surface

14 Foaming Martin J . Schick

Consultant New York, New York Irving R. Schmolka

Consultant Grosse lie, Michigan I. INTRODUCTION 836 H. THEORY 836 A. General 836 B. Foam Characteristics and Nature of Surfactant 837 C. Stability and Rupture of Isolated Films 838 D. Interaction Between Foam Films and Plateau Borders 844 E. Stabilization of Foams by Liquid Crystals 846 m . TEST METHODS 847 IV. FACTORS AFFECTING FOAMING OF NONIONIC SURFACTANTS 849 A. Structure of Surfactants 849 B. Electrolytes 859 C. Foam Stabilizers 861 D. Foam Inhibitors 864 E. Low Foamers 865 V. FOAMING OF NONIONIC SURFACTANTS IN COMPOSITIONS 868 A. Heavy-Duty Laundry Detergents 868 B. Light-Duty Dishwashing Liquids 869 C. Machine Dishwashing Powders 871 D. Personal Care Industry 871 E. Miscellaneous 872 References 872

835

15 Polymer-Surfactant Interactions Shuji Saito Momotani Juntenkan Ltd. Osaka, Japan

I. INTRODUCTION 881 H. INTERACTIONS OF IONIC SURFACTANTS 882 A. Significance of Hydrophilic Head Group of Surfactants in the Interactions with Nonionic Polymers 882 B. Some Aspects of the Interactions 885 C. Interactions with Ionic Polymers Including Polypeptides and Proteins 888 HI. INTERACTIONS OF NONIONIC SURFACTANTS 892 A. Interactions with Nonionic Polymers 892 B. Interactions with Polymeric Acids 893 C. Interactions with Water-Dispersible Polymeric Acid 911 D. Adsorption to Solid Acids 913 E. Solubilization Properties of the Complexes 916 F. Flocculation of Nonionic Surfactant-Stabilized Colloids by Polymeric Acids 917 G. Interactions with Proteins 918 VI. CONCLUDING REMARKS 920 References 921 I. INTRODUCTION When surfactants are employed in practice, they are almost without exception mixed with various substances either unintentionally or for improving their performances. This is also true for polymers in solution. When a surfactant and a polymer happen to be mixed in aqueous 881

16 Configuration and Hydrodynamic Properties of the Polyoxyethylene Chain in Solution Frederick E. Bailey, Jr. and Joseph V. Koleske Union Carbide Corporation South Charleston, West Virginia

I. INTRODUCTION 928 H. SOLUTION PROPERTIES 929 A. Solubility 929 B. Molecular Weight Distribution 935 C. Molecular Weight Determination 937 D. Dilute Solution Viscosity/Rheology 938 E. Concentrated Solution Viscosity/Rheology 945 m . CONFIGURATION OF THE POLYOXYETHYLENE MOLECULE IN SOLUTION 949 A. Calculation of Dimensions from Hydrodynamic Theories 950 B. Molecular Expansion Factor 953 C. Hindrance Parameters 954 D. Thermodynamic Properties in Aqueous Solution 956 IV. DIELECTRIC BEHAVIOR 957 V. INTERFACIAL BEHAVIOR 958 VI. ASSOCIATION COMPLEXES 959 Vn. POLYPROPYLENE OXIDE 963 LIST OF SYMBOLS 963 References 964

927

17 Structure and Dynamics by NMR and Other Methods Anthony A. Ribeiro Department of Radiology Duke University Medical Center Durham, North Carolina Edward A. Dennis Department of Chemistry University of California at San Diego La Jolla, California

I. INTRODUCTION 972 H. PHASE DIAGRAMS AND AGGREGATION STATES OF NONIONIC SURFACTANTS 972 A. Lyotropic Mesomorphism in Aqueous Media 973 B. Thermotropic Mesomorphism in Aqueous Media 973 C. Nonaqueous Solvents 974 HI. NMR CHARACTERIZATION AND ASSIGNMENTS OF NONIONIC SURFACTANTS 975 A. *H nmr Studies 975 B. 13C nmr Studies 979 IV. NMR INVESTIGATIONS OF DILUTE ISOTROPIC STATES 984 A. }H Chemical Shift Studies 985 B. *H Relaxation Studies 987 C. 13C Chemical Shift Studies 989 D. 13C Relaxation Studies 989

RIBEIRO AND DENNIS

972

V. NMR INVESTIGATIONS OF MESOMORPHIC STATES AT HIGH CONCENTRATIONS 992 A. 13C nmr Studies 992 B. ^ nmr Studies 995 VI. NMR INVESTIGATIONS OF CLOUD POINT STATES 996 VH. POLYOXYETHYLENE CHAIN CONFIGURATIONS AND CONFORMATIONS 997 A. X-ray and Theoretical Considerations 997 B. Laser Raman and nmr Considerations 999 Vm. CONFORMATIONAL ISSUES 1001 A. Water Effect on Micelle Packing 1001 B. Classical vs. Nonclassical Micelle Structure 1002 LX. CONCLUSIONS 1004 References 1006 I. INTRODUCTION The elucidation of the structure, conformation, mobility, and dynamics of nonionic surfactants in solution has been the subject of several recent physicochemical investigations. Although it is still not possible to present a definitive picture of the structure of these surfactants in solution, there has been considerable progress in this area, so that reasonable possibilities can now be considered. The phase diagrams and background on the aggregation of nonionic surfactants are covered first in Sec. n, followed by a summary of the experimental investigations of nonionic surfactants and polyoxyethylene chain conformations carried out by high-resolution nmr spectroscopy, laser Raman spectroscopy, and other contemporary physicochemical techniques in Sees. m-VII. Conformational issues are discussed in Sec. VDI. Finally, in Sec. DC we attempt to summarize our present knowledge of the structure and dynamics of nonionic surfactants gained by the application of physical techniques. Other solution properties (cmc, micelle molecular weight, aggregation numbers, and so on) of nonionic surfactants and their use in the solubilization of membrane phospholipids have been reviewed previously [1-3]. A comprehensive review on nmr of surfactant solutions was published in 1976 [4]. II.

PHASE DIAGRAMS AND AGGREGATION STATES OF NONIONIC SURFACTANTS

The most common nonionic surfactants contain a polyoxyethylene chain as the hydrophilic portion and either an alkyl or alkylphenyl group

18 Stability of the Polyoxyethylene Chain Max Donbrow

School of Pharmacy The Hebrew University of Jerusalem Jerusalem, Israel I. INTRODUCTION 1012 H. DEGRADATION OF POLYOXYALKYLENE-CONTAINING MOLECULES 1013 A. General Aspects 1013 B. Initiation Kinetics and Induction Period 1014 C. Peroxidation of Polyoxyethylene Chains 1015 D. Stability and Primary Decomposition Paths of Polyoxyalkylene Hydroperoxides 1016 E. Methods of Study of Autoxidation and Degradation in Polyoxyglycols 1021 F. Relation of Oxidation Rate to System Parameters 1024 G. Degradation Products and Reaction Schemes 1026 H. Polymer Structure, Phase, and Crystallinity 1031 I. Mechanical Degradation 1032 m. AUTOXIDATION OF NONIONIC SURFACTANTS 1035 A. Changes in Physical Properties During Surfactant Degradation 1035 B. Peroxide Measurement in Surfactant Solutions 1041 C. Conditions Affecting Decomposition of Nonionic Surfactants: Concentration, Temperature, Catalysts, and Pretreatments 1043 IV. STABILIZATION OF POLYOXYALKYLENE DERIVATIVES 1059 A. Purification Methods in Stabilization 1059 B. Storage Conditions 1059 C. Antioxidants and Preservatives 1060 1011

1012

DONBROW

V. SOLUBBLIZED AND MIXED SYSTEMS CONTAINING POLYOXYALKYLENE DERIVATIVES 1065 References 1067 I. INTRODUCTION Except for molecules containing known labile groups, the main body of nonionic surfactants composed of saturated alkyl and polyoxyalkylene chains have been erroneously considered to be relatively stable under normal conditions of preparation, storage, and use. In fact, the polyether chains show behavior similar to that of simple ethers, undergoing autoxidation very readily. This can lead to profound changes in the physical properties and behavior of the surfactant, a point frequently overlooked, perhaps as a result of the limited amount of research published on surfactant stability. Hydrolysis of ester or amide groups in nonionic surfactants is a complicating factor complementary to the effects of autoxidation. Studies on the oxidative degradation of polyglycol polymers are especially important in revealing the mechanisms underlying the decomposition of analogous chains in surfactants in which analytical problems are much more severe, particularly for low surfactant concentrations and in multicomponent systems. Methods used in elucidating degradation will also be considered briefly and instability in multicomponent systems will be reviewed together with the stabilizing effects of antioxidants. It should be added that the alkyl chain of nonionic surfactants is not necessarily immune to degradation. The presence of activating substituents, e.g., unsaturation or aromaticity, can increase their reactivity and involvement in autoxidation under sufficiently vigorous conditions [la] though, in general, the rapidity of the reaction in the ether chains permits the alkyl chain reaction to be neglected. Apart from environmental considerations, the chemical stability and degradability of nonionic surfactants is important both in theoretical studies, where structure modification and the presence of impurities can lead to serious errors, and for practical applications, in which the shelf life of products may be limited by changes resulting from degradation of nonionic surfactant constituents. Among factors influencing such decomposition are the storage conditions of the product, the prior history of the surfactant in terms of its mode of manufacture, purification and storage before use as well as any special treatments given, such as bleaching or sterilization, and, finally, the nature and quantities of the other materials present in the system which may potentiate degradation or stabilize the surfactant.

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Subject Index Acetal derivatives, 21,1028 Acrylamide, 394 N-Acyl a-amino acids oligoethylene glycol esters, 139 Adsorbent aluminum oxide, 74, 75, 90 aluminum hydroxide, 62 antimony sulfide, 617 arsenic sulfide, 84, 615, 617, 645 calcite, 93 calcium carbonate, 61, 62, 605, 645 calcium phosphate, 62 carbon black (Graphon), 53, 71, 73, 87, 89, 95, 96, 605, 607, 608, 611, 614, 623 cation exchange resin, 64, 65 cellulose, 605 charcoal, 53, 71, 73, 89, 90 clay, 605, 611, 613, 614 B-copper phthalocyanine blue, 67, 82,605 copper sulfide, 62 cotton, 68, 84 dyes, 95 electrodes, 63, 80, 81 ferric hydroxide, 62 fibers, 68, 84, 605 griscofulvine, 605 inorganic salt, 61 iron oxide, 605 kaolin, 74, 90, 91 Na- and Ca-magadiite, 78

magnesium hydroxide, 62 mercury, 63, 64, 79, 605, 623 metal powders, 63, 97 Na- and Ca-montmorillonite, 75, 76-78, 613, 792, 793 nylon, 69, 605 paraffin wax, 646 pigment, 64, 605 polyacrylic acid, 660, 662 polybutylmethacrylate, 83, 658 polycarbonate membranes, 64, 65, 610, 613, 666 polyester, 69, 70, 85, 605 polyethylene, 64, 605 polymers, 64, 605, 610, 612 polymethylmethacrylate, 610 polystyrene latex, 66, 81, 82, 602, 608-610, 614, 616, 617, 641, 646, 648, 662, 665-667 polytetrafluoroethylene (PTFE), 64, 611, 613, 614, 666 polyvinylacetate, 660 polyvinylchloride, 66, 81, 82 scheelite, 93 silica (Si0 2 ), 56, 57, 60, 75, 605, 611-614, 616, 637, 645, 666 silica, methylated, 60, 612 silica, pyrogenic, 58 silica gel (Aerosil), 58,74,95-97,915 silicate layer, 75 silver iodide, 78-80, 605, 614-619, 621-624, 632, 642, 646, 647, 666 styrene-divinylbenzene copolymers, 65 1123

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1124

[Adsorbent] Sudan Red G, 67 sulfamine, 605 sulfathiazole, 605 titanium dioxide, 74, 605, 645 viscose, 69 zeolite A, 92 zinc oxide, 75 Adsorption (see also Mono- and multilayers), 15, 45, 602-616 from aqueous solution, 52 of cationic exchange resins, 913 competitive, 619, 620, 628 dielectric contribution, 603 by high polarity surfaces, 611 ideal mixed layers, 90 infrared spectroscopy, 59, 611 isotherms (see Langmuir isotherms) kinetics, 34 layer thickness, 603, 613, 618, 620, 627, 631, 638, 644, 648, 651, 652, 658, 696 by low polarity surfaces, 605 mechanism, 47 microcalorimetry, 61 from nonaqueous solutions, 96 osmotic mixing energy, 604, 633 preferential, 66 standard chemical potential, 25 temperature, 24 thermodynamics, 50 Aerosol OT, 525, 740, 742 Alkylamine, 394 Alkylamine oxide, 394 Alkylarsine oxide, 399 Alkylbenzene sulfonate, 90, 91 Alkyglucoside, 23 Alkylglycerol, 400 Alkylphosphine oxide, 388 Alkylphosphate, 388 Alkylphosphonate, 388 Alkylsulfinyl alcohol, 86, 607 Alkylsulfone diimine, 390 Alkylsulfosuccinate, 93 Alkylsulfoxide, 390 Alkylsulfoximine, 390

SUBJECT INDEX

Amberlite IR-118, 913 IR-120B, 914 IRA-401, 914 IRC-50, 913 200C, 914 Autoxidation, 1015-1027,1031, 1032, 1035-1059

Biodegradation, 795 Bile salts, 918 Biomembranes, 918 Birefringence, electrical, 712, 727, 733, 745, 1001 Bovine serum albumin (BSA), 889891, 919, 920

Carboxymethylcellulose, 759, 785 Cellex CM, 914 Cement, 102 Critical micelle concentration (cmc), 112,124, 277, 302, 314, 316, 328, 410 (see also Micelles) dye solubilization, 112, 191 effect of alkyl chain length, 124 effect of connecting group, 139 effect of electrolytes, 150 effect of pressure, 144 effect of solvent, 153 effect of temperature, 133 effect of urea, 151 electrical conductivity, 170,171, 173 iodine solubilization, 114,124,191, 316 keto-enol tautomerism, 114, 115, 124,151 mixed micelles, 159, 161-176

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SUBJECT INDEX

1125

Orange OT, 315 interaction of clay/det./cellulose, surface tension, 112, 114, 124, 129, 792 159, 161, 191, 277 kinetics, 760, 788 TCNQ solubilization, 114,118,124, light-duty dishwashing, 821 151, 153,161,167, 317 (see also machine dishwashing, 821 TCNQ) polyalkylene oxide block vapor pressure osmometry, 191 copolymers, 802 Coagulation, 637, 642, 647, 650, 653 polyoxyethylene alcohols, 795 critical coagulation concentration, polyoxyethylene alkylphenols, 800 619, 644, 646 polyoxyethylene fatty acid esters, Cosurfactant, 355 795 Crown ethers, 22, 529 rinse aids, 822 CVP (Carbomer, Carbopole), 911sugar-based surfactants, 802 913, 915 Diffusion coefficient, 36, 84, 89, 265, 268, 732, 839 Dimethyldecyl phosphine oxide, 615, 617, 623, 644 Dimethyldodecyl phosphine oxide, 87, 608 Debye-Bueche equation, 950, 999 Dipole Debye-McAulay equation, 931 interactions, 5, 34 Decomposition of nonionic surfacmoment, 5, 32 tants, 1043-1058 Direct force measurements, 657 effect of hydrophobic group, 1056 Disjoining pressure, 577 Dispersions, 100, 601 polyoxyethylene alcohols, 1043 Dispersion stability, 601, 602, 642-665 polyoxyethylene fatty acid esters, 1051 effect of additives, 658-665 effect of electrical double layer, polyoxyethylene sorbitans, 1051 Demulsification 642-644 coalescence, 437, 458, 512 effect of particle size, 649-651 flocculation, 437, 458 effect of surfactant concentration, instability, 437 644-649 Detergency, 99, 753 (see also Soil effect of surfactant type, 644-649 removal) effect of temperature, 651-658 of alkyl ether sulfates, 811 polymer, T p 658 cold water, 822 stability ratio, 625, 637, 644, 647 in compositions, 813 Distearyldimethyl ammonium effect of anionic/nonionic mixtures, chloride, 92 807 DLVO theory 577, 624-626, 759, 846 effect of cationic/nonionic mixtures, attractive energy potential, 577, 810 624, 626, 666, 667 effect of enzymes, 820 potential energy of interaction, 624, effect of EO distribution, 801 625 effect of phosphate builders, 805 repulsive energy potential, 577, 624, 626, 666, 667 hard surface, 823 Dodecyl sulfobetaine, 623 heavy-duty laundry, 814

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1126

ED? (see HLB temperature) Electrical double layer, 602 (see also Interaction of particles and Dispersion stability) Electrocapillarity, 80 Electrokinetics Debye-Htickel K, 616 diffuse layer potentials, 616, 617, 620, 626, 627, 665, 666 Helmholtz planes, 616 ^-potential, 67, 90, 466-470, 616621, 623, 627, 628, 643, 644, 648, 665, 666 Stern layer, 604, 616-620, 666 streaming potential, 610 Electrophoresis, 79, 82 Emulsification ETP of mixtures of oil, 517 inversion method, 513 PIT method, 512, 513 (see also HLB temperature) PIT of mixtures of oil, 517 PIT of phase volume ratio, 518 PIT of EO chain length, 519 PIT of hydrocarbon chain length, 521 PIT of surfactant concentration, 521 PET of partition between phases, 523 Emulsifiers application, 461 nonionic, 437 Emulsions centrifugation, 457 cohesive energy, 504 differential thermal analysis (DTA), 508 emulsion inversion point (EIP), 493, 506-510 (see also HLB temperature) phase inversion temperature (PIT), 493, 508-510 (see also HLB temperature)

SUBJECT INDEX

testing, 457 Emulsion, multiple, 549 diameter ratio, 552 liquid vesicles, 565 mechanical agitation, 554 oil layer extent, 585 oil layer permeability, 579, 580 oil layer thinning, 574 O/W/O, 550, 571 phase compartments, 554 phase inversion, 557 stability, 588-596 structure, 550 two steps, 560 weighted HLB, 563 W/O/W, 549 W/O/W edible, 568 W/O/W evaluation, 562 Emulsion, phases continuous, 436 external, 436 internal, 436 Emulsion, stabilization, 462, 463 electrical, 466 liquid crystals, 470, 471, 473, 649 steric, 466 surfactant association, 470 surfactant-cosurfactant association, 479 EO chain (see Polyoxyethylene chain)

Flocculation, 660-663 critical flocculation concentration (cfc), 917 critical flocculation temperature (CFT), 662 critical precipitation concentration (cpc), 917 by polymeric acids, 917 Flocculation rates, Coulter counter, 460 light scattering, 458

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SUBJECT INDEX

photodenaitometry, 458 photomicrography, 460 photon correlation spectroscopy, 458 Flory-Fox equation, 951, 999 Flory-Huggins equation, 407, 408, 609, 634, 738, 956 Flotation, 100 Foam, inhibitors, 864 Foam, stability, 837-844 Bacon's test, 849, 872 black films, 843, 844, 846, 854, 859861 critical thickness, 843 disjoining pressure, 842 dynamic conditions, 839 dynamic test, 848, 865 evaporation, 846 film drainage, 837, 845, 848, 861 film rupture, 837, 838, 845 gas diffusion, 846 Gibbs film elasticity, 837-839, 841, 842 hydrostatic pressure, 845 of isolated films, 837, 838 lifetime, 845, 846 liquid crystals, 846 manual dishwashing test, 849 Plateau borders, 844, 845 Ross-Miles test, 848, 865 rotating wire cage, 841 Schlag test, 848 static conditions, 842 static test, 848 surface elastic modulus, 838 surface dilational modulus, 838, 839 surface transport, 838 surface viscosity, 864 Foam, stabilizers N, N-bis(hydroxyethyl)lauramide, 861 dimethylamine oxide, 869 N, N-dimethyldodecylamine oxide, _ ' 861, 863 lauric diethanolamide, 869 lauric isopropanolamide, 869

1127

Foaming characteristics, 837 effect of electrolytes, 859 effect of EO distribution, 859 effect of hydrophilic group, 849-855 effect of hydrophobic group, 855858 effect of surfactant structure, 849 test methods, 847 theory, 836 Foaming, compositions heavy-duty laundry detergents, 868 light-duty dishwashing powders, 869 machine dishwashing powders, 871 personal care products, 871 Form factors, 686 (see SANS) Free radicals, 1013-1021, 10281031, 1060, 1061 activation, 1013-1015, 1017 chain reaction, 1013,1060 hydroperoxide, 1013, 1015-1028, 1033, 1041-1052, 1056-1060, 1064, 1066, 1067 initiation, 1013-1018,1033, 1043, 1052, 1059, 1061, 1066 propagation, 1013-1021,1027-1031 termination, 1013, 1016, 1027, 1030-1032, 1060 Freundlich equation, 49, 67, 920

Gibbs adsorption equation, 3, 15, 17, 18, 21, 22, 25, 124, 174 Gibbs-Duhem equation, 244, 246, 287 Gibbs free energy, 410 Gibbs phase rule, 415 Gouy-Chapman theory, 617

H

Hamaker constant, 603, 604, 629-632, 647, 739, 741, 743

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1128

Heat of adsorption, 61, 72, 73, 86, 606, 607 of immersion, 52, 72, 86 of micellization, 209 of solubilization, 214 of solution, 188 of wetting, 51, 52 High-flux isotope reactor (HFIR), 703 HLB, 438, 439, 442, 462, 463, 483, 493, 931, 1035 effective, 472, 481, 494, 524, 526, 528, 530, 534, 537, 539 effect of additivity, 537-539 effect of alcohol, 530-532 effect of chain length, 524, 536 effect of cosurfactant, 525, 532 effect of electrolyte, 528-530 effect of polyethylene glycols, 532 effect of surfactant blends, 535 effect of surfactant locus, 534 effect of surfactant modification, 524, 525 effect of temperature, 526, 527 experimental aspects, 442-451 group numbers, 440 numbers for surfactants, 443-445 optimum ratio, 537 phenol index, 451, 507, 533 required numbers, 446, 447, 509, 515 theoretical aspects, 452-455 HLB range by dispersibility, 448 effect on droplet size, 473 HLB temperature catastrophe theory, 476 EIP (emulsion inversion point), 351, 448, 476, 493, 494, 502, 514 EIP determination, 507 PIT (phase inversion temperature), 349-351, 362, 448, 476, 493496, 500-502, 514 PIT determination, 507 range, 376, 378, 413, 418, 420 THLB, 348

SUBJECT INDEX

Hydrophile-lipophile balance (see HLB)

Interaction forces attractive, 407 dispersion, 410 electrostatic, 378, 379, 886 hydrophobic 378, 885 intermicellar, 261, 404, 406, 409 pairwise potential, 410 repulsive, 404, 407 zwitterionic, 379 Interaction parameter, 8, 174, 809, 864 Interactions, particles 602, 624 effect of electrical double layer, 604, 616-624, 626-628, 664-667 effect of London dispersion forces, 603, 628-632 effect of solvation forces, 635-637 effect on stability of dispersions, 637-642 effect of steric interactions (see Steric stabilization) Interactions, polymer/surfactant, 359, 661,881 effect of hydrophilic group, 895 effect of hydrophobic group, 894 effect of inorganic electrolytes, 904 effect of nonionic polymers, 910 effect of organic electrolytes, 905 effect of pH change, 899 effect of surfactant mixtures, 906 ionic polymer/ionic surfactant, 888 nonionic polymer/ionic surfactant, 882,885 nonionic polymer/nonionic surfactant, 892 polymeric acid/nonionic surfactant, 893, 911 polypeptide/ionic surfactant, 888 protein/ionic surfactant, 888

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SUBJECT INDEX

protein/nonionic surfactant, 918 test methods, 885, 886 Interactions, polyoxyethylene, 927 association complexes, 959-963 electrically conducting complexes, 962 electrolyte/polyoxyethylene, 928 ion association, 962 one-to-one complexation, 961 polyacrylic acid/polyoxyethylene, 936, 959, 961 polyelectrolyte/polyoxyethylene, 928 polymethacrylic acid/ polyoxyethylenes, 961 solvents/polyoxyethylenes, 929 stepwise complexation, 961 urea/polyoxyethylene, 959 Interface gas/liquid (see Monolayers) liquid/liquid, 476, 480 solid/liquid, 46, 47, 609-624 Interfacial tension, nonionic surfactants, 476 equivalent alkane carbon number (EACN), 352, 455, 483, 518 mixtures, 480 normal distribution, 478 single species, 478 ultralow, 483, 500-502 K

Kinetics of micelle formation, 266 (see also Micelles) of monolayer formation, 34, 36 (see also Monolayers) Kirkwood-Riseman theory, 951 Kubelka-Munk equation, 760

Langmuir balance, 3, 7, 9, 12, 14

1129

equation, 25, 28, 29, 49, 51, 58, 61, 65, 70, 78, 81, 96, 97, 161, 339 isotherms, 48, 191, 340, 605, 607612, 614, 615, 624, 648, 665 Laplace pressure, 326 Laser Raman spectroscopy, 999 Lewis acids, 213 bases, 213 Lipids, 918 bilayers, 580, 637 black membranes, 566, 580 liposomes, 566, 580 vesicles, 565 Liquid crystals, 649 (see also Phases) Low foamers, 865 capped polyoxyethylene adducts, 865 Pluronic ® polyols, 865, 867 polyalkylene oxide block copolymers, 865 Tetronic ® polyols, 867 Lyotropic mesomorphism, 973 Lyotropic series (Hofmeister), 31, 150, 307, 528, 660, 861, 882, 932

M Marangoni effect, 838 Macroemulsions, 435 (see Emulsions) definition, 436 Mark-Houwink equation, 933 Mesophases, 387, 399, 404, 411, 412, 424, 608, 649, 678-680, 727 Micellar catalysis, 219 esterolysis of p-nitrophenyl acetate, 221, 222 hemin (CN)2 complex, 220, 221 hydration of acetaldehyde, 222 hydration of 1,3-dichloroacetone, 223, 224 a complex, 220 Micellar interactions (see also Interaction forces), by SANS, 678680,710

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SUBJECT INDEX

1130

Micellar shape, 176, 308, 309, 404, 405 408, 659,1001, 1002, 1005 Micellar size, 176,196 cryoscopy, 197 distribution, 194, 256, 328 effect on solubilization, 318 effect of solvent, 206 effect of temperature, 207 fluorescence-quenching, 176, 735 laser light scattering, 205, 659, 712 light scattering, 176, 197, 204, 678, 681, 712 nmr self-diffusion, 176,197, 264, 404, 409, 413, 659, 735, 745 SANS, 409, 678, 680, 710, 712 sedimentation, 176, 206 ultrasonic absorption, 176 vapor pressure osmometry, 197, 206 Micelles in aqueous media, 109, 972 catalysis (see Micellar catalysis) cmc {see cmc) disappearance (CDM), 153-155,157 effect of water structure, 139, 152, 308, 613, 660, 661, 666, 885, 904, 1001 formation, 371, 380, 404, 405, 407, 411-414 free energy of conformation, 405 free energy of formation, 405 free energy of transfer, 405 heat of formation (see Heat) of homogeneous nonionic surfactants, 112 ideal mixtures, 90 kinetic model, 273 kinetics, 266 of mixtures, 287, 356 of mixtures of homogeneous nonionic surfactants, 158 of mixtures of nonionic and anionic surfactants, 159 of mixtures of nonionic and cationic surfactants, 175 in nonaqueous media (see Reversed) noninteracting, 241

rate processes, 263 relaxation time, 266, 271 reversed, 185, 191, 406, 413, 974 shape (see Micellar shape) single-component, 247, 252 single-component in mixed solvents, 249 size (see Micellar size) swollen, 496-498 thermodynamic parameters (see Thermodynamics) two-component, 258 water-induced, 209, 210 Microbial surfactants, 570 Microemulsions O/W, 369, 376-378, 412, 417, 495, 680, 694, 710, 738, 740, 742, 746, 937 W/O, 218, 219, 571 W/O/W, 571 a-Monoglycerides, 400 Monolayers, surface absorbed, 1, 2, 4, 15, 22, 27, 30-34, 37-39, 53, 79, 502, 606-616, 619, 623, 656 compressibility, 6 effect of electrolyte, 13 equation of state, 2 gaseous, 4, 5,10 effect of hydrophobic group, 9, 20 interaction, electrical, 4 interaction forces, 4 kinetics, 34, 36 liquid condensed, 10, 163 liquid expanded, 4, 6,163 vapor expanded, 4 spread, 4-6, 12, 13, 27, 37-39 thermodynamics, 24, 30, 31 transitions, 507 water evaporation, 15 Monolayers, interfacial, 497

N Neutron spin-echo spectroscopy, 708 Nuclear magnetic resonance (nmr)

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SUBJECT INDEX

characterizations, 975-996 of cloud point states, 996 of dilute isotropic states, 984 13 C chemical shift, 989 *H chemical shift, 985 13 C relaxation, 989 X H relaxation, 987 dynamics of nonionic surfactants, 971 mesomorphic states, 992 U C nmr studies, 992 2 H nmr studies, 992 of nonionic surfactants, 975 U C nmr studies, 979 X H nmr studies, 975 structure of nonionic surfactants, 971,999

1131

liquid crystallline, 298, 371, 379, 386, 399, 410, 413, 414, 973, 995 lower consolute boundary (LCB), 678, 738, 745 lower critical end point temperature T lc , 348 lower critical solution temperature (LOST), 189, 281-283, 299, 304, 376, 386, 404, 407-409, 414, 423, 424, 426, 495, 738, 742, 930, 939, 973 micellar, 344 miscibility gap, 415, 495 multicomponent systems, 243, 412, 417 pseudo-binary, 349 reversed bicontinuous cubic, 387 separation, 299 separation temperature, Tc, 678-680, 712, 743 surfactant, 377, 495, 498, 500 Oil recovery, tertiary, 100 ternary systems, 341, 344, 346, 412, Osmotic compressibility, 688-701 413, 418, 425, 500-502, 972 Oxidation rate, 1024-1026 upper critical end point temperature, Tuc, 348 upper critical solution temperature (UCST), 376, 408, 414, 423, 495, 679, 738, 742 PEO alkylethers (polyoxyethylene Winsor regimes, 378 (see also alcohols), 892, 894, 896-907, Winsor R-values) 909-914, 916, 917, 919 Photon correlation spectroscopy, 708 Permeation of water, 579, 580, 583 Phototropism of dyes, 313 Peterlin, 951, 999 PIT (see HLB temperature) Phase Pluradot ® HA-430, 871 anomalous, 376 Plurafac ® RA-40, 871 behavior, 369, 378, 404 Poisson-Boltzman equation, 405, 617 binary systems, 299, 302, 370, 379, Polyaciylamide, 886, 888 404, 411, 526 Polyacrylic acid (PAA), 888, 894-917 bicontinuous isotropic, 387, 404 Polyalkylene oxide copolymer, 930 equilibria, 369, 379, 380, 412, 418 Polyamino acid, 885 face-centered cubic, 412 Polyethylene glycol (PEG) 532, 928 inversion (see HLB temperature) Polyethylene oxide (PEO) (polyoxyisotropic cubic, 394, 412 ethylenes), 882, 886, 892-896, isotropic liquid, 299, 344, 655, 678 899, 900, 910, 915-917 lamellar (hexagonal), 298, 344, 371, Poly-y-benzyl-L-glutamate, 939 380, 386-388, 394, 403, 404, Polymethacrylic acid (PMA), 894, 411, 412, 424, 425, 427, 650, 973 902, 913, 916

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1132

Polymethylmethacrylate, 939 Polyoxyalkylenes solubilization, 1065 mixtures, 1065 Polyoxyethylene alcohols, 7, 9, 18, 29, 71, 379, 605 Polyoxyethylene alkylphenols, 6, 9, 19, 53, 387, 609 Polyoxyethylene-a.a'-dialkylethers, 12,22 Polyozyethylene chain configuration, 927, 949, 997 helix, 1000 meander, 999 random coil, 1002 zigzag, 999 conformation, 310, 503, 959 effect of micellar structure, 1002 effect of water on micelles, 1001 energy calculations, 999 degradation, 942-944,1013-1034 acid catalysts, 1020, 1021,1026, 1045, 1048-1050,1054-1056, 1059 concentration dependence, 1017, 1018, 1024, 1025, 1031, 1032, 1034, 1043,1044 degradation products, 1023-1031 hydroperoxides, 1016 (see also Free radicals) induction period, 1014 initiation kinetics, 1014-1027, 1033, 1034,1040-1057,10611065 mechanical, 1032 metal catalysts, 1014-1021, 1026, 1036-1038,1045, 1047-1053, 1056, 1057,1059, 1062-1067 peroxidation, 1015 (see also Autoxidation) reaction schemes, 1026-1031 temperature dependence, 1017, 1031, 1034, 1041-1043, 10451049, 1052,1057, 1061 test methods, 1041-1043

SUBJECT INDEX

dielectric behavior, 942-944, 10131034 distribution, 519-521 effect of terminal hydroxyl groups, 953 hydrodynamic properties, 927, 928 calculations of dimensions, 950 expansion factor, 953 steric hindrance parameter, 955 interfacial behavior, 958 molecular weight, 935 diffusion, 934 intrinsic viscosity, (see Rheology of polyoxyethylene chain) light scattering, 934, 935, 937 osmometry, 935, 936 photon correlation spectroscopy, 935 ultracentrifugation, 935, 937 molecular weight distribution, 935 relaxation time, 957 rheology (see Rheology of polyoxyethylene chain) stability, 1011 thermodynamics, 956 heat capacity, 956 heat of dilution, 956 heat of mixing, 956 Polyoxyethylenes, 928-963 Polyoxyglycols, autoxidation, 1021 degradation, 1021 test methods, 1021-1024 Polyoxypropylene (polypropylene oxide), 892, 928, 963 Polyoxypropylene alcohols, 29 Polyoxypropylene-polyoxyethylene alkylphenols, 609 Polysaccharides, 379 Polystyrene, 939 Polyvinylacetate (PVAc), 883, 886, 892,896 Polyvinylalcohol (PVA), 882, 892 Polyvinylpyrrolidone (PVP), 882, 883, 886, 887, 891-893, 899, 911, 913

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SUBJECT INDEX

Pulsed-gradient spin-echo nmr (PGSE) XH FTNMR, 732

y-Radiation, 1015-1018, 1022, 1025, 1027, 1031-1033 Radiotagged C14, 755, 780 Raoult's law, 247 Renormalization group theory (RGT), 744 Rheology of polyoxyethylene chain concentrated solutions, 945 dilute solutions, 938 drag reduction, 945 effect of electrolytes, 948 friction reduction, 945 glass-transition, 958 hard-sphere radius, 952 hydrodynamic volume, 952 intrinsic viscosity, 933, 937, 938, 941, 942, 951, 953, 956 Mark-Houwink constants, 938 pseudoplastic behavior, 947 shear dependence, 941 shear gradient, 928 structural turbulance, 945

Sedimentation, 448, 608 Silicon nonionic surfactants, 23 Small angle neutron scattering (SANS), 609, 659, 677 contrast variations internal and external, 693 external for C^Eg, 729 critical exponents for C„Em, 743 dispersions, 694, 710 dynamic SANS, 708 dilute solutions, 724 concentrated solutions, 727

1133

form factors for polydisperse particles, 691 for single particles, 686 interactions, 677 attractive, 700, 737, 738, 741, 743 electrostatic repulsions, 698 hydration forces, 701 micellar, 710 particle-particle, 696, 697 micellar growth of C„Em, 732 SANS data for C..E,,,, 710 C8E4 and C8Es, 722 C8E4, 678, 722, 727 CgEs, 722, 724, 725, 727, 739 daEg, 727, 737, 745 CUJES, 678, 712, 718, 720, 722,

733-737, 746 CiaEg, 678, 714, 717, 718, 722, 724, 725, 727, 729, 732-734, 743-746 CioE4, 744, 745 CjsEg, 727 model 1 for C ^ a , 714 model 2 for C12Eg, 717 simulation scattering of Ci2E6, 722 static data for C12Eg, 720 spectrometer, 703 static SANS concentrated solutions, 727 dilute solutions, 681, 703, 712 theory, 681 Small angle X-ray scattering (SAXS), 682, 684 Sodium carboxymethylsuccinate (CMOS), 805 Sodium nitrilo acetate, 805 Sodium (TSPP) or potassium (TKPP) tetrapyrophosphate, 805 Sodium tripolyphosphate (STPP), 805 Soil redeposition, 759, 785 Soil removal, 756 from cellulose, 780, 783, 785, 792

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1134

[Soil removal] effect of interfacial tension, 766, 773-776 effect of substrate, 780 of mineral oil, 762-770 of natural soil, 770-773 from nylon, 780, 783 of oily soil, 756-761, 780, 785 of particulate soil, 783, 784 from polyester, 761, 780, 783, 785 by surfactant mixtures, 776-780 from Teflon, 774, 780 roll-up mechanism, 756 test methods, 755 theory, 756 Solubility in apolar solvents, 186 cloud point, 139, 281, 299, 301, 302, 304, 305, 320, 321, 323, 376, 379, 387, 407, 496, 505-507, 526, 533, 658, 659-661, 663, 678, 937, 973, 996 cohesive energy density, 187, 188, 206,453 double cloud point, 303-305, 348 effect of temperature, 188 gap, 376, 380, 415 haze point, 349, 353, 497 hydrotrope, 660, 661 Krafft point, 139, 305, 306 parameter (SP), 153-155, 157,187, 188, 206, 453, 610, 929 precipitation temperature, 929 salting in, 307, 308 salting out, 307, 321, 324, 613, 660, 661, 931, 932, 940 second virial coefficient, 935 9-temperature, 932, 940, 949 Solubilization, 209, 297 absorption spectra, 887 acid-base indicator equilibria, 218, 221 in aqueous systems, 308, 496 dye, 899 effect of cloud point, 320 effect on cmc, 314

SUBJECT INDEX

effect of electrolytes, 306, 353 effect on micellar size, 318 effect of O/W partition coefficient, 337,338 effect of O/W ratio, 328 effect of solubilizate, 330 effect of surfactant, 330 effect of temperature, 213, 320 ear spectroscopy, 311 fluorescence probe, 311, 887 infrared spectroscopy, 313 kinetics, 361 locus, 308, 310, 326 in nonaqueous systems, 496 nmr spectroscopy, 216, 217, 311 polar substances-surfactant interactions, 217, 218 polymer surfactant complex, 916 of water, 210, 213-217, 413, 420 water-surfactant interactions, 216, 217 ultraviolet spectroscopy, 311, 313 X-ray diffraction, 311 Yellow OB, 359, 916 Solutions apparent specific volume, 145-147, 149 compressibility. 144-147,149 freezing point lowering, 277 light scattering, 277, 278 membrane osmometry, 277 multicomponent systems, 243 neutron scattering, 277 quasi-elastic light scattering, 277 phase approximation, 246 sedimentation rate, 277 vapor pressure osmometry, 277 Sorbitan esters, 12 Stabilization of polyoxyalkylenes, 1059 by antioxidants, 1060, 1062 by preservatives, 1060 by purification, 1059 by storage conditions, 1059 Steric stabilization, 604, 632-635, 650, 665, 759

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SUBJECT INDEX

denting potential, 635 interpenetration domain, 633, 635 interpenetration-plus-compression domain, 633, 635 Surface area, 2, 3, 7, 9 dilational modulus, 37 (see also Foam stability) Gibbs elasticity, 37 (see also Foam stability) excess, 3,16, 48 potential, 15, 31, 32, 36 pressure, 2, 3, 4, 27, 79, 129, 163, 165 rheology, 34, 37 tension, 5, 15, 17, 19, 21, 22, 24, 27, 31, 34, 37-39 (see also Surface pressure) Surfactants, homogeneous nonionic, 110 Szyskowski equation, 25-29, 38

TCNQ (7, 7, 8, 8-tetracyanoquinodimethane), 114, 118 Temkin equation, 29, 37 Thermotropic mesomorphism, 973 Thermodynamics, 233 enthalpy effect, 410 entropy of mixing, 407, 408 free energy of mixing, 186 of micellar parameters, 284 of micelle formation, 131, 134,135, 137-139, 141, 208, 209, 233, 236

1135

of monolayers, 24, 30, 31 Traube's rule, 20, 23, 129, 286

Viscosity, 610, 652, 735

W

Wetting, 45, 46, 51, 67 agent, 102 contact angle, 51, 610 heat of (see Heat) interfacial energy, 759, 783 tension, 51 time (Draves test), 68, 84, 90 Wilhelmy method, 34, 36 Winsor, R-values, 341, 345, 378, 495

X-ray diffraction, 75, 78, 613, 614, 997, 1001

Young equation, 757 Z ZeoUte A, 92, 805, 818