Applied Surface and Colloid Chemistry

HANDBOOK OF APPLIED
SURFACE AND COLLOID
CHEMISTRY
Volume 1 - 2
Edited by

Krister Holmberg
Chalmers University of Technology,
Goteborg, Sweden

Associate Editors

Dinesh O. Shah
University of Florida,
USA

Milan J. Schwuger
Forschungszentrum JUlich GmbH,
Germany

JOHN WILEY & SONS, LTD
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Library of Congress Cataloging-in-Publication Data
Handbook of applied surface and colloid chemistry / edited by Krister Holmberg.
p.cm.
Includes bibliographical references and index.
ISBN 0-471-49083-0 (alk. paper)
1. Chemistry, Technical. 2. Surface chemistry. 3. Colloids. I. Holmberg, Krister, 1946TP149 .H283 2001
660 - dc21

2001024347

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ISBN 0-471-49083-0
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Contributors List
Joshua J. Adler

John Daicic

Department of Materials Science and Engineering, and
Engineering Research Center for Particle Science and
Technology, PO Box 116135, University of Florida,
Gainesville, FL-32611, USA

Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Dennis S. Everhart
Kimberly Clark Corporation, 1400, Holcombe Bridge
Road, Roswell, GA-30076-2199, USA

Bjorn Bergenstahl
Department of Food Technology, Center for Chemistry

and Chemical Engineering, Lund University, PO Box
124, SE-221 00 Lund, Sweden

Vance Bergeron
Ecole Normale Superieure, Laboratorie de Physique
Statistique, 24 Rue Lhomond 75231, Paris CEDEX 05,
France

Lennart Bergstrom

Valentin B. Fainerman
International Medical Physicochemical Centre, Donetsk
Medical University, 16 Hych Avenue, Donetsk 340003,
Ukraine

Michele Ferrari
CNR - Instituto di Chimica Fisica Applicata dei Materiali, Via De Marini 6, 1-16149 Genova, Italy

Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

David T. Floyd

Michal Borkovec

Degussa-Goldschmidt Care Specialties, PO Box 1299,
914, East Randolph Road, Hopewell, VA-23860, USA

Department of Inorganic, Analytical and Applied Chemistry, CABE, University of Geneva, Sciences II, 30 quai
Ernest Ansermet, CH-1211 Geneva 4, Switzerland

Johan Froberg
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Norman L. Burns
Amersham Pharmacia Biotech, 928 East Arques Avenue,
Sunnyvale, CA 94085-4520, USA

Per M. Claesson
Department of Chemistry, Surface Chemistry, Royal
Institute of Technology, SE-100 44 Stockholm, Sweden
and Institute for Surface Chemistry, PO Box 5607, SE114 86 Stockholm, Sweden

Burghard Gruening
Degussa-Goldschmidt Care Specialties, Goldschmidtstrasse 100, D-45127 Essen, Germany

Karina Grundke
Institute of Polymer Research Dresden, Hohe Strasse 6,
D-01069 Dresden, Germany

Michael F. Cox

Syed Hassan

Sasol North America, Inc., PO Box 200135, 12024 Vista
Parke Drive, Austin, TX-78726, USA

Department of Chemical Engineering, UMIST, PO Box
88, Manchester, M60 IQD, UK

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Heinz Hoffmann

Bjorn Lindman

Lehrstuhl fur Physikalische Chemie I der Universitat
Bayreuth, Universitatsstrasse 30, D-95447 Bayreuth,
Germany

Department of Physical Chemistry 1, Chemical Center,
Lund University, PO Box 124, SE-221 00 Lund, Sweden

Krister Holmberg

Department of Organic Chemistry, University of Florence, Via G. Capponi 9, 50121 Florence, Italy

Giuseppe Loglio
Department of Applied Surface Chemistry, Chalmers
University of Technology, SE-412 96 Goteborg, Sweden

James J. Lu
Lothar Huber
Adam Bergstrasse IB, D-81735 Munchen, Germany

Paul D. T. Huibers
Department of Chemical Engineering, Massachusetts
Institute of Technology, Cambridge, MA 02139-4307,

USA

Stephen T. Hyde
Applied Mathematics Department, Research School
of Physical Sciences, Australia National University,
Canberra 0200, Australia

James R. Kanicky
Center for Surface Science and Engineering, Departments of Chemical Engineering and Anesthesiology, PO
Box 116005, University of Florida, Gainesville, FL32611,USA

Bengt Kronberg
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Hubert Kuhn
Department of Physical Chemistry, University of Essen,
Universitaetsstrasse 3 - 5 , D-45141 Essen, Germany

Markus Lade
Institute for Technical Chemistry, Technical University
of Berlin, Sekr. TC 8, Strasse der 17 Juni 124, D-10623
Berlin, Germany

Department of Mechanical and Industrial Engineering,
Univeristy of Toronto, 5 King's College Road, M5S 3G8
Toronto, Ontario, Canada

Alexander V. Makievski
International Medical Physicochemical Centre, Donetsk

Medical University, 16 Ilych Avenue, Donetsk 340003,
Ukraine

Martin Malmsten
Institute for Surface Chemistry and Royal Institute
of Technology, PO Box 5607, SE-114 86 Stockholm,
Sweden

Anna Matero
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Reinhard Miller
Max-Planck-Institute of Colloids and Interfaces, Am
Mtihlenberg, D-14476 GoIm, Germany

Helmuth Mohwald
Max-Planck-Institute of Colloids and Interfaces, Am
Miihlenberg, D-14476 GoIm, Germany

Juan-Carlos Lopez-Montilla
Center for Surface Science and Engineering, Departments of Chemical Engineering and Anesthesiology, PO
Box 116005, University of Florida, Gainesville, FL32611,USA

Hubert Motschmann
Oliver Lade
Institute for Physical Chemistry, University of Cologne,
Luxemburger Strasse 116, D-50939 Cologne, Germany

Max-Planck-Institute of Colloids and Intefaces, Am

Miihlenberg, D-14476 GoIm, Germany

Brij M. Moudgil
C. N. Catherine Lam
Department of Mechanical and Industrial Engineering,
University of Toronto, 5 King's College Road, M5S 3G8
Toronto, Ontario, Canada

Department of Materials Science and Engineering, and
Engineering Research Center for Particle Science and
Technology, PO Box 116135, University of Florida,
Gainesville, FL-32611, USA

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Michael Mulqueen

Mark W. Rutland

Department of Chemical Engineering, Massachusetts
Institute of Technology, Cambridge, MA 02139-4307,
USA

Department of Chemistry, Surface Chemistry, Royal
Institute of Technology, SE-100 44 Stockholm, Sweden
and Institute for Surface Chemistry, PO Box 5607, SE114 86 Stockholm, Sweden

A. Wilhelm Neumann
Department of Mechanical and Industrial Engineering,

University of Toronto, 5 King's College Road, M5S 3G8
Toronto, Ontario, Canada

Lutz Nitschke
Karwendelstrasse 47, D-85560 Ebersberg, Germany

Magnus Nyden
Department of Applied Surface Chemistry, Chalmers
University of Technology, SE-412 96 Goteburg, Sweden

UIf Olsson
Department of Physical Chemistry 1, Center for Chemistry and Chemical Engineering, PO Box 124, S-221 00
Lund, Sweden

Wolfgang von Rybinski
Henkel KgaA, Henkelstrasse 67, D-40191 Dusseldorf,
Germany

Antje Schmalstieg
Thaerstrasse 23, D-10249 Berlin, Germany

Reinhard Schomacker
Institute for Technical Chemistry, Technical University
of Berlin, Sekr. TC 8, Strasse des 17 Juni 124, D-10623
Berlin, Germany

Christoph Schunicht
Degussa-Goldschmidt Care Specialties, Goldschmidstrasse 100, D-45127 Essen, Germany

Samir Pandey

Center for Surface Science and Engineering, Departments of Chemical Engineering and Anesthesiology, PO
Box 116005, University of Florida, Gainesville, FL32611,USA

Dinesh O. Shah
Center for Surface Science and Engineering, Departments of Chemical Engineering and Anesthesiology, PO
Box 116005, University of Florida, Gainesville, FL32611,USA

Alexander Patist
Cargill Inc., Central Research, 2301 Crosby Road,
Wayzata, MN-55391, USA

Robert J. Pugh
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Pankaj K. Singh
Department of Materials Science and Engineering, and
Engineering Research Center for Particle Science and
Technology, PO Box 116135, University of Florida,
Gainesville, FL-32611, USA

Dale S. Steichen

Heinz Rehage
Department of Physical Chemistry, University of Essen,
Universitaetsstrasse 3 - 5 , D-45141 Essen, Germany

Akzo Nobel Surface Chemistry AB, SE-444 85 Stenungsund, Sweden

Tharwat F. Tadros

Brian H. Robinson
School of Chemical Sciences, University of East Anglia,
Norwich, Norfolk, NR4 7TJ, UK

89, Nash Grove Lane, Wokingham, Berkshire, RG40
4HE, UK

Klaus Tauer

Madeleine Rogerson
School of Chemical Sciences, University of East Anglia,
Norwich, Norfolk, NR4 7TJ, UK

Max Planck Institute of Colloids and Interfaces, D14424 GoIm, Germany

William Rowe

Fabienne Testard

Department of Chemical Engineering, UMIST, PO Box
88, Manchester, M60 IQD, UK

Service de Chemie Moleculaire, CE Saclay, Batelle 125,
F-999 91 Gif-sur-Yvette, France

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Staffan Wall

John Texter
Strider Research Corporation, 265 Clover
Rochester, NY 14610-2246, USA

Street,

Department of Chemistry, Physical Chemistry, Goteborg
Universitet, SE-412 96 Goteborg, Sweden

Fredrik Tiberg

Guenther W. Wasow

Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden

Karl-Marx-Alle 133, D-10243 Berlin, Germany

Klaus Wormuth

Gordon J. T. Tiddy
Department of Chemical Engineering, UMIST, PO Box
88, Manchester, M60 IQD, UK

Werner Ulbricht
Lehrstuhl flir Physikalische Chemie I der Universitat
Bayreuth, Universitatsstrasse 30, D-95447 Bayreuth,
Germany

Institute for Technical Chemistry, Technical University
of Berlin, Sekr. TC 8, Strasse des 17 Juni 124, D-10623
Berlin, Germany

Thomas Zemb
Service de Chemie Moleculaire, CE Saclay, Batelle 125,
F-999 91 Gif-sur-Yvette, France

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Foreword
I am delighted to have been given the opportunity to
write a Foreword for this important, landmark book in
Surface and Colloid Chemistry. It is the first major book
of its kind to review, in such a wide-ranging and comprehensive manner, the more technical, applied aspects
of the subject. Yet it does not skip the fundamentals. It
would have been wrong to have done so. After all, chemical technology is the application of chemical knowledge
to produce new products and processes, and to control
better existing ones. One cannot achieve these objectives without a thorough understanding of the relevant
fundamentals. An attractive feature of this book is that
the author of each chapter has been given the freedom to present, as he/she sees fit, the spectrum of the
relevant science, from pure to applied, in his/her particular topic. Of course this approach inevitably leads
to some overlap and repetition in different chapters, but
that does not necessarily matter. Fortunately, the editor
has not taken a "hard-line" on this. This arrangement
should be extremely useful to the reader (even if it
makes the book look longer), since one does not have
to search around in different chapters for various bits of
related information. Furthermore, any author will naturally have his own views on, and approach to, a specific

topic, moulded by his own experience. It is often useful
for someone else, particularly a newcomer, wanting to
research a particular topic, to have different approaches
presented to them. (There is no absolute truth in science, only commonly accepted wisdom!). For example,
someone primarily interested in learning about the roles
that surfactants or polymers play in formulating a pharmaceutical product, might well gain from also reading
about this in a chapter of agrochemicals, or food detergents. Alternatively, someone wishing to learn about
paper making technology might also benefit from delving into the chapter on paints. It is very useful to have all
this information together in one source. Of course, there
are, inevitably, some gaps. The editor himself points out
the absence of a comprehensive chapter on emulsions,
for example, but to have covered every nook and cranny
of this field would be an impossible task, and have taken

forever to achieve! A refreshing feature of this book is
its timeliness.
The book will be of tremendous use, not only to
those working on industrial research and development,
over a whole range of different technologies which are
concerned with surface and colloid chemistry, but also
to academic scientists in the field, a major proportion
of whom interact very strongly with their industrial colleagues. It will compliment very well, existing textbooks
in surface and colloid science, which, in general, take
the more traditional approach of reviewing systematically the fundamental (pure) aspects of the subject, and
add in a few examples of applications, by a way of
illustration.
I personally will find this book an extremely useful
teaching aid, and I am certain many of my colleagues
and universities (particularly at post-graduate level), but
also to an activity more and more of us in the field

are becoming involved in, namely presenting various
aspects of surface and colloid science to industrialists, at
a specialist schools, workshops, awareness forums, etc.
I believe that Krister Holmberg was the ideal choice
to have edited this book. Not only does he have a
wide experience of different aspects of the field, but
he has successively worked in Industry, been Director of an internationally recognised research institute
(The Ytkemiska Institutet - The Institute for Surface
Chemistry - in Stockholm), and is now heading up the
Department of Applied Surface Chemistry at Chalmers
University of Technology. He has done an outstanding
job in putting this book together, and has produced an
extremely valuable reference source for all of us working with surfaces and colloids.

Brian Vincent
Leverhulme Professor of Physical Chemistry and
Director of The Bristol Colloid Centre
School of Chemistry, University of Bristol
BS8 ITS, UK

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Preface
This book is intended as a comprehensive reference
work on surface and colloid chemistry. Its title, "Handbook of Applied Surface and Colloid Chemistry",
implies that the book is practically oriented rather than
theoretical. However, most chapters treat the topic in a
rather thorough manner and commercial aspects, related
to specific products, etc. are normally not included. All

chapters are up-to-date and all have been written for the
specific purpose of being chapters in the "Handbook".
As will be apparent to the user, the many topics of the
book have been covered in a comprehensive way. Taken
together, the chapters constitute an enormous wealth of
surface and colloid chemistry knowledge and the book
should be regarded as a rich source of information,
arranged in a way that I hope the reader will find useful.
When it comes to the important but difficult issues
of scope and limitations, there is one clear-cut borderline. The "Handbook" covers "wet" but not "dry" surface chemistry. This means that important applications
of dry surface chemistry, such as heterogeneous catalysis involving gases, and important vacuum analysis
techniques, such as Electron Spectroscopy for Chemical
Analysis (ESCA) and Selected-Ion Mass Spectrometry
(SIMS), are not included. Within the domain of wet surface chemistry, on the other hand, the aim has been to
have the most important applications, phenomena and
analytical techniques included.
The book contains 45 chapters. The intention has
been to cover all practical aspects of surface and
colloid chemistry. For convenience the content material
is divided into five parts.
Part One, Surface Chemistry in Important Technologies, deals with a selected number of applications of surface chemistry. The 11 chapters cover a broad range of
industrial and household uses, from life-science-related
applications such as Pharmaceuticals and food, via detergency, agriculture, photography and paints, to industrial
processes such as paper-making, emulsion polymerization, ceramics processing, mineral processing, and oil
production. There are several more areas in which surface chemistry plays a role and many more chapters

could have been added. The number of pages are limited, however, and the present topics were deemed to
be the most important. Other editors may have made a
different choice.
Part Two, Surfactants, contains chapters on the four

major classes of surfactants, i.e. anionics, nonionics,
cationics and zwitterionics, as well as chapters on
polymeric surfactants, hydrotropes and novel surfactants. The physico-chemical properties of surfactants and
properties of liquid crystalline phases are the topics of
two comprehensive chapters. The industrially important
areas of surfactant-polymer systems and environmental
aspects of surfactants are treated in some detail. Finally,
one chapter is devoted to computer simulations of surfactant systems.
Part Three, Colloidal Systems and Layer Structures
at Surfaces, treats four important colloidal systems, i.e.
solid dispersions (suspensions), foams, vesicles and liposomes, and microemulsions. A chapter on emulsions
should also have been included here but was never
written. However, Chapter 8, Surface Chemistry in the
Polymerization of Emulsion, gives a rather thorough
treatment of emulsions in general, while Chapter 24,
Solid Dispersions, provides a good background to colloidal stability, which to a large part is also relevant to
emulsions. Taken together, these two chapters can be
used as a reference to the field of emulsions. Part Three
also contains chapters on two important layer systems,
i.e. Langmuir-Blodgett films and self-assembled monolayers.
Part Four, Phenomena in Surface Chemistry, consists
of extensive reviews of the important phenomena of
foam breaking, solubilization, rheological effects of
surfactants, and wetting, spreading and penetration.
Part Five, Analysis and Characterization in Surface
Chemistry, concerns a selected number of experimental
techniques. As with the selection of topics that make up
Part One, this list of 12 chapters could have been longer
and another editor may have made a different choice of
topics within the given number of chapters. However,

the experimental methods chosen are all important and I
hope that the way this part is organized will prove useful.

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Most books related to analysis and characterization
are divided into chapters on different techniques, such
as "Fluorescence" or "Self-diffusion NMR", i.e. the
division is by method. By contrast, the division here
is by problem. As an example, when the reader wants
to find out how to best measure micelle size he (or
she) does not need to know from the beginning which
methods to consider. The reader can go directly to
Chapter 38, Measuring Micelle Shape and Size, where
the relevant information is collected.
All 45 chapters can be regarded as overview articles. They all cover the area in a broad way and in
addition they often give in-depth information on specific sub-areas which the author has considered particularly important. Each chapter also gives references
to literature sources for those who need deeper penetration into the area. Each of the chapters is written
as a separate entity, meant to stand on its own. This
means that each chapter can be read separately. However, those knowledgeable in the field know that the
topics of the "Handbook" chapters are not isolated.
For example, there are obviously many connections
between Chapter 25, Foams and Foaming, and Chapter 31, Foam Breaking in Aqueous Systems, Chapter 27,
Micro emulsions, has much in common with both Chapter 32, Solubilization, and Chapter 40, Characterization
of Microemulsion Structure, while Chapter 19, Physicochemical Properties of Surfactants, deals among many
other things with lyotropic liquid crystals which is
the topic of Chapter 21 and which has strong links
to Chapter 39, Identification of Lyotropic Liquid Crystalline Mesophases. Such connections will lead to some
overlap. However, this is natural and should not present

any problem. First, a certain overlap is unavoidable if
each chapter is to be an independent entity. Secondly,
different authors will treat a particular topic differently
and these different views can often complement each
other. Since both of these aspects are helpful to the
reader, small overlaps have not been a concern for the
editor.
The "Handbook of Applied Surface and Colloid
Chemistry" is unique in scope and the only work of
its kind in the field of surface and colloid chemistry.
There exist comprehensive and up-to-date books lean-

ing towards the fundamental side of surface chemistry,
with Hans Lyklema's "Fundamentals of Interface and
Colloid Science" being one good example. There are
excellent books on surfactants and there are good textbooks on surface chemistry in general, such as "The
Colloidal Domain" by Fennell Evans and Hakan Wennerstrom and "Surfactants and Interfacial Phenomena"
by Milton Rosen. However, there exists no substantial
work like the "Handbook of Applied Surface and Colloid Chemistry" which covers applied surface chemistry
in a broad sense. Against this background, one may say
that the book fills a gap. I hope therefore that the "Handbook" will soon establish itself as an important reference
work for researchers both in industry and in academia.
I am grateful to my co-editors, Milan Schwuger of
Forschungzentrum Julich and Dinesh O. Shah from the
University of Florida for helping me to identify the
chapter authors. We, the editors, are extremely pleased
that we have managed to raise such an interest for
the project within the surface chemistry community.
Almost all of those that we approached expressed a
willingness to contribute and the result has been that the

contributors of the "Handbook" are all leading experts
in their respective fields. This is the best guarantee for
a balanced treatment of the topic and for an up-to-date
content.
On behalf of the entire editorial team, I would like
to thank all those who contributed as chapter authors.
Four persons, Bjorn Lindman, Robert Pugh, Tharwat
Tadros and Krister Holmberg, have written two chapters
each. The rest of the 45 chapters have been written by
different individual authors. In total 70 individuals from
10 countries contributed to the work. I hope that when
they see the "Handbook" in print they will regard the
result to be worth the effort. Finally, I would like to
thank Dr David Hughes at Wiley (Chichester, UK) for
his constant encouragement and patience.

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Krister Holmberg
Chalmers University of Technology
Sweden
Goteborg, January 2001


Contents

Contributors List .................................................................................................

ix

Foreword ............................................................................................................

xiii

Preface ...............................................................................................................

xv

Part I. Surface Chemistry in Important Technologies
1. Surface Chemistry in Pharmacy ...........................................................................

3

1.1

Introduction ...............................................................................................

3

1.2

Surface Activity of Drugs ...........................................................................

4

1.3

Effects of Drug Surface Activity on Formulation Structure and
Stability ......................................................................................................

6

1.4

Drug Delivery through Dispersed Colloidal Systems .................................

8

1.5

Drug Delivery through Thermodynamically Stable Systems .....................

15

1.6

Responsive Systems .................................................................................

24

1.7

Biodegradable Systems ............................................................................

26

1.8

Acknowledgements ...................................................................................

30

1.9

References ................................................................................................

30

2. Surface Chemistry in Food and Feed ...................................................................

39

2.1

Introduction ...............................................................................................

39

2.2

Colloids in Liquids .....................................................................................

39

2.3

Interparticle Interactions in Liquids ............................................................

42

2.4

Surface-Active Components .....................................................................

44

2.5

Particles and Surfaces in Air .....................................................................

48

2.6

Concluding Remarks .................................................................................

51

2.7

References ................................................................................................

51

v
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vi

Contents
3. Surface Chemistry in Detergency .........................................................................

53

3.1

Introduction ...............................................................................................

53

3.2

Surface Tension and Wetting ....................................................................

54

3.3

Adsorption at the Solid/Liquid Interface ....................................................

58

3.4

Complexation and Ion Exchange ..............................................................

61

3.5

Liquid/Liquid Interface ...............................................................................

65

3.6

Phase Behaviour of Surfactant Systems ...................................................

67

3.7

Foaming ....................................................................................................

71

3.8

References ................................................................................................

72

4. Surface Chemistry in Agriculture .........................................................................

73

4.1

Introduction ...............................................................................................

73

4.2

Surface Chemistry in Emulsifiable Concentrates ......................................

74

4.3

Surface Chemistry of Emulsion Concentrates ...........................................

76

4.4

Surface Chemistry in Suspension Concentrates .......................................

78

4.5

Surface Chemistry in the Application of Agrochemical Formulations ........

80

4.6

References ................................................................................................

83

5. Surface and Colloid Chemistry in Photographic Technology ...........................

85

5.1

Introduction ...............................................................................................

85

5.2

Surfaces and Particles in Photographic Technology .................................

90

5.3

Particles and Colloids in Photographic Technology ..................................

94

5.4

Coupler Dispersions ..................................................................................

99

5.5

Adsorber Dyes and Filter Dyes .................................................................

101

5.6

Matte Beads ..............................................................................................

103

5.7

References ................................................................................................

104

6. Surface Chemistry in Paints ..................................................................................

105

6.1

Introduction ...............................................................................................

105

6.2

Competitive Adsorption of Surfactants ......................................................

105

6.3

The Binder-Emulsion Preparation and Film Formation .............................

107

6.4

Pigment Dispersant ...................................................................................

113

6.5

Wetting of the Substrate ............................................................................

119

6.6

Use of Speciality Surfactants ....................................................................

121

6.7

Bibliography ..............................................................................................

122

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Contents

vii

7. Surface Chemistry of Paper ...................................................................................

123

7.1

Introduction ...............................................................................................

124

7.2

Fibre Properties .........................................................................................

125

7.3

Paper Formation .......................................................................................

128

7.4

Internal Sizing of Paper .............................................................................

138

7.5

Dry and Wet Strength of Paper .................................................................

145

7.6

Surface Treatment of Paper ......................................................................

146

7.7

Wettability and Absorbency of Paper ........................................................

154

7.8

Characterization of Paper Properties ........................................................

162

7.9

Acknowledgements ...................................................................................

171

7.10

References ................................................................................................

171

8. Surface Chemistry in the Polymerization of Emulsion .......................................

175

8.1

Introduction ...............................................................................................

175

8.2

A Little Relevant Thermodynamics ...........................................................

176

8.3

Emulsification ............................................................................................

179

8.4

Stability of Emulsions ................................................................................

186

8.5

Comminution or Condensation Techniques-What Makes the
Difference? ................................................................................................

190

8.6

Polymerization of (or in) Monomer Emulsions ...........................................

191

8.7

Fixation of an Emulsion by Radical Polymerization in Aqueous

Media-Fact or Fancy? ...............................................................................

196

References ................................................................................................

198

9. Colloidal Processing of Ceramics ........................................................................

201

8.8
9.1

Introduction ...............................................................................................

201

9.2

Powder Processing of Ceramics ...............................................................

202

9.3

Interparticle Forces and Colloidal Stability ................................................

203

9.4

Deagglomeration and Dispersion ..............................................................

206

9.5

Rheological Properties of Ceramic Suspensions ......................................

208

9.6

Consolidation ............................................................................................

212

9.7

Drying and Binder Burnout ........................................................................

216

9.8

Acknowledgements ...................................................................................

217

9.9

References ................................................................................................

217

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viii

Contents

10. Surface Chemistry in Dispersion, Flocculation and Flotation .......................... 219
10.1

Introduction ...............................................................................................

219

10.2

Surface Chemistry .....................................................................................

220

10.3

The Electrical Double-Layer ......................................................................

222

10.4

Zeta Potential (Electrokinetic Potential) ....................................................

224

10.5

Electrostatic Forces ...................................................................................

226

10.6

Manipulating Surface Behaviour by Polymer Adsorption ..........................

229

10.7

Manipulating Surface Behaviour by Surfactant Adsorption .......................

232

10.8

Particle Processing ...................................................................................

238

10.9

References ................................................................................................

249

11. Surface Chemistry in the Petroleum Industry .....................................................

251

11.1

Introduction ...............................................................................................

251

11.2

Fundamentals ...........................................................................................

252

11.3

Applications ...............................................................................................

259

11.4

Summary ...................................................................................................

266

11.5

References ................................................................................................

266

Part II. Surfactants
12. Anionic Surfactants ................................................................................................

271

12.1

Introduction ...............................................................................................

271

12.2

Soap ..........................................................................................................

272

12.3

Alkyl Sulfates .............................................................................................

273

12.4

Alkyl Ether Sulfates ...................................................................................

275

12.5

Alkyl Ether Carboxylates ...........................................................................

275

12.6

α-Olefinesulfonates ...................................................................................

276

12.7

α-Sulfo Fatty Acid Methyl Esters ...............................................................

277

12.8

Esters and Amides of Fatty Acids .............................................................

278

12.9

Petrol Sulfonates .......................................................................................

278

12.10 Alkylbenzene Sulfonates ...........................................................................

278

12.11 Alkane Sulfonates .....................................................................................

282

12.12 Esters of Phosphoric Acid .........................................................................

285

12.13 Sulfosuccinates .........................................................................................

289

12.14 Anionic Surfactants with Special Properties ..............................................

291

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12.15 Acknowledgements ...................................................................................

292

12.16 Bibliography ..............................................................................................

292

13. Nonionic Surfactants ..............................................................................................

293

13.1

Introduction ...............................................................................................

294

13.2

Nonionic Hydrophobes ..............................................................................

294

13.3

Nonionic Hydrophiles ................................................................................

298

13.4

Common Nonionic Surfactants .................................................................

301

13.5

References ................................................................................................

308

14. Cationic Surfactants ...............................................................................................

309

14.1

General Introduction ..................................................................................

310

14.2

The Synthesis and Manufacture of Cationic Surfactants ..........................

311

14.3

Cationic Surfactants in Fabric Softening ...................................................

314

14.4

Cationic Surfactants in Biocides ................................................................

318

14.5

Cationic Surfactants in Hard Surface Cleaning .........................................

321

14.6

Cationic Surfactants in Laundry Detergents ..............................................

326

14.7

Cationic Surfactants in Personal Care ......................................................

327

14.8

Cationic Surfactants in Paper Processing .................................................

331

14.9

Cationic Surfactants in Conveyor Lubricants ............................................

332

14.10 Cationic Surfactants in Road Construction ...............................................

334

14.11 Cationic Surfactants in Viscose/Rayon Production ...................................

337

14.12 Cationic Surfactants in Oilfield ..................................................................

337

14.13 Cationic Surfactants in Agricultural Formulations .....................................

341

14.14 Cationic Surfactants in Organoclays .........................................................

343

14.15 Cationic Surfactants in Mining ...................................................................

344

14.16 Acknowledgements ...................................................................................

347

14.17 References ................................................................................................

347

15. Zwitterionic and Amphoteric Surfactants ............................................................

349

15.1

Introduction ...............................................................................................

349

15.2

Chemistry of Zwitterionic Surfactants ........................................................

350

15.3

Chemistry of Amphoteric Surfactants ........................................................

355

15.4

Analysis of Zwitterionic and Amphoteric Surfactants ................................

361

15.5

Physico-Chemical Properties ....................................................................

362

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15.6

Ecological and Toxicological Properties of Zwitterionic and
Amphoteric Surfactants .............................................................................

364

15.7

Application Properties ...............................................................................

365

15.8

Applications ...............................................................................................

367

15.9

References ................................................................................................

369

16. Polymeric Surfactants ...........................................................................................

373

16.1

Introduction ...............................................................................................

373

16.2

Solution Properties of Polymeric Surfactants ............................................

374

16.3

Adsorption and Conformation of Polymeric Surfactants at
Interfaces ..................................................................................................

377

16.4

Stabilization of Dispersions Containing Polymeric Surfactants .................

381

16.5

References ................................................................................................

384

17. Speciality Surfactants .............................................................................................

385

17.1

Gemini Surfactants ....................................................................................

385

17.2

Cleavable Surfactants ...............................................................................

390

17.3

Polymerizable Surfactants ........................................................................

397

17.4

Bibliography ..............................................................................................

405

18. Hydrotropes .............................................................................................................

407

18.1

Introduction ...............................................................................................

407

18.2

Structure of Hydrotropic Compounds ........................................................

408

18.3

Function and Mechanism ..........................................................................

409

18.4

Applications ...............................................................................................

415

18.5

References ................................................................................................

419

19. Physico-Chemical Properties of Surfactants ......................................................

421

19.1

Different Surfactant Systems ....................................................................

421

19.2

Surfactants Start to Form Micelles at the CMC .........................................

422

19.3

The CMC Depends on the Chemical Structure .........................................

423

19.4

Temperature and Cosolutes Affect the CMC ............................................

425

19.5

The Solubility of Surfactants May Be Strongly TemperatureDependent .................................................................................................

427

19.6

Driving Forces of Micelle Formation and Thermodynamic Models ...........

428

19.7

The Association Process and Couterion Binding Can Be Monitored
by NMR Spectroscopy ..............................................................................

430

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19.8

Hydrophobic Compounds Can Be Solubilized in Micelles .........................

431

19.9

Micelle Size and Structure May Vary ........................................................

431

19.10 A Geometrical Consideration of Chain Packing Is Useful .........................

432

19.11 Kinetics of Micelle Formation ....................................................................

433

19.12 Surfactants May Form Aggregates in Other Solvents Than Water ...........

434

19.13 General Comments on Amphiphile Self-Assembly ...................................

435

19.14 Micelle Type and Size Vary with Concentration ........................................

435

19.15 Micellar Growth Is Different for Different Systems ....................................

437

19.16 Surfactant Phases Are Built Up by Discrete or Infinite Self-Assemblies .....

439

19.17 Nonionic Oxyethylene Surfactants Display Special Temperature Effects .....

440

19.18 Clouding Is a Characteristic Feature of Polyoxyethylene-Based
Surfactants ................................................................................................

442

19.19 Bibliography ..............................................................................................

442

20. Surfactant-Polymer Systems ................................................................................

445

20.1

Introduction ...............................................................................................

445

20.2

Polymers Can Induce Surfactant Aggregation ..........................................

445

20.3

Attractive Polymer-Surfactant Interactions Depend on Both Polymer
and Surfactant ...........................................................................................

447

20.4

Surfactant Association to Surface-Active Polymers Can Be Strong ..........

449

20.5

The Interaction between a Surfactant and a Surface-Active Polymer
Is Analogous to Mixed Micelle Formation ..................................................

451

The Phase Behaviour of Polymer-Surfactant Mixtures Resembles
That of Mixed Polymer Solutions ..............................................................

452

Phase Behaviour of Polymer-Surfactant Mixtures in Relation to PolymerPolymer and Surfactant-Surfactant Mixtures ..............................

456

20.8

Polyelectrolyte-Surfactant Systems Show a Complex Behaviour .............

458

20.9

Polymers May Change the Phase Behaviour of Infinite Surfactant SelfAssemblies ........................................................................................

460

20.6
20.7

20.10 Surfactant Binding Strongly Affects Adsorbed Polymer Layers and
the Swelling of Chemical Gels ..................................................................

462

20.11 There Are Many Technical Applications of Polymer-Surfactant
Mixtures .....................................................................................................

462

20.12 Bibliography ..............................................................................................

463

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Contents

21. Surfactant Liquid Crystals .....................................................................................

465

21.1

Introduction ...............................................................................................

465

21.2

Liquid Crystals ...........................................................................................

466

21.3

Surfactant Solutions: Micelles ...................................................................

467

21.4

Liquid Crystal Structures ...........................................................................

472

21.5

Origins of the Formation of Surfactant Liquid Crystals - WaterContinuous Phases ...................................................................................

479

Origins of the Formation of Surfactant Liquid Crystals - Reversed
Phases ......................................................................................................

480

21.7

Phase Behaviour of Nonionic Surfactants .................................................

480

21.8

Block Copolymer Nonionic Surfactants .....................................................

491

21.9

Zwitterionic Surfactants .............................................................................

493

21.10 Ionic Surfactants .......................................................................................

493

21.11 The Influence of Third Components: Cosurfactants, Mixed
Surfactants, Oils, Hydrotropes, Electrolytes and Alternative Solvents ......

497

21.12 Conclusions and the Future ......................................................................

502

21.13 References ................................................................................................

504

22. Environmental Aspects of Surfactants ................................................................

509

21.6

22.1

Introduction ...............................................................................................

509

22.2

Use and Environmental Relevance of Surfactants in Different Fields
of Application .............................................................................................

510

22.3

Environmental Legislation .........................................................................

512

22.4

Analysis of Surfactants in the Environment ...............................................

513

22.5

Criteria for Ecological Assessment and Biological Testing Procedures ......

514

22.6

Anionic Surfactants ...................................................................................

520

22.7

Nonionic Surfactants .................................................................................

525

22.8

Cationic Surfactants ..................................................................................

529

22.9

Amphoteric Surfactants .............................................................................

532

22.10 Environmental Behaviour under Real Conditions and Risk Assessment ......

534

22.11 References ................................................................................................

535

.....................................
23. Molecular Dynamics Computer Simulations of Surfactants

537

23.1

Introduction ...............................................................................................

537

23.2

Surfactants Adsorbed at Surfaces and Interfaces .....................................

537

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23.3

The Molecular Dynamics Method ..............................................................

539

23.4

Molecular Dynamics Computer Simulations of Surfactant
Monolayers at Air/Water and Oil/Water Interfaces ....................................

541

23.5

Molecular Dynamics Computer Simulation of Micelles .............................

544

23.6

The Dissipative Particle Dynamics Simulation Method .............................

546

23.7

Limits and Restrictions of the Molecular Dynamics Technique for
Surfactant Simulations ..............................................................................

547

References ................................................................................................

550

23.8

Part III. Colloidal Systems and Layer Structures at Surfaces
1. Solid Dispersions ....................................................................................................

3

1.1

Introduction ...............................................................................................

3

1.2

Synthesis of Solid Particles .......................................................................

4

1.3

Surface Electrical Properties .....................................................................

9

1.4

Stability of Solid Particles ..........................................................................

13

1.5

Electrostatic Interactions ...........................................................................

13

1.6

Aggregation Processes .............................................................................

15

1.7

Rheology ...................................................................................................

19

1.8

References ................................................................................................

20

2. Foams and Foaming ...............................................................................................

23

2.1

Introduction and Background ....................................................................

23

2.2

Classification of the Stability of Foam .......................................................

25

2.3

Rupture Mechanisms of Thin Liquid Foam Films ......................................

26

2.4

Theories of Foam Stability ........................................................................

26

2.5

Test Methods for Foam Stability ...............................................................

31

2.6

Research Techniques for Studying Foam Stability ...................................

34

2.7

Industrial Material and Food Foams ..........................................................

37

2.8

References ................................................................................................

43

3. Vesicles ....................................................................................................................

45

3.1

Introduction ...............................................................................................

45

3.2

Properties of Vesicles ...............................................................................

46

3.3

Phase Structure and Phase Transition .....................................................

46

3.4

Dynamic Processes involving Vesicles .....................................................

47

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Contents
3.5

Vesicle Formation .....................................................................................

47

3.6

Phospholipid Vesicles with Fatty Acids .....................................................

49

3.7

Interactions between Phospholipids and Fatty Acids: Considerations
of Autopoiesis ............................................................................................

50

3.8

Summary ...................................................................................................

52

3.9

References ................................................................................................

52

4. Microemulsions ......................................................................................................

55

4.1

Introduction ...............................................................................................

55

4.2

Phase Behaviour .......................................................................................

57

4.3

Links between the Phase Behaviour, Microstructure and Interfacial Tensions ...

70

4.4

Applications of Microemulsions .................................................................

73

4.5

References ................................................................................................

74

5. Langmuir-Blodgett Films .......................................................................................

79

5.1

Langmuir-Blodgett Films ...........................................................................

79

5.2

Molecular Assemblies with Functions .......................................................

85

5.3

Final Remarks ...........................................................................................

95

5.4

References ................................................................................................

95

6. Self-Assembling Monolayers: Alkane Thiols on Gold ........................................

99

6.1

Introduction ...............................................................................................

99

6.2

Properties and Characterization ................................................................

100

6.3

Self-Assembled Monolayers to Control Interfacial Chemistry ...................

103

6.4

Patterned Self-Assembled Monolayers .....................................................

109

6.5

Self-Assembled-Monolayer-Protected Metal Clusters ...............................

113

6.6

Conclusions ...............................................................................................

114

6.7

References ................................................................................................

114

Part IV. Phenomena in Surface Chemistry
7. Wetting, Spreading and Penetration .....................................................................

119

7.1

Introduction ...............................................................................................

119

7.2

Thermodynamics of Wetting .....................................................................

121

7.3

Dynamics of Spreading .............................................................................

134

7.4

Wetting Caused by Capillary Penetration .................................................

136

7.5

References ................................................................................................

140

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8. Foam Breaking in Aqueous Systems ...................................................................

143

8.1

Introduction ...............................................................................................

143

8.2

Types of Antifoamers and Mechanisms ....................................................

147

8.3

Ageing Effects with Chemical Defoamers .................................................

154

8.4

Physical Methods of Defoaming ................................................................

155

8.5

References ................................................................................................

156

9. Solubilization ..........................................................................................................

159

9.1

Introduction ...............................................................................................

159

9.2

Solubilization in Binary Solutions ..............................................................

162

9.3

Solubilization in Initially Ternary Systems .................................................

173

9.4

Conclusion: Open Problems .....................................................................

185

9.5

References ................................................................................................

186

10. Rheological Effects in Surfactant Phases ............................................................

189

10.1

Introduction ...............................................................................................

189

10.2

The Rheological Behaviour of Aqueous Surfactant Solutions ...................

191

10.3

The Rheology of Bilayer Phases ...............................................................

199

10.4

The Rheology of Cubic Phases .................................................................

204

10.5

Shear-Induced Phenomena in Surfactant Solutions .................................

205

10.6

References ................................................................................................

214

Part V. Analysis and Characterization in Surface Chemistry
11. Measuring Equilibrium Surface Tensions ...........................................................

217

11.1

Introduction ...............................................................................................

217

11.2

Capillary Rise ............................................................................................

218

11.3

The Wilhelmy Plate Method ......................................................................

219

11.4

The Du Nouy Ring Method ........................................................................

220

11.5

The Drop Weight Method ..........................................................................

220

11.6

Pendant/Sessile Drop and Bubble Methods .............................................

221

11.7

The Spinning Drop Method .......................................................................

222

11.8

The Maximum Bubble Pressure Method ...................................................

223

11.9

Conclusions ...............................................................................................

223

11.10 References ................................................................................................

223

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Contents

12. Measuring Dynamic Surface Tensions ................................................................

225

12.1

Introduction ...............................................................................................

225

12.2

Dynamic Surface and Interfacial Tension Methods ...................................

226

12.3

Maximum Bubble Pressure Tensiometry ..................................................

227

12.4

Oscillating Jet Method ...............................................................................

229

12.5

Drop Volume Technique ...........................................................................

230

12.6

Drop and Bubble Shape Tensiometry .......................................................

232

12.7

Drop and Bubble Pressure Techniques ....................................................

234

12.8

Ring and Plate Tensiometry ......................................................................

236

12.9

Acknowledgements ...................................................................................

237

12.10 References ................................................................................................

237

13. Determining Critical Micelle Concentration .........................................................

239

13.1

Introduction ...............................................................................................

239

13.2

Importance of CMC ...................................................................................

240

13.3

Methods to Determine CMC ......................................................................

241

13.4

Methodical Differences in Determining CMC ............................................

244

13.5

Factors Influencing CMC ...........................................................................

245

13.6

Micellization in Non-Aqueous Media .........................................................

246

13.7

Determining CMC in Non-Aqueous Media ................................................

247

13.8

Factors Influencing CMC in Non-Aqueous Media .....................................

248

13.9

References ................................................................................................

248

14. Measuring Contact Angle .......................................................................................

251

14.1

Introduction ...............................................................................................

251

14.2

Background Theory ...................................................................................

252

14.3

Contact Angle Measurement .....................................................................

253

14.4

Acknowledgements ...................................................................................

277

14.5

References ................................................................................................

277

15. Measuring Micelle Size and Shape .......................................................................

281

15.1

Introduction ...............................................................................................

281

15.2

NMR Relaxation and Self-Diffusion ...........................................................

281

15.3

Fluorescence Techniques .........................................................................

290

15.4

Small-Angle Scattering Techniques ..........................................................

292

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15.5

Static and Dynamic Light Scattering .........................................................

294

15.6

References ................................................................................................

296

16. Identification of Lyotropic Liquid Crystalline Mesophases ...............................

299

16.1

Introduction: Liquid Crystals Versus Crystals and Melts ...........................

299

16.2

Lyotropic Mesophases: Curvature and Types 1 and 2 ..............................

301

16.3

A Note on Inhomogeneous Lyotropes .......................................................

321

16.4

Molecular Dimensions Within Liquid Crystalline Mesophases ..................

323

16.5

Acknowledgements ...................................................................................
References ................................................................................................

327
327

Color Plates .....................................................................................................

a1

17. Characterization of Microemulsion Structure ......................................................

333

16.6

17.1

Introduction ...............................................................................................

333

17.2

Experimental Techniques ..........................................................................

334

17.3

Curvature and Curvature Energy ..............................................................

336

17.4

Useful Experimental Systems: The Oligoethylene Oxide Surfactants .......

337

17.5

Phase Behaviour .......................................................................................

338

17.6

Structural Inversion and the Spectrum of Microstructures ........................

342

17.7

Characterization of a Droplet Microemulsion ............................................

344

17.8

The Droplet to Bicontinuous Transition .....................................................

351

17.9

Sponge Phases .........................................................................................

352

17.10 References ................................................................................................

355

18. Measuring Particle Size by Light Scattering .......................................................

357

18.1

Introduction ...............................................................................................

357

18.2

Particle Size Distribution ...........................................................................

358

18.3

Static Light Scattering ...............................................................................

360

18.4

Dynamic Light Scattering ..........................................................................

365

18.5

Simultaneous and Time-Dependent Methods ...........................................

368

18.6

Conclusion ................................................................................................

369

18.7

References ................................................................................................

369

19. Measurement of Electrokinetic Phenomena in Surface Chemistry ..................

371

19.1

Introduction ...............................................................................................

371

19.2

Theory of Electrokinetic Phenomena ........................................................

372

19.3

Measurement of Electrokinetic Phenomena .............................................

375

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Contents
19.4

Surface Characterization and Electrokinetic Phenomena .........................

379

19.5

References ................................................................................................

382

20. Measuring Interactions between Surfaces ..........................................................

383

20.1

Introduction ...............................................................................................

383

20.2

Surface Force Techniques ........................................................................

384

20.3

Measurements between Solid Surfaces in Air ..........................................

389

20.4

Measurements in Aqueous Electrolyte Solutions ......................................

393

20.5

Measurements in Aqueous Surfactant Systems .......................................

397

20.6

Measurements in Non-Aqueous Systems .................................................

404

20.7

References ................................................................................................

407

21. Measuring the Forces and Stability of Thin-Liquid Films ..................................

415

21.1

Introduction ...............................................................................................

415

21.2

Measurements of Forces in Thin-Liquid Films ..........................................

417

21.3

Disjoining Pressure Components/Interpretation ........................................

424

21.4

Common Black Film Stability ....................................................................

431

21.5

References ................................................................................................

433

22. Measuring Adsorption ...........................................................................................

435

22.1

Introduction ...............................................................................................

435

22.2

Adsorption at Particle Surfaces .................................................................

436

22.3

Measurement of Surfactant Adsorption at a Solid Macroscopic Surface .......

443

22.4

References ................................................................................................

444

Index .................................................................................................................. 573

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PART 1

SURFACE CHEMISTRY IN
IMPORTANT TECHNOLOGIES

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