Colloidal Silica Fundamentals and Applications

COLLOIDAL SILICAFundamentals and Applications

2006 by Taylor & Francis Group, LLC

DANIEL BLANKSCHTEINDepartment of Chemical EngineeringMassachusetts Institute of TechnologyCambridge, Massachusetts

S. KARABORNIShell International PetroleumCompany LimitedLondon, England

LISA B. QUENCERThe Dow Chemical CompanyMidland, Michigan

JOHN F. SCAMEHORNInstitute for Applied Surfactant ResearchUniversity of OklahomaNorman, Oklahoma

P. SOMASUNDARANHenry Krumb School of MinesColumbia UniversityNew York, New York

ERIC W. KALERDepartment of Chemical EngineeringUniversity of DelawareNewark, Delaware

CLARENCE MILLERDepartment of Chemical EngineeringRice UniversityHouston, Texas

DON RUBINGHThe Procter & Gamble CompanyCincinnati, Ohio

BEREND SMITShell International Oil Products B.V.Amsterdam, The Netherlands

JOHN TEXTERStrider Research CorporationRochester, New York

SURFACTANT SCIENCE SERIES

FOUNDING EDITOR

MARTIN J. SCHICK19181998

SERIES EDITOR

ARTHUR T. HUBBARDSanta Barbara Science Project

Santa Barbara, California

ADVISORY BOARD


1. Nonionic Surfactants, edited by Martin J. Schick (see also Volumes 19, 23, and 60)2. Solvent Properties of Surfactant Solutions, edited by Kozo Shinoda

(see Volume 55)3. Surfactant Biodegradation, R. D. Swisher (see Volume 18)4. Cationic Surfactants, edited by Eric Jungermann (see also Volumes 34, 37,

and 53)5. Detergency: Theory and Test Methods (in three parts), edited by W. G. Cutler

and R. C. Davis (see also Volume 20)6. Emulsions and Emulsion Technology (in three parts), edited by Kenneth J. Lissant7. Anionic Surfactants (in two parts), edited by Warner M. Linfield (see Volume 56)8. Anionic Surfactants: Chemical Analysis, edited by John Cross9. Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato

and Richard Ruch 10. Anionic Surfactants: Biochemistry, Toxicology, Dermatology, edited by

Christian Gloxhuber (see Volume 43)11. Anionic Surfactants: Physical Chemistry of Surfactant Action, edited by

E. H. Lucassen-Reynders 12. Amphoteric Surfactants, edited by B. R. Bluestein and Clifford L. Hilton

(see Volume 59)13. Demulsification: Industrial Applications, Kenneth J. Lissant 14. Surfactants in Textile Processing, Arved Datyner15. Electrical Phenomena at Interfaces: Fundamentals, Measurements,

and Applications, edited by Ayao Kitahara and Akira Watanabe16. Surfactants in Cosmetics, edited by Martin M. Rieger (see Volume 68)17. Interfacial Phenomena: Equilibrium and Dynamic Effects, Clarence A. Miller

and P. Neogi18. Surfactant Biodegradation: Second Edition, Revised and Expanded, R. D. Swisher19. Nonionic Surfactants: Chemical Analysis, edited by John Cross20. Detergency: Theory and Technology, edited by W. Gale Cutler and Erik Kissa21. Interfacial Phenomena in Apolar Media, edited by Hans-Friedrich Eicke

and Geoffrey D. Parfitt22. Surfactant Solutions: New Methods of Investigation, edited by Raoul Zana23. Nonionic Surfactants: Physical Chemistry, edited by Martin J. Schick24. Microemulsion Systems, edited by Henri L. Rosano and Marc Clausse25. Biosurfactants and Biotechnology, edited by Naim Kosaric, W. L. Cairns,

and Neil C. C. Gray26. Surfactants in Emerging Technologies, edited by Milton J. Rosen27. Reagents in Mineral Technology, edited by P. Somasundaran and Brij M. Moudgil28. Surfactants in Chemical/Process Engineering, edited by Darsh T. Wasan,

Martin E. Ginn, and Dinesh O. Shah29. Thin Liquid Films, edited by I. B. Ivanov30. Microemulsions and Related Systems: Formulation, Solvency, and Physical

Properties, edited by Maurice Bourrel and Robert S. Schechter 31. Crystallization and Polymorphism of Fats and Fatty Acids, edited by Nissim Garti

and Kiyotaka Sato32. Interfacial Phenomena in Coal Technology, edited by Gregory D. Botsaris

and Yuli M. Glazman33. Surfactant-Based Separation Processes, edited by John F. Scamehorn

and Jeffrey H. Harwell34. Cationic Surfactants: Organic Chemistry, edited by James M. Richmond


35. Alkylene Oxides and Their Polymers, F. E. Bailey, Jr., and Joseph V. Koleske36. Interfacial Phenomena in Petroleum Recovery, edited by Norman R. Morrow37. Cationic Surfactants: Physical Chemistry, edited by Donn N. Rubingh

and Paul M. Holland38. Kinetics and Catalysis in Microheterogeneous Systems, edited by M. Grtzel

and K. Kalyanasundaram39. Interfacial Phenomena in Biological Systems, edited by Max Bender40. Analysis of Surfactants, Thomas M. Schmitt (see Volume 96)41. Light Scattering by Liquid Surfaces and Complementary Techniques, edited by

Dominique Langevin42. Polymeric Surfactants, Irja Piirma43. Anionic Surfactants: Biochemistry, Toxicology, Dermatology. Second Edition,

Revised and Expanded, edited by Christian Gloxhuber and Klaus Knstler44. Organized Solutions: Surfactants in Science and Technology, edited by

Stig E. Friberg and Bjrn Lindman45. Defoaming: Theory and Industrial Applications, edited by P. R. Garrett46. Mixed Surfactant Systems, edited by Keizo Ogino and Masahiko Abe47. Coagulation and Flocculation: Theory and Applications, edited by Bohuslav Dobis48. Biosurfactants: Production Properties Applications, edited by Naim Kosaric49. Wettability, edited by John C. Berg50. Fluorinated Surfactants: Synthesis Properties Applications, Erik Kissa51. Surface and Colloid Chemistry in Advanced Ceramics Processing, edited by

Robert J. Pugh and Lennart Bergstrm52. Technological Applications of Dispersions, edited by Robert B. McKay53. Cationic Surfactants: Analytical and Biological Evaluation, edited by John Cross

and Edward J. Singer54. Surfactants in Agrochemicals, Tharwat F. Tadros55. Solubilization in Surfactant Aggregates, edited by Sherril D. Christian

and John F. Scamehorn56. Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache57. Foams: Theory, Measurements, and Applications, edited by Robert K. Prudhomme

and Saad A. Khan58. The Preparation of Dispersions in Liquids, H. N. Stein59. Amphoteric Surfactants: Second Edition, edited by Eric G. Lomax60. Nonionic Surfactants: Polyoxyalkylene Block Copolymers, edited by

Vaughn M. Nace61. Emulsions and Emulsion Stability, edited by Johan Sjblom62. Vesicles, edited by Morton Rosoff63. Applied Surface Thermodynamics, edited by A. W. Neumann and Jan K. Spelt64. Surfactants in Solution, edited by Arun K. Chattopadhyay and K. L. Mittal65. Detergents in the Environment, edited by Milan Johann Schwuger66. Industrial Applications of Microemulsions, edited by Conxita Solans

and Hironobu Kunieda67. Liquid Detergents, edited by Kuo-Yann Lai68. Surfactants in Cosmetics: Second Edition, Revised and Expanded,

edited by Martin M. Rieger and Linda D. Rhein69. Enzymes in Detergency, edited by Jan H. van Ee, Onno Misset, and Erik J. Baas70. Structure-Performance Relationships in Surfactants, edited by Kunio Esumi

and Minoru Ueno


71. Powdered Detergents, edited by Michael S. Showell72. Nonionic Surfactants: Organic Chemistry, edited by Nico M. van Os73. Anionic Surfactants: Analytical Chemistry, Second Edition, Revised and Expanded,

edited by John Cross74. Novel Surfactants: Preparation, Applications, and Biodegradability, edited by

Krister Holmberg75. Biopolymers at Interfaces, edited by Martin Malmsten76. Electrical Phenomena at Interfaces: Fundamentals, Measurements,

and Applications, Second Edition, Revised and Expanded, edited by Hiroyuki Ohshima and Kunio Furusawa

77. Polymer-Surfactant Systems, edited by Jan C. T. Kwak78. Surfaces of Nanoparticles and Porous Materials, edited by James A. Schwarz

and Cristian I. Contescu79. Surface Chemistry and Electrochemistry of Membranes, edited by

Torben Smith Srensen80. Interfacial Phenomena in Chromatography, edited by Emile Pefferkorn81. SolidLiquid Dispersions, Bohuslav Dobis, Xueping Qiu,

and Wolfgang von Rybinski82. Handbook of Detergents, editor in chief: Uri Zoller Part A: Properties,

edited by Guy Broze83. Modern Characterization Methods of Surfactant Systems, edited by

Bernard P. Binks84. Dispersions: Characterization, Testing, and Measurement, Erik Kissa85. Interfacial Forces and Fields: Theory and Applications, edited by Jyh-Ping Hsu86. Silicone Surfactants, edited by Randal M. Hill87. Surface Characterization Methods: Principles, Techniques, and Applications,

edited by Andrew J. Milling88. Interfacial Dynamics, edited by Nikola Kallay89. Computational Methods in Surface and Colloid Science, edited by

Malgorzata Borwko90. Adsorption on Silica Surfaces, edited by Eugne Papirer91. Nonionic Surfactants: Alkyl Polyglucosides, edited by Dieter Balzer

and Harald Lders92. Fine Particles: Synthesis, Characterization, and Mechanisms of Growth,

edited by Tadao Sugimoto93. Thermal Behavior of Dispersed Systems, edited by Nissim Garti94. Surface Characteristics of Fibers and Textiles, edited by Christopher M. Pastore

and Paul Kiekens 95. Liquid Interfaces in Chemical, Biological, and Pharmaceutical Applications,

edited by Alexander G. Volkov96. Analysis of Surfactants: Second Edition, Revised and Expanded,

Thomas M. Schmitt97. Fluorinated Surfactants and Repellents: Second Edition, Revised and Expanded,

Erik Kissa98. Detergency of Specialty Surfactants, edited by Floyd E. Friedli99. Physical Chemistry of Polyelectrolytes, edited by Tsetska Radeva

100. Reactions and Synthesis in Surfactant Systems, edited by John Texter101. Protein-Based Surfactants: Synthesis, Physicochemical Properties,

and Applications, edited by Ifendu A. Nnanna and Jiding Xia102. Chemical Properties of Material Surfaces, Marek Kosmulski


103. Oxide Surfaces, edited by James A. Wingrave104. Polymers in Particulate Systems: Properties and Applications, edited by

Vincent A. Hackley, P. Somasundaran, and Jennifer A. Lewis105. Colloid and Surface Properties of Clays and Related Minerals, Rossman F. Giese

and Carel J. van Oss106. Interfacial Electrokinetics and Electrophoresis, edited by ngel V. Delgado107. Adsorption: Theory, Modeling, and Analysis, edited by Jzsef Tth108. Interfacial Applications in Environmental Engineering, edited by Mark A. Keane109. Adsorption and Aggregation of Surfactants in Solution, edited by K. L. Mittal

and Dinesh O. Shah110. Biopolymers at Interfaces: Second Edition, Revised and Expanded, edited by

Martin Malmsten111. Biomolecular Films: Design, Function, and Applications, edited by James F. Rusling112. StructurePerformance Relationships in Surfactants: Second Edition, Revised

and Expanded, edited by Kunio Esumi and Minoru Ueno113. Liquid Interfacial Systems: Oscillations and Instability, Rudolph V. Birikh,

Vladimir A. Briskman, Manuel G. Velarde, and Jean-Claude Legros114. Novel Surfactants: Preparation, Applications, and Biodegradability: Second Edition,

Revised and Expanded, edited by Krister Holmberg115. Colloidal Polymers: Synthesis and Characterization, edited by

Abdelhamid Elaissari116. Colloidal Biomolecules, Biomaterials, and Biomedical Applications,

edited by Abdelhamid Elaissari117. Gemini Surfactants: Synthesis, Interfacial and Solution-Phase Behavior,

and Applications, edited by Raoul Zana and Jiding Xia118. Colloidal Science of Flotation, Anh V. Nguyen and Hans Joachim Schulze119. Surface and Interfacial Tension: Measurement, Theory, and Applications,

edited by Stanley Hartland120. Microporous Media: Synthesis, Properties, and Modeling, Freddy Romm121. Handbook of Detergents, editor in chief: Uri Zoller Part B: Environmental Impact,

edited by Uri Zoller122. Luminous Chemical Vapor Deposition and Interface Engineering,

HirotsuguYasuda123. Handbook of Detergents, editor in chief: Uri Zoller Part C: Analysis, edited by

Heinrich Waldhoff and Rdiger Spilker124. Mixed Surfactant Systems: Second Edition, Revised and Expanded, edited by

Masahiko Abe and John F. Scamehorn125. Dynamics of Surfactant Self-Assemblies: Micelles, Microemulsions, Vesicles

and Lyotropic Phases, edited by Raoul Zana126. Coagulation and Flocculation: Second Edition, edited by Hansjoachim

Stechemesser and Bohulav Dobis127. Bicontinuous Liquid Crystals, edited by Matthew L. Lynch and Patrick T. Spicer128. Handbook of Detergents, editor in chief: Uri Zoller Part D: Formulation,

edited by Michael S. Showell129. Liquid Detergents: Second Edition, edited by Kuo-Yann Lai130. Finely Dispersed Particles: Micro-, Nano-, and Atto-Engineering, edited by

Aleksandar M. Spasic and Jyh-Ping Hsu131. Colloidal Silica: Fundamentals and Applications, edited by Horacio E. Bergna

and William O. Roberts132. Emulsions and Emulsion Stability, Second Edition, edited by Johan Sjblom


COLLOIDAL SILICA

Edited by

Horacio E. BergnaH. E. Bergna Consultants

Wilmington, Delaware

William O. RobertsWilmington, Delaware

A CRC title, part of the Taylor & Francis imprint, a member of theTaylor & Francis Group, the academic division of T&F Informa plc.

Boca Raton London New York

Fundamentals and Applications


Published in 2006 byCRC PressTaylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300Boca Raton, FL 33487-2742

2006 by Taylor & Francis Group, LLCCRC Press is an imprint of Taylor & Francis Group

No claim to original U.S. Government worksPrinted in the United States of America on acid-free paper10 9 8 7 6 5 4 3 2 1

International Standard Book Number-10: 0-8247-0967-5 (Hardcover) International Standard Book Number-13: 978-0-8247-0967-9 (Hardcover) Library of Congress Card Number 2005050208

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Library of Congress Cataloging-in-Publication Data

Colloidal silica : fundamentals and applications / edited by Horacio E. Bergna, William O. Roberts.p. cm. -- (Surfactant science series ; v. 131)

Includes bibliographical references and index.ISBN 0-8247-0967-51. Silica. 2. Colloids. I. Bergna, Horacio E., 1924- II. Roberts, William O., 1936- III. Series.

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Preface

Colloidal phenomena have an essential importance in our

lives. Living tissues are colloidal systems and therefore

the diverse processes involved in our metabolism are for

the major part of colloidal nature.

Industrial use of colloidal silicas is growing steadily in

both traditional areas and ever-increasing numbers of

novel areas. Colloidal silicas are found in fields as

diverse as catalysis, metallurgy, electronics, glass, cer-

amics, paper and pulp technology, optics, elastomers,

food, health care and industrial chromatography.

However in spite of the apparent simplicity of silicas

composition and structure, fundamental questions remain

about the formation, constitution, and behavior of col-

loidal silica systems. As a result, a broad and fascinating

area of study is open to scientists interested in fundamental

aspects of silica chemistry and physics and to technol-

ogists looking for new uses of silica and for answers to

practical problems.

This book is dedicated to the field of colloidal silica

and although it is aimed at technical people not familiar

with colloid science and silica chemistry, we have

introduced new information on colloid science related to

silica chemistry found in the current literature. In this

respect the reader is encouraged to review the selected

books listed in the reference list at the end of each chapter.

The work presented here includes both theoretical and

experimental aspects of some of the most significant areas

of colloidal silica science and technology. This book

constitutes an update of the science and technology of

colloidal silica since Ralph K. Iler, the distinguished

silica scientist, published the definitive book on silica

chemistry in 1979 and the American Chemical Society

published Colloid Chemistry of Silica in 1994.

The book will increase the readers understanding of

the most important problems in this area of science. It is

written by some of the most outstanding silica scientists

of Argentina, Australia, Canada, China, Japan, Europe,

New Zealand, Russia, Ukraine, the United Kingdom, and

the United States.

In sum we believe that this book is useful not only

to technical people unfamiliar with the subject but also

to colloid and silica chemists.


Editors

Horacio E. Bergna is

chairman of H.E. Bergna

Consultants. Bergna

received his licenciado

and doctorate in chemistry

at the National University

of La Plata in Argentina

and worked on his doc-

toral thesis (honors) on

clay electrokinetics under

Marcos Tschapek at the

National Institute of

Soils in Buenos Aires,

Argentina. Bergna taught at the School of Chemistry

in La Plata and worked at the Laboratory of Testing

Materials and Technological Research of the Province of

Buenos Aires. He did post-doctoral work at the Sorbonne

in Paris and the Massachusetts Institute of Technology,

where he worked with E.A. Hauser as a guest of the

Department of Chemical Engineering and as a research

staff member of the Division of Industrial Cooperation

with J. Th. Overbeek, A. Gaudin and P. de Bruyn. He

studied humanities at the City of London College and

Columbia University.

Bergna is the author of 30 papers and holds 31 U.S.

patents and more than 200 foreign corresponding patents

in subjects such as colloidal silica syntheses, silica,

alumina, aluminosilicates, zeolites, vanadyl phosphate

catalysts, submicron grained products for metallurgy,

and binders for foundry sands. Bergna received 18 Oscar

Awards for the patents received by Dupont.

In 1990, Bergna organized and chaired the Ralph

K. Iler International Symposium on the Colloid Chemistry

of Silica held at the 200th ACS National Meeting.

Bergna co-authored the colloidal silica section of the

1993 edition of the Ullman Encyclopedia of Chemistry

and guest edited two special issues of the Elsevier inter-

national journal Colloids and Surfaces. He edited and

co-authored Colloid Chemistry of Silica, published by the

American Chemical Society, 1994.

In 1997 Bergna received the Pedro J. Carriquiriborde

Prize from the Argentine Chemical Society in Buenos Aires.

William O. Roberts

earned his bachelors

degree in chemistry at the

Massachusetts Institute of

Technology and his Ph.D.

at Syracuse University.

In 1963, he began work-

ing under Ralph Iler at

the DuPont Experimental

Station in Wilmington,

Delaware. There he

helped to develop micro-

grain cutting tools, and

this evolved into a production venture that eventually

moved to the DuPont plant in Newport, Delaware. In

1972, when the Newport facility closed, Roberts returned

to Wilmington to work at the Chestnut Run technical

facility. He remained there until his retirement in 1999.

Various assignments there involved catalyst work and

colored pigments, but the bulk of his last 27 years were

spent on Ludoxw colloidal silica. The technical service lab-

oratory at Chestnut Run was the main source of new product

development for Ludoxw, and Roberts developed two new

colloidal silica-based products that were patented.

Because of DuPonts involvement in the colloidal

silica industry, Roberts became their representative to

the Investment Casting Institute (ICI), for which he

served on the Ceramics Committee, and eventually

became chairman. He was elected to the ICI Board of

Directors and served for 13 years until his retirement.


ASSOCIATE EDITORS

Michael Baloga

DuPont Company

Jonathan L. Bass

The PQ Corporation (retired)

John Dietz

DuPont Company (retired)

F. Dumont

Free University of Brussels

James S. Falcone, Jr.

West Chester University

Michael L. Hair

Xerox Research Center of Canada

Bruce A. Keiser

Nalco Chemical Company

Geoffrey Meadows


Alan Palmer


Robert E. Patterson

The PQ Corporation

William O. Roberts


William A. Welsh

W.R. Grace & Company

Paul C. Yates



Contributors

Cheryl A. Armstrong

Department of Chemistry

Colorado State University

Pueblo, Colorado

F.J. Arriagada

Department of Materials Science and

Engineering and the Particulate

Materials Center

Pennsylvania State University

University Park, Pennsylvania

Michael R. Baloga

DuPont Company

New Johnsonville, Tennessee

Bhajendra N. Barman

FFFractionation, Inc.

Salt Lake City, Utah

Jonathan L. BassThe PQ Corporation

Conshohocken, Pennsylvania

Theo P.M. Beelen

Schuit Institute of Catalysis

Eindhoven University of Technology

Eindhoven, The Netherlands

Horacio E. Bergna

DuPont Experimental Station


J.D. Birchall


Keele University

Keele, Staffordshire, UK

G.H. Bogush

Department of Chemical Engineering

University of Illinois

Urbana, Illinois

E.J. BottaniResearch Institute of Theoretical and

Applied Physical Chemistry (INIFTA)

La Plata, Argentina

Harald Bottner

Fraunhofer Institute for Physical

Measurement Techniques

Freiburg, Germany

C. Jeffrey Brinker

Sandia National Laboratories and Center for

Micro-Engineered Ceramics

University of New Mexico

Albuquerque, New Mexico

U. Brinkmann

Degussa AG

Hanau-Wolfgang

Dusseldorf, Germany

A. Burneau

Laboratory of Physical Chemistry and

Microbiology for the Environment

Villers-le`s-Nancy, France

C. Carteret




I-Ssuer Chuang



Fort Collins, Colorado

A.A. Chuiko

Institute of Surface Chemistry

National Academy of Sciences of Ukraine

Kiev, Ukraine

Bradley K. Coltrain

Eastman Kodak Company

Corporate Research Laboratories

Rochester, New York

J.B. dEspinose de la Caillerie

Quantum Physics Laboratory

The City of Paris Industrial Physics and

Chemistry Higher Educational Institution

Paris, France


L.E. Cascarini de TorreResearch Institute of Theoretical and

Applied Physical Chemistry (INIFTA)

La Plata, Argentina

F. Dumont

Free University of Brussels

Brussels, Belgium

M. Ettlinger

Degussa AG

Hanau-Wolfgang, Germany

James S. Falcone, Jr.Department of Chemistry

West Chester University

West Chester, Pennsylvania

Horst K. Ferch

Degussa AG

Department of Applied Research and

Technical Services

Silicas and Pigments

Degussa AG

Frankfurt, Germany

Lawrence E. Firment

DuPont Company


D. Neil FurlongDivision of Chemicals and Polymers

Common wealth Scientific and Industrial

Research Organization

Clayton, Australia

J.P. Gallas

Department of Material Sciences and Radiation

University of Caen

Caen, France

Miguel GarciaDepartment of Chemistry


Pueblo, Colorado

J. Calvin Giddings

Field-Flow Fractionation

Research Center


University of Utah


Dhanesh G.C. GoberdhanAtomic Energy Authority

Harwell Laboratory

Oxford, UK

Chad P. Gonzales



Pueblo, Colorado

A.G. Grebenyuk



Kiev, Ukraine

Peter Greenwood

Eka Chemicals (Akzo Nobel)

Bohus, Sweden

Vladimir M. Gunko



Kiev, Ukraine

Michael L. Hair

Xerox Research Centre of Canada

Mississauga, Ontario, Canada

Marcia E. Hansen

FFFractionation, Inc.


Thomas W. Healy

School of Chemistry

University of Melbourne

Parkville, Victoria, Australia

H. Hommel




Paris, France

B. Humbert




Alan J. Hurd

Ceramic Processing Science Department

Sandia National Laboratories

Albuquerque, New Mexico


Bruce A. KeiserNalco Chemical Company

Naperville, Illinois

Larry W. Kelts

Corporate Research Laboratories

Eastman Kodak Company

Rochester, New York

Martyn B. Kenny


Brunel University

Uxbridge, Middlesex, UK

D. Kerner

Degussa AG


J.J. Kirkland

DuPont Experimental Station

Central Research and Development Department


T. Kobayashi

Kyushu Institute of Technology, Tobata

Fukuoka, Japan

Hiromitsu Kozuka

Institute for Chemical Research

Kyoto University

Uji, Kyoto-Fu, Japan

R. Krasnansky

Department of Chemistry and Biochemistry

University of Notre Dame

Notre Dame, Indiana

A.P. Legrand




Paris, France

Donald E. Leyden

Department of Chemistry (retired)

Condensed Matter Sciences Laboratory



Guangyue Liu

Field-Flow Fractionation Research Center


University of Utah


Luis M. Liz-MarzanDepartment of Chemistry

University of Vigo

Vigo, Spain

V.V. Lobanov



Kiev, Ukraine

J.-L. Look


University of Illinois

Urbana, Illinois

Gary E. Maciel




Sally J. Markway



Pueblo, Colorado

Egon Matijevic

Center for Advanced Materials Processing

Clarkson University

Potsdam, New York

Akihiko Matsumoto

Atomic Energy Authority

Harwell Laboratory

Oxford, UK

A.J. McFarlanDepartment of Chemistry

University of Ottawa

Ottawa, Ontario, Canada

A.R. Minihan

Unilever Research Port Sunlight

Bebington, UK

I.F. Mironyuk



Kiev, Ukraine

David T. Molapo





Myeong Hee MoonField-Flow Fractionation

Research Center


University of Utah


Barry A. Morrow




Paul Mulvaney

School of Chemistry

Nanotechnology Laboratory

University of Melbourne

Victoria, Australia

K. Osseo-Asare

Department of Materials, Science, and Engineering

and the Particulate Materials Center

Pennsylvania State University

University Park, Pennsylvania

Jan-Erik Otterstedt

Emeritus of Engineering Chemistry

Chalmers University of Technology

Gothenburg, Sweden

Euge`ne Papirer

Research Center for Physicochemistry

National Center for Scientific Research (CNRS)

Mulhouse, France

Robert E. Patterson

Research and Development Center

The PQ Corporation

Conshohocken, Pennsylvania

Charles C. Payne

Nalco Chemical Company

Naperville, Illinois

A.A. PentyukInstitute of Surface Chemistry


Kiev, Ukraine

V.K. Pogorelyi



Kiev, Ukraine

Kristina G. ProctorDepartment of Chemistry

Condensed Matter Sciences Laboratory



John D.F. Ramsay

Atomic Energy Authority

Harwell Laboratory

Oxford, UK

S. Kim Ratanathanawongs



University of Utah


William O. Roberts



Sumio SakkaInstitute for Chemical Research

Kyoto University

Uji, Kyoto-Fu, Japan

George W. Scherer

Princeton University

Princeton, New Jersey

R. Schmoll

Degussa AG


Helmut Schmidt

Institute for New Materials

Saarland University

Saarbrucken, Germany

J. Shimada

Kyushu Institute of Technology, Tobata

Fukuoka, Japan

Kenneth S.W. Sing

Brunel University


Uxbridge, Middlesex, UK

P. Somasundaran

Langmuir Center for Colloids

and Interfaces

Columbia University

New York, New York


Stephen W. SwantonAtomic Energy Authority

Harwell Laboratory

Oxford, UK

Dennis G. Swartzfager

DuPont Company


J.K. Thomas

Department of Chemistry and Biochemistry

University of Notre Dame

Notre Dame, Indiana

V.V. Turov



Kiev, Ukraine

Brenda L. Tjelta


University of Utah



K.K. Unger

Department of Inorganic and

Analytical Chemistry

Johannes Gutenberg University

Mainz, Germany

Alfons van Blaaderen

Soft Condensed Matter Group

Debye Institute

Utrecht University

Utrecht, The Netherlands

Rutger A. van Santen




Alain M. Vidal

Research Center for Physicochemistry

National Center for Scientific

Research (CNRS)

Mulhouse, France

E.F. Voronin



Kiev, Ukraine

A. VrijVant Hoff Laboratory

University of Utrecht

Utrecht, The Netherlands

D.R. Ward


Bebington, UK

William A. Welsh


Columbia, Maryland

W. Whitby


Bebington, UK

Peter W.J.G. Wijnen




Paul C. Yates



Akitoshi YoshidaCentral Research Institute

Nissan Chemical Industries, Ltd.

Chiba, Japan

K. Yoshinaga

Kyushu Institute of Technology, Kobata

Fukuoka, Japan

V.I. ZarkoInstitute of Surface Chemistry


Kiev, Ukraine

L. Zhang

Langmuir Center for Colloids

and Interfaces

Columbia University

New York, New York


A.N. ZhukovDepartment of Colloid Chemistry

St. Petersburg State University

St. Petersburg, Russia

L.T. ZhuravlevInstitute of Physical Chemistry

Russian Academy of Sciences

Moscow, Russia

Yu.L. ZubInstitute of Surface Chemistry


Kiev, Ukraine

C.F. ZukoskiUniversity of Illinois


Urbana, Illinois


Table of Contents

Chapter 1 Colloid Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Horacio E. Bergna

Chapter 2 The Language of Colloid Science and Silica Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Horacio E. Bergna

Chapter 3 Colloid Chemistry of Silica: An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Horacio E. Bergna

Chapter 4 Silicic Acids and Colloidal Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

Horacio E. Bergna

Part 1

Preparation of Sols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Bruce A. Keiser

Chapter 5 Science and Art of the Formation of Uniform Solid Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Egon Matijevic

Chapter 6 Silica Nucleation, Polymerization, and Growth Preparation of

Monodispersed Sols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Akitoshi Yoshida

Chapter 7 The Formation and Interfacial Structure of Silica Sols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

John D.F. Ramsay, Stephen W. Swanton, Akihiko Matsumoto,

and Dhanesh G.C. Goberdhan

Chapter 8 Synthesis and Characterization of Colloidal Model Particles Made

from Organoalkoxysilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

A. van Blaaderen and A. Vrij

Chapter 9 Synthesis of Nanometer-Sized Silica by Controlled Hydrolysis in Reverse

Micellar Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

F.J. Arriagada and K. Osseo-Asare

Chapter 10 Formation of Silica Gels Composed of Micrometer-Sized Particles by the

SolGel Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

Hiromitsu Kozuka and Sumio Sakka


Chapter 11 Silica Aquasol Process to Prepare Small Particle Size ColloidalSilica by Electrodialysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

Horacio E. Bergna

Chapter 12 Manufacturing and Applications of Water-Borne

Colloidal Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

William O. Roberts

Chapter 13 Enterosorbent Silics: Properties and Clinical Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177

A.A. Chuiko, A.A. Pentyuk, and V.K. Pogorelyi

Chapter 14 Industrial Synthetic Silicas in Powder Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187

Horst K. Ferch

Chapter 15 High Ratio Silicate Foundry Sand Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

Horacio E. Bergna

Chapter 16 Spray Dried Silica for Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223

Horacio E. Bergna

Chapter 17 Preparation of Monodisperse Ultrafine Hybrid Silica Particles by

Polymer Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229

K. Yoshinaga, J. Shimada, and T. Kobayashi

Chapter 18 Monodisperse Core-Shell Silica Colloids from

Alkoxysilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233

Alfons van Blaaderen

Chapter 19 Preparation of Silica Solid Microspheres by Hydrolysis of Tetraethyl Ortho Silicate

(TEOS) and Silica Porous Microspheres by Spray Drying

Aggregated Colloidal Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

Horacio E. Bergna

Part 2

Stability of Sols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

F. Dumont

Chapter 20 Stability of Aqueous Silica Sols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

Thomas W. Healy

Chapter 21 Stabilization Against Particle Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

Paul C. Yates


Part 3Surface Chemistry of Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

Michael L. Hair

Chapter 22 The Surface Chemistry of Silica The Zhuravlev Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

L.T. Zhuravlev

Chapter 23 Surface Structure of Amorphous and Crystalline Porous Silicas: Status and Prospects . . . . . . . . 267

K.K. Unger

Chapter 24 Infrared Study of Chemical and HD Exchange Probes for Silica Surfaces . . . . . . . . . . . . . . . 277

B.A. Morrow and A.J. McFarlan

Chapter 25 Infrared Studies of Chemically Modified Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

Barry A. Morrow and David T. Molapo

Chapter 26 Fourier Transform Infrared and Raman Spectroscopic Study of Silica Surfaces . . . . . . . . . . . . . . 295

B. Humbert, C. Carteret, A. Burneau, and J.P. Gallas

Chapter 27 Adsorption on Silica and Related Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311

L.E. Cascarini de Torre and E.J. Bottani

Chapter 28 Structure of Disperse Silica Surface and Electrostatic Aspects of Adsorption . . . . . . . . . . . . . . . 331

A.A. Chuiko, V.V. Lobanov, and A.G. Grebenyuk

Chapter 29 Variable-Temperature Diffuse Reflectance Fourier Transform Infrared

Spectroscopic Studies of Amine Desorption from a Siliceous Surface . . . . . . . . . . . . . . . . . . . . 361

Donald E. Leyden and Kristina G. Proctor

Chapter 30 Surveying the Silica Gel Surface with Excited States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367

R. Krasnansky and J.K. Thomas

Chapter 31 Surface Chemistry and Surface Energy of Silicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379

Alain M. Vidal and Euge`ne Papirer

Chapter 32 Diffuse Reflectance FTIR Spectroscopic Study of Base

Desorption from Thermally Treated Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

Kristina G. Proctor, Sally J. Markway, Miguel Garcia, Cheryl A. Armstrong, and Chad P. Gonzales

Chapter 33 Salient Features of Synthesis and Structure of Surface of Functionalized

Polysiloxane Xerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397

Yu.L. Zub and A.A. Chuiko


Chapter 34 Multinuclear NMR Studies of Silica Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425

Gary E. Maciel and I-Ssuer Chuang

Chapter 35 Modified Silicas: Synthesis and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457

A.A. Chuiko

Chapter 36 Electric Surface Properties of Silica in Nonaqueous

Electrolyte Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461

A.N. Zhukov

Chapter 37 Chemical Reactions at Fumed Silica Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465

Vladimir M. Gunko and A.A. Chuiko

Chapter 38 Structural and Adsorptive Characteristics of Fumed Silicas in

Different Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499

Vladimir M. Gunko, V.I. Zarko, V.V. Turov, E.F. Voronin, I.F. Mironyuk, and A.A. Chuiko

Chapter 39 Adsorption of Surfactants and Polymers on Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531

P. Somasundaran and L. Zhang

Part 4

Particle Size and Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

Jonathan L. Bass

Chapter 40 New Separation Methods for Characterizing the Size of Silica Sols . . . . . . . . . . . . . . . . . . . . . 537

J.J. Kirkland

Chapter 41 Characterization of Colloidal and Particulate Silica byField-Flow Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549

J. Calvin Giddings, S. Kim Ratanathanawongs, Bhajendra N. Barman, Myeong Hee Moon,

Guangyue Liu, Brenda L. Tjelta, and Marcia E. Hansen

Chapter 42 Formation of Uniform Precipitates from Alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565

C.F. Zukoski, J.-L. Look, and G.H. Bogush

Part 5

Silica Gels and Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573

William A. Welsh

Chapter 43 Synthetic Amorphous Silicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575

U. Brinkmann, M. Ettlinger, D. Kerner, and R. Schmoll


Chapter 44 Adsorptive Properties of Porous Silicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

Martyn B. Kenny and Kenneth S.W. Sing

Chapter 45 Silica Gels from Aqueous Silicate Solutions: Combined 29Si NMR and Small-Angle

X-Ray Scattering Spectroscopic Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597

Peter W.J.G. Wijnen, Theo P.M. Beelen, and Rutger A. van Santen

Chapter 46 Interpretation of the Differences between the Pore Size Distributions of

Silica Measured by Mercury Intrusion and Nitrogen Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 605

A.R. Minihan, D.R. Ward, and W. Whitby

Part 6

SolGel Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613

George W. Scherer

Chapter 47 SolGel Processing of Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615

C. Jeffrey Brinker

Chapter 48 The Chemistry of Hydrolysis and Condensation of Silica SolGel Precursors . . . . . . . . . . . . . . 637

Bradley K. Coltrain and Larry W. Kelts

Chapter 49 Chemistry and Properties of Porous, Organically Modified Silica . . . . . . . . . . . . . . . . . . . . . . . 645

Helmut Schmidt and Harald Bottner

Chapter 50 Evaporation and Surface Tension Effects in Dip Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653

Alan J. Hurd

Part 7

Silica Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663

Michael R. Baloga

Chapter 51 Nanostructuring Metals and Semiconductors with Silica from

Monolayers to Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

Luis M. Liz-Marzan and Paul Mulvaney

Chapter 52 Surface Chemistry of Silica Coatings of Titania . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689

D. Neil Furlong

Chapter 53 Dense Silica Coatings on Micro- and Nanoparticles by Deposition of

Monosilicic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 701

Horacio E. Bergna, Lawrence E. Firment, and Dennis G. Swartzfager


Part 8Uses of Colloidal Silicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 711

Robert E. Patterson and James S. Falcone, Jr.

Chapter 54 Applications of Colloidal Silica: Past, Present, and Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . 713

Charles C. Payne

Chapter 55 The Uses of Soluble Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721


Chapter 56 Attrition Resistant Catalysts, Catalyst Precursors and Catalyst

Supports and Process for Preparing Same . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725

Horacio E. Bergna

Chapter 57 Some Important, Fairly New Uses of Colloidal Silica/Silica Sol . . . . . . . . . . . . . . . . . . . . . . . 737

Jan-Erik Otterstedt and Peter Greenwood

Chapter 58 SiliconAluminum Interactions and Biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757

J.D. Birchall

Chapter 59 Silica in Biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765


Chapter 60 Preparation and Uses of Silica Gels and Precipitated Silicas . . . . . . . . . . . . . . . . . . . . . . . . . . . 779

Robert E. Patterson

Chapter 61 Foundry Mold or Core Compositions and Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789

Horacio E. Bergna

Chapter 62 Silica Supported Catalysts and Method of Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807

Horacio E. Bergna

Chapter 63 Molded Amorphous Silica Bodies and Molding Powders for

Manufacture of Same . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 815

Horacio E. Bergna and Frank A. Simko, Jr.

Chapter 64 High Ratio Silicate Foundry Sand Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831

Horacio E. Bergna

Part 9

NMR of Silica Edge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853

Chapter 65 On the Silica Edge: An NMR Point of View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855

A.P. Legrand, H. Hommel, and J.B. dEspinose de la Caillerie


Part 10Research in Russia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 861

Horacio E. Bergna

Chapter 66 Colloid Chemistry of Silica: Research in the Former Soviet Union . . . . . . . . . . . . . . . . . . . . . . 863

L.T. Zhuravlev

Part 11

Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889

Horacio E. Bergna

Chapter 67 Integrated Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891

Horacio E. Bergna


Dedication

This book is dedicated to Ralph K. Iler who devoted his career to exploratory and industrial research in the chemistry of

colloidal material. He is recognized worldwide for his unique contributions to a unified understanding of the colloidal

chemistry of silica and silicates.

Ralph K. Iler not only made outstanding contributions to science and industry, but he was an individual sensitive to

the beauty of nature and the works of humanity.

Dr. Ilers biography and portrait appear in Colloid Chemistry of Silica (American Chemical Society, Washington,

D.C., in 1994). His book The Chemistry of Silica, published in 1979, is the definitive book on silica chemistry and a

primary source of reference.

The ACS book mentioned above and the current volume, Colloidal Silica: Fundamentals and Applications,

constitute an updating of Dr. Ilers book.


1 Colloid Science

Horacio E. BergnaDuPont Experimental Station

CONTENTS

Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Subdivision of Particles and

the Colloidal State . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Colloid Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . 3

History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

DEFINITION

Colloid science is generally understood to be the study of

systems containing kinetic units which are large in com-

parison with atomic dimensions [1]. Such systems may

be those in which the particles are free to move in all direc-

tions, or they may be derived systems, as a coagulum or a

gel (discussed subsequently), in which the particles have

lost their mobility either partially or entirely, but have

maintained their individuality.

The colloidal state of subdivision comprises particles

with a size sufficiently small (1 mm) not to be affectedby gravitational forces but sufficiently large (.1 nm) toshow marked deviations from the properties of true solutions.

SUBDIVISION OF PARTICLES AND

THE COLLOIDAL STATE

Matter can be subdivided into progressively smaller parts,

fragments or particles, until the dimensions of molecules,

ions and atoms are reached. The subdivision process pro-

duces matter of progressively smaller particle size. In the

size range much larger than the atomic range but much

smaller than particles observable with the naked eye, the

physical and chemical properties of the surface of these

particles assume a preponderant role in the behavior of

the system.

This range, where units are made up of a few hundred to

perhaps a few billion atoms is said to be in the colloidal state.

The range of colloidal dimensions does not have rigorous

boundaries, since the threshold of increment varies for differ-

ent properties in tens or hundreds of angstrom units.

However, it can be stated that the colloidal range comprises

particles with size between around 10 and 10,000 A units.

In other words, colloidal particles are those with a size

or with one dimension between 10 and 10,000 A units

(1 nm and 1 mm). Considering the size of the constituentatoms, this means that colloidal particles are made of

associations or colonies of approximately 103 to 109

atoms. These atoms can be arranged in a crystalline or in

an amorphous structure. It is pertinent to remark that the

colloidal particles may either be crystalline or amorphous

terms colloidal or crystalline state.

linear scale in comparison with the wavelength of

common radiations and expands the comparison to mesh

openings of common sieves and microscope ranges.

The characteristic properties of the colloidal range

vary gradually toward both ends of the dimensional

boundaries and they tend to undergo a sudden increment

The process of subdivision of matter implies creation

of new surfaces. Subdivision of matter increases its

surface/volume ratio. A cube of 1 m of edge, for instance,has a volume of 1 m3 and a surface area of 6 m2. The mass

of the same cube when the cube is subdivided in one thou-

sand smaller cubes of 10 cm of edge occupies, of course,

the same volume of the mass of the original cube, but

the total surface area of all the new cubes is now 60 m2.

The surface: volume ratio increases ten times.

In the colloidal range, the surface: volume ratio is

extremely high. All properties related to surfaces are

therefore accentuated in this range. The limit or boundary

between two homogeneous phases, the interface, shows

characteristic properties. These properties of the inter-

face, the surface properties, play a predominant role in

colloidal systems. This is why it is sometimes said that

1


in nature (Figure 1.1). There is no antinomy between the

Figure 1.2 helps to situate the colloidal range in a

near one or both ends of the range (Figure 1.3).

FIGURE 1.1 Crystalline and amorphous structures.

Hair Bacteria

Coarse Fine Mud ClayCellRed Blood

CoalPowder

CigaretteSmoke

Pigments

NH4Cl Smoke

Pollen Powdered Milk

FlourSmog

Mist, Clouds

Virus Atoms

COMMONPARTICLES

Naked EyeLow Magnification

Microscope

Electron Microscope

Ultra-MicroscopeVISIBILITY

MESHSIZE

STATE OFDISPERSION

COARSEDISPERSIONS

COLLOIDALDISPERSIONS

30 60100

325

ca. 109Atoms

ca. 103Atoms

Wavelength Infrared Visible UltraViolet X-ray

104 105 106 107 108

11 nm1Size in cm

Sand Sand

FIGURE 1.2 Particle sizes of dispersed systems.

2 Colloidal Silica: Fundamentals and Applications


colloidal properties are those of a large surface concen-

trated in a small volume.

COLLOID SYSTEMS

Colloid systems are mostly based on very small particles

dispersed in a solution. This is why it is sometimes said

that colloidal properties are those of a large surface

concentrated in a small volume.

Colloidal particles are commonly found distributed

as a separate phase, the disperse phase, into another

substance or substances, the dispersant or continuous

phase. In this sense, colloidal systems are heterogeneous

systems.

Either of the two phase can be in any of the states of

matter: solid, liquid, or gas. A very common case is the

dispersion in a liquid of colloidal particles of a solid.

All three dimensions need not be in the colloidal

range: in fibers or needle-shaped particles only two dimen-

sions are in this range and in thin films or disk-shaped par-

ticles only one dimension is in colloidal range. Nor must

the units of a colloidal system be discrete: continuous-

network structures, the basic units of which are of colloidal

dimensions, also fall in this class, for example, porous

solids and foams in addition to gels.

Today the science that they helped create is common

knowledge to scientists and even many non scientists.

This prompted Prof. Robert B. Dean to write that nearly

everything we see is colloidal. The common molecules

of inorganic chemistry and the common small molecules

of organic chemistry are molecules of substances which

are rarely encountered in a pure state in everyday life.

When you get up in the morning you wash with colloidal

soap, pout on your colloidal clothes, read a colloidal news-

paper while eating a colloidal breakfast. The house you

live in and the pavement you walk on are both colloidal;

even you, yourself consist entirely of colloidal materials.

The mineral kingdom is partly colloidal, the vegetable

and animal kingdoms wholly so. Colloid Science is the

link joining chemistry to all the biological sciences. It is

also the most frequently encountered branch of applied

chemistry in industrial practice [2].

History

Colloid science, as defined at the beginning of this chapter,

is a discipline which determines and attempts to explain

and predict the properties of substances based on certain

dimensions. The term colloid science was created by

Wolfgang Ostwald in 1929. A. Buzagh and E.A. Hauser

joined Ostwald in pointing out that the term colloid

chemistry was outdated and should be supplanted by

the words colloid science since this is a field which

cannot be considered as merely an appendix to physical

chemistry [3].

As early as 1747, Pott made a semisolution of silica,

and as early as 1820, a reference is made to the preparation

of a sol of hydrated silica [4].

Selmi (1843) was the first to investigate colloids

systematically. He prepared colloidal solutions of sulphur,

Prussian blue and casein, performing numerous exper-

iments. He came to the conclusion that these were not

true solutions but suspensions of small particles in water [5].

Graham (1861) is usually regarded as the founder

of classical experimental colloid science. He classified

all substances into two groups: crystalloids and col-

loids. According to him the former could be easily

crystallised, but not the latter. Colloids can be dissolved

or dispersed and exposed to a semipermeable membrane

the so called crystalloids pass through the membrane

easily, but the colloids do not. This procedure is called

dialysis. By 1864, silica were being prepared not only by

the dialysis of gels but also by hydrolysis of silicate esters.

The name colloid was proposed by Graham (1862),

because he considered all colloids to be more or less like

glue and for this reason he gave them the Greek name

KOALO. For colloids in a liquid suspension he used thename sol. When the sols transformed into solid jellies

under suitable conditions he called them gels.

The work of Graham was of fundamental importance

but his classification of all substances into crystalloids

and colloids is not always right; many colloids, like

some proteins, can be crystallized. On the other hand,

almost all so-called crystalloids can be prepared in the

colloidal state.

Faraday (1857) was another scientist who made inter-

esting discoveries about colloids. He observed that a

narrowly defined beam of light passing through a gold

sol (colloidal suspension) appears as a whitish path.

PARTICLE SIZE

PRO

PERT

Y

FIGURE 1.3 Plot of property vs. particle size.

Colloid Science 3


The phenomenon was further studied by Tyndall and now

bears his name, the Tyndall effect [7].

Schulze (1883) investigated the stability of colloidal

solutions (sols) working mainly with inorganic colloids.

He investigated thoroughly the phenomenon of floccula-

tion or coagulation, to find out the flocculating power

of different reagents.

Freundlich investigated adsorption phenomena and

enunciates his law of adsorption in 1903. Siedentopf and

Zigmondy (1903) invented the ultramicroscope based on

the previously mentioned observation, of Faraday and

Tyndall. The ultramicroscope was of great utility to

study colloids until the invention of the electron

microscope.

Important contributions toward the solution of the

problem of particle size as well as sedimentation, move-

ment and coagulation of particular were made by

Smoluchowski (1906), Svedberg (1906), Perrin (1908),

and Einstein (1908).

P.O. von Weimarn (18791935), James W. McBain

(18871953), Harry N. Holmes, Harry B. Weiser (1887

1950), and Lloyd H. Reyerson also made important contri-

butions to the development of modern Colloid Science.

REFERENCES

1. Verwey, E.J.W.; Overbeck, J.Th.G. Theory of the Stab-

ility of Lyophobic Colloids. Elservier, 1948.

2. Dean, Robert B. Modern Colloids, D. Van Nostrand

Company, Inc. New York, 1948.

3. Hauser, E.A. Silicic Science; Van Nostrand: Princeton,

NJ, 1955; p. 54.

4. Fremy, E. Am. Chem. Phys. 1853 (3), Bd 38, S 312344.

5. Jirgensons, B.; Straumanis, M.E. A Short Textbook of

Colloid Chemistry. Pergamon Press Ltd., London, 1954.

6. Graham, T. Am. Chem., 1862, Bd 123, S 860861.

7. Jirgensons, B.; Straumanis, M.E. A Short Textbook of

Colloid Chemistry. Pergamon Press Ltd., London.



2 The Language of Colloid Scienceand Silica ChemistryHoracio E. BergnaDuPont Experimental Station

CONTENTS

Sols, Gels, and Powders . . . . . . . . . . . . . . . . . . . . . . . . 5

This section provides brief explanations for the most

important terms that may be encountered in a study of

the fundamental principles, experimental investigations

and industrial applications of colloid science and silica

chemistry.

The definition of some important terms has been given

Others are given subsequently.

SOLS, GELS, AND POWDERS

A stable dispersion of solid colloidal particles in a

liquid is called a sol. Stable in this case means that

the solid particles do not settle or agglomerate at a

significant rate. If the liquid is water, the dispersion

is known as an aquasol or hydrosol. If the liquid is

an organic solvent, the dispersion is called an organo-

sol. The term gel is applied to systems made of a con-

tinuous solid skeleton made of colloidal particles or

polymers enclosing a continuous solid skeleton made

of colloidal particles or polymers enclosing a con-

tinuous liquid phase. Drying a gel by evaporation

under normal conditions results in a dried gel called

a xerogel. Xerogels obtained in this manner are often

reduced in volume by a factor of 5 to 10 compared

to the original wet gel as a result of stresses exerted

by capillary tension in the liquid.1

An aerogel is a special type of xerogel from which

the liquid has been removed in such a way as to

prevent any collapse or change in the structure as liquid

is removed [1]. This is done by drying a wet gel in an

autoclave above the critical point of the liquid so that

there is no capillary pressure and therefore relatively

little shrinkage. The product is mostly air, having

volume fractions of solid as low as about 0.1% [2],

hence the term aerogel.1

An aerosol is a colloidal dispersion of particles in gas.

Fumed or pyrogenic oxides, also known in the case of

silica as aerosols, are powders made by condensing a pre-

cursor from a vapor phase at elevated temperatures [3].

(Usage has converted Aerosil, the trademark of Degussas

pyrogenic silica, into a generic term that includes other

pyrogenic silicas, such as the Cabot Corporations

Cab-O-Sil.) Dried gels obtained by dispersing aerosols in

water and then drying are called by some authors aero-

silogels. Powders obtained by freeze-drying a sol are

known as cryogels.1

Commercial colloidal silicas are commonly available

in the form of sols or powders. The powders can be xero-

gels, dry precipitates, aerogels, aerosols, or dried and cal-

cined coacervates. The ultimate unit for all of them is a

silica particle, the size of which determines the specific

surface area of the product.

The formation of silica sols, gels, and powders a

genealogical tree of colloidal silicas can be seen

1The Colloid Chemistry of Silica, edited by Horacio E. Bergna, American

Chemical Society, Washington, DC, 1994.

5


in the Colloid Science section of this book, Chapter 1.

represented in Figure 4.4 of Chapter 4.

Hydrogen

Oxygen (air)

Si-tetrachloride b

a c

d

e

fg

HCl-adsorption

pyrogenicsilica gel

a: vaporizerb: mixing chamberc: combustion chamber

d: coolinge: separation

f: purificationg: silo

FIGURE 2.1 Flow chart of production process.

FIGURE 2.2 Collisions of flame-formed particles form larger aggregates and agglomerates.



FIGURE 2.3 Growth in size of fumed silica particles as they are carried further from the flame is shown by these four electronmicrographs. All samples were taken from the same flame but at different distances from the flame front: upper left, 8 ms

residence time, specific surface 360 m2/g; upper right, 13 ms, 350 m2/g; lower left, 86 ms, 200 m2/g; lower right, 137 ms,150 m2/g.

The Language of Colloid Science and Silica Chemistry 7


3 Colloid Chemistry of Silica:An OverviewHoracio E. BergnaDuPont Experimental Station

CONTENTS

Colloidal Dispersions and Colloid Science . . . . . . . . 11

Commercial Colloidal Silicas . . . . . . . . . . . . . . . . . . 12

Sols, Gels, and Powders. . . . . . . . . . . . . . . . . . . . . . . 12

Colloidal Silica Stability and Aggregation . . . . . 13

Gelation, Coagulation,

Flocculation, and Coacervation . . . . . . . . . . . . . . . . 15

Fractal Approach to Colloid Systems . . . . . . . . . . . . 17

Silica Nucleation, Polymerization, and Growth:

Preparation of Monodisperse Silica Sols. . . . . . . . . 19

Stability of Silica Sols . . . . . . . . . . . . . . . . . . . . . . . . 20

Silica Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Silanol Groups, Siloxane Bridges, and Physically

Adsorbed Water . . . . . . . . . . . . . . . . . . . . . . . . . 22

Concentration of Hydroxyl Groups on the

Silica Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

Dehydration of the Silica Surface . . . . . . . . . . . . 27

Dehydroxylation of the Silica Surface . . . . . . . . 27

Rehydroxylation of the Silica Surface . . . . . . . . 28

Structurally Bound Water in Silica Particles . . . 30

Coalescence and Sintering . . . . . . . . . . . . . . . . . . 30

Particle Size and Characterization Techniques. . . . . 31

The Concept of Zeta Potential . . . . . . . . . . . . . . 31

Colloidal Dispersions. . . . . . . . . . . . . . . . . . . . . . . . . 31

Electrokinetic Effects and the Concept of

Zeta Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

SolGel Science and Technology. . . . . . . . . . . . . . . 31

Gels and Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Uses of Silica From the Caves of Altamira and

Cro-Magnon to Silicon Valley and Outer Space . . 33

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

Silicon dioxide is the main component of the crust of the earth. Combined with the oxides of magnesium,

aluminum, calcium, and iron, it forms the silicate minerals in our rocks and soil.

Over millions of years silicon dioxide, or silica, has been separated from the original silicate rocks by the

action of water to appear as quartz. In a few places it was deposited in the amorphous form as opal.

Our English word silica has a very broad connotation: it includes silicon dioxide in all its crystalline,

amorphous, soluble, or chemically combined forms in which the silicon atom is surrounded by four or six

oxygen atoms. This definitely excludes all the organosilicon compounds made by man in which carbon

atoms have been linked directly to silicon atoms commonly referred to as silicones, which do not

occur in nature. Silica is soluble enough in water to play important roles in many forms of life. It forms

the skeletons of diatoms, the earliest form of life that absorbed sunlight and began to release oxygen into

the atmosphere. Many plants use silica to stiffen stems and form needles on the surface for protection.

As animals developed, the role of silica became less obvious. But each one of us contains about half a

gram of silica, without which our bones could not have been formed, and probably also not our brains.

Silica has played a key role since the beginning of civilization, first in flint for tools and weapons and in

clay and sand for pottery. The high strength and durability of Roman cement 2000 yr ago is now known to be

due to the use of a special volcanic ash that is an almost pure form of amorphous colloidal silica. Today

there is active research on the use of the somewhat similar silica fume from electric furnaces to make a

super-strong Portland cement.

Our present technology would be very different without the silica for the catalysts of our oil refineries, for

the molds for casting the superalloys in our jet engines, for modern glass and ceramics, electronic micro-

circuits, quartz crystals, and fiber optics.

Ralph K. Iler, Alexander Memorial Lecture, Australia, 1989. Reprinted with permission from Chemistry in

Australia, October 1986, p. 355.

9


Silicon dioxide, silica, can be natural or synthetic,

crystalline or amorphous. This book is concerned mostly

with synthetic amorphous silica in the colloidal state.

The building block of silica and the silicate structures

is the SiO4 tetrahedron, four oxygen atoms at the corners

of a regular tetrahedron with a silicon ion at the center

cavity or centroid (Figure 3.1). The oxygen ion is so

much larger than the Si4 ion that the four oxygens of aSiO4 unit are in mutual contact and the silicon ion is

said to be in a tetrahedral hole [1]. Natural silicas

can be crystalline, as in quartz, cristobalite, tridymite,

coesite, and stishovite, or amorphous, as in opal. Crystal-

line silica polymorphs are divided according to their

framework density (SiO2 groups per 1000 A3) into pykno-

sils and porosils, and the latter are further divided into

clathrasils and zeosils depending on whether the pores

are closed or open, that is, accessible to adsorption (see

Familiarity with the structure of crystalline silica is

helpful in understanding the bulk and surface structure

of amorphous silica. All forms of silica contain the

Si22O bond, which is the most stable of all Si22Xelement bonds. The Si22O bond length is about0.162 nm, which is considerably smaller than the sum of

the covalent radii of silicon and oxygen atoms

(0.191 nm) [2]. The short bond length largely accounts

for the partial ionic character of the single bond and is

responsible for the relatively high stability of the siloxane

bond. Although in most silicas and silicates the silicon

atom is surrounded by four oxygen atoms, forming the tet-

rahedral unit [SiO4]42, a sixfold octahedral coordination

of the silicon atom has also been observed in stishovite

and coesite [3]. The arrangements of [SiO4]42 and

[SiO6]82 and the tendency of these units to form a three-

dimensional framework structure are fundamental to

silica crystal chemistry.

The silicates are built up in a manner analogous to that

of the polyborates and the polyphosphates by sharing of

oxygen atoms. In practice, two different SiO4 groups may

share only one oxygen atom, but any or all of the four of

the oxygen atoms on a SiO4 group may be shared with adja-

cent groups. Sharing of two oxygen atoms per unit yields a

chain, three oxygen atoms a sheet, and four oxygen atoms a

three-dimensional network [1]. The crystalline silicas

quartz, tridymite, and cristobalite are in truth network sili-

cates, each silicon being bound to four oxygens and each

oxygen being bound to two silicons. Quartz is the stable

form of crystalline silica below 8708C, tridymite below14708C, and cristobalite below 17108C, but either of thetwo high-temperature forms can exist for long periods of

time at room temperature and atmospheric pressure

without turning to quartz [2].

The polymorphism of silicas is based on different lin-

kages of the tetrahedral [SiO4]42 units [2]. Quartz has the

densest structure, and tridymite and cristobalite have a

much more open structure. All three forms exist in a- andb-forms, which correspond to low- and high-temperaturemodifications, respectively. The a- and b-modificationsdiffer only slightly in the relative positions of the tetrahe-

dral arrangements. This similarity is evident from the fact

that the conversion aN b is a rapid displacing transform-ation that occurs at relatively low temperatures. Quartz is

the most stable modification at room temperature; all

others forms are considered to be metastable at this temp-

erature [2].

In amorphous silica the bulk structure is determined, as

opposed to the crystalline silicas, by a random packing of

[SiO4]42 units, which results in a nonperiodic structure

The structure, Si22O bond length, and Si22O22Si bondangle in crystalline and amorphous silicas have been

studied by x-ray, electron, and neutron diffraction and by

infrared spectroscopy. Three strong absorption bands at

800, 1100, and 1250 cm21 measured by infrared trans-

mission techniques are attributed to fundamental Si22Ovibrations and do not differ greatly in the various silica

modifications, whereas in the high-frequency region

(28004000 cm21) certain distinct differences are

adjacent SiO4 tetrahedra that shows the Si22O22Si bondangle [4]. Diffraction measurements have shown a differ-

ence between the Si22O22Si bond angle of quartz(1428), cristobalite (1508), and fused quartz (1438).

Silicate glasses are conventionally regarded as silicate

frameworks in which cations are distributed at random.

However, Gaskell et al. [5], using neutron scattering with

FIGURE 3.1 Methods of representing the tetrahedralcoordination of oxygen ions with silicon: (a) ball and stick

model, (b) solid tetrahedron, (c) skeletal tetrahedron, and (d)

space-filling model based on packed spheres. (Reproduced with



(Figure 3.2). As a result of the structural differences the

observed [2]. Figure 3.3 is a schematic representation of

various silica forms have different densities (Table 3.1).

Chapter 23).

permission from reference 95. Copyright 1974.)

isotopic substitutions of Ca in a calcium silicate glass,

revealed a high degree of ordering in the immediate

environment of Ca over distances approaching 1 nm. The

technique was later extended to obtain a direct measure-

ment of the Ca22Ca distribution and provided what they

considered strong evidence that such glasses and possibly

other amorphous oxides are more extensively ordered

than previously seemed possible. These findings on silicate

glasses made some researchers review the largely discre-

dited notion, originally based on the observation of broad

x-ray diffraction peaks centered in the range of the crystal-

line silicas strong peaks, that amorphous silica may also

have limited domains with a high degree of ordering.

COLLOIDAL DISPERSIONS AND

COLLOID SCIENCE

As previously pointed out, this book deals mostly with col-

loidal silicas, that is, disperse systems in which the dis-

perse phase is silica in the colloidal state of subdivision.

The colloidal state of subdivision comprises particles

with a size sufficiently small (1 mm) not to be affectedby gravitational forces but sufficiently large (.1 nm) toshow marked deviations from the properties of true sol-

utions. In this particle size range, 1 nm (10 A) to 1 mm(1000 nm), the interactions are dominated by short-range

forces, such as van der Waals attraction and surface

forces. On this basis the International Union of Pure and

Applied Chemistry (IUPAC) suggested that a colloidal

dispersion should be defined as a system in which particles

of colloidal size (11000 nm) of any nature (solid, liquid,

or gas) are dispersed in a continuous phase of a different

composition or state [6]. If the particles are solid they

may be crystalline or amorphous. The disperse phase

may also be small droplets of liquids, as in the case of

emulsions, or gases, as for example in foams.

By way of comparison, the diameters of atoms and

molecules of classical chemistry are below 0.5 nm. On

the other end of the colloidal range, at about 1000 nm,

the region of suspensions begins. Thus, colloid science,

concerned with the intermediate range, is generally under-

stood to be the study of systems containing kinetic units

that are large in comparison with atomic dimensions [7].

Such systems may be those in which the particles are

FIGURE 3.2 Two-dimensional representation of random versusregular packing of (Si22O4)

42 tetrahedra: amorphous (top) and

crystalline silica. (Crystalline diagram reproduced with

q

FIGURE 3.3 Schematic representation of adjacent SiO4tetrahedra that shows the Si22O22Si bond angle. Small circle,Si; large circle, O. (Reproduced with permission from

TABLE 3.1Density (d ) of Crystalline and Amorphous Silicas

SilicaDensity

(g/ml at 273 K)

Coesite 3.01

a-Quartz 2.65

b-Quartz 2.53

b-Tridymite 2.26

b-Cristobalite 2.21

Amorphous silica 2.20

Elsevier Science Publishing Co., Inc.

Colloid Chemistry of Silica 11


permission from reference 96. Copyright 1960.)

reference 97. Copyright 1976 John Wiley & Sons, Inc.)

Source: Reproduced with permission from reference 2. Copyright 1979

free to move in all directions, or they may be derived

systems, as a coagulum or a gel (discussed subsequently),

in which the particles have lost their mobility either par-

tially or entirely, but have maintained their individuality.

All three dimensions need not be in the colloidal

range: fibers or needle-shaped particles in which only

two dimensions are in this range and thin films or disk-

shaped particles in which only one dimension is in this

range may also be treated as colloidal [7]. Nor must the

units of a colloidal system be discrete: continuous-

network structures, the basic units of which are of colloidal

dimensions, also fall in this class, for example, porous

solids and foams in addition to gels.

A more modern approach to colloidal dispersions is

based on fractal geometry. The fractal approach, as

explained later, provides a new basis for the definition

and characterization of colloidal systems.

COMMERCIAL COLLOIDAL SILICAS

Commercial colloidal silicas are produced by many

companies both in the Americas, in Europe, and in

Japan as dispersions in water or organic solvents

in different particle sizes. Current types are listed in

SOLS, GELS, AND POWDERS

A stable dispersion of solid colloidal particles in a liquid is

called a sol. Stable in this case means that the solid particles

do not settle or agglomerate at a significant rate. If the liquid

is water, the dispersion is known as an aquasol or hydrosol.

If the liquid is an organic solvent, the dispersion is called an

organosol. The term gel is applied to systems made of a

continuous solid skeleton made of colloidal particles or

polymers enclosing a continuous liquid phase. Drying a

gel by evaporation under normal conditions results in a

dried gel called a xerogel. Xerogels obtained in this

manner are often reduced in volume by a factor of 5 to 10

compared to the original wet gel as a result of stresses

exerted by capillary tension in the liquid.

An aerogel is a special type of xerogel from which the

liquid has been removed in such a way as to prevent any

collapse or change in the structure as liquid is removed

[8]. This is done by drying a wet gel in an autoclave

above the critical point of the liquid so that there is no

capillary pressure and therefore relatively little shrinkage.

The product is mostly air, having volume fractions of solid

as low as about 0.1% [8], hence the term aerogel.

An aerosol is a colloidal dispersion of particles in gas.

Fumed or pyrogenic oxides, also known in the case of

silica as aerosils, are powders made by condensing a

TABLE 3.2Properties of Commercial Silica Sols Listed by Manufacturer

Stabilizer

Sol(Manufacturer) Grade

SiO2(%) Type (%)

RatioSiO2:Na2O pH

ParticleDiameter

(nm)

SpecificSurface(m2 g21)

TechnicalBulletin


Columbia, MD

HS-40 40 Na2O 0.41 95 9.7 12 230 E10260 (1976)

HS-30 30 Na2O 0.32 95 9.8 12 230 E10260 (1976)

TM 50 Na2O 0.21 240 9.0 21 130 E10260 (1976)

SM 30 Na2O 0.56 54 9.9 7 360 E10260 (1976)

ASa 40 NH3 9.0 21 130 E10260 (1976)

LS 30 Na2O 0.10 300 8.2 12 130 E10260 (1976)

WPb 35 Na2O 0.62 130 11.0 21 130 E08913 (1976)

(AS)c 30 NH3 9.6 1314 210230 A82273 (1974)

AMd 30 Na2O 0.13 230 9.0 15 210 A21163

Positively charged sols Al2O3 coating

Ondeo Nalco Naperville, Il. 1115 15 Na2O 0.8 19 10.4 4 750 CTG-1115

2326 14.5 NH3 0.01 9.0 5 600 CTG-2326

1130 30 Na2O 0.65 46 10.2 8 375 CTG-1130

1030 30 Na2O 0.40 75 10.2 13 230 CTG-1030

1140 40 Na2O 0.40 100 9.7 15 200 CTG-1140

1050 50 Na2O 0.35 143 9.0 21 143 CTG-1050

1034A 34 H 3.0 19 158 CTG-1034

Max

2327 40 NH3 0.10 9.3 23 130 CTG-2327



Tables 3.23.6 and 3.8.

precursor from a vapor phase at elevated temperatures.

(Usage has converted Aerosil, the trademark of Degussas

pyrogenic silica, into a generic term that includes other pyro-

genic silicas, such as the Cabot Corporations Cab-O-Sil.)

Dried gels obtained by dispersing aerosils in water and

then drying are called by some authors aerosilogels. Powders

obtained by freeze-drying a sol are known as cryogels.

Commercial colloidal silicas are commonly available

in the form of sols or powders. The powders can be xero-

gels, dry precipitates, aerogels, aerosils, or dried and cal-

cined coacervates. The ultimate unit for all of them is a

silica particle, the size of which determines the specific

surface area of the product.

powders a genealogical tree of colloidal silicas.

COLLOIDAL SILICA STABILITY AND

AGGREGATION

unit of all colloidal silicas. In a restricted sense the term

TABLE 3.4

Grade 215 830 1430 1440 2040 2050 9950 2040 NH4 2034DI

SiO2 wt % 15 30 30 40 40 50 50 40 34

Particle size nm 4 10 14 14 20 20 100 20 20

Na2O wt % 0.83 0.55 0.40 0.50 0.38 0.47 0.12

pH 11.0 10.5 10.3 10.4 10.0 10.0 9.0 9.0 3.0

Density g/cm3 1.10 1.22 1.21 1.30 1.30 1.40 1.40 1.30 1.23

Viscosity mPas 5 8 7 16 13 50 15 15 7

TABLE 3.3

Grade 15/500 30/360 30/220 30/80 305 40/220 40/130 50/80 F 45 30 NH3/220 CAT80

SiO2 wt % 15 30 30 30 30 40 40 50 45 30 40

Surface area m2/g 500 360 220 80 220 220 130 80 80 220

Particle size nm 6 9 15 40 15 15 25 40 40 15 40

Na2O wt % 0.40 0.55 0.30 0.13 0.30 0.40 0.18 0.22 0.20 ,0.10

pH 10.0 10.0 9.7 9.6 9.5 9.7 9.0 9.3 9.5 9.0 4.0

Density g/cm3 1.1 1.2 1.2 1.2 1.2 1.3 1.3 1.4 1.36 1.2 1.32

Viscosity mPas ,5 ,8 ,7 ,6 ,10 ,25 ,10 ,15 ,15 ,10 ,15

TABLE 3.5aSilica Typical Values

ProductMetalOxide

Wt. %MetalOxide Media

% H2O(Karl Fischer)

SpecificGravity

SG of SiO2

pH50/50 wt.

in water5 wt.% in

aqueous slurry

MeanParticle

DiameterParticleCharge

nm mm

DP5480 Silica 30 EG 1.0 1.3 3.0 50 NegativeDP5540 Silica 30 EG 1.0 1.3 3.0 100 NegativeDP5820 Silica 30 EG 1.0 1.3 3.0 20 NegativeNyasil 5 Silica 92 Powder N/A 2.2 4.0 1.8 N/ANyasil 20 Silica 95 Powder N/A 2.2 4.0 1.4 N/ANyasil 6200 Silica 96 Powder N/A 2.2 4.0 1.7 N/

Colloidal Silica Fundamentals and Applications

Documents

anionic surfactants

nonionic surfactants

cationic surfactants

amphoteric surfactants

chemical analysis

surfactant biodegradation

hiltonsee volume

kozo shinodasee volume