Liquid Detergents (Surfactant Science Series) PDF

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Liquid Detergents

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SURFACTANT SCIENCE SERIES
CONSULTING EDITORS
MARTIN J. SCHICK
Consultant
FREDERICK M. FOWKES
(19151990)
New York, New York
1. Nonionic Surfactants, edited by Martin J. Schick (see also Volumes 19,
23, and 60)
2. Solvent Properties of Surfactant Solutions, edited by Kozo Shinoda (see
Volume 55)
3. Surfactant Biodegradation, R. D. Swisher (see Volume 18)
4. Cationic Surfactants, edited by Eric Jungermann (see also Volumes 34,
37, and 53)
5. Detergency: Theory and Test Methods (in three parts), edited by W. G.
Cutler and R. C. Davis (see also Volume 20)
6. Emulsions and Emulsion Technology (in three parts), edited by Kenneth J.
Lissant
7. Anionic Surfactants (in two parts), edited by Warner M. Linfield (see
Volume 56)
8. Anionic Surfactants: Chemical Analysis, edited by John Cross (out of print)
9. Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato
and Richard Ruch (out of print)
10. Anionic Surfactants: Biochemistry, Toxicology, Dermatology, edited by
Christian Gloxhuber (see Volume 43)
11. Anionic Surfactants: Physical Chemistry of Surfactant Action, edited by E.
H. LucassenReynders (out of print)
12. Amphoteric Surfactants, edited by B. R. Bluestein and Clifford L. Hilton
(see Volume 59)
13. Demulsification: Industrial Applications, Kenneth J. Lissant (out of print)
14. Surfactants in Textile Processing, Arved Datyner
15. Electrical Phenomena at Interfaces: Fundamentals, Measurements, and
Applications, edited by Ayao Kitahara and Akira Watanabe
16. Surfactants in Cosmetics, edited by Martin M. Rieger (out of print)
17. Interfacial Phenomena: Equilibrium and Dynamic Effects, Clarence A.
Miller and P. Neogi
18. Surfactant Biodegradation: Second Edition, Revised and Expanded, R. D.
Swisher
19. Nonionic Surfactants: Chemical Analysis, edited by John Cross

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20. Detergency: Theory and Technology, edited by W. Gale Cutler and Erik
Kissa
21. Interfacial Phenomena in Apolar Media, edited by HansFriedrich Eicke
and Geoffrey D. Parfitt
22. Surfactant Solutions: New Methods of Investigation, edited by Raoul
Zana
23. Nonionic Surfactants: Physical Chemistry, edited by Martin J. Schick
24. Microemulsion Systems, edited by Henri L. Rosano and Marc Clausse
25. Biosurfactants and Biotechnology, edited by Naim Kosaric, W. L.
Cairns, and Neil C. C. Gray
26. Surfactants in Emerging Technologies, edited by Milton J. Rosen
27. Reagents in Mineral Technology, edited by P. Somasundaran and Brij
M. Moudgil
28. Surfactants in Chemical/Process Engineering, edited by Darsh T. Wasan,
Martin E. Ginn, and Dinesh O. Shah
29. Thin Liquid Films, edited by I. B. Ivanov
30. Microemulsions and Related Systems: Formulation, Solvency, and Physical
Properties, edited by Maurice Bourrel and Robert S. Schechter
31. Crystallization and Polymorphism of Fats and Fatty Acids, edited by
Nissim Garti and Kiyotaka Sato
32. Interfacial Phenomena in Coal Technology, edited by Gregory D.
Botsaris and Yuli M. Glazman
33. SurfactantBased Separation Processes, edited by John F. Scamehorn
and Jeffrey H. Harwell
34. Cationic Surfactants: Organic Chemistry, edited by James M. Richmond
35. Alkylene Oxides and Their Polymers, F. E. Bailey, Jr., and Joseph V.
Koleske
36. Interfacial Phenomena in Petroleum Recovery, edited by Norman R.
Morrow
37. Cationic Surfactants: Physical Chemistry, edited by Donn N. Rubingh
and Paul M. Holland
38. Kinetics and Catalysis in Microheterogeneous Systems, edited by M.
Grätzel and K. Kalyanasundaram
39. Interfacial Phenomena in Biological Systems, edited by Max Bender
40. Analysis of Surfactants, Thomas M. Schmitt
41. Light Scattering by Liquid Surfaces and Complementary Techniques,
edited by Dominique Langevin
42. Polymeric Surfactants, Irja Piirma
43. Anionic Surfactants: Biochemistry, Toxicology, Dermatology. Second
Edition, Revised and Expanded, edited by Christian Gloxhuber and Klaus
Künstler
44. Organized Solutions: Surfactants in Science and Technology, edited by
Stig E. Friberg and Björn Lindman
45. Defoaming: Theory and Industrial Applications, edited by P. R. Garrett
46. Mixed Surfactant Systems, edited by Keizo Ogino and Masahiko Abe
47. Coagulation and Flocculation: Theory and Applications, edited by
Bohuslav Dobiáš

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48. Biosurfactants: Production • Properties • Applications, edited by Naim
Kosaric
49. Wettability, edited by John C. Berg
50. Fluorinated Surfactants: Synthesis • Properties • Applications, Erik Kissa
51. Surface and Colloid Chemistry in Advanced Ceramics Processing, edited
by Robert J. Pugh and Lennart Bergström
52. Technological Applications of Dispersions, edited by Robert B. McKay
53. Cationic Surfactants: Analytical and Biological Evaluation, edited by John
Cross and Edward J. Singer
54. Surfactants in Agrochemicals, Tharwat F. Tadros
55. Solubilization in Surfactant Aggregates, edited by Sherril D. Christian
and John F. Scamehorn
56. Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache
57. Foams: Theory, Measurements, and Applications, edited by Robert K.
Prud'homme and Saad A. Khan
58. The Preparation of Dispersions in Liquids, H. N. Stein
59. Amphoteric Surfactants: Second Edition, edited by Eric G. Lomax
60. Nonionic Surfactants: Polyoxyalkylene Block Copolymers, edited by
Vaughn M. Nace
61. Emulsions and Emulsion Stability, edited by Johan Sjöblom
62. Vesicles, edited by Morton Rosoff
63. Applied Surface Thermodynamics, edited by A. W. Neumann and Jan K.
Spelt
64. Surfactants in Solution, edited by Arun K. Chattopadhyay and K. L.
Mittal
65. Detergents in the Environment, edited by Milan Johann Schwuger
66. Industrial Applications of Microemulsions, edited by Conxita Solans and
Hironobu Kunieda
67. Liquid Detergents, edited by KuoYann Lai
ADDITIONAL VOLUMES IN PREPARATION
Surfactants in Cosmetics: Second Edition, Revised and Expanded, edited by
Martin M. Rieger and Linda Rhein
Powdered Detergents, edited by Michael S. Showell
Enzymes in Detergency, edited by Jan H. van Ee, Onno Misset, and Erik J.
Baas

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Liquid Detergents
edited by
KuoYann Lai
ColgatePalmolive Company
New York, New York
M ARCEL DEKKER, INC.
N EW YORK • BASEL

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Library of Congress CataloginginPublication Data
Liquid detergents / edited by KuoYann Lai.
p. cm. — (Surfactant science series ; v. 67)
Includes index.
ISBN 0824793919 (hardcover : alk. paper)
1. Detergents. I. Lai, KuoYann. II. Series.
TP992.5.L56 1996
668'.14—dc20
9644787
CIP
The publisher offers discounts on this book when ordered in bulk quantities.
For more information, write to Special Sales/Professional Marketing at the
address below.
This book is printed on acidfree paper.
Copyright © 1997 by Marcel Dekker, Inc. All Rights Reserved.
Neither this book nor any part may be reproduced or transmitted in any form
or by any means, electronic or mechanical, including photocopying,
microfilming, and recording, or by any information storage and retrieval system,
without permission in writing from the publisher.
Marcel Dekker, Inc.
270 Madison Avenue, New York, New York 10016
Current printing (last digit):
10 9 8 7 6 5 4 3 2
PRINTED IN THE UNITED STATES OF AMERICA

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Preface
Liquid detergents play very important roles in our daily lives for personal care,
household surface care, and fabric care. We use these products just about
every day from washing our hands, hair, dishes, clothes to cleaning various
surfaces in our homes. In the last three decades, liquid detergents have gained
an increasing popularity largely due to the convenience they offer over other
forms. During this period, there have been significant advances in both science
and technology in this area. Numerous papers have been published in
professional journals and trade magazines, thousands of patents have been
granted, and large number of new products have been introduced to the
marketplace. The objective of this volume is to provide a comprehensive
review of these advances.
This is the first book specifically devoted to the review and discussion of liquid
detergents. It is intended primarily for scientists and engineers working in the
detergent industry and the detergent raw materials industry around the world.
Researchers in other industries—such as those in the petroleum industry who
are involved in enhanced oil recovery and those in textile processing—as well
as those in academia will also useful information in this volume.
Consistent with the overall aim of the Surfactant Science Series, this volume
covers both theoretical and applied aspects of liquid detergents. There are a
total of 14 chapters. Chapter 1 gives a concise account of the past, present,
and future of liquid detergents. The rest of the volume is structured into two
parts—theories and applications. Chapters 2–6 present an indepth discussion
of theories of common importance to most liquid detergent systems including
hydrotropy, phase equilibria, rheology, polymeric stabilizers, and nonaqueous
surfactant systems. Chapters 7–13 cover the technological aspects of liquid
detergents in various practical applications from light and heavyduty liquid

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detergents, liquid automatic dishwasher detergents, liquid soaps, shampoos
and conditioners, and fabric softeners to specialty liquid household surface
cleaners. Chapter 14 focuses on the manufacturing aspects of liquid detergents.
It is hoped that this volume will not only serve as a handy reference to
researchers but also stimulate many new innovations in the detergent field.
I want to take this opportunity to express my sincere thanks to Colgate
Palmolive Company for permitting me to undertake this project and to the
leadership team at its Global Technology Division for their strong support.
Special thanks also go to all the contributors of this book not only for sharing
their expertise and extensive experience but also for patiently enduring the
unavoidable delays of a multiauthored book.
I would also like to express my gratitude to Dr. Martin Schick, the consulting
editor of this series, for his valuable suggestions, encouragement and patience;
and to the publisher, Marcel Dekker Inc., in particular, Ms. Anita Lekhwani,
Associate Acquisitions Editor, and Mr. Joseph Stubenrauch, Production
Editor, for their patience and invaluable help.
Finally, I want to thank my wife, Jane, and my children, Melody, Amy, and
Peter for their endurance and support in the last several years. It was with their
love and understanding that I was able to devote numerous evenings and
weekends to complete this task.
KUOYANN LAI

Contents
Preface
Contributors
1. Liquid Detergents: An Overview
Arno Cahn
2. Hydrotropy
Stig E. Friberg and Chris Brancewicz
3. Phase Equilibria
Guy Broze
4. Rheology of Liquid Detergents
R. S. Rounds
5. Polymeric Stabilizers for Liquid Detergents
Madukkarai K. Nagarajan and Hal Ambuter
6. Nonaqueous Surfactant Systems
Marie Sjöberg and Torbjörn Wärnheim
7. LightDuty Liquid Detergents
KuoYann Lai, Elizabeth F. K. McCandlish, and Harry Aszman
8. HeavyDuty Liquid Detergents
Amit Sachdev and Santhan Krishnan
9. Liquid Automatic Dishwasher Detergents
Philip A. Gorlin, KuoYann Lai, and Nagaraj Dixit

10. Shampoos and Conditioners
Clarence R. Robbins
11. Liquid Soaps
Richard E. Reever
12. Fabric Softeners
Alain Jacques and Charles J. Schramm, Jr.
13. Specialty Liquid Household Surface Cleaners
Karen Wisniewski
14. Manufacture of Liquid Detergents
R. S. Rounds
Index

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Contributors
Hal Ambuter Specialty Chemical Division—Product Development, The
BFGoodrich Company, Brecksville, Ohio
Harry Aszman Research and Development, Global Technology, Colgate
Palmolive Company, Piscataway, New Jersey
Chris Brancewicz Department of Chemistry and Center for Advanced
Materials Processing, Clarkson University, Potsdam, New York
Guy Broze Advanced Technology Department, ColgatePalmolive Research
and Development, Inc., Milmort, Belgium
Arno Cahn Arno Cahn Consulting Services, Inc., Pearl River, New York
Nagaraj Dixit Research and Development, Global Technology, Colgate
Stig E. Friberg Department of Chemistry and Center for Advanced Materials
Processing, Clarkson University, Potsdam, New York
Philip A. Gorlin Research and Development, Global Technology, Colgate
Alain Jacques Fabric Care, ColgatePalmolive Research and Development,
Inc., Milmort, Belgium
Santhan Krishnan Research and Development, Global Technology, Colgate

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KuoYann Lai Global Materials and Sourcing (AsiaPacific Division), Global
Technology, ColgatePalmolive Company, New York, New York
Elizabeth F. K. McCandlish Research and Development, Global
Technology, ColgatePalmolive Company, Piscataway, New Jersey
Madukkarai K. Nagarajan Specialty Chemical Division—Product
Development, The BFGoodrich Company, Brecksville, Ohio
Richard E. Reever Richard Reever and Associates, Inc., Minnetonka,
Minnesota
Clarence R. Robbins Research and Development, Global Technology,
ColgatePalmolive Company, Piscataway, New Jersey
R. S. Rounds Fluid Dynamics, Inc., Piscataway, New Jersey
Amit Sachdev Research and Development, Global Technology, Colgate
Charles J. Schramm, Jr. Research and Development, Global Technology,
Marie Sjöberg Institute for Surface Chemistry, Stockholm, Sweden
Torbjörn Wärnheim* Institute for Surface Chemistry, Stockholm, Sweden
Karen Wisniewski Research and Development, Global Technology,
*Current affiliation: Pharmacia & Upjohn, Stockholm, Sweden

1
Liquid Detergents: An Overview
ARNO CAHN
Arno Cahn Consulting Services, Inc., Pearl River, New York
I. Introduction
II. LightDuty Liquids
III. HeavyDuty Liquids
IV. Liquid Automatic Dishwasher Detergents
V. Shampoos and Conditioners
VI. Liquid Soaps
VII. Fabric Softeners
VIII. Specialty Liquids
IX. Manufacture and Raw Materials
References
I. Introduction
Liquid detergents are convenience products. Compared with powdered detergen
dissolve more rapidly, particularly in cold water, they generate less dust, and they
dose. It is not surprising, therefore, that liquid forms of household cleaning produ
developed by manufacturers.
With the exception of fabric softeners and shampoos, the solid form of cleaning p
preceded the liquid form. This is true of manual and automatic dishwashing, laund
general personal washing products. As a result,

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the technical history of liquid detergents is to a large extent one of emulating the
performance features of the powder models.
All other factors—soil, water hardness, and temperature—being equal,
cleaning performance is a function of the concentration and type of the active
ingredients that are delivered into the cleaning bath. Almost by definition, the
liquid form involves a dilution of the active ingredients, that is, a given volume
of a powdered detergent can generally deliver more active ingredients than an
equal volume of a liquid detergent. The task to provide performance equality
with powders is therefore not insignificant. It is made even more difficult when
inorganic salts are used to provide certain specific performance features. These
salts often pose problems of solubility and compatibility with the organic
surfactants of the formulation. Finally, formulation problems are most severe
when the active component is less stable in an aqueous environment than in a
solid matrix.
These considerations apply principally to the heavyduty liquids, the largest of
the liquid detergent categories, but they also come into play with liquid
automatic dishwasher detergents.
The situation is different for products designed for lightduty, hand dishwashing
and for softening fabrics. These liquids are generally superior in performance to
their powdered counterparts to the extent that these existed in the first place.
This is also true of shampoo formulations, for which there is no common solid
equivalent.
This chapter gives an essentially historical overview of the various categories.
Historically, soapbased shampoos and the liquid potassium oleate
formulations found in washroom dispensers were probably the earliest
commercial liquid detergents.
II. LightDuty Liquids
On a truly commercial scale, the age of liquid detergents can be said to have
begun in the late 1940s when the first liquid detergent for manual dishwashing
was introduced. This liquid consisted essentially of a nonionic surfactant:
alkylphenol ethoxylate. In use, it produced only a moderate amount of foam in
the dishpan.
This proved to be a serious detriment. To be successful, consumer product
innovations must show a large measure of similarity to the conventional
products they are intended to displace. In this case, copious foam was the
essential performance attribute that needed to be as close to that which could
be generated from powders and soap chips.
The requirement for copious foam levels has a technical basis and is more than
a mere emotional reaction to a visual phenomenon. With soapbased products,
the appearance of a permanent foam signaled that all hard water ions had

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been removed by precipitation as calcium and magnesium carboxylates and
that excess soap was now available to act as a surfactant.
The foaming requirements for lightduty liquids were met by the next series of
product introductions in the early 1950s. These formulations were based on
highfoaming anionic surfactants. They were capable of maintaining adequate
levels of foam throughout the dishwashing process and possessed sufficient
emulsifying power to handle the load of grease in the dishpan to produce
“squeaky clean” dishware.
In practice, this was accomplished by a mixture of anionic surfactants—
alkylbenzenesulfonate, alcohol ether sulfate, and alcohol sulfates—sometimes
in combination with nonionic surfactants. To maintain foam stability,
alkanolamides were incorporated. In some products, alkanolamides were
subsequently replaced by longchain amine oxides.
The formulation of lightduty liquids overcame a second major technical hurdle
inherent in the formulation of all liquid detergents: to maintain homogeneity in
the presence of significant levels, about 30% or more, of moderately soluble
organic surfactants. Coupling agents or hydrotropes were introduced for this
purpose, specifically the shortchain alkylbenzenesulfonates, such as xylene,
cumene and toluenesulfonates, as well as ethanol.
Lightduty liquids have maintained a significant market volume to this day. This
is somewhat surprising because the primary function of these products is to
wash dishes. In newer homes and apartments, this function has been taken
over by automatic dishwashing machines and the special detergents developed
for use in these machines. Both have expanded greatly since their introduction
in the late 1950s. Some part of the persistence of lightduty liquids is no doubt
a result of their use as finefabric detergents for washing delicate laundry items
by hand.
Over the years, minor additives have been incorporated into lightduty liquid
formulations, principally to support marketing claims for special performance
features. For a period of time in the 1960s, antimicrobials were incorporated
into some products designed to prevent secondary infections of broken skin
during dishwashing. After an absence of some 30 years, antimicrobials are
again appearing in lightduty liquids. Their return is no doubt connected with
increasing awareness of the possible presence of bacteria in foods, especially
in chicken. Other commercial products contained protein as a skin benefit
agent.
Improving the condition of skin as a result of exposure to lightduty liquid
solutions proved to be technically very difficult. Exposure times are relatively
short, about 20 minutes, three times a day under the best of circumstances, and
use concentrations are low, about 0.15%. The combination of low use levels
and short exposure times makes it difficult to overcome the adverse effects of
skin exposure to other inimical influences, such as dry air in heated homes and
strong household chemicals.

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Generally speaking, lightduty liquid compositions are relatively nonirritating to
skin. Mildness to skin could therefore be claimed by these products with
reasonable justification. During the 1960s and 1970s, the cosmetic image was
further enhanced by opacifying lightduty liquids and conferring upon them a
lotionlike appearance. In more recent years, dishwashing efficacy—effective
emulsification of grease—combined with persistent foam, has been the main
objective of technical product improvement.
In line with cleaning efficacy, solid particles have also been incorporated into
some lightduty liquid formulations with the objective of raising the
effectiveness of the products in removing solid cakedon soil from dishes.
III. HeavyDuty Liquids
Once lightduty liquid products had established an attractive market position,
the development of heavyduty liquids could not be far behind. Here, too, the
requirement of similarity to the existing products had to be met, in this case
powdered laundry detergents. The powdered laundry detergents of the 1950s
were characterized by the presence of high levels of builder, specifically
pentasodium tripolyphosphate (STPP), and relatively low levels, about 15%,
of surfactants. In formulating a heavyduty liquid, therefore, the major technical
objective was to find ways of stably incorporating maximum levels of builder
salts.
The first commercially important heavyduty liquid was introduced into the
U.S. market in 1958. The product was built with tetrapotassium
pyrophosphate, which is more soluble than STPP. Even so, in the presence of
a surfactant system of sodium alkylbenzenesulfonate and a mixture of
alkanolamides, the formulation could tolerate only 15–20% of tetrapotassium
pyrophosphate.
Incorporation of an antiredeposition agent, another ingredient present in
laundry powders, proved to be another major technical hurdle.
Antiredeposition agents, generally carbohydrate derivatives, such as
carboxymethylcellulose, had been introduced into laundry powders to prevent
greying after a number of repeat wash cycles.
In one product, the patented solution to this problem consisted of balancing
two antiredeposition agents of different specific gravity such that the tendency
of one to rise in the finished product was counterbalanced by the tendency of
the second agent to settle out of the product [1].
Even though the first major commercial heavyduty liquid composition was
formulated with a builder system, the concentrations of builders and surfactants
it delivered into the washing solution were lower than those provided by the
conventional detergent powders. As a liquid, however, the product possessed
a unique convenience in use, particularly for fullstrength application to specific
soiled areas of garments. Convenience was accompanied by effectiveness,

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because the concentration of individual ingredients in the neat form approached
that of a nonaqueous system.
This is illustrated by the following consideration. Recommended washing
product use directions lead to washing solutions with a concentration of about
0.15% of the total product. At a surfactant level of about 15% in the product,
the final concentration of surfactant in the wash liquor is about 0.0225%. The
efficacy of surfactant in providing observable cleaning at such low
concentration attests to the power of the interfacial phenomena that underlie
the action of surfactants.
By contrast, a heavyduty liquid containing 20% surfactant, applied full
strength, leads to a surfactant concentration of 20%, some three orders of
magnitude larger than in the earlier case. At these—almost nonaqueous—
concentrations, solution phenomena, such as those operating in nonaqueous
dry cleaning, are likely to be responsible for cleaning efficacy. The popularity
of heavyduty liquids for pretreating stains was thus based not only on
convenience but also on real performance.
In the mid1960s, the branchedchain surfactants were replaced by more
biodegradable analogs in all laundry products. In heavyduty liquids, sodium
alkylbenzenesulfonate, derived from an alkylbenzene with a tetrapropylene side
chain, was replaced by its straightchain analog, referred to as sodium linear
alkylbenzenesulfonate (LAS).
The conversion to more biodegradable surfactants was prompted by the
appearance of foams on river. The appearance of excessive algal growth on
stagnant lakes prompted a second environmental development that proved to
be beneficial to the expansion of heavyduty liquids: the reduction or
elimination of the sodium tripolyphosphate builder from laundry detergents.
Restrictions on the use of phosphate in laundry detergents were imposed by a
number of states and smaller administrative agencies beginning in 1970.
Because no totally equivalent phosphate substitute was immediately available,
the performance of heavyduty laundry powders was adversely affected. As
the wholewash performance differential between powders and liquids
narrowed, the usage of heavyduty liquids for the whole wash expanded,
markedly so in areas where phosphate had been banned.
In the first nonphosphate version of the commercial product, phosphate was
replaced by NTA (trisodium nitrilotriacetate), a powerful builder, comparable
to the condensed phosphates in its efficacy in sequestering calcium ions in the
washing solution. Because of reports of adverse teratogenic effects in
laboratory experiments, this builder was withdrawn from the market late in
1971. It was replaced by sodium citrate, an environmentally more acceptable
but inherently less powerful calcium sequestrant. At the same time, surfactant
levels were increased by a factor of about 3. What had happened in practice
(if not in theory) was that higher levels of surfactants had been introduced to
compensate

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for the loss in the building contribution to washing efficacy provided earlier by
phosphate.
The 1970s saw the introduction of several heavyduty liquids that carried this
substitution to its ultimate, being totally unbuilt and consisting solely of
surfactants at levels ranging from 35% to about 50%. These compositions
were distinguished from lightduty liquids by the presence of surfactants with
longer hydrophobes and, of course, by the presence of laundry auxilaries, such
as fluorescent whiteners and antiredeposition agents. With the exception of a
few products based on surfactants only, most heavyduty liquids are
formulated with a mixture of anionic and nonionic surfactants, with anionics
predominating.
The steady expansion of phosphate bans across the United States,
accompanied by an expanding perception of the convenience and efficacy of
heavyduty liquids, led to an expansion of this product category in the two
decades beginning 1970. This expansion was fueled not only by the publicity
that normally accompanies the introduction of new brands but also by some
significant product improvements. The first of these to appear late in the early
1980s was the incorporation of proteolytic and, later, amylolytic enzymes. In
liquid detergents, with their relatively high level of water, proteolytic enzymes
must be stabilized to prevent degradation during storage [2,3].
Enzymes make a significant and demonstrable contribution to washing efficacy,
not only in the removal of enzymespecific stains, such as grass and blood, by
proteinases, but also in an increase in the level of general cleanliness. The latter
effect is the result of the ability of a proteolytic enzyme to act upon
proteinaceous components of the matrix that binds soil to fabric.
Enzymes had been used in detergent powders in the United States and Europe
as early as 1960. They were subsequently withdrawn in the United States, but
not in Europe, when the raw proteinase of the time proved to have an adverse
effect on the health of plant workers. Improvements in the enzymes, specifically
encapsulation, eliminated their dustiness and made it possible to use these
materials in detergent plants without adverse health effects.
The second product innovation was the incorporation of a fabricsoftening
ingredient. Again, a powdered version of a “softergent” that had been on the
market for some time served as the model product. In the powder, the
mutually antagonistic anionic surfactants and cationic softening ingredients
could be kept apart so that they would not neutralize their individual benefits in
the wash cycle. In a liquid, this proved to be unattainable. As a result, the
choice of surfactants in liquid softergents was restricted to nonionics.
Although the incorporation of enzymes and fabric softeners strengthened the
market position of heavyduty liquids, it did not solve the basic problem of
limited general detergency performance in normal washing. As noted earlier,
heavyduty liquids came close to the performance of the first nonphosphate
laundry powders. With time, however, the performance of nonphosphate
laundry

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powders improved as new surfactant systems and new nonphosphate builders,
notably zeolite in combination with polycarboxylate polymers, were
introduced.
The last decade saw a partial conversion of some major brands from unbuilt to
built compositions. The first of these products employed a builder system
consisting of sodium citrate in combination with potassium laurate [2]. In the
most recent versions, potassium laurate has been replaced by a smallmolecule
ether polycarboxylate sequestrant, a mixture of sodium tartrate monosuccinate
and sodium tartrate disuccinate [3]. In these built products, the stabilization of
enzymes is technically more difficult than in unbuilt systems. A combination of
lowmolecularweight fatty acids, lowmolecularweight alcohols, and very low
levels of free calcium ions proved to be the solution to this problem.
At the height of their popularity, heavyduty liquids accounted for 40–45% of
the heavyduty laundry products category in the United States. Not
unexpectedly, the market share of heavyduty liquids has declined somewhat
as new developments in laundry powders, notably the introduction of a
bleaching function and of concentrated, higher density detergent powders, has
reinvigorated this product category.
If the emulation of the performance of laundry powders is to continue in the
future, and there is no reason to doubt this trend, the incorporation of a stain
removal and bleaching function into heavyduty liquids should be the next
technical improvement in these products. Indeed, the first product claiming a
bleaching ingredient has made its appearance at this writing.
In laundry powders, effective bleaching has been attained in the last decade by
incorporating a combination of sodium perborate and an activator. In Europe,
sodium perborate has been used for many decades as a major (about 20%)
ingredient of laundry detergents. At temperatures near 100°C, sodium
perborate alone provides effective bleaching. As washing temperatures have
decreased over the past 15 years, a need has arisen for an activator that reacts
with sodium perborate to form unstable peroxy intermediates, which in turn can
effect bleaching at the lower temperatures.
To prevent premature reaction with the oxygen source, usually sodium
perborate, the activators can easily be encapsulated in powdered detergent
products. In an aqueous environment, this is technically much more difficult.
One approach toward the incorporation of activated perborate into heavyduty
liquids is to remove the aqueous environment and formulate nonaqueous
systems [5]. To attain product homogeneity, these formulations require
significant levels, about 20%, of organic solvents, such as propylene glycol
and/or ethanol. Nonaqueous systems have been patented extensively,
particularly in Europe, but so far have not been reflected in major new product
introductions.
Nonaqueous liquids could be considered “superconcentrated” and as such are
in tune with the recent trend to concentrated laundry powders. However, the

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need for organic solvents combined with the high level of surfactants present in
these formulations represents a burden on the environment and adds to the
cost of such products. In Europe, specifically in Germany, discharge into the
environment is a serious problem that is likely to inhibit expansion of both
aqueous and nonaqueous heavyduty liquids.
Such superconcentrated, nonaqueous heavyduty liquids have not made an
appearance in the marketplace, but “concentrated” products have been
introduced, in consonance with a general trend toward compaction initiated by
the introduction of compact or concentrated detergent powders. Two technical
approaches toward more concentrated products have been followed. The first,
originating in Europe, results in an opaque product containing relatively high
levels of builder salts in suspension. A stable suspension is achieved by salting
out the surfactant system by an excess of electrolyte (which includes the builder
salts) to form lamellar or spherulitic surfactant aggregates that are capable of
suspending builder in excess of its solubility in the formulation. The relatively
high builder levels contribute to improved wholewash performance, especially
in the European liquids, which contain sodium tripolyphosphate as the builder
[4].
A second approach toward compaction yields clear, isotropic liquids that
appear to be preferred by U.S. consumers. Technically, this involves a difficult
balancing act because conventional hydrotroping agents, such as cumeneor
xylenesulfonates, may lose their efficacy in a system enriched in organic
components. As the system becomes more organic in nature, higher levels of
solvents, such as ethanol, are required in combination with neutralization of
acidic functionalities (LAS or citric acid) with alkanolamines, such as mono
and triethanolamine. In general, the phase stability of the system becomes more
sensitive to changes in active levels because the stable operating region of the
phase diagram is narrowed relative to more dilute systems.
IV. Liquid Automatic Dishwasher Detergents
The development of liquid automatic dishwashing detergents continued the
pattern of emulating the composition of solid products in a liquid form. Liquid
automatic dishwashing detergents were first introduced in 1986 at a time when
the market penetration of heavyduty liquid laundry detergents was on a
pronounced upswing, without an upper limit in sight. A liquid version of the
automatic dishwashing detergent powders therefore appeared to be attractive
and timely.
These liquid detergent products are suspensions rather than true solutions.
Nonetheless, the technical problems of formulating thick but flowable
suspensions are considerable. Again, the primary task was to incorporate as
much of

Page 9
the important ingredients—principally builders in this case—as possible. Even
approaching the levels of sodium tripolyphosphate and sodium carbonate
present in the powdered versions gives rise to a very thick suspension that can
be coaxed out of the container only with considerable difficulty. Making the
suspension thixotropic by incorporation of the appropriate clay materials and,
optionally, polycarboxylate polymers provides a solution to the flow problem
[6]. Before use by the consumer, the product must be shaken to reduce
viscosity and promote flow.
Another major technical problem is the inadequate stability in an aqueous
environment of chlorinated isocyanurates, the organic chlorine source used in
powders. Sodium hypochlorite satisfies the stability requirements but, on the
other hand, reacts with the surfactant types used in powder formulations. The
specification of surfactants for use in liquid automatic dishwashing products
therefore includes not only the universal requirement of low foam levels (and
ideally the capability of destroying the foams generated during the dishwashing
process by proteinaceous soil) but also stability to sodium hypochlorite. To a
large extent, these requirements have been met by the alkyldiphenyl oxide
disulfonate surfactants.
In some commercial liquid automatic dishwashing formulations, the surfactant is
omitted altogether. In practice, this is a possible solution because detergency in
hard surface cleaning, such as dishwashing, is accomplished primarily by the
phosphate builder. However, in the absence of surfactant there is little
defoaming of natural soils and no contribution to the “sheeting” of water just
before drying. Such sheeting minimizes the formation of water spots on dishes
that have gone through the dishwashing process.
V. Shampoos and Conditioners
Shampoos are liquid detergents designed to clean a particular substrate, that is,
hair and scalp. They bear some resemblance to hand dishwashing liquids in that
they are essentially unbuilt surfactant solutions.
Esthetic properties, such as appearance (clear or pearlescent), viscosity, and
fragrance, are perhaps more important in this product group than in any other
product category discussed in this book. Development and maintenance of an
adequate foam level is at once a performance property and also a esthetic
property in that it is noticed and evaluated by the user.
Shampoos almost always contain additives with activity in areas other than
cleaning and foaming, designed to provide specific performance attributes that
confer such properties as luster, manageability to hair, and elimination of
dandruff.
The concentration in use of shampoos is estimated as near 8%. This is an order
of magnitude greater than the use concentrations of laundry and dishwashing

Page 10
liquids. Mildness to skin and low irritation to eyes are therefore important
requirements for shampoos.
Salts, generally sodium but also triethanolammonium, of longchain alcohol
sulfates and alcohol ether sulfates are the most widely used surfactants in
shampoo formulations. Alkanolamides act as viscosity regulators as well as
foam stabilizers.
The most general benefits associated with the use of conditioners is a reduction
in static charge on hair and hence a greater ease of combing, that is, improved
manageability. Cationic, quaternary surfactants and cationic polymers provide
these benefits as a result of electrostatic adsorption on hair. In analogy with
“softergents,” the mutual antagonism of the cationic conditioners and the
anionic surfactants that provide the primary shampoo function of removing oily
soil presents a problem in the development of conditioning shampoos. Some
anionic surfactants, notably carboxylated nonionics, have been found to be
more tolerant toward cationic surfactants than the alcohol sulfates or alcohol
ether sulfates.
The history of shampoos is long, beginning well before the days of synthetic
surfactants. The advent of the latter greatly expanded options for the
formulator and at the same improved the esthetics of the products.
VI. Liquid Soaps
Liquid soaps is the popular description given to this product category. This
definition is technically not quite accurate. These products may contain some
fatty acid salts, but they are predominantly solutions of (synthetic) surfactants
rather than of soap.
Apart from the potassium oleate solutions mentioned earlier, the history of
liquid soaps is relatively short. It offers a relatively representative illustration of
the development of a product category or subcategory in the U.S. market. The
first liquid soap was first introduced by a smallish U.S. company in the late
1970s. The product proved to be sufficiently attractive to U.S. consumers to
capture a significant market share in the personal washing category. In short
order, many competitive brands were introduced that saturated the field and, it
seemed, stunted the growth of the category. In the most recent stage, the field
reduced to fewer, larger brands and the category has reached a relatively firm
level from which slow and steady growth can be anticipated.
Liquid soaps can be stored and dispensed with the convenience characteristic
of all liquids. Beyond these generic attractions, they possess an esthetic
advantage over conventional personal washing bars in that during use, and
particularly during occasional use, they are not subject to the visual and
physical deterioration in appearance of personal washing bars. Stored in an
aqueous

Page 11
matrix (residual water from washing), bars tend to slough and crack to various
degrees. The cracks, in turn, can collect soil, which leads to a less than
attractive appearance.
Liquid soaps can be considered successors to the potassium oleate solutions
noted earlier. Presentday products, however, are formulated principally with
nonsoap surfactants, including olefinsulfonate, alkyl sulfates, and alkyl ether
sulfates. Some products, however, still depend on potassium salts of fatty acids
as the principal constituent.
As in other personal products, specialty surfactants also find application in
liquid soap formulations. These include alkyl phosphate esters, sarcosinates,
and sulfosuccinates. As expected from consumer products that contact skin, a
number of specialty ingredients can be found in products making specific
marketing claims. These ingredients include glycerin, aloe vera, and
antimicrobial phenolics. Small levels of calcium sequestrants, such as EDTA,
and sodium citrate, are also present.
VII. Fabric Softeners
Fabric softeners or conditioners, as the name implies, are products that confer
softness to washed textile goods. They first made their appearance in the U.S.
market in the 1950s. The major active ingredient in fabric softening
compositions is a cationic surfactant, a di(longchain)alkyldimethylammonium
halide or methosulfate. The positive charge on the nitrogen atom, combined
with the high molecular mass associated with the long alkyl chains, ensured
adsorption of the compound on the substrate and a soft feel of the conditioned
fabric.
In contrast to most other liquid detergent categories, fabric softeners are not
true solutions. The longchain quaternary salts do not dissolve to form an
isotropic solution.
Cotton is the primary target substrate for fabric softeners. On repeated
washing, the fine structure of cotton at the surface of the fabric becomes
dendritic, that is, many fine spikes of cotton fibers are formed that protrude
from the surface of the textile. Electrostatic repulsion holds these spikes in
place, but in the presence of the cationic softening agent, they are smoothed
out. Synthetic fabrics, such as polyester and nylon, are not subject to this
phenomenon. Much of the “softening” with these substrates is provided by the
mechanical flexing action in the drier. However, the mechanical action causes a
buildup of static electricity on synthetic fabrics, which can result in considerable
sparking when garments made of synthetic fibers are withdrawn from a clothes
drier. Fortunately, the agents that confer softening to cotton fibers also reduce
the buildup of static charges on synthetics.

Page 12
In a conventional fabric softener formulation, the level of the quaternary
surfactant is about 5%. Low concentrations of “leveling agents” can also be
present. These materials, often nonionic surfactants, assist in uniform deposition
of the softening quaternary. In addition, a buffering system is used to assure an
acidic pH. Finally, a solvent, such as isopropanol, present at levels of about
10–15%, assures a viscosity range suitable for easy dispensing from the bottle.
As an additive to improve ease of ironing and to reduce the wrinkling
tendencies of the treated textile, silicone derivatives, such as polydimethyl
siloxanes, have been incorporated into liquid fabric softener compositions [7].
As an alternative softening quaternary, imidazolinium compounds have been
introduced with a claim of superior rewet performance. This can be a useful
performance feature because with continuing usage and buildup of cationics on
the substrate, the water absorption of the substrate can be adversely affected.
The use of anionic detergents in the main wash can mitigate this phenomenon
because the anionic surfactant can combine with the cationic fabric softener to
form a combination that is removed as part of the oil on the fabric.
Since the late 1970s, concentrated fabric softener products have been
marketed in the United States and in Europe. In these products, the
concentration of the softening cationic is about three times as high as in the
conventional products.
In the most recent past, the environmental acceptability of the dialkyldimethyl
ammonium quaternary has been questioned, particularly in Western Europe. In
response, the nature of the alkyl group has been modified and a moderately
extensive patent literature has arisen covering these modifications. For the most
part, the patented structures include an ester linkage, generally at the third
carbon atom, which makes for a more rapid biological breakdown of the
parent compound [8].
The liquid fabric softeners just described are also referred to as rinse cycle
softeners. The reason is that these products are added to the rinse cycle of the
wash when no or very little of any anionic residue from the detergent used in
the main wash can be expected to be present. As in all textile treatments, fabric
softening and conditioning are inherently more effective when they are carried
out in a liquid bath, that is, when a rinse cycle softener is employed. Adding a
product to the rinse cycle softener represents a measure of inconvenience to
the user. Before special ports for the automatic addition of rinse cycle became
a widespread feature of washing machines, the use of a rinse cycle softener
usually required an appropriately timed second trip to the washing machine.
It is not surprising, therefore, that alternative means of softening products were
sought and developed. Here, however, the usual situation was reversed, in that
now greater convenience rested with “solid” products, that is, flexible sheets
treated with a fabric softening compositions that performed their softening

Page 13
and static reducing functions in the clothes drier rather than in the washing
machine.
Softergents, mentioned earlier in connection with heavyduty liquids, can be
viewed as representing the ultimate in convenience. These products require no
additional effort beyond laundering. As noted, this convenience is bought at
some cost in both the washing and softening performance.
VIII. Specialty Liquids
In addition to the major liquid detergent categories discussed earlier, several
more specialized liquid product categories have been marketed for a number
of years. In terms of function, character, and formulation ingredients, this is the
most fragmented group of products considered here.
The largest group comprises the “general” hard surface cleaners. In addition,
there is a large variety of specialties within specialty liquids, such as window
cleaners, bathroom cleaners, and toilet bowl cleaners.
The major category of general hard surface cleaners has evolved into two
principal types: allpurpose cleaners and solvent cleaners. Allpurpose liquids
are essentially dilute versions of heavyduty liquids. Again, a solid product that
required dissolution before use was the model for the liquid cleaners. Early
versions of the liquid cleaners were based on low levels of tetrapyrophosphate
builder and surfactant and, additionally, auxiliaries, such as alkanolamide and a
sufficient amount of hydrotrope, to keep the composition homogeneous. For
sanitizing products, the auxiliaries include compounds with antimicrobial
efficacy, such as pine oil or antimicrobial cationics. With the advent of
phosphate bans, sodium citrate has emerged as the most common phosphate
replacement in these products.
For increased efficacy in removing particulate soil adhering to the substrate,
some generalpurpose cleaners incorporate a soft abrasive, such as calcium
carbonate. The resulting products are milky suspensions with about 40–50%
of suspended calcium carbonate [9]. Keeping these compositions
homogeneous through extended storage is a technical challenge. One approach
to solving this problem is to provide “structure” to the liquid medium.
Surfactants present as a lamellar phase are capable of structuring liquids. Most
recently, a composition containing both soft abrasive and bleach has been
introduced [10].
These hard surface cleaners have not escaped the recent trend toward
compaction. Here, the approach toward “ultra” products is based on the use
of shorter chain surfactants that combine the soil penetration efficacy of
solvents with the grease emulsification of traditional surfactants. These
surfactants are also said to require no builders because their performance is not
affected by water hardness.

Page 14
Solvent cleaners are generally free of builder salts and depend for their efficacy
on solventtype compounds, such as glycol ethers. Solvent cleaners are less
effective on particulate soil, such as mud tracked into the house from the
outside, but target their efficacy against oily soils, particularly on oily soil on
modern plastic surfaces.
Window cleaning products constitute a specialty within the solvent cleaner
category. Because any residue left on glass after drying leads to streaking or an
otherwise undesirable appearance, these products are highly dilute aqueous
solutions containing extremely low surfactant levels—most often nonionic
surfactants—and a combination of glycol ethers and isopropyl alcohol as the
solvent system.
Bathroom cleaners, sometimes referred to as tubtileandsink cleaners,
represent “subspecialty” liquids that must be effective against a combination of
sebum soil deposited from skin detritus during bathing or showering and the
hardness deposits deriving from hard water itself or from its interaction with
soap, that is, calcium salts of fatty acids. One subset in this group depends on
acids for removing this combination. The acids contained in the products range
from the strong hydrochloric and phosphoric acids to moderately strong
organic acids, such as glycollic acid. Other products are formulated at a basic
pH, incorporating an calcium sequestrants, such as the sodium salt of
ethylenediaminetetraacetic acid (EDTA), surfactants, and, in the case of
products with disinfecting action, antimicrobial quaternaries.
Like bathroom cleaners, toilet bowl cleaners are formulated to remove mineral
deposits, principally iron salts, that form an unsightly deposit at the water level.
Again, acids ranging in strength from hydrochloric to citric are found in these
products.
Another subsegment of the specialty liquids is that of the drain cleaners. These
are strongly basic products based on combinations of sodium hydroxide and
sodium hypochlorite.
IX. Manufacture and Raw Materials
In principle, the manufacture of liquids is simple, involving only the formulation
of a generally aqueous solution or suspension. For light and heavyduty liquids,
which contain sodium salts of surfactant acids, neutralization can be carried out
in situ, that is, as a first step in the mixing process. The heat of neutralization
must be dissipated before addition of the more temperaturesensitive
ingredients, such as the fragrance. Heat must also be dissipated in the
production of products that require heat input to solubilize individual
ingredients.
The raw materials for the liquid household products discussed in this book are
relatively few in number, including the “workhorse” surfactants, builders,

Page 15
hydrotropes, and a small number of special function ingredients. Cost
constraints on the finished products are one of the important limiting factors.
The situation is different for the personal liquid detergents and liquid soaps and
especially so for shampoos and conditioners. Cost constraints are relaxed, and
the range of performance claims based on specific and unique ingredients is
now very much expanded. Although the variety of the essential surfactants is
still manageable, the number of specialty surfactants and special function
ingredients is very much greater.
A detailed discussion of these ingredients is beyond the scope of this chapter.
Details of the characteristics, properties, and manufacture of the raw materials
can be found in other reference works [11].
In the following, the raw materials found in liquid detergent compositions are
listed to provide a convenient summary for further reference. For the large
scale categories of light and heavyduty liquids, for automatic dishwasher
detergents, and for fabric softeners, the list is fairly complete. For specialty
liquids, shampoos and conditioners, and to a lesser extent for liquid soaps, only
limited examples of special functional ingredients have been selected.
I. Lightduty liquids
A. Surfactants
1. Alkylbenzenesulfonate (linear alkylate sulfonate, LAS) salts
2. Alkyl ether sulfate salts
3. Alkyl sulfate salts
4. Betaines
5. Alkylpolyglycosides
B. Foam stabilizers
1. Fatty acid alkanolamides (mono and di)
2. Alkyldimethylamine oxides
C. Hydrotropes
1. Shortchain alkylbenzenesulfonates (xylenesulfonate salts)
2. Ethanol
II. Heavyduty liquids
A. Surfactants
1. Alkylbenzenesulfonate salts
A. Surfactants
4. Alcohol ethoxylates
5. Nmethylglucamides

Page 16
B. Builders
1. Sodium citrate
2. Sodium salts of tartrate mono and disuccinate mixture
C. Hydrotropes
1. Salts of shortchain alkylbenzenesulfonates (xylenesulfonate,
cumenesulfonate, toluenesulfonate)
2. Ethanol
D. Bases: Alkanolamines
E. Other special functional ingredients
1. Enzymes (proteinase, amylase, lipase): stain remover
2. Borax (cleaning aid)
3. Sodium formate, calcium chloride (enzyme stabilizing system)
4. Hydrogen peroxide (bleach)
5. Propylene glycol (solvent)
III. Liquid automatic dishwasher detergents
A. Surfactants
1. Alkyldiphenyl oxide disulfonate salts
2. Hydroxyfatty acid salts
B. Builders:
1. Pentasodium tripolyphosphate
2. Tetrasodium pyrophosphate
3. Sodium carbonate
4. Sodium silicate
C. Bases: Sodium and potassium hydroxide
D. Other special functional ingredients
1. Sodium hypochlorite (bleach)
2. Clay (smectite, bentonite): viscosity regulator, suspending agent
3. Polyacrylate sodium salts (viscosity regulator)
4. Monostearyl acid phosphate (suds depressant)
IV. Shampoos and conditioners
2. Clay (smectite, bentonite): viscosity regulator, suspending agent
3. Polyacrylate sodium salts (viscosity regulator)
4. Monostearyl acid phosphate (suds depressant)
IV. Shampoos and conditioners
A. Surfactants
3. Acylaminopropyl betaines
4. Olefinsulfonate salts
B. Foam stabilizers/viscosity regulators: Fatty acid alkanolamides

Page 17
C. Other special functional ingredients
1. Polyquaternium 7 (cationic conditioner)
2. Glycol monostearate (opacifier)
3. Aloe vera (luster promoter)
4. Jojoba (luster promoter)
5. Derivatives of hydrolyzed keratin (skin and hair conditioner)
V. Liquid Soaps
A. Surfactants
1. Alcohol sulfate salts
3. Olefinsulfonate salts
4. Fatty acid salts
B. Sequestrants
1. EDTA
2. Sodium citrate
C. Foam stabilizers/viscosity regulators: Fatty acid alkanolamides
D. Other special functional ingredients
1. Phenolic antimicrobials
2. Glycerin
VI. Fabric conditioners
A. Surfactants
1. Dialkyldimethylammonium halide or methosulfate salts
2. Monoalkyltrimethylammonium halide salts
3. Alkylimidazolinium salts
5. Alkyl (ethylene oxide/propylene oxide) nonionics
B. Solvents
1. Isopropanol
2. Ethanol
C. Other special functional ingredients: Polydimethylsiloxanes (leveling agent)
B. Solvents
1. Isopropanol
2. Ethanol
C. Other special functional ingredients: Polydimethylsiloxanes (leveling agent)
VII. Specialty liquids
A. Surfactants
2. Alcohol sulfate salts

Page 18
3. Alkanesulfonate salts
5. Alkylphenol ethoxylates
B. Builders/sequestrants
1. Sodium carbonate
2. Sodium sesquicarbonate
3. Sodium citrate
4. EDTA
C. Acids/alkalis
1. Hydrochloric acid
2. Phosphoric acid
3. Glycollic acid
4. Sodium hydroxide
5. Sodium metasilicate
6. Alkanolamines
D. Hydrotropes: Shortchain alkylbenzenesulfonate salts (toluene, cumene)
E. Bases: Alkanolamines
F. Other special functional ingredients
1. Pine oil (disinfectant)
2. Benzalkonium cationics (antimicrobials)
3. Sodium hypochlorite (bleach)
4. Calcium carbonate (soft abrasive)
5. Alumina (suspending aid)
6. Alkyl glycol ethers (solvents)
7. Isopropanol (solvent)
References
1. I. Reich and H. Dallenbach, U.S. Patent 2,994,665 to Lever Brothers
Company (1963).
2. J. C. Letton and M. J. Yunker, U.S. Patent 4,318,818 to the Procter &
References
1. I. Reich and H. Dallenbach, U.S. Patent 2,994,665 to Lever Brothers
Company (1963).
2. J. C. Letton and M. J. Yunker, U.S. Patent 4,318,818 to the Procter &
Gamble Company (1982).
3. R. D. Bush, D. S. Connor, S. W. Heinzman, and L. N. Mackey, U.S.
Patent 4,663,071 to the Procter & Gamble Company (1987).
4. B. J. Akred, E. T. Messenger, and W. T. Nicholson, British Patent
2,153,839 A to Albright & Wilson Limited (1985).
5. G. Broze, D. Bastin, and L. Laitem, U.S. Patent 4,749,512 to Colgate
Palmolive Company (1988).
6. M. Julemont and M. Marchai, British Patent 2,116,119 A to Colgate

Page 19
7. R. J. Dumbrell, J. P. Charles, I. M. Leclerq, R. M. A. de Bakker, P. C. E.
Goffinet, B. A. Brown, R. E. Atkinson, and F. E. Hardy, British Patent
1,549,180 to the Procter & Gamble Company (1979).
8. J. C. Letton, U.S. Patent 4,228,042 to the Procter & Gamble Company
(1980).
9. U.S. Patent 4,129,527, F. P. Clark, R. C. Johnson, and J. Topolewski to
the Clorox Company (1978).
10. C. K. Choy, F. I. Keen, A. Garabedian, and C. J. Spurgeon, U.S. Patent
4,695,394 to the Clorox Company (1987).
11. G. Barker, in Surfactants in Cosmetics (M. M. Rieger, ed.), Marcel
Dekker, New York, 1985.

2
Hydrotropy
STIG E. FRIBERG and CHRIS BRANCEWICZ
Department of Chemistry and Center for Advanced Materials Processing, Clarks
Potsdam, New York
I. Introduction
II. Historical Review
III. Fundamentals
IV. Cleaning and Washing
V. Summary
References
I. Introduction
Liquid detergent concentrates commonly contain hydrotropes to avoid excessive
the formulation and to improve their detergency. Both functions rely on the funda
properties of hydrotropes.
In this chapter, historical knowledge about the function of hydrotropic molecules i
reviewed, followed by a description of hydrotropic action in liquid detergents usi
commercial hydrotrope with an unusual structure.
II. Historical Review
The term “hydrotropy” was coined in 1916 by Neuberg [1,2], who found that aq
solutions of certain salts possessed the ability to enhance the solubility in water of
otherwise waterinsoluble substances. He found that the alkali metal salts of benz
salicylic acid, benzenesulfonic acid and its

Page 22
many derivatives, naphthoic acid, and various other hydroaromatic acids
displayed hydrotropic activity. In his study, Neuberg investigated a large
number of organic solutes, such as carbohydrates, alcohols, aldehydes,
ketones, hydrocarbons, esters, ethers, lipids, fats, and oils.
The second phase or period of activity started 30 years later, with an emphasis
on chemical engineering and industrial applications. McKee [3] showed that
concentrated aqueous solutions of very soluble neutral salts of organic acids,
such as sodium benzoate (NaB), salicylate (NaS), benzenesulfonate (NaBS),
ptoluenesulfonate (NaPTS), xylenesulfonate (NaXS), cumenesulfonate
(NaCS), and cymenesulfonate (NaCyS), increased the solubility of a wide
variety of organic and some inorganic compounds in water. He noted that most
hydrotropic solutions precipitated the solubilized solute on dilution with water
and showed that this permits easy recovery of the hydrotrope for further use.
Lumb [4] studied the ternary phase diagrams of systems consisting of water
octanolpotassium alkanoates and, based on their similarities, postulated that
the hydrotropy exhibited by the lower alkanoates (e.g., butyrate) and
surfactant solubilization were essentially the same phenomenon. On the other
hand, Licht and Wiener of the University of Cincinnati [5] agreed with McKee
[3]. They attributed the increase in solubility to a “saltingin” effect rather than
by a similarity in structure to surfactants.
The final comparison with surfactant phase equilibria was made two decades
later when Lawrence [6], Friberg and Rydhag [7], and Pearson and Smith [8]
presented phase diagrams for hydrotropes. These phase diagrams
demonstrated hydrotropic solubilization as an extension of surfactant
solubilization into less ordered systems.
In modern times, hydrotropes have found many applications. Their use includes
the pharmaceutical field, with solubilization of drugs, specifically temazepam [9]
and the coronary vasodilator nifedipine [10]. Hydrotropes have shown
promise in enhancing the action of drugs with such combinations as
theophylline with insulin [11] and have been utilized to improve transdermal
delivery systems [12].
In chemical engineering, the original McGee [3] approach was recently
continued in such processes as catalysis and extraction [13,14]. It is also used
in the paper and pulp industry [15–19].
The application in liquid detergents is a direct consequence of the fundamentals
of hydrotropic solubilization. Hence, in this chapter we first describe
hydrotropic action in general, followed by a treatment of an unusual
hydrotropic agent in the context of detergency.
III. Fundamentals
There are two essential features of hydrotrope solubilization: comparatively
large concentrations of hydrotrope are required to initiate solubilization, and the

Page 23
maximum amount solubilized into the aqueous hydrotrope solution is large
compared with what is found in an aqueous micellar solution of a surfactant.
These two characteristics are illustrated in Fig. 1 [7]. The dashed line shows
the strongly enhanced solubility of octanoic acid in a sodium xylene sulfonate
solution at concentrations in excess of 20% by weight of the hydrotrope. The
contrast between a solubility of less than 1% for concentrations at 15% of the
hydrotrope and the rapid increase to more than 30% by weight of octanoic
acid at higher concentrations illustrates the typical properties of hydrotrope
mediated
Fig. 1
The solubility of octanoic acid into an aqueous solution of a
hydrotrope sodium xylene sulfonate, dashed line, requires
high concentrations of the hydrotrope to initiate solubilization
(~20%), but the solubilization increases steeply to large values for
small increases in hydrotrope concentrations above those
values. The surfactant (sodium octanoate), on the other hand
(solid line), requires lower concentrations to start the
solubilization (~5%) but the maximum solubilization is limited.

Page 24
solubilization. The contrast between the values for the dashed and solid lines
illustrates the distinction of hydrotrope solubilization from that by a surfactant,
in this case sodium octanoate. The solubilization of the octanoic acid with the
surfactant is initiated at a much lower concentration than with the hydrotrope,
but the maximum amount of the acid solubilized remains at a modest level of
less than 8%.
The comparison with surfactant solubilization offers an immediate explanation
for the high concentration of hydrotrope required to initiate the solubilization. It
has been well known for many years [20] that a surfactant with a shorter
hydrocarbon chain has an increased value of the critical micellization
concentration (CMC). The CMC is the concentration at which solubilization
begins.
Hence, the high hydrotrope concentration for initial solubilization (Fig. 1) is
reasonable and expected because the phenyl group is analogous to only three
to four carbons in a straight chain. The very high hydrotrope concentration for
initial association of the molecules and the accompanying solubilization are
given a rational explanation.
The much higher values of solubilized material for the hydrotrope in
comparison with the values for the surfactant (Fig. 1) are understood first after
a more complete phase diagram is considered for the two compounds. Figure
2 reveals the essential features of the two solubilized mechanisms. Increased
amounts of octanoic acid in the surfactantwater solution give rise to several
phases, four of which are illustrated in Fig. 2. Area a in Figure 2 consists of an
aqueous solution of normal micelles, the structure of which is shown in Fig. 3a.
At higher surfactant concentrations a liquid crystalline phase containing
cylindrical surfactant associations stacked in a close packed hexagonal array is
formed. This region is labeled area d in Fig. 2, and its structure is shown in Fig.
3d.
At increasing concentrations of octanoic acid, a lamellar liquid crystal is
formed, as shown in Fig. 2, region c. This phase has a structure of “infinite”
bilayers of surfactant interlaced with layers of water, as shown in Fig. 3c.
A further increase in the content of the solubilizate results in the formation of an
octanoic acid solution of inverse micelles, which contain water solubilized in
their cores. This region is shown as area b in Fig. 2, and the structure of an
inverse micelle is depicted in Fig. 3b. The essential feature of the phase
diagram is the presence of the lamellar liquid crystal region, which separates
the normal micellar solution (Fig. 3a) from the solution of inverted micelles (Fig.
3b).
This is in strong contrast to the conditions with hydrotrope (Fig. 2) for which
only one solubility region (Fig. 2) of significance is found with increasing

Page 25
Fig. 2
When water and octanoic acid (solid lines) are combined with
sodium octanoate, four phases are obtained: a and b are
micellar solutions (Fig. 3a and b), and c and d are liquid
crystals (Fig. 3c and d). The combination with a hydrotrope
sodium xylene sulfonate, dashed line, gives a single area of
an isotropic solution (e).
Fig. 3
The amphiphile organization in a normal micelle (a),
in an inverse micelle (b), in a lamellar liquid crystal
(c), and in a liquid crystal of hexagonally packed
amphiphile cylinders (d).

Page 26
amounts of octanoic acid. As shown by the dashed line, a continuous isotropic
liquid phase reaches from the aqueous corner to 80% octanoic acid without
interruption.
With this information, the reason for the “anomalously” high solubilization by
the hydrotrope is obvious. Its solubility region is not interrupted by the
formation of a liquid crystal; the shift from water continuous to octanoic acid
continuous solution now takes place without a phase transition.
It is essential to realize that the phase changes when octanoic acid is added to
the watersodium octanoate combination are not a question of solubility. The
octanoic acid is certainly soluble in the liquid crystalline phase, region c (Fig. 2)
and infinitely so in its own solution, region b (Fig. 2). The different phases
found in the surfactant system are only a matter of molecular organization of the
system components, not of their mutual solubility.
The similarity between the solubilization action of surfactant and hydrotrope
(Fig. 4) is now immediately evident. The surfactant and hydrotrope solubility
regions are analogous with the surfactant requiring lower concentrations
because of its greater hydrophobic character. Hence, the difference between
regions in Fig. 2 is not a distinction in solubility; numerous phases in the
surfactant system in Fig. 2 are a result of packing restrictions imposed by the
length of the hydrocarbon chains. The transition between normal and inverse
micelles requires a lamellar packing for two hydrocarbons chains of eight
carbons each. As the structures in Fig. 5 suggest, a combination of the bulky
hydrotrope and the long hydrocarbon chain of a solubilizate does not stabilize a
lamellar packing, and the transition from normal to inverse association
structures takes place via disordered aggregates, as shown in Fig. 4b.
IV. Cleaning and Washing
These processes are mainly concerned with the removal of “oily dirt,”
depending to a high degree on the complex phase equilibria encountered in the
surfactantwater“oily dirt” system [21].
Two treatments have been published [22,23] on the action of a nontraditional
hydrotrope structure in such systems. Instead of the usual bulky molecule (Fig.
5), this compound [24] is a dicarboxylic acid of considerable chain length (Fig.
6).
The fundamental phenomena have been investigated of the action of this
hydrotrope in a liquid cleaner. In such an application, the hydrotrope functions
in the formulation concentrate by preventing gelation. In addition, under the
dilute conditions in the washing process, the hydrotrope facilitates the removal
of oily dirt from the fabric. In the following section these two functions are
related to the phase equilibria of wateramphiphile systems.
The formula for the dicarboxylic acid (Fig. 6) has a hydrophilic lipophilic
balance similar to that of octanoic acid, but the influence of the two acids on

Page 27
Fig. 4
The total solubility region in the surfactant system (a) is similar
to that of the hydrotrope (b); the only difference is that the
change from normal to inverse association structures takes place
via an ordered lamellar liquid crystal (a phase separation) in
the surfactant case (a), and in the hydrotrope system the
transition takes place over disordered aggregates within the
solution (b).
amphiphilic association structures is entirely different, as can be seen in Fig. 7
[25]. The octanoic acid causes the formation of a liquid crystal when added to
a solution of water in hexylamine. The size of the lamellar liquid crystalline
region is large (Fig. 7a). Addition of the dicarboxylic acid, on the other hand,
gives no liquid crystal, and it may be concluded that its action in con

Page 28
Fig. 5
The reason for the difference in transition structures, Fig. 4, is that the
carboxylic acid and the surfactant (octanoic acid and sodium octanoate)
are of similar chain length and a lamellar packing is easily
stabilized. The difference in structure in the hydrotrope and fatty
acid combination (sodium xylene sulfonate and octanoic acid), on
the other hand, results in a disordered structure.
centrated systems is similar to that of the common shortchain hydrotropes
despite its long hydrocarbon chain (Fig. 7b).
Activity in dilute systems was investigated using a model system from Unilever
[26] in which octanol mimicks the oily dirt. A lamellar liquid crystal was
present at low concentration of the oily dirt [23], in the absence of the
hydrotrope (Fig. 8). After addition of the hydrotrope, the amount of model oily
dirt solubilized without liquid crystal formation was greatly enhanced. Clearly,
this hydrotrope functions not only as a destabilizer of liquid crystals in the
formulation concentrate but also as a destabilizer of liquid crystals under the
dilute conditions of the washing process.
Fig. 6
The dicarboxylic acid hydrotrope has an elongated structure.

Page 29
Fig. 7
The combination of water and hexylamine with octanoic
acid (a) gives a huge area of a lamellar liquid crystal
(LC); the combination with the dicarboxylic acid in Fig. 6
results in an isotropic liquid solution only (b).
The molecular mechanism behind the destabilization of liquid crystals was
clarified later [27]. The specific disordering brought forward by the hydrotrope
in the watersurfactantoily dirt liquid crystal was first determined, followed by
an investigation into the conformation of the diacid molecule itself [22].
The order of the hydrocarbon chains in a liquid crystal is directly obtained from
nuclear magnetic resonance (NMR) spectra using amphiphiles with deuteriated
chains. Each methylene group and the terminal methyl group give a NMR
signal doublet, and the difference in frequency between the two signals is
proportional to the order parameter [27]. Using a lamellar liquid crystal model
system of “oily dirt,” surfactant, and water, the influence of the hydro

Page 30
Fig. 8
The solubilization of a model compound for oily dirt was small
in a surfactant solution at concentrations below the CMC
() because of the formation of a liquid crystal. A
combination of hydrotrope and surfactant gave an
increased solubilization (—) caused by the hydrotrope
destabilization of the liquid crystal.
trope on the structure could be directly determined using NMR. Addition of
the hydrotrope molecule resulted in a narrowing of the difference between the
NMR signals due to a disordering of the liquid crystal, as shown in Fig. 9 [26].
It was assumed that this was the primary factor in the destabilization of the
liquid crystal.
Next, the diacid conformation was determined after it was added to the oily
dirt liquid crystalline phase. Figure 10 shows two possibilities for the
conformation of the hydrotrope in the liquid crystal.
In one form of the diacid (Fig. 10b), both polar groups are located at the
interface between the amphiphile polar groups and the water; the other
possibility is that only the terminal carboxylic group is found at this site (Fig.
10a).
The two conformations result in different interlayer spacing (Fig. 10), and a
determination of this dimension was used to distinguish between the two
alternatives. Lowangle xray diffraction gives the interlayer spacing directly
from the maxima in the diffraction pattern.
Interpretation of the results is straightforward; if addition of the diacid to a
lamellar liquid crystal model dirt system did not increase the interlayer spacing,
the conformation in Fig. 10b is correct; if an increase took place, then Fig. 10a
would describe the structural organization of the diacid molecule.
The interlayer spacing with the diacid added was very close to the host liquid
crystal (Fig. 11), and the first conformation (Fig. 10b) is obviously the one
encountered in the liquid crystal. As a comparison, the addition of oleic acid
with one polar group located at the interface, gave the expected increase in
interlayer spacing, as shown in Fig. 11. Destabilization of the lamellar liquid

Page 31
Fig. 9
Addition of a hydrotrope, Fig. 6, to a lamellar liquid
crystal gave a reduction of the order parameter of
the surfactant hydrocarbon chain ( ); addition of a
surfactant gave no change in order ( ).
Fig. 10
A hydrotrope, Fig. 6, conformation with only one polar group at the
water/amphiphile interface (left) results in an enhanced interlayer spacing
d compared with the value d for a conformation with both polar
1 2
groups at the interface (right).

Page 32
Fig. 11
The lowangle xray values for interlayer spacing in a lamellar liquid crystal
(×) was unchanged with the addition of a hydrotrope ( ), Fig. 6. Addition
of a longchain compound, oleic acid, gave the expected increase ( ).
crystalline phase is not only affected by the diacid; it appears to be a general
property shared by other hydrotropes, such as alkanols, shortchain
quaternary ammonium salts, xylenesulfonates, and glycols, as shown by
Pearson and Smith [8] and Darwish et al. [28].
In some cases, the oily dirt is less polar than the model system by Kielman and
Van Steen [26]; for less polar fatty oils the concept of hydrotropic breakdown
of a liquid crystal is also useful [29].
V. Summary
The function of hydrotropes in the detergency is discussed against their
interaction with lyotropic liquid crystals. The main activity of the hydrotrope as
a part of a liquid detergent is to avoid gelation in both concentrated and dilute
surfactant systems.
This ability is directly related to a detergent's phase equilibria with hydrophobic
amphiphiles. These phase equilibria illustrate and explain the two basic
characteristics of hydrotropes: that is, their high association concentration and
their pronounced solubilizing power.

Page 33
References
1. C. Neuberg, Biochem. Z., 76:107 (1916).
2. C. Neuberg, J. Chem. Soc., 110(II):555 (1916).
3. R. H. McKee, Ind. Eng. Chem. Ind. Ed., 38:382 (1946).
4. E. C. Lumb, Trans. Faraday Soc., 47:1049 (1951).
5. W. Licht and L. D. Wiener, Ind. Eng. Chem., 41:1528 (1949).
6. A. S. C. Lawrence, Nature (London), 183:1491 (1959).
7. S. E. Friberg and L. Rydhag, Tenside, 7:80 (1970).
8. J. T. Pearson and J. M. Smith, J. Pharm. Pharmacol., 26:123 (1974).
9. A. D. Woolfson, D. F. McCaffer, and A. P. Launchbu, Int. J. Pharm.,
34:17 (1986).
10. N. K. Jain, W. Patel, and L. N. Taneja, Pharmazie, 43:254 (1988).
11. T. Nishihata, J. H. Rytting, and T. Higuchi, J. Pharm. Sci., 70:71 (1981).
12. D. W. Osborne, Colloids Surf., 30:13 (1988).
13. V. G. Gaikar and M. M. Sharma, Solvent Extr. Ion Exch., 4:839 (1986).
14. A. Mahapatra, V. G. Gaikar, and M. M. Sharma, Sep. Sci. Technol.,
429:23 (1988).
15. G. E. Styan and A. E. Bramhall, Pulp Puu. Can., 80:725 (1979).
16. D. E. Bland, Res. Rev. Aust. CSIRO Chem. Technol., 27 (1976).
17. P. J. Nelson, Appita, 31:437 (1978).
18. D. E. Bland, J. Skicko, and M. Menshun, Appita, 31:374 (1978).
19. E. L. Springer and L. L. Zoch, Pap. 6:815 (1979).
20. K. Shinoda, Colloidal Surfactants, Academic Press, New York, (1963),
pp. 9–15.
21. K. H. Raney and C. A. Miller, J. Coll. I. Sc., 119:539 (1987).
22. T. Flaim and S. E. Friberg, J. Coll. I. Sc., 97:26 (1984).
23. J. M. Cox and S. E. Friberg, J. Am. Oil Chem. Soc., 58:743 (1981).
24. B. F. Ward, Jr., C. G. Force, A. M. Bills, and F. E. Woodward, J. Am.
Oil Chem. Soc., 52:219 (1975).
25. T. Flaim, S. E. Friberg, C. G. Force, and A. Bell, Tenside Detergents,
20:177 (1983).
26. H. S. Kielman and P. J. F. Van Steen, Faraday Disc., 191 (1979).
24. B. F. Ward, Jr., C. G. Force, A. M. Bills, and F. E. Woodward, J. Am.
Oil Chem. Soc., 52:219 (1975).
25. T. Flaim, S. E. Friberg, C. G. Force, and A. Bell, Tenside Detergents,
20:177 (1983).
26. H. S. Kielman and P. J. F. Van Steen, Faraday Disc., 191 (1979).
27. S. E. Friberg, S. B. Rananavare, and D. W. Osborne, J. Coll. I. Sc.,
109:487 (1986).
28. I. A. Darwish, A. T. Florence, G. M. Ghaly, and A. M. Saleh, J. Pharm.
Pharmacol., 40:25 (1988).
29. S. E. Friberg and L. Rydhag, J. Amer. Oil Chem. Soc., 48:113 (1971).

3
Phase Equilibria
GUY BROZE
Advanced Technology Department, ColgatePalmolive Research and Developm
Milmort, Belgium
I. Introduction
II. What is a Phase Diagram?
A. Twocomponent phase diagrams
B. Threecomponent phase diagrams
C. Recording phase diagrams
III. Phase Diagrams for Ionic SurfactantContaining Systems
A. Ionic surfactant: water
B. Ionic surfactant, water, and organic material ternary systems
C. Ionic surfactant, water, protondonating material, and hydrocarbon
quaternary systems
IV. Phase Diagrams for Nonionic SurfactantContaining Systems
A. Nonionic surfactant and oil
B. Nonionic surfactant and water
C. Nonionic surfactant, water, and oil
D. Effects of system parameters on phase behavior
References
I. Introduction
All liquid detergents contain at least one surfactant in the presence of other materi
electrolytes, oily materials, and other impurities. Unlike academic research, the fo
work with industrialgrade raw materials

Page 36
containing significant amounts of molecules, the properties of which differ from
those of the main product. The understanding of how a given property of a give
“pure” system is affected by “impurities” is accordingly of essential practical
importance. Understanding the principles by which a given product behaves
(as is or under use conditions) allows us to replace counterproductive trial
anderror by more efficient methods with a broader range of potential
applications.
II. What Is a Phase Diagram?
A phase diagram is a graphic representation of the phase behavior of a system
studied. The solidliquidvapor behavior of a single compound as a function of
temperature and pressure can be represented by a phase diagram. Phase
diagrams usually involve more than one component. They are very useful tools
for formulation, because they allow the formulator to define not only the
acceptable composition of a product but also the order of addition of the
different raw materials.
A. TwoComponent Phase Diagrams
1. Temperature and Composition
Whether a given proportion of two (liquid) compounds will mix is defined by
thermodynamics. Although, in regular systems, the entropy of mixing is always
positive and accordingly favorable to mixing, the enthalpy of mixing can be
positive or negative depending on the energy of formation of the heterocontacts
at the expense of the homocontacts.
An exothermic mixture usually leads to mixing in all proportions. If the mixing is
endothermic, the number of coexisting phases and their composition depend on
temperature. Increasing temperature usually results in an increase in the mutual
solubilities of the two compounds, eventually leading to complete miscibility
above a critical temperature, the upper consolute temperature (UCT). Note
that some abnormal systems can also present a lower consolute temperature
(LCT). Both UCT and LCT are thermodynamic critical points. At a critical
point, the compositions of the two phases in equilibrium become identical.
Figure 1 is a schematic representation of a twocomponent phase diagram
characterized by UCT. The left axis corresponds to pure A, and the right axis
corresponds to pure B. the abscissa corresponds to different AB
compositions. It is very common to express the compositions in weight
fractions, although not compulsory. Mole fractions or volume fractions can also
be used. The central, shaded area corresponds to the twophase domain. The
clear zone around it is single phase.

Page 37
Fig. 1
Phase diagram of two substances that are
only partly miscible at low temperature
and become fully miscible above the
“upper consulate temperature.”
2. Tie Lines and Lever Rule
When a mixture separates in two phases, it is important to know the
compositions and the amounts of the two phases in equilibrium. A tie line links
the two compositions in equilibrium. This means that any composition located
on the same tie line will separate in two phases, the compositions of which are
defined by the points of contact of the tie line with the phase boundary.
The relative amounts of the two phases is determined according to the lever
rule (Figure 2). If the compositions are expressed in weight fractions, the
weight fraction of phase A is CB/AB and the weight fraction of phase B is
AC/AB.
B. ThreeComponent Phase Diagrams
Practical systems involve more than two components. A threecomponent
system can be represented in an equilateral triangle (Figure 3). A corner of the
triangle represents a pure component, a side represents binary mixtures of the
components represented by the adjacent corners, and any point in the triangle
represents one and only one tricomponent composition.
Fig. 2
Lever rule, allowing quantification of the proportion of the two
coexisting phases in a twophase domain of a phase diagram.

Page 38
Fig. 3
Method of determining the composition
of a threeingredient mixture.
The weight fraction of component A in the composition represented by P in the
triangle is given by the ratio of the lengths of the segments perpendicular to the
sides Pa/(P b + Pb + Pc). Similarly, the amount of B is given by Pb/(P a + Pb +
Pc) and the amount of C by Pc/(P a + Pb + Pc).
Of course, such a phase diagram is isothermal. The effect of temperature on a
threecomponent phase diagram can be visualized in three dimensions, with
temperature at the elevation axis. The phase diagram looks like a triangular
prism, with every horizontal slice corresponding to one temperature.
1. Fields and Densities
There is an important difference among the thermodynamic functions of state as
far as phase equilibria are concerned. Some thermodynamic functions of state,
such as temperature and pressure, have the same value in all the phases of a
system at equilibrium. They are actually the forces driving a system to its
equilibrium. Such functions are referred to as fields [1].
The other thermodynamic functions of state generally present different values in
the different phases of a system at equilibrium. Typical examples are the
volumes of the phases and their composition. Such functions are densities.
A thermodynamic expression of functions of state can be expressed as a sum
of field variables multiplied by their conjugated density. For example,
G = U + PV TS + ini
where U is the internal energy, PV is the product of the field variable pressure
and the density variable volume, TS is the product of the field variable
temperature and the density variable entropy; and ini is the product of the
field variable chemical potential of i and the density variable number of moles
of i.

Page 39
The chemical potentials are the field functions conjugated with the
concentrations.
2. Phase Rule
For a multicomponent system, the phase rule [2] allows us to know the number
of independent variables necessary to define completely (from a compositional
point of view) a system. This number is called the number of degrees of
freedom or the variance of the system. The variance ƒ is given by the relation
ƒ = C + 2
where C is the number of chemically independent ingredients in the system,
is the number of coexisting phases at the equilibrium, and the last term takes
care of temperature and pressure.
For isobar systems, such as all systems under atmospheric pressure, the last
term should be 1. Similarly, isobar and isotherm systems have 0 as the last
term.
A direct implication of the phase rule is that a threecomponent system in one
phase at atmospheric pressure and at 25°C has a variance equal to 2. This
means that two dimensions are necessary to describe such a system. Another
implication is that such a system could show a maximum of three coexisting
phases.
A system based on five components will need, according to the phase rule, a
fourdimension hyperspace to be completely described. To represent such a
system, some variables are usually grouped. The accuracy of the
representation is, of course, imperfect.
A more accurate procedure is to set a variable to a constant value. This is
impossible with a composition because it is a density and is different in each of
the coexisting phases. The phase rule determines the number of independent
variables a system needs to be represented but does not introduce any
restriction on the choice of the independent variables. It is accordingly much
better to fix a field variable to reduce a system of one dimension. Instead of
using concentrations (density variables), a representation as a function of the
chemical potentials is easier to read and is more accurate. The problem is that,
in practice, it is very complicated to work at defined chemical potentials.
3. Tie Lines and Critical Points
Let us consider two liquids A and B that are not very soluble in each other.
Addition of liquid C increases the miscibility of B in A and of A in B. C behaves
like increasing temperature in the binary phase diagram. The major difference is
that the tie lines are no longer parallel to the baseline, and the critical end point
is no longer at the maximum of the miscibility gap (Figure 4). This is because C
does not partition evenly between the two coexisting phases.

Page 40
Fig. 4
A Winsor II ternary phase diagram.
In the present case, it goes preferably in B. The critical end point is located
near the A corner. An isothermal critical end point is usually referred to as a
plait point.
4. ThreePhase Domain
In some cases a threephase region can be observed (Figure 5). The
coexistence of three phases in equilibrium in an isothermal threecomponent
phase diagram is a zerovariant situation. Of course, an infinity of different
compo
Fig. 5
A Winsor III ternary phase diagram.

Page 41
sitions fall inside the threephase triangle, but the compositions of the three
coexisting phases do not change with the initial composition. They are
represented by the three corners of the threephase triangle. All that change
are the relative amounts of the three phases.
C. Recording Phase Diagrams
There are basically two methods of recording phase diagrams: the titration
technique and the constant composition method. Both have advantages and
drawbacks.
1. Titration Method
In the titration method, a mixture is titrated by another. Typically, a mixture of
two of the ingredients is titrated by the third. The weight of titrant to reach a
phase boundary is carefully recorded and plotted on the phase diagram. The
process is then repeated to cover the whole domain to be investigated. Such a
method is relatively quick and can give a good idea of the phase boundaries.
There are nevertheless two major drawbacks to this method.
First, this method gives the phase diagram at one temperature only. To
determine the phase diagram at another temperature, the process must be
repeated. The temperature domain practically available with the titration
method is limited, because everything must be kept at the same temperature.
The second drawback of the titration method is that it is usually used in an out
ofequilibrium condition. In some systems, such as those involving lyotropic
liquid crystals, the time needed to reach equilibrium can be very long; besides,
metastable phases can also be encountered.
A phase diagram recorded by the titration method should be used as a guide
only and should never be applied to longterm stability prediction.
2. Constant Composition Method
In the constant composition method, a series of compositions, covering the
composition range to be studied, are prepared in test tubes, which are closed.
The test tubes are shaken thoroughly and allowed to stand in a thermostatic
bath. The test tubes containing turbid solutions are allowed to stand until they
separate into two or more completely clear phases. The number of clear
phases can be reported on the phase diagram, and the phase domains can be
mapped.
This method is very long, but it allows one to approach the true equilibrium
conditions, and the tubes can be used at other temperatures. Another
advantage of this method is that, when a system gives more than one phase, it
is possible to analyze the phases and to know exactly where the phase
boundaries are, as well as the orientation of the tie lines.

Page 42
III. Phase Diagrams for Ionic SurfactantContaining Systems
A. Ionic Surfactant: Water
1. Krafft Point
The Krafft point can be defined as the temperature Tk above which the
amphiphile solubility in water greatly increases [3]. The reason is that the water
solubility of the amphiphile, which increases with the temperature, reaches the
amphiphile critical micelle concentration (CM in Figure 6). When the solubility
curve is above CM, the dissolved amphiphile is forming micelles and the
amphiphile activity in water solution no longer increases. There is accordingly
no longer a limitation to solubilization.
The Krafft point is a triple point because at this temperature, three “phases”
coexist [4]: hydrated solid amphiphile, individual amphiphile molecules in
solution (monomers), and amphiphile molecules involved in micelles.
Tk increases as the hydrophobic chain length increases. The Krafft points of the
sodium salts of the classic amphiphiles (alkyl sulfates, sulfonates, and
benzenesulfonates) are below room temperature. The Krafft point is also a
function of the counterion, the alkalineearth cations giving higher Krafft points:
sodium laurylsulfate, Tk = 9°C; Ca salt, 50°C; Sr salt, 64°C; and Ba salt, 105°
C.
Because the Krafft point imposes a limitation in formulation processes, the
following rules to reduce Tk can be of essential interest:
Chain branching and polydispersity reduce Tk.
Complexation of Mg and Ca reduces Tk.
Fig. 6
The Krafft point is the temperature
at which the solubility of the
amphiphile becomes higher than its
critical micelle concentration.

Page 43
The presence of an unsaturation decreases Tk.
A very efficient way to reduce Tk is to incorporate two or three oxyethylene
monomers between the hydrophobic chain and the polar head group (alcohol
ethoxy sulfates).
Of course, in each case, other properties of the amphiphile, such as the surface
activity, can be consequently be modified.
2. Phase Diagram
The phase diagram of sodium dodecyl sulfate/water is representative of many
ionic systems (Figure 7) [5]. Liquid (L1) is the aqueous micellar phase; Ha is
the hexagonal lyotropic liquid crystal, sometimes called the middle phase; and
La is the lamellar lyotopic liquid crystal, sometimes called the neat phase. On
the surfactantrich side, several hydrated solid phases are present.
As a general rule, in any (real) phase diagram, at any point representative of a
region and on its boundaries, the number of phases and their nature are similar.
A tie line is the line joining the points representative of two coexisting phases. If
the total composition of a mixture C falls in a twophase region, it separates in
the two phases located at both sides of the tie line that passes the formulation
point (A and B). The weight distribution of the two phases is given by the lever
rule.
Fig. 7
Typical phase diagram of a wateranionic surfactant system.

Page 44
B. Ionic Surfactant, Water and Organic Material Ternary Systems
1. Organic Material = Hydrocarbon
Let us consider an isotherm of a waterionic amphiphile binary mixture above
the Krafft point (for example, watersodium octanoate) [6]. At an amphiphile
concentration of 7% (the critical micellar concentration), the micellar isotropic
solution L1 appears and lasts up to 41%.
Between 41 and 46% is the miscibility gap between L1 and H1, the hexagonal
phase, which lasts up to 52%. Above 52% is the miscibility gap between H1
and the hydrated crystal.
If a nonpolar component (aliphatic hydrocarbon or tetrachloromethane) is
added, almost nothing happens (Figure 8a). The solubility of decane in either
the micellar solution or the liquid crystal is very limited. This is true of any
molecule exhibiting only dispersion cohesive forces.
2. Organic Material = Polar but Not ProtonDonating Material
The solubility of a molecule exhibiting dipoledipole cohesive forces and low H
bonding cohesive forces, such as methyl octanoate, is higher than that of a
hydrocarbon, but nothing special happens in the center of the phase diagram.
3. Organic Material = ProtonDonating Material
If the third component is a nonwatersoluble alcohol (five carbons or more),
amine, carboxylic acid, or amide, the phase topography is profoundly
modified.
The phase diagram presented in Figure 8b [7] shows in addition to L1 and H1 a
huge lamellar phase, a narrow reverse hexagonal phase H2, and, even more
important, a “sectorlike” area of reverse micelles L2. This means that the
solubility in ndecanol of a sodium octanoatewater mixture containing
between 25 and 62% amphiphile is by far more important (30–36%) than pure
water (4%) and pure sodium octanoate (almost nil). This phase is essential to
obtain water in oil (w/o) microemulsions.
The solubility of ndecanol in the L1 phase is also important (up to 12% at the
“end” of the L1). The L1 phase is responsible for the observation of oilinwater
(o/w) microemulsions. The La domain, generally located in the middle of the
diagram, points toward the water side for a critical surfactant/cosurfactant
ratio. (A 1:2 sodium octanoate to ndecanol ratio leads to a lamellar phase
with as little as 17% surfactantcosurfactant.) In some cases, such as octyl
trimethyl ammonium bromidehexanolwater, the lamellar phase already exists
for 3% hexanol + 3% OTAB!
The practical interest of a lamellar liquid crystal lies in its suspending capability.
A lyotropic liquid crystal exhibits a viscoelastic behavior that allows

Page 45
Fig. 8
(a) Typical ternary phase diagram of water, an amphiphile
(sodium octanoate), and a hydrocarbon (octane). (b) Typical
ternary phase diagram of water, an amphiphile
(sodium octanoate), and a coamphiphile (decanol). This
phase diagram was established by Ekwall in 1975.
suspension of solid particles for a very long time. The lamellar phase is
additionally characterized by an ideal critical strain to provide the suspension
with good resistance to vibrations and convections, without impairing its
flowability by a slimy aspect.

Page 46
C. Ionic Surfactant, Water, ProtonDonating Material, and
Hydrocarbon Quaternary Systems
The solubilization of an oil, such as decane, in the micellar isotropic solution L1
or in the reverse micellar isotropic solution L2 can be very important. L1 leads
to water in oil (w/o) microemulsions and L2 to oilinwater (o/w)
microemulsions.
Note that the “cosurfactant” is an amphiphile with (generally) a lower molecular
weight than the “main” amphiphile, the “surfactant.”
1. WaterinOil Systems
As illustrated by Figure 9, the L2 phase is able to solubilize a very large amount
of an hydrocarbon, such as decane or hexadecane. In fact, a composition
containing up to 75% decane and water/surfactant/cosurfactant proportions
corresponding to the L2 phase is still clear, fluid, and isotropic, forms
spontaneously, and is thermodynamically stable. The structure of this
microemulsion can be (to some extent) regarded as a dispersion of tiny water
droplets (reverse micelles) in a continuous phase of the hydrocarbon. The
surfactant and cosurfactant are at the water/oil interphase. This type of system
is often referred to as a waterinoil microemulsion.
The term “microemulsion” to qualify such systems is not well chosen: it conveys
the idea of an actual emulsion characterized by submicrometer (below 0.1 m)
droplets. As is well known, an emulsion is not thermodynamically stable and
cannot be represented by a single phase domain in a thermodynamic phase
diagram. On the other hand, the socalled microemulsions must be considered
real micellar solutions containing oil in addition to water and surfactants.
Fig. 9
A “waterinoil” microemulsion.

Page 47
These solutions, although very far from “ideal” in the thermodynamic sense, are
nevertheless always real in the thermodynamic sense.
Another great difference between the microemulsions and the emulsions is that,
in the very general case, a microemulsion requires significantly more surfactant
than an emulsion.
These waterinoil microemulsions exhibit other important characteristics:
The domain of existence is large. Significant compositional changes can occur
without crossing a phase boundary. Such behavior is particularly important for
manufacturing processes, because it tolerates some “freedom” during
formulation.
They are very stable in a large temperature range, usually from the Krafft point
up to the boiling point. Moreover, the phase boundaries are almost insensitive
to temperature.
The phase topography remains almost unchanged even up to 75% of the ionic
amphiphile is replaced by a nonionic amphiphile.
To obtain a wide waterinoil microemulsion, it is essential to adjust carefully
the cosurfactant structure (usually its chain length) and its relative amount.
Although trial and error is still the most commonly used method of obtaining
microemulsions, a tentative rule is to combine a very hydrophobic cosurfactant
(ndecanol; C10OH) with a very hydrophilic ionic surfactant (alcohol sulfates)
and a less hydrophobic cosurfactant (C6OH) with a less hydrophilic ionic
surfactant (octyl trimetyl ammonium bromide). For very hydrophobic ionic
surfactants, such as dialkyl dimethyl ammonium chloride, even a watersoluble
cosurfactant, such as butanol or isopropanol, is adequate (this rule derives at
least partially from the fact that an important feature of the cosurfactant consists
of readjusting the surfactant packing at the solvent/oil interface).
2. OilinWater Systems
We stated earlier that the solubility of decane in the L1 phase is almost nil. For
a welldefined surfactant/cosurfactant ratio, huge quantities of decane (or any
hydrocarbon) can be solubilized from the L1. A thin, snakelike single phase
domain develops toward the oil pole (Figure 10). This phase can be regarded
as amphiphile micelles swollen with oil.
Generally, the oilinwater microemulsion phases are only metastable systems.
As every metastable system, o/w microemulsions need an activation energy to
separate, and sometimes this activation energy is so large that the separation
almost never occurs. Such systems are not thermodynamically stable and could
accordingly not be considered in a phase diagram. On the other hand, they
form spontaneously and are stable (because of the high activation energy for
separation) for a very long time.

Page 48
Fig. 10
An “oilinwater” microemulsion.
A typical example of a very stable metastable system is a mixture of one
volume of oxygen with two volumes of hydrogen. The mixture is spontaneous
and stable for a very long time, without being thermodynamically stable. The
final thermodynamically stable state is obtained by adding a catalyst (platinum
foam) or a flame to the mixture.
Although not thermodynamically stable, o/w microemulsions form
spontaneously and are accordingly useful (ease of manufacture).
Nonthermodynamic stability implies some constraints:
The position of a o/w microemulsion can depend on the order of mixing of the
raw materials and on the shear imposed on the system.
Their domain of existence is generally narrow.
The system can be sensitive to freeze and thaw cycles.
IV. Phase Diagrams for Nonionic SurfactantContaining Systems
The phase topography of a ternary system involving water, a hydrocarbon, and
a polyethoxylated fatty alcohol depends on the hydrocarbon chain length,
branching, degree of insaturation, aromaticity, and so on, on the amphiphile
structure (hydrophobic and hydrophilic chain length), and also on temperature,
which exerts a very strong influence on the configuration (and accordingly on
the solubility) of the polyoxyethylene segments in water solution. A review has
been presented by Kalhweit et al. in a series of papers [8–11].

Page 49
The phase topography is strongly influenced by the more elementary behavior
of the binary amphiphileoil and amphiphilewater systems.
A. Nonionic Surfactant and Oil
Polyethylene oxide is not soluble in a hydrocarbon, such as hexane or decane.
If a fatty chain is attached to a short segment of polyethylene oxide (4–8 EO
units), the nonionic amphiphile obtained exhibits a solubility profile in oil
depending on temperature.
At low temperatures, a miscibility gap is obtained, translating the nonsolubility
of the polyethylene oxide chain in the oil. At high temperatures, the effect of the
energy is preponderant and the amphiphile is soluble in all proportions in the
oil.
As predicted by the FloryHuggins theory, such a system shows a lower
miscibility gap characterized by an upper critical point, the temperature Ta
which depends on both the oil and the amphiphile structure (Figure 11a). The
critical composition is usually not far from the pure oil side.
Figure 11b shows the lower miscibility gap between some nalkanes and C6E5
(nhexanol ethoxylated with 5ethylene oxide molecules). The upper critical
temperature Ta rises with increasing the oil chain length (its hydrophobicity).
The critical temperature Ta is often referred to as the haze point temperature,
and the miscibility gap between oil and amphiphile plays an essential role in the
ternary phase diagram.
Fig. 11
(a) The haze point temperature. (b) Set of phase diagrams showing how
the haze point temperature is affected by the structure of the oil.

Page 50
B. Nonionic Surfactant and Water
1. Cloud Point
The phase diagram of the binary system nonionic amphiphilewater is more
complicated (see Figure 12). A “classic” upper critical point exists, but usually
below 0°C. At higher temperatures, most nonionic amphiphiles show an upper
miscibility gap, which is actually a closed loop with an upper as well as lower
critical point. The lower critical point Tb is often referred to as the cloud point
temperature. The upper critical point often lies above the boiling temperature of
the mixture (at 0.1 MPa pressure).
The position and the shape of the loop depend on the chemical nature of the
amphiphile. The cloud point temperature Tb plays an essential role in three
component phase diagram topography.
The closed loop can be regarded as a vertical section through a “nose” in the
concentrationtemperaturepressure space, at constant pressure (see Figure
13a). When the pressure rises, the surface covered in the temperature
concentration phase by the phase separation loop decreases and vanishes at a
critical pressure P*.
The shrinking of the loop of the system waterC4E1 with increasing pressure is
given in Figure 13b. The critical conditions for the loop to vanish are T* = 95°
C, P* = 80 MPa, and C* = 28 wt%.
To show the multidimensional nature of these phenomena, note that similar
effects (shrinking of the loop, f.i.) can be achieved by the addition of
“hydrotropic” electrolytes at constant pressure or by increasing the
hydrophilicity of the amphiphile. Figure 13c exhibits the loop areas of butanol
(C4EO), ethylene glycol butyl ether (C4E1), and diethylene glycol butyl ether
(C4E2). The last does not exhibit a loop at 0.1 MPa (± 1 atm), but the system
behaves actually as if the nose were “lurking.” Although no phase separation
occurs in
Fig. 12
The phase behavior of a
waternonionic amphiphile
system.

Page 51
Fig. 13
(a) The effect of pressure on the size of the “closed loop.” (b)
Closed loop of the system waterethylene glycol butyl ether at
different pressures. (c) Effect of the hydrophilic group of the
amphiphile on the shape of the closed loop. (From Ref. [16], with
permission.)
water, the lurking nose exerts some influence on the threecomponent phase
diagram. Another way to look at the same phenomenon is to consider that, in
conditions close to T = 90°C and C = 30 wt%, the C4E2water system is such
that the mixing entropy is just high enough to maintain the molecules in a single
phase, the enthalpic term being positive (endothermic). As soon as a third
incompatible ingredient (the oil f.i.) is incorporated, the entropy is no longer
able to maintain the molecules in a single phase, and phase separation occurs.

Page 52
TABLE 1
min b
(°C) Cb (wt%)
Amphiphile HLB (wt%)
C4E1 10.3 58.9 48.7 29.0
C6E3 12.7 47.4 45.4 13.5
C8E4 12.6 29.6 39.6 6.9
C10E5 12.5 19.7 40.3 3.5
C12E6 12.4 10.6 48.0 2.2
In Table 1, the HLB is calculated according to the empirical equation
HLB = 20 MH/M
where MH is the molar mass of the hydrophilic group and M the total molar
mass of the product. g min is the minimum amphiphile concentration required for
the homogenization of a 1:1 mixture of water and ndecane at around 40°C
(wt%). Tb and Cb are the coordinates of the lower critical points (cloud point).
Although the HLB seems to be correlated with the cloud point, it cannot give
any information on the amphiphile efficacy (g min). Even if the HLB remains
constant, increasing both the polar part and the nonpolar part of a surfactant
molecule significantly improves its efficacy (at least its wateroil compatibilizing
efficacy).
2. Liquid Crystals
The closed loop is not the only characteristic of the nonionic surfactantwater
binary phase diagram. Like the ionic surfactantwater mixture, the nonionic
surfactants, at a higher concentration in water, exhibit lyotropic mesophases.
Figure 14 shows a typical binary phase diagram exhibiting the full lyotropic
mesophase sequence:
I1: cubic, isotropic phase
H1: direct hexagonal phase (middle phase)
V1: special cubic (viscous phase)
La: lamellar phase (neat phase)
Note the presence of the twophase domains surrounding each mesophase, the
critical point on top of each, and the zero variant threephase situation.
Although very difficult to determine with accuracy, the miscibility gaps always
exist, as well as the threephase situations. Of course, the critical temperatures
and concentrations corresponding to each mesophase depend on the chemical
nature of the amphiphile, the pressure, and the optional presence of an
electrolyte.
critical point on top of each, and the zero variant threephase situation.
Although very difficult to determine with accuracy, the miscibility gaps always
exist, as well as the threephase situations. Of course, the critical temperatures
and concentrations corresponding to each mesophase depend on the chemical
nature of the amphiphile, the pressure, and the optional presence of an
electrolyte.

Page 53
Fig. 14
Binary phase diagram of a
waterethoxylated nonionic amphiphile
phase diagram, including lyotropic
liquid crystal domains. (From Ref.
[11], with permission.)
Figure 15 shows some examples of nonionic amphiphilewater binary phase
diagrams [10,12]. As a rule, amphiphiles with hydrocarbon chain length of 8 or
fewer carbon atoms exhibit only the loop (in a domain depending on the
ethoxylation) and no mesophase.
Longer chain amphiphiles show one or more mesophases, one being
preponderant. The type of main mesophase (the one exhibiting the highest
critical temperature) depends on the relative volumes of the EO and
hydrocarbon chains. If the volumes are similar, the lamellar phase is
preponderant. This is the case with C12E6. If the volume of the EO chain is
significantly higher than the volume of the hydrocarbon chain, the hexagonal
phase will melt at higher temperature (C12E7); if the volume of the EO chain is
much higher than the volume of the hydrocarbon chain, the cubic phase I1 may
appear.
In some cases, such as C12E5, the lamellar phase La (or the H1) interferes with
the loop (with the cloud point curve) and induces the socalled critical phase,
L3. L3 is an isotropic, often lactescent phase, exhibiting a zerovariant three
phase critical point at its lower temperature of existence. The nature of the
three phases in presence at the critical conditions are W (water with a minute
amount of amphiphile), L3 and La. The L3 phase seems to have a beneficial
action on cleaning performance, maybe because of the presence of the critical
point.
C. Nonionic Surfactant, Water, and Oil
From the phase behavior of both binary mixtures (wateramphiphile and oil
amphiphile), it is now possible to account, at least qualitatively, for the three
component phase diagram as a function of temperature. The presence of a
haze point on the oilamphiphile phase diagram (critical point a) at temperature
Ta shows that the surfactant is more compatible with the oil at high temperature

Page 54
Fig. 15
Real examples of waterethoxylated
nonionic amphiphile binary phase
diagrams. (From Ref. [10], with
permission.)

Page 55
than at low temperature. The presence of a cloud point on the water
amphiphile phase diagram (the lower critical point ) at temperature Tb shows
that (at least in the neighborhood temperature domain) the amphiphile is less
compatible with water at high than at low temperatures. As a consequence (the
other parameters being kept constant), the amphiphile behavior depends on
temperature.
At low temperature, these mixtures are more compatible with water than with
oil. The phase diagram corresponding to this situation is illustrated in Figure 16,
a1 or a2. The tie line orientation is directly deduced from the partitioning of the
amphiphile between water and oil: because under the current conditions the
surfactant is more compatible with water than with oil, the majority of the
amphiphile is in the water phase and only a limited amount of amphiphile is
present in the oil. Accordingly, the tie lines point in the direction of the oil
corner. Diagrams a1 and a2 (Figure 16) are referred to as Winsor I (WI). If
the temperature at which the phase diagram is recorded lies above Ta (the haze
point), a critical point CPa is present near the oil corner (although pure
amphiphile and pure oil are miscible, the presence of a small amount of water
“recalls” the lack of compatibility between amphiphile and oil). On the other
hand, if the temperature lies below Ta, no critical point appears in the three
component phase diagram (it seems to lie for a negative water concentration).
At high temperatures, these mixtures are more compatible with oil than with
water. The phase diagram corresponding to this situation is c1 or c2 in Figure
16. The amphiphile partitioning now favors the oil, and the tie lines point in the
direction of the water corner. c1 and c2 are referred to as Winsor II (WII). A
critical point CPb is found if the temperature lies below the cloud point
Fig. 16
Evolution of waterethoxylated nonionic amphiphileoil ternary phase
diagrams with temperature (rising from a to c).

Page 56
Tb but more often, the critical point lies outside the Gibbs triangle (T > Tb ).
In WI and WII representations, the critical point CPb or CPa is called a plait
point. If the temperature difference between the temperature T at which the
phase diagram is recorded and the critical point of the binary mixture. Tb or Ta,
increases, the distance from the plait point to the oilamphiphile axis for CPb
and wateramphiphile for CPa increases, too. An important characteristic of a
ternary system is the line that links the plait points as a function of temperature.
The plait point curve is really the trace of the partitioning of the amphiphile
between oil and water. The closer to the oil is the plait point, the amphiphile is
more in the water, and vice versa.
At low temperatures, the amphiphile is more compatible with water because
water interacts strongly with the hydrophilic head group. Accordingly, the
hydrodynamic volume of the head group is greater than the hydrodynamic
volume of the hydrocarbon tail. At high temperatures, head group hydration is
reduced and so is hydrodynamic volume, which becomes smaller than the
hydrodynamic volume of the hydrocarbon tail. There is necessarily a
temperature at which the hydrodynamic volumes of the two antagonistic parts
of the amphiphile molecule are equal. This particular temperature, represented
by , is the phase inversion temperature (also called the HLB temperature).
The phase inversion temperature is a characteristic (and is accordingly a
function) of the nature of the oil, the amphiphile, and the brine (if electrolytes
are present). If the pressure can vary (as in oil recovery), it also changes . It
is important to realize that can be higher than both CPb and CPa when the
amphiphile solubility is very small in water and total in oil.
The topography of the phase diagram at the phase inversion temperature
depends on the mutual incompatibilities between oilamphiphile, water
amphiphile, and wateroil. Even with a polar oil and water containing a
chaotropic (hydrotropic) electrolyte, the wateroil incompatibility is high
enough to guarantee a miscibility gap from 0 to 100°C.
With the amphiphile, the situation is not as simple. We showed that, at , the
amphiphile is equally compatible with water and oil, but no assumption is made
about the degree of compatibility. Two limit cases can occur:
1. The amphiphile is either very compatible with both water and oil or not very
incompatible. The phase diagram will look like Figure 16 b1, with a plait point
only for an equal amount of oil and water and with the lines parallel to the
wateroil side. (equal partitioning). This plait point corresponds to the merger
of the CPa and CPb lines, and the projection of the plait point curves on the oil
watertemperature phase diagram should look like Figure 17a or b.
2. The amphiphile is equally (and significantly) incompatible with both water
and oil. The phase diagram will now look like Figure 14 b2. A threephase
triangle (3PT) appears.

Page 57
Fig. 17
Transition from an infratricritical situation (a and b) to a supertricritical
situation (d and e) through a tricritical point (c). (From Ref. [11], with permission.)
Three phases are now in equilibrium:
1. A waterrich phase (W)
2. An oilrich phase (O)
3. An amphiphilerich phase (S)
The amphiphilerich phase is also called the surfactant phase or the middle
phase. The last terms, due to Shinoda, results from the physical appearance of
a threephase body:
1. A dense, waterrich phase at the bottom
2. A light, oilrich phase at the top
3. A phase containing most of the amphiphile in the middle
It is worth noting that with higher molar volume amphiphiles, such as C12E4, a
significant amount of the amphiphile can be present in the oil phase, even at .
Here, too, the plait points CPa and CPb will be or will not be inside the Gibbs
triangle depending on the relative positions of , Ta, and Tb .
If the phase diagram exhibits a threephase triangle, it is called a Winsor III
(WIII) system. In such a situation, the plait point curves do not merge but
“cross” each other and stop at two terminal critical points (see Figure 17d or
e).
The sequence of the evolution of a threecomponent system when temperature
has risen can be summarized as follows. If the amphiphile is strongly
incompatible with oil and water,
WI WIII WII
If the amphiphile is compatible or is weakly incompatible with oil and water,
WI WII
A way to modify amphiphile compatibility with oil and water is to change its
molecular weight, keeping the proper balance between oleophobicity and
hydro
Page 58
phobicity. A highmolecularweight amphiphile like C12E6 will show a WIWII
WII sequence, although a lowmolecularweight amphiphile like C4E2 will show
(with decanol acetate as the oil) a WIWII sequence.
By varying the amphiphile (in)compatibility through its molecular weight, it is
possible to pass from a WIWII to a WIWIIIWII sequence. At a certain
point, a situation as illustrated in Figure 15c will occur: the plait point curves
just merge critically and the threephasetriangle (3PT) collapses. This situation
corresponds to a tricritical point, an essential concept in theoretical
thermodynamics.
When the system is such that a 3PT appears (by far the most common case),
the 3PT exists from a temperature T1 lower than to a temperature Tu above
. To some extent, the difference between T1 and Tu is a measure of how far
the system is from the tricritical conditions. (Note that is not necessarily the
average of Tu and T1.)
The thermal evolution of a typical system, with broken critical lines (see Fig.
18), can be summarized as follows:
At T < T1, the phase diagram is a typical WI.
T1 is the temperature of the critical end point of the CPb curve. At T = T1, the
phase diagram is still a WI, but with a critical tie line from which the three
phase triangle will appear a fraction of Kelvin above.
For T1 < T < , the corner of the threephase triangle corresponding to the
amphiphile phase remains close to the water side but moves “clockwise” in the
Gibbs triangle.
For T = , the amphiphile corner of the threephase triangle reaches “12
o'clock” (phase inversion temperature).
For < T < Tu the corner of the threephase triangle corresponding to the
amphiphile phase keeps on “moving clockwise” to the oil phase.
Tu is the temperature of the critical end point of the CPa curve. At T = Tu, the
amphiphile corner of the threephase triangle merges with its oil corner and the
threephase triangle collapses in a critical tie line of a WII phase topography.
At T > Tu, the phase diagram is a typical WII.
It is important to remark on the shape of the line joining the three corners of the
threephase triangle (G lines). It is a single, gauche line, with a minimum at T1
on the water side of the critical tie line and a maximum at Tu on the oil side of
the critical tie line. These branches can be identified (Ga, Gb , and Gg), each
corresponding to the compositions of each corner of the threephase triangle.
It is important to note that Ga has nothing to do with CPa and that Gb has
nothing to do with CPb . Gi are composition curves, and CPi are critical point
curves.
At a critical end point, however, the critical point curve meets the extreme of
u
the critical tie line. These branches can be identified (Ga, Gb , and Gg), each
corresponding to the compositions of each corner of the threephase triangle.
It is important to note that Ga has nothing to do with CPa and that Gb has
nothing to do with CPb . Gi are composition curves, and CPi are critical point
curves.
At a critical end point, however, the critical point curve meets the extreme of
the composition curve (CPa meets Ga at Tu and CPb meets Gb at T1).

Page 59
Fig. 18
Detailed evolution of the phase diagram of a
wateroilethoxylated nonionic amphiphile (low
molecular weight) with temperature. (From Ref.
Another important characteristic of these systems is that the best compatibility
capacity is achieved at T = , when the hydrodynamic volumes of both parts
of the surfactant are equal. Under phase inversion conditions, the amount of
amphiphile needed to compatibilize a mixture of equal amounts of oil and water
is minimal. The phase inversion conditions are accordingly looked for to
minimize the amphiphile quantity needed to achieve a given task.
Winsor behavior is not the only characteristic of wateroilnonionic amphiphile
systems. The lyotropic mesophases appearing on the wateramphiphile binary
phase diagrams expand to some extent in the Gibbs triangle (Figure 19).
Amphiphiles based on alcohols lower than C8 do not generate liquid crystal at
all (amphiphiles based on C4 and less do not even give micelles). C10 and
above alcoholbased nonionic amphiphiles exhibit lyotropic liquid crystals, at
least usually up to Tu. Figure 19 shows the typical and general behavior of
ternary system with an amphiphile giving liquid crystals. At temperature below
T1, each lyotropic mesophase appearing on the wateramphiphile binary

Page 60
Fig. 19
Ternary phase diagrams involving nonionic amphiphiles
generating lyotropic liquid crystals with water. (From Ref.
phase diagram expand in the Gibbs triangle. At a temperature close to ,
generally only the lamellar liquid crystal phase is present, and points toward the
amphiphile corner of the threephase triangle. Above Tu, all the liquid crystals
are molten.
D. Effects of System Parameters on Phase Behavior
1. Nonionic Surfactant Structure
Tu, T1, and increase if more and more hydrophilic amphiphiles are used. This
is easily explained by the HLB concept: a more hydrophilic amphiphile will
remain in water up to a higher temperature.
Another fundamental effect of the amphiphile is a result of its molecular weight
(or molar volume): increasing the molecular weight of an amphiphile at constant
HLB results in the fact that much less amphiphile is required to compatibilize
equal amounts of water and oil, as illustrated by Figure 20.
2. Effect of Oil
(a) Molar Volume. Increasing the oil molar volume results in an increase in Tu,
T1 (if they exist), and . This is illustrated in Figure 21 for aliphatic

Pag
Fig. 20
Effect of the molecular weight of the amphiphile on the shape of the ternary phase diagra
(From Ref. [10], with permission.)
hydrocarbons, alkyl benzenes, and alkanol acetate mixtures with water and
diethylene glycol monobutyl ether (C4E2).
Increasing the oil molar volume corresponds to increasing the oilwater
incompatibility: another result is the increase in the temperature difference betwee
Tu and T1. This is illustrated by the alkyl benzene series, which presents a tricritica
point for an alkyl chain length between 6 and 7.
(b) Polarity. Because increasing the oil polarity (by shifting from aliphatic
hydrocarbons to alkyl benzenes to alkanol acetates) decreases the wateroil
incompatibility, it is not surprising that the Winsor transitions (Tu, T1, and ) occu
at lower temperatures and the supertricriticality decreases.
The polarity of the oil can be estimated from Hansen's threedimensional solubilit
parameters. Hansen separated Hildebrand's solubility parameter into three
independent components: d for the dispersion contribution, p for the polar
contribution, and h for the H bonding contribution. As an estimation of the oil
polarity, we define Dph as the square root of the square of the polar
Fig. 21
Effects of oil molar volume and polarity on the characteristics of
ternary phase diagrams obtained with water and diethylene
glycol butyl ether.

Page 62
component plus the square of the H bonding component of the solubility
parameter, using the table published by Barton [13].
For ternary mixtures of alkanes, alkyl benzenes, or alkanol acetates with water
and C4E2, the phase inversion temperature can be satisfactorily expressed as
(°C) = 1.016V 0.00121V2 44.72Dph + 4.747D2ph 2.74 (1)
V is the oil molar volume in ml/mol and Dph is the oil polar character in MPa½ .
The effects of the molar volume and that of the polarity appears to be
independent, at least in this specific case.
3. Effect of Electrolytes
It is possible to modify the behavior of water by adding electrolytes.
Electrolytes usually reduce the solubility of uncharged organic ingredients in
water. Although the great majority of electrolytes exert a saltingout action,
several exceptions exist, such as perchlorates and thiocynates. These salts are
saltingin.
The saltingout or in characteristics of electrolytes were discovered at the end
of the nineteenth century by Hofmeister [14] and remain a mystery. It has been
established that this effect has nothing to do with ionic strength: different salts at
the same ionic strength present different saltingout or in characteristics.
Besides, unlike a classic electrostatic effect, it is almost linear with salt
concentration (at least in the low concentration range).
In water, the effects of anions are much more pronounced than the effects of
cations. The sequence of anions of increasing salting out character in aqueous
solutions is as follows:
Nitrate < chloride < carbonate < chromate < sulfate
On the other hand, perchlorates and thiocyanates are saltingin electrolytes. A
saltingout electrolyte strengthens the structure of water and makes it less
available to hydrate organic molecules; saltingin electrolytes would, on the
other hand, disrupt the structure of water, creating “holes.” It is noteworthy
that saltingin electrolytes usually have a positive enthalpy of solubilization in
water (endothermic solubilization).
In practice, saltingout electrolytes make water even more incompatible with
oil. The result is a decrease in the Winsor transition temperatures and an
increase in the supertricritical character. The amount of amphiphile necessary
to compatibilize water and oil generally increases in the presence of a salting
out electrolyte. Of course, all these tendencies are inverted with a saltingin
electrolyte. Figure 22 illustrates the effects of different electrolytes on a C4E2
C13 acetatewater system.

Page 63
Fig. 22
Effect of the nature of the electrolyte and its concentration
on the characteristics of ternary phase diagrams obtained
with water, diethylene glycol butyl ether, and
tridecanol acetate.
4. Effect of LowMolecularMass, WaterSoluble Organic Molecules
Water can be made less incompatible with oil by adding small, uncharged,
watersoluble organic molecules, such as amides and substituted ureas [15].
High saltingin performance is obtained with organic molecules with the
following characteristics:
Amphiphilic structure
Hydrophobic segment short enough to prevent aggregation
Concentration well below the solubility limit
Typical examples are urea derivatives, especially butyl urea.
5. Emulsions
Unlike the systems described above, emulsions are not thermodynamically
stable systems. They are dispersions of one liquid phase within another, helped
with a surfactant. Oilinwater emulsions are dispersions of oil droplets in a
continuous aqueous phase and waterinoil emulsions are dispersions of water
in an oily continuous phase. Multiple emulsions may also exist: an aqueous core
surrounded by an oil phase, itself dispersed in an aqueous continuous phase.
The size of the dispersed droplets ranges from a fraction of a micron to 50
microns. Accordingly, emulsions are milky, nontransparent systems. They are
also subject to phase separation on aging, and their behavior does not depend
only on their composition, but also on the process of producing. To date, the
formulation of emulsions remains highly empirical.

Page 64
The general principle behind emulsion formulation is that one must generate a
large surface of contact between water and oil. It is easier to do this if the
interfacial tension between water and oil is as low as possible. Surfactants are
accordingly very helpful. The choice of the surfactant depends on the nature of
the oil and the desired structure of the emulsion. Oilinwater emulsions should
be formulated with surfactants exhibiting a hydrophilic head group larger than
their lipophilic tail, and reciprocally.
The physical stability of emulsions depends on a lot of internal and external
factors. The size of the droplets is very important, as it directly conditions the
rate of separation , according to Stokes' law
126290064a.gif
Where is the difference of density between the solid particle and the liquid,
r is the radius of the droplet and is the viscosity of the continuous phase.
It has to be pointed out that Stokes' law is valid only in the case of a single
droplet not interacting with the continuous phase. The observed separation rate
may be very different than the one predicted; nevertheless, it is important to
keep it in mind.
The dispersed droplets necessarily collide with each other. The collisions can
be elastic (they just bounce) or inelastic. In such a case, they can just stick
together and form a cluster. This is called “flocculation” and it usually induces
viscosity modifications long before visible phase separation is observed. When
two droplets stick together, the film separating them may break and the
droplets can join to form a larger droplet. This is called “coalescence.”
One may think that better emulsion stability would be obtained with higher
surfactant quantity. This is not true. Optimum stability is obtained with an
optimum amount of surfactant. One possible explanation of emulsion
destabilization with too much surfactant is that the surfactant in excess forms
micelles, which bombard emulsion droplets, due to Brownian motion. If two
droplets happen to be close together, even if they do not attract each other,
they are pushed into contact by the no longer balanced collisions, as there are
less micelles between the two droplets than in the bulk.
References
1. Griffiths, R. B., and Wheeler, J. C., Phys. Rev., A2, 1047–1064 (1970).
2. Ricci, J. E., The Phase Rule and Heterogeneous Equilibrium. Van
Nostrand, New York, 1951.
3. Krafft, F., Ber. Deutsche Chem. Ges., 32, 1596–1608 (1899).
4. Shinoda, K., Solvent Properties of Surfactant Solutions, Vol. 2, Marcel
Dekker, New York, 1967, pp. 12–16.

Page 65
5. Kekicheff, P., GabrielleMadelmont, C., and Ollivon, M., J. Colloid Int.
Sci., 131, 112–132 (1989).
6. Ekwall, P., Mandell, L., and Fontell, K., Mol. Cryst. Liq. Cryst., 8, 157–
213 (1969).
7. Friman, R., Danielsson, I., and Stenius, P., J. Coll. Interface Sci., 86,
501–514 (1982).
8. Kalhweit, M., Lessner, E., and Strey, R., J. Phys. Chem., 87, 5032
(1983).
9. Kalhweit, M., Lessner, E., and Strey, R., J. Phys. Chem., 88, 1937
(1984).
10. Kalhweit, M., Strey, R., and Haase, D., J. Phys. Chem., 89, 163 (1985).
11. Kalhweit, M., and Strey, R., Angew. Chem. Int. Ed. Engl., 24, 654
(1985).
12. Mitchell, D. J., Tiddy, G. J. T., Waring, L., Bostock, T., and McDonals,
M. P., J. Chem. Soc., Faraday Trans., 1, 79, 975–1000 (1983).
13. Barton, A. F. M., Handbook of Solubility Parameters and Other
Cohesion Parameters, CRC Press, Boca Raton, FL, 1983.
14. Hofmeister, F., Arch. Exp. Patol. Pharmackol., 24, 247 (1888).
15. Broze, G., Comm. J. Com. Esp. Deterg., Barcelona, 20, 133 (1989).
16. Schneider, G., J. Phys. Chem. (Munich), 37, 333 (1963).

4
Rheology of Liquid Detergents
R. S. ROUNDS
Fluid Dynamics, Inc., Piscataway, New Jersey
I. Introduction
II. Patent Survey of Liquid Detergent Formulations
III. Rheological Measurements
A. Steady Shear Viscometry
B. Dynamic Mechanical Spectroscopy
C. Extensional Viscometry
IV. Product Delivery Vehicles
A. Dispersed Systems
B. Highly Concentrated Dispersions
C. Gels and Microgels
D. Stability
V. Fundamental Research in Liquid Detergents
A. Surfactant Solutions
B. Surfactant Liquid Crystal Gels
C. PolymerSurfactant Interactions
VI. Conclusions
References

Page 68
I. Introduction
Common household liquid detergent products can exhibit remarkable
rheological properties, depending on the structured or unstructured delivery
system selected for a specific formulation. Whether solution, dispersion, or gel,
these products can display rich rheological attributes, including solidlike
properties in the quiescent state with transitions to fluid flow, allowing flow
through dispensers, and facile application to intended organic and inorganic
surfaces. Thixotropy is a commonplace property, as are yield stresses and
pseudoplasticity, and dilatancy and rheopexy are also observed.
The most general survey of the rheology of commercial liquid detergents shows
clearly that these fluids span the entire range of the viscoelastic spectrum,
including both personal and home care products. Consumers have a wide
range of product selections within most product categories, ranging from low
viscosity solutions to highly elastic gel compositions, depending on individual
preferences. Rheology design and control is a difficult task, however,
considering the complexity of many of these formulations, consisting of
surfactants, surfactant mixtures, electrolytes, hydrotropes, polymers, various
conditioners, builders, fragrances, pigments and dyes, and so on, with many
potential associative interactions. Fundamental rheological research has
provided insight into various mechanisms available to product formulators to
regulate rheological attributes of these complex fluids.
The complex nature of the rheology of surfactant systems has been known and
studied for many decades. The elasticity of specific surfactants in the presence
of electrolytes was deduced initially from simple observations of elastic recoil
and steady shear viscosity measurements. In 1926, for example, Hatschek and
Jane [1] determined ammonium oleate, in excess ammonia, to have a highly
structured order, with both significant elastic and timedependent properties.
Similar results were reported by Winsor for potassium oleate in the presence
of potassium salts, such as potassium acetate or carbonate [2]. Research
continued to determine the nature of this phenomena, exploring the morphology
of the surfactant in aqueous solutions in the presence of various additives.
The existence of viscoelastic surfactant systems in the dilute regime sparked
interest in defining the organization of the micelles in these systems. In 1954,
Pilpel speculated about the presence of long, interlinked cylindrical micelles
forming coherent, yet transient network structures as the basis for the formation
of viscoelastic surfactant gels [3,4]. His research was directed at gels formed
from soaps in the presence of fatty alcohols, perfluoro compounds, and various
simple electrolytes. Further, Nash [5,6] investigated conditions of gel formation
in dilute, twocomponent, cetyltrimethylammonium bromide (CTAB)/naphthol
solutions, also proposing the formation of long, cationic filaments resulting in
polymerlike viscoelastic behavior.

Page 69
These early research efforts were a preface to the extensive rheology research
of surfactant systems currently in progress. Interest in the rheology of surfactant
systems and multicomponent liquid detergent products has continued to grow,
playing a more comprehensive role in the characterization of these complex
fluids and guiding product development research in the academic and industrial
sectors. Both steady shear and dynamic mechanical measurements elucidate
the structure and morphology of surfactant micelles and their corresponding
mechanical properties, in concert with other characterization techniques,
leading to fundamental structureproperty relationships. In addition, a
considerable effort has been directed towards theoretical modeling of the
observed rheological behavior. Much of the growing emphasis on the rheology
of liquid detergents and their product components has been advanced by the
development of sophisticated, programmable, rheological testing
instrumentation with highsensitivity transducers, required for the
characterization of these fluid systems.
This chapter broadly summarizes the technical literature and reviews the
fundamentals of rheological measurements relevant to detergent systems.
Rheological profiles of various commercial liquid detergents and their
components will also be presented from personal care and household care
product categories, emphasizing product delivery vehicles and including both
steady shear and dynamic mechanical and extensional properties. The
principles of rheology, with definition of terms and derivation of appropriate
mathematical expressions, are not included, however, because excellent
references are available in these subject areas [7–26].
II. Patent Survey of Liquid Detergent Formulations
The importance of the rheology of liquid detergents is well reflected in the
patent literature. Frequently, mechanical properties such as viscosity, yield
stresses, thixotropy, and various viscoelasticity parameters are the principle
objects of the invention, reflecting the importance of these properties in defining
product aesthetics and consumer experience in product usage.
Rheology or, at least, consistency, is a dominant liquid detergent patent theme.
Several examples include a thickened aqueous abrasive cleanser with “use
favorable” rheology [27], a thickening colloidal suspension stabilized through
association with surfactant for incorporating whitening agents in a bleach
composition [28], stable, lowviscosity liquid detergents consisting of lamellar
dispersions or vesicles within an aqueous continuous phase [29], and acrylic
maleic acid builder copolymers as dispersion stabilizers and viscosity
modifiers for structured and unstructured liquid detergents [30]. One patent

Page 70
discloses a liquid detergent composition that increases viscosity upon dilution
to provide benefits to the consumer during use [31]; another presents viscosity
improvers for aqueous solutions of nonionic surfactants for applications in
shampoos, hand soaps, fabric care, and hard surface care detergents [32]. The
patent literature teaches many methods of rheology modification and control
throughout product shelf life, although full rheological characterizations are not
typically provided.
The recent patent literature has seen a new emphasis on the viscoelastic nature
of liquid detergents. One example is a linear viscoelastic automatic dishwasher
detergent composition with improved physical stability and flow properties
incorporating a polymeric thickening agent [33,34], providing an alternative to
claythickened dispersions. Whereas many previous patents describe viscosity
or yield stress values within the product definition, this patent defines the
viscoelastic nature of the liquid detergent product through dynamic mechanical
properties, including the strain dependence of the storage and loss modulus.
Viscoelastic gel detergent compositions are also the subject of a patent issued
to Lever Brothers Co., with creep compliance data provided to support
evidence of gel formation [35]. A lowfoaming automatic dishwashing
detergent composition gel is also the subject of a patent issued to the Drackett
Company. “Gel” characteristics are supported only by the presence of a yield
stress, extrapolated from Brookfield viscosity data [36].
Gelled or thickened laundry detergents and hard surface cleaners containing
bleach compounds have seen considerable growth during the past few years.
Thickened aqueous bleach compositions formed through the addition of a
viscoelastic surfactant system, comprised of surfactant ions and organic
counterions, have also been proposed [37], suitable as hard surface cleaners,
with delivery through manual spray nozzle dispensers. Advantages include
reduced misting as a result of the viscoelastic nature of the solution, as well as
suitable rheology for adherence to vertical surfaces [38], good phase stability,
bleach stability, and stable viscosity. The Proctor and Gamble Company has
patented liquid or gel laundry compositions containing amido peroxy acid
bleach showing good stability in the presence of perfume ingredients [39],
stable cleansers containing chlorine bleach and phytic acid [40], and a stable
thickened aqueous bleach composition formulated with hypochlorite and a
mixture of highmolecularweight polycarboxylate polymer and amine oxide
surfactant, applicable to toilet bowl cleansers, bathroom tiles, and shower
walls. Akzo Nobel NV has also been granted a patent for a stable yet
pourable aqueous bleachcontaining composition with waterinsoluble peroxy
acid suspended in a mixture of two or more polymers. The preferred organic
peroxy acid is cited as 1,12diperoxydodecanedioic acid [41].
Additional patents have also been granted for various thickened hard surfaces
cleaners and drain clearing compositions [42–45]. Viscoelasticity is highlighted,

Page 71
formed through association of quaternary ammonium compounds with suitable
counterions, for example, providing consumeracceptable pour properties. Of
particular interest is a patent issued to the Clorox Co. for viscoelastic
formulations, citing a Trouton ratio of greater than 50 for select compositions
[46].
An unusual gel delivery vehicle for a detergent composition based on the phase
behavior of surfactant systems is described in another patent issued to Procter
and Gamble, containing ethoxylated alkyl sulfate surfactant in hexagonal liquid
crystal form [47].
We have reviewed only a small segment of the vast liquid detergent patent
portfolio, yet the emphasis on product rheology, viscoelasticity, and extensional
flow behavior is noteworthy. A significant industrial focus is directed toward
the development of liquid detergents with tailored rheological attributes
appropriate for the intended application.
III. Rheological Measurements
Rheological and viscometric measurements relevant to the study of commercial
liquid detergent compositions and their many components are very diverse, and
selection of the appropriate measurement tool is dependent on (1) the
objective of the measurement and (2) the nature of the fluid under investigation.
The nature of the liquid composition or the delivery system is an important
consideration in the selection of rheological test methods, and this is addressed
in greater detail in the following sections.
A. Steady Shear Viscometry
Viscosity is a very obvious material property requiring specification in the
design of a liquid detergent product. It is one design element that directly
influences the acceptability of the complete product formulation, its ease of
manufacture, the package and dispenser orifice design, product appearance,
and numerous consumerperceived product attributes. As such, it is necessary
to complete viscosity measurements accurately within the appropriate shear
rate or shear stress range of interest. Process engineers, for example, may
require constitutive equations describing the steadystate viscosity function at
shear rates and temperatures experienced during manufacture, for specification
of process equipment and determination of process conditions and process
simulations. These requirements are quite distinct from those concerned with
transient viscosity behavior or the flow resistance of products encountered by
the consumer throughout product usage, such as dispensing from a container,
pouring, application to a surface, and drainage.
If a product is being evaluated for dispensability through a packaging orifice,
the shear rate to be used in the viscometric study must be estimated from

Page 72
the geometry of the orifice and the discharge rate or linear velocity of the fluid
through the orifice. The objective of this measurement is very clearly to define
fluid response, under conditions simulating product dispense. This is a transient,
converging flow, occurring very rapidly, and flow resistance at the inception of
flow, or + = ƒ(t), or during an accelerated flow, = ƒ(d /dt) for short flow
durations, may be the most appropriate testing format. A creep measurement is
a reasonable alternative if estimates of the forces involved are available. A
summary of several viscometric tests commonly applied to the characterization
of liquid detergents and their raw materials is provided in Figure 1, with
examples of typical fluid responses.
Viscosity measurements require a fundamental understanding of the definition
of viscosity describing the proportionality between the stress tensor and the
rate of deformation tensor :
=
Viscosity, a scalar, is a function of the invariants Ii of the rate of deformation
tensor . For viscometric flow of incompressible fluids,
= ƒ(I2)
I2 = ( : ) = i j ij ji
Viscometric measurements require simple, unidirectional flow in restricted
geometries such that analytic solutions of the differential equations describing
the flow exist, directly enabling viscosity calculations [48].
Rotation viscometers, especially those equipped with computer control and
data acquisition firmware, can very effectively be used to generate flow curves
or determine viscosity functions, = ƒ( ), for most fluid systems. Newtonian
fluids can be readily distinguished from nonNewtonian fluids and time
dependent shear effects can be easily quantified. Many liquid detergents and
their components are not simple Newtonian or nonNewtonian fluids but
exhibit either thixotropy or rheopexy. These timedependent shear effects can
significantly complicate the generation of flow curves, because an additional
variable, duration of shear, that is, = ƒ( ,t), must be considered. In addition
to viscosity measurements of both Newtonian and nonNewtonian fluids,
rotational viscometry is often used to evaluate yield stresses, normal stress
differences, timedependent properties, and structural parameters.
Steady shear viscometers are commercially available with normal force
transducers, needed to calculate normal stress differences. These
measurements are of critical importance in viscometry to define completely the
rheological state of a fluid, because practical implications of normal stress
effects can occur in processing liquid detergents. The Weissenberg effect in
mixing, for example,

Page 73
FIG. 1
Experimental test methods frequently applied to the
characterization of liquid detergents, with examples of typical
fluid responses.
is perhaps the best known. These measurements, however, are difficult to
complete for low viscosity fluids.
If we assume simple unidirectional flow between a cone and plate testing
geometry, as shown in Fig. 2, the expressions for viscosity and primary nor

Page 74
FIG. 2
Cone and plate viscometric fixture with derivation of
equations for the calculation of viscosity and first normal
stress coefficient.
mal stress coefficient, 1, in terms of experimental variables are provided.
Normal force is the sole experimental parameter generally measured in
commercial viscometric instruments, leaving the secondary normal stress
coefficient, 2, undetermined.
For liquid detergents that are simple, isotropic, Newtonian solutions, viscosity
determinations are sufficient to fully characterize resistance to flow, if normal
stresses are not present. Examples of such products include most liquid hand
dishwashing detergents and certain personal care, hard surface cleaners and
laundry detergent products. Linear Newtonian flow curves, = ƒ( ), for
several commercial products, selected from household hard surfaces cleaners
marketed in the United States, are shown in Fig. 3. We have included one
concentrated detergent that shows obvious deviation from Newtonian
behavior, in the shear rate range of 0–25 s1. Hard surface cleaners, hard
surface cleaners containing bleach, liquid laundry detergents, and shampoos
are among products that can occur as simple, isotropic, Newtonian fluids or as
unstructured systems. It is interesting to note that products that are represented
as “gels” are frequently viscous Newtonian fluids, although there are occasional
exceptions.
Many consumer products exhibit more complex flow behavior in viscometric
evaluations, depending on the composition and physical form of the liquid
composition and more rigorous rheological characterizations are required fully
to

Page 7
FIG. 3
Viscosity as a function of shear rate for a representative sampling of U.S. home
care liquid detergent products, determined at 25°C using the Rheometrics Scientific
RFSII with parallel plate test geometry.
appreciate flow resistance in a manufacturing environment, flow behavior during
product use, physical product appearance, and so on. These products, including
dispersions and gellike fluids, are generally nonNewtonian, viscoelastic, and
may also exhibit time dependent mechanical properties. Figure 4 contains
representative flow curves, = ƒ( ), for several personal care products
which exhibit nonlinear viscosity functions, that is, nonNewtonian fluids. Liquid
detergent products fully embrace the full viscoelastic spectrum, as we see when
representative commercial detergents are characterized in oscillatory
measurements.
Thixotropy, a decrease in viscosity occurring with increasing time of shear at
constant shear rate, is a wellknown viscometric property often displayed by
various structured liquid detergent products, especially dispersed systems;
rheopexy is a more novel response. Figures 5 and 6, for example, show the
viscosity as a function of time for two commercial personal care products during
stress growth measurements at 0.05 s1, for a 60 s time interval. These two liquid
detergents, both dispersions, exhibit very different responses to the same

Pa
FIG. 4
Viscosity as a function of shear rate for several randomly selected personal care
cleansers, determined at 25°C using the Rheometrics Scientific RFSII with parallel plate
tooling.
FIG. 5
+
Viscometric behavior, = ƒ(t) of a commercial skin cleanser in response to
a constant shear rate of 0.05 s1 at 25°C. Data obtained using the Rheometrics
Scientific RFSII with parallel plate tooling.

Page 77
FIG. 6
Rheopectic behavior of a commercial conditioning shampoo, determined
through stress growth measurements, + = ƒ(t) at 0.005 s1 and 25°C using
the Rheometrics RFSII and parallel plate geometry.
applied deformation. In Fig. 5, we see thixotropy following a stress overshoot;
while the second detergent (Fig. 6) appears to be thickening, or rheopectic,
under identical experimental conditions. In further experimentation, the product
exhibiting rheopexy showed no equilibration to an equilibrium shear stress
following an increase in shear duration to 6000 s.
The ease with which the internal physicochemical microstructure is eroded in
shear and the kinetics of the structural reformation following shear are
characteristics of structured fluids that can be investigated using rotational
viscometry. Such products, for example, may appear to be very thick and rich
in composition yet relatively easy to dispense. For these complex fluids,
phenomenological characterizations have attempted to define structural
parameters predictive of the timedependent viscosity functions [49–52]. A
review of various models attempting to model thixotropic behavior is provided
by Ultrecht et al. [53].
Thixotopy is a truly complex phenomenon, involving longrange interactions
between product components yielding threedimensional network structures,
or coagulation structures, with potential reversible transitions. In the structured
state, such fluids may exhibit significant elasticity and timedependent inelastic
flow when exposed to a sufficient external force. Equations predictive of time
and

Page 78
sheardependent flow behavior for thixotropic fluids, with and without yield
stress, are unavailable at this time, although limited empiricisms have been
developed for specific dispersions.
B. Dynamic Mechanical Spectroscopy
When detergents are formulated as structured viscoelastic fluids, dynamic
mechanical spectroscopy can be an essential tool in the definition of the
strength and cohesiveness of the internal ordering, in addition to susceptibility
to strain. Measurements of storage and loss modulus as a function of strain can
easily quantify the facility with which the structure can be degraded, the ability
of that internal microstructure to reform, and the extent of reformation. The
same measurements, completed as a function of deformation period, define the
“architecture” of the fluid in the most general sense. Dramatic differences occur
between unstructured versus structured liquid detergents, solutions versus gels,
dilute versus concentrated dispersions, and so on. Both measurements, G', G''
= ƒ( ) and G', G'' = ƒ( ), are valuable in defining the structured state.
Oscillatory rheometers are now designed under controlled strain or controlled
stress modalities, capable of applying a sinusoidal strain or stress to the
fluid under test. Under controlled strain operating conditions, the two
independent variables are the frequency and the amplitude of the applied
deformation 0, shown in Fig. 7, with examples of typical responses of ideal
fluids, both viscous, elastic, and a representative viscoelastic substance. There
are two dependent variables: the amplitude 0 of the fluid response and the
phase angle between the applied deformation and the measured oscillatory
response. It is typically assumed that the oscillatory response is sinusoidal,
similar to the applied deformation, although there are fluid systems for which
this assumption may be incorrect. The harmonics associated with these
measurements and the resulting errors have been discussed in the literature
[54]. For structured fluids exhibiting yielding behaviors, nonlinear waveforms
are frequently encountered [55,56].
Figure 8 com+pares the storage and loss modulus as a function of strain for
two shampoo products, one which is unstructured in its commercial form A, a
simple viscous solution, and the other, a structured viscoelastic gellike fluid B.
As we would expect, for the unstructured shampoo, G " > G', and both
parameters are independent of strain or deformation amplitude. The structured
gel, however, exhibits a noticeably different response: G' > G " and G', G " = ƒ
( ). For structured elastic detergents, it is often observed that the elastic
modulus, G', decreases appreciably with increasing strain, reflecting the
sensitive nature of the internal structure.
Figure 9 summarizes the dynamic mechanical properties of a gelled laundry
spot remover. This product exhibits a clearly defined linear viscoelastic region
and a retarded frequency dependence in the frequency range of 0.01–100
rad/s

Page
FIG. 7
Sinusoidal strain and the corresponding responses
of a purely elastic, a viscous, and a viscoelastic fluid.
FIG. 8
Storage and loss modulus as a function of strain for two liquid detergent
products determined at a frequency of 10 rad/s and 25°C.

Pag
FIG. 9
Viscoelasticity of gel laundry strain remover. (a) Complex moduli as a function
of strain at 10 rad/s; (b) complex moduli as a function of frequency at a strain of
0.02. Measurements were completed at 25°C using the Rheometrics Scientific RFSII and
parallel plate geometry: 50 mm diameter and 0.9 mm plate spacing.

Page 81
similar to the structured shampoo and reflecting gellike behavior. In this range,
G' > G", or tan <1, where tan is defined as G "/G'.
To demonstrate further the breadth of the viscoelastic spectrum embraced by
liquid detergents, Fig. 10 summarizes tan = ƒ( ) and tan = ƒ( ) for body
cleansing shower and bath personal care products. Although many of these
products appear to be quite similar in their viscometric properties under certain
shear conditions, many consumer perceived product attributes indicate
significant differences, which are well captured in dynamic mechanical
rheological characterizations [57].
C. Extensional Viscometry
Very limited research has been published on the elongational flow properties of
surfactant solutions, yet elongational or “stretching” flows are frequently
encountered by liquid detergents in process environments and in use by the
consumer. During manufacture, elongational flow may be experienced during
spray drying or atomization, mixing, flowthrough pumps and pipeline
transport, converging flows, filling, high shear dispersing, and other
mechanisms. During consumer use, examples include the simple act of
dispensing a liquid detergent from an orifice, application of a liquid detergent to
a surface through a spray nozzle and rubbing or coating a surface with the
detergent. Extensional flows represent a very important area of study for
commercial liquid detergents and diluted aqueous solutions, representing
consumer usage conditions.
Research has shown that polymeric systems experience conformational
changes in extensional flows. In certain cases, dilatancy and chain scission can
occur [5863]. Recently, research has been extended to include surfactant
systems. For example, relative elongational viscosity as a function of
elongational rate has been determined for a cationic surfactant, C16TASal, in an
aqueous solution at a concentration at 600 and 900 ppm, with evidence of a
shearinduced structuring [64]. The effect of preshearing on the elongation
viscosity is also determined at preshearing rates of 203600 s1. For example,
preshearing at 80 s1 produces the greatest increase in elongational viscosity at
a surfactant concentration of 900 ppm, attributed to the formation of a shear
induced structured state. At the higher preshearing rates, the elongation
viscosity is reduced and the relative elongation viscosity appears to be a
decreasing function of elongation strain rates. Data are also presented for dilute
polyethylene oxide solutions.
Extensional viscosity measurements have been completed for dilute
polyacrylamide and xanthan gum solutions in flowthrough opposing jets
[65,66], showing the difference in flexible chain versus rigid rodlike polymer
conformations. A commercial instrument based on this design is available from

Page 82

Page 83
FIG. 10
Comparison of the strain and frequency dependence of tan for a representative
sampling of shower and bath body cleansers from the U.S. and European markets.
Data obtained at 25°C using the Rheometrics Scientific RFSII and parallel plate
test geometry. (a) Unstructured Newtonian or nearly Newtonian products. (b)
Highly structured elastic formulations. (c) Comparison of the frequency
dependence of both structured and unstructured products determined at = 0.02
and 25°C using the Rheometrics Scientific RFSII and parallel plate geometry.
Rheometrics Scientific, Inc. (Piscataway NJ), believed to be the only
commercially available extensional viscometer. Other flow configurations for
extensional viscosity measurements have been proposed in various academic
communities [67–70].
Spinnability and viscoelasticity for aqueous solutions of alkyl and
oleydimethylamine oxides and sodium alginate have also been investigated
[71]. Both ductile failure and polymeric viscoelasticity are reported. Equally
significant are interfacial elongational viscosities, also known as dilational
viscosities, referring to the elongational viscosity of an interface. This is a
critical parameter in foam stability, a very important characteristic for many
liquid detergents [72,73]. A comprehensive theoretical review of surface
rheology is provided by Edwards and Wason [74–77].

Page 84
IV. Product Delivery Vehicles
Liquid detergent products can be broadly divided into three distinct delivery
systems: (1) isotropic, clear, unstructured solutions, (2) structured opaque or
translucent dispersion, and (3) structured transparent gels, as shown in Fig. 11.
As we can see, there is overlap in this systems definition, as concentrated
particulate dispersions can exhibit gellike behavior, although differentiation is
provided by the clarity of the vehicle. Each of these three delivery systems has
unique rheological characterization requirements to define effectively their
rheological states in a process environment, throughout shelflife and during
consumer use. In rheological measurements, the second classification, opaque
or translucent dispersions, is the most difficult to characterize. Depending on
the volume fraction of the immiscible phase(s), the particle size distribution,
shape of particulates, surface charge, presence of adsorbed components, and
degree of flocculation, such systems can be highly elastic fluids, with both time
and sheardependent properties. The importance of the product delivery
vehicle and its influence on rheology is summarized very effectively by
Goodwin for dispersions in Fig. 12 [78].
From the perspective of the product development scientist, the product
delivery vehicle, composition and internal ordering of product components,
determines rheological behavior. Our discussions regarding the rheological
properties of commercial liquid detergents is based on fundamental product
delivery systems, that is, solutions, dispersions, or gels. Dispersions include
both solid
FIG. 11
Representation of the three major product delivery
systems used in liquid detergent formulations and
corresponding rheological features.

Page 85
FIG. 12
Generalized structure/property diagram of dispersions. (From Ref. 78.)
inliquid colloidal and large particulate suspensions, in addition to liquidliquid
emulsions.
A. Dispersed Systems
Fundamental rheological studies of controlled model systems provide an
excellent overview of the rheological behavior of these complex systems. For
dispersions, comprehensive theoretical and experimental studies have been
completed, providing very basic evaluation of both material and process
variables influencing product rheology. Although it is well beyond the scope of
this chapter to provide a detailed review of the rheology of dispersions, a brief
overview of the technology is provided.
For liquid detergents, dispersions are a very common type of delivery system,
because of insolubility or immiscibility of vital product components in aqueous
solvents, such as inorganic solids used as builders in heavyduty liquid
detergents and conditioning oils formulated into shampoos. It becomes a
formidable task to the product development scientist to generate acceptable
rheological properties of colloids, large particulate suspensions, or emulsions
while ensuring longterm stability against phase separation or sedimentation.
From a rheological and physicochemical perspective, the primary distinction
between these dispersed systems is in the size, volume fraction, surface
chemistry, and deformability of the dispersed phase. For example, foams, in
fact, may also be considered dispersions, similar to emulsions, with a low
density, gaseous dispersed phase [79–82].

Page 86
The introduction of an immiscible phase into a solvent system frequently alters
the rheological characteristics of the solvent carrier fluid, the modification of
properties being a function of the size and shape of the dispersed phase, its
volume fraction, and the physical chemistry of both the continuous (solvent)
and dispersed (particulate) medium. Flow of dispersions is governed by a
multitude of thermodynamic and spatial steric factors, including Brownian,
hydrodynamic, gravitation, van der Waals, and electrostatic forces [83,84].
The viscosity of a dispersion is frequently described in terms of the relative
viscosity r, which is the ratio of the suspension viscosity, , to the viscosity of
the continuous phase, 0, as a function of the volume fraction of the dispersed
phase n:
The dramatic influence of the volume fraction of the dispersed phase on the
relative viscosity of a dispersion is shown in Fig. 13. As one approaches the
maximum packing fraction of the immiscible dispersed phase, the viscosity
increase is appreciable, reflecting the solidlike behavior such highly
concentrated systems can develop. To demonstrate further the influence of
dispersion characteristics on the relative viscosity of dispersions, the effect of
particle aspect ratio is well illustrated in Fig. 14 [85]. At constant volume
fraction, particles with higher aspect ratio produce the highest relative viscosity.
Similarly, the same relative viscosity can be obtained at lower volume fraction
with higher aspect ratio particles. In detergent systems, anisotropic particulates
are
FIG. 13
Functional representation
of the dependence of the
relative viscosity on the
volume fraction of the
dispersed phase.

Page 87
FIG. 14
Relative viscosity of suspensions as
a function of particle aspect ratio at constant
volume fraction. (From Ref. 85.)
common product components, influencing the flow characteristics of the full
formulation. To control product viscosity, aspect ratio is clearly a most
significant variable. The impact of median particle size on the critical shear rate
at which thickening occurs, compiled from a survey of colloids and large
particulate suspensions, is summarized in Fig. 15 [86].
Many semiempirical models have been derived expressing the dependence of
the relative viscosity as a function of volume fraction. One example, suggested
by Krieger and Dougherty [87], represents the relative viscosity as
where the reduced shear stress is r is given by
where d is the particle diameter and the subscripts refer to the relative viscosity
in the zero shear and high shear rate limits, 0 and , respectively. In a further
extension of the KriegerDoughtrty model, the relative viscosity function has
been proposed as

Page 88
FIG. 15
Critical shear rate producing shear thickening of colloid and large
particulate dispersed systems as a function
of mean particle size. (From Ref. 86.)
where m is maximum packing volume fraction and the exponent a is a function
of m .
Because of the prevalence of solidinliquid suspensions throughout many
industries and the need to process and formulate these dispersions efficiently,
particulate suspensions have been studied extensively [88–108]. For both
colloidal dispersions and large particulate suspensions, the influence of many
material variables has been studied, such as volume fraction of the dispersed
phase, n, particle size distributions, particle geometry, particleparticle
interactions, polymer additives, presence of surfaceactive agents, and the
nature of the continuous phase. The emphasis of these studies has been very
broad, capturing steady shear properties, dynamic mechanical properties,
relaxation phenomena, and transient flow phenomena at flow inception and
cessation. Timedependent shear effects have also been investigated, including
shear thinning and shear thickening under numerous deformation conditions.
Rheooptics has been also effectively applied to the evaluation of structural
changes in dispersions during flow. For example, the dynamics of colloidal
particles in sheared, nonNewtonian fluids and structured liquid detergent
systems has been examined using birefringence and dichroism [109,110].
An introduction to the general rheological properties solidliquid dispersions is
provided by Onogi and Matsumoto [111]. The existence of the second plateau
in dynamic mechanical measurements, noted for dispersions but absent for

Page 89
polymer solutions and melts, is discussed, attributed to relaxation process as a
result of internal particulate ordering, and is strongly dependent on particle
content, and related to the presence of “apparent” yield stresses. This
secondary plateau is apparent in numerous commercial liquid detergent
products, with further decreases in dynamic moduli with decreasing frequency,
bringing to question the existence of yield stress phenomena. Experimental data
are reviewed for dispersions whose flow behavior is governed by attractive
Londonvan der Waals forces and those with strong repulsive forces caused
by particle surface charge.
An extensive review of various rheological models proposed for twophase
flows, including the composition of colloidal and large particle suspensions
used in numerous studies, with experimental details, is provided by Utracki
[112]. Although the compositions of the dispersions used in these studies are
quite distinct from those used in detergent formulations, they provide
fundamental knowledge and various empiricisms governing the flow
characteristics of twophase composites.
Although admittedly limited, studies have also been completed in systems more
directly applicable to the detergent industry. In one example, the interaction of
alcohol ethoxylates, sodium ether sulfate, sodium alcohol sulfate, and linear
sodium alkylbenzene sulfonate with aluminabased thickening agents has been
determined as a function of surfactant composition, surfactant concentration,
pH, and temperature in 5 wt% alumina dispersions in steady shear viscometry
[113]. Studies have also been completed showing the complex rheological
features dispersions can exhibit, especially when polymer surface modification
occurs [114–118]. Built heavyduty liquid detergents have also been
evaluated, especially those containing particulate sequestration agents [119–
123]. In a further example, Papenhuijzen examines the influence of particle
interactions in the rheology of dispersed liquid detergent systems, with models
of the breakage and reformation of network chains [124]. Proposed is a chain
like model of dispersed phase particles forming a network structure through the
medium.
A recent theoretical derivation of suspension relative viscosity functions in
generalized Newtonian media has included liquid detergent suspensions in the
data analysis of the proposed model for the Einstein coefficient [125,126].
Normal stress differences have also been determined for an anionic viscous
isotropic detergent solutions in the presence of electrolyte [127].
The microstructure and viscosity of liquid detergents comprised of highly
concentrated multilayered vesicles, or lamellar droplets, a novel suspension
medium, has been described by Jurgens and van de Pas [128,129]. The effect
of shear and shear history is addressed, with thixotropic and rheopectic shear
effects evident and the effect of shear history on the dispersed phase
photodocumented through electronic microscopy. Rheopexy is found for shear

Page 90
rates in excess of 1 s1, with no equilibration following a 24 h shearing interval.
Good correlation of the viscosity behavior of these complex dispersions is
cited with the following viscosity relationship:
p
assuming K >> 1, such that
where the consistency index K' and the parameter p is as defined by Sisko
[130]. Volume fractions were estimated from conductivity measurements using
the Bruggeman equation for dispersions of spheres [131].
In concentrated dispersions, both dilatancy and rheopexy can occur. Because
these are flow properties that can influence product performance and handling
characteristics, there may be a need either to eliminate or further enhance these
attributes in a product formulation. A broad review of shear thickening in
nonaggregating solid particulate suspensions in Newtonian liquids is provided
by Barnes [86], with a summary of parameters controlling shear thickening
behavior. Shear thickening of concentrated colloidal dispersions is well
documented [132–135]. Further, the influence of soluble polymers in the
presence of surfactants on the rheology of suspensions has been evaluated,
showing the effect of polymer adsorption, bridging, flocculation, depletion
flocculation, and stability [136–141]. Although most commercial products in
dispersion form are truly complex systems containing multiple solid
components with dissimilar aspect ratios, one or more immiscible liquid
elements, and perhaps, aeration, fundamental studies of the rheology of well
defined systems provide mechanisms for optimization, when product rheology
requires modification.
Colloidal dispersions comprised of finely divided, submicron particulates in
Newtonian and nonNewtonian fluids have been the subject of considerable
research in theoretical and experimental rheology [142–149], including normal
stress measurements [150–153]. Phase diagrams of colloidal dispersions
determined from rheological measurements as a function of dispersed phase
volume fraction detect distinct sol/gel transitions, which significantly impact
overall rheological properties as a function of particle concentration and ionic
strength [154]. For specific application to liquid detergents, the transitions from
liquid to solid behavior of charged particle colloids are most critical [155].
Research has further evaluated the effect of dispersed phase geometry,
including anisotropic rods and disks, applicable to the evaluation of various
rheology modifiers, such as clays, in product formulations [156–161]. In one
study, a correlation scaling model is proposed for the temperature dependence
of the relative viscosity of colloids containing both electrically charged and
neutral

Page 91
dispersed phases, as shown in Fig. 16, applied to unpurified and purified
bentonite clays, in the temperature range of 20–40°C. A single master curve is
obtained at each concentration for the unrefined clay, while the purified clay
does not follow this scaling analysis at higher volume fraction, indicating a clear
change in interactive forces driven by temperature and concentration [162].
Although the influence of particle anisotropy is not well understood or
systematically investigated, the influence of particle size distribution is more
recognized as a mechanism for modification of rheological behavior [163,164].
A
FIG. 16
Rheogram of (a) unpurified bentonite and
(b) purified bentonite as a function
of temperature. (From Ref. 108.)

Page 92
very broad overview of the rheology of clay dispersions, including dynamic
mechanical and steady flow behavior, is provided by Amari and Watanabe
[165].
A general overview of the physical chemistry of colloidal systems (d < 1 m)
and large particulate suspensions (d > 1 m) is available in the following
references, including stability [166], depletion stabilization and depletion
flocculation [167], steric stabilization [168], chemical complexation at
solid/liquid interfaces [169], interparticle van der Waals forces in concentrated
suspensions [170], electrostatic stabilization [171], polymerically stabilized
particles [172,173], and adsorbed highmolecularweight polyelectrolytes
[174].
Liquidliquid suspensions, or emulsions, have not been neglected in rheological
research studies [175–189], and comprehensive theoretical and experimental
studies have been completed defining the shear modulus G, yield stress y , and
effective viscosity e in concentrated systems [190]:
where is the interfacial tension, R32 the Sauter mean drop radius the volume

fraction of dispersed phase, n the maximum packing volume fraction, and m
the viscosity of the continuous phase, and Ca is the capillary number, defined
as mR32g /s. For those formulating emulsified liquids for personal and household
care detergents, volume fraction, particle size, surface chemistry and interfacial
tensions determine rheological behavior. As in all dispersions, adsorbed
species at the interface is an important factor, because this directly influences
the volume fraction of the dispersed phase.
For those faced with the technical challenge of developing liquid detergents
with tailored rheological properties, a vast portfolio of research is available to
support that activity. Many of the primary variables influencing the rheological
behavior of dispersions have been determined, at least providing numerous
options for product modification to effect the necessary changes in mechanical
properties. Although many surfactantbased dispersions exhibit unique
rheological properties, mechanical behavior nevertheless remain functionally
dependent on the geometry of the dispersed phase, surface charge, volume
fraction, the nature of the continuous phase, and associativity of all components
and the nature of the applied flow field.

Page 93
B. Highly Concentrated Dispersions
At volume fractions approaching the maximum packing fraction for mono and
polydisperse solidliquid and liquidliquid dispersions, solidlike behavior is
frequently observed in the quiescent state. The high viscosity of these systems,
the ability to retain their shape under the influence of gravitational forces, and
the ability to suspend particulates without sedimentation indicates the presence
of a yield stress. Methods have been reviewed for the measurement of yield
stresses in these complex fluids [193–200].
Fluids that exhibit yield stress values frequently display additional anomalous
flow behavior, such as wall slippage. This significantly complicates all
rheological measurements, and effective corrections must be applied
[200,201]. Nonlinear torque waveforms in response to sinusoidal strain
deformations have also been observed, and a model has been developed that
predicts the response of an elastic Binghamtype fluid to oscillatory shear for
high volume fraction ( = 0.92) oilinwater emulsions [202]. Other structural
constitutive equations have been developed based on network theory [203–
205]. Of particular interest is the extension of the CoxMerz rule proposed for
concentrated suspensions and gels exhibiting yield stress behavior [206]. A
good correlation has been developed for steady shear viscosity and complex
dynamic viscosity in terms of an effective shear rate.
For the experimentalist, rheological measurements of concentrated and highly
structured dispersions can be quite difficult. Reproducible measurements in
even simple shearing flows are often complicated by the disturbance of fluid
structure in normal handling, such as loading in the selected test fixture. As a
result, various methods are applied either to preshear the test fluid before
testing or to allow a restructuring interval before testing following sample
loading, for example. The dependence of rheological profiles on fluid shear
history is one of the overwhelming difficulties in effectively characterizing these
structured materials.
C. Gels and Microgels
There has been a dramatic increase in the use of gels as the delivery vehicle of
liquid detergent products, especially in the personal care category, because of
an increased understanding of the viscoelasticity of various gelling and
thickening agents.
Gels can be formed by various mechanisms, including interactive solid
particulates, physically or chemically crosslinked polymers, and ordered
surfactants or anisotropic surfactant phases. The fundamental criterion is that
connectivity through chemical or physical association occurs with sufficient
strength, forming a continuously defined network structure. One of the best
known is the

Page 94
electrostatically stabilized gels formed from refined clays, forming the “house of
cards” structure. Others include polysaccharides, such as xanthan guns,
strongly dependent upon the conformation of the polymer in solution and
additional physical interactions through hydrogen bonding, for example [210].
Polymers are often used as rheology modifiers or gelling agents for liquid
detergent systems, and understanding of the characteristics of these aqueous
polymeric solutions, solutions versus gel behavior, in various ionic solution
environments and in the presence of surfactants is easily obtained through
rheological measurements. The steady shear and dynamic mechanical
properties of numerous gelling and thickening agents frequently used in the
formulation of liquid detergents are well documented in the literature under
general conditions frequently occurring in product compositions [211]. The
utility of dynamic mechanical measurements in defining the fundamental
properties of solutions and gels is well illustrated in Fig. 17, describing the
change in the frequency dependence of the storage modulus, G' and the loss
modulus G'' during gelation as a function of temperature [212]. Beginning with
a simple solution we see the influence of a growing crosslink density on both
components of the complex modulus, with complete gelation at Fig. 17d. The
transition from solution to a true gel network structure is most apparent.
FIG. 17
Gelation of polystyrene in carbon disulfide with G' and G'' as a
function of frequency. (From Ref. 212.)

Page
The rheology of microgel solutions, frequently used in liquid detergent formulation
comprised of carbomers, for example, has been determined, including dynamic
mechanical characterizations as a function of polymer concentration, with an
evaluation of creep behavior and steady shear viscosity [213]. The dynamic mod
of Carbopol 941, as a function of concentration, is summarized in Fig. 18. Typic
of many commercial gel structures, concentrated microgel rheology is compared t
a cellular, deformable spheric model, equally applicable to emulsions and foams.
These polyacrylate gelling agents are known to be tolerant to hypochlorite bleach
lending their use to various household care liquid detergents [214].
As an example of an additional gelling mechanism, carboxymethylcellulose in free
acid form (HCMC), less hydrophilic than sodium carboxymethylcellulose, can als
form rheological gels as a result of quasicrystalline microaggregation of HCMC
detected by electron microscopy and dependent on the degree of substitution of t
NaCMC [215]. Gelation is observed for a degree of substitution (DS) of 0.8 as
function of aging time, but none is found for DS = 2. Gelling for this system
proceeds for a 60 day interval.
FIG. 18
Dynamic mechanical characterization of Carbopol 941 at concentrations of
0.53 to 6.16% as a function of frequency. (a) G' = ƒ( ). (b) G' = ƒ( ). (c) G" = ƒ( ).
(d) G" = ƒ( ). (From Ref. 213.)

Page 96
Discussions of the gelation would be incomplete without reference to the
relationship between the storage modulus of a gel G' and the crosslink density
n [216]:
G' = gnKT + Gen
where: K = Boltzmann constant
T = temperature K
g = constant < 1
and Gen is the influence of entanglements on the elasticity. This expression has
been used to determine gelation kinetics from measurement of time rate of
change in the storage modulus G'/ t during the gel formation process, as
shown in Fig. 19 [217].
Dynamic mechanical measurements are quite sensitive to the internal ordering
within the fluid composition. Through carefully designed experiments, not only
can the development of a continuous network structure be effectively
monitored through measurements of the elastic modulus G' as a function of
time, leading to an understanding of factors controlling gelation kinetics, but the
integrity of the final state can be well represented by such determinations,
related to the physics of the final gel. Both qualitative and quantitative measure,
dynamic mechanical spectroscopy is an increasing effective probe of the
rheology of liquid detergents and their various product components.
FIG. 19
Gelation kinetics determined from the change in
storage modulus, G', as a function of
gelling time. (From Ref. 217.)

Page 97
D. Stability
Dispersion stability is a critical subject for those processing and formulating
liquid detergents. Such formulations can be difficult to stabilize effectively
throughout the shelf life of the product and shelf life monitoring can be labor
and time consuming. Predictive methods and accelerated product aging studies
are generally employed with varying degrees of success. This may include such
techniques as thermal cycling, incubation, centrifugation, vibration or simulated
shipping tests, in addition to rheological characterizations.
Although progress has been made in the development of stability criteria for
polydisperse model suspensions, accurate predictive tools for commercial
formulations are generally unavailable. Recent developments have occurred in
rheology, however, to assist in the prediction of product stability. The most
significant contribution is the realization that the dynamic mechanical properties
of these complex fluids may be indicative of long term stability [218]. Studies
have shown that the strength of the internal microstructure as determined from
the strain and frequency dependence of the storage and loss modulus as a
function of temperature may be predictive of incipient product failure. Dynamic
mechanical measurements as a function of strain, frequently used to identify the
linear viscoelastic region, have been isolated as one potential indicator of
dispersion stability.
A review of the technical literature has been included in the following section
demonstrating the importance of surfactant phase behavior, component
interactions, and effect of electrolytes and total solution environment on the
rheological properties of liquid detergent systems. Such fundamental studies
can lead to a greater understanding of the rheology of commercial consumer
products, expanding into new and more effective product delivery vehicles.
V. Fundamental Research in Liquid Detergents
In research, rheology is a very useful tool and highly effective probe of the
internal microstructure of surfactant systems. Viscometric and oscillatory
rheometry can explore the architecture of surfactant solutions, especially when
coupled to other analyses, such as smallangle neutron scattering, microscopy,
nuclear magnetic resonance (NMR), and flow birefringence. Fundamental
research of liquid detergents using dynamic mechanical measurements can
probe the quiescent versus sheared physical state of the fluid as a function of
many material variables determining the kinetics of structural formation or
degradation and definition of the physical state of the fluid. Viscometric
measurements have also been used to investigate micelle geometry and
structural transitions. Another important industrial application of the rheological
sciences is in the investigation of interactions between product components
through appropriately

Page 98
designed rheological measurements, with counterions, polymers, cosurfactants,
and so on, identified to modify or tailor rheology for a given consumer function.
A. Surfactant Solutions
Solution viscosity is a most basic structureproperty measurement as defined
by the relationship between the stress tensor and the rate of deformation
tensor . In surfactant solutions, the viscosity depends on the tensioactive
agent concentration, solvent, presence of ionizable groups, surface charge
density, ionic strength of the carrier fluid, pH, and temperature. In addition,
viscosity behavior depends on surfactant molecular weight and geometry,
showing a strong dependence on micelle shape and size. Critical primary
transitions such as micellar spheretorod configurations can often be identified
from viscosityconcentration determinations in the dilute regime. Table 1
summarizes common viscometric parameters generally used to describe
solution behavior as a probe of surfactant micelle architecture.
Hydration is an important factor in the viscosity behavior of dilute surfactant
solutions because water bound to the micelles, forming the hydration layer,
contributes to the size of the micelles. It also determines the effective
concentration of surfactant partitioning the aqueous phase into the free and
bound water of hydration. This is demonstrated by Mukerjee [219], for
example, estimating the hydration of micelles of sodium lauryl sulfate and
dodecyl, tetradecyl and trimethylammonium chlorides from reduced and
intrinsic viscosity data, using appropriate corrections for electroviscous effects.
The viscosity of dilute surfactant solutions in the spherical micelle region can be
described by a modified form of the Einstein viscosity equation [220,221]:
where is the volume fraction of solvated micelles and c m c represents the

viscosity of the solution at the CMC. This is accurate for uncharged, dilute,
TABLE 1 Definition of Viscosity Functions
Viscosity/function Definition
Reduced viscosity = /c
red sp
Relative viscosity = /
r 0
Specific viscosity = rl

sp
Intrinsic viscosity [ ] = [(ln r)/c] c = 0

Page 99
noninteractive dispersions. The viscosity of ionic surfactants is strongly
dependent on the surface charge density. For micellar solutions, a modification
of the Einstein equation for this first electroviscous effect [222] is given as
When hydrodynamic factors become relevant at higher concentrations, a
second electroviscous effect becomes operative because of the electrostatic
repulsion between micellar aggregates, creating an additional resistance to flow
with further increases in bulk solution viscosity.
The isotropic phase of any surfactant solution is typically Newtonian, although
there are exceptions. Throughout the isotropic region, viscometric behavior is
dependent on micelle size, micelle concentration, geometry, and various intra
and intermicellar interactions, and in keeping with this functionality, viscosity is
not constant throughout the isotropic phase. This is represented
comprehensively by Schafheutle and Kinkelmann [223]. Lines of constant
reduced viscosity within the isotropic phase of a novel surfactant with rigid
rodlike hydrophobic moiety terminally substituted with monodisperse oligo
(ethylene glycol) units is provided in Fig. 20. The reduced viscosity (ml/g)
varies significantly throughout the isotropic phase and along the phase
boundaries of the various phases. This shows quite definitively the complex
dependence of viscometric behavior on micellar dimensions and dispersion
characteristics within
FIG. 20
Reduced viscosity isocontours within the
isotropic phase. (From Ref. 223.)

Page 100
the isotropic phase. This aqueous surfactant system exhibits Newtonian
behavior at shear rates from 0 to 60 s1 at all temperatures and concentrations
included in this study.
In the following sections, various examples are provided of rheological studies
of nonionic, anionic, cationic and mixed surfactant solutions. These studies
were selected to exemplify the critical relationship between surfactant
morphology and viscometric or rheological behavior.
1. Nonionic Surfactants
Because the rheology of liquid detergents is inherently dependent on surfactant
architecture, or phase, rheology can be a useful tool in developing phase
diagrams. For example, the phase diagram of a ternary nonionic surfactant, [p
(1,1,3,3tetramethylbutyl)phenyl]poly(oxyethylene) (Triton X100),
dioctylphthalate, and water system has been determined by Otsubo and
Prud'homme [224]. For this system, the isotropic phase is Newtonian within
the broad shear rate range of 0.1250 s1 and pseudoplastic behavior occurs
within the anisotropic phase. Viscosity measurements of the binary surfactant
water system as a function of concentration identify three distinct regions.
Below 33 wt% surfactant, a micellar microemulsion occurs and for
concentrations greater than 58 wt% surfactant, an inverse microemulsion has
been identified. At intermediate concentrations, rheological measurements
identify a liquid crystalline phase with typical nonNewtonian viscosity
behavior. This extensive study further documents the abrupt change in flow
properties at phase boundaries.
The reduced viscosity as a function of micellar concentration for
polyoxyethylene alkyl ethers of the type CH2[CH2]m1[OCH2CH2]1.25mOH has
been determined for several carbon chain lengths ranging from C8–C14 and
from E10–E19 [225] and there is a linear increase in viscosity with increasing
polyoxyethylene concentration. For the same surfactant, the intrinsic viscosity
as a function of alkyl chain length for various ethylene oxide/carbon chain
length ratios reveals an abrupt discontinuity between C16 and C18. It is
speculated that this is a result of the intrusion of anhydrous polyoxyethylene
into the micellar core, altering hydration within the micelle mantle.
Many additional viscometric studies of surfactant solutions have addressed the
dependence of bulk solution viscosity on micelle geometry. Robson and
Dennis, for example, calculate the size, shape, and hydration of a commercial
grade of the nonionic surfactant micelle, [p (1,1,3,3tetramethylbuytyl)phenyl]
poly(oxyethylene), from intrinsic viscosity data [226]. Several of the major
difficulties associated with these calculations are demonstrated: the coupling of
both hydration and shape factors. Based on geometric considerations and
viscosity data, they argue against the presence of spherical micelles and
support the formation of an oblate micelle. A spherical micelle could occur,
however,

Page 101
if several ethylene oxide groups are embedded into the hydrophobic core. The
deviation from spherical micelle geometry is also suggested by Wright [227]
from birefringence data, and Tanford et al. [228] also argue the nonspherical
geometry of polyoxyethylene ethers in aqueous solutions from sedimentation
and intrinsic viscosity data. Calculations indicate a disklike globular micelle
with random coil polyethylene oxide chains in the outer micelle mantle.
2. Anionic Surfactants
Alkylbenzene sulfonate is a very important industrial surfactant. It is a common
lowcost surfactant in household detergents. With the increasing emphasis on
concentrated liquid detergents, an awareness of the phase behavior of this
surfactant and resulting rheology is critical.
Sulfonation conditions, reaction pathways, byproducts, and impurities can
have a significant impact on the rheology and phase behavior of linear (LAS)
and branched (ABS) alkylbenzene sulfonate. Because this surfactant is
frequently processed at high active ingredient concentrations, the relationship
between specific reaction conditions and final surfactant rheology is important
for processing and controlling product formulations. The viscosity of caustic
sodaneutralized sodium linear alkylbenzene sulfonate is found to be strongly
dependent on the molar ratio of SO3/alkylbenzene and also the sulfonation
process, HF versus A1C13[229]. The tetralin content appears to control and
actually reduce the viscosity of 25% active LAS solutions. Although this study
includes very limited viscosity data, it demonstrates the influence of both
process and material variables on surfactant viscosity at concentrations
frequently encountered during the manufacture of this surfactant.
Similarly, Rybicki investigated the dilute solution viscosity of sodium
dodecylbenzene sulfonate as a function of various commercial detergent
builders, on the partial molar volume of hydrated micelles [230]. The relative
viscosity of one commercial linear sodium dodecylbenzene sulfonate, average
molecular weight of 343.9 g/mol, is presented in Fig. 21, and two transitions
are noted. The first CMC is the micellar monomersphere transition and the
second attributed to a further, as yet unidentified, structural change in the
micelle. Figure 22 summarizes micellar hydration volume as a function of
temperature and sodium metasilicate concentration showing the influence of
electrical doublelayer thickness on viscosity. It is also shown that the partial
molar volume of hydrated micelles depends on ionic strength, independently of
the type of electrolyte. Figure 23 shows the effect of electrolyte concentration
for several salts, (NaPO3)6, Na2SiO3, and Na2SO4, on A3, a coefficient of the
Vand equation, related to the partial molar hydrated micelle volume at 293 K
[231]. The effect of salt on the double layer as a function of temperature is
very clear. With increasing salt concentration, the electroviscous effect is
reduced and partial

Page 102
FIG. 21
Reduced viscosity sodium dodecylbenzene sulfonate
as a function of surfactant concentration
at 25°C. (From Ref. 230.)
molar volume of the hydrated micelle is similarly reduced for this anionic
surfactant. This alters the effective volume fraction of the dispersed phase,
consisting of spherical micelles, with a significant influence on solution viscosity.
The alkyl sulfates are also important industrial surfactants used in a very broad
range of consumer products. Similar to the sulfonates, reaction byprod
FIG. 22
Micelle hydration volume of sodium
dodecylbenzene sulfonate for several
sodium metasilicate concentrations as a
function of temperature. (From Ref. 230.)

Page 103
FIG. 23
Coefficient of the Vand equation, A3 as a
function of electrolyte concentration at
25°C. (From Ref. 230.)
ucts of the alcohol sulfates, including sodium chloride and sodium sulfate,
influence the viscosity behavior of sodium lauryl sulfate solutions [232]. Each of
the salts and the free oil, primarily unreacted alcohol, has a very clear impact
on surfactant viscosity. A micelle model illustrating the increase in sodium
dodecyl sulfate (SDS) viscosity with inorganic salts and free oil is also
provided and in each case, the increase is attributed to the increase in effective
volume fraction of the dispersed phase. With inorganic salts, this is caused by
the sodium cation association with the sulfate groups through electrostatic
interactions at the micelle surface; the free oil does not appear to interact at the
surface. It is thought that the free oil acts as a “cosurfactant,” participating in
the micelle itself. This increases the effective volume fraction of the micelles
producing a similar increase in solution viscosity. This is, however, energetically
unfavorable, and thought to be a precursor to the formation of a
microemulsion.
Akhtar and Alauddin [223] investigated the viscometric properties of sodium
dodecyl sulfate in simple aqueous solutions and aqueous solutions containing
cyclohexanol, investigating changes in micelle size and shape and also the
micellar location of the solubilized alcohol. Viscosity measurements of the
aqueous detergent as a function of SDS concentration identify a transition at
0.2 mol/kg, attributed to a postmicellar transition from spherical to rodshaped
micelles. The temperature and concentration dependence of the average
aggregation number of SDS have been investigated with smallangle neutron
scatter

Page 104
ing experiments. The increase in SDS aggregation number, quantifying the
number of monomers per micelle, at this transition concentration necessitates a
change in shape [234].
The effect of simple electrolytes, both NaCl and HCl, on the relative viscosities
of SDS as a function of concentration has been determined by Gamboa and
Sepulveda [235]. Na+ counterions appear to produce a greater increase in
viscosity than H+, because it is a more strongly bound counterion, and all
solutions demonstrate highly nonlinear viscometric behavior. The lengths of the
rodlike micelles are calculated from the viscosity data for both sodium lauryl
sulfate (SLS) and cetyltrimethylammonium salts.
Soap solutions have long been known for their interesting viscometric behavior.
This is evident from isoviscometric contours for potassium laurate and
potassium carbonate solutions, further demonstrating the complexity of the
isotropic phase [236]. Within the isotropic phase, there is a dramatic variation
in viscosity values initially attributed to the formation of complex emulsions
from dispersed anisotropic liquid crystalline surfactants in isotropic surfactant
solution.
Pilpel derives expressions from geometric and energy considerations of soap
aggregation to support long interlinked rodlike or cylindrical micelle formation
in soap gels in an attempt to clarify the observed rheological behavior [237].
The systems in this investigation include sodium oleate, elaidate and oleylsulfate
and the introduction of longchain alcohols and other compounds. The
development of viscoelastic effects is thought to occur through a cascade of
intermediate micellar stages as suggested by Philippoff [238]. Pilpel estimates
that the van der Waals energy per molecule decreases nearly 90% in the
transition from spherical to cylindrical micelles for specific soap gels, with a
corresponding Coulombic energy decrease of approximately 5%. This
decrease in both van der Waals and Coulombic energy in the micellar
transitions supports the stability of the rodlike micelles at higher salt
concentrations. He proposes one geometry of a cylindrical micelle to be
approximately 9 Å, with a length of 200 Å. Early xray diffraction studies of
soap systems support the speculation that cylindrical elongated structures
occur.
3. Mixed Surfactants: Anionic/Nonionic Systems
The flow behavior of SDS and alkyl polyoxyethylene ethers, C12–18 and E10–40,
has been determined by Uchiyama and Abe [239]. Although the relative
viscosity of the alkyl polyoxyethylene ether is greater than that of SDS, for the
mixed surfactant system there is a maximum in the relative viscosity at an SDS
mole fraction of 0.3. Increasing the ethylene oxide content has a significant
effect in both the single Cm En and mixed surfactant solutions. A maximum also
occurs at the same molar ratio, 0.3, with the exception of the C16E40 system.

Page 105
In addition, the effect of sodium chloride on the relative viscosity of the
SDS/C18E20 mixed surfactant system as a function of SDS mole fraction has
also been investigated by Uchiyama and Abe. The relative viscosity is found to
be a decreasing linear function of SDS mole fraction, and no effect is observed
on the relative viscosity of the single nonionic surfactant solutions. In the mixed
surfactant system, salt addition is presumed to decrease the electroviscous
effect with a decrease in the CMC and an increase in aggregation number.
Addition of the nonionic surfactant increases the degree of ionic dissociation of
the mixed micelle. The degree of ionic dissociation also increased with
increasing alkyl chain lengths and decreasing EO groups. The maximum in the
relative viscosity is assumed to be a result of the electroviscous effect of the
mixed micellar solution, which is greatest at the SDS molar ratio of 0.3.
Zwitterionic surfactants, such as alkydimethylamine oxides, can exhibit
complex viscometric properties individually and in the presence of ionic
surfactants. At low concentrations, viscoelastic rodlike entangled networks
are thought to occur [240]. The zero shear viscosity of the nonionic surfactant
is very strongly dependent on concentration and surfactant molecular weight.
For example, oleyldimethylamine oxides are known to form rodlike micelles
and viscoelasticity is observed at concentrations as low as 1% by weight. The
uncharged surfactant in aqueous solution appears to behave as a simple
Maxwell fluid with a single shear modulus and structural relaxation time. The
influence of both cationic and anionic surfactants has been determined from
rheology, light scattering, and electric birefringence measurements.
The zero shear viscosity of a mixed oleyldimethylamine oxide (ODMAO)
system is strongly influenced by the amount of ionic surfactant. Both SDS and
tetradeyltrimethylammonium bromide are evaluated for their influence on the
flow behavior of the uncharged surfactant. A comparison of the C14DMAO
and SDS influence on the zero shear viscosity of ODMAO is provided in Fig.
24. The anionic surfactant has a considerably greater influence in the surfactant
mixture.
In dynamic mechanical measurements, it is observed that SDS has the effect of
decreasing the frequency dependence of the elastic modulus. A highly
structured composition is evident at the 46:4 concentration, as shown in Fig.
25. In the concentration regime used in this study, the shear modulus remains
fairly constant and is not affected by the anionic surfactant and the primary
influence is through the structural relaxation time. It is suspected that the
introduction of charge to the nonionic surfactant stiffens the rodlike network
and that adhesive hydrophobic interaction occur at micellar interfaces. The
zero shear viscosity and structural relaxation time are determined by the
intermicellar bond energy, which is sensitive to charge density, surfactant chain
length, and electrolyte concentration. This study also evaluates the effect of
other cationic

Page 106
FIG. 24
Effect of SDS and tetradecyltrimethylammonium salt on
the zero shear viscosity of oleyldimethylamine oxide at
25°C and surfactant concentrations of 50 mM.
(From Ref. 240.)
surfactants, such as tetra and hexadecyldimethylamine oxide, on the
viscoelasticity of the zwitterionic surfactant solutions.
The rheology of a mixed zwitterionic and anionic surfactant,
hexadecyldimethylammonioprophane sulfone, SDS, and water, has been
studied by Saul et al. [241], including both isotropic and hexagonal phases.
Rheological results
FIG.25
Storage modulus G' as a function of frequency for
oleyldimethylamine oxide/SDS aqueous mixtures at overall
concentrations of 50 mM and 25°C. (From Ref. 240.)

Page 107
are interpreted in terms of the coexistence of both spherical and cylindrical
micelles. Both viscosity and first normal stress difference data are presented for
various regions of the phase diagram and high shear rate viscosity data are also
provided in the shear rate range of 428, 1235, and 2570 s1. The phase
diagram of this surfactant mixture is provided as determined from both NMR
and rheological measurements.
4. Cationic Surfactants
Cationic surfactants in dilute solutions can form long rodlike micelles that
produce very unusual rheological properties. These elongated micellar
structures can mimic entangled polymers and crosslinked gellike systems,
depending on the surfactant head group, concentration and electrolyte, additive
environment. The dramatic elasticity of these very dilute solutions has been well
documented, and research in the rheological behavior of dilute cationic
surfactants spans a number of decades [242–253]. This includes
comprehensive examples of dynamic mechanical characterizations, steady
shear viscosity functions, stress growth and stress relaxation behavior, and
modulus and normal stress measurements.
For example, Nash investigates conditions whereby naphthol and
cetyltrimethylammonium bromide (CTAB) interact to form elastic gels using a
simple qualitative rheological test and fluorescence technique [254]. The
formation of very long filaments is identified as a plausible mechanism for
elasticity, and estimates are given for a 1 mM solution forming a filament length
of nearly 30,000 km. His detailed study investigating the micelle
“polymerization” mechanism covers the effect of many additives to the cationic
surfactant.
Dilute aqueous solutions of specific cationic surfactants can develop sheared
induced structures. This has been observed in stress growth steady shear
viscometric measurements of dilute aqueous solutions of CTASal [255].
Within the shear rate range of 0.59–0.99s1, the viscosity is Newtonian and no
time dependence is observed. At 1.35s1, however, following a considerable
induction time period, we see dramatic rheopectic behavior. Equally
remarkable is the very broad range of rheological properties exhibited in the
dilute solutions. In a narrow concentration range, 3–5 mmol/dm3, Gravsholt
identifies rheopectic, thixotropic, nonNewtonian power law, and Newtonian
viscosity behavior. Although Newtonian in the unsheared quiescent state, these
dilute cationic solutions develop a metastable supramolecular structure under
mechanical stress, forming novel viscoelastic systems.
The counterion or ion pair is critical in forming viscoelasticity in dilute cationic
detergents and the development of longrange order. An example is provided
by Gravsholt using CTAx ( = substituted benzoic acid) [256]. Salicylate, m
chlorobenzoate, and p chlorobenzoate give rise to viscoelastic behavior,
whereas ochlorobenzoate, mhydroxybenzoate, and p hydroxybenzoate

Page 1
TABLE 2 Viscoelastic Cationic Surfactant Systems
Surfactant Counterion
Cetylpyridinium chloride Nasalicylate
Cetyltrimethylammonium bromide Nasalicylate
Cetyltrimethylammonium chloride NaSCN
Cetrytrimethylammonium chloride 2Amimobenzenesulfonate
C8F17SO3NA (C2H5) 4NOH
C9F19CO2Na (CH3) 4NOH
Surfactant
Tetradecyldimethylaminoxide Sodium dodecyl sulfate
Tetradecyldimethylaminoxide C7H15CO2Na
Uncharged compound
Cetyltrimethylammonium bromide Chloroform
Cetylpyridinium chloride 4Propylphenol
Source: From Ref. 257.
have no apparent impact on micellar structure. The CMC and minimum or critical
concentrations needed to develop viscoelasticity are noted as well. Table 2
summarizes several cationic surfactant systems exhibiting viscoelastic properties
[257].
The unusual viscometric behavior of the cationic surfactants containing mainly
pyridinium or trimethylammonium head groups at dilute concentrations has been
attributed to the formation of rodlike micellar structures of length L and mean
separation distance D, leading to a dynamic threedimensional network structure
[258]. Simply stated, viscoelasticity occurs when L > D.
The zero shear viscosity of dilute rodlike solutions can be calculated from Doi
Edwards [259] as
where ˆc is the number of rods/unit volume and L represents rod length. The
critical overlap condition occurs at
Table 3 summarizes length of rodshaped micelles for cetylpyridinium salicylate
(CPySal) as a function of temperature and concentration [260].
critical overlap condition occurs at
Table 3 summarizes length of rodshaped micelles for cetylpyridinium salicylate
(CPySal) as a function of temperature and concentration [260].

Page 1
TABLE 3 Length (Å) of Rodlike Micelles as a Function of Temperature and Concentratio
for Cetylpyridinium Salicylate Solutions
c (mmol/dm) 20°C 30°C 40°C 50°C
1 120 70 40 —
2 210 140 90 60
4 430 270 160 150
6 640 400 280 200
7 750 460 315 240
Surfactant systems are dynamic systems with constant redistribution of monomeri
species. This exchange leads to a lack of permanence to any entanglement or
crosslink site and the evolution of the “living network” model. The rodshaped
micelles can undergo a continuous process of bond formation and cleavage,
distinguishing long micellar rodshaped surfactants from polymers.
It is known that anionic cosurfactants, specific organic counterions, and nonionic
compounds, including esters and aromatic hydrocarbons, induce viscoelasticity in
cationic solutions [261,262]. The efficiency of these compounds in favoring
specific micellar aggregate structures, rodlike micelles, is critical in the
development of supermolecular structures capable of significant viscoelastic
effects. The specific architecture of the interactions between the micelle and
additive and their orientation is also critical. Research has demonstrated, for
example, the importance of molecular orientation in determining the overall
rheological response. This is shown quite clearly through the influence of para,
meta, and orthotoluic acid on the steadystate zero shear viscosity of CPyCl
[257]. The largest increase in viscosity occurs with p toluic acid: it is suspected
that the COO group orients perpendicularly to the micellar interface, providing a
mechanism for micellemicelle linkage, or “micelle polymerization,” similar to the
effect observed for sodium salicylate [263]. This study and others highlight the
importance of surfactant architecture on rheological properties and a micellar chai
model for the origin of viscoelasticity in cetyltrimethylammonium bromide solution
has been presented, based on the premise that the counterions serve as “crosslin
agents” capable of building micellar chain structures. The orientation of sodium
salicylate, sodium mchlorobenzoate, and mhydroxylbenzoic acid has been
investigated, and results from Fourier transform NMR studies suggest that the
orientation of the COO carboxylic group is likely the key to the origin of
viscoelasticity. Only when the COO projects out of the micellar surface are
conditions favorable for chain formation and viscoelasticity favored. Cryo
transmission electron microscopy (TEM)

Page 110
and both steady shear and dynamic rheological measurements of
cetyltrimethylammonium chloride in the presence of sodium salicylate as the
binding counterions support the premise that threadlike or wormlike elongated
micellar structures occur [264]. In addition, polar and hydrophobic interactions
are critical in the increased viscosity exhibited by cationic surfactants in the
presence of salts and other surfactants. It has been proposed that the increased
solution viscosity is a result of increased ion pair stability [265].
It has been speculated by Hoffmann and his colleagues that only two
parameters are needed adequately to define the rheology of these cationic
detergents. These are the shear modulus, representative of the structure of the
detergent, and the relaxation time, representative of the dynamic nature of the
system, both calculated from the zero shear viscosity. Using this hypothesis,
four distinct zones as a function of detergent concentration are identified [266].
The nonlinear viscoelasticity of aqueous CTAB solutions with excess sodium
salicylate has been determined by Shikata et al. [267,268]. The nonlinear
properties were found to be dependent on the concentration of excess
salicylate. A 1:1 complex of CTAB and NaSal molar ratio form rodlike
micelles, and three behavior modes are described. When the NaSal
concentration is significantly less than CTAB, dilute flexible polymer solution
behavior is observed and the relaxation spectrum is found to follow the Rouse
theory of polymer solutions without entanglement. At higher concentration of
NaSal but still below the 1:1 ratio, full entanglement behavior typical of
concentrated polymer solutions occurs. When NaSal concentration exceeds
CTAB, the viscoelastic behavior is quite different. Unlike polymer systems,
Maxwell behavior with the single relaxation time is evident. The relaxation time
does not appear sensitive to CTAB concentration and temperature but is highly
dependent on the free salicylate concentration in solution. It is speculated that
the free salicylate ion is a prerequisite for scission reaction and that micellar
relaxation occurs not through reptation but as a result of micellar monomer
exchange kinetics. Although there are similarities to polymer solutions at lower
ratios, the dynamic nature of the “living” network [269] becomes evident at
higher mole ratios of salicylate.
Stress growth measurements at the inception of flow completed by Shikata et
al. indicate the presence of shearinduced structures for dilute CTAB/NaSal
solutions at low shear rates. Dramatic rheopectic behavior is documented in
Fig. 26 at a shear rate of 0.481. Viscometric measurements at various salt
concentrations and shear rate ranges are summarized with evidence of damping
oscillation. The long induction period for shearinduced structuring of cationic
surfactants solutions in simple shearing flows appears to follow a simple scaling
law for CTABsodium salicylate solutions in which the induction time is
inversely proportional to the applied shear rate [270]. There also appears to
be a critical shear rate at which shear thickening occurs for 2 mM CTAB
sodium salicylate within the temperature range of 10–36°C. The critical shear
rate for

Page 111
FIG. 26
Stress growth behavior of dilute
aqueous CTAB/NaSal solutions at
low shear rates and concentrations
C = 0.1 and C = 0.15 M.
D s
(From Ref. 268.)
the development of the nonequilibrium metastable micellar shearinduced
ordering increase with increasing temperature. One could conclude that there is
a critical strain required to induce the reorganization of micelles in this
surfactant system.
5. Mixed Surfactants: Anionic/Cationic Systems
The effect of salts on the rheology of cationic surfactants has been actively
investigated, yet little research on mixed surfactant systems has been
completed to date.
Tetradecyldimethylaminoxide (TDMAO) and sodium dodecyl sulfate do not
individually exhibit timedependent nonNewtonian viscosity functions in
solution, yet mixed solutions of these surfactants are known to show rheopectic
and dilatant characteristics [271–273]. This is evident from the stress growth
behavior of the TDMAO/SDS solution in the presence of sodium chloride at a
shear rate of 50 s1 [274]. Following a lengthy induction interval, shear
thickening occurs at a moderate shear rate of 50 s1, for this anionic/cationic
surfactant pair containing sodium chloride. For this system, it appears that
induction time follows a simple scaling law, inversely proportional to shear rate.
For the same surfactant system, dilatancy is exhibited as well. The steadystate
viscosity increases with increasing shear rate, reaching a maximum at
approximately 60 s1, and timedependent and shear thickening behavior is
attributed to the shear induced coagulation of rodlike micelles.

Page 112
Theoretical and experimental research has been extensive in cationic surfactant
systems. This is undoubtedly a result of the complexity of these systems and
the dynamic nature of the micellar matrix with a continuous exchange of
surfactant monomers from solution to micelle and the shear induced structural
states that can be achieved. Theoretical models have been proposed [275–
278] and there is good experimental evidence that relaxation processes are
dominated by the kinetics related to micellar chain scission and reformation.
This is seen from the exponential stress decay. If dominated by reptation, as
noted by Cates, a nonexponential stress decay would be operative. Diffusion
would be the ratecontrolling factor.
B. Surfactant Liquid Crystal Gels
Both isotropic and microemulsion phases of liquid detergent systems are
typically Newtonian. Hexagonal, cubic, and lamellar phases, however, exhibit
distinct nonNewtonian behavior. At these higher concentrations, within
mesomorphic phases, mechanical properties can be nonlinear and time
dependent. Gellike properties, similar to those of crosslinked polymers, may
also occur with formation of yield stresses. In general, thixotropy, rheopexy,
dilatancy, and pseudoplasticity have been demonstrated in the surfactant
literature within the anisotropic phases.
Lyotropic liquid crystals are particularly interesting surfactant phases because
of the high fluidity of these systems, the apparent yield stresses they can exhibit
and the various shear effects that can occur. These are also difficult systems to
characterize because of the orientation of the micelles in the test geometry and
the dependence of rheological properties on defects occurring within the liquid
crystal matrix [279].
1. Nonionic Surfactant Systems
Repetitive flow curves for C12E4(60 wt%) demonstrate significant thixotropy in
qualitative thixotropic loop measurements [280]. One might suspect that this
thixotropy is associated with a loss of structure with shear at this shear rate.
This obvious shear effect is most likely a result of realignment, orientation, and
reduction of defects within the liquid crystal in simple shear. Disruption of the
liquid crystal lamellar geometry in shear results in both dilatant and rheopectic
behavior caused by the transition from twodimensional order to a highly
irregular surfactant dispersion.
Defects in the liquid crystalline morphology can significantly influence
viscometric flow properties [281]. It has been shown that viscosity increases
significantly with a high incidence of internal defects. This phenomenon
complicates measurement and interpretation of the rheology of these systems.
The rheology of ternary phosphated polyoxyethylene nhexane, and water
lyotropic liquid crystals have been determined in qualitative thixotropic loop

Page 113
measurements using a FerrantiShirley cone and plate viscometer and a Deer
variable stress rheometer [282], with measurements completed within the
lamellar and hexagonal phases of both phosphated nonylphenol ethoxylate and
phosphated fatty alcohol ethoxylate at 25°C. Qualitatively, thixotropic loop
measurements within the considerable shear rate range show rheopectic
hysteresis for specific segments of the lamellar liquid crystal phases and a
thixotropic response within the hexagonal and intermediate amorphous gel
phase. A comparison of the lamellar, hexagonal, and gel phases as a function
of water content at a shear rate of 90.45 s1 shows the lamellar liquid crystal
phase to be the most viscous under these experimental conditions, coupling
both time and shear rate variables. The maximum exhibited by the hexagonal
liquid crystal at 40% water represents a phase boundary. Such thixotropic
loop measurements are difficult to interpret because of the combined effects of
both time of shearing and shear rate and constant shear rate experiments, or
stress growth measurements, are better suited to characterize these ordered
systems.
2. Anionic Surfactants
Lamellar liquid crystals can exhibit shear effects in various concentrations
within this anisotropic phase. Stress growth measurement at 0.05 s1 for an
alkyl ether sulfate, C12E7SO4Na, at a concentration of 70% by weight is
presented in Fig. 27. Following a stress overshoot, significant viscosity
reduction occurs with increasing time of shear. Note that following a shearing
interval of 600 s, a shear steady viscosity has not been achieved. In simple
shear, this lamellar liquid crys
FIG. 27
Stress growth behavior at 25°C and 0.5 s1 of
aqueous C12E7SO4Na gels (70% weight active)
using 25 mm parallel plate geometry.

Page 114
tal appears to be thixotropic. The cause of this time dependent shear effect,
however, is not fully understood. This may be the result of reduction in liquid
crystal defects, slippage along the twodimensional planar matrix, or other
experimental anomalies.
Dynamic mechanical properties for the same alkyl ether sulfate as a function of
strain are summarized in Fig. 28. This liquid crystal appears to be highly elastic
and gellike because the storage modulus is nearly frequency independent and
exceeds the loss modulus by nearly an order of magnitude for strains greater
than 0.1. The strain dependence of the storage and loss modulus indicates the
presence of a yield stress.
A comparative study of the thermotropic and lyotropic mesophases of
ammonium dodecanoate at 30, 40, and 50°C shows both systems to be
Bingham plastics with high yield stresses within the lamellar phases [283]. The
activation energy for viscous flow for the thermotropic mesophase consisting of
a ternary system of ammonium laurate, water, and noctanol was found to be
more than an order of magnitude greater than that for lyotropic mesophase.
Sodium soap mesophases also exhibit unusual behavior in thixotropic loop
measurements [284]. Ternary sodium caprylate, decanol and water systems in
various anisotropic phases were evaluated using a FerrantiShirley viscometer
including both lamellar and hexagonal phases. The most unusual behavior was
observed for the lamellar phases, strongly dependent upon water
concentration. As in previous surfactant lamellar liquid crystal studies, the
distribution of water within the liquid crystal matrix plays a key role in the
overall rheological behavior of these aqueous surfactants.
3. Cationic Surfactants
The ternary lamellar liquid crystal of hexadecyltlrimethylammonium bromide
(CTAB), hexanol, and water was determined in couette flow at 25°C and
varying water concentration from 30–80% [285]. Viscometric measurements
were obtained through constant shear rate experiments applied as a series of
shear rate pulses with the shear stress response obtained for samples
containing 30, 40, and 50% water. An increase in water content to 60%
produces markedly differing results. This sample, also within the lamellar liquid
crystal phase, exhibits rheopexy while subjected to a train of shear rate pulses
at 77.5 s1. This is attributed to the formation of a nonequilibrium metastable
microstructure. Xray diffraction shows no change in the repeat distance of the
lamellar liquid crystal, and it is hypothesized that shearing creates large oriented
domains as evidenced from polarized microscopy. In steady shearing flow,
Newtonian behavior is observed at low shear rates and twofold cooperative
coordination at higher shear rates.

Page 115
FIG. 28
(a) Storage and loss modulus at 25°C and 10 rad/s of
aqueous C12E7SO4Na gels (70% weight active) at 25°C
and a strain of 0.005 using 25 mm parallel plate geometry.
(b) Storage and loss modulus of aqueous C12E7SO4Na
lamellar liquid crystal gels (70% weight active) at 25°C
and a strain of 0.005 using 25 mm parallel plate geometry.

Page 116
C. PolymerSurfactant Interactions
Most commercial detergent preparations contain both polymers and
surfactants and these components can be interactive [286]. Complexation can
have a significant influence on rheological behavior, depending on the topology
of the association, and several associative complexes are represented in Fig.
29 [287]. Type 3 contains a surfactant species, a divalent cationic surfactant
capable of physically crosslinking the polymer chain. Depending on the
concentration of
FIG. 29
Representation of
polymersurfactant
complexes. (From Ref. 287.)

Page 117
both surfactant and polymer, this can lead to gel formation, depending on the
flexibility of the polymer backbone, the geometry of the micelle, and the
polarity and charge distribution.
Viscosity measurements provide an excellent tool to study polymersurfactant
interactions. This is demonstrated very effectively for various polymer
surfactant pairs [288–291]. Nagarajan and Kalpakci have studied
polyethylene oxide and dextran in the presence of cationic, anionic, and
nonionic surfactants [292]. Polyethylene oxide with a flexible backbone shows
a significant interaction with anionic micelles, including sodium dodecyl sulfate,
sodium dodecyl benzene sulfonate, and 8phenyl hexadecane benzene
sulfonate, and minimal complexation with cationic systems, such as dodecyl
amine hydrochloride, didodecyl dimethyl ammonium bromide, and ethyl
hexadeyl dimethyl ammonium bromide. It appears that polymers with rigid
backbones, such as dextran, do not favor complexation with either anionic or
cationic surfactants. The absence of surface binding has also been confirmed
through surface tension measurements.
Hydrogels have been formed from nonionic surfaceactive graft copolymers
and unmicellized anionic surfactants [293]. It is suspected that comicelles are
formed between surfactant monomers and polymer hydrocarbon side chains
for hydrophobically modified hydroxyethylcellulose and sodium dodecyl sulfate
with gel formation at critical concentrations of the polymer and surfactant.
Dynamic mechanical rheology properties are presented supporting the
formation of a gel network structure.
Further, Goddard et al. have studied the interaction of a cationic cellulosic
ether polymer with anionic, cationic and nonionic surfactants [294]. Gelation
occurs with anionic surfactants, especially SDS; higher chain length cationic
surfactants, such as C12–C14 TAB, show no interaction with the polymer. In
addition, interactions are not apparent with nonionic surfactants although
surface tensions measurements indicate the contrary.
Many other references are available to the reader to explore fully the
implications of polymersurfactant interactions in liquid detergent systems
[295–304]. Various physical and electrochemical methods, such as
sedimentation, light scattering, viscometry, potentiometry, polarography,
conductivity, and ultracentrifugation, are combined to evaluate hydrodynamic
properties and conformation of the complexed pair. This includes both
polymeric acids and bases and their salts and nonionic watersoluble polymer
solutions, both dilute and concentrated systems. For example, the interaction of
lowmodularweight polymers in concentrated aqueous surfactant systems has
been reported by Mast and colleagues [305]. Their research, involving both
polyethylene oxide and hydrophobically modified polyethylene oxide in high
surfactant and salt concentrations, demonstrates the importance of viscometric
measurements and rheological characterizations in exploring polymersurfactant
complexation.

Page 118
VI. Conclusions
The rheology of liquid detergents is a fascinating research area because of the
breadth of rheological properties that can occur. Depending on the chemistry
and morphology of the surfactant micelles, and the various interactions that can
develop in the presence of additives, even dilute solutions well below the
CMC, can exhibit nonNewtonian flow behavior. Many types of flow
anomalies have been documented, including dilatancy, pseudoplasticity,
rheopexy, and thixotropy, and yield stresses are also not uncommon. Further,
rheological characterizations are complicated by the dependence of these flow
anomalies on the magnitude of the applied external flow field. Systems that
appear Newtonian can exhibit nonNewtonian behavior within relatively
narrow ranges of shear rates and strains. This is further complicated by the
time scales of these effects, because shearinduced structural transitions occur
following induction periods that vary in duration depending on the composition
of the surfactant system.
Characterization of commercial liquid detergent products can be relatively
straightforward. Interpretation of these rheological characterizations, however,
is a challenge. Data analysis requires a more fundamental understanding of the
internal mechanisms binding the surfactant system under investigation. Coupling
of rheological characterizations with other analytical techniques such as
microscopy, CryTEM, xray diffraction, SANS, NMR, and flow
birefringence, a greater understanding of the morphology of the liquid detergent
and resulting rheology can be obtained. There has been an increasing emphasis
in this area, leading to greater insight into the structureproperty relations of
liquid detergents.
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(1993).

5
Polymeric Stabilizers for Liquid Detergents
MADUKKARAI K. NAGARAJAN and HAL AMBUTER
Specialty Chemical Division—Product Development, The BFGoodrich Compan
Ohio
I. Introduction
II. Carbomer Resin Usage History
A. Automatic machine dishwashing gel
B. Liquid cleaner with abrasives
C. Liquid laundry detergents
D. Specialty liquid cleaner products
III. The Technology of Carbomer Resins
A. Chemistry of carbomer resins
B. Powder properties
C. Dispersion properties
D. Carbomer microstructure properties
E. Carbomer thickening mechanisms
IV. Handling Carbomer Resins
A. Wetting time
B. Dispersion viscosity
C. Dispersion techniques
D. Formulating with carbomer resins
E. Stability evaluations
References

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I. Introduction
The market share of liquid detergents steadily increased during the 1980s and
1990s. Their consumer popularity is due in part to ease of handling and
dispensing from the packaging container, better dissolution properties in
comparison with powders, and perceived performance benefits. However, the
conversion from a powder detergent to a liquid or a gel is not without its
difficulties for the formulator. First, although the selection of the performance
active materials remains more or less the same, the liquid formulator needs to
achieve product phase stability over the trade life of the product. Second, the
formulator must also consider the rheological behavior of the product (i.e.,
viscosity, flow characteristics, etc.) to meet the product's and customer's inuse
application requirements. Much research and development effort has been
spent in investigating and employing solvents, hydrotropes, and complex
surfactant combinations to achieve these ends. However, these functional
ingredients generally are not suitable for systems that require suspension of
insoluble materials and do not deliver the appropriate rheological profile for
some applications. For some of these applications, a rheological modifier or
additive is required.
The use of highly cost efficient polymeric resins in liquid detergents spurred
much commercially fruitful formulation technology research in the 1980s and
1990s. Enhanced stability of liquid detergents and new application concepts
were achieved and marketed with the incorporation of a small quantity of
lightly crosslinked polyacrylic acid network polymers known to the industry as
carbomers [1]. Due to their multifunctionality (they thicken, suspend, and
provide emulsion stabilization), unique rheological profile, broad compatibility,
and high weight efficiency, carbomer resins have become the predominant
polymer used in the industry for stabilization of liquid detergents.
The history of carbomer usage, carbomer resin chemistry, properties of
carbomer powder and aqueous dispersions, carbomer microstructural
properties, rheology of carbomercontaining systems, carbomer thickening
mechanisms, influence of electrolytes on carbomer properties, and handling of
carbomer resin in practical liquid detergent formulations are reviewed in this
chapter.
II. Carbomer Resin Usage History
A. Automatic Machine Dishwashing Gel
The automatic machine dishwashing gel (ADG) is a unique formulation in terms
of its product requirements. The product requires the thickening of a high ionic
strength continuous phase (silicates, carbonates, metal hydroxides) and the
suspension of a significant level of insolubles (phosphates). It must also have

a rheological profile that will (1) allow the product to flow easily under normal dis
pressures, (2) not splash or splatter upon dispensing, and (3) rapidly regain its str
dispensing and exhibit a “yield value” such that the product will not leak out of th
dishwasher cup. A typical recipe, with and without a polymeric stabilizing agent, f
laboratory, is given below.
Weight percent
Ingredient Control Exp
Sodium hydroxide (dry basis) 20.0
Carbopol 674 resin (BFGoodrich) 0
Sodium tripolyphosphate 13.0
(anhydrous)
Fatty alcohol ethoxylate (HLB:10) 1.0
Demineralized water 67.0
100.0
The control formulation phase separated, with solids settling to the bottom of the
container, within 1 day. On the other hand, the experimental formulation was ho
stable for over 3 months, as illustrated in Fig. 1.
FIG. 1
Alkaline slurry detergent stabilized by carbomer resin. Left:
Control; solids settled with phase separation. Right:
Experimental; homogeneous emulsion, stable
for over 3 months.

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During the early ADG formulation development, use was made of high levels
(5–15%) of linear polyacrylic acid in the preferred molecular weight range of
85,000–95,000 [2]. The researchers discovered that high total solids levels
(65–80%) could easily be stabilized in industrial warewashing machine slurry
detergents through the use of linear polyacrylates. The linear polyacrylate also
increased the water softening capacity, thus enabling the reduction of
phosphate levels to comply with antieutrophication legislation. Subsequent
patents disclosed similar high solids slurries or gels but with the incorporation
of low (e.g., 0.5%) levels of carbomer resins for improved stability, improved
aesthetics, and much greater formulation flexibility. Moreover, significantly
higher (to 98%) cup retention was noticed for ADLs stabilized with carbomer
resins than with the linear polyacrylic acid alone. Bush and Braun [3] were
among the early researchers to note that gelled dishwashing detergents
employing carbomer resin(s) as stabilizing agents leaked less from the
dishwashing machine's dispenser cups than even granular solid dishwashing
detergents and also described procedures for measuring “cup retention”
values. Their investigations showed that the degree of cup retention was not
dependent on the viscosity but more on the degree of cohesiveness of the gel,
i.e., its ability to hold together or its gelatinousness. Such a property is “yield
value,” which indicates the minimum shearing stress to produce continuous
deformation or flow. They measured yield value of their gels as
where the viscosity is measured using a Brookfield viscometer.
During the late 1980s and early 1990s, the research and patent activity in the
use of carbomer resins to stabilize and modify the rheological profile of ADGs
became intense. Gabriel and Roselle [4], for example, used a binary mixture of
carbomer resins to adjust the yield value and hence the degree of stability of
ADL formulations. On the other hand, Koring et al. [5] employed layered
clays such as laponite XLS as costabilizers for carbomer resins to achieve
improved product phase and active chlorine stability in bleachcontaining ADL
systems. Elliot and Kiefer [6] recommended the use of specially synthesized
carbomer thickeners wherein the crosslinking agent contained saturated
hydrocarbon or aromatic structures to improve both the phase and active
chlorine stability. Dixit et al. [7] suggest using, in addition to carbomer
stabilizer, a potassium/sodium weight ratio of about 1 to minimize the amount
of undissolved solid particles. They further recommend controlling the bulk
density of the ADL formulation through the incorporation of air such that the
bulk density of the entire composition is approximately equal to the bulk
density of the continuous phase.

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B. Liquid Cleaner with Abrasives
Another good example to illustrate the stabilization benefits from the use of
carbomer resins in liquid detergents is the abrasivecontaining cleaner products
used for cleaning hard surfaces such as washbasins and bathtubs.
Commercially available powder abrasive cleaners are composed of finely
divided mineral substances (such as silica, calcite, and pumice), surfactants,
bleaching agents, and small amounts of optional specialpurpose ingredients
such as defoamers. In the early liquid analogs of abrasive cleaner products,
higher fatty acid alkanolamides and ethoxylated higher fatty acid alkanolamides
were often used as dispersion stabilizers for the insoluble abrasives [8]. The
viscosities of these liquid abrasive cleaner products were made extremely high,
often higher than 5000 mPa. s, to maintain product phase stability over a long
period of time. As a result, these products had poor fluidity and were difficult
to dispense from a bottle. Moreover, the insoluble abrasive particles often
settled to the bottom of the container, necessitating instructions to shake the
bottle before use in order to achieve a homogeneous product during use.
Imamura and Shiozaki, in their patent on liquid abrasivecontaining cleanser
composition [9], describe the use of small amounts (0.3%) of carbomer resin
to stabilize liquid cleaners containing abrasive, nonionic surfactant, and
hydrotrope. The pH was adjusted to be between 5 and 9 using mono or
triethanolamine as a pH regulator. The viscosity of such a composition was in
the range of 1500 mPa. s, easily pourable and stable for long period of time
under varied storage temperatures. In addition to providing dispersion stability,
the liquid abrasivecontaining cleaner product with polymeric carbomer
thickener also possessed vertical cling or antisag properties that are desirable
in hard surface cleaning situations.
C. Liquid Laundry Detergents
1. Industrial Liquid Laundry Detergent
A highly concentrated heavy duty, built liquid laundry detergent product for
mechanically metered industrial and institutional (I&I) use is described by
Borgerding and Claus [10]. Its composition consists of alkali metal hydroxide,
surfactants, sodium aluminosilicate (zeolite 4A) builder and/or complex
phosphates, sodium (linear) polyacrylate of molecular weight 50,000–200,000
as a cobuilder, sodium carboxymethylcellulose as an antiredeposition agent,
and small amounts of a carbomer resin as a suspending aid. Rek [11]
describes the use of carbomer resins to stabilize high alkaline slurry detergents
employing a mixture of complex phosphates and silicates and specially selected
nonionic surfactants. Sodium salts of carbomer resins are also used to ensure
phase stability in an interesting invention by Boskamp [12,13]. In his
compositions,

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Boskamp recommends certain combinations of borax, polyols (such as
glycerol), or dicarboxylic acid salts and an antioxidant (such as sodium sulfite)
to achieve enzyme and physical stability. Stable, homogeneous, aqueous built
laundry detergents stabilized by linear alkalisoluble (e.g., Acrysol ASE95
from Rohm and Haas Company) or crosslinked, alkaliswellable (e.g.,
Acrysol ASE108) acrylic emulsions are described by Jones and Brabant
[14]. In general, an acrylic emulsion polymer is used at 3–10 times the
concentration of a carbomer resin to obtain equivalent physical stability.
2. Consumer Liquid Laundry Detergent
The industrial laundry detergents just discussed tend to employ high levels of
either insoluble (e.g., zeolite) or only partly soluble (e.g., complex phosphate
salts) builders, whereas consumer liquid laundry detergents employ water
soluble detergent builders such as sodium citrate, sodium nitrilotriacetate,
sodium laurate, alkali metal silicates, sodium (linear) polyacrylates, and sodium
tetrapotassium pyrophosphate (to some extent). These formulas therefore have
a higher ionic strength in the aqueous phase and present new challenges for the
formulator.
Structured liquid detergent formulations have been described [15] in which
carbomertype resins were used to achieve product stability and, curiously
enough, to provide a “viscositylowering” characteristic. The overall benefit
from the use of carbomer stabilizers, in this instance, is that pourable liquid
detergent compositions are obtained with viscosities in the range of 600–7500
mPa. s. Certain interesting formulating ideas useful for making concentrated
liquid laundry detergents with total surfactant concentration as high as 60 wt%
but with low viscosities (i.e., 40–200 mPa. s at room temperature) have been
described by Nagarajan et al. [16]. In such formulating scenarios, carbomer
resins incorporated at 0.1–2.0% enable the lowering of viscosities of highly
concentrated surfactant solutions and also provide soil antiredeposition
properties. The carbomer concentrations are generally lower in predominantly
nonionic surfactant formulations (e.g., 0.05–0.20%) than in anionic surfactant
systems (0.20–0.50%). This is due to the additional thickening provided by
cooperative structures formed via hydrogen bonds between the carboxyl group
of the carbomer resin and the polyol groups of the nonionic surfactants.
Other formulating approaches have been used in (1) liquid cleaning products
with skin feel additives by Hoskins and Kessler [17], who used a mixture of
carbomer resin and guar gum as stabilizers or viscosity modifiers in liquid
cleaner products containing up to 30 wt% anionic, nonionic, cationic, and
zwitterionic surfactants; (2) liquid cleanser compositions for toilet bowls by
Tagata et al. [18], who used anionic synthetic and fatty acid based surfactants
and carbomer resins as viscosity modifiers; and (3) liquid detergents mild to the
skin by Deguchi et al. [19], who described alkyl glycoside (40 wt%) based

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products with a mixture of synthetic carbomers, natural gums, and polyvinyl
alcohol as viscositymodifying agents.
D. Specialty Liquid Cleaner Products
In the carbomer usage examples reviewed above, the term “polymeric
stabilizer” had a very restricted and narrow meaning. In these early research
formulations, the carbomer resin was included primarily to suspend insoluble or
sparingly soluble detergent ingredients to minimize or prevent phase separation.
As more and more liquid formulators become familiar with how to incorporate
carbomer resins in their formulations and with their function, they are also
enlarging the scope and meaning of the term polymeric stabilizer. We have
already seen this somewhat in earlier examples: vertical cling, cup retention,
viscosity lowering, viscosity building, viscosity control, rheology modifier, and
structure building are some of the terms gradually being introduced into the
liquid detergent literature under the general blanket of “polymer stabilizer.”
Ambuter [20] has formulated several stable specialty liquid detergent products
that accentuate the multitude of functions and roles that the carbomer resins
can provide. Carbomer resins provide thickening, shear thinning with quick
viscosity regain, and antisagging properties in laundry prespotters. The use of
carbomer resins can provide “no drip” vertical cling characteristics to glass and
generalpurpose cleaners. The thickening provided by carbomer resins can
reduce splashing in high alkalinity and bleachcontaining formulas such as oven
cleaners and mold and mildew cleaners. Another unique function of carbomers,
especially those that include a hydrophobic comonomer, is to stabilize oilin
water emulsions such as solventbased hand cleaners and degreasers. The
ability of carbomer resins to hydrogen bond also makes possible thickening
formulations containing organic acids. We are of the opinion that more
functionrelated benefits from the use of carbomer polymer stabilizers will be
added in the future by liquid detergent formulators to enlarge the scope of what
is meant today by “polymeric stabilizers in liquid detergents.”
III. The Technology Of Carbomer Resins
A. Chemistry of Carbomer Resins
Brown of The BFGoodrich company is credited with the invention of the
original carbomer resin [21]. Carbomer resins are prepared by the
precipitation polymerization of acrylic acid, which forms the polymer
backbone, and small amounts of a crosslinking agent possessing polyallyl
functionality [22]. The International Cosmetic Ingredient Dictionary of the
Cosmetics, Toiletries and Fragrance Association (CTFA) defines a
homopolymer carbomer as a lightly

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crosslinked polymer prepared from acrylic acid and a polyalkenyl polyether
crosslinking agent. A schematic diagram of a segment of homopolymer
carbomer resin is given in Fig. 2. While the acrylic acid and polyallyl cross
linking agent have different degrees of unsaturation, the resulting carbomer
resin is a fully saturated entity with no unsaturation or double bonds. It is also
known [23] that the organic solvent used in the polymerization process has
much influence on the quality, performance, and environmental acceptability of
carbomer resins.
Recent developments [24–26] in carbomer resin technology include
hydrophobically modified copolymer carbomer resins in which small amounts
of a C10–C30 alkyl acrylate are included in the polymerization step as a
comonomer. In the schematic diagram of a segment of copolymer carbomer
structure (Fig. 3), these hydrophobic surfactant comonomer moieties are
incorporated into the homopolymer carbomer resin structure shown in Fig. 2.
The homopolymer and copolymer carbomer resins are threedimensional
network polymers. The corresponding twodimensional carbomer structures
shown in Figs. 2 and 3 are only illustrative and not exact. Also, like most
polymeric materials, there will be a distribution of molecular structures with a
most probable or average structure for any given carbomer resin. The ultimate
chemical structure of any particular carbomer is very sensitive to a large
number of factors in the polymerization process such as crosslinker type,
allylic functionality, crosslinker level, polymerization solvent, total solids in the
solvent during polymerization, polymerization temperature, drying temperature,
FIG. 2
Schematic structure of a segment of homopolymer
carbomer resin. Monomer: acrylic acid.
Crosslinking agent: polyalkenyl polyether.

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FIG. 3
Schematic structure of segment of hydrophobically
modified copolymer carbomer resin. Monomer: acrylic
acid. Comonomer: C –C alkyl acrylate.
10 30
Crosslinking agent: polyalkenyl polyether.
extent (time) of polymerization and drying, and a host of other processrelated
factors. These varied threedimensional structures or physical morphologies
may lead to large or sometimes subtle differences in the performance of the
resin during end use. However, the differences in chemical composition
between several carbomer resin types or grades are small and in many
instances insignificant.
In the following sections, commercial carbomer resins are used as examples for
the discussion of physicochemical properties. Carbopol® 941, 940, and 934
are carbomer resins polymerized in benzene. Carbopol® ETD™ 2020 and
Carbopol® Ultrez™ 10 are “easytodisperse” resins [27–29] polymerized in
a cyclohexane and ethyl acetate cosolvent system.
B. Powder Properties
1. Glass Transition Temperature
Eisenberg et al. [30] report that the glass transition temperature (Tg) of linear
polyacrylic acid is on the order of 103°C. The Tg varies with moisture content
and reaches an extrapolated value of 140°C for the pure linear anhydride. The
viscosity average molecular weights (Mv) of the linear polyacrylic acid samples
used in Eisenberg's work ranged between 18,000 and 313,000 daltons
(implied by Mv). The anhydride formation is primarily by an intramolecular

Page 138
process. The simultaneous dehydration and decarboxylation are both first
order reactions. The decarboxylation is a much slower process than the
dehydration process in the overall drying process of polyacrylic acid chemistry.
The Tg of most grades of carbomer resins, determined by differential scanning
calorimetry, is in the range 103–110°C. The Tg of carbomer resins falls very
sharply with the addition of water and is expected to be at or below room
temperature for dilute carbomer dispersions in water. The small differences in
the Tg's of several carbomer resins is consistent with the differences between
their chemical compositions. The lower Tg for wet carbomer or dilute aqueous
carbomer dispersions suggest rapid molecular movements of polyacrylic acid
backbones leading to chain entanglements—a characteristic feature of
carbomers and important in determining the rheological behavior of dilute
carbomer dispersions.
2. Particle and Bulk Density
Carnali and Naser [31] used pycnometry in noctane to determine a particle
density of 1.449 g/mL for purified (dialyzed) Carbopol 941 and 940 resins.
The particle densities of several commercially available carbomer resins were
determined, without any purification steps, employing standard pycnometric
methods [32] in 2,2,4trimethylpentane and are given in Table 1. The available
data suggest that the polymerization solvent and process lead only to small
differences in the carbomer resin's particle density. In Table 1 we also include
the bulk densities of the carbomer resins reported by their manufacturers.
3. Particle Size
A typical scanning electron microscopy photomicrograph of carbomer resin
power, at 20,000× magnification, is shown in Fig. 4. Visual examination of the
photomicrographs gave the following results [33]:
Size range ( m)
Carbomer :Smallesta Average :Largest
Carbopol934 0.043 0.20 0.25
Carbopol 940 0.046 0.20 0.24
a
Only a few particles of this size were observed.
Cohen [33] also obtained independent confirmation of 0.18–0.20 m being
the smallest particle diameter in typical carbomer resin powder from B,E,T
surface area (20–23 m2/g) and particle density (1.42 g/mL). Carbomer
powder, as manufactured, consists of aggregates of primary particles
generated

Page 139
TABLE 1 Particle and Bulk Densities
for Some Carbomer Resins
Particle Bulk Carbopol 941 1.427 no

density density data
Carbomer (g/mL) (g/cm3
Carbopol 940 1.448 0.23
Carbopol 934 1.444 0.23
Carbopol 1.396 0.28

Ultrez 10
Carbopol 1.333 0.30

ETD 2020
during the initial stages of its precipitation polymerization. In these secondary
particle agglomerates, the constituent primary particles are held together by
rather strong coulombic and van der Waals forces. The size distribution of
secondary particle agglomerates in carbomer resin powder is generally
determined by automated Coulter counter apparatus. Employing the Coulter
counter procedure, the average particle sizes (diameters) of the Carbopol 934
and Ultrez 10 resins were found to be 2–6 and 3–10 m; respectively.
4. Solubility
Carbomer resin powders are not soluble in commonly used solvents, including
water. However, the secondary particle agglomerates, upon dispersion in
water, swell to many times their original volume and disperse through the
break
FIG. 4
Scanning electron photomicrograph of carbomer
resin × 20,000. White bar is 1 m.

Page 140
down of the interparticle forces originally holding the secondary particle
aggregates together. In many instances the aqueous carbomer resin dispersions
exhibit remarkable clarity, but the resins are not soluble.
5. Hygroscopicity
Carbomer resin powders are hygroscopic and pick up moisture easily when
left open to the atmosphere. The following moisture uptake data were
collected when Carbopol 934 powder, contained in a petri dish, was left open
to a laboratory atmosphere at 70% relative humidity:
Time % 0.67 4.0

(h) Weight
gain
1.00 5.6
1.50 7.6
2.00 9.0
4.00 13.5
6.00 15.6
The equilibrium moisture content at 50% relative humidity and room
temperature is reported to be 8–10 wt% for most carbomer resin powders.
6. Molecular Weight
The weight average molecular weight (Mw) of uncrosslinked linear polymer
(Carbopol 907, for example), polymerized under the same process conditions
as for the crosslinked carbomer grades, is 603,300 daltons as determined by
gel permeation chromatography (GPC) using polyacrylic acid standards. For
Carbomer 907 linear polymer, the number average molecular weight (Mn) is
146,300, giving a value of 4.124 for the polydispersity index (Mw/Mn). The
viscosity average molecular weight (Mv) of the Carbomer 907 linear polymer is
524,700 as calculated from the above GPC data. The weight percent of low
molecular weight linear polymer impurities in the Carbomer 907 linear
carbomer is 1.7, 0.26, and 0.005 for the molecular weight cuts below 20,000,
1000, and 500, respectively.
Since carbomer resins do not dissolve in water or any organic solvents, their
molecular weight determination by standard physicochemical methods is an
intractable problem. To date, the molecular weights of carbomer resins have
not been unequivocally determined.
In addition to the overall molecular weight, carbomer resins can be
characterized by microstructural features like the molecular weight between
adjacent

Page 141
crosslink sites (Mc). The calculation of Mc is dependent on both the
experimental method and data used and the theoretical model used for deriving
Mc values. Thus for the Carbopol 941 resin, Taylor and Bagley [34] reported
an Mc of 5 × 106 calculated from shear modulus data, whereas Carnali and
Naser [31] determined a value of 237,600 from the viscometric determination
of the equilibrium swelling ratio. (See also Section III.D in this chapter.) With
Mc values on the order of several hundred thousands, the overall molecular
weight of carbomer resins may be estimated to be in the billions. Cohen [33]
calculated the molecular weight of carbomer resin from the estimated
dimensions of its primary particle (see Section III.B.3) and the polymer's
particle density (see Section III.B.2) to be on the order of 4.5 × 109 daltons.
Nae and Reichert [22] proposed an approach for the theoretical calculation of
Mc based on the network structure and the stoichiometry of the polymerization
reaction. They assumed that the reaction went to 100% completion and that
there were no loops, side chains, or unreacted chain ends in the carbomer
structure. The values of Mc calculated using this approach are far too small and
do not reflect the complexities of the precipitation polymerization reaction or
the actual final structure.
7. Acid Dissociation Constant
Carbomer resin is a week acid. The total carboxyl content in 1 g of carbomer
is approximately the same as in the acrylic acid monomer from which it is
made, with a stoichiometrically negligible amount of crosslinking agent. The
carbomer's total carboxylic content, on weight basis, is therefore determined as
In the absence of unequivocal molecular weight information for carbomer
polymers, Charman et al. [35] reported an apparent pKa for carbomers as 6.8.
This value was estimated from a first derivative plot of pH versus the volume of
added sodium hydroxide solution to a known weight of hydrated carbomer
resin [i.e., d(pH)/d(volume)]. The pKa values obtained for five different
carbomer resins were similar. The pKa of 6.8 for carbomer resins is greater
than the pKa of linear polyacrylic acid (5.3) and acrylic acid monomer (4.3)
[36, 37]. These data indicate that the acidity of the crosslinked polymeric
species is approximately 100fold less than in monomeric form. This decrease
in apparent acidity of the polymeric species is primarily due to the weakening
inductive effects that affect the ionization potential of neighboring carboxylic
acid groups. Therefore, it is fair to surmise that the carboxyl functional groups
within the network polymer are dissimilar and that the acidity of carbomer resin

Page 142
is a function of the degree of ionization. The pHdependent viscosity of
carbomer dispersions is a function of the degree of ionization of the polymeric
species and reflects the carbomer's apparent pKa value. Thus, carbomer resins
exhibit a pHindependent viscosity region of pH 5–9 (Fig. 4 in Ref. 26).
Similarly, the decrease in viscosity of carbomer dispersions at high pH values is
due to the increased counter ion concentrations (which disturb the electrostatic
repulsion between the ionized carboxyl groups placed randomly along the
polyacrylic backbone) and an overall decrease in the hydration of the cross
linked polymer.
It is interesting to note that Charman et al. [35] also found that the apparent
pKa of carbomer resins reverts to that of monomer acrylic acid, 4.3, when
determined in the presence of 0.05–0.20% calcium chloride in the titrating
solution. Apparently, the binding interaction of calcium with ionized carboxylate
sites in the polymer was sufficient to significantly reduce the induction effects
due to ionized carboxylate moieties on adjacent carboxylic acid sites in the
polymer backbone. In a practical sense, carbomer resins possess 100fold
more acidity in the presence of calcium ions, which are commonly found in
liquid detergent use situations. The use of added reserve alkalinity or buffering
agents in liquid detergent formulations containing carbomer resins therefore
seems prudent.
C. Dispersion Properties
1. Intrinsic Viscosity
High molecular weight polymers possess the unique capacity to greatly
increase the viscosity of the liquid they are dissolved or dispersed in, even
when present at concentrations that are quite low. In carbomer resins, the
viscosity increase is due to the voluminous character of the waterswollen
carbomer microgels [37]. The capacity of a polymer to enhance the viscosity is
characterized by its “intrinsic viscosity,” a structurerelated parameter
introduced by Staudinger and Heuer [38]. The units in which intrinsic viscosity
is expressed, dL/g, originate from Einstein's rigidsphere model, which relates a
polymer's specific volume and its specific viscosity [39]. Factors affecting the
intrinsic viscosity of a carbomer resin include
1. pH, which also influences the degree of neutralization of the carbomer and
hence the ionic strength.
2. Ionic strength, including any ionizable additive in the detergent formulation,
such as EDTA or ionic surfactants.
3. Electrolyte type, including both cations and anions.
4. Carbomer type.

Page 143
5. Nonaqueous solvent ingredients, which influence the ionic strength via
changes in the dielectric constant of the medium.
The same factors influence the molecular confirmation and the resultant specific
volume of the swollen polymer.
The influence of pH on the intrinsic viscosity of several types of carbomer
resins is discussed in a paper by Ishikawa et al. [40]. Generally, the intrinsic
viscosity increases with an increase in pH and reaches an asymptotic value
above pH 6–7. Ishikawa et al. determined the intrinsic viscosity of carbomers
using dilute solution capillary viscometry and the Huggins relationship,
discussed later in this chapter. Carnali and Naser [31], using dilute solution
viscosity measurements, determined the intrinsic viscosities of unneutralized
Carbopol 940 and 941 (pH about 3) resins as a function of ionic strength.
They found a linear relationship between the intrinsic viscosity and the inverse
square root of ionic strength at very low salt concentrations, which leveled off
at higher ionic strengths.
We have also determined the intrinsic viscosities of several carbomer resins by
dilute solution viscometric procedures [41]. We chose a TrisHClNaCl buffer
[42] as the background electrolyte. The buffer was prepared using Tris
(hydroxymethyl)aminomethane and HCl buffer solution at pH 7.60 with
additional sodium chloride to bring the ionic strength to 0.171 (equivalent to
1.0 wt % sodium chloride). To this, an appropriate amount (00.04 dL/g) of
carbomer resin was added, and the solution was neutralized to pH 7.3–8.2
with sodium hydroxide. The viscosities of these dilute polymer solutions were
then measured using a Physica LS100 low stress rheometer. The viscosity
obtained was constant (Newtonian behavior) to within 2% in the shear rate
range of about 50–200 s1, and the relative viscosity varied between 1.03 and
1.29, which is well within Flory's recommendations [37]. The specific viscosity
was then plotted as a function of polymer concentration, referred to as Huggins
plots [43] (Fig. 5). The intrinsic viscosity was then obtained using the equation
(1)
where
sp = / 0 1
where
sp = specific viscosity
0 solvent viscosity
solution viscosity
[ ] intrinsic viscosity
c = polymer concentration

solution viscosity
c = polymer concentration

Page 144
FIG. 5
Huggins plot for Carbopol 940 resin
(in 1% TrisNaCl buffer; pH 7.6).
The intrinsic viscosities, determined as the viscosity at zero concentration, for
several carbomer resins are summarized in Table 2.
2. Intrinsic VolumeSwelling Ratio
Einstein [39] (see also Ref. 31) showed that the viscosity of a fluid in which
small rigid spheres are dilutely and uniformly dispersed (i.e., random close
TABLE 2 Intrinsic Viscosities for Some Carbomer
Resins
Intrinsic Slopea Carbopol 941 7.59 35.0

viscosity K' (dimensionless)
Carbomer (dL/g) Carbopol 940 4.49 12.8
Carbopol 934 3.85 8.3
Carbopol 2.60 9.9

Ultrez 10
Carbopol 1.89 43.6

ETD 2020
Conditions: Ionic strength 0.171; TrisNaCl equal
to 1.0 g/dL NaCl; pH 7.60. aSlope calculated from
Huggins equation [see Eq. (1)].

Page 145
packing model) is related to the volume fraction occupied by all the rigid
spheres. We specify here Qi as intrinsic volumeswelling ration, which is given
by the volume of the swollen polymer divided by the volume of the dry
polymer. The following relation then holds:
(2)
where
Qi intrinsic swellability
p particle density
With the particle densities given in Table 1, Eq. (2) can be used to calculate Qi.
The results of these calculations are given in Table 3.
3. Overlap Concentration
Taylor and Bagley [44] were the first to explain the extraordinary viscosity
building properties of carbomer resins, even at low concentrations, in terms of
a twophase microgel model. According to their model, carbomer resin
dispersions consist of swollen, deformable gel particles closely packed in
intimate contact [45]. Under high dilution or at high ionic strength conditions,
the gel particles are no longer tightly packed, the (interstitial) solvent is present
in excess, the viscosity drops precipitously, and the thickening action almost
disappears. Steeneken [46] further developed this model by taking into
account the existence of two concentration regimes (Fig. 6). In the dilute
regime, the dispersion is essentially nonhomogeneous with a low viscosity
governed by the polymer volume fraction of the swollen microgel. The swollen
microgels are farther apart, and the dispersion is either already unstable (i.e.,
separated in two
TABLE 3 Intrinsic Volume Swelling Ratio for
Some Carbomer Resins
Particle Intrinsic volume Carbopol 941 1.427 446.6

density swelling ratio
Carbomer (g/mL) (dimensionless) Carbopol 940 1.448 263.8
Carbopol 934 1.444 214.1
Carbopol 1.396 142.2

Ultrez 10
Carbopol 1.333 101.5

ETD 2020
Conditions: Ionic strength 0.171; TrisNaCl
equal to 1.0 g/dL NaCl; pH 7.60.

Page 146
FIG. 6
Thickening mechanism for carbomer dispersions.
(Adapted from Fig. 3 in Ref. 46.)
phases) or will become unstable over time. This dilute dispersion is Newtonian
and does not have a yield value [47]. In the higher concentration regime, the
dispersion becomes homogeneous with a high viscosity governed by the rigidity
of the microgel. Here, the swollen microgels are compressed, and the
dispersion is stable. This system is now viscoelastic and has a definite yield
value. Between these two limiting cases, a broad transition region exists where
the viscosity is governed by both the polymer volume fraction and the rigidity
of the microgel. At a critical concentration in this transition region, the
microgels are fully swollen and just touch each other. The resin concentration
at this point is called the “overlap concentration” (c*. At c*, the viscosity of the
system rises sharply (Fig. 7 and Table 4). Assuming Einstein's rigidsphere
model (nondraining case) and a random closepacking volume fraction of
0.637 [48], the critical overlap concentration is calculated employing the
equation
(3)
where c* = critical overlap concentration and = volume fraction = 0.637 for
hard spheres.
The resin parameters [ ], Qi, and c* are all indicative of the thickening (or
viscositybuilding) efficiency of a polymer resin in a chosen environment (i.e.,
the solvent or background electrolyte). Thus,

Page 147
FIG. 7
Viscosity building by carbomer resins (in 1% TrisNaCl
Buffer; pH 7.6).
Relative High High Low High

thickening
[ ] Qi c* efficiency
Low Low High Low
Table 4 summarizes the results of such calculations for several carbomer resins.
Since c* is derived from the polymer's intrinsic viscosity, it is also depen
TABLE 4 Overlap
Concentration for Some
Carbomer Resins
Overlap Carbopol 941 0.20

concentration
Carbomer (g/dL) Carbopol 940 0.35
Carbopol 934 0.41
Carbopol 0.61
Ultrez 10
Carbopol ETD 0.84
2020
Conditions: Ionic strength
0.171; TrisNaCl equal to 1.0
g/dL NaCl; pH 7.60.

Page 148
FIG. 8
Microgel model for aqueous carbomer dispersions. After shear
stops, the original high viscosity is recovered quickly
(i.e., viscoelastic behavior).
dent on the pH, ionic strength of the electrolytes present, type of electrolyte,
carbomer type, and the presence of nonaqueous solvents in the detergent
formulation.
4. Viscosity
Most carbomer resin dispersions show pseudoplastic flow behavior and exhibit
a shear thinning character to a varying degree (Fig. 8). The rheological data
obtained for a 1 wt% carbomer resin mucilage, neutralized to pH 7–8, using a
controlled stress rheometer, are shown in Figs. 9–11. All three ways of
representing the flow curve data—viscosity vs. shear rate, viscosity vs. shear
stress, and shear stress vs. shear rate—are equivalent.
FIG. 9
Viscosity versus shear rate flow curves for carbomer
resins.

Page 149
FIG. 10
Viscosity versus shear stress flow curves
for carbomer resins.
Carbomer resin manufacturers usually specify singlepoint viscosities of various
grades of their products, where the viscosity is measured using a Brookfield
spindle viscometer. With the advent of more and more sensitive modern
computerized rheometers, it has been our experience that the instrumental error
is usually high at low shear rates (e.g., > 20% standard error) and low
FIG. 11
Shear stress versus shear rate flow curves for
carbomer resins.

Page 150
at high shear rates(<5% standard error at high shear rates). Therefore,
reporting viscosities measured at two or three shear different rates might be a
better option for quality control and product specification purposes.
5. Yield Value
An examination of Figs. 9 and 10 graphically illustrates the carbomer resin's
plastic flow behavior with a definite yield stress. Many researchers have
developed and proposed test methods and procedures to calculate the yield
value.
Almost 40 years ago, Meyer and Cohen [49] drew attention to the ability of
carbomer resins to exhibit yield values even at low concentrations such as 0.1
wt%. They used an empirically derived yield value determination procedure
based on a Brookfield spindle viscometer. They also semiquantitatively related
the yield values of carbomer suspensions to their ability to produce
“permanent” suspensions in practically useful systems. Voet and Brand [50]
describe a procedure based on a plate plastometer that became the basis for
the British Pharmacopea (B.P.) plastometer test method (as in B.P. 1980
Appendix YJ, A79). An elegant and visually demonstrative, although time
consuming, suspended sphere test method for yield value determination has
been described by a carbomer resin manufacturer [51]. Data on equilibrium
strain vs. stress behavior of “atrest” carbomer dispersions, obtained by
employing stress rheometry, were used by Ketz and coworkers [45] to
estimate the yield stress in these systems. Controlled shearstress flow curves
(rotational tests) were used by Farooq et al. [52] in determining the yield stress
of automatic machine dishwashing liquid detergent formulations containing
carbomer and inorganic alumina in their study on synergistic interactions in
polyacrylatealumina gel dispersions. Magnin and Piau [53], from their detailed
study using different experimental approaches for determining yield value,
found that several artifacts arise from surface roughness, slip moisture
evaporation, and other experimental conditions used in the test.
We summarize here some important aspects of the yield value concept as
applied to systems containing carbomer resins:
1. Yield value is the initial resistance to applied stress.
2. Yield value (rather than viscosity) is the dominant factor in determining the
suspending ability of carbomer resin.
3. The actual units in which yield value is expressed are dependent on the
measurement method. Hence, only the relative magnitude of yield value,
determined by the same experimental procedure, is important when discussing
the role of carbomer resins in liquid detergents. The general units are force per
unit area, the same as for shearing stress.
4. The yield behavior in carbomer resincontaining systems begins only after
the overlap concentration of the resin is exceeded.

Page 151
5. Like other carbomer resin properties, the yield value is affected by pH, ionic
strength, ion type, carbomer type, and solvents, if any, in the liquid detergent
formulation.
6. Yield value, in general, decreases linearly with the inverse square root of the
total ionic strength in the dispersion at low ionic strengths and reaches a plateau
value at higher ionic strengths.
Typical yield values of some carbomer resins are given in Table 5. The data
were determined by applying the Casson rheology model [47] to a controlled
stress flow curve using internally standardized run parameters. The Casson
rheology model relationship is given by the equation
(4)
where
= shear stress (Pa)
o
= yield stress (Pa)
h = infinite shear viscosity (Pa. s)
g = shear rate (s1)
6. Microviscosity
Davidson and Collins [54] determined the viscosity of the continuous phase in
carbomer dispersions by an elegant morphological technique involving
photographic diffusion coefficient measurements in a neutralized carbomer
mucilage doped with monosized polystyrene latex particles. They used
Einstein's equation for Brownian motion of spherical particles to derive these
waterlike or microviscosities. Lockhead et al. [26] used a quasielastic light
scattering technique to measure the StokesEinstein microdiffusion coefficient
of gelsol particles in the interstitial waterlike fluid in carbomer resin thickened
systems.
TABLE 5 Rheology Profile Data for Some Carbomer Resins
Viscosity at
Thixotropy 2.041 s1
Carbomer Rigidity(Pa) (Pa/s/cm3) Yield point(Pa)
(mPa s)
Carbopol 941 25.5 4.6 13.5 10,700

Carbopol 941 425.0 42.9 13.5 75,800
Carbopol 934 736.9 304.9 94.5 74,500
Carbopol Ultrez 983.3 309.0 108.1 84,300
10
Carbopol ETD 325.8 11.5 147.2 63,200
2020
Conditions: 1.00 wt% neutralized carbomer mucilages; pH 7.38.2; temperature 25** C

Page 152
FIG. 12
Macro and microviscosity curves for carbomer microgel.
(Microviscosity data from Refs. 26 and 54.)
Figure 12 illustrates this macro vs. microviscosity concept in a typical
neutralized (pH 7–8) carbomer resin mucilage. The limiting high shear rate
viscosity obtained in the Casson rheology model fit for controlled shear stress
flow curve data, calculated via Eq. (4), can be considered as an approximate
(or proportional) measure of microviscosity. The microviscosity in neutralized
carbomer resin systems is affected by, among other factors, the soluble linear
polyacrylic polymer impurities and the amount of linear polyacrylic acid
segments attached to the particlelike carbomer microgel. Pertinent
microviscosity data extracted from Casson rheology model analysis of
controlled stress flow curve data of several carbomer resins are also included
in Table 5.
7 Thixotropic Index
Thixotropy is defined as a decrease in viscosity under shear stress, followed by
a gradual recovery to the original viscosity when the stress is removed.
Thixotropy is dependent upon the shearstress history of the sample and time.
It is measured by the hysteresis loop area (in Pa/s) or relative hysteresis
volume (in Pa/s/cm3) from the combined “up” and “down” flow curve (see Fig.
13). A conceptual analog for understanding thixotropy can be drawn from the
readily

Page 153
FIG. 13
Thixotropic loop for carbomer resins.
observable differences between ordinary Jello and wet sand. Jello has low
thixotropy, and wet sand has high thixotropy. From this analogy, we can relate
low thixotropy in carbomer resins (like Jello) to high gel strength, fast release of
bound actives (if any), rapid relaxation after a brief stress period (a quick
recovery to the original state), smaller (microgel) particle size, and good
(optical) clarity. Similarly, a high thixotropy in carbomer resins (like wet sand)
signifies low gel strength, slow active release, slow relaxation, large particle
size, and poor clarity or cloudiness. Thixotropic indexes for several carbomer
resins are included in Table 5.
8. Microgel Rigidity (or Compliance)
A vast amount of published literature supports the fact that neutralized
carbomer resin dispersions consist of two phases: a discontinuous phase of
(water) swollen carbomer particles (“microgels”) dispersed in a waterlike
continuous phase (“interstitial fluid”) [26,31,34,44–46, 54]. It is known [31,
40, 45, 46, 52] that these highly swollen carbomer microgels are deformable
under stress and can be characterized by steadystate compliance or its
reciprocal, the rigidity coefficient (total shear modulus, G0). Creep relaxation
curves for some carbomer resins are shown in Fig. 14 and may be used to
determine the microgel rigidity coefficients (Table 5). The data reported in Fig.
14 were obtained using a controlled stress creep test on 1 wt % neutralized
carbomer mucilages and adjusting the run parameters so that the maximum
strain reached was well

Page 154
FIG. 14
Creep relaxation curve for carbomer resins (in 1%
TrisNaCl buffer; pH 7.6). Resins were subjected to
5 Pa stress for 20 s, followed by 0 Pa stress for 180 s.
within the linear viscoelastic range (<10–15% deformation) of the particular
test sample.
Microgel rigidity is another dimension, quite apart from polymer swelling, of the
viscosifying effect due to carbomer resins. It is also directly responsible for the
elastic component in carbomer rheology. This particle nature of carbomer
resins is particularly useful at the high electrolyte concentrations normally found
in liquid detergents.
D. Carbomer Microstructure Properties
The internal microstructure properties of carbomer resins such as molecular
weight between adjacent crosslink sites (Mc) and the crosslink density ( c)
were calculated from the corresponding intrinsic volumeswelling ratios (Qi),
the application of FloryHuggins' swelling thermodynamics, and rubber
elasticity theory.
When a network polymer, such as carbomer resin, swells in a fluid medium,
there are two opposite and equal forces operating: (1) a favorable mixing due
to increased entropy as the fluid spreads through the added volume, with a
driving force favoring swelling [55; see also Ref. 37, p. 52, Eq. (41)],
Gmix = RT [In (l c) + c + c2] (5)
where

Page 155
= Flory's chi parameter = 0.44
c = 1/Qi
and (2) an opposing elastic retractive force [56] because the polymer chains
between network junctions are required to assume elongated conformations:
(6)
where
Mc = molecular weight between adjacent crosslink sites
V1 = molar volume of the fluid (18.01 for water)
R = gas constant
T = temperature in Kelvin
When equilibrium is established, the following holds:
(7)
Mc can now be calculated from Eq. (7). The appropriate units for Mc are
g/mol, which can be converted to other required units such as Mc in g/mol ×
1/72 = Mc in number of acrylic acid monomer units per link, where 72 is the
formula weight for acrylic acid monomer.
The crosslink density ( c) of the carbomer is calculated from the
corresponding Mc values as
or
where Nav is the Avogadro number, 6.022 × 1023.
Table 6 summarizes the abovementioned microstructure parameters.
E. Carbomer Thickening Mechanisms
Carbomer resin is a special case of nonlinear, branched polymer chains that
interconnect to form a threedimensional network structure. In dispersions
consisting of network polymers the dominant structural feature are (water)

E. Carbomer Thickening Mechanisms
Carbomer resin is a special case of nonlinear, branched polymer chains that
interconnect to form a threedimensional network structure. In dispersions
consisting of network polymers the dominant structural feature are (water)

TABLE 6 Microstructure Parameters for Some Carbomer Resins
Molecular weight between adjacent Crosslink de
Carbomer crosslinks (× 103 monomer units/link) networ
Carbopol 941 156.7 7.
Carbopol 940 63.7 19
Carbopol 934 44.5 27
Carbopol Ultrez 10 20.8 54
Carbopol ETD 2020 11.4 97
Conditions: Ionic strength 0.171; TrisNaCl equal to 1.0 g/dL NaCl; pH 7.60.
swollen microgels. Polymer microgel particles viscosify a solution essentially thro
mechanisms. At concentrations below c*, the viscosity increases in direct propor
magnitude of polymer swelling. In this region, the most efficient carbomer resins h
rigidity compressible microgels, high intrinsic viscosity, and high intrinsic swellabili
Carbopol 941 and 940). This concept is supported by experimental data as sho
which is a magnification of Fig. 7 at the lower carbomer concentrations. Above c
governing factor in building viscosity is the microgel rigidity. It is seen that the rigi
concentration behavior illustrated in Fig. 16 parallels the viscosityconcentration (
behavior of carbomer resins. In this regime, the viscosity of the system increases i
proportion to the microgel particle rigidity.
FIG. 15
Viscosity building by carbomer resins (in 1% TrisNaCl
buffer; pH 7.6).

Page 157
FIG. 16
Rigidity building by carbomer resins (in 1% TrisNaCl
Buffer; pH 7.6).
It is interesting to note here that both high crosslink density and high microgel
rigidity (as in Carbopol Ultrez 10) yield the most efficient resins for viscosity
building beyond c*. The Carbopol ETD 2020 resin, though exhibiting a high
crosslink density, is less efficient than the Carbopol Ultrez 10 resin at low
ionic strengths because of its lower rigidity.
Carbomer Crosslink density Rigidity
Carbopol 934 27.1 736.9
Carbopol ETD 2020 97.7 983.3
Carbopol Ultrez 10 54.6 325.8
At considerably higher ionic strengths, the Carbopol ETD 2020 resin can be
expected to outperform other resins because it is hydrophobically modified to
provide better electrolyte tolerance.
Because of the dual mechanism of viscosity building by carbomer resins, an
interesting crossover phenomenon occurs. Lowswelling carbomer resins (e.g.,
Carbopols Ultrez 10 and 934) have a lower viscosity at low polymer
concentrations; however, at higher polymer concentrations, this situation is
reversed (see Figs. 7 and 15). This illustrates the unique rigidparticle nature of
the Carbopol Ultrez 10 resin as compared to Carbopol 940 and 934. In fact,
the fundamental data given in this chapter show that the Carbopol Ultrez 10
resin

Page 158
is capable of replacing either Carbopol 940 or 934 in certain liquid detergent
product formulations.
IV. Handling Carbomer Resins
A. Wetting Time
Significant time and money can be saved by using the Carbopol ETD 2020
and Ultrez 10 resins rather than traditional carbomer resins [27–29]. The
surface modification of these resins with high molecular weight surfactants is
responsible for the dramatic reduction in powder wetting times. Wetting time
data for these carbomer resins are compared with data for other carbomer
resins in Table 7. The wetting time is determined as follows. Dry 2.5 g of
Carbopol resin in a vacuum oven at 80°C and 29 in. mercury for 1 h to
remove any superficial moisture in the sample. Add all of the resin onto the
surface of 500 mL of demineralized water without any agitation. The Carbopol
Ultrez 10 polymer will begin to wet in seconds and incorporate into the water.
Note the time when the dry power is no longer visible on the water surface.
This time is the wetting time. The shorter the wetting time, the easier it is to
disperse the carbomer resin in water.
B. Dispersion Viscosity
One of the unusual features of the Carbopol ETD 2020 and Ultrez 10 resins
are their lower dispersion viscosities (viscosity of unneutralized carbomer in
water) (Table 8), giving them several important processing and/or costsaving
advantages. Unlike other carbomer resins, it is possible to prepare a very
concentrated dispersion stock solution. Pumpable concentrations as high as 5
wt % can be easily made, saving valuable production time and freeing up water
TABLE 7 Wetting Times for Some Carbomer Resins
Wetting time
Carbomer (min)
Carbopol 941 >50
Carbopol 940 >50
Carbopol 934 >50
Carbopol Ultrez 10 5
Carbopol ETD 2020 15

TABLE 8 Dispersion Viscosities for Some Carbomer Resins
Weight percent concentration of the resin
Carbomer 0.50 1.00 2.00 3.00 4.00
Carbopol 941 2,970 4,630 5,560 6,980 16,450
Carbopol 940 680 4,150 10,580 26,350 57,600
Carbopol 934 17 105 2,820 7,260 19,750
Carbopol Ultrez 10 7 9 41 164 1,130
Carbopol ETD 2020 17 108 740 3,410 7,010
Conditions: Units, mPa. s; Brookfield viscometer, 20 rpm; pH 2.53.5; temperature 23°C.
for use in other parts of the process. Additionally, because of the lower viscosity
concentrated Carbopol Ultrez 10 resin stock dispersions, foam created during th
of mixing will dissipate faster.
The low dispersion viscosity of high concentrations of the Carbopol ETD 2020 a
resins is primarily due to the enhanced particle behavior of these resins. These tw
thicken systems more because of their higher rigidity than because of their swellin
(see Section III.C.2). With other carbomer resins, the situation is exactly the reve
accounts for their higher dispersion viscosities.
C. Dispersion Techniques
Carbomer resins owe much of their exceptional utility to their hydrophilic nature
for water. These dry powder resins are highly hygroscopic and hydrate very rapi
added to water or polar solvents. Similar to other hygroscopic powders, carbom
clump or incompletely wet out when haphazardly dispersed into polar media. The
the wet agglomerates quickly solvate and form a tough exterior layer that prevent
wetting of the interior particle. When this occurs, the mixing time required to achi
hydration of each polymer particle is governed by the slow diffusion of the solven
solvated layer to the dry interior. This also will result in dispersion defects such as
texture, reduced viscosity, or the presence of partially wet agglomerates resembli
in the final product. Therefore, to avoid lengthy mixing times and to prepare high
reproducible carbomer resin dispersions, good dispersing techniques must be ap
The method by which a carbomer resin should be incorporated into a formulation
on a number of factors such as the carbomer type, quantity and concentration of
being prepared, type of process equipment available, and the formula compositio

1. Direct Batch Dispersions
Dispersions from 200 g to several thousand kilograms can be prepared by slowly
resin into the vortex of a rapidly stirred solution. To take advantage of the resin's
size, techniques or devices that sprinkle the powder as discrete particles are the
effective, for example, a coarse sieve or a noncorrosive 20 mesh screen (since th
form of the resin is acidic). The ideal method should efficiently sprinkle the resin a
controlled rate as well as break up the soft agglomerates of dry powder formed
electricity or humid conditions. This allows each particle to wet out in the water v
Agitation enhances the rate of solvation of the resin. In general, high shear rates d
resin very rapidly; however, extremely high shear mixers such as Waring Blendor
homogenizers should be employed carefully because they can break down the po
molecularly, resulting in permanent viscosity loss. Moderate agitation equipment i
preferred choice. The primary consideration is to incorporate the resin so that lar
wet agglomerates do not form. Orifices with an openblade impeller are the most
Conventional impellers such as propellers or turbines do not impart excessively hi
rates, and mucilages can be mixed for extended periods of time with virtually no
polymer efficiency [1].
Impeller type Comments
Cowles blade Not recommended due to high shear.
Paddle blade Frequently used when blending operations follow the initial
carbomer.
Threeblade marine Preferred choice for dispersing carbomer and making emulsi
Foddler impeller Poor mixing due to low shear.
Hi lift impeller High shear; use with caution.
When preparing dispersions with high carbomer resin concentrations and in mixin
with a large vessel heighttoimpeller diameter ratio, two impellers on one comm
recommended. The top impeller serves to rapidly disperse the resin before undes
partially hydrated lumps are formed, while the bottom blade provides dispersion i
The mixer should be positioned in the vessel so that a vortex of 1–1.5 impeller di
generated. It is also best to angle the impeller so that the dry resin will come in co
the impeller blades rather than the impeller shaft. Adjust the agitation speed and a
of the resin to avoid the formation of a continuous film of the dry resin on the surf
layer

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could lead to the formation of lumps of nonhydrated resin. Also, be sure to
scrape any resin from the sides of the beaker and impeller shaft throughout the
dispersion process. Continue the agitation for about 20 min or until a lumpfree
dispersion is attained.
Once a homogeneous dispersion is obtained, air entrapment (foaming) can be
avoided or minimized by eliminating or reducing the vortex. Elimination of the
vortex can be accomplished by repositioning the mixer. If the mixer cannot be
repositioned, the vortex can be reduced by decreasing the motor speed.
2. Large Quantity Batch Dispersions
An eductor or a flocullant disperser (Fig. 17) can quickly prepare batch
dispersion quantities of up to hundreds of liters with reduced dusting. Liquid
flows through the venturi of the eductor throat, causing an increase in the liquid
velocity and a decrease in pressure, the Bernoulli effect. This exerts a partial
vacuum on the powder inlet, pulling the particles of resin from the eductor
funnel or hose into the turbulent liquid stream. This process rapidly wets out the
resin and minimizes lumping. The resulting liquid polymer slurry is then directed
into an agitated mix tank. The flow of liquid is continued until the desired
solution concentration is reached. Note that an eductor that is capable of solid
particle dispersion must be used.
FIG. 17
Diagram of an eductor.

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3. Large Quantity Continuous Dispersions
A mechanical inline powder disperser can continuously produce large
quantities of resin dispersion [1]. Mechanical dispersers couple the principle of
a highvelocity eductor with the mechanical working configuration of an inline
homogenizer. Each polymer particle is instantaneously dispersed, wetted, and
expelled prior to swelling. This highly turbulent, highshear mixer operates at
such a rate that lump formation and polymer degradation from mechanical
shearing are eliminated. The valved powder hopper feed of the mechanical
disperser can significantly reduce the level of air entrapment or foaming.
Dispersed particles are expelled directly into a tank with low to moderate
agitation.
If inline mixers such as colloid mills or homogenizers are used, the resin should
be initially wetted out with moderate agitation. Therefore, mixing time using the
highshear mixers will be minimized. If a homogenizer is employed, strive to
use the lowest shear rate and the shortest mixing time to achieve a
homogeneous mixture.
4. Dispersing Resin in Nonpolar Liquids
The addition of the resin can be greatly simplified if the formulation contains a
solvent that does not swell the carbomer polymer. In a pure solvent or at high
solvent concentrations in water, the resin can be directly added with minimal
agitation. Concentrations of carbomer in solvent can reach as high as 10%
using this method. Note that if the resinsolvent slurry is to be added to water,
vigorous mixing should be used.
Premixing or wetting the resin with a nonpolar liquid (such as mineral oil,
mineral spirits, kerosene, or silicone oil) or low HLB nonionic surfactant is also
often an easy method of incorporating the powder. This is a preferred
technique for using carbomers to stabilize oilinwater emulsions [1]. For
example, the resin can be added directly into the oil phase with minimal
agitation. This mixture may then be added to the aqueous phase, or vice versa,
with vigorous mixing. In some cases, heated oils will plasticize the resins and
cause agglomeration. If this occurs, repeat the procedure at a reduced
temperature or add a separate, lowtemperature oilresin slurry to the
emulsion.
5. Other Dispersion Techniques
To reduce agitation and mixing time, carbomer resin can be initially dry
blended with other dry ingredients such as mineral fillers or abrasives. Doing so
separates the resin particles from each other so that they do not form a swollen
“skin” when exposed to water. The blend is usually freeflowing and free of
lumps if the polymer constitutes less than half of the total dry weight. Avoid
blending carbomer resin with polyvinylpyrrolidone (PVP), cellulosic polymers,
or other gums. These blends may give waterinsoluble complexes or may
prevent proper swelling of the resin.

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If a persistent foam is generated, it can be broken by partially collapsing the
resin with the addition of a very low level of a strong acid before neutralization.
This reduces the viscosity and yield value of the slurry and allows the
entrapped air to escape. HCI is effective at 0.5% of the weight of the resin. A
1.0% weight dispersion would require approximately 0.005 wt % or 50 ppm
HCI. This level of acid does not result in a significant contribution of salt when
neutralizing the resin and does not significantly affect the viscosity of the end
product.
It is best to use deionized water, distilled water, or deaerated tap water. If
fresh tap water is used, you may produce a cloudy gel due to the presence of
tiny air bubbles. The bubbles can actually be observed forming on the soft gel
clusters prior to neutralization. After neutralization, the bubbles are trapped by
the gel's yield value so that the only way to remove them is by centrifuge or
vacuum.
6. Dispersing Carbopol ETD, Ultrez, and EZ Resins
The development and commercialization of easier dispersing carbomer
technology has greatly improved the dispersibility of carbomer resins,
especially in water. These resins behave differently in their dispersion as well as
hydration rates (see Sections IV.A and IV.B) and need to be processed and
handled in a slightly different manner [57].
The appearance of these resins in water (before neutralization) is much
different from that of traditional resin dispersions. When a Carbopol ETD resin
is first added to nonagitating water, the powder begins absorbing water. Within
a few seconds, soft clusters of hydrated resin begin to settle to the bottom of
the vessel. Within several minutes, all of the dry powder particles will wet out,
and most of the polymer will be below the surface in the form of these clusters.
The total wetting time is dependent upon the amount of resin added, vessel
geometry, and, most important, water temperature. Unlike traditional resins,
Carbopol ETD resins can be dispersed more quickly by increasing the
temperature of the water to which they are added (Fig. 18).
In fullscale production, a Carbopol ETD resin may be added to water by any
of the following techniques.
1. No Agitation. The resin can be added onto the surface of the water without
any agitation. The powder will wet out without lumping.
2. Moderate Agitation. In this case, a steep vortex pulls powder from the
water surface into the agitator blades. Large quantities of Carbopol ETD resin
can be quickly dispersed by such equipment without lumping. In production,
control the mixing time from batch to batch, as long periods of highshear
mixing can lower the final product viscosity. Note that under highshear
agitation, dispersions of Carbopol ETD resins can foam if

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FIG. 18
Carbopol Ultrez 10 wetting time as a
function of temperature (1 gm dropped
into 200 ml of water at rest).
quantities of air are entrained. Low levels of an antifoaming agent can be added
to the water prior to the addition of the resin to minimize or eliminate foaming.
3. Mild Mixing. In this mixing scenario, a very shallow vortex is created, but
the powder is not pulled into the agitator blades. Instead, the powder is
trapped in one mass at the water surface and coagulates around the agitator
shaft. Dispersing a Carbopol ETD resin under these mixing conditions could
result in lump formation. For best results, scatter the Carbopol ETD powder
onto the water surface over several minutes while mixing, using a small scoop.
Although the Carbopol ETD resins wet at a much faster rate than other resins,
they have been found to have a slower rate of hydration. This may manifest
itself as a lower initial viscosity, higher formulation texture and graininess, and,
in some high ionic systems, a lower final viscosity. To avoid these potential
issues, a partial neutralization of the mucilage to pH 3.5–4.0 has been found to
be of great benefit. The gel clusters will then relax, and the viscosity will build
slightly while other ingredients are being added.

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D. Formulating with Carbomer Resins
Among the myriad of detergent formulations and types, detergent formulations
can be grouped into three categories:
1. Aqueous systems
2. Polar solvent and nonaqueous systems
3. Liquid emulsion systems
The performance and role of carbomer resins in each of these matrices is very
different. Additionally, the method of incorporating the resin into the final
formulation can be quite different. Some general guidelines are provided
below; note that some formulations may require different processing methods.
1. Aqueous Systems
In aqueous systems, the best method to achieve the maximum thickening and
suspending properties of carbomer resins is to neutralize the resin with an
inorganic base (metal hydroxide) or an organic base (low molecular weight
amines) before adding the other raw materials. This procedure is quite
common and can be used for a wide variety of detergent formulations such as
automatic dishwashing gels, abrasive cleaners, and laundry prespotters [20].
Procedure 1A
1. Disperse the resin into all of the available formulation water. Concentrations
of carbomer resin in water can be as high as 6–7% with certain resins.
2. Using moderate agitation (avoid vortex formation), add the neutralizing agent
(s) and/or any other high pH or alkaline materials (silicates, etc.). Thickening
will occur immediately.
3. Continue moderate agitation and add in any insoluble materials that require
suspension (such as phosphates, zeolites, carbonates, and abrasives). Heating
and the selective use of some high shear mixing may be required during this
step to achieve the complete dispersion hydration of some materials (especially
phosphates).
4. Under low agitation, add in any surfactants and/or other minor components.
5. Under low agitation, add in any oxidizing agents (chlorine bleach, hydrogen
peroxide) followed by any aesthetics.
This procedure is very straightforward and has three major advantages: (1)
The process can be completed in one mixing vessel, (2) elaborate mixing or
processing equipment is not required, and (3) the insoluble materials are added
to the formulation after the polymer has been neutralized, when the formulation

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has a high enough yield value to be able to suspend these particles. However,
there are two major drawbacks or limitations of this procedure. First, the
viscosity at step 2 may reach a level higher than that of the final formulation,
requiring the use of a higher horsepower motor. This is due to the ionic strength
profile during the batch cycle. The formula will reach its maximum viscosity
with the addition of the first alkaline material. With the subsequent addition of
more alkaline materials, the ionic strength will continue to increase and result in
a gradual reduction in the volume of each microgel, resulting in a lowering of
the product viscosity. Second, after neutralization, the polymer can be
subjected to high shear rates, which can reduce its efficiency. Nonetheless, this
is the most frequently used procedure for product formulations with
carbomers.
A variation on Procedure 1A is to vary the addition point of the carbomer
slurry [58,59].
Procedure 1B
1. Using the abovementioned procedures, create a 5–6 wt % dispersion of
the resin in water.
2. With the remaining water, formulate a “premix” of carefully selected raw
materials, usually composed of the neutralizing agents and any other high pH or
alkaline materials.
3. Add the polymer slurry to the premix by either (a) slowly adding the
polymer slurry to the premix under moderate to high agitation or (b)
simultaneously combining the polymer slurry and premix through a static mixer
(or another type of singlepass, inline high shear mixer) and into an agitated
third vessel.
4. Under low agitation, add in any surfactants, minor components, oxidizing
agents, and aesthetics.
The use of this procedure addresses the two major deficiencies of Procedure
1A. First, temporary high viscosities are avoided as the carbomer microgels
are neutralized at their final product ionic strength. Second, the amount of high
shear the polymer is subjected to after neutralization is minimized, especially if
an inline static mixer is employed. The drawback of this procedure is the
requirement for more, and more complex, processing equipment. The use of
two vessels is required if the polymer slurry is created in one vessel and then
added to another vessel containing the premix. Three vessels are required if the
polymer slurry and premix are created in separate vessels and combined
through a static mixer into a third vessel. Additionally, since the premix does
not contain any carbomer resin, any insolubles will settle to the bottom of the
premix vessel if it is left unagitated.
A third variation on this method is to first dry blend the carbomer resin with
another one of the powder raw materials in the formula.

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Procedure 1C
1. Dry blend the carbomer resin with another powder raw material (i.e., an
abrasive, noting the recommended procedure and limitations described earlier).
2. Disperse this powder blend into all or some of the water, using the above
mentioned procedures.
3. Proceed using either Procedure 1A or 1B by (a) sequentially adding the
remaining raw materials (starting with the high pH and high alkaline materials)
to the polymer slurry created in step 2 or (b) creating a premix of the
remainder of the water and selected raw materials—add the polymer slurry of
step 2 to this premix using the procedures described in 1B.
4. Under low agitation, add in any surfactants, minor components, oxidizing
agents, and aesthetics.
The primary advantage of this method is to improve the initial dispersibility of
the carbomer resin into the water phase. This procedure does require the use
of more complex processing equipment to perform the initial dry powder
blending step.
2. Polar Solvent and Nonaqueous Systems
Polar and some nonpolar solvents can be thickened with neutralized carbomer
resins. Key in this procedure is the selection of an appropriate amine to form a
solventsoluble salt of the resin. The amine salt must be soluble in the solvent
system; if not, the carbomer salt will precipitate and no thickening will occur.
The theory governing solvent thickening is complex and is based on matching
solubility parameters, hydrogen bonding, and dipole moment properties of the
solvent and the solute [57,60,61]. Less polar or nonpolar solvents may be
thickened by neutralizing the carbomer resin with a longchain nonpolar amine
that is soluble in the solvent. An alternative approach is to modify the solvent
system by adding 5–25% of a more polar solvent that is miscible with the
major solvent. This enables the use of a more polar amine or, in some cases,
inorganic bases.
Procedure 2A: Nonaqueous Thickening with Neutralization
1. If there are more than two solvents, disperse the carbomer resin in the least
polar solvent.
2. Add the amine to the most polar solvent.
3. With moderate agitation, add the carbomer resin (or carbomer dispersion if
more than two solvents are used) to the solventamine premix.
4. Continue mixing until the mucilage is uniform.
This method can be used to thicken a wide variety of solvents for a wide
variety of detergent applications. For example, ethanol can be thickened for
use

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as a solid fuel or as a handsanitizing gel. Mineral spirits can be thickened via a
blend with methanol for use as a hand cleaner [60].
There are two mechanisms that govern the mechanism of carbomer properties.
The predominant one for most formulations is the use of neutralization to
achieve ionization of the carboxyl groups and swell the microgel structure
through ionic repulsion. A second thickening mechanism involves the use of a
hydroxyl donor in conjunction with a carbomer resin. The combination of the
hydroxyl compound(s) and the carboxyl groups on the carbomer will result in
thickening through the formation of hydrogen bonds. To thicken polar solvents
without neutralization in an aqueous or nonaqueous matrix, the following
procedure can be used.
Procedure 2B: Nonaqueous Hydrogen Bonding
1. Combine the hydroxyl donor(s) and any water.
2. Slowly disperse the carbomer resin into this solution using the techniques
described above.
3. Continue stirring until thickening occurs; heating to 70°C usually hastens this
process.
4. Cool product to room temperature.
5. Add in remaining materials (surfactants, builders, dispersants, aesthetics,
etc.).
This method can be used to thicken a wide variety of materials for a wide
variety of detergent applications. For example, organic acids (citric, acetic,
hydroxyacetic acids) can be thickened using this mechanism for use in bathtub
and tile detergent applications. Nonaqueous formulations using a low molecular
weight glycol carrier can be thickened and used to suspend builders,
surfactants, enzymes, and peroxygen bleach (perborate, percarbonate) for
laundry and automatic dishwashing gels.
3. Liquid Emulsion Products
Carbomer resins can act as emulsifiers and emulsion stabilizers in oilinwater
emulsions and as emulsion stabilizers in waterinoil emulsions. The resin can
function as emulsifiers via dual neutralization with an inorganic base and an oil
soluble amine. This sets up a bridge between the oil phase and the water phase
by forming salts soluble in both phases. The portion of the molecule neutralized
with the inorganic base is soluble in the water phase, and the portion
neutralized with the amine is soluble in the oil phase. The bridging of both
phases forms an emulsion with excellent chemical and physical stability. When
carbomer resins are neutralized with an inorganic base or an amine, they impart
viscosity and yield value to the water phase of an emulsion. The oilinwater
emulsion is then stabilized because the yield value permanently suspends

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the oil droplets. Carbomer resins build viscosity in oilinwater emulsions by
thickening the continuous phase.
Carbomer resins can be used to stabilize emulsions in a number of detergent
applications. Several oils can be emulsified in water to be used in such
applications as hand cleaners and solvent degreasers (such as dlimonene and
mineral spirits).
There are two methods to produce stable waterbased emulsions using
carbomer resins: direct and indirect. In the direct method, the polymer is added
carefully to the water phase.
Procedure 3A
1. Disperse the carbomer into the water, following the above
recommendations.
2. Add all other waterphase ingredients.
3. Combine all oils and slowly add to the polymer slurry with rapid mixing.
4. Neutralize using an inorganic acid and/or an amine.
5. Controlled homogenization may be useful, but emulsion instability could
result from prolonged exposure to a high shear rate.
Emulsions prepared in this manner result in large oil droplets, which in some
oils causes instability. In these instances, the particle size of the oil droplets can
be reduced using ~0.5% of a nonionic surfactant containing aromatic groups
such as nonylphenoxypolyethyleneoxy. The surfactant can be added as a
separate phase at step 3 or combined originally in the oil phase.
In the indirect method, the polymer is first added to the oil phase. The
advantage of this approach is that the polymer will disperse easily in this non
swelling medium. In some cases, however, this method is less successful for
creating stable emulsions, especially when the carbomer resin begins swelling in
the oil phase after several minutes or has poor dispersibility in the oil phase.
Procedure 3B
1. Disperse the carbomer resin in the oil phase; continue mixing until a smooth
and homogeneous dispersion n obtained.
2. Under vigorous agitation, add the oil phase to the water phase.
3. Any nonionic surfactant required can be added at this point.
4. Add a suitable amount of an appropriate neutralizing base.
5. Continue mixing until the desired emulsion consistency is achieved.
E. Stability Evaluations
It has been said that the first purchase of a product is achieved through
marketing and advertising; subsequent purchases are made as a result of
product
5. Continue mixing until the desired emulsion consistency is achieved.
E. Stability Evaluations
It has been said that the first purchase of a product is achieved through
marketing and advertising; subsequent purchases are made as a result of
product

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performance. However, not only does the product have to meet its cleaning
performance targets, but also the product must be delivered to the consumer in
the same product form and consistency with the same level of actives
regardless of the product age or its storage history. Product that is separated
into many phases (on a macroscopic or microscopic level) will decrease
product performance, drive consumer dissatisfaction, erode consumer
confidence and brand loyalty, create potential safety issues during product
usage, and result in major expense to the formulator if a product recall is
required.
The determination and assessment of the physical stability of a formulation is
very timeintensive and, overall, a very subjective and inexact science.
Consumer products can be exposed to static temperatures from below 0°C to
over 50°C for varying lengths of time but most often with extreme temperature
cycles (i.e., freezing at night to warm in the day to refreezing at night). The goal
of the R&D formulator becomes one of trying to predict a product's stability
profile in the trade without having to conduct a fullscale trade stability study,
as the latter is very costly and consumes vast amounts of time. The formulator
must attempt to duplicate or imitate every possible temperature and storage
condition in a laboratory setting that the product will observe in the trade, and
in a short period of time.
Many different stability test designs and methods have been developed to
decrease the complexity and streamline this required phase in a product
formulation cycle.
1. Visual Inspection
Upon initial observation of a formula, most skilled formulators can ascertain
and observe signs of impending instability. Such observations as incomplete
dispersion and suspension of particulates, immediate formation of a surface
layer, and product striations throughout the bulk can be made by the
formulator. The skill and experience of the formulator play a large role in
observing instability issues at this point in the product's life.
A relatively quick and easy method to assess stability, especially that of an
emulsion, is to analyze a portion of the product under a microscope. A wide
range in the size of the particles is a good indication of potential instability. The
more uniform the particle size, the more stable an emulsion. Also, the smaller
the particle size, the more stable the emulsion. These observations can be
made both on “fresh product” and on product that has been allowed to age
under various temperature profiles.
2. Static Temperature Testing
The majority of formulators will employ some base level of static temperature
testing and usually several freezethaw cycles. This is the formulators' closest
tool to imitating realworld conditions. As a first step, the formulator needs

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to determine the temperature range that the product will be exposed to in the
trade. This can easily be obtained for the geographies that the product will be
sold in through the use of various weather reporting services. Product should
then be placed into containers and stored at temperatures throughout this
range, ideally at 10°C intervals from the product's freezing point to the
maximum trade temperature.
Ideally, the product should be stored in its final trade package to eliminate or
pick up any packaging incompatibilities with any of the raw materials in the
formulation. If the package container is clear, the stability testing should be
conducted in lighting conditions similar to those encountered in the trade to
explore and examine any instability issues due to UV light. In order to best
conduct visual observations on the product, it is best to have clear packaging
containers. This will enable observations to be made without having to pour the
product out of the container. Pouring the product out of one container and into
another results in the product being remixed (potentially eliminating any signs of
instability), exposed to the air, and potentially contaminated. Therefore, it is
best to conduct stability testing in clear containers (with and without UV
exposure) as well as in their final opaque container. Also, the product should
be placed in the container with as little headspace as possible. The water in the
product may evaporate and recondense, forming a liquid layer on the surface
that may be mistakeningly identified as a broken emulsion or phase separation.
There are numerous tests that can be conducted on aged product. Of foremost
importance is a visual observation of the product. The stability tester should
observe the product for phase separations, crystal growth, precipitation,
flocculation, color and clarity, rheology, form transitions (i.e., liquid to gel), etc.
If viscosity stability over time is a concern or observed to be an issue
(especially with products containing chlorine bleach), several samples should
be placed in testing. One of the samples can then be taken from the test for
rheological analysis without creating the problems of sampling out of a bulk
storage container. If the stability of key actives (bleach, enzymes, perfume,
dyes, pigments, etc.) is a potential issue, then the sample for rheology testing
could also be used to analyze for the percent retained activity of these
materials.
The frequency of observations is an important consideration and variable. The
product ideally should be observed on a weekly basis for the first 2 months,
followed by biweekly observations until the sixth month, and then on a monthly
basis thereafter. This protocol will allow the tester to observe any extreme
changes in stability that will usually occur within the first few weeks and build
up a history of and familiarity with the product for those changes that occur
only over a prolonged period of time.
An advantage that a liquid formulation has over its powder/granule equivalents
in the realm of stability testing is that humidity is not a factor that needs

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to be assessed, because most liquids are stored in tightly closed plastic
containers. However, the formulator may want to assess the effect on product
stability of a cap that is not placed tightly back on the bottle or in the correct
manner.
In terms of using static stability testing to predict trade life stability, the
generally accepted rule of thumb is that 1 month at 50°C is generally equal to
1–2 years of shelf life.
3. Cycle Temperature Cycling
Since it is unrealistic to assume that a product in the trade will be subjected to
only a static temperature, the use of temperature cycling has become a vital
supplement to static stability testing. The purpose of the cycling is to evaluate
the effect of alternating temperatures on the product stability, especially the
formation of crystals in lowtemperature cycling and supersaturation in elevated
temperature cycling.
Lowtemperature cycling is most commonly performed—especially freeze—
thaw cycling. In lowtemperature cycling, the product is allowed to freeze at
least two different temperatures: at the product's freeze point and at a
temperature significantly below this temperature. The use of both a slow and a
rapid freeze will examine two different types of stresses on the system causing
the formation of different types and structures of crystals. The product is
allowed to freeze at this temperature for either a prescribed duration of time
(e.g., 8 h) or until the product is completely frozen (which could be 2–3 days
at the product's actual freezing point). The product is then cycled to a warmer
temperature. This temperature is usually room temperature (25°C) but can be
just slightly above the freezing point, or gradually warmed to room
temperature, or at a very elevated temperature (e.g., 40°C). After the product
has “thawed,” it is placed again at the colder temperature and the cycle is
repeated, usually for three to five cycles. Observations are made at each
temperature, and the time required for the product to regain its flow
characteristics is recorded.
The use of carbomer resins in detergent formulations provides a definite
advantage in terms of freezethaw stability. The volume of the carbomer
microgel is not very sensitive to changes in temperature over the temperature
range that most detergent products experience in the trade. Because the
microgel's volume remains constant, there is little change in product viscosity as
a function of temperature (Fig. 19). The yield value provided by the carbomer
microgel structure also serves to keep any developing crystals isolated so that
large networks will not be formed. This could be thought of as inhibiting or
prohibiting crystal growth.
Elevated temperature cycling is the reverse of the above. Here the product is
exposed to elevated storage temperatures for a prescribed period of time and

Page 173
FIG. 19
Viscosity versus temperature for carbomer resins
(neutralized to pH 7 with sodium hydroxide).
then cycled back to room temperature. Three to five cycles are normally
performed with observations at each temperature.
Again, the purpose of the static temperature and temperature cycling is to
attempt to imitate the conditions that the product will be exposed to in the
trade and observe how the product responds to these conditions. However,
this testing is timeconsuming due to the quantity of product required and the
resources required to monitor the stability on a periodic basis. In an attempt to
reduce these resource and time constraints, much research has been devoted
to finding other ways to predict longterm storage stability.
4. Centrifugation
The use of a centrifuge to separate a product into density layers, remove
entrapped air, force precipitation for various analytical techniques, etc., is well
known and widely practiced. This technique has therefore been used to help
determine the stability of a product, especially high solids suspensions and
emulsions. The principle is to increase the gravitational force on any suspended
particles to accelerate instability. If the product does not separate or
precipitate when subjected to the applied centrifugal force, it is more likely to
be phasestable. The selection of the amount of centrifugal force and the time
of application of this force is critical. Virtually all suspended solids will
eventually precipitate at high centrifugal forces. The best correlations of the use
of centrifugation with actual product instability have been found at a speed of
500

Page 174
rpm for 5 min. Additionally, the results of this test are usually used as a tool to
screen for instability rather than stability. If the product separates or
precipitates, the product will most likely not be stable over time. However, if
the product passes this test, it is not a guarantee of stability. Therefore, this tool
becomes very useful to rapidly screen several samples prior to placing them in
a large temperature stability test.
5. Rheological Testing
The use of rheological tools to indicate and predict instability has become
increasingly of interest to R&D formulators. Reboa and Fryan [62] presented a
paper on the use of dynamic and oscillatory testing to predict the physical
stability of concentrated dispersions containing particulates. The advantage in
oscillatory testing versus other rotary rheological testing is the fact that this test
does not lead to structural breakdown by forcing particles to flow past each
other. This rheological testing probes the atrest structure of the matrix without
breaking it as in conventional shear viscometry.
This method is composed of two parts. First, a strain sweep test (vary dynamic
strain level at a constant frequency) is performed to determine the linear
viscoelastic region. Second, a frequency scan is performed in the viscoelastic
region over a temperature range. These two tests generate the elastic (G') and
viscous (G'') moduli of the product. Plotting the ratio of the elastic to viscous
moduli (G'/G'') as a function of frequency and temperature generates a three
dimensional surface that is a fingerprint of the dispersion's colloidal stability. To
suspend solid particles, G' must be greater than G " or sedimentation will
occur. Therefore, plotting the response of this ratio as a function of frequency
and temperature will give an indication as to the stability and robustness of the
formulation to various stresses.
Acknowledgments
We thank John J. Kovacs for much of the original experimental data reported
in this chapter. We also thank The BFGoodrich Company, Cleveland, Ohio,
for encouragement, support, and permission to publish this material.
References
1. Carbopol—High performance polymers for detergents; (Detergent
Technical Binder) The BFGoodrich Company, Specialty Chemicals,
Cleveland, OH.
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Corporation (1979).
3. W. G. Bush and V. D. Braun, U.S. Patent 4,226,736 to The Drackett
Company (1980).

Page 175
4. S. Gabriel and B. J. Roselle, U.S. Patent 4,859,358 to The Procter &
5. R. J. Koring, M. Goedhart, S. P. Christiano, K. J. Krupa, and H. S.
Kielman, Eur. Patent Appl. 407187, to Unilever NV (1990).
6. D. L. Elliot and L. A. Kiefer, U.S. Patent 4,867,879 to Lever Brothers
Company (1989).
7. N. Dixit, M. Shevade, and R. Round, U.S. Patent 5,053,158 to Colgate
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6
Nonaqueous Surfactant Systems
MARIE SJÖBERG and TORBJÖRN WÄRNHEIM*
Institute for Surface Chemistry, Stockholm, Sweden
I. Introduction
II. Micellar Aggregation
III. Concentrated Surfactant Systems
A. Liquid crystals
B. Microemulsions
IV. Concluding Remarks
V. Nomenclature
References
I. Introduction
The interest in studying surfactant aggregation in polar solvents other than water h
quite recently; indeed, much of the advances in the field are less than 10 years ol
majority of have been published during the last years.
The research can be motivated, mainly, by two different types of arguments. First
consideration of amphiphile aggregation, such as a description of the hydrophobi
leading to micelle and liquid crystal formation, for example. What can be learned
comparing water with other po
*
Current affiliation: Pharmacia & Upjohn, Stockholm, Sweden.

Page 180
lar solvents? Much work has been performed to elucidate the properties of the
solvent that are essential to obtain a hydrophobic (or “solvophobic”)
interaction. Comparisons of critical micelle concentrations in different solvents
with parameters characterizing the solvent are numerous in the literature [1,2].
Second, there are technical applications in which amphiphile aggregates and
structures are needed to promote a specific effect but circumstances may
prevent the particular use of water because of certain reactions, corrosion
problems, and so on. Of particular interest in this context are alcoholbased
systems for cleaning purposes [3]; another interesting area is chemical reaction
in an aprotic solvent, such as formamide [4–6].
This review deals with the first, fundamental point, in particular the formation of
micelles and the mapping of phase equilibria. This is a logical starting point,
because a prerequisite for most applied work is some knowledge of the
relevant phase diagrams.
Methodological questions have often been raised when studying nonaqueous
systems: many early studies on micellization were performed using indirect
methods for detecting aggregation [7–10]. This has caused considerable
confusion as a result of apparently irreconcilable results. Also, recently, several
studies have pointed out the difference between a proper micellization process
and ordinary aggregation. As discussed later, depending on combination of
solvent and surfactant [11–14], it is possible to have a cooperative aggregation
(micelle formation) as well as a more gradual aggregation process.
II. Micellar Aggregation
Micellization has long been studied in a large number of nonaqueous polar
solvents, such as different alcohols, formamide, fused salts [15,16], hydrazine,
and hydrogen fluoride [17]. However, most early investigations used indirect
methods for the detection of surfactant aggregation. Not until recently have
studies more directly, using, for example, nuclear magnetic resonance (NMR)
relaxation rate measurements (Fig. 1), proved the existence of aggregates in
the solution phase of polar solvents other than water.
Hydrazine is a solvent that has many properties similar to water. Studies of
surfactant aggregation in hydrazine have shown that the free energy G for the
micellization of sodium alkylsulfates is close to that of water [18]. The enthalpic
and entropic contribution's H and S, however, are very different in these
two solvents: in water, the entropic contribution favors aggregation; in
hydrazine, the enthalpic contribution predominates. The conventional view of
the micellization process in water, often stated as if the structural properties of
water would be necessary to obtain a driving force for aggregation, was
challenged. It was concluded that the structure of water was not determining
the aggregation process [18].

Page 181
Fig. 1
2
HNMR frequency variable relaxation rate
measurements in the system deuterated
C16TABrsolvent. (a) MFA show no variation of
the relaxation rate with frequency, suggesting no
slow (aggregate) motions of the surfactant. In
contrast, the data from (b) FA and (c) EG show a
clear frequency dependence. A fit of the relaxation
data to a motional model suggests similar micellar
radii in FA and EG, around 14 Å, in contrast to
approximately 20 Å in water. (From Ref. 14.)

Page 182
The nonaqueous polar solvent that has been studied most extensively in this
context is probably formamide. Lattes et al. have thoroughly studied the
aggregation of surfactants in formamide [19–22]. They started by observing
the aggregation of longchain phosphonium salts in formamide and found the
critical micelle concentration (CMC) to decrease with increasing chain length,
as anticipated [19]. They have also investigated the sodium dodecyl sulfate
(SDS)formamide and the C16TABrformamide systems. A sharp rise in
solubility of the surfactant with increasing temperature was noted in these
systems and was interpreted as a Krafft point, that is, the temperature at which
the monomeric solubility of the surfactant exceeds the CMC. The CMC as
well as the Krafft point for both surfactants was found to be considerably
higher in formamide than in water. They noted that other studies of surfactant
aggregation in formamide, in which aggregates were not found, have been
performed at temperatures below the Krafft point [23–25].
The C16TABrformamide system has been widely studied with a number of
different techniques, such as NMR relaxation and selfdiffusion [14,22,26,27],
xray smallangle scattering [21], positron annihilation [25], or Raman
spectroscopy [28]. Most studies agree that aggregates start to form at
considerably higher surfactant concentration than in water and that they are
considerably smaller than in water. An aggregate radius of 9 Å was found at a
concentration close to the CMC [21] and it was found to be ~ 15 Å at five
times the CMC [14]. This corresponds to an aggregation number of
approximately onethird that in water. An aggregate growth with concentration
has been verified both in a study of solvent binding to aggregates [26] and in a
study of conterion binding [27]. An increase in micellar size with increasing
surfactant concentration was also found in the SDSformamide system [29].
An investigation of counterion binding of a cationic surfactant, C16TAF, in
formamide, ethylene glycol, and water showed that the degree of counterion
binding is very different in the different solvents, depending on the dielectric
constant of the solvent [27]: high in water and ethylene glycol but lower in
formamide. Calculations confirmed that the effects of the dielectric constant
(Table 1) could account for this trend [27]. This observation supports the
study of BinanaLimbele [11], who found the micelles to be small and highly
ionized in formamide and therefore not suitable for conductivity investigations.
Micelles of cationic surfactants have been found to form both in glycerol [30]
and in ethylene glycol [14]. The micelle formation of C16PyBr in ethylene glycol
and glycerol was studied with surfactantselective electrodes [31]. The
monomer concentration could in this way be measured at different total
surfactant concentrations, and it was concluded that there is some premicellar
aggregation and that the CMC is not very well defined. The dissociation of
C16PyBr micelles in mixtures of water and ethylene glycol has been studied,
and it was

Page 1
TABLE 1 Interfacial Tension Between Solvent and Hydrocarbon and Dielectric Constant
for the Solvent
Solvent Interfacial tension Dielectric

(mN/m)a constant
Water 50b 78
Glycerol 29.7c 42
Formamide 27.3c 109
Ethylene glycol 17.2c 37
Nmethylformamide 12.5c 182
a
At 20°C.
b
Against hexadecane.
c
Against dodecane.
Source: Ref. 56.
concluded that the degree of counterion association decreases with increasing
amount of ethylene glycol in the solvent [32]. This is consistent with earlier
estimations of the counterion binding in the waterethylene glycol system, where
conductivity measurements suggested a decrease in counterion association when
ethylene glycol was added to the water [58].
The solvent Nmethylsydnone have some interesting features; it has a high cohesi
energy but is not hydrogen bonding. The results from this system are to some
extent contradictory. Evans et al. found no aggregates of C16PyBr using a number
of different techniques [33], but Auvray et al. found aggregates in the solution
phase of the C16PyBrNmethylsydnone system using smallangle xray scattering
[34].
Aggregation of nonionic surfactants in these nonaqueous solvents could, in
principle, be more energetically favorable than for ionic surfactants because, at
least in water, the repulsive interaction between the polar head groups is smaller.
The CMC of different polyethylene glycol alkyl ethers (CiEj ) has been determine
in different nonaqueous solvents [13,35–38]. Different CiEj formamide systems
have been investigated using NMR selfdiffusion [13]. Micelles formed but were
concluded to be smaller than in water. In contrast to what is found in water, no
micellar growth occur at high temperatures, at high surfactant concentration, or
when approaching the lower consolute temperature. The same systems were late
examined in a calorimetric study [12], and it was found that the enthalpies of
micelle formation of CiEj in formamide are much smaller and not as temperature
dependent as in water. The aggregation numbers were found to be smaller, and f
the C12Ej surfactants, the smooth titration curves indi

Page 184
cate that the micelle formation extends over a significant concentration region
[12].
The kinetics of micelle formation of nonionic surfactants in formamide has been
studied using ultrasonic relaxation measurements. The data were consistent
with a multistep bimolecular scheme of the type previously used for ionic
surfactants in water, and polydispersity of the micelles and rate constants for
the equilibrium could be obtained [39]. The results showed that the
polydispersity decreases with increasing alkyl chain length, and the association
of a monomer to the micelle was found to be diffusion controlled, in line with
earlier findings for ionic surfactants in water.
The aggregation of fluorinated surfactants in nonaqueous solvents has also been
studied. These surfactants form aggregates at lower concentrations than
ordinary hydrogenated surfactants in water. Chrisment et al. studied nonionic
fluoroalkyl lipopeptides in DMSO and found progressive and very limited
aggregation in this solvent [40]. In addition, the lithium salt of nonadecafluoro
decanoic acid has been studied with 19FNMR in formamide, N
methylformamide, and ethylene glycol [41].
It is evident from all these investigations that micelles are formed in non
aqueous, polar solvents but that the aggregates, comparing the same surfactant,
are generally smaller than in water. Small micelles, with a large part of the
hydrocarbon chain of the surfactant in contact with the solvent, are very
unfavorable in water because the interfacial tension between water and
hydrocarbon is high; the contact area between the solvent and the hydrocarbon
chain of the surfactant must consequently be minimized. In the nonaqueous
solvents investigated the interfacial tension between solvent and hydrocarbon is
smaller (Table 1) and smaller aggregates are thus less energetically unfavorable
from this point of view.
III. Concentrated Surfactant Systems
A. Liquid Crystals
The first report of a nonaqueous lyotropic liquid crystal in a polar solvent
appeared in 1979, in which Friberg and coworkers revealed the existence of a
lamellar (D) phase in the lecithin (dialkylphosphatidylcholine)ethylene glycol
system [42]. In a series of papers, a large number of lecithindiol systems have
been characterized, and detailed structural properties of the systems have been
elucidated [43–50].
The interlayer distance in the D phase with ethylene glycol, is shorter than in
water, indicating an enhanced disorder in the lipid layers [42]. It was suggested
that the primary solvation shell of the phosphatidylcholine group contains one
bound solvent molecule per polar head group, with several more

Page 185
loosely associated as determined by 2HNMR measurements [43,45]. The
similarities to interactions in the aqueous systems have been probed by
comparative NMR measurements [45]. 1H and 31PNMR were employed to
determine qualitatively the dynamics of the acyl chain and the polar head group
[46]. It has also been noted that the D phase under certain conditions may
align in the magnetic field of the NMR [47].
Extensive phase studies reveal that lecithin readily form D phases with the
homologous series of , diols, from ethylene glycol up to 1,7heptanediol,
although the swelling decreases with increasing molecular size of the solvent
[44].
Oligomers and polymers of ethylene oxide [48], and polyethylene glycol alkyl
ether also form D phases with lecithin, the latter as mixed lamellae containing
the acyl part of the lecithin and the alkyl chain of the ethers [49]. Solubilization
of alcohols and hydrocarbons in the D phase formed with ethylene glycol has
been studied [50].
The similarity of the interactions in the aqueous and the ethylene glycol systems,
respectively, is emphasized by forcedistance curves derived from osmotic
pressure measurements, which are similar for lecithin bilayers in water and
ethylene glycol [51].
The existence of lamellar phases with lecithin has also been demonstrated for
ethylammonium nitrate [52]. For lecithin and formamide, Nmethylformamide,
or N,Ndimethyl formamide, respectively, full phase diagrams have been
determined [53] showing a gradual disappearance of liquid crystalline phases
with increasing methylation of the solvent (Fig. 2). The lamellar phase is stable
with Nmethylformamide but disappears with N,Ndimethylformamide.
To summarize, lecithin studies give a quite complete picture of how the solvent
affects the phase behavior of a zwitterionic surfactant with a large hydrophobic
moiety. Lecithin forms lamellar lyotropic liquid crystals with a wide variety of
solvents; a sufficiently hydrophilic solvent—and indeed even amphiphilic
compounds with a hydrophilic moiety—stabilizes lamellar phases. The
mechanism for stabilization of the lamellar phase in aqueous zwitterionic
systems is still controversial, however, leading to difficulties in pursuing the
theoretical interpretation.
Full and partial phase equilibria have been determined in a large number of
systems with ionic surfactants, and there are numerous combinations of
surfactant and solvent that form liquid crystals.
The first report of a liquid crystal formed in a binary system containing a single
alkylchain ionic surfactant dealt with the C16TABrformamide system.
C16TABr forms a hexagonal and a lamellar phase in formamide, in analogy to
the aqueous system [54]. Later, the formation of a cubic phase between the E
and D phases was reported [55,56]. The phase diagram has been revised
[56,57], and there is now a consensus that the phase sequence is E I D

Fig. 2
Phase diagrams of dioleyllecithin and (a) water, (b) formamide, (c) methylforma
dimethylformamide. (From Ref. 53.)

Page 187
(with increasing concentrations of surfactant) and that the liquid crystals form at
higher temperatures and melt at lower temperatures than in water. C16TABr
and the homologous series of alkyltrimethylammonium bromide have been
extensively characterized (Fig. 3), and there are reports of liquid crystals
formed in glycerol [56], ethylene glycol [56], and mixtures of ethylene glycol
and water [58], as well as in Nmethylsydnone [59]. Also, xray scattering
techniques have been used to probe in more detail the structures of the cubic
phases in formamide systems [57].
An extensive comparison between the aggregation of C16TABr and C16PyBr in
a series of solvents, formamide, Nmethylformamide, N,Ndimethyl
Fig. 3
Phase diagrams of C16TABr and different solvents: (a) water, (b) glycerol,
(c) formamide, (d) ethylene glycol, and (e) methylformamide. For notations,
see Sec. V. (From Refs. 55 and 56.)

Page 188
formamide, glycerol, ethylene glycol, or Nmethylsydnone, revealed some
interesting differences between the surfactants. With formamide, ethylene
glycol, and glycerol, the phase sequence was E I D for both surfactants,
and with N,Ndimethylformamide, the least polar solvent, only D phases
formed. However, only C16PyBr showed the sequence E I D with N
methylformamide and Nmethylsydnone [59].
Thus, in general, if liquid crystals form, the phase sequence for an ionic
surfactant in water, L I E I D with increasing surfactant
concentration, is also followed in other polar solvents. (This overall picture
does not give a detailed accurate representation of either aqueous or
nonaqueous systems [59,60] but accounts for most available observations.) In
systems in which the forces promoting amphiphile association are weaker,
there still may occur a lamellar phase at a very high concentration of surfactant.
It should be noted that this bilayer packing resembles the fully crystalline lattice
of a nonsolvated ionic surfactant [61], suggesting that a low concentration of
ionic surfactant in a particular solvent may be misleading if taken as a more
absolute sign that the solvent promotes surfactant association.
Considering solely the phase diagram, the main effects of exchanging water for
another more weakly polar solvent in these systems is to decrease their
existence regions. In addition, there are also more subtle phenomena in
nonaqueous systems. It has been demonstrated that for alkylpyridinium
chlorides and bromides in glycerol and formamide, cubic phases can occur
intermediate to the L1 and E phase region, where they are not stable in water
[60].
E, I, and D phases have been observed in an SDSformamide system. In other
solvents—ethylene glycol, glycerol and Nmethylformamide—only a lamellar
phase is formed [62].
Finally, binary phase diagrams of the homologous series of potassium soaps
(with alkyl chain length C12–C22) and ethylene glycol, butylene glycol, or
glycerol, respectively, have been determined [63]. They essentially confirm the
conclusions pointed out previously; the phase diagrams for soaps with glycerol
show large, qualitative similarities to the aqueous systems, with a decrease in
the regions where the liquid crystalline phase exists.
Nonaqueous systems also form liquid crystals analogous to aqueous systems in
ternary systems, with an added weakly hydrophilic component. SDS has been
extensively employed in studies of ternary systems and quaternary systems with
glycerol or formamide, a longchain alcohol, and, sometimes, hydrocarbon
[64]. In the SDSglyceroldecanol system, the lamellar phase swells
extensively, even more so than in water. 2HNMR order parameters showing
the conformational freedom of the alkyl chain are considerably reduced
compared with the aqueous system [64], suggesting a tilted structure of the
surfactant alkyl chains or a general decrease in order. The SDSformamide
decanol system shows simi

Page 189
lar features in the phase diagram [64]. Measurements of NMR quadrupolar
splittings of the solvent and the counterion have been performed, suggesting a
similar interface between the lamellar surface and the solvent, as in water.
Added toluene seems to penetrate the bilayer to some extent [64].
Addition of longchain alcohols increases the stability of the aggregated
surfactant relative to the crystalline surfactant in aqueous systems (i.e., lowers
the Krafft point). This occurs in nonaqueous systems as well as in the ternary
systems C16TABrethylene glycoldecanol [65] or SDSglyceroldecanol [64].
Although no liquid crystals form at room temperature in the binary systems, a
D phase occurs when decanol is added.
Finally, aerosol OT (sodium diethylhexylsulfosuccinate) is another extensively
studied ionic surfactant. The surfactant is reported to form a thermotropic
liquid crystalline phase in the pure state (of inverse hexagonal structure) [66],
and it forms in addition a lamellar and cubic phase with formamide [67] and
glycerol [68] as with water. With ethylene glycol and Nmethylformamide, no
liquid crystals except the inverse hexagonal occur [67].
Formation of liquid crystals by nonionic surfactants of the polyethylene glycol
alkyl ether type, CiEj , with nonaqueous solvents has to our knowledge only
been considered in a single paper [13], in which the phase diagrams of C12E3,
C12E4, C16E6, and C16E8, respectively, with formamide as solvent have been
determined. No liquid crystals are stable for the C12Ej surfactants; however,
there is a clouding, a lower consolute temperature, in the C12E3 system [69].
The C16Ej series follows the same trend as the aqueous systems [70]: C16E4
gives a D phase, C16E6 an E phase, and C16E8 and I phase, most likely of the I1
type (Figs. 4 and 5). As with ionic surfactants, the regions where the liquid
crystalline phase exist are smaller, and fewer phases are present, comparing
formamide with water as solvent [13,70].
Monoglycerides form an inverse hexagonal phase with glycerol, as in water
[71]. Mixtures of triethanolamine and oleic acid form a nonaqueous lamellar
liquid crystal with a surfactant bilayer of soap and acid and with intercalated
ionized and unionized alkanolamine as solvent [72]. The lamellar phase also
solubilizes other polar compounds, such as glycerol and ethylene glycol [72].
Liquid crystals form in a similar way with dodecylbenzenesulfonic acid and
triethanolamine [73].
These and other systems reported to contain a nonaqueous liquid crystalline
phase are listed in Table 2.
B. Microemulsions
The first reports of nonaqueous microemulsions, isotropic solutions containing
a hydrophilic and a lipophilic component stabilized by a surfactant, were made

Page 190
Fig. 4
Phase diagrams of nonionic surfactants in
formamide: (a) C16E4formamide, (b)
C E formamide, (c) C E formamide.
16 6 16 8
For notations, see Sec. V. (From Ref. 13.)
by Palit and McBain in 1946 [74] and by Winsor in 1948 [75]. Both groups
used glycols as polar solvent. The microemulsion regions were only observed
visually, so that no structural information could be obtained.
Three groups reported independently the observation of microemulsions with
nonaqueous polar solvents in 1984. The group headed by Lattes found
microemulsions in the C16TABrformamidecyclohexane system with butanol
as cosurfactant [76–78], and Friberg and Podzimek detected a narrow
microemulsion

Page 191
Fig. 5
Phase diagrams of nonionic surfactants in water: (a) C16E4water,
(b) C E water, (c) C E water. For notations, see Sec. V.
16 6 16 8
(From Ref. 13.)
region in the lecithinethylene glycoldecane system (Fig. 6) [79]. The third
group, Robinson et al., investigated glycerol in heptane microemulsions with
AOT as surfactant [80] using dynamic light scattering to study the aggregation.
Systems reported to contain some sort of nonaqueous microemulsion are listed
in Table 3.
Lattes et al. investigated the C16TABrformamidebutanol system with
cyclohexane or isooctane, respectively, as the oil component [6,76–78]. In
both systems, conductivity measurements could give indications of percolation.
When an xray scattering study was conducted on the latter system, no
discrete droplets could be detected. When increasing the hydrocarbon volume
of the surfactant to didodecyldimethylammonium bromide [(C12)2DABr],
microemulsions form without cosurfactant in formamide and in ethylene glycol
using dodecane and toluene as the oil [65]. The microemulsion region formed
in the (C12)2DABrwaterdodecane system was investigated as the water was
gradually replaced by formamide, resulting in a very small microemulsion region
in

TABLE 2 Nonaqueous Lyotropic Liquid Crystalline Phases Reported in the Literaturea
Surfactant Solvent Additive Phases detectedb
Lecithin EG D
Lecithin 1,3Propanediol D
Lecithin 1,4Butandiol D
Lecithin 1,5Pentanediol D
Lecithin 1,6Hexanediol D
Lecithin 1,7Heptanediol D
Lecithin (EG)1–4 D
Lecithin PEG D
Lecithin C12Ej D
Lecithin EAN D
Lecithin FA D, I, F
Lecithin MFA D, I, F
Lecithin DMF I, F
Lecithin EG Methanol D
Lecithin EG Decanol D
Lecithin EG Decane D
C16TABr FA E, I, D
C16TABr G E, I, D
C16TABr EG E, I, D
C16TABr MFA D
C16TABr NMS D
C16TABr EG Decanol D
C16TACl FA I, E, …
C16TASO4 EG E, D
C14TABr G E, I, D
C14TABr EG E, D
C20PyBr FA …I…
C18PyBr FA …I…
C14TABr G E, I, D
C14TABr EG E, D
C20PyBr FA …I…
C18PyBr FA …I…
C16PyCl FA I, E, I …
C16PyCl G E, I, D
C16PyCl MFA E, I, D
C16PyCl DMF D
C16PyCl EG E, I, D
C16PyCl NMS E, I, D
SDS FA E, I, D
SDS FA Decanol D
SDS FAH2O Decanol D (E)
SDS FA Decanol + toluene D
SDS G D
SDS EG D

TABLE 2 Continued
Surfactant Solvent Additive Phases detectedb R
SDS MFA D 6
SDS G Decanol D 6
KC22 G E, D 6
KC18 G E, I, D 6
KC16 G E, D 6
KC14 G E, I, D 6
KC12 G E, D 6
KC22 EG E, D 6
KC18 EG E, I, D 6
KC22 BG D 6
KC18 BG I, D 6
AOT FA D, I, F 6
AOT G Decanol D … 6
AOT G Decane D … 6
AOT G p Xylene D … 6
TEAO TEA G, EG D 7
DBSA TEA G, EG, TEG D 7
C16E4 FA D 1
C16E6 FA E 1
C16E8 FA I, E 1
a
For notations, see Sec. V.
b
Dots indicate that the entire phase diagram has not been investigated.
Fig. 6
Phase diagram of the system lecithinethylene
glycoldecane at 25°C, showing a narrow
microemulsion region. (From Ref. 79.)

TABLE 3 Nonaqueous Microemulsion Phasesa
Surfactant Solvent Hydrocarbon Cosurfactant Referenc
C16TABr FA Cyclohexane Butanol 76–78
C16TABr FA Isooctane Butanol 6, 21, 77,
CTbPB FA Cyclohexane Butanol 76–78
KC10(F) FA Fluorinated decene Fluorinated 77, 78, 96

hexanol
KC10(F) FA Fluorinated decene Fluorinated 77, 78, 97,

hexanol
(C12) 2DAB FA, EG Dodecane, toluene 65
C16TABr G nHeptane, 81
chloroform
C11NH 3Cl EG Cyclohexane 75
NaO1 PG Benzene 74
TEAO1 G p Xylene Oleic acid 99
SDS FA Toluene Hexanol 83
SDS FA Toluene Decanol 84
SDS FA Pentanol, 24, 86

hexanol,
heptanol,
octanol
SDS FA p Xylene Pentanol, 24, 86

hexanol, octanol
SDS MFA, DMF Xylene Pentanol, 24

octanol
SDS FA, EG, PG, PC, Dodecane Alcohols 100

DMSO,
acetonitrile
SDS G Hexanol 87
SDS G p Xylene Hexanol 89
SDS G Decane Hexanol 88
SDS G Decanol 64
SDS EG Toluene Decanol 101
AOT DMF, MFA, FA, Toluene, dodecane 67

EG
AOT G Decanol 68
AOT G Decane, p xylene 68
AOT G nHeptane 80, 90

AOT DMF, MFA, FA, Toluene, dodecane 67
EG
AOT G Decanol 68
AOT G Decane, p xylene 68
AOT G nHeptane 80, 90
AOT G Isooctane 102
AOT EG Benzene 75
AOT EG, PG Toluene 103

TABLE 3 Continued
Surfactant Solvent Hydrocarbon Cosurfactant Referen
Triton X114 DMSO Dodecane Pentanol 106
Triton X114 Acetonitrile Dodecane Pentanol 106
C12E4 FA Dodecane 91
CiEj G + PG Alkanes 104
CiEj EG, PG Alkane with > 17 105

carbons
Lecithin EG Decane 79
a
Isotropic solution phases, containing both a nonpolar and a polar component together wi
surfactant, reported in the literature. F, denotes fluorinated surfactant; for other notations
the pure formamide system. When comparing the formamide and the ethylene gl
toluene systems, it was found that the formamide system needs considerably less
to form microemulsions than ethylene glycol (Fig. 7). NMR selfdiffusion measur
were carried out in the formamide microemulsion, and the diffusion pattern was f
resemble that of a bicontinuous aqueous one. In the ethylene glycol microemulsio
at higher surfactant content), there were no indications of nonpolar and polar do
8).
Robinson et al. have investigated the glycerolinoil microemulsion stabilized by
using a mixture of nheptane and chloroform as oil with dynamic light scattering,
hydrodynamic radius of the droplets and an area per surfactant head group, and
measurements [81]. A similar study was also conducted on the AOTglycerolhe
system and reversed micelles with glycerol was found in both systems [80].
Turning to the anionic surfactants, SDS is the one that has been most frequently i
Friberg et al. have studied a number of SDSstabilized formamide microemulsion
different hydrocarbons and cosurfactants [82–84]. The system containing toluen
hexanol showed a microemulsion region, but from light scattering studies it was c
be a nonstructured solution [83]. When increasing the alkyl chain length of the alc
decanol, however, two isotropic solutions could be observed; the formamide sol
no indication of an organized structure, but in the decanol solution, some kind of i
micelles were found [84].
Lindman et al. examined different microemulsions using SDS and formamide but
the oil to p xylene and using alcohols of different alkyl chain length, going from pe
octanol [24,85,86]. Both ternary and quaternary systems were investigated with t
different NMR techniques, selfdiffusion and frequency variable relaxation measu
The selfdiffusion study gave no

Page 196
Fig. 7

Phase diagrams of the systems (a) (C12) 2
TABrformamidetoluene and (b) (C12) 2TABrethylene
glycoltoluene at 25°C, showing the microemulsion
regions (L) in the systems. (From Ref. 65.)
indication of any organized structures, but from relaxation measurements, a
fraction of the SDS molecules was observed to aggregate into some sort of
interface when octanol was used as cosurfactant. Microemulsion regions were
observed when using methylformamide and dimethylformamide as polar
components and octanol as cosurfactant, but these phases were found to be
nonaggregated solutions [24,85].
Another polar solvent that has been used in SDSstabilized microemulsions is
glycerol. Hexanol or decanol has been used as cosurfactant, and systems both
with and without oil have been studied. The ternary system with hexanol as
cosurfactant was examined with smallangle neutron scattering and NMR self

Page 197
Fig. 8
NMR selfdiffusion measurements in the systems (a)

(C12) 2TABrformamidetoluene and (b) (C12) 2
TABrethylene glycoltoluene at varying mass ratio
= (toluene/toluene + polar solvent). D/D0 is the ratio of the
diffusion coefficient of the polar solvent (open circles) or
toluene (closed circles) in the microemulsion to the
diffusion coefficient of the pure component. (From Ref.
65.)
diffusion measurements by two different groups, and both found the
microemulsions to be structureless solutions [87,88]. The same result was
found from a selfdiffusion study of quaternary systems with p xylene or
decane as the oil component [88,89].
AOT is another widely used anionic surfactant in aqueous microemulsions.
AOTglycerol microemulsions have been carefully studied by two different
groups, that of Friberg and that of Robinson. Friberg studied ternary phase
diagrams with decanol, decane, or p xylene as the third component, and
isotropic solution phases were detected in all systems [68]. Robinson et al.
studied two other ternary systems with heptane or octane as the third
component

Page 198
[80,90]. They found inverse micelles with glycerol in both systems using
dynamic light scattering in the heptane system and quasielastic neutron
scattering in the octane system. The latter study gave information about the
lateral diffusion coefficient of AOT in the micelles, and it was found to be half
that in the corresponding aqueous system, even though glycerol has a viscosity
that is ~ 1500 times larger than water. These facts led to the conclusion that
the AOT molecules cannot be anchored to any large extent in the dispersed
phase.
Finally, we report on the work that has been accomplished on nonaqueous
microemulsions with nonionic surfactants. The C12E4 surfactant was found to
stabilize microemulsions of formamide and dodecane [91]. The ternary phase
diagrams were studied at different temperatures and the solubilization of
hydrocarbon shown to be very temperature dependent (Fig. 9). It was also
observed
Fig. 9
Phase diagrams of the system C12E4formamidedodecane at (a) 30°C, (b) 40°C,
and (c) 50°C, showing the growth of the threephase region in which a
solution phase is formed at the lowest possible surfactant concentration.
(From Ref. 91.)

Page 199
that the temperature intervals of the threephase regions are dependent on the
hydrocarbon used; larger aliphatic hydrocarbons give threephase regions at
higher temperatures, observations completely analogous to the corresponding
aqueous systems.
In a smallangle neutron scattering study, Schubert and Strey [92] investigated
the order/disorder transition in microemulsions of nonionic surfactants, water
formamide mixtures, and oil. As the water content of the systems was
decreased, a more disordered microstructure was observed. Even with pure
formamide as polar solvent, however, the existence of internal interfaces,
although uncorrelated, could be detected.
As a brief conclusion it can be noted that many nonaqueous microemulsions
reported do not contain an organized structure: they are simply molecular
solutions. Because the degree of organization already in many aqueous
microemulsion is low, in particular for quaternary systems containing ionic
surfactant and cosurfactant, this is not really surprising. In some systems,
however, more structured microemulsions have been found, but this may
require other surfactants and cosurfactants than in the aqueous systems.
IV. Concluding Remarks
Evidently, the mapping of surfactant aggregation in nonaqueous polar solvents
is extensive, and investigations of many different combinations of surfactants
and solvents are available in the literature. Furthermore, a wide range of
experimental techniques have been used. The results from different studies are
quite consistent and most of the authors agree on some basic trends.
Qualitatively, the general aggregation behavior is similar to water. That is,
surfactant aggregation in the form of micelles, liquid crystals, or microemulsions
is possible in polar solvents other than water. However, there are indeed
quantitative differences between these nonaqueous systems and aqueous
systems. For example, the Krafft temperatures of ionic surfactants and CMC
values are higher and the aggregation numbers of the micelles are lower in
these nonaqueous solvents. The existence regions for liquid crystal phases in
nonaqueous solvents are reduced and the phase diagrams are less complex
than in water. Also, the microemulsions formed in nonaqueous solvents often
have a more disordered microstructure than in water. It is tempting to, in a
qualitative manner, ascribe these differences to the less extensive solvophobic
interaction in polar solvents other than water.
There are, of course, other ways of expressing and discussing this solvophobic
interaction than, for example, comparing interfacial tensions between solvent
and hydrocarbon, as in Table 1. The nonaqueous solvents that have been
reported to promote the aggregation of surfactant molecules have one property
in common: they all have high cohesive energy. That is, the net at

tractive interactions between the solvent molecules are strong. Hildebrand et al. [
derived a cohesive energy parameter from the heat of vaporization of the solvent.
measure of the cohesive energy is the Gordon parameter [94], /V1/3 ( = surfac
V = molar volume). This parameter has the advantage that it can be used for both
fused salts.
Different authors [11,95] have tried to determine a limiting value for the cohesive
which a certain solvent should be able to promote surfactant aggregation. Howev
curiously often overlooked that the hydrophobicity of the surfactant must also be
account in this context. A surfactant with a long hydrocarbon chain or a fluorinate
hydrocarbon chain is able to aggregate in solvents in which a less hydrophobic su
remain in monomeric form, just as in water.
V. Nomenclature
AOT aerosol OT (sodium diethylhexylsulfosuccinate)
BG butylene glycol
(C12) didodecyldimethylammonium bromide
2DAB
CiEj nonionic surfactant of the polyethyleneglycol alkyl ether type; alkyl
contains i carbon atoms and the polar group j ethylene glycol units
CMC critical micelle concentration
CxNH3Br cationic surfactant of the alkylammonium bromide type; alkyl chain
carbon atoms
CxPyBr cationic surfactant of the alkylpyridinium bromide type; alkyl chain
carbon atoms
CxTABr cationic surfactant of the alkyltrimethylammonium bromide type; alk
contains x carbon atoms
CxTASO4 cationic surfactant of the alkyltrimethylammonium sulfate type; alkyl
contains x carbon atoms
CTbPB cetyltributylphosphonium bromide
D lyotropic liquid crystalline phase with lamellar structure
DBSA dodecylbenzenesulfonic acid
DMF N,Ndimethylformamide
D lyotropic liquid crystalline phase with lamellar structure
DBSA dodecylbenzenesulfonic acid
DMF N,Ndimethylformamide
DMSO dimethysulfoxide
E lyotropic liquid crystalline phase with hexagonal structure
EAN ethylammonium nitrate
EG ethylene glycol
F lyotropic liquid crystalline phase with reverse hexagonal structure
FA formamide
G glycerol

I general notation for lyotropic liquid crystalline phase with cubi
KCx potassium soap with x carbon atoms in the alkyl chain
MFA Nmethylformamide
NaOl sodium oleate
NMS Nmethylsydnone
PC propylene carbonate
PEG polyethylene glycol
PG propylene glycol
SDS sodium dodecyl sulfate
TEA triethanolamine
TEAO triethanolammonium oleate
TEG triethylene glycol
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7
LightDuty Liquid Detergents
KUOYANN LAI
Global Materials and Sourcing (AsiaPacific Division), Global Technology, Colg
Company, New York, New York
ELIZABETH F. K. McCANDLISH and HARRY ASZMAN
Research and Development, Global Technology, ColgatePalmolive Company, P
New Jersey
I. Introduction
II. Typical Composition and Ingredients
A. Typical composition
B. Ingredients
III. Hand Dishwashing
A. Variables
B. Mechanism of cleaning
C. Factors affecting dishwashing detergent performance
IV. Test Methods and Performance Evaluation
A. Evaluation of cleaning performance
B. Evaluation of foam performance
C. Evaluation of mildness
D. Other tests
V. Formulation Technology
A. Formulation
B. Guidelines and examples
VI. New Products and Future Trends
A. Line extensions
B. Clear, colorless products
A. Line extensions
B. Clear, colorless products
C. Increased use of nonionics
D. Environmental and regulatory concerns
E. Dish liquids with added benefits
F. Concentrates
References

Page 208
I. Introduction
Lightduty liquid detergents (LDLDs) are primarily used for washing dishes
and pots and pans by hand. They are also used for washing delicate fabrics,
cars, and, to a lesser extent, general household cleaning.
The first LDLD was developed in the late 1940s. Like other liquid detergents,
LDLDs offer the advantage of convenience and are well accepted by
consumers in the developed countries and some developing countries.
Despite the increasing popularity of automatic dishwashing machines and the
continuing growth of automatic dishwasher detergents in the developed
markets, LDLDs for hand dishwashing continue to grow slowly in these
markets. The estimated tonnage in 1992 was 1.3 million ton in Europe,
550,000 ton in the United States, and 270,000 ton in Japan [1]. The annual
growth rate was estimated at 2% for Europe, 1.5% for Japan, and 0.5% for
the United States. Similar growth rates are predicted for the future.
Although commercial hand dishwashing liquids available in the marketplace
vary greatly in AI (active ingredient) level, esthetics, and positioning, they
typically exhibit physical and chemical characteristics as summarized in Table
1.
Literature articles specifically devoted to the discussion of LDLDs are limited
[2–9]. The advances in technology in this area are primarily documented in
patents.
This chapter attempts to review LDLDs, focusing on hand dishwashing
applications: typical composition and ingredients, the hand dishwashing process
and chemistry involved, the test methods and performance evaluation, the
formulation technology, and new products and future trends.
II. Typical Composition and Ingredients
A. Typical Composition
A lightduty liquid detergent consists of ingredients for cleaning, foaming,
solubilization, preservation, fragrance, color, and other additives, such as thick
TABLE 1 Typical Physical and Chemical
Characteristics of LightDuty Liquid Detergents
Characteristic Typical value
Viscosity, cps 100–500
pH 6–8
Cloud point, °C <5
Clear point, °C <10

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eners, antiirritants, and antibacterial agents. A typical composition of an LDLD
is shown in Table 2.
B. Ingredients
1. Surfactants
Surfactants are the primary ingredients that provide the cleaning performance
for an LDLD. They also provide foams that are an important sensory signal to
consumers. Therefore, the cleaning and foaming capabilities of a surfactant are
the key considerations for LDLD usage. The other factor that has become
increasingly important in many developed markets in recent years is the
mildness of a surfactant to human skin. Among the four classes of surfactants,
anionic, nonionic, and amphoteric surfactants all have been used in LDLDs in
varying degrees. Cationic surfactants as a class have not been found suitable
for use in LDLDs.
Historically, anionic surfactants [10] have been the predominant surfactants of
choice for LDLDs. This is a result in part of their good cleaning and excellent
foaming properties and in part their availability and economy.
The anionic surfactants most commonly used in LDLDs are linear alkylbenzene
sulfonate (LAS), alkyl polyoxyethylene sulfate (also referred to as alkylethoxy
sulfate, AEOS), paraffin sulfonate (PS, also referred to as secondary alkane
sulfonate, SAS) [11], fatty alcohol sulfate (FAS), and olefin sulfonate
(AOS). The anionic surfactants tend to be two of the following: LAS, AEOS,
and SAS. In the United States, LAS and AEOS are the main anionic
surfactants; in Europe, SAS is more commonly used than LAS [2].
Nonionic surfactants [12] have been used to a much lesser extent in LDLDs
than anionic surfactants. This is primarily because of their low foaming
properties and higher cost. Recently, however, nonionic surfactants have been
used increasingly [1], recognizing the many advantages they offer over anionic
sur
TABLE 2 Typical Dishwashing Detergent Composition
Ingredient %
Surfactants 10–50
Foam stabilizers 0–5
Hydrotropes 0–10
Salts <3
Preservatives <0.1
Fragrance 0.1–1
Dyes <0.1
Other additives 0–3
Water Balance

Page 210
factants, such as mildness, higher active level, better compatibility with other
ingredients, and some synergistic effects with certain anionic surfactants.
Additionally, technology has been developed for boosting and stabilizing foams
of nonionic surfactant systems [13].
Nonionic surfactants used in LDLDs are primarily ethoxylated alcohols with
varying degrees of ethoxylation. Alkylpolyglycosides (APGs) [14–16] and
fatty acid glucamides [17–20] have also become important new surfactants for
LDLDs in recent years. Major manufacturers, such as ColgatePalmolive,
Henkel, Kao, and Procter & Gamble, started using these new classes of
nonionic surfactants in their products in the early 1990s. These are further
discussed in Sec. VI.
Amphoteric surfactants [21] typically exhibit good cleaning and foaming
properties. More importantly, they offer excellent mildness. Because of their
higher cost, however, amphoteric surfactants have not been used in LDLDs to
a significant extent. In the last few years, with the increased attention to the
mildness aspect of the product, amphoteric surfactants have gained popularity
for use in LDLDs. The most widely used amphoteric surfactants are betaines,
especially cocoamidopropylbetaine.
Table 3 lists the surfactants commonly used in LDLDs and their chemical
structures.
2. Foam Stabilizers
Foam is an important visual signal for LDLDs. There is no direct correlation
between foam and cleaning, but consumers in general use foam volume and
foam persistence to judge the performance of an LDLD. There are wide
varieties of stabilizers for foams [22]. Among the most commonly used in
LDLDs are the following:
1. Fatty alkanol amides, such as LMMEA (lauric/myristic monoethanol amide),
LMDEA (lauric/myristic diethanol amide), CDEA (cocodiethanol amide), and
CMEA (cocomonoethanol amide)
2. Amine oxides, such as DMDAO (dimethyldodecyl amine oxide) and
DMMAO (dimethylmyristyl amine oxide)
Fatty alkanol amides and amine oxides commonly used as foam stabilizers in
LDLDs can be found in the literature [22,23].
3. Hydrotropes
Hydrotropes are often added to an LDLD to help solubilize surfactants or
other materials to ensure its stability. The fundamental properties of
hydrotropes and their hydrotropic action in liquid detergents are discussed in
Chap. 2. The hydrotropes most widely used in LDLDs are sodium xylene
sulfonate (SXS),

TABLE 3 Surfactants Commonly Used in LightDuty Liquid Detergentsa
Chemical description Chemical structure
Anionic surfactants
Alkylbenzene sulfonate
Paraffin sulfonate
Alkyl sulfate Na+
ROSO3
Alkylethoxy sulfate Na+
R(OCH2CH2) nOSO3
Na+
Olefin sulfonate H3C(CH2) mCH=CH(CH2) nSO3
Nonionic surfactants
Alcohol ethoxylate R(OCH2CH2) nOH
Fatty acid glucamide
Alkylpolyglycoside
Amine oxide

Amphoteric surfactant
Cocoamidopropyl betaine

a
R = alkyl group.

sodium cumene sulfonate (SCS), sodium toluene sulfonate (STS), urea, and etha
shown in Table 4. Isopropanol, propylene glycol, and polyethylene glycol ethers
used as hydrotropes for LDLDs. SXS, SCS, and ethanol are hydrotropes used
for LDLD formulation as a result of nearly colorless and odorless properties. Ure
effective and cheap hydrotrope. Two concerns raised by some formulators using
hydrotrope [9,24] are as follows:
1. Formulations containing urea usually tend to be of higher pH and exhibit ammo
Storage at higher temperature worsens this problem.
2. Because of its high nitrogen content, urea is a good nutrient for bacteria. There
adequate bacteriostats or bactericides are needed to avoid problems.
These concerns, however, can be overcome with proper pH adjustment and pre
The addition of hydrotrope to an LDLD affects its viscosity, and clear and cloud
obviously depends on the type and quantity of the hydrotrope used.
TABLE 4 Hydrotropes Commonly Used in LightDuty Liquid Detergents
Hydrotrope Chemical structure
Sodium xylene sulfonate (SXS)

Sodium toluene sulfonate (STS)

Sodium cumene sulfonate (SCS) 126290212c.gif

Urea

Ethanol CH3CH2OH

4. Minor Ingredients
Minor ingredients are added to an LDLD mostly for esthetic reasons. These inclu
fragrances, dyes, preservatives, chelators, and viscosity modifiers. They are adde
at less than 1% of the formula.
The fragrance and color of an LDLD are of critical importance to its success. Th
of the fragrance types and colors creates the image for the product. Fragrances a
must be compatible with other ingredients in the product and compatible with the
materials to be used for the final product. They must also not adversely affect the
performance of the product and not cause other problems, such as skin irritation.
Preservatives are often needed to prevent microbial growth in LDLDs. Preservati
commonly used are formaldehyde, glutaraldehyde, ethanol, benzoic acid, Kathon
Dowicil®, Bronopol®, and various esters of hydroxybenzoic acid and others.
Chelators are also used to assure no precipitation occurs on aging. The most co
problem is iron, which is introduced as an impurity from surfactants and salts. Th
used most often in LDLDs are ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetetraacetic acid (HEDTA), and citrate.
Viscosity modifiers are used to achieve the desired product viscosity of an LDL
include alcohols, salts, and polymers. Hydrotropes as just discussed also serve a
modifiers. Among the most commonly used viscosity modifiers are ethanol, sodiu
potassium chloride, sodium sulfate, magnesium salts, urea, and various celluloses
polymers (see Chap. 5).
5. Special Additives
Other additives may also be added to an LDLD to provide additional benefits to
Table 5 lists some examples [25–32] of additives that can be incorporated into a
TABLE 5 Special Additives for LightDuty Liquid Detergents
Special additive Benefits R
Protein Mildness to skin
Opacifier Product esthetics
Abrasives Cleaning tough soils
Lemon juice Enhanced cleaning
Polymers Rinsing and feel to hands
Bleach (oxygen based) Prevents discoloration
Antibacterial ingred. Antibacterial on hands

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III. Hand Dishwashing
A. Variables
1. Mechanical Action
Mechanical action is very important in hand dishwashing. When people wash
dishes they actively rub the surface. This mixes the surfactant with the soil and
accelerates the cleaning. It also physically removes soil.
The amount of mechanical action used in hand dishwashing is extremely
variable and hard to quantify. This is illustrated by the wide range of
dishwashing performance tests (see Sec. IV). Consumers may soak items that
are difficult to clean in a very low mechanical action environment. Under these
conditions, surface chemistry is very important. Consumers may also scrub
vigorously directly on the soiled area, break up the soil particles, and suspend
them. At this point interfacial processes become important again. All individuals
have their own techniques. Individuals vary the amount of effort they use
depending on the type and distribution of the soil on the item. However, they
usually do not use enough sustained mechanical action to make a stable oilin
water emulsion.
As is true in automatic dishwashing machines, much of the cleaning occurs from
water and mechanical action alone. Large food particles, sugars, many
starches, and some protein soils are readily removed by rinsing with plain
water. Some food soils, such as bakedon starches or polymerized fats, are
extremely resistant. These require vigorous, direct mechanical action. In some
cases, vigorous chemical action is used, as in oven cleaners, but this
mechanism is not within the scope of LDLDs.
2. Washing Methods
Dishwashing methods are extremely diverse. A single person may use different
methods depending on the number of dishes, the soil load, the availability of
water, and local tradition.
(a) Neat Dishwashing. Neat dishwashing refers to the practice of placing the
dishwashing liquid directly on the item to be washed or directly on the washing
tool (sponge, brush, rag, and so on). The item is usually rinsed first. In neat
dishwashing, the surfactant concentration ranges from a few percent to 30% or
more, depending on the active ingredient level of the product. In developed
countries, neat dishwashing is used when there are only a few dishes to wash
or when one particular item is especially soiled. Neat dishwashing is also a
common habit in Brazil, India, and Japan [33].
(b) Dilute Methods. Dilute dishwashing is the widely used practice of filling a
tub, sink, or pot with water and adding the dishwashing liquid (1–10 g) [34].
The dishes are either submerged in the bath all at once or submerged one

Page 215
at a time and then washed. Typical surfactant concentrations range from 0.1 to
0.3% for U.S. consumers and from 0.06 to 0.3% for European consumers.
The sinks range in size from 5 to 20 L [17].
(c) Dip and Dab Methods. The dip and dab method is intermediate between
dilute and neat usage. Dip and dab consists of adding product (10100 g) [33]
to a small bowl and filling the bowl with water. The soiled item is then washed
with this solution, but not submerged as in the dilute method. The dip and dab
method generally has much higher concentrations (1–3%) than the dilute
method (0.1–0.3%) [17].
(d) Rinsing. Once plates are washed, they are generally rinsed with clean
water. This is especially important when higher concentrations of dishwashing
liquid are used. Some consumers in Germanspeaking countries do not rinse.
They scrape the plates extremely thoroughly so there is a minimum soil load,
wash in very dilute solutions, and dry with a towel.
3. Soils
The principal type of soil encountered in dishwashing is oily soil. Proteins,
carbohydrates, and mixed soils (bones and large particles) are relatively easily
removed. Bakedon soil requires more vigorous treatment, either mechanical
or chemical [35]. The type of oily soil is almost exclusively triglycerides. The
hydrocarbon chains in food triglycerides are predominantly C12–C16, although
higher and lower chains are present. Siliceous particles or clays are not of
interest to hand dishwashing, although they are to laundry. An important
consideration in applying the theory of surfactants to hand dishwashing is that
triglycerides are considerably more polar than hydrocarbons and considerably
higher in molecular weight. The theory has been developed for hydrocarbons,
and the fundamental physical chemistry has been focused on them. As a result,
the chemistry of dish cleaning presents interesting opportunities for further
research.
4. Surfaces
Dishwashing must consider soil and surfactant adsorption to both polar and
nonpolar surfaces. Metals (aluminum, stainless steel, carbon steel, cast iron,
silver, and tin), siliceous surfaces (china, glass, and pottery), and organics
(polyethylene, polypropylene, polyethylene terephthalate (PET),
polytetrafluoroethylene (PTFE), and wood) present a wide variety of surface
characteristics. They span the range of high interfacial free energy (metals) to
low interfacial free energy (hydrocarbon polymers) surfaces [36,37].
5. Water
(a) Water Temperature. The water temperature used in hand dishwashing is
highly variable and depends on the climate and the availability of hot water. In
tropical places the ambient temperature of water is 30–37°C. Many

Page 216
edible fats are at least partly liquefied at this temperature. In temperate zones
the water can be close to 0°C, depending on its source and time of year. A
source of hot water is essential under these conditions. A typical wash
temperature is 32–43°C [2]. The maximum temperature at which dishes are
washed is about 50°C. Above this temperature the water becomes
dangerously hot. Hotter water is used for tough jobs, but the items are left to
soak and are not handled, unless perhaps gloves are used. Raising the washing
temperature can markedly increase the amount of cleaning [38].
(b) Effect of pH. Although the pH is an important variable in formulating dish
liquid, the pH is not an major variable in dishwashing. Because most
consumers do not generally wear gloves, only pH values near neutral are mild
enough to the skin to be used. Some dish liquids have a pH as low as 5 or as
high as 8, but the majority are close to 7. Hydrolysis of fatty soils is not an
appreciable cleaning method under these circumstances, especially at
temperatures under 40°C.
(C) Effect of Water Hardness. As discussed later, increasing the water
hardness generally increases the efficacy of LDLDs. Increased hardness
increases grease removal and increases the number of plates washed with a
given amount of surfactant. Water hardness has a variable effect on foam [13]
depending on the range of hardness and the anionic or nonionic nature of the
surfactant. If dishes are washed and then air dried, hard water increases the
likelihood of getting spots on the dishware.
B. Mechanism of Cleaning
Aside from mechanical action, there are several mechanisms of cleaning dishes.
These mechanisms operate differently depending on whether the soil is solid or
liquid. Solid soil (from solid fats or other solids) is broken up and suspended in
the bath. Liquid soil is usually removed by (1) rollup, (2) emulsification, and
(3) direct solubilization. It is possible, using heat or surfactants, to liquefy solid
oils, thereby making them candidates for rollup and better candidates for
emulsification[39]. There may be a fourth mechanism: the formation of
microemulsion or liquid crystalline phases.
1. Rollup
The first mechanism of cleaning hard surfaces is the rollup of liquid soils or
soils that have been liquefied by heat or surfactant penetration [40]. The theory
of wetting of hard surfaces by soils and of adsorption of surfactant is described
in detail elsewhere [36,41–44]. Only a brief overview, from a dishwashing
perspective, is given here.
An unwashed dish presents the classic picture of an oily soil in air on a solid
substrate (see Fig. 1). In this situation, the equilibrium contact angle is re

Page 217
Fig. 1
Oily soil on an unwashed plate in air.
lated to the surface tensions (or, alternatively, surface free energies) by the
YoungDupree equation
plateair = oilair cos + plateoil
When the soiled plate is placed in a detergent bath, all the interfaces undergo
changes. The surfactant begins to modify the soil and the plate by adsorbing to
surfaces and penetrating the soil.
A new equilibrium is established after a few minutes:
platebath = oilbath cos + plateoil
The equation can be rearranged to give
In the presence of a detergent, the interfacial tensions tend to be very low. In
general, platebath and oilbath are less than plateoil. As a result, plateoilbath becomes
larger than plateoilair (see Fig. 2).
In the ideal situation is 180°. Now the soil does not wet the plate at all. There
is essentially no contact area between the plate and the oily soil. Minor currents
in the bath lift the droplet; other surfactant molecules emulsify it and suspend it
in solution. If plateoilbath is less than 180°, however, even though
Fig. 2
Oily soil on an unwashed plate in a detergent bath.

Page 218
Fig. 3
Removal of an oil droplet by hydraulic forces when the
contact angle is between 90° and 180°.
greater than 90°, mechanical forces can still remove the droplet of soil from the
surface (see Fig. 3).
If the contact angle is greater than 90°, it is theoretically possible for hydraulic
currents to reduce the area of contact to zero while maintaining the contact
angle [45]. If the contact angle is less than 90°, the droplet cannot be removed
completely by hydraulic currents. A neck forms in the drop so that part of the
drop pulls away and a small amount of material is left behind (see Fig. 4). The
remainder can be removed by emulsification or solubilization.
As a practical matter, contact angles of 180° are very rare. In practice it is
extremely difficult to remove all the oil from the plate by rollup, even if the
contact angle is high. When the contact angle is high, even though it is not
180°, agitation keeps a large portion of the oil off the surface and suspended in
the bath. This produces effective cleaning if the plate is promptly rinsed [45].
2. Emulsification
Emulsification is probably the primary mechanism of cleaning in hand
dishwashing. An emulsion is a suspension of liquid particles in a second liquid
phase. The particles are much larger, about 500 nm or greater, than micelles.
The suspension is not thermodynamically stable [46]. Depending on the food
soil and the state of liquefaction of the fats, solidinwater suspensions are also
formed during dishwashing. That these emulsions and suspensions are rather
Fig. 4
Removal of oily soil when the contact angle is less than 90°.

Page 219
unstable is not important because, by and large, people drain the dirty
suspension and rinse the dish.
3. Solubilization
Solubilization is the spontaneous dissolving of a normally insoluble substance in
a relatively dilute surfactant solution [46]. The soil goes directly into or around
the micelles. The solution is thermodynamically stable. Because the micelles in
a dilute solution are generally too small to scatter light, the final solution looks
very much like the initial solution (unless the solute is colored). The size of the
micelle is determined mainly by the length of the carbon chain. Micelles range
between 5 and 100 nm in diameter and typically contain about 50–100
monomers [47]. Anionic micelles are partly neutralized by counterions and
carry only 50–70% of the theoretical charge [48].
The location of the soil within the micelle depends on the type of soil. Alkanes
are thought to wedge themselves between the surfactant tails. They do not
form a pool of oil in the middle. In contrast, amphiphiles with polar head
groups tend to solubilize with their heads in the hydrophilic region of the
micelle. It is not clear where benzene and the aromatics fit in a micelle [49].
The oily soils encountered in dishwashing are overwhelmingly triglyceride and
relatively polar compared with alkanes. Triglycerides are also considerably
higher in molecular weight than typical hydrocarbon or polar fatty soils. It is not
clear where triglycerides fit in a micelle.
The amount of soil that can be solubilized depends in part on the micelle shape.
For a given number of surfactant molecules, the transition from spherical
micelles to rods is thought to decrease the amount of polar organics that can be
solubilized. In contrast, the solubility of alkanes increases in going from spheres
to rods [49]. In a typical cleaning situation there is not usually enough
surfactant to solubilize all the oils, especially if the surfactants are mainly
anionic. A greater portion of the oil is solubilized if the surfactants are nonionic.
High solubilizing power is an important factor in good detergency [13].
Although in general detergency reaches a maximum when the critical micelle
concentration (CMC) is reached (after accounting for surfactant adsorbed to
the soil and the substrate), for some surfactantsoil combinations detergency
continues to increase above the CMC [50].
4. Formation of SurfactantRich Liquid Crystal Phases
A recent review [42] describes several cases in which the maximum soil
removal occurs when the soil is incorporated into an intermediate phase, such
as a microemulsion or liquid crystal. These intermediate phases form at the
interface between the soil and the washing bath. The intermediate phases grow
up to a point and then, as a result of agitation, break off into the bath, where
they are emulsified into the aqueous solution.

Page 220
The soils for which this occurs extensively are mainly hydrocarbons, polar fatty
soils, or mixtures of hydrocarbons with triglycerides. The surfactants used are
ethoxylated alcohols. It is much harder to form these intermediate phases using
triglyceride soils. Relatively high (65°C) temperatures are required. Because
triglycerides are the main fatty soil in dishwashing and dish detergents rely
mainly on anionics, it is not clear that these phases form to an appreciable
extent in hand dishwashing. However, practical triglyceride soils are always
contaminated with polar components (such as hydrolysis products, proteins,
and polar lipids). Also, increasingly, nonionics of various sorts are being used
in dish liquids. Last, undiluted or slightly diluted (more than 1% surfactant)
washing methods are used by many consumers. Thus it is possible that this
mechanism is relevant under certain circumstances.
C. Factors Affecting Dishwashing Detergent Performance
1. Effect of Surfactant Type
Detergents in general do a better job of cleaning if they contain a mixture of
surfactants. It is best if the mixture includes a variety of types of surfactants as
well as a variety of chain lengths. This can be illustrated in Fig. 5, which shows
performance for secondary alkane sulfonate (SAS) and mixtures as a function
of carbon chain length.
Fig. 5
Miniplate test of SAS (and mixtures) as
a function of the C chain length.
Concentration: 0.3 g/L of active substance.
(Source: From Ref. 11, reproduced by
permission.)

Page 221
Micelle formation with different chain lengths is energetically favored compared
with micelle formation with the same chain length [51]. It is also an advantage
to mix anionic and nonionic surfactants. The mixture shows a reduction in
CMC compared with the individual components because the nonionic allows
the mutual repulsion between the anionic head groups to decrease. A practical
advantage to having mixtures of surfactants is that in dishwashing there is a
wide variety of soils and surfaces. A mixture has the right surfactant for any
given soilsubstrate combination.
2. Effect of Carbon Chain Distribution
Several authors describe the effect of alkyl chain length on performance. For
linear alkylbenzene sulfonate (LAS), a widely used surfactant in LDLDs, the
most important factor in the performance is the carbon chain distribution [52].
The optimum chain length of LAS for foam stability in a typical LDLD
formulation varies depending on water hardness. This is illustrated in Table 6
for a formulated product of 24% LAS, 6% alkylpolyoxyethylene sulfate
(AEOS), and 2% amide (LMMEA).
The location of the phenyl group on the alkyl chain (within the limits of
commercially available LAS) had little effect on the performance [52]. For
SAS, an anionic surfactant widely used in European LDLDs, more plates are
cleaned in the C14–C15 region than at longer or shorter lengths. This is true for
SAS alone and for SAS/AEOS mixtures (see Fig. 5) [11].
As stated earlier, alcohol ethoxylate surfactants were historically used to a
limited extent in LDLDs because they are low foamers. In recent years, their
use has increased. They provide an example of the effects of carbon chain
length. In this case both carbon chain and ethylene oxide content have an effect
on detergency. It is thought that reducing the carbon chain increases the
solvency of the surfactant and improves its ability to penetrate soil [53]. The
best performance varies with the surfactant concentration, as shown in Table 7.
The best ethylene oxide level was found to be 50–60% by weight for all chain
lengths [53].
TABLE 6 Optimum Chain Length of LAS as a Function of
Hardness
Hardness (ppm) Optimum foam stabilitya
0 C13
50–150 C11–C12
>150 C10–C11–C12
a
Product formulation: 24% LAS, 6% AEOS, and 2% LMMEA.

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TABLE 7 Optimum Chain Length as a Function of Concentration
Concentration (%) Optimum chain length in alcohol
ethoxylate surfactants
>1 C6–C8
0.1–1 C8–C10
<0.1 C10–C12
3. Effect of Inorganic Ions
An important effect in the formulation of dish liquids is the presence of
inorganic ions. These come in as impurities in all commercial surfactants. They
are present as calcium and magnesium carbonates, sulfates, and chlorides in
hard water. They are deliberately added as viscosity modifiers of concentrated
product in the bottle and as important performance boosters. In the last
capacity, the calcium or preferably magnesium can be added either as an
inorganic salt, such as MgSO4, or as the counterion of an anionic surfactant.
One of the effects of increased electrolyte concentration is lowering of the
CMC. This has direct implications for detergency. Electrolytes do this for ionic
surfactants, mainly anionics in dish liquids, by “screening” the ionic head groups
in a micelle from each other. Adding salts decreases the CMC in the following
order for lauryl sulfate:
Li > Na > K > Cs > N(CH3)4+ > N(C2H5)4+ > Ca, Mg
The larger the polarizability of the ion and the larger the valence, the greater is
the decrease in the CMC. The smaller the radius of the hydrated ion, the
greater is the decrease in the CMC [54].
A similar effect occurs in the electrical double layer that surrounds the surface
of an object to be cleaned. Items with a relatively highly charged surface, such
as glass, ceramics, and metals with oxide coatings, first repel surfactants with a
like charge and attract surfactants with an opposite charge. Adding salts causes
a decrease in the adsorption of the oppositely charged surfactant and an
increase in the adsorption of the likecharged surfactant. In dishwashing liquids,
many of the surfaces to be cleaned are negatively charged. Because the
principal surfactants used in dishwashing detergents are anionic, adding salts
increases the adsorption of anionics onto a negatively charges surface [55]. In
the nonpolar items, such as those of polypropylene or polyethylene,
electrolytes also increase the adsorption of ionic surfactants because the mutual
repulsion between the head groups is decreased [56].
There is also an effect of ionic strength of the stability of the emulsions formed
as the dishes are cleaned. Emulsions in general decrease in stability with
increasing electrolyte concentration. Oil droplets in water are surrounded by an

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electrical double layer because these droplets generally carry a negative
surface charge. Emulsions that are stabilized by charged particles, for example
those formed by ionic surfactants, are stabilized by having a low electrolyte
concentration. In the presence of electrolyte, the thickness of the electrical
double layer is decreased. This decreases the stability of the emulsion [51].
Fortunately, the emulsions formed in dishwashing need not last very long. If the
stability of the emulsion is too low, then redeposition of soil can be a problem.
Some modern patent technology of dishwashing includes substantial amounts
of both anionic and nonionic surfactants. Nonionic emulsions are much less
affected by ionic strength.
The most important effect of electrolytes is the effect of Ca2+ and Mg2+ ions on
dishwashing performance. Numerous patents teach the beneficial effects of
both ions on dishwashing performance [18,20,57]. It is thought that Mg2+ ions
form a complex with anionic surfactants. This complex allows the anionic
surfactant to adsorb more readily on surfaces with a surface negative charge. A
preferred mode of adding magnesium to a dish liquid is to use the MgO or Mg
(OH)2 to neutralize the surfactants after they are formed by sulfonation or
sulfation. This method is preferred because adding magnesium using salt
generally requires adding additional hydrotrope. Magnesium is preferred over
calcium because the calcium surfactant salts are much less soluble. It is also
possible to add divalent metals to the formula as simple salts, such as MgSO4
[9]. A similar effect was found using a formulation of 24% LAS, 6% AEOS,
and 2% LMMEA (amide). The maximum number of plates washed (see Sec.
IV for performance evaluation) at 0 ppm was only about 7; the maximum
number of plates for 50 and 150 ppm was 17 and 20 respectively (see Fig. 6)
[52].
It should be noted that hardness ions are generally undesirable in laundry
applications because they are detrimental to detergency [29,58]; however, this
is not invariably true [55]. This is particularly not true for dishwashing, as
illustrated in Fig. 7.
4. Effect of Raw Material Variations
Some LAS mixtures appear to be selfhydrotroping; others need extra
hydrotrope [59]. Commercial LAS contains various amounts of the 2phenyl
isomer and dialkyltetralin sulfonates. The 2phenyl content significantly affects
the solubility, and the tetralins considerably reduce the viscosity. This variation
in 2phenyl isomer and tetralin content is a result of the industrial process used
to make the linear alkylbenzene. Linear alkylbenzene sulfonate is made from
the three primary processes that use different catalysts, AlCl3, HF, and
DETAL, resulting in different amounts of 2phenylalkanes and dialkyltetralins.
Material from the AlCl3 process is considered high in 2phenyl content and
high in dialkyltetralins, material from the HF process is considered low in 2
phenyl

Page 224
Fig. 6
Effect of water hardness on the foam stability optimum
(24% LAS, 6% ES, and 2% amide). (Source: From Ref.
52, reproduced by permission.)
Fig. 7
Impact of water hardness ions on dishwashing performance for
LAS/FES = 4:1 (plate test, 2 ml beef tallow per plate). Index
100% = 285 ppm (tapwater); 45°C; 0.15 g/L of surfactant. (Source:
From Ref. 9, reproduced by permission.)

Page 225
content and low in dialkyltetralins, and material from the DETAL process is
considered high in 2phenyl content and low in dialkyltetralins.
Another consideration is the source of the hydrophobic end of the surfactant. It
is well known that oleochemical fatty alcohols have even numbers of carbons
and petrochemical fatty alcohols have odd and even numbers. As discussed
earlier, the carbon chain length has an effect on dishwashing performance.
However, when alkyl sulfates, alkylpolyoxyethylene sulfates, and dishwashing
compositions were made out of laurylrange hydrophobes, there was no
difference in performance or physical properties between those from
oleochemical and petrochemical sources [60].
IV. Test Methods and Performance Evaluation
There is no universally accepted single test method for the performance
evaluation of dishwashing detergents. This is because of the wide variations in
soils, washing conditions, and consumer habits in dishwashing. Numerous test
methods for performance evaluations exist in the literature. These test methods
can essentially be classified into four categories:
1. Evaluation of cleaning performance
2. Evaluation of foam performance (volume and stability)
3. Evaluation of mildness
4. Other tests
Discussed here are some of these tests. It is by no means inclusive of all
available tests. Rather, these are only a few examples to illustrate the wide
variations that exist for the evaluation of the various performance attributes of a
dishwashing detergent.
A. Evaluation of Cleaning Performance
Cleaning performance is the most important characteristic of a dishwashing
detergent as consumers purchase the product for cleaning dishes. Greasy soils
are the most common consumer complaint regarding washing dishes. The
literature is replete with formulations directed at efficacious grease cleaning.
Consequently, test methods for cleaning performance are generally focused on
greasy soils. The three basic means for measuring the cleaning performance of
LDLDs are as follows:
1. Gravimetric measurements
2. Turbidity measurements
3. Plate counts

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1. Gravimetric Measurements
Gravimetric tests are probably the most common for evaluating the cleaning of
dishwashing products. Examples are (1) the cup test, (2) the grease removal
test, and (3) the static soaking test.
(a) The Cup Test. The cup test [18] measures the product's ability to remove
greasy soils chemically from surfaces under normal use conditions of
temperature, water hardness, and concentration. It is important that the
temperature of the solution in the cup be below that of the melt temperature of
the greasy soil or combination of soils. Otherwise, a true reading of the
product's performance is not obtained because the soil will melt. The
procedure consists of melting the greasy soil and pouring it into a beaker or by
smearing it onto the sides of a beaker. Combinations of greases can also be
used. The solution of the test product is made, poured into the beaker, and
allowed to stand in contact with the grease for a fixed time. The amount of
grease remaining in the beaker after the solution is poured off is determined.
Results are reported as percentage soil removed by the following formula:
Obviously, higher percentage soil removal reflects better greasy soil cleaning.
(b) Grease Removal Test. Another gravimetric grease evaluation is the grease
removal test [61]. In this test a solid greasy soil is applied to microscope slides
or test tubes by dipping into the melted greasy soil. After allowing the grease to
solidify, the substrates are repeatedly dipped into solutions of test compositions
under specific conditions of temperature, water hardness, and concentration
for the intended market. The substrates are dried and weighed and the
percentage soil removal calculated following the same formula as just outlined.
(c) Static Soaking Test [13]. This test measures the amount of soil (Crisco,
vegetable shortening derived from cottonseed and soybean oils and
manufactured by Procter & Gamble) removed from a plate after soaking for a
fixed time in a test solution under specific conditions. The plates are transferred
to an ice bath following immersion in the warm test solution to stop the soil
removal. The plates are dried and weighed and the percentage soil removal is
calculated as
Similarly, a higher percentage of soil removal reflects better greasy soil cleaning
ability.

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2. Turbidity Measurements
Turbidity measurements involve measuring turbidity using a light source, usually
transmission, colorimetry, or a turbidimeter, as a means to measure the
product's ability to emulsify grease.
(a) Emulsion Stability Test [62]. This test measures a liquid detergent
composition's ability to keep greasy soils emulsified. It is performed by placing
an oil, like corn oil, into a vial containing a solution of detergent. The vial is
agitated for a fixed number of rotations at a fixed rate and allowed to stand for
a fixed time. Readings are taken with a turbidimeter or colorimeter at given
time intervals. Higher tubidity values or lower colorimetry values indicate more
stable emulsions [62].
(b) The Cup Test [63]. Tubidity measurements can also be used in this test.
Here, a fiber optic probe is used to measure percentage transmission as the
solution is mixed at a constant rate. Measurements are taken as a function of
time. The lower the transmission values as time progresses, the better is the
greasy soil removal capability of the test product.
3. Dishwashing Test (Plate Count)
Dishwashing tests provide the best performance information about the entire
product because they use soils and wash conditions as close as possible to
those encountered by consumers under normal conditions. The foam end point
is usually the indicator of the product's performance. This is consistent with
consumers' expectations: they usually equate a product's performance with its
foaming ability. Dishwashing tests that use foam as the end point are discussed
later in this section under Foam Stability Tests.
Another indicator of a product's performance is the number of plates washed
to the cleaning end point. In this test [64], the product is placed directly on a
sponge and soiled plates are washed until plates can no longer be cleaned.
Performance is equated with the number of plates washed, with the greater the
number of plates washed indicating the better the cleaning ability.
Although the plate wash test provides a more accurate account of a product's
performance, it has some drawbacks. This type of test usually takes a long
time to complete. Less timeconsuming tests are used to screen potential
formulations before conducting actual plate wash tests. An example is the
miniature dishwashing test that is discussed later. Another limitation of this test
is that it is subjective and thus can vary from operator to operator.
B. Evaluation of Foam Performance
Foam volume and foam stability tests are widely used for evaluating LDLDs.
Foam volume tests measure the amount of foam a composition can generate
with and without soil. Foam stability, sometimes referred to as foam mileage,

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measures the ability of a detergent to maintain its foam with soil present or
while oil is introduced.
1. Foam Volume Tests
Foam volume is an important characteristic of lightduty dishwashing
detergents, higher foam heights being desirable because consumers generally
equate foaming with cleaning performance [3]. An ASTM method [65] for the
evaluation of foam volume of light duty dishwashing liquids is more commonly
known as the RossMiles foam test. This method is widely used for evaluating
the foaming ability of a detergent or surfactants in general. Numerous other
foam volume tests are cited in the patent literature that differ significantly from
the RossMiles test. These test methods are faster and easier for foam volume
evaluation [61,66].
Foam volume tests can be conducted with soil or without soil. One foam
volume test without soil [67] is conducted by placing a solution of a
composition into a cylinder. The cylinder is shaken or inverted a fixed number
of times or for a set amount of time. The foam height is measured in
centimeters or milliliters. A foam volume test with soil is conducted the same
way but with soil added to the test solution. The soil can either be added with
the solution initially or added after foam is generated.
2. Foam Stability Tests
Various types of foam stability or foam mileage tests are found in the literature.
All use the same basic theme of generating a foam under constant agitation
followed by the addition of soil to the solution until the foam collapses.
Foam mileage tests measure the product's ability to resist foam depletion in the
presence of soil. The amount of soil needed to break the foam is an indication
of the product's ability to retain the foam while soiled dishes are washed. The
more soil it takes to break the foam, the better is the product's performance.
Examples of some foam mileage tests are briefly described here.
(a) Soil Titration Method (STM). The STM test [68] involves generating a
foam under constant agitation, followed by titrating with a soil at a constant
mass flow rate until a foam end point is reached. The amount of soil needed to
collapse the foam is measured. Products requiring more soil have better foam
stability.
A foam performance ratio (FPR) is calculated by
This test was developed to screen potential formulas because hand
dishwashing tests are time consuming and are operator dependent. This test
was found to correlate with a hand dishwashing test [68]. Figure 8 shows the
good correla

Page 229
Fig. 8
Correlation between the hand dishwashing and the
foam performance ratio. (Source: From Ref. 68,
reproduced by permission.)
tion between foam performance ratio and number of plates washed at ambient
and elevated temperatures.
(b) Tergotometer Test. The Tergotometer test is commonly used in
evaluating the detergency of laundry products. It was modified [63] for the
evaluation of LDLDs. The Tergotometer provides constant agitation in which
a dilute solution of test composition is added and foams are generated. Small
metal plates covered with soil are periodically added until the foam height is
reduced to a foam end point or a fixed foam height. The number of small metal
plates added to the foam end point reflects the foam stability of a composition.
(c) Piston Plunger Test. Another foam mileage test is referred to as the piston
plunger test [69]. In this test, similar to the Tergotometer test, foams are
generated and soil is added until the foam is depleted. The soils used in this test
are commercial foods, such as Crisco shortening and Ragu spaghetti sauce.
The amount of soil needed to break the foam is an indication of the product's
efficacy.
(d) Dishwashing Test (Foam End Point). An ASTM method [70] exists for
the evaluation of the performance of hand dishwashing detergents based on
foam stability. The objective of this test is to provide a standard test for the
formulator and suppliers, a screening test for formulations, and quality control.
One method described uses a dishcloth to wash the front and back of each
dish at a fixed time interval. Dishes are continually washed to a foam end point
as determined by a thin layer of foam covering half the surface. Standard soils
are described, an example being a mixture of oils (Wesson and corn), grease
(lard), oleic acid, gelatin, salt, flour, and water.
Another example of a dishwashing test [69] consists of soiling dishes with

Page 230
Crisco by spreading a fixed amount on the dish. A basin of water is prepared
in which the temperature, water hardness, and product concentration are
adjusted to meet the habits and practices for the intended market. Foam is
generated by a mixer or by manual agitation. The plates are washed using
standard washing implements, such as sponges or cloths. It is common to fix
the time and number of strokes used to wash the plates to minimize variability.
The cleaned plate is then stacked, and the process continued until the foam end
point is reached. Again, the foam end point is when half the surface of the
water is covered with foam. The plates washed are counted and used as a
relative measure of the product's performance.
(e) Miniature Dishwashing Test. A miniature dishwashing test [71] was
developed as a means to reduce the time required for actual washing tests.
Instead of using actual plates, “miniplates” (small watch glasses) are used. This
test still uses foam end point as a means of determining a product's
performance, but it scales down the number and size of the plates washed, thus
reducing the time for completing an evaluation.
(f) Modified SchlachterDierkes Test. In the modified SchlachterDierkes
test [72], product is placed in a graduated cylinder and inverted to generate
foams. Soil increments are added at fixed intervals until the foam collapses.
The results are recorded as the number of soil increments, the higher value
being better foam stability.
(g) Total Foam and Foam Mileage. In the total foam and foam mileage test
[18], graduated cylinders are charged with test solution consistent with
conditions for the intended market. The cylinders are stationed side by side
and rotated to generate a foam, and initial foam heights are measured. Soil is
added and the cylinders are again rotated. The foam height is again recorded.
Soil is repeatedly added to a low foam height. A control is tested with each run
and compared with the test product. Total foam and foam mileage is
determined by the following:
C. Evaluation of Mildness
Mildness has become an increasingly important product attribute of lightduty
dishwashing detergents. Mildness assessments typically involve clinical and
sensory evaluations of skin irritation. Clinical irritation is usually evaluated by
trained clinicians on the observable changes of the skin caused by exposure to

Page 231
an LDLD. Erythema (redness), dryness, and flaking are most commonly
evaluated. Sensory irritation is the consumer or panelist evaluation of the
product's mildness. Common sensory signals are feelings of dryness, tightness,
or roughness, lack of softness or smoothness, and red appearance. Mildness
evaluations are usually conducted in both in vitro and in vivo testing.
1. In Vivo Tests
Hand immersion and patch tests are the two common types of in vivo testing
used for evaluating the mildness of LDLDs. Each has its own advantages and
disadvantages, as discussed here.
(a) Hand Immersion Tests. Hand immersion tests consist of panelists
immersing their hands into a solution of the test composition or commercial
product for a given period of time. The test conditions are generally those
encountered by the consumer during regular dishwashing. Temperature, water
hardness, product concentration, and time must all be properly controlled.
After immersion, the hands are rated during and after use for different
attributes, such as skin smoothing, hand feel (sticky or slimy), hand roughening,
and redness. The rating can be done by the panelist comparing the feel
between two test compositions or can be evaluated by a trained observer.
Patel et al. [73] used hand immersion testing to measure the skinsmoothing
properties of a dishwashing detergent that incorporates a skinsmoothing
compound. In this test, panelists immersed their hands in a solution of test
composition at a fixed temperature for short periods of time, rinse under tap
water, and towel dry. The panelists evaluated their hands for smoothness as
they dried them.
The hand immersion test is analogous to dishwashing tests in that the test
composition is evaluated under close to realistic conditions as experienced by
consumers and provide a more accurate account of a product's mildness. The
same drawbacks are encountered with the hand immersion test as with
dishwashing tests: it usually takes a long time to complete and is subjective. In
addition, only two products can be compared by panelists at one time.
(b) FroschKligman Soap Chamber Test. The FroschKligman soap
chamber test [74] is designed to evaluate the mildness of surfactant
compositions on individuals with hypersensitive skin. An individual is
considered hypersensitive if the treated site appears confluently red 24 h after
occlusion with 0.75% sodium lauryl sulfate for 6 h. Once screened, a panelist
is exposed for 5 weekdays to a solution of product or test composition. The
exposure time varies from 24 h on the first day to 6 h on days 2–5. On the
following Monday, the panelist is evaluated for scaling, redness, and fissuring
based on the rating scales shown in Table 8.
The total score is determined by summing the averages of the three
parameters. The advantages of the FroschKligman test are that multiple
products can

TABLE 8 Rating System for the FroshKligman Soap Chamber Test
Erythema Scaling Fissures
1+ slight redness, spotty or 1+ fine 1+ fine cracks

diffuse
2+ moderate, uniform redness 2+ moderate 2+ single or multiple bro
3+ intense redness 3+ severe with large flakes 3+ wide cracks with hem

or exudation
4+ fiery red with edema
be evaluated at once (up to eight), predicting erythema and dryness, and it takes
to complete the evaluation and thus is a good screening test. The disadvantage wi
that the exposure is unrealistic and is expensive. Consumers do not have their han
with the wash solution for 24 h periods or even 6 h per day.
(c) Patch Test. Similar to the FroschKligman test, this test is generally used to s
potential compositions. In this type of test, a “patch” or chamber is used to keep
of diluted product against the skin for a given period of time. The arms are the ar
used. The solution usually used for this test is one that consumers normally use fo
dishes. The duration of product contact to the skin can vary from one application
repeated applications for longer than 24 h. In one variation [69], plastic disks are
keep a solution of test product on the forearm for a 24 h period. The arms are th
after another 24 h without contact with product. Scores are then given with the le
product having the lowest score. In another variation [75], a sealing “Finn
chamber” (aluminum disk) is used for 24 h and the skin is evaluated 1 h after rem
disk. This process is repeated for a second time. An overall rating is determined
the rating for the degree of reaction by the rating for the observed symptom. The
used and the symptoms with their rating are shown in Table 9.
The total irritation is calculated by summing the scores of all the observed sympto
example, redness is observed with slight reaction and dryness with moderate rea
total irritation for that area is then (3 x 2) + (1 x 3) = 9.
(d) Human Repeat Insult Patch Test (HRIPT). HRIPT is similar to FroschKli
chamber and patch testing because the product is patched onto skin. This test is
used for cosmetic products to determine allergic reaction. Manufacturers of LDL
beginning to use this type of testing as

TABLE 9 Reaction Rating Scale and Symptoms Ratings for Patch Test
Reaction Rating Symptom R
No visible reaction 0 Vesicles
Reaction only just visible 1 Edema
Slight reaction 2 Redness
Moderate reaction 3 Flaking
Serious reaction 4 Dryness
Wrinkles
Semitransparency
Glasslike
such products as Palmolive Sensitive Skin (ColgatePalmolive) and Clear Ivory (
Gamble, P&G) are becoming borderline cosmetic products. This test is conducte
patching product at a high concentration (5%) three times a week for 3 weeks, f
a rest period without patching for 2 weeks. The product is again patched at the s
concentration on a site not previously used. The new sites are evaluted for erythe
(redness) and edema (swelling) after 48 and 72 h of exposure and are compared
initial patching. The panelist is considered to have an allergic reaction if the levels
erythema and edema are higher than the initial values.
(e) 21 Day Cumulative Patch Test. The 21 day cumulative patch test [76] uses
patches made of nonwoven fabric impregnated with the test liquid that are place
back and occluded with tape. The patches are removed after every 24 h period
after 30 minutes, and a new patch is applied. Testing continues for 21 days or unt
maximum reading occurs. A numeric score or cumulative irritation index is calcula
each test liquid according to Table 10.
This is done on a daily basis and totaled after 21 days. The lower the reading, the
irritating is the liquid. Variations in this test include varying the concentration and
testing (a petrolatum ring is used instead of a patch that confines the liquid).
TABLE 10 21 Day Cumulative Patch Test Numeric Score Index
Index Description
0 Negative reading (questionable erythema not covering entire patch area)
1 Definite erythema covering entire patch area
2 Erythema and induration
3 Vesiculation
4 Bullous reaction

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2. In Vitro Tests
In vitro tests are generally used to screen formulations because this type of
testing is relatively easy to perform, is inexpensive, and can be correlated with
an in vivo test. The most common type of in vitro test as evidenced in the
patent literature is protein denaturation.
(a) Protein Denaturation. Protein denaturation by surfactants is considered
one of the major causes of skin irritation and roughness induced by surfactants
[77]. Consequently, simple and reproducible methods for evaluating protein
denaturation by surfactants have been developed. These tests work by
measuring the amount of protein that has been denatured after the protein and
test composition have been in contact with each other for a given period of
time.
Prottey et al. [78] have developed a method that can be used to predict the
mildness of surfactants and thus dishwashing liquids. They found a correlation
between the changes observed in the stratum corneum phosphatase specific
activity during normal dishwashing conditions and dryness and flakiness. Figure
9 shows the correlation of hand dryness and acid phosphatasespecific activity
after hand immersion in various surfactants. A commercial manufacturer of
LDLDs used this method to show that a liquid detergent composition exhibited
good mildness [79].
In the protein denaturation test developed by Prottey et al. [78], the interaction
of detergents with acid phosphatase enzyme is performed on skin. Others have
developed a protein denaturation test that uses wheat germ [80]. Another
protein denaturation method mixes an aqueous protein solution of egg yolk
albumin and detergent [81]. The mixture is subjected to chromatography and
Fig. 9
Correlation of hand dryness and acid phosphatase.
(Source: From Ref. 78, reproduced by
permission.)

Page 235
compared with the chromatogram of the egg yolk solution alone. Mildness is
determined by the amount of denaturation: the milder the composition, the less
the percent denaturation. Yet another method uses ovalbumin and human
serum albumin and measures protein denaturation via gelpermeation
chromatography (GPC) [82]. Figure 10 is an example of a chromatogram
using this type of method.
Percentage denaturation is then calculated as
Where: H0 = peak height of GPC elution of protein
Ht = peak height of GPC elution of protein after mixing with surfactant
(b) Zein Test. The zein test [83] is based on the principle of the correlation
between the skin compatibility of a surfactant and its solubilization potential for
zein (Indian corn protein). The test actually determines the solubility of the zein
in the presence of anionic surfactants. Zein is insoluble in water, but surfactant
solutions cause part of the zein to dissolve. It has been shown [83] that there is
a correlation between the surfactant's ability to dissolve zein and its irritation
potential: the higher the solubility of zein, the more irritating the surfactant. The
method is based on mixing the surfactant or test composition in water and zein
at 25°C under constant stirring for 2 h. The solution is filtered and processed in
a centrifuge. The zein value is calculated as
Fig. 10
GPC elution curve protein,
surfactant, and mixtures of protein.
(Source: From Ref. 82,
reproduced by permission.)

Page 236
where A is the amount of nitrogen measured in the filtered solution using a
microKjeldahl method and B is the amount of nitrogen in the surfactant
solution without zein. The proposed irritation potential based on zein value is
shown in Table 11.
(c) Collagen Swelling Test. The collagen swelling test [84] is used to
determine the irritation potential of anionic surfactants and products containing
anionic surfactants. In this test, a correlation was found between the swelling of
a collagen film and the irritation potential. The more the collagen films swell, the
higher is the irritation potential. The test is conducted by treating the collagen
film with the test surfactant or composition and placing it into a vial with a
buffer and tritiated water. After incubating for 24 h, the collagen films are
rinsed to remove any tritiated water and placed in a scintillation vial. The films
are digested and treated and then analyzed for radioactivity. The swelling is
defined as milliliters water uptake per gram dry collagen.
The example shown in Fig. 11 illustrates that LAS and SLS exhibit a high
irritation potential compared with AEOS (3EO), Tween 20, and water
because they produce a high level of swelling. Similar results for LAS and SLS
were reported by Putterman et al. [85] for isolated stratum corneum.
(d) Other In Vitro Tests. Other in vitro tests have been developed for
evaluating the irritation potential of surfactants or compositions, for example the
following:
1. Extraction of Coomassie Brillant Blue R 250 dye from a matrix of gelatin
[86]: more dye extracted is an indication of a surfactant's irritancy
2. Swelling of guinea pig stratum corneum [85], in which swelling is an
indication of irritation potential
D. Other Tests
Various other tests are used by formulators to aid formulation or to evaluate
some specific benefits. Interfacial tension measurements, the drainage test, and
the rinsing test are among the examples.
(a) Interfacial Tension Measurement. The emulsification capability of
surfactant systems is often screened using interfacial tension measurements.
Low
TABLE 11 Irritation Potential Based on Zein Value
Irritation classification Zein value (mg N2/100 ml)
Nonirritant 0–200
Slight irritant 200–400
Severe irritant >400

Page 237
Fig. 11
Water uptake as a function of surfactant concentration using
the collagen swelling test. (Source: From Ref. 84, reproduced
by permission.)
interfacial tensions are usually an indication of the surfactant's effective ability to
emulsify grease and oily soils [18].
(b) Drainage Test. Faster drying and spotfree utensils may be other
consumerdesired benefits of LDLDs. A test method to measure the draining
of lightduty liquids was described in U.S. Patent 5,154,850 [66]. In this test
plates are immersed in a solution of product for a fixed number of times,
removed, and dried under ambient conditions. This cycle is repeated, with the
final dipping followed by rinsing. The plate is allowed to dry and the water
spots are counted. A product that provides good drainage leaves few or no
spots on the utensils.
In another drainage test [87], various regular kitchen utensils, such as drinking
glasses, glass dinner plates, and ceramic dinner plates, are washed in test
compositions under controlled conditions. The utensils are then rinsed and
placed in a rack to dry. The time at which drainage begins and the percentage
area dried by this drainage are recorded.
(c) Rinsing Test. Although copious and longlasting foams are desirable for
LDLDs, consumers also want the foam to be easily rinsed away from the
dishes so as not to leave residue that could appear as spots. A test method
was disclosed in U.S. Patent 5,154,850 for the evaluation of the rinsability of
foam generated for an LDLD [66]. This involves making a solution of product,
charging it to a container and stirring. The solution is discharged from bot

Page 238
tom of the container, leaving residual foam in the container. Tap water is added
to the container with residual foam and stirred again. The stirring and draining
steps are repeated until no foam remains in the container. The product that
needs fewer additions of water is considered to have better rinsing
characteristics.
V. Formulation Technology
A. Formulation
Formulating an LDLD is both a science and an art. It requires a good balance
among product performance, esthetics, safety, and cost. From the consumer
point of view, the important attributes for a liquid hand dishwashing detergents
are listed in Table 12. Consequently, liquid dishwashing detergents are
formulated to deliver against these consumerrelevant attributes.
Formation of LDLDs typically involves (1) selecting appropriate raw materials
for the desired performance, (2) developing formulas and optimizing for
performance, (3) optimizing product esthetics, (4) testing product safety, (5)
optimizing product cost, and (6) aging for product stability, and (7) validating
with consumers.
The following section presents a review on formulation against these
performance attributes with the intent of providing some guidelines.
B. Guidelines and Examples
1. Formulating for Effective Cleaning
The most important performance attribute of a LDLD is cleaning. As discussed
earlier, cleaning of dishes with an LDLD relies primarily on the interfacial
properties provided by the surfactants. Various surfactants exhibit different
interfacial properties and thus varying ability in removing different soils from
TABLE 12 Important Attributes of a Hand
Dishwashing Liquid Detergent
Effective cleaning
Copious and longlasting foam
Mildness to hands
Pleasant fragrance
Convenient to use
Safe to humans
Safe to dishes and tableware
Storage stability
Economic to use

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various surfaces. In general, a combination of surfactants is necessary for an
LDLD to be effective against the wide spectrum of soils encountered in the real
world.
A significant number of patents on LDLDs have been issued in the United
States, Europe, and Japan in recent years. Listed in Table 13 are recent U.S.
patents [27,28,29,62,88–110] on LDLD formulated for effective cleaning. The
technology utilized in these patents ranges from special surfactants, surfactant
mixtures, salts, and microemulsions to the use of special additives, such as
lemon juice and abrasives.
2. Formulating for High and LongLasting Foam
It is wellrecognized that foam is the most important visual signal consumers
use to judge the performance of an LDLD. This is despite the lack of direct
correlation between the foaming and cleaning properties of an LDLD, as
discussed earlier. Therefore, it is critically important that the formulators create
an LDLD with copious and longlasting foam.
Copious foam usually requires the use of highfoaming surfactants, typically
anionic or amphoteric surfactants [10,21,111] or a mixture of surfactants.
Longlasting foam often requires foam stabilizers [22] in addition to a proper
surfactant mixture. Table 14 is a summary of recent U.S. patents [26,72,112–
132] on LDLDs formulating for good foaming properties. The technologies
involved are either using novel surfactants or surfactant blends or novel foam
stabilizers.
3. Formulating for Mildness
For some consumers, mildness to skin is an important attribute of a LDLD,
especially those who have sensitive skins.
There are essentially two approaches to formulate an LDLD for mildness: (1)
use mild surfactants, such as nonionic surfactants, zwitterionic surfactants, or a
combination; and (2) use additives that are antiirritants, such as modified
proteins or polymers. Recent U.S. patents [13,25,30,66,133–151] on LDLDs
claiming a mildness benefit are summarized in Table 15.
4. Formulating for Desirable Esthetics
The esthetic attributes of LDLDs are just as important as their performance.
This includes color, fragrance, cloud and clear points, viscosity, and product
stability. Color, fragrance, and viscosity are usually chosen based on consumer
preference. The cloud and clear points must be adequate for the temperature
to which the product is likely to be exposed.
(a) Cloud and Clear Points. The cloud point is the temperature at which the
product begins to turn cloudy or hazy upon cooling. The clear point is the
temperature at which the cloudy product turns clear again upon warming. In

Pa

Page 24

Page 2

Page

North America and Europe, it is desirable that the cloud point be below 5°C and
the clear point not exceed 10°C.
The cloud and clear points of an LDLD can be adjusted using hydrotropes [6,15
such as sodium xylene sulfonate, sodium cumene sulfonate, alcohols, or urea. Fig
12 shows the significant effect of SXS on the clear point of an LDLD formulation
is hypothesized that hydrotropes act by destabilizing liquid crystalline phases that
might form and separate from the bulk mixture [153].
(b) Viscosity. The viscosity of an LDLD is very important for its consumer
acceptability and its dispersibility on dilution [154]. The viscosity of an LDLD is
typically in the range of 100–500 CPS. In some markets, such as Malaysia and
Hong Kong, consumers like much thicker product with viscosity in the range of
2000–3000 CPS. The viscosity of an LDLD is a strong function of its active
ingredient level, the isomer distribution in the surfactant, the relative amount of
different surfactants, and the salt levels. Salt can be both a viscosity builder and a
viscosity reducer. An example of a simple system is sodium AEOS (2.8 EO) at
15% concentration. The viscosity first increases with the addition of NaCl and th
decreases as the amount of NaCl increases [155]. AEOS with narrow EO
distribution thickens much more than AEOS

Pag

Page 2

with a conventional, broad EO distribution. Other factors that affect salt thickenin
are carbon chain legnth and carbon chain distribution [155].
Salt also has a significant effect on the viscosity of LAS. Depending on the cation
of the LAS, salt in the range 0–2% can have a modest or great effect on the
viscosity [154].

Page 246
Fig. 12
Effect of sodium xylene sulfonate on clear point of a premium
LDL blend. (Source: From Ref. 6, reproduced by permission.)
Fatty alkanolamides are mainly used as foam stabilizers, but they can also have
a significant effect on the viscosity of an LDLD formulation. Other viscosity
modifiers include hydrotropes, such as alcohol, SXS, SCS, urea, and water
soluble polymers.
(c) Physical Stability. Physical stability is another important product attribute
that cannot be overlooked. Consumers do not want to purchase a product that
changes physically over time. This may include precipitation, phase separation,
or microbial contamination.
Aging studies are typically conducted to achieve physical stability of product at
market age. Various aging conditions are necessary to simulate the conditions
the product may encounter from warehousing and transportation to storage in
stores and at home. This includes elevated temperature, such as 50°C, and low
temperature—just above the freezing point.
The other standard aging study normally conducted is to expose the product to
sunlight to simulate storage of product at home near a kitchen window for
color and fragrance stability.
During aging, periodic examinations of product are made to check for pH,
color, fragrance, appearance and containers for any changes and deviations
from room temperature samples. Any unacceptable changes and deviations
need to be investigated to identify the cause and to determine corrective
measures. The

Page 247
entire series of aging studies must be repeated when corrections are made to
the formula.
To be sure that the product can withstand microbial contamination, adequacy
of preservation studies must be conducted. If the product is not able to control
the growth of microorganism, incorporation of a suitable preservative is
necessary.
(d) Product Safety. In addition to performance and esthetics, already
discussed, the safety of the final product cannot be overlooked in formulating a
dishwashing detergent. This includes safety to humans, safety to surfaces it
cleans, and safety to the environment. Typically, eye and skin irritation tests are
required. The safety testing and product labeling requirements may vary from
country to country. It is important to ensure that all safety testing is conducted
in accordance with government regulatory requirements.
5. Other Formulation Technology
Other formulation technology may include ways to concentrate an LDLD
product and formulating for cost effectiveness and improved odor stability.
Table 16 lists recent U.S. patents [31,156–165] on these formulation
technologies.
Liquid hand dishwashing detergents have gone through continued evolution in
recent years. Many new products have been introduced to the marketplace.
There are also some significant formulation changes as a result of the advances
in new technologies and the changes in consumer habits and practices.
A. Line Extensions
A perennially popular way of expanding the market for a product is to produce
line extensions. In a line extension, the same brand name is applied to a
different form of the product. Sometimes there is an alternative physical form,
such as a concentrate, powder, or liquid. Sometimes the line extension has new
esthetics, such as new color, degree of translucency, or opacity or fragrance.
Last, there might be other new features, such as increased mildness,
antibacterial efficacy, or presence of a special ingredient. This trend continued
to be strong in the early 1990s because of the expense in introducing a new
brand name and the difficulties of attracting customer attention in a crowded
market [166].
In the United States competition is particularly keen because of a trend to slow
growth in the overall LDLD volume. The cooking and eating habits of
consumers are changing to lower fat, easier, simpler meals and increased use
of prepared food, all of which translates into less dish liquid use [167]. Line
extensions are a way of combating this trend.

Page

B. Clear, Colorless Products
Since 1990 there has been a broad trend in the consumer market to clear, water
white products. Colorless products present the consumer with a new esthetic
experience. Colorless detergent connotes mildness, purity, and safety to the
environment. Products as diverse as beer and deodorant have been formulated a
clear variants [168,169].
As part of this trend, at least three clear dishwashing liquids have appeared in the
United States and spread to Europe (Palmolive Sensitive Skin from

Page 24
Colgate and Ivory and Dawn Free from P&G). Ivory was formerly an opacified
product. One method was developed [31] to enhance the stability of colorless
detergent compositions. It involves the addition of 0.05–0.5% oxygen bleach,
preferably H2O2, and 0.01–2% chelating agent, preferably citric acid, as a way to
keep the percentage transmittance at 97% after 6 months at 140°F. Table 17
shows two LDLD compositions utilizing such technology for a stable colorless
LDLD. Also, there are recent patents on the use of purer and lighter colored raw
materials [170,171].
C. Increased Use of Nonionics
The appearance of dishwashing liquids using more nonionic surfactants is another
recent trend. Small amounts of nonionics, such as amides and amine oxides, have
long been used as foam boosters. As discussed earlier, nonionics have not been
widely used traditionally because of their low foaming characteristics. By proper
formulation, it is possible to have a satisfactorily foaming dish liquid that contains
at least 50% ethoxylated fatty alcohol [13]. Examples of nonionic surfactant
based compositions having foaming properties equal to or better than those of a
conventional anionic surfactantbased dishwashing liquid are listed in Table 18.
New nonionics are becoming available that are relatively high sudsing.
Alkylpolyglycosides (APGs) are a prime example [172]. Although APGs are not
as foamy as anionics, such as ethoxylated alcohol sulfates, they are much foamier
TABLE 17 Examples of Stable Colorless Liquid Dishwashing Detergent Compositions
Using H2O2
Ingredient A (%) B (%)
NH 4C12–13alkylEO1sulfate 15.5 28.5
NH 4C12–13alkylEO6.5sulfate 12
Tetronic 704 0.1
Cocoamidopropylbetaine 0.9
C12dimethylamine oxide 5 2.6
NaCl 1
MgCl2 3.3
Ammonium xylene sulfonate 4 3.0
Ethanol 5.5 4
Perfume 0.09 0.18
Citric acid 0.1
Disodiumdiethylene pentaacetate 0.1
H2O2 0.18 0.17

Pa
TABLE 18 Examples of HighFoaming Nonionic SurfactantBased Liquid Dishwashing
Detergent Compositions
Ingredient A (%) B (%) C (%
Neodol 918 16 19
Neodol 916 19
Ammonium lauryl sulfate 6 6 6
Cocoamidopropylbetaine 4 4 4
LMMEA 3 5 5
Ethanol 5 5 5
SXS 7 7 7
Water, fragrance, color Balance
than nonionics. By the RossMiles foam method (0.1% solution, 49°C, after 5
minutes), a C12 alcohol sulfate would have 18.5 cm foam, a C12 alkyl polyoxyethy
(6.5 EO) alcohol would have 2.5 cm foam, and a C12 APG would have 15 cm fo
[173]. APGs of varying hydrophobes and degrees of polymerization are availabl
least three commercial dishwashing detergents contain APGs, one in Europe, one
the United States, and one in Japan [174,175]. In addition to being relatively high
foamers, APGs have some other useful properties. They are completely
biodegradable, ecologically safe, and mild to the skin and offer wetting properties
similar to those of anionic surfactants. Both the hydrophile and hydrophobe come
from oleochemical resources [176]. Table 19 shows examples of LDLDs formul
with APGs [116].
Polyoxyalkalenes and fatty acid glucamides are also part of the trend to the incre
use of nonionics in dish liquids. Fatty acid glucamides interact strongly with anioni
surfactants to give suds boosting, interfacial tension lowering, and irritancy reducti
[177]. The glucamides are completely and rapidly biodegradable in the Sterm tes
They are highly removed in activated sludge sewage treatment [178]. A partial p
diagram has been reported. There are two crystal structures of polymorphs, one
extended and one bent [179]. Examples of LDLDs formulated with fatty acid
glucamides are listed in Table 20 [18,20].
D. Environmental and Regulatory Concerns
Products with an environmental positioning are a continuing trend, especially in
Europe [180]. In 1992, Pril, a leading German brand, was reformulated to have
mildness and environmental friendliness platform. One feature of both

TABLE 19 Examples of Liquid Dishwashing Detergent Compositions Using Alkyl Polygly
Ingredient A (%) B (%)
Ammonium C11–12alkylbenzene sulfonate 17.5 —
Magnesium C11.4alkylbenzene sulfonate 6.4 —
Ammonium C12–13alkylpolyoxyethylene (EO0.8) sulfate 6.1 —
Ammonium C12–13alkylsulfate — 15.7
Sodium C12–16 olefin sulfonate — 10.4
Cocomonoethanolamide — 5.5
C12–13alkyl polyglycoside1.7 5.0 5.9
C12alkyl dihydroxyethylamine oxide — —
MgCl2∙6H2 — 5.6
Ammonium xylene sulfonate 3.0 —
Ethanol 3.7 4
Water, perfume, minors Balance
APG and fatty acid glucamides is that both hydrophobic and hydrophilic ends ca
“naturally derived” or from “renewable resources.” Neither is a natural product.
are intensively processed. There is considerable debate over whether oleochemic
petrochemical sourcing is better for the environment [181].
Government regulations are a continuing source of challenge to the makers of con
detergent products. For example, in Europe, the Directive on the Classification,
Labeling of Dangerous Substances of the European Economic Community (EEC
published [182]. Since then, the directive has been amended to require manufact
consumer products
TABLE 20 Examples of Liquid Dishwashing Detergent
Compositions Using Methyl Ester Glucamide
Surfactant A (%) B (%)
C12–14alkyl EO8 16
AEOS 15
Amine oxide 4
Glucamide 8 10
Betaine 2 3
C9–11EO8 8 4
Mg 0.025 0.25
Glucamide 8 10
Betaine 2 3
C9–11EO8 8 4
Mg 0.025 0.25

Page 252
according to the hazards posed to the consumer (toxic, corrosive,
carcinogenic, eye or skin irritant, and so on) and package and label them
accordingly [183,184]. The member states of the EEC had to incorporate the
directive into their laws by October 1993. The method of classification is
basically either directly to test the final composition or to estimate the hazards
by using a calculation (called the conventional method). The calculation
depends on the sum of the hazards of the individual components and their
percentage in the final composition. The products must be classified according
to their concentration when they are sold to the public. LDLDs with
concentration above 20% AI must be sold in packages with irritant warning
labels, even though the the LDLD is mild when diluted for use. Labeling
requirements affect the composition of dish liquids by accelerating the
incorporation of milder surfactants.
E. Dish Liquids with Added Benefits
Another trend is the addition of new benefits. This is in part a reflection of the
overall trend of making consumer products multipurpose [185]. An example
is the introduction of a combination dishwashing liquid and antibacterial hand
soap by Colgate Palmolive in 1994. About twothirds of the people who wash
their hands in the kitchen use dish detergent [186], possibly because it is
handy. This product has the benefit that, in addition to washing dishes, when
used undiluted it kills possibly pathogenic germs on hands. Colgate's product
was quickly followed by Dial dishwashing liquid, which also claimed
antibacterial hand soap properties. The interest in antibacterial properties fits a
growing concern about germs on the part of the public [187].
F. Concentrates
Dish detergents in developed markets have become more concentrated as part
of a general trend that can also be seen in laundry detergents and hard surface
cleaners [188–190]. The trend toward dish liquid concentrates in formerly
dilute markets started in Europe in 1992. In Germany (previously a 20–25%
AI market), the market was evolved into concentrated products with the
introduction of Unilever's Sunlight Progress, Colgate's Ultra Plus, Henkel's Pril
Supra, and P&G's Fairy Ultra. It remains to be seen whether products with
even higher active levels (40–50%) will be accepted by consumers in the
United States and Europe.
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8
HeavyDuty Liquid Detergents
AMIT SACHDEV and SANTHAN KRISHNAN
New Jersey
I. Introduction
II. Physical Characteristics of HDLDs
A. Structured liquids
B. Unstructured liquids
C. Nonaqueous liquids
III. Components of HeavyDuty Liquid Detergents and Their Properties
A. Surfactants
B. Builders
C. Enzymes
D. Bleaches
E. Optical brighteners
F. Detergent polymers
G. Miscellaneous ingredients
IV. Product Evaluation Methods
A. Physical properties
B. HDLD detergency evaluation
V. Future Trends
Appendix
References

Page 262
I. Introduction
Heavyduty liquid detergents (HDLDs) were introduced into the laundry
market much later than powder detergents. The first commercial heavy duty
liquid detergent appeared in the United States in 1956. Liquid detergents were
introduced in the Far East/Pacific countries and Europe only in the 1970s and
1980s, respectively (Fig. 1).
Heavyduty liquids have several advantages over powder detergents. The
liquid detergents readily and completely dissolve in water, especially cool or
cold water. They can be easily dispensed from the bottle or refill package with
relatively less messiness than powder detergents, and they do not tend to cake
FIG. 1
Commercial North American (above) and European and Asian/Pacific
HDLDs.

Page 263
in storage as powders often do when exposed to moisture. Furthermore, liquid
detergents lend themselves to pretreatment at full strength directly on stains and
thus provide a convenient way to remove tough stains.
A typical heavyduty liquid detergent consists of all or some of the following
components: surfactants, builders, optical brighteners, enzymes, polymers, and
fragrance. In addition, it may contain other special ingredients designed for
specific functions.
Both anionic and nonionic surfactants are used in the formulation of liquid
detergents. Surfactants are primarily responsible for wetting the surfaces of
fabrics as well as the soil, helping to lift the stains off the fabric surface and to
stabilize dirt particulates or emulsify grease droplets [1–4]. The main anionic
surfactants are sodium alkylbenzene sulfonate, alkyl sulfate, and alkyl
ethoxylated sulfate. Nonionic surfactants used are primarily ethoxylated fatty
alcohols. Other surfactants are also used in HDLDs and are discussed in a
subsequent section.
Builders are formulated into detergents mainly to sequester the hardness of the
water as well as to disperse the dirt and soil particulates in the washwater.
Common builders used are sodium and potassium polyphosphates, silicates,
carbonates, aluminosilicates, and citrates [5].
Optical brighteners are colorless dyes that absorb ultraviolet radiation and emit
bluish light, making fabrics look whiter and brighter. Most detergents contain
brighteners in their composition, their content adjusted more or less to reflect
regional consumer preferences and marketing claims.
The enzymes in HDLDs usually consist of a protease and an amylase. In
addition, the detergent may also contain lipase and cellulase enzymes. The
function of the protease is to digest protein stains such as blood and
proteinaceous food stains, while the amylase acts on starchy stains. Lipase
attacks fatty chains in greasy stains and is good at cleaning certain oily soils.
Cellulase is an enzyme that acts on cellulase and is being used in detergents for
removing prills in cotton fabrics, thereby restoring reflectance of the fabric
surface and making colors look brighter [6].
Liquid laundry detergents may be classified into two main types: unstructured
liquids and structured liquids. Unstructured liquid detergents typically are
isotropic, have a large and continuous water phase, and are the most
widespread type of liquid detergents in the U.S. market. Structured liquid
detergents are those consisting of multilamellar surfactant droplets suspended in
a continuous water phase. These structured liquids are capable of suspending
insoluble particles such as builders (phosphates, zeolites). These liquids are in
use in Europe and in Asian and Pacific countries. A further type of liquid is one
where the continuous phase is nonaqueous. Only one commercial example of
this type of liquid detergent is known.

Page 264
The sections that follow describe the physical characteristics of heavyduty
liquids, followed by detailed descriptions of typical formulation components of
liquid detergents and their functions. A brief section on evaluation
methodologies follows. Finally, emerging trends in the formulation and
detergency of heavyduty liquids are discussed. A comprehensive tabulation of
the patents relevant to HDLDs is given in the Appendix at the end of this
chapter.
II. Physical Characteristics of HDLDs
The physical form and appearance of laundry liquids can vary greatly among
various regions of the world. These differences in types of liquid detergents
from region to region is largely dictated by the laundry habits and personal
choices of the consumers in that particular market. HDLDs can be broadly
classified into two main types: structured and unstructured liquids. A third type,
nonaqueous liquids, have been actively studied and are also discussed in this
chapter.
Structured liquids are opaque and usually thick and are formed when surfactant
molecules arrange themselves as liquid crystals [7–9]. This form of liquid
detergent is largely marketed in Europe and the Asian/Pacific regions.
Unstructured liquids, on the other hand, are usually thin, clear, or translucent
and are formed when all ingredients are solubilized in an aqueous medium.
Figure 2 gives examples of unstructured and structured HDLDs. Nonaqueous
liquids, in which the continuous medium consists of an organic solvent, can be
either structured or unstructured.
A. Structured Liquids
1. Introduction
The general tendency of liquids containing high levels of anionic surfactants and
electrolytic builders is to structure themselves with the formation of liquid
crystalline surfactant phases [7–12]. This trend can be accelerated with the use
of longer or branched chain alkyl groups and by using a higher electrolyte level
[13]. The resulting liquid is opaque, extremely thick, unpourable, and
frequently physically unstable. It may also subsequently separate into two or
more layers or phases: a thick, opaque surfactantrich phase containing the
flocculated liquid crystals and a thin, clear electrolyterich phase. The
challenge, therefore, in developing such a liquid is to not only to prevent phase
separation of the product but also to reduce the viscosity to a pourable level. A
pourable level depends, of course, on the preferences, requirements, and
convenience of the consumer. Viscosities of commercially available structured
liquids vary from 500 to 9000 cps.

Page 265
FIG. 2
Examples of an unstructured (left) and a structured (right)
HDLD.
2. Lamellar Structures
The liquid crystalline phase in a structured liquid is frequently in the form of
spherical lamellar bilayers or droplets [14–18]. The internal structure of these
droplets is in the form of concentric alternating layers of surfactant and water.
This configuration is often compared to the structure of an onion, which has a
similar concentric shelllike structure (Fig. 3). It has been determined that the
physical stability of these types of liquids is achieved only when the volume
fraction of the bilayer structures is high enough to be spacefilling. This
corresponds to a volume fraction of approximately 0.6 [7,8,19]. An
excessively high value of this volume fraction, however, will lead to
flocculation, high viscosity, and an unstable product. A stable dispersion of the
lamellar droplets makes it possible to suspend solids and undissolved particles
between the lamellae and in the continuous electrolyte phase. This capability
allows the use of relatively high builder/electrolyte levels. Many patents have
been issued for structured liquids that have the capability of suspending
undissolved solids. The suspended solids include bleaches [20,21], builders
such as zeolites [22], and softeners [23,24].
There are a number of factors that determine whether or not a lamellar droplet
can form. As a general rule these bilayer structures will develop if the surfactant
headgroup is smaller than twice the trans crosssectional area of the alkyl
chains of the surfactants [8,13]. This ratio of the areas of the alkyl chain and
the surfactant headgroup is referred to as the packing factor of the surfactant
system. Among the elements that can accelerate the formation of these struc

Page 266
FIG. 3
Schematic diagrams of a nonflocculated lamellar dispersion, a lamellar
droplet, and the internal structure of a lamellar droplet. (Reproduced with
permission from Ref. 10.)
tures is the use of longer chain alkyl chains, branched alkyl groups, dual alkyl
groups, and higher levels of electrolytes. Conversely, by using short, straight
chain alkyl groups, lower electrolyte levels, or hydrotropes, the onset of the
liquid crystalline phase can be delayed.
A lamellar droplet is held together by an intricate balance of various interand
intradroplet forces [10,11]. Any alteration or imbalance in these forces can
have a direct impact on the stability of the structured liquid. Electrostatic
repulsion between the charged headgroups of the anionic surfactants is
compensated by attractive van der Waals forces between the hydrophobic
alkyl chains of the anionic and nonionic surfactants. In addition, there are also
osmotic and steric forces between the hydrated headgroups of the nonionic
surfactants. These particular interactions can be either attractive or repulsive
depending on the “quality” of the solvent [8]. The resultant force has a direct
influence on the size of the water layers, the size of the droplet, and eventually
the stability of the liquid.
3. Stability of Structured Liquids
The balance of attractive forces between the surfactant layers and the
compressive/repulsive forces due to steric and/or osmotic interactions makes
highly concentrated formulations possible. But a singlephase structured liquid,
by its

Page 267
very nature, is never in a state of complete equilibrium. However, for practical
purposes a stable structured liquid is achieved when the inter and intralamellar
forces are manipulated in such a way that phase separation is minimized or
avoided. Depending on the extent of concentration of the ingredients, various
methods can be employed to stabilize these structured liquids (Fig. 4).
The most basic means of achieving stabilization and viscosity reduction is by
the addition of electrolytes. The addition of cations in the form of electrolytes
such as sodium citrate has the effect of screening out some of the repulsive
forces between the negatively charged anionic headgroups. Also, the
electrolytes in the continuous layer provide an element of stability by giving it
ionic strength. This screening out process reduces the size of the intralamellar
water layer and consequently the size of the entire droplet. This reduction of
the lamellar size frees up some extra volume in the continuous phase and
therefore provides an additional element of stability. Increasing the amounts of
citrate works only up to a certain point beyond which there is a greater amount
of undissolved salt that will be have to be suspended between the lamellar
droplets and can lead to excessive thickening. Another consequence of adding
large
FIG. 4
Schematic diagrams depicting the stability of (a) unstable and (b) stable
structured HDLDs.

Page 268
amounts of electrolyte is the further erosion of the intralamellar water layer.
This water layer has to be maintained at a level that is sufficient to hydrate the
headgroups of the nonionic surfactants. Saltingout electrolytes [25], of which
sodium citrate is an example, also hydrate and therefore compete with the
nonionics and other ingredients for the water. Excessive shrinkage of the water
layer can therefore result in product instability.
(a) Free Polymers. The addition of electrolytes assists in lowering viscosities
and in stabilizing the structured liquid only up to a certain degree [26–28].
Polyethylene glycol and polyacrylates are examples of free polymers. These
polymers are nonstructuring, and consequently they do not have the capability
of adsorbing onto the lamellar dispersions. Instead they function by means of
osmotic compression, which results in shrinkage of the lamellar droplet. The
consequence of this reduction in the volume of the individual droplets is a
higher void fraction in the liquid. This polymer can therefore be used only up to
the point at which the optimum void fraction is achieved. Further increases in
the free polymer often lead to depletion flocculation, which is also
accompanied by large increases in viscosity as well as phase separation.
Concentrating the structured liquid by merely forming thinner lamellar layers
and increasing the volume fraction of the lamellae can have implications for the
rheology and pourability of the product. The best pourability characteristics are
obtained when the volume fraction of the lamellar phase is as low as possible
and the lamellae are relatively large. A compromise between these two
pathways or strategies has to be achieved in order to formulate a stable,
concentrated liquid with acceptable rheological traits. This task becomes
increasingly difficult at even higher concentrations. With only a limited void
fraction available, the lamellar droplets, even though they are reduced in size,
begin flocculating.
(b) Deflocculating Polymers. Free polymers are effective in reducing the size
of the lamellar dispersion and thereby imparting stability. However, at ever
increasing concentrations of surfactants and builders, simply reducing the
intralamellar water layer is not sufficient to prevent flocculation. The problem
was successfully addressed by researchers at Unilever, who were able to
prevent flocculation by altering the interlamellar forces [13,19,29–31]. This
was achieved by means of a deflocculating polymer that could be considered
to be bifunctional. These polymers consisted of a hydrophilic backbone
attached to a hydrophobic side chain. The hydrophilic component is
fundamentally like a free polymer or copolymer in both structure and function.
The hydrophobe side chain is typically a long alkyl chain. Figure 5 shows a
schematic of an example of a Unilever deflocculating polymer—an acrylate
lauryl methacrylate copolymer. The unique aspect of this polymer is its ability
to not only utilize its hydrophilic component to induce osmotic compression
within the lamellar bilayers

Page 269
FIG. 5
An example of a Unilever deflocculating polymer.
(Reproduced with permission from Ref. 13.)
but also to employ its hydrophobic side chain to adsorb onto the surfactant
layers. This hydrophobicity also permits the deflocculating polymer to attach
itself to the outer surface of the lamellar droplet and consequently be able to
influence the interlamellar interactions. This trait prevents or at least lessens the
likelihood of flocculation occurring.
The stability of these structured liquids, therefore, is obtained when the lamellae
are not only smaller, but also well separated (Fig. 4). This results in not only a
singlephase, stable liquid but also a product with good flowability
characteristics. Table 1 shows the list of ingredients typically found in a
structured HDLD.
B. Unstructured Liquids
1. Introduction
Heavy duty liquids on the current U.S. market are predominantly in the thin,
clear, and unstructured form. All manufacturers market laundry liquids that are

TABLE 1 Example of Structured HDLD Formation
Ingredient Function
Sodium linear alkylbenzene sulfonate Anionic surfactant
Sodium alkyl ether sulfate Anionic surfactant
Alcohol ethoxylate Nonionic surfactant
Sodium carbonate Builder
Zeolite Builder
Sodium perborate Bleach
Polymer Stabilizer
Protease Enzyme
Fluorescent whitening agent Brightener
Boric acid Enzyme stabilizer
Preservative
Fragrance
Colorant
unstructured, thin, and clear. Besides the obvious differences in the physical appe
properties between the structured and unstructured liquids, there are other dissim
the formulation of these liquids that can have a direct impact on the cleaning perfo
the product. Unstructured liquids are commonly formulated with higher amounts
surfactants in conjunction with lower builder levels (see Table 2). This is in contra
structured liquids, which need more builders and electrolytes to sustain the struct
TABLE 2 Example of Unstructured HDLD Formulation
Ingredient Function
Sodium linear alkylbenzene sulfonate Anionic surfactant
Sodium alkyl ether sulfate Anionic surfactant
Alcohol ethoxylate Nonionic surfactant
Sodium citrate Builder
Monoethanolamine Buffer
Soap Defoamer
Protease Enzyme
Fluorescent whitening agent Brightener
Boric acid Enzyme stabilizer
Ethanol Solvent
Sodium xylene sulfonate Hydrotrope
Preservative
Page 271
phase. The physical appearance and stability of structured liquids are very
dependent on surfactant ratios, whereas the clear, unstructured liquids allow far
greater flexibility in choosing surfactant ratios as long as a single phase is
maintained. The main advantage in structured liquids is their ability to suspend
undissolved and insoluble solids. The unstructured, clear liquids, on the other
hand, by their very nature do not permit the use of insoluble materials. This
results in the use of only soluble builders, and at relatively low levels, and
precludes the use of other useful builder ingredients such as zeolites.
It cannot be said that one form of liquid has a distinct advantage over the other.
The formulation and marketing of either form may be dependent on such
factors as efficacy targets, consumer preferences and habits, choice and
availability of raw materials, and cost considerations.
2. Stability of Unstructured Liquids
Unlike structured liquids, unstructured, thin, clear liquids can be developed
only if the onset of the formation of liquid crystals is delayed or broken up. This
can be accomplished by two different methods: (1) by adding hydrotropes and
solvents that can disrupt or prevent any liquid crystal formation and also aid in
solubilizing the other components in the formulation or (2) by increasing the
water solubility of the individual components. More than likely a combination
of the two techniques is used to develop a stable liquid. The respective costs of
these approaches ultimately determines their use in the final formulation. Some
of the methods used to formulate stable, singlephase, thin, clear, unstructured
liquids are summarized below.
Compounds such as sodium xylene sulfonate (SXS), propylene glycol, and
ethanol are useful in disrupting and preventing the formation of lamellar
structures that can opacify and thicken the liquid. SXS is especially useful in
solubilizing LAS. Propylene glycol and ethanol have the additional benefit of
contributing to enzyme stability. The main drawback of using these compounds
is that they do not contribute to the detergency performance of the product.
Their principal function is to aid in achieving the thin, clear appearance by
solubilizing various ingredients and preventing precipitation and phase
separation.
It is possible to form concentrated liquid detergents that do not require
additional ingredients to assist in the maintenance of a clear appearance. This is
usually accomplished by minimizing the use of LAS and electrolytes and
maximizing the use of nonionics.
The use of ingredients with increased water solubility is probably the most
effective tool for producing a singlephase thin, clear liquid. Potassium salts
generally tend to be more soluble than their sodium cation counterparts. In
these formulations, a higher level of potassium citrate than sodium citrate can
be successfully incorporated. Detergency performance is not affected by
replacing the Na+ cation with K+.

Page 272
Citrate compounds are saltingout electrolytes—they may tie up water
molecules in the liquid and as a result help force the formation of liquid crystals
or lamellar structures. It is sometimes possible to reverse this trend by adding
saltingin electrolytes, compounds with high lyotropic numbers (>9.5) that can
raise the cloud point of the liquid formulation [25]. This permits increased
concentration without the onset of structuring.
Ethanolamines such as monoethanolamine (MEA) and triethanolamine (TEA)
can also be invaluable in enhancing the solubility of the ingredients. These
compounds are bifunctional in that they have characteristics common to both
alcohols and amines. As a result, salts of MEA and TEA are more soluble than
those prepared with Na+. Neutralizing sulfonic acid with MEA is a very
effective way of freeing up additional water to allow for further concentration.
In addition, any free alkanolamine that is not tied up as a salt behaves like an
alcohol and can aid in solubilizing other ingredients. These compounds also
provide detergency benefits by buffering the washwater.
C. Nonaqueous Liquids
Nonaqueous liquids may be classified as structured or unstructured depending
on the level of surfactants and other components in their formulation [32].
These detergents have several advantages over aqueous formulations.
Nonaqueous detergents can contain all the primary formulation components,
including those that are not compatible with or are difficult in aqueous systems.
The liquid matrix is a nonionic surfactant or a mixture of nonionic surfactants
and a polar solvent such as glycol ether [33–36]. Builders such as phosphates,
citrates, or silicates can be incorporated, although zeolites containing about
20% water are not generally recommended [37]. Phosphatefree formulations
have also been reported [38]. Bleaches, such as tetraacetyl ethylenediamine
(TAED) activated sodium perborate monohydrate, can be included in these
formulations. Since these formulations do not contain water, enzymes may be
added with minimal need for stabilizers. Softening ingredients can also be
included [39,40]. Furthermore, excellent flexibility in the concentration of the
detergent can be attained because only the active cleaning ingredients can be
included in the formulation. The density of the finished product can be as high
as 1.35 g/mL for structured liquids, requiring low dosages for equivalent
cleaning. However, the two major challenges facing this technology are
physical stability of the product and dispensability and solubilization in the
washing machine.
III. Components of HeavyDuty Liquid Detergents and Their
Properties
Heavyduty laundry liquid formulations vary enormously depending upon the
washing habits and practices of the consumers in a given geographic region.

Page 273
The degree of complexity can range from formulations that contain minimal
amounts of cleaning ingredients to highly sophisticated compositions consisting
of superior surfactants, enzymes, builders, and polymers. This section
describes the ingredients found in typical HDLD formulations.
A. Surfactants
Surfactants are the major cleaning components of HDLD formulations
throughout the world. Unlike powder detergents, physical and phase stability
considerations greatly limit the use of other cleaning ingredients, chiefly
builders. Surfactants contribute to the stain removal process by increasing the
wetting ability of the fabric surface and stains and by assisting in the dispersion
and suspension of the removed soils.
An HDLD formulator has a vast array of surfactants from which to choose
[41]. A comprehensive listing and description of these surfactants are beyond
the scope of this article. The choice and levels of surfactants used in
commercial HDLD products depend not only on their performance and
physical stability characteristics but also on their cost effectiveness.
This section briefly describes the anionic and nonionic surfactants commonly
used in commercial HDLD formulations. Cationic surfactants, though also used
on a large scale, are mostly used in fabric softener products. Linear
alkylbenzene sulfonates (LAS), alcohol ethoxylates, and alkyl ether sulfactes
are three of the most widely used types of surfactants in liquid laundry
detergents [42]. Recently, various external considerations, such as
environmental pressures, have prompted manufacturers to change their
surfactants mix to include newer natural types of surfactants [43–45].
1. Linear Alkylbenzene Sulfonate (LAS)
The excellent costperformance relationship of linear alkylbenzene sulfonates
(LAS) makes them the dominant surfactants used in laundry detergents [46].
Recent trends in Europe and North America indicate a gradual reduction in
their use in HDLDs. Nevertheless, their use in laundry liquids globally is still
substantial, especially in the developing regions of the world.
De Almeida et al. [47] and Matheson [48] provide a comprehensive
examination of the processing, production, and use of linear alkylbenzene in the
detergent industry. Linear alkylbenzene sulfonates are anionic surfactants and
are prepared by sulfonating the alkylbenzene alkylate and subsequently
neutralizing it with caustic soda or any other suitable base. The alkylate group
is typically a linear carbon chain of length ranging from C10 to C15, with a phenyl
group attached to one of the secondary carbons on the alkyl chain (Fig. 6).
The alkylate portion of the molecule is hydrophobic, whereas the sulfonate
group provides the water solubility and the hydrophilicity. Most commercial
alkylates are mixtures of various phenyl isomers and carbon chain homologs
[49]. The

Page 274
FIG. 6
Structures of typical HDLD surfactants.
position of the phenyl group depends on the manufacturing method. Systems
using AlCl3 or HF catalysts are the most common. Table 3 lists a typical
isomeric and homolog distribution in linear alkylbenzene produced using the
HF process.
The length of the carbon chain and the isomeric distribution strongly influence
the formulatability and performance of the surfactant. It has been determined
that the surface activity of this surfactant increases with longer carbon chain
lengths [50]. A longer alkyl chain increases the hydrophobicity of the molecule,
lowers its CMC, and generally provides better soil removal charac

TABLE 3 Homolog and Isomeric Distribution of Linear Alkylbenzene Prepared Using the
Percent
Compound C10 C11 C12 C13 C10–13 ØC11.5
5Phenyl decane 29.8 0.06


6/5Phenyl undecane 0.4 43.1

4Phenyl undecane 0.2 21.4

6Phenyl dodecane 0.6 22.2 0.07


6/7Phenyl tridecane 0.06 33.2

5Phenyl tridecane 0.05 22.2
4Phenyl tridecane 0.02 15.3
3Phenyl tridecane 13.3
2Phenyl isomer 20.2 15.2 12.0 9.9 14.8
Source: Ref. 4.
2Phenyl isomer 20.2 15.2 12.0 9.9 14.8
Source: Ref. 4.
teristics [51–54]. LAS offers superior and very cost effective detergency perfor
especially on particulate soils. However, due to its high sensitivity to water hardn
best utilized only with an accompanying builder [55]. Figure 7 shows the increase
to hardness ions for LAS with longer carbon chain lengths. Without the assistanc
builders, the soil removal efficacy of LAS drops rapidly with increasing water har
[4,56] (Fig. 8).
The amount and type of LAS in HDLDs depend largely on the physical form of t
liquid—unstructured or structured. In unstructured liquids, solubility consideration
the use of shorter carbon chain lengths ( C11). The choice of cations can also en
solubility. Potassium and amine cations such as MEA and TEA can be used inste
sodium ions to improve stability [57]. An increase in the proportion of the 2phen
the LAS can also increase solubility [58] and sometimes improve the hardness tol
the surfactant [59]. In structured liquids, on the other hand, a longer alkyl chain c
desirable for the formation of surfactant lamellae. The choice of

Page 276
FIG. 7
Ca2+LAS precipitation boundary diagrams. (Reproduced with
FIG. 8
Soil removal data for LAS as a function of water hardness.
Results are shown for surfactant with builder (STPP) and
electrolyte. (Reproduced with permission from Ref. 4.)

Page 277
the counter ion can also affect stability because ions such as Na+ and K+ have
different electrolytic strengths, which can also impact phase stability.
A disadvantage of using LAS in HDLDs is their detrimental effect on enzymes.
With the increasing use of enzymes it becomes necessary to devote a sizable
portion of the formulation space and cost to enzyme stabilization. Alternative
approaches using surfactants more compatible with enzymes can be employed.
2. Alcohol Ethoxylates
Figure 6 shows the general structure of a nonionic alcohol ethoxylate
surfactant. Its hydrophobic group is linear with the carbon chain length ranging
typically from C10 to C15. The hydrophilic ethoxylate group can vary in size
from an average of 5 to 7 mol of ethylene oxide [60–62]. Alcohol ethoxylates
are marketed commercially under the trade names Neodol (Shell Chemical
Co.), Genapol (Hoechst AG), Tergitol (Union Carbide Co.), and Alfonic
(Vista Chemical Co.). The feedstocks for the alcohol can be derived from
natural coconut oil sources as well as from petroleum feedstocks. These
surfactants are sold in a 100% concentration and are typically in liquid form.
Alcohol ethoxylate usage in HDLDs depends on the type or the physical form
of the liquid detergent. Its high aqueous solubility makes it a useful ingredient in
unstructured liquids. This solubility can be further enhanced by increasing the
degree of ethoxylation and decreasing the carbon chain length. However, these
modifications can sometimes have negative ramifications for cleaning
performance. The choice of carbon chain length and the degree of ethoxylation
depend on the physical stability and cleaning requirements of individual
formulations. Structured liquids, on the other hand, can tolerate only a limited
amount of the nonionic alcohol ethoxylate surfactant, as the stability of these
liquids is dependent on the optimum distribution of the size and packing
configuration of lamellar droplets. Excessive use of nonionic surfactants can
disturb this somewhat delicate equilibrium and cause phase separation of the
HDLD.
Nonionic surfactants like alcohol ethoxylates demonstrate superior tolerance to
hard water ions. This characteristic is especially useful in unstructured HDLD
formulations because solubility constraints limit the amount of builder that can
be incorporated. They also provide excellent cleaning benefits and are
commonly used in conjunction with LAS in HDLD formulations [54,63].
Studies have shown that in LAScontaining products, alcohol ethoxylates can
lower the critical micelle concentration (Fig. 9) as well as provide
improvements in the detergency [63]. Superior cleaning is observed, especially
on oily soils such as sebum on polyester fabrics [64]. The presence of alcohol
ethoxylates in an LAScontaining formulation was found to improve
detergency, especially at higher

Page 278
FIG. 9
Critical micelle concentration (CMC) as a function of
nonionic surfactant content in a LAS/NI solution.
hardness levels (Fig. 10). Improvements have also been detected when narrow
EO range surfactants (Fig. 11) are used [65].
This insensitivity to calcium ions also provides a very important benefit in the
stabilization of enzymes (see Sec. III.C). It has been shown that these
surfactants are not as detrimental to the preservation of enzymes in HDLDs as
NaLAS. With increasing reliance on the use of enzymes in the laundry cleaning
process, nonionic surfactants like alcohol ethoxylates play an important role in
enhancing enzyme stability.
3. Alkyl Ether Sulfates (AEOS)
Alkyl ether sulfates are also anionic surfactants that are manufactured by
sulfating alcohol ethoxylate surfactants [66]. Figure 6 shows the structure of the
molecule, which consists of the alcohol ethoxylate connected to a sulfate
group. The EO groups typically range in size from 1 to 3 moles.
These surfactants provide numerous benefits that make them an attractive
option to HDLD formulators. They are commonly used in both structured and
unstructured liquids. Their high water solubility makes it possible to use a wide
range of levels in unstructured liquids. They can also be successfully
incorporated in structured liquids.
Unlike NaLAS, alcohol ether sulfates are more tolerant to hardness ions and
as a result do not require an accompanying high level of builder in the
formulation. Figure 12 shows the relative insensitivity of alkyl ether sulfates to
hardness ions. The addition of small amounts of NaAEOS to LAS was found
to improve interfacial properties. They are more friendly to enzymes, which can
also reduce the cost of enzyme stabilizers in the formulation. They are also
milder to the skin and as a result are used in hand dishwashing formulations.
The

Page 279
FIG. 10
Detergency performance at 100°F of LAS and LAS/AE blends.
Formulation also contained 25% STPP, 10% silicate, and 35%
sodium sulfate. (Reproduced with permission from Ref. 63.)
superior detergency performance of this surfactant is demonstrated by its
superior efficacy in most stain categories.
4. Alkyl Sulfates
Alkyl sulfates are anionic surfactants (Fig. 6) that are used primarily in Europe
as a substitute for LAS [43]. Environmental considerations have prompted
manufacturers to use surfactants of this type, which can be derived from
oleochemical sources. The carbon chain length can range from C10 to C18.
Tallow alcohol sulfate is a common form used in HDLDs. It provides excellent
detergency and good foaming and solubility characteristics.

Page 280
FIG. 11
Typical ethoxylate adduct distribution in narrowrange
and broadrange C alcohol surfactants with similar
12–14
cloud points. (Reproduced with permission from Ref. 62.)
FIG. 12
Data showing the hardness tolerance of alkyl ether
sulfate surfactants. (Reproduced with permission from Ref. 4.)

Page 281
5. Polyhydroxy Fatty Acid Amides (Glucamides)
Polyhydroxy fatty acid amides (Fig. 6) are currently used in light duty and
heavy duty laundry liquids. Recent advances in the technology for the
manufacture of these surfactants has made their use economically feasible [67–
69]. The use of natural or renewable raw materials improves their
biodegradation characteristics. Several patents have been filed for detergent
formulations containing glucamides that claim superiority in cleaning efficacy for
oily/ greasy and enzymesensitive stains [70–73]. Synergies with other anionic
and nonionic surfactants have been reported [72,73]. Their improved skin
mildness qualities can be useful in lightduty liquid applications [74]. Enzyme
stabilization characteristics in glucamide formulations are also enhanced relative
to LAScontaining HDLDs.
6. Methyl Ester Sulfonates
Methyl ester sulfonates are anionic surfactants (Fig. 6) that are also derived
from oleochemical sources and have good biodegradability characteristics.
They are currently used in only a limited number of markets, primarily in Japan
[44]. Their good hardness tolerance characteristics (Fig. 13) and their ability to
also function as a hydrotrope makes these surfactants a good candidate for
liquid detergents [74]. They have also been found to be good cosurfactants
for LAScontaining formulations. They can only be used in products with low
alkalinity due to the likelihood of hydrolytic cleavage of the ester linkage under
high pH conditions.
7. Other Surfactants
Once used as a major surfactant in detergent formulations, soap is now used
only as a minor ingredient in HDLDs. Its function is primarily to provide foam
FIG. 13
Detergency as a function of water hardness in
methyl ester sulfonate/LAS formulations.

Conditions: 25°C, surfactant 270 ppm, Na2CO3
135 ppm, silicate 135 ppm. (Reproduced with

Page 282
control in the washing machine. European liquid formulations contain higher
soap levels than their counterparts in North America because of increased
foaming tendencies in European machines. Soap also aids in the cleaning
process. However, it can leave behind an encrustation of soap scum on fabric
surfaces. A variety of other surfactants are also used, primarily for specialty
applications [76]. They include amine oxides, amphoterics, and betaines.
B. Builders
The primary function of builders in the detergency process is to tie up the
hardness ions Ca2+ and Mg2+. They also provide other valuable benefits
including maintaining the alkalinity of the wash solution and functioning as
antiredeposition and soildispersing agents and, in some cases, as corrosion
inhibitors [77–81].
The level of builders used in liquid formulations depends largely on three main
criteria: (1) the aqueous solubility of the builder, (2) the physical form of the
liquid, and (3) the cost effectiveness of the ingredient. Due to inherent solubility
constraints in formulating stable liquid detergents, the usage level of builders in
HDLDs is significantly lower than in granulated detergents. This is especially
true in the case of unstructured liquids, where the solubility limitations of the
builder largely dictate its level in the formulation. In structured liquids, however,
a certain amount of electrolytic builder is necessary to induce structuring, which
allows the incorporation of significantly higher amounts of builder. Insoluble
builders can also be added by suspending them in the liquid. Builder ingredients
such as zeolites, phosphates, silicates, or carbonates can account for 20% or
more of the total formulation.
1. Mechanisms
Builder compounds decrease the concentration of the washwater hardness by
forming either soluble or insoluble complexes with the calcium and magnesium
ions. The mechanisms by which these ingredients function can be broadly
grouped into three classes: (1) sequestration, (2) precipitation, and (3) ion
exchange. All three methods have the ultimate effect of lowering the
concentration of hardness ions that could interfere with the cleaning process by
rendering the surfactants less effective.
In sequestration (chelation), the hardness ions Ca2+ and Mg2+ are bound to the
builder in the form of soluble complexes. Phosphates, citrates, and NTA are
examples of this class of builder compound. Table 4 lists the calciumbinding
capacities of various builders. Other strongly chelating compounds exist,
phosphonates and EDTA for example, but they are generally not extensively
used in HDLDs. The most efficient builder is sodium tripolyphosphate.
Unfortunately, tripolyphosphate has been identified as a possible cause of
eutrophi

TABLE 4 Sequestration Capacity of Selected Builders

Structure Ch
Sodium diphosphate

Sodium triphosphate

1Hydroxyethane1,1dip

Amino tris methyleneph

Nitrilotriacetic acid

TABLE 4 Continued

Structure Chemical name
N(2Hydroxyethyl)im

Ethylenediamine tetra

1,2,3,4Cyclopentane
(table continued on next page)

(table continued from previous page)

Structure Chemical name
Citric acid

OCarboxymethyl tartr

Carboxymethyl oxysuc

Source: Ref. 82.

Page 286
cation of lakes and rivers. It is severely controlled and even banned in several
countries. As a result, most countries in North America and Europe have
converted to nonphosphate formulations. Other regions are also gradually
imposing restrictions on the use of phosphates.
Carbonates are examples of builders that precipitate out the calcium ions in the
form of calcium carbonate. Precipitation builders, however, can leave behind
insoluble deposits on the clothes and washing machine parts. Aluminosilicates
such as zeolites are ionexchange compounds: they remove calcium and
magnesium ions and exchange them with sodium ions.
Most builders also contribute significantly to detergency by providing alkalinity
to the washwater. A high pH (>8) solution aids in the removal of oily soils such
as sebum stains by saponifying them. Insoluble fatty acids found in oily soils are
converted to soluble soap in the presence of alkalinity.
2. Builder Classes
(a) Inorganic. In regions where phosphorus compounds are still permitted in
detergent products, polyphosphates such as tripolyphosphates and
pyrophosphates are unsurpassed in their cost effectiveness and cleaning ability.
These ingredients are not only very good chelating agents but also provide a
soilsuspending benefit. Stains, once removed from the fabric, can be
suspended in the washwater by electrostatic repulsion, thereby preventing soils
from redepositing onto the clothes. To a certain extent phosphates also buffer
the washwater. The solubility of tripolyphosphates can be enhanced by using
the potassium salt. This would be the more appropriate for unstructured
liquids. In structured liquids, the sodium salt can be incorporated at much
higher levels.
Carbonate compounds offer an economical means of reducing the calcium
content and also raising the alkalinity of the washwater. They lower the
concentration of the calcium by precipitating it in the form of calcium
carbonate. This could lead to fabric damage in the form of encrustation, which
becomes especially apparent after repeated washing cycles. Fortunately, this is
not a major problem in unstructured HDLDs, because the amount of carbonate
used in the formulation is limited by solubility restrictions. Compounds such as
sesquicarbonates and bicarbonates that are less likely to lead to the formation
of calcium carbonate precipitates have better solubility characteristics and can
be used to a greater extent in unstructured liquids. On the other hand,
structured liquids offer the potential of incorporating much higher amounts of
these compounds. Carbonates are also good washwater buffers and can
provide the alkalinity needed for improved efficacy.
Another class of ingredients that are effective at providing alkalinity are the
sodium silicates [83]. Although they can also be good sequestrants and are
used as such in powder formulations, they provide this benefit only at higher
con

Page 287
centrations. Once again, the solubility restrictions prevent the incorporation of
any substantial amounts in unstructured liquids. At the low levels at which they
can be used, they are valuable as alkaline buffers. The use of sodium silicates in
HDLDs is limited to the liquid silicates, which have SiO2/Na2O ratios from 3.2
to 1.8.
Aluminosilicates [Mz (zAlO2: y SiO2)] are another type of builders, of which
zeolite A is a common example [84]. Zeolite A is a sodium aluminosilicate with
an Al/Si ratio of 1:1 and a formula of Na12(SiO2∙ A O2)12∙ 27H2O. It acts as a
builder by exchanging sodium ions inside the lattice with calcium ions from the
washwater. Zeolites are not effective in providing alkalinity and are normally
used in conjunction with carbonates. They are insoluble in water and are
therefore not suitable for formulating unstructured liquids. In structured liquids,
zeolites are suspended as solid particles.
(b) Organic. The restrictions placed on the use of phosphate compounds in
detergent formulations have led to a variety of organic compounds that could
function as builders but must also be readily biodegradable. Although some of
these compounds do approach the sequestration level of phosphates, they are
not as costeffective [85].
Various polycarboxylate compounds, those with at least three carboxylate
groups, have now become widely used as replacements for phosphates as the
builder component of HDLDs. In liquid detergent formulations, citrate
compounds have become commonplace. Though their chelating ability is
relatively low (Fig. 14), citrate compounds are used in HDLDs for a variety of
reasons. Citrate's high aqueous solubility makes it useful in unstructured liquids,
whereas in structured liquids its high electrolytic strength can aid in salting out
and stabilizing the formulation. In addition, it is used in enzymecontaining
formulations where maintenance of the pH at less than 9.0 is crucial to the
stability of the enzyme. Citric acid itself has also been patented as an ingredient
in protease stabilization systems [87].
Ether polycarboxylates have been determined to provide improvements over
the calcium and magnesiumchelating ability of citrates. In a series of patents
assigned to Procter & Gamble, it has been claimed that a combination of
tartrate monosuccinates and tartrate disuccinates (Fig. 15) delivers excellent
chelating performance [88–90]. Data shown in Fig. 16 indicate a high level of
calciumbinding capacity.
Salts of polyacetic acids, e.g., ethylenediamine tetraacetic acid (EDTA) and
nitrilotriacetic acid (NTA), have long been known to be very effective chelating
agents [91]. The chelating ability of NTA has been found to be comparable to
that of TPP. Unfortunately, questions regarding the toxicity of this compound
have all but prevented any largescale use in HDLDs. Currently, NTA usage is
primarily limited to a few powder formulations in Canada. The high chela

Page 288
FIG. 14
Sequestration of water hardness ions by detergent
builders. ( ) Sodium polyacrylate M w = 170,000; ( )
STPP; ( ) NTA; ( ) EDTA; (
) sodium citrate; ( )
CMOS; ( ) sodium carbonate; ( ) zeolite A.
FIG. 15
Ether polycarboxylate builders.

Page 289
FIG. 16
Effect of builder level on calcium ion concentration. (From
Ref. 89.) CMOS, sodium carboxymethoxysuccinate; ODS,
sodium oxydisuccinate; STP, sodium tripolyphosphate;
TMS, tartrate monosuccinate; TDS, tartrate disuccinate.
tion power of EDTA has been used in compositions where metal impurities of
iron and copper can be detrimental to the product stability, as, for example, in
peroxide bleachcontaining liquids.
Polymeric polyelectrolytes have also found applications as builder ingredients
[92,93]. High molecular weight polyacrylates and acrylic maleic copolymers
can be very effective in tying up calcium ions in the wash (Fig. 17). However,
concerns about their biodegradability and aqueous solubility have significantly
limited their use in liquid formulations. These polymer systems can also aid in
soil dispersion and in antiredeposition. In products containing carbonates, these
polymers can disrupt calcium carbonate crystallite formation and as a result
prevent encrustation on clothes.
Fatty acids such as oleic and coco fatty acid (saturation level) added to
HDLDs can serve a multifunctional role. Though they primarily provide a foam
suppression capability, they can also precipitate out some of the calcium ions in
the wash by forming calcium soap. This could, however, pose a problem
because soap scum is insoluble and may impact the overall cleaning result.
C. Enzymes
Enzymes have become integral components of most liquid detergent
compositions as they continue to play an increasingly larger role in the stain
removal

Page 290
FIG. 17
Sequestration of water hardness ions by sodium

polyacrylate polymers. ( ) M w=2100; ( )M w=5100;
( )M w=20,000; ( )M w=60,000; ( )M w=170,000,
( ) M =240,000. (Reproduced with permission from
w
Ref. 86.)
process. This has come about because of many recent advances in enzyme
technology and has resulted in more efficient and effective strains. The ability of
these enzymes to target specific classes of stains can provide the formulator
with the flexibility to tailor the development of products for consumers with
different requirements and preferences. In addition, enzymes are especially
effective when the liquid detergent is used as a prespotter.
There are four types of enzymes currently being used in HDLDs: protease,
lipase, cellulase, and amylase [6,94]. They are all proteins and are derived
from various living organisms. Their role is to catalyze the hydrolysis of large
biological molecules into smaller units that are more soluble and as a result are
washed away relatively easily. The optimum conditions for the functioning of
these enzymes depend on individual strains or types. Generally, the rates of
these enzymatic reactions rise with increasing temperatures and are usually
optimum within an alkaline pH range of 9–11.

Page 291
Proteases are by far the most widely used of all detergent enzymes. Introduced
in the 1960s, they have since become one of the more important components
of the detergent formulation [6]. Proteases aid in the removal of many soils
commonly encountered by the consumer such as food stains, blood, and grass.
These enzymes hydrolyze or break up the peptide bonds found in proteins,
resulting in the formation of smaller and more soluble polypeptides and amino
acids. Since most enzymes have to function at high pH conditions, subtilisin, a
bacterial alkaline protease, is commonly used in laundry detergents. This
particular protease does not hydrolyze any specific peptide bond in the
proteinaceous stain but cleaves bonds in a somewhat random manner.
Amylase enzymes work on food stains of the starchy variety, like rice,
spaghetti sauce, and gravy. These enzymes hydrolyze the 1–4glucosidic
bonds in starch, which leads to the formation of smaller watersoluble
molecules. Amylase randomly hydrolyzes the bonds in the starch polymer to
form dextrin molecules. Amylase, on the other hand, cleaves the maltose
units that are situated at the end of the starch polymer.
The use of lipases in detergents is a relatively recent occurrence. The first
commercial detergent lipase was introduced in 1988 [(6,94]. These enzymes
target the oily/greasy stains that are some of the most difficult stains to remove.
The major components of most oily stains encountered in households are
triglycerides. Lipases catalyze the hydrolysis of mostly the C1 and C3 bonds in
the triglyceride molecule, yielding soluble free fatty acids and diglyceride (Fig.
18). In practice, it has been determined that lipases work best subsequent to
the first wash (Fig. 19). It is believed that the temperatures encountered in a
typical drying process are needed to activate the enzyme. Though most oily
stains can also be cleaned using traditional surfactant methods, the main benefit
of lipases is their ability to perform at relatively low concentrations and low
temperatures.
With greater emphasis given to the care of the fabric, cellulase enzymes have
become increasingly important in detergent products [94]. Repeated washing
often leads to cotton fabrics looking faded and worn. This appearance is
attributed to the damaged cellulose microfibrils on the fabric surface. Cellulase
en
FIG. 18
Lipasecatalyzed conversion of insoluble oily (triglyceride) soils.

Page 292
FIG. 19
Effect of lipase enzyme (Lipolase) on lard/Sudan Red stains as a
function of the number of wash cycles. Conditions: Powder
detergent, temp 30°C, Tergotometer, pH 9.7. (Reproduced with
zymes are able to hydrolyze the (1–4) bonds along the cellulose polymer,
resulting in smaller units that are carried away in the wash (Fig. 20). The
removal of these damaged microfibrils or pilling gives the clothing a less faded
appearance (Fig. 21).
FIG. 20
Hydrolysis of cellulose fibers by cellulase enzyme.

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FIG. 21
Effect of cellulase on the color clarity and pilling tendency of a
cotton fabric. European machine at 40°C using a new black
cotton fabric. (Reproduced with permission from Ref. 6.)
1. Enzyme Stabilization
Enzymes are highly susceptible to degradation in heavy duty laundry liquids.
With increasing emphasis on the use of enzymes as cleaning agents, it becomes
all the more important that these enzymes be protected against premature
degradation or at least maintain their performance throughout the shelf life of
the product.
Many factors contribute to the denaturation of the enzymes in HDLDs. They
include free water, alkalinity, bleaches, and calcium ion concentration. The
presence of free water in the formulation is a major cause of enzyme
degradation. This process is greatly accelerated at increasingly alkaline
conditions. Generally, enzymecontaining commercial HDLDs are maintained
within a pH range of 7–9 (Fig. 22). However, this constraint can affect the
detergency, as most enzymes attain their optimum efficacy at pH ranges of 9–
11. Certain additional ingredients, especially bleaches, can also have a major
detrimental effect on enzyme stability.
It is believed that ingredients that are capable of depriving the enzyme's active
site of calcium ions are detrimental to enzyme stability. It is hypothesized that
calcium ions bind at the bends of the polypeptide chain, resulting in a stiffer and
more compact molecule [96–98]. Builders and surfactants that have affinities
toward calcium ions are examples of such ingredients. The degree of stability
also varies greatly with the type of surfactant or builder used. Linear
alkylbenzene sulfonate and alkyl sulfate surfactants have been found to be
more detrimental to enzymes than alcohol ethoxylates or alkyl ether sulfates
[95]. The

Page 294
FIG. 22
Effect of product pH on protease stability in an HDLD containing
alcohol ethoxylate and alcohol ethoxy sulfates. (Reproduced with
degree of ethoxylation also affects the status of the enzyme. In ether sulfates,
improved stability is observed with increasing EO groups up to five to seven
EO groups [96]. LAS is more likely to bind with the calcium ions in the
product than other more hardnesstolerant surfactants such as alkyl ether
sulfates or the nonionic alcohol ethoxylate surfactants. This has been
considered a possible cause of faster enzyme degradation in LAScontaining
HDLDs (Fig. 23). Similarly, in formulations with builders or chelants, additional
calcium is sometimes added to shift the equilibrium to favor the enzyme's active
sites and prevent premature deactivation.
Other mechanisms for enzyme denaturation in the presence of surfactants have
also been proposed. One hypothesis is that the high charge densities of the
ionic surfactants increase the probability of their binding strongly onto protein
sites. This causes conformational changes of the enzyme, which subsequently
lead to further enzyme deactivation [95,99].
The task of stabilizing enzymes is further complicated by the fact that
increasingly HDLD formulations contain more than one enzyme (e.g., protease,
lipase, and cellulase) system. In such systems, not only do the enzymes have to
be protected against denaturation, but also enzymes such as lipase and
cellulase, which are themselves proteins, have to be shielded from the
protease.

Page 295
FIG. 23
Effect of surfactant type on protease stability. AE, Alcohol ethoxylate;
AE253S, Alcohol ethoxy sulfate; LAS, linear alkylbenzene sulfonate.
(a) ProteaseOnly HDLDs. All stabilization systems function either by binding
to the active site of the enzyme or by altering the equilibria of the formulation to
favor the stable active sites. The system is effective in protecting the enzyme
only if the stabilizing molecule binds strongly to the enzyme while in a
formulation but easily dissociates from the enzyme's active sites when it
encounters the dilute conditions in the wash.
Letton and Yunker [100] and Kaminsky and Christy [101] describe protease
stabilization systems composed of a combination of a calcium salt and a salt of
a carboxylic acid, preferably a formate. These ingredients are moderately
effective in enzyme stabilization and are relatively inexpensive. Care has to be
taken, however, when adding divalent ions such as calcium to HDLDs to
prevent the possibility of precipitation.
An improvement over this earlier system was attained with the addition of
boron compounds such as boric acid or borate salts [102–104]. It has been
hypothesized that boric acid and calcium form intramolecular bonds that
effectively crosslink or staple an enzyme molecule together [103,104]. The
use of polyols such as propylene glycol, glycerol, and sorbitol in conjunction
with the boric acid salts has further enhanced the stability of these enzymes
[105–107].

Page 296
The patent art contains numerous examples of enzyme stabilization systems that
use borates, polyols, carboxylate salts, calcium, and ethanolamines or
combinations thereof [87,108–111].
(b) Mixed Enzyme HDLDs. In HDLD formulations with additional enzymes
besides protease, it becomes increasingly difficult to stabilize all the enzymes.
Amylases, lipases, and cellulases are themselves proteins and hence are
susceptible to attack from the protease. Various approaches to stabilizing a
mixed enzyme system have been documented in the patent literature. One
approach attempts to extend the stabilization techniques developed to stabilize
proteaseonly formulations and apply them to mixed enzyme liquids [112–
114].
Compounds that bind even more tightly to the protease active sites and as a
result inhibit this enzyme's activity in the product during shelf storage have been
identified. However, this method is effective only if the enzyme inhibition can be
reversed under the dilute conditions of the washwater. Various boronic acids
[115–119] (e.g., arylboronic acids and amino boronic acids), peptide
aldehyde [120], peptide ketone [121], and aromatic borate ester [122]
compounds have been found that deliver this type of performance. It is
believed that boronic acids inhibit proteolytic enzyme by attaching themselves
at the active site. A boronserine covalent bond and a hydrogen bond between
histidine and a hydroxyl group on the boronic acid apparently are formed
[118]. The patent literature also describes methods of stabilizing the cellulase
enzymes in mixed enzyme systems with hydrophobic amine compounds such
as cyclohexylamine and nhexylamine [123].
Recently, alternative methods have also been developed to stabilize these
complex enzyme systems. The technique of microencapsulation [124] is
designed to physically prevent the protease enzyme from interacting with the
other enzymes (Fig. 24). This is accomplished by a composite emulsion
polymer
FIG. 24
Enzyme microencapsulation. (Reproduced with permission
from Ref. 6.)

Page 297
system that has a hydrophilic portion attached to a hydrophobic core polymer.
The protease is stabilized by trapping it within a network formed by the
hydrophobic polymer.
D. Bleaches
Bleaches play a significant role in detergent formulations because they can
affect cleaning efficacy, which is easily perceived by consumers. Bleaching
action involves the whitening or lightening of stains by the chemical removal of
color. Bleaching agents chemically destroy or modify chromophobic systems
and degrade dye compounds, resulting in smaller and more watersoluble
molecules that are easily removed in the wash. Typical bleachsensitive stains
include food, coffee, tea, fruits, and some particulate soils. Bleaches can also
aid in minimizing “dinginess,” which gives clothes a gray or yellow tint caused
by a combination of fabric fiber damage and dirt buildup.
There are two types of bleaches used in the laundry process: hypochlorite and
peroxygen bleaches. Although hypochlorite bleaches by themselves are
effective bleaches, they lead to color fading and fabric damage and are difficult
to incorporate into detergent formulations. Peroxygen bleaches, on the other
hand, though not as effective, can be formulated into detergents and cause
minimal color fading or fabric damage. They also bleach out food stains as the
chromophores found in these stains are susceptible to peroxide bleaches.
Fabric dyes, however, are not as active as food dyes and are therefore not
easily affected by the peroxygen compounds.
Most detergents with bleach formulations are in the powder form.
Unfortunately, the aqueous nature of the HDLDs does not easily permit the
formulation of bleach components. This is especially true in unstructured
liquids, where the stability of the peroxygen components is severely
compromised. Nevertheless, attempts have been made to produce HDLDs
that also contain bleaches.
1. Peroxygen Bleaches
Detergent formulations containing peroxide bleach contain either hydrogen
peroxide or compounds that react to form hydrogen peroxide in the wash. The
most direct source for peroxide bleaching is hydrogen peroxide. Numerous
attempts have been made to develop stable HDLDs containing hydrogen
peroxide [125–127]. The stability of this ingredient in aqueous formulations,
however, is of concern. Hydrogen peroxide is very susceptible to
decomposition in aqueous environments, largely because trace impurities of
metal ions such as iron, manganese, and copper can catalyze its decomposition
[128]. Alkalinity also accelerates this process. For these reasons HDLDs
containing hydrogen peroxide are maintained at an acidic pH and usually also
contain a strong chelating agent to sequester metal ions. A free radical
scavenger is also sometimes

Page 298
added to further enhance stability. Polyphosphonate compounds and butylated
hydroxytoluene (BHT) are examples of chelating agents and free radical
scavengers, respectively, that are used in hydrogen peroxidecontaining
formulations [129]. Still, the bleaching performance of these products is
inadequate, especially at low temperatures. These limitations have prompted
manufacturers to look to other methods to develop bleach HDLDs.
Inorganic peroxygen compounds such as sodium perborate tetrahydrate or
monohydrate and sodium percarbonate can also be used as sources of
hydrogen peroxide. These insoluble compounds release hydrogen peroxide on
contact with the washwater. The challenge is to stabilize them within an HDLD
formulation. The ability of structured liquids to suspend solids between the
surfactant lamellae or spherulites can be made use of in these products [130–
133]. It is possible to suspend sodium perborate in highly concentrated
structured liquids. The minimization of contact with water prevents the
peroxygen compounds from decomposing prematurely. It has also been found
that the use of solvents further improves their stability [134]. Hydrophobic
silica can enhance stability in unstructured liquids [135]. The most effective
method of formulating with perborates and percarbonates is with nonaqueous
liquids. The complete absence of water and a high level of solvents significantly
enhance the stability of bleaches in the product.
2. Peracid and Activated Peroxygen Bleaches
Peroxy carboxylic acids or peracids are far more effective bleaching
compounds than peroxygen molecules, especially at low and ambient
temperatures. The high reactivity and low stability of these compounds have so
far prevented them from being used in commercial detergent bleach
formulations. Peracids are somewhat stable in aqueous solutions of neutral pH,
and they equilibrate with water in the acid pH range to form hydrogen peroxide
and carboxylic acids. However, in alkaline conditions these compounds
undergo accelerated decomposition. Nevertheless, attempts have been made
to develop HDLDs that take advantage of the ability of structured liquids to
suspend insoluble solids. Patents have been issued for liquid detergent
formulations that incorporate peroxy acids such as diperoxy dodecane dioic
acid [136,137] and amido and imido peroxy acids [138,139]. These product
formulations are also maintained at acidic pH to reduce the premature reaction
of the peracid.
An alternative and more desirable method of bleaching is by forming the
peracid in the washwater. This is accomplished by reacting a bleach activator
compound with a source of hydrogen peroxide such as perborate,
percarbonate, or hydrogen peroxide itself in an aqueous environment. In this
reaction, referred to as perhydrolysis (Fig. 25), the bleach activator undergoes
nucleophilic attack from a perhydroxide anion generated from hydrogen
peroxide, resulting in the formation of percarboxylic acid. This formulation
strategy is used effec

Page 2
FIG. 25
Bleach activator (nonanoyloxybenzene sulfonate) reactions. (Reproduced with permission
from Ref. 94.)
tively in powder detergents where perborate and percarbonate compounds are
used along with activators such as tetraacetyl ethylenediamine (TAED) and sodiu
nonanoyl oxybenzene sulfonate (NOBS).
Unfortunately, in liquid detergents the challenge is to incorporate hydrogen
peroxide and an activator compound in an aqueous formulation and prevent thes
two components from reacting prematurely in the product itself. A novel method
uses emulsions formed by nonionic surfactants with varying HLB values to protec
a soluble activator, acetyl triethyl citrate, from other ingredients, including hydrog
peroxide, in the product [140–142]. An acidic pH and the addition of a strong
chelating compound aid in achieving product stability. Other patents using NOBS
[143], glycol and glycerin esters [144], and a lipaseanhydride combination [14
have been issued.
E. Optical Brighteners
It has been found that fabrics, especially cotton, begin to appear yellowish after
repeated washing cycles. Virtually all modern liquid detergent formulations contai
very small amounts (<1.0%) of optical brighteners or fluorescent whitening agent
that absorb ultraviolet light (300–430 nm) and reemit it as fluorescent visible blu
light (400–500 nm) [146–149]. This visible blue light offsets some of the yellow
hues from the fabric and as a result provides a whitening/brightening effect.

Page 300
The most widely used class of fluorescent whitening agents (FWA) are known
as cyanuric chloride diaminostilbene or CC/DAS types. The chromophore in
these molecules is triazinylaminostilbene (Fig. 26). The basic molecule can be
altered by the addition of various substituent groups including alkoxy, hydroxy,
or amino groups. The choice of these substituent groups can control the
solubility, substantivity, and overall performance of the brightener. These
brightener molecules are highly susceptible to electrophilic attack. As a result,
they are ineffective and unstable in the presence of chlorine bleach. For this
reason, it is common for detergent manufacturers to recommend that users wait
to add chlorine bleach until at least 5 min into the wash. Another class of
brighteners have been developed that are more resistant to chlorine bleach
(Fig. 27). These include distyrylbiphenyl derivatives such as disodium 4,4'bis
(2sulfostyryl)biphenyl, and triazolylstilbene.
F. Detergent Polymers
1. Soil Release Agents
Greasy and oily soils on polyester or polyestercontaining fabrics are among
the more difficult stains to displace. Removal of these soils from cotton fabrics
is far easier. This difference in cleaning can be attributed to the hydroxyl and
carboxyl groups on the cellulosic fibers that give the surface of the cotton a
hydrophilic nature and subsequently permit surfactants and water to more
easily wash away adsorbed soils. The surface of polyester fabrics, on the other
hand,
FIG. 26
CC/DAS or DASCbistriazinyl derivatives of 4,4'diaminostilbene2,2'disulfonic
acid. (Reproduced with permission from Ref. 146.)

Page 301
FIG. 27
Chlorinestable fluorescent whitening agent: disodium
4,4'bis(2sulfostyryl) biphenyl and a triazolylstilbene type. (Reproduced
with permission from Ref. 146.)
is hydrophobic, because they are essentially composed of copolymers of
terephthalic acid and ethylene glycol. This hydrophobicity not only creates an
affinity toward oily soils but also makes them more difficult to remove.
The use of soil release agents in liquid laundry detergents is meant to address
some of these issues [150]. These ingredients are usually polymeric and are
composed of hydrophilic as well as hydrophobic segments. The hydrophobic
functionality of the polymer allows it to be deposited and remain adsorbed
during the washing and rinsing cycles onto the hydrophobic fibers of the
polyester fabric. Once adsorbed the polymer can also hydrophilize the surface
of the fabric. In this way the polymer can not only make it easier for water and
other cleaning agents to diffuse into the soil/fabric interface but also prevents
soils from adsorbing strongly onto the fabric. Consequently, soil release
polymers are most effective only after the fabric has been treated with them.
For this reason the greatest impact is observed after the first wash cycle.
A typical soil release polymer consists of segments of hydrophobic ethylene
terephthalate and hydrophilic polythylene oxide (Fig. 28). A major drawback
initially with these polymers was their limited aqueous solubility. This in turn led
to lower performance, especially in particulate soil removal, due to weaker
adsorption on fabric surfaces. The low solubility also limited the use of soil
release polymers in unstructured liquids and sometimes led to instability of the
product. Some of these obstacles have been overcome by using lower
molecular weight polymers and by introducing endcapping groups [94,151].
These changes have led to improved solubility and better soil removal
characteristics (Fig. 29).

Page 302
FIG. 28
Segments of a PETPOET soil release polymer. (Reproduced with
2. Dye Transfer Inhibition: Polyvinylpyrrolidone (PVP)
Colorsafe detergents are becoming a significant portion of the detergent
market worldwide. Few technologies have been able to demonstrate real color
safety in washing. Inhibition of dye transfer is one way whereby the color
freshness of the fabric can be maintained after repeated washing. Polymers
such as PVP are employed that inhibit the transfer of fugitive dyes from
colored fabrics onto other items in the washing machine [152,153].
Polyvinylpyrrolidone (PVP) is a nonionic watersoluble polymer that interacts
with watersoluble dyes to form watersoluble complexes with less fabric
substantivity than the free dye. Additionally, PVP inhibits soil redeposition and
FIG. 29
A soil release polymer with endcapping groups. (Reproduced with

Page 303
is particularly effective with synthetic fibers and synthetic cotton blends. The
polymer comprises hydrophilic, dipolar imido groups in conjunction with
hydrophobic, apolar methylene and methine groups. The combination of
dipolar and amphiphilic character make PVP soluble in water and organic
solvents such as alcohols and partially halogenated alkanes and will complex a
variety of polarizable and acidic compounds. PVP is particularly effective with
blue dyes and not as effective with acid red dyes.
G. Miscellaneous Ingredients
A variety of other ingredients also serve valuable functions in HDLD
formulations.
1. Buffers
An alkaline pH in the washwater can greatly improve the cleaning ability of the
detergent. Certain oily or greasy soils can be removed from the fabric surface
by saponification at high pH. In addition, enzymes reach an optimum
performance level within a pH range of 8–11. Examples of buffering
compounds used in HDLDs include carbonates, liquid silicates, borates, and
amines such as monoethanolamine (MEA) and triethanolamine (TEA).
However, in enzymecontaining formulations, care should be taken to prevent
the product pH from exceeding a level that could lead to enzyme degradation.
2. Antiredeposition Agents
Compounds that prevent soils from redepositing onto the fabric surface from
the washwater are known as antiredeposition agents. These molecules can
prevent redeposition either by suspending or dispersing the soil in the wash or
by forming a barrier on the fabric surface. High molecular weight polyacrylates
can be used as soil suspension agents. Carboxymethylcellulose (CMC) has
been widely used as an antiredeposition agent for cotton fabrics. It functions by
forming a protective layer on the surface of the cellulosic fibers. Low aqueous
solubility, however, greatly limits its use in unstructured liquids.
3. Defoamers
Soap is extensively used to minimize excessive foaming in washing machines.
Siliconebased defoamers are also highly effective.
4. Hydrotropes
It is sometimes necessary to use hydrotropes to solubilize all ingredients in an
unstructured liquid. Examples of hydrotropes include sodium xylene sulfonate
(SXS), sodium cumene sulfonate (SCS), and sodium toluene sulfonate (STS).
An extensive description of these ingredients is presented elsewhere in this
volume (Chapter 2).

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A number of ingredients, though used in small amounts, serve very important
roles. For example, preservatives are needed to inhibit the growth of germs in
the aqueous product. Fragrances and dyes help cover the odor and color of
the base liquid and enhance the aesthetics of the product.
IV. Product Evaluation Methods
A. Physical Properties
The acceptability and formulation success of a laundry liquid can depend on
several important physical properties. Foremost among these characteristics is
the physical stability of the product. The consumer expects the final product to
be uniform and singlephase. Accelerated aging tests at temperatures the
product is likely to encounter in its lifetime are conducted to test the storage
stability. In addition, a test is generally carried out to check the ability of the
liquid to withstand repeated freezethaw cycles and still remain a single phase.
Rheology and flowability tests are especially crucial in characterizing structured
liquids. The LADD section in this volume provides a good description of the
basic rheological concepts (Chapter 9). HDLDs have to maintain desirable
pouring characteristics in order to be considered acceptable by the consumer.
The stability of the fragrance is also of utmost importance to the product.
Fragrance characteristics are analyzed in conjunction with the accelerated
physical stability tests.
The importance of preserving enzymes has been discussed earlier in this
chapter. The activity of enzymes is usually measured by performing an assay
specific to the enzyme being tested. It is also recommended that wash tests be
conducted over an extended time range on enzymesensitive stained fabrics to
determine the extent of enzyme loss as a function of time.
B. HDLD Detergency Evaluation
The mechanisms underlying the detergency and soil removal process have been
reviewed by many other authors [154–162]. This section briefly summarized
the test methods used to characterize the performance of liquid laundry
detergents. There are typically three stages of testing during product
development: (1) laboratory evaluation, (2) practical evaluation, and (3)
consumer tests.
1. Laboratory Tests
(a) Soil Removal. Soil removal testing on a laboratory scale is conducted in
laundrometers, such as Tergotometers, which are designed to simulate the
actual laundry process. The Tergotometer consists of a series of 1 liter stain

Page 305
less steel buckets, each with an agitation mechanism. Soiled fabric swatches
are placed in the wash solution to measure stain removal and other attributes of
the detergent product. These instruments offer the advantage of providing a
controlled environment in which the effects of various variables can be
measured. The effects of water temperature, water hardness, agitation rate,
detergent concentration, etc., can then be determined.
Table 5 shows the categories and typical examples of soils that are artificially
deposited on a range of fabrics such as cotton, polyester, and blends. These
soils represent stains that can be removed by physical as well as by chemical
mechanisms. The removal of stains in the watersoluble and particulate
categories is largely dependent on mechanical agitation and the interfacial
forces created by the detergent surfactants. Bleachable or oxidizable and
enzymatic stains are examples of soils that are more responsive to the chemical
nature of the wash liquor.
The detergency can be evaluated either visually by an expert panel that rates
the degree of soil removal or by instrumental techniques [163–165]. In the
latter method, the stain removal factor R is expressed as
R = 100 [(Lc Lw)2 + (ac aw)2 + (bc bw)2]½ (1)
where
L = reflectance
a = redness/greenness
b = yellowness/blueness
c = unstained fabric washed in treatment conditions
w = stained fabric washed in treatment conditions
(b) Brightening. The brightening performance of detergent formulation is
determined by washing a set of large unsoiled swatches representing various
types of fabrics. This can include swatches of cotton, nylon, cotton blends,
terry towels, and polyester fabrics. The swatches are washed for one to three
cycles, and their brightness is subsequently measured by using the
reflectometer. The b component (blue/yellow) of the light reading is measured
for this test.
(c) Soil Release. Clean swatches are first prewashed, typically for one to three
cycles, using the detergents to be tested. After the prewash, the swatches are
stained with a variety of soils, usually greasy particulate and food stains.
Subsequently, the swatches are washed again. At each stage, the reflectance
reading of the fabric swatches is recorded.
(d) Antiredeposition. Once soil is removed from the fabric, the possibility
exists that this soil can redeposit onto the fabric. The likelihood or the extent of
this occurring for a particular detergent product can be measured by an

TABLE 5 Listing of Laundry Soils Used in Detergent Evaluations
Watersoluble soils Particulate soils Proteins sourc

Fats/oils
Inorganic salts Metal oxides Animal fats Bloot
Sugar Carbonates Vegetable fats Eggs
Urea Silicates Sebum Milk
Perspiration Humus Mineral oils Cutaneous

scales
Carbon black Waxes
Source: Ref. 4.

Page 307
antiredeposition test. In this test, clean swatches along with typical soils are
added to the wash solution. Representative particulate soils include vacuum
cleaner dirt and Bandy Black clay; a mixture of triolein and mineral oil and an
artificial sebum composition serve as oily/greasy soils [166,167]. The washing
experiments can be conducted in a laboratoryscale Tergotometer or in a
commercial washing machine. Generally, approximately one to three cycles for
a laboratory scale and 5–10 wash cycles for a washing machine are necessary
for the entire test. The degree of soil deposited is measured instrumentally by
the reflectance readings.
(e) Color Loss or Color Transfer. Colored fabrics tend to lose color and
fade after repeated detergent washes. In addition, white or undyed fabrics can
sometimes acquire a small degree of color from the transfer of dyes when
washed with colored fabrics. Test methods have been developed to measure
the contribution of detergents to this color loss. Detergent manufacturers
perform these tests on a laboratory scale as well as on a practical level.
In a typical laboratoryscale test [168,169] conducted in a Tergotometer, a
nylon fabric dyed red and cotton fabrics dyed at different levels of blue are
added to the wash bucket along with a clean undyed white cotton fabric. The
white cloth is meant to be a scavenger of dyes lost in the wash and provides an
indication of color transfer. Various detergents can be tested and ranked
according to their color loss properties. After the wash, the fabric swatches are
instrumentally evaluated with a colorimeter. The E value provides the degree
of colorfastness of the fabric in a particular detergent.
E = [(Lw L0)2 + (aw a0)2 + (bw b0)2]½ (2)
where L = reflectance, and the subscripts w and 0 signify after the wash and
before the wash, respectively.
The practical evaluations use commercial washing machines and actual colored
clothing materials in the test. The clothes are washed repeatedly with detergent
over a 10–50 cycle range. The clothes are then evaluated visually by an expert
panel. Instrumental measurements can also be taken.
2. Practical Evaluation
Further performance evaluations are also conducted in commercial washing
machines. Although this method does not permit testing in as controlled a
fashion as with the laundrometers, it can be used to predict more consumer
relevant behavior. Soiled fabric swatches added to commercial washing
machines need to be accompanied by additional clothing as ballast to provide
more realistic clothestodetergent and clothestowashwater ratios.
Fabric bundle tests are also an effective and realistic method of evaluating the
detergency of HDLDs. In this test, articles of clothing are distributed among

Page 308
volunteers to be used in their normal manner. They are periodically returned to
be washed and evaluated. The evaluation can be conducted visually or
instrumentally.
3. Consumer Tests
The final and most important component of the analysis of laundry detergents is
the consumer test. A select group of consumers are provided with product and
instructed to use it with their normal laundry loads. Their feedback on various
aspects of cleaning and product aesthetics is collected and analyzed. These
data play a significant role in any decision regarding the composition of the
liquid laundry detergent.
V. Future Trends
There are several current and emerging trends in the laundry detergent industry,
and liquid detergents have been or are a part of each of them. Over several
years the trend in detergents has been toward concentration, first in powder
detergents and later in liquids. Concentration refers to reduction in dosage that
is required for equivalent cleaning; therefore, the detergent itself becomes more
efficient. Concentration also has other benefits such as reduced packaging
waste, consumer convenience, and economy to the manufacturer (distribution,
package costs, amount of fillers, etc.).
Another trend that is emerging via the use of more efficient surfactants,
polymers, and enzymes, either individually or in combination, is better and
faster cleaning at ambient temperatures. The rapid expansion of the detergent
market in developing countries is focusing attention on cleaning at ambient or
low temperature conditions. Furthermore, in developed countries the increasing
pressure to reduce energy in washing machine use also points to the need to
clean better at lower temperatures. The focus on less energy use has also
placed more importance on such cleaning parameters as redeposition of soils,
faster cleaning, foaming characteristics of the detergent, and rinseability of the
detergent and soils from the fabric surface.
Manufacturers and consumers have recently been emphasizing the care aspects
of the washing process. This includes the care of fabrics, of fabric colors, of
the environment, and also of the hands where hand washing is predominant.
Detergents have been introduced worldwide with claims that address these
aspects directly.
An other emerging trend has been the increasing use of enzymes in liquid
detergents, especially the use of enzyme cocktails. Mixtures of protease,
amylase, lipase, and cellulase in several combinations are being used to
address the removal of specific categories of stains, ambient temperature
cleaning, and soaking practices of the consumers and to promote fabric
protection and care. The

Page 30
patent literature has many references to stabilization of mixed enzyme systems
(see Appendix Table A).
Appendix
Recent patents related to heavyduty laundry liquids are tabulated in Tables A–J.

Page 310

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9
Liquid Automatic Dishwasher Detergents
PHILIP A. GORLIN and NAGARAJ DIXIT
New Jersey
KUOYANN LAI
Global Materials and Sourcing (AsiaPacific Division), Global Technology, Colg
Company, New York, New York
I. Introduction
II. Mechanics and Chemistry of Automatic Dishwashing
A. Components of automatic dishwashing machines
B. Mechanical cleaning
C. Thermal cleaning
D. Chemical cleaning
III. Components and Their Functional Properties
A. Builders
B. Surfactants
C. Defoamers
D. Oxidizing agents
E. Enzymes
F. Thickening agents
IV. Rheology and Stability of LADDs
A. Flow properties
B. Dynamic properties
V. Evaluation of Performance
A. Spotting and filming
B. Soil removal
A. Spotting and filming
B. Soil removal
C. Stain removal
D. Foaming
E. Fine china overglaze

VI. Formulation Technology
VII. Auxiliary Products
A. Liquid prespotters
B. Rinse aids
VIII. Future Trends
A. Nonphosphate products
B. Nonhypochloritecontaining products
C. Enzymatic products
D. Concentrated products
E. Lowtemperature cleaning
References
I. Introduction
The concept of using mechanical devices for dishwashing was documented as ear
with the issuance of a U.S. patent to Houghton [1]. Since then, several companie
manufacture and market automatic dishwashing machines for home as well as for
use [2,3]. However, it was not until the early 1950s that both mechanical dishwa
detergents became widely available to consumers. Today, an estimated 50% of t
in the United States, 25% in Europe, and 8% in Japan have automatic dishwashe
The automatic dishwasher detergents (ADDs) originally introduced into the U.S.
powder form. These products have subsequently undergone major changes in co
deliver better cleaning performance. Typical compositions of powder automatic d
detergents sold in the United States and Europe are shown in Table 1.
Even today, powders continue to dominate the United States market, commandi
of the market share [5]. Recently, the marketplace has seen the advent of liquid f
automatic dishwasher detergents (LADDs). Clarification of what constitutes a “li
mentioning here. Commercially, the products are marketed under different names
liquids, liquigels, liquid gels, or gels. Technically these products are concentrated
The liquid matrix predominantly comprises an aqueous phase and thickening agen
are typically either a swellable clay or waterdispersible polymer and optionally a
The mechanical properties of these products are such that the product can be dis
the container without prior shaking.
Automatic dishwasher detergents in the liquid form offer the following advantages
powders:
are typically either a swellable clay or waterdispersible polymer and optionally a
The mechanical properties of these products are such that the product can be dis
the container without prior shaking.
Automatic dishwasher detergents in the liquid form offer the following advantages
powders:

Page 327
TABLE 1 Conventional Machine Dishwashing Powder
Formulation
Ingredient % by Weight
Sodium TPP 15–45
Sodium silicate 15–60
Sodium carbonate 0–25
Chlorocyanurates 0–7
Nonionic surfactant 0–6
Sodium sulfate 0–40
Water Balance
1. They offer convenience in dispensing and dosing.
2. They dissolve quickly in the wash water.
3. They are free from lumping or caking during storage.
4. They do not release irritating dust upon handling.
The market entry of firstgeneration automatic dishwasher liquids dates to
1986 in the United States and to 1987 in Europe with the introduction of
Palmolive Automatic and Galaxy, respectively, by ColgatePalmolive [6].
Soon afterward, Procter & Gamble and Lever Brothers introduced similar
liquid products. The category has since been steadily growing. Today, LADDs
account for about 30 and 15% of total sales of the ADD market in the United
States and Europe, respectively [7].
The firstgeneration LADDs were essentially powder compositions in the liquid
form, in which functional components were suspended or dispersed in a
structured liquid matrix. The liquid matrix consisted of water, and the common
structuring additives used were bipolar clays and a cothickener comprising a
metal salt of a fatty acid or hydroxy fatty acid. These liquid products, although
minimizing some of the shortcomings of the powders, suffered from two major
disadvantages. First, the rheological properties of these products were such
that the bottle needed to be shaken before dispensing the product. Second, the
shelf life stability of the products did not meet consumer expectations. This
problem was soon recognized by the manufacturers, and esthetically superior,
nonshake, stable, and translucent products were introduced to the market in
1991 as “gels.” All the liquid products marketed today in the United States are
essentially in gel form using polymeric thickeners.
The discussion in this chapter focuses on the technology behind the
development of currently marketed liquid automatic dishwasher detergents.
Powder ADDs, which in most areas utilize analogous technology, are not
discussed except in comparison.
The discussion in this chapter focuses on the technology behind the
development of currently marketed liquid automatic dishwasher detergents.
Powder ADDs, which in most areas utilize analogous technology, are not
discussed except in comparison.

Page 328
II. Mechanics And Chemistry Of Automatic Dishwashing
Cleaning in an automatic dishwasher is accomplished by a combination of three
types of energy: mechanical, thermal, and chemical. In general, a combination
of machine (mechanical), hot water (thermal), and detergent (chemical) is
necessary for complete cleaning of dishware. Before these effects can be
discussed in more detail, the basic components and mechanics of an automatic
dishwasher must be described.
A. Components of Automatic Dishwashing Machines
In keeping with LADDs, automatic dishwashers have been improving over
time to offer the consumer greater convenience and performance. Two views
of a typical automatic dishwashing machine sold in the North America is shown
in Fig. 1. European machines are similar except for some minor but important
differences. These differences allow the use of different detergent technologies
in the two markets.
One difference is in the materials used to manufacture the interiors of the
machines. Machines sold in North America contain allplastic interiors. In
contrast, European machines contain stainless steel interiors. This difference is
important not only because plastic can tolerate a more corrosive detergent but
it is also more economical than stainless steel.
Automatic dishwashing machines typically contain two racks that hold the items
to be washed. All machines contain at least one spray arm, which spins as a
result of the pressurized wash solution being pumped through the arm nozzles.
This allows an even distribution of the wash liquor over all the items being
washed. The main spray arm is located underneath the bottom rack and directs
the water pumped upward through it. In some machines, a second and even a
third spray arm are located below and above the top rack, respectively. The
wash liquor is recycled throughout the complete cycle by means of a pump that
continually circulates it through the spray arms. A strainer in the wash tank
removes large soil particles throughout the recirculation process. For each
program cycle (wash or rinse) a new water supply is introduced.
Machines generally contain two detergent dispensing cups, one of which has a
lid and is therefore closed through part of the machine cycle. A significant
difference between American and European machines is that the latter contain
a gasketed closed cup. This prevents the detergent from prematurely leaking
out of the cup. Many American machines lack such a gasket. Instead, the
detergent is formulated as a viscous gel that does not flow unless stressed. All
European machines, and some American, also contain a rinse aid dispenser,
which provides a does of rinse aid during the final cycle. These dispensers must
be filled only about once a month. Rinse aids are especially useful in hard water
areas (see Sec. VII).
A typical dishwashing program consists of several cycles of differing function.
The number of each type of cycle and their order depends on the brand

Page 329
FIG. 1
Front and side views of an automatic dishwasher. (Courtesy of the
General Electric Company.)
of machine and the wash program selected. Typically, two or three programs
are available, corresponding to heavy, normal, and light wash loads. All
programs consist of a rinse, a main wash, at least one rinse after the main
wash, and a drying cycle that is optionally heated. In addition, a shorter
prewash before the initial rinse can be selected. The rinse cycles are
mechanically similar to the wash cycles, except that no detergent is present. In
programs containing two wash cycles (heavy or potscrubber cycle), both
dispensing cups are filled with detergent. If only a main wash cycle is to be
used (normal or light cycle), only the closed cup is filled. In either case, it is
essential that the detergent be structured so that it does not leak out of the
closed cup before the cup opens. Otherwise, the main wash is underdosed,
resulting in ineffective cleaning. Proper structuring of gel detergents is discussed
later (Sec. IV).

Page
The most important differences between European and North American machine
designs are in the condition of the incoming wash water. As discussed later, the
presence of hardness ions (Ca2+ and Mg2+) in the wash decreases the overall
effectiveness of cleaning. This is especially a problem in hard water areas and can
only be overcome by softening of the water. Table 2 lists the typical water hardn
conditions encountered in the major countries that use automatic dishwashers [9].
European machines circumvent this problem by softening the water before it is
introduced into the wash. This is accomplished by a builtin ion exchanger that
works by replacing the hardness ions with sodium ions. Regeneration of the ion
exchanger with sodium chloride is required periodically. In contrast, North Ameri
machines contain no watersoftening device and must therefore rely on the deterge
for sequestration of the hardness ions. The presoftening of the wash water by
European machines allows detergents that contain lower builder levels to be
formulated.
Another difference between the North American and European dishwashing
programs concerns the temperature of the incoming water. In North America, the
wash water is preheated by the household water heater and is introduced into the
machine at temperatures of 110–140°F. In contrast, European machines receive
cold water and heat it via machine heating coils during the wash and rinse cycles.
The final temperature the water reaches in this manner is therefore higher than in
American machines, reaching 140–160°F. Schematic pro
TABLE 2 Typical Water Hardness Levels in Different Countries
Hardness (ppm CaCO3)
Country 0–90 90–270 >27
United States 60a 35 5
Japan 92 8 0
Western Europe (total)b 9 49 42
Austria 1.8 74.7 23.
Belgium 3.4 22.6 74
France 5 50 45
Germany 11 42 47
Great Britain 1 37 62
Italy 9 75 16
Switzerland 2.8 79.7 17.
Spain 33.2 24.1 42.
a
Including 10% with home watersoftening appliances.
b
These values are calculated from the data for the countries indicated below with regard to
their individual population figures.

Page 331
files of water temperature versus time for U.S. and European machines are
shown in Figs. 2 and 3, respectively.
B. Mechanical Cleaning
Probably the most important cleaning component of cleaning in automatic
dishwashing is the mechanical component, which primarily arises from the
kinetic energy of the water being pressurized through the rotating spray arm
nozzles. As the wash water is pumped through the spray arms, the water jets
sprayed from the rotor arms help to dislodge soils that adhere to the dishware.
Therefore, an increase in kinetic energy, which can be accomplished by either
more water or higher pressure, results in more efficient removal of soils from
substrates [10]. It has been suggested that the mechanical energy of the
machine itself is responsible for 85% of the soil removal during the cleaning
cycle; the detergent contributes the other 15% [11].
C. Thermal Cleaning
Most soil removal during an automatic dishwashing cycle is positively affected
by thermal energy, which is delivered by the hot water. Thermal energy is in a
sense a secondary effect, contributing to the effectiveness of both the
mechanical and chemical components of cleaning. Typical machine dishwashing
tem
FIG. 2
Typical U.S. dishwashing cycle.

Page 332
FIG. 3
Typical European dishwashing cycle.
peratures in the United States are 110–140°F. The water temperature is
dictated by the household hotwater heater, which supplies the water. In
contrast, the wash temperature in Europe approaches 160°F. This is because
the machine itself contains a heating element that heats the water.
High temperatures have some advantageous effects on chemical processes
involved in cleaning. For example, the solubility of slightly soluble salts
increases with temperature. Otherwise, the deposition of such salts on
glassware is the cause of much of the inorganic filming observed in hard water
regions. Thermal energy also aids in the removal of fatty soils from items being
washed. Above their melting point, fats are more easily removed because the
intermolecular forces binding them to the dishware and the cohesive forces of
the soil are both lower. The activity of most oxidizing agents also increases with
temperature.
D. Chemical Cleaning
A typical washload consists of several types of soils that must be solubilized or
degraded by a combination of the detergent and machine. Detergents must
control both food soils introduced by the items washed and inorganic scale
produced by hardness ions in the wash water. Food soils consisting of
proteinaceous, starchy, or fatty materials not only must be effectively removed
from the dishware, but they must also be prevented from redepositing on items
be

ing washed. Redeposition on glasses is of particular importance because it leads t
undesirable spotting and filming. Soils that produce stains are also a problem in a
dishwashing. For example, coffee, tea, wine, and tomato sauce leave highly visibl
wash items unless properly treated during the wash.
Removal of food soils from wash surfaces can only be accomplished once the att
forces between surface and soil are overcome. Generally, dehydrated soils intera
strongly with surfaces as a result of stronger van der Waals interactions between
surface [10]. On the other hand, the soilsurface interaction decreases as the surfa
becomes more hydrophobic because of fewer available polar sites. Exceptions ar
hydrophobic soils, such as fats, which interact strongly with hydrophobic surfaces
III. Components And Their Functional Properties
Liquid automatic dishwasher detergents are chemically complex mixtures, consisti
variety of components working in unison to clean the items placed in the dishwas
machine. Each component performs a vital function, either alone or in conjunction
others. LADD ingredients can be broadly classified into two categories: those tha
cleaning function and those that modify the rheology or esthetics of the liquid. In t
the typical components found in LADDs are discussed. A typical LADD compos
the functions of the individual components are listed in Table 3.
TABLE 3 Typical Compositions and Functions of LADD Products
Component Amount (%) Function
Builder 5–30 Sequestration, soil suspensio

emulsification
Silicate 3–15 Anticorrosion, alkalinity, sequ
Surfactant 0–2 Spot/film prevention, sheeting

dispersion
Bleach 0.5–2 Stain removal, soil removal,

disinfectant
Caustic 1–5 Alkalinity
Defoamer 0–1 Foam prevention
Thickener 0.5–2 Gel structure
Color/fragrance <0.5 Esthetics
Water Balance Solubilizer, flow properties

Page 334
A. Builders
Builders as a class perform several essential functions in the automatic
dishwashing process. Ideally, a builder should possess the following properties:
a high and rapid sequestration capacity for hardness ions in the wash water,
soildispersing properties, chemical stability and compatibility with other
detergent components, low toxicity, high biodegradability, and low cost. The
chemical structures of some common builders are shown in Fig. 4.
The presence of alkaline earth (Ca2+ and Mg2+) ions during an automatic
dishwashing cycle can lead to undesirable spotting and filming on items being
washed. This occurs through the formation of insoluble metal complexes with
proteinaceous soils, fatty acids, anionic surfactants, and carbonate. Research in
the field has led to a better understanding of the causes of spotting and filming
on items being washed, especially glassware [12,13]. Fatty soils, in
combination with calcium ions, result in filming of glasses. However, organic
soils do not deposit film in soft water. In addition, inorganic filming (as CaCO3)
is also a problem under hard water conditions. Both types of film can be
controlled or even prevented by efficiently sequestering the hardness ions in the
incoming wash water. This problem is obviously of greater concern in hard
FIG. 4
Chemical structures of selected builders.

Page 3
water areas. Spotting, in contrast, cannot be controlled by sequestration of
hardness ions. Both fatty and proteinaceous soils can deposit as spots under all
water conditions.
Because of the different mechanisms responsible for soil deposition on glassware,
formulations of LADD products rely on two different approaches to control this
problem. First, compounds that sequester the hardness ions (builders) are used. I
this manner, the calcium and magnesium form watersoluble complexes and are
removed with the wash water. In general, Ca2+ sequestration is of greater
importance than that of Mg2+. This is not only because Ca2+ is generally present i
higher concentrations in water supplies, but also because Casoil and CaCO3
complexes are more stable and less soluble than the magnesium analogs. An
important factor in the selection of builders is therefore their clacium binding affini
KCa, usually reported as the pK Ca [14]. The equilibrium present in solution is show
in the equation:
>
where L is the complexing ligand. The pK Ca of builders typically used in LADDs
are listed in Table 4. Also listed are the calcium binding capacities in terms of mg
CaO per g builder [15]. Of course, for two molecules with equal binding
constants, that with the lower molecular weight is more efficient. The second
approach to spot or film prevention involves the use of compounds that either
inhibit the deposition and precipitation of Ca2+ complexes by slowing crystallizati
or reduce the growth of existing crystallites, known as the threshold effect.
TABLE 4 p K Ca Values for Typical ADD Builders
Builder pK Ca Ca binding capacity
(mg Ca2+/g) [15]
Sodium TPP 6.0 198
Nitrilotriacetic acid 6.4 448
Sodium citrate 3.6 400
Sodium carbonate 286
LMW polyacrylate 4.5 440
Acrylate/maleic copolymers 4.5 480
Zeolite A 198

Page 336
Generally, combinations of builders are used in LADD products, the reason
being that some builders are more effective sequestrants of calcium, others
more effectively bind magnesium, and yet others provide soil dispersion.
Studies have also shown synergistic effects in many cases. For example, Lange
has reported that interactions between silicate and phosphate show surface
activity greater than what each component alone would contribute [16].
Experiments have shown that combinations of lowmolecularweight
polyacrylates and soda ash tolerate higher concentrations of Ca2+ in the wash
water than equal amounts of either sequestrant individually [14,17]. Builders
also work synergistically with surfactants to increase the detergency of the
liquid. By tying up free hardness ions, they prevent the formation of insoluble
Casurfactant complexes.
1. Phosphates
Details of the chemistry of phosphorous compounds pertinent to detergent
applications are discussed in a comprehensive review by van Wazer [18].
Phosphates are the universal builder in LADDs because of their high
performance tocost ratio. The term “phosphate,” when used in reference to
LADDs, actually refers to oligophosphate ions, most common being the
tripolyphosphate pentaanion (TPP), the pyrophosphate tetraanion, and the
cyclic trimetaphosphate trianion. The structure of TPP is shown in Fig. 4. All
polyphosphates hydrolyze to simple orthophosphate over time. The
rate of hydrolysis increases with increasing temperature or decreasing pH [18].
For tripolyphosphate in typical LADD conditions, the hydrolysis halflife is
very slow, on the time scale of years [18], and is thus of little concern for
typical alkaline LADD compositions.
These builders are generally available as sodium, potassium, or mixedmetal
salts, the last two being more soluble in water but also more costly. The wide
spread use of sodium TPP (STPP) in LADD formulations can be attributed to
the many functions it performs during the wash cycle. Besides its efficient
sequestration of hardness ions, STPP works to disperse and suspend soils,
enhance the surface action of anionic surfactants, solubilize proteinaceous soils,
and provide alkalinity and buffering action. Pyrophosphates have been included
in some LADD formulations because of their better solubility properties
relative to tripolyphosphate [19].
Phosphates are currently the primary builder in all LADD products sold in
North America, although various regulations limiting their use have been in
place for the past 20 years. The concern with phosphates is that large amounts
in the wastewater results in the eutrophication of lakes and ponds, leading to
excessive algal growth. Because of this concern, government regulations
banning their use in laundry detergents and limiting their use in ADD products
were passed in the early 1970s.

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2. Silicates
After phosphates, silicates are the most ubiquitous builders in use in LADD
formulations. Like tripolyphosphate, silicates are multifunctional. A combination
of phosphate and silicate is therefore generally used in ADD formulations. In
addition to their sequestering properties, silicates provide alkalinity, soil
suspension, and anticorrosion properties. A detailed treatment of the synthesis,
chemistry, and applications of silicates has been undertaken by Iyler [20].
Other reviews are also available [21,22].
Silicates used in detergents vary according to the SiO2/Na2O ratio present.
They are synthesized by the reaction of sand and sodium carbonate at elevated
temperatures. Commercially, ratios of 0.5–4 are available, depending on the
ratios of starting materials used [23]. An important transition occurs at a mole
ratio of about 2. Below a mole ratio of SiO2/Na2O of 2, monomeric or dimeric
silicate tetrahedra exist [22]. In contrast, mole ratios greater than 2 result in
higher molecular weight silicates because of polymerization. The equilibrium
between monomeric and polymeric silicate is affected by the pH of the
solution. As the solution becomes more alkaline, the amount of monomeric
species increases. For LADD formulation purposes, disilicates with an
SiO2/Na2O ratio of 1:2–3 are generally used. At lower ratios, metasilicates
form that render the detergent too alkaline, at which point safety problems
because of their corrosiveness may become a concern.
3. Zeolites
A related class of siliceous builders are the aluminosilicates (zeolites). Zeolite
A, in particular, has been studied as a builder in detergent formulations,
generally as a phosphate replacement. It consists of alternating SiO2 and AlO2
building blocks forming a threedimensional cage structure, with sodium ions balancing
the charge. It works by ion exchange, replacing Ca2+ in solution with Na+. This is a
different mode of action compared with the other builders, which form soluble complexes
with calcium and magnesium. Because of the relatively small pore size of zeolite A (4.2
Å), the larger, hydrated Mg2+ dications cannot be efficiently exchanged.
Studies have shown zeolites to be slower than STPP in removing Ca2+ from
the wash solution [24]. In addition, their insolubility in aqueous solutions has
limited use to powder detergents, especially in the laundry industry. A
comprehensive review of the chemistry of aluminosilicates in detergent
compositions is available [25]. Recently, patents for LADD products utilizing
zeolites have appeared in the literature [26–28]. The attraction is a result of
their low cost and low toxicity.

Page 338
4. Carbonate
Sodium carbonate (Na2CO3) has been used in detergent formulations for many
years both to sequester calcium ions (at pH > 9) in the wash water and as an
alkalinity source. The structure of the carbonate dianion is shown in Fig. 4.
Currently, all powder ADDs contain high levels of sodium carbonate (15–
40%), mainly as a source of alkalinity. In LADDs in which caustic can be
incorporated into the compositions, the need for sodium carbonate is less
important.
Because complexation with Ca2+ results in the insoluble CaCO3, which
deposits on items being washed, carbonate alone is not an effective builder
system. In contrast, tripolyphosphate forms a soluble calcium salt, preventing
the deposition of insoluble salts. Sodium sesquicarbonate
(Na2CO3∙NaHCO3∙2H2O) and sodium bicarbonate (NaHCO3) have not been
used in LADD formulations, except when buffering action is needed.
5. Citrate
A builder that was recently studied as a possible phosphate replacement is
sodium citrate. The structure of the citrate trianion is shown in Fig. 4. Several
properties of sodium citrate restrict its use in LADD formulations. First, it is
incompatible with hypochlorite, precluding its use in most LADD compositions.
It is also inferior to STPP in its sequestration efficiency for calcium ions.
Finally, it is almost three times more expensive than STPP. This combination
renders citrate unsuitable as a replacement for STPP. In Europe, where the
different wash conditions allow the use of milder peroxygen bleaches or
enzymes and the water is presoftened, citratebuilt products are possible.
6. Organic Polymers
Polymers of carboxylic acids are being increasingly used in LADD formulations
because they can perform several functions necessary to ADD components.
Lowmolecularweight polycarboxylates (<250,000 amu) are useful as both
builders and soildispersing agents. Because these two functions in LADD
formulations are usually performed by sodium tripolyphosphate (STPP), much
effort has been directed toward the use of lowmolecularweight
polycarboxylates as phosphate replacements. In particular, the soildispersing
properties of lowmolecularweight polycarboxylates make them very
attractive in LADD formulations because other builders, such as carbonate,
silicate, aluminosilicates, nitrilotriacetate, citrate, and even tripolyphosphate, act
mainly as sequestrants.
The most often used polycarboxylates consist of acrylic, maleic, and olefinic
monomers, either as homo or copolymers. Modifications to the side groups
can be made to alter the hydrophobicity of the polymer. In addition, the
relative ratios of monomers in copolymer structures can be varied to control
the properties of the polymer. Both acrylic acid homopolymers and acrylic
acid/maleic

Page 339
anhydride copolymers are commercially available in a wide range of molecular
weights (1000–250,000 amu). The structures of both types are shown in Fig.
4. They are sold under the trade names Acusol (Rohm & Haas) [29] and
Sokalan (BASF) [30], among others.
As calcium sequestering agents, the copolymers are generally better than
analogous acrylic homopolymers because of their greater concentration of
COO groups per monomeric unit. The differences are rather small, though. In
addition, the calcium binding capacity increases with increasing molecular
weight [17]. The degree to which the carboxylate groups are ionized also
affects the polymer properties. Polycarboxylates that exhibit only partial
ionization in the wash have been found to be better sequestrants [31]. The
degree of ionization determines the amount of association between COO
groups and the degree to which the polymer coils. Two mechanisms have been
proposed for sequestration of Ca2+ and Mg2+ by polycarboxylic acids [32].
Through electrostatic binding, the hardness ions interact with electrostatic fields
created by the polymer. In contrast, site binding relies on preferential binding of
large cations (e.g., Ca2+) over smaller cations (e.g., Na+ or K+) along specific
binding sites [32].
Capolycarboxylate complexes are not very soluble and will precipitate and
deposit on glassware under high Ca2+ concentrations. In fact, research at
BASF [14] has shown that a combination of soda ash and lowmolecular
weight polycarboxylates works better at preventing filming on glassware than
either soda ash or the polymer alone. This is because soda ash binds the
calcium but is not deposited as CaCO3 because of the dispersing properties of
the polymer. In this manner, a higher concentration of Ca2+ can be tolerated.
In addition to their role as calcium sequestrants, polycarboxylates perform two
other major functions [14]. In fact, because they are usually used in
combination with other sequestrants (phosphate, carbonate, and citrate), which
behave more as sequestrants of hardness ions, it is these properties that make
them so important. First, they prevent the crystal growth of calcium
precipitates, especially CaCO3 (threshold effect). They also reduce the growth
of crystallites already formed. In general, lowmolecularweight
polycarboxylates (<10,000 amu) are more effective than higher molecular
weight polycarboxylates. Equally important, polycarboxylates are effective
dispersants of particulate soils. In this role, lowmolecularweight polymers are
again more efficient than higher molecular weight analogs.
7. Other Builders
A very effective STPP replacement not used in LADD compositions is
nitrilotriacetic acid (NTA), commonly manufactured as the monohydrate. Its
structure is shown in Fig. 4. It is superior to STPP in sequestration of hardness
ions, contribution to the alkalinity of the detergent, and solubility under highpH
conditions. Because of these properties, it was once considered for use in no

Page 340
P LADD products. However, concerns about its toxicity have prevented
widespread use. There is some controversy regarding its possible role as a
carcinogen [33,34]. Only sporadic use in the laundry detergent category is
now observed in Canada and parts of Europe.
The last class of builder to be mentioned here is the ether carboxylates, or
oxydicarboxylates. These have not found use in marketed LADD products,
mainly because of their high cost and incompatibility with hypochlorite.
Nonetheless, some favorable characteristics have been identified for effective
Ca2+ binding [35]:
1. A pK Ca > 5 is desired with minimum molecular weight.
2. Carboxylate and ether oxygens on carbons are preferred.
3. Ether oxygens are preferred over ketal oxygens.
4. The order of preference is substituted malonate > malonate > succinate >
acetate > propionate.
5. The total ionic charge should be >2 but <5, except for 2:1 complexes.
6. A close steric fit of >4 donor oxygens around Ca2+ is desired.
7. A minimum number of degrees of freedom in the carbon backbone is
desired.
B. Surfactants
The role of surfactants in the automatic dishwashing process is very different
from their role in the hand dishwashing process. In contrast to lightduty liquid
detergents (LDLDs; see Chap. 7), which consist mainly of and rely on a
combination of surfactants for foaming, grease cutting, and soil removal,
LADDs contain surfactants only as a minor additive. The grease and soil
removal is instead accomplished by the high alkalinity and bleach present. In
addition, the high wash temperature helps to melt fatty soils and to denature
proteinaceous soils. Surfactants provide sheeting action on the items being
washed to prevent soils from depositing as spots or film. However, their
tendency to produce a large amount of foam is detrimental to the automatic
dishwashing process. The reason is that dishwashing machines work by
pumping the wash solution through spray arms, which spin because of the
water pressure. Foam decreases the water pressure and therefore the cleaning
efficiency of the machine (see Sec. II). In surfactantcontaining compositions,
defoamers are often used which reduce foaming by interfering with the
formation of micelles (next section).
Surfactants suitable for LADD formulations must be low foaming. In addition,
if the product is to contain chlorine bleach, the surfactants must be resistant to
oxidation. In LADD formulations, only anionic and nonionic surfactants have
found use. Cationic or amphotheric surfactants have not been used because of

Page 341
their relatively high cost and/or incompatibility with other detergent ingredients.
Anionic surfactants are available as alkali metal salts that dissociate in aqueous
solution. Typical hydrophilic “head groups” useful in LADD formulations
include carboxylates, sulfonates, sulfates, phosphates, and phosphonates.
These surfactants are bleach stable unless the hydrophobic tail is oxidizable. A
drawback to the use of anionics in LADDs is that they produce too much
foam. Nonetheless, because of their bleach stability, alkyl ether sulfonates,
such as the Dowfax line (Dow Chemicals), have been used at low
concentration in LADD products. The bleach compatibility of a series of
anionic surfactants is reported by Rosen and Zhu [36] and in a Dow Chemical
bulletin [37].
Nonionic surfactants have also been investigated as components of LADD
compositions. The hydrophilicity of nonionic surfactants arises from the polar
linkages within the molecule. Typical nonionic surfactants include polythylene
glycol ethers, fatty acid alkanol amides, amine oxides, and ethylene
oxide/propylene oxide (EO/PO) block polymers. The last is especially
effective in LADD formulas, although their incompatibility with chlorine bleach
has restricted their use to powder or bleachfree gel formulas. The relative
hydrophobicity of the EO/PO polymeric surfactants can be controlled by
variations in the EO/PO ratio, hydrophobicity increasing with PO content.
Nonionic surfactants possess several advantages over anionics as far as
automatic dishwashing is concerned. At temperatures above their cloud points,
foaming is reduced nearly to zero. In addition, nonionics are much more
effective in lowering the surface tension of water and are therefore much better
detergents.
C. Defoamers
The formation of foam during the automatic dishwashing cycle is detrimental to
the mechanical washing efficiency of the machine. To prevent foaming, LADD
products often contain defoamers. The most commonly used hypochlorite
stable defoamers in LADDs are anionic surfactants, such as alkyl phosphate
esters and ethoxylated esters [38–40] and silicone oils [41]. The structures of
the first two types are shown in Fig. 5. Also described in the patent literature is
the use of aliphatic alcohols or acids as defoamers [42].
The wash temperature has a significant effect on foaming because of its effect
on the solubility of the defoaming surfactant. Nonionic surfactants are effective
only above their cloud points. Careful consideration must therefore be taken
when formulating with nonionics. Water hardness also plays a role in foam
formation. In hard water, Ca2+ and Mg2+ form complexes with fats or anionic
surfactants. These insoluble complexes interact with the foam, breaking up the
micellar structure.

Page 342
FIG. 5
Chemical structures of phosphate
ester defoamers. R refers to an alkyl
group.
D. Oxidizing Agents
The primary role of bleach in automatic dishwashing is in the removal of food
based stains by oxidation of the responsible molecules. These include
anthocyanins (berries), humic acid polymers (coffee and cocoa), tannins (tea
and red wine), and carotinoid dyes (carrots and tomatoes). In addition,
bleaches contribute to overall cleaning and disinfecting of dishware. They
accomplish this by oxidizing food soils, thereby solubilizing them. Several
factors contribute to the bleaching activity in the automatic dishwashing
process. The most important are listed here [43]:
1. All bleaches work faster with increasing temperature.
2. Trace amounts of metal impurities dramatically increase the rate of catalytic
decomposition of bleaches.
3. The rate of bleaching increases with increasing bleach concentration.
However, bleach selfdecomposition also increases.
4. The bleach activity is often dependent on pH.
Two general types of bleaches have been used in automatic dishwashing
detergents: hypochorite and peroxygen bleaches. “Chlorine bleaches” refer
here to complexes that either contain or deliver hypochlorite (OCl) in solution.
The compounds used in detergent products are typically alkali or alkaline earth
hypochlorites, liquid sodium hypochlorite being the most common. Solid
calcium hypochlorite has also received attention, although its low solubility and
its contribution of Ca2+ to the wash liquor has limited its use in LADD
products. Generally, NaOCl is added in amounts resulting in 1–2% active
chlorine.
One drawback to the use of chlorine bleaches is that in addition to oxidizing
soils, the bleach also oxidizes some ingredients often used in the formula

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tions. Because of these unwanted side reactions, care must be taken when
formulating with chlorine bleach. For example, enzymes, nonionic surfactants,
sodium citrate, and other useful LADD components are easily and rapidly
oxidized by hypochlorite. A study of the stability of sodium hypochlorite in the
presence of surfactants has been published by Rosen and Zhu [36]. Even when
using only bleachstable detergent ingredients, the bleach present decreases
over time as a result of autodecomposition. Two different pathways contribute
to bleach degradation [43]:
2NaOCl *** 2NaCl + O2
3NaOCl *** NaOCl3 + 2NaCl
The first pathway accounts for about 95% of the consumption of OCl in the
absence of metallic catalysts [44]. The decomposition is affected by pH,
concentration, temperature, salt content, and photolysis [36,44] and can lead
to loss of product performance upon prolonged storage.
The peroxygen bleaches, typically perborate or percarbonate salts, produce
peroxide in aqueous solutions. The effectiveness of peroxide as an oxidizing
agent at relatively low wash temperatures (120–140 °F) is unfortunately
minimal. Peracids [RC(O)OOH], which can be generated by the activation of
carboxylic acids by peroxide or can be added directly, have not found use in
LADD compositions despite their relatively high oxidation potentials because
of their instability in aqueous solution.
As mentioned earlier, European wash conditions are somewhat different from
those encountered in the United States. In particular, the water temperature
during wash cycles is higher in Europe. This difference has important
consequences regarding the formulation of detergents. The higher wash
temperatures present in European dishwashing allow the use of milder oxygen
bleaches in place of chlorine bleaches. As bleaching agents, the activity of
peroxides and peracids increases with temperature. Under typical North
American conditions, they are not suitable replacements for hypochlorite.
However, they are more effective under European conditions. The use of
peroxygen bleaches allows more freedom in formulations because many
LADD components are incompatible with hypochlorite but not with peroxide.
Because of the instability of peroxide in alkaline aqueous systems, their use is
limited to nonaqueous LADDs.
E. Enzymes
The use of enzymes in detergent formulations became a practical matter in the
mid1960s, when Novo Industry began production of proteinases by microbial
fermentation. These enzymes were stable at the high temperatures and
alkalinity encountered in dishwashing.

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Several types of enzymes have found uses in LADD compositions [4,45].
Most common are proteinases, amylases, and lipases, which attack
proteinaceous, starchy, and fatty soils, respectively. Proteinases work by
hydrolyzing peptide bonds in proteins. Proteinases differ in their specificity
toward peptide bonds. The typical proteinase used in LADD formulations,
bacterial alkaline proteinase (subtilisin), is very nonspecific. That is, it attacks
all types of peptide bonds in proteins. In contrast to proteinases, amylases
catalyze the hydrolysis of starch. They attack the internal ether bonds between
glucose units, yielding shorter, watersoluble chains called dextrins. Lipases
work by hydrolyzing the ester bonds in fats and oils. Often, combinations are
used because of the specificity of each kind of one type of soil. The
commercially available enzymes are listed in Table 5.
F. Thickening Agents
LADD products currently in the marketplace are not real liquids but are, in
fact, gels thickened by a structuring agent. Two main kinds of thickeners are
used in LADD products currently available to consumers: these are water
swellable, highmolecularweight (HMW) crosslinked polyacrylates (MW >
1,000,000) and clays, such as bentonite or laponite. Cothickeners are often
added to improve the stability of the gel. For example, colloidal alumina or
silica [46–48], fatty acids or their salts [47,49–59], and others have been
described in the patent literature as effective additives. It has also been found
that incorporated air bubbles can also contribute to the stability of
polyacrylatethickened gels [67–70]. The effect of such thickening systems is
to make the gel viscoelastic and thixotropic. This means that the gel is viscous
when unstressed, but the
TABLE 5 Commercially Available Detergent Enzymes
Type Trade name Manufacturer
Proteinase Esperase Novo

Savinase
Durazym
Alcalase
Maxapem Gistbrocades
Optimase Solvay
Opticlean
Amylase Termamyl Novo
Maxamyl Gistbrocades
Maxatase
AmylaseLT Solvay
Lipase Lipolase Novo

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viscosity decreases because of shear thinning upon application of an applied
stress. The rheological properties of LADD products are discussed in the next
section.
Currently, products on the market are thickened mainly by polyacrylic acids,
although some use a mixture of polymer and a clay. This is in contrast to the
early LADD products, which used exclusively clay thickeners and therefore
suffered from stability problems [6]. The products, because they were clay
suspensions in an aqueous medium, tended to separate in a relatively short
period of time. The introduction of bleachcompatible polymeric thickeners in
the early 1990s corrected this problem [71].
IV. Rheology And Stability Of Ladds
As discussed earlier, LADDs are complex, multicomponent mixtures consisting
of both organic and inorganic compounds dispersed in a liquid matrix. Such
compositions can exhibit a broad range of rheological characteristics, from
simple Newtonian to complex pseudoplastic flow. Shown in Figs. 6 and 7 are
flow and viscosity profiles of Newtonian and nonNewtonian fluids as a
function of applied shear rate. A number of mathematical models have been
proposed [72] to describe the flow characteristics of various systems. These
are called constitutive equations and are used to predict flow behavior in
complex systems.
FIG. 6
Generic examples of shear stress versus shear rate plots for different
rheological systems. (Reproduced by permission from Ref. 72.)

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FIG. 7
Generic examples of viscosity versus shear rate plots for different
rheological systems. (Reproduced by permission from Ref. 72.)
Clearly, the response of fluids to an applied shear can be linear or nonlinear
and depends on two major factors: shear rate and structural or mechanical
properties of the system, which in turn depend upon the interaction between
the components, including the rheological additives. It is the latter that primarily
determine the flow properties of LADDs. The intent of this section is to discuss
various rheological properties and test methods pertinent to LADDs.
Interested readers may refer to Chap. 4, which deals with the rheology of
complex liquids and suspensions, and other books [72–75] and review articles
[76–78] covering this subject. Heywood [79] discusses the criteria for
selecting various commercial viscometers.
The ideal rheological characteristics of LADDs from the consumer point of
view are as follows:
1. The product must be homogeneous and phase stable.
2. The flow properties of the product should be such that it can be readily
dispensed to the dishwasher cup from the bottle without dripping.
3. Once the product is in the dishwasher cup, it should recover its structure
and viscosity such that the product stays in the cup until the wash cycle begins.
The third attribute is the most important for dishwashers sold in the United
States because a majority of dishwasher cups are primarily designed for
powders. They are therefore ungasketed and do not prevent improperly
structured gel products from leaking prematurely.

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A. Flow Properties
1. Viscosity
This is a fundamental rheological property that is universally measured and
reported for all liquid products. Different types of viscometers are used to
measure these properties. A major disadvantage of determining the viscosity
for complex fluids is that the value obtained depends on instrument, type of
spindle, and rotational speed. Therefore, one should be extremely careful when
comparing the viscosities of the liquid products described in the literature.
2. Yield Value
Another rheological attribute of LADDs commonly referred to in the patent
literature is yield value (also referred as yield stress). The significance of the
yield value is that it indicates shear stress or shear rate necessary to induce
flow, which is a characteristic of the system. This is only an apparent yield
stress, because everything flows even at zero stress if given enough time.
Several methods based on viscometers [80,81] and stress rheometers [82,83]
have been proposed and described for measuring this parameter. One of the
methods described [84] utilizes a Brookfield RVT model viscometer and a T
bar spindle. The viscometer readings are recorded at 0.5 and 1.0 rpm after 30
s or after the system is stable. Shear stress at zero shear is equal to two times
the 0.5 rpm reading minus the reading at 1.0 rpm. The yield value is then
calculated as
Yield value = 18.8 × stress at zero shear
According to this patent, the yield value for LADDs should be in the range 50–
350 dyn/cm2.
Another method described in the literature [81] is based on Brookfield
viscosity measurements at two different shear rates, and the yield value is
calculated according to the equation
where is the shear rate and 1 and 2 are viscosities at shear rates at 1 and

2 1, respectively.
3. Thixotropy
The most desirable type of flow encountered in LADDs is thixotropy. Such
systems follow a shear thinning pattern very similar to pseudoplastic systems,
but when the shear is removed the structure rebuilds in a timeindependent
manner instead of instantaneously. A rheological profile of a thixotropic liquid
shows a characteristic hysteresis loop, the size of which is related to the

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degree of thixotropy and structure recovery time. A typical thixotropic loop
shows the relationship between the viscosity or stress versus shear rate. An
example for a commercial LADD is shown in Fig. 8. Such flow curves are
typically obtained by plotting viscosity or shear stress with increasing shear rate
(up curve), followed by decreasing shear rate (down curve).
Some systems exhibit flow behavior opposite of thixotropic systems, that is
viscosity increases with increasing shear rate. Such fluids are referred to as
dilatant or rheopectic. This type of behavior is not common for liquid products
containing a low concentration of the dispersed phase.
B. Dynamic Properties
The vast majority of concentrated dispersions, such as LADDs, exhibit both
viscous and elastic properties. These systems are therefore referred to as
viscoelastic. The flow properties discussed in the previous section are not
sufficient for complete rheological characterization of visoelastic fluids.
Dynamic mechanical properties, characterized by the storage modulus G' and
loss modulus G'', are normally measured to quantify viscoelastic properties.
The storage modulus represents the mechanical energy stored and recovered
and is a direct measure of the elasticity of the fluid. The loss modulus is a
measure of mechanical energy lost thermodynamically as heat. This type of
energy dissipation occurs when the sample is undergoing viscous flow. For
predominantly elastic materials G' > G'', and for predominantly viscous
materials G' > G".
FIG. 8
Shear stress versus shear rate for a commercial LADD. The rheograms were
recorded on a CarriMed CSL 100 stresscontrolled rheometer using a 4 cm
acrylic parallel plate configuration with gap setting of 1000 m.

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Both G' and G " are related to the complex modulus G* and complex viscosity
* by the following relationships:
where is the angular frequency of the oscillation.
The relative magnitudes of the two moduli provide significant information
regarding the strength of internal association or structure in fluids and
dispersions. These moduli are measured as a function of strain, frequency, or
time. For some dispersions, the magnitudes of G' and G " may remain constant
as a function of either frequency or strain. Such materials are referred to as
linearly viscoelastic.
Plots of G' and G " versus % strain for the three major commercial gel LADDs
sold in the United States are shown in Figs. 9–11. In this experiment, a strain is
applied to the sample and the stress response is measured.
The elasticity and viscosity of a gel are essential criteria for ease of dispensing
and cup retention in the dishwasher. For example, a patent issued to Corring
and Gabriel [85] claims that viscosities of 1000–20,000 cP under 51 shear,
200–to 5000 cP under 21 s1 shear, and a steadystate viscoelastic
deformation compliance value of at least 0.01 are ideal for product
dispensability and cup
FIG. 9
G' and G" versus % strain for a commercial LADD. The rheograms were recorded on
a CarriMed CSL 100 stresscontrolled rheometer using a 4 cm acrylic
parallel plate configuration with gap setting of 1000 m.

Page 350
FIG. 10
Plots of the G' and G" vs % strain for a commercial LADD. The rheograms were
recorded on a CarriMed CSL 100 stresscontrolled rheometer using a 4 cm acrylic
retention (as measured on a Haake Rotovisco RV100 viscometer). A series
of patents issued to Dixit and coworkers [51,52,55,67,68] emphasizes the
importance of linear viscoelasticity as defined by tan as an important
rheological characteristic for LADDs.
FIG. 11
Plots of the G' and G" vs % strain for a commercial LADD. The rheogran were
recorded on a CarriMed CSL 100 stresscontrolled rheometer using a 4 cm acryl

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Essential to the development of new LADD products is the evaluation of their
performance. It is important that the test conditions closely reproduce the
conditions encountered by the consumer under typical household situations;
therefore, prototype formulas are usually tested in actual dishwashing machines
using real food soils.
Typically, performance evaluation tests are run using a variety of soiled items,
because a combination of soils are typically encountered by consumers. For
example, spotting and filming on standard glass tumblers are run in conjunction
with plates and cutlery soiled with egg, oatmeal, spinach, tomato sauce, and
various other common food soils. In addition, the ability of the ADD product
to remove tough stains, such as coffee, tea, and blueberry, is assessed on a
variety of substrates during these multisoil test cycles.
Ideally, testing should be conducted using machines from all major
manufacturers, because differences exist in detergent dosing amounts, water fill
amounts, and lengths and order of cycles. It is also important that performance
tests be carried out at different water hardnesses, because regional variations
exist. Water hardness for testing purposes can be controlled by the addition of
simple salts of calcium and magnesium to deionized water. A 2:1 mole ratio
commonly is used because this is the Ca2+/Mg2+ ratio encountered in most
water supplies.
A. Spotting and Filming
The standard method for the testing of ADD products in the area of spot or
film prevention on glassware is described in ASTM D3556 [86]. The test
entails the washing of glass tumblers using commercial automatic dishwashing
machines. Initially the glasses are coated with whole milk, and a soil consisting
of margarine and powdered, nonfat milk (40 g in an 8:2 ratio) is added before
starting the cycle. The soil can be introduced by spreading on dinner plates or
by adding directly to the wash. This combination of soils provides the fats and
proteins generally present during typical household wash cycles. Optionally, a
similar soil mixture that also contains cooked cereal can be added, providing a
source of starch. For completeness, a combination of dinner plates, dessert
plates, and silverware is placed in the machine for ballast.
It is recommended that at least five complete cycles be run during a test,
coating the glasses with milk and adding the soil at the beginning of each cycle.
This is to ensure that product performance remains acceptable after repeated
cycles. Detergents that are underbuilt, for example, lead to heavy filming on the
glasses only after several cycles. The two test parameters that are typically
varied during spot/film tests are the water temperature and hardness. To dis

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criminate between similar products, it is often useful to run the tests under
stress conditions, that is, low temperature and high water hardness. In contrast,
to determine how a detergent might perform under normal household
conditions, higher temperatures and lower water hardnesses should be used.
The ASTM procedure also describes a rating method for judging the spotting
and filming on glasses. The readings are done visually using a fluorescent light
box to highlight spotting and filming on the glasses being inspected. The
performance of a product is rated on a 1–5 scale for both spotting and filming,
as shown in Table 6. The use of photometry to rate the spotting and filming on
glassware eliminates the possibility of subjective judging by humans. Several
systems have been described in the literature that take advantage of this
technique [87].
B. Soil Removal
When testing the performance of ADD products, it is often useful to determine
the ability of the detergent to remove tough food soils from items being
washed. In selecting the soils to be used, the following criteria must be met.
The soils must be representative of what consumers encounter in their kitchen,
but they must not be removed so easily that all products are rendered equal in
cleaning efficiency. The soils can be roughly divided into two classes: water
soluble or dispersible and waterinsoluble. Examples of the former are sugars,
starch, flour, or egg whites; the latter soils might be animal or vegetable fats.
Egg yolks have proven to be an especially useful soil for performance testing of
ADD products. They contain a very high protein content and thus are not
saponified by the heat and alkalinity during the wash cycle as are fatty soils.
Their efficient removal from dinner plates can only be accomplished by
detergents that target proteinaceous soils. Often, CaCl2 is mixed into the egg
mixture to make a cohesiveadhesive egg complex capable of remaining on the
dishes throughout the complete cycle [88]. Otherwise, the mechanical energy
from the water jets alone removes the egg from the plate. Typically, 2–3 g
CaCl2/25 g egg yolk are added. This more closely stimulates typically soiled
plates, which might derive a small amount of calcium from milk or salts
TABLE 6 Rating Scale for Spotting and Filming of Glassware
Rating Spotting Filming
1 No spots None
2 Random spots Barely perceptible
3 ¼ surface covered Slight
4 ½ surface covered Moderate
5 Virtually completely covered Heavy

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present. A known weight of the egg soil should be spread on dinner plates.
The degree of egg removal after the cycle is determined either visually or by
weight difference. An added bonus of this test is that it provides a
proteinaceous soil to the wash liquor, making the spotting and filming scores
more realistic. Studies have shown proteinaceous soils to be a source of
spotting on glasses [12]. It is important to place the egg plates consistently in
the same position in the dishwasher to minimize spray arm effects.
The Association of Home Appliance Manufacturers has published a set of
standards for testing of the automatic dishwashing process [89]. A multisoil test
is described for testing of detergents. The items to be washed are soiled as
listed in Table 7. The test procedure also describes how to load the items into
the dishwasher and other test parameters. Variations in the types and number
of soils and items used for a multisoil test are permissible. It is desirable,
though, to use a soil combination that contains the major types of soils
(proteinaceous, fatty, and starchy), because some ADD products might
effectively remove some soils but not others. This is especially true of formulas
that contain enzymes.
C. Stain Removal
Besides the prevention of spots and film and the removal of food soils from
items being washed, LADD products must also effectively remove stains. For
TABLE 7 Recommended Multisoil Test
Item Soil Quantity
Dinner plates Mashed potato 1 tsp
Raspberry preserves 1 tsp
Ground beef ½tsp
Egg yolk 1 tsp
Coffee grounds 1/8 tsp
Butter plates Cream corn ¼tsp
Oatmeal ¼ tsp
Flatware
Knives Peanut butter ¼ tsp
Spoons Cream corn Coated
Forks Egg yolk Coated
Serving spoon Cream corn, potato Coated
Serving fork Egg yolk Coated
Coffee cups Coffee Coates
Saucers Coffee Coated
Glasses Tomato juice Coated

Serving fork Egg yolk Coated
Coffee cups Coffee Coates
Saucers Coffee Coated
Glasses Tomato juice Coated
Serving bowls Cream corn 1 tsp
Mashed potato 1 tbsp

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this purpose, LADDs often employ bleaching agents that act by oxidizing the
chromophore responsible for the stain color. Generally, as the oxidizing
potential of the bleach increases, its effectiveness also increases. The common
method employed to gauge stain removal is to allow either coffee or tea to dry
in a porcelain, plastic, or glass cup. The cups are then run in a standard soil test
[89].
D. Foaming
The minimization of foam generated by detergent and food soils during wash
cycles in the automatic dishwashing process is a prerequisite for efficient
mechanical cleaning by the machine spray arms. Foam decreases the water
pressure pumped through the rotors, decreasing the kinetic energy of the water
jets. As stated in Sec. II, mechanical action has been estimated to be
responsible for 85% of the cleaning in a machine dishwashing cycle. Lowering
of the wash pressure therefore has a noticeable effect on overall cleaning.
Because of this, ADD formulations, especially those containing anionic
surfactants, often contain defoamers.
A standard test method has been developed for the measurement of foam
during an automatic dishwashing cycle. This method is described in the CSMA
Compendium, Method DCC001 [90]. The test involves the measurement of
the machine spray arm rotational velocity (rpm) at 1 minute intervals over a 10
minute wash cycle. The rotor rpm decreases in the presence of foam because
the water pressure being pumped through the spray arm is lower. To measure
the revolutions per minute, a magnetically activated “Reed” switch is used and
the spray arm is fitted with a magnet. The detergent is dosed normally, and a
highfoaming soil is added before the cycle begins. The recommended soil is
nonfat powdered milk (10 g) or a powdered milk and egg white combination
(1:1).
The efficiency score for a particular detergent is obtained by taking the average
of the arm speed readings and dividing by the average reading for the control.
In this experiment, the control is the same experiment without the detergent or
soil. As in other performance tests, it is good practice to use the same machine
for all comparative experiments to eliminate variations due to the use of
different machines. Different machines have slightly different motors, which
produce slightly different rotor velocities.
E. Fine China Overglaze
Fine china is often decorated with colored patterns made from various metal
salts or oxides. Two methods are commonly used: underglaze, in which the
color is applied before the glaze, and overglaze, in which it is applied after the
glaze. The overglaze pattern on fine china is incompatible with the high alka

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linity characteristic of ADD products. Unless the china is somehow protected
from hydroxide ions during the wash, the overglaze and color are attacked and
destroyed. To protect against this, LADDs are generally formulated with
sodium silicate, which acts by coating the china with a protective siliceous
layer, preventing the alkali from coming in contact with the overglaze itself.
Silicate works in a similar manner to protect metal machine parts from
corrosion.
A procedure has been developed to test the effectiveness of ADD products in
fine china overglaze protection. This method is described in ASTM D3565
[91]. Segments of a china plate are soaked in a 0.3% ADD solution held at
96.0–99.5°C in a steam bath. Two controls are also set up, consisting of a
sodium carbonate solution and water only. The segments of the china plate are
placed in supporting wire mesh to avoid contact with the bottom of the steel
beakers used. The solutions are heated for 6 h, after which the china segments
are removed and rubbed vigorously with a 1.5 inch square of muslin. The plate
segment is then washed, dried, and visually inspected for fading. An effective
detergent should prevent any sign of wear.
VI. Formulation Technology
The formulation of LADDs comprises a balance among performance,
esthetics, and cost. For the consumer to accept the product, it must possess
several attributes, listed in Table 8. In formulating LADDs, the components
used must not only clean the dishware effectively but must also yield a stable,
physically attractive product with specific rheological characteristics. As far as
cleaning is concerned, the product must prevent spotting and filming on glass
items and remove food soils encountered under typical conditions. To meet
these criteria, LADDs utilize a combination of components.
The bulk of food removal from soiled dishes is accomplished by two
mechanisms. Fatty soils are removed by a combination of the high temperature
and alkalinity present, which melts and saponifies fats. Proteinaceous and
starchy soils, on the other hand, are attacked by oxidation and hydrolysis. The
removal of tough stains, such as coffee or tea, can only be accomplished by
strong
TABLE 8 Important Attributes of LADDs
Effective cleaning
Convenient to use
Safe to dishes and tableware
Safe to dishwasher
Stable upon storage
Safe to humans
Economical to use

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bleaching agents, such as hypochlorite. Hypochlorite also has a sanitizing effect
on the washed items. More effective soil removal is accomplished by the use of
enzymes, which selectively and efficiently attack fats, starches, or proteins.
Listed in Table 9 are relevant patents that disclose novel cleaning technologies
in LADDs.
Equally important when formulating LADDs is making a product that is stable
and easy to handle. LADDs are concentrated suspensions that must be
properly structured to prevent separation upon storage. The product must also
be thickened for two reasons: to prevent it from prematurely leaking out of the
machine dispenser cup and to make it easier to control when dosing. However,
the product must be shear thinning so that it easily flows under an applied
stress. Early LADDs were thickened by clay thickeners. More recently, the
use of highmolecularweight polymeric thickeners, optionally with fatty acid or
other surfactant cothickeners, has solved the separation problems. Patents in
this area are listed in Table 10. Patents that disclose processing or
manufacturing methods used in LADD production are listed in Table 11.
Other important considerations must be taken into account when formulating
LADDs. Because of the corrosiveness of typical LADDs, ingredients must be
added that protect both the machine itself and fine items, such as china and
silverware. Generally, silicate is added for this purpose, but its inherent
alkalinity in aqueous solutions is not always desired. In Table 12, several
patents are listed that describe other anticorrosion agents.
As previously mentioned, a hurdle in formulating bleachcontaining LADD
products is that many useful ingredients are not stable toward hypochlorite.
Table 13 lists patents that claim bleachstable nonionic surfactants, and Table
14 lists patents relating to the stabilization of LADD components.
VII. Auxiliary Products
A. Liquid Prespotters
The automatic dishwasher detergents in today's marketplace, both liquid and
powder versions, deliver cleaning performance acceptable to most consumers.
However, one area in which consumers would like to see product
improvement is in cleaning of bakedon, cookedon, and driedon food soils.
These soils are tenaciously stuck to the surfaces and are hard to remove unless
strong mechanical forces are applied. To make the cleaning task of such hard
toremove soils easier, special liquid formulations, often referred to as
“prespotters,” have been developed.
The idea of a prespotter is to spray the product onto the soiled surface and
allow it to stand at ambient temperature over a period of 30–60 minutes before
they are cleaned in the dishwasher. This process allows the soil to soften and
debond or the adhesive forces between the soil and the substrate to loosen.
The

TABLE 14 Patents Relating to Stabilization of LADD Components
Patent and year Inventor(s) and company Technology
US 5384061 (1995) Wise (Procter & Gamble) Chlorine bleach ingredient, phytic

[128] stabilizing agent
US 5258132 (1993) Kamel et al. (Lever Bros.) Wax encapsulation of bleach, enz

[129] catalysts
US 5230822 (1993) Kamel et al. (Lever Bros.) Wax encapsulation of bleach, enz

[130] catalysts
US 5225096 (1993) Ahmed et al. (Colgate Alkali metal iodate

[131] Palmolive)
US 5185096 (1993) Ahmed (ColgatePalmolive) Alkali metal iodate

[132]
US 5229027 (1993) Ahmed (ColgatePalmolive) Watersoluble iodide/iodine mixtu

[133]
US 5200236 (1993) Lang et al. (Lever Bros.) Solid core particles encapsulated

[134]
EP 533239 (1993) Tomlinson (Unilever) Encapsulated bleach reducing age

[135]
US 5141664 (1992) Corring et al. (Lever Bros.) Encapsulation of bleach, bleach p

[136] surfactants, or perfumes
EP 414282 (1991) Behan et al. (Quest) Encapsulation of perfume in micr

[137]
US 4919841 (1990) Kamel et al. (Lever Bros.) Blend of hard and soft waxes for

[138] perfumes, enzymes, or surfactant
encapsulation

Page 366
conditioned soiled substrate can be easily removed by mechanical and
chemical forces in the dishwasher.
Several prespotter formulations are disclosed in the patent literature. Acidic
compositions that contain a mixture of nonionic surfactants and hydrotropes
[139], thickened alkaline products with hypohalite bleaches [140,141], and
enzymecontaining formulas [142] have all been developed for use as
prespotters. Although these products are effective at cleaning tough soils, no
product has made it to the marketplace, possibly because of economic factors.
However, LADD products can be used as prespotters by applying them
directly to soiled items.
B. Rinse Aids
As discussed earlier, consumers judge the performance of the automatic
dishwasher detergents based on overall cleaning, filming, and spotting on
dishware, glasses, and utensils. Spots and film on glass surfaces are readily
noticeable because of differences in the refractive indices of the glass and the
deposits. It is generally recognized that deposits on glasses are predominantly
water soluble minerals, such as salts of alkaline earth ions present in the water,
with proteins and fats of the soil as minor components. Clearly, the condition of
the final rinse cycle water largely determines the degree of spotting and filming
on glasses. Laboratory assessment indicates that water hardness exceeding
200 ppm as CaCO3 results in poor performance on glasses and silverware
unless the calcium ions are sequestered.
To minimize the mineral deposits and surfaceactive soil components on
articles cleaned in the dishwasher, special formulations called rinse aids are
often used for both home and institutional dishwashers. In the United States, an
estimated 40% of households use rinse aids [143]. Rheologically, the rinse aid
liquids are Newtonian, with viscosities in the range of 50–200 cP. Their role is
to reduce the interfacial tension between the dishware and glassware and the
wash water. In this way, a uniformly draining film of wash water is acheived on
the items. Otherwise, uneven wetting results in spotting and filming on the items
being dried.
Typically, rinse aid formulations for household dishwashers are composed of
aqueous solutions containing nonionic surfactant(s), a complexing agent, such
as citric acid or polyphosphate, hydrotropes (also known as coupling agents),
fragrance, and color. Suitable preservatives are also added to the formulations
to prevent the product from bacterial and fungal growth [144]. The pH of the
formulations span from acidic to alkaline. Normally the rinse aid solution is
injected during the final rinse cycle of dishwashing. A typical dosage of the
product per rinse is about 0.3–1.0 g/L, depending upon the level of nonionic
surfactant in the formulation. Most rinse aids contain between 20 and 40%

surfactant levels. Excessive or underdosage may have an adverse effect on the sp
and filming on glasses.
1. Ingredients for Rinse Aids
(a) Nonionic Surfactants. The heart of the rinse aid formulation is the surfactant,
virtually all formulations contain nonionic surfactants. The primary function of the
surfactant is to produce rapid sheeting action, achieving a quick and uniformly dr
film that prevents the nonuniform drying of the hard water minerals on the utensil
Systematic studies have shown that the nonionic surfactants must satisfy the criter
rinse aid applications, the most important of which are discussed here:
1. The nonionic surfactant must be an efficient wetting agent with low foaming
characteristics, because excessive foaming influences not only the cleaning but als
rinsing effectiveness.
2. The foaming properties of the nonionic surfactants depend upon the temperatu
because of their inverse solubility temperature relationship. Above the cloud poin
are nonfoamers, and some nonionic surfactants may even function as defoamers
their cloud point temperature. Therefore, the nonionic surfactant selected for rins
formulations must have a cloud point below the temperature of the rinse water.
3. The aqueous surface tensions of the surfactant solutions must be low, in the ra
40 dyn/cm2. The surface tensions should be preferably measured at temperatures
to rinse water temperatures.
The nonionic surfactants commonly used in the rinse aid formulations along with t
structures are shown in Table 15.
(b) Sequestering Agents. Sequestering agents, such as polyphosphates, are add
rinse formulations to condition the rinse cycle water (deactiva
TABLE 15 Nonionic Surfactants for Rinse Aids
Surfactant Structure
Alkyl phenoxy polyethenoxy ethanol [145] R(C6H4)O(CH 2CH2O)nCH2CH3
Block polymers of ethylene and propylene oxide [146– RO(CH2CH2O)n(CH2CH[CH3]O)
148]
Alkyl phenoxy polyethenoxy benzyl ethers [149] R(C6H4)O(CH 2CH2O)nCH2C6H5
Alkyl polyethenoxy benzyl ethers [150] R(CH2CH2O)nCH2C6H5
Ethoxylated alcohols R(OCH2CH2) nOH

Page 368
tion of alkaline earth metal ions) and to prevent or delay the formation of
waterinsoluble compounds, such as calcium bicarbonate or carbonate. These
insoluble precipitates may deposit on glasses and appear as spots or film.
The addition of acidic additives, such as citric acid, is very popular in European
formulations. The theory behind their use is that if sufficient acid is present in
the final rinse solution, the acid converts the carbonate and bicarbonate ions
into water and carbon dioxide, preventing the formation of insoluble salts.
Citric acid formulations may also keep the dishwasher surfaces and nozzle of
the spray arms free of limestone deposits. It is also believed that citrate may
contribute to the brilliancy or shiny appearance of siliceous surfaces [151].
(c) Hydrotropes. Hydrotropes (Chap. 2) or coupling agents play an important
role in formulating rinse aid products. Their main functions include increasing
the solubility of the nonionic surfactant in water and thus maintaining the clarity
of the formulations. Judicious selection of the hydrotropes is important since
they may contribute to the foaming and potentially reduce the sheeting
efficiency of the nonionic surfactant. Most effective are certain alkylnaphthalene
sulfonates and sulfosuccinate esters, since they increase the solubility of the
nonionic surfactants without leading to excessive foaming. Other hydrotropes
utilized in the rinse aid formulations include propylene glycol, isopropanol, and
urea. In general, alcohols are not effective solubilizers in rinse aid formulas
[151].
2. Typical Rinse Aids
Typical examples of rinse aid formulations are shown in Table 16 [8]. Several
patents describing rinse aid compositions have been issued. These are listed in
Table 17.
TABLE 16 Examples of Rinse Aid Formulations
I II
Ingredients (wt/wt %) (wt/wt %)
Plurafac RA 30a 50 17.5
Plurafac RA 40a 1 17.5
Isopropanol 24 12
Citric acid, dehydrated — 25
Deionized water 16 28
a
BASF Corporation

TABLE 17 Patents Relating to Rinse Aids
WO 94/07985 (1994) De Smet et al. (Procter & Lime soap dispersant, lipase enzym

[152] Gamble)
US 5294365 (1994) Welch et al. (BASF) Hydroxypolyethers

[153]
US 5104563 (1992) Anchor et al. (Colgate Lowmolecularweight polypropyle

[154] Palmolive) interacts with anionic or nonionic
surfactants
GB 2247025 (1992) van Dijk et al. (Unilever) Phospholipase A1 and/or A2

[155]
EP 252708 (1988) van Dijk et al. (Unilever) Nonplateshaped colloids, such as

[156] silica
US 4443270 (1984) Biard et al. (Procter & Ethoxylated nonionic, organic chel

[157] Gamble) agent, watersoluble Mg, Zn, Sn, Bi
salts
US 4416794 (1983) Barrat et al. (Procter & Ethoxylated nonionic, organic chel

[158] Gamble) agent, aminosilane

Page 370
VIII. Future Trends
The majority of LADDs marketed today deliver performance that is
acceptable to consumers. However, economic, environmental, or regulatory
pressures necessitate formulators of LADDs to continue to improve products.
Several trends in LADD development appear to be evolving.
A. Nonphosphate Products
The low costperformance ratio of phosphates, especially alkali metal
tripolyphosphates, make them the “workhorse” of detergents. Although
phosphate builders are safe for human beings, they are unfortunately beneficial
to algae growth. Therefore, large amounts of phosphate in waste streams lead
to eutrophication of lakes and streams. For this reason there have been
concerns, especially in Europe, about the heavy use of phosphates in detergent
products. In certain states of the United States, the quantity of phosphates
used in LADDs is regulated by the local governments. Therefore, one of the
challenges to automatic dishwasher detergent manufacturers today is finding a
substitute for polyphosphate. Ideally, the phosphate substitute must satisfy
several criteria including the following:
1. Free of phosphorus and nitrogen
2. Soluble in water with readily biodegradable characteristics
3. Chemically stable and compatible with oxygen and/or chlorine bleach
4. Performance characteristics equal to phosphates
5. Safe to humans
6. Economically practical
Although many builder systems meet most of these criteria, they provide
inferior performance attributes. In particular, filming and spotting on glasses is a
concern in hard water areas. This is probably the primary reason that
nonphosphate liquid products have not found their way into the marketplace.
The search for an alternative to phosphates will continue, as evident from the
patent activity in the last 5–10 years. Many reviews have appeared that
compare the characteristics of the more heavily studied alternatives
[17,26,35,159–168]. Table 18 lists the recent patents on phosphatefree
LADD formulations.
B. NonHypochloriteContaining Products
Another trend appears toward products containing no hypochlorite bleach.
The reason is that the strong oxidizing nature of hypochlorite makes it
incompatible with easily oxidized components, such as nonionic surfactants,
fragrances, and enzymes. There is also some concern regarding the possible
formation of chlorinated organics [7]. Oxygen bleaches, such as perborates or
percarbonates,

TABLE 18 Patents Relating to PhosphateFree LADDs
WO 94/29428 (1994) Ambuter et al. (Procter & Concentrated, enzymes and stabilizi

[159] Gamble) system
WO 94/05763 (1994) Rattinger et al. (Unilever) Pyridine carboxylates

[160]
EP 561452 (1993) van Dijk et al. (Unilever) Biodegradable polyamino acid

[169]
US 5169553 (1992) Durbut et al. (Colgate Binary mixture of proteinase and am

[170] Palmolive) nonaqueous
WO 91/03541 (1991) Beaujean et al. (Henkel) Aluminosilicate, stabilizing electrol

[26] and system
EP 476212 (1990) Boutique et al. (Procter & Citrate, C10–C16 alkylor alkenyl

[161] Gamble) substituted succinic acid
DE 3832478 (1988) Dixit (ColgatePalmolive) Aluminosilicate, polycarboxylates

[171]

Page 372
which liberate peroxide in solution, are being studied to replace chlorine
bleach. Being weaker oxidizing agents than hypohalite bleaches, they are
compatible with some oxidizable LADD components. However, there are two
main disadvantages of peroxide bleaches. First, they display acceptable
performance only at elevated temperatures. Second, they are difficult to
formulate in liquid products because of chemical stability problems.
The search for chlorine bleach alternatives, as well as development of
technologies for stabilizing peroxide bleaches, will continue.
Microencapsulation technology for formulating the LADDs containing chlorine
bleaches has shown limited success [129,130,134,138].
C. Enzymatic Products
Although they are incorporated into powder automatic dishwashing detergents,
the use of enzymes into LADDs is a relatively unexplored area. Cleaning action
by enzymes is highly selective and occurs only under specific wash conditions.
Formulating LADDs with enzymes is challenging because of the chemical
incompatibility of most of the enzymes in aqueous products containing chlorine
bleach and caustic. Considerable progress has been made in improving the
compatibility of different types of enzymes. Research will continue to develop
superior enzymes that are effective and efficient, providing cleaning action
under broad range of washing conditions. It is also possible that innovative
packaging based on compartmentalization will be developed to overcome the
chemical incompatibility of enzymes with other LADD components.
D. Concentrated Products
Although compact ADD powders are marketed in the United States, compact
liquids have not yet been introduced. Following the trend set by other cleaning
products in the marketplace, LADDs are expected also to evolve into
concentrated products. For example, the patent literature reveals that
concentrated LADDs can be developed using a nonaqueous solvent system
[92,96–98,105,170,172]. Two nonaqueous ultraconcentrated LADDs
appeared in Great Britain in the early 1990s. Two variants were marketed by
Marks and Spencer, one with enzymes and one without. The recommended
dosage for these products was onequarter the normal amount. Other markets
have not yet followed suit.
E. LowTemperature Cleaning
In an average U.S. machine dishwasher cycle, water temperature ranges from
110 to 140°F; in Europe it is around 160°F. Typical wash cycles last from 5 to
20 minutes, and two wash cycles are generally incorporated into the washing
process. In addition, from two to five heated rinse cycles are also gener

Page 373
ally present. Clearly, in mechanical dishwashing a good amount of energy is
utilized. Energy can be conserved by lowering the temperature of the wash
water. At present, technology does not exist that delivers consumeracceptable
performance at lower wash temperatures. The detergent industry may be
forced to develop cleaning technology at reduced wash temperatures, though,
if government regulations mandate the lowering of wash temperatures. This
could be a challenge and an opportunity for detergent manufacturers to
develop LADDs that meet both regulatory demands and consumer satisfaction.
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149. W. D. Niederhauser and E. J. Smialkowski, U.S. Patent 2,856,434 to
Rohm & Haas (1958).
150. L. M. Rue, T. E. Brunnelle, and W. G. Mizuno, U.S. Patent 3,444,242
to Economics Laboratory (1969).
151. E. J. Parker and K. F. Schoene, HAPPI 25:83 (1988).
152. B. L. A. De Smet, J. G. L. Pluyter, and L. A. Jones, WO Patent
94/07985 to Procter & Gamble (1994).
153. M. C. Welch, J. G. Otten, and G. R. Schenk, U.S. Patent 5,294,365 to
BASF (1994).
154. M. J. Anchor and R. R. Roelofs, U.S. Patent 5,104,563 to Colgate
Palmolive (1992).
155. W. van Dijk, A. Gerardus, and T. M. Bastein, British Patent GB
2247025 to Unilever (1992).
156. J. van Dijk, H. S. Kielman, L. Los, and R. C. S. Verheul, European
Patent 252708 A2 to Unilever (1988).
157. D. Biard and R. Lodewick, U.S. Patent 4,443,270 to Procter & Gamble
(1984).
158. C. R. Barrat, J. R. Walker, and J. Wevers, U.S. Patent 4,416,794 to
159. H. Ambuter and T. S. Alwart, WO Patent 94/29428 to Procter &
Gamble (1994).
160. G. B. Rattinger, B. Cotter, and M. J. Fair, WO Patent 94/05763 to
Unilever (1994).
161. J. Boutique and K. J. M. Depoot, European Patent 476212A1 to
162. E. A. Matzner, M. M. Crutchfield, R. P. Langguth, and R. D. Swisher
Tenside Det. 10:239 (1973).
163. M. S. Niewenhuizen, A. P. G. Kieboom, and H. van Bekkum, J. Am.
Oil Chem. Soc. 60:120 (1983).
164. H. C. Kemper, R. J. Martens, J. R. Nooi, and C. E. Stubbs, Tenside
Det. 12:47 (1975).
162. E. A. Matzner, M. M. Crutchfield, R. P. Langguth, and R. D. Swisher
Tenside Det. 10:239 (1973).
163. M. S. Niewenhuizen, A. P. G. Kieboom, and H. van Bekkum, J. Am.
Oil Chem. Soc. 60:120 (1983).
164. H. C. Kemper, R. J. Martens, J. R. Nooi, and C. E. Stubbs, Tenside
Det. 12:47 (1975).
165. S. Santhanagopalan, H. Raman, and S. K. Suri J. Am. Oil Chem. Soc.
61:1267 (1984).
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European Patent 561452 A1 to Unilever (1993).

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170. P. Durbut, F. Ahmed, and J. Drapier, U.S. Patent 5,169,553 to Colgate
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(1988).
172. P. Durbut, D. Kenkare, and N. S. Dixit, European Patent 611206 A2 to

10
Shampoos and Conditioners
CLARENCE R. ROBBINS
New Jersey
I. Introduction
II. General Formulas
III. Structures of Ingredients
A. Structures of shampoo ingredients
B. Structures of hair conditioner ingredients
IV. Safety Concerns and Considerations, Including Hair Damage
A. General safety considerations
B. Damage to hair from shampoos, grooming, and weathering
V. Different Types of Shampoos and Conditioners
VI. Cleaning Hair
A. Types of hair soils
B. Soils from hair preparations
C. Environmental soils
D. Detergency mechanisms
E. Transport of hair lipid
F. Methods of evaluating hair cleaning
G. Cleaning efficiency of shampoos
VII. Adsorption onto Hair
A. General characteristics
B. Kinetics of ionic reactions with keratin fibers
VII. Adsorption onto Hair
A. General characteristics
B. Kinetics of ionic reactions with keratin fibers
C. Binding of ionic ingredients to hair
D. Reactions of neutral materials with human hair

VIII. Shampoo Lather
IX. Viscosity Control in Shampoos and Conditioners
References
1. Introduction
According to legend, the word shampoo is derived from a Hindustani word mea
squeeze.” Shampoos have a long and varied history. However, hair conditioners
widely used until the midtwentieth century following the introduction of “cold” pe
types of products that created combing problems and damaged hair.
The primary function of shampoos is to clean both the hair and the scalp of soils
primary function of hair conditioner products was and is to make the hair easier t
Nevertheless, shampoos and conditioners have important secondary functions, su
control, extra mildness, static control, conditioning in a shampoo, and even fragra
satisfaction, that have either created new market segments or have become prima
purchase.
The two principal actions of shampoos and hairconditioning products involve cle
varied types from the hair and the sorption or binding of conditioning ingredients t
most important for both these products are interactions that occur at or near the f
near the first few cuticle layers (see Fig. 1).
FIG. 1
Structure of a human hair fiber.

Page 383
The first section of this chapter describes general shampoo and hair conditioner
formulations. The second part is concerned with chemical structures of the
main types of ingredients used in shampoos and hair conditioners. A brief
discussion of some safety concerns and considerations for these types of
products including damaging effects to hair caused by shampooing and by the
actions of combing and brushing follows. Cleaning of hair and the different
types of soil found on hair, including their origin and the ease or difficulty in
their removal and methods to evaluate hair cleaning, are then described. The
next section is concerned with deposition or the attachment and the affinity of
conditioning ingredients to hair, including both wholefiber and surface binding.
Foam properties and their measurement and viscosity control and evaluation
are also described.
II. General Formulas
Shampoos consist of several types of ingredients that usually include many of
the following types of components:
Primary surfactant for cleaning and foaming
Secondary surfactant for foam and/or viscosity enhancement
Viscosity builders: gums, salt, amide
Solvents to clarify or lower the cloud point
Conditioning agents
Opacifier for visual effects
Acid or alkali for pH adjustment
Colors (D&C or FD&C colors) for visual effects
Fragrance
Preservative
UV (ultraviolet) absorber, usually for products in a clear package
Specialty active ingredients, such as antidandruff agents and conditioning
agents
Hair conditioners, on the other hand, are very different compositionally from
shampoos. These are usually composed of many of the following types of
ingredients:
Oily and/or waxy substances, including mineral oil, longchain alcohols, and/or
triglycerides or other esters, including true oils and waxes, silicones, and/or
fatty acids
Cationic substances: monofunctional quaternary ammonium compounds or
amines or polymeric quaternary ammonium compounds or amines
Viscosity builders, usually gums
Cationic substances: monofunctional quaternary ammonium compounds or
amines or polymeric quaternary ammonium compounds or amines
Viscosity builders, usually gums
Colors
Preservatives

Page 384
III. Structures of Ingredients
A. Structures of Shampoo Ingredients
The principal primary surfactant used in the United States for shampoos is
ammonium lauryl sulfate; in many other countries, sodium or ammonium laureth
sulfate (with an average of 2 or 3 mol ethylene oxide) is the current leader.
These two surfactants are used alone or blended together for shampoos
because of their ability to clean sebaceous oil and because of their excellent
lathering properties.
Olefin sulfonate has been used to a limited extent in lower priced shampoos.
This surfactant is represented by the following structures:
Olefin sulfonate consists of a mixture of these four surfactants in about equal
quantities. The commercial shampoo material is 14–16 carbon atoms in chain
length; therefore, R = 10–12 carbon atoms.
Generally a carbon chain length of 12–14 carbon atoms or a cocotype
distribution, which is approximately 50% C12, is used for the primary surfactant
in shampoos. This chain length is preferred because of the excellent foam
character of C12 systems. Longer or shorter chain length surfactants are used
only in specialty systems.
Secondary surfactants are used for foam modifiers, for added cleaning, or even
for viscosity enhancement. The principal secondary surfactants used in
shampoos are amides, such as cocodiethanolamide, lauric diethanolamide, or
cocomonoethanolamide. Betaines are excellent foam modifiers. They are
becoming more popular, and cocoamidopropylbetaine is the most widely used
betaine in shampoos today.
Baby shampoos and some light conditioning shampoos employ nonionic
surfactants, such as PEG80 sorbitan laurate, and amphoteric surfactants, such
as cocoamphocarboxyglycinate or cocoamphopropylsulfonate, to improve the

Page 385
mildness of anionic surfactants through surfactant association and at the same
time to provide cleaning and improved lather characteristics.
Conditioning agents for shampoos are varied and may generally be classified as
follows:
Lipid type
Soap type or salts of carboxylic acids
Cationic type including cationic polymers
Silicone type, including dimethicone or amodimethicones (see structures later)
Opacifiers, such as ethylene glycol distearate, or soaptype opacifiers are often
used for visual effects and to provide the perception that something is
deposited onto the hair to condition it.
The pH is usually adjusted with a common acid, such as citric acid or even
mineral acid or ordinary inexpensive alkaline materials.
For additional details on product compositions, consult Refs. 1–3, product
ingredient labels, and the books by Hunting [4,5].
B. Structures of Hair Conditioner Ingredients
Cream rinses, on the other hand, are basically compositions containing cationic
surfactant in combination with longchain fatty alcohol or other lipid
components. Distearyl dimethylammonium chloride and cetyl
trimethylammonium chloride are typical cationic surfactants used in many of
today's hairconditioning products. Amines like dimethyl stearamine or
stearamidopropyl dimethylamine are other functional cationics used in these
products. Hype compounds, such as proteins, placenta extract, and vitamins,
which are usually nonfunctional, are also used.

Page 386
Typical lipids used in these products are cetyl alcohol and/or stearyl alcohol,
glycol distearate, or even silicones like dimethicone or amodimethicones.
For additional details on product compositions, consult Refs. 1–3, product
ingredient labels, and the books by Hunting [4,5].
IV. Safety Concerns and Considerations, Including Hair Damage
A. General Safety Considerations
Shampoos and conditioners are among the safest consumer products, if used
for their intended purpose and according to the directions on the package
label. Cautionary eye warning labels appear on most medicated products and
on some cosmetic brands because many of these products can cause eye
irritation if product accidentally flows into the eyes.
Warnings against internal consumption also appear on many shampoo labels
and on a few cream rinses or hair conditioners. Many conditioners contain no
cautionary warnings because they are so mild and of such low toxicity,
primarily because they are formulated at such low concentration (generally less
than 2% by weight of surfactant).
Bergfeld [6] has reviewed the most frequent adverse effects of hair products
from patients at the Cleveland Clinic Dermatology Department over a 10 year
period and has found relatively few adverse effects from shampoos; the
majority of these are a result of sensitization, an immunological reaction, rather
than irritation or hair breakage. Furthermore, Bergfeld attributes these few
adverse effects either to preservatives or medicated ingredients of these
products rather than to the surfactant active ingredients.
Ishihara [7] surveyed five large hospitals in Japan for contact dermatitis in
1970. Only 0.2% of the cases of the total number of outpatients at all derma

Page 387
tologic clinics were caused by adverse reactions to all hair preparations. Only
0.008% of these adverse reactions were caused by shampoos, and these few
cases involved contact dermatitis. From these results, Ishihara concluded that
most cases of contact dermatitis from shampoos are not serious enough to be
treated in a hospital.
B. Damage to Hair from Shampoos, Grooming, and Weathering
Chemical and physical damage to hair results from shampooing, combing and
brushing, and normal exposure of scalp hair to sunlight, and the changes that
are ultimately detected in hair can be detected at the morphological level by
electron microscopy. These effects may be viewed as aging of hair (not the
person) or of weathering damage. Weathering effects include damage to hair
by environmental factors, such as sunlight, air pollutants, wind, seawater, or
even chlorine in pool water.
Damage by hair grooming is produced by combing and brushing or even blow
drying, the use of curling irons, and other physical processes that are used in
grooming hair. Sunlight, pool water, and cosmetic products, such as permanent
waves, bleaches, hair straighteners, and even some hair dyes, chemically alter
or damage the hair. These chemical modifications generally increase hair's
propensity to physical damage manifested by progressive cuticle erosion and
fiber splitting resulting from the combination of chemical action and the abrasive
effects of hair grooming aids and the procedures described earlier [8]. A
detailed description of hair damage from rubbing actions is described by
Robbins [9].
Virtually every time a person shampoos or conditions the hair, he or she combs
or brushes it or uses grooming aids and procedures. Therefore, combing and
brushing of air is a fundamental part of the shampoo and hairconditioning
processes. Furthermore, Okumura [10] has suggested that a large amount of
cuticle damage occurs in the lathering step during the actual shampooing of
hair. Kelly and Robinson [11] have concluded that shampooing and towel
drying of hair damage hair. However, these scientists conclude that combing
and brushing damages hair more than the lathering step of shampooing, and
furthermore, brushing is more damaging than combing.
Garcia et al. [12] have developed a mathematical model to predict cuticle
wear, and these scientists conclude that cuticle erosion from grooming
accelerates as one moves closer to the tip end of the hair.
Gould and Sneath [13] examined root and tip end sections of scalp hair by
transmission electron microscopy and observed holes or vacancies in the thin
cross sections. These holes were greater (more frequent and larger) in tip ends

Page 388
than in root ends. These scientists attribute these holes to damaging effects by
shampooing.
It is becoming increasingly clear that shampooing and combing or brushing of
hair over time actually produces cuticle erosion, and ultimately normal cleaning
and grooming practices contribute to cortical damage as evidence by fiber
splitting [9]. In addition, sunlight [14] and cosmetic damaging treatments, such
as bleaches, permanent waves, and some hair dyes or even chlorinated water,
can accelerate these physical damaging effects to hair.
V. Different Types of Shampoos and Conditioners
Shampoos can be classified in many different ways; for compositional
considerations, however, perhaps the best classification is according to the
following four types:
1. Cleaning shampoos
2. Conditioning, including two in one shampoos
3. Baby or mild shampoos
4. Medicated shampoos
Cleaning shampoos generally consist of one or more detergents along with an
amide or amphoteric type of foam booster combined with a polymeric
thickening agent and salt to control the viscosity. Obviously, other additives,
such as color additives, fragrance, and preservative, are generally also used,
although there is a movement in many environmentally conscious countries to
make product without the addition of preservatives. Nevertheless,
preservatives are still an important component of shampoos and conditioners
and are added to prevent microbial contamination and degradation.
Conditioning shampoos usually consist of similar ingredients: as indicated
earlier, however, soaptype conditioners, cationic ingredients, or neutral
ingredients like silicones are usually a part of these products.
Baby shampoos generally contain milder surfactants, such as nonionics, and
they also contain less anionic detergent along with amphoterics that associate
with anionics to moderate the potential irritation of the anionic surfactants.
Medicated shampoos, such as antidandruff products, usually contain zinc
pyrithione, selenium sulfide, or even salicylic acid or coal tar (see Table 1).
The OTC monograph on dandruff recommends three classes of potential
antidandruff ingredients [15]:
Category I. Active ingredients considered safe and effective for use for
dandruff, seborrheic dermatitis, and psoriasis.
Category II. Ingredients not recognized as safe and effective or misbranded.
Category III. More data are required.

Actually, at this time only two categories are recognized: category I, as defined h
category II. All other ingredients are not recognized as safe and/or effective in thi
recent classification.
Five ingredients are currently recognized as safe and effective for use against dan
United States, and these are listed in Table 1. The OTC monograph recommend
ingredient at specific concentration levels for specified purposes (products and a
as listed in Table 1.
Other ingredients either reported or shown to be effective against dandruff and d
the OTC monograph, the published literature, or the patent literature include alkyl
isoquinolinium bromide, allantoin, benzethonium chloride, magnesium omadine, cli
[1imidazopyl1(p chlorophenoxy)3,3dimethylbutan2one], octopirox [1hy
methyl6(2,4,4trimethylpentyl)2(1H)pyridine], ethanolamine, and ketoconazol
last ingredients have not been described in category I by the OTC monograph.
Conditioners may be classified as cream rinses, deep conditioners, and other typ
include combination products, such as conditioning mousses or setting lotions. Th
products contain gums or resins in addition to conditioner additives.
Cream rinse conditioners generally consist of monofunctional cationic ingredients,
described previously, along with such lipids as longchain alcohols and other fatty
ingredients, such as mineral oil, longchain esters, amides, or even waxes. Deep c
may be similar compositionally; however, these tend to be formulated at a higher
and contain more fatty or waxy substances. Silicone or amodimethicones are also
three types of conditioner products.
VI. Cleaning Hair
Cleaning hair and requirements for a shampoo arise from the fact that dirty huma
contains different soils, although the predominant soil is lipid, primarily sebaceous
Hair contains both internal and external lipid; however, we have demonstrated th
and dirty hair contain the same
TABLE 1 Active Ingredients for Antidandruff Products
Ingredient Concentration specified (%) Use spec
Coal tar preparations 0.5–5.0 Shampoos
Salicylic acid 1.8–3.0 Body and scalp
Selenium sulfide 1 Topical use
Sulfur 2.0–5.0 Topical use
Zinc pyrithione 1.0–2.0 Shampoos
0.1–0.25 Hair groomers

Page 390
quantity of internal lipid; therefore, the hair soils are located at or near the fiber
surface, and cleaning of hair involves removing soils at or near the fiber surface.
Cleaning ingredients must be safe, requiring low toxicity, low sensitization
potential, and low skin and eye irritation potential. Low temperatures (35–45°
C) are used to shampoo hair, and short cleaning or reaction times (minutes) are
employed in the shampoo process.
Low substantivity of the detergent for hair is generally preferred, except in
conditioning, for which adsorption is necessary (see later). Essentially no
degradation of the hair substrate by the cleansing system is desirable, and the
cleansing system should be capable of removing a variety of different soils
without complicating interactions between shampoo ingredients and the soils.
The most common test criteria used to assess the cleaning efficiency of
shampoo products relate to the amount of soil left on the hair surface.
However, the rheological and other physical properties of the soil have recently
been shown to be important, too. Specific properties of hair fibers versus
assemblies, attributes of the product (fragrance, later, and viscosity), and the
rate of resoiling are also relevant to haircleaning efficacy. The next section is
concerned primarily with the different types of soil found on hair, their origin,
and their removal by existing surfactant systems.
A. Types of Hair Soils
Hair soils may be classified as one of four types:
1. Lipid soils are the primary hair soil and are principally sebaceous matter.
For a more complete description of the chemical composition of sebaceous
soil, see Table 2.
2. Soils from hair preparations represent another important group consisting of
a variety of different cationic ingredients, polymers, and lipophilic ingredients.
Lipid soils are either sebaceous in origin or from hair products. They may exist
on hair surfaces either as neutral lipid (oils, waxes, and silicones) or as
calciumbridged fatty acids or neutralized or free fatty acids.
3. Protein soils are from the skin but probably in most cases do not constitute
a serious soil removal problem.
4. Environmental soils vary and consist of particulate matter from air
(hydrocarbons and soot) and minerals from the water supply.
B. Soils from Hair Preparations
A variety of different soils from hair products may be found on hair surfaces,
and it is essential for a good shampoo to remove these soils without
complicating interactions between the surfactant and the soil. Hair products
provide

Page 391
TABLE 2 (Spangler) Synthetic Sebum with
Essential Components of Natural Sebum
Lipid ingredient %
Olive oil (TG) 20
Coconut oil (TG) 15
Palmitic acid (FFA) 10
Stearic acid (FFA) 5
Oleic acid (FFA) 15
Paraffin wax (P) 10
Squalene (S) 5
Spermaceti (WE) 15
Cholesterol (C) 5
lipid soils, cationic soils, polymeric soils, silicone soils, and metallic ions or fatty
acids that can bridge metallic ions to hair.
Neutral lipids are found in many different types of hair products, including
some conditioners, pomades, and men's hair dressings. As indicated earlier,
monofunctional cationic ingredients, such as stearalkonium chloride and cetyl
trimethylammonium chloride, are the primary active ingredients of creme rinses
and other hairconditioning products, and the increased usage of such products
over the last decade makes this soil type even more common.
Cationic polymers, such as polymer JR (polyquaternium10), a quaternized
cellulosic material [16], Merquat polymers (polyquaternium6 and 7),
copolymers of dimethyl diallyl ammonium chloride and acrylamide [17], and
Gafquat polymers (polyquaternium11), a copolymer of polyvinyl pyrrolidone
and dimethylaminoethyl methacrylate) [18], have all been used and are
currently being used in conditioning shampoos, setting lotions, or mousses.
Neutral and acidic polymers, such as polyvinyl pyrrolidone, copolymers of
polyvinyl pyrrolidone, and vinyl acetate and copolymers of methyl vinyl ether
and halfesters of maleic anhydride, are all used in hairstyling and hairsetting
products.
Fatty acids, such as lauric, myristic, or palmitic, have in the past been
commonly used conditioning ingredients in conditioning shampoos. Fatty acids
interact with calcium and magnesium ions in the water supply and deposit on
the hair. It is believed that at least part of this type of conditioning agent binds
to the hair through metal ion bridges [19]. The “harder” the water, the greater
is the amount of deposition of fatty acid conditioner on the hair [20]. Thus the
primary sources of calciumbridged fatty acids on hair are conditioning
shampoos and soap bar products that react with metal ions in the water
supply. In

Page 392
moderate to high hard water areas, fatty acids from sebum may also be a
source of metal ionbridged fatty acid on the hair fiber surface.
C. Environmental Soils
Hair is an excellent ionexchange system. Therefore, other metallic ions, such
as copper (2+) [21], can adsorb to hair, especially after frequent exposure to
swimming pool water. It has been suggested that metallic ions, such as
chromium, nickel, and cobalt, may also sorb to hair from swimming pool water
[22]. Sorption of metallic ions, such as calcium or magnesium, occurs even
from low concentrations in the water supply. However, fatty acids present in
hair products enhance the adsorption of most of these metallic ions to the hair
surface, as described earlier. Heavy metals, such as lead and cadmium, have
been shown to collect in hair from air pollution [23], and other metals, such as
zinc, are available from antidandruff products.
Other soils that shampoos must remove are proteinaceous matter arising from
the stratum corneum, sweat, and other environmental sources. We have
already described metallic ion contamination from the water supply, from
swimming pools, and from sweat. In addition, particulate soils from the
environment include hydrocarbons, soot, and metal oxide particles, which
should also be removed by shampoos [21].
D. Detergency Mechanisms
Although mechanical action is involved in shampooing or cleaning hair, it may
be assumed to be constant for any given person. Therefore, detergency
mechanisms are the main approach in producing differences in hair cleaning,
that is, in removing soils at or near the fiber surface.
Detergency mechanisms include emulsification, solubilization, and rollup [24]
and generally consider soils as either oily (liquid soils) or particulate (solid
soils). The removal of oily soils involves diffusion of water to the soil/fiber
interface and rollup of the soil, which generally determines the rate of soil
removal, although solubilization, emulsification, and soil penetration are also
involved. Rollup of oil on a fiber surface is caused by interfacial tensions of
(oil on fiber) fo, and (water on fiber) fw, and between (oil and water) ow, and
the oily soil rolls up when the combination of these interfacial tensions R is
positive in the expression, where is the contact angle of the oil droplet on the
fabric or substrate:
R = fo fw + ow cos
In other words, to clean oily soils from hair involves emulsification,
solubilization, and rollup of the oily soil. This includes emulsification and
solubili

Page 393
zation of the lipids of Table 2 and oil soil rollup. To maximize rollup, the
detergent must make the fiber surface more hydrophilic [24]. Thus, the
removal of lipid soil from hair is controlled by the hydrophilicity of the fiber
surface, and anything that can be done to make the fiber surface more
hydrophilic, such as bleaching or washing with anionic surfactants in water,
should facilitate oily soil removal. This is one of the reasons that damaged hair,
which is generally more hydrophilic at the surface, is so sensitive to oil removal.
On the other hand, the removal of particulate soils is not controlled by the
hydrophilicity of the fiber surface. Particulate soil removal depends on the
bonding of the particle to the surface and the location of the particle [24].
When the soil particle consists of nonpolar components, its adhesion depends
mainly on van der Waals forces, for example waxes or polymeric resins or
even some cationic polymer deposits. The removal of these soils is easier for
noncationic polymers because adhesive binding for cationics can include a
combination of ionic and van der Waals forces.
Some soils (e.g., conditioners containing cationic surfactant plus oily
substances or some plasticized resins) are intermediate in classification, and
their removal may involve a more complicated cleaning mechanism.
E. Transport of Hair Lipid
After shampooing, the surface of hair is relatively free of lipid, or at least its
concentration is considerably reduced. Sebum (produced by the sebaceous
glands) and epidermal lipid (produced by the cells of the horny layer of the
scalp) are transferred to the hair because of its greater surface area and
absorptive capacity. Creeping of sebum along the hair has also been suggested
[25], although Eberhardt [26] has shown that creeping does not occur along
single hair fibers. Eberhardt suggests that transport occurs primarily by
mechanical means, that is, by contact of hair with scalp (pillows and hats),
rubbing (combing and brushing), and haironhair contact.
Distribution of sebum along the fibers by combing and brushing is very
important, and wicking as occurs in textile assemblies might also be involved
[27,28]. The net result is that the rate of accumulation of lipid is fastest for oily
hair; after the lipid accumulates beyond a given level, it interferes with the
appearance and overall esthetics of the hair, causing fibers to clump or to
adhere together.
The composition of the lipid itself may influence its transport, because
ingredients that either lower the surface tension of the sebum or increase its
fluid nature (make it less viscous) can facilitate transport and even increase the
perception of oiliness. In addition, other ingredients left behind on the hair
surface, such as conditioning agents, may exacerbate oiliness in an analogous
manner.

Page 394
Hair characteristics, such as fineness, degree of curvature, and length, are also
relevant to the transport of lipid and to the influence of lipid on hair assembly
properties. For example, fine, straight mediumlength hair provides optimum
characteristics for the transport of sebum. This type of hair provides the
maximum amount of hair clumping by a given amount of lipid. On the other
hand, curly, coarse, long hair tends to inhibit transport and also minimizes the
influence of tress compacting. Among all hair properties, increasing fiber
curvature provides the greatest influence against the cohesive forces of hair
lipid and the resultant compacting of tresses [29].
F. Methods of Evaluating Hair Cleaning
Several methods have been described to evaluate the ability of different
shampoos or detergents to clean soil from the hair [11,21,22,30–37]. Most of
these methods have been developed to evaluate the removal of lipid soil from
the hair [21,31,32,38]. Some of these methods are soil specific [31] or are
more sensitive with specific soil types [21,34]; others work for most soils [33].
Haircleaning methods may be classified according to the following categories:
chemical and physical properties, microscopic methods, or subjective or
sensory evaluation procedures. Chemical or physical methods may involve
either direct analysis of the hair itself [21,34] or analysis of hair extracts
[30,31]. For direct analysis of hair, chemical methods, such as ESCA [35] or
infrared spectroscopy, may be used. Physical methods, such as fiber friction
[34] or light scattering [33] or examination of interfiber spacings [21], on the
other hand, are less soil specific than chemical methods and offer the ability to
look at a variety of soil types, but sometimes these methods are less
distinguishing in so doing.
Microscopic methods have also been used to evaluate hair cleanliness [30].
However, sensory evaluation of hair greasiness on hair swatches [36] and
subjective assessments from halfhead and consumer tests are also useful. The
latter evaluations are in a sense the final word in the estimation of cleanliness by
shampoos. Most procedures involve evaluation of either single soils (primarily
hair lipid) or shortterm effects of different products. One area of concern that
has received relatively little attention is longterm effects that might result from
gradual buildup or from gradual interactions between different hair products or
between hair lipid and different hair products. This is an important area for
future research for shampoos.
G. Cleaning Efficiency of Shampoos
To evaluate shampoo efficiency, one must consider the different soil types
separately and then together and also attempt to distinguish between cleaning

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soil from hair and the deposition of ingredients from the shampoo formulation
itself.
1. Cleaning Lipid Soil
For efficiency in removing lipid soil from hair, the literature does not provide a
consensus. For example, Shaw [30] concludes that a onestep application of
anionic shampoo removes essentially all the hair surface lipids and that
differences in cleaning efficiencies cited (for different surfactants [30]) reflect
differences in the amount of internal hair lipid removed. To support this
conclusion, Shaw cites results from scanning electron micrographs (SEM) of
hair washed with anionic surfactant (monoethanolamine lauryl sulfate)
compared with SEM photographs of hair washed with ether. In addition, Shaw
cites in vitro studies showing that various shampoos remove 99% of an artificial
lipid mixture deposited on the hair.
Robbins [39] independently arrived at a similar conclusion, suggesting that
shampoo surfactants in a normal twostep shampoo operation are very
effective in removing “surface” lipid; although because of their limited
penetration into hair, they are less effective in removing internal lipid.
Table 3 offers some evidence for the effectiveness of current shampoos for
removing a sebaceous soil from wool fabric in moderately soft water (80 ppm
hardness). These data show that a cocomonoglyceride sulfate (CMGS)
shampoo at only 5% concentration (5% shampoo, when diluted provides only
1% AI) under these laboratory conditions nearly approaches the efficiency of
boiling
TABLE 3 Shampoo Versus Chloroform Extraction of Animal Hair: % Synthetic
Sebum Removeda
% Shampoo concentration CMGS formula Soap CTG formula
0.5 63 18
2.0 86 53
5.0 91 77
a
Percentage values were obtained by extracting the same wool swatches in
boiling chloroform for 4 h in a Soxhlet after shampooing and comparing the
residue weight versus total soil deposited. For practical purposes, boiling
chloroform for 4 h is 100% sebum removal. Test procedure: Preweighed wool
swatches were soiled with synthetic sebum and reweighed to determine the
amount of soil deposited. These swatches were washed in a tergitometer with
CMGS and soapcontaining (conditioning) shampoos at varying concentrations.
The swatches contained approximately 10% sebum, an exceptionally large
amount of soil. The temperature was 105–110°F, time 30 s, and a 200:1 solution
to wool ratio and 2–30 s water rinsings were used.

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chloroform in a 4 h Soxhlet extraction for removing lipid soil from wool
swatches. On the other hand, the soapcontaining shampoo of Table 3 is not
very effective in removing this lipid from hair. The normal usage concentration
of shampoos is 20–25%. The solutionhair ratio in normal usage is lower than
in this experiment; however, this probably does not make a substantive
difference. Wool swatches were used in this experiment instead of hair,
because most shampoos are too effective to provide distinctions in removing
sebum from hair under these conditions.
There are recent publications [40,41] showing that fatty acids, paraffin waxes,
and certain triglyceride components of sebum are more difficult to remove from
hair than the other components, although a detergent like sodium laureth2
sulfate is highly effective in removing virtually all sebaceous components.
There are only limited published data with regard to the removal of other
nonsebaceous types of soils by shampoos. However, there are data showing
incomplete removal of monofunctional cationics by anionic detergents [42],
and although limited data are available, the removal of polycationic soil should
be even more difficult.
2. Cleaning Other Soils
The original hair spray lacquers of the 1950s were more difficult to remove
from hair than the anionic and neutral polymers of today's hairsetting products.
However, no systematic study of the ease or difficulty in removing these
ingredients from hair could be found. Gloor [41] has examined the influence of
hair spray on reoiling; however, no systematic study of the effects of hair spray
on the ease of removal of hair lipid has been reported.
Calciumbridged fatty acid may be deposited onto hair even in shampoos
containing anionic surfactant. It is also well known that acid rinses may be used
to remove calciumbridged fatty acid from hair, and anionic sulfate surfactants
appear to remove fatty acid deposits from hair. However, copper (cupric ion)
adsorbs strongly to hair and is reported to be resistant to removal by anionic
surfactant [22].
Published literature regarding the efficacy of anionic surfactant systems for
removing particulate soils, such as soot and hydrocarbons, could not be found.
One may speculate that two important variables with this kind of soil are
particle size and the type of chemical bonding between the particle and the
hair. As particle size decreases below the region of about 1 m, the resistance
to removal should increase. However, when van der Waals attractive forces
are the primary adhesive forces, removal probably occurs. When hydrogen
bonding and/or ionic bonding are involved, the particle is more resistant to
removal.

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VII. Adsorption Onto Hair
A. General Characteristics
The binding of ingredients to hair fibers is fundamental to the action of
conditioning agents whether from a shampoo or a conditioner medium. The
amount of sorption or uptake of an ingredient by hair from an aqueous solution
is governed by its attraction or binding interactions to the keratin, its
hydrophilicity or binding interactions to the aqueous phase, and the diffusability
of the ingredient into the hair.
It is useful to consider deposition onto hair as represented by two distinct
driving forces. The first involves chargecharge interactions, which cationic
ingredients are attracted to a negatively charged hair fiber surface. This
mechanism has been studied to the greatest extent. The second important
driving force for deposition onto human hair involves hydrophobic interactions,
which a neutral hydrophobic material, like a silicone polymer, is driven from an
aqueous medium onto a hair fiber surface primarily by entropy.
The binding interactions to keratin are influenced by the charge of the
ingredient, its molecular size, the isoelectric point of hair, the pH of the
surrounding medium, other salts or components in the formulation, and
ingredients that are attached to the fiber surface. The attraction to the aqueous
phase is governed primarily by the charge of the ingredient and the ratio of
polar to nonpolar substituent groups. Penetration into the fibers or diffusion
rates are governed primarily by molecular size, the condition of the hair, pH,
and reaction temperature.
Because the isoelectric point of hair is so low, approximately 3.67, its surface
bears a net negative charge near neutral pH, at which most shampoos are
formulated. Although anionic surfactants bind to the hair surface, the number of
sites is comparatively small, relative to sites for cationic ingredients. Lauryl and
laureth sulfate salts and salts of olefin sulfonate are also moderately hydrophilic.
They appear to rinse well (but not completely) from hair and therefore serve as
good cleaning agents.
More anionic surfactant binds to hair with decreasing pH, suggesting that low
pH shampoo formulations leave more anionic surfactant behind after
shampooing than neutral pH shampoos.
The diffusion of anionic surfactants into hair is slow, and it takes days for an
averagesized surfactant to completely penetrate cosmetically unaltered hair.
Although some penetration of surfactant can and does occur, the major
interactions and effects of the active ingredients of shampoos and conditioners
occur at or near the fiber surface, that is, near the first few micrometers of the
periphery of the hair.

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One objective of highcleaning shampoos is to minimize sorption and/or
deposition of its ingredients. On the other hand, the effects caused by
conditioning shampoos and creme rinses are primarily a result of adsorption of
ingredients at or near the fiber surface, and so the objective with conditioning is
to maximize the deposition of the conditioning agents.
Soaps and surfactants, lipids, cationic ingredients, and even polymers or
polymer association complexes have been used as conditioning ingredients in
shampoos and/or conditioning products. Soaps deposit their hydrophobic salts
on the hair or bind by metal bridging. Cationic surfactants and polymers attach
substantively to hair by ionic bonds enhanced by van der Waals attractive
forces. On the other hand, the substantivity of most polymer association
complexes or silicones is probably a result of their hydrophobic nature,
enhanced by van der Waals forces and possibly by ionic bonds and entropy.
Cream rinses are analogous to conditioning shampoos in causing hair effects
chiefly by the adsorption of ingredients to hair. Above its isoelectric point (pH
3.67 for undamaged hair), more cationic than anionic surfactant binds to the
hair surface, and cationics are difficult to remove by rinsing. As a result,
cationic surfactants are said to be substantive to hair. Similar to anionic
surfactants, diffusion of cationic surfactants into hair is slow.
The more important interactions occur at or near the fiber surface (first few
micrometers of the fiber periphery), accounting for the low surface friction and
the ability of creme rinses to make hair comb more easily. More modern cream
rinse conditioners contain a high concentration of a fatty alcohol, such as cetyl
alcohol, or a similar fatty material in addition to a cationic surfactant. Dye
binding studies suggest that conditioning alcohols binds to hair along with
cationic ingredient (absorption maximum shifts), resulting in easier combing and
more effective conditioning than by the cationic surfactant alone.
The condition of the hair also affects the uptake and the diffusion of cream
rinse and shampoo ingredients. Diffusion is faster into altered or damaged hair
than into unaltered hair. Bleaching (oxidation) also lowers both the isoelectric
and the isoionic points of hair, thereby attracting more cationic surfactant to the
hair.
Thus, although diffusion occurs more easily into cosmetically altered hair, the
more important hair effects are produced by conditioner and conditioning
shampoo ingredients binding at or near the fiber surface. Only in severely
damaged tip ends might internal binding be more important, and even here the
distinction may be essentially semantic.
B. Kinetics of Ionic Reactions with Keratin Fibers
1. Summary
Reactions of hair fibers with solute in solution may be considered a multistep
process:

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1. Diffusion through solution
2. Adsorption or interaction at the fiber surface
3. Diffusion or transport into the fibers
4. Reaction at internal sites in the fibers
Whenever diffusion through solution is rate determining, reactant
concentrations are generally low, the rate is dependent on agitation, and the
reaction is usually characterized by low activation energies (3–5 kcal/degree
mol).
Fiber surface adsorption is generally rapid for ionic ingredients, and the surface
becomes filled (with respect to solute) during the first few minutes of reaction.
Diffusion into the fibers is generally the ratedetermining step of most hair fiber
reactions and is usually characterized by higher activation energies (10–30
kcal/degree mol).
Because ionic reactions are generally more rapid than diffusion, they are usually
not rate determining. However, reactions that involve breaking and formation
of covalent bonds can sometimes be slower than diffusion into the fibers and
therefore can be rate determining, for example, reduction of the disulfide bond
by mercaptans at acidic pH.
Penetration into the fibers is governed by the following factors:
Reaction temperature
Molecular size
Crosslink density of fibers
Fiber swelling
Reaction time
The rate of penetration generally increases with increasing temperature and
fiber swelling, whereas it decreases with increasing crosslink density and
molecular size of the penetrating species. Obviously, the extent of penetration
increases with time.
Liquid water at room temperature penetrates across the entire fiber in less than
15 minutes and in less than 5 minutes at 92°F [43], whereas more than 6 h is
required for single fibers to equilibrate in a humid atmosphere, and even longer
for a fiber assembly. Such dyes as methylene blue (molecular weight 320)
and orange II (molecular weight 350) generally require over an hour to
penetrate through the cuticle layers to the cortex. Similar penetration times are
expected for the typical anionic and cationic surfactants used in shampoos and
hair conditioners.
2. Transcellular and Intercellular Diffusion
Two pathways have been described for diffusion into human hair [45]: (1)
transcellular diffusion and (2) intercellular diffusion. The transcellular route
involves diffusion across cuticle cells through both high and low crosslinked
hair conditioners.
2. Transcellular and Intercellular Diffusion
Two pathways have been described for diffusion into human hair [45]: (1)
transcellular diffusion and (2) intercellular diffusion. The transcellular route
involves diffusion across cuticle cells through both high and low crosslinked
proteins. Intercellular diffusion involves penetration between cuticle cells

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through the intercellular cement and other proteins low in cystine content (low
crosslinked density regions).
Transcellular diffusion is the generally accepted route because of the much
greater amount of surface area available for this type of penetration.
Intercellular diffusion was first proposed as far back as 1937 by Hall [46] and
was recently demonstrated clearly by Leeder et al. [47] for metal complex
dyes; a large cationic dye (rhodamine B, 479 daltons); triphenyl pyrazine, a
neutral molecule (311 daltons); and for the highmolecularweight anionic
oligomeric Synthappret BAP (>3000 daltons).
For shampoos and conditioners, both diffusion routes probably occur in most
circumstances. The intercellular route, is probably preferred for larger
molecules, however, because the lowsulfur, nonkeratinous proteins are more
easily swollen than the highly crosslinked regions. With decreasing molecular
size, the transcellular route probably becomes increasingly important because
of the much greater surface available for this type of diffusion.
C. Binding of Ionic Ingredients to Hair
The interactions of ionic ingredients (i.e., acids, alkalies, and neutral salts) with
keratin fibers are of major importance to shampoos, cream rinses, ionic
conditioners, and the group of hair dyes referred to as rinses. In this section,
we consider the acidcombining capacity, which relates to the total number of
basic groups in the fibers and defines the capacity for the fiber to bind anionic
detergent ionically, and the basic binding capacity, which defines the capacity
for the fiber to bind cationic detergent ionically. Unexpectedly, the surface of
the fiber is essentially negatively charged and has a greater capacity for cationic
binding than the fiber interior, as reflected in the isoelectric point near pH 3.67
and the isoionic point of about 6.5–7.
1. Maximum AcidCombining Capacity
The acidcombining capacity provides indirect information about the
combination of highmolecularweight organic anions with whole or total hair
fibers, and organic anions are the primary ingredient of shampoos. The
maximum acidcombining capacity of human hair fibers, from reaction with
simple acids, such as hydrochloric, phosphoric, or ethyl sulfuric acids, is
approximately 0.75 mmol/g for unaltered human hair and about 0.82 mmol/g
for wool fiber [48]. This value approximates this number of dibasic amino acid
residues in the fibers [49], that is, the combined amounts of arginine, lysine,
and histidine. The primary sites for interaction with acid (protons) are probably
the carboxylate groups of aspartic and glutamic acids (ionized by interaction
with the dibasic amino acid residues) and the dibasic amino acid groups
themselves.
This acidbase reaction involves protonation of a basic site on or in the fiber,
forming a positive charge on the fiber that attracts a negative ion to it.

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Steinhardt and Harris [48] have shown that the uptake of chloride ion by wool
corresponds to the uptake of hydrogen ions during reaction with hydrochloric
acid, and we in our laboratories have shown the same to be true of human hair.
Maclaren [50] has taken advantage of this counterion effect and has developed
a test for the acidcombining capacity of keratin fibers by measuring the uptake
of the anion of orange II dye (p hydroxy1naphthyl azobenzenesulfonic acid)
from formic acid solution. We have used this test to study the variation in the
acidcombining capacity of hair among individuals, by cosmetic treatments, and
from environmental effects (next section).
2. Variation in the AcidCombining Capacity of Unaltered Hair
Hair samples were collected from 20 female Whites ages 10–30 who had
never bleached, dyed, or permanentwaved their hair. These hair samples
were analyzed by Maclaren's method for the acidcombining capacity. The
average uptake was 0.70 mmol/g. Analysis of variance indicated significant
differences among these hair samples beyond the = 0.01 level. This tells us
that there are differences in the ability of undamaged human hair to take up
anionic surfactants from shampoos.
3. Variation in the AcidCombining Capacity of Altered Hair
Bleaching decreases the acidcombining capacity of both human hair [51] and
wool fibers [52]. Analysis of hair samples bleached to different extents shows
that the acidcombining capacity decreases with increased bleaching (see
Table 4). This result shows that bleached hair takes up less anionic surfactant
from shampoos than nonbleached hair and that there is a continued decrease in
the ability of hair to adsorb anionic surfactant with increased bleaching. On the
other hand, bleached hair should pick up more cationic surfactant, and the
adsorption of this type of species should increase with increased bleaching.
Amino acid analysis of these same hair samples shows no change in the basic
amino acid residues. Therefore, the decrease in acid combination (anionic sur
TABLE 4 AcidCombining Capacity of Bleached Hair
Acidcombining
capacitya Cysteic acid
Sample description (mmol/g hair) (mmol/g hair)
Control (unbleached) 0.67 0.03
One bleach 0.60
Two bleaches 0.52
Three bleaches 0.48
Four bleaches 0.43
Frosted hair 0.30 .066
a
By the method of Maclaren [50].

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factant combination) must be a result the formation of cysteic acid in the fibers,
which forms a strong ionic bond with the basic amino acid residues and inhibits
their interaction with weaker acids, such as formic acid, thus decreasing the
uptake of orange II dye or anions of high affinity, such as lauryl sulfate.
Because the exocuticle and its A layer are highly crosslinked with cystine [53]
and are near the fiber surface, one would expect a large increase in cysteic
acid in the cuticle and in all probability a decrease in the isoelectric point of
hair. This should produce a decrease in aciddye combination and an increase
in the combination of cationic conditioning agents at or near the fiber surface
with increased bleaching or oxidative weathering.
In our laboratories, we have shown that the acidcombining capacity of human
hair decreases with weathering [54], although only to a small extent, and this
change results in a decrease in the ability of hair to take up anionic surfactant
from shampoos. This study involved a comparison of root and tip ends of five
samples of long hair (longer than 18 inches) that was visually lighter in the tip
ends than the root ends. The acidcombining capacity varied from
approximately 3 to 13% less in the tip ends. The most severely affected sample
was hydrolyzed and analyzed for amino acids and found to contain significantly
less lysine and histidine and a larger amount of cysteic acid in the hydrolyzates
of the tip ends.
This result is presumably from reaction with the elements. Such hair reacts
more strongly with cationic conditioning agents than nonweathered hair, so
that weathered hair should show more reaction with cationic surfactants in the
tip ends than the root ends, and it does. In addition, weathered hair also shows
more reaction with anionic detergents because of the increased penetration rate
from the degradation reactions of the oxidizing agent.
4. Reaction with Hydrogen Ions and Cationic Surfactants
In neutral dyeing or surfactanthair interactions, competition of cations with
hydrogen ions plays a role. When the concentration of hydrogen ions is low
and cations of low affinity are present, the adsorption of anion is influenced by
the concentration and affinity of cations for hair. If the cation affinity is high
enough that it is adsorbed, a counterion must accompany it to maintain
electrical neutrality. In the presence of lowaffinity cations, such as sodium or
potassium hydrogen ions can be taken up until quite high pH values are
reached [55]. However, competition between hydrogen ions and other cations
occurs at high concentrations or when cations of high affinity are employed.
5. Base Binding Capacity and Cationic Binding
The base binding capacity of human hair is approximately 0.4 mmol/g or about
onehalf the acidcombining capacity of human hair. This demonstrates the
difference between the whole fiber and the fiber surface with regard to the ratio

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of acidic to basic amino acid side chains and is an index of the relative reaction
of the whole fiber to cationic surfactants that occurs via ionic bonding.
Longchain quaternary ammonium compounds, such as surfactants or
conditioner additives, have a high affinity for human hair, and they compete
quite effectively with hydrogen ions for sites on hair, even at acid pH in many
cream rinse formulations. Furthermore, greater binding of cationic surfactants
occurs to hair with increasing pH, because of the increased ionization of
carboxyl side chain groups that occurs with increasing pH, creating additional
sites for ionic binding with the cationic surfactant.
6. Influence of Cations on the Combination of Hydroxide Ions with
Keratin Fibers
Quantiative cation affinities have not been determined for human hair; however,
Steinhardt and Zeiser [56] have shown that for a series of quaternary
ammonium halides, as with anions, the affinity for keratin increases with
increasing molecular weight.
Organic ions of small size (below 150 daltons) differ very little in affinity and
are similar to inorganic alkali metal cations, but above 150 daltons, the affinity
of organic cations increases rapidly. The high affinity of hexadecyl
trimethylammonium and larger cations (conditionertype actives) is a result of
the ionic bond, van der Waals attractive forces, and the relatively low
hydrophilic nature of the molecule.
Scott et al. [57] have shown a similar phenomenon for human hair by
comparing the sorption behavior of hexadecyl and dodecyl
trimethylammonium bromides. These scientists found that under similar
conditions of adsorption and desorption, greater amounts of the larger
hexadecyltrimethylammonium bromide combined with hair, attesting to its
greater affinity. This is probably an entropyrelated phenomenon (see later).
Cations of low affinity, at high concentrations, increase the interaction of
hydroxide ion with keratin. This has been described by Steinhardt and Zeiser
[56] as an effect of salt on the base binding behavior of keratin.
Cations of high affinity also produce a greater effect in increasing the interaction
of hydroxide ion with keratin [56].
7. LowMolecularWeight Organic Bases
Similar to the interactions of lowmolecularweight carboxylic acids with hair,
the interactions of lowmolecularweight organic bases involve more than
simply the backtitration of conjugate acids. Barnett [58] has described the
interaction of mono, di, and triethanolamines at 25% concentration and
higher with human hair. The reactions of these species with hair involve
extensive swelling and ultimately lead to decomposition and disintegration of
the hair.

Page 404
8. Interactions of Salts Near Neutrality and Effect on Surfactant
Interactions
The interactions of surfactants and ionic dyes with keratin fibers, near neutral
pH (5–8), have not been studied as thoroughly as acid and basic dyeing.
However, Vickerstaff [59] suggests that the mechanisms for neutral dyeing is
analogous to the action of surfaceactive agents at an air/water interface, where
they orient with the hydrophobic tail extending into the air and the hydrophilic
group in the water. Another analogy is the electrophoresis of proteins in
sodium dodecyl sulfate, where the hydrophobic portion of the surfactant binds
to the protein and the charged group projects toward the solvent or gel.
Thus, a mechanism for neutral interactions of surfactants with keratin fibers
depicts the surfactant attaching to the fiber by its hydrophobic tail and the
hydrophilic group (e.g., the sulfonate group) projecting toward the solution
[60]. Evidence for a change in mechanism for the binding of surfactants to
human hair as the pH of the system changes from acid to neutral has been
provided by Robbins and Fernee [61]. A “leading ion mechanism” has also
been proposed by Peters [55] for interactions near neutrality. For this
mechanism, the fiber surface bears a net negative charge because of its low
isoelectric point (pH 3.7). Positively charged ions are attracted to the
negatively charged surface, thus helping it to overcome the electrical barrier for
anions. This view elevates the importance of the counterions (cations in
particular) in neutral dyeing or surfactant binding to hair near neutral pH. The
effect of salt addition on dye uptake is consistent with this mechanism, because
the addition of electrolyte near neutral pH increases the amount of dye [62] or
surfactant [63] that combines with keratin fibers.
Most surfactant interactions with hair are above the critical micelle
concentration, and aggregation introduces complexities to the mechanisms.
However, because sorption of sodium lauryl sulfate continues to increase
above the critical micelle concentration [64], higher concentrations of
aggregate near the fiber surface may be capable of providing higher
concentrations of monomer for diffusion into the fiber, because it is probably
monomer rather than aggregate that diffuses into the fiber.
D. Reactions of Neutral Materials with Human Hair
Reactions of neutral materials with human hair have been studied to a lesser
extent than ionic ingredients. However, the deposition of waterinsoluble
dispersed silicones as occurs from modern two in one shampoos onto human
hair is most likely driven by a hydrophobic mechanism rather than by an ionic
mechanism. This is therefore an entropydriven process which greater
randomness in the products versus reactants favoring the deposition onto the
hair as opposed to a highly structured alignment to keep the waterinsoluble
particles

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dispersed. This phenomenon is largely responsible for the greater binding of
anionic and cationic surfactants to hair with increasing molecular weight.
Interestingly, nonionic surfactant has been shown to decrease the sorption of
sodium lauryl sulfate, probably by decreasing the concentration of monomer
available at the surface. Ethoxylation to sodium lauryl sulfate decreases the
sorption, too, although it is not clear at this time whether this action is simply an
effect on diffusion rate or on the anion affinity or both these parameters.
VIII. Shampoo Lather
Shampoo lather does not directly influence the physical behavior of hair fibers.
However, shampoo lather can influence the consumer's perception of hair
characteristics. Lather is so important to consumers preferences that it is a
fundamental property of shampoos.
The most useful work leading to the present understanding of shampoo lather
was described by Neu [65] and by Hart and colleagues [66–68]. Neu pointed
out that the traditional RossMiles [69] shampoo foam evaluation using an
active concentration of about 0.1–0.2% is unrealistic and does not simulate
consumer preferences for shampoo lather. He suggested lather testing at an
order of magnitude greater in active surfactant concentration than used in the
RossMiles test. Neu used a kitchen food mixer to generate shampoo lather
for laboratory evaluation.
Lather produced from this type of apparatus is more similar to that obtained on
hair under shampooing conditions than provided by cylinder shake test
methods, as in RossMiles.
Hart and DeGeorge [66], following the lead of Neu, used a Waring blender to
generate shampoo lather and measured drainage rates to provide an index of
lather viscosity. Hart and DeGeorge [66] distinguished between foam and
lather for shampoo evaluation, pointing out that “foam” is a broad generic term
consisting of “any mass of gas bubbles in a liquid film matrix,” whereas lather is
a special type of foam formed during shampooing and other processes and
“consists of small bubbles that are densely packed,” thus resisting flow. It has
been shown that the foam drainage test produces results that relate better to
actual inuse salon testing [70].
Conclusions from Hart's work are as follows. A synthetic sebum load lowers
lather quality. This is consistent with the known observation that the second
shampoo application lathers better than the first shampoo application because
more sebaceous soil is encountered in the first application. Hart also
demonstrated that the traditionally known “foam booster” additives, such as
lauramid DEA or cocamidopropyl betaine, should more correctly be called
lather modifiers (amides modify lather feel and tend to make a thicker,
creamier lather) but these additives do not boost lather; they tend to suppress
shampoo

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lather. These foam modifiers actually associate with surfactant to strengthen the
film structure of the lather.
Other structuring agents not typically thought of as foam modifiers are
polymeric gums, such as methylcellulose or hydroxyethylcellulose, that have
been traditionally added to thicken shampoos. Such a polymer at a level as low
as 0.2% can often create a nice thick creamy lather from a loose largebubble
foam, presumably by enhancing the film strength of the lather.
It is hoped that this summary provides a useful beginning to a better
understanding of shampoo lather and lather testing. However, it should be
understood that lather drainage rates are only one of the important parameters
of shampoo lather. Lather feel and the rate of lather generation are two other
important components of shampoo lather, for which reliable quantitative
predictive methods are not yet available.
IX. Viscosity Control in Shampoos and Conditioners
To control the viscosity of many shampoos, salt is added to the surfactant
system, and the interaction between salt and the longchain surfactants tend to
form a lamellar or liquid crystalline structure that helps to stabilize or control the
consistency of the shampoo. If one plots the salt concentration versus the
viscosity in such a system, one typically finds an optimum above which
additional salt decreases the viscosity. In developing such a system in which
viscosity is controlled by salt addition, it is recommended that one select the
appropriate salt concentration on the ascending part of the viscositysalt
concentration curve. The selection of surfactant, amide, and other components
are critical to the viscositysalt concentration control in such a system.
Furthermore, impurities, such as salt contaminants in surfactants, must be
carefully controlled to obtain the appropriate viscosity when salt control of
viscosity is employed.
Polymeric gums, such as methylcellulose or hydroxyethylcellulose, have also
been used in shampoos to help control viscosity. In such systems, the salt
concentration is also critical to viscosity control.
Solvents, such as propylene glycol, glycerine, carbitols, or other alcohols, are
sometimes used in shampoos to help solubilize, to clarify product, or to lower
cloudclear points. Such ingredients often tend to lower product viscosity,
presumably by interfering with surfactant association.
References
1. D. Powers, Cosmetics, Science and Technology. Chap. 17 (Sagarin (ed.),
Interscience, New York, 1957.
2. T. Gerstein, Cosmet, Perfumery 90, 35 (March 1975).

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3. C. Radar and W. Tolgyesi, Cosmet. Perfumery 90, 29 (March 1975).
4. A. L. L. Hunting, Encyclopedia of Shampoo Ingredients, Micelle Press,
Cranford, NJ, 1983.
5. A. L. L. Hunting, Encyclopedia of Conditioning Rinse Ingredients,
Micelle Press, Cranford, NJ, 1987.
6. W. F. Bergfeld, in Hair Research (Orfanos, Montagna, and Stuttgen, eds.),
SpringerVerlag, Berlin, 1981, p. 507.
7. M. Ishihara, in Hair Research (Orfanos, Montagna, and Stuttgen, eds.),
SpringerVerlag, Berlin, 1981, p. 536.
8. J. A. Swift and A. C. Bews, J. Soc. Cosmet. Chem. 23, 695 (1972).
9. C. Robbins, in Chemical and Physical Behavior of Human Hair, 3rd ed.,
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Van NostrandReinhold, New York, 1979, p. 107.

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(9), 121 (1983).

11
Liquid Soaps
RICHARD E. REEVER
Richard Reever and Associates, Inc., Minnetonka, Minnesota
I. Introduction
II. Formula Market Trends
A. Formulation systems
B. Market size and dynamics
III. Anatomy of Liquid Soap Formulas
A. Skincleaning agents
B. Skinconditioning agents
C. Product physical property regulators
D. Preservative systems
E. Product esthetic regulators
F. Special additives
IV. Antibacterial Liquid Soaps
V. Mildness
A. Sensitive skin products
B. Mildness testing
VI. Future Category Trends for BodyCleansing Products
References

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I. Introduction
The mass market liquid soap personal cleansing category in the United States
has evolved from rather simple beginnings. In the 1960s and early 1970s,
“liquid soap” cleansing products consisted of institutional and hospital health
care handwash products—many based on medicated formulas, some using
simple liquid fatty acid coco soaps and some using the forerunners of today's
blended detergent formulations.
In Europe the liquid cleansing category for personal cleansing was continuing to
grow and become accepted as a popular choice especially in the shower area.
Some smaller companies would stimulate this new category in the United
States responding to different set of consumer trends.
In 1982, Frank wrote an early overview of the formulation technology and the
market trends that accompanied the beginning of this new market category [1].
In 1992, Lundmark added a very complete update on the technology as well
as the market growth that accompanied the now substantial category [2]. It is
interesting that both authors were key individuals in small companies thought to
be responsible for stimulating growth in the new liquid soap category: Frank in
1982 with Jovan, Inc. and Lundmark in 1982 with Minnetonka, Inc. These
were two of the small companies known at the time as innovators and astute
readers of new consumer trends.
In 1977, Minnetonka, Inc. developed a liquid soap product to be sold through
specialty department stores called the Incredible Soap Machine, an artistically
decorated liquid pump dispenser containing a rich pearly sodium lauryl sulfate,
cationic, and glycerin conditioning skin cleanser formula. At a retail price of
$4.95 for a 16 ounce container, this single item became the largest single sales
growth item in the company. During 1978 and 1979, Minnetonka reworked
the specialty product with a revised decorate package (improved formula) and
in 1980 nationally launched Softsoap brand liquid soap. The product entered
the market with a 10.5 fluid ounce package at a retail price of $1.59 and
achieved first year reported sales of $35 million [3]. The primary consumer
drivers for the success of this products were as follows:
Decorator package designs
A “no soap bar mess” advertising campaign
An inexpensive highquality formula
II. Formula Market Trends
To describe product formulas it is first important that the category of liquid
soaps be technically defined. In fact, most early products were not and are not

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today technically “soaps.” In the early 1980s there was correspondence
between industry and the FDA that aided in clarifying the acceptance of using
the term “soap” in a statement of identity for a liquid skin cleaning product that
contained primarily synthetic detergent ingredients. Because a soap for the
purposes of the FD&C act was considered to be comprised primarily of alkali
salts of fatty acids and soaps were exempt from certain cosmetic labeling
requirements and were instead regulated by the Consumer Product Safety
Commission, the FDA allowed these synthetic detergentbased products to be
labeled as liquid soaps as long as they were “properly qualified as cosmetics.”
It became the custom of the industry that “properly qualified” meant using
proper ingredient labeling disclosure and using the FDAapproved colors [4].
The trade and probably more importantly the consumer seemed to accept that
liquid soaps became any liquid formulas used to clean skin and generally
dispensed from pump dispensers.
A. Formulation Systems
Initially, all liquid soap products marketed from 1980 to 1985 had to meet only
very simple requirements:
Attractive packaging
Pleasant aesthetic qualities: fragrance, color, feel on the skin
Good cleaning: good lather, cleaned well, gentle to skin
Ease of use: pump dispenser
Good value: priced in line with bar soaps
Many of the early liquid formulas were based upon shampoo technologies. The
raw materials were in abundant supply, and methods of manufacture allow
small batch processes with simple turbine mixers in a wide variety of
acceptable mixing vessels. Many companies rapidly entered the market. It was
estimated in 1982 that over 50 different products entered the market [1].
Many of these included established large companies with longstanding brand
names but also included many lowprice regional and private label brands;
many of these were shortlived.
B. Market Size and Dynamics
The Softsoap brand continued to hold the lead market share, primarily because
of its highquality formula and decorator design image. As the segment
evolved, competitors focused on adding product benefits and, when possible,
leveraging these benefits with the wellestablished “equity” of their brand
names.
Procter & Gamble entered the market with Ivory, one of the only fatty acid
soapbased formulas with the same Ivory Clean position as the well
established

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bar soap. Jergens added a lotionenriched formula based on the skin lotion
equity of the company. In 1988, Dial entered the market with its own special
germkilling equity, to be discussed shortly.
The financial size of the market had grown to an estimated “stagnated” $115
million by 1988, primarily driven by product formulations and claim positions
that offered only basic simple cleaning and skinconditioning properties [5]. By
the end of 1993, with the successful boost from the antibacterial germkilling
claim, the market grew to over $289 million, exceeding 10% of the total soap
market, and included market shares as follows: ColgatePalmolive Softsoap
(28%), Dial liquid (21%), liquid Neutrogena (10%), Jergens (8%), and Liquid
Dove by Lever (7%), with new or reformulated entries from Ivory (Procter &
Gamble), liquid Safeguard (Procter & Gamble), and liquid Lever 2000 (Lever)
[6,7].
By mid1993, all major liquid soap producers were beginning to emphasize
new formula technologies with emphasis on special consumer skin care needs
as well as a new packaging response to an ever increasing environmental and
cost and valueaware consumer. All major brands started to offer a larger
package or series of larger sizes, with better cost value to the consumer and a
major emphasis on refilling the pump container. General estimates proposed
that sales of refill packages were estimated to become nearly 50% of the total
sales for some of the liquid soap brands.
III. Anatomy of Liquid Soap Formulas
Many good references exist that provide detailed starting formulas for a wide
variety of liquid soaps. A good overview of starting formulas for a wide variety
of liquid soap compositions appears in the text by Flick [8]. The most concise
way to simplify the structural parts of these compositions from the formulator's
point of view is as follows:
Skincleaning agents (surfactants)
Skinconditioning agents
Product physical property regulators (pH, viscosity)
Preservative systems
Product esthetic regulators (color, fragrance)
Special additives (antibacterial additives; see Tables 1–7)
A. SkinCleaning Agents
As illustrated by Flick, the skincleaning portion of the formulas is most usually
comprised of mixtures of surfactants, with a primary “deepcleaning”
surfactant, usually anionic, blended with lower levels of nonionic and ampho

TABLE 1 ColgatePalmolive Regular Liquid Soaps: Key Ingredients and Functions
Ingredients Softsoap original (aloe) [67]
Surfactants (cleansing agents/emulsifiers) Sodium C14–16 olefin sulfonate (AOS)
Sodium lauryl sulfate (SLS)
Sodium lauriminodipropionate
Sodium cocoamphodiacetate
Lauramide DEA
Humectants (conditioning agents) Glycerin
Polyquaternium7
Quaternium22
Silk peptide hydrolyzed
Silk protein (aloe vera extract)
Pearlescent agents Glycol stearate
Preservative system DMDH hydantoin
Color system FD&C Green No. 3
D&C Yellow No. 10
pH adjuster Citric acid
Viscosity adjuster Sodium chloride

TABLE 2 ColgatePalmolive Antibacterial Soaps: Key Ingredients and Functions
Ingredients Softsoap regular [69]
Surfactants (cleaning agents/emulsifiers) Sodium C14–16 olefin sulfonate (AOS)
Cocamidopropyl betaine
Lauramide DEA
Humectants (conditioning agents) Glycerin
Polyquaternium7
Aloe vera gel
Silk peptide hydrolyzed
Silk protein
Pearlescent agents
Preservative system DMDM hydantoin
Tetrasodium EDTA
Color system FD&C Yellow No. 5
D&C Red No. 33
FD&C Red No. 40
Antibacterial active ingredient Triclosan
pH adjuster Citric acid

TABLE 3 Dial Antibacterial Soaps: Key Ingredients and Functions
Ingredients Dial Regular [70]
Surfactants (cleaning Ammonium lauryl sulfate (ALS) AL
agents/emulsifiers) SLES SLE
Lauramide DEA Lau
Humectants (conditioning agents) Glycerin PE
Isostearamidopropyl morpholine Iso
lactate La
Gly
PEG
Vita
Gua
chl
Pearlescent agents Gly
Preservative system DMDM hydantoin DM
Tetrasodium EDTA Tetr
Color system FD&C Yellow No. 5 FD
FD&C Red No. 5 FD
Antibacterial active ingredient Triclosan Tric
pH adjuster Citric acid Citri
Viscosity adjuster Sod

TABLE 4 Lever Regular Liquid Soaps and Antibacterial Liquid Soaps: Key Ingredients an
Dove Beauty Wash (face and hands
Ingredients
Surfactants (cleansing agents/emulsifiers) Sodium cocoyl isethionate
Sodium Isethionate
SLES
Sodium alkyl benzene sulfonate
Sodium tallowate
Sodium cocoate
Disodium cocamido MEA sulfosuc
Disodium oleamido MEA sulfosuc
Humectants (conditioning agents) Propylene glycol
Stearic acid
Pearlescent agent Stearic acid
Preservative system Quaternium15
Trisodium EDTA
Methylparaben
Propylparaben
Antibacterial active ingredient
Hectorite

TABLE 5 Kao/Jergens Regular Liquid Soaps and Antibacterial Liquid Soaps: Key Ingredie
Ingredients Jergens Antibacterial Plus [18] Jergens
Surfactants (cleansing ALS AOS

agents/emulsifiers) AOS ALS
Cocamidopropyl betaine Cocamid
Cocamide DEA Cocamid
Sodium stearate Sodium
Humectants (conditioning agents) Polyquaternium7 (plus Jergens Polyqua

Lotion) Lotion)
Pearlescent agents Glycol distearate Glycol di
Preservative system DMDM hydantoin DMDM

Tetrasodium EDTA Tetrasod
Color system
Antibacterial active ingredient Triclosan
Viscosity adjuster Sodium chloride Sodium
teric materials. The most common early liquid soap formulas used true fatty acid
anionic. Extensive research was presented in a number of patents, most often by
larger soap marketers. Some representative patents of this work can be seen in e
ColgatePalmolive and a superfatted saturated and unsaturated potassium soap s
Stiros of Procter & Gamble [9,10]. For a company with
TABLE 6 Procter & Gamble Regular Liquid Soaps: Key Ingredients and Functions
IVORY Skin
Ingredients IVORY Regular [72] LiquiG
Surfactants (cleansing SLES SLES

agents/emulsifiers) SLS SLS
Cocamidopropyl betaine Lauramide DE
Lauramide DEA Cocamidoprop
Octoxynol9
Humectants (conditioning agents)
Pearlescent agents Styrene/acrylate copolymer
Preservative system DMDM hydantoin DMDM hydan
Tetrasodium EDTA Tetrasodium E
Color system
pH adjuster Citric acid Citric acid
Viscosity adjuster Sodium chloride Sodium chlori

TABLE 7 Procter & Gamble Antibacterial Liquid Soaps: Key Ingredients and Functions
Ingredients Safeguard Regular [73] Safegu
Surfactants (cleansing SLS SLS

agents/emulsifiers) SLES SLES
Cocamidopropyl betaine Cocamidopr
Lauramide DEA Lauramide
Humectants (conditioning agents) Guar hydro
chloride
Pearlescent agents Glycol diste
Preservative system DMDM hydantoin DMDM hy

Tetrasodium EDTA Tetrasodiu
Color system FD&C Red No. 4 FD&C Red

FD&C Yellow No. 5 FD&C Yello
Antibacterial active ingredient Triclosan Triclosan
pH adjuster Citric acid Citric acid
Viscosity adjuster Sodium sulfate Sodium sulf
extensive raw material and manufacturing emphasis in the soap area, these formul
economies of scale. They suffered from certain chemical and physical deficiencies
synthetic detergent systems, most notably in pH, flash foam in hard water, and, in
fragrancing with a wide latitude of light fragrances. Procter & Gamble and Neutr
few major companies to launch “true soap” formulas, and in later years Procter
formula for liquid Ivory from a potassium soap system to a sodium lauryl sulfate,
sulfate system (Table 6).
In the following analysis of general classes of liquid soap ingredients, the form of
ingredient names as listed in the most recent edition of the International Cosmet
Dictionary [11].
Some of the most widely used anionic surfactants are the alkyl and alkyl ether sul
sulfate (SLS), sodium laureth sulfate (SLES), and the various other anionic salts
triethanolamine, and magnesium—all offered ease of formulation, ease of manufa
for value if purchased in large quantities. Sodium lauryl sulfate is typically supplie
solution and can be easily blended with simple manufacturing equipment and at m
when blended properly, can allow systems that provide excellent cleaning, copio
rinsing.
Many formulas use a blended surfactant system to allow optimizing performance,
manufacturing ease. AOS ( olefin sulfonates), such as the ingredient sold with t
sodium C14–16 olefin sulfonate, or

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a trade name example, Witconate AOS (Witco Corporation), is one of these
coanionics that is widely used. Typically supplied in a cost effective 40% solids
solution, the material has been reputed to have interesting cleaning and
mildness properties while offering a reduction in cost of formula per anionic
active ingredient level [12]. The types of anionic surfactants listed here
generally create a type of lather with an “open structured frothy” foam.
Nonionic surfactants in the alkanolamide class, such as the CTFA names
lauramide DEA or cocamide DEA, are usually included at a lower ratio
concentration of active anionic for the functions of viscosity builders, flash foam
enhancers, and foam stabilizers. Examples of amphoteric surfactants that are
also commonly coblended with the aforementioned anionic and nonionics are
such compounds as cocamidopropyl betaine (Mackam 35, Mcintyre Group,
Ltd.) to reduce skin irritation and at carefully controlled ratios to increase the
“creamy character” of the lather. Ideal liquid soap formula ranges for
optimizing foam building, rinsing, mildness, and viscosity building (with a lower
requirement for inorganic salts) can be obtained with AOS anionics, lauric
alkanolamides, and cocamidopropyl betaine at solids ratios of 9:1:1 [12]. The
first performance evaluation the consumer makes in using a liquid soap is the
degree of flash foam, initial development of foam volume. The next is
generally foam volume, followed by a creamy or silky character depending on
the desired claim or product position.
A typical liquid soap formula, such as the original SoftSoap brand formula as
listed in Table 1, is generally comprised of a mixture of these different types of
cleaning agents to achieve the desired performance.
Typical laboratory tests have been designed to measure the level of flash foam
and foam volume and are usually calibrated to a laboratory individual's
personal means of testing. Such methods as the carefully repeated shaking of a
fixed concentration of product in a graduated cylinder, with a resultant
measurement of foam rate, volume, and stability, can be quick and reliable. A
long standing laboratory method for foam volume is the method detailed by
Ross and Miles [13]. Possibly the most reliable consumer data come from
actual use of the product under home use conditions or in controlled clinical
settings.
B. SkinConditioning Agents
As the cleaning process continues, the user begins to focus on the feel of the
product on the skin. Generally it is desirable to have a feeling of lubricity and
smoothness during the cleaning and rinsing process but not an excessive feeling
of a sticky feeling or a feeling of residual material on the skin after rinsing. The
degree of a clean skin feeling to a soft or smooth skin feeling is balanced
toward the product positioning or claim and is adjusted by the use of skin
conditioning ingredients. Classes of ingredients used for skin feel include

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humectants, such as glycerin, proteins, and skin refatting agents, such as PEG
7 glyceryl cocoate. Another widely used class of materials that imparts skin
feel is the class of watersoluble anioniccompatible cationic salts and
polymeric compounds. Much of the research experience for these materials
comes from many years of application research in the hair care area. Many
researchers have studied the similarity of substantivity of these materials to skin
and hair proteins from both a theoretical and an experimental basis [14,15].
Examples of this class are such materials as the polyquaternium7 series
(Merquat 550, Calgon Corporation). Numerous formulas in Tables 1, 2, 3,
and 5 show the wide use of this material. One of the key benefits of this
material appears to be the high degree of skin feel provided at a very low
formula concentration used. This is particularly useful to produce a smooth skin
feel without a sticky negative afterfeel on product rinsing. Other classes of
cationic salts compatible with high levels of anionics are represented by the
research of Gesslein et al. in a U.S. patent issued to the Inolex Chemical
Company covering alkyl or alkylamido dimethyl 2, 3dihydroxypropyl
ammonium salts sold under the trade name Lexquat series [16]. For all these
materials care must be used to select concentrations of additives that balance
the skin feel desired with the possible suppression of lather.
C. Product Physical Property Regulators
Liquid soaps are typically dispensed from pump dispensers directly onto wet
skin. In this use they must possess a thickness or viscosity sufficient not to
appear “runny” to the user or not to slip through the fingers but at the same
time must have the ability to disperse quickly into foam with only a minimum
amount of rubbing. This rheology is well known to those skilled in the art of
formulation and is very dependent on selection and blending of the surfactant
portions of the formula with auxiliary additives, such as polymers, nonionics,
cationics, and electrolytes. Typically an electrolyte viscosity response titration
curve is conducted on the finished base formula with the electrolyte of choice,
commonly sodium chloride, and a safe margin is determined that allows normal
process adjustments without the product becoming too stringy (too low in
viscosity). Great care in final formula selection is critical because this
relationship can be highly sensitive to seemingly minor ingredients, such as
product pH, fragrance types and levels, conditioning additives, natural extracts
based on glycols, and of course the key cleaning surfactants and their
manufacture. The product pH requires a separate study to ascertain not only
the desired range and limits (per the previous reference) but also a study to
ascertain the product pH stability with age, raw material variations, and
interdependence of such items as finished product color over a range of
product pH.

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D. Preservative Systems
General laboratory testing by this writer has established that typical liquid soap
formulas for use in handwashing will be in the range of 75–85% water. The
remaining solids are organic materials that are sensitive to microbiological
contamination: generally the lower the level of solids the higher the potential for
possible contamination. To fortify the product against contamination during
manufacture and extended age in use, it is necessary to add antimicrobial
preservatives. Formaldehyde, once widely used as very effective preservative,
has been largely discontinued as a pure additive, but various formaldehyde
donor materials, such as DMDM hydantoin, are now commonly used [17].
Other additives that enhance preservative effectiveness, such as tetrasodium
EDTA, are also found.
Care must be taken with proper selection of ingredient and concentrations
because some known consumer skin sensitivities exist. Also, proper care on
selection, age, and challenge testing is a standard procedure.
E. Product Esthetic Regulators
As with most toiletries, the esthetics of the product fragrance, color, clarity, or
pearly appearance can be as important to consumer perception as the base
formula chemistry. The fragrance of a product must be carefully developed to
enhance the overall product position. In the author's opinion, this element
should be treated as a critical development step and researched thoroughly.
The fragrance must be selected with emphasis that the ultimate consumer will
attempt to smell the product in the bottle (at the point of purchase), then of
course as it is used, will likely want or not want it to have residual fragrance on
the skin (depending on the product claims or concept), and finally will make an
evaluation as he or she leaves the washing area on how much or little is
“fragrancing the air” around the washing area.
In kitchen use the fragrance must be clean, fresh, and not in conflict with the
food preparation process. For a moisturizing product the fragrance must
emphasize skin softness and not be in conflict with this concept. A very
interesting range of fragrances is represented by the currently marketed
products and ranges from very light subtle floral of the SoftSoap family to the
fruity green almond floral of the Jergens lotion product to the woody, lavender
herbal floral of liquid Dial.
Colors are also an important part of product positioning and have become
almost a part of functionality, with the color family of gold and amber
representing germ killing (see Tables 2, 3, and 7) to a complete freedom of
color representing the ultramild sensitive skin formulas (see Tables 1, 3, and 6).

Page 422
The addition of glycol stearate to provide an opaque and “pearled” look has
been an established part of certain marketed formulas, for example, the original
SoftSoap formula in Table 1. In early testing before the initial market decision,
formulations with this pearled appearance were actually rated superior in skin
conditioning to an otherwise equivalent formula series in consumer testing.
Certain currently marketed liquid soaps with strong skin conditioning product
positions use a pearled or opaque appearance to fortify this position.
F. Special Additives
Each product formulation contains a number of special additives to fortify
certain product or advertising claim positions or appeal to certain consumer
preferences. One interesting claim was made on the package and in advertising
by Jergens Liquid Antibacterial Plus in 1991 [18]. The claim was that the
product not only kills germs on hands but also “eliminates odors that linger on
your hands, like onions, diapers and cleaning products” (see Table 5). From
general consumer work done in the fragrance and product concept area, it was
well known that in food preparation areas, such as kitchen use of liquid soaps,
a product that had a fragrance that was too sweet or strongly floral could be in
conflict with the intended use. Apparently, to overcome this possible objection
of the original sweet floral almond fragrance of the original Jergens liquid lotion
soap, a change in fragrance was made to a cleaner, more neutral “malodor
counteractant” scent, along with a strong claim that would appeal to kitchen
users.
Chemical components of the fragrance of a liquid soap capable of
counteracting kitchen malodors can be comprised of certain aromatic
compounds, such as the acetic and propionic acid compounds represented in
the patent work of Schleppnik [19,20].
IV. Antibacterial Liquid Soaps
As previously mentioned, the antibacterial ingredients and claims have been the
most important new additives responsible for a significant boost in sales of the
category since 1990.
At the time of this writing, there are extensive discussions taking place between
U.S. manufacturers and the U.S. Food and Drug Administration that could
have a significant impact on the category. This chapter does not deal in detail
with these issues: interested readers are directed to the historical and pending
record of industry and FDA Federal Register references for the proposal to
establish a Monograph for overthecounter antimicrobial products (1974 and
1978–1994 [21–23]. The current pending discussions in summary relate to the
following issues:

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All leading liquid hand soap products use for the active ingredient (2,4,4'
trichloro2'hydroxydiphenyl ether) (Triclosan in the United States; Irgasan
DP300, Ciba Geigy Corporation; see Tables 2–5 and 7).
The FDA has expressed some concerns regarding the need for more
information on the safety and effectiveness of this material for these intended
products and has listed this ingredient as category III [23].
The FDA has expressed to industry that the category term “antimicrobial
soaps” or “antibacterial soaps” not be included in the tentative final monograph
(TFM), in obvious conflict with the fact that this is the consumer category that
has been established by the industry since these products were introduced in
1989, instead, FDA proposed “antiseptic handwash” for this category [23].
The FDA in their current TFM has used professionally directed soaps, such as
health care personnel handwash and surgical scrub products, to establish the
types of effectiveness tests for the category.
Currently it has been reported that a joint industry task force has been
established with the Soap and Detergent Association (SDA) and Cosmetic
Toiletry and Fragrance Association (CTFA), and feedback meetings are being
held with FDA to try to resolve many of these issues surrounding the OTC
topical antiseptic TFM and the existing antimicrobial soap category [24].
Extensive discussions covering such topics as methods for testing the efficacy
of these products seem to be opening up the opportunity to have different
methods of testing established for the different product types—mass market
everyday use soaps versus health care professional handwash and surgical
scrub products—and such tests as the following are being indicated for the
mass “handwashes”: the cup scrub test, the “agar patch test,” the modified
CADE technique, and modified forms of the general health care handwash test
[24]. The comment period for the currently pending June 1994 TFM has been
extended to June 1995, with the deadline for any new data currently extended
to December 15, 1995 at the time of this writing [24].
A number of good reference publications have demonstrated in vivo tests that
are helpful to researchers both in the rapid evaluation of the effectiveness of
antimicrobial formulas, including handwash products, as well as part of the final
clinical efficacy documentation [25–28]. In 1992, Lever Brothers Company
positioned Liquid Lever 2000 Antibacterial Soap with package claims that
stated for the Triclosan formula “…not only kills germs but actually keeps them
from coming back—all day” (Table 4) [29].
An interesting new crosscategory approach to antibacterial liquid soaps
occurred in 1994, when both the ColgatePalmolive Company through the
Palmolive brand and the Dial Corporation through the Dial brand introduced

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a combined dishwashing liquid and antibacterial handsoap in one formula, both
using Triclosan as the active ingredient and labeled as OTC drugs [30].
V. Mildness
The addition of antibacterial ingredients and germkilling claims created
significant growth in the category, but probably the most significant formulation
trend to cross over the entire category in the 1990s has been the trend toward
improved skin mildness. In a recent review of current population trends, it was
stated that as the nation's elderly population grows, so will the demand for
much milder cosmetics, softer colors, and treatment and care for aging skin
[31]. Much of the direction from cosmetic raw material supplier formularies as
well as the patent art in this area of liquid skin cleansing is directed at more
skincaring materials and compositions. The Lever Brothers Company has long
incorporated a blended isethionate chemistry with fatty acid tallowate/cocoate
soap chemistry to achieved improved mildness to skin; a simple representation
of this chemistry is reviewed in a 1987 patent [32].
Much of the Lever patent art is aimed at varying ratios of fatty acid soaps and
sodium isethionate/sodium cocoyl isethionate to provide clinically verified
reductions in irritation. A number of these patents speak to compositions that
create physical products from solids to liquid cream to transparent gel
structures, and many are aimed at emphasizing their mildness benefits toward
consumer facial cleansing [33–36].
In 1991, Lever Brothers entered the U.S. bodycleansing category with Liquid
Dove Beauty Wash for face and hands with a creamy liquid dispenser formula
based on sodium cocoyl isethionate/sodium isethionate chemistry blended with
sodium laureth sulfate and disodium sulfosuccinates and low levels of sodium
tallowate and sodium cocoate fatty acid soaps (Table 4). The primary new
package claim for this product in 1991 was that Liquid Dove “doesn't dry like
soap” and was “milder than any liquid soap on the market” [37]. In 1992,
Lever introduced similar isethionate/sodium laureth sulfate chemistry but
eliminated the fatty acid soaps and used polyquaternium10 (a polymeric
cationic) and cyclomethicone for skin conditioning (Table 4). One of the
package claims emphasized the skin mildness of the formula as “won't dry your
skin like the leading antibacterial liquid” [29]. In 1994, the Lever 2000
Antibacterial formula package was revised to showed some modification in
label claim to “unique formula includes special skin care ingredients so it's
better for your skin.” The formula also reflected revisions to replace sodium
laureth sulfate and ammonium laureth sulfate and the replacement of
cyclomethicone/polyquaternium10 skin conditioners with polyquaternium39
and guar hydroxypropyltrimonium chloride [38]. To reinforce skin mildness,
many of the early

Page 425
leading formulas in the liquid soap category, especially those that added
antibacterial formulations, added at least two distinct antibacterial formula
variations, generally a “regular” and an “extra conditioning formula.” Colgate
with SoftSoap, Dial, and Procter & Gamble with the Safeguard brand
introduced a second moisturizing or extra conditioning formula that usually
contained the same basic surfactant system but then used a pearlescent agent,
usually from the family of glycol stearates, along with an increased
concentration of skin substantive conditioners from the higher molecular weight
polymeric cationics (Tables 2, 3, and 7). Most of the technology for these
formula variations were previously publicly disclosed through previously
marketed similar conditioning hair shampoo formulas or was widely disclosed
publicly by formularies of raw material suppliers but two interesting Procter &
Gamble patents illustrate the dual benefit of materials like the cationic guar
series to skincleansing products [39,40]. U.S. Patent 4,812,253 by Small et
al. discusses the benefit of mild surfactants and polymeric skin feel ingredients
like cationic guar in both clinically verified skin mildness and panelisttested
improvements in smooth skin feel [39]. General claims of these extra
conditioning antibacterial formulas are as follows:
Extra softeners for dry skin [41]
With moisturizer, helps protect against dry skin [42]
Kills germs and moisturizes, a combination of moisturizers and naturally
derived skin conditioners that leave hands feeling soft and smooth [43].
A. Sensitive Skin Products
One of the most recent trends in formula liquid soap formulations between
1992 and 1995 was the addition of clear, waterwhite colorless formulas
positioned as ultramild for people with sensitive skin (Tables 1, 3, and 6).
Colgate's Softsoap brand launched a product in 1992 with claims that the
formula was “free of colors, soaps and other harsh ingredients that can irritate
sensitive skin” [44].
This formula uses a gentle cleansing surfactant blend of anionic and a new
category of nonionic (alkyl polyglucoside) material that has the capability for
good, is gentle in skin cleansing, and has a good viscosity build and easy rinse
properties (Table 1) [68]. A survey article by Salka et al. provides a good
overview of the chemical and physical and positive dermatological properties
of these materials [45].
The naturally sourced origin (positive for environmental concerns), along with
their mildness and high activity of supply, gives these materials a high
opportunity for growth across household and personal care categories [30].

Page 426
IvoryProcter & Gamble launched a waterwhite variant in 1994 based upon
its previous SLES/SLS formula, with general claims that it was “so gentle you
could use it on your face” (Table 6) [46].
Dial Corporation in 1995 has extended its antibacterial liquid soap line with a
waterwhite formula based on SLES/cocamidopropyl betaine and decyl
polyglucose, claiming the following:
Free of dyes
Free of harsh perfumes
Dermatologist approved
Hypoallergenic (Table 3) [47]
B. Mildness Testing
In his review of Sensitive Skin, Simion points out that although consumer
surveys indicate that 50% or more female consumers believe they have
sensitive skin, cosmetic researchers and dermatologists and consumers are not
always in agreement as to what constitutes sensitive skin [48]. Simion goes on
to describe some very good strategies as guidance for the formulator of
sensitive skin products, emphasizing two important key directives: (1) the
avoidance of known irritants and allergens and (2) the product should be
subjected to a series of tests including “inuse” testing to confirm acceptance to
a sensitive skin population [48].
In describing hypoallergenic claim support, Jackson et al. also reinforced that
although no legal or regulatory definition exists for “hypoallergenic” products, it
is imperative for the formulator to provide products by composition and a
carefully designed battery of tests that produces a “lower than typical rate of
allergic contact dermatitis” [49].
It is therefore imperative that the product development team be continually
updated on published dermatological profiles on all formula raw materials as
well as the current status on all testing methods both in vitro and in vivo for all
similar products in the desired category. It is wise to continue to review the
published experience of even commonly used materials. A common ingredient
in most of the leading liquid soaps is the amphoteric cocamidopropyl betaine.
Several recent references are listed here that voice different opinions but
possibly leave some questions about the complete safety of this ingredient in
sensitive skin formulas [50,51].
Much of the original comparison data for irritancy testing of skincleansing
products continue to use certain benchmark tests, such as the Frosh and
Kligman soap chamber test [52]. However, the articles by Simion and Jackson
along with the following represent good overview publications for additional
perspectives [53–56].

Pa
VI. Future Category Trends for BodyCleansing Products
The most significant growth of the liquid soap category could be in the near future
trends of the growth of the body cleansing or shower gel segment if the U.S.
consumer will adopt their use. Advertising Age has listed the category growth at
$158 million in sales (mid1995) up from just over $50 million in 1994, with And
Jergens spending over $50 million in advertising to launch Jergens Body Shampo
1994 [57,58]. Recent articles listed the major entries of Procter & Gamble, Unil
and Coty in addition to Dial and Colgate's Softsoap, one of the early U.S. entran
[57,49]. As another potential measure of growth, Zimmerman states that in some
countries liquid body cleansers account for up to 86% of the liquid soap category
[58].
As yet another perspective on the potential usage levels of the products and how
may relate to the potential size of the segment, many of the currently marketed
products have label directions that state that containers have of the order of 5 ml
use, or 5–6 showers per fluid ounce. This would create 40–50 showers per 8 ou
container or usage that would be comparable to hair shampoos, a market size tha
could become two to three times the current liquid handwash market (Tables 8–
and product label directions).
The currently marketed products have a total solids level (measured as ovendried
nonvolatiles) in the range of 26–50%, nearly twice that of the liquid handwash
products [60]. It is believed that this higher active level is needed to develop
satisfactory foaming levels in use. In addition, all the newest entries include either
sponge or polymer/foam applicator or “pouf” to increase the foaming performanc
The major claim positions of the products are summarized in Table 12. Clearly, a
these products emphasize skin care claims. With the high level of solids and the hi
portion of surfactants to create lather, much of the empha
TABLE 8 Key Ingredients and Functionsa
Function Ingredient
Surfactants (cleansing agents) Cocamidopropyl betaine
Sodium cocoyl isethionate
Sodium laureth sulfate
Ammonium laureth sulfate
Conditioning agents Dimethicone
Guar hydroxypropyltrimonium chloride
a
Category: Body. Product: Caress Moisturizing Body Wash by Lever Bros. Co., Dove
Moisurizing Body Wash.

P
Function Ingredient
Surfactants (cleansing agents) Sodium magnesium laureth sulfate
Sodium lauroamphoacetate
Conditioning agents Soybean oil
PEG6 caprylic/capric glycerides
Glycerin
Maleated soybean oil
Polyquaternium10
a
Category: Body. Product: Oil of Olay Moisturizing Body Wash by Procter & Gamble.
Function Ingredient
Surfactants (cleansing agents) Potassium C9–15 alkyl phosphate
(MAP)
Sodium cocoamphoacetate
Conditioning agents Polyquaternium 10
Sucrose octaacetate
Propylene glycol
a
Category: Body. Product: Jergens Body Shampoo, Andrew Jergens Company.
Function Ingredient
Surfactants (cleansing agents) Lauramide DEA
Sodium cocoamphoacetate
Sodium myreth sulfate
Conditioning agents PEG7 glycery cocoate
Glycerin
Isostearamidopropyl morpholine lactate
Linoleamidopropyl PGdimonium chloride
Phosphate
Special additives Triclocarban (active ingredient)
a
Category: Body. Product: Dial Plus Moisturizing Antibacterial Body Wash, Dial Corp.

TABLE 12 Body Cleansing Products: Key Product Claims
Product Key claim
Caress Moisturizing Body Wash Moisturizes as you shower
Leaves skin silky soft, smooth
Dove Moisturizing Body Wash Adds moisture, leaves skin feeling soft
Oil Of Olay Moisturizing Body Leaves skin feeling soft and moisturized in one step
Wash may not need a body lotion
Jergens Body Shampoo pH balanced, enables your skin to retain more of its
moisture
Dial Plus Moisturizing Body Wash Incredible softening of skin, trusted antibacterial
protection
sis in the formulas is on the mildness of the surfactant blends selected as well as a
skinconditioning chemistry. Fox, in a 1995 patent survey article, lists a number o
covering the mild surfactant and skinconditioning systems and references the pas
on mildtoskin monoalkyl phosphate surfactants, also illustrated in their currently
Body Shampoo product (Table 10) [61]. Kao has a number of research activitie
cleansing arena, covering various types of blended surfactant systems represente
patents, including alkyl saccharide surfactants with cationic polymers [62], alkyls
and silicone additives [63], and nonionic saccharide surfactants with enhanced an
skin and hair cleansing [64].
Dove and Caress brand moisturizing body wash products use a 1992 patented c
a mild surfactant blend in combination with a cationic guar derivative and an insol
emulsified silicone (dimethicone) [65].
Dial Corporation currently has the only marketed body wash with an antibacterial
and a shower claim position for “antibacterial protection” (Tables 8–12). Clearly,
important consumer claim and if regulatory action is quiet in this area, others may
to enter this arena. Abamba in a 1993 article may have also projected some addi
European concepts that, if this new category is well received in the United States,
new innovative products [66].
If one looks at the true market age of the liquid soap market, (a little over 15 yea
category with other established categories, such as hair care, at over twice that a
wash market, still in its U.S. infancy, one can only envision many exciting years of
product activity ahead.

Page 430
Acknowledgment
The author thanks Mr. Joseph Mabee, Technical Service Manager, Colgate
Palmolive Company for his assistance in providing thoughtful and stimulating
discussions as well as a creative outline for some of the key tables in this
chapter.
References
1. E. M. Frank, Cosmet. Toil. 97(7), 49–54 (1982).
2. L. Lundmark, Cosmet. Toil. 107(12), 49–53 (1992).
3. Business Week, 1/12/81.
4. CTFA Labeling Manual, 5th ed., Cosmetic Toiletry and Fragrance
Association, Washington, D.C., 1990, pp. 8, 147, 166.
5. Soap and Cosmet. Chem. Spec. 6, 22 (1989).
6. S. J. Ilgenfritz, Wall Street Journal (B8) 8/26/93.
7. C. Canning, HAPPI 30(12), 38–46 (1993).
8. E. Flick, Cosmetic and Toiletry Formulations, 2nd ed., Noyes
Publications, Park Ridge, NJ, 1989.
9. Straw, US 4,387,040 to Colgate Palmolive (1983).
10. Stiros, US 4,310,433 to Procter and Gamble (1982).
11. International Cosmetic Ingredient Dictionary, 5th ed. Vol. 1 (J.
Wenninger and G. N. McEwen, eds.), CTFA, Washington, D.C., 1993.
12. R. Reever, presented at Am. Oil. Chem. Soc. Spring Meeting,
Philadelphia, PA, May 1985.
13. J. Ross and G. D. Miles, Oil Soap, 18, 99 (1941).
14. G. V. Scott et al., J. Soc. Cosmet. Chem. 20, 135–152 (1969).
15. G. D. Goddard et al., J. Soc. Cosmet. Chem. 26, 539–550 (1975).
16. B. Gesslein, J. Guth, et al., US 4,978,526 to Inolex Chemical Company
(1990).
17. Cosmet. Toil. 108(10), 88 (1993).
18. Commercial package label, Jergens Antibacterial Plus Liquid Soap, 1991,
AndrewJergens Company.
19. A. Schleppnik, US 4,187,251 (1980).
20. A. Schleppnik, US 4,310,512 to Bush, Boake and Allen, Inc. (1982).
21. Food and Drug Administration, OTC topical antimicrobial products, Fed.
Reg. 39(179), 33103–33141 (1974).
AndrewJergens Company.
19. A. Schleppnik, US 4,187,251 (1980).
20. A. Schleppnik, US 4,310,512 to Bush, Boake and Allen, Inc. (1982).
21. Food and Drug Administration, OTC topical antimicrobial products, Fed.
Reg. 39(179), 33103–33141 (1974).
22. Fed. Reg. 43(4), 1243–1244 (1978).
23. Fed. Reg. 59(116), 31402–31452 (1994).
24. FDC Reports—The Rose Sheet 16(14), 1–3 (1995).
25. M. Casewell, and N. Desai, J. Hosp. Infect. 4, 350–360 (1983).
26. S. Selwyn, J. Hosp. Infect. 6(Suppl.), 37–43 (1985).
27. M. Finkey, H. Maibach, et al., J. Soc. Cosmet. Chem. 35, 351–355
(1984).
28. F. Yackovich and J. Heinze, J. Soc. Cosmet. Chem. 36, 231–236
(1985).
29. Commercial package label, Lever 2000 Antibacterial Liquid Soap, 1992
Lever Bros. Co.

Page 431
30. Chemical Week 156(3), 40–44 (1995).
31. U.S. Industrial Outlook 1994, U.S. Dept. CommerceInternational Trade
Association, Chap. 33, Cleaning Preparations and Cosmetics, 1994.
32. M. Caswell et al., US 4,695,395 to Lever Brothers Company (1987).
33. D. Rosser et al., US 4,975,218 to Lever Bros. Co. (1990).
34. A. Greene et al., US 5,132,037 to Lever Bros. Co. (1992).
37. Commercial package label, Liquid Dove Beauty Wash, 1991, Lever Bros.
Co.
38. Commerical package label, Liquid Lever 2000 Antibacterial Soap, 1994,
Lever Bros. Co.
39. L. Small et al., US 4,812,253 to Procter and Gamble (1989).
40. R. Metcalf et al., US 4,820,447 to Procter and Gamble (1989).
41. Commercial package label, Softsoap Extra Conditioning Antibacterial
Soap, 1992, SoftSoap Enterprises, Inc.
42. Commercial package label, Safeguard Antibacterial Liquid Soap, 1992,
Procter and Gamble.
43. Commercial package label, Liquid Dial Plus Moisturizing Antibacterial
Soap, 1995, Dial Corp.
44. L. Kintish, Soap Cosmet. Chem. Spec. 68(12), 34–36 (1992).
45. T. Forster, H. Hensen, B. Salka, et al., Cosmet. Toil. 110(4), 23–28
(1995).
46. Commercial package label, Ivory Skin Cleansing LiquiGel, 1994, Procter
& Gamble.
47. Commercial package label, Dial Sensitive Skin Antibacterial Liquid Soap,
1995, Dial Corp.
48. F. A. Simion and A. H. Rau, Cosmet. Toil. 109(2), 43–50 (1994).
49. E. M. Jackson, T. J. Stephens, and L. A. Rhein, Cosmet. Toil. 109(7),
83–85 (1994).
50. P. D. Pagetto et al., Am. J. Contact Derm. 5(1), 13–16 (1995).
51. J. E. Hunter and K. L. Hintze, presented at 51st Scientific Conference
CTFA, San Francisco, CA, October 1994.
52. P. J. Kauffman and M. J. Rappaport, in Cosmetic Safety (J. Whittam,
ed.), Marcel Dekker, New York, 1987, pp. 179–204.
50. P. D. Pagetto et al., Am. J. Contact Derm. 5(1), 13–16 (1995).
51. J. E. Hunter and K. L. Hintze, presented at 51st Scientific Conference
CTFA, San Francisco, CA, October 1994.
52. P. J. Kauffman and M. J. Rappaport, in Cosmetic Safety (J. Whittam,
ed.), Marcel Dekker, New York, 1987, pp. 179–204.
53. B. H. Keswick, K. D. Ertel, and M. O. Visscher, J. Soc. Cosmet. Chem.
43(4), 187–193 (1992).
54. J. L. Lichtin and K. L. Gabriel, J. Soc. Cosmet. Chem. 43(6), 313–330
(1992).
55. M. Paye et al., Skin Res. Technol. 1(1), 30–35 (1995).
56. M. Reiger, Cosmet. Toil. 110(4), 31–50 (1995).
57. P. Sloan, Advertising Age 65(6), 48 (1994).
58. T. Zimmerman, Advertising Age (special supplement S6), June 26, 1995.
59. T. Branna, HAPPI 32(6), 91–92 (1995).
60. Private communication testing laboratory data, Minnetonka Research
Institute, Inc., 1995.
61. C. Fox, Cosmet. Toil. 110(4), 59–73 (1995).
62. J. Kamegai et al., US 5,057,311 to Kao Corp (1991).

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63. H. Takamura, J. Kamegai, and H. Hirota, US 5,035,832 to Kao Corp.
(1991).
64. J. Kamegai et al., US 5,234,618 to Kao Corp. (1993).
65. E. Reid and A. Murray, US 5,085,857 to ChesebroughPond USA Co.
(1992).
66. G. Abamba, Cosmet. Toil. 108(11), 83–89 (1993).
67. Commercial package label, Softsoap Original Aloe, 1995, Colgate
Palmolive Co.
68. Commercial package label, Softsoap Sensitive Skin, 1992, Colgate
Palmolive Co.
69. Commercial package label, Softsoap Regular Antibacterial Liquid, 1995,
ColgatePalmolive Co.
70. Commercial package label, Dial Regular Antibacterial Liquid, 1995, Dial
Corp.
71. Commercial package label, Jergens Lotion Enriched, 1991, Andrew
Jergens Co.
72. Commercial package label, Ivory Regular Liquid, 1993, Procter &
Gamble.
73. Commercial package label, Safeguard Regular Antibacterial Liquid Soap,
1991, Procter & Gamble.
74. Commercial package label, Caress and Dove brands Moisturizing Body
Wash, 1994, Lever Bros. Co.
75. Commercial package label, Oil of Olay Moisturizing Body Wash, 1994,
Procter & Gamble.
76. Commercial package label, Jergens Refreshing Body Shampoo, 1995,
Andrew Jergens Co.
77. Commercial package label, Dial Plus Moisturizing Antibacterial Body
Wash, 1995, Dial Corp.

12
Fabric Softeners
ALAIN JACQUES
Fabric Care, ColgatePalmolive Research and Development, Inc., Milmort, Belgi
CHARLES J. SCHRAMM, JR.
New Jersey
I. Introduction
II. Commercial Applications
A. Business aspects
B. Product types
III. Mechanism of Softening
A. Softness
B. Substantivity
IV. Softening Compounds
A. Organics
B. Inorganics
V. Aspects of Formulation and Industrial Manufacture
A. Chemical factors
B. Mechanical factors
C. Case study
VI. Environmental and Regulatory Aspects
VII. Future Trends
References

Page 434
I. Introduction
Fabric softeners for domestic use are primarily designed to give a pleasant feel
to garments, to impart freshness or another pleasant smell, and to control the
static electricity that impairs the comfort of handling and wearing clothes when
ambient humidity is low.
The need for fabric softeners was prompted by the move from soaps to
synthetic detergents and by the utilization of automatic washing machines. In
the predetergent age, clothes were washed only with soap. The fibers were
then covered with a thin film of insoluble calcium and magnesium soap formed
from the water hardness. This film gave enough lubrication of the fibers to
maintain an acceptable feel. The introduction of automatic washing machines
together with more powerful synthetic detergents has changed the washing
conditions for users and also for the clothes.
The original feel and handle of fabrics is altered by the following:
Higher mechanical friction in the washing machine
High washing temperatures
The ability of the detergents to remove original textile finishes, not only greasy
stains
The mineral incrustations formed from water hardness or from inorganic salts
present in detergents
The industry realized very quickly that cationic fatty materials can maintain or
restore the original feel of fabrics. As a result, it was not long before domestic
products appeared on the market [1–6]. Fabric softeners were introduced first
on the U.S. market around 1955 and about 10 years later in Europe. This type
of product is also widespread in Japan and is still expanding and growing
worldwide. The data of worldwide rinse cycle fabric softeners growth shown
in Table 1 exemplify the important growth of this category. They are an
estimate based on United Nations published information.
TABLE 1 Fabric Softener Worldwide Volume
Growth
Year Worldwide volume (ton)
1966 160,000
1985 2,060,000
1991 3,700,000
Source: United Nations published data.

Page 435
II. Commercial Applications
A. Business Aspects
1. Textile Market
Treatment of fabrics and fibers with softeners and lubricants was standard
practice in textile processing before becoming a part of the home laundering
regimen. Softening imparts lubricity and flexibility, which minimizes damage
during the processing of fabrics and fibers. Softening also provides a pleasant
feel to enhance consumer acceptance of an item at the point of purchase.
Some softener materials, cationic softeners, utilized in textile processing have
also found application in the home. Application methods and desired end
benefits of textile processing allow for the use of a much wider range of
softener actives. In textile processing, concentrated softener suspensions or
solutions can be sprayed or padded directly onto the cloth.
Fabric treated in this manner eliminates the need for materials that exhibit high
rates of exhaustion and substantivity. Thus, such anionics as soaps and fatty
alcohol sulfates and nonionics, such as waxes, ethoxylated fatty alcohols, and
ethoxylated fatty acids, are effective textile softeners. Although these materials
have limited durability to home laundering, they are quite satisfactory for textile
processing.
2. Home Market
For fabrics of high synthetic fiber content, the buildup of static cling is a
problem in areas of low humidity or where automatic clothes dryers are
frequently used. Cationic softener materials with a wide range of structures
have been used to meet the needs of the home market. Cationic softeners
exhibit a high degree of fabric substantivity and high exhaustion rates from
dilute solution. Effective softener materials have the general structure of one or
two long hydrocarbon chains attached to a cationic hydrophilic group. Two
longchain hydrocarbon groups each with 16–18 carbon atoms are preferred.
Acceptable levels of softening may be achieved when deposition reaches 0.1–
0.2% by weight of fabric [5]. The most effective softener materials are virtually
deposited quantitatively from the rinse solution. Thus, softening is quite
economical, requiring roughly 3–6 g active softener per rinse.
Consumer perception of fragrance is important. In the bottle, fragrance must
be pleasant and not overwhelming. Fragrance must be sufficiently substantive
to be perceived on wet and dry fabric. A pleasant fragrance to some extent
makes up for reduced levels of fabric softening. Fragrance in the rinse is
important where automatic dosing machines are not prevalent (such as the
United States) because consumer perception of a pleasant fragrance is the first
indication that the product is efficacious.

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3. Industrial and Institutional Market
The industrial and institutional market utilizes many of the same materials used
in the home market. Lowcost actives are more frequently utilized. Less
emphasis is also placed in product esthetics, such as fragrance, color, and
packaging. Softening efficacy, static reduction, and ease of handling are looked
on as the primary benefits.
B. Product Types
The primary consumer benefits of fabric softeners are obviously softness and
freshness. Table 2 lists some of the additional positive benefits delivered by
fabric softeners. Static control is important to consumers utilizing electrical
dryers or living in areas with a dry climate. Other benefits, such as ease of
ironing and wrinkle reduction, are of less significance to consumers.
Some misuse conditions can cause drawbacks. Fabric staining can result if the
softener is placed directly onto a garment. Greasy feel may occur if they are
strongly overdosed. Continued use of certain types of softener formulations
may cause reduced water absorption and/or yellowing.
Fabric softeners are available to consumers in many forms.
1. Rinse Cycle
Liquid fabric softeners are typically added to the rinse water at the last rinse
cycle after the main wash. This product form is the form most used by
consumers. These products are offered to consumers in a wide range of
concentration from regular strength to up to 10 times concentrated. Some
products are intended for direct use; others (such as a 10 times concentrated
product) require predilution before use. In the early 1980s, the concentrates
were introduced primarily for cost and convenience reasons. Subsequently,
they have been sold in socalled ecopacks to help to reduce packaging waste.
This trend has occurred
TABLE 2 Fabric Softener Effects on Fabrics
Positive effects Side effects
Softness, fluffiness Occasional fabric staining
Fragrance Reduced water absorption
Static control Yellowing
Ease of ironing Greasy feel
Fiber protection
Bacteriostat
Reduced drying time

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in both Europe and the United States. Rinse cycle softener products constitute
the fabric softener form that delivers the greatest level of perceived softening
efficacy.
2. Dryer Cycle
Dryer sheets are added to the tumble dryer along with the damp laundry
before drying. Where electrical dryers use is very high, such as the United
States, dryer sheets are a very important segment. Dryer sheets are convenient
and deliver effective antistatic properties with a low level of active ingredient.
3. Wash Cycle
Wash cycle softeners are added to the main wash along with the detergent.
These products are a compromise between convenience and efficacy.
Products that would not be prohibitively expensive generally deliver a lower
level of softening than rinse softeners or antistatic properties than dryer
softeners.
The products may be either a wash cycle additive fabric softener (WCFS) or
softergent (detergent softener combination). Commercial WCFS products
intended for use with the consumer's choice of detergent were not widespread.
In the United States, a product called Rain Barrel by S. C. Johnson & Son,
Inc. was marketed during the mid1980s as a WCFS. This product contained
a low level of distearyldimethylammonium chloride softener. Interaction of
softener with surfactants in detergent systems would be expected to have
limited the efficacy of this type of WCFS. As indicated by Puchta et al. [7], a
product for effective delivery of softening and antistatic benefits with a broad
range of detergent systems would require a high use level of softener. The high
cost associated with delivering perceptible consumer benefits may be the
reason for the limited availability of this product form.
Detergent systems incorporating a fabric softener material were quite popular
in the United States between roughly 1981 and 1989. The combination
product allowed controlled balancing of softening and detergency. These
products delivered consumerperceptible softening and antistatic benefits while
maintaining acceptable detergency. In the 1990s, the softergent product form
has become a significantly lesser part of the U.S. market. This trend was the
result of the industry increasing the softening efficacy of rinseadded softeners
and increasing the detergency of detergent products. Softergents progressively
became a less acceptable compromise between softening and detergency.
Fabric softeners are probably the most cosmetic of the laundry products. This
is why the right choice of color, fragrance, and even texture to fit the product
concept is very important. In recent years, fabric softeners have become
extraordinarily diversified in terms of colors and perfumes.

Page 438
III. Mechanism of Softening
A. Softness
There are many causes for the hardening of fabrics, as discussed earlier.
Softeners counteract this harshening in several ways.
One way to counteract the alteration of fabrics by the washing process is to coat
the fibers with a protective film of a fatty material acting as a lubricant. Figure 1
shows the state of the fibers of a cotton bath towel after 12 cumulative wash
cycles with and without using a fabric softener.
The fabric treated with fabric softener shows fibers with a smooth surface and
little surface residue. Fibers from fabric without softener treatment show
significant surface residue that appears to connect adjacent fibers. The less
damaged state of the fibers of the sample treated with fabric softeners leads to a
more pleasant feel of the fabric.
The use of a fatty lubricant material that reduces surface friction explains the
ease of fabric ironing. Reduction of interfiber friction reduces some of the
tendency for static electricity generation from the rubbing together of dissimilar
materials when fabrics are tumbled in an automatic dryer.
Another role of this fatty material is as a vehicle to carry perfume to the clothes.
FIG. 1
These electron micrographs show how the protective film left by fabric softeners
prevented
residue build up on fibers (a) with fabric softener and (b) without fabric softener.

Page 439
In hard water areas, the same type of lime scale buildup results on fibers as
occurs on the heating element of European washing machines. To counteract
this, it has been the usual practice of some consumers to add vinegar to the
rinse water. In fact, the use of organic acids has received very little attention
from the formulators of fabric softeners. Fabric softener use alone can to some
extent counter the negative feel caused by lime scale buildup.
Another approach to improve the feel of fabrics is to increase the flexibility of
the fibers [1]. The simplest material that plasticizes the fibers is water. This is
the basis for incorporating waterbinding materials, such as polyglycols, in
softening compositions. To be effective, these components must be sufficiently
small molecules to penetrate the fibers. In practice, the use of such materials
has been of less importance than the use of organic fatty materials, which
constitute the bulk of fabric softeners and which bind more readily to fabrics.
As a result, the primary mechanism through which fabric softeners act is fiber
lubrication.
As far as dryeradded fabric softener is concerned, the transfer of the
lubricating materials from the softener sheet onto the clothes results from the
combination of temperature, humidity, and friction occurring in the dryer.
B. Substantivity
Several factors alter the deposition of rinseadded softeners onto the fabrics.
Details are available from several papers by Bücking et al. [8], Hughes and
Koch [9], Okumura et al. [10], Smith et al. [11], Hughes et al. [12,13], and
Linfield et al. [14].
There is an agreement on the very high exhaustion rate of the rinse liquor and
on the important uniform deposition of the softener on the fabrics. For instance,
Linfield et al. [14] showed that softener exhaustion increases with pH
increasing from 5 to 8 and with temperature increasing from 21 to 32°C.
Higher levels of water hardness seems to improve the deposition. The
presence of ethoxylated fatty alcohols [6,15] and of an excess of anionic
surfactants [10,11] impairs deposition. Also, Okumura et al. [10] showed that
reducing the particle size of the dispersion improves the deposition of the
softener.
Laughlin [16] analyzed the existing results to clarify the mechanism of the
cationic softener deposition. He suggests an ionexchange reaction between
the carboxylate groups of cotton (and the associated counterions) and the
cationic salts coupled with physical adsorption. This is in agreement with the
nonstoichiometric deposition of cationic softener versus the number of
carboxylic groups [17] and deposition on more neutral fibers [7].
Recently, Crutzen has described a mechanism in which the driving force of
deposition of ditallowdimethylammonium chloride onto cellulose is purely
hydrophobic [18]. The hydrophobicity of the softener forces the softener out
of

Page 440
the rinse water and causes it to deposit onto available surfaces. The softener
binds to the fabric by weak London dispersion forces. The high level of
deposition of softener onto cellulose relative to other fabric types results from
the large specific surface area of cellulose.
IV. Softening Compounds
Softening materials used by the detergent industry fall into three classes:
organics; inorganics; and silicones. Organic fabric softeners are the most
frequently utilized form and are found in wash, rinse, and dryer products.
Montmorillonite clays are the principle type of inorganic softener and are used
in washcycle detergent products. Silicone softeners are used in small
quantities and generally as a minor component in combination with organic
softeners.
A. Organics
The preferred materials used in domestic fabric softeners are predominantly
fatty quaternary ammonium cationic salts. A very large number of materials
have been patented [19], but only a few of these have been of practical
importance.
Early fabric softener formulas were based on simple aqueous dispersions of di
hard tallow dimethylammonium chloride (DHTDMAC), shown in Fig. 2, or of
imidazolinium methosulfate (DHTIMS), shown in Fig. 3, at a level of around
5%.
Hughes and Koch [1] have studied DHTDMAC deposition based on
colorimetric and radiometric techniques, finding that better than 90%
deposition onto cotton occurred over a wide range of pH and temperature.
Early use of the DHTDMAC, DHTIMS, and other softener actives in textile
manufacturing, for the control of friction during processing and improvement of
final fabric feel, is discussed by Evans [2]. Foley [3] broadly reviewed early
developments in fabric softener technology indicating that DHTDMAC and
DHTIMS represented 95% of the cationic softeners in use and that these
softeners are effective at a level of 0.1–0.2% by weight of the fabric treated.
Fuller and Ackerman [4a]
FIG. 2
Dihydrogenated tallow dimethylammonium
chloride.

Page 441
FIG. 3
Ditallow imidazolinium.
and Ackerman [4b] discussed factors for choosing which softener type was
the appropriate choice under the different use conditions of wash, rinse, and
dry. Milwidsky [5] reviewed recommendations for processing DHTDMAC
and DHTIMS dispersions and the importance of controlling dispersion pH. He
also discussed product esthetics, such as perfume, color, and the potential
need to include fluorescent whitening agents. Egan [6] and Billenstein and
Blaschke [20] report on synthetic procedures for the manufacture of
DHTDMAC, DHTIMS, and other aminebased fabricsoftening materials.
Puchta [19] has discussed the use of DHTDMAC and DHTIMS in dryer
products, rinse cycle products, wash cycle products, and softenerdetergent
combined products. His discussion demonstrates the wide application of these
two softener actives. Laughlin also discusses DHTDMAC and DHTIMS at
length in his review of fabric softeners [16]. He indicates that the importance of
these two materials is based on the existence of straightforward manufacturing
techniques for their preparation, as well as their softening effectiveness.
The 1970s saw the commercial development of improved softening systems
still based on the same quaternaries but used in synergistic combinations with
other fatty materials. There are two groups of synergistic combinations, the
cationicanionic systems and the cationicnonionic systems. Typical examples
of the first group are the systems based on DHTDMAC and on fatty alcohols,
ether sulfates, or alkyl sulfonates [21]. The second group is illustrated by
compositions based on combinations of DHTDMAC with various cosofteners:
glyceryl monostearate [22]; stearic acid [23,24]; tallow alcohol [25]; and
lanolin derivatives [26]. In all these compositions, the weight ratio of
DHTDMAC to the cosoftener was always higher than 1.
Some compositions with lower levels of DHTDMAC, or even free of it have
been commercialized. U.S. Patent 4,806,255 [27] describes mixtures of cyclic
amines with a lower content of DHTDMAC. Patents U.S. 4,933,096 [28] and

Page 442
FIG. 4
Structure of one type of esterquat.
4,844,823 [29] refer respectively to ester cyclic amines and to mixtures of
socalled esterquat with various cosofteners. These cationic materials with ester
bonds allow the softener molecule to biodegrade more quickly than other
cationic softeners. Figure 4 shows one form of esterquat and Fig. 5 the
structure of ditallow ester imidazoline.
B. Inorganics
1. Clays
Clay fabric softening agents have been utilized principally in detergent fabric
softener combination products. These softergent products combine a standard
heavyduty built anionic detergent system with clay softeners. Commercial
products include the heavyduty powders, such as Australian Fab [30] and
U.S. Bold [31].
Clays of the smectite type are utilized in fabricsoftening systems. Sodium and
calcium montmorillonite clays are the most frequently utilized smectite clays.
Patents [32,33] have also included such forms of clay as hectorites and
saponites and have claimed additional antistatic benefits for these clays. Mont
FIG. 5
Structure of ditallow ester imidazoline.

Page 443
morillonite clays are unique in their structure compared with typical soil clays.
Montmorillonite clays, particularly the sodium forms, are highly dispersible to
extremely small platelike particles with sizes in the range of a few hundredths
of a micrometer to several micrometers. Each platelike particle is composed
of several clay unit layers like a deck of cards. The clay particles have been
shown by electrokinetic studies [34,35] to have a net negative surface
potential. As a result, potential interaction between anionic surfactant and clay
softener would be minimal, making the clay ideally suited for inclusion into
anionicbased detergent systems.
Extensive fundamental studies are available [36–38] involving sodium
montmorillonite deposition onto and removal from cellulose. These studies
demonstrated that low levels of sodium montmorillonite clay (0.04% by
weight) were rapidly and irreversibly deposited onto cellulose at extremely low
clay concentrations. Typical claycontaining softergents utilize high levels of
clay softener, up to or exceeding 20% of the product. That high levels of clay
are generally employed suggests that fabric softening by clay requires high
levels of deposition (all the clay is depositing) or that deposition of clay is
concentration dependent (only a fraction of clay employed deposits). High clay
use levels are possible because the cost of most montmorillonites utilized as
softeners are generally of the order of the sodium sulfate filler.
Nonionic surfactants must be avoided in the formulation of effective clay
softergents. Fundamental studies by Schott [39] indicated that ethoxylated
alcohol surfactants were the most effective in removal of montmorillonite clays
from cellulose. Even more critical was the observation by Schott [39] that the
presence of the nonionic surfactants prevented the deposition of sodium
montmorillonite onto cellulose.
Lowcost clays utilized as softeners are colored by impurities, generally light
brown or gray. This has not been reported to contribute to discoloration of the
fabrics upon which they deposit. Colored, powdered clay intimately mixed
with other detergent components before or after spray drying discolors the
detergent powder, leading to an unesthetic product. For this reason, users of
clay softeners have developed methods for agglomeration of clay powder into
detergentsized aggregates. The agglomerates are added later to the detergent
powder. They do not harm product esthetics, appearing as a few dark
speckles in a mostly white powder. Softergents containing clay as the sole
softening agent deliver lower softening levels than the combination detergent
plus separate rinse cycle softeners. A limitation with clays is that they do not
deliver antistatic benefits, particularly necessary in areas of high dryer use, such
as the United States. The patent literature [40–46] contains numerous
examples that address these deficiencies. These softergents combine separate
clay softener and organic softening agents. This presents the added
complication of potential interaction between organic softener and both clay
softener and anionic detergent compo

Page 444
nents. One combination softergent minimizes the potential interaction between
organic softener and other components by utilizing a neutral amine softener
[44–46]. Another approach has been the preparation of a selfcontained
cationic softener agglomerate [40–43]. The agglomerate contained agents that
inhibit dispersal in the wash water. This prevents interaction of cationic softener
with clay and detergent components both in the wash and in the product itself.
Clay softeners are effective softening agents ideally suited for use in those areas
of the world where antistatic benefits are of low importance and low cost of
the active softener is critical. In the wash cycle, clay softenerorganic softener
combinations are unique in their ability to approach the softening efficacy of the
combination detergent plus separate rinse cycle softener.
2. Silicones
Silicone softeners include both polydimethylsiloxane polymers as well as a
wide range of organomodified polydimethylsiloxanes. The silicones were first
utilized by the textile industry primarily as lubricants in fiber and fabric
manufacture [47]. Silicone softeners are also applied with permanent press
finishes to improve garment wear life and permanent press finish durability
[48,49]. Organomodified polydimethylsiloxanes, particularly epoxy modified,
were found to offer a significant improvement over conventional unreactive
silicones [49,50]. The improvement was in terms of both a greater degree of
softening and good durability of polymer to laundering. Aminofunctional
polydimethylsiloxanes softeners were found to have the same advantages as
reactive silicones [51,52]. Two additional benefits were found with
aminofunctional silicone softeners. Knit fabrics became more elastic, with
better stretch recovery. The softener also additionally delivered antistatic
benefits and wrinkling resistance [53]. These two benefits and the fact that the
amino functional silicone are readily adsorbed from dilute solution onto cotton
fabrics in conjunction with traditional cationic organic softeners led to their use
in rinse cycle softeners in the middle to late 1980s [54,55]. Although their use
level was never high (0.1–1.0% by weight) as a result of their high cost, amine
silicones did bring a consumerperceptible new dimension to rinse cycle fabric
softeners. Changing market forces have resulted in the removal of silicone
softeners from most consumer fabric softener products.
V. Aspects of Formulation and Industrial Manufacture
An important aspect of the formulation of liquid rinse cycle softener is control
of the viscosity. It is desirable to deliver a product that displays some
consistency. For the consumer this makes the dosage operation easier and acts
as a signal of efficacy. It is equally desirable to stabilize the viscosity at a
reason

Page 445
able level to avoid clogging troubles in the dispensers of the automatic washing
machines. The complexity of this problem increases as the concentration of the
softener increases.
This section discusses the critical parameters governing the viscosity of
concentrated liquid softeners and the involved structural changes in the product
when a viscosity increase occurs. The major drawback to the preparation of
concentrated aqueous dispersions of DHTDMAC is the sharp viscosity
increase with concentration as reported by Hein [56] and shown in Fig. 6.
Before discussing the formulation aspect, it is worth describing the structure of
the DHTDMAC in aqueous dispersions. The dispersion phase of DHTDMAC
consists of hydrated particles with a structure similar to that of multilayered
liposomes, which are called vesicles. The DHTDMAC molecules form
concentric bimolecular lamellar layers with entrapped water. According to
Okumura et al. [10], the DHTDMAC vesicles range in size from below 1–10
m. The bimolecular layer has a width of 50 Å, and the intralamellar spacing is
100–400 Å. Okumura et al. [10] calculated that the water of hydration is
around 7 mol H2O/mol DHTDMAC. Such results can vary with the conditions
of the preparation of the dispersion.
Controlling the viscosity of aqueous dispersions of DHTDMAC is possible by
applying the principles of emulsification from the chemical and mechanical
standpoints. The DHTDMAC aqueous dispersion is contemplated as an oilin
water emulsion.
FIG. 6
Viscosity of an aqueous dispersion of DTDMAC according to
Hein [56].

Page 446
A. Chemical Factors
It is widely known that emulsifiers form an interfacial film around the droplets
of the dispersed phase and protect the droplets against coalescence, provided
the emulsifers are well located at the interface. The selection of the right
emulsifier can be made according to the HLB system. ICI has published a list
of applications and some suggested emulsifier blends and their HLB values
[57].
Table 3 and Fig. 7 demonstrate the influence of the emulsifier HLB on the
stability of DHTDMAC dispersion. Table 3 shows the dependence of the
emulsifier viscosity on the HLB value of the emulsifier. In this specific case, two
emulsifiers were used (SPAN and Tween). The required HLB value is around
16.
Figure 7 shows the effect of the emulsifier concentration on the emulsion
stability when using an optimized surfactant. In this specific case, nonylphenol
ethoxylated 10:1 was used. Two concentrations of emulsifier lead to stable
dispersions. The highest is preferred because it allows a higher formula
flexibility.
Another approach to producing stable dispersions of DHTDMAC vesicles is
to take advantage of the vesicle structure itself. James and Ogden [58]
suggested that the DHTDMAC bilayers of the vesicles work as a
semipermeable membrane and that osmotic transfers are possible when
electrolytes are used. Addition of electrolytes in the continuous phase (water)
causes an osmotic transfer of water from inside the vesicles to the continuous
phase. The net result is a reduction of the vesicle size, that is, the dispersed
phase volume, and an increase in the continuous phase volume. This osmotic
effect tends to “dilute” the dispersion, which decreases the viscosity and
stabilizes the dispersion to separation.
According to the DLVO theory [59], the use of electrolytes can decrease the
emulsion stability by decreasing particle surface charge and thus reducing
interparticle repulsion. Because of the two adversary effects of electrolytes, the
TABLE 3 Determination of the Required HLB
Emulsifier mixture 3% by weight Viscosity
after 24 h
Calculated HLB SPAN 80 (%) Tween 20 (%) (cP)
14 22 78 Gel
15 14 86 670
16 6 94 230
17 100 280
18 4 96 Gel

Page 447
FIG. 7
Determination of the optimum emulsifier content. Viscosity of the fabric softener
versus the content of emulsifier.
Curve of DHTDMAC dispersion stability versus electrolyte content exhibits a
maximum of stability at finite electrolyte levels.
Additional slight stability improvements can also be obtained by limiting the
solvent content in the raw materials and by using hydrophilic polymers, such as
polyethylene glycols (steric hindrance), to prevent coalescence.
B. Mechanical Factors
In addition to the osmotic phenomenon, particle size also drastically affects the
stability and the rheological behavior of the emulsions. For concentrated fabric
softeners, the influence is so strong that, with exactly the same composition,
either thin liquids or nonpourable gels can be obtained by changing the particle
size distribution.
Mixing conditions are a key factor in setting the particle size of the product.
The mixing conditions can be carefully optimized when defining the
manufacturing procedure by scaleup experimentation.
The mechanical energy imparted to the dispersion by the propeller can be split
into shear and flow. The shear magnitude is related to the impeller head given
by the equation
H = K1N2D2
where H is the head developed by the impeller, K1 is a proportionality constant
that varies with the shape of the impeller and of the mixing vessel, N is the

Page 448
speed of rotation, and D is the diameter of the impeller. The flow rate is
defined by the equation
Q = K1ND3
where Q is the flow rate, K1 is a constant determined by the shape of the
impeller and of the mixing vessel, N is the rotation speed of the agitator, and D
is the diameter of the impeller.
The reader interested in more details about the mixing principles and their
application to emulsification and to scaleup experimentation should refer to the
books dedicated to this subject [60,61].
C. Case Study
The magnitude of the flow and of the shear alters the particle size of the
emulsion and consequently phase stability and rheological behavior. Table 4
lists the composition of a concentrated DHTDMAC emulsion stabilized with an
emulsifier and with CaCl2 electrolyte. This formulation is used to illustrate the
influence of mixing parameters on product stability.
All experiments were performed in 200 kg size batch, using different types of
impellers with different flow and impeller head values. The resulting particle size
distributions were recorded with Coulter N4 (photon correlation
spectroscopy) and particle concentration with a Coulter Counter. Rheology
measurements were made by Rheomat 30, Rheometrics System 4 (oscillatory
response), and Brookfield RVT.
This emulsion, when prepared with the correct process parameters, exhibits
excellent stability over aging (initial viscosity = 80 ± 20 cP; less than 200 cP
after 6 week aging in the range of 4–43°C). The typical particle size
distribution is bimodal, the first peak is around 0.2–0.3 m; the second is at
TABLE 4 Fabric Softener Formulation Used for Case Study
Material % wt/wt
DHTDMAC 13.2
Tallow amine 15:1 EO 1.91
Stearic acid 0.59
Perfume 0.30
Calcium chloride (2H2O) 0.7–0.9
Dyes 0.005
(0.25% of a 2% stock)
Preservative 0.05
Water Balance
Source: Ref. 54.
Page 449
1.0–2.0 m. The particle size distribution, as shown graphically in Fig. 8, is
described by the mean diameter resulting in both populations and by the
percentage of population of the small particles (around the first mode), both
populations together being 100%.
Under some conditions, this emulsion can exhibit two typical instability forms,
thickening or clearing over aging. Of course, these product alterations are a
result of a structural change.
1. Thickening
The thickening phenomenon was observed for the samples prepared with
highshear mixing devices.
It is demonstrated here that the smaller particles induce flocculation of the
emulsion. Therefore, the interaction between closely packed particles leads to
higher viscosity of the emulsion. (The average distance between particles was
estimated at 60% of the average particle diameter.) This was calculated
according to the equation
where A m = average distance between particles; Dm = average diameter of
particles; max = maximum ratio of phase volume = 0.74 for spheres; and =
actual ratio of phase volume = 0.184 (assuming no water inside the vesicles).
FIG. 8
Typical DTDMAC aqueous dispersion particle size distribution
containing two subpopulations.

Page 4
TABLE 5 Particle Size Distribution Versus Impeller Head
Impeller head Average diameter ''Small particle'' (%)
(M) ( m)
0.11 1.24 31
0.21 0.80 36
0.36 0.77 48
0.77 0.73 50
1.18 0.69 51
1.82 0.68 65
3.24 0.48 58
5.05 0.30 67
As indicated in Table 5, the particle size is decreased with the increasing shear of
the mixing device measured by the impeller head.
The decrease in particle size does not significantly change the viscosity of the fres
emulsions, as shown in Table 6, but allows the particles to draw nearer each othe
and to interact upon aging. Table 7 reports the viscosity changes after accelerate
aging (16 cycles from 0 to 50°C, 1°C/minute) versus initial particle size.
More than a simple viscosity measurement is needed to describe the rheological
changes in the samples. Measurements of shear stress versus shear rate (Rheoma
30) were made and the results are reported according to the power (OstwaldD
Waele model) and Casson laws.
TABLE 6 Viscosity of Liquid Softener After Making Versus Particle Size Distribution
Average diameter ( m) “Small particle” (%) Viscosity (cP)
1.24 31 56
1.13 38 58
1.10 33 68
0.80 36 68
0.77 48 66
0.73 50 76
0.69 51 70
0.68 65 84
0.48 58 86
0.30 68 236

Page 451
TABLE 7 Dependence of Emulsion Stability of
Viscosity on Initial Particle Size Distribution
Averaged "Small" particles Viscosity after
diameter ( m) (%) 16 cycles (cP)
1.24 31 216
1.13 38 156
1.10 33 308
0.80 36 708
0.77 48 860
0.73 50 490
0.69 51 558
0.68 65 Above 800
0.48 58 Above 800
0.30 68 Above 800
2. Power Law
The measurements of shear stress versus shear rate, plotted on logarithmic
scales, are represented by a linear expression over a limited range of shear rate
(7–158 s1). The equation that represents this behavior is called the power law
or the OstwaldDe Waele model:
n
= m
where = shear stress; = shear rate; m = consistency; and n = flow index.
For pseudoplastic (shear thinning) materials, n is less than 1. Obviously, for n
= 1, the model reduces to the Newtonian. If the shear rate = 1 s1, then the
consistency magnitude will represent the value of the apparent viscosity.
Table 8 gives the values of the consistency and of the flow index after aging for
different samples produced with various particle sizes. The results show
TABLE 8 Power Law: Consistency and Flow Index
Versus Particle Sizea
Mean diameter ( m) M (poise) N Flow
index
1.24 0.32 0.73
0.89 0.60 0.68
0.69 0.90 0.58
0.48 2.20 0.46
0.30 3.30 0.41
a
Shear rate 7158 s1.

Page 452
that the flow index n of aged samples decreases and that the consistency
increases as the particle size decreases. The samples depart from Newtonian
behavior upon aging, as the particle size decreases. This means that particles
more strongly interact upon aging. This stronger interaction is responsible for
the “thicker” aspect of the emulsion.
3. Casson Law
Many materials which exhibit an apparent yield stress and which do not exhibit
a linear shearstress rate relationship can be described by the Casson model.
The representation of this flow behavior is
1/2 1/2c + c for >

= c
and
= 0 for < c
where c = yield stress and c = slope.
The basis of the theory lies in a consideration of the rate of energy dissipation
in a dispersion of relatively long chain aggregates. Under very high shear rate
(“infinite”), one can assume that the bonds between particles are broken and
that the aggregates are destroyed. Table 9 shows the dependence of the two
main parameters of the Casson law; the yield stress and the viscosity under
infinite shear rate, on the impeller head or the related particle size.
The results showed that the higher the impeller head (or consequently the lower
the particle size), the higher was the yield stress (or the stronger the interactions
between particles). On the other hand, the change in the viscosity under infinite
shear rate is very small and of the same order of magnitude as before aging.
The high shear rate appears to break the bonds between the particles, and then
the viscosity is only slightly reduced depending on the particle size.
Overall, the rheological study indicates that when small particles are generated
by a high shear mixing, they interact strongly to form a network floc that can be
separated under high shear.
TABLE 9 Casson Law: Yield Stress and Viscosity Under
Infinite Shear Rate Versus Impeller Head (Aged Samples)
Yield stress Viscosity under infinite
Impeller head (m) (Pa) shear rate (cP)
0.11 0.2 76
0.42 0.7 64
1.18 0.5 89
3.24 2.0 94
5.05 3.7 84

Page 453
The following experiments confirmed the flocculation phenomenon. Different
samples of concentrate were diluted to different concentrations ranging from
104 to 108 g oily phase (active ingredients)/100 g water. Effective mixing was
used to deflocculate the samples. Suspensions were then allowed to flocculate
under controlled conditions of time and temperature (15 minutes, 25°C). It
was expected to find a lower degree of flocculation for the samples with higher
dilution because the flocculation rate is proportional to the concentration of
particles. When the flocculation rate is rapid, the number of particles should be
greatest for the most diluted samples after the 15 minutes flocculation time.
The flocculation phenomenon was monitored with a Coulter Counter. The
Coulter Counter measures the number and size of particles in a set volume. In
this study, the number of particles in 50 l was counted for each sample. Table
10 shows the number of particles counted in the different samples after 15
minutes flocculation at 25°C. Also shown is the relative particle count and the
relative particle count corrected for concentration in reference to the most
concentrated sample. As expected, the results showed that the most diluted
sample has the lowest degree of flocculation.
The flocculation phenomenon also allows us to explain another observation
made during particle size measurement with the Coulter Counter. The
concentration index recorded by the Coulter was increasing over the
measurement time from around 5 to 10%. The concentration index is
proportional to the weight percentage of solids in the sample volume measured.
The concentration index is based on only those particles observed by the
instrument. The increasing concentration index can be explained by the
flocculation occurring during the time of the experiment. The 20 m tube
aperture of the Coulter can detect particles with diameter ranging from 0.4 to
10 m. The typical particle size distribution of the concentrate is bimodal, with
the lower distribution at around 0.2–0.3 m. These particles are not detected
by the Coulter Counter at the beginning of the experiment, when the dispersion
is deflocculated, because of the mixing used for the dilution of the sample
required by the Coulter procedure. During measurement, the diluted sample is
subjected to flocculation, leading to aggregates of larger size (the small
particles flocculate first because
TABLE 10 Flocculation: Particle Concentration Versus Dilution
Ratio of relative
Concentration (g number of
organic phase/ 100 g Number of particles Relative number of particles to dilution
water) in 50 l particles factor
104 203,452 1 1
105 24,859 0.122 1.22
106 5,836 0.029 2.9
107 1,817 0.009 9
108 2,441 0.012 120

Page
of their more rapid Brownian motion), which can be detected by the Coulter
Counter. The flocculation and formation of additional large particles result in an
increase in the concentration index.
4. Phase Separation
Another form of instability of concentrated softeners is a form of phase separatio
we call clearing. In a product that shows clearing, two layers appear on aging, th
bottom layer being more translucent and clearer than the top. The viscosity of ea
layer remains quite stable and low. This phenomenon is reversible and disappears
soon as the sample is gently moved.
This instability is caused by the presence of a bimodal population. The small
particles (submicrometer) remain evenly distributed; the larger particles move up,
forming the top layer because of the difference in density between the dispersed
the continuous phases. If the interactions between the particles are weak, the
viscosity remains low and clearing occurs according to Stoke's law.
Table 11 shows the typical average particle size of the two particle populations
separately observed in the two layers of a sample exhibiting a noticeable clearing.
The cationic matter concentration of each individual phase is also shown.
VI. Environmental and Regulatory Aspects
For more than 30 years, the most common softening material around the world h
been the socalled ditallow dimethylammonium chloride. It has been extensively
used, for example, in 1980, the annual consumption of this material was 27,000 t
in Germany. Despite this high consumption for a long period of time, there has be
no clear evidence of any negative impact on the environment (1981 Aachen
Symposium, Cationic Surfactants and Environment). In 1991, the major
manufacturers have been led to replace this conventional DHTDMAC by other
materials exhibiting an improved environmental acceptability on the basis of
standard testing procedures.
The EEC Commission has published the criteria for classifying (risk phrase labeli
dangerous substances on the basis of environmental effects in the 12th Commissi
Amendment 91/325/EEC. They include acute aquatic toxicity and
TABLE 11 Clearing: Population in the Two Layers
Population particle % Particles in each
size ( m) bimodal part of the (g/L)
Layer population Cationic concentrati
Bottom 0.2 68 75
1.5 32
Top 0.3 38 150
1.8 62

Page 455
biodegradability limits and, in some cases, chronic toxicity effect limit, as well
as the potential of the substance to accumulate. Testing procedures are
recommended. Figure 9 shows the criteria used to determine the need to label
a material as dangerous to the environment.
The acute aquatic toxicity of the conventional DHTDMAC was found as low
as less than 1 mg/L on the basis of a EC50 test on DAPHNIA MAGNA. The
European industry progressively abandoned DHTDMAC during 1991 and
1992. This move has introduced some diversity in the formulations because the
single DHTDMAC has been replaced by at least three other materials.
The new molecules are all characterized by ester bonds, which makes them
break down faster and more easily [28,29,62–64]. They are also designed to
generate intermediates that are not toxic and fully biodegrade. Typical
examples of these new molecules are NmethylN,Ndi(2(C16–18acyloxy)
ethyl)N(2hydroxyethyl)ammonium methosulfate [32]; 2,3di(C16–18
acyloxy)propyltrimethylammonium chloride [61]; and 2(C16–18alkyl)3
(C16–18acyloxy)ethylimidazoline [65].
VII. Future Trends
Table 12 lists patents [66–103] covering the years 1991–1995. These patents
indicate some of the trends for future fabricsoftening products. Most of the
FIG. 9
EEC criteria for environmental labeling of raw materials.

Page 459
patents relate to rinse cycle liquid products, although there are several rinse
cycle softener powders.
In Europe there is much continued interest in new softening molecules. Some of
the new molecules are intended solely to meet new biodegradability standards,
although all new actives for Europe must meet the condition of good
biodegradability. Until governmental regulations become more stringent outside
Europe, changes in actives will be slower in the rest of the world. Many of the
new molecules are intended to be more highly active softeners. The more
highly active softeners enable products to be more cost effective or more easily
concentrated. The interest in actives for highly concentrated products appears
in all areas of the world.
Several of the patents in Table 12 relate to softening systems that deliver
benefits in addition to softening. Improved ease of ironing, reduced wrinkling,
color protection, and soil release are all benefits claimed to be delivered with
fabricsoftening systems. There are patents that claim to improve on one
particular aspect of softening, such as resiliency. claims have been made for
improved fragrance delivery.
Patent activity indicates that fabric softeners are a product of continued interest
to the detergent industry and the consumer.
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50. Union Carbide Silicones, Technical Literature SUI554 (1985).
51. A. J. Sabia and A. M. Czech, Am. Dyestuff Rep. 82, 58 (1993).

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57. HLB System, ICI United States, Inc., Wilmington, DE (1976).
58. A. D. James and P. H. Ogden, JAOCS 56, 542 (1979).
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60. C. Fox, The current state of processing technology of emulsions and
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61. J. Y. Oldshue, Fluid Mixing Technology, McGrawHill, New York,
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62. J. Waters, B. Wirral, H. H. Kleiser, M. J. How, M. D. Barratt, R. R.
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64. A. P. Singh, G. A. Turner, E. Willis, EP Patent 0,0409,504 to Unilever
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13
Specialty Liquid Household Surface Cleaners
KAREN WISNIEWSKI
New Jersey
I. Introduction
II. AllPurpose Cleaners
A. Historical background
B. Cream cleansers
C. Liquid allpurpose cleaners
D. Test methods
III. Spray AllPurpose Cleaners
A. Historical background
B. Allpurpose spray cleaners
C. Glass cleaners
D. Glass and surface cleaners
E. Test methods
F. Bleach spray cleaners
IV. Bathroom Cleaners
A. General bathroom cleaners
B. Mildew removers
C. Test methods
D. Toilet bowl cleaners
V. Conclusion and Future Trends
References
Page 464
I. Introduction
Household hard surface cleaners are defined in this discussion as formulations,
powder or liquid, used to clean hard surfaces in the home, excluding dishes.
Also excluded from this discussion are household products that are used
primarily as treatments rather than cleaners per se: polishes, floor waxes,
tarnish removers, and drain cleaners (decloggers). Metal cleaners, surface
descalers, and other such industrial liquid cleaners are not discussed. The
formulation of liquid bleach products is an art in itself, so bleach is discussed
here briefly as an adjunct to allpurpose cleaning. Household surface cleaners
are now moving to added benefits beyond simple cleaning of the hard surface.
Added benefits for cleaners are well established in other areas (e.g.,
conditioning with shampooing, softening with laundering, and tartar control in
toothbrushing), but such advantages are arriving late in hard surface cleaning.
The starting point for this discussion is the history of the development of
household cleaners [1]. Powder cleaners are covered briefly as part of the
evolution of this field of cleaners. In general, powder cleaners tend to have
large market share in developing countries, liquid allpurpose cleaners and
cream cleansers dominate in Western Europe, and liquid cleaners, especially
those dispensed through trigger sprayers, enjoy popularity in North America
and Australia and New Zealand. Therefore, this discussion focuses on
developments in North America and Western Europe. The area of household
cleaning may be seen as one of the most challenging for the formulator because
the household cleaning regimen can be said to have the most varied chemistry
of any cleaning field. This is in response to the variety of cleaning tasks in the
home and the demands of the consumer.
To illustrate the problem for the product developer, one has only to enumerate
the soils and surfaces. The soils can vary from simple dust and hair to dirt, hard
water spots, and fingerprints to hardened grease, soap scum, and excrement.
Although the usual household cleaning tasks are concentrated in only two
rooms of the house, kitchen and bathroom, the number of different surfaces
encountered are many. In the United States, for example, there may be
Formica, ceramic tile, grout, lacquered wood, vinyl flooring, painted surfaces,
brass, stainless steel, enamel, porcelain, aluminum, chrome, glass, marble,
methyl methacrylate, and other types of plastics. All these materials may occur
within only two rooms of the same home!
From a scientific point of view, one can see that these surfaces run the gamut
from highenergy (ceramic and metal) to lowenergy (plastic) surfaces. Soils
also can vary, from very nonpolar (motor oil) to very polar (lime scale). The
tenacity of the soil adherence therefore varies according to the combination of
soil and surface. In general, the better the soil wets the surface, the better is

Page 465
the adherence. It is a wellaccepted principle of adhesion that two substances
in intimate contact with each other tend to adhere very well, this being a
necessary (but not sufficient) condition. Highenergy surfaces tend to be easy
to wet, making them generally easy to soil. An example is the relative tenacity
of soap scum on ceramic as opposed to plastic surfaces.
Once wetting has occurred, the soil can then “bond” to the surface. What is
often forgotten in adhesion is that van der Waals forces can be strong enough
to account for the adhesion of soils to surfaces. Simple dispersion forces are
about 5 kcal/mol, and hydrogen bonds between 4 and 40 kcal/mol, whereas
covalent bonds can be as weak as 15 kcal/mol [2]. It can be seen from these
numbers that if good molecular contact is made between the soil and surface, a
bond can be made. This is especially easy if the soil is liquid or is deposited
from a liquid medium. Of course, the contribution of other mechanisms, such as
electrostatic attraction, tends to strengthen the bond between soil and surface,
if they are present. (Also, if the surface tends to be rough, then there exists the
possibility of purely mechanical adhesion as well, with the soil physically
located in nooks and crannies of the surface.) If an attempt is made to break
the adhesive boundary, a likely course is that one or the other of the materials
tends to break within itself. Therefore, in cleaning, the soil can be broken down
into successively thin layers removed from the surface, unless the fundamental
bond between the soil and the surface can be compromised. Very thin layers
can be even more difficult to remove than the original thicker layer [3]. For
household cleaning this implies that the most tenaciously held soil is that most
intimately in contact with the surface, and this should be the target of truly
efficacious cleaning. Upper layers of the soil are relatively easy, by this
analysis, to remove compared with the fundamental layer. In the beginning of
cleaning history, the soil was simply abraded off, which inevitably damaged the
unsoiled areas of the surface. In recent times, the discovery of more chemical,
rather than mechanical, means of removing soil has greatly improved this
situation.
A wellformulated modern cleaner avoids abrasion as a primary mechanism of
cleaning and depends on more chemical than mechanical means. This is
generally accomplished in three steps: wetting, penetration, and removal. In
some ways, water may be looked upon as the primary cleaning element. Given
enough time, enough volume, and the right temperature, water is capable of
cleaning almost any soil/surface combination. However, the times involved can
be of the order of days, or the temperatures required close to boiling.
Cleaning solutions can be viewed as water with ingredients added to speed the
cleaning action or lower the temperature at which effective waterbased
cleaning takes place. Surfactants, of course, lower the surface tension of water,
thereby increasing the wetting of the soil by the cleaning solution. This is

Page 466
especially important for hydrophobic soils like grease. Solvents help the
cleaning solution to penetrate into the soil, softening it, sometimes even partially
dissolving the soil. Other active ingredients, such as acids, bleaches, and
alkaline compounds, can then more effectively react with the soil to change its
composition to make it more liquid, less polymerized, or less tenacious, for
example, and easier for the cleaning solution to remove. The surfactant then
helps to emulsify or otherwise lift the soil from the surface into the cleaning
solution. The mechanical action of wiping or scrubbing also aids the wetting,
penetration, and lifting of the soil by spreading, roughening, and breaking up
the soil. The cleaning solution is then removed, leaving a clean surface. The
best cleaners are effective at performing these tasks on even the most
fundamental layers of soil, restoring the surface to its original state.
A cleaning task for the consumer is usually one or two soils on any one of the
surfaces. Also, besides removing the soil, one must consider the safety of the
chemical strategy used to remove the soil on the underlying surface. This has
grown to become a more desired benefit in recent time [4]. Acid, as one
example, may help to remove soap scum, but this would not be a good
approach on a marble sink. Germ killing is also considered part of the
household surface cleaning task by many consumers, especially on bathroom
or food preparation surfaces [4]. To meet some of these target concerns, the
chemistry of the cleaner may be focused, but this can also limit the useful scope
of the product.
As seen in this discussion, the evolution of cleaners develops from simple soap
powders into liquid formulations to more specialized products. “Allpurpose
cleaners” are the backbone of this development. Along with specialized
formulas for specific cleaning problems, it is also seen that in some cases these
products are augmented by specialized packaging. Generally, the packaging
contributes more to the convenience of the product than the efficacy.
The trend in the United States and Europe most recently has been to more
“niche” products, such as toilet bowl cleaners and dedicated bathroom
cleaners. These types of products tend to show the greatest growth and have
maintained this high growth position for about 10 years [5,6]. This is shown in
Fig. 1 for North America. However, liquid “allpurpose” cleaners continue to
sell well. In Fig. 1, spray allpurpose cleaners and glass and surface cleaners
are probably grouped with liquid cleaners. These spray versions can
sometimes be considered niche products themselves and can account for as
much as 33% of the allpurpose cleaner segment. In Europe also, special
purpose cleaners, such as bathroom cleaners, are the largest growth segment
[7].
The most recent trend in allpurpose cleaners per se is the entry of “ultras,”
formulas that give double or triple the cleaning strength of the formulas already
common in the marketplace. This has already happened in Europe and North
America. These products use less packaging, occupy less storage space, and

Page 467
Fig. 1
Sales amounts for household cleaners in North America. (From Ref. 1.)
give consumers more flexibility in the dilution of the product. However, they
also require more careful measuring on the part of the consumer if they are to
reap the full value of the product. As seen in the section on allpurpose
cleaners, the range of concentration of active ingredients in recent allpurpose
cleaner patents is sufficient for these products to be formulated either as normal
strength products or as ultras.
Nevertheless, allpurpose cleaners are generally the beginning points for entry
and for specialization in a given market. The niche products are the fastest
growing part of household cleaning in mature markets, and yet they are starting
to appear in developing markets as well. Strangely, allpurpose cleaners
(APCs) can be considered specialty products themselves, growing out of the
real allpurpose cleaner of the past, a heavyduty cleaning powder. This can
still be true in less mature cleaning markets.
II. AllPurpose Cleaners
A. Historical Background
1. Powder Cleaners
The evolution of household cleaners begins with allpurpose cleaners.
Specialization to handle the multiple problems of household cleaning arose
relatively recently. Before the 1930s [8], consumers had only soap powders
with which to do all their household cleaning, which included not only kitchen
and bath surfaces but also laundry and dishes. Glass windows were nearly the
only sur

Page 468
face that could not be effectively cleaned with this product. This multiple use of
a basic cleaning product continues in many developing regions of the world.
In the 1920s, powdered products began to appear in the U.S. market that
were formulated especially for general household cleaning. These were
generally highly built, very alkaline formulations designed to dissolve in warm or
hot water for such tasks as floor mopping, grease removal, and bathroom
cleaning. “Built” formulas refer, of course, to the use of compounds like
phosphates, silicates, and carbonates, which mitigate the effects of hard water
and also buffer the system to high pH levels. At first they still used soap but
later began to use the modern anionic surfactants (such as alkyl
benzenesulfonates). A typical example of this kind of formula is given in Table
1.
These cleaners were more effective than their predecessors, but they also
required a large amount of rinsing. The builders that boosted cleaning efficacy
also increased the amount of residue left behind when cleaning solution dried
on a surface. Depending on water temperature and hardness, these cleaners
could also be difficult to dissolve completely in a bucket of water. Being some
what hygroscopic powders, they also tended to cake and solidify once the
container, usually a cardboard box, was opened.
2. Cleansers
As far back as the 1880s, a product was sold as a pressed cake of soap with
abrasive [9]. However, modern powder cleansers also started to appear at
roughly the same time as powder allpurpose cleaners (approximately 1930–
1935). The addition of abrasives to the basic cleaning product helped use
mechanical as well as chemical energy to do cleaning, but obviously made
these products unsuitable for general use. In this sense, cleansers can be
thought of as some of the first “specialty” cleaners because the presence of
abrasive made them appropriate for very tough cleaning jobs but also limited
their usefulness because they could scratch softer surfaces. This tends to be the
continuing theme of specialty cleaners: the formulation delivers more directed
power at a par
TABLE 1 Powdered AllPurpose Cleaner Formulas
Amount
Ingredient Examples (wt/wt %)
Anionic surfactant Soap, alkylbenzene sulfonate 1–10

(usually one only)
Builder Phosphates, carbonates, silicates 50–60

(usually a mixture)
Sodium sulfate Processing and delivery aid 30–50
Perfume, color, others 0.5–1.0

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TABLE 2 Powdered Cleanser Formulas
Amount
Anionic surfactant Soap, alkylbenzene sulfonate (usually 1–5

one only)
Builder Phosphates, carbonates, silicates 5–30

(usually a mixture)
Abrasive Silica, feldspar, calcite 60–90
Disinfectant Usually hypochlorite generating 0–2

compound (i.e., trichlorocyanuric
acid)
Perfume, color, 0.25–0.5
others
ticular cleaning problem and then disqualifies itself from other tasks because of
this adaptation. A typical cleanser formula is shown in Table 2.
Both powder allpurpose cleaner and powder cleansers are in the U.S. market
still and maintain large shares of the market in developing areas of the world.
Powder cleansers are still a major part of the abrasive cleaning subcategory,
but powder allpurpose cleaners in the United States are represented only by
one major brand (Spic and Span).
The formulas have had to react to modern pressures, the largest of which was
the limitations and bans of phosphates. These builders are usually not used or
are used in very small quantities in most household cleaners outside of
automatic dishwashing detergents. Usually carbonates, bicarbonates, and
silicates are used along with more modern ingredients, such as citrates and
polyacrylates. A small amount of nonionic surfactants may also be used,
although alkyl benzene sulfonates now dominate as the surfactant of choice.
Hydrotropes, such as sodium cumene sulfonate and sodium xylene sulfonate,
may also be added to aid the dissolution and cleaning of the main surfactant. In
these choices, household surface cleaner formulation has mirrored the
developments in fabric care.
Cleansers have also undergone some formulation changes that are specific to
their group. One major change was the addition of bleach to major cleanser
brands in the 1950s. Cleaners had been used in the past to “sand out” stains,
with some degree of surface damage. With the introduction of such ingredients
as the isocyanurates (like trichlorocyanuric acid, TCCA), usually in the range
of 0.5% available chlorine, stains could be removed as a result of hypochlorite
bleaching rather than muscle. This addition also opens the possibility of
disinfectant claims for the product. However, this addition also brings with it
more demands on the formulator because the formula is harder to stabilize.
Such compounds as TCCA decompose with water to form hypochlorite
bleach. This

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is good for the usual use conditions but confers water sensitivity on the formula.
Usually small amounts (<5%) of waterabsorbing compounds are added to
prevent the premature activation of the bleach. However, two factors work
against the formulator. The normal packaging of cleansers is cardboard
cylinders that are not able to be resealed tightly, and the product is usually
stored under a sink. Under these conditions, prolonged storage of the product
usually results in a loss of bleaching ability.
The largest recent change in cleansers has come in abrasives. These have
generally become softer as time goes on, going from sand originally to using
calcium carbonate (calcite) now in the major brands. This constitutes a change
on the Moh's hardness scale from about 7 to 3 [10]. This is a reaction to
changing times: many household surfaces are now plastics of various kinds and
are easily scratched by silica. For instance, where glazed ceramics in the
bathroom could be scrubbed for years without seeing signs of wear, today's
methyl methacrylate shower enclosures would show damage after a single
vigorous use of a silica cleanser. The major exception to this trend is the
increasing use of solid polymer countertop, such as Corian, which encourages
the use of strong abrasives to rub out nicks and stains in the surface.
B. Cream Cleansers
Both cleansers and allpurpose cleaners are now also available in liquid forms,
which were the next stage of their evolution. The liquid form has two main
advantages. Liquids can be formulated in a concentrated form that can be
diluted by the consumer before use to the desired strength. This dilution
operation is easier for the consumer because the liquid form mixes easier and
dissolves better than the powder form that preceded it. The liquids can also be
used straight from the container on heavily soiled areas; the powder cleaners
had to be made into a paste for effective use.
From the formulator's point of view, there is a mixed bag of advantages and
disadvantages. Water is an even less expensive diluent than the sodium sulfate
or abrasives that were used in powder forms. However, because all the
ingredients are dissolved or dispersed, this makes possible more interactions
between the ingredients than in a powder. Fortunately, the liquid form
broadens the choice of surfactant because it need not be available in powder
form.
Liquid cleaners with suspended abrasives—cream cleansers—first started to
appear in the United States and Europe in the 1980s. This chapter does not go
into detail on the formulation of these products because although they are fluid
household surface cleaners, they should be properly considered suspensions,
not true liquid formulas. Their arrival on the market so recently is a result of the
difficulty of producing stable suspensions of abrasive particles; the
advancement

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of polymer science and clay technology during the last 30 years is a large part
of the successful formulation of this product.
Unlike their parent product, powder cleansers, the cream cleansers almost
always use the gentler calcite abrasive. This, combined with their liquid form,
helps to convey the image of less harsh cleaning to the consumer. This is
especially important to consumers who have softer, plastic surfaces in their
bathrooms, such as fiberglass (polymethyl methacrylate) shower enclosures,
which are much more easily marred than the traditional vitreous materials [11].
The patent art for this kind of cleaner begins in the mid1960s [12–14], but
there continue to be abundant patents written up to the present time. The main
point of most art is the stable suspension of the abrasive particles, and this is
achieved largely by raising the viscosity of the system. Imanura [15] uses
crosslinked polyacrylic acid as an aid to suspending the abrasive. Another
patent uses styrene/polysaccharides copolymers to thicken the formula [16].
On the other hand, Brierly and Scott's patent [17] gives an example of the use
of clays to thicken the formula, their aim being the stabilization of the formula
during high shear processing steps. Alternatively, the same inventors also give a
method for stabilizing the cleanser at high shear using monoalkylolamides [18].
Other recent art uses colloidal alumina associated with a surfactant to suspend
the abrasive [19,20]. Another approach is to use stearate soap to thicken a
formula in which the aluminum oxide is used as the abrasive [21]. A somewhat
novel approach by Straw et al. [22] uses neither of the usual approaches, but
instead generates a liquid crystal phase to suspend the abrasive. In all cases the
viscosity of the product is quite high, of the order of 500–5000 cP.
The most challenging formulations also contain hypochlorite bleach as well as
trying to suspend an abrasive. Because many suspending or thickening agents
are sensitive to oxidation, it becomes difficult to assemble a product lacking
syneresis. For cream cleansers, the most successful approach for bleach
containing formulas seems to be alumina/surfactant thickening systems [23,24].
The alumina particle size is very small, and the calcium carbonate is used as the
abrasive.
Sometimes the abrasive is given as an optional ingredient in an otherwise
completely liquid cleaning formula. In one example of this type, the abrasive is
combined into a terpene/limonene solventbased cleaner while remaining stable
[25].
A generalized formula for liquid cleaners is seen in Table 3. The evolution of
cleansers more or less stops at this point, with only recent patent art on using
“soluble abrasive” as the next step [26,27]. This is probably intended to defeat
the largest consumer complaint about cleansers, either powder or liquid: the
difficulty of completely rinsing away the abrasive after use. Cream cleansers
can be even more difficult to rinse away because of the agents used to keep
the

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TABLE 3 Cream Cleanser Formulas
Amount
Anionic surfactant Soap (stearate), alkylbenzene sulfonate 1–15
Nonionic surfactant Ethoxylated alcohols, amine oxides 0–10
Builder Phosphates, carbonates, silicates (usually 1–20

mixture)
Solvent Alcohol, glycol ether, limonene 0–7
Thickening agent Polyacrylate polymer, clay, alumina 0–10
Abrasive Usually calcite (CaCO3) 10–55
Bleach Usually hypochlorite 0–1
Hydrotrope Sodium cumene sulfonate, sodium xylene 0–5

sulfonate
Perfume, color, others 0–1
Water 40–80
abrasive suspended, such as clays. Except for this, the new competitors in this
area, such as thickened bleach cleaners, are being formulated without abrasive
but in the same realm of viscosity.
C. Liquid AllPurpose Cleaners
1. Historical Background
Simple allpurpose cleaners were introduced in liquid form starting in the 1930s.
Liquid allpurpose cleaners were for many years differentiated mainly by the
specific “active” ingredient that they contained. The simplest liquid cleaner was
ammonia with some added soap, which has been used for over 100 years. This
is an effective grease cleaner but is very unpleasant and harsh to use. Simple
household bleach solutions date back to the early 1900s [28]. This is an effective
stain remover but not good for tough oily soils. Liquid disinfectant solutions go
back to the 1870s [29], but these were targeted more to the elimination of germs
than to soil removal. The closest products to modern formulations begin with
pine oil formulas, dating back to 1929 [30]. These gave good grease cleaning
with a more pleasant (and safer) odor. However, there are consumers who
dislike pine odor and would prefer a different cleaner. Modern, nonpine formulas
were introduced between 1955 and 1965 in the United States.
Liquid allpurpose cleaners at that time still incorporated many of the
characteristics of their dry predecessors. They still used the popular anionic
surfactants, such as alkyl benzene sulfonate, and builders with high alkalinity to
achieve their goals. However, they had three important differences. First, liq

Page 473
uids dissolve (or disperse) more quickly than powders. This means the cleaning
solution can be prepared by the consumer quickly at ambient water
temperatures. Second, they are not as limited by their solubility. Higher
amounts can be added to the cleaning solution without the precipitation that
could be encountered with the older powder cleaners. Last, they are neater to
dispense and store.
However, these advantages are not given without some drawbacks as well.
Although they might have had a weakness on greasy soil, powder allpurpose
cleaners were not particularly deficient in cleaning; they were deficient in
convenience. In general, this tends to be the greatest component in the
evolution of household cleaners. A major change in form or formulation is not
motivated by claims of superior cleaning; these claims tend to be made among
cleaners of the same form. The major motivation seems to be increasing
convenience for the consumers while maintaining cleaning efficacy. This may be
achieved by more convenient dispensing or shortening the number of steps in
the cleaning process. It may be the transfer from muscular effort on the part of
the consumer to chemical energy supplied by the cleaner.
Part of the high efficacy of powder detergents was their high concentration of
builder salts. To formulate the same level of builders into liquid detergents
required even higher levels of surfactant. This usually results in higher foaming.
Although high foam may be preferred in such applications as shampoos and
dishwashing detergents, such a sustained foam is undesirable in household
cleaning. Many surfaces that are washed with allpurpose cleaners are large
and horizontal, such as floors and countertops. If a cleaner has a slowly
collapsing foam, the consumer must laboriously rinse the surface. Even in areas
where rinsing is relatively easy, such as a bath or shower enclosure, the extra
effort and time spent rinsing a highfoaming product is undesirable to a
consumer. The immediate “flash” foam produced when the cleaner is first used
serves as a signal of its efficacy. Once this message is communicated, the foam
should collapse to give easier rinsing.
Continuing to use the high levels of builders used in powders would also have
meant continuing another rinsing problem; residue if the cleaning solution is left
to dry on surfaces. A consumer does not consider a surface clean unless it
shines. Residue from the cleaner left on the surface, even if all the soil has been
removed, diminishes a consumer's evaluation of the cleanliness of the surface.
Residues from crystalline compounds, such as builder salts, tends to dull the
native shine of a smooth surface. The degree of shine left on the surface is an
important indicator to the consumer of the degree of cleanliness of the surface.
In an effort to counteract the foaming and residue effects, formulators begin
decreasing builders, using solvents, and exerting more effort in finding
surfactant synergies.

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2. Solvents
Solvents became useful when the product form changed to liquids. Their main
role is to penetrate and soften grease to facilitate its removal by the surfactant.
Their fluid form made them attractive to use in liquid formulations, although the
solubility of good greasecutting solvents in water is very low. Some examples
of these are pine oil and dlimonene. These are still very popular today as
greasecutting solvents, not only for their efficacy, but more recently because
of their “natural” origins. This reflects on the current marketing ploy of playing
on some consumers' opinion that vegetableextracted chemicals are intrinsically
safer or more ecologically sound than petroleumbased chemicals. Although
the first pine cleaners appeared in the early part of the century, formulations
built around pine oil still occur in the patent art, most recently as an alternative
to more volatile organic solvents [31].
Much more common and more easily formulated because of their higher water
solubility are the glycol ether solvents. This approach dates back as far as the
early 1970s [32,33]. Earlier formulations made use of the simpler ethylene
glycol monoalkyl ethers (Cellosolves), but this use has been largely
discontinued because of health hazards [34]. The diethylene glycol monobutyl
ether is most favored, although the use of the propylene glycols is increasing.
As the chain length rises the health hazards decrease, but the solubility in water
also decreases. This increases the difficulty of formulating stable products.
However, stable products are made, as evidenced by recent patent art that
touts the use of tripropylene glycols and their ethers for concentrated floor
cleaning products [35]. In this case, the glycol ether is claimed not only as part
of the cleaning system but also as a way of enhancing the shine on a vinyl floor
surface. In Fig. 2, a comparison is made of the streaking and filming
characteristics based on solvent changes alone. There is also mention in other
art of longer chain lengths in the ether portion of the glycol ethers being used as
well [36].
Alcohols are sometimes used in dilutable allpurpose cleaners, but they are
usually tertiary or benzyl alcohols [37,38]. The greasecutting ability of the
lower alcohols is inferior to these and to the glycol ethers. Lower carbon
alcohols find their main use in glass and lightduty cleaners.
The aim of modern formulation is to minimize builder concentration to alleviate
the problems in rinsing and residue cited earlier. Part of this is done with the
solvent choice and the other half with the surfactant synergies.
3. Surfactant Innovations
One important area is actually surfactants working in negative synergy to give
quickbreaking foams even with high total surfactant concentrations. This is
most commonly done by including a small amount of soap in the formulation.
Interest has also been shown in the counterion, a potassium soap combined
with paraffin solvent, claimed to give a much reduced tendency for stable foam
[39].

Page 475
Fig. 2
Streaking/filming as a function of glycol ether.
(From Ref. 28.)
This brings up the point that the choice of counterion is also important for
efficacy of the main anionic surfactants used in the cleaning formula. It has been
known for some time now that divalent metal salts of alkyl benzene sulfonate,
paraffin sulfonates, and the like are better grease cleaners than the analogous
sodium salts [40]. These are more difficult to use because of their lower water
stability, but they can be formulated with some of the more effective
greasecutting solvents [41,42]. It has also been claimed that if ammonium salts
of the anionic surfactants are used less residue is left on the surface [43].
Many formulations continue to depend mainly on anionic surfactants for
detergency. However, there is a growing trend toward the use of other
surfactants beyond the workhorse anionics that have served for so long [44].
There are, for example, allpurpose cleaners that depend more on nonionic
surfactants [45]. Nonionics are less sensitive to water hardness, can be
synthesized to target HLBs, and have lower foaming. Much of the pioneering
work in this area was and is done by the primary suppliers of the materials,
such as the work of Shell on primary alcohol ethoxylates [46], and the more
recent work by Henkel and

Page 476
Kao on alkylpolyglycosides [47–49]. The sugarderived polyglucosides [50]
show good surfactant qualities and are becoming favored because of the
“environmental” claims that can be made for vegetable rather than petroleum
feedstock material. They also show mildness to the consumer's skin. On the
other hand, ethoxylated alkyl phenols are falling out of favor because of their
low biodegradability [51]. Some formulators claim that is possible to achieve
effective cleaning with nonionics while completely excluding anionic materials
[52–55]. It is now claimed that some shortchain nonionics can give superior
cleaning [56]. The claim in all nonionic formulas is that they are less sensitive to
water hardness. There are also cases in which longer chain, block copolymer
nonionics are used. In one particular case [57], the nonionic is used not only
for its cleaning but for its residual spotting/filming characteristics. The general
practice, however, is to use a combination of both anionic and nonionic
components [58]. In part, this may be because nonionic surfactants have a
lower tendency to foam, and foam is expected by consumers as a sign that the
“active” is working. Therefore, including a certain amount of anionic surfactant
helps to signal the consumer that the detergent is present [59].
As noted earlier, greasecutting solvent is included in nearly every allpurpose
cleaning formula. These solvents are generally kept to low levels because of
volatility and general safety considerations. It is interesting to note, therefore,
that recent claims are being made for surfactants also to have solventlike
cleaning functions [60].
A new subclass of formulations in this area is the microemulsion. These special
phases were used in such areas as oil recovery as early as the 1970s and have
been exploited more recently in organic synthesis and analytical extractions.
However, microemulsions have come much more slowly to the household
cleaning area. Much has been written recently on microemulsions [61,62], their
advantages over regular emulsions being increased stability, spontaneous
formation, and oilsolubilizing potential. They are also transparent, giving the
esthetics of a true solution. There are examples in the literature that are
formulas intended for industrial cleaning of computer components or metal
parts [63,64]. In these formulas, the highly hydrophobic solvent (usually a
chlorinated hydrocarbon) is delivered to the surface in an aqueous media. The
clear advantage of the microemulsion in these cases is the ability to stabilize the
solvent in a mixture with other hydrophilic components.
A similar approach can be taken to deliver high amounts of a hydrophobic but
more consumerfriendly, greasecutting solvent, such as pine oil or dlimonene.
Examples may be found that use these insoluble grease removal solvents as the
essential oily material in a microemulsion, sometimes with glycol ether solvents
added as the cosurfactant [65,66]. All microemulsions formulated for
household cleaning so far have far more hydrophilic components than hydro

Page 477
phobic, opposite to the industrial examples. Surfactant types vary, one of these
examples using an anionic/nonionic mixture and the other all nonionic. Still
another example uses an anionic/nonionic surfactant mix with glycol ether
cosurfactant but uses the perfume as the oily material essential to form the
microemulsion [67,68].
4. Added Benefits
The addition of any added benefits tends to narrow the scope of a cleaner, and
so there are a few general types included in allpurpose cleaners. The most
popular is the dimension of disinfection or antimicrobial action. An excellent
overview of disinfectants in general is given in the Encyclopedia of Chemical
Technology [69]. Biguanides, alcohols, aldehydes, and phenols, as well as
quaternary ammonium compounds (“quats”) and oxidizing agents, are used
[70]. The most commonly used of these are pine oil (included in the alcohol
group), quats, and alkali metal hypochlorites (rather than oxygen bleaches,
which are weaker disinfectants). Sometimes they can be combined, as in the
quats and alcohols [71,72]. Pine oil gives the most freedom of formulation,
bleach the least.
The main restriction to using quats is, of course, that association of the quats in
solution with most anionic surfactants inactivates the disinfecting action of this
cationic compound. The action of quats is well known to be boosted by the
addition of common chelating agents [73,74], the sodium salts of ethylene
diamine tetraacetic acid (EDTA) the most common used. Pine oil can have a
narrow spectrum of antimicrobial effectiveness that can be broadened by
adjunct compounds, such as quats or some organic acids [75].
The broadest spectrum disinfection, at a low price, is delivered by bleach,
which is often a compensating factor for the difficulty of formulation.
Formulation with bleach usually prevents the use of most common nonionics,
paraffin sulfonate, alkylbenzene sulfonates, betaines, longchain unsaturated
quats, and so on. The surfactants most often used with hypochlorite bleach are
amine oxides, soaps, and sodium alkyl sulfates. It has been known for some
time that amine oxides interact with anionic surfactants at certain ionic strengths
to generate liquids with dynamic viscosities from 10 to about 5000 cP [76–
79]. In this way, bleachcontaining formulas can be thickened by the use of the
surfactants alone [80]. Therefore, bleach allpurpose cleaners can have three
benefits in addition to the primary cleaning: removal of oxidizable stains,
disinfection, and increased cling or residence on vertical surfaces.
Most bleach cleaners, however, are simple, waterthin solutions. The most
common formulations are a simple combination of hypochlorite bleach, sodium
hydroxide (to achieve a pH of 10–12), amine oxide surfactant, and a low
quantity of perfume. Despite their simplicity, however, these types of products
are very effective stain removers and disinfectants.

Page 478
There is an interest in nonhypochlorite disinfection, as evidenced by patent art
for institutional use. Examples can be focund that use peroxyacids to achieve
antimicrobial effects [81]. The advantage of these formulas would be lack of
the odor and corrosion that can be encountered in hypochlorite formulas.
Besides disinfection, there are few other added benefits of major market
importance. The next most important is the special class in which a polymer
film is left behind on the surface. The most common example of this are really
not allpurpose cleaners, but are the “mop and shine” products for floor
cleaning. This subset is intended solely for floor cleaning and leave behind a
film intended to mimic the shine and soil resistance of waxing a floor. Unlike
waxes, however, these polymer films do not need to be buffed to make them
glossy [82]. The only drawback to this kind of formula is the possible buildup
of polymer on the surface. These polymer films tend to be slightly colored, and
so repeated layers can yellow the surface. The aim of inventions in the field is
therefore to give polymers that deposit on the surface readily in formulations
that avoid buildup [83].
This concept of polymer adsorption for greater shine and soil resistance has
since been extended to other household surfaces, going from specialized floor
products back to allpurpose cleaners. These generally use nonionic polymers,
such as polyethylene glycol, polyvinyl pyrrolidone, or other film formers
[84,85]. One very interesting invention states that by the use of a
polyalkoxylated alkylolalkane and vegetable oil surfactant a formula may be
made that shines shiny surfaces but imparts no gloss to matte surfaces [86].
Another recent interesting invention is the formulation of an insect repellent into
an allpurpose cleaner [87–89]. The key here is that the active ingredient is not
an insecticide but simply a repellent that makes it possible to leave it behind
routinely in the cleaning process without concerns about repeated human
contact.
5. Formulation Technology
Table 4 gives ranges for common ingredients for allpurpose cleaner
formulation. Although it is not explicit from the previous discussion, “regular”
allpurpose cleaners are intended to be dilutable. The consumer may use them
full strength from the bottle for cleaning a very heavily soiled small area, or may
dilute them in the range of 1:32 to 1:128, with a dilution rate of 1 part cleaner
to 64 parts solution being most common. Recent allpurpose cleaners launched
in North America and Europe are operating at the top of the dilution range;
these are the ultra or concentrated products, similar in concept to the ultra
laundry detergents. There are also some patents appearing for household
surface cleaners that are touting the concentration of the formula [90,91]. If a
such concentrated formula can be made stable, the manufacturer gains the
advantages of less packaging, smaller shipping weights, and less storage space.
The con

Page 479
TABLE 4 Liquid Dilutable AllPurpose Cleaner Formulas
Amount
Anionic surfactant Alkylbenzene sulfonate, paraffin sulfonate, 0–35

ethoxylated alcohol sulfate, soap
Nonionic surfactant Ethoxylated alcohol, amine oxide, alkanol amide 1–35

fatty acid
Hydrotropes Sodium cumene sulfonate, sodium xylene 0–10

sulfonate
Builder or chelator Carbonates (more rarely phosphates), silicates, 0–10

citrates, EDTA sats, polyacrylates
pH adjustment Ammonia, sodium hydroxide, magnesium 0–10

hydroxide, alkanolamines
Solvent Alcohol (pine oil, benzyl alcohol, or lower carbon 0.5–50

number alcohols) glycol ether (Carbitol, Dowanol,
others), dlimonene
Disinfectant Hypochlorite bleach, pine oil, low carbon number 0–15

alcohols quaternary ammonium compounds
“Shine” polymers Polyacrylate, polyethylene glycol, polyvinyl 0–25

pyrrolidone
Perfume, color, 0.1–3
others
Water Q.S.
sumer gains advantages in more easily stored containers and less packaging to
recycle while the absolute cleaning potential in its delivered form increases. These
types of concentrated allpurpose cleaners should be considered as existing
toward the top of the surfactant concentrations listed in Table 4.
With higher concentrations of surfactant, the formulas also tend to become
thicker. In most cases, the increase in viscosity is minor, but in some cases it can
become significant. If the product is meant to be dilutable by a consumer, then
the perception of pouring and dispersability of the product cannot be adversely
affected by the viscosity. The ways to decrease the viscosity in these cases is to
decrease the surfactant association that is responsible. Many of the commonly
used solvents can affect the solubility of the surfactant and therefore redistribute
the relative amount of monomer versus associated forms. Changes as a result of
ionic strength can have the same effect, and so the addition of simple salts to the
formula can also remedy the problem. Of course, if it is desirable to thicken the
product, this can be done most easily through

Page 480
the addition of various polymers, such as polyacrylates, polethyleneoxides,
cellulose gums, and polyglycols, depending on which is most compatible with
the surfactant system.
The pH of most allpurpose cleaners is between 8 and 12. Generally this is the
best range for grease cleaning in that the alkalinity can (to a small degree)
saponify some portions of a grease, thereby assisting the surfactant/solvent
system in removing soil. However, high pH can also damage some sensitive
surfaces, such as aluminum, as well as being irritating to skin. In the interest of
giving consumers more advantages, formulators strive to work at pH values as
close to neutral as possible to reduce these negative effects. That means that
more care has to go into optimizing the surfactant system and sometimes more
reliance on greasecutting solvents. For instance, pine cleaners tend to be
acidic, but the pine oil, more than the pH, contributes to the grease cleaning.
This approach also has its dangers, because some surfaces, such as paint and
wallcoverings, can be sensitive to solvents.
Fragrance is a very important part of household cleaners, often overlooked in
the technological drive for formula performance. However, fragrance can often
be the driving attribute in a consumer's evaluation of a product. Fragrance can
sometimes be difficult to incorporate stably into a product because of its low
solubility (oily nature) and chemical reactivity (presence of aldehydes, esters,
ketones, and so on). One way of easing the addition of a perfume oil into a
formula is to premix the fragrance with either surfactant (a lower HLB
component) or with the solvent. Higher concentration formulas, rich in
surfactant, often have enough solubilization power to make the addition of the
fragrance less difficult than in more dilute products, such as glass cleaners.
As can be seen from the preceding discussion, allpurpose cleaners started
with the oldest surfactant, soap, and have progressed to more powerful
surfactants and then further developed sophisticated surfactant synergies. As
these developments are made, there is less and less reliance on the old
inorganic “builders” and more interest in solvents, particularly those with
greasecutting ability. Only concerns about human toxicity limit the choice of
solvent.
In the course of formulating the allpurpose cleaner, there may be a need for
other minor ingredients in addition to the main cleaners—the surfactant,
solvent, or builder. These ingredients include hydroptropes, hard water control,
and buffers. These ingredients do not include any added for special benefits,
such as shine enhancement, disinfection, or soil release.
When builders are used in a formula, they also fill the function of hard water
controls and buffering agents. However, the high electrolyte concentration
imparted by the use of these builders may make it necessary to use a
hydrotrope. (See Chap. 2.) In general, hydrotropes are organic compounds
that

Page 481
enhance the solubility of other species. In cleaning formulations they facilitate
the dissolution and continued solubility of the main detergent surfactant in a
liquid formula. Many times the solubility of the surfactant is limited by high salt
content or other factors. Examples are given in Table 4. As the use of inorganic
builders decreases over time, the use of the hydrotropes is also decreasing.
However, hypochlorite bleaches also increase the electrolyte concentration, as
can the inorganic thickeners in cream cleansers. In these cases, the use of a
hydrotrope may also be required.
When, as in many modern formulas, builders are excluded or limited to
decrease visible cleaner residue, other means are necessary to control water
hardness and buffer the formula. In some areas where the water hardness is
very high (above 250 ppm as CaCO3), even modern anionic surfactants can be
partially precipitated. Soap is very easily precipitated. The most common
remedy is to add one of the salts of EDTA (ethylenediaminetetraacetic acid) or
NTA (nitrilotriacetate) to chelate the water hardness ions and therefore
maintain the anionic surfactant efficacy. Of course, this problem does not occur
with nonionic or cationic surfactants.
The other problem when builders are eliminated is stabilizing the pH of the
formula. Many anionic surfactants can impart a slightly acid pH to the solution
when dissolved. If the aim of the formula is largely grease cleaning, this is most
efficiently done at basic pH. Therefore, the pH can be adjusted using common
bases, such as ammonia or sodium hydroxide. Ammonia is useful in that it is
volatile and therefore leaves no residue, but it also imparts a distinctive odor
that is not pleasing to some consumers. However, neither of these choices are
good buffering agents. If the pH of the formula is to be maintained in a lower
range (pH 8–9) or if the formula pH tends to drift over time, then alkaline
buffering agents, usually one of the alkanolamines, are used.
D. Test Methods
There are several key performance areas to test for allpurpose cleaners. As
may be deduced from the previous discussion, these are cleaning, ability to
foam, and residue/shine. Unfortunately, very few published standardized
methods exist in this area, especially residue/shine. Although foam height and
soil removal are easily quantitated, the impact of various amounts of residue
and its distribution on a surface are not. Most residue/shine tests are based on
the evaluation on scales from 1 to 10 by panels of observers of prepared
samples. Usually the method is described in a corresponding patent. A usual
general method is to apply the cleaning solution, either by wiping or by
pipetting, onto a clean glossy surface, usually of a dark color. Black ceramic
wall tile is convenient for this purpose. The solution is left to dry on the surface,
and a panel of observers rates their impression of residue on the resulting
pattern.

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1. Cleaning Tests
For cleaning tests, the methods for applying soil, simulating the cleaning
process, and judging the result are well estabilished [92,93]. What is not well
established is the precise identity of the soil used. For allpurpose cleaning, the
target soil usually investigated is “grease.” It is meant to replicate the soil left on
kitchen surfaces from normal household cooking practices. Of course, the type
of oil or fat used in cooking can vary widely around the world, from vegetable
oils and margarine to beef fat, lard, and butter. Even among the vegetable oils,
there can be differences between olive and corn oils, because of the
distribution of chain lengths and unsaturation. These factors affect how the
grease is changed by heating and exposure to the air in thin films [94].
In many cases, a pure grease soil is not used. Sometimes the soil is colored
with carbon black to make it more visible. However, this also has the effect of
introducing a solid particulate into the soil mix [95,96]. Other particulates have
also been introduced, such as humus, clay, ferrous oxide, soot, and filtered
vacuum cleaner dust [97,98]. However, the grease component of the soil
usually predominates. If the grease soil is liquid (such as vegetable oil), then it
can be sprayed on the surface neat. Mixtures of particulates with oils are also
spread on surfaces using paint rollers. However, liquid soils usually require
longer aging periods before they can be used. Soils can also be prepared by
dissolving solid greases (tallow) in various solvents (napthenic hydrocarbons,
chloroform, and others) and then spraying the solution or dispersion. The
solvent flashes off, leaving a solid grease layer (usually without particulate).
These soils need shorter aging times because their solid form makes them more
difficult to clean than oily soils. However, there are two concerns with this type
of procedure: (1) the proper protection of laboratory workers from these
hazardous solvents, and (2) the contamination of the greasy soil with any
residual solvent that might influence the cleaning process.
The soil is applied to typical kitchen surfaces, such as vinyl floor tile, sections
of Formica, ceramic tile, pieces of enamel, aluminum, stainless steel, and
painted wall sections. The local point of sale is the determinant of the choice of
surface, so knowledge of local materials of construction is necessary. It is
sometimes necessary to alter the surface to make the soil tenacious. This is
sometimes done with a light sanding of the surface to roughen it or with
chemical etching, such as strong acid or strong base treatments of susceptible
surfaces. It is preferred to alter the composition or aging of the soil to increase
tenacity, although surface roughening is sometimes considered accelerated
“aging” of a surface.
Once the soil has been aged, usually at ambient temperature, cleaning
experiments can be carried out. The usual apparatus for this testing is a
Gardner abrader (Fig. 3). This consists of a testing platform and a carrier for
holding cleaning utensils that is motor driven back and forth along the platform.
Clean

Page 483
Fig. 3
Gardner straight line abrader machine.
ing utensils fitted in the machine are also chosen according to local habits and
practices. They can be sponges, mohair, folded cloth, folded paper towel, or
scrub brushes. Small pieces of sponge wrapped around solid blocks are the
usual choice. The utensil holder is usually made to hold two separate sponges
so that the cleaners can be tested side by side. Often, variations in the
individual quality of a surface and its applied soil make it necessary to do direct
comparisons of cleaners on the identical item. Also, a standard amount of
weight is applied to the utensil holder to simulate the force a person employs in
the wiping process. This force is usually in the range of 200–500 g per sponge,
including the weight of the carrier and the loaded sponges.
In some cases, such as spray cleaners, the test product can be applied directly
to the surface and a wetted utensil used for cleaning, but for most general or
more concentrated allpurpose cleaners the solution is loaded onto the utensil.
The utensil is usually wetted so that it is wet but not dripping water. The
cleaning solution can be used neat or dilute depending on the intention of use. If
floor cleaning is simulated, the cleaner is diluted according to label instructions,
usually in the range of 1:64. If tough soil spot cleaning is simulated, then the
cleaner is used neat. It can be applied to the utensil in two ways. Either a
specified amount of cleaner is poured or pipetted onto the sponge, or the
utensil mounted in its holder is soaked in a shallow pool of the cleaner for a
specified time. The utensil is then fixed in the holder on the abrader.
The abrader is then set in motion, making reciprocal sweeps back and forth
over the soiled surface, which is fixed on the testing platform. Cleaning can be
done in two ways: a fixed number of strokes can be used, or the process
continued until one or both sides of the testing surface is completely clean. The
first method can be used to compare cleaners at different number of strokes to

Page 484
generate data on the “kinetics” of cleaning. The second method mimics the
practice of the consumer, which is to wipe until the surface is clean. In this
case, the number of strokes needed to give 100% cleaning is tallied for at least
one cleaner. The slower cleaner can then be continued until it is completely
clean and its higher number of strokes recorded or its amount of lesser soil
removal tallied when the superior side reaches 100%.
Soil removal can be judged by eye, but the more common methods use a
reflectometer. First, the “new” surface is measured before soiling. Most
conveniently this is done on a white surface. The surface is soiled, usually with
a colored soil. As mentioned before, the soil may be colored with carbon
black or other particulates giving a gray or brown appearance. It may also be
colored with oil soluble dyes. After soiling, another reflectometer reading is
made. The cleaning is done, and the surface is then usually rinsed to eliminate
cleaner residues or loosely held soil. Then the final “cleaned” measurement is
made. The percentage soil removal is calculated as
where: Rc = reflectance of the cleaned surface
Rs = reflectance of the soiled surface
Rn = reflectance of the surface before soiling
Another method of grease testing was shown by a consumer organization [99].
Although the choice of ingredients for the grease soil in this test is not the most
consumer relevant, depending on mineral oil and petroleum jelly rather than
household kitchen grease, the method by which the grease was removed is
interesting. In this test, the greasy soil was applied in a narrow strip
perpendicular to the travel of the sponges in the abrader apparatus. Clean
areas were on both sides of the soiled strip. In this way, these experimenters
measured not only the soil removal from the greasy area but also the tendency
of the cleaner to smear the soil onto previously clean areas, so that a cleaner
that performs poorly on soil redeposition or one that adsorbs the soil poorly
into the cleaning implement is judged inferior by this test.
Other, special soils may also be tested. A “sticky” kitchen soil has been cited
in the patent literature [100], consisting of vegetable shortening and allpurpose
flour. This soil was baked on.
For cleaners containing bleach, it is desirable to test the stain removal ability of
the cleaner. In this case, a tea stain on an enamel surface is usually done.
Enamel on steel plates are boiled in a concentrated tea solution. They are air
dried, rinsed with deionized water, and then repeated until the uniformity and
degree of staining desired is reached [101]. This soil is cleaned and evaluated
in the same manner as the grease soil.

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Although grease is the main soil target, followed by particulate soil, for all
purpose cleaners, they may also be tested against other nonkitchen problems,
such as soap scum. Soap scum testing is described in the section on bathroom
cleaners.
2. Foam Level Testing
Foam tests of allpurpose cleaners are done similarly to other fields. One of the
most common is the cylinder test. The cleaner may be placed, neat or diluted,
in a glass graduated cylinder. The cylinder is then inverted a specified number
of times, and the resulting foam height noted. This immediate reading is referred
to as “flash foam.” The cylinder then may sit undisturbed for various lengths of
time and the gradual collapse of the foam recorded in decreasing foam heights.
Another test is the RossMiles foam test [102]. In this method the solution is
dropped over a specified distance into a receiver. The foam produced by this
fall is measured immediately and after 5 minutes. Different foam esthetics are
preferred around the world, although generally it is preferable that the foam
collapses because this is perceived to decrease the effort of rinsing.
3. Surface Safety
Another area of investigation is surface safety. Households contain many
different surfaces that may be soiled. If a consumer uses these products as true
allpurpose cleaners, they are carried from room to room, encountering many
of these surfaces. It is wise to test the effect of a cleaning formulation on
various items, depending on local materials. This is done most simply by
immersing a solid block of material in the cleaner or by allowing a pool of the
cleaner to contact a representative surface. The length of time for the test is left
to the experimenter's discretion. The compatibility of a cleaner with a variety of
surfaces is part of the designation of an allpurpose cleaner. Evaluating surface
safety becomes even more important when aggressive substances, such as
strong solvents or bleach, are included in the formula. Inclusion of these types
of ingredients tends to limit the formulation's use, relegating it to the category of
a specialty cleaner in some consumer's minds. This is especially true of bleach
cleaners, whose aggressiveness to many colored surfaces is well known.
4. Disinfectancy
Disinfectancy tests are usually regulated by the local government. For example,
in the United States, the rules and procedures for disinfectancy are set out by
the Environmental Protection Agency, and in France they are given by
AFNOR (Association Francaise de Normalisation). The usual test for
disinfectancy, for both disinfectant compounds and cleaning formulations, is the
use dilution test [103]. They usually consist of challenging a use dilution of the
cleaner with specified microorganisms, followed by incubation. The
disinfectancy of the

Page 486
formula is determined by the number of surviving cultures at the end of the
incubation period. The usual score for successful disinfection is lack of
subsequent growth in 59 of 60 tubes. U.S. regulations specify three different
levels of disinfection claim, as well as a sanitization claim, depending on the
organism(s) used in the test [104].
5. Miscellaneous Testing
If the product is not a disinfectant formula, it may be advisable to conduct
adequacy of preservation tests. In these tests, the formula, as made for sale, is
challenged with various microorganisms. This test sample is incubated for a
time, and the amount of growth measured. Aging tests for the shelf life of the
formula are also advisable, usually run for up to 12–18 weeks at both room
temperatures and elevated temperatures.
Other tests may be required by various governments. Eye irritancy warnings on
the product, for example, may be required depending on the outcome of
standard irritancy tests. There are also many regulations or labeling procedures
regarding the biodegradability of cleaning formulas and their ingredients. In
these ecologically aware days, many primary suppliers of surfactants and other
active ingredients perform their own biodegradation tests. An excellent
overview of the field of biodegradability and various testing methods is given in
this surfactant series [105]. It is wise for the formulator to inquire about these
tests, especially if the product is intended for use in Western Europe or other
ecologically conscious areas.
III. Spray AllPurpose Cleaners
A. Historical Background
Spray allpurpose cleaners began to emerge on the U.S. markets in the 1950s.
In the beginning they were pump sprayers, but the late 1970s saw the
development of the more ergonomic trigger sprayers. These are now coupled
with bottles shaped to give convenient gripping (Fig. 4). These formulations
extend the convenience of the liquid form by marrying it to a very convenient
dispensing container. The trigger sprayers deliver more product to the surface
than the older pump forms and with reduced hand fatigue [106]. The formula in
the spray bottle is generally in readytouse concentration, as opposed to the
formula in the regular bottle, which is meant to be diluted by the consumer.
These spray cleaners are used predominantly for spot cleaning and special
needs rather than for larger area cleaning (i.e., floors). They are also generally
used for lighter soil loads (fingerprints or thin films of oil) than for tougher soils
(thick layers of aged grease on range hoods), which are reserved for more
concentrated products, the regular dilutable cleaners. This marriage of cleaning
for

Page 487
Fig. 4
Modern spray trigger packaging: (a) allpurpose spray cleaners; (b) glass
and glass and surface cleaners.
mula to specific package form, tailoring the action of the cleaner to the way it is
dispensed, is an important trend in household surface cleaning.
Allpurpose cleaners, as powders, were dispensed from boxes or bags. This
could be a messy operation, and spills are difficult to clean. Liquid allpurpose
cleaners are dispensed from bottles, usually equipped with screwoff caps.
Therefore, these were not only less messy to dispense, but they were easier to

Page 488
close tightly to eliminate spills. The caps could also be used to measure the
product so that the appropriate amount of cleaner could be specified by the
formulator without the need of a measuring device separate from the container.
The more convenient formula is accompanied by the more convenient
dispensing system.
Spray cleaners are also of this type. The formula is already at the concentration
appropriate for use, and the dispenser easily spreads a small amount of
cleaner. Aerosol packaging has played a smaller role in this area than in others,
such as furniture polishes and hair care. It has survived most often when a thick
foam meant to stick to vertical surfaces is needed, as in oven cleaning or
bathtub enclosures. In the future it can be expected that as packaging
innovation continues, specialized formulas will be matched to them to create
more convenient and targeted cleaning systems for consumers to use.
In theory, almost any dilutable cleaning formula—pine, disinfectant, grease
cleaning, bleach, and so on—can be “watered down” to give an effective spray
cleaner. The trigger sprayers used with these formulas tend to exaggerate the
foaming qualities of the cleaner, so the surfactant levels are generally at the
lower end of ranges given in Table 4. (Even at these concentrations, a spray
cleaner is much more concentrated than the solutions generally used for floor
cleaning, for which the cleaner has been diluted 30–60 times.) Also, these
convenience cleaners are generally used without rinsing, so that minimum
ingredients must be used to minimize residue. Any crystalline ingredients must
also be minimized to reduce buildup on the trigger itself when residual cleaner
dries on the nozzle.
These are general restrictions on spray cleaners. About the same time that all
purpose cleaners were developing into sprays, formulas were also becoming
less all purpose. One of the first specialties to appear were glass cleaners. At
the present time there are also formulas adapted for bathroom cleaning, stain
removal, carpet cleaning, oven cleaning, and so on. These types of
specialization also impose their own special restrictions. One of the largest
areas of specialization is grease cleaning, which in very developed markets can
be subdivided into three different soil loads.
B. AllPurpose Spray Cleaners
Most closely related to the dilutable cleaner packaged in bottles are the all
purpose spray cleaners. These are used for the heaviest soil in spot cleaning:
small greasy areas, such as stove tops, small spills, and sticky spots like drops
of jelly on countertops. The small, quick nature of the job does not justify
getting out a bottle and a bucket, and the difficulty of the soil load calls for
something close to the concentration of the dilutable allpurpose cleaner. As a
general trend, these spray formulations are richer in solvent and more poor in

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surfactant than their dilutable counterparts. Also in common with the dilutable
cleaners, the main trends in formulation are greater emphasis on safer solvents,
increasing use of nonionic surfactants, and decreasing use of builders and other
salts. Typical formula ranges for this type of cleaner are given in Table 5.
A survey of the literature reveals a preoccupation with streakfree cleaning
when the allpurpose spray cleaners are in spray form [107,108]. One of the
drawbacks of these spray cleaners is that even the low level of builders,
chelators, buffers, and so on, still leave a residue that is perceptible on very
shiny or transparent surfaces. The traditional answer to this problem was to
then go back and clean these types of surfaces with a glass or window cleaner
to remove the allpurpose cleaner residue.
C. Glass Cleaners
Glass cleaners are made to have the least possible residue. Formulas of this
kind go back to the late 1960s [109]. However, this is usually accomplished
by ultralow levels of ingredients, which results in very light duty cleaning. Glass
cleaners have sufficient ingredients to remove common window soils, such as
fingerprints, dust, and water spots. They are not intended for heavyduty soil
loads like kitchen grease or sticky food spots. The main consideration for glass
cleaners is that they deliver the minimum cleaning while leaving no streaks or
TABLE 5 Spray AllPurpose Cleaner Formulas
Amount

ethoxylated alcohol sulfate
Nonionic Ethoxylated alcohol, alkanol amide fatty acid, 1–10

surfactant amine oxide
Builder or chelator Carbonates (more rarely phosphates), silicates, 0–10

citrates, EDTA salts, NTA
pH adjustment Ammonia, sodium hydroxide, magnesium 0.1–10

hydroxide, alkanolamines
Solvent Alcohol (pine oil, benzyl alcohol, or lower carbon 0.5–20

number alcohols), glycol ether (Carbitol,
Dowanol, others), dlimonene
Disinfectant Pine oil, C2–3 alcohol, quaternary ammonium 0–5

compounds
Antistreak Polystyrene/maleic anhydride, polyethylene 0–5

polymers glycol, others
Perfume, color, 0.1–2
others
Water Q.S.

Page 490
residues that would be readily apparent on transparent surfaces. For this
reason, volatile ingredients are desired in glass cleaners. This will be curtailed in
the future because of volatile organic compound legislation.
The trend previously noted for grease or allpurpose sprays continues for glass
cleaners. Glass cleaners depend even more on solvent content and less on
surfactants than the allpurpose sprays, which depend more on solvent and less
on surfactant than the dilutable allpurpose cleaners. This is readily apparent if
Table 6 is compared with Tables 4 and 5. Two other differences are also
apparent. One is that the more powerful greasecutting solvents (e.g., pine oil
and dlimonene) tend not to be used in glass cleaners because of their lower
volatility and oily character. Volatility is an important consideration in glass
cleaners. The solvents that are used in glass cleaners, especially the low carbon
number alcohols, may not be the best greasecutting solvents, but they give
very quick drying of the cleaner. If the cleaner does not dry quickly, the
cleaner film may not be evenly rubbed out by the consumer, resulting in
streaking. The streaks will not apparent until the cleaner completely dries, and
so it is desirable that this happen while the consumer is engaged in the cleaning
task, not later.
The other difference noticeable from comparison of the tables is the use of
different groups of surfactants: amphoterics [110,111] and amido nonionics.
There seems to be advantages to these types of surfactants for less streaking.
In the first example cited, it is claimed that because of the way the formula is
constructed, it does not lose its performance (cleaning and lack of streaking)
TABLE 6 Spray Glass Cleaner Formulas
Amount

ethoxylated alcohol sulfate
Nonionic surfactant Ethoxylated alcohol, alkanol amide fatty acid, 0.01–3

carbamates, amine oxide
Amphoteric Betaines, sulfobetaines 0–10

surfactant
Builder Carbonates, silicates, citrates 0–2
pH adjustment Ammonia, sodium hydroxide, alkanolamines, or 0–5

acetic acid
Solvent Lower carbon number alcohols, glycol ether 0.5–40

(Carbitol, Dowanol, others)
Antistreak, antifog Silanes, ethoxylated silicones, polyethylene 0–1

polymers glycol, polyvinyl alcohols
Perfume, color, 0.001–0.5
others
Water Q.S.

Page 491
when perfume is added. It should be commented that perfume can be a source
of streaking and residue problems in glass cleaners, and in most glass cleaners
the perfume is kept to a minimum.
Most glass cleaners are also alkaline, to aid in cleaning the most common
window soil, greasy fingerprints. The alkalinity is usually produced by “fugitive”
compounds, such as ammonia, which minimizes residue, obviously an
important consideration in glass cleaning. However, the formula sometimes
needs better buffering than ammonia can provide, so the use of alkanolamines
and carbamates is also well established. The key is to avoid crystalline
compounds (traditional builders) to avoid noticeable residue on the transparent
glass surface. The only acid glass cleaners are those that contain acetic acid.
These depend on the reputation for good cleaning developed by the home
remedy of vinegar and newspaper for cleaning windows.
Streaking is caused by the drying of the residual product on glass in droplets
larger than 0.25 m, which can scatter visible light [112]. Only if there is no
residue, or the residue breaks up into droplets smaller than this size, can
streaking be avoided. Lubricity is also a factor in window cleaning. Unlike
other cleaners, window cleaners are formulated to evaporate quite rapidly.
This can cause some difficulty in wiping the cleaner in its final stages. Ammonia
salts of surfactants and builders tend to be favored in window cleaners. Not
only is ammonia a volatile compound that can conveniently be used to adjust
the pH, it also seems that these ammonia salts increase the lubricity of the
formula during wiping [113].
These cleaners are also trying to deliver added benefits. They usually fall in the
category of antifogging, of which there is voluminous patent art [114,115].
Some of these claim that in addition to the antifogging effects, usually achieved
through the deposition of a polymer film, there are also antisoiling benefits.
Antisoiling benefits alone can be achieved with silanes [116], which can react
with siliceous surfaces. Another patent claims the use of polyglycols as both
adjuncts to the surfactant system as well as giving the antifogging and antisoiling
benefits [117,118]. Another benefit claimed is the uniform draining of water
from the glass surface [119], which tends to decrease water spotting. This was
also achieved with a film using polyvinyl alcohol and/or cationic polymers. This
is a major benefit when the cleaner is also intended to be used on automobile
windshields or to clean outside windows.
These cleaners, in common with the allpurpose sprays, are also delivered in
trigger spray packages. They were at one time packaged as aerosol sprays,
but protest against aerosol packaging has largely eliminated them.
D. Glass and Surface Cleaners
Another recent development in the marketplace is the introduction of “glass
and surface” cleaners. These are cleaners that are presented as able to clean
greasy

Page 492
soil and yet leave no residue. This gives the advantage to the consumer of
having to only buy one product to do both the jobs of glass cleaner and all
purpose cleaner. In practice, they cut grease less than allpurpose cleaners and
streak more than window cleaners. However, they also streak less than the all
purpose sprays and cut grease better than window cleaners. In general, their
formulations are between those of the allpurpose cleaners and window
cleaners. They share with the window cleaners high solvent levels and minimal
builder concentrations. However, they also have surfactant levels closer to
those of the allpurpose cleaners. There are some advantages claimed for
betaines in the literature of these cleaners [120–122]. These inventions are
usually synergistic mixtures of betaines and other surfactants that are claimed to
give good grease cleaning while minimizing streaking or residue. Modified
sulfobetaines have also been claimed in glass and general cleaning formulations
[123], for which it is pointed out that the solvent/buffering system of the
product also has a role with the surfactant in keeping filming and streaking to a
minimum. More exotic surfactants have also been used, for the benefits of
good cleaning with less streaking, such as amidesubstituted soaps [124]. Like
the glass cleaners, glass and surface cleaners also may contain polymeric
ingredients to decrease streaking [125]. They are also delivered in bottles
equipped with trigger sprayers.
E. Test Methods
1. Cleaning Methods
The test methods for these spray cleaners are similar to those described for
dilutable allpurpose cleaners. Grease cleaning is tested the same way with
surfaces. Amounts of soil are sometimes adjusted to lower levels, especially for
glass or glass and surface cleaners. Another adjustment that can be made is
that the product may be sprayed directly on the soiled test surface rather than
applied to the sponge. The cleaning tests may also use paper towels or mohair
cloth instead of sponges, depending on the local consumer habit.
For window or glass and surface cleaners, the test substrate is often glass. This
allows not only for testing soil removal on the surface of interest, but the same
surface may be evaluated for residue [126]. The soil tested may also be
changed for glass cleaners. In this case, the main task is not cooking grease but
the grease of fingerprints. Therefore, the soil is changed from animal or
vegetable fat to synthetic sebum [127]. For glass and surface cleaners, either
soil may be used because it is used for both glass and generalpurpose
cleaning.
2. Streak and Residue Testing
The major difference in this area, especially for any cleaner promoted for use
on glass, is the emphasis on residue/streak testing. The most challenging sur

Page 493
face is glass mirror because of its reflectivity. Streaks or residues are readily
apparent. A given amount of cleaner is wiped on the surface in a specified
number of strokes, sometimes as low as one. If more than one stroke is used,
all the strokes are done in the same direction: no perpendicular or circular
wiping is done. The usual applicator is a soft, lintless cloth or paper towel
[128]. The area is left to dry. A panel of observers rate the prepared surfaces,
taking care to view the surface from several angles. Streaks or residue are not
always apparent from a single lighting condition, and the surface should be
tipped several ways for proper observation. Alternatively, streaking can also
be evaluated using the product on black ceramic tiles and using a glossmeter to
measure the residue on the surface [129].
3. Other Testing
Foam level becomes a question of the interaction of the formulation with the
spray trigger. The inherent foaming character of the formulation can be tested
by the methods used for other household cleaners. However, this foam profile
may be changed by the trigger used. The degree of foaming should also be
evaluated by spraying the product out of the trigger.
There are other characteristics that are also caused entirely by being a sprayed
product. Although some of these attributes are part of the testing of the actual
packaging itself, they should also be done with the formulation. It is desirable
to test the area covered by a single spray and the volume of product delivered.
One could also measure the amount of time it takes the product to run down
the surface or its “cling.”
Surface safety is evaluated the same as for the dilutable cleaners, by allowing
the product to sit on a surface for a predetermined amount of time. Safety
profiles for spray cleaners can be quite different from dilutable cleaners
because of the different proportions of solvent or surfactant generally used.
F. Bleach Spray Cleaners
Bleach spray cleaners for general household use have emerged with the
bleachcontaining allpurpose dilutable cleaners. These constitute yet an even
more specialized niche than the glass or glass and surface cleaners because of
the sensitivity of many household surfaces to bleach. The majority of such
sprays on the market are hypochlorite bleach based and are close or identical
in formula to the dilutable bleach allpurpose cleaners. That is, they contain
about 1–2% hypochlorite bleach, a low level of bleachcompatible surfactant
(usually amine oxide), an alkalinity agent like sodium hydroxide, and possibly
some builder salt, such as phosphate or silicate. These cleaners combine a
medium level of grease cleaning with the obvious stainremoving properties of
the bleach. The trigger sprayer used with the product can either deliver the
usual aerosol or, more usually, a loose foam.

Page 494
IV. Bathroom Cleaners
Bathroom cleaners, along with bleach cleaners, are the largest category of
specialty liquid cleaners. These products are formulated and packaged with the
specific soil and cleaning problems associated with modern bathrooms. All
purpose cleaners are also used to clean bathroom surfaces, but they are not
targeted at soils, such as soap scum, and so suffer some deficiency compared
with the specialty products. As mentioned in the beginning, this specialization is
a twoedged sword. Although these cleaners are very efficient on targeted
soils, the ingredients to accomplish this often limit their use in other
circumstances. Most often, as will be seen, the concern is with surface safety.
Also, there are psychological barriers. There is no reason an acid toilet bowl
cleaner could not be used to clean hard water stains from a kitchen sink, but
very few consumers would be willing to do this.
Three categories of bathroom cleaners are discussed here: general bathroom
cleaners, mildew removers (with some crossover to bleach cleaners), and toilet
bowl cleaners. “Automatic” toilet bowl cleaners are not discussed because of
the dominance of solid, not liquid, forms in this group.
A. General Bathroom Cleaners
Around the world, there seems to be a consensus that the main problem in
bathroom cleaning is soap scum, followed by the related problem of hard
water deposits [130]. Allpurpose cleaners have some effect on soap scum,
but tend to have difficulty with hard water spots. General bathroom cleaners
tend to target these problems and tailor their chemistry accordingly. These
types of cleaners are usually moderately alkaline or strongly acidic. Some
make disinfectant claims, and others do not. Although worldwide bathroom
cleaners are commonly packaged similarly to dilutable allpurpose cleaners in
squared or handled bottles, in North America this particular subset of specialty
cleaners is dominated by trigger spray packaging.
1. Alkaline Bathroom Cleaners
Alkaline bathroom cleaners are direct descendants of the allpurpose cleaners.
They tend to have somewhat higher builder levels than modern allpurpose
cleaners, presumably to try to chelate some of the hard water ions that
contribute so significantly to tough bathroom soils. Many of these types of
cleaners also have disinfectant claims. Bleach bathroom cleaners fit this general
description, but because of their destaining ability are discussed in a later
section. This category includes general bathroom cleaners that use
alkyldimethylbenzylammonium chlorides as their disinfecting agent. Use of this
quat to achieve disinfectant places the constraint of nonanionic ingredients on
the formulation. Generally nonionic surfactants are used. These cleaners, like
their disinfectant

Page 495
and nondisinfectant allpurpose cleaning forerunners, have moderate soap
scum removal abilities and poor water stain cleaning. However, they do find
application in areas where many surfaces are acid sensitive [131], such as
countries where many bathroom surfaces are marble. Still, the most activity in
bathroom cleaners recently has been in acidic bathroom cleaners.
2. Acidic Bathroom Cleaners
Acidic bathroom cleaners have some distinct advantages to common bathroom
soils. First, the main matrix for the soil referred to as “soap scum” is soap that
has been precipitated for water hardness ions. Embedded in this matrix may be
skin flakes, lint, or dirt, for example (see Fig. 5), but the waxy precipitated
soap serves to hold the mass together and make it adhere to surfaces. Acid
can work to reverse this chemical reaction, turning some part of the soap fatty
acids into liquid components (notably oleic acid). This would serve to soften
the soil overall and thereby make it more easily removed. Second, if there
were any ion bridging of the soil to a receptive surface (ceramic), similar to the
bridging effects found in ore flotation, then strong acid could be used to disrupt
this bonding, freeing the soil from the surface. Acid is also effective at
dissolving hard water spots, stains, and encrustations, these being mostly
CaCO3, Mg CO3, and similar salts.
Fig. 5
Photomicrograph of homegenerated soap scum. Magnified 50 times;
visible are water spots (large circles), skin flakes (dark speckling), and
fabric fibers within the soap scum matrix.

Page 496
There are also some minor advantages to acid cleaners. Although an acid
cleaner can sting any open wound, in general moderate acid pH is kinder to
skin than alkaline pH. Acids are generally more effective at removing rust or
copper stains than alkaline products. The most effective of these acids, such as
oxalic acid, have chelating effects that also aid in the cleaning action, similar to
EDTA salts at high pH levels. Disinfectant quaternary ammonium surfactants
are also compatible with acids, although the same restriction as to choice of
cleaning surfactant holds at low pH as well as at high. It was long thought that
the most effective pH for quaternary disinfectant action was high pH: hence its
common use in alkaline bathroom and allpurpose cleaners. However,
disinfection has been documented at a variety of pH levels depending on the
organism [132].
However, acid also has one main disadvantage. Many bathroom surfaces may
be acid sensitive. Certainly marble fixtures top the list; the beautiful shine of a
wellpolished marble surface is easily destroyed by even one application of an
acid cleaner. The cement grout between wall tiles is another sensitive surface.
The modern addition of latex to the grout mixture helps resist acid attack but
cannot stop it completely. In Europe, many ceramic tiles and enamel surfaces
are also acid sensitive, prone to accelerated wear if an acid cleaner is used. As
seen in the examples cited here, the use of more moderate pH values (in the
range of 2.5–5) will slow the damage but it will not stop it completely.
There is also a minor disadvantage to acids if used in trigger spray products. In
these cases, the respirable mist produced by the sprayer may irritate the nose
and throat of the consumer. This can be mediated to some extent by the
delivery of the product, discussed later.
The beginnings of this field are predictably centered around the kind of acid
used. Very strong mineral acids are generally avoided in favor of better
buffering organic acids. Indeed, several patents give claims that the
performance of a higher pKa acid is superior to that of a strong acid at
comparable pH levels [133]. A synergy between different acid mixtures [134]
or the advantages of a particular acid are usually claimed [135,136]. The
patent literature also gives examples in which this fundamental weakness of
acids, their attack on certain surfaces, is claimed to be circumvented. Usually
this includes the use of phosphoric acid or derivatives [137,138]. One recent
invention cites the use of an esterase to generate acid under mild pH conditions
to enhance cleaning performance [139].
Interestingly, many of these bathroom cleaning formulas began using
zwitterionic, amide nonionic, and ethoxylated alkyl surfates just about the time
that such surfactants were becoming popular in spray allpurpose and glass
and surface cleaners [140–142]. They also use similar solvents to the all
purpose

sprays, leaning heavily on the glycol ethers. Table 7 gives a comparison of alkalin
bathroom cleaners. Figure 6 gives a general comparison of the soap scum cleanin
types of formulas.
One of the other problems of bathroom cleaning is that many of the surfaces with
vertical. There should be an advantage to increasing the residence time of the cle
One way to do this is to produce a thick foam with the cleaner by combining the
right delivery system, usually a trigger spray or aerosol. The cleaner is formulated
formed [143]. However, the foam cannot be too persistent or it becomes a rinsin
Another way to increase the residence time is to thicken the product, usually with
[145,146]. Once again, care must be taken to make sure that the thickened prod
very interesting alternative approach gives a thixotropic gel that forms a waterim
preventing the cleaner from drying out and thereby increasing the time of action o
There are also cleaners that are formulated with polymer thickeners to reduce mi
case, the object is to increase the particle size of the droplets formed upon sprayi
number of droplets that continue to float in the air. The longer a particle floats, th
TABLE 7 Spray Bathroom Cleaner Formulas
Ingredient Examples (
Anionic surfactant Alkylbenzene sulfonate, paraffin sulfonate, ethoxylated

alcohol sulfate
Nonionic surfactant Ethoxylated alcohol, alkanol amide fatty acid, carbamates,
amine oxide
Amphoteric surfactant Betaines, sulfobetaines
Builder Carbonates, citrates
Alkalinity Sodium hydroxide, alkanolamines
Acid Phosphoric, dicarboxylic, citric, sulfamic acetic
Solvent Lower carbon number alcohols, glycol ether (Carbitol,
Dowanol, others)
Disinfectant Quaternary ammonium surfactants
Perfume, color, others
Water

Page 498
Fig. 6
Relative soap scum cleaning; experiments done with
formulas at different pH values with and without glycol
ether solvents.
consumer will breathe it. Considering the aggressive chemistry used in many
bathroom cleaners, this can be irritating and unpleasant. Any cling given to the
product on the surface then becomes a side benefit to reducing the irritation.
However, thickening can also slow the diffusion of active ingredient to the soil
or stain, thus counteracting the effect of increasing residence time. Therefore
the benefits of reduced misting and increased residence must be balanced with
rinsing ease and slowed diffusion. These properties can also be important for
bleach sprays, as discussed later.
Added benefits are also arriving in this field, paralleling their arrival in all
purpose cleaning. The newest of these, as in allpurpose cleaning, is the
inhibition of soiling [149]. One recent entry into the North American market
claims to waterproof surfaces “to keep dirt from sticking and building
up” [150]. This would be a desirable trait in bathroom cleaning: many soils are
tenacious, the surface area to be cleaned is large, and the opportunity to resoil
intrinsic to the use of the room.
B. Mildew Removers
Nonbleachcontaining cleaners generally show little effectiveness against the
black stains caused by mold and mildew. Bleach cleaners are effective at
removing this stain and usually have the added benefit that they tend to kill the

Page 499
offending organism at the same time. Oxygen bleach products are not apparent
in this category, because they often lack the speed and effectiveness of
hypochlorite bleach that the consumer is accustomed to using. Mildew
removers are actually a subset of the general bleach cleaners described before,
although they usually predate the bleach cleaners intended for general
household use. The advantage of bleach cleaning specifically in the bathroom
are that most of the major surfaces tend to be bleach resistant, the
disinfectancy supplied by the bleach is highly desirable, and there is a
prevalent, highly colored stain to be removed.
Mildew removers are very closely related to the spray bleach cleaners
discussed earlier. The main distinction between general household bleach
cleaners and mildew removers is the concentration of bleach. In the household
cleaners the bleach level rarely exceeds 2% available chlorine, but in mildew
cleaners the level may reach as high as 3%. This is testament to the tenacity of
the melanin stain that molds and mildews are able to produce, particularly in
porous substrates like grout. Beyond this difference, the types and amounts of
surfactants tend to be similar, as are the choice of alkalinity agent and the
presence of any builders.
These cleaners should not only be tested for their stainremoving ability but
also for their soap scum cleaning. Although such alkaline products generally
show poor soap scum cleaning compared with the acid bathroom cleaners,
many consumers use them for general bathroom and tile cleaning.
One of the main problems with these types of cleaners has been the mist
produced by the trigger sprayer. The situation is similar to the irritation
described for general bathroom cleaners. Although this mode of delivery
contributes much to the convenience of the product, it also makes the product
very unpleasant to use. The respirable particles produced with their high
alkalinity and bleach can be very irritating to the consumer. One way to
combat this is to thicken the product, and there is literature to show that this
can be done with polymers [151] or with surfactants [152]. The important
aspects to balance are reducing the mist produced by the product while still
achieving a consumeracceptable spray pattern. If the product becomes very
thick, the spray pattern often collapses to a narrow stream. For some uses, this
kind of pinpoint application may be preferable, but for other consumers, a
more broad spray pattern is expected.
Newer products are also claiming not only to remove mildew stain or kill
mildew but also to keep it from recurring. Once again, this is another incidence
of the trend in household cleaners to give added benefits. Many products are
so efficient at removing the mildew stains that a further step to ease the cleaning
problem must be taken to differentiate new products. A commercial entry
made using this claim also uses a packaging innovation relatively new to
household cleaning—a dual bottle with a single trigger sprayer (Fig. 4b).
Evidently the

Page 500
chemistries used in this product are not compatible on storage. One bottle
contains the solution used to remove the mildew stain (bleach), and the other
contains the ingredients used to keep the mildew from recurring. Both solutions
are delivered simultaneously when the single trigger, with dual dip tubes, is
pulled. Once again, packaging works with chemistry to give a new product
benefit.
C. Test Methods
1. Soap Scum and Hard Water Cleaning Methods
The test methods for evaluating bathroom cleaners are very similar to those for
evaluating allpurpose cleaners. The Gardner straight line abrader is still used,
with sponges or other appropriate utensils for cleaning tests. The substrate
usually used for evaluation is ceramic tile, this surface being generally
representative of ceramic, porcelain, and enamel. The same equation is used to
measure percentage soil removed after measurements with either a
reflectometer or a glossmeter. In this case, as in allpurpose cleaning, the main
discrepancy among cleaning methods is the choice of soil composition and
application. Usually the soil is applied by being dissolved or dispersed in a
solvent such as isopropanol or chloroform, and then sprayed on the surface.
The soap scum is usually calcium stearate, calcium oleate, or calcium palmitate
or a mixture of all three. It may or may not be mixed with other soil
components. The most common is carbon black or charcoal, which also colors
the soil so that it can be seen on a white tile [153]. Conversely, the pure white
calcium fatty acid can be used on glossy black tiles. This last choice has the
added advantage that glossy black tiles are often used for residue and shine
tests.
Hard water spotting is usually a much easier soil to clean than soap scum or
mildew. It is related to soap scum in that it has the same root cause, hard
water. Water spots may be produced by applying hard water (150 ppm as
CaCO3, with a Ca/Mg ratio of 3:2) to a glossy tile surface. This should be
allowed to air dry. Multiple applications of the hard water may be necessary to
build a tenacious, visible soil. The ease of removal of the spots gives the
strength of the cleaner. For more difficult hard water problems, such as lime
buildup around water faucets, a quick test can be done. If a cleaner can
dissolve a piece of chalk, it is a good indication that it can remove these kinds
of scale.
2. Mold and Mildew Cleaning
The last important bathroom soil is mold and mildew stain. A distinction must
be made with regard to this soil. Cleaning tests are a measure of the cleaner's
ability to remove the melanin stain produced by the organism. This is not
necessarily a measure of the cleaner's ability to kill or retard the organism caus

Page 501
ing the stain. To do this, formal disinfection or mildicide test must be
performed. The usual place for mold growth is the grout between wall tiles, so
it is important that grout as well as tiles be included as the cleaning surface. A
nutrient medium is applied to the surface, and this is inoculated with the
organisms of interest (usually Aspergillus niger). The culture is incubated for
several weeks, and then the surfaces are inspected for mildew growth.
Cleaning tests may then be performed, with special attention going to the
cleaning on the grout surfaces [154]. Alternatively, cleaners can also be tested
for mold inhibition. In this case, the cleaners are applied to the surface before
the introduction of the medium and microorganisms. The tiles are allowed to
incubate, with periodic checks on the growth (or nongrowth) of the mold.
For claims pertaining to killing mildew, controlling its growth, or general
disinfecting action, local government regulations should be consulted. In the
United States, this means following the tests set out by the Environmental
Protection Agency (EPA) [155]. The tests usually require production samples
of cleaner to be used against test organisms grown according to specified
methods. The application of the cleaner and the time of contact are usually also
prescribed.
3. Other Tests
The residue and shine, foam, disinfectancy, and surface safety tests are done as
described in the section under allpurpose cleaning. Greasecleaning tests may
also be performed with the bathroom cleaners because such bathroom soils as
lipstick and bath oils have an oily component. The other nonperformance tests
(eye irritancy and biodegradability, for example) are also outlined in the section
on allpurpose cleaners.
D. Toilet Bowl Cleaners
Toilet bowl cleaners are also a product in which great specialization has taken
place in the form of the dispenser. The most modern of the toilet bowl
packages feature shaped necks that allow the product to be squirted directly
under the rim of the toilet (Fig. 7). This allows consumers to keep themselves,
and their hands, out of the toilet bowl. With more traditional packaging, the
consumer would have to reach down in the toilet to squirt the product under
the rim.
Toilet bowl cleaners also include products placed in the toilet tank to be
released on flushing into the toilet bowl. Many of these products are solid
“pucks” or blocks and are beyond the scope of this review. Others are liquid
formulas with very elaborate dispensing devices. The device can be built to
release the cleaning liquid at the beginning or end of the flushing cycle. If
delivered at the end of the flush, it usually is held with the water in the tank,

Page 502
Fig. 7
Modern toilet bowl cleaner packaging.
thereby imparting its benefits to the tank as well as the bowl. The cleaning
liquids contained in the devices are generally very simple lowviscosity
formulas. Their compositions are given in patents mainly devoted to the
intricacies of the mechanical devices [156,157]. Typically they contain
traditional anionic or nonionic surfactants (0.5–10%), perfume (0.01–1%), and
high amounts of dye (1–10%). The concentrations are higher than might be
expected because they are significantly diluted in use, either in the bowl or in
the tank. The color of the water is used as a signal to the consumer that the
cleaner is present (and is esthetically pleasing to some) and so is much higher
than generally found in household cleaners. Sometimes disinfectant quaternary
ammonium surfactants (0–5%) are used. Often, these kinds of products also
make extended benefit claims (by virtue of their residence in the bowl) for
inhibiting bacterial growth [158] or inhibiting stains [159].
Originally, toilet bowl cleaners, like allpurpose cleaners, were powders based
largely on sodium bisulfate [160]. They were packaged in dispensers very
much like powder abrasive cleaners. In fact, many products that have been
mentioned in this review are used to clean the toilet. General bathroom
cleaners, liquid and powder abrasive scourers, allpurpose cleaners, and even
simple household bleach are used by consumers for this task. Modern cleaners
specialized for toilet bowl cleaning, however, have one factor in common these
other formulas generally lack: high viscosity. The viscosity of toilet bowl
cleaners is generally between 300 and 1000 cP. Only cream cleansers have
higher viscosities. When applied to the rim of the bowl, they gradually flow
down the

sides. The high viscosity also increases the contact time of the cleaner with the su
aiding in soil removal. The consumer need not spread the cleaner over the surfac
scrubbing should be decreased. Other than this common denominator, toilet bow
like general bathroom cleaners, are either acid or alkaline.
1. Acidic Toilet Bowl Cleaners
Acidic toilet bowl cleaners are by far the largest group. The greatest cleaning pro
outside of the obvious organic soils, is hard water buildup. Toilets function most
as water storage tanks and therefore suffer the same evaporation and scale probl
tanks. Acids are especially efficacious against this type of problem. The usual arr
are used in this field (similar to those used in general bathroom cleaners), althoug
levels are targeted. The use of oxalic acid, which is particularly good at removing
be especially beneficial in this type of cleaner if rust stains are a local problem. A
the formulas used for acidic toilet bowl cleaners is given in Table 8.
Newer toilet bowl cleaner formulations are moving to the newer classes of surfac
the rest of household cleaning [161]. More nonionic surfactants than anionic surfa
used. These acid formulas are generally selfthickening, using a high concentratio
electrolytes combined with the surfactant to produce the high viscosity. It is also i
that toilet bowl cleaners give lower foam than allpurpose cleaners. It is desirable
the foam disappear quickly. Nonionic surfactants are preferred over anionics for
purposes. Thickeners, such as polyacrylates, are sometimes used to supplement t
viscosity of the surfactant system.
TABLE 8 Acid Toilet Bowl Cleaners
Ingredient Examples
Anionic surfactant Alkylbenzene sulfonate, paraffin sulfonate, ethoxylated
alcohol sulfate
Nonionic surfactant Ethoxylated alcohol
Cationic surfactant Quaternary ammonium
pH adjustment Phosphoric, hydrochloric, oxalic, citric
Electrolyte Nitrate, chloride
Bleach Persulfate salts, hydrogen peroxide
Thickening agents Polyoxyethylene, cellulose gums
Abrasive Calcite, silica
Perfume, color, others
Water

Page 504
This is also one area in which peroxide compounds are widely used. Persulfate
salts have long been used in powder toilet bowl cleaners, so that bleaching and
acidic cleaning were combined in a single formula. Persulfate salts are now
making appearance in liquid formulas as well. In one formula, it is claimed that
the dilution on adding to the toilet bowl helps the cleaning because the pH level
rises rapidly, destabilizing the bleach [162].
Disinfection is also a benefit desired by consumers in toilet bowl cleaning. This
can be achieved with quaternary ammonium surfactants, as in bathroom and
allpurpose cleaners. “Quats” are effective bactericides at both low (1–4) and
high (8–12) pH values and so are compatible with very acid toilet bowl
cleaners. One of the problems with disinfection is knowing whether the product
has been used at the proper dilution, and one toilet bowl cleaner formula gives
the signal via a pHdependent dye [163].
Similar to the technology used to produce cream cleaners, there are also
formulas that can produce liquid toilet bowl cleaners with suspended abrasives
[164]. The main difference between the cream cleansers and this type of
product is that the suspending system should be acid stable instead of alkaline
and/or bleach stable.
2. Bleach Toilet Bowl Cleaners
The other category of popular toilet bowl cleaners are those containing bleach.
The chemistry to produce these formulas is very similar to that for thickened
bleach allpurpose cleaners. The most common examples uses amine oxide
and anionic surfactant combinations to thicken the formula, sometimes
supplemented by a polymer [165]. The formula can also be selfthickened, as
in the acid systems, by the interaction of surfactant and electrolyte [166]. The
same surfactants are used in these formulas as with other bleach formulas, and
similar alkalinity agents. The bleach levels tend to be in the range of 0.5–5%
available chlorine.
New formulas have appeared in the patent art using oxygen bleaches instead of
hypochlorite. These formulas have the advantage of low pH and therefore
would be more useful for the typical toilet bowl problems, such as mineral, as
well as having a bleaching ability that consumers find attractive. One of these
formulas uses persulfate salts, long known as powerful oxidizing agents but
difficult to stabilize as liquid systems [167,168]. Another approach is to use
peroxyacids, such as peracetic acid, in which the bleaching agent and the lime
scale remover are combined in the same compound, thereby combating the
two most common toiletcleaning problems [169].
3. Test Methods
Not much is published on the subject of testing the efficacy of toilet bowl
cleaners. References to “toilet soil” are made in some patent literature, but the
details

Page 505
of the ingredients of the soil are not made clear. The efficacy testing is done by
soil solubilization efficiency and, if bleach is present, soil discoloration. Tests
can be made against hard water stains, as is described in the bathroom
cleaning section. As with other household cleaners, the normal disinfectancy
tests for a locality can be used.
For intank automatic cleaners, the most important test is usually lifetime of the
product. In the most brute force method, the product is installed in a real toilet.
The toilet is then repeatedly flushed to determine how long the product will last,
measuring either the persistence of some ingredient, such as color or bleach in
the bowl water, or the physical remains of product in the tank.
V. Conclusion and Future Trends
The area of household hard surface cleaning has advanced at a rapid rate in 60
years. From its beginnings in simple soap powders, it has branched out into
many types of specialized cleaners (see Fig. 8). It is at present a dynamic field,
Fig. 8
Lineage of specialty household cleaners.

Page 506
full of both formulation and packaging innovation. These advances tend to
work in synergism, as in the development of trigger sprayers and spray all
purpose cleaners. The following summarizes some of the highlights and future
trends.
In welldeveloped markets, the drive is to supply the consumer with greater
convenience through added benefits, such as twoinone cleaners. Included in
this trend is the combination of bleach with various allpurpose cleaners and
cleansers. This is a recent development that gives the consumer more effective
stain removal combined with traditional cleaning (solid soil removal). Although
cleaning is always the main requirement, the household surface cleaners of the
future will do more: prevent tenacious soil adhesion, reduce fogging, give more
shine, and so on. Disinfection may be viewed either as an added benefit or as
an integral part of cleaning. These kinds of added benefits are just making their
appearance in household hard surface cleaning.
Giving more benefits is at times at odds with the concomitant trend to give
easier cleaning through greater chemical targeting of soils (grease or mildew) or
special needs, that is, streakfree window cleaners. The chemistry needed to
target these problems often limits the scope of their use in the household. An
example is the inadequacy of window cleaners for overall grease cleaning in the
household. Another example is the compromise of bleach cleaners: greater
stain removal, but limited to use on bleachresistant surfaces.
The overall direction is, however, to let the chemistry do more work and
relieve the consumer of a mechanical contribution to the cleaning process. This
is being achieved through continuing invention of new surfactants and solvents,
studies of ingredient synergies, and the increasing use of polymeric ingredients
for various added benefits. This, coupled with changing household surfaces,
would account for the decrease in the consumers' use of abrasive cleaners.
Liquid cleaners are now sufficient for nearly every cleaning job, leaving only
special “tough” jobs for cleansers, such as very worn surfaces and bakedon
soils.
Dilutable allpurpose cleaners are also tending to become more concentrated,
giving the consumer use and storage advantages. At the same time there is a
proliferation of very dilute cleaners that exist as convenience spray products,
largely as targeted cleaners mentioned earlier.
Powder products for household cleaners are now in the minority of products
and are decreasing every year. The household cleaning category in developed
countries is dominated by the ease and convenience of liquid products. It is
expected that the same trend will eventually emerge in developing countries.
Packaging continues to evolve in this area in synergy with changing chemistries.
Redesigns of toilet bowl cleaner bottles and the invention of the trigger sprayer
have already greatly changed the array of products in the hard surface
category. New dualchamber packages offer the most exciting possibili

Page 507
ties. Mixtures that have limited shelf life can be stored separately and
dispensed simultaneously. These are prime examples of how new containers
can augment the convenience, safety, or delivery of a cleaner to its target. The
importance of packaging innovations to the field of household cleaners cannot
be underestimated.
More attention is being paid to the safety of household surface cleaners. There
are at least three aspects of safety: less irritating to the consumer, less
aggressive to the household surfaces, and more environmentally agreeable.
The sheer volume and variety of chemistry in this field are challenging, and only
promises to continue in that direction. Likewise, the increase in the number of
products, and their overlapping claims should also continue.
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American Society for Testing Materials, Philadelphia, PA, 1992.

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14
Manufacture of Liquid Detergents
R. S. ROUNDS
Fluid Dynamics, Inc., Piscataway, New Jersey
I. Introduction
II. Structured and Unstructured Liquid Detergent Delivery Systems
III. Liquid Detergent Process Patent Technology
IV. Continuous Versus Batch Process
V. Unit Operations in Liquid Detergent Manufacture
A. Transport phenomena in agitated vessels
B. Product shelf life
VI. Summary
References
I. Introduction
Commercial liquid detergents are available to consumers as low, moderate, an
Newtonian and nonNewtonian solutions, freeflowing or thick, opaque dispersio
pastes. Despite the differences in composition and consistency of these diverse d
systems, the manufacturing processes typically involve the same fundamental unit
Viscous nonNewtonian dental creams and lowviscosity Newtonian hard surfac
example, both require dispersive and distributive mixing, dissolution of various co
heat transfer for heating and cooling, solids and liquids conveying, pipeline transp
and filling. The primary differentia

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tion in the processing of these various products lies in the industrial equipment
required for each unit operation and the difficulty of each operation.
Many, if not all, transport functions and corresponding unit operations in the
processing of liquid detergents are linked to rheology. This is most apparent
from mathematical simulations and dimensional analyses used to describe these
phenomena in manufacturing. Depending on the delivery system of a liquid
detergent selected for a specific consumer application, mass transfer, heat
exchange, and fluid flow or mixing characteristics can be cumbersome, and
generally, manufacturing conditions are selected to minimize any obstacles
created by adverse fluid dynamics.
In this chapter, we review basic process requirements for both structured and
unstructured liquid detergents. In addition to an overview of the process patent
literature, a general review is provided for the manufacture and handling of
both Newtonian and nonNewtonian fluid compositions.
II. Structured and Unstructured Liquid Detergent Delivery Systems
The physicochemical state of a liquid detergent frequently determines
manufacturing requirements and, for the purposes of this review, we adopt the
adopt the nomenclature of van de Pas [1] and broadly partition liquid
detergents into two general material categories: structured versus unstructured
liquid detergents. The unstructured fluid category includes both Newtonian and
marginally nonNewtonian single and multiplephase detergents, in which the
dispersed phases are not highly interactive and the volume fraction of the total
dispersed phase is relatively low. These products may show minor deviation
from Newtonian behavior but display neither significant elasticity nor time
dependent shear effects. Fluids of this type can generally be processed as
Newtonian fluids. This broad liquid detergent classification includes many but
certainly not all personal and household care liquid detergents, including certain
shampoos, conditioners, lightduty liquid laundry detergents, hard surface
cleaners, and hand dishwashing detergents. The second category, structured
detergents, refers to highly nonNewtonian, viscoelastic dispersions, including
physically or chemically crosslinked gels, which is an increasingly popular
form of both personal and household care products. These complex fluids may
exhibit yield stresses and shear effects, such as thixotropy, rheopexy,
pseudoplasticity, and dilatancy, and generally are viscoelastic products with
appreciable elasticity. Dispersions and emulsions are common with this product
segmentation. For example, dental creams exemplify the “structured detergent”
category, in addition to phosphate and certain nonphosphate built heavyduty
detergents, fabric softeners, and select shampoos, conditioning shampoos,
conditioners, automatic dishwashing liquids, and so on.

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Experience has shown structured fluids to be more difficult to manufacture
because of the complexity of their rheological profiles. In addition to elasticity,
dilatancy, and rheopexy, certain structured fluid compositions may exhibit
solidlike properties in the quiescent state and other flow anomalies under
specific flow conditions. For emulsions and solid particulate dispersions, near
the maximum packing volume fraction of the dispersed phase, for example,
yield stresses may be excessive, severely limiting or prohibiting flow under
gravity, demanding special consideration in nearly all unit operations. Such
fluids pose problems in pumping, mixing, filling, and filtrations and in storage or
holding vessels, with potential for a negative cumulative effect on both heat and
mass transfer. In addition, impaired drainage characteristics can contribute to
material loss during production, increasing operating costs substantially.
It is understood that manufacturing of liquid detergents that are unstructured in
their commercial form may involve intermediate streams that are, in fact,
structured fluids, such as surfactant solutions at high active concentrations,
within anisotropic mesophase boundaries, or concentrated polymeric solutions
and gels. Whether the source is raw material, premix, or final product,
manufacturing operations for each of these classifications are discussed with a
focus on any specific requirements or limitations as a result of the
physicochemical form.
III. Liquid Detergent Process Patent Technology
Patent activity is very aggressive in the personal and household care detergent
industry, based on the total number of worldwide patents issued annually. A
review of the current patent literature highlights the complexity of liquid
detergent compositions and their manufacturing requirements. In process
technology, the influence of process variables on product efficacy, stability, and
viscosity control is common patent subject matter, disclosed for both
structured and unstructured systems.
Liquid detergent process patents frequently define both compositional and
process requirements, such as raw material concentrations and specifications,
order of addition of critical components, thermal history, premix or adjuvant
preparation methods, product or process stabilizers, distributive and dispersive
mixing requirements, and process instrumentation. These patents apply to the
production of primary raw material constituents, such as surfactants, builders,
conditioning agents, rheology regulators, hydrotropes, disinfectants, and bleach
additives in addition to the specification of fully formulated detergent systems.
One patent for the manufacture of a liquid detergent composition, containing
surfactant and water insolubles, describes air injection for increased dispersion
stability [2]. The preparation of admixtures is disclosed, in addition to the
process for air incorporation. Also issued is a process patent for the produc

Page 516
tion of a pearlescent aqueous dispersion, containing fatty acid glycol ester and
a wetting agent, for use in shampoos, hair rinses, cosmetics, and other
detergents [3]. The primary advantage of the process described is
pearlescence achieved in the absence of crystallization. In a further example, a
patent has been granted for the production of an opalescent, stable dispersion
obtained through multistage emulsion polymerization of nvinylpyrrolidone and
styrene, using both anionic and nonionic emulsifiers, for use in bath foams,
shampoos, and various cosmetic preparations [4].
Process requirements maximizing product stability are often disclosed in the
liquid detergent patent literature. In one example, Neutrogena Corporation has
been assigned a patent for a coal tar shampoo prepared with a novel,
reproducible, and specific process whereby detergent clarity, color, and
viscosity are maintained for extended periods of time [5]. A patent describing
the process for the production of a stable liquid detergent containing surfactant,
aluminosilicate, a watersoluble detergent builder, and a stabilizing agent
discloses the partial gelatinization of an aqueous zeolite mixture to promote
dispersion stability [6]. Dispersion stability is also the subject of a patent issued
to the ColgatePalmolive Company for stable fabricsoftening heavyduty
liquid detergents, including the process for the manufacture thereof [7,8].
Further, a patent has been issued to Lever Brothers for the process of making
a colorfast heavyduty liquid detergent, whereby the sequence of addition of
the builder is specified [9]. It is noted that the builder is required to be added
to the batch process vessel before the neutralization of the anionic detergent,
from acid to salt, by an alkalimetal hydroxide. Advantages include rapid
neutralization, with a potential for reduced batch cycle time. A process for the
preparation of an aqueous liquid detergent compositions formulated with clay
as a fabric softener is described in a patent issued to Conopco, Inc., yielding a
stable finished product with no undesirable increase in viscosity following clay
incorporation [10].
In structured fluid detergent delivery systems, considerable effort is directed at
maintaining or enhancing product shelf life and phase stability, and the patent
literature teaches various methods intended to increase the physical stability of
surfactantbased compositions. One technology presented in the patent
literature imparts an integral physicochemical microstructure within the
detergent system for the retardation of phase separation. For these detergent
systems, processing requirements are frequently vital to the formation of the
required internal ordering of product components. In this notable example, the
use of aqueous dispersions of a multilayered lamellar liquid crystal phase to
stabilize structured liquid detergent systems has been proposed and several
patents issued [11–15]. In the proposed examples, which are anionic/nonionic
surfactant paired compositions, both rheopexy and thixotropy are found to
occur. High shear is required during detergent manufacture to obtain the
appropriate lamellar

Page 517
liquid crystal particle size distribution, and it is suggested that a high shear
device in a recirculation loop can be applied if the shear rate is greater than
1000 s1, preferably within the range of 4000–15,000 s1. As taught in these
patents, mixing is the strategic engineering element to successfully producing
this stable, internally structured liquid detergent. Several patents have also been
assigned to the ColgatePalmolive Company for a linear viscoelasticity
aqueous liquid automatic dishwasher detergent composition with exceptionally
good physical stability [16,17] and a process for producing the linear
viscoelastic detergent [18]. This patent discloses the dispersal of a crosslinked
polyacrylic acid in water, neutralization and gelation with alkali metal
hydroxide, addition of builder and silicate, and emulsification of fatty acid and
detergent in an aqueous solvent. Further, air incorporation to the gel is
disclosed further to promote dispersion stability.
The importance of order of addition of detergent components throughout the
mixing process as a critical process variable is demonstrated in a patent issued
by Unilever for the incorporation of perfumes in liquid detergents in laundry
and personal care products via a structured emulsified liquid crystalline or
vesicle delivery vehicle [19]. The selective premixing of various components is
further cited as a prerequisite for the process of manufacturing structured
lamellar concentrated heavyduty liquid detergent compositions in an additional
patent issued to the Lever Brothers Co. [20]. By strict adherence to
component order of addition and premix compositions, viscosity can be
reduced and draining characteristics improved. Steady shear viscosity data at
21 s1 is included in the patent, defining the criteria for stability.
Lever Brothers Co. has also been assigned a patent for the process of
producing an anticorrosion aqueous liquid detergent composition containing
particulate alkalimetal silicate. This detergent contains 5–25% soap and/or
synthetic detergent and 5–40% detergent builder [21]. A process patent has
also been issued for the making of a siliconecontaining shampoo, detailing the
thermal requirements of various adjuvants and the final mixing process [22].
Numerous patents exist for the manufacture of specific surfactants and other
raw materials used in the formulation of liquid detergents. For example, a
patent has been granted for the design of a reactor and process of
saponification [23], claimed to the applicable to the preparation of various
liquid detergent cleaning agents. In this patent, saponification is described for
batch processing on a semicontinuous basis. Another example is a patent
describing the efficient manufacture of an amphoteric surfactant for use in
shampoos by reacting aminocontaining compounds with acid halide alkali salt
[24]. Further, a patent has been issued for the production of a fatty acid
monoglyceride monosulfate salt surfactant describing the complete sulfation of
glycerol, reaction with fatty acid, hydrolysis, and neutralization [25].
Advantages of this process include reduced concentration of sulfating agent
and high active concentration with low inor

Page 518
ganic sulfate concentration. The Procter & Gamble Company also holds a
patent for the production of alkyl ethoxy carboxylate surfactant compounds
through the reaction of an ethoxylated fatty alcohol with a hindered base and
anhydrous chloroacetic acid or its salt [26]. Use of this surfactant is found in
cleaning compositions, such as shampoos, laundry detergents, and liquid
dishwashing products. An additional Procter & Gamble patent has been
assigned for the cosulfation of ethoxylated and unsaturated fatty alcohols
producing acid sulfate compounds that, upon neutralization, form mixed
surfactant systems for use in heavyand lightduty liquid detergents, shampoos,
and other cleaning compositions [27].
Liquid detergents contain many product components, including surfactants,
salts, soluble and insoluble builders, polymers, viscosity modifiers, fragrances,
colorants, stabilizers, hydrotropes, and other ingredients, which are often
interactive and capable of affecting product efficacy and synergistically
influencing rheological attributes. Throughout the process patent literature, the
manufacture of liquid detergents appears to require a regimented order of
addition of ingredients, with the appropriate shear and thermal history, to
obtain the appropriate consistency, appearance, stability, and performance and
minimize product aging following manufacture.
IV. Continuous Versus Batch Process
Structured and unstructured liquid detergents can be processed batchwise or
continuously, depending on the specific production and volume requirements.
Unstructured liquid detergents, especially those lacking significant solid
components, are well suited for continuous versus batch processing. Examples
of such detergents may include certain shampoos and liquid duty liquids,
including hand dishwashing detergents. With the development of highprecision
mass flow meters, proportional metering systems, and inline multiplestage
dispersers, both dynamic and static, continuous processing is frequently the
optimum process selection. If well designed, the process can be adequately
controlled to ensure adherence to specifications, meeting high volume
production demands with favorable manufacturing costs.
There are various minor components in most liquid detergents, such as
colorants, pH adjusters, and fragrance, and metering of these low
concentration yet critical components can be achieved with good accuracy in
continuous operations. For pH adjustment, which frequently controls product
viscosity, adequate sensors and product controls are required to ensure
consistent product quality.
Continuous processes depend on various types of mixing devices, both static
and dynamic, to disperse and/or blend formulation components. Several
commercial examples of inline static mixers for both turbulent and lamellar
flow are shown in Fig. 1, exposing the internal flow elements, and an example
of

Page 519
a commercial flow configuration containing three inline static mixers is
provided in Fig. 2. The primary advantage of such mixers, namely minimum
space requirements, is clearly seen. Continuous processes are not restricted to
unstruc
Fig. 1
(a) Turbulent flow configuration inline static mixer. (Courtesy of
LIGHTNIN, a unit of General Signal Corporation.)
(b) Inline static mixer with mixing elements. (Courtesy of Chemineer, Inc.)

Page 520
Fig. 2
Commercial application of three inline static mixers. (Courtesy of
LIGHTNIN, a unit of General Signal Corporation.)
tured detergents, and applications exist for structured systems as well. A
dynamic inline mixer, applicable to the blending of highviscosity fluids,
containing a helical ribbon impeller, is shown in Fig. 3. The dynamic mixing
element has been removed from the inline flanged assembly and positioned on
supports in a horizontal position to show the mixer impeller. In operation, the
mixer would be rotated 90° and installed in the pipeline.
In industrial practice, commercial liquid detergent manufacturing processes may
occur on a semicontinuous basis through a combination of both batch and in
line static and/or dynamic mixers. This may be the result of special process
requirements in the preparation of product intermediates:

Page 521
Fig. 3
Inline helical ribbon blender. (Courtesy of LIGHTNIN, a unit of
General Signal Corporation.)
Inorganic solids dispersal and hydration
Polymer hydration and swelling
Surfactant neutralization
Thermal gelation of select components
Liquefaction of component(s)
Emulsification

Page 522
Thermal and temporal equilibration
Ion exchange
An example of a complete continuous process suitable for liquid detergent
manufacture is provided in Fig. 4. This flexible and continuous manufacturing
process can produce multiple product variants. Viscosity measurements, pH
adjustment, level control, feedback process control to the metering pumps
from the level controller at the buffer tank feeding the filler line, and an inplace
water flushing cleaning system demonstrate the advantages of such production
systems, in addition to the limited space requirements. These metering systems
have found successful application in the production of fabric softeners,
shampoos, dishwashing detergents, and other liquid detergent products [28].
Fig. 4
Complete continuous manufacturing process. (Courtesy of Bran + Luebbe, Inc.)

Page 523
V. Unit Operations in Liquid Detergent Manufacture
The manufacture of liquid detergents involves many of the basic engineering
unit operations common throughout the chemical process industries. Depending
on the specific detergent formulation, each unit operation can contribute
significantly to the physical, mechanical, and visual properties of the finished
product. For this reason, quality control and manufacturing process controls
are important, particularly for structured detergents. For structured liquid
detergents containing multiple dispersed phases, such factors as particle size
distribution of both solid and immiscible liquid components, particle geometry,
hydration kinetics and extent of hydration, interactions between components,
kinetics governing each association under diffusioncontrolled static conditions
and shear environments, and anisotropic surfactant phases can determine
efficacy and many consumerperceived product attributes.
Several critical unit operations are briefly reviewed with an emphasis on the
process requirements of each liquid detergent classification, both structured
and unstructured systems, emphasizing momentum, material, and energy
transfer operations.
A. Transport Phenomena in Agitated Vessels
Mathematical simulation of heat, mass, or momentum transfer in agitated
vessels is often untenable, because of the threedimensional components of the
material and energy balances and the large number of material and process
variables. In such cases, dimensional analysis is the preferred method of
correlation. Numerous references are available for a review of dimensional
analysis in engineering applications [29–31].
Dimensionless groups provide an excellent overview of the critical parameters
influencing heat, mass, and momentum transfer, and several are defined here:
Dimensionless number Definition
Reynolds number NR DV /
Froude number NFr V2/gD
Brinkman number NBr V2/k T
Nusselt number (heat) hD/k
Nusselt number (mass)
Prandtl number NP r Cp m/ k
Peclet number NP e NRNPr
Schmidt number NSc

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where:
D = diameter
V = velosity
k x = masstransfer coefficient
Cp = specific heat (constant pressure)
k = thermal conductivity
h = heattransfer coefficient
= diffusivity of B in A
Using such dimensionless groups, one can easily deduce the importance of fluid
properties, namely, resistance to flow, on many of the production steps in the
manufacture of a liquid detergent. For example, the power needed to provide
agitation in a mixing vessel, known as the Power number Np, can be expressed
as [32]
Np = ƒ(NR,N Fr,S i)
where Si are factors relating to the design of the agitation system, that is, single
or multiple impellers, agitator placement, and design. In mixing, fluid viscosity is
clearly a significant material variable, influencing the power drawn during
mixing.
Similarly, under nonisothermal conditions, as might be experienced in heat
exchange by forced and free convection in an agitated vessel, the equations of
change for the energy function can be expressed as
The time rate of temperature is a function of the dimensionless groups, which
include resistance to flow or viscosity as one of the physical governing the
heatexchange process.
In mass transfer, the primary variables to be considered include all physical
properties, including density of relevant phases, viscosity, diffusivity. When
liquidsolid mass transfer in agitated vessels is the interest, factors related to
particle geometry, such as shape and size, must be considered, as well as
process design, including vessel geometry, agitator configurations, and speed
[33]. Because fluid viscosity functions is the distinguishing feature between
structured and unstructured fluids, it is clear that rheology is a major factor in
the processing of liquid detergents.
1. Momentum Transfer
Momentum transfer involves all unit operations in which fluid motion occurs.
The most common examples of this operation include pipeline transport,
mixing, and the filling operation. In liquid detergent manufacture, mixing is un
the processing of liquid detergents.
1. Momentum Transfer
Momentum transfer involves all unit operations in which fluid motion occurs.
The most common examples of this operation include pipeline transport,
mixing, and the filling operation. In liquid detergent manufacture, mixing is un

Page 525
doubtedly the most important momentum transfer unit operation, occuring inline
or in agitated batch vessels [34]. Mixing appears to be a very simple and
straightforward procedure, but it can be extremely complex [35–39] and
perhaps the most difficult of the unit operations used in liquid detergent
manufacture.
Each mixer configuration imposes a strain distribution to the fluid being
processed, which may influence the overall characteristics of the final product.
As such, mixing can be the critical production step determining the physical and
mechanical characteristics of the finished product. The physical stability of the
product, immediate and longterm aging effects, efficacy, texture, appearance,
and rheology are some of the important product characteristics that can be
altered by the total shear or strain history a product experiences during mixing.
Scaleup from laboratory to pilot plant through to production volumes
becomes a significant challenge, because it is difficult to reproduce exactly the
fluid velocity profiles and residence times, or total strain, a fluid experiences
during its process history.
Equally important is the influence of fluid properties on the efficiency and
power requirements of the mixing operation. This is especially true of
structured liquid detergents with appreciable elasticity and shear sensitivity. For
these structured systems, there is a strong interdependence between rheology
and mixing efficiencies. A basic understanding of the flow characteristics of the
finished liquid detergent product and all intermediate streams or product
components is a key to the selection and optimization of the mixing process.
Research devoted to the processing and mixing of complex nonNewtonian
fluids has not been extensive. This is unfortunate because many commercial
fluids, including structured liquid detergents, can be nonNewtonian fluids, with
appreciable normal stresses, and guidelines or process design criteria for
viscoelastic fluids are generally unavailable. Most dispersions at high solids
content and gels fall within this category, creating significant challenges in the
design of an efficient batch, continuous, or semicontinuous manufacturing
process.
(a) Mixing of Structured Versus Unstructured Liquid Detergents. Several
common radial and axial flow open impellers used in batch mixing of lowto
mediumviscosity unstructured or weakly structured liquid detergents, are
provided in Fig. 5. In addition to the type of impeller, impeller diameter, vessel
height and diameter, impeller locations, and baffles are design variables to be
specified for a particular application. Placement of baffles to minimize vortexing
and facilitate mixing and the type and location of impellers depend on the
specific mixing needs. Because of the size and scale of most industrial mixing
vessels, multiple impellers are generally needed to obtain an adequate degree
of mixedness. A simple schematic of a batch mixer is provided in Fig. 6,
showing all relevant engineering dimensions.

Page 526
Fig. 5
(a) Pitch blade impeller, (b) highefficiency impeller,
(c) straight blade turbine impeller with stabilizer, (d) welded disk impeller.
(Courtesy of Chemineer, Inc.)
For highviscosity structured and unstructured surfactant systems, one example
of an alternative mixer design, consisting of three topentering coaxial agitators,
surfacesweeping anchor, counterrotational blades and rotor/stator
homogenizer, is provided in Fig. 7. Details of this turboemulsifier are provided
in Fig. 8, showing the presence of a powder inductor through the vessel
bottom near the highspeed homogenizer turbine, variablespeed drive,
jacketing

Page 527
for heating and cooling, and provisions for vacuum or pressurized operation.
For highviscosity systems, common marine propellers and turbines are
generally unsuitable, providing limited bulk flow to the process fluid under
normal operating conditions. The efficiency of the mixing operation and the
effec

Page 528
Fig. 6
Batch mixing vessel with baffles and dual impellers with indicated
engineering dimensions.
tiveness of the flow field that is generated in the bulk of the fluid have a
significant impact on blending times and the kinetics of these operations that are
governed by effective mass, heat, and momentum transfer. For reference, Fig.
9 broadly summarizes the viscosity limitations of most commonly used
industrial agitators [40].
Large jacketed 316 stainless steel construction mixing vessels with variable
drive agitators are expensive. Because of the high capital cost, space
requirements, and high operating costs associated with such vessels in batch
operations, they are typically required to be multifunctional and capable of
performing many of the manufacturing elements of a liquid detergent. At large
production batch volumes of 10–20 or larger, this places a great demand on
the impeller/drive selections and placement of these impellers and baffles within
the mixing vessel.
Most industrial batch operations do not utilize single vessels for the
manufacture of a liquid detergent, and multiple vessels of various sizes and
specifications are used to perform discrete functions. Vessels with and without
tem

Page 529
Fig. 7
Ross Turboemulsifier. (Courtesy of Charles Ross and Son,
Hauppauge, NY.)
perature control, may be selected to prepare polymeric solutions or surfactant
premixes or dissolve various solid components uniformly before the final
blending operation. Further, intermediate product components may be
prepared in sufficient bulk to support multiple production batches. This is
generally desirable when production of intermediates is time consuming,
excessively increasing

Page 530
Fig. 8
Detailed schematic of Turboemulsifier. (Courtesy of Charles Ross and Son,
Hauppauge, NY.)
Fig. 9
Viscosity limitations of various impeller configurations. (From Ref. 88.)

Page 531
individual batch cycle times. In continuous operations, this approach may also
be applied to various product intermediate streams metered through a final
multistage inline dispenser. This may be achieved with static inline mixers or
dynamic multiplestage dispersers, depending on the specific product
requirements. Use of multiple supporting vessels, frequently of smaller size, can
reduce cost by application of special requirements, such as heat transfer or
high shear, only where needed.
In batch mixers, impellers impose flow, or momentum transfer, to the fluid
mass contained within the vessel. The power consumption during mixing for a
given fluid viscosity and density is proportional to the rotational speed of the
impeller and the impeller diameter, and flow is achieved by the momentum
transferred to the fluid by the motion of the impellers. Placement of the agitator
is determined by the mixing requirements when the vessel is fully charged and
also by requirements during batch filling and discharge. Agitator placement is
coordinated with ingredient order of addition to limit, for example, excessive
foaming in the presence of surfactants. The order of addition of formulation
components can also be balanced to limit undesirable rheological properties
and promote the formation of the desired microstructural state.
For unstructured liquid detergents, standard methods can generally be used to
size and specify mixing equipment. Pseudoplastic behavior with low order of
magnitude normal stresses would most likely not present serious mixing
problems. Structured detergents, however, and intermediates may require
special consideration. Significant deviation from Newtonian behavior cannot be
ignored in the specification of a production agitation system, because this can
produce significant errors in the estimation of power requirements for a
particular application. This is especially true of fluids capable of developing
solidlike mechanical properties in the quiescent state.
The influence of elasticity on the mixing unit operation is well illustrated by
Prud'homme and Shaqfeh [41]. A correlation of dimensionless mixing torque
versus Reynolds number is provided for three Newtonian fluids, two of which
exhibit significant elasticity, as determined by the magnitude of the primary
normal stress differences. For Rushton turbines, the results indicate a fourfold
increase in torque during mixing for fluids exhibiting high normal stress
differences, indicating that the fluid rheology must be considered in the
assessment of torque and power requirements for various agitation systems.
Power consumption is an important mixing design parameter, dependent upon
impeller diameter D, rotational speed N, and fluid properties, including
viscosity and density r, and power consumption of impellers is usually
provided as correlations of power number Np to Reynolds number NR. For
fluids exhibiting timeindependent powerlaw viscosity functions.
= Kgn
the generalized Reynolds number in agitation can be expressed as

Page 532
Power characteristics for the mixing of nonNewtonian fluids have been
determined for various impellers and other critical mixer design variables using
pseudoplastic, dilatant, and Bingham slurries and polymeric solutions frequently
encountered in the manufacture of liquid detergents, such as clay dispersions,
cellulosic, and carbomer solutions [42,43]. This research has also provided
correlations of the mean fluid shear rate and impeller speeds for various
impeller geometries and fluid viscosity functions. Typical agitators used in these
investigations include anchors, paddles, fan paddles, and turbines in agitated
vessels with and without baffling. Results clearly indicate that power
requirements for mixing of nonNewtonian fluids can be much greater than for
Newtonian systems.
Power consumption and blend times in the mixing and agitation of Newtonian
and nonNewtonian fluids are not equivalent, and in fact, blend times can be
much longer for nonNewtonian fluids when comparing fluids with comparable
apparent viscosity values. Through dimensional analysis, the dimensionless
blend or mix time m be expressed as
m = ƒ(NR, N Fr, S i)
Su and Holland report that power input per unit volume and mixing time are
substantially higher for pseudoplastic fluids than for Newtonian counterparts
[44]. Godleski and Smith [45] report blend times nearly 10–50 times longer
for nonNewtonian aqueous dispersions of hydroxyethylcellulose compared
with equivalent viscosity Newtonian fluids using flatblade turbine agitators.
Blending times for the pseudoplastic, timeindependent cellulosic fluids are also
noted to increase even further in baffled vessels. This study suggests a strong
dependence of mixing efficiencies on fluid rheology.
There have been contradictory results reported in the literature, however,
regarding the influence of fluid elasticity on the mixing unit operation [46–49].
Further research is apparently required to define adequately the influence of
viscoelasticity on mixing in agitated vessels for a broad range of fluid properties
and mixer configurations.
Carreau et al. [50] have investigated the behavior of Newtonian, inelastic, and
elastic nonNewtonian highviscosity pastelike fluids in helical ribbon
agitators, showing that the efficiency of mixing both pseudoplastic and
viscoelastic fluids is lower than for Newtonian fluids, decreasing significantly
with increasing fluid elasticity. Ranking the three fluid systems, the efficiency
rating is such that
Viscoelastic < pseudoplastic < Newtonian

Page 533
As with open impellers, elastic fluids are apparently more difficult to process in
helical ribbon mixers. To quantify this effect, the mixing efficiency of a highly
elastic Separan solution is only 20–40% that of glycerol, which is Newtonian.
The effect of fluid rheology on the power consumption on helical ribbon
agitators has also been evaluated [51] and power consumption as a function of
generalized Reynolds number for shear thinning but inelastic fluids defined.
When shear thinning effects are small and elasticity is negligible, deviations from
the Newtonian power curve are slight. At low Reynolds numbers, this is also
true for viscoelastic fluids. At higher fluid velocities, fluid elasticity begins to
dominate the power curve. Further, it appears that shear thinning delays the
effect of elasticity on mixing efficiency for structured fluids. The transient and
extensional nature of the flow field is stressed as a key factor in the increased
energy required to obtain a required degree of mixedness. Fluids that exhibit
both shear thinning and elasticity show deviations from the Newtonian power
curves at higher Reynolds numbers than viscoelastic fluids with minimal shear
effects.
Power needed to maintain mixing may not be the same as the power needed at
the inception of flow when processing structured liquid detergents. An
interruption in the process sequence can introduce a transient power
requirement quite different from the steadystate design criteria. The rheology
of structured liquid detergents systems are quite complex and can introduce
many variables not applicable to unstructured systems. When yield stresses are
significant and delays are expected at any part of the mixing process, slip drive
couplings to the motor drive may be required. This may prevent damage to
agitator motors and shaft assemblies when agitation is restarted. For pumping,
mixing, and any fluid transport operations, fluids with yield stresses require
shear stresses in excess of the yield stress to initiate and maintain flow.
Depending on the magnitude of the yield stress, this can be problematic.
In a batch mixer, a sufficient shear stress exceeding the yield stress may occur
only near the impeller, producing flow in the immediate vicinity of the impeller
but with stagnation zones throughout the remaining fluid bulk. This has an
overwhelming impact on the efficiency of the mixing operation and can be
further complicated in the presence of baffles. One solution is to utilize large
surface sweeping agitators, such as gate, anchor, or pattern mixers to minimize
regions experiencing stagnation. Discharging vessels containing these types of
fluids can also be difficult, resulting in residual material on the vessel surfaces
that cannot be fully evacuated. For example, in discharging a vessel under
gravity, a film thickness (z, t) can be calculated remaining on the vessel wall as
a function of draining time t and distance from the initial fluid height z, as shown
in Fig. 10. For Newtonian fluids, from the unsteadystate mass balance, the
film thickness can be expressed as [52,53]

Page 534
Fig.10
Film thickness on vessel wall during drainage.
where:
= viscosity
= density
g = gravitational constant
As we would expect, film thickness is directly proportional to fluid viscosity
and inversely related to density.

Page 535
For a comprehensive overview of the mixing unit operation, for both structured
and unstructured fluids, various references are available describing the specific
requirements for the design and specification of complete mixing systems [54–
75]. A general discussion of the effects of elongational flow experienced by a
fluid during processing on product rheology is also available [76].
(b) Dispersive Mixing. There are liquid detergents that require specific
particle size distribution of certain components to maximize efficacy and
substantivity, for both solidliquid and liquidliquid dispersions. Examples of
such products include hair conditioners, shampoos, conditioning shampoos,
bodycleansing bath gels, and fabric softeners. In conditioning shampoos
containing silicone oils, substantivity and effective deposition on hair are
functions of particle size, ionic charge of the particles, and silicone oil viscosity
[77]. Formulation and processing of these systems can be extremely
demanding.
Emulsions are difficult to process batchwise if a strict control on particle size
distribution is required. Processing may also be hindered by the complex
rheological properties that emulsions can exhibit. Very strict mixing controls are
therefore not unusual to ensure that product during manufacture, at the filling
line, and on the market shelf is within specification.
Fundamental mixing studies on simple twocomponent systems has provided
insight into the effect of mixing parameters on critical emulsion properties, such
as particle size distribution. For example, Nagata [78] has shown the
distribution of sizes of the dispersed liquid phase as a function of agitator
speeds. As we might expect, a normal distribution occurs at higher speeds. In
a similar study, the effect of surface tension was determined for several liquid
dispersed phases from benzene to paraffin oil [79].
Because of the very broad distribution of shear rates that fluids experience in
batch mixers, control of particle size distributions may not be possible. There
are, however, alternative agitation systems that can be used in tandem to
achieve a more controlled distribution of emulsion droplets or particulate
solids. These include colloid mills, inline dynamic dispersers in recirculating
lines, and other high shear flowthrough devices. These devices can be very
successful in tailoring emulsion and dispersion characteristics. An example of a
colloid mill with optional rotor/stator options is provided in Fig. 11, capable of
producing stable emulsions to the submicrometer range. This rotor/stator
design provides fourstage shearing action for effective dispersion and
deagglomeration. Figure 12 details a twostage tandem shear pipeline inline
mixer with two turbines and mating stators on a single shaft to provide greater
high shear dispersal. Use of external inline mixers positioned in batch mixer
recirculation loops is an effective process method for achieving a high degree
of dispersive mixing [80].
(c) Pumping of Newtonian and NonNewtonian Fluids. For liquid detergent
products known to be shear sensitive or containing particulates, pump selec

Page 536
Fig. 11
(a) Greerco colloid mill. (b) Standard colloid mill rotor/stator
combination with plain, smooth milling surfaces for most
emulsions and dispersions. (c) Specialty rotor/stator with
grooved miling surfaces for viscous emulsions. (Courtesy of
Greerco Corp., Hudson, New Hampshire.)
tion is an important process variable. Whether driven by centrifugal force,
volumetric displacement, mechanical impulse, or electromagnetic force, an
understanding of fluid exposure to high shear in close clearances is required.
An internal schematic of a rotary gear pump is shown in Fig. 13, showing the
close clearances between impeller surfaces and pump casing, with two
alternative rotary screw pumps illustrated in Figs. 14 and 15.

Page 537
2. Heat Transfer
Forcedconvection heat transfer is a common unit operation in the production
of liquid detergents. Whether experienced in jacketed process vessels, agitated
vessels with immersion coils, or other forms of heat exchange, there are
multiple causes for thermal regulation during detergent manufacture.
Temperature may be controlled to increase the dissolution rates of various
components, accelerate hydration, moderate phase behavior of the product
intermediates, regulate viscosity, or reduce yield stresses, for example.
Many liquid detergent products contain components that serve as product
viscosity modifiers, added to achieve the desired consistency of the
commercial product. Cellulosic polymers, for example, are an excellent
example of such an additive, and various polysaccharides are capable of
gelation under specific thermal conditions. In such cases, heat transfer during
manufacture may be required to complete hydration and effect the necessary
conformational change in the select polymer system [81] in the appropriate
aqueous environment. Products requiring controlled heattransfer process may
include various dental creams, shampoos, built liquid detergents, and hard
surface cleaners.
Heat transfer may also be required to maintain isothermal or adiabatic
conditions in the presence of endothermic and/or exothermic reactions as the
result of mixing product components, surfactant neutralization, and other
chemical reactions. In these cases, heattransfer requirements may be severe to
minimize exposure of the bulk fluid to high temperatures for extended time
periods, resulting in irreversible thermal degradation.

Page 538
Fig. 12
(a) Greerco 4 inch twostage sanitary tandem shear pipeline mixer.
(b) Exploded view of tandem shear turbine/stator assembly.
(Courtesy of Greerco Corp., Hudson, New Hampshire.)
3. Mass Transfer
Liquidsolid and liquidliquid mass transfer is highly dependent upon surface
area or particle size. Mass transfer is involved in simple wetting, dissolution,
hydration, swelling of product components, ion exchange, electric doublelayer
formation, dispersion stabilization through adsorption or absorption, and sur

Page 5
Fig. 13
Gear pump. (From Ref. 60.)
Fig. 14
Tworotor screw pump. (From Ref. 60.)
Fig. 15
Singlerotor screw pump with elastomeric lining. (From Ref. 60.)

Page 540
factant phase equilibration, among others. Both momentum and heat transfer
are frequently concurrent in the effectiveness and efficiency of most mass
transfer operations.
(a) Solids Hydration: Builders and Polymers. Solidliquid suspensions are
frequently encountered in the production of liquid detergents. For example, the
chelating agent sodium tripolyphosphate (STPP), in anhydrous form, is a
common builder in both laundry and automatic dishwasher detergents, forming
a hexahydrate when exposed to an aqueous environment. It is known that
material and process variables can influence phosphate hydration kinetics [82–
86]. The shear exerted on the slurry during hydration, rate of phosphate
addition, order of addition of various components, the electrolytic solution
environment, temperature, tripolyphosphate characteristics, including phase I/
phase II crystalline form, particle size distribution, and pH, for example, can
influence the rate and extent of STPP dissolution. Formation of the
hexahydrate may result in an increase in consistency of the phosphate slurry,
limiting the solids concentration during processing. The rheology of phosphate
liquid detergents is critically dependent upon the characteristics of the
anhydrous phosphate phase I/II ratio, which influences the rate and degree of
hydration. Modification of the hydrating characteristics of form II phosphate to
minimize undesirable processing effects is the subject of a patent issued to
Lever Brothers Co. [87].
The agitation rate and solids suspension should be sufficient to maximize
available surface area, especially when mass transfer is occurring. The
dependence of the masstransfer coefficients on relative power is shown in Fig.
16 [88]. The masstransfer coefficient is much higher when complete off
bottom
Fig. 16
Dependence of masstransfer coefficients on solids suspension. (Adapted
with permission from Ref. 88.)

Page 541
solids suspension is achieved. Even when suspension of solids is the process
objective, as in phosphate hydration, for example, it is necessary to determine
whether complete solids suspension and uniformity throughout the continuous
phase is required or offbottom suspension with a solids gradient throughout
the vessel is adequate. A general review of mass transfer in mechanically
agitated vessels involving both particulate suspensions is provided in Ref. 89.
Phosphate hydration in the primary detergent mixing vessel represents a good
example of the challenges facing a process development or manufacturing
engineer in the specification of a multifunctional mixing vessel. If we assume
that the phosphate hydration or other solids dispersal will occur early in the
manufacturing process, the immediate requirements of the mixing vessel is that
an agitator is adequately positioned to keep all solids suspended during the
hydration process. If this occurs as a highly concentrated dispersion with a
minimum of solvent, solids suspension may be difficult to achieve and the extent
of hydration limited, placing constraints on the impeller selection and location
within the mixing vessel.
A major difficulty associated with solids dispersion and hydration is settling in
the event of a process interruption. Depending on the duration of the
interruption, redispersal of solids may be difficult to achieve. An excellent
example of this is provided in Fig. 17, showing the agitation times required to
redisperse solids after settling [90]. Depending on the nature of the solid being
process
Fig. 17
Agitation requirements to redisperse settled solids. (From Ref. 88.)

Page 542
ing, particle size and shape, degree of compaction, and impeller location,
redispersal may not be possible. Adequate characterization of the slurry during
process development is needed to anticipate such difficulties. Depending on the
impeller location relative to the compacted solids region, precautions may be
necessary to protect the agitator motor drive. In certain instances, compaction
may occur when agitator motion is reintroduced as a result of the forces
exerted on the settled solids by the surrounding flow field.
Polymer processing during the manufacture of a liquid detergent represents
another difficult processing step because certain polymers may undergo rapid
hydration when introduced to an aqueous solvent. This complicates the mixing
operation and may require a predispersion of the polymer with a second inert
powdered ingredient or predispersion of the polymer solid in a nonaqueous
solvent or high shear dispersion. This can also be achieved in a dynamic inline
mixer through a transfer or recirculating line attached to a mixing vessel, as
previously discussed, or a powder inductor, as shown in Fig. 8. High shear
dispersion reactors or mechanical dry powder dispersers are known to reduce
blending times favorably, while increasing the concentration of polymer that can
be dispersed, even for certain hydrophilic carbomer polymers [91].
When mixing hydrating species, the order of addition of components can again
be significant. Polymer hydration, for example, can be significantly hindered in
the presence of specific salts. In general, with liquid detergents of limited shelf
life, the order of addition of ingredients can be critical in finished product
attributes. This is especially true of structured high solids dispersions. The
order of addition can influence phase stability, rheology, and many other
product properties.
B. Product Shelf Life
Liquid detergents can be dynamic systems in a metastable thermodynamic state
during and following manufacture. Depending on the complexity of the
formulation and concentration of surfactants, polymers, and other additives,
changes in consistency, texture, appearance, and color, for example, can be
experienced following manufacture, and this is not unusual for many detergent
systems. Controlling this effect, however, is necessary to ensure consistent
product throughout shelf life and represents the underlying necessity of effective
heat, mass, and momentum transfer during product manufacture.
For example, a product may exhibit a Brookfield viscosity of several thousand
centipoise at the filling line, yet viscosity may continue to increase or decrease
following production for a period of time. Most undesirable is progressive
thinning or thickening for extended time periods. Depending on the mechanism
responsible for the thickening or thinning behavior, this may be

Page 543
accelerated through effective heat and mass transfer at the relevant
manufacturing step. Possible causes of such phenomena include continuing
hydration of polymeric and solid species, occlusion of solvent in porous solids,
and surfactant phase equilibration. Heat transfer may well be used to increase
the rate of each of these effects during manufacture, thereby moderating any
changes in consistency following production, driving the product to a more
stable pseudoequilibrium or steady state.
Heat transfer can occur in both batch or continuous configurations. Both types
of processes require fluid motion to obtain an effective heat transfer to the bulk
of the fluid. In batch processing using jacketed vessels, helical coils, or coils in
a baffle configuration, for example, sufficient agitation is required for heat
transfer through the medium; continuous systems rely on flow rate to achieve
effective heat transfer to satisfy process requirements. Effective heat transfer in
batch operations for structured liquid detergents may require scrapers or
anchortype impellers to increase heattransfer coefficients in jacketed vessels.
Effective mass transfer is as important because product stability can be
seriously compromised in colloids and suspensions, both liquidsolid and
liquidliquid phases, if the morphology of the interface is not properly formed
and interactions sufficiently developed. Phase separation is the major
consideration in such complex systems and is easily affected by poor process
history.
VI. Summary
Liquid detergents are seldom in equilibrium during processing or throughout
shelf life. Few of the reactions are driven to completion during manufacture yet
continue throughout product shelf life. Ion exchange, crystallization, phase
equilibration, adsorption, absorption, diffusion, and so on may continue to
occur from the point of manufacture to the point of use. If these proceed
without significant change in physical properties, there may be little reason for
concern, unless efficacy is impaired. Unfortunately, however, these can result in
viscosity increases with product age, induce physical phase separation, shift
particle size distributions, or alter color and fragrance, for example, leading to
product changes that are consumer perceptible. With a rigorous statistical
experimental design during process development, many of these characteristics
can be understood and successfully controlled.
Both structured and unstructured liquid detergents have process requirements
and limitations. The order of addition of ingredients and the shear history
experienced during processing can determine the physical state of the detergent
and ultimate stability. Any additional unit operations, such as pumping, pipeline
transfer, and filling, must be defined in a manner that does not irrevers

Page 544
ibly alter the structured phase. The objective throughout manufacturing is to
deliver a consistent product to the consumer with minimal variability
encountered during production.
Specification of raw materials used in the manufacture of liquid detergents is
critical to controlling process effects. Although some detergents are relatively
insensitive to broad fluctuations in raw material characteristics, others are
extremely sensitive to minor variability. Apparent in the patent literature,
surfactant chemistry can be a critical component. For example, when
manufacturing with a surfactant/solvent composition near a phase boundary, a
minor change in electrolyte concentration, surfactant composition, and
concentration can significantly alter product characteristics.
Mixing is an important unit operation in the production of a liquid detergent.
Effective mixing of liquid detergents requires a basic understanding of the
rheology of the system being manufactured. A preliminary investigation of the
fluid properties, such as viscosity behavior, normal stress differences, time
dependence or shear effects, yield stresses, and structural kinetics, including
deformation and recovery, are relevant and necessary in anticipation of specific
agitation requirements. As we have seen, the elastic effects are particularly
important to identify and monitor during processing, and processing of liquid
detergents, depending on the physical form of the product, can be a significant
engineering challenge.
References
1. J. C. van de Pas, Tenside Surf. Det. 28, 158 (1991).
2. Japanese Patent 60,076,598 to the Lion Corp. (1985).
3. H. Yamamoto, M. Kinosita, and S. Konisi, Japanese Patent 61,268,797 to
the Lion Corp. (1986).
4. H. Auweter, A. Nuber, C. J. Tschang, and A. Sanner, DE 3,818,868 to
BASF AG (1989).
5. J. Fong, V. Noukarikia, and E. Jungermann, WO 8,603,679 to the
Neutrogena Corporation 1986).
6. M. Kukzel and J. W. Leikhim, US Patent 4,405,483 to the Procter &
Gamble Co. (1982).
7. P. A. Grand, and P. N. Ramachandran, US Patent 4,619,774 to the
8. P. A. Grand and P. N. Ramachandran, US Patent 4,469,605 to the
9. L. R. Mazzola, US Patent 4,800,037 to Lever Brothers Co. (1987).
10. R. J. Green and J. C. Van De Pas, US Patent 5,002,688 to Conopco,
Inc. (1990).
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10. R. J. Green and J. C. Van De Pas, US Patent 5,002,688 to Conopco,
Inc. (1990).
11. P. L. Dawson, C. Upton, and J. C. Van de Pas, WO 91/09108 to
Unilever PLC (1991).

Page 545
12. S. G. Hales, E. Khoshdel, P. G. Montague, J. C. Van de Pas, and A.
Visser, WO 91/09109 to Unilever PLC (1991).
13. C. J. Buytenhek, M. S. Mohammadi, J. C. Van de Pas, and C. L. De
Vries, WO 91/09107 to Unilever PLC (1991).
14. J. C. Van de Pas, Tenside Surf Det. 28, 3 (1991).
15. A. Jurgens, Tenside Surf Det. 26, 3 (1989).
16. A. Delsignore, N. S. Dixit, R. Rounds, and S. Makarand, US Patent
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Page 549
Index
Acetyl trimethyl citrate, 299
Acidcombining capacity of bleached hair, 401
Acrylatelauryl methaacrylate copolymer, 268
Acrylic/maleic copolymer, 334
Activated peroxygen bleaches, 298
Activator, 7
Acusol, 339
Adequacy of preservation tests, 486
Aerosol OT, 189
AFNOR (Association Francaise de Normalization), 485
Aging tests, 486
Alcohol ethoxylates, 277
Aldehydes, 477
Alfonic, 277
Alkalinity, 286
Alkanolamide, 10
Alkylate, 273
Alkyldiphenyl oxide disulfate, 9
Alkylether sulfate, 114, 278
dynamic mechanical properties of, 114
Alkylisoquinolinium bromide, 389
Alkylphosphate ester, 11, 341
Alkylpolyglycosides (APG), 201, 249
Alkylpolyoxyethylene oxide (AEOS), 209
Alkyl sulfate, 279
Allantoin, 389
Alkylpolyglycosides (APG), 201, 249
Alkylpolyoxyethylene oxide (AEOS), 209
Alkyl sulfate, 279
Allantoin, 389
All purpose cleaners (see also Liquid all purpose cleaners), 467
All purpose liquids, 13
All purpose spray cleaners (see also Spray liquid all purpose cleaners), 488
formulas, 489
Aloe Vera, 11
Aluminosilicates, 287
Amido peroxy acid, 298
Ammonium lauryl sulfate, 384
Amphiphile aggregation, 179
Amphiphile compatibility, 58
Amphiphile efficacy, 52
Amphiphilerich phase, 57
Amylase (see also Enzymes), 290291, 344
Amylolytic enzymes (see also Enzymes), 6
Anisotropic particulate, 86
Anthocyanins, 342
Antibacterial liquid soaps (see also Liquid soaps), 422
key ingredients & functions, 414418
Anticorrosion agents, 356
Antidandruff ingredients, 388

Page 550
Antidandruff shampoos, 388
active ingredients, 389
Antifogging, 491
Antimicrobial phenolic, 11
Antimicrobials, 3
Antimicrobial soaps, 423
Antiredeposition agents, 4, 6, 303
test for, 307
Antisagging, 135
Antiseptic handwash, 423
Antisoiling, 491
Apparent yield stresses, 89
Aromatic borate ester, 296
Aspergillus niger, 501
Association concentration, 32
Atomization, 81
Automatic dishwasher detergents (see also Liquid automatic dishwasher
detergents), 326
powder formulation, 327
Automatic dishwashing:
mechanics and chemistry, 328
Automatic dishwashing machines:
components, 328
European dishwashing cycle, 332
European vs. American machines, 329330
U.S. dishwashing cycle, 331
Baby shampoos (see also Shampoos), 384, 388
Batch mixing vessel, 528
Bathroom cleaners, 13, 14, 494
B
Baby shampoos (see also Shampoos), 384, 388
Batch mixing vessel, 528
Bathroom cleaners, 13, 14, 494
acidic, 495
alkaline, 494
test methods, 500
Benzethonium chloride, 389
Benzoic acid, 213
Bernoulli effect, 161
Betaines (see also Cocoamidopropylbetaine), 210, 384
Biguanides, 477
Binghamtype fluid, 93
Biodegradability, 459, 486
Biodegradable analog, 5
Biodegradation, 281
Birefringence, 101
Bleach activator, 7, 298
Bleach cleaners, 477
Bleach degradation, 343
Bleaches, 265, 297
Bleaching function, 7
Bleaching ingredients, 7
Bleach spray cleaners, 493
Bleachstable surfactants, 356
Bleach toilet bowl cleaners, 564
Body cleansing products, 429
Boronic acids, 296
Brighteners, 263
Bronopol, 213
Brookfield spindle viscometer, 148, 347
Bruggeman equation for dispersion of spheres, 90
Buffers, 272, 303
Bronopol, 213
Brookfield spindle viscometer, 148, 347
Bruggeman equation for dispersion of spheres, 90
Buffers, 272, 303
Builder, 4, 16, 17, 263, 265, 282, 334
calcium binding capacities, 335
chemical structures, 334
classes, 286
mechanism of function, 282
patents, 312
pKCa values, 335
sequestration capability of selected builders, 283285
Built heavyduty liquid detergents, 89
Butylated hydroxytoluene (BHT), 298
Calcite, 470
Calcium sequestrant, 5, 14
Carbomer dispersions:
microviscosity, 151
thickening mechanism, 146, 155
viscosity of, 148, 158
Carbomer resins:
chemistry of, 135
copolymer of, 136
for automatic machine dishwashing gel, 130
hygroscopicity, 140
particle density, 139
scanning electron photomicrograph, 139

Page 551
solubility of, 139
technology, 135
Carbomers, 130
acid dissociation constant of, 141
bulk density of, 138139
crosslink density, 155156
dispersion in nonpolar liquids, 162
dispersion properties, 142
dispersion technique, 159
formulating with, 165
glass transition temperature of, 137
handling of, 158
intrinsic viscosity, 142
factor affecting, 142
values, 144
intrinsic volume swelling ratio, 145
microrigidity, 153
microstructure properties, 154
molecular weight of, 140
overlap concentration, 145, 147
particle size of, 138
powder properties of, 137
thixotropy indexes, 151152
thixotropic loop, 153
viscosity building by, 156
wetting time, 158
yield value, 148, 150, 151
Carbonate, 334, 338
Carbopol, 95, 163164
Carboxylated nonionics, 10
yield value, 148, 150, 151
Carbonate, 334, 338
Carbopol, 95, 163164
Carboxylated nonionics, 10
Carboxymethylcellulose, 4, 303
Carotinoid dyes, 342
Casson law, 452
Casson rheology model, 151152
Cellosolves, 474
Cellulase (see also Enzymes), 290291
Centrifugation, 97, 173
Cetyltrimethylammonium bromide (CTAB), 68
Cetyltrimethylammonium chloride, 385, 386, 391
Chain scission, 81
Characterization of liquid detergents (see also Liquid detergents):
experimental test methods, 73
Chemical cleaning, 332
Chlorinated isocyanurates, 9
Chlorine bleaches, 342
Chromophore, 300
Citrate, 334, 338
Clays, clay softeners, 442
Cleaning efficacy, 281
Cleaning shampoos (see also Shampoos), 388
Cleaning tests for APC, 482
Cleansers, 468
Clear point, 239, 243
effect of sodium xylene sulfonate, 246
Climbazole, 389
Cloud point, 50, 55, 56, 239, 243
Cocoamidopropylbetaine, 210
Cocoamidopropylhydroxysultaine, 385
Cocoamphocarboxyglycinate, 384385
Cloud point, 50, 55, 56, 239, 243
Cocoamidopropylbetaine, 210
Cocoamidopropylhydroxysultaine, 385
Cocoamphocarboxyglycinate, 384385
Cocoamphopropylsulfonate, 384
Cocomonoethanolamide (CMEA), 210
Cocomonoglyceride sulfate (CMGS), 395
Coefficient of the Vand equation, 103
Collagen swelling test, 236
Colloidal dispersions, 90
Colloid mills, 162
greerco, 536
standard, 536
Colorless products, 248249
Complex fluids, 93
Concentrated products:
dishwashing detergents, 252
LADD, 372
Conditioning agents:
types of, 385
Conditioning mousses, 389
Conditioning shampoos (see also Shampoos), 388
Cone and plate viscometric fixture, 74
Consumer tests, 308
Contact angle, 218
Continuous manufacturing process (for liquid detergents), 522
Continuous vs. batch process, 518
Corian, 470
Coronary vasodilator nifedipine, 22
Cosmetic Toiletry and Fragrance Association (CTFA), 423

Page 552
Cotton, 11
Coulter counter, 139
Coupling agents, 3
CoxMerz rule, 93
Cream cleanser, 470
formulas, 472
Creep measurement, 72
Critical micellization concentration (CMC), 24, 182, 219
Critical phase, 53
Critical points, 36, 39, 55
Crosslink density, 96, 154
Crosslinked polyacrylates, 344
Crosslinked polymer, 136
Crosslinker, 136
Crosslink sites, 154
Cubic isotropic phase, 52
Cumulative patch test, 233
Cup retention values, 132
The cup test, 226227
Cyanuric chloride diaminstilbene, 300
Cyclohexylamine, 296
Cylinder test, 485
Dandruff, 9
Dandruff control, 282
Decarboxylation, 138
Deep conditioners, 389
Deer variable stress rheometer, 113
Defoamers, 303, 341
Defoaming, 9
Deep conditioners, 389
Deer variable stress rheometer, 113
Defoamers, 303, 341
Defoaming, 9
Deflocculating polymers, 268
Degree of flocculation, 84
Degree of substitution, 95
Depletion flocculation, 268
Detergency, 21, 222, 271, 272, 275, 277, 279, 281, 286, 304, 392
Detergent polymers, 300
Dextrins, 344
Diacid, 30
Dielectric constant for solvent, 183
Diethylene glycol monobutyl ether, 474
Differential scanning calorimetry, 138
Dilatant, 348
Dilatancy, 81
Dilational viscosities, 83
Di(long chain)alkyl dimethylammonium halide, 11
Dilute methods—dishwashing, 214
Dimensionless groups, 523
Dimethicone, 386
Dimethyldodecyl amine oxide (DMDAO), 210
Dimethylmyristal amine oxide (DMMAO), 210
Dimethyl steramine, 385
Dinginess, 297
Dip and dab methods—dishwashing, 215
Diperoxydodecanedioic acid, 70, 298
Direct batch dispersions (of carbomers), 161
Direct hexagonal phase, 52
Dishwashing detergents (see also Light duty liquid detergents):
cleaning evaluation, 225227
compositions based on alkylpolyglucamides, 250
Direct hexagonal phase, 52
Dishwashing detergents (see also Light duty liquid detergents):
cleaning evaluation, 225227
compositions based on alkylpolyglucamides, 250
compositions using methylester glucamide, 251
concentrates, 252
foam performance evaluation, 227230
mildness evaluation, 230236
nonionic surfactantbased compositions, 250
performance evaluation, 220, 225
test methods, 225238
typical composition, 209
Dishwashing test, 227, 229
Disinfectancy, 485
test for, 485
Disinfectants, 477
Disinfection, 504
Disinfection claim, 486
Disodium 4,4'bis(2sulfostyryl)biphenyl, 300
Disordered aggregates, 26
Dispensability, 72, 272
Dispersed systems, 85
Dispersion:
stabilizer, 69
structure/property diagram, 85

Page 553
Dispersive mixing, 535
Distearyldimethylammonium chloride, 385, 386
Distyrylbiphenyl derivatives, 300
Ditallowdimethylammonium chloride, 439, 440
Ditallow ester imidazoline, 442
Ditallow imidazoline, 441
DLVO theory, 446
Dowfax, 341
Dowicil, 213
D phase, 184
Drainage test, 237
Dryer sheets, 437
Dye transfer inhibition, 302
Dynamic mechanical measurements, 96, 97
Dynamic mechanical properties, 70, 97, 114
Dynamic moduli, 95
Edema, 233
Eductor, 161
EEC criteria for environmental labeling of raw materials, 455
Einstein coefficient, 89
Einstein viscosity equation, 98
Elasticity modulus, 78
Elastic modulus, 174
Elevated temperature cycling, 172
Elongational flow properties:
of surfactant solutions, 81
Elongational rate, 81
Elongational viscosity, 81
Emulsification, 218
of surfactant solutions, 81
Elongational rate, 81
Elongational viscosity, 81
Emulsification, 218
Emulsifiers, 445
determination of optimum content, 447
Emulsions, 92, 218
oilinwater, 93
Emulsion stability tests, 227
Encapsulation, 6
Environmental protection agency, 485
Enzymes, 6, 263, 289, 343
commercially available detergent enzymes, 344
denaturation of, 293
stabilization of, 281, 293, 296, 309
types of, 290
Enzymespecific stains, 6
Equilibrium contact angle, 216
Erythema, 233
ESCA, 394
Ethanolamines, 272, 389
Ester quat, 442
Ether carboxylates, 340
Ether polycarboxylates, 287
Ethoxylated alcohols, 210
Ethoxylated phosphate diesters, 342
Ethylenediaminetetraacetic acid (EDTA), 287
Ethylene glycol monoalkyl ether, 474
Ethylene terephthalate, 301
European Economic Community (EEC), 251
Eutrophication, 336, 370
Extensional viscometry, 81
F
European Economic Community (EEC), 251
Eutrophication, 336, 370
Extensional viscometry, 81
Fabric bundle tests, 307
Fabric conditioners:
raw materials, 17
Fabric softeners, 11, 433459
effect on fabrics, 436
environmental & regulatory aspects, 454
formulation, 444, 448
future trends, 455
industrial manufacture of, 444
patents, 456458
product types, 436
Fatty acid glucamides, 211, 250
Fatty alcohol sulfate (FAS), 209
FerrantiShirley cone and plate viscometer, 113
Fiber friction, 394
Fields, 37
Filming, 354
Film thickness, 533, 534
Fine China overglazes:
evaluation for LADDs, 354
“Finn chamber”, 232

Page 554
“Fish eyes”, 159
Flash foam, 419, 485
Flexibility, 435
Flocculant disperser, 161
Flocculation, 265, 453
FloryHuggins theory, 49
Flowability, 269
Fluorescent whiteners, 6
Fluorescent whitening agents (FWA), 299
Foam booster, 405
Foam end point, 227
Foaming of LADDs, 354
Foam level testing for APCs, 485
Foam mileage, 230
Foam performance:
evaluation of, 227
Foam performance ratio (FPR), 228
Foam stability, 83
tests for, 228
Foam stabilizers, 10, 15, 16, 17, 210
Foam volume test, 228
Foam vs. lather, 405
Formaldehyde, 213
Free polymers, 268
FroschKligman soap chamber test, 231
“Fugitive” compounds, 491
Gafquat polymers, 391
Gardener abrader machine, 482, 483
Gear pump, 539
G
Gafquat polymers, 391
Gardener abrader machine, 482, 483
Gear pump, 539
Gel, 70, 74, 93
electrostatically stabilized, 94
Gelation, 26
kinetics, 96
of polystyrene carbon disulfide, 94
Gelling agents, 94
Gel Permeation chromatography (GPC), 140
Genapol, 277
Gibbs triangle, 57, 59
Glass and surface cleaners, 491
Glass cleaners, 489490
formulas, 490
Glass transition temperature, 137
Glucamides, 210, 211, 250
Glutaraldehyde, 213
Glycerin esters, 299
Gravimetric measurement, 225226
Grease emulsification, 13
Grease removal test, 226
Greerco colloid mill, 536
Hair:
acidbinding capacity of, 401
adsorption onto, 397
basebinding capacity of, 402
binding of ionic ingredients to, 400
breakage, 386
damage from shampoo, grooming and weathering, 387
diffusion into, 399
basebinding capacity of, 402
binding of ionic ingredients to, 400
breakage, 386
damage from shampoo, grooming and weathering, 387
diffusion into, 399
isoelectric point of, 397
manageability, 9, 10
reaction with cationic surfactants, 402
reaction with hydrogen ion, 402
reaction with neutral materials, 404
structure of, 382
Hair cleaning:
methods of evaluation, 394
Hair conditioners, 383
structure of ingredients, 385
Hair lipid:
transport of, 393
Hair setting, 391
Hair soils, 390, 392
Hair styling, 391
Hand dishwashing, 214
effect of pH, 216
test, 228
variables in, 214
washing methods, 214
Hand immersion tests, 231
Hard surface cleaners, 13
Haze point, 55
Heat transfer, 537
Heavyduty liquids:
advantages over powder, 263
components, 272
detergency evaluation, 304
Heavyduty liquids:
components, 272
detergency evaluation, 304
future trends, 308

Page 555
with mixed enzymes, 296
raw materials, 15
nHexylamine, 296
High foaming anionic surfactants, 3
HLB, 52, 446
HLB temperature, 56
Homogenizers, 162
Homopolymer, 136
Household hard surface cleaners, 464
“House of cards” structure, 94
Hugging plots, 143
Human repeat insult patch test, 232
Humic acid polymers, 342
Hydration, 97
Hydrazine, 180
Hydrogels, 115
Hydrophobic interaction, 179, 180
Hydrophobicity, 58, 269
Hydrotropes, 3, 15, 18, 21, 210, 303, 368
applications, 22
commonly used in LDLDs, 212
Hydrotropic activity, 22
Hydrotropic solubilization, 22
Hydrotropy, 2133
Hype compounds, 385
Hypoallergenic products, 426
Hypochlorite, 297
Hypochloritestable defoamers, 341
Imidazolinium compounds, 12
Hypochlorite, 297
Hypochloritestable defoamers, 341
Imidazolinium compounds, 12
Imidazolium methosulfate (DHTIM), 440
Imido peroxy acid, 298
Immunological reaction, 386
Impeller:
high efficiency, 526
pitch blade, 519, 520
straight blade turbine, 526
Incompressible fluids:
flow of, 72
Incubation, 97
Inline dynamic mixers, 521
Inline helical ribbon blender, 521
Inline mixers, 162
Inline static mixers, 519, 520
Inorganic ions—effect on dishwashing, 222
Insect repellent, 478
Intercellular diffusion, 399
Interfacial elongational viscometers, 83
Interfacial tension (solvent/hydrocarbon), 183
Interfacial tension measurement, 236
Interfiber spacing, 394
Interlamellar forces, 268
Interlamellar spacing, 30
Intrinsic viscosity, 100, 142, 143
Intrinsic volumeswelling ratio, 144
Inverse micelles, 24
Invitro tests, 231
Invivo tests, 234
Ionexchange, 282
Inverse micelles, 24
Invitro tests, 231
Invivo tests, 234
Ionexchange, 282
Isotropic liquid phase, 24
Isotropic liquid solution, 29
Isotropic phase, 99
Isotropic unstructured solution, 84
Kathon, 213
Ketoconazale, 389
Kinetics of ionic reactions with keratin fibers, 398
Krafft point, 42, 44, 182
KriegerDougherty model, 87
Lamellar bilayers, 265
Lamellar dispersion, 69
Lamellar droplets, 89, 265, 266
Lamellar liquid crystal, 29
Lamellar packing, 26
Lamellar phase, 52, 53, 184
Lamellar structures, 265
Large quantity batch dispersions (of carbomers), 161
Large quantity continuous dispersion (of carbomers), 162
Lather feel, 406
Lather vs. foam, 405
Lather modifier, 405
Laundry auxiliaries, 6
Laundry prespotter, 135

Page 556
Laundry soils, 306
Lauric/myristic diethanol amide (LMDEA), 210
Lauric/myristic monoethanol amide (LMMEA), 210
Leading ion mechanism, 404
Leveling agents, 12
Lever rule, 37
Lightduty liquid detergents, 207259
aging studies, 246
formulating for desirable esthetics, 239
formulating for effective cleaning, 238, 240
formulating for longlasting foam, 239, 242
formulating for mildness, 239, 244
formulation guidelines, 238
formulation technology, 238247
ingredients, 208
line extension, 247
minor ingredients, 213
new products and future trends, 247
physical stability, 246
product safety, 247
special additives, 213
typical composition, 207, 208
viscosity, 243
Lightduty liquids (see also Lightduty liquid detergents):
raw materials, 15
dLimonene, 474
Linear alkylbenzene sulfonate (LAS), 209, 273
Linear Newtonian flow curves, 74
Lipase (see also Enzymes), 290, 291, 344
Liquid all purpose cleaners, 472
Linear alkylbenzene sulfonate (LAS), 209, 273
Linear Newtonian flow curves, 74
Lipase (see also Enzymes), 290, 291, 344
Liquid all purpose cleaners, 472
formulas, 479
with insect repellent, 478
minor ingredients, 480
test methods, 481486
Liquid automatic dishwasher detergents (LADDs), 8, 325
concentrated products, 372
enzymatic products, 372
flow properties, 347
future trends, 370
ideal rheological characteristics, 346
important attributes, 355
nonhypochloritecontaining products, 370
nonphosphate products, 370
performance evaluation, 351
raw materials, 15
thixotropy, 347
typical compositions, 333
thixotropy, 347
viscosity, 347
yield value, 347
Liquid cleaners with abrasives, 133
Liquid crystals, 28, 52, 184, 264
destabilizer, 28
disordering of, 30
Liquid crystal matrix, 112
Liquid crystal phase, 24, 264
destabilizer, 28
disordering of, 30
Liquid crystal matrix, 112
Liquid crystal phase, 24, 264
Liquid detergents:
fundamental research, 97
manufacture of, 513
overview, 119
process patent technology, 515
rhelogy of, 67
stability evaluation, 169
Liquid laundry detergents (see also Heavyduty liquid detergents):
consumer, 134
industrial, 133
Liquidliquid suspensions, 92
Liquid prespotters, 356
Liquid soaps, 10, 409432
antibacterial soaps, 414
formulas, 412
future trends, 427
key ingredients and functions, 413
mildness, 424
mildness testing, 426
preservative systems, 421
product esthetic regulators, 421
product physical property regulators, 420

Page 557
raw materials, 17
sensitive skin products, 425
Loss modulus, 78, 94, 348
as a function of strain, 79
Lower consolute temperature (LCT), 36
Lowswelling carbomer resins, 157
Light scattering, 394
Low temperature cycling, 172
Lubricity, 435, 491
Luster (of hair), 9
Lyotropic liquid crystals, 32, 110
Lyotropic mesophase, 59
Magnesium omadine, 389
Manageability (of hair), 9, 10
Mass transfer, 538
Maximum acidcombining capacity (of hair), 400
Maxwell behavior, 110
Mechanical action (in hand dishwashing), 214
Mechanical cleaning, 331
Mechanism of cleaning—dishwashing, 216
Medicated shampoos, 388
Merquat polymers, 391
Mesophase, 53
Methyl ester sulfonates, 281
Micellar aggregation, 180
Micellar solution, 23
Micelle geometry, 97
Micelle polymerization, 109
Micelles, 24
Micellar solution, 23
Micelle geometry, 97
Micelle polymerization, 109
Micelles, 24
Micellization, 180
Microemulsion, 47, 189, 476
oilinwater, 47
waterinoil, 48
Microencapsulation, 296, 372
Microgel rigidity, 153, 154
Microgel rigidity coefficient, 153
Microgels, 93, 145, 146, 150, 153
Microscopy, 97
Microviscosity, 151
Middle phase, 52, 57
Mildew removers, 494, 498
Mildness to skin, 4
Mineral incrustation, 434
Miniature dishwashing test, 230
Miniplate test, 220
Miscibility gap, 49
Mixing of liquid detergents:
structured vs. unstructured, 525
Model dirt, 29
Modified SchlachterDierkes test, 230
Moh's hardness scale, 470
Mold and mildew cleaning, 500
Momentum transfer, 524
Monoethanolamine (MEA), 272, 303
Montmorillonite clays, 443
Multilayered vesicle, 89
Neat dishwashing, 214
Montmorillonite clays, 443
Multilayered vesicle, 89
Neat dishwashing, 214
Neat phase, 52
Neodol, 277
Newtonian flow, 345
Newtonian fluid, 72
pumping of, 535
NMR, 30, 97, 185
NMR relaxation, 182
Nonaqueous liquids, 264, 272
Nonaqueous lyotropic liquid crystalline phase, 192
Nonaqueous microemulsions, 189
Nonaqueous system, 5, 7, 179
Nonflocculated lamellar dispersion, 266
Nonhypochloritecontaining LADDs, 370
Nonhypochlorite disinfection, 478
Nonionic surfactantbased dishwashing detergents, 250
NonNewtonian fluid, 72
pumping of, 535
Nonphosphate products—LADDs, 370
Nonsoap surfactants, 11
NTA (trisodium nitrilotriacetate), 5, 287, 334, 339
Nutralization, 14
Nylon, 11
Oblate micelle, 100

Page 558
Olefin Sulfonate (AOS), 209
Oleophobicity, 58
Oleyldimethylamineoxide (ODMAO), 105
Oligophosphate ions, 336
Optical brighteners, 299
Organic peroxy acid, 70
Organic polymers, 338
Organic solvent, 7
Organomodified polydimethylsiloxanes, 444
Orthophosphate, 336
Oscillatory rheometers, 78
Osmotic compression, 268
Osmotic interactions, 266
OstwaldDeWaele model, 451
Overlap concentration, 146
Oxydicarboxylates, 340
Paraffin sulfonate, 209
Patch test, 232
Patents:
builders, 312
cleaning technology in LADDs, 357358
corrosion inhibition in LADDs, 363
detergents with bleach, 312
detergents with softener, 313
dye transfer, 317
enzyme stabilization, 309
fabric softeners, 456458
formulating LDLDs for effective cleaning, 240
formulating LDLDs for longlasting foams, 242
enzyme stabilization, 309
fabric softeners, 456458
formulating LDLDs for effective cleaning, 240
formulating LDLDs for longlasting foams, 242
formulating LDLDs for mildness, 244245
formulating LDLDs—miscellaneous examples, 248
LADD processing, 362
nonaqueous liquids, 315
phosphatefree LADDs, 371
rinse aids, 369
stabilization of LADD components, 365
structured liquid composition, 314
suds control, 317
surfactants for HDLDs, 311
surfactants for LADDs, 364
thickeners in LADDs, 359361
Peptide, 291
Peptide aldehyde, 296
Peptide ketone, 296
Peracids, 298, 343
Perborate salts, 343
Percarbonate salts, 343
Peroxygen bleaches, 297, 343
Phase behavior:
effect of electrolytes, 62
effect of oil, 61
effect of organic molecules, 63
effect of polarity, 62
effect of system parameters, 60
effect of surfactant structure, 60
of LAS, 101
Phase diagrams, 22, 36, 100, 186, 190, 191, 193, 196, 198
of colloidal dispersions, 90
effect of surfactant structure, 60
of LAS, 101
Phase diagrams, 22, 36, 100, 186, 190, 191, 193, 196, 198
of colloidal dispersions, 90
of ionic surfactantcontaining system, 42
of nonionic surfactantcontaining system, 48
recording of, 41
three component, 37
topology of, 56
two component, 36
Phase equilibria, 35
Phase inversion temperature, 56
Phase rule, 39
Phase separation, 268, 454
Phase stability, 8
Phase topology, 48, 49
Phenols, 477
Phosphate diesters, 342
Phosphatefree LADDs, 370
Phosphate hydration, 541
Phosphates, 336
Pine oil, 474, 477
Placenta extract, 385
Plate counts, 225
Polyacrylamide, 81
Polyacrylates, 268

Page 559
Polyacrylic acid, 334
Polycarboxylate polymers, 7, 9, 287
Polycarboxylates, 338, 339
Polydimethylsilicone polymers, 444
Polyester, 11
Polyethylene glycol, 268, 478
Polyethylene oxide, 301
Polyglucosides, 476
Polymeric polyelectrolytes, 289
Polymeric surfactants, 341
Polymerization, 136
Polymer JR, 391
Polymer processing, 542
Polymer stabilizers (for liquid detergents), 130, 135
Polymersurfactant complexes, 114
Polymersurfactant interaction, 114
Polyoxyalkalenes, 250
Polypeptide, 291
Polysaccharides, 94
Polyvinylpyrrolidone (PVP), 162, 302, 478
Positron annihilation, 182
Potassium oleate, 10
Potassium taurate, 7
Pourability, 268
Powder cleaners, 464, 467
Powdered all purpose cleaner:
formulas, 468
Powdered cleanser:
formulas, 469
Powdered laundry detergents, 4
formulas, 468
Powdered cleanser:
formulas, 469
Powdered laundry detergents, 4
Power law, 451
Power number, 524
Precipitation, 282
Preservatives, 213
Preshearing rates, 81
Prespotter, 290
Principles of rheology, 69
Product delivery vehicles, 84
Product shelf life, 542
Product stability, 97
Propylene glycols, 474
Protease (see also Enzymes), 290, 291, 344
HDLDs, 295
Protease stabilization, 287, 295
Protein, 3
Proteinases, 6
Protein denaturation, 234
Proteolytic enzymes, 6
Pseudoplastic flow, 148, 345
Pyrophosphate, 286, 336
Quaternary ammonium compounds, 477
“Quats”, 477
Raman spectroscopy, 182
Rate of deformation tensor, 72, 98
Raw material variation—effect on dishwashing, 223
Reduced viscosity, 100
Reflectometer, 305, 484
Raman spectroscopy, 182
Rate of deformation tensor, 72, 98
Raw material variation—effect on dishwashing, 223
Reduced viscosity, 100
Reflectometer, 305, 484
Regular liquid soaps:
key ingredients and functions, 417
Relative viscosity, 86
Relaxation process, 89
Reynolds number, 531
Rheogram:
of unpurified bentonite, 91
of purified bentonite, 91
Rheological characterization, 97
Rheological measurements, 71
Rheological models:
review of, 89
Rheological studies:
of anionic surfactants, 101
of cationic surfactants, 107
of mixed surfactants:
anionic/cationic systems, 110
anionic/nonionic systems, 104
zwitterionic/anionic systems, 106
of nonionic surfactants, 100
Rheology:
of LADDs, 345
of LAS and ABS, 101
principles of, 69
Rheopectic, 77, 88, 348
Rheopectic behavior:
of a commercial conditioning shampoo, 77

Rheopectic, 77, 88, 348
Rheopectic behavior:
of a commercial conditioning shampoo, 77

Page 560
Rheopexy, 72, 89
Rinse aids, 366
formulations, 368
ingredients, 367
Rinse cycle fabric softeners, 12
worldwide volume, 434
Rinsing in dishwashing, 215
Rinsing test, 237
Rodlike micelle, 111
Rollup, 216, 392
RossMiles test, 228, 485
Ross turboemulsifier, 529
Rotation viscometers, 72
Rubber elasticity theory, 154
Salting electrolytes, 272
Saltingin effect, 22, 62
Salting out: 8, 62
electrolytes, 268, 272
Sanitization claims, 486
Sanitizing products, 13
Sarcosinates, 11
Scanning electron micrographs (SEM), 395
Screw pumps:
single rotor, 539
tworotor, 539
Seborrheic dermatitis, 388
Sensitization, 386
Sequestering agents (see Sequestrants)
Sequestrants, 17, 18, 367
Seborrheic dermatitis, 388
Sensitization, 386
Sequestering agents (see Sequestrants)
Sequestrants, 17, 18, 367
Sesquicarbonates, 286
Setting lotions, 389
Shampoo (see also Shampoos and conditioners), 382408
baby shampoos, 384
efficiency, 394
general formulas, 383
lather, 405
safety considerations, 386
structures of ingredients, 384
types, 388
Shampooing:
detergency mechanism, 392
Shampoos and conditioners (see also Shampoo), 9, 381408
raw materials, 16
viscosity control, 406
Shear stress vs. shear rate plots, 345
Shear thickening, 90
Shear thinning, 148
Sheeting, 9
Silicates, 337
Silicone oils, 341
Silicones, 444
Silicone softeners, 444
Simulated shipping tests, 97
Skin benefit agent, 3
Skin conditioners, 424
Skin conditioning agents, 419, 427, 428
Skin feel ingredients, 419
Sinusoidal strain, 79
Skin conditioners, 424
Skin conditioning agents, 419, 427, 428
Skin feel ingredients, 419
Sinusoidal strain, 79
Smallangle neutron scattering, 97, 199
Smoothness (of skin), 419
Soap aggregation, 104
Soap and detergent association (SDA), 423
Soap scum cleaning, 498
test methods for, 500
Soap solution, 104
Soda ash, 339
Sodium bicarbonate, 338
Sodium carbonate, 338
Sodium citrate, 5, 7
Sodium cumene sulfonate (SCS), 212
Sodium hypochlorite, 9
Sodium laureth sulfate, 384
Sodium linear alkylbenzenesulfonate (LAS), 5
Sodium nonanoyl oxybenzene sulfonate (NOBS), 299
Sodium perborate, 7
Sodium perborate tetrahydrate, 298
Sodium percarbonate, 298
Sodium sesquicarbonate, 338
Sodium silicates, 286
Sodium soap mesophase, 114
Sodium tartrate disuccinate (TDS), 7, 288
Sodium tartrate monosuccinate (TMS), 7, 288
Sodium toluene sulfonate (STS), 212
Sodium xylene sulfonate (SXS), 212

Page 561
Soft abrasives, 13
Softeners (see also Fabric softeners), 265
Softening (of fabrics):
compounds, 440
mechanism, 438
“Softergents”, 6, 13, 437
Softsoap, 411
Soil release agents (see also Soil release polymers), 300302
Soil release polymers, 301
endcapping groups, 301
patents, 316
PETPOET, 302
Soil removal:
laboratory tests for HDLDs, 304
Soil titration method (STM), 228
Sokalan, 339
Solid hydration:
builders and polymers, 540
Solubilization, 219, 272
Solubilizing power, 32
Soluble abrasives, 471
Solution phenomena, 5
Solution viscosity, 98
Solvent cleaners, 14
Solvents, 474
Solvophobic interaction, 180, 199
Spangler synthetic sebum, 391
Specialty liquid household surface cleaners, 13, 135, 463512
future trends, 505
Solvophobic interaction, 180, 199
Spangler synthetic sebum, 391
Specialty liquid household surface cleaners, 13, 135, 463512
future trends, 505
lineage, 505
Specialty liquids (see Specialty liquid household surface cleaners),
Spherical micelles, 100
Spherulitic surfactant aggregates, 8
Spinnability, 83
Spotting and filming, 351
rating scale, 352
Spray all purpose cleaners, 486493
formulas, 489
streak and residue testing, 492
Spray bathroom cleaner:
formulas, 497
Spray trigger packaging, 487
Stability, 97
of LADDs, 345
Stable structured liquid, 267
Stain removal:
Standard colloid mill, 536
Static soaking test, 226
Steady shear viscometers, 72
Stearalkonium chloride, 391
Stearamidopropyldimethyl amine, 385
Steric interaction, 266
StokesEinstein microdiffusion coefficient, 152
Storage modulus, 78, 94, 348
STPP, 4, 283, 314, 336
Strain sweep test, 174
Storage modulus, 78, 94, 348
STPP, 4, 283, 314, 336
Strain sweep test, 174
Streaking, 14, 491
effect of solvent, 475
Stress growth behavior, 113
Stress growth measurement, 110, 113
Stress overshoot, 77
Stress tensor, 72, 98
“Stretching” flow, 81
Structural relaxation time, 105
Structured HDLDs—examples, 270
Structured liquid detergents, 134, 263
manufacture of, 514
stability of, 266, 269
Structured viscoelastic fluid, 78
Structuring agents, 344, 406
Substantivity, 439
Sulfosuccinate, 11
“Super concentrated”, 7
nonaqueous heavyduty liquids, 8
Surface charge, 84
Surface free energy, 217
Surface rheology, 83
Surface safety, 485
Surfactant liquid crystal gels, 112
Surfactant morphology, 100
Surfactant phase, 57
Surfactantrich liquid crystal phase, 219
Surfactant types and dishwashing performance, 220

Page 562
Surfactants:
for heavyduty liquid detergents, 274
for lightduty liquid detergents, 211
for liquid automatic dishwasher detergents, 340
for rinse aids, 367
surfactant viscosity, 103
Suspension, 8
Suspension viscosity, 86
Tannins, 342
Temazepam, 22
Tergitol, 277
Tergotometer test, 229, 304
Tetraacetylethylenediamine (TAED), 299
Tetradecyldimethyl amine oxide (TDMAO), 111
Tetragenic effects, 5
Thermal cleaning, 331
Thermal cycling, 97
Thickened aqueous bleach composition, 70
Thickening agents, 344
Thixotropic index, 152
Thixotropic loop, 348
Thixotropy, 9, 72, 75, 152, 347
Threephase triangle, 57, 58
Threshold effect, 339
Tie line, 37, 39, 55
Toilet bowl cleaners, 13, 14, 494, 501
acidic, 503
bleach, 504
formulas, 503
Toilet bowl cleaners, 13, 14, 494, 501
acidic, 503
bleach, 504
formulas, 503
packaging, 502
test methods, 504
Total foam, 230
Total irritation, 232
Transcellular diffusion, 399
Transport phenomena in agitated vessels, 523
Triazinylaminostilbene, 300
Triazoylstilbene, 300
Trichlorocyanuric acid (TCCA), 469
Triclosan, 423
Triethanolamine (TEA), 272, 303
Triglyceride, 291
Tripolyphosphate (TPP) (see also STPP), 286, 334
Tripropylene glycol, 474
Trouton ratio, 71
Turbidimeter, 227
Turbidity measurements, 225, 227
Turboemulsifier:
detailed schematic, 530
Unit operations:
in liquid detergent manufacture, 523
Unstructured heavyduty liquid detergents—examples, 270
Unstructured liquid detergents, 263, 269
manufacture of, 514
stability of, 271
Upper consolute temperature (UCT), 36
Urea, 212
manufacture of, 514
stability of, 271
Upper consolute temperature (UCT), 36
Urea, 212
Vesicles, 69
Vibration, 97
Viscoelastic cationic surfactant systems, 108
Viscoelastic gel detergent, 70
Viscoelasticity, 70, 89, 109
of gel laundry stain remover, 80
Viscometers, 347
Viscometric measurements, 71
Viscometric properties of zwitterionic surfactants, 105
Viscometric tests, 72
Viscosity, 71, 72, 86
as a function of shear, 76
of ionic surfactants, 99
of lightduty liquid detergents, 243
steadystate, 71
transient, 71
Viscosity limitations of various impeller configurations, 530
Viscositylowering characteristics, 134
Viscosity modifier, 69
Viscosity regulator, 10, 16, 17
Viscosity vs. shear rate plots, 346
Viscous modulus, 174

Page 563
Viscous phase, 52
Vitamins, 385
Wall slippage, 93
Wash cycle softeners, 437
Wash liquor, 5
Washwater buffers, 286
Water hardness:
effect on dishwashing, 216, 224
effect on foam stability, 224
in different countries, 330
Waterinoil microemulsion, 47
Weissenberg effect, 73
Whitening agents (see Fluorescent whitening agents)
Window cleaners (see also Glass cleaners), 13, 14
Winsor behavior, 59
Winsor II, 56
Winsor III system, 57
Winsor III ternary phase diagram, 40
Winsor transition temperature, 63
Xanthan gum, 81
Xray scattering techniques, 187
Xray smallangle scattering, 182
Yield stress, 93
Yield value, 132, 347
YoungDupree equation, 217
Z
Yield stress, 93
Yield value, 132, 347
YoungDupree equation, 217
Zein test, 235
Zein value, 235
Zeolite, 7, 265, 287, 337
Zero shear viscosity, 105, 106
Zwitterionic surfactants:
viscometric properties of, 105

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C4E1 10.3 58.9 48.7 29.0

C6E3 12.7 47.4 45.4 13.5

C8E4 12.6 29.6 39.6 6.9

C10E5 12.5 19.7 40.3 3.5

C12E6 12.4 10.6 48.0 2.2

WI WIII WII

where is the interfacial tension, R32 the Sauter mean drop radius the volume

where is the volume fraction of solvated micelles and c m c represents the

Specific viscosity = r­l

Intrinsic viscosity [ ] = [(ln r)/c] c = 0

C8F17SO3NA (C2H5) 4NOH

C9F19CO2Na (CH3) 4NOH

c (mmol/dm) 20°C 30°C 40°C 50°C

4 430 270 160 150

6 640 400 280 200

7 750 460 315 240

Ingredient Control Exp

Carbomer :Smallesta Average :Largest

Carbopol934 0.043 0.20 0.25

Carbopol 940 0.046 0.20 0.24

Particle Bulk Carbopol 941 1.427 no

Carbopol 940 1.448 0.23

Carbopol 934 1.444 0.23

Carbopol 1.396 0.28

Carbopol 1.333 0.30

Time % 0.67 4.0

Intrinsic Slopea Carbopol 941 7.59 35.0

Carbopol 934 3.85 8.3

Carbopol 2.60 9.9

Carbopol 1.89 43.6

Particle Intrinsic volume Carbopol 941 1.427 446.6

Carbopol 934 1.444 214.1

Carbopol 1.396 142.2

Carbopol 1.333 101.5

Relative High High Low High

Low Low High Low

Overlap Carbopol 941 0.20

Carbopol 941 25.5 4.6 13.5 10,700

Carbomer Cross­link density Rigidity

Carbopol 934 27.1 736.9

Carbopol ETD 2020 97.7 983.3

Carbopol Ultrez 10 54.6 325.8

Carbomer 0.50 1.00 2.00 3.00 4.00

Carbopol 941 2,970 4,630 5,560 6,980 16,450

Carbopol 940 680 4,150 10,580 26,350 57,600

Carbopol 934 17 105 2,820 7,260 19,750

Carbopol Ultrez 10 7 9 41 164 1,130

Carbopol ETD 2020 17 108 740 3,410 7,010

Solvent Interfacial tension Dielectric

Formamide 27.3c 109

N­methylformamide 12.5c 182

Surfactant Solvent Additive Phases detectedb

Lecithin MFA D, I, F

Lecithin DMF I, F

C16PyCl MFA E, I, D

C16PyCl NMS E, I, D

SDS FA­H2O Decanol D (E)

AOT G Decanol D … 6

AOT G Decane D … 6

AOT G p ­Xylene D … 6

TEAO TEA G, EG D 7

DBSA TEA G, EG, TEG D 7

C16TABr FA Cyclohexane Butanol 76–78

Specific viscosity = rl

Carbomer Crosslink density Rigidity

Nmethylformamide 12.5c 182

SDS FAH2O Decanol D (E)

AOT G p Xylene D … 6

TEAO1 G p Xylene Oleic acid 99

SDS FA p Xylene Pentanol, 24, 86

SDS G p Xylene Hexanol 89

AOT G Decane, p xylene 68

AOT G nHeptane 80, 90

AOT G Decane, p xylene 68

AOT G nHeptane 80, 90

Triton X114 DMSO Dodecane Pentanol 106

Triton X114 Acetonitrile Dodecane Pentanol 106

plateair = oilair cos + plateoil

platebath = oilbath cos + plateoil

Sodium C12–16 olefin sulfonate — 10.4

5Phenyl decane 29.8 0.06

2Phenyl decane 20.1 0.2

2Phenyl undecane 0.1 14.9

3Phenyl dodecane 0.3 12.9 0.2

Watersoluble soils Particulate soils Proteins sourc