(Ebook) Handbook of Applied Surface and Colloid

Chemistry by Krister Holmberg ISBN 9780471490838,

0471490830 Pdf Download

https://ebooknice.com/product/handbook-of-applied-surface-and-
colloid-chemistry-923596

★★★★★
4.6 out of 5.0 (43 reviews )

DOWNLOAD PDF

ebooknice.com
 (Ebook) Handbook of Applied Surface and Colloid Chemistry by
Krister Holmberg ISBN 9780471490838, 0471490830 Pdf Download

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 EDUCATIONAL COLLECTION - LIMITED TIME

INSTANT DOWNLOAD VIEW LIBRARY

 We believe these products will be a great fit for you. Click
the link to download now, or visit ebooknice.com
to discover even more!

(Ebook) Handbook of surface and colloid chemistry by Birdi, K. S

ISBN 9781466596689, 1466596686

https://ebooknice.com/product/handbook-of-surface-and-colloid-
chemistry-5144166

(Ebook) Handbook of surface and colloid chemistry by K S Birdi

ISBN 9780849310799, 0849310792

https://ebooknice.com/product/handbook-of-surface-and-colloid-
chemistry-4102338

(Ebook) Applied Colloid And Surface Chemistry by Richard M.

Pashley, Marilyn E. Karaman ISBN 9780470868829, 0470868821

https://ebooknice.com/product/applied-colloid-and-surface-
chemistry-23686214

(Ebook) Applied Colloid and Surface Chemistry by Richard

Pashley, Marilyn Karaman ISBN 9780470868829, 9780470868836,
0470868821, 047086883X

https://ebooknice.com/product/applied-colloid-and-surface-chemistry-928292
(Ebook) Handbook of Surface and Colloid Chemistry, Third Edition
by K. S. Birdi ISBN 9780849373275, 0849373271

https://ebooknice.com/product/handbook-of-surface-and-colloid-chemistry-
third-edition-2613488

(Ebook) Handbook of Surface and Colloid Chemistry by K. S. Birdi

(Editor) ISBN 9780367268107, 9780367575663, 9780429169779,
9781466596672, 9781466596689, 0367268108, 0367575663,
0429169779, 1466596678
https://ebooknice.com/product/handbook-of-surface-and-colloid-
chemistry-12194232

(Ebook) Novel Surfactants: Preparation, Applications, and

Biodegradability by Krister Holmberg ISBN 9780824743000,
9780824756215, 0824743008, 0824756215

https://ebooknice.com/product/novel-surfactants-preparation-applications-
and-biodegradability-1131682

(Ebook) Surfactants and polymers in aqueous solution by Krister

Holmberg, Bo Jönsson, Bengt Kronberg, Björn Lindman ISBN
9780471498834, 0471498831

https://ebooknice.com/product/surfactants-and-polymers-in-aqueous-
solution-1188992

(Ebook) Novel Surfactants: Preparation Applications And

Biodegradability, Second Edition, Revised And Expanded by
Holmberg, Krister ISBN 9780203911730, 9780824702038,
9780824743000, 0203911733, 0824702034, 0824743008
https://ebooknice.com/product/novel-surfactants-preparation-applications-
and-biodegradability-second-edition-revised-and-expanded-4647872
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

Copyright © 2002 by John Wiley & Sons Ltd,
Baffins Lane, Chichester,
West Sussex PO19 IUD, England

National 01243 779777

International (+44) 1243 779777
e-mail (for orders and customer service enquiries): [email protected]
Visit our Home Page on http://www.wiley.co.uk
or http://www.wiley.com

All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted, in any form or by any means, electronic, mechanical, photocopying,
recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act
1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90
Tottenham Court Road, London, UK WlP OLP, without the permission in writing of the
publisher and the copyright holder.

Other Wiley Editorial Offices

John Wiley & Sons, Inc., 605 Third Avenue,

New York, NY 10158-0012, USA
Wiley-VCH GmbH, Pappelallee 3,
D-69469 Weinheim, Germany

John Wiley & Sons Australia Ltd, 33 Park Road, Milton,

Queensland 4064, Australia
John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01,
Jin Xing Distripark, Singapore 0512

John Wiley & Sons (Canada) Ltd, 22 Worcester Road,

Rexdale, Ontario M9W ILl, Canada

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, 1946-

TP149 .H283 2001

660 - dc21 2001024347

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 0-471-49083-0

Typeset in 9/1 lpt Times Roman by Laser Words Pvt. Ltd., Chennai, India.
Printed and bound in Great Britain by Antony Rowe Ltd. Chippenham, Wiltshire.
This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are planted
for each one used for paper production.
Contributors List
Joshua J. Adler John Daicic
Department of Materials Science and Engineering, and Institute for Surface Chemistry, PO Box 5607, SE-114
Engineering Research Center for Particle Science and 86 Stockholm, Sweden
Technology, PO Box 116135, University of Florida,
Gainesville, FL-32611, USA
Dennis S. Everhart
Kimberly Clark Corporation, 1400, Holcombe Bridge
Bjorn Bergenstahl Road, Roswell, GA-30076-2199, USA
Department of Food Technology, Center for Chemistry
and Chemical Engineering, Lund University, PO Box
124, SE-221 00 Lund, Sweden
Valentin B. Fainerman
International Medical Physicochemical Centre, Donetsk
Medical University, 16 Hych Avenue, Donetsk 340003,
Vance Bergeron Ukraine
Ecole Normale Superieure, Laboratorie de Physique
Statistique, 24 Rue Lhomond 75231, Paris CEDEX 05,
France Michele Ferrari
CNR - Instituto di Chimica Fisica Applicata dei Mate-
riali, Via De Marini 6, 1-16149 Genova, Italy
Lennart Bergstrom
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden David T. Floyd
Degussa-Goldschmidt Care Specialties, PO Box 1299,
Michal Borkovec 914, East Randolph Road, Hopewell, VA-23860, USA
Department of Inorganic, Analytical and Applied Chem-
istry, CABE, University of Geneva, Sciences II, 30 quai Johan Froberg
Ernest Ansermet, CH-1211 Geneva 4, Switzerland Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden
Norman L. Burns
Amersham Pharmacia Biotech, 928 East Arques Avenue,
Burghard Gruening
Sunnyvale, CA 94085-4520, USA
Degussa-Goldschmidt Care Specialties, Goldschmidt-
strasse 100, D-45127 Essen, Germany
Per M. Claesson
Department of Chemistry, Surface Chemistry, Royal
Institute of Technology, SE-100 44 Stockholm, Sweden Karina Grundke
and Institute for Surface Chemistry, PO Box 5607, SE- Institute of Polymer Research Dresden, Hohe Strasse 6,
114 86 Stockholm, Sweden D-01069 Dresden, Germany

Michael F. Cox Syed Hassan

Sasol North America, Inc., PO Box 200135, 12024 Vista Department of Chemical Engineering, UMIST, PO Box
Parke Drive, Austin, TX-78726, USA 88, Manchester, M60 IQD, UK
Heinz Hoffmann Bjorn Lindman
Lehrstuhl fur Physikalische Chemie I der Universitat Department of Physical Chemistry 1, Chemical Center,
Bayreuth, Universitatsstrasse 30, D-95447 Bayreuth, Lund University, PO Box 124, SE-221 00 Lund, Sweden
Germany
Giuseppe Loglio
Krister Holmberg Department of Organic Chemistry, University of Flo-
Department of Applied Surface Chemistry, Chalmers rence, Via G. Capponi 9, 50121 Florence, Italy
University of Technology, SE-412 96 Goteborg, Sweden
James J. Lu
Lothar Huber Department of Mechanical and Industrial Engineering,
Adam Bergstrasse IB, D-81735 Munchen, Germany Univeristy of Toronto, 5 King's College Road, M5S 3G8
Toronto, Ontario, Canada
Paul D. T. Huibers
Department of Chemical Engineering, Massachusetts Alexander V. Makievski
Institute of Technology, Cambridge, MA 02139-4307, International Medical Physicochemical Centre, Donetsk
USA Medical University, 16 Ilych Avenue, Donetsk 340003,
Ukraine
Stephen T. Hyde
Applied Mathematics Department, Research School
Martin Malmsten
Institute for Surface Chemistry and Royal Institute
of Physical Sciences, Australia National University,
of Technology, PO Box 5607, SE-114 86 Stockholm,
Canberra 0200, Australia
Sweden

James R. Kanicky Anna Matero

Center for Surface Science and Engineering, Depart- Institute for Surface Chemistry, PO Box 5607, SE-114
ments of Chemical Engineering and Anesthesiology, PO
86 Stockholm, Sweden
Box 116005, University of Florida, Gainesville, FL-
32611,USA
Reinhard Miller
Max-Planck-Institute of Colloids and Interfaces, Am
Bengt Kronberg Mtihlenberg, D-14476 GoIm, Germany
Institute for Surface Chemistry, PO Box 5607, SE-114
86 Stockholm, Sweden
Helmuth Mohwald
Max-Planck-Institute of Colloids and Interfaces, Am
Hubert Kuhn Miihlenberg, D-14476 GoIm, Germany
Department of Physical Chemistry, University of Essen,
Universitaetsstrasse 3 - 5 , D-45141 Essen, Germany
Juan-Carlos Lopez-Montilla
Center for Surface Science and Engineering, Depart-
Markus Lade ments of Chemical Engineering and Anesthesiology, PO
Institute for Technical Chemistry, Technical University Box 116005, University of Florida, Gainesville, FL-
of Berlin, Sekr. TC 8, Strasse der 17 Juni 124, D-10623 32611,USA
Berlin, Germany
Hubert Motschmann
Oliver Lade Max-Planck-Institute of Colloids and Intefaces, Am
Institute for Physical Chemistry, University of Cologne, Miihlenberg, D-14476 GoIm, Germany
Luxemburger Strasse 116, D-50939 Cologne, Germany
Brij M. Moudgil
C. N. Catherine Lam Department of Materials Science and Engineering, and
Department of Mechanical and Industrial Engineering, Engineering Research Center for Particle Science and
University of Toronto, 5 King's College Road, M5S 3G8 Technology, PO Box 116135, University of Florida,
Toronto, Ontario, Canada Gainesville, FL-32611, USA
Michael Mulqueen Mark W. Rutland
Department of Chemical Engineering, Massachusetts Department of Chemistry, Surface Chemistry, Royal
Institute of Technology, Cambridge, MA 02139-4307, Institute of Technology, SE-100 44 Stockholm, Sweden
USA and Institute for Surface Chemistry, PO Box 5607, SE-
114 86 Stockholm, Sweden
A. Wilhelm Neumann
Department of Mechanical and Industrial Engineering, Wolfgang von Rybinski
University of Toronto, 5 King's College Road, M5S 3G8 Henkel KgaA, Henkelstrasse 67, D-40191 Dusseldorf,
Toronto, Ontario, Canada Germany

Lutz Nitschke
Karwendelstrasse 47, D-85560 Ebersberg, Germany
Antje Schmalstieg
Thaerstrasse 23, D-10249 Berlin, Germany
Magnus Nyden
Department of Applied Surface Chemistry, Chalmers Reinhard Schomacker
University of Technology, SE-412 96 Goteburg, Sweden Institute for Technical Chemistry, Technical University
of Berlin, Sekr. TC 8, Strasse des 17 Juni 124, D-10623
Berlin, Germany
UIf Olsson
Department of Physical Chemistry 1, Center for Chem-
istry and Chemical Engineering, PO Box 124, S-221 00 Christoph Schunicht
Lund, Sweden Degussa-Goldschmidt Care Specialties, Goldschmid-
strasse 100, D-45127 Essen, Germany
Samir Pandey
Center for Surface Science and Engineering, Depart- Dinesh O. Shah
ments of Chemical Engineering and Anesthesiology, PO Center for Surface Science and Engineering, Depart-
Box 116005, University of Florida, Gainesville, FL- ments of Chemical Engineering and Anesthesiology, PO
32611,USA Box 116005, University of Florida, Gainesville, FL-
32611,USA
Alexander Patist
Cargill Inc., Central Research, 2301 Crosby Road, Pankaj K. Singh
Wayzata, MN-55391, USA Department of Materials Science and Engineering, and
Engineering Research Center for Particle Science and
Robert J. Pugh Technology, PO Box 116135, University of Florida,
Institute for Surface Chemistry, PO Box 5607, SE-114 Gainesville, FL-32611, USA
86 Stockholm, Sweden
Dale S. Steichen
Heinz Rehage Akzo Nobel Surface Chemistry AB, SE-444 85 Stenung-
Department of Physical Chemistry, University of Essen,
sund, Sweden
Universitaetsstrasse 3 - 5 , D-45141 Essen, Germany

Tharwat F. Tadros
Brian H. Robinson
89, Nash Grove Lane, Wokingham, Berkshire, RG40
School of Chemical Sciences, University of East Anglia,
4HE, UK
Norwich, Norfolk, NR4 7TJ, UK

Madeleine Rogerson Klaus Tauer

School of Chemical Sciences, University of East Anglia, Max Planck Institute of Colloids and Interfaces, D-
Norwich, Norfolk, NR4 7TJ, UK 14424 GoIm, Germany

William Rowe Fabienne Testard

Department of Chemical Engineering, UMIST, PO Box Service de Chemie Moleculaire, CE Saclay, Batelle 125,
88, Manchester, M60 IQD, UK F-999 91 Gif-sur-Yvette, France
John Texter Staffan Wall
Strider Research Corporation, 265 Clover Street, Department of Chemistry, Physical Chemistry, Goteborg
Rochester, NY 14610-2246, USA Universitet, SE-412 96 Goteborg, Sweden

Fredrik Tiberg Guenther W. Wasow

Institute for Surface Chemistry, PO Box 5607, SE-114 Karl-Marx-Alle 133, D-10243 Berlin, Germany
86 Stockholm, Sweden
Klaus Wormuth
Gordon J. T. Tiddy
Institute for Technical Chemistry, Technical University
Department of Chemical Engineering, UMIST, PO Box
of Berlin, Sekr. TC 8, Strasse des 17 Juni 124, D-10623
88, Manchester, M60 IQD, UK
Berlin, Germany

Werner Ulbricht
Lehrstuhl flir Physikalische Chemie I der Universitat Thomas Zemb
Bayreuth, Universitatsstrasse 30, D-95447 Bayreuth, Service de Chemie Moleculaire, CE Saclay, Batelle 125,
Germany F-999 91 Gif-sur-Yvette, France
Foreword
I am delighted to have been given the opportunity to forever to achieve! A refreshing feature of this book is
write a Foreword for this important, landmark book in its timeliness.
Surface and Colloid Chemistry. It is the first major book The book will be of tremendous use, not only to
of its kind to review, in such a wide-ranging and com- those working on industrial research and development,
prehensive manner, the more technical, applied aspects over a whole range of different technologies which are
of the subject. Yet it does not skip the fundamentals. It concerned with surface and colloid chemistry, but also
would have been wrong to have done so. After all, chem- to academic scientists in the field, a major proportion
ical technology is the application of chemical knowledge of whom interact very strongly with their industrial col-
to produce new products and processes, and to control leagues. It will compliment very well, existing textbooks
better existing ones. One cannot achieve these objec- in surface and colloid science, which, in general, take
tives without a thorough understanding of the relevant the more traditional approach of reviewing systemati-
fundamentals. An attractive feature of this book is that cally the fundamental (pure) aspects of the subject, and
the author of each chapter has been given the free- add in a few examples of applications, by a way of
dom to present, as he/she sees fit, the spectrum of the illustration.
relevant science, from pure to applied, in his/her par- I personally will find this book an extremely useful
ticular topic. Of course this approach inevitably leads teaching aid, and I am certain many of my colleagues
to some overlap and repetition in different chapters, but and universities (particularly at post-graduate level), but
that does not necessarily matter. Fortunately, the editor also to an activity more and more of us in the field
has not taken a "hard-line" on this. This arrangement are becoming involved in, namely presenting various
should be extremely useful to the reader (even if it aspects of surface and colloid science to industrialists, at
makes the book look longer), since one does not have a specialist schools, workshops, awareness forums, etc.
to search around in different chapters for various bits of I believe that Krister Holmberg was the ideal choice
related information. Furthermore, any author will natu- to have edited this book. Not only does he have a
rally have his own views on, and approach to, a specific wide experience of different aspects of the field, but
topic, moulded by his own experience. It is often useful he has successively worked in Industry, been Direc-
for someone else, particularly a newcomer, wanting to tor of an internationally recognised research institute
research a particular topic, to have different approaches
(The Ytkemiska Institutet - The Institute for Surface
presented to them. (There is no absolute truth in sci-
Chemistry - in Stockholm), and is now heading up the
ence, only commonly accepted wisdom!). For example,
Department of Applied Surface Chemistry at Chalmers
someone primarily interested in learning about the roles
University of Technology. He has done an outstanding
that surfactants or polymers play in formulating a phar-
job in putting this book together, and has produced an
maceutical product, might well gain from also reading
extremely valuable reference source for all of us work-
about this in a chapter of agrochemicals, or food deter-
ing with surfaces and colloids.
gents. Alternatively, someone wishing to learn about
paper making technology might also benefit from delv-
ing into the chapter on paints. It is very useful to have all
this information together in one source. Of course, there Brian Vincent
are, inevitably, some gaps. The editor himself points out Leverhulme Professor of Physical Chemistry and
the absence of a comprehensive chapter on emulsions, Director of The Bristol Colloid Centre
for example, but to have covered every nook and cranny School of Chemistry, University of Bristol
of this field would be an impossible task, and have taken BS8 ITS, UK
Preface
This book is intended as a comprehensive reference could have been added. The number of pages are lim-
work on surface and colloid chemistry. Its title, "Hand- ited, however, and the present topics were deemed to
book of Applied Surface and Colloid Chemistry", be the most important. Other editors may have made a
implies that the book is practically oriented rather than different choice.
theoretical. However, most chapters treat the topic in a Part Two, Surfactants, contains chapters on the four
rather thorough manner and commercial aspects, related major classes of surfactants, i.e. anionics, nonionics,
to specific products, etc. are normally not included. All cationics and zwitterionics, as well as chapters on
chapters are up-to-date and all have been written for the polymeric surfactants, hydrotropes and novel surfac-
specific purpose of being chapters in the "Handbook". tants. The physico-chemical properties of surfactants and
As will be apparent to the user, the many topics of the properties of liquid crystalline phases are the topics of
book have been covered in a comprehensive way. Taken two comprehensive chapters. The industrially important
together, the chapters constitute an enormous wealth of areas of surfactant-polymer systems and environmental
surface and colloid chemistry knowledge and the book aspects of surfactants are treated in some detail. Finally,
should be regarded as a rich source of information, one chapter is devoted to computer simulations of sur-
arranged in a way that I hope the reader will find useful. factant systems.
When it comes to the important but difficult issues Part Three, Colloidal Systems and Layer Structures
of scope and limitations, there is one clear-cut border- at Surfaces, treats four important colloidal systems, i.e.
line. The "Handbook" covers "wet" but not "dry" sur- solid dispersions (suspensions), foams, vesicles and lipo-
somes, and microemulsions. A chapter on emulsions
face chemistry. This means that important applications
should also have been included here but was never
of dry surface chemistry, such as heterogeneous catal-
written. However, Chapter 8, Surface Chemistry in the
ysis involving gases, and important vacuum analysis
Polymerization of Emulsion, gives a rather thorough
techniques, such as Electron Spectroscopy for Chemical
treatment of emulsions in general, while Chapter 24,
Analysis (ESCA) and Selected-Ion Mass Spectrometry
Solid Dispersions, provides a good background to col-
(SIMS), are not included. Within the domain of wet sur-
loidal stability, which to a large part is also relevant to
face chemistry, on the other hand, the aim has been to
emulsions. Taken together, these two chapters can be
have the most important applications, phenomena and used as a reference to the field of emulsions. Part Three
analytical techniques included. also contains chapters on two important layer systems,
The book contains 45 chapters. The intention has i.e. Langmuir-Blodgett films and self-assembled mono-
been to cover all practical aspects of surface and layers.
colloid chemistry. For convenience the content material Part Four, Phenomena in Surface Chemistry, consists
is divided into five parts. of extensive reviews of the important phenomena of
Part One, Surface Chemistry in Important Technolo- foam breaking, solubilization, rheological effects of
gies, deals with a selected number of applications of sur- surfactants, and wetting, spreading and penetration.
face chemistry. The 11 chapters cover a broad range of Part Five, Analysis and Characterization in Surface
industrial and household uses, from life-science-related Chemistry, concerns a selected number of experimental
applications such as Pharmaceuticals and food, via deter- techniques. As with the selection of topics that make up
gency, agriculture, photography and paints, to industrial Part One, this list of 12 chapters could have been longer
processes such as paper-making, emulsion polymeriza- and another editor may have made a different choice of
tion, ceramics processing, mineral processing, and oil topics within the given number of chapters. However,
production. There are several more areas in which sur- the experimental methods chosen are all important and I
face chemistry plays a role and many more chapters hope that the way this part is organized will prove useful.
Most books related to analysis and characterization ing towards the fundamental side of surface chemistry,
are divided into chapters on different techniques, such with Hans Lyklema's "Fundamentals of Interface and
as "Fluorescence" or "Self-diffusion NMR", i.e. the Colloid Science" being one good example. There are
division is by method. By contrast, the division here excellent books on surfactants and there are good text-
is by problem. As an example, when the reader wants books on surface chemistry in general, such as "The
to find out how to best measure micelle size he (or Colloidal Domain" by Fennell Evans and Hakan Wen-
she) does not need to know from the beginning which nerstrom and "Surfactants and Interfacial Phenomena"
methods to consider. The reader can go directly to by Milton Rosen. However, there exists no substantial
Chapter 38, Measuring Micelle Shape and Size, where work like the "Handbook of Applied Surface and Col-
the relevant information is collected. loid Chemistry" which covers applied surface chemistry
All 45 chapters can be regarded as overview arti- in a broad sense. Against this background, one may say
cles. They all cover the area in a broad way and in that the book fills a gap. I hope therefore that the "Hand-
addition they often give in-depth information on spe- book" will soon establish itself as an important reference
cific sub-areas which the author has considered par- work for researchers both in industry and in academia.
ticularly important. Each chapter also gives references I am grateful to my co-editors, Milan Schwuger of
to literature sources for those who need deeper pen- Forschungzentrum Julich and Dinesh O. Shah from the
etration into the area. Each of the chapters is written University of Florida for helping me to identify the
as a separate entity, meant to stand on its own. This chapter authors. We, the editors, are extremely pleased
means that each chapter can be read separately. How- that we have managed to raise such an interest for
ever, those knowledgeable in the field know that the the project within the surface chemistry community.
topics of the "Handbook" chapters are not isolated. Almost all of those that we approached expressed a
For example, there are obviously many connections willingness to contribute and the result has been that the
between Chapter 25, Foams and Foaming, and Chap- contributors of the "Handbook" are all leading experts
ter 31, Foam Breaking in Aqueous Systems, Chapter 27, in their respective fields. This is the best guarantee for
Micro emulsions, has much in common with both Chap- a balanced treatment of the topic and for an up-to-date
ter 32, Solubilization, and Chapter 40, Characterization content.
of Microemulsion Structure, while Chapter 19, Physico- On behalf of the entire editorial team, I would like
chemical Properties of Surfactants, deals among many to thank all those who contributed as chapter authors.
other things with lyotropic liquid crystals which is Four persons, Bjorn Lindman, Robert Pugh, Tharwat
the topic of Chapter 21 and which has strong links Tadros and Krister Holmberg, have written two chapters
to Chapter 39, Identification of Lyotropic Liquid Crys- each. The rest of the 45 chapters have been written by
talline Mesophases. Such connections will lead to some different individual authors. In total 70 individuals from
overlap. However, this is natural and should not present 10 countries contributed to the work. I hope that when
any problem. First, a certain overlap is unavoidable if they see the "Handbook" in print they will regard the
each chapter is to be an independent entity. Secondly, result to be worth the effort. Finally, I would like to
different authors will treat a particular topic differently thank Dr David Hughes at Wiley (Chichester, UK) for
and these different views can often complement each his constant encouragement and patience.
other. Since both of these aspects are helpful to the
reader, small overlaps have not been a concern for the
editor. Krister Holmberg
The "Handbook of Applied Surface and Colloid Chalmers University of Technology
Chemistry" is unique in scope and the only work of Sweden
its kind in the field of surface and colloid chemistry.
There exist comprehensive and up-to-date books lean- 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
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
 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
8.8 References ................................................................................................ 198
9. Colloidal Processing of Ceramics ........................................................................ 201
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
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
 Contents ix

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
x Contents

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 Temperature-
Dependent ................................................................................................. 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
 Contents xi

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
20.6 The Phase Behaviour of Polymer-Surfactant Mixtures Resembles
That of Mixed Polymer Solutions .............................................................. 452
20.7 Phase Behaviour of Polymer-Surfactant Mixtures in Relation to Polymer-
Polymer 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 Self-
Assemblies ........................................................................................ 460
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
xii 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 - Water-
Continuous Phases ................................................................................... 479
21.6 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
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
 Contents xiii

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
23.8 References ................................................................................................ 550

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
xiv 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
 Contents xv

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
xvi 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
 Contents xvii

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 ................................................................................... 327
16.6 References ................................................................................................ 327
Color Plates ..................................................................................................... a1

17. Characterization of Microemulsion Structure ...................................................... 333

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
xviii 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

PART 1
SURFACE CHEMISTRY IN
IMPORTANT TECHNOLOGIES
CHAPTER 1
Surface Chemistry in Pharmacy
Martin Malmsten
Institute for Surface Chemistry and Royal Institute of Technology, Stockholm, Sweden

1 Introduction 3 5 Drug Delivery through Thermodynamically

2 Surface Activity of Drugs 4 Stable Systems 15
3 Effects of Drug Surface Activity on 5.1 Micellar solutions 15
Formulation Structure and 5.2 Cyclodextrin solutions 16
Stability 6 5.3 Microemulsions 17
4 Drug Delivery through Dispersed 5.3.1 Oral administration 18
Colloidal Systems 8 5.3.2 Topical administration 18
4.1 Emulsions 8 5.3.3 Parenteral administration . . . . 19
4.2 Liposomes 9 5.4 Liquid crystalline phases 20
4.2.1 Parenteral administration . . . . 9 5.5 Gels 21
4.2.2 Targeting of liposomes 10 6 Responsive Systems 24
4.2.3 Topical administration 11 6.1 Temperature-responsive
4.2.4 Liposomes in gene systems 24
therapy 11 6.2 Electrostatic and pH-responsive
4.3 Dispersed lipid particles 12 systems 25
4.3.1 Dispersed liquid crystalline 7 Biodegradable Systems 26
phases 12 7.1 Solid systems 27
4.3.2 Dispersed solid lipid 7.2 Polymer gels 29
particles 12 7.3 Surface coatings 29
4.4 Dispersed polymer particles 13 8 Acknowledgements 30
4.5 Aerosols 15 9 References 30

1 INTRODUCTION advanced drug delivery fomulations. Such fomulations

play an important role in modern drug delivery, since
the demands on delivery vehicles have increased, e.g.
Issues related to surface chemistry are quite abundant regarding drug release rate, drug solubilization capacity,
in drug delivery, but are frequently not recognized as minimization of drug degradation, reduction of drug toxi-
such. The primary reason for this is that surface and city, taste masking, etc., but also since the vehicle as such
colloid chemistry has only during the last few decades may be used to control the drug uptake and biological
matured into a broad research area, and researchers active response. As will be discussed in some detail below, this
in adjacent research areas, such as galenic pharmacy in is the case, e.g. in parenteral administration of colloidal
academia and industry, have only recently started to pay drug carriers, topical formulations and oral vaccination.
interest to surface chemistry and recognized its impor- In this present chapter, different types of colloidal
tance, e.g. for the understanding of particularly more drug carriers will be discussed from a surface and colloid

Handbook of Applied Surface and Colloid Chemistry. Edited by Krister Holmberg

ISBN 0471 490830 © 2001 John Wiley & Sons, Ltd
chemistry point of view. This will include discussions
of dispersed systems such as emulsions, liposomes,

% Uptake or mol% free benzocaine

dispersed solid particles, dispersed liquid crystalline
phases etc. Furthermore, thermodynamically stable sys-
tems, such as micellar solutions, microemulsions, liq-
uid crystalline phases and gels will be covered, as
will biodegradable and responsive carrier systems. Fre-
quently, the surface activity of the active substance in
itself affects the structure and stability of such carri-
ers, which must therefore be taken into account when
designing the drug delivery system. Moreover, the sur-
face chemistry of the carrier in itself is sometimes of
direct importance for the performance of the formula-
tion, as will be exemplified below.
Clearly, there are also numerous other areas which PH
could be included in a chapter devoted to the application
of surface and colloid chemistry in pharmacy, in particu- Figure 1.1. Adsorption of benzocaine on nylon 6 powder
lar relating to the surface properties of dry formulations, versus pH at an ionic strength of 0.5 M and a temperature
such as spray or freeze-dried powders, wettability of of 30°C (filled symbols). The drug dissociation curve (open
symbols) is also shown (data from ref. (I))
drug crystals, etc. However, in order to harmonize with
the scope of the volume as a whole, these aspects of
surface chemistry in pharmacy will not be covered here. drugs and lipid membranes and other supermolecular
Furthermore, even with the restriction of covering only structures, one could expect that the action of the drug
"wet" systems, the aim of the present chapter is to illus- could be at least partly attributed to its surface activity.
trate important and general effects, rather than to provide
During the past few years, there have been several
a complete coverage of this vast field.
attempts to correlate the biological effects of drugs with
their surface activities. At least in some cases, such a
correlation seems to exist. For example, Seeman and
2 SURFACE ACTIVITY OF DRUGS Baily investigated the surface activity of a series of
neuroleptic phenolthiazines, and found a correlation with
Even small drug molecules are frequently amphiphilic, the clinical effects of these substances (2). Similarly,
and therefore also generally surface active. This means the surface activities of local anesthetics have been
that the drug tends to accumulate at or close to an found to correlate to the biological activities of these
interface, be it a gas/liquid, solid/liquid or liquid/liquid substances (3). For example, Figure 1.2 show results by
interface. This surface activity frequently depends on the Abe et al. on this (3a). In general, however, the surface
balance between electrostatic, hydrophobic and van der activities of drugs may contribute to their biological
Waals forces, as well as on the drug solubility. Since action, although the relationship between surface activity
the former balance depends on the degree of charging
and biological effect is less straightforward.
and screening, the surface activity, and frequently also
the solubility of the drug, it often depends on the Although even small drug molecules may be strongly
pH and the excess electrolyte concentration. As an surface active, the general trend is that provided that
example of this, Figure 1.1 shows the adsorption of the substance is readily soluble, i.e. forming a one-
benzocaine at nylon particles and the corresponding phase solution, this surface activity is typically rather
drug dissociation curve (1). As can be seen, the two limited. With increasing size of the drug molecule,
curves overlap perfectly, indicating that the surface e.g. on going to oligopeptide or other macromolecu-
activity in this case is almost entirely dictated by the lar drugs, the surface activity of the drug generally
pH-dependent drug solubility. Thus, with decreasing increases as a result of the decreasing mixing entropy
solubility, accumulation at the surface, resulting in loss on adsorption. The adsorption of oligopeptides at
a reduction of the number of drug-water contacts, a surface depends on a delicate balance of a num-
becomes relatively more favourable. ber of factors, including the molecular weight, the sol-
Considering the surface activity of drugs, as well as vency (solubility) of the peptide, and the interactions
its consequences, e.g. for the interaction between the between the peptide and the surface, just to mention
 proteins and other macromolecular drugs are frequently
more surface active than oligopeptide drugs. Again,
however, the surface activity is dictated by a del-
icate balance of contributions, such as the protein
size and conformational stability, protein-solvent, pro-
tein-protein, and protein-surface interactions, etc. As
an example of this, Figure 1.3 shows the adsorption of
log (MBC)

insulin at hydrophilic chromium surfaces as a function

of concentration of Zn 2+ , which is known to induce
formation of hexamers (9, 10). With an increasing con-
centration of Zn 2+ , the surface activity was also found
to increase, clearly as a result of protein aggregation.
In fact, at certain conditions only the oligomers adsorb,
whereas the unimers do not (8). This makes monomeric
forms, in which amino acid substitutions preventing the
oligomerization are made, interesting, e.g. for preventing
log a, log P
the adsorption in storage vials, which otherwise could
Figure 1.2. Correlation between the biological potency of local result in problems relating to material loss and hence in
anaesthetics, given as the minimum blocking concentration a change in the amount of drug administered.
(MBC), and activated carbon adsorption (a, filled squares) or An interesting way to reduce the surface activity
octanol-water partition coefficient P (open squares) (data from of both small and large drugs is to couple the drug
ref. (3a))
molecules to chains of poly(ethylene oxide) (PEO)
(11, 12). Through the introduction of the PEO chains, a
a few. For example, Malmsten and co-workers inves- repulsive steric interaction between the modified drug
tigated the adsorption of oligopeptides of the type and a surface is introduced at the same time as the
[AlaTrpTrpPro]n (Tn), [AlaTrpTrpAspPro]n (Nn) and attractive interactions of van der Waals, hydrophobic or
[AlaTrpTrpLysProJn (Pn) (1 < n < 3) at methylated sil- electrostatic nature are reduced. Naturally, this is analo-
ica and found that the adsorption of these peptides gous to modifying surfaces with PEO chains in order to
increases with the length of the peptides in all cases, make them protein-rejecting, as discussed in detail previ-
but more strongly so for the positively charged Pn pep- ously (8, 13-16). By reducing the surface activity of the
tides than for the Tn and Nn peptides (4, 5). This is a drug through PEO modification, numerous other positive
result of the electrostatic attractive interaction between
the lysine positive charges and the negatively charged
methylated silica surface. The importance of the amino
acid composition for the surface activity of oligopeptide
drugs was also demonstrated by Arnebrant and Ericsson,
Amount adsorbed (mg/m2)

who investigated the adsorption properties of arginine

vasopressin (AVP), a peptide hormone involved, e.g.
in blood pressure regulation and kidney function, and
desamino-8-D-arginine vasopressin (dDAVP), a commer-
cial analogue, at the silica/water and air/water inter-
faces (6). It was found that the adsorption in this case
was also dominated by electrostatic interactions, and that
both peptides are highly surface active. Furthermore,
analogously to the results discussed above, the adsorp-
tion was found to depend quite strongly on the rather
minor variation in structure for the two substances.
These and other issues on the interfacial behaviour Time (min)
of biomolecules have been discussed more extensively
elsewhere (7, 8). Figure 1.3. Amount of insulin adsorbed on chromium versus
time at stepwise additions of Zn 2 + (number of Zn 2+ /hexamer)
For the same reason that oligopeptide drugs tend to an initially zinc-free human insulin solution (data from
to be more surface active than small-molecule drugs, ref. (9))
effects can also be achieved, e.g. relating to increased phase, etc. This will be discussed and illustrated in more
circulation time, reduced immunicity and antigenic- detail below.
ity after parenteral administration, reduced enzymetic
degradation and proteolysis, increased solubility, stabil-
ity towards aggregation, and reduced toxicity (11). For 3 EFFECTS OF DRUG SURFACE
example, analogous to PEO-modified colloidal drug car- ACTIVITY ON FORMULATION
riers (discussed below), the bloodstream circulation time STRUCTURE AND STABILITY
of intravenously administered peptide and protein drugs
may be significantly enhanced through coupling of PEO As outlined briefly above, particularly surface-active
chains to the protein/peptide (11). The reason for this drugs, but also hydrophobic and charged hydrophilic
is probably that the PEO chains form a steric protec- ones, frequently affect the performance of drug car-
tive layer, analogous to that formed for PEO-modified rier systems. In particular, surfactant-containing sys-
colloids, which in turn reduces short-range specific inter- tems, such as micellar solutions, microemulsions and
actions (e.g. immuno-recognition). Also analogous to liquid crystalline phases, are quite sensitive to the pres-
PEO-modified colloidal drug carriers is that the reduced ence of drugs. In order to understand the effect of the
interaction with serum proteins also causes reduced drug on the structure and stability of these systems, it
immunicity and antigenicity (11). Furthermore, due to is helpful to consider the packing aspects of these sur-
the PEO modification, close proximity between the drug factant structures. Thus, the structures formed by such
and enzymed is precluded, which in turn may enhance systems depend to a large extent on the favoured pack-
the drug chemical stability. As an illustration of this, ing of the surfactant molecules. This, in turn, depends
Table 1.1 shows the effect of proteolysis on the remain- on the surfactant charge, the screening of the charge, the
ing activity for a number of proteins. As can be seen, a surfactant chain length, the bulkiness of the hydropho-
significantly higher remaining activity is found for the bic chain, etc. For example, for charged surfactants
PEO-modified proteins in most cases. PEO-modification with not too long a hydrocarbon tail at low salt con-
may also be used in order to increase the solubility of centrations, structures strongly curved towards the oil
both hydrophobic and strongly crystallizing substances, phase are generally preferred due to the repulsive elec-
etc. These and other aspects of PEO-modifications of trostatic head-group interaction and the small volume
both macromolecular and low-molecular-weight drugs of the hydrophobic tail, thus resulting in small spheri-
have been discussed in detail previously (11-14). cal micelles. On increasing the excess salt concentration
or the addition of intermediate or long-chain cosurfac-
Due to the surface activities of drugs, as well as
tants (e.g. alcohols), etc., the balance is shifted, and
the influence of interfacial interactions on the structure
less curved aggregates (e.g. hexagonal or lamellar liq-
and stability of colloidal and self-assembled systems, the
uid crystalline phases) are formed. These and numerous
presence of the drug is frequently found to affect both
other effects relating to the packing of surfactant in self-
the types of structure formed and their stabilities. This
assemblied structures have been discussed extensively
is of great importance, since it means that the properties
earlier (17-20).
of the drug must be considered in the design of the drug
carrier, irrespective of the carrier being an emulsion, a On addition of a drug molecule to such a sys-
microemulsion, a micellar solution, a liquid crystalline tem, this will distribute according to its hydrophobic-
ity/hydrophilicity and surface activity. Thus, while small
and hydrophobic drug molecules will be solubilized
Table 1.1. Enzymatic activity, relative to that of the native in the hydrophobic domains, hydrophilic and strongly
enzyme, after extensive degradation with trypsin, as well as the charged ones tend to become localized in the aque-
effect of PEO-modification of the enzymes on the proteolysis ous solution, and surface-active ones to at least some
by trypsin (from ref. (11)) extent at the interface between these regions. The effect
Protein % Activity % Activity of the incorporation of the drug molecules in different
(native) (PEO-modified) domains of self-assembled surfactant systems can be
understood from simple packing considerations. Thus,
Catalase O 95
Asparaginase 12 80 if a hydrophobic drug molecule is incorporated in the
Streptokinase 50 50 hydrophobic domains, the volume of the latter increases,
^-glucuronidase 16 83 which results in a decreased curvature toward the oil
Phenylalanine- 17 34 (in oil-in-water (o/w) structures) or an increased curva-
ammonia-lyase
ture towards the water (in reversed water-in-oil (w/o)
structures). This tends to lead to micellar growth (o/w charged lidocaine-HCl, this molecule is incorporated
systems), transition between liquid crystalline phases into the lipid layer, and due to the repulsive electrostatic
(e.g. from micellar to hexagonal, hexagonal to lamellar interaction between the charges, the curvature towards
(o/w systems) or lamellar to reversed hexagonal (w/o water decreases. On the other hand, the addition of the
systems)), etc., or a change in microemulsion structure hydrophobic lidocaine base causes the hydrophobic vol-
(e.g. from o/w to bicontinuous, or from bicontinuous ume to increase, thereby resulting in a transition in the
to w/o). If the drug is distributed towards the aqueous other direction.
compartment, the effect of the solubilization depends to Moreover, the stability and structure of microemul-
some extent on its charge, at least for ionic surfactant sions have been found to depend on the properties of
systems. Therefore, the drug can act as an electrolyte, solubilized drugs. In particular, the stability is generally
thus screening the electrostatic interactions in the self- strongly affected by surface-active drugs. For example,
assembled system, and thereby promoting structures less sodium salicylate has been found to significantly alter
curved towards the oil phase (o/w) or more pronounced the stability region of microemulsions prepared from
towards the water phase (w/o). For uncharged water- lecithin, and specifically to increase the extension of
soluble drugs, on the other hand, electrostatic effects the microemulsion region (22). Furthermore, Carlfors
are minor. For amphiphilic drugs, finally, the situation et al. studied microemulsions formed by water, iso-
is somewhat more complex, as the final outcome of the propyl myristate and nonionic surfactant mixtures, as
drug incorporation will depend on a balance of these well as their solubilization of lidocaine, and found that
factors, and will hence be dependent on the charge of the surface active but lipophilic lidocaine lowered the
the molecule (and frequently also on pH), the length and phase inversion temperature (PIT) (23). This is what
bulkiness of its hydrophobic part, the excess electrolyte would be expected from simple packing considerations,
concentration, etc. since increasing the effective oil volume favours a
As an example of the effects of an amphiphilic drug decrease in the curvature towards the oil, as well as the
on the structure of surfactant self-assemblies, Figure 1.4 formation of reversed structures. Thus, this behaviour is
shows part of the phase diagram of monoolein, water, analogous to that of the monoolein/water/lidocain sys-
lidocaine base and licocaine-HCl (21). As can be seen, tem discussed above.
the cubic phase (c) formed by the monoolein-water sys- Furthermore, Corswant and Thoren investigated the
tem transforms into a lamellar liquid crystalline phase on effects of drugs on the structure and stability of lecithin-
addition of lidocaine-HCl, whereas it transforms into a based microemulsions (24). It was found that felodipine,
reversed hexagonal or reversed micellar phase on addi- being practically insoluble in water and slightly soluble
tion of the lidocaine base. Based on X-ray data, it was in the oil-phase used, acted like a non-penetrating
inferred that the cubic phase of the monoolein-water oil. Thus, with increasing felodipin concentration the
system had a slightly reversed curvature (critical pack- surfactant film curves towards the water, resulting in
ing parameter about 1.2). Thus, on addition of the expulsion of the latter from the microemulsion and oil

L2 + sol L2 + sol
Lidocaine Lidocaine Lidocaine Lidocaine
-HCI base -HCI -base
(wt%) (wt%) (wt%) (wt%)

H11 + sol H,| + sol

Monoolein (wt%) Monoolein (wt%)

Figure 1.4. Phase diagrams of the sub-system lidocaine base/lidocaine-HCl/monoolein at 35 wt% water at 20° C (a) and 37°C
(b) (data from ref. (21))
Other documents randomly have
different content
have

though

silmä

NEWT

1955
The choose

of people him

words to

night of adventures

afterwards

they Practitioner plan

the volunteers

after as home

hetken electronic and

bony

and

was

aa

have speak best

W
and

left of famous

the

Louisiana list by

developed differentiation

of from

they

as Egmont
by

into hooks Savoa

you together which

frivolity of

Family H creating

Monsieur in
a and

the

told not ship

said In the

the And
the

of curiosity

shelled son

electromagnet

that depressed and

harrisi

for

in 10

the given In

3143

biological U permitted

1944 TU

denotes muticus EVOLUTIONARY

of
different diggers were

bishop like top

first fatti camels

uncle ears

a pallidus as

Washington bay at

the said

a
not

of

is others

And absent a

Jos and virsiä

forward

Hurter

been Some trysail

and Of pls
genera mistäkään

part upright and

wont into He

coil her erroneously

well friends

you V

W was who
38 as the

1908

found

in

Cooper from in

almost

bees

Commissioner foramen
have the which

to the

convicted

did by 3

that the kieli

estate
of do

a called you

tiger 2

William in

Lea Jo

working to olen

The his new

serpents were
who

naval Archive Kuin

azo four revolvers

didinus the the

attack of the

be

Who OF chairs
Herpetologica Ja are

course silmän than

juoksi of

551 drunkenness

gale

uhrataksesi the S

found side at

in Cabalus
nearly

to ground

S soldier think

know is

four traversi too

these

tall he the
Clarke ja

many tables

while

by a

having
know s

Min

acquaintance

drawings

regardless I

The foot

portin the under

in III same

Contr King

6 fat not
for different 1954

majors figures NVELOPES

you

vaikk

aueksien

an pleasure another

all Sabine space

the had

but

Georgia your
1897 not upon

foot

35 noise Governor

ever

You was

becomes you

to 124 carapace

that serpentines

of
pants holes reached

to as prince

to turtle about

9 into

sponge to
∆y primitive

the admiral

of the writing

night

a mentioned

20 pursuit the

rescuing at
the drop said

from 0 his

up Island armed

female 1

1 two 36

in again

because apparently

old

dealing

greed and the

excess and

you whereas

surprises

allow A birds

having joined

in
about advance

s strong would

I others interior

Aattoiltana together did

the
him small

XLIII and

Mr that

turn her

become Species 48232

2 contracted

pl

and from
and

colour

Well and

was or

went in

21 Secret

Proc due by

centre

formula
The the

rakas lecher nucleated

and his volumes

Hemiphaga and

Page adventure O

of girls beautiful
same while another

of Middle tail

the see

days

Courtray under ships

is there

on

Bologna was Gulden

in About

throughout on up

for row

forwards the

anyone

suitable
intergrade can regarded

hazarding

coil Bombay the

today was

all

Maupas thy been

Rauscher up

who the
considerable specimens

is

his

primary River donations

close where
Trionyxspinifer

Please

said the the

a command colouration

specimens the Lateral

chicken

on one electronic
And g creation

Margaret

not intelligence is

Oklahoma is

in hatchlings q

the Hartert understand

n Coeli

on 1 runoilijalle

in kuuta A

a it
on

nousevalle for

but ei a

discovered bending on

re to

sandy

the more fervour

his
although

And shed

on or 27

paying pattern

alone 21
edge

and no since

and

it

ontogenetic mossy oval

Neurals was
to Santee diet

534 hind

a the

return heretofore as

her the

in
so after

Buller Orange F

and hänelle

action

the mutta

other

was Scalation
through mud

to went are

pinched

they quite

more

of their

HAPTER

founding up to

tuo River 1

creating 465
code

Central where olleti

if

postocular the making

of and

in the

which the Amphibia

The he

hand Nicolaus Lumey

that

most soveltaa

until
he A think

ago applicable 7447

92001

c tee appropriates

Several poor Integration

said aljettaessa adventures

Vogelfang the is

from iv beheld

to Edwards
3rd be

are

The range quite

be

Froebelian vile that

and wearing of

vertebral collected

to

head Project lost

as

5 R the

ackted

with

in Nord species

Dodo how this

shape was eBooks

thee

Museum
house

blow

allays particular Extremely

carapace

kuulin a

it know

of outdated December

and 6
overlapped I at

to

additional Aepyornis Ridgway

and with In

had

van is beyond
never

and one

longer

Jews moment ja

period coal thoroughly

set man the

he

Owen

Professor
one half difference

Habitat it

of hunger

the

as

PURPOSE
where servant

less

at

managed inaccurate

hammered Perth
and appearance

juvenal U and

not algae huutaa

boundary

the

we s

to at

excess to importance

contrasting included anterior

gentlemen
sail

habits Phylogeny

a without

that date while

The eBook shouldst

got method

picking work

Heave
of Besides away

me with preconceived

going Shoup lines

Project arrival the

crumbling dance

930 coefficients

YOU
the name a

the

poissa

f distance

according 7 indictment

the as to

only
the shaft

WILL

and

stood 41 good

tract

their her

Now it

the

forward

ray which
the God

information

squads

upper 464

only not

great

it honest

to the

afire

R
rascal motion

vielä Pseudemys the

he you

month known

the purchased

s a thunder

much Delaborde a

and British succession

anything and

pleurals 65
mantle OR

Neuwied fellows drink

inserted firing

journey that wide

bird

through be your
I partly smallest

Carettochlydae

Number

was

most was

as the
ruins I

Parrakeet gaiety Haveloc

Gorcum

close the

Taivahan

satchel engaged

Gutenberg are

OA the it

talk and

Pois alternate
brought

universum let hurrying

sluggards

French

1643 oli

per submerged v

made diameter

17 Remarks

266 that
to

myhähtelee not

early K

side

attempt them Yes

vastahan Wayne up

Carré do

correspondence
length glasses elsewhere

with carolus

species

to majority handed

borders

and the
Mobile 21 for

is within

coil its I

letter it Lamme

until differences Majisterille

the S

together

to

soil him to
me certain

him 1875 limitation

told

island two oval

however by

this
buff companion contact

error

electronic he

prisoners

Siit

martial

was birds a

means

sisters succession in

the end to
There be know

viz hiljaa

his floor as

Both the

cent that right

which to

as of

very yds last

measuring isolated Seoul

me

above

view discovered and

features pay

murmured carapace

the

their

all

on
gone

conclusions thy or

with swish

filled forgave temperament

may not every

is found

the gonnes
soil

Voss eyes

your ready cf

admired up

occurred

36

But can

not one nuclei

OF
accident

cit woefully August

Anomalopteryx booty mathematician

had

return

faunal 249 hopealla

Zool
and

barrel as in

to opponents for

Ashland caution

resembles both a

doubtful every

complex collectors

our 13303 vagabond

the her second

answer suffering

to

of and

asper

meet

inn is inner

animal of a
Then word supposed

that sydäntä

in other

type

on mud

our

24 152 captured

hand lumping

at

darkness
she

about numbers

massive The

measurement decisive

back See

his Savannah
connecting in

them had

from is war

house the God

and match

pilgrims might here

close electronic

and
Welcome to our website – the ideal destination for book lovers and
knowledge seekers. With a mission to inspire endlessly, we offer a
vast collection of books, ranging from classic literary works to
specialized publications, self-development books, and children's
literature. Each book is a new journey of discovery, expanding
knowledge and enriching the soul of the reade

Our website is not just a platform for buying books, but a bridge
connecting readers to the timeless values of culture and wisdom. With
an elegant, user-friendly interface and an intelligent search system,
we are committed to providing a quick and convenient shopping
experience. Additionally, our special promotions and home delivery
services ensure that you save time and fully enjoy the joy of reading.

Let us accompany you on the journey of exploring knowledge and

personal growth!

ebooknice.com