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. 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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 Valentin B. Fainerman 124, SE-221 00 Lund, Sweden 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, Michele Ferrari France 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 Karina Grundke Institute of Technology, SE-100 44 Stockholm, Sweden 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 Alexander V. Makievski Department of Chemical Engineering, Massachusetts International Medical Physicochemical Centre, Donetsk Institute of Technology, Cambridge, MA 02139-4307, Medical University, 16 Ilych Avenue, Donetsk 340003, USA Ukraine Stephen T. Hyde Martin Malmsten Applied Mathematics Department, Research School 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 Antje Schmalstieg Karwendelstrasse 47, D-85560 Ebersberg, Germany Thaerstrasse 23, D-10249 Berlin, Germany Magnus Nyden Reinhard Schomacker Department of Applied Surface Chemistry, Chalmers 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- 14424 GoIm, Germany Norwich, Norfolk, NR4 7TJ, UK 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 Thomas Zemb Lehrstuhl flir Physikalische Chemie I der Universitat Service de Chemie Moleculaire, CE Saclay, Batelle 125, Bayreuth, Universitatsstrasse 30, D-95447 Bayreuth, F-999 91 Gif-sur-Yvette, France Germany 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. Part Three, Colloidal Systems and Layer Structures When it comes to the important but difficult issues at Surfaces, treats four important colloidal systems, i.e. of scope and limitations, there is one clear-cut border- solid dispersions (suspensions), foams, vesicles and lipo- line. The "Handbook" covers "wet" but not "dry" sur- 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. Goteborg, January 2001 There exist comprehensive and up-to-date books lean-