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 233

Denver G. Hall

6. SOLUBILIZATION 2 9 7
Raymond A. Mackay

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 549

Sachio Matsumoto

11. 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 881

Shuji Saito

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 1011

Max Donbrow
Author Index 1073
Subject Index 1123
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
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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
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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
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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 simplifica-
tions 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 popula-
tion 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 non-
ionic 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 devia-
tions 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
298 MACKAY

C. Other Systems 359

D. Rate of Solubilization 361
References 363

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 incor-
porate 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 micel-
lization.
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 jour-
nals, 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.
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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
370 SJ0BLOM, STENIUS, AND DANIELSSON

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 crystal-
line without swelling appreciably with water. This will usually be the case
well below the melting point of the surfactant.

/
/
/
/
! W + L2
60 r
o L2
e
3

I JU r ' 1
L
1 a
I
; w + u i

25
i
i
i
i •

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 emulsifi-
cation 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 emulsify-
ing 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 two-
phase 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
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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
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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
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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 Inter-
actions 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
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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 Cylin-
ders 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. Nonscatter-
ing Techniques 732
G. Attractive Interactions Between Nonionic Micelles 737
H. Surfactant-Dependent Critical Exponents for C„Ems 743
IV. CONCLUSIONS 745
References 746
677
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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 discus-
sion of detergency would be repetitious; therefore, this chapter empha-
sizes those aspects of detergency which are relevant to nonionic sur-
factants. 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 deter-
gency 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 sur-
factants 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 solubiliz-
ing 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 oxi-
dative sensitivity to the heat and large volumes of air used in the spray-
drying 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
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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
972 RIBEIRO AND DENNIS

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 possibili-
ties 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 autoxi-
dation 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 es-
pecially important in revealing the mechanisms underlying the decompo-
sition 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 substitu-
ents, 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 de-
composition 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.

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
 Page links created automatically - some may be erroneous
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
 Page links created automatically - some may be erroneous

1124 SUBJECT INDEX

[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 mul-
tilayers), 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
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), 889-
891, 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
 Page links created automatically - some may be erroneous
SUBJECT INDEX
Orange OT, 315
surface tension, 112, 114, 124, 129,
159, 161, 191, 277
TCNQ solubilization, 114,118,124,
151, 153,161,167, 317 (see also
TCNQ)
vapor pressure osmometry, 191
Coagulation, 637, 642, 647, 650, 653
critical coagulation concentration,
619, 644, 646
Cosurfactant, 355
Crown ethers, 22, 529
CVP (Carbomer, Carbopole), 911-
913, 915
Debye-Bueche equation, 950, 999
Debye-McAulay equation, 931
Decomposition of nonionic surfac-
tants, 1043-1058
effect of hydrophobic group, 1056
polyoxyethylene alcohols, 1043
polyoxyethylene fatty acid esters,
1051
polyoxyethylene sorbitans, 1051
Demulsification
coalescence, 437, 458, 512
flocculation, 437, 458
instability, 437
Detergency, 99, 753 (see also Soil
removal)
of alkyl ether sulfates, 811
cold water, 822
in compositions, 813
effect of anionic/nonionic mixtures,
807
effect of cationic/nonionic mixtures,
810
effect of enzymes, 820
effect of EO distribution, 801
effect of phosphate builders, 805
hard surface, 823
heavy-duty laundry, 814
1125
interaction of clay/det./cellulose,
792
kinetics, 760, 788
light-duty dishwashing, 821
machine dishwashing, 821
polyalkylene oxide block
copolymers, 802
polyoxyethylene alcohols, 795
polyoxyethylene alkylphenols, 800
polyoxyethylene fatty acid esters,
795
rinse aids, 822
sugar-based surfactants, 802
Diffusion coefficient, 36, 84, 89, 265,
268, 732, 839
Dimethyldecyl phosphine oxide, 615,
617, 623, 644
Dimethyldodecyl phosphine oxide, 87,
608
Dipole
interactions, 5, 34
moment, 5, 32
Direct force measurements, 657
Disjoining pressure, 577
Dispersions, 100, 601
Dispersion stability, 601, 602, 642-665
effect of additives, 658-665
effect of electrical double layer,
642-644
effect of particle size, 649-651
effect of surfactant concentration,
644-649
effect of surfactant type, 644-649
effect of temperature, 651-658
polymer, T p 658
stability ratio, 625, 637, 644, 647
Distearyldimethyl ammonium
chloride, 92
DLVO theory 577, 624-626, 759, 846
attractive energy potential, 577,
624, 626, 666, 667
potential energy of interaction, 624,
625
repulsive energy potential, 577, 624,
626, 666, 667
Dodecyl sulfobetaine, 623
 Page links created automatically - some may be erroneous
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, 616-
621, 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
 Page links created automatically - some may be erroneous
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, 859-
861
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, 855-
858
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, 1028-
1031, 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
 Page links created automatically - some may be erroneous
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, 493-
496, 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 sur-
factant, 892
polymeric acid/nonionic surfactant,
893, 911
polypeptide/ionic surfactant, 888
protein/ionic surfactant, 888
 Page links created automatically - some may be erroneous
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 surfac-
tants, 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, 607-
612, 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 copoly-
mers, 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 Inter-
action forces), by SANS, 678-
680,710
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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 surfac-
tants, 112
ideal mixtures, 90
kinetic model, 273
kinetics, 266
of mixtures, 287, 356
of mixtures of homogeneous non-
ionic surfactants, 158
of mixtures of nonionic and anionic
surfactants, 159
of mixtures of nonionic and cation-
ic surfactants, 175
in nonaqueous media (see Re-
versed)
noninteracting, 241
SUBJECT INDEX
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 sol-
vents, 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)
 Page links created automatically - some may be erroneous
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
Oil recovery, tertiary, 100
Osmotic compressibility, 688-701
Oxidation rate, 1024-1026
PEO alkylethers (polyoxyethylene
alcohols), 892, 894, 896-907,
909-914, 916, 917, 919
Permeation of water, 579, 580, 583
Peterlin, 951, 999
Phase
anomalous, 376
behavior, 369, 378, 404
binary systems, 299, 302, 370, 379, Polyaciylamide, 886, 888
404, 411, 526
bicontinuous isotropic, 387, 404
equilibria, 369, 379, 380, 412, 418
face-centered cubic, 412
inversion (see HLB temperature)
isotropic cubic, 394, 412
isotropic liquid, 299, 344, 655, 678
lamellar (hexagonal), 298, 344, 371, Poly-y-benzyl-L-glutamate, 939
380, 386-388, 394, 403, 404,
411, 412, 424, 425, 427, 650, 973
1131
liquid crystallline, 298, 371, 379,
386, 399, 410, 413, 414, 973, 995
lower consolute boundary (LCB),
678, 738, 745
lower critical end point tempera-
ture 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
ternary systems, 341, 344, 346, 412,
413, 418, 425, 500-502, 972
upper critical end point tempera-
ture, Tuc, 348
upper critical solution temperature
(UCST), 376, 408, 414, 423,
495, 679, 738, 742
Winsor regimes, 378 (see also
Winsor R-values)
Photon correlation spectroscopy, 708
Phototropism of dyes, 313
PIT (see HLB temperature)
Pluradot ® HA-430, 871
Plurafac ® RA-40, 871
Poisson-Boltzman equation, 405, 617
Polyacrylic acid (PAA), 888, 894-917
Polyalkylene oxide copolymer, 930
Polyamino acid, 885
Polyethylene glycol (PEG) 532, 928
Polyethylene oxide (PEO) (polyoxy-
ethylenes), 882, 886, 892-896,
899, 900, 910, 915-917
Polymethacrylic acid (PMA), 894,
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, 1034,1040-1057,1061-
1065
mechanical, 1032
metal catalysts, 1014-1021, 1026,
1036-1038,1045, 1047-1053,
1056, 1057,1059, 1062-1067
peroxidation, 1015 (see also Au-
toxidation)
reaction schemes, 1026-1031
temperature dependence, 1017,
1031, 1034, 1041-1043, 1045-
1049, 1052,1057, 1061
test methods, 1041-1043
SUBJECT INDEX
dielectric behavior, 942-944, 1013-
1034
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 poly-
oxyethylene 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 inter-
actions, 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 1135

denting potential, 635 of monolayers, 24, 30, 31

interpenetration domain, 633, 635 Traube's rule, 20, 23, 129, 286
interpenetration-plus-compression
domain, 633, 635
Surface
area, 2, 3, 7, 9
dilational modulus, 37 (see also Viscosity, 610, 652, 735
Foam stability)
Gibbs elasticity, 37 (see also Foam
stability) W
excess, 3,16, 48
potential, 15, 31, 32, 36 Wetting, 45, 46, 51, 67
pressure, 2, 3, 4, 27, 79, 129, 163, agent, 102
165 contact angle, 51, 610
rheology, 34, 37 heat of (see Heat)
tension, 5, 15, 17, 19, 21, 22, 24, 27, interfacial energy, 759, 783
31, 34, 37-39 (see also Surface tension, 51
pressure) time (Draves test), 68, 84, 90
Surfactants, homogeneous nonionic, Wilhelmy method, 34, 36
110 Winsor, R-values, 341, 345, 378, 495
Szyskowski equation, 25-29, 38

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

TCNQ (7, 7, 8, 8-tetracyanoquino- 997, 1001
dimethane), 114, 118
Temkin equation, 29, 37
Thermotropic mesomorphism, 973
Thermodynamics, 233
enthalpy effect, 410 Young equation, 757
entropy of mixing, 407, 408
free energy of mixing, 186
of micellar parameters, 284 Z
of micelle formation, 131, 134,135,
137-139, 141, 208, 209, 233, 236 ZeoUte A, 92, 805, 818