Chemistry of Silica - Ralph Iler

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Silica, the major component-Olthe
earth's solid surface and. the constituent of ordinary sand,'becomes involved
at some point in a great many phasesof .' .
modern technology and science. It is an
essential material in many, if not all,
. forms of life. Its role in human disease,
aging, and health is Just beginning to be
explored. Here is a comprehensive account of the basic chemistry invOWed in
a wide range of research and development activities, as well as a wealth of information on production and production control.
Beginning with the solubility of different.
. forms of silica and the factors that influence dissolution and deposition, the solution chemistry of silica Is Introduced.
The author also compares and recommends analytical methOds. The digest
of all currently available information
provides a solid background as to the
nature of soluble silicates and particularly the mechanism of polymerization
of sHicic acid and formation of colloid.
:.'For the first time, the mechanism by
which silica sots, powders and gels -are
formed and their properties controlled
Is clearly described. Next, the many
types and uses of commercial concentrated sols, gels, and u'trafine powders
are examined, fotl~ by a discussion
of the biochemical properties and many
applications of the surface chemistry of
silica. The finat chapter draws together
all aspects of the occurrence and importance of silica in different life forms.
Those engaged in research, development, and production in the many diverse fields and Industries in which silica plays a vital role-such as chemistry, biology, medicine, agriculture, metallurgy, and mining-will find THE
CHEMISTRY OF SILICA an indispensable reference.
795
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THE CHltMISTRY
OF SILICA
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Solubility, Polymerization, Colloid and

Surface Properties, and Biochemistry
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RALPH K. ILER
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A Wiley-Interscience Publication
JOHN WILEY & SONS
New York Chichester Brisbane Toronto
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To my wife, Mary, with gratitude for her never-ending

patience during the seemiaaly interminable
writing of this book
'-
Preface
This book was at first intended to be an updated second edition of my
earlier book, The Chemistry of Silica and Silicates (Cornell University
Press, 1955). It necessarily covers much of the same subject matter, but
with 2500 new references to consider, it had to be reorganized and expanded
to such an extent that it constitutes an almost entirely new work.
The purpose of the book is to present a complete and coherent account of
the chemistry of amorphous silica, including soluble silica and silicate
precursors of soluble silica, polymerization to polysilicic acids, colloidal sols
and gels, and the surface chemistry of silica. In discussing practical applications of sols and gels, emphasis is placed on the chemistry involved. The.last
chapter on silica in living organisms is especially important in view of the
growing recognition that silica is present in many biological systems and
can function as an essential trace element.
Since publication of my earlier book in 1955, the literature on colloidal
metal silicates, including minerals, and on silicic esters has grown
enormously. Consequently these areas had to be omitted.
The title, The Chemistry of Silica, may be misleadingly broad but is
offset by a more definitive subtitle, "Solubility, Polymerization, Colloid and
Surface Properties, and Biochemistry."
It is remarkable that silica, the major component of the earth's solid surface, has never become a separate branch of study or instruction. Science
students graudate with little or no knowledge of its properties or chemistry.
Yet sooner or later, in such diverse fields as industrial chemistry,
electronics, agriculture, mining, metallurgy, petroleum, power development,
and even biochemistry and medicine, problems arise involving this common
element oxide. This book is written not only for those already engaged in
these areas, who may find it a useful guide to the literature, but also for
".'
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Preface
those in other fields who need specific information not otherwise easily
available.
RALPH
K. ILER
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Wilmington, De/aware
November /978
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Acknowledgments
I am indebted to the Cornell University Press for permission to include
some of my earlier book* with the following credit:
Reprinted from Ralph K. lIer: THE COLLOID CHEMISTRY OF
SILICA AND SILICATES. Copyright
1955 by Cornell University.
Used by permission of the publisher. Cornell University Press.
I am also grateful to John Wiley and Sons for permission to include in
Chapter 5 portions of my monograph on "Colloidal Silica" in Col/Did and
Surface Science. VoL 6. 1973. edited by Egon Matijevic.
.
This work would have been impossible without the generosity of E. I.
duPont de Nemours & Co. in making available to me. as a retiree. the
facilities of the Lavoisier Library at the duPont Experimental Station.
It is impossible to mention all those who have kindly reviewed drafts of
portions of the manuscript and given invaluable advice. My friend and
fellow scientist. Dr. Paul C. Yates has been very helpful with sound
technical counsel.
.
To the late Mildred Syvertsen. who played an indispensible role in all my
earlier publications. I remain grateful for help in collecting references and
typing much of the present manuscript. The assistance of Patricia Cullen in
final typing. of Joseph A. Pankowski. Jr. in preparing illustrations and of
Jennifer J. Stiles in assembling indexes. is sincerely appreciated.
R.K.1.
Now out of print.
,
ix
Contents
Introduction
Previous Books and Reviews of Silica Chemistry

Selection of References
Terminology
References
. 1 The Occurrence, Dissolution, and Deposition of Silica
The Silica-Water System

Thermodynamics of the System
Relating Particle Size and Composition
Energy Change with Changing Particle Size and Composition
Soluble Silica-Monosilicic Acid
Volatility in Steam
Soluble Silica in Nature
Phases of Silica
Anhydrous Crystalline Silicas
Relation between density
.
.and . refractive index
. Hydrated Crystalline Silicas
Amorphous Silicas
Microscopic sheet. ribbon, and fiberlike forms. Common
amorphous forms. Hydrated amorphous silica. Biogenic sili
The Solubility of Silica _ .
Solubility of Quartz at Ordinary Temperature
Cleaning the surface
Solubility of Quartz under Hydrothermal Conditions
I
I
2
3
6
7
9
10
12
13
15
15
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19
21
30
30
32
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Solubility of Cristobalite and Tridymite

Solubility of Other Crystalline Forms of Silica
Adsorbed Silica on Crystalline Silica
Solubility of Amorphous Silica
Establishment of solubility equilibrium, Effect of heating,
Solubility in water: pH 0-8. Possible solubility minimum at
pH 7. Solubility in nitric acid. Solubility in NaCIO. solutions,
Effect of electrolytes. Solubility under hydrothermal conditions
Solubility of Hydrated Amorphous Silica
Apparent High Solubility at High pH
Calculation of solubility and dissociation constant
Effect of Particle Size on Solubility in Water
Interfacial Energy
Effect of Impurities on Solubility
Effect of Organic Compounds on Solubility
Catechol and Related Compounds
Polyhydroxy Organic Compounds
N-Oxides
Organic Bases
Living Tissues
Solubility in Alcohols .
Methanol. Higher alcohols
Solubility in Molten Salts"
Rate of Dissolution of Silica'
Mechanism
Effect of pH on Rate
Relation Between Rate of Dissolution and Particle Size
Rate of Dissolution of Very Small Particles
Rate of solution as particle dissolves
Rate of Dissolution of Particles of Different Sizes
Dissolution of Crushed Powders
Neutral Solutions-Effect of Salts
Retardants of Dissolution
Rate of Dissolution in Presence of Catechol
Rate of Dissolution in Aqueous HF
. Comparative Rates of Dissolution
Removal and Deposition of Silica from Water
32
33
34
40
46
47
49
54
56
58
59
59
59
60
60
61
62
62
62
65
65
69
72
73
74
75
75
76
76
76
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Contents
32
Removal of Silica from Water

78
Precipitation mechanisms, Nucleation of quartz, Adsorption and
precipitation by hydrous oxides, Removal by ion exchange
83
Deposition of Silica from Water
Rate of deposition of monomeric silica, Silicification of biogenic
materials, Rate of deposition of colloidal silica
3
34
40
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46
47
49
54
56
58
59
59
59
10
60
61
62
62
62
65
65
69
72
73
74
75
75
76
76
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76
xiii
Methods of Analysis
Atomic Absorption
Chemical Methods
Methods Involving Silicomolybdic Acid
The beta silicomolybdate method, A recom mended procedure,
Interfering substances, Molybdenum blue method, For
biological sample.
Methods of Concentrating Silica for Analysis
Depolym erizing Colloidal Silica before Analysis
Standard Silica Solutions
Miscellaneous Colorimetric Methods
Detection of Colloidal Silica on Surfaces
Rapid Titration of Total Silica as Fluosilicate
Titration as the Silicomolybdic Acid
References
94
94
95
95
100
101
101
101
102
102
103
104
Water-Soluble Silicates
116
Sodium and Potassium Silicates

Manufacture
Commercial Solutions
Soluble Crystalline Sodium and Potassium Silicates
Properties of Solutions
Fields of Use
The Nature of Silicate Solutions
Theory
Physical Studies :
Effects of diluting silicate solutions. Effect of alkali metal
salts and other coagulants
Conversion to Suicic Acids
Reaction with molybdic acid. Conversion to esters of silicic
acids. Conversion to trirnethylsilyl derivatives of silicic acid
117
117
119
120
120
121
123
126
130
137
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Silicates with Coordination Numbers Four and Six

Solutions of Polysilicates
Sodium Polysilicate .
Potassium Polysilicate
Lithium Silicates
Lithium Polysilicates
Uses for Lithium Silicates and Polysilicates
Organic Base Silicates
Mixed Organic Base-Alkali Metal Base Silicates
Other Organic Base Silicates
Complex Metal Ion Silicates
Organic Chelates of Silicon
Catechol Derivatives
Humic Acids
Other Organic Cornpounds :
Hydrated Crystalline Alkali Metal Polysilicates
Silicates Convertible to Crystalline Forms of (H 2Si 2Os),c
Precipitation of Insoluble Silicates
Soluble Silicate Glasses
Peroxy Silicates
References
142
143
144
145
145
146
149
150
153
154
154
155
156
157
157
158
160
161
163
164
165
Polymerization of Silica
172
General Theory of Polymerization

Overall Effect of pH on Gelling
Monosilicic Acid
Preparation
Dissolving silica, Hydrolysis of monomeric silicon compounds,
Dissolving monomeric silicates in acid
Characteristics of Silicic Acid
Diffusion constant. Ionization constants. Increase in ionization
constant with polymerization, Isoelectric point. Point of zero
charge, Stability of monomeric silica
Reactions of Monosilicic Acid
Phosphoric andboric acids, Sulfuric acid, Iron and uranium,
Chromium, Aluminum, Divalent cations
Characterization of Silicic Acids
174
177
177
178
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Contents
142
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144
145
145
146
149
ISO
153
154
154
155
156
157
157
158
160
161
3
164
165
172
174
177
177
178
Is,
180
on
189
xv
Contents
Reaction with Molybdic Acid

..
Alpha and beta silicic acids, Measurement of reaction rates,
Reaction rate constants, Composition of molybdic acid
reagents, Other observations
Separation of Silicic-Acids
Particle Size and Surface Area by Titration
Correction for soluble silica
Coagulation with Gelatin-Salt
Mechanism of Condensation and Hydrolysis
Catalytic Effect of HF
Polymerization: pH 2-7
Formation ofOligomers Oligomers as Particles
Nucleation Theory
Particle Growth in Acidic Solution
Depolyrnerization in Acidic Solution
Polymerization by Aggregation-Gel Formation
Molecular versus Particle Chains
Mechanism of Interparticle Bonding
Formation of Chains of Particles and Networks
Partial Coalescence of Particles in Chains
Development of Microgel and Viscosity
Isolating "gel phase" or "rnicrogel", Effect of electrolytes and
coagulants. Gel density and structure, Increase in viscosity
Formation of Larger Particles by Coacervation
Polymerization above pH 7
Spontaneous Growth of Particles
Final Size of Particles versus Temperature
Viscosity of Sols before Aggregation Begins
Viscosity of Sols of Very Small Particles at Low pH
. Decrease in Viscosity on Conversion of Microgel to Sol
Thermal Effects
Energy of activation. Heat of polymerization
Summaries of Investigations
Investigations at Low pH
Iler; Alexander, Heston, and Iler: Schwarz and Knauff:
Bechtold; Goto; Okkerse: Audsley and Avcston: Weitz, Franck,
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195
202
203
206
209
211
213
214
215
218
220
220
222
222
223
225
227
231
239
239
239
242
244
244
247
248
249
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xvi
and Giller; Bechtold, Vest, and Plambeck; Acker: H~ebbel

. and Wieker
Investigations Through the Neutral pH Range
268
Merrill and Spencer; Ashley and Innes; Baumann; Coudurier,
Baudru, and Donnet; Marsh, Klein, and Vermeulen; Ginsberg
and Sheidina
Investigations Above pH 7
281
Greenberg and Sinclair; Greenberg; Goto; Tarutani; Iler: IIer
and Sears; Richardson and Waddams; Makrides et al.
Polysilicic Acids
287
Preparation of Polysilicic Acid
288
Hydrogen-Bonded Complexes with Polar Organic Compounds
288
Method of comparing hydrogen-bonding activity, Structure
versus activity, Liquid hydrogen bonded complexescoacervates, Complex of silicic acid with amine salt,
Interaction of silicic acid with phosphoric acid ester
Combinations with Organic Polymers
297
Prevention of hydrogen bonding by negative charge on silica,
Cationic organic compounds
29~
Miscellaneous Interactions with Organic Materials
Interaction with proteins-e-tanning. Esterification of
polysilicic acid
Activated Silica Sols-Water Treatment
301
Reaction of Polysilicic Acid with Metal Cations
303
References
304
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312
Definition of Colloidal Silica and Historical Development

Growth and Stabilization of Discrete Particles
Increasing Particle Size by Adding ..Active" Silica
Methods of Making Particles Under 10 nm in Size
Stabilization Against Particle Growth
Stabilization Against Aggregation
.. , Stabilization by ionic charge, Addition of salt to lower
viscosity, Sterk stabilization .
Porous Particles
312
313
313
317
318
323
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268
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287
288
288
297
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301
303
304
312
312
313
313
317
318
323
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328
Contents
Elongated Particles
Particles with Non-Siliceous Cores
Methods of Making Sols
Neutralizing Soluble Silicates With Acids
Electrodialysis
Ion Exchange
Peptizing Gels
Hydrolysis of Silicon Compounds
Dissolution of Elemental Silicon
Dispersion of Pyrogenic Silica
Purification. Concentration, Preservatives
Ion Exchange
Dialysis and Electrodialysis
Washing Procedures
Concentration
Evaporation of water, Centrifugation, Ultrafiltration,
Electrodecantation
Preservatives
Characterizing Sols
Chemical Analysis
Measuring pH. Electrolyte concentration
Particle Characteristics
Particle size. Specific surface area
Ionic Charge on Particles
Nature of ionic charge. Counterions and double layer
Viscosity
Aggregation of Particles
Definitions
Gelling
Effect of pH. Effect of particle size and concentration.
Electrolytes and organic liquids. Temperature. Theory of
strength of gels
Coagulation
Mechanism. Coagulation by electrolytes. Monovalent cations
as bridging agents. Coagulation by divalent metal ions.
Coagulation by polyvalent cations-basic metal salts. Effect
of silica concentration and other factors. Effect of
particle' size. Partly dehydrated surface
xvii
330
330
331
33 I
332
333
334
335
335
336
337
337
338
338
338
343
344
344
345
355
360
364
364
366
372
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Flocculation
Flocculation with cationic surfactants, Flocculation with
organic polymers
Coacervation
Silica spheres by coacervation
Aggregation into Ordered Structures-Precious Opal
Opal structure, Other ordered aggregates, Formation of
uniform inorganic particles, Synthesis of opal
Adsorption of Silica Particles on Surfaces
Sols of Silica Particles with Modified Surfaces
Negatively Charged Surfaces
Aluminosilicate ions, Other anions
Positively Charged Particles
Polyvalent metal oxide coatings, Polyvalent organic cations
Organic Modified Surfaces-Organosols
Organic ions, Esteri fication, Silylation
Commercial Colloidal Silicas
Uses of Colloidal Silicas
Making Catalysts, Gels, Adsorbents
Inorganic Binder, Stiffener
Molded refractory bodies, Binders for fibers, Refractory
coatings, Molds for casting metals
Frictionizing Effects
Fibers, Paper, Steel rails, Other surfaces
Antisoiling Surfaces
Hydrophilizing Surfaces
Modifying Adhesion
Increasing adhesion, Decreasing adhesion
Coating Compositions
Coatings on ships: tanks
Reinforcing organic polymers
Polishing Agent for Silicon Wafers
Surfactant Effects
Dispersing effects; Antifoaming effects
Modifying Viscosity-e-Gelling .
Miscellaneous Optical Effects. Color, Photography
Use in Biological Research-. Density Gradient
-
'
384
396
398
405
407
407
410
,
412
415
415
420
420
, -..
425
426
427
428
430
432
433
433
434
435
436 <..
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Contents
Contents
384
Source of Chemically Reactive Silica

Soluble silicates, Silica bodies, GI3~\ compositions, Forming
solid silicates-cements, Other rea..' \ions and uses
Colloidal Silicates'
References
396
398
xh
437
439
439
r:
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405
407
407
Definitions
Types of Gels
Types of Powders
Physical Characterization ?f Gels and P'lwders
Ultimate Particle Size
410
412
5 Silica Gels and Powders
I.
415
420
Characterizing Pores by Adsorption h'Jtherms
426
427
428
430
432
433
433
434
135
\-t36
463
464
465
476
478
Particle size and packing, Loss of SUrface area by particle

packing
420
425
462
462
Electron micrographs, Specific sur(:II,;C area, Low angle X-ray

scattering
Aggregate Size-Powder Particles, Gd Granules
Pore Characterization
415
462
-.:
488
Pore volume, Pore size and size dislt'ibution, Miscellaneous

effects in micropores,
Nature of Silica Surface
Aggregate Strength-Interparticle B'IIIIJing
505
506
Electron micrographs, Partial diss,'lltlion method, Mechanical

strength of the aggregate
.
.
Silica pels
Sources of Silica Gel
From soluble silicates andminernb,From colloidal silica,
From hydrolysis of silicon com pou lids
Factors Controlling' Gel Characterist it:;
Size of pri~'~~ypa~iicles::'-pHefft.''', Wet gel strength.,
Particle size and packing density ill dried gels, Increased
porosity with 'removable fillers
Forming and Shaping Gel Particles
Wet Gel Treatments
Gel reinforcement
510
511
516
526
528
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Drying and Shrinkage-Xerogels

Drying from low surface tension liquids
Drying without Shrinkage-Aerogels
Hydrothermal Treatments
Liquid or vapor phase
Heating in Air, Vacuum
Sintering uniform structures, Alkali metals, impurities,
crystallization
Special Gel Structures
Submicroporous gels-impervious silica, Porous glass,
Specific adsorbents
Precipitated Silica Powders
Silica Precipitated from Sodium Silicate Solution
Silica coagulated with sodium ions, Coagulation by adding
sodium or ammonium salts, Coagulation with calcium,
polyvalent metal ions, Coagulation with organic materials
Silica Precipitated from Fluoride Solution
Silica Precipitated from Organic Liquids
Silica Precipitated from Colloidal Silica Sols
Silica Precipitated from Vapor: Pyrogenic Silica
, "vaporized Si02, Oxidation of SiO vapor, Oxidation and
hydrolysis of SiCI. vapor, Oxidation and hydrolysis of silicon
esters vapors, Hydrolysis of SiF. vapor
Naturally Occurring Silica Powders
Microcrystalline Hydrated Silicas
Hydrophobic-Organophilic Silica Powders '
Adsorbed Organic Cations
Adsorbed Polyvalent Metal Cations with Organic Anions
Surface Esterification
Organosilicon Coatings
'.
Organic Polymer Coatings
Silica Gels with Ion-Exchange Surfaces
Inorganic Ion-~xchang'e .Sites
Organic-Linked Ion-Exchange Sites
Commercial Silica Gels and Powders
Uses of Silica Gels and Powders
533
537
539
544
549
554
554
563
564
564
565
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569
570
571
572
573
574
575
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576
577
578
578
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533
Reinforcing and Other Effects in Organic Solids

In rubber, In silicone elastomers, In various organic polymers
Reducing Adhesion
Increasing AdhesionIncreasing Viscosity,Thixotrophy
Mechanism, Lubricating grease, Paints, coatings, inks,
. Parmaceuticals and cosmetics, Miscellaneous compositions
Optical Effects-Flatting
Surfactant Effects
Stabilizing emulsions, Hydrophilic surface, Antifoam agent
Hydrophobing Effects
"Dry" water
Absorbent
Catalysts
Aerogels, Base for mitochondria, Spillover
Reactive Silica
Cloud Seeding
Chromatographic Column Packings
. References
537
539
544
549
554
554
563
564
564
ui
Contents
I
I
J65
6 The Surface Chemistry of Silica
568
569
570
571
572
573
574
575
576
576
577
578
578
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Reviews and Summaries

Nature of the Silica Surface
Structure of the Underlying Silica
Definition of Surface
The Hydroxylated Surface
. State of water at th-.7 hydroxylated surface, Electrical
. conductivity ofthe surface, Distinguishing adsorbed water
from silanol groups, Internal hydroxyl groups and trapped
water, Hydroxyl~groups per square nanometer, Theoretical
. concentration of surface hydroxyl groups
Dehydration and Rehydration
Surface Energies
Heat of Wetting Silica Surface
Physical Adsorption of Non-Ionic Low Molecular Weight
Compounds
582
587
587
588
593
594
594
595
596
597
597
598
599
622
623
624
624
625
625
637
645
646
648
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'
.
,
,.
I
:.
Contents
Adsorption of Vapors
Effect of dehydroxylation on adsorption
Adsorption from Solution-Nonionic
Nonaqueous solutions, Aqueous solutions, nonionic, hydrogen
bonding
Ionization and Surface Charge
The Hydroxylated Surface
The Dehydroxylated Surface
Nature of the Anionic Charge Sites
The "Site-Binding" theory
Forces Involved in Adsorption of Ions
Univalent cations: Metals and lower amines, Alkaline earth
metals and magnesium cations, Polyvalent metal cations
(Table 6.3)
Nonionic Reactions of the Silica Surface (Table 6.4)
Hydrophilic Coatings on Silica
Hydrophobic Silica Surface
Organic Cations and Bases
Hydrophobing effects, Cationic dyes, Aluminosilicate surfaces
Hydrocarbon Groups Attached through Polyvalent Metals
Surface Esters with Alcohols
Surface coverage, Reaction conditions, Methyl esterified silica,
Reaction of alcohols with dehydroxylated surface, Reaction of
hydrocarbons with dehydroxylated surface, Esterification in
micropores, Substituted alcohols, Hydrolysis of ester groups
Organic Groups attached by C-Si Bonds
Adsorption on Hydrophobic Surfaces
Adsorption ofwater, Adsorption of inert gases
Adsorption of Organic Polymers on the Silica Surface
From Aqueous Solution
Polyethylene oxide, Polyvinyl alcohol, Cationic polymers,
Proteins, Adsorption of polymers on dehydroxylated silicas,
Effect of salts
From Nonaqueous Solvents
Deposition of Multilayers of Charged Polyions and Particles
The Surface of Alumina-Silica
648
654
659
659
661
663
665
676
679
680
680
688
689
.695
699
702
704
709
710
710
'-.::..'
........;.... _-
Contents
Contents
648
Active Sites, Free Radicals, Active Oxygen, Ozone

References
xxiii
712
714
,,54
jen
7 Silica in Biology
659
659
661
663
665
676
679
680
680
:es
'88
689
rca,
of
s
695
699
702
704
709
710
710
730
Introduction
730
Origin of Life
730
731
Earliest Life Forms
Biological Disintegration of Rocks
733
Association with Primitive Organisms
733
Viruses
734
Bacteria
734
Fungi and Lichens
734
Algae and Diatoms
734
Sponges
739
Gastropods, Sea Cucumbers, Limpets
739
Plants
740
741
Nature of Silica Deposits in Plants
Strengthening Plant Parts
742
Equisetum, Bamboo, Grasses, Spiny plants, Job's Tears, Palms,
Wood
Mechanism ofAbsorption, Movement, and Deposition of Silica 747
Relation of Soluble Silica to Soil Fertility
748
Beneficial and Protective Effects of Silica
750
Insects
752
Fish, Amphibians, Reptiles, Birds
753
Mammals: Man
753
Essential Role of Silica in Mammals
756
Toxicity of Silica
757
Cytotoxicity
761
Silica in Biochemical Combinations
Combination with polysaccharides, Combination with proteins.
Denaturation of proteins, coagulation of blood, Combination
with specific compounds, enzymes, Combination in
.
phosphorus compounds: Nucleic acids, DNA, RNA,
Mutations, atherosclerosis, cancer
i. 1
~l-r~.,
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~.
~.
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t
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r
:1f
-;
.._...-.
__
._t1t!'~A:.::9~n2"W~WCU"'~I_ aa,..,,"~-...,'_.
_ - - ' -
-.
Silicosis-Pneum oconiosis- Fibrinogenesis

Mechanism of silicosis, Amorphous versus crystalline silica
and particle size, Susceptibility to silicosis, An unusual
compound in silicotic tissues, Solubility theory, Silica
antagonists to prevent silicosis
Asbestosis-M icroaciculosis
Beneficial Effects of Silica
Silicon Metabolism
Silica Gel as a Culture Medium
Organosilicon Compounds
Analytical Problems
Conclusion
References
Contents
769
782
783
783
784
785
786
787
787
Author Index
803
Subject Index
835
1
J
Ir
f.
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.--;.----
xxiv
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Contents
769
THE CHEMISTRY OF SILICA
'<:...
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Introduction
PREVIOUS BOOKS AND REVIEWS OF SILICA CHEMISTRY
Numerous outlines or surveys of the chemistry of silica. especially the water-silica

system. have appeared over the past half-century. Properties of silica have been
described by Sosman (la) and more recently by BrUchner (Ib), The state of
knowledge of soluble silicic acid and colloidal silica was summarized in 1937 by
Fricke and HUttig (2). and the general aspects of "silicic science" were reviewed by
Hauser in 1955 (3). At the same time. Iler exhaustively covered the rapidly developing theory and practice of the colloid chemistry of silica and silicates. including new
surface chemistry and the role of silica in biology (4). Following an initial book on
the physical chemistry of silicates in 1954 (5). Eitel authored a monumental series of
six volumes on silicate science from 1964 to 1975 (6). The colloidal aspects of silica
are summarized in Volume I and brought up to date in Volume IV. A review of the
solubility of silica in water. the nature of soluble silica." and its equilibrium with
polymer species was published by Stober (7). Similar reviews. each with a particular
emphasis. were written by Greenberg (8). Wittman (9). Coyle (10). Maher (I I). and
Kolthoff and Elving (12).
. Alexander has given an entertaining personal account of his researches in silica
chemistry (13). More recent summaries have been prepared by Kukolev (14) and
Hinz(!5).
SELECTION Of REfERENCES
!'
The major references used are those in which most variables have been deli ned. Thus
when pH has not been recorded in an aqueous system. or the source or characteristics of the silica used in experiments are not well deli ned. less attention is given,
There has been enormous duplication of experimental work. particularly in countries where earlier work was not recognized because of lack of availability to the
literature or language difficulties. In such cases original work has been emphasized.
and secondary work is cited only as conlirmation.
Patents are cited when the technical information is not otherwise available in the
literature. Where possible. United Stales patents arc cited because of general
availability throughout the vor ld upon request. But where equivalent U.S. patents
could not be located. the patents in other countries arc cited.
Introduction
TERMINOLOGY
,
'7; . :;'
~
'The term "silanol" is used for any OH group attached to silicon and will be understood to include what has otherwise been referred to as "siloxanol" and "silicol"
groups. The term "polymerization," strictly speaking, means a linking together of
monomer units to form a polymer of the same composition, but, in the silica system
the monomer, Si(OH)., condenses to form polymer that ultimately has the composition (SiO z)II' However, the term "polymerization" has been so widely used for the
formation of condensation polymers that it will also be so used here.
"Silica" is used as a short convenient designation for "silicon dioxide" in all its
crystalline, amorphous, and hydrated or hydroxylated forms. This word does not
occur in many other languages, which generally use the term "silicon dioxide."
However, the latter implies only the composition SiO z In analysis, the term "silica"
indicates only that the silicon content is given in terms of weight' of SiO z regardless
of the form in which it is actually present.
"
!.
;
REFERENCES
..
+':
I".
~.
iI ,
:1:
la. R. B. Sosrnan, The Phases of Silica, Rutgers University Press. New Brunswick, N.J .
1965.
r:
I'
,", ,
lb. R. Brilchner, "Properties and Structure of Vitreous Silica:' J. Non-Cryst, Solids. 5,

123, 177 (1911).
.,
,,
~:
-'
2. R. Fricke and G. F. HUttig. Handbuch der Allgemeine Chemle, Vol. 9. Hydroxides and
Oxyhydrates, Akademische Verlag. Leipzig, 1937, p. 146.
'
,~
3. E. A. Hauser, Silicic Science, Van Nostrand. Princeton. N.J., 1955.
.;.:"
4. R. K. Iler, The Colloid Chemistry of Silica and Silicates. Cornell University Press.
Ithaca, N.Y. 1955.
"
i
l~
1 I. P. K. Maher. Kirk-Othrner Encyclopedia of Chemical Technology. 2nd ed.. Vol. 18.

Wiley. New York. 1969. p. 61.
12. I. M. Kolthoff, P. J. Elving, and E. B. Sandell. "Analytical Chemistry of Silicon."
Treatise on Analytical Chemistry. Part II. Vol. 2. Wiley-Interscience, New York. 1962.
, p. 120.
.
...
13. G. B. Alexander. Silica and Me. Doubleday. Garden City. New York. 1967.
.'
..
-J
J:
;1
.
:)
":{ f.
10. T. D. Coyle. Kirk-Othmer Encyclopedia of Chemical Technology. 2nd ed . Vol. 18.

Wiley. New York. 1969. p. 46.
"
7. W. Stober~ Kolloid Z. 147, 131 (1956).

,9. A': Wittman. Oesterr. Chem, Z . 62, 245. (1961).
,-
6. W. E~tel. Silicates Science. Vols. I-VI. Academic. New York. 1964-1975.
-,
8. S: (Greenberg.J. Chem, Educ. 36, 218 (1959).
..-
,
I
";
5. W. Eitel. The Physical Chemistry of the Silicates. University of Chicago Press. Chicago.
III.. 1954.
,,
14. G. V. Kukolev, Chemistry of Silicon and Physical Chemistry of the Silicates. Vols. 1-3.
translated from Russian by E. H. Murch. National Lending Library of Science and
Technology. Boston Spa. England. 19?1; reviewed inJ. Am. Ceram, Soc. 55,126 (1972).
15. W. Hinz, Silikate: Grundlagen der Sllikatwlssenschaft und Silikattechnlk, Vol. 2. Verlag ',-,
Bauwesen, East Berlin. 1971.
ntroduction
,
i
be underI "silicol"
agether of
ca system
composied for the
. in all its
does not
dioxide."
n "silica"
regardless
I
i
CHAPTER
The Occurrence, Dissolution,

and Deposition of Silica
vick, N.J.
Solids. S,
i
xi
and
sity Press
..
!.
Silica is by far the major component of the earth's crust. yet much remains to be
learned of its chemistry and, in particular, its solubility behavior in water. The manner of its deposition to form such curiosities as quartz crystals containing inclusions
of mineral oil, mercury, or liquid carbon dioxide remains' a mystery (I). Flint, which'
our remote ancestors recognized as the strongest and toughest stone available, was
apparently formed in some instances from the siliceous skeletons of ancient sponges
by a mysterious process of solution transport. Within some plants and marine
organisms, soluble silica is transported and deposited in characteristic intricate patterns. Only recently has it been recognized that soluble silica, even in trace amounts.
plays a role in the development of mammals.
Chicago.
THE SILICA-WATER SYSTEM
Vol. 18.
Vol. 18.
Silicon."
irk, 1962.
loIs. 1-3.
ence and
6(1~"2).
2..... clg
As water is a unique liquid, so is amorphous silica a unique solid. They are much
alike, both consisting mainly of oxygen atoms with the smaller hydrogen or silicon
atoms in the interstices. As pointed out by Weyl and Marboe (2), "Some properties
of water and silica are so similar that the transition between hydrated silicic acids
and the aqueous mat-ri is a gradual one." Washburn (3) noted that water and arnor. phous silica both have a temperature of minimum .volume. Ephraim (4) observed
another similarity between silica and water in that water is much less dense than
expected from close packing of the constituent atoms and from X-ray diffraction
studies. Bernal and Fowler (Sa) concluded that water molecules are arranged in a
rather open structure like quartz. and undcrcooled water has a still III are open structure,like tridymite. Another model has been proposed by Weres and Rice (5b).
These ideas lead to the suggestion that there is some relationship between the
density of water and the solubility of the various forms of silica. since both are
related to the close packing of oxygen atoms. Both silica and water consist. from the
stlWi4pQint of volume. largely of oxygen atoms. which are packed together with a
characteristic nnck inu density. The small hvdr oucn and silicon atoms lit between the
The Occurrence. Dissolution. and Deposition of Silica
..
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oxygen atoms, contributing little to the volume. In pure orthosilicic acid, Si(OH). (if
it could be prepared). the small silicon and hydrogen atoms. lying in the interstices
between the large. oxygen atoms, would be more or less evenly distributed
throughout the mass. Polymerization of silicic acid to form solid silica and water
amounts to separation into two phases: in silica. the silicon atoms surround
themselves with oxygen atoms in a region of closer packing, and in water hydrogen
atoms surround themselves with oxygen in a region of more open packing. In amorphous SiO" there are 1.17 grams of oxygen per cubic centimeter; water of density
1.0, there is 0.89 gram of oxygen per cubic centimeter.
There is no evidence that silica is "soluble" to any appreciable degree in any
liquid other than water. However, that statement may depend on the definition of
"soluble." The dissolution of silica involves a chemical reaction or hydrolysis in an
excess of water:
L
,
Thus it is not a simple solution such as that of sugar in water, where the sugar
molecule exists intact in solution as in the crystal1ine state. Instead. it is analogous
to a hypothetical equilibrium of silica and ether in an excess of ether:
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Since low condensation polymers such as [(HO)2SiO]. appear to be clear watermiscible fluids resembling a poly hydroxy organic compound like glycerol (6). the
monomer, "soluble silica" or Si(OH). would probably be a clear liquid if it could be
isolated in anhydrous condition, In a pure state it might ~ven crystallize.
The unusual nature of the silica-water system has been noted by J. A. Kitchener
(7), who pointed out that the endless confusion in the literature concerning the
silica-water interface has arisen because the hydration and solubility characteristics
have not been understood. For example. there is the question as to why silica sols
are extraordinarily stable 'at pH 2 where the zeta potential is zero and become
increasingly sensitive to electrolytes at higher pH. where the potential is highest-in
contradiction to the generally accepted electrical double layer theory. Another
mystery is that crystalline quartz becomes coated with a film of amorphous silica
even though the solution is undersaturated with soluble silica with respect to a surface of amorphous silica.
The dissolution and deposition of silica in water involves hydration and dehydration reactions catalyzed by OH - ions:
(SiO z).. + 2 HzO
hydration
I
dehydration
(Si0 2) x _1 + Si(OH).
For massive amorphous silica, the equilibrium concentration of Si(OH). at 25C

corresponds to 70 ppm as SiO:. This is the "solubility" of anhydrous nonporous -.
amorphous Si02 However, except for fused StO, glass, the common forms of arnor- '--""
~--
1c
t-
m of Silica
The Silica-Water System
,i(OH). (if
ces
int
listriouted
and water
surround
hydrogen
In amorof density
phous silica consist of extremely small particles of amorphous silica. or porous

aggregates, the surface of which is hydrated as SiOH groups. These exhibit a
somewhat higher solubility so that most powders and gels have a solubility of
100-130 ppm sto;
On the other hand, crystalline silica, such as quartz, almost universally present as
"sand," has a much lower solubility, of the order of 6 ppm SiO z.
Supersaturated solutions of monomeric Si{OH). are formed when silica is
dissolved in water at high temperature under pressure and then cooled, or when an
aqueous solution of soluble silicate is acidified:
ee in any
inition of
ysis in ~
the sugar
analogous
Supersaturated solutions of silicic acid in pure water are thermodynamically unstable because condensation polymerization through dehydration takes place. All
higher polymers of whatever size, molecular weight, or state of hydration can be
represented by a general formula containing n silicon atoms. The polymerization of
additional monomer 'molecules or the deposition of silica can be represented as
follows:
[SiIlO ZIl _C/UIZI(O H )lIz]
+ m Si(OH).
-=
[Sill+mOzlI-clIZlzl+zmlz-p,(OH)IlZHm-p,] + 2pm HzO

:ar -vater>1,
the
t could be
Kitchener
rning the
acteristics
silica sols
j become
ghest-in
Another
ous silica
to a sur-
where n = number of silicon atoms in a polysilicic acid molecule or particle or

polymeric network
x = number of OH groups per silicon atom in the polymer, not exceeding 4
m = the number of monomeric silicic acid molecules added to the polymer
p = fraction of the hydroxyl groups per monomeric silicic acid molecule that
are converted to water during the polymerization reaction
dehydra-
Thus when p = 1, the monomer is converted to SiO z within the polymer molecule
without change in the number of OH groups in the polymer. There are, of course,
restrictions such as n and In having to be integers and the values of x and p being
limited by the possible structures of polymers and conditions of polymerization.
However, for the case where dense amorphous silica is being deposited on extensive, massive silica surfaces from slightly supersaturated monomer solution. especially at high temperature and neutral or alkaline pH. x is very small. p is unity. and
n is large. Thus the deposited silica may be essentially dense and anhydrous:
at 25C
onnorous
o
or-
Even vitreous or glassy silica contains some water. probably as SiOH groups. At a
given temperature and humidity there is an equilibrium "solubility" of water in vitreous silica, according to Hetherington and Jack (8). Flame-fused quartz contains
0.04 wt, % OH, whereas electrically fused material contains only 0.0003% as
detected byInfrared absorption at 2.73 micron wavelength. By extrapolation to'
-~"-
The: Occurrence. Dissolution. and Deposition of Silica
30C. Moulson and Roberts (9) concluded the equilibrium concentration of water in
ps.
silica glass may be as high as 0.22% H 2 0 . probably present as internal SiOH .
Let us return to the behavior of soluble silica in water. When the solution is hfghly
supersaturated and insufficient solid silica surface is available to permit rapid
deposition of soluble silica. new small nuclei particles are formed by intercondensa_
tion on monomer and low polymers. Silica is also deposited on these until supersajjj,
ration is relieved.
It is in this manner that colloidal particles of silica are formed. These. in turn.
may be aggregated to form silica gel or may be laid down as opal. both of which are
highly porous with an extensive internal surface covered with SiOH groups. Thus
"hydrated" silicas are formed. Very slow deposition may produce quartz. .
I'.
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I.
Thermodynamics of the System
\
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The heat of formation of silica by the reaction
)
\
Si(c) + O 2 (g)
{;.
SiC: (s)
was reported (10. II): ~H~ISOK ... - 217.5 == 0.5 kcal mole':' i for alpha quartz. and
-215.9 0.3 for amorphous silica.
Greenberg and Price (12) give somewhat different estimated values:
I\
,
j
I
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~:.
Alpha quartz (q)

Colloidal silica (cs)
Vitreous silica (vs)
'1 '
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1
~
AF
(cal mole:")
HfuaoK
(cal rncle ")
'J. ",
f .:
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-210.260
-205.570
- 1220 (~Fq - AFcs 200C)

- 550 (~Fvs - AFcs 25C)
for the overall equilibrium
I
I
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f.
,
Greenberg (13) calculated the following values for the thermodynamic functions:
I
I
AH (kcal mole-I)
~F~9S0K (kcal mole ' ')
.;lS~9"oK (cal deg" ' mole:")
Amorphous Silica
Quartz
+2.65 == 0.28
+3.98 == 0.04
-2.82 == 0.50
+ 7.34 0.37
+5.20 0.04
+4.53 0.71
According to these data. the heat of formation of quartz from amorphous solid silica
is ~H = -4.69 kcal mole:", which is .....areatcr than the value -1.78 found bv
. W~'et
/'
!
I1 .
~
..
1.
and Deposition of Silica
mcenrration of water in
ir
11 SiOH groups.
:n the solution is highly
lable to permit rapid
med by intercondensa1 these until supersatu-
irmed, These. in turn,

ipal, both of which are
h SiOH groups. Thus
rce quartz.
r~'Silica-
Wat.r System
a1. (14). The latter is closer to the value 0.54 :I: 0.2 more recently calculated by
Cochran and Foster (15).
Other reported values for the above hydration reaction of amorphous silica were
given by Morey, Fournier, and Rowe (16), who found
Kitahara (17a) measured the solubility of amorphous silica between 9 and 100C
and calculated AHa.o K .. 3.2 kcal mole:".
Walther and Helgeson (17b) calculated the thermodynamic properties of aqueous
silica and the solubility of quartz and its polymorphs over a wide range of temperatures and pressures. The thermodynamic constants derived from all available data
were evaluated as follows:
Constant
Entropy, So (cal deg " mole-I)
Volume, VO (em! rnole ")
Gibbs free energy, AG (cal mole:")
Enthalpy, AH (cal mole:")
Alpha Quartz
Amorphous Silica
9.88
22.69
-204.65
-217.65
14.34
29.0
-202.89
. -214.57
'or alpha quartz, and

Coefficients were also given with equations for calculating the values over a wide
range of temperatures and pressures.
.
alues:
Relating Particle Size and Composition

. AFcs 200C)
. AF c 25C)
/narnic functions:
Quartz
+ 7.34
+5.20
+4.53
:I:
:I:
:I:
0.37
0.04
0.71
.rphous solid silica

I f(\""d by Wise et
In most sols that consist of discrete spherical particles of amorphous silica, the
interior of the particles consists of anhydrous Si02 with a density of 2.2 gem -'. The
silicon atoms located at the surface bear OH groups which are not lost when the
silica is dried to remove free water."
The relation of particle composition to particle size can be calculated purely from
geometry and densities of the components. Let
.
.
.
n, = total number of silicon atoms in a particle
n, = number of silicon atoms at the particle surface
d . = diameter of particle on anhydrous basis (nm)
d" ~ diameter of hydroxylated particle (nm)
x = ratio of SiOH groups to total Si atoms
= ns/n t assuming one OH per surface silicon
w ... weight of one anhydrous Si0 2 particle (grams)

WIt
weight of one surface hydroxylatcd particle

= average number of silicon atoms across the diameter of a particle
.--.;.
10
..
surface had decreased and the particles have grown to a certain size. Further spon-
t.
.,I
t~
I
taneous changes are unlikely to occur.

One point that has not been considered in the foregoing discussion is that the
energy values have been generally determined on types of silicas that have already
reached a relatively stabilized state of particle growth. On the other hand. for much
finer silica, for example, with a specific surface of more than 600 m Z g-l, the radius
of curvature of the surface is then less than 25 A, and the silanol groups must be
spread apart so that less hydrogen bonding can occur between neighboring hydroxyl
groups. In turn. it might be expected that this would increase the heat of "wetting,
decrease the heat of dehydration, and decrease particle density and surface energy.
Under these conditions, it is certain that particle growth occurs with decrease in the
radius of curvature, but energy data on such materials have not been obtained,
particularly in regard to surface energy of the silanol-water interface.
,J .
SOLUBLE SILICA-MONOSILICIC ACID
I.
I,
1
1.
1
The soluble form of silica is monomeric, containing only one silicon atom and
generally formulated as Si(OH). This is often called monosilicic acid or orthosilicic
acid. The state of hydration is not known. although at high pressure there is some
indication that one water molecule is linked to each OH group, probably by
hydrogen bonding, so the hydrated molecule is represented by Willey (20) as
Si(OH: OH z).'
The structure of monosilicic acid is assumed to involve silicon coordinated with
four oxygen atoms as in amorphous vitreous silica and in crystalline quartz.
Although there are rare minerals such as the stishovite form of SiO z (21) or thaumasite (22), in which silicon is coordinated with six oxygen atoms, silicon in most
oxides and silicates is surrounded by only four oxygen atoms. If the monomer had
the structure HzSi(OH)., one would expect it to be a strong acid like the analogous
HzSiF., but in fact it is a very weak acid.
It is essentially non ionic in neutral and weakly acidic solution and is not
transported by electric current unless ionized in alkaline solution . .lt is not salted out
of water nor can it be extracted by neutral organic solvents.
It remains in the monomeric state for long periods in water at 25C, as long as
the concentration is less than about 2 x 10 -3 M. but polymerizes. usually rapidly. at
higher concentrations. initially forming polysilicic acids of low molecular weight and
then larger polymeric species recognizable as colloidal particles.
The question often arises as to whether the term "soluble silica" should include
the low polymers such as tetrarner or decarner, which are classed as "oligorners." It
becomes a matter of definition. "Soluble" materials have been recognized as those
that pass through a dialysis membrane. whereas colloids do not: but even though
membranes can now be made with pores sufficiently small to separate dextrose from
sucrose. we think of sucrose as being "soluble," On the other hand. sucrose is certainly not colloidal.
For the purpose of this book. the following terminology is used:
~--...;;.-.-.-
Deposition of Silica
size. Further spon-
Soluble silica (or monosilicic acid). Si(OH)4'

Polysilicic acid (oligomers). Polymers with molecular weights (as Si0 2) up to
about 100,000, whether consisting of highly hydrated "active" silica or dense
spherical particles less than about 50 A in diameter.
Colloidal silica. More highly polymerized species or particles larger than about 50
A, although sometimes down to 10-20 A.
Silica sol. May refer broadly either to polysilicic acid or colloidal silica.
cus.. is that the

that have already
ier hand, for much
m2 g the radius
01 groups must be
ghboring hydroxyl
ie heat of wetting,
nd surface energy.
lith decrease in the
lot been obtained,
Ice.
r
',
11
The arbitrary borderline of 50 A or mol. wt. 100,000 is based on the general

observation that below this point the polymer species are generally unstable, having
only a transient existence owing to gelling or particle growth.
Also, as has already been shown, it is below this size range that less than half of
all the silicon atoms are present as Si02 that is, as "silica," whereas more than half
are each associated with at least one hydroxyl group. The term "silicic" acid is thus
justifiable.
The preparation and reactions. for example. polymerization. of dilute solutions of
monosilicic acid are further described in .Chapter 3. Meanwhile, some of its characteristics are noted, as follows, prior to discussing solubility:
silicon atom and

acid or orthosilicic
.sure there is some
'oup, probably by
Jy Willey (20) as
1. It is characterized by its rapid rate of reaction with molybdic acid to form the
yellow silicomolybdic acid.
2. It is generally inert in neutral solution if the concentration is below the saturation
level with respect to amorphous silica. Thus it is almost universally present at a
concentration of a few parts per million in most natural waters and in living
organisms.
3. It combines with metal ions to an increasing degree with increasing pH, thus
reducing the concentration of free monosilicic acid. (Ferric and uranyl ions react
at a pH as low as 2, whereas most other metal ions combine only at higher pH.)
4. Above pH 9 it is ionized first to (HO)3SiO - or at still higher pH to (HO)2Si022-.
The first equilibrium constant (13.23) is approximately (25C)
c. dinated with
crystalline quartz.
Si02 (21) or thauns, silicon in most
the monomer had
like the analogous
lution and is not

.lt is not salted out
[(HO)3SiO-]
[OH-] [Si(OH)4]
t 25C. as long as
usually rapidly. at
ilecular weight and
1.5
104
. or
[(HO)3SiO-] [H -]
ca" should include

as "oligorners." It
ecognized as those
t: but even though
.rate dextrose from
LOd. sucrose is cer-
[Si(OH)4]
Even though the silica solution is neutral. if it is passed through a bed of strongbase cation-exchange resin in the free-base form. the soluble silica in contact with
the resin is ionized and is then held as silicate ions. In a mixture of Si(OH)4 in
equilibrium with colloidal silica particles at pH 7-8, the particles bear a negative
charge. According to Goto, Okura, and Kayarnu (24) electrophoresis and trans-
.,
.l.
....
port studies show that the colloid. not the "molecularly soluble" Si(OH)., is the
charge carrier. When the mixture is passed through a mixture of strong-bas'
anion- and cation-exchange resin, monosilicic acid is removed. but not the
colloidal particles. [After a time the particles dissolve surticiently to reestablish
the equilibrium concentration of Si(OH).]
5. It is converted to H 2SiF. by reaction with HF in aqueous solution:
;I'
.
til:
,
'
l:
--The Occurrence. Dissolution. and Deposition of Silica
12
~ ...
. :.
!;.,. ~"
n
~ .
t!r..
"1( :'
Si(OH).
+ 6 HF
== 2 H+
+ SiFi- + 4 H20
6. It is converted to a complex anion by reaction with o-dihydroxy aromatic compounds, such as catechol, in neutral solution:
Si(OH).
+ 3 o-C 2H.(OH)2 + 2 NH.+ + 20H-
(o-C 2H.02)3Sj2- + 2 NH. + + 8 H20
Volatility in Steam
Although Si(OH). is nonvolatile at ordinary temperature and polymerizes quickly
when heated, nevertheless at elevated temperature and pressure in'water its solubility
is greatly increased and it can exist in equilibrium as the vapor phase in the steam,
as shown by Kennedy (25). This is of importance in very high pressure boilers in
power plants where deposits build up on turbine blades unless all silica is remover
from the feed water. Brady (26) supposes the volatile species is Si(OH). 0,.
(HO)3SiOSi(OHh. Astrand (27) found that volatility increased with decreasing
alkalinity in experiments conducted up to 350C and 300 atm. This. of course. suggests that Si(OH). is more volatile than the silicate ion. Wendlandt and Glemser (28)
reviewed evidence from earlier workers and calculated the equilibrium constants
involved whence the species in the vapor were related to the density of the water
vapor:
. ,
.. I.
I
Quartz
Gas Density Range (g em -3)
Si0 2 + 2 H20 == Si(OH).

2 Si0 2 + 3 H20 == (HO)3SiOSi(OH)3
Si0 2 + H20
== OSi(OH)2
Up to 0.05
Up to 0.45
Above 0.65
Similarly. Martynova, Fursenko, and Popov (29) found that in a solution saturated with soluble silica at 263-364C about a third of the silica in the vapor was
present as disilicic acid, whereas in the range lSI-223C it was all monomeric.
Heitmann (30) concluded that deposition in turbines was minimal if the silica
concentration was less than 0.01 ppm. iron concentration less than 0.005 ppm. and
the conductivity less than 0.1 micromho cm -I. According to Heitmann's measurements (3 I). the silica concentration in the vapor phase ranges from O. I rng kg -I r
400C to 5 mg kg:" at 600C at a pressure of 0.3 kg em -2, but increases to mor.. _
than 100 mg kg -I under an applied pressure of 300 kg ern -2.
isition of Silica
,i(OH)., is the
.r ~"'ng-base
b, lot the
to reestablish
romatic com-
erizes quickly
r its solubility
in the steam,
ure boilers in
:a ie removed
H). or
th decreasing
,f course, sug. Glemser (28)
urn constants
of the water
~-
' -.,
r,
: (g cm -3)
"
:'~.
~ -.
solution satu.he vapor was

meric.
I if the silica
~05 ppm, and
nn's measure.1 rn~. kg-I at
ea.
0 more
_ _ _ _ _ _t;;...'
"'';--'..
13
Soluble Silica in Nature
Silica is constantly dissolving and precipitating over a large part of the earth's surface. The sedimentary cycles have been described in complex detail by Siever (32).
Soluble silica is mainly derived from the weathering of minerals which, in some
cases, results in amorphous silica residues that then dissolve. Very little can come
from the "sands of seashore," or quartz, which is soluble to only a few parts per
million; furthermore, the rate of dissolution is extremely slow. River waters range
from S to 3S ppm Si0 2, a few up to 7S ppm, and by the time they reach the sea may
range from 5 to 15 ppm. Seawater varies widely but the silica content may range
from 2 to 14 ppm (33). However, Lisitsyn and Bogdanov (34) report that surface
waters in the Pacific Ocean contain only 0.0001-0.3 ppm Si02 Plankton convert
6 X 10' tons Si0 2 from soluble to suspended form each year, but this is only 0.16%
of the available silica.
In addition to the silica carried into the sea by fresh water, additional soluble
silica comes from the suspended colloidal clays and related minerals. Tests show
that common colloidal silicates like clay will dissolve in seawater sufficiently to give
a silica concentration of 10 ppm (35).
Concentrations of silica of around 2 ppm were reached in dilute salt solution with
mica and kaolin and up to 15 ppm with montmorillonite (36). When seawater was
enriched with soluble silica to 25 ppm Si02 , it remained at that level for a year in the
absence of these minerals, but when the latter we~e then added, the silica was
removed from solution down to the 2-15 ppm level that was reached when the
minerals alone were added. Since many ocean waters contain 2-10 ppm Si0 2 , it is
possible that this value is reached as the equilibrium solubility of colloidal aluminosilicate in suspension. The above experiment is consistent with the fact that in pure
water, pure amorphous silica dissolves to give a concentration of monosilicic acid of
100-110 ppm, but in' the presence of polyvalent metal cations such as iron, aluminum, and other metals, colloidal silicates are formed with a much lower solubility
with respect to monosilicic acid. lIer (37) has shown that soluble aluminum reduces
the solubility of amorphous silica from about 110 to less than 10 ppm.
Willey (38, 39) has studied the natural interaction of soluble alumina and soluble
silica in 0.6 N sodium chloride solution. Addition of aluminum ion to 200 ppm
Si(OH). retards polymerization. Probably there is formed a colloidal complex which
reacts as monomer when put into the strongly acidic molybdate reagent. A very low
concentration of soluble silica also causes the precipitation of alumina.
Soluble silica as determined by the molybdate: method is not necessarily present as
Si(OH). Bogdanova (40) reported that in natural waters that contained only about 5
ppm total silica, 4-9% of the silica was polymeric but was converted to monomer by
acid. It is most likely that the "polymeric" silica was actually very small colloidal
particles of aluminum silicate that liberated monomer when acidified..
Silica is continuously removed from seawater by biochemical processes. Diatoms
and sponges as well as plants remove silica which is stored within the organism.
Although Calvert (41) believes that the concentration of silica in the sea is mainly
controlled by biological activity, Harder (42) reports that amorphous hydroxides of
AI, Fe, Mn, or Mg can react with and precipitate soluble silica, thus reducing the
concentration to as low as 3 ppm. Both processes are no doubt operative.
-'.;..... -
-The Occurrence. Dissolution. and Deposition of Silica
14
Amorphous silica is probably more soluble in seawater at great depths owing to

the higher pressure. Willey (20) and Jones and Pytkowicz (43) found that at about
OC, the solubility increased with pressure as follows:
Willey (OC)
-'
Ib in. -2
ppm Si02
15
4,000
8,000
12,000
18,000
64
74
80
85
94
"
Jones (2C)
Ib in.- 2
ppm Si02
15
56
7,500
62
15,000
70
The salt at this concentration no doubt promoted more rapid establishment of equilibrium but would have little effect on solubility.
Hot springs in some areas produce a supersaturated solution of silica. Knowing
the solubility of quartz, Fournier and Rowe (44) have shown that the total silica
content of the water permits an estimate of the subterranean temperature at which
the water has become saturated with respect to quartz, which is the major phase that
usually determines the solubility. Typical results are as follows:
..
Dissolved Silica
(ppm)
660 .
425 .' .
245
.'
I.
.
:>
,-
j .
Estimated
Temperature (OC)
Maximum Measured Temperature

in Drill Hole (0C)
246-252
215-220
178-180
250
220
170
~-
The method is, of course, not dependable if the water encounters previously
deposited amorphous silica at any point. Also, the loss of water as steam must either
be prevented or taken into account.
. Major studies of silica in geothermal waters have been made in 1956 by White.
Brannock: and Murata (45) and in 1970 by Fournier (46). all of the united States
Geological Survey. Detailed analyses of waters from Yellowstone National Park,
Wyoming, have been published by Rowe, Fournier, and Morey (47).
Soluble silica is found in essentially all plants and animals. For example. human
blood contains I ppm. Ingested monosilicic acid as an undersaturated solution
rapidly penetrates all tissues and body fluids and is excreted apparently without any
effect (48). Plants, especially grasses. including the grains and rice. take up silica and
deposit it in the tissues as characteristic microscopic amorphous opaline particles.
which are later found in the soil and in the intestinal tracts of grazing animals (49).
The widespread occurrence and possible role of silica in living systems are more fully
discussed in Chapter 7.
In regard to the weathering of soils. it is noted that aluminosilicates (clays)
. undergo weathering in the tropical regions with dissolution of silica, leaving a .-'
residue high in alumina (bauxite) whereas in colder regions alumina seems to be
removed preferentially, leaving more highly siliceous residues (50).
....
15
Phases of Silica
sition of Silica
A possible explanation is that in the tropics the decomposing vegetation produces

tannins and other catechol-like materials that are known to dissolve silica in neutral
solution. In colder regions, .less organic matter is likely to be present and the pH
may be lower because more dissolved carbon dioxide is present, so that alumina is
preferentially dissolved.
ths owing to
hat '1bout
PHASES OF SILICA
Since different phases of silica exhibit different solubility behavior, they are briefly
described. By far the commonest crystalline form is quartz, the main constituent of
common sand. However, under certain conditions in nature and in the laboratory,
other forms are produced. These forms in turn may be divided into the following
classes:
nent of equi-
1. Anhydrous crystalline Si02

2. Hydrated crystalline Si0 2xH 20.
3. Anhydrous amorphous silica of microporous anisotropic form such as fibers or
sheets.
4. Anhydrous and hydrous amorphous silica of colloidally subdivided or
microporous isotropic form such as sols, gels, and fine powders.
:a. Knowing
e total silica
ure at which
or phase that
S. Massive dense amorphous silica glass.

Temperature
Of these, 2, 3, and 4 exhibit extensive external or internal surfaces and are thus
pertinent to the present study.
(0C)
Anhydrous Crystalline Silicas

Sosman (51) classified the more common phases as follows:
s previously
1 must either _
Thermodynamically
Stable at Atmospheric
Pressure
;6 by White,
mited States
tional Park,
Quartz low
Quartz high
Tridymite S-1
Tridyrnite S-II
Tridyrnite S-lIl
Tridymite S-IV
Tridymitc S-V
Tridyrnite S- VI
Tridyrnite 1\1:1
Tridymitc M-I r
Tridymitc M-1I1
Cristobalite low
Cristobalitc high
nple, human
ted solution
without any
up silica and
ne particles.
mirnals (49).
-e more fully
cates (clays)
a, l-uving a
se,
to be
_ _ _ _ _ _ _---..J:.
"
Thermodynamic
Stability Range (OC)
To 573
573-867 - tridyrnite
To'64
64-117
117-163
163-210
210-475
475-IHO - cristobalite
To 117
117-163
Above 163
To
~72
272-1723
16
The different forms of quartz. tridyrnite, and cristobalite are transformed spontaneously with temperature so that from the standpoint of solubility there are only
the three phases to be considered.
The next group of three phases are those formed only under conditions of high
temperature and pressure. '
Thermodynamically Stable Range
Therrn odynam ically
Stable at High Pressure
:! .
't .
rI '
(
Keatite
Coesite
Temperature (OC)
400-500
From 300
To
1700
1200-1400
Stishovite
Pressure (kilobars)
0.8-1.3
15
40
160
r
L
E
i
I
L
r
I'
Surveys of these phases and their properties have been published by Fronde! (52).
Sosman (53). and Fldrke (54). Wells relates the structure of the different forms of
silica to various crystalline silicates (55).
Quartz, the commonest phase found in nature. ranges from huge crystals. to amorphous-looking powders a few microns in size. to shapeless masses of chalcedony agate
or flint consisting of densely packed. interlocked microscopic crystals. The
transformations between the three common forms and vitreous silica is as follows:
quartz
tridymite
147QOC
~
~'.
cristobalite
vitreous
t',
.!~
.j'
.'
j
1
i
f
I
,,
~ . .
f
j .;
i '
~
e
"
;;
.";
L.
i .
.,
.t
The transformation to tridymite apparently requires traces of certain impurities or

mineralizers.
The three phases metastable at ordinary pressure were recognized only recently.
Keatite was discovered by Paul Keat (56) in 1954. and its formation via cristobalite
and transformation to quartz were studied by Carr and Fyfe (57). Hoover (58), in a
patent filed in 1954. described the preparation of a very similar if not identical
material from "silicic acid". that is. hydrated amorphous silica powder. by heating it
in water at about 3000 atm pressure and 500-625C in the presence of about 1%
alkali based on silica.
Coesite was discovered by Coes, in 1953 (59). It is made from amorphous silica in
the same temperature range as for keatite, but at 10 times the pressure and with
weakly acidic catalysts such as boric acid or ammonium chloride (59). It was found
in nature in 1960 at Meteor Crater, Arizona. apparently formed under the high
temperature and pressure conditions of the im pact.
Similarly. stishovite was first made in the laboratory in 1961 by Stishov and
Popova (60) and discovered in Meteor Crater by Chao. Shoemaker. and Madsen. in
1962 (61). A most interesting story of the isolation of substantial amounts of coesite
and stishovite from the crater is told by Bohn and Stober (62.63).
There arc also some unusual anhydrous crystalline forms. as follows (64).
\.
~-_.
:ion of Silica
med spononly
re
ft - - :
ons
of high
mge
kilobars)
1.3
5
o
o
'ondel (52),
nt forms of
Is. to arnoredony agate
/stals. The
'ollows:
17
Phases of Silica
~
Silica W is a fibrous crystalline silica with a density of 1.97 g em -, described by

Weiss and Weiss (65), formed in the gas phase by oxidizing silicon monoxide vapor
at 1200-1400C and deposited as paperlike films. It is unstable above about 1400C.
It is fairly stable in dry air, but is converted by moisture to amorphous hydrated
silica, still retaining a swollen fibrous form. In this transformation. only about 0.08
mole of H 20 is taken up per mole of Si0 2, forming SiOH groups. Silica W can have
no true equilibrium solubility in water. Instead, it must decompose rapidly in water
to give monosilicic acid. When the powder is suspended in water and within 2 min
centrifuged to obtain a clear solution. then titrated with NaOH solution at pH
10.2-10.5 (thymolphthalein). 2 equivalents of base are required per mole of Si0 2 in
solution (66). After the solution has been aged for 1 hr, only 0.1 equivalent is
required .. Initially. therefore, the solution must have been supersaturated with
Si(OH)4, which when titrated with base, requires 2 equivalents of alkali. but after the
monomer has polymerized. much less alkali is required to neutralize the surface
acidity of the colloid. If the solution is mixed with silver salt an orange. light-sensitive AgSiO, is precipitated. In absolute methanol the fibers swell and form a
polymeric methyl ester containing one methoxy group per silicon atom which, when
heated in vacuum at 300-500C, yields cyclic methyl esters [(CH,OhSiO]II.'.u,
_When hydration of the fiber by water is followed by suitable technique under the
microscope it can be seen that the reaction starts at the end of the fiber and proceeds
rapidly along its length as the crystal swells and is converted to hydrated amorphous
silica:
vitreous -
npurities or
Iy recently.
cristobalite
er (58). in a
ot identical
'y heating it
f about 1%
ous silica in ...
re and with
t was found
er the high
Stishov and
Madsen. in
lS of cocsitc .
4).
Anhydrous fibrous silicas formed in connection with high temperature metallurgical operations were noted as long ago as 1852 by Schnabel and 1859 by Rose.
Soft. silky fibers of more than 98% Si0 2 were classed as aphanitic (invisible) silica.
.' and also known as lussatite. Around 1910. in the mouths of electric furnaces making
silicon carbide. a sort spongy gray deposit called "elephant's ear" was identified as
microfibrous amorphous silica (67). It is likely that all of these were silica W.
. Melanophlogite, a long known but strange and little understood mineral. is found
in volcanic sulfur deposits in Sicily. Skinner and Appleman reviewed its history and
showed that it was a new cubic polymorph of silica (68). It has a cubic. very open
structure. containing 92.4% SiO; and about 5.7t:(. SO, (2.2SC;c as sulfur). 1.2%
carbon. and 0.81 % hydrogen. The density is 2.052 0.013 g COl -'. The initial
refractive index is 1.467. but when these volatile materials are driven off by heating.
the crystalline silica residue has a refractive index of 1.425 0.002 and a density of
1.99 g COl -'. which arc substantially lower than those of amorphous or glassy silica.
The silica crystal is stable up to about 900C. above which it changes into cristo. balite. However. ,vhen crystals arc subjected to grinding in a mortar at ordinary
temperalure. the open structure collapses to fine-grained quartz. Its solubility h~IS
not been measured. and it is doubtful if il can ha v c a true equilibrium solubility in
-~
18
I,
I'
I.
I,
. '; .
,
J.
- The Occurrence. Dissolution. and Deposition of Silica
water. The heat-purified material will probably react with water rapidly to give a
highly supersaturated solution of Si(OH)4' similar to the behavior of silica W.
The nature of the hydrocarbon and sulfur content is still not clear. However. calculations based on density data would seem to support earlier suggestions that the
sulfur must be present as S03 or H 2S0 4 within the silica lattice. The optical characteristics of the mineral show that the organic matter occurs in films between the
faces of the crystals. On the other hand, calculations based on the difference in
densities of the original mineral and the pyrolyzed silica crystals show that the sulfur
compounds at least must be within the crystal lattice. Kamb offers evidence (69) that
the silica structure is a clathrate with S02. H 20. and CH 4 in the lattice analogous to
the known 12 A gas hydrates of water, 6X .46H 20, where X is CH 4, H 2S, CO 2, S02.
C12 etc., and in fact the structure is the complete analogue of 6C1 2 H 20.
Silica 0 crystallizes from lithium silicate glasses during devitrification at low
temperature. It has a crystal lattice similar to quartz and may simply be "high
quartz" stabilized below 573C. the normal transition temperature, to low quartz
(53. 70) by inclusions of metal ion impurities. The only way pure material can be
obtained is by neutron bombardment of quartz.
Silica X is a microcrystalline form obtained as spherical aggregates of radial
fibers up to 12 microns in diameter by heating pure amorphous hydrated silica
("silicic acid") with 2% KOH solution in sealed tubes at 150C for a few weeks. The
refractive index of 1.484 0.004 is close to that of cristobalite. It is anhydrous.
maintaining its structure up to about 600C. above which it is converted to cristobalite (71a. 71b).
Silica lite. a very unusual new form of anhydrous crystalline silica hornogeneousl..
permeated by uniform pores 6 A in diameter and having a density of only 1.76 g
ern -3, has been described by FJanigen et al. (71 c) and patented by Grose and
Flanigen (71d). The pores constitute 33% of the volume of the crystal. A most
remarkable feature is that this silica is hydrophobic; the pores are lined with oxygen
atoms that are highly hydrophobic and organophilic or oleophilic. Thus the crystals
preferentially absorb hexane in the presence of water. which does not enter the pores
even at saturation pressure.
This type of silica is made first as a crystalline quaternary ammonium silicate. for
example, tetrapropylammonium silicate: (TPA).O .48Si0 2 H 20. It is then heated to
red heat to remove the organic matter and water. leaving uniform cylindrical channels throughout the three-dimensional crystalline framework of silica.
A similar but even more hydrophobic. anhydrous. microporous crystalline silica
was obtained by Flanigen and Patton (7le) by conducting the hydrothermal synthesis in the presence of some ammonium fluoride. which facilitated the formation of
crystals 2-15 microns in size at only 100C rather than at the higher temperature
and pressure required for making silicalitc. After crystallization from solution a
typical composition was about 88% by weight of silica. 11.0% tetrapropylarnmonium
oxide. and 0.9% fluorine, but after calcination at 600C the porous crystalline
product was essentially pure Si02 (containing less than 0.1 % fluorine) with a mean'
refractive index of 1.39 0.01 and a specific gravity of" 1.70 0.05. These value"
arc the same as those of silicalite and fall on the same curve with other forms 0
silica in Figure 1.1.
"'~
-..,.
on of Silica
to give a
W
veve. callS
that the
.al characetween the
Terence in
: the sulfur
e (69) that
alogous to
CO2, S0 2.
on at low
, be "high
.ow quartz
-ial can be
; of radial
ated silica
veeks. The
anhydrous,
I to cristoog,
usly
mly 1.76 g
Grose and
J. A most
ith oxygen
he crystals
r the pores
Relation Between Density and Refractive Index
The anhydrous crystalline phases were arranged in order of increasing density and
refractive index, and found to have a linear relationship, by Skinner and Appleman
(68). Stishovite falls on the s~me line (72) (Figure 1.1).
It will be noted that the line for silica polymorphs has been extrapolated to meet
that of two forms of water. It seems odd that neither of these lines extrapolates to a
refractive index of 1.0 (for a vacuum) at zero density.
The analogous structures of Si0 2 and H 20 have been compared by Kamb (69),
who points out that the ratios of the densities of the various phases or polymorphs of
Si0 2 and water to those of the corresponding forms of Ice I and cristobalite are very
similar, and for each type of silica there is an ice counterpart with the same type of
crystal structure.
Hydrated Crystalline Silicas
Until the advent of X-ray diffraction, it was not clear whether solids containing only
silica and water were definite compounds. that is, had a definite stoichiometry or
structure. In 1905, Tschermak (73) believed that he had obtained definite hydrates
based on ratios of silica to water corresponding to Si0 2 : 2 H:O, 2 Si0 2 : 2 H20, 3
Si02 : 2 H20 , etc. by carefully leaching the metals out of certain crystalline silicates
and drying in air. Then Van Bemmelen (74) and Theile (75) gave evidence that no
definite silicic acids were thus produced.
Nevertheless, since then numerous instances have been found where definite
crystalline materials. having characteristic X-ray diffraction patterns and crystal
structures. have been made by extracting the cations from certain crystalline silicates
.
with a c i d . '
2.0
x
o
silicate, for
heated to
rical chan-
19
Phases of Silica
>
i=
illine silica
nal syntherrnation of
emperature
solution .1
irnmoniurn
crystalline
ith a mean
11:S" values
:r .
s of
COESITE
~ 1.5
QUARTZ
0::
l.l.
KEATITE
W
0::
' - - - - - - CRIST06:'UTE
<l:
W
TRIDYMiTE
::E
AMORPHOUS
' - - - - - - MELANOPHLOGITE
to
2
DENSITY
Figure 1.1.
G -CM-)
Density versus refractive index of various forms of silica.
20
I
f
,j
I~
-,
i
I
11
....
! :,;
<
.<
1:
1
\
Jj
I
1
tI
)
>
"
'
..~
:
"
-:-- -.-
Th~ Occurrence. Dissolution. and Deposition of Silica
There is no instance of a hydrated silica being crystallized directly from a solution

of silica and water. Yet there is the peculiarity that certain hydrates. once formed,
exhibit what seems to be a characteristic solubility. implying that since an equilibrium is reached, silica must pass from solution to the solid phase as well as the
reverse. However, the data are conflicting.
Sodium disilicate, Na 2Si20s , may be converted to hydrated silica. Thus !?y treating
the silicate with concentrated cold acid, washing out salts with water and water with
acetone, and drying in vacuum at 40C, a crystalline "disilicic acid" is obtained (76,
77). Such layerlike structures are termed "lepidoidal" (scalelike) or phylloidal (Ieaflike). Liebau distinguished two types of layer structures. They are internally
hydrogen bonded and exhibit only weak acidity (78).
Crystalline Na:Si0 34H20 gives another form of silica. Here treatment with dry
HCI gas at -25C gave definite silica hydrates containing 2.0. 1.5, and 1.0 moles of
H 20 per mole of Si02, as the product was dried under vacuum at progressively
increasing temperatures. The silica was anhydrous at 90C (79).
From gillispite, BaFeSi40 10 , Pabst (80) obtained flakes of crystalline hydrated silica consisting of Si 40 l o 4 - ions linked into sheets with the composition 4 H 4Si 40 l o +
2 H 20; density calculated 2: 15, found 2.05; refractive index 1.45 0.0 I.
From sheetlike KHSi 20S ' Le Behan, Kalt, and Wey (81) obtained by treatment
with a dilute acid a still different leaflike disilicic acid, H 2Si 20 s .
From the zeolite mordenite, Chen and Smith (82) obtained silica having the same
zeoli tic skeleton by repeatedly heating the hydrogen form in steam at 538C and
extracting the liberated aluminum with acid. The pores are apparently lined with
siloxane oxygen bonds and are hydrophobic, retaining high hydrocarbon sorption
capacity.
Chrysotile asbestos, JHO).Mg, .Si40 10 , treated with acid yields fibrous hydrated
silica. By reacting the silica with (CH3)3SiCI as rapidly as it is liberated, it is
converted to the trimethylsilyl derivative which. in organic solvent. is a highly
swollen mass of ribbons of silica only a few angstroms thick. When solvent is
removed the ribbons roll up again into tubes or fibers with a structure similar to that
of the original fibrous mineral. The fibrous product by X-ray diffraction shows a
prominent 15 Ad-spacing (83).
Magadiite, NaSi 70 133H 20, is a mineral first found in Kenya by Eugster (84) and
later in Oregon and California. However, a similar structure had been synthesized
years before by McCulloch (85) by prolonged aging of a mixture of microamorphous
silica and alkali (Si0 2 : Na 20 = 4-5) in concentrated suspension at 100C. lIer (86,
87) prepared it in good yield from a mixture of sodium silicate and colloidal silica
(Si0 2 : Na 20 = 4.6) and made a number of derivatives by esterification and ion
exchange. McCulloch reported the product to have a Si0 2 : Na 20 ratio of 9.4, and
IIer found 8.0. whereas the ratio of magadiite was l-l.O. However. lIer found his
material. when treated with acid, to exchange all the sodium for hydrogen ions. and
the crystalline silicic acid had the same X-ray pattern (within 2C;C d-spacings) as
reported by Gude and Sheppard (88) for "silhydrite." 3Si0 2 H~O. which is a
crystalline silicic acid found in association with magadiite. The acid obtained by
leaching magadiite was reported to be somewhat di ffercnt. The structure of rnaga- '; .....~-
-~
...
ion of Silica
Phases of Silica
a solution
ce r~"rned.
an _..ilibNell as the
diite has been further studied by Brindley (89). McAtee, House. andEugster (90).
Bricker (91a) measured the stability constant:
-14.3
by treating
water with
tained (76.
oidal (leafinternally
it with dry
o moles of
ogressively
/drated sil-{.Si.0 1o +
;..,
i~
treatment
21
,.
and also calculated the free energy of formation as j.Go = -1762.2 kcal mole",
where G = standard molal Gibbs free energy.
There is probably a family of similar high-silica crystalline silicates having characteristic crystal structures. and from which corresponding crystalline silicic acids
could be obtained. Thus, along with magadiite, is found kenyaite, with a Si02: Na20
ratio of 22; its formula is N aSi l1 0 2o.(OH). 3H 20 (84). lagaly and co-workers (91b,
91c) have further described these "phyllosilicic acids" in regard to structure and ionexchange properties (see Chapters 2 and 5).
Lepidoidal silica is a term that has been used in the past to describe silica in the
form of extremely thin flakes or scales. Such silicas are usually hydrated and may
have a crystalline structure or may be amorphous. depending on how they are made.
Three types that have been described are as follows:
I
g the same
D8C and
lined with
n
.tion
5
hydrated
ated, it is
) a highly
solvent is
ilar to that
n shows a
er (84) and
ynthesized
irnorphous
:. lIer (86.
oidal silica
n and ion
)f 9.4. and
found his
1 ions. and
lacings) as
/hich IS a
otained by
:c
uga-
1. A synthetic silica [(Si,O,)Oa](OH), prepared from siloxane [HO~i-~iH]n
...
w
obtained by the hydrolysis of calcium silicide.

2. Sheetlike, crystalline forms of silica obtained by extracting layer-type basic copper silicate with acid (92, 93).
3. Flakelike gels made by freezing sols of colloidal silica or sols of hydrolyzed
HSiCla and oxidizing the product (93).
.
These hydrated silicas are similar only in physical form and are entirely different
in structure. (The type made by freezing is amorphous to Xvrays and is considered in
the following section.) A comparison of the chemical behavior of types 1 and 3 has
been made by Kautsky and Reise (94).
Kautsky and associates (92. 93) have studied in some detail the lepidoidal silica
obtained from a synthetic layerlik e colloidal copper silicate which they formulate as
[(Si,O,)(OH)12][OCuOH]. It has a very high specific surface area similar to the copper mineral chrysocolla (95, 96). which has a specific surface area greater than 300
m2 g", The corresponding silica has ion-exchange properties. but all the original
copper cannot be put back into the structure once it has been removed.
Amorphous Silicas
Amorphous silica may be broadly divided into three types:
I. Vitreous silica. made by fusing quartz.
2. Silica M. an amorphous silica formed when either amorphous or crystalline

silicas arc irradiated with high speed neutrons. The density of amorphous silica
_.~-
,
,
22
increases and that of crystalline silica decreases. It is thermally unstable and is

transformed to quartz at 930C in 16 hr. Actually the silica M from different
crystalline forms may differ slightly from each other. The density is 2.26. as compared with 2.20 for vitreous or microamorphous silicas (53).
3. Microamorphous silica; which includes sols, gels, powders. and porous glasses
which generally consist of ultimate particles less than a micron in size or have a .
specific surface area greater than about 3 m 2 g-l. (These are discussed in detail in
Chapters 4 and 5.)
Frondel (97) states that amorphous silica is not truly amorphous but consists of
regions of local atomic order, or crystals of extremely small size, which by careful
X-ray diffraction studies appear to have the cristobalite structure. Nevertheless. by
ordinary diffraction procedures this material gives only a broad band. with no
multiple peaks as are ordinarily obtained with macroscopic crystals. and is referred
to here as "amorphous."
In nature, microamorphous silicas have either been condensed from the vapor
.phase ejected in volcanic eruptions or deposited from supersaturated solutions in
natural waters and in living organisms. Except for silica deposited in plants or
diatoms, natural microamorphous silicas are generally too impure to permit a
study of solubility. (The formation and properties of natural opal .are discussed in
Chapter 4.)
Microamorphous silicas made in the laboratory can be divided into three classes:
I. Microscopic sheets, ribbons, and liberlike forms obtained by special processes.

2. Common amorphous forms consisting of ultimate spherical particles of Si0 2 less
than 1000 A in diameter, the surface of which consists of anhydrous Si0 2 or
SiOH groups. These particles may be separate or linked together in three-dimensional networks as shown in Figure 1.2:
(a) Discrete or separate particles as in sols.
(b) Coherent three-dimensional aggregates with siloxane bonding at the points of
contact, as in gels.
(c) Voluminous three-dimensional open networks of aggregated particles as in
aerogels, pyrogenic silicas, and certain dispersible silica powders.
3. Hydrated amorphous silica. here designated as a separate class in which most. if
not all, of the silicon atoms each retains one or more hydroxyl groups in the silica
structure. This type of polymeric structure is obtained if monosilicic acid or
oligosilicic acids in water are concentrated and polymerized at ordinary or low
temperature and in slightly acidic solution. It is now believed that under these
conditions the silica polymerizes to extremely small spherical units less than
20-30 A in diameter, which. when concentrated. link together into a three-dimensional gel mass, trapping water in the interstices. which are of molecular dimensions and retain water which can be desorbed only above about 60C.
Ordinarily such structures are not retained because in making sols and gels the pH is \._
--~._.
:ion of Silica
able and is
m
23
Phases of Silica
8
"<rent
26, i1~ comous glasses

e or have a
in detail in
consists of
by careful
rtheless, by
d, with no
i is referred
I
the vapor
ioluticns in
:t plants or
o permit a
liscussed in
I
ee classes:
OCI..
Figure 1.2. Ultimate particles in common forms or colloidal silica. Aggregation is actually in
three dimensions but here represented only in two. A, sol; B, gel; C, powder.
...
of Si02 less
'us Si0 2 or
iree-dimen-
not kept sufficiently acidic nor is the temperature kept below 60C during processing to the final state.
Microscopic Sheer, Ribbon, and Fiberlike Forms
te points of
Sheet or flakelike amorphous silica particles are obtained in various ways:
tides as in
I. Formation at the gas-liquid interface: hydrolysis of gaseous SiF. and

simultaneous polymerization of the silicic acid in water at 100 or OC produced
. opaque "scales" of silica: so does hydrolysis of-SiCI. vapor at IOO"C (98). The
scales appear to be films of silica gel formed at the. gas interface when the
extremely reactive vapors meet the water surface. The remarkably "fluffy"
character of the powder made from SiF. by Jacobson (99) is shown by its very
low bulk density of 0.025 g ern -3 and the fact that it appears to now as water
does. The irregular gel flakes, a micron or so in diameter and perhaps a tenth as
thick, contain 92.86% Si0 2 and 7.14% H20.
.
2. Formation by freezing silica sols: When a solution of colloidal silica or polysilicic
acid is frozen, the growing ice crystals exclude the silica until it remains as a
concentrated sol between the ice crystals and then polymerizes and forms a dense
gel. When the ice is melted the silica is obtained usually as irregular flakes
ich most, if
in the silica
cic acid or
iary or low
rnder these
s less than
iree-dirnenliar dirnen:?
.,
Is L
H is
.
-
..
...
\,;
formed between the flat surfaces of the ice crystals. Lepidoidalsilica formed in
this way from polysilicic acid of low molecular weight has been extensivelv
studied by Kautsky and associates (92-94). The gel structure is of high densit,
owing to the high concentration of the silicic acid before it polymerizes to gel,
and the specific surface area of the microporous mass is around 900 m 2 g-1 so the
ultimate silica particles can only be 20-30 A in diameter. Kautsky reported that
the vacuum-dried powder contained about 10% H 20; if the water was all present
as SiOH groups and each OH group occupied 12.5 A on the surface of the ultimate particles, then the specific surface area is calculated to be 930 m 2 g-1 SiO z'
Kautsky investigated the capacity to exchange hydrogen for copper ions from
solution (0.1 M Cu(NH3)4S03 + 0.3 M NH 40H) in 200 hr. The product
contained one copper atom per silicon (-SiOCuOH) and had surface area (by
BET-method adsorption) of 870 m 2 g ",
3. Leaflets of silicon oxyhydride (HSi0 1. s ) up to 5 mm in diameter are formed when
HSiCl 3 in ether is hydrolyzed by very gradual addition of a theoretical amount of
water. The product appears to "crystallize" when the concentrated ether solution
is evaporated, It is possible the silica forms at the silica-water interface but
remains invisible because of the close refractive index until the ether "evaporates
(l00).
4. Sheets of silica consisting of a single layer of colloidal particles are formed when
silica is coagulated under the influence of cationic surfactants (101). The
mechanism of formation is discussed in Chapter 4.
5. Highly elongated forms of silica, other than libers formed from glass, have bee'
obtained either by conversion from fibrous precursors or by unidirectional craz-
ing or cracking during drying of thin films of sols.
Silicon monoxide has long been known to oxidize to fibrous silica. Nemetschek and
Hofmann (102) investigated the material condensed from vapor from the reaction of
silica and silicon metal. Under the electron microscope it was found to consist of a
mat of remarkable hollow tubes and spiral fibers of amorphous silica less than 0.04
micron in diameter and many microns long. The morphology was compared with the
fibers of halloysite and chrysotile (103).
Silica W, an unstable crystalline silica fiber (65), as previously mentioned. is
converted to amorphous silica fibers by traces of moisture. These are very similar to
those obtained via silicon monoxide.
Fibers of amorphous anhydrous silica. I-50 microns in diameter. grow outward
from an electrically heated platinum surface exposed to nitrogen-diluted SiF 4 and
water vapor at 1100C, according to Haller (104). The mechanism of formation is
unknown. It may be that the silica is being deposited at the base of the fiber simply
because the temperature is highest at the platinum surface under the end of the liber
around which silica vapor is condensing. Once a nucleus of viscous silica is formed it
probably does not wet the platinum, so that surface tension pulls it up into a drop,
the outer, cooler portion of which solidifies and moves away. while more silica is
added at the hotter base. This suggested mechanism is consistent with the observe
I, .-
,I
II
i
~
.
I
.'f
~.,~
:':":
.---~.-.-
on of Silica
Phases of Silica
formed in
ext- .';vely
gh ~ . sity
zes to gel,
: g-1 so the
icrted that
all present
of the ultiz g-1 sio,
ions from
ie product
:e area (by
tion that there are often spherical beads on the end of the fiber and that the fibers
wave about as they are growing.
.med when
amount of
er solution
erface but
evaporates
'med when
101). The
Common Amorphous Forms

The formation and properties of silicic acids. sols. gels. and powders are described in
subsequent chapters in detail, but a brief description of the nature of microarnor.
pho us silica should preface a discussion of solubility.
There are two broad classes, as follows.
~
r
I
"
:;
.:
f'
h: ">een
iona .:raz-
f~
~.
j)::
t..:.
.'
~,
tr.
~!~.
e-
tschek and
reaction of
onsist of a
j than 0.04
ed with the
ntioned, is
. similar to
w outward
SiF. and
rmation is
ber simply
)f the fiber
s formed it
Ito a drop.
re silica is
e r ':rvaj
2S
r;--
t"
":'i"
(".
-.-
::
1. Anhydrous amorphous silica particles formed at high .temperature, such as

"pyrogenic" or "fumed" silicas, are recovered from the gas phase as voluminous,
extremely finely divided powders. They are made in one of the following ways:
(a) Vaporizing silicon dioxide in an arc or plasma jet and condensing it in a
stream of dry inert gas.
(b) Oxidizing the more volatile silicon monoxide in the vapor phase with air and
condensing the SiO z
(c) Oxidizing silicon compounds in the vapor state, such as SiH SiCI or
HSiCI 3 , with dry oxygen or in a hydrocarbon flame.
When water vapor is present the surface of the particles may be partly hydrated
as SiOH groups.
Surface-hydroxylated
amorphous silica particles are nucleated and grown from
2.
aqueous solution supersaturated with monomer. Si(OH). The unique feature of
this system is that, unlike a solution of sugar from which sugar molecules
crystallize unchanged, Si(OH). does not crystal1ize as such. but must undergo a
dehydration reaction to form SiO z This reaction is slow at ordinary temperature,
so that Si(OH). can deposit SjO, on the surface of a growing quartz crystal only
from extremely dilute solution and at an extremely slow rate. If the concentration
of Si(OH). exceeds about 2 X 10- 3 M, condensation to polysilicic acids occurs. as
previously described. and colloidal particles are formed.
Ordway (105) has shown by molecular models that tetrahedral networks of silica
built up by the condensation process from Si(OH)4 are amorphous and are spherical
unless a nucleus of crystalline structure is initially present. However. it is obvious
that if the rate of condensation of Si(OH). onto the crystaline nuclei cannot keep up
with the rate of addition of Si(OH). to the system. the latter will accumulate until
amorphous networks are nucleated.
Under almost all conditions. soluble silica comes out of solution as spherical.
amorphous particles that. depending on concentration. temperature. and pH. remain
as a sol. are aggregated into a gel network. or arc coagulated as a precipitate.
As initially formed, the amorphous particles may contain some uncondensed
SiOH groups within the amorphous SiO z network. but in further processing these
are largely eliminated, leaving only SiOH groups on the surface.
:r.-',,~-
:.r.
-~-
26
!
I
F
,
r
~
Microamorphous silica is not easily crystallized. When an ionic material such as a

salt is rapidly precipitated from a highly supersaturated solution. it may initially be
amorphous. but it rapidly rearranges to the ordered crystalline state. However. in
the case of silica in which bonds are largely covalent, such rearrangement can occur
only at elevated temperature or in the presence of a solvent such as water under
hydrothermal conditions. Silica. in effect, is a polymeric material. Walton (106) has
pointed out why an intermediate amorphous phase is likely to be precipitated if the
material is of high molecular weight or polymeric.
Carr and Fyfe (57) observed that amorphous silica in water crystallizes via cristobalite and keatite to quartz at 335C in 840 hr under 15.000 psi pressure. but in 18
hr at 45.000 psi.
Hydrated Amorphous Silica
. !
).~
~
As will be seen, the highly hydrated silicas. which are generally stable up to 60C,
must be considered separately because they seem to differ in solubility from the
anhydrous or only surface-hydrated forms.
Two solid insoluble hydrated amorphous silicas were made by Signer and Gross
(107) by starting with cyclohexyl esters of the formulas
!
I
.!
and
The first is a ring tetrarner: the second is a cage-like sphere of silica in which each
silicon atom is linked to one ester group. By removing the cyclohexyl groups with
anhydrous HI. they obtained white amorphous powders which were extremely hygroscopic, corresponding to
[(HOhSiO l,r
and
It can be seen that even if the low molecular weight silicic acid counterparts were
initially produced. condensation of silanol groups between adjacent molecules. forming siloxane bonds and water molecules. could occur rapidly. However. the water is
still held so tenaciously that the overall chemical analysis is not changed. while the
mass becomes cross-linked arid insoluble.
Natural opal may contain from 5.25 to 13.7% water. which is locked within the
structure and does not evaporate (108). Opal is generally nonporous in the sense that
it does not adsorb gases or liquids.
Highly hydrated silica gels which retain water tenaciously at ordinary temperature
can be obtained by reacting hydrated sodium silicate crystals with anhydrous acid so
that the silicic acid is liberated and simultaneously polymerized in a very dense state
(109).
Similar gels were obtained by hydrolyzing ethyl silicate in distilled water at 17C
to obtain a sol containing about 0.5% Si0 2 After a few days this became viscous as
aggregates were formed. which then formed a precipitate that was filtered off as a
wet gel and stored over water at 15-17C. Removal of all traces of HCI from this
"
)f Silica
ch as a
all" "~
:vel, .
1 occur
. under
)6) has
j if the
cristot in 18
27
Phases of Silica
ester retards hydrolysis and is not even desirable. Unfortunately, the pH" was not
recorded but was probably below 6 if traces of acid were present (110, Ill). When
the wet gel was dehydrated under vacuum at 11C, a plot of residual water versus
vapor pressure in the range from 7 to 1 torr revealed definite steps corresponding to
2.5, 2.0, 1.5, 1.0, and 0.5 molar ratios of water to silica.
From the vapor pressure of water at each stage of hydration, corresponding to
0.5, 1.0, 1.5, and 2.0 molar ratios, measured at a series of temperatures from 35 to
600C, Thiessen and Koerner found a linear relationship between log p and T.-I, and
calculated the average heat of hydration, h, per mole of water over the temperature
range TI - T2:
h = 2.3R
60C,
im the
Gross
where R
Pili' p/(.
PWI' PW.
gas constant
dissociation pressure of the hydrate at T T 2
"
vapor pressure of water at T h T2
h was 1.2-1.5 kcal mole-I H 20 .

It was mentioned earlier that Greenberg (13) found for the reaction
h
f'
-It
Si0 2(amorphous) + m H 20(l) = H.SiO.(aq)

j,H kcal mole:" = 2.65 0.28
is v..
ely hy-
s were
. form-ater is
rile the
lin the
se that
:rature
reid so
estate
: 17C
ous as
ff ~ - "'
m '.
If one assumes the heat of solution of H.SiO. to be negligible and that m = 2, then
AH per mole of water would be 1.32 0.14, which agrees with the above value
obtained by quite a differentmethod by Thiessen and Koerner.
The formation of definite hydrates in a system now known to be amorphous is difficult to accept. The stepwise rem oval of rnonolayers of adsorbed water from a large
.fixed area of silica surface is more plausible if it can be assumed that the removal of
one layer, by coincidence. corresponds to about 0.5 mole of water per silicon atom.
If this is so. no formation of water by condensation of SiOH groups is involved, and
the above relation to Greenberg's data is only a coincidence.
as is discussed in Chapter 3, it is
Based on what is now known of
- this system.
,
likely that the sol made by hydrolyzing. ethyl silicate contains polysilicic acid or
silica particles that are so small that a substantial fraction of the silicon atoms are at
the surface of the particles and bear OH groups.
Initially, such particles aggregate into short chains to form a very open threedimensional network of gel filling the aqueous phase. As water is removed the structure gradually collapses. but at ordinary temperature there is a layer of water
probably several molecules deep associated by hydrogen bonding to the silanol surface. Thus a hydrated silica gel is obtained from which the vapor pressu re of water is
less than that of liquid water. The stepwise removal of water may correspond to the
removal of successive layers of water molecules from the silica surface. As this water
is removed from between the silica particles the gel structure shrinks and the parti-
..
....-~-
28
cles move closer together until the silanol surfaces corne into contact as alI free
water is removed.
This stage is probably reached in this particular type of gel at the point where
there are 2.75 moles water per SiO z, as shown in Figure 1.3. The water content of
the gel at 2 torr was plotted versus temperature (Ref. 110, p. 171). Since water
removal in the range 200-300C is known to involve dehydration of silanol groups,
the linear portion above 70C represents this process, whereas below this temperature it is only adsorbed water that is being removed. Therefore, the silanol content at
70 0 is about 0.27 moles HzO, or 0.54 OH groups per silicon atom.
From this the specific surface area of the silica can be calculated, since the area
per OH group is about 12.5 Az on a highly hydroxylated surface:
0.54 x 6 x 1023 x 12.5

60 X 10ZO
690 mZg- 1 Si0 2
When water is adsorbed on a silanol surface, there is one H 20 per SiOH group.
Hence a monolayer of water corresponds to 0.54 HzO per Si0 2 Inspection of the
steps in the adsorption curves (110) indeed indicates that each corresponds
approximately to 0.5 HzO per SiO z
Nevertheless, it must be admitted that by this theory it is difficult to explain
definite HzO: SiOz ratios of 1.0 and 0.5 identified in gels made by hydrolyzing
cyclohexyl esters of cyclic tetrasilicic acid, [(HOhSiO].. and of the polycyclic
decamer [(HO)zSi z0 3 ]a as described by Signer and Gross (107), or [(HOhSiO]z from
hydrolysis of SiSz by Schwarz (112).
0.5
0.4
c.;;
o
"N 0.3
:I:
~
a:
0.2
a:
<t
..J
~ 0.1
o
o
100
200
300
TEMPERATURE _OC
Figure 1.3. Bound' water content of hydrated amorphous silica In vacuum at increasing
temperatures. [Data from Thiessen and Koerner (110).)
-~ ..
29
ion of Silica
Phases of Silica
as all free
On the other hand. removal of layers of water from an aluminum oxide surface in distinct steps has been noted by de Boer (113a). Thus the foregoing explanation cannot
be ruled out. since highly hydrated gels made by neutral or low pH and at room
temperature generally have specific surface areas in the range 600-800 m2 g-I.
oirn .. Ilere
content of
ince water
101 groups,
S temperacontent at
Biogenic Silicas
ce the area
JH group.
tion of the
orresponds
to explain
ydrolyzing
polycyclic
iiC" 'rom
increasing
f
1_-'
These are of many types found in widely different kinds of living organisms as
isolated particles. skeletal structures. and surface elements. In most cases, when
freed from organic matter, the silica exhibits characteristic patterns and shapes (see
Chapter 7). Essentially all biogenic silica is amorphous. It often has a substructure
of extremely small particles less than 50 A in diameter which have a surface of
SiOH groups. These are joined together in close-packed three-dimensional structures, some of which are isolated microscopic masses; others are solids permeated by
holes like Swiss cheese; and still others are like an interconnected mass of rods. The
ultimate particles in this size range can coalesce into denser structures as the
intervening pores become finer. Further deposition of silica can obliterate the
particulate appearance and lead to an impervious solid. Thus specific surface areas
observed in biogenic silicas vary widely from several hundred m2 g-1 to very low
values in those cases where the porosity has collapsed until the pores no longer
admit the nitrogen used for the measurement. These wide variations in structure and
porosity are also seen in synthetic silica gels but the latter do not exhibit the characteristic patterns usually seen in biogenic silicas.
The biogenic silica structure must be interpenetrated by organic tissue to effect the
deposition. Also, where the silica plays the role of a stiffening and strengthening
agent it is interlaminated or interpenetrated by biopolymer: in plants by cellulose. or
in diatoms by a protein, silicalemrna.
.
Many microcrystalline silica minerals such as flint, chert, and chalcedony can be
formed from biogenic silica by compaction and microcrystallization. Kieselguhr
(diatomite), which. was originally amorphous, is found in various stages of
transformation. The changes over millions of years can be noted, for example, by
the decrease in solubility and changes in other properties. Furthermore silica
undergoes continuous dissolution and biogenic redeposition in the oceans. Hurd and
associates (l13b-e) studied the properties of biogenic silica of ages up to 40 million
years, with emphasis on differences insolubility, density, and refractive index, comparing these with the values for known crystalline forms. which were thoroughly
reviewed.
Kastner, Keene. and Gieskes (1131) have examined the transformation of
amorphous biogenic silicas in the form of siliceous "oozes" on the ocean bottom to
partially crystalline geological deposits. They reviewed the complex background
literature and gave experimental data showing more rapid transformations when the
silica was embedded in carbonate (chalk). The remarkable 80 million year shrinkage
of the silica skeletons of large sponges to dense round boulders of flint in the chalk
beds of England is probably an example of this phenomenon.
."
30
..
Th_e Occurrence. Dissolution. and Deposition of Silica
THE SOLUBILITY OF SILICA

Before the solubility of microamorphous silica, which is a basic factor in the
behavior of silica as a colloid, is considered in detail, the solubility of crystalline
phases of silica is briefly re~iewed.
Solubility of Quartz at Ordinary Temperature

Prior to the outstanding investigation by Van Lier, published in 1960 (114, 115).
there was speculation that quartz might exhibit no true equilibrium solubility in
water at ordinary temperature, although Gardner (116) reported 6 ppm in 1938.
Solubility data were very confusing until it was found that traces of certain metal
impurities and especially the presence of an amorphous or at least disturbed layer on
the crystal surface caused variable results, especially at temperatures below 150C.
In 1952, Dempster and Ritchie (117) reported that siliceous dusts have a layer of
high solubility that gradually blends into the solid core, which adsorbs basic dyestuffs (118). Alexanian (119) found by electron diffraction that quartz possesses a
surface layer of amorphous silica about 100 A thick. which is removed by HF but is
re-formed in ambient humidity. Waddams found that the quartz surface in water
released "mosaic" silica, presumably as particles of colloidal size, since they scattered light (120). This was confirmed by Sakabe et al. (121), who found that in neutral or alkaline aqueous suspension, quartz released both soluble silica and colloidal
particles of crystalline nature, 0.01-0.3 microns in size. Stober and Arnold (122)
found that the amount of silica released was much more than a monomolecular
layer, and that it decreased with successive changes of water. When quartz was
intensively pulverized in water, the disturbed surface layer can amount to as high as
35%, with a specific sur-face area of 70 m 2 g-l, and the solubility is increased from
less than 10 to 70 ppm at 25C (123). Paterson and Wheatley (124) made similar
observations.
The disturbed layer on ground quartz particles 1.5 microns in diameter was
examined by Koopmans and Rieck (125), by gradually dissolving it in dilute HF
while following the X-ray peak intensity. The layer thickness was 0.1-0.2 microns.
Similar studies by Lidstrom (126), who also used nmr, indicated a disturbed layer up
to 2 microns thick may exist, but upon aging in water and removal of the outer portion, the remaining underlying disturbed and strained layer returned to the normal
crystalline state.
Cleaning the Surface

Van Lier (l14) studied the dissolution of ground quartz of particle size 3-15 microns. He found a more soluble disturbed surface layer, 0.3 microns thick, which
could be removed by stirring 10 g of the powder into 50 ml 9-15% HF for 5 min to
dissolve 25% of the silica: then the residue was washed with 0.1 N NaOH and then
water to remove fluoride and alkali, and dried and stored in a desicator. When this
powder was suspended in 0.1 N NaOH at 26C, the rate of dissolution remained
10
of Silica
31
The Solubility of Silica
or
the
crystalline
constant and was far less than for the untreated powder. More recently, Henderson.
Syers, and Jackson (127) have further studied the effects of HF treatment. Van Lier
found that cleaned quartz has a well defined solubility in water at autogenous
pressure, which can be ex.pressed by the equation:
log c
= 0.151 -
1162T-'
where c is the molar concentration of Si(OH).. and T is absolute temperature. Solubility in parts per million, as calculated from the equation, is shown as fine A in
Figure 1.4; at 25C it is II ppm.
From these data, the standard heat of dissolution is +5.32 kcal rnole", the free
enthalpy of dissolution is +5.11 kcal mole:", and the entropy change is zero according to Van Lier.
Morey, Fournier, and Rowe (128) obtained values somewhat lower than those of
Van Lier's. They found in one case that if quartz powder was tumbled in water at
c
1000
500
Figure 104. Solubility of various forms of silica in water and salt solutions at .0-500C at
autogenous pressure unless otherwise noted. Quartz: A. Van Lier equation (dashed line) (114):
B, Morey (133): C. Morey-IOOO bars (133): D. Willey-in seawater (38): E. Mackenzie and
Gees (244b): F. Morey. Fournier, and Rowe (128). Cristobalite: G. Fournier and Rowe (137).
Amorphous: II. Stober (144): I, Elmer and Nordberg (153): J. Lagerstrom. in 0.5 M NaCIO.
(162): K. Willey (20): L. Jones and Pytk owicz (43); M, Goto (see also Figure 1.7) (167a); iV.
Okkersc (165); O. Jorgensen, in 1.0 M NaCIO. (161).
-~---
.J
32
-The Occurrence, Dissolution, and Deposition of Silica
25C. the silica increased to 80 ppm after a year, and so was highly supersaturated.
and then dropped to 6 ppm, the true solubility. It is not known why the quartz surface already present could not accept the silica, but new nuclei had to be created to
reach equilibrium.
Siever (129) also investigated the solubility of quartz with results compatible with
those of Van Lier,
Solubility of Quartz Under Hydrothermal Conditions
It is impossible to review the extensive investigations in this highly specialized field.

Some of the publications are as follows.
Kennedy and associates developed data against which subsequent work was often
compared (25, 130, 131). In 1954, extensive studies were made by Wyart and
Sabatier (132), who measured the solubility of quartz, tridymite, cristobalite, and
vitreous silica in both water and steam phases at up to 480 bars and 470C.
Increased solubility of quartz with pressure had earlier been examined up to 600C
by Morey (133), and more recently by Heitmann (30); Anderson and Burnham (134)
examined solubility in water and salt and alkali solutions up to 900C and 6 kilobars. Solubility was only slightly reduced by the presence of salt, .but increased in
direct proportion to the base added. The solubility of quartz under hydrothermal
conditions is described in three papers by Kitahara (135) with special attention to
supercritical conditions up to -500C and 900 bars. The heat of solution of quartz
calculated from solubility data was 7.8 kcal mole:". In 1965, Heitmann (30) surveyed
the solubility of silica in water and stream and assembled data based on more than
1000 experiments up to 650C and 300 kg cm -2, on the basis of which a complete
solubility diagram was constructed. Verifying earlier work, the solubility of silica is
shown to increase with increasing density of steam or water, and reach a maximum
near the critical point of water. The thermodynamic properties and solubility of
quartz up to 600C and 5 kilobars pressure are being summarized by Hegelson (136).
. .~
..
Solubility of Cristobalite and Tridymite

There is some question whether true equilibrium can be established for cristobalite
and tridymite. There appears to be no instance where these crystals have been grown
under hydrothermal conditions in preference to quartz. Fournier and Rowe (137)
believed that precipitation of crystalline silica under hydrothermal conditions would
generally result in quartz. For this reason, in their study of the solubility of cristobalite, they left water in contact with the solid for long times without changing
temperature, so as not to supersaturate the solution any more than necessary. and
then suddenly quenched the system and measured the concentration of monomeric
silica, which was the only type of silica in the water. In Figure 1.4, line G strongly
suggests that a definite solubility value was established.
"-\
, ,
v............
"
---. ..I
/";
.
l
n of Silica
From the slope of the line,
.aturated,
rar: lJr
;re<t~_ ~
33
dinS
to
dT
tible with
Thus
-AHO
log S
4.576T
constant
zed field.
and
was often
'yart and
alite, and
i 470C.
to 600C
lam (134)
id 6 kiloreased in
-otherrnal
ention to
of ouartz
si,
fed
"
lore than
complete
)f silica is
naximum
ubility of
y Hegel-
AH
where AH is the differential heat of solution of cristobalite. The solubility at 25C,

by extrapolation, is 27 ppm, or 0.45 millimolal.
whence
'
From their corresponding data for the quartz system,
~F~98.K
.'
~"
'istobalite
.en grown
= 4.58 kcal rnole "
,.
,,-t
= 5.46 kcal mole>'
Thus the free energy change going from cristobalite to quartz was estimated to be
-0.90 0.3 kcal rnole ", which is in reasonable agreement with 0.57 0.75 kcal
rnole" calculated from the heats of formation from elements:
Quartz:
Cristobalite:
196.582 0.30
0.75
197.151
iwe (137),
ins would
of cristochanging
sary, and
onomeric
: strongly
Solubility of Other Crystalline Forms of Silica
For measuring the solubility of silica in water Stober (138) adopted a standard buffered salt solution (Ringer's solution) containing 0.9% NaCI. which expedites equilibration but does not affect solubility.ind 0.1 ~ NaHCO J which buffers the solution
at pH 8.4. where dissolution occurs 1110st rapidly without appreciable formation of
silicate ions that would occur at higher pH.
.':~'rl'; ,',
.
. ..;;... ...
1,
if
11.'
~\
L
34
;,.
Tire-Occurrence. Dissolution. and Deposition of Silica
!il.
Stober compared the solubilities of different crystalline forms using ground
powders of different particle sizes and treated with N aOH solutions to remove
disturbed material from the crystal surfaces. Dissolution behavior proved to be very
complex. Solubility in the sense of a dynamic equilibrium between silica in solution
and in the solid phase apparently exists only with crystalline quartz, and amorphous
or vitreous silica (139).
.j
J.
The dissolution of the other crystalline phases, crystobalite, coesite, tridyrnite, and
stishovite, with increasing concentration of Si(OH), is accompanied by adsorption of
Si(OH), on the crystal surface, which inhibits further dissolution. Thus the final
concentration of soluble silica depends on relative rates of dissolution and adsorption, and may reach the limiting solubility of amorphous silica.
Stishovite, which differs from the other forms by having a more dense octahedral
structure, with a higher surface concentration of SiOH groups. behaved most peculiarly. In 0.1 % HF solution it was completely insoluble, coesite dissolved slowly, and
quartz dissolved most rapidly. Yet in Ringer's solution quartz reached its equilibrium solubility of about 12 ppm in a few days, but coesite continued to dissolve for a
month as the silica concentration reached more than 25 ppm, and stishovite
dissolved rapidly until the soluble silica reached 190 ppm, at which point amorphous
silica was apparently nucleated and the silica concentration began to decrease (140).
Extensive further studies were summarized by Stober (141), and a theory of solubility was formulated.
Adsorbed Silica on Crystalline Silica

Holt and King discovered in 1955 that when powdered quartz was added to water,
the concentration of' dissolved silica, Si(OH)" increased rapidly at first but
thereafter very slowly. This was traced to a form of silica that amounted to 16% ora
monolayer on the crystal surface and that dissolved rapidly. Furthermore, when this
material was removed by treatment with alkali. the cleaned surface then adsorbed
soluble silica from solution, to reestablish the layer. Using Si(OH), containing
radioactive 31Si, they found that at pH 5 it did not exchange with the surface: at pH
9 it exchanged with adsorbed Si(Oti)" but not with the cleaned crystal surface
(142, 143).
Stober investigated the solubility behavior of several modifcations of silica and
developed a theory and equation for the behavior of adsorbed monosilicic acid in
retarding or preventing approach to true solubility equilibrium (144).
Stober believed that the interaction of Si(OH)~ and the silica surface involved the
following steps:
;. !
1. At the surface Si-O-Si bonds are split by hydrolysis. averaging two bondings per
tetrahedra. forming a hydrated silicic acid molecule adsorbed on the surface.
2. The Si(OH), is desorbed into solution.
3. Si(OH), is adsorbed onto the surface at equilibrium as the reverse process occurs.
followed by condensation and addition of Si0 2 to the surface.
C 1:
I
,.
Ii:
.~
"
ion of Silica
.ng ground
to -ornove
I tc,
very
He formulated the following equations. For the adsorption of Si(OH). the equation
is
35
in solution
amorphous
nJlC
lyrnite, and .
'sorption of
lS the final
nd adsorp-
where nod. = surface concentration of adsorbed Si(OH).

no = surface concentration of complete mololayer
c = silicic acid concentration in solution
b = adsorption constant
octahedral
most pecuslowly, and
its equilibssolve for a
stishovite
amorphous
ease (140).
iry of solu-
Adsorption occurs only on the bare surface not covered by Si(OH).:

(2)
where nH
t
k
A
R
d to water,
: first but
.016% ofa
. when this
n adsorbed
containing
face: at pH
tal surface
(I)
1 + be
silicic acid released by hydrolysis per unit of surface area

time
kinetic constant for hydrolysis
activation energy of hydrolysis
gas constant
= temperature (0 K)
It is assumed adsorption equilibrium is established rapidly relative to the other steps.

Thus equation I can be inserted into equation 2:
no
- - - k exp
+ be
.
,
(3)
. Condensation involves adsorbed molecules only:

(4)
. silica and
cic acid in
ivolved the
JOdi ngs per

rface.
.ess occurs,
where n;
k'
A'
silicic acid condensed per unit of surface area

kinetic constant for condensation
activation energy for condensation
Since temperature is assumed constant and values of k, k', A. and A' do.not change.
new constants can be introduced:
k cxp
-(~~)
K'
= k' cxp
-~i)
-=fhe Occurrence, Dissolution. and Deposition of Silica
36
Combining equations gives
dn
dt
dnH
dn,
dt
dt
= -- +
-(K -K'bc)
__
0
1 + be
where n is the concentration of adsorbed monomer at time t.

The concentration of silicic acid, c, can be expressed in terms of volume of"
solvent, V, and total surface area of solid silica, F.
noFbc
= Co -
Vel
+ bc)
+ -
It
0
dn
-dt
dt
where Co = initial concentration of Si(OH). in solution.

Differentiation gives the relation of changes in concentrations on the surface and
in the volume, respectively:
rV
dn
dt ==
l"F +
nob ] de
(I + be)2 dt
Substituting for dnjdt and integrating gives
~'
c~l
[b InO + bc) _ Vbc _ bnoF + ,V(I - bctJ' In

_
K
I + be;
noF
noF(l + bet:)
\.'
ct:)
where c, is the equilibrium solubility concentration for the two-phase system soluble
silica plus amorphous silica. defined as c, = K] bK'.
The amorphous silica phase presumably might appear in solution as colloidal
particles or as a built-up layer at some points on the crystal surface.Btdber used the
experimental value of c, of liD ppm (micrograms of SiD, per milliliter). For no. the
value of 600 p.g m -, was calculated on the basis of 10 micromoles m -2 (l45) or 6
Si(OH). nm -2,
Experimental data were obtained by measuring. at many times over 3-4 weeks,
the amount of silica dissolved into 500 rnl of Ringer's solution at pH 8.2 at 25C
from IO m' of silica surface. Using particles of different sizes. Stober found a relatively constant rate of solution per unit of surface area.
For quartz. he used six different sizes of particles ranging from about 0.07 to 1.3
microns with specific surface areas of 33.6-1.7 m' g-I. From the curve of con centration of dissolved silica versus time. the constants for the above equation were
determined as
b
K
0.7 ml J.Lg- 1
1.7 day "
The final concentrations of soluble silica ranged from II to 13 ppm in excellent -",
agreement with Van Lier's value of It ppm (115) for the solubility of quartz.
\~~
.on of Silica
37
The Solubility 'of Silica
For vitreous silica, b = 0.7 ml J.Lg- 1 (as for quartz) but a much higher value for the
hydrolysis constant, K, indicated a much higher hydrolysis rate than for quartz.
With b = 0.7 ml J.Lg -1 assumed, the following values were found:
Modification
volume of _
urface and
em soluble
s colloidal
er used the
For no, the
(145) or 6
3-4 weeks,
.2 at 25C
und a rela-
0.07 to 1.3
concentra-
arion were
n:
'tz.
-llcnt
Quartz
Vitreous
Cristobalite
. Stishovite
Tridymite
Coesite
K(day-1)
(Hydrolysis)
1.7
90
K'(day-1)
(Condensation)
0.2
1.17
4.0
20
2.4
0.4
When the phases other than quartz and amorphous silica are suspended in water, the
final concentration of soluble silica is not a saturation concentration, but the result
of a competition between silica passing into solution as Si(OH). and Si(OH).
readsorbing on the surface to an ever-increasing extent, blocking further dissolution.
Thus a limiting concentration is reached that depends on the area of solid surface
exposed per unit volume of solution.
When the same sample of silica having an area of I m 2 is put each day into 50 ml
of fresh Ringer's solution (pH 8.4) for 24 hr, the amount of soluble silica dissolving
each day reaches a steady value, which is characteristic of the particular modification of silica used:
Modification
Vitreous (glass)
Stishovite
Cristobalite
. Tridymite
Quartz
Coesite
Specific Surface
(rn" g-l)
Limiting Silica
. Concentration (ppm)
8.8
21.6
39
11
.. 8.5
12.0
lOA
10.6
6
4.5
2.9
0.7
If Stober's views are correct and cristobalite, for example, has no true equilibrium
solubility, then calculations based on published solubility cannot be valid. The need
for a more accurate definition of solubility has been pointed out by. Weill and Bottinga (146). Data presented as "solubility" of different forms of silica is often only
an indication of the rate of solution or the limiting concentration reached under
particular conditions. Thus a reportthat opal is 15-18 times as soluble as anhydrous
silica at pH 12.8 merely indicates the relative rate of dissolution (147).
Similarly, solubility data by Kopeikin and Mikhailov (148) for quartz (7 ppm),
cristobalite (12 ppm), tridymite (16 ppm), vitreous silica (88 ppm), and amorphous
. silica (120 ppm) are, in the cases of tridymitc and cristobalitc, higher than the limiting concentrations observed by Stober, no doubt because different techniques were
II
38
Jhe Occurrence. Dissolution. and Deposition of Silica
used. Of these. only the values for quartz and amorphous silica represent true solubility.
The relation of "rapidly soluble silica" on micron-range quartz particles to
"disturbed layer" was further investigated by Bergman. Cartwright. and Bentley
(149) with the conclusion that particles smaller than 1 micron in diameter contained
too much of the rapidly soiuble material to be explained by a monomolecular layer
of soluble silica. For example. 8% was rapidly soluble on 0.3 micron particles. It is.
clear that such "disturbed" material must be removed from quartz particles before
the behavior of adsorbed Si(OH). can be studied.
The dissolution and deposition of silica on quartz was examined by Beckwith and
Reeve (150), who noted an apparent equilibrium solubility of 18-20 ppm for HFcleaned quartz in 0.1 N sodium acetate solution at pH 7.7. The deposition of monosilicic acid was much faster at pH about 7 than in more acidic solution.
An unexplained phenomenon observed by Baumann (151) is that when cleaned
quartz powder was suspended repeatedly in a buffered pH 8.5 solution of 88 ppm
soluble silica, silica was adsorbed until the total far exceeded a monolayer coverage
(Figures l.Sa and I.Sb). The adsorption rate increased with increase of pH from 3 to
9 and was proportional to the second or third power of the initial concentration and
decreased with surface coverage. The kinetics show that the soluble silica is held not
by physical but chemical bonds. During seven repeated 40 day exposures to fresh 88
ppm solutions. the powder kept on adsorbing until four monolayers had been laid
down. The adsorbed silica was not ordinary crystalline quartz. because it could be
dissolved more rapidly than quartz. Yet it was much less soluble than amorphous
silica, because it continued to be deposited from a solution containing less than 30
. ppm of soluble silica, whereas the solubility of ordinary amorphous silica is 110- I20
ppm.
Baumann proposed that the true solubility of quartz may be less than II ppm. He
thinks that quartz stops dissolving when the concentration of soluble silica reaches
::E
100
Q.
a..
I
Ei
a::
....
z
ILl
U
50
u
<
u
:J
(i)
0
0
10
20
30
40
DAYS
Figure 1.5a. Residual soluble silica in solution in contact with quartz surface after indicated
.
number of days at 25C. Curves are numbered according to the number or times the SOlution,.l
was changed. Initia! concentration was 80 ppm in all cases. [Data by Baumann {I 51 ).]
eposition of Silica
<t
resent true solu-
...J
en
.rt.
rticles to
ht, and Bentley
meter contained
nnolecular layer
n particles. It is
particles before
IL.
lQ
w
~
...J
o
Z
::!:
o
w
CD
a::
>y Beckwith and

!O ppm for HFosition of mono-
o(/'l
o
<t
IL.
>no
a::
w
at when cleaned
nion of 88 ppm
iolayer coverage
of pH from 3 to
incentration and
silicais held not
sures to fresh 88
rs had been laid
ause it could be
than amorphous
.in -ss than 30
silil._ .rs 110-120
han II ppm. He
lie silica reaches
CD
::!:
::>
z 0
1234567
NUMBER OF 40-DAY TREATMENTS
WITH SOLUTIONS INITIALLY 80 PPM
SIUCA
Figure l.Sb. Number of layers of monomeric silica adsorbed on quartz versus the number of
40 day treatments at 25C. [Data from Baumann (151).]
::!:
&
50
z
o
a::
w
~
ou
25
/B
----....
<t
--
."./
.".""
..
~~~-------------C
...J
en
o
0123456
NUMBER OF ADSORBED MONOLAYERS OF SILICA
ice after indicated

tirr '. the solution
10
t, ,
'0..
',J
Figure 1.5c. Concentration of soluble silica in solution in equilibrium with adsorbed

monolayers of silica at 25C: A. after 40 days: B. extrapolated to 100 days: C. solubility of
quartz. [Data from Baumann (151 ).1
39
40
II
1
II ppm because at this concentration enough Si(O H). is adsorbed to stop further
dissolution at 25C. On the other hand, II ppm is the solubility value extrapolated
from solubility data at higher temperatures where it is known that true solubility
equilibrium is reached and that quartz crystals grow when the solution is supersaturated.
It is suggested that at 25C the adsorbed layers of silica are very slow to assume
the ordered structure of the underlying crystal lattice, but nevertheless crystallization
is slowly occurring just as it does more rapidly at higher temperatures.
A possible explanation for the above observations is as follows: the first adsorbed
layer of Si(OH)4 is held tirst by hydrogen bonds and then condensation by siloxane
bonds in a fairly regular arrangement almost matching the very regular array of
underlying silicon atoms. It is the regularity of the silanol groups on the quartz surface that permits almost perfect molecular matching and very strong adsorption of
the Si(OH)4' Each subsequent layer becomes less regular, and thus the adsorption
constant is lower and the apparent solubility of that layer becomes higher. Even in
the fourth layer, the regularity is still so pronounced that the solubility is still only'
about 25 ppm.
From a plot of Baumann's data for the concentration of silica in solution after 40
days versus the number of molecular layers of Si0 2 (Figure 1.5c) it appears that
after the second layer, the solubility increases with the number of layers as the
atomic arrangement becomes more disordered.
From a plot of the data in Figure 1.5a as parts per million in solution versus the
logarithm of time (days), the more nearly linear curves permit a reasonable
extrapolation to 100 days. As shown in Figure 1.5c the amount of silica in solution
continues to drop, suggesting that in all cases it is approaching the solubility of
quartz. It is therefore likely that if this quartz powder with multilayers of adsorbed
silica on the surface were left to age for a year or so instead of 40 days. or if the
suspension were heated to 100C, for example, the adsorbed material would become
further converted to the structure of quartz and its solubility decrease to that of
quartz.
Solubility of Amorphous Silica

A given sample of amorphous silica exhibits a reproducible equilibrium solubility in
water. However, reported solubility values for amorphous silicas range from 70 to
more than 150 ppm at 25C. Such variations are apparently due to differences in
particle size, state of internal hydration, and the presence of traces of impurities in
the silica or absorbed on its surface during the measurements.
As a basis of comparison, it is of interest to note the solubility data for silica of
which the particles are large enough that size has no effect.
Based on data for smaller particles, an extrapolation of Alexander's (152) data
indicates the solubility of massive amorphous silica to be 90 ppm for silica from
pure sodium silicate. and 60-70 ppm for silica from commercial water glass. which
probably contains traces of impurities that reduce solubility. Similar extrapolated ~~'
values are described below (Figure 1. lOb).
....
-~-
.ion of Silica
top further
xtr>-olated
e ~. . Jility
; supersatu-
VitreouS silica has the same solubility as other amorphous silica. Because of the
mall specific surface area of powdered silica glass in comparison with that of
~icroamorphous or colloidal silicas, workers found it difficult to establish solubility
equilibrium. Stober (144) found that at pH 8.4 in Ringer's solution (0.9% NaC!,
0.1 % NaHC03 ) at 25C, at least 15 days was required to reach equilibrium when 20
m2 of silica surface was exposed per liter, regardless of particle size; Without the use
of this solution, which has an optimum catalytic effect, it would probably have been
impossible to establish equilibrium. The solubility was found to be about 100 ppm.
A highly porous, vitreous silica which equilibrated much more rapidly was used by
Elmer and Nordberg (153) in a study- of solubility in nitric acid solutions. Their
values for high dilution at pH 3 were 160 ppm at 36C, 260 ppm at 65C, and 400
ppm at 95C. They found the solubility was identical to that of a commercial dried
silica gel, provided care was taken not to abrade the gel by disturbing it during the
test. .
There have been several surveys of the solubility of amorphous silica. as follows.
In 1955. Baumann (154) concluded that amorphous silica had a uniform solubility
in the neutral pH region. that the dissolved species was almost entirely monomeric,
and that in the pH range from 3 to 6 the rate of dissolution increased linearly with
increasing pH. In the same year, Krauskopf (155) presented an excellent summary
of previous studies of the dissolution and precipitation of silica at modera,te temperatures, and emphasized the recognition of the differences between soluble. ionic, and
colloidal silica. relating these to the solubility behavior of silica in natural waters.
, to assume
'stalllzaticn
st adsorbed
by siloxane
ar array of
quartz sursorption of
adsorption
er. Even in
is still only'
ion after 40
ppears that
yers as the
versus the
reasonable
ir
ution
olubiuty of
)f adsorbed
'S, or if the
uld become
: to that of
1
solubility in
from 70 to
fferences in
npurities in
for silica of
(152) data
silica from
;Iass. which
xt: 'Iated
41
Establishment ofSolubility Equilibrium
Equilibrium is established only very slowly. unless the amorphous silica is so finely
divided or microporous as to furnish an area of hundreds or thousands of square
meters of surface per liter of water. Stober (144) has shown that Si(OH). is adsorbed
on the surface of amorphous silica, retarding its dissolution. as has already been
described in the case of quartz. The surface of vitreous silica appears to consist of
SiOH groups. and if Si(OH). is absorbed by hydrogen bonding and then is partially
condensed the surface may then at least partly consist of =Si(OH)2 groups. referred
to as vicinal hydroxyl groups. Depending then on the state of the surface of amorphous silica before it is isolated and dried. there may be found different numbers of
hydroxyl groups per unit of surface area.
Likewise. the amount of silica passing into solution when a powder is first placed
in water may depend on its state before it was dried. However. this should not affect
the final equilibrium solubility of the silica.
According to Baumann (154). when amorphous silica powder (Aerosil) is placed
in water at 25C. the approach to equilibrium is different at high and low pH. Below
pH 7. the concentration of soluble silica increases for several days and approaches
the final solubility value asymptotically. Above pH 7. the silica concentration rises
rapidly in the first day to form a supersaturated solution containing. for instance.
155 ppm at pH 9. Then the concentration drops over a period of 3-4 days to the
solubility characteristic of the pH and type of silica. such as 125 ppm.
Baumann proposes that the initial rate of dissolution at this pH is greater than the
----_.
42
TheOccurrence. Dissolution. and Deposition of Silica
,..
rate of deposition, thus leading to temporary supersaturation. and that there is an

oversupply of low molecular weight silicic acid, the excess of which then polymerizes
to form colloidal 'particles. This was shown by filtering the silica powder from the
. supersaturated solution and showing that the concentration of Si(OH)4 dropped
slowly to the equilibrium value at about the same rate as when the original solid was
present.
Another possible explanation is that in the Aerosil powder, there might be some
extremely small particles only a few angstroms in diameter, which have a higher
solubility than the average larger particle.
Effect ofHearing
!.
Silica gels made from sodium silicate and SiCI 4 respectively, were dried and samples
heated to a series of temperatures up to 900C. These all showed the same solubility
in water as reported by previous workers, according to Morachevsky and Piryutko
(156) (see Figure 1.4).
Solubility in Water: pH 0-8

:
I:
I:
I,
In 1855, Struckman (157) concluded that amorphous silica dissolved in water at

ordinary temperature to the extent of 100-150 ppm. To this day, a single figure has
not been agreed upon because of the extreme variations in the form in which amorphous silica can occur. Curves of currently available data are shown in Figure 1.6.
,I
i
::i:
a.
a.
I
ct
500
::i
en
en
::J
i
:r:
a.
D::
200
::i:
1.
j!
<!
u,
>-
t:
-..l
100
co::>
-..l
en
a
o
10
pH
Figure 1.6. Solubility of amorphous silica versus pH: O. Alexander. 25C; ., Cherkinskii
and Knyaz'kova (160) 19C; Baumann. 20C; Baumann, 30C; Dashed line from Cherkinskii \ .
equation: log eM = -2.44 - 0.053 (pH).
'--'
43
.ition of Silica
t there is an
pc <erizes
ier ... In the
H). dropped
tal solid was
Alexander. Heston, and Her (158) were the first to show that microarnorphous
silica as powder made by collecting the smoke from burning SiH. or as colloidal
silica in sol form both exhibited about the same solubility. In retrospect, these silicas
probably had specific surface areas of 240 and 500 m 2 g " ', respectively, and the solubility at pH 7-8 was about 100 and 130 ppm, respectively. A silica gel, made under
conditions that we now know give a high specific surface area of more than 600 m 2
g-I, was soluble to the extent of 200 ppm at 25C. and the dissolved silica was
.
proved to be monomeric by chemical and physical methods.
Goto, Okura and Kayama (159) in 1953 showed that earlier data indicating a
minimum solubility at pH 3 were in error, and that solubility was constant from pH 2
to 8, then increased rapidly at higher pH.
ght be some
ive a higher
and samples
ne solubility
.nd Piryutko
in water at
le figure has
which amor'igu"~ 1.6.
Possible Solubility Minimum at pH 7

Baumann (154) collected data from other sources for comparison with the data of
Alexander plotted in Figure 1.6; these data seem to confirm that the solubility
reaches a minimum at pH 7-8, but the reason for the slightly higher solubility at
lower pH is not known. However. Cherkinskii and Knyaz'kova (160) verified the
data (see Figure 1.6) and proposed that silica is amphoteric and is cationic below pH
7. They give equations assuming that all the "soluble" silica is actually polymeric
and cationic at low pH. There is no experimental basis for such a theory: all of the
soluble silica has been shown to be monomeric, and there is no evidence for cationic
silica above the isoelectric point of pH 2.
Solubility in Nitric Acid

Elmer and Nordberg (153) have furnished data on solubility of porous vitreous silica
in nitric acid solutions up to 9 N:
log C = "";0.168N - 0.332
log C = -0.167N - 0.584
log C = ':'0. 184N - 0.796
at 95C
at 65C
at 36C
where C = concentration of SiO z (mg ml- I )

N = nitric acid normality
Thus in 7 N nitric acid at 95C the solubility was only about 30 ppm, as compared
to 400 ppm in water, whereas at 36C it was 8 versus 160 ppm. It was pointed out,
therefore, that to extract impurities from amorphous silica with nitric acid. strong
acid should
be used. The solubilities in water (N = 0) are included in Figure 1.4 at I.
.
~.
Solubility in NaCiO. Solutions

t.
11
Ch~rkinskii
........
1.;inskii
A careful study by Jergenson (161) showed that there arc still mysteries to be
explained regarding the solubility of amorphous silica. ln spite of all previous work
indicating that the solubility in water is 100-120 ppm. and that solubility is not
--
II
...
TlreOccurrence, Dissolution. and Deposition of Silica
affected by the presence of salt, he reported 77.7 == 1.1 ppm at 25C in eM NaCIO.
solution. This value was reached only after 3-5 months, but was highly reproducible.
Jergensen suggested that in the presence of salt a uniform. reproducible. ordered
layer of silica hydrate is developed on the solid surface, and this is less soluble than
other forms of microamorphous silica: However, the lower solubility may be
explained instead by the larger radius of curvature of the surface of the final aged
amorphous silica.
Furthermore, he gave evidence that silica powders put into the perchlorate solution first formed a supersaturated solution in 10 days. The degree of supersaturation
depended on the amount of silica that had been added to the system. The supersaturation was higher with silica preheated to higher temperature (up to 700C).
However, silica that had previously been equilibrated with the solution did not cause
supersaturation and followed the dissolution rate
de
dt
k(Cc
C)3
where C; = 77.7 ppm

C = concentration at time t
k = 1.2 x 10-12 mg ? hr " '
The solubility value of 77.7 ppm was obtained by approaching equilibrium from
the undersaturated and supersaturated sides.
Jergensen found that in water, equilibrium concentrations were variable. ranging
from 108 to 121 ppm. It was concluded that sodium perchlorate exerted a catalytic
effect in the formation of a uniform solubility-defining surface, regardless of the type
of silica used.
It would be interesting to determine if the silica that had been equilibrated with
perchlorate solution would then show the same low solubility when equilibrated in
water. Unfortunately, the effect of pH was not examined: raising the pH slightly
above neutrality should have reduced the time needed to reach equilibrium.
The mystery is deepened by the fact that in an investigation of the behavior of
silica and silicate ions in 0.5 M solutions of ,NaCIO Lagerstrom (162) concluded
that the solubility of amorphous silica is 0.002 M (I 20 ppm) at 25C and 0.0036 M
(216 ppm) at 50~C, which are the values obtained by other investigators (see Figure
1.4).
. Effect of Electrolytes
The effect of electrolytes on the solubility of amorphous silica powder (750 m 2 g-l
over the pH range 7-11 was examined by Greenberg and Price (12). Up to 0.1 N,
NaCI or Na 2SO. had essentially no effect on the solubility or on the ionization
constant of silicic acid as measured around pH 10. Even the use of Ca(OH)2 solutions instead of NaOH, up to 0.04 N, did not change the solubility at a given pH in
the range from 8 to 10.
.~.
--
...;.....
4S
tion of Silica
M NaCl0 4
:prc- ~ib\e.
ole. .rered
soluble than
ity may be
e final aged
Silica gel dissolves in H:zSiF. in an amount to give a F: Si ratio around~5. Over an

acid concentration range from 0.03 to 3 M the ratio changes only from about 5.2 to
5.0, and is the same at 0 and 25C. A detailed study of the effect of acid strength on
this ratio was described by Ryss and Plakhotnik (163).
The solubility of amorphous silica at 40C in various strengths of solutions of
N a 2CO" K2CO" NaOH, and KOH ranging from 0.1 to 2.0 N as published by Drnitrevskii et al. (l64a) may prove useful in industrial research.
.lorate soluersaturation
e supersatuto 700C).
id not cause
brium from
ole,... .iging
I a catalytic
i
of the type
Solubility under Hydrothermal Conditions
.j
As shown in Figure 1.4, the variation in the solubility of amorphous silica with
temperature is probably represented by a common slope for different samples under
the same experimental conditions. However, at a given temperature the values are
spread over a considerable range, for example, at 25C from 70 to 180 ppm.
The maximum temperature is around 200C since amorphous silica crystallizes at
. an increasing rate above this point, depending on what impurities are present.
Willey (20) measured the effect of pressure on the solubility of amorphous silica in
seawater at OC. The solubility increased from 65 to 71 ppm when ,the pressure was
increased from I to 150 atm and then linearly to 94 ppm at 1200 atm.
Pressure also has a marked effect on the rate of crystallization. Oehler (l64b)
found that silica gel crystallized to microcrystalline quartz (chert) even 'at 165C at
3000 bars.
Because of the rapid decrease in solubility upon cooling, sampling has been a
problem. Fournier and Rowe (l64c) devised improved means of quenching and dilut-. ing samples that had been equilibrated with silica at high ternperature and pressure
in the autoclave. Their data are expressed by the equation
-731
log C = --" + 4.52
T
brated with
iilibrated in
p.H slightly
n.
behavior of
) concluded
d 0.0036 M
(see Figure
where C = mg SiO, kg- 1 (or ppm) and T is the absolute temperature. According to
this equation the solubilities at the vapor pressure of the solution are as follows:
Ternperature (OC)
Solubility (mg kg " ')
25
100
117
32\
Solubility under a constant pressure of 1039 bars is

:750 rn" g-'
p to 0.1 S.
: ionization
~OH)1
Jog C
-810
T
+ 4.82
solu-
giwn pH in
The differential heat of solution, !},H. is 3.7\ 0.05 kcal rnole"' and the differential entropy. ;j,S, is 13.9 0.05 cal rnolc' '.
--
TOe Occurrence. Dissolution. and Deposition of Silica
46
Solubility of Hydrated Amorphous Silica
1
!
i
,;
,,
f. ~
:)
;I .
.j
:.
I
~
, I
1
j
..
r: ~
There is a question whether silica in a dense but highly hydrated form is Jess soluble
than anhydrous amorphous silica. When silicic acid of low molecular weight. with a
particle size of only 10-20 A, is concentrated as soon as it is made at pH 2. at which
further polymerization is slowest, a very dense hydrated gel is obtained with pores
under 20 A diameter. The effect of pH in forming such gels has been discussed in
detail by Okkerse (165).
Gels can be made with pores so small that nitrogen molecules cannot enter. Iler
has prepared gels from polysilicic acid obtained by hydrolyzing ethyl silicate in an
alcohol-water mixture with HCI catalyst at 25C, and then diluting to 1% SiO z at
pH 2. The particle size was calculated to be 19 A based on the specific surface area
of 1405 m Z g ? by a titration procedure. Part of the sol was vacuum-dried and the
glass-clear silica gel had a specific surface area by nitrogen adsorption of only 45 m 2
g-l.
Another part of the sol was adjusted to pH 6 and aged for I hr at 25C, then
readjusted to pH 2. The particle size had grown to 23 A as indicated by a surface
area of 1215 m 2 g-l. When this sol was dried in the same manner. the gel. which
looked the same as the previous one, had a specific surface by nitrogen adsorption of
.
626 m 2 g-l.
Thus when silica particles smaller than 20 A diameter are closely packed into a
gel, most of the pores between the particles are too small to be penetrated by
nitrogen. Such fine-pored gels are obtained only from very small particles that are
rapidly brought together before they can link together into a very open network.
At the point where such gels solidify, they still contain much water, but because
the pores are so small the vapor pressure is far less than that of free water. As
described in a previous section, these "hydrated" silicas sometimes appear to give up
water stepwise, as though definite hydrates were present.
When such gels are dried, the pores become so small that even nitrogen molecules
cannot penetrate, and the specific surface area by the BET method becomes very
small. It would therefore not be surprising if the rate of dissolution should also be
very low. However, there is no reason to believe that at equilibrium this form of
silica should be any less soluble than microamorphous or vitreous forms. In fact,
because of its hydration. since many of the silicon atoms are linked to hydroxyl
groups. the true solubility might be expected to be higher than the other forms.
On the other hand, Spychalski (166) reported that solubility decreased with'
increasing hydration. He gave the following tentative "solubilities" of hydrated
silicas at various stages of dehydration. as prepared by Thiessen and Koerner (I 10.
Ill) by hydrolyzing ethyl silicate:
Composition
Si0 2 2.5H 20
Si02 2.0 H20
Si0 21.5H 2 0
Si0 21.0H 20
Si0 2 O.5 H20
"Solubility" as ppm in
Water at 18-2rC
18
44
58
61
120
on of Silica
ess ~ .ubte
ght, with a
2. at which
with pores
iscussed in
enter. lIer
icate in an
% Si0 2 at
irface area
ed and the
only 45 m 2
!5C, then
I a surface
gel, which
sorption of
:ked into a
etrated by
es that are
-~"
...
47
However, there is no indication that solubility equilibrium had beef reached.

Nevertheless, there is a consistent relation in that the "solubility." as he measured it,
was inversely proportional to the state of hydration.
Possibly in microporous gels in which water is strongly hydrogen-bonded in the
pores at low temperature, the solubility would be much greater at higher temperature, where hydrogen bonds are less stable. Okkerse (165) measured the rates of
solution and solubility of microporous (717 m 2 g-l) and macroporous (293 m 2 g-I)
silicas in a veronal-NaCI-NaAc-HCI buffer at pH 2, 4, 6, and 8 at 60C. In every
case, the rate of dissolution of the microporous gel was at least twice as fast as the
other. After 200 hr at pH 4-8, both gels exhibited the same solubility of about 200
ppm, which is close to the value for other amorphous silicas in Figure 1.4.
Apparent High Solubility at High pH
From pH 9 to 10.7, there is an apparent increase in the solubility of amorphous
silica, owing to the formation of silicate ion in addition to the monomer which is in
equilibrium with the solid phase. Since the silicate ion is instantly converted to
monomer in acid solution, both monomer and silicate ion are included in the
determination as "soluble silica" by the molybdate reagent. In this range, amorphous silica is in solubility equilibrium with neutral monomer as well as silicate ions:
(Si0 2) % + 2 H 20 = Si(OH). + (Si0 2) %_ 1
Si(OH). + OH- = Si(OHh- (or HSiOi)
.wc
ut because
water. As
. to give up
: molecules
.ornes very
rld also be
.is form of
IS. I n fact.
J hydroxyl
.rrns.
eased with
f hydrated
erner (110.
Above pH 10.7, all the solid phase of amorphous silica dissolves to form soluble
silicate, since at higher pH the concentration of Si(OH). _is greatly lowered by
conversion to ionic species. so that no amorphous solid can remain in equilibrium.
Measurement by Alexander, Heston, and lIer (158) on the solubility of a very
pure amorphous silica (Linde silica) in water at different pH values (adjusted with
HCI or NaOH) show the following variations. as measured by the molybdate
method:
pH
Solubility of Amorphous
Silica (25C) (ppm)
6-8120
9
138
9.5
180
10
310
10.6
876
The increase in the total "soluble" silica can be explained on the basis of the
following equilibrium. assuming that the concentration of Si(OH). in solution does
not change with pH:
Si(OI-l).
+ 01-1-
H 3SiO; + '-1 20
[H 3SiO.1 = 1.85 x 10 [Si(OII).][OH-1
--.;.......
48
"Fhe Occurrence. Dissolution. and Deposition of Silica
The equilibrium constant calculated from these solubility data agrees reasonably
well with that found by Roller and Ervin (23) in a study of the association of silicate
ions in the CaO-Si0 2-H 20 system. These authors found at 30C a value of 1.5 x
10, Thus it is clear that the solubility of silica increases at high pH because of the
formation of silicate ion in addition to Si(OH). in solution.
Subsequent measurements have been made with additional precision.
At 90C. Van Lier (115) measured the total amount of silica dissolved at equilibrium from quartz in 10- 1 to 10- M NaOH and noted the change in pH. From these
~~
where
Since the ionization constant for water at 90C is 12.42.
[OH] [Si(OH).]
.'f
103 2
1.6 X 103
The effect of pH on solubility of silica at temperatures from 0 to 200C was

measured by Goto (t67a) and is shown in Figure 1.7. At 22-100C the solubility was
about 30% higher than for most powders and gels. as shown in Figure 1.7. This is
1500
::!:
00I
:J
iii 1000
(/l
:::>
::t
00:
oCt
500
90C---73C------
>-
I-
---~~
-J
iii
-~
::>
...J
o
(/l
a
5
B
pH
10
II
Figure I. 7. Solubility of amorphous

silica versus pH at di Iferent tern peratu res
[from Goto (167a)].
ion of Silica
Effect of Particle Size on Solubility in Watee., -
reasonably
of ~;Iicate
undoubtedly because the colloidal particles were smaller than 50 A. since they were
prepared at room temperature from sodium silicate by ion exchange. However, at
155 and 200C in water, the particle size of the silica undoubtedly increased and the
solubility was the same as reported by others (see Figure 1.4).
ie I.
.5
ause of the
49
Calculation 01 Solubility and Dissociation Constant

at equilib- _
From these
Where the ionization constant and solubility are not known, as for example at some
unusual pH. Van Lier (114) has shown how the ion concentration and solubility can
be calculated easily from data on pH and total soluble silica. which includes both
monomer and ionic silica as determined by the molybdic acid reagent. In general
terms their method is as follows.
Let S, = concentration of total soluble silica at pHI
S2 = concentration of total soluble silica at pH 2
So = concentration of Si(OH) which is the solubility of silica in neutral water
Then concentration of ionic silica at pH 1 = S1 - So
concentration of ionic silica at pH 2 = S2 - So
Since the decrease in H ion concentration is accompanied by a corresponding
increase in concentration of H 3SiO. -. then
20r - .... was

lub.. j was
1.7. This is
By rearrangement.
The concentrations of silicate ion can be obtained by difference and the ionization
constant calculated. using the appropriate value for the ionization constant of water:
C
25
50
90
100
K
14.944
13.996
[3.26
12.42
12.26
EFFECf OF PARTICLE SIZE ON SOLUBILITY IN \VATER

amorphous
em
'lures
The behavior of polysilicic acids. colloidal silica.ind silica gels cannot be understood without taking into account the fact that the solubility or silica is higher when
The-occurrence. Dissolution. and Deposition of Silica
the silica surface is convex. and lower when it is concave. It is a matter of'the radius
of curvature of the surface; the smaller the radius the greater the effect on solubility
(l67b).
As shown in Figure 1.8 smaller particles with a smaller positive radius of curvature have a higher equilibrium solubility. On the other hand. in a crevice. such as
where two particles are in contact, the radius of curvature is negative and the equilibrium solubility is low.
There are two important practical consequences:
-j
".
2. If there has been an aggregation or flocculation of colloidal silica particles. so

that two or more particles are brought together, then at the point of contact the
.:
\,
Si02
INCREASING
POSITIVE CURVATURE
SOLUBILITY, PPM
200
100
S=77
10
OF CURVATURE-NANOMETERS
Figure 1.8. Variation in solubility of silica with radius of curvature of surface. The positive
radii of curvature are shown in cross-section as particles and projections from a silica surface.
Negative radii are shown as depressions or holes in the silica surface. and in the crevice
between two particles.
1. When very small individual silica particles are brought into the same solution as
larger ones. especially at pH 9-10 where hydroxyl ions catalyze dissolution and
deposition of silica. the smaller ones dissolve and the larger ones grow.
INCREASING
NEGATIVE CURVATURE
~"J,
~.
'".po"";
''''i'
SI
Effect of Particle Size on Solubility in WatCI- -
on of Silica
radius of curvature is negative and extremely small, the solubility of silica in this
region is very low, and silica dissolves from the particle surfaces and is deposited
around the point of contact to minimize the negative radius of curvature, thus
forming a coalescence or neck between particles.
the radius
\ s('I-'l,ility
; of curva.e, such as
j the equi-
Even at low pH the same phenomenon occurs if the particles of silica are less than
about 5 nm in diameter, so that the solubility changes rapidly with radius of curvature.
The coalescence between adjacent silica particles in an aggregated gel structure by
this spontaneous process or by adding soluble silica to be deposited at the points of
contact between particles is described by Alexander, Broge, and lIer (168) and is
further discussed in Chapter 5.
Kitahara (169) shows that the effect of pH, salt, and temperature have the same
influence on the rates of polymerization of monosilicic acid as they have on the gelling of sol, showing that both phenomena, that is, the growth of particles and the
cementing together of particles once they are in contact, are influenced by the same
factors; that is, those jhat affect the rate of dissolution and deposition of monomeric
silica.
.
Greenberg (13) concluded that although theoretically solubility is a function of
particle size, there was no published data to bear this out. Alexander (152) was the
first to obtain data that showed that for a given type of silica, solubility increased
with decreasing size. Silica containing different impurities or having different
degrees of hydration within the particles cannot be used for comparison.
The. Ostwald-Freundlich equation, applied to solubility (known as the
Thompson-G,ibbs effect), is as follows:
.olution as
lution and
irticles, so
.ontact the
. 5,
= exp(2 EVR -IT-1r 1)
. 5,
;".
r
F..
r'
where S, = solubility of particle or radius r

5, = solubility of a nat surface or particle of infinite radius (nm)
E = interfacial surface energy (ergs em -2)
V = molar volume = 27~2 ern" for amorphous silica
R= gas constant (8.3 X 107 ergs mole ? deg ")
T ~ temperature (degrees absolute)
." r = radius of curvature (cm) .
. d= particle diameter (nm)
E .: I04.6(J0 7 )(r )log(5 , / 5 ,) at 25C
-.
The positive
lica surface.
l~
reVlce
......
Thus
. s:
Jog l o
c,
o.
[~:]
= 2.85 x 10- 7
Tr
5.7
Td
('
:.~------~--
52
II'
!:
~~
t;
ii
&:
1:'
! ..
1"
r '
i...
:~
*
~.:.t
,.~
,r~
"
1'1
tI
i I
r I
i I
;I
I
I!
!
..:..,-..
Theoccurrence. Dissolution. and Deposition of Silica
There have been past indications that very small silica particles are ibnormally
soluble, but no measurements were made.
In studying the solubility of finely ground quartz, Stober and Arnold (122) concluded that the silica which dissolves very rapidly at first when immersed in water is
much more than an adsorbed layer of Si(OH)., but instead is a minute fraction of
the powder which is finer than 0.1 micron and is thus, owing to the
Thompson-Gibbs effect, much more soluble.
.
The radius of curvature of the silica-water interface is of critical importance even
with a porous silica solid. Charles (170) found that the rate of dissolution of porous
high silica glass could be explained on the basis of a high local solubility of the silica
surface owing to its small radius of curvature.
Over millions of years the conversion of the amorphous siliceous remains of large
sponges to solid rounded flint boulders in chalk beds is an extreme example of the
conversion of a high surface area form of silica, through dissolution and deposition,
to a dense low area form. Examination of flint boulders with inclusions of oyster
shells and belemnites indicates that a once highly extended skeleton of a sponge had
been drawn together into a round black boulder (171). Between the flint and the
CaC03 there is a film 10 nm thick of intermediate hydrated calcium silicate, along
which the soluble silica must have been transported.
Another mysterious phenomenon is "ambient pyrite," Grains a f~w microns in
diameter have moved through solid chert (an extremely tine-grained quartz). leaving
a trail of coarse-grained quartz. This was described by Tyler, Knoll. and Barghoorn
(l72)(Figure 1.9).
One explanation is that there is a slow transport of silica from the more soluble
tine grains ahead of the crystal of pyrite to the growing quartz crystals behind the
pyrite. The pyrite is hydrophobic in nature and not chemically bonded to the surrounding silica. Thus it is possible that the pyrite grain is pushed ahead by, the growing quartz crystals. The resulting pressure ahead of the grain on the finer crystals of
quartz must also increase their already higher solubility. However, organic matter is
known to be present, and it is postulated that gas evolution and pressure buildup are
also involved..
The particle size effect is probably also involved in a phenomenon described by
Baumann (173). Amorphous silica powder condensed from a name consists of fine
spherical particles generally less than ISO A diameter. When such a pov..' der is placed
in water, a supersaturated solution of silica is obtained, no doubt owing to a very
small percentage of more soluble particles under 50 A diameter. The dissolved
monomeric silica then rapidly polymerizes to polysilicicacids. but these later disappear as supersaturation is relieved by deposition of silica on the larger amorphous
particles in suspension.
Agitation of granular silica in water may cause abrasion. liberating very fine
particles which then give erroneously high solubility data. Morey. Fournier. and
Rowe (16) measured the solubility of amorphous silica in the form of commercial
pure silica gel, crushed vitreous silica (fused quartz), colloidal silica formed by cooling a supersaturated solution (720 ppm) dissolved from quartz, and colloidal silica
from supersaturated hot spring waters. The silica gel and colloid from supersaturated solutions showed a reproducible solubility of 115 ppm at 25C. However. silica
\ .
.,-.--
--~ ..
:ion of Silica
abnormally
-,
I (I.., , conl in water is

fraction of
ng to the
rtance even
n of porous
of the silica
tins of large
mple of the
deposition,
1S of oyster
sponge had
.int and the
icate, along
microns in
rtz), leaving
I Barghoorn
.luble
behind the
to the surly the growr crystals of
lie matter is
buildup are
10,
lescribed by
isists of fine
Ier is placed
19 to a very
ie dissolved
later disapamorphous
19 very Ii ne
rurnicr. and
commercia!
ned by coollloidal silica
-- .<. :.,:...
..
-.
'
..
;,;-'.-;-' ~.
..~
.
~:
-. .
;.-:-;",-".,~.,.:-_.,;.
'
.",-,.~:....
...... .
~.'
'-:,.
';.,'
",
-.
'
-.;".
"j
~ ... ~.!:. -.'.
..: .
....
.:,:;:'i-t~.~;,~:?,_:<;::':" ''C-'~';r :=J
\
"',"-,
(b) :
,~
"; :;~,~;;
...._.
..
.~_~ __~:-'~-~~J
Figure 1.9. Ambient pyrite grains in chert. (a) Biwabik Formation. Mesabi Range. Finegrained dark material: organic matter. Black grains: pyrite. Trails: coarse-grained quartz.
Matrix: line-grained quartz (chert) (200x). (h) Magnified pyrite crystal and trail of coarse
quartz grains (2200x). (Courtesy of Professor E. S. Barghocrn, Harvard Univcrsity.)
rsatuwever, silica
1 ~
53
The Occ~rrence. Dissolution. and Deposition or Silica

"
glass evidently underwent self-abrasion during the continuous tumbling. generating

subcolloidal fragments of extremely high solubility, so that the monomer level
reached more than 300 ppm.
Interfacial Energy
II'1 "
i .!
I .
One problem in calculating the solubility of small particles is that the surface energy
is not accurately known. There are very few substances of which the solubility of
particles of uniform size and less than toO A diameter have been measured. According to Walton (174), a combination of these requirements has not previously been
achieved, but recently using radiotracer measurements and the electron microscope.
such measurements have been made on strontium sulfate particles, from which the
solid-water interfacial energy was calculated to be 84 8 ergs ern -2.
In the case of amorphous silica, Alexander's data gave E = I.l X 105 cal ern -2, or
46 ergs em:". For purpose of calculations, Iter (175) used both 80 ergs em -2, based
on some preliminary experimental data, and 133 ergs em -2, based on the surface
tension of glass extrapolated to zero alkali content (176), 275 ergs ern -2, minus the
energy of wetting of the siloxane surface by water, 142 ergs ern -'.
In the case of quartz, the interfacial energy was taken to be the surface energy of
the crystal, 980 ergs em -2 (177) minus the heat of wetting, 564 16 ergs em -2 (178),
leaving an interfacial energy of 416 ergs cm -'.
As discussed earlier under the topic of thermodynamics, calculations based on
data now available involve small differences between large numbers, and about all
that can be said is that the interfacial energy of the amorphous SiOH-H 2 0 surface
.
is low and probably of the order of 50-100 ergs crn "".
Some further preliminary experiments by lIer have given the results shown in
Figures 1.10a and b. On commercial silica sols made from the same type of sodium
silicate, but not all at the same temperature or necessarily containing the same trace
impurities, line A was obtained. On sols of very small particles made by polymerizing pure silicic acid for various times at pH 8 and 25C, then stabilizing at pH 2.2
and aging to a constant monomer concentration, line B was obtained.
The particle size was calculated" on the basis of specific surface areas determined
by a titration procedure, and assuming the particle is anhydrous SiO,. The values of
E, the interfacial energy calculated from the slopes of the lines A and B, using the
equation
"
E = 0.1754Tdlog
Sr
S;
are 54 and 46 ergs em -2.

In view of the scatter of data for line A, it is quite possible the slope could be the
same as that of line B, in which case both would give a value of E, the same as
reported earlier by Alexander, 46 ergs cm- I
The difference between the two groups of sols is that in making the commercial \"
--
-....
-~
...
tion of Silica
. generating
nor
level
:J
200
en
en
s::c:
a..
a::
150
:E
<t
\A
l.L..
....>:J
ffi
::>
100
...J
oen
PARTICLE
10
12
DIAMETER - NANOMETERS
(a)
Figure 1.10a. Relation between solubility of amorphous silica at 25C in water and particle
size at pH 8: A. particles made at 80-IOOC; B, particles made at 2S-S0C.
:E 1000
a..
a..
r-------.------"""'l'""".....,
<t
:J
en
en .500
s::c: 400
,/
a.
~ 300
:E
<t
,/
'Co
~ 200
o
O
0.5
1.0
RECIPROCAL OF PARTICLE
DIAMETER -NANOMETERS
(b)
Figure 1.10b. Relation between log solubility of amorphous silica at 25C in water and reciprocal of particle: size: at pH 8: A, particles made: at 80-IOOC: 8, particles made at 25-S0C.
5S
The Occurrence, Dissolution. and Deposition of Silica
sols (line A). particle growth was carried out at temperatures above 80C. whereas
the particles made by aging silicic acid (line B) were all grown at lower temperatures
and probably are internally more hydrated with trapped silanol groups.
A dependable value for the interfacial energy remains to be determined for both
amorphous silica and quartz. '
Since the interfacial surface energy for the quartz-water surface may be as high as
416 ergs em:", 10 nm quartz particles may have a solubility of 28 ppm, and 3 om
particles. 93 ppm (18).
.-
EFFECT OF IMPURITIES ON SOLUBILITY
i,.
.r
.i
I
Certain impurities such as aluminum in minute amounts not only reduce the rate of
dissolution of silica, but by chemisorption on the surface of silica, even in amounts
less than a monomolecular layer. reduce the solubility of silica at equilibrium. Jephcott and Johnston (179a) have shown that the apparent solubility of amorphous finely
divided silica in water, which they lind to be 0.017% at 37C. is reduced to
0.003-0.0097%' when aluminum' oxide is added to the system and to less than
0.0001 % when powdered aluminum is present. Since it was also shown that the addition of silica to a suspension of alumina depressed the solubility of alumina. it seems
likely that a surface containing both Si0 2 and AI 203 is formed on both the silica and
alumina phases and has a lower solubility than either oxide. Earlier Denny. Robson.
and Irwin (I 79b) had shown similar effects of iron and aluminum.
This observation emphasizes the point that in attempting to measure the solubility
of silica in the form of coarse particles, where the surface area of the silica in the
system is rather low. it may be very difficult to obtain an accurate measure of solubility unless traces of aluminum and other metals forming insoluble silicates are
ridigly excluded from the system.
The fact that the amorphous silica on the ocean floor, found in enormous deposits
of skeletons of diatoms. does not dissolve in seawater. has been a mystery. Lewin
(180) found that as soon as these organisms died. silica began to dissolve. but only
slowly. and the concentration in solution reached only 30 ppm. Removal of organic
matter had no effect, but treatment with hot concentrated nitric acid greatly
increased the rate of dissolution. as did treatment with mixed oxalate and EDTA
solutions at pH 6.8. This clearly indicated certain metal ions were retarding the
dissolution of silica in tris buffer at pH 9.0.
The nitric acid-cleaned silica. which was free from organic material as well as
metal ions. was immersed in 4-10 mi\{solutions of selected metal salts at a series of
pH values and washed. and the rate of dissolution was measured in a standard manner at pH 9.0. Metals with no effect at pH 2-9 were La. Mo. and Cr. and at pH
4-11 were Ca and Mg: at pH 8. which is that of seawater. AI. Be. Fe. G~. Gd. and Y
all retarded dissolution. However. Al was unique in that when applied over the range
from 5 to 9. it rendered the silica completely insoluble at pH 9.
The amount of aluminum on the silica surface required to reduce the solubility of
silica has been measured by Iler (ISla). When only one aluminum atom was
absorbed on the surface as an anionic aluminosilicutc site per 2 nrn", at which point
--
.... .;..._n of Silica
whereas
per-v-res
i for both
high as
and 3 nm
1S
he rate of
amounts
irn. Jephous finely
-duced to
less than
the addi it seems
silica and
Robson,
solubility
:CCi
he
e of solucates are
5 deposits.
'y. Lewin
but only
If organic
j greatly
.d EDTA
rding the
s well as
series of
ard mannd at pH
id, and Y
the range
ubility of
tom was
lie!
nt
Effect of Impurities on Solubility.
57
only 5% of the surface was occupied. the rate of dissolution as well as \he equilibrium solubility of the surface were drastically reduced. The surface of colloidal silica
in the presence of an aluminum citrate complex became saturated with aluminum at
pH 8 when 1.4 aluminosilicate sites nm-z were present (about 25% coverage) and the
solubility of silica was reduced to 10 ppm. The effect of extremely low concentrations of aluminum ion on the solubility of quartz was reported by Baumann (18Ib).
The quartz surface was first equilibrated with a buffer solution at pH 8.5 at 25C
until a concentration of about 6 ppm SiO z was reached. Then to different suspensions, different amounts of aluminum ions were added at concentrations of 3-60 J.l.M
(0.15-3.0 ppm equivalent of Al z0 3 ) . Over a 10 day period the amount of silica in
solution dropped drastically. Even with only 3 J.l.M aluminum present the soluble
silica decreased to 3 ppm SiO z, and with 12 J.l.M to zero. It is significant that similar
amounts of iron had no effect. Perhaps this should not be surprising when it is
recalled that quartz often is found in association with iron oxide.
Lieflander and Stober (182) found that when the surface of colloidal silica powder
was covered with an amount of aluminum corresponding to 3.6 aluminum atoms
nm -z, that is. about hal f the surface covered. the silica was essentially insoluble.
The effect of impurities AP+, Ca!", Mgz+. SO/-, and F- on the solubility of
silica gel in water and 0.1-2.0 N solutions of Na ZC0 3 , KZC0 3 NaOH, and KOH
were studied by Dmitrevskii (183). The ions F- and SO/- have no effect on solubility, but the polyvalent cations decreased solubility or led to formation of insoluble
silicates.
The effect of impurities on the solubility of glass in alkaline solutions has been
discussed by Weil and Marboe (184). Calcium, zinc, and aluminum hydroxides at
low levels greatly retard attack by alkali. It is interesting that in strongly alkaline
solution. silica offsets the effect of these hydroxides, no doubt by removing them
from solution as insoluble silicate. Thus under certain conditions the addition of
silica to a solution of alkali can increase its rate of attack on glass. Similarly. traces
of iron or copper from screens used to sieve glass powders can reduce the rate at
which water attacks the glass and leaches alkali.
Boehm and Schneider (185) caused alumina to be adsorbed on the surface of a
pyrogenic silica by suspending it in a dilute solution of aluminum chloride and
adding enough NaOH to neutralize two-thirds of the chloride. thus forming basic
aluminum chloride. The silica surface adsorbed one Al atom per SiOH group and
the solubility of the silica dropped from 123 to 6 rpm.
A practical application of this phenomenon is to- insolubilize the silica in a porous
glass membrane at low pH by including 0.3 g I-I of AICI 3 6H zO in the feed solution.
or by treating the membrane every 100 hr with the aluminum salt. Iron or zirconyl
chloride was not as effective (186).
The dissolution of silica from glass in water (187). from biogenic amorphous silica
in seawater (18S). and from kaolin. talc. and mica dusts in Ringer's 'solution or
serum (189) were all accelerated by removing metal ions from the surface hy extraction with acid or cornplexing with citrate ion in neutral solution.
The reaction of-silica gel with MgCI 2 at p H 9A to form magnesium silicate evidently involves the dissolution or silica. Smirnovu. Dushina. and Alcskovskii (190)
..............
58
The Occ~r~ncc:. Dissolution. and Deposition of Silica
found that introduction of aluminum into the gel (SIO z:AI 2 0 3 = 2: 1) permitted
only adsorption of magnesium onto the surface. but none reacted.
Magnesium ion insolubilizes amorphous silica only to the extent that it converts
silica to magnesium silicate. In the case of Quartz it combines with the amorphous
silica associated with the surface: and thus lowers the solubility at least to that of
pure quartz (191).
.Calcium ion has no effect on the solubility of silica up to about pH 9.S. where calcium silicate begins to form (192).
The effect of phosphoric acid on silica has been examined by Mitsyuk (l93), who
found that H,P04 is adsorbed on silica gel from water. The amount corresponds to
about one H 3P04 molecule per surface silicon atom, indicating formation of a surface compound of silicon phosphate. Once treated with as little as 0.06% H,P0 4 , the
rate of dissolution of the silica in water is greatly reduced. The addition of H 2 S 0 4 to
the dilute H,P0 4 solution prevents the formation of an adsorbed film and accelerates
dissolution. In strong H,P0 4 there is further reaction as silica is converted to SiP z0 1
in which silicon is coordinated with six oxygen atoms.
.
Lithium hydroxide differs from NaOH and KOH in the reaction of concentrated
solutions with silica (194). In 1 N solutions all three bases dissolve microamorphous
silica at about the same rates, but in 2.2 N solutions LiOH does not react. Also: the
addition of LiOH to strong solutions of the other alkalis retards the rate of dissolution of silica. apparently by the formation of an insoluble film of lithium silicate on
the silica surface. It should be pointed out that lithium silicate is soluble in water
below about 60C, and the system acts 'much like the other alkali silicates. but at
higher temperature lithium silicate is insoluble, and comes out of solution as a gel or
precipitate. It appears that the less hydrated form of the lithium ion behaves more
like calcium does.
Fluoride ion affects solubility only at low pH. and then only to the extent that it
.
- converts silica to SiF.z- ion.
Pressure increases the solubility of amorphous silica in seawater at oc. Willey
(20) reported the following: at 1 atm the solubility as SiO z was 65 ppm. This
increased to 71 ppm at 150 atm and thereafter linearly to 94 ppm at 1250 atm.
f
I:
I'
I
i
,f
,
!'
,.i.
>
'.
EFFECTS OF ORGANIC COMPOUNDS ON SOLUBILITY

Broadly speaking, organic compounds can either retard dissolution by covering the
silica surface with a strongly sorbed liIm or accelerate dissolution by removing the
soluble Si(OH)4 that is in equilibrium with the surface by converting it to a soluble
complex.
The simplest example of the former is the effect of treating a pyrogenic silica with
trirnethylchlorosilane, which coats the surface with a chemisorbed monolayer of
SiOSi(CH 3)3 groups. In undisturbed suspensions of treated and untreated powders.
the rate of dissolution of the treated material in neutral 1% NaHCO J solution at
25C is only 15% as fast as the untreated. When 'shaken. however. the coated silica
aggregates are apparently broken apart. leaving bare spots on the ultimate particles
which then dissolve much faster. The difference is noted mainly below pH 7 (195).
>.
, of Silica
Effects of Organic Compounds on Solubilit)'--
xrrnitted
Catechol and Related Compounds
co., .ts
10rphous
o that of
here cal93), who
ponds to
of a surjPO., the
12S0. to
celerates
o SiP 20 7
:entrated
lorphous
~Iso: the
, dissolulicate on
in water
s, hilt at
,
;a
or
/es more
it that it
A 6-coordinated structure is suggested for the complex anion formed between catechol and silica, reported by Rosenheim, Raibmann, and Schendel (196). The ammonium salt, crystallized from, alcohol, has the composition (NH.)2Si(C,H.02)3 and
dissolves in water without decomposition of the anion. The compound is prepared by
boiling freshly precipitated silica in an ammoniacal solution of pyrocatechol out of
contact with air. Since silica is not soluble in ammonium hydroxide (because silica
does not form silicate ions below about pH 10.8). it is evident that the combined
action of ammonia and catechol converts silica to some soluble form other than a
simple silicate ion. The corresponding potassium, barium, guanidinium, and
pyridinium salts were prepared.
Numerous investigations have shown that o-dihydroxy aromatic compounds are
unique in forming complex ions with silicon that are not hydrolyzed in aqueous solution, but are destroyed by atmospheric oxygen, forming dark insoluble residues.
polynuclear complexes can also be formed and many salts, especially of organic
bases, have been prepared from a variety of silicon tricatecholate derivatives. Weiss,
Reiff, and Weiss (197) found that catechol solution will attack quartz and dissolve
amorphous silica at pH 7-8.' If the partly dissolved silica is washed, it retains
strongly adsorbed catechol.
Vlacil and Bock (198) have shown that silica can be extracted from the aqueous
. phase with nitrobenzene if the concentration of catechol in the water is 0.5 M. that
_of diphenylguanidine in the organic phase is more than 0.25 M. and the pH is
suitably adjusted. By this means silica can be concentrated for analysis.
, Her examined aqueous ammonium catecholate as an etching solution for different
forms of silica. In a mixture of 20% catechol, ~O% concentrated ammonium
hydroxide (28% NH 3). and 40% water. vitreous silica dissolved at a rate of 0.5
Quartz dissolved at about half that rate.
micron hr- I at 90C (0.2 mg cm -2 hr
r
:, Willey
m. This
n.
:ring the
,ving the
1 soluble
lica with
layer of
iowders,
ution at
ed silica
pa
19~J'
\:5
59
').
Polyhydroxy Organic Compounds
Since boric acid forms stable complexes with polyhydroxy aliphatic compounds such
as glycols and polyalcohols, these common compounds might be expected to have
some effect on silica: apparently they do. not. Richardson (199) examined nine sugars
and seven polyhydric alcohols. and found no influence on solubility. For some
unexplained reason he found glycine- to. retard the rate of dissolution of quartz by
10-20%.
. .
N-Oxides
An apparently unique type of compound thal strongly interacts with silicic acid and
silica surfaces by hydrogen bonding is l-hydroxypyridine IV-oxide. It will be noted
that, as in catechol. there are two oxygen atoms closely spaced. so that they can
either chelate with .1 silicon atom or hydrogen-bond to adjacent SiOH groups on
polysilicic acid.
The Occu-rfence. Dissolution. and Deposition of Silica
Gardner and Katritzky (200) prepared and characterized about 24 amino- and
hydroxypyridine oxides. and showed that 2-hydroxypyridine l-oxide exists as the
strongly hydrogen-bonded l-hydroxypyrid-2-one. Weiss and Harvey (201) described
the water-soluble monovalent 6-coordinated silicon chloride salt. soluble in water
and alcohol. The tetrachloroferrate (III)
H
/C.. . . . .
HC' _ C-O
II
HC~
N=O
'C/
H
,
,.
salt is soluble in tetrachlorethane.

Iler examined the pl-l-titration behavior of silicic acid in the presence of 2hydroxypyridine I-oxide by titrating 16 mM (1000 ppm Si02 ) silicic acid silica from
pH 10.5 to 3.0 in the presence and absence of a 43 mM concentration of the Noxide. At no point did the titration curves differ. indicating that no complex had
formed. In another experiment. a solution of Si(OH). containing 100 ppm as SiO:z
was mixed with a 200-fold excess of the above N-oxide at pH 6.15 and .aged for a
few hours. Tests with molybdic acid showed that the reaction rate with silica
monomer was the same as a control, indicating either that no complex was formed
at this pH or that it dissociated very rapidly. However. the rate of dissoiution of
monomer from colloidal silica particles at pH 1.4 was apparently doubled in the
presence of a 20 mM concentration of the N-oxide, indicating some type of interaction at low pH.
.
Schlipkoter and Brakchaus (202) investigated the interaction of polyvinylpyridine
in connection with the problem of silicosis. (The extensive literature on this general
subject is reviewed in Chapter 7.)
. Organic Bases
Organic bases in water interact with silica in a manner that would be expected from
the resulting pH. Strong quaternary ammonium bases like tetramethylammonium
hydroxide dissolve silica rapidly. forming the silicate salt.
In a search for an organic medium that would dissolve silica. Meyer and Yen
(203) found that quinoline plus KOH pellets. dissolved crushed quartz at a
substantial rate, in fact, faster than saturated aqueous KOH.
LivingTissues
.,
According to Foucalt and Col1ette (204), finely divided silica dissolves more rapidly
in the peritoneal cavity of a rat than at. 37C in a buffer solution at pH 7A. The
- !
.. ..=....-..
of Silica
ino- and
:s a'" the
Effects of Organic Compounds on SoJubiJi4'-_
61
reason is unknown. but it would not be surprising if there are compounds present
having a catechol-like structure that are responsible.
les, .d
in water
Solubility in Alcohols
Methanol
At 25C, amorphous silica is essentially insoluble in methanol. Her' prepared
colloidal dispersions of 90 A silica particles at pH 9-9.5 in methanol-water mixtu res
and observed the approach to solubility equilibrium from the initially undersaturated
solution and from a heated and cooled supersaturated solution over a period of 2
months.
Equilibrium solubilities were as follows:
ce of 2ica from
f the Nplex had
as SiD:
~ed for a
th silica
s formed
iu ti,.., of
:d. he
~ interacIpyridine
5 general
Wt. % Methanol
Solubility
at 25C (mg 1-1)
140
25
50
75
90
75
40
15
5
Obviously,. the solubility is strongly related to .water content and is very low in
anhydrous methanol.
On the other hand. at 200C under pressure, silica "dissolves" to a higher extent
in anhydrous methanol than in water, as shown in a careful study by Kitahara and
Asano (205). They reported the solubility to be at a minimum at around 80%
methanol-20% water.
Just as silica reacts with water for form Si(OH)~. silica combines to some extent
with anhydrous methanol:
ted from
.rnoniurn
and Yen
'tz at a
e ra oidly
7.'.
he
Ester form~tionis evidently Involved," since silica did not dissolve in acetone under
the same conditions. Also it was shown that the surface of the silica gel used as a
source of silica was fully esterilied. However. it is not certain that the dissolved
species was the ortho ester or esters ofpolysilicic acids. The polymerization of the
dissolved silica on cooling suggests that the dissolved species may have contained
some silanol groups either from traces of water in the system or from residual
silanol groups on the gel that was used. even though the latter had been dehydrated
at high temperature.
Kitahara and Asano found that at 500C. methanol dissolved up to 1.9 g 1- 1 SiD:.
maximum solubility being observed when the gel was dehydrated to a maximum
: y....
"the..Occurrence. Dissolution. and Deposition of Silica
62
extent at SOO-700C. Gels heated to still higher temperatures no doubt'sintered with

loss of surface area. accounting for lower solubility.
The maximum degree of esterification of the surface of the resulting silica gel was
5.0 methoxy groups nm -2. This means that the surface was covered with a closepacked layer of methyl gro,!ps. which explains its hydrophobic character.
Higher Alcohols
Using silica gels dehydrated under optimum conditions and suspended in anhydrous
alcohols, the following solubilities were observed by Kitahara (206) at 500C:
Alcohol
Solubility (ppm)
CH 30H
1890
164
8
C2 H $O H
n-C 3 H 70 H
The surface of the resulting gels was fully esterified with ethoxy and propoxy groups,
there being 3.0 alkoxy groups nm -2 (205,207-209).
SOLUBILITY IN MOLTEN SALTS

The solubilities of silica in molten NaCl and KCI under argon have been measured
(210) at 900-1100C. The values were 1.8 and 1.7 ppm at 900C, and only increased
by I.S-fold at 1100C. It was no doubt important to exclude oxygen and moisture,
which rapidly oxidize these salts to alkali, which then would combine with the silica.
RATE OF DISSOLUTION OF SILICA

Mechanism
f.
t
I
I
The rate at which silica dissolves in water is influenced by many factors, but regardless of the type of silica involved, the dissolution process requires the presence of a
catalyst. The dissolution of silica in water is, in effect, a depolymerization through
hydrolysis, and the "solubility" is the concentration of Si(OH). reached as a steady
. state in the depolymerization-polymerization equilibrium. The "catalyst" is a
material that can be chemisorbed and increases the coordination number of a silicon
atom on the surface to more than four, thus weakening the oxygen bonds to the
underlying silicon atoms.
The hydroxyl ion is the unique catalyst in alkaline solutions and hydrofluoric acid
in acid solutions. The structure of amorphous silica is an even more open arrangement than that of cristobalite, to which it is closely related. On the surface there are
spaces between oxygen ions sufficiently large to accommodate hydroxyl ions. Such a
of Silica
ered with
~
as
a close-
ihydrous
-.
groups,
ae ~ed
ncr",_.,;ed
noisture,
re silica.
regard.nce of a
through
a steady
it" is a
a silicon
Is to the
63
Rate of Dissolution of Silica
surface then bears an ionic charge and silica is constantly being exchanged in an
equilibrium between solution and surface, as indicated. The first step is the adsorption of OH- ion, after which a silicon atom goes into solution as a silicate ion. If the
pH is much below II, the silicate ion hydrolyzes to soluble silica, Si(OH)., and OHions and the process is repeated (Figure 1.11). Hydrofluoric acid no doubt acts in the
same way, the first step being chemisorption of a F- ion, which is about the same
size as OH- ion.
Catechol and related compounds dissolve silica in neutral solution, but it is not
certain that a catalytic effect is involved. It is likely that these materials simply combine with Si(OH). as rapidly as it is liberated from the surface by the catalytic action
of OH - ion and thus keep the solution from becoming saturated. Above pH II the
hydroxyl ions act in the same way, converting Si(OH). to silicate ions, thus keeping
the solution unsaturated so that silica continues to dissolve. But below pH 11, even
down to pH 3, the OH- ion is only the catalyst that controls the rate at which silica
dissolves until the solution reaches saturation.
The dissolution mechanism has been discussed in detail by Strelko (211), who
considers analogous mechanisms for dissolution of silica not only by catechols but
also HF, H 3PO., and possibly in acidic acetyl acetone, all of which are known to
form silicon compounds in which silicon is coordinated by six -surrounding fluorine
or oxygen atoms.
However, the catalytic effects of F- and OH- ion are not identical. as is obvious
from the fact that silica dissolves in NaOH solution but not NaF. It requires the
presence of H+ and F-. Stober made the important observation that stishovite,
which is the only form of silica in which silicon atoms are surrounded by six instead
of the usual four oxygen atoms. is insoluble in aqueous HF but dissolves even in
weak alkali (140). The first step in the action of HF on any type of silica is to
convert the SiOH surface groups to SiF groups. These two surfaces are physicalIy
very different. The SiOH surface is completely hydrophilic, whereas the SiF surface
is hydrophobic. since there are no hydrogen atoms to hydrogen-bond with water.
Consequently, in the case of stishovite, which is much denser than quartz. the surface is converted to a close-packed monolayer of hydrophobic fluorine atoms,
physically similar to a fluorocarbon surface. This. in effect, excludes water from the
~I
Si-O-Si.,J.OH
~I
Si-o~siloH
,r---~
OH
S+OH
l_
oric acid
arrangehere arc
.~
'la
+Si(OH):\o~
SI-O ::"S~,OH
0/
Figure 1.11. Proposed mechanism of dissolution of silica in water in the presence of hydroxyl
ions. The dotted line represents the interface between silica on the left and water on the right.
...
~--.
-.

surface so that no dissolution can occur. On the more open quartz structure. the
fluorine atoms are not as densely packed and water is not excluded from the surface:
there is still room for F- ions to penetrate the surface and raise the coordination
number of silicon. so that dissolution can occur.
As for the effect of hydroxyl ion, it is not possible to see how it could catalyze the
dissolution of stishovite in which silicon has already reached its maximum coordination number. No data seem to be available on the effect of pH on the dissolution
rate of stishovite, but it is interesting that at pH 8.4 it dissolves about as fast as vitreous silica when compared on the basis of equal areas of surface being'exposed to
the solution. Furthermore, it continues to dissolve past the saturation level for vitreous or amorphous silica. The concentration of soluble silica can reach as high as
190 ppm, at which point colloidal particles are nucleated (139). It is likely that stishovite is hydrolytically unstable and would eventually decompose completely to
amorphous silica. Whether or not pH has an effect on the rate of hydrolysis is not
known.
As for other forms of silica, equations for the polymerization-depolymerization
kinetics and equilibrium have been formulated by Stober (195) to explain solubility
behavior.
The relative rates of dissolution of different forms of silica at pH 8.5 have been
reported by Stober ( 139):
Type of Silica
"I
Fused glass
(vitreous)
Quartz
Cristobalite
Tridymite
Coesite
Stishovite
Rate of Dissolution
(10- 8 g rnl " day-I)
39.0
:2.8
6.0
4.5
0.7
11.0
The measurements were made with powders having surface areas of I J 01 2 suspended
in 500 ml volumes.
In determining the rate of dissolution of amorphous silica powders. the possible
existence of a porous. rapidly soluble layer must be considered. Yates and Healy
(212a) have shown that BDH-precipitated silica. widely used as a standard for study.
has a surface layer that is impermeable to nitrogen but permeable to alkali. This
"gel" layer dissolves more rapidly than the remainder of the silica and must be
taken into account when the rate of dissolution is being measured.
After an initial rapid period the rate of dissolution. expressed as rnoles Si0 2 rn ?
hr- I becomes constant and is characteristic of the particular kind of silica. When
BDH silica was first heated to 800C for 36 hr, the characteristic rate decreased by
50% and approached that reported by Stober (139. 144) for vitreous silica. The
original SDH probably contained some internal uncondensed OH groups.
.,"
~.
'.~
...;
:.
.;, ...
~ ..
.,";".'- .
ition of Silica
.ructure, the
th -..face;
Effect of pH on Rate
::00. ~_.Iation
Below pH 3, Elmer and Nordberg (153) found that the initial rate of dissolution
reached a maximum at 0.8 N HNO", corresponding to pH 0.1, and declined above
this pH. However, BaumannJl54) has shown that from pH 3 to about 6, the rate of
dissolution increased in proportion to the hydroxyl ion concentration. There may
therefore be a small minimum between pH 0.1 and 3.0 that has gone unnoticed.
Between pH 2 and 9, Baumann found a region from pH 3 to 6 where the rate of
dissolution was proportional to the OH- ion concentration, whereas outside the
range the pH depended less on pH (Figure 1.12). Because of the overall shape of the
curve, he examined the possibility that at low pH silica became a cation, but this
could not be supported by a pH titration of soluble silica with hydrochloric acid.
More than likely, there is a catalytic effect of H+ ion which becomes evident in the
range from pH 2 to 0; on the other hand, above pH 6 rate of diffusion or rate of
desorption of the silicic acid from the surface may limit the overall rate of dissolu-
catalyze the
m coordina~ dissolution
s fast as vit~ exposed to
level for vith as high as
:ely that stiimpletely to
olysis is not
65
ymerization
in solubility
tion.
5 have been
Relation Between Rate of Dissolution and Particle Size
....
It is logical to assume that the rate of depolymerization or dissoluti~n of colloidal

silica particles would be proportional to the specific surface area of the silica particles. Thus different solvents such as dilute hydrofluoric acid, molybdic acid. or dilute
alkali, all of which convert the monomeric silica permanently to other silicon corn-
+2
i=
+1
::::>
-J
tf)
suspended
~
0
u,
0
the possible
and Healy
'd for study,
alkali. This
nd must be
-I
a::
2
<:>
0
-2
-J
-3
:s Si0 2 m :"
ilica. When
ecreased by
silica. The
10
pH
Figure 1.12. Log rate of dissolution of amorphous silica versus pl-l. Slope of dotted line indicates that between pH J and .5 the rate is approximately proportional to the hydroxyl ion
concentration. [Baumann (I 54}]
......
-.
TfiC Occurrence. Dissolution. and Deposition of Silica
,
j.
pounds. may therefore be employed to measure surface area. The difficulty,

however, is that the types of silica particles studied have been so varied and illdefined that this approach has not been of any value until recently, when sols of uniform discrete solid particles have become available. Even then the value of the
method is in doubt unless one can be sure that the samples of silica under study all
have the same composition and structure.
In a patent issued to Balthis (212b) a method is described whereby a sample of
deionized silica sol is put into an excess of 0.0 I N NaOH solution at 30C and over
a period of 90 min samples of the solution are removed and the 'amount of
monomeric silica is determined by reaction with the molybdic acid reagent. The rate
of dissolution of the silica to form monomeric silicate in the alkaline solution was
related to A, the specific surface area of the silica (in .square meters per gram)
determined by other means, by the following equation:
where K D is a constant defined as the specific depolymerization rate for the

particular type of silica, dm/d, is the rate of monomer formation per 100 min, and m
is the fraction of original silica converted to monomer at time t, in minutes.
For the particular type of silica particles involved, which was highly porous. the
value of K was ISS at the point where 20% of the silica was converted to monomer.
For a dense silica particle prepared at elevated tern perature by the buildup process
according to Bechtold and Snyder (213). the value of K was about 8 at the same
stage of dissolution. The porous and dense particles com pared were of about the
same size, being 18 and 16 nm in diameter. respectively.
It is therefore obvious that the rate of dissolution in alkali cannot be used as a
dependable method for determining specific surface area unless it is certain that all
the samples being evaluated have the same particle structure. or at least have been
made under the same process conditions from the same materials.
The method is probably valid. for example. as em ployed by Goto (214). who used
it to compare the particle sizes of silica polymerized from monomer in a pH range
from 7 to 10. In this case the particles were depolymerized by diluting the sol a hundredfold with I g 1-1 of sodium carbonate solution. giving a pH of 10.8, the original
silica sols containing 2 g I-I Si0 2 Goto used an equation developed by Suite, Hirai.
and Taki (215), which assumes that the rate of dissolution of particles is proportional to their surface area.
Instead of an alkaline solution. a dilute solution of NaF and Hel to generate HF
was employed by Goto (216a) to measure the specific surface area of colloidal silica
from the rate of dissolution in this acid medium. The samples from the reaction mixture were removed. the reaction was stopped by adding aluminum salt to combine
with the fluoride, and the dissolved silica was then determined by the molybdic acid
method.
-..;:.-_.
In of Silica
difficulty,
:d ~ ~ illols _ .milue of the
r study all
Based on Goto's data, as summarized by Okura, Goto, and Murai (216b). the
initial rate of dissolution of colloidal silica particles of different sizes at a concentration of 20 mg I-I, at 25C, in 0.12 N HCI containing 300 mg I-I F- ion, was
expressed as ppm passing into solution per minute per milligrams of SjO, initially
present. The observed relation of rate of dissolution to the specific surface area of
the silica particles initially present was interpolated as follows:
sample of
: and over
.mount of
:. The rate
[ution was
per gram)
orous, the
m0-"mer.
rp I .:ess
the same
about the
who used
pH range
sol a hunie original
ito. Hirai.
is propornerate HF
)idal silica
ction mix) combine
ybdic acid
A, Specific Area
D, Particle Diameter
(rn" g ")
(nm)
R, DissolutionRate
(mg mg -I min -I)
600
800
1000
1200
4.3
3.4
2.7
2.26
0.045
0.075
0.150
0.300
The particle diameter was calculated from specific' surface area assuming a density
of 2.2 g ern-3. The data are approximately represented by the empirical equation R
= 1.7(IO)-loA3. The data resemble similar data obtained by Her for particles of
similar size dissolving in dilute alkali, as will be discussed.
The many different factors that can influence the rate of dissolution of silica particles in addition to the surface area have been reviewed by O'Connor and Greenberg
(217). The temperature, degree of crystallinity, previous mechanical and heat treatment, and previous treatments with water. alkali. or acid all had their effects. They
found that the theoretical rate equations for dissolution hold only if the silica is completely dispersed as individual particles and that in aggregated or flocculated
material not all the surface' area is available to solution. They formulated the rate of
solution as follows:
.e for the
lin, and m
used as a
in that all
have been
67
de
dr
,.'
where c = concentration of dissolved silica (moles 1-1)

. S = area of surface of solid silica phase (rn" I-I)
k 1 = rate constant for dissolution
k z = rate constant for deposition
t = time
At equilibrium. dcf dt = 0 and c;
de
-
ell
k./k 2 from which

= kzS(c. - c)
where c, is the equilibrium concentration or "solubility" of silica.
.., ...:;- ...
!
68
In neutral solution. where a considerable excess of silica is' present. S is

approximately constant. and if c = 0 at t = O. then
log
c, - c
Ce
II
= k'St
where k' .. -k 2 O'Connor and Greenberg presented experimental data showing that
this expression held very well when an amount of silica was used so that S was
constant. But when different amounts of a given silica powder were suspended. the
times required to reach equilibrium were not proportional to the surface areas. In a
granule of silica powder consisting of aggregated ultimate silica particles, it is
obvious that the particles inside cannot dissolve as rapidly as the outer particles.
In alkaline solution above pH II, the rate of deposition is zero, so that
de
.!
dt
I ~
:1
;i
;;
il
!,
Letting Cp = moles per liter of amorphous silica in suspension consisting of n

particles of density 2.2 and diameter d,
I.
Cp
!!
j1
-dCp
-dt-
It
:!
II
;t'
U
. 1
; i;
:r
,.
iI
,~ ,~
TrcJ3
2.2n
60
= s =
k: n 1!3C p 2 3
Integration gives
where CPo is concentration of suspended silica at time t = O. and k 1 * and k 3 are

constants.
Greenberg (218) found that at 40C above pH I I. the rate is independent of
hydroxyl ion concentration and proportional to the amount of silica introduced into
a fixed quantity of 0.025 N NaOH (pH 12.4) solution. where the Na 2 0 : S i 0 2 ratios
were I :0.66 to 1:2.
The energy of activation for dissolution in water was 17.8 and in alkali was 18
kcal mole:". Earlier. Greenberg had measured the rates of dissolution of both quartz
and amorphous silica powders in alkali, and concluded the energy of activation in
alkali was 21.5 kcal mole " '. also that above pH II the addition of Na 2SO. did not
affect the rate, and that the rate was profoundly influenced by the nature of the silica
structure.
A modification of the method of measuring dissolution rate was used by McNally
and Rosenberg (219) to determine the surface area of extremely small colloidal silicparticles which are below the practical resolution limits or the electron microscope. _
.:-, ...
on of Silica
sent, S is
om. They carried out the dissolution reaction using 1.6 g of colloidal Si0 2 in I liter
0.0025 N NaOH, and followed the rate of depolymerization by noting the change in
electrical conductivity of the solution with time. Where R, is the electrical resistance
after all the silica is dissolved and R o the resistance of the mixture before the silica
dissolves, a plot of (R, - R O} 1/ 3 versus time gave a constant slope which was related
to the particle diameter by measuring the slope for particles known to be 23 nm in
diameter, and assuming the slope is inversely proportional to the particle size as
small as 1.4 nm. The sol contained 14% silica, had a molecular ratio of Si0 2 : Na 2 0
of about 14: I, and the particles could not be resolved by electron microscopy.
However, the assumption that in such a solution all the silica is present as uniform
"particles is questionable, since a considerable portion of the silica must be present as
silicate ions.
In the method used by Balthis (2l2b) the assumption is made that the rate.
expressed in terms of the fraction of silica dissolved per 100 min, can be measured at
a given time, t. However, it is easier to use the integrated equation
owing that
hat S was
ended, the
areas. In a
icles, it is
tides.
69
(l - m}I!3 = 1 - k'Aol
isting of n
and plot the cube root of the fraction of silica remaining undissolved ".versus time to
obtain a line the slope of which is a combination of A o, the original specific surface
area of silica, and k', a constant proportional to the characteristic depolymerization
rate of the particular type of silica involved. The latter can be expressed in terms of
milligrams per square meter per minute, as measured, for example, at pH 12 and at
25C.
" Rate of Dissolution of Very' Small Particles
and k, are
Goto (216a) has shown that the rule that the rate of dissolution is proportional to the
surface area does not hold for particles of less than 5 nm diameter. As discussed
earlier, smaller particles exhibit much higher equilibrium solubility and this must be
"taken into account. Thus the rate of solution in alkali should be proportional to both
the surface area and the solubility of silica.
oendent of
duced into
5i02 ratios
ali was 18
oth quartz
tivation in
O. did not
.r the silica
rate of solution
dt
KAS
where K = constant
A = area of silica
S = solubility of the particle. depending on the size
m = fraction of silica dissolved at time t
From the earlier discussed relation or solubility and particle size:
f McNally
:Jicl . silica
.ros __ ,IC. 5
dm
=
log
SrI
S,
5.7T- 1d-\
70
The-Occurrence. Dissolution. and Deposition of Silica
where Stj is the solubility of particle of diameter d. in nanometers, at time t; S, is the

solubility of a flat silica surface with infinite radius of curvature; is the interfacial
energy in ergs ern -2; and T is the temperature in degrees Kelvin.
Where two particle sizes are considered,
where Stt is the solubility of diameter d and So that of diameter do. Let B
l3.IEr- l
0:
Rate of Dissolution as Particle Dissolves

1
If silica is assumed anhydrous with a density of 2.2, the specific surface area A
1373 d :',
'
:1
_i
,i
particle at t = 0
= area at time t
do = diameter at time zero
d diameter at time I (nm)
m
fraction of silica dissolved
Let A o
A
= area of a
- ;i:
.~ i
.
Then
A
-=
~J
(I - m)2/3
(I - m)I/3
. I
do
,
i
I,
I
Sd == So [exp (-Bd;I)] [exp Bd;' (1 - m)-1/3]
- 1
dm
dt
B
KAS
13.IET-l
KAoSo [exp (_Bd;I)] [1 - m ]-2/3 [exp Bd;l {I _ m)-lf3]
B ... 0.044
when T
= 298
For a given type and particle size of silica the rate decreases as the particles are
reduced in size because the surface area is reduced by the factor (1 - m )2f3 but as
the size becomes smaller it is increased by the increasing solubility, as expressed in
the final term in the above equation. Thus, since do is a constant in a given experiment, the relative rate of dissolution can be calculated from the equation
.K'
dm
dr
: ..J,
(I - m)2/3 [exp (O.044d;') (I _ m)-lf3J
. :
:
71
tion of Silica
e t; Sj is the
e iP"'rfacial
The relative rate can be plotted versus m, the fraction dissolved, as shown in Figure
1.13. It will be noted that, for particles of 3 nm diameter, there should be less than
:::30% variation in rate while up to half of the silica dissolves, as long as E is assumed
to be in the range of 20-100 ergs cm-t.
Apparently there are no published data on the rate of dissolution of particles
under 5 nm diameter. In a preliminary study, the writer has made a sol by hydrolyzing ethyl silicate in a water-alcohol mixture with HCI and then diluting and neutralizing to pH 2.1 to obtain a 1% SiOt starting sol of 1.9 nm particles, By raising
the pH to 6.0 for 2 min and reducing it again to 2.1 the particles increase in size to
2.1 nrn. If held at pH 6 for 1 hr the size reaches 2.8 nm.
Particle growth at pH 6 is more rapid at higher temperature; when the pH is
adjusted and the sol heated to 60C for 1 hr, cooled to 25C, and stabilized at pH
), Let B
e area A
z
o
r=
3
1.5
~lJJ
C-J
La..u
o~
lJJO:
~~
0:<
lJJu
~:J
~(j'j
1.0
-J-J
lJJ<
O:u
~a:
I-lJJ
<:1:
-Ja..
=>(f)
~<
<
u, 0.5
uo
0.5
1.0
FRACTION OF PARTICLE DISSOLVED
iarticles are
n )2/3 but as
expressed in
iven experi-
.... _--
II
i
Ii
I
Figure 1.13. Calculated relative . rates of dissolution of amorphous silica particles with
assumed values for E and initial particle diameters:
Curve
E (ergs ern -2)
do (nm)
A
B
175
175
100
100
100
20
20
C
D
E
F
G
3
2
3
4
2
3
--
.The Occurrence. Dissolution. and Deposition of Silica
72
2.1, the particle size is 3.5 nm. The particle size is calculated from the specific surface area determined by a rapid titration of a sample containing 200 g I-I NaCI
from pH 4.0 to 9.0. corrected for the monomer present at the start which consumes
I equivalent of alkali per Si(OH). molecule.
The rate of dissolutionof silica was measured in an excess of 0.01 N NaOH solution at 25C, by following the amount of total soluble and ionic silica by the
molybdic acid method.
As shown in Figure 1.14 the experimentally determined rate of dissolution of
particles of a given size remained reasonably constant while 10-70% of the silica was
dissolving. According to the foregoing calculations for Figure 1.13 this could be true
for a 3 nm particle only if E is about 100 ergs cm ? and for a 2 nm particle if E is
even lower.
Rate of Dissolution of Particles of Different Sizes

Next must be considered the relation between the measured dissolution rates when
starting with particles of different sizes.
Since with very small particles the rate does not change much as the silica
dissolves, the average rate is about the same as the initial rate. where m = 0 and
thus
K'
dm
dt
d ;' [exp (0.044 Ed;I)]
This expression assumes that the rate of dissolution is proportional to the specific
surface area of the silica (proportional to do -I) and to the solubility as related to
o 1.00
ILl
2.1
s
CJ)
<t
~
-l
iii
.... 0.50
3.0
o
z
o
----------3.5
i=
u
a::
u,
TIME - MINUTES
Figure 1.14.
Fraction of silica dissolved versus time for particles of indicated initial diameters
in nanometers,
....
on of Silica
oecific surI-I NaCl

I cc
.nes
--73
100
aOH soluica by the
...w
z
s
50
:;)
150
a::
w
solution of
~ silica was
uld be true
:icle if E is
a.
0
100
:J
0
l/l
l/l
10
<l:
::J
iii
...z
rates when
w
u
a::
w
a.
the silica
n = 0 and
152345
PARTICLE DIAMETER
NANOMETERS
.he specific
related to
3.5
Figure 1.15. Calculated versus experimental rates (circles)

of dissolution of silica of different particle diameters and
assumed values of E (ergs em -Z).
particle size. As-seen in Figure 1.15 it requires a value of E of 150-200 ergs em:" to
give a line parallel to the one from experimental data. (The data are empirically
plotted as log of the relative rate versus log of particle diameter in nanometers. and
only the slope is significant.)
There is therefore a discrepancy between theory and experiment. To explain the
constant rate of dissolution as particles dissolve requires a value for the interfacial
energy, E, in the range 50-100 ergs ern -:z. On the other hand. to explain the much
faster rate when starting with smaller particles requires a value for E in the range
150-200 ergs em -2.
In the case of particles approaching 2 nm in diameter, a larger fraction of the
silicon atoms is linked to OH groups on the surface. Thus the rate of dissolution
would be higher than anticipated because fewer siloxane bonds have to be broken
per molecule of Si(OH). that is liberated. In any case. the above considerations indicate that much remains to be learned about silica particles or "polymer molecules"
in the size range below 5 nrn, where the silica is labile and becomes unusually soluble.
.
Dissolution of Crushed Powders

al
eters
The more rapidly dissolving layer on the outside of finely crushed quartz. tridyrnitc,
cristobalite, and vitreous silica was examined by Bergman and Paterson (220) by
74
...;.,.--
"ftreOccurrencc:. Dissolution. and Deposition or Silica
measuring the rate of its removal in dilute alkali. It was concluded that the more
rapidly dissolved layer was from one to five monolayers of Si02 in average depth.
the finer particles having the greatest thickness. This was true of all the polymorphic
forms of silica. However. there is reason to believe that much of the "easily soluble"
material consisted of the corners and edges of the irregular fragments which have a
higher solubility owing to the very small radius of curvature, rather than a uniform
layer.
The dissolution rate of amorphous silica in 0.0 I N NaOH solution has been
measured at 23-88C by a rotating disk method by Anatskii and Ratinov (221, 222).
De Keyser and W olIast (223a) have been able to use the constant of the rate of
dissolution of a solid, obtained by the rotating disk method, to calculate the rate of
solution of powders of which the particle size has been measured by the cumulative
sedimentation method.
.
The nature of the "disturbed layer" on the surface of crushed quartz was
described at the beginning of the section on solubility, and its abnormal solubility is
discussed in Chapter 7 in relation to a theory of silicosis. When crushed powders are
to be used for solubility measurements it is essential that the highly soluble outer
layers and fine fractions be eliminated. The problems involved in obtaining quartz
with a reproducible dissolution behavior have been described by Baumann (223b),
who found that subsequent adsorption of silicic acid from solution or heating the
cleaned powder above 800C can reestablish a layer which is abnormally soluble.
Neutral Solutions-Effect of Salts

-i
II
!I
,
i
Rate measurements on fine amorphous powder and colloids have been made by
Doremus et aJ. (224) and by Friedberg (225). The effects of pH, temperature. and
presence of salts were similar to those reported by others. More than 50 years ago,
Dienert and Wandenbulcke (226) reported the basic facts that colloidal silica passed
into solution as soluble silica. which was detectable calorimetrically with molybdic
acid, and that alkalinity and salts were good catalysts for dissolution. They made an
observation which apparently has n~ver been followed up. They claimed that when
salt is present. the dissolution rate is faster in a quartz container than in platinum
. and that in the absence of added salt. colloidal silica would pass into the soluble
state when heated with water in quartz. but not in platinum. However. pH measurements were not made.
In a study of the attack of water on glass. Wiegel (227) found that glass was more
resistant to attack by water than by salt solution. Also when alkali was first
extracted from glass by acid. it was then more resistant to attack by water. no doubt
because there was no soluble electrolyte to build up in the water. Finally. he found
that copper. zinc. tin. and aluminum all reduced the amount of alkali extractable
from glass by water. while nickel. cobalt, and magnesium increased it.
It thus appears that in very pure water. in the absence of impurities which can
leach from silica into water. silica is remarkably inert (167a). remaining undissolved
for long periods of time. whereas it rapidly dissolves in seawater. Impurities have
such marked effects in neutral solution that it is doubtful if reproducible rates of';
In
of Silica
the more
ige ~epth,
lyr. ..Jhic
y soluble"
ich have a
a uniform
7S
dissolution of amorphous or colloidal silica can be obtained unless unusual precautions are taken to start with very pure silica and avoid all possible contaminants.
Van Lier (114) found that NaCI increased the rate of solution of quartz in water
by factors of about 4, 14, and 67 in 10- 3 , 10- 2, and 10- 1 N solutions.
Retardants of Dissolution
has been
221,222).
he rate of
:he rate of
:umulative
uartz was
olubility is
iwders are
uble outer
ing quartz
nn (223b),
eating the
oluble.
made by
ature, and
years ago,
ica passed
molybdic
y made an
that when
, platinum
he soluble
measurewas more
was first
. no doubt
. he found
As discussed earlier there has been much study of the effect of impurities, especially
aluminum, on the solubility of silica, but only limited research on the effect on the
rate of dissolution.
The rate of dissolution of fused silica from a flask was measured by Sasaki (228);
the rate was proportional to the base concentration. Zinc and aluminum both greatly
diminished the rate of solution. Complete inhibition in 0.1 N NaOH was observed at
concentrations of 3.4 x 10- 3 N aluminum and 5 x 10- 3 N zinc.
Hudson and Bacon (229a) examined inhibitors to prevent the attack of 3% NaOH
solution on glass at 125F. By far the best was beryllium, which almost stopped
attack at a concentration of 10 mg atoms per kilogram of solution (about 2 g I-I
BeSO. 4H 20 ). Catechol. then zinc, were next best at this concentration. Surprisingly, aluminum in this strong alkali was little better than barium, lead, and other
heavy metals, none of which were very effective because they were precipitated from
solution.
Porous glass membranes used for hyper filtration were stabilized against dissolution by having 0.3 g 1-1 of AICI36H 2 0 in the feed solution (229b).
Rate of Dissolution in Presence of Catechol

It is interesting that in 3% NaOH solution catechol is a strong inhibitor of the dissolution of glass (224). However, in neutral and slightly alkaline solutions catechol is a
solvent.
It was pointed out above that it strong ammoniacal solution of catechol dissolved
vitreous silica at a rate of 0.5 micron hr" ' at 90C and attacked quartz at half that
rate. This corresponds to a dissolution rate of about 1100 mg m -2 hr- I for vitreous
silica. and 550 mg m -2 hr " for quartz.
Measurements by Bach and Sticher (230) were made on HF-c1eaned quartz surfaces using 0.2 M catechol solution at pH 9.6. From 17 to 40C the rate of attack
was
log v. = 0.0295T - 20.87
xtractable
which can
ndissolvcd
-it" 'lave
c r... ..:s of
At 25C the rate is 0.8 x 10- 12 g cm " sec-t, which is 2.9 x 10- 2 rng m ? hr- '. The
extrapolated rate at 95C is 3.6 mg m -2 hr " ',
Extensive data on the rates of dissolution of different forms of silica in dilute
alkali and in the presence of catechol were reported by Baumann (231 a). It was
noted that in dilute alkali the rates of solution declined as the solid phase was
- --.
76
TherOccurrence. Dissolution. and Deposition of Silica
consumed, but remained constant when catechol was used. Vitreous silica dissolved
much more rapidly than quartz. but stishovite was completely insoluble (231 b).
The declining rate in alkali may have been due to the accumulation of traces of
aluminum in the solution as the silica dissolved. When readsorbed on the silica surface as aluminosilicate ions t-hese would reduce the rate of solution. However. catechol can complex both silicon and aluminum so that the rate remained constant.
(See also discussion of chelates in Chapter 2.)
'.
Rate of Dissolution in Aqueous HF

Bergman (232) conducted extensive measurements on the rates of solution of quartz
and tridymite in 0.1 and 1.0 M H F solution at 25C. Reasonably reproducible rates
expressed as milligrams per square meter per hour were obtained using particles in
the micron size range. Tridymite dissolved in 0.1 M HF about seven times faster
than quartz and vitreous silica about 45 times faster, but in 1.0 M HF there was little difference.
In 0.1 M HF, cristobalite and tridymite dissolved about 10 times faster than
quartz and vitreous silica 100 times faster. based on unit surface area (233).
There have been several studies of the etching rate of HF on silica in relation to
processes in the electronics industry. A patented mixture of HF and NH.F gives a
desirable etching rate for thin films (234).
. Judge (235) concludes that the rate of attack of HF on Si02 films is due to HF 2 and HF. the former acting four to five times faster than the latter. Pliskin and
Lehman (236) uses a solution of 2.26% HF and 2.15% HNO a to etch Si0 2 films on
silicon. The film formed by oxidation at 1000C. which is probably nonporous. is
etched at the rate of 2 A sec-t, which is 1600 mg rn ? hr ". Using vitreous silica
spheres. Leko measured the rates of dissolution in HF solutions up to 20%
concentration and at 20-80e. Conditions for removing a certain thickness of silica
can be calculated from the data (237).
A fundamental study of the attack of HF on vitreous silica, preceded by a literature review. was published by Blumberg and Stavrinou (238). They developed equations for the reaction rates and determined the velocity constants. At 32C. the
typical value was k , = 5 x 10- 8 g SjO, sec- 1 em -2 M H~'
Comparative Rates of Dissolution

.~
Miscellaneous data have been collected in Table 1.1. and an attempt made to put the
rates on a comparative basis.
REMOVAL AND DEPOSITION OF SILICA fROM WATER

.. Removal" of silica from water is considered here from the standpoint of lowering
the silica content without regard to the means of disposal. This may occur by deposi-
~":"'I;:~
.;~~.
'""
.
--
"
In of Silica
Table 1.1
II b\
ft.
of
silica surever, cate, constant.
Type of
Silica
Solvent
Quartz
Water
Temperature
(OC)
Ratl:
(approx.)
(mg m -2 hr " ')
25
90
25
4 x 10-
0.001
0.029
0.2 M catechol
(pH 9.6)
Ringer's solution
(0.9% NaCI.
0.1% NaHC0 3 )
NaOH (0.05-0.4 N)
of quartz
cible rates
iarticles in
mes faster
.re was lit-
'.
relation to
.F gives a
Vitreous
e to HF 2 " and
lis
)2 films on
.porous, is
eous silica
p to 20%
5S of silica
Iy a literaiped equa32C. the
;:
Van Lier (115)
Stober (139)
25
37
25
0.13 a
0.5 a
0.015 b
O.IOMHF
1.00 M HF
Saturated catechol in
cone. NH.OH
0.8 M catechol
(pH 8.5)
25
25
90
2.8-3.0
110
550
Bergman (220)
Bergman (220)
Baumann. Klosterkotter, and Robock
(23Ib)
Bergman (232)
Bergman (233)
Her (unpublished)
25
0.008
Baumann. Klosterkdtter. and Robock

(23Ib)
Ringer's solution
NaOH (0.05-0.4 N)
1-5% HF
24-14% NH.F
J.l3 M HF
0.34 M HN0 3
1.0 M HF
25
25
25
0.08
0.6 a
2-10 x 10
25
1600
32
1800
0.1 MHF
32
180
0.1 MHF
25
25
136-150
0.083
90
1100
Stober (139)
Bergman (220)
Strauss and Bauer
(234)
Pliskin and Lehman
(236)
Blumberg and
Stavrinou (238)
Blumberg and
Stavrinou (238)
Bergman (232. 233)
(23 Ib)
lIer (unpublished)
(pH 8.5)
Satd. catechol-NH.OH
Cristobalite
0.1 MHF
25
24
Bergman (232. 233)
Tridymite
0.1 MHF
25
28
Bergman (232. 233)
Coesite
0.8 M catechol
25
0.0025

(23lb)
to put the
Reference
0.006
0.8 M catechol
I
!
..
25
0.1 NNaOH
aster than
.. ~
dissolved
t~
(pH 8.5)
t:
~
;.:
I'
~.
~~'.
a
b
Rate for "rapidly soluble" surface layer.

Rate after surface layer removed,
.;
rl "ring
by L",Josi.
f.
f
'~~
t
:.!
'"~
!I
It
tt:
77
;c:. ,..~~;.;:; ....-;:
'i
78
.The Occurrence. Dissolution. and Deposition of Silica
tion, adsorption. or precipitation. On the other hand. "deposition" of silica involves

the formation of solid silica either as a coating or a solid surface, or as crystals.
However. the deposition of soluble silica on particles that remain in water as a sol is
considered separately in Chapters 3 and 4; the biogenic removal of silica and deposition in living organisms are reviewed in Chapter 7.
.
Since silica exists in water both in soluble and colloidal forms, the mechanisms of
removal and deposition are quite different. and often must be considered separately.
Removal of Silica from Water
The removal of silica from water is involved in several types of practical problems.
Most important is removal from feedwater to high pressure boilers in steam power
plants, where even traces of silica can lead to formation of deposits on turbine blades
and scale formation on heat transfer surfaces. Another is removal from cooling
water where silica is deposited on equipment as the temperature is reduced rn:~ as
evaporation occurs. Of growing importance is the silica in geothermal steam and
water, where high silica levels lead to serious problems in -developing power from
these sources. An artifical but economically serious problem has also arisen in
industry from decrees that traces of colloidal silica must now be removed from some
industrial waste streams. even though the level is below that in some natural waters
which are not considered harmful (239). Glacial streams are often milky with suspended silica.
Since it is not possible here to review the large volume of literature on water treatment, only general principles are considered, along with some examples.
Precipitation Mechanisms.
In considering the phenomenon of precipitation it should be pointed out that two
entirely different mechanisms may be involved:
NUCLEATION. Most discussions of precipitation concentrate on the question of how
particles are initially formed. The mechanism has been considered in detail, for
example. by Nielsen (240) and Walton (174) in their treatises on precipitation. The
formation of amorphous silica particles by polymerization of Si(OH)4 involves some
aspects of the theory of nucleation. This is dealt with in Chapter 3.
I
I
COAGULATION. In this case, a precipitate is formed by coagulation of already existing colloidal particles. It does not involve nucleation and is often considered as a
separate subject.
Nucleation of Quartz
The formation of quartz must definitely involve nucleation. Although quartz is not a
colloidal form of silica. its genesis is discussed briefly.
Quartz crystals apparently never are precipitated in suspension. as, for example,
in the case of 8aS0 4 Instead of quartz, colloidal particles are nucleated in suspen-
'-,
n of Silica
involves
; cr"..rals.
as ~ . is
id deposi1
anisms of
parately.
oroblems.
irn power
ne blades
n cooling
ed f;"~! as
team and
wer from
arisen in
rom some
'al waters
with susiter treat-
that two
of how
letail, for
.tion. The
lves some
:)0
ady existered as a
tz is not a
e,
-ilc,
n Sl._tJcn-
Removal and Deposition of Silica from
Wat~.L
79
sion in supersaturated solution from hot springs and also are formed in other natural
waters (32,241).
Solid amorphous silica (opal) and quartz crystals, as in geodes. are formed on
solid sufaces. In a comprehensive investigation of the behavior of silica in hotspring water, White Brannoc~, and Murata (45) pointed out that there was no evidence quartz could be formed within any reasonable time under ordinary conditions.
In nature, amorphous silica appears to be deposited from the highest concentration
of silica, then chalcedony (extremely tine-grained fibrous form of quartz) from a
lower concentration, and finally macroscopic quartz crystals from lowest concentrations just exceeding the saturation level for quartz. Over millions of years most
amorphous silicas in the presence of water are eventually transformed to chalcedony
or chert and quartz.
As early as 1909, Leitrneier (242) reported that quartz could be obtained in the
laboratory as microscopic spheroliths by heating 1% by weight of microamorphous
silica ("silicic acid") in an aqueous suspension of Al(OH)3 at 80C for 144 days.
Only recently was it shown by Harder and Flehmig (243) that even at 20C, quartz
crystals were nucleated in a suspension of Fe(OH)3 or AI(OHh in only 14 days. The
solutions were very dilute: 2 ppm Fe3+ or AI3+ and 0.4-5 ppm Si02 In some manner, amorphous hydroxides of Fe3+, AI, Mn, and Mg can absorb and hold up to 9
moles of Si02 per mole of hydroxide, The silica is converted to quartz crystals
10-100 microns in size, the quartz also being accompanied by "quartzin," a form' of
rodlike or fibrous quartz elongated along the z-axis.
Quartz crystals will not grow from solution saturated with amorphous silica,
containing around 80-110 ppm 0 r monomeric silica, because the latter is adsorbed
on the quartz surface in a disoriented' state, as discussed earlier in connection with
the solubility of quartz. The metal hydroxides combine with Si(OH). in some manner to repress its solubility to the point where quartz will nucleate and grow (244a).
A suitably low degree of supersaturation, without the presence of metal
hydroxides, was attained by Mackenzie and Gees (244b). who ground quartz crystal
to less than 6 microns in size and shook the powder in seawater at a concentration of
0.5% at 20C for up to 3 years. The concentration leveled off at 4.4 0.3 ppm and
new micron-sized quartz crystals were observed to have been formed. No supersaturation occured in sea water. The concentration of soluble silica rose to 3 ppm in I
month and 4.4 ppm in 1 year, but the pH remained at 8.1. It was speculated that the
silica was not deposited on the quartz surfaces already present. because they were
covered by organic or inorganic impurities such as iron oxide. The presence of traces
of iron or aluminum in the system might also explain why the observed solubility is
somewhat lower than the 9.5 ppm value that would be expected by extrapolating
Van Lier's data to 20C (see Figure 1.4). As shown by Willey (38) and by Iler (37).
the presence of traces of alumina reduces the equilibrium solubility of silica.
Adsorption and Precipitation by Hydrous Oxides
Silica, both soluble and colloidal. can be removed from water to varying low levels
in neutral or slightly alkaline solution by coprecipitation with insoluble metal
I~:~-I
80
;1/
!i:il
n:
I
I,
Ii
i
I
hydroxides in situ or by adsorption upon freshly formed hydroxides added 'to the
water.
lIer found at pH 3-4 Si(OH). is not adsorbed on the surface of crystalline
alpha alumina that has been cleaned by treatment with HF followed by ammonia to
remove fluoride ions and then thoroughly washed. However. such a surface does
strongly adsorb colloidal or polymeric silica at this pH (245).
On the other hand. at pH 7 and higher. Si(OH). begins to ionize to silicate ions in
increasing degree, and these are adsorbed and can form a silicate-type bond with a
variety of hydroxides that are in a highly dispersed state. For example. Wohlberg
and Bucholz (246) have reviewed the literature on the reduced solubility of silica in
the presence of metal salts and hydroxides. It was concluded that alumina should be
the best adsorbent. but aparently it is not widely used. Magnesium is the commonest
reagent, but requires a relatively high pH and recirculation of sludge. and has to be
operated hot (247a). Willey (247b) has shown that zinc ions at about pH 8.3 can
precipitate dissolved silica that is in excess of 2 ppm, and the precipitate has the
Si: Zn composition of 5: J.
In laboratory studies, silica was adsorbed and precipitated by hydroxides of aluminum, iron. manganese, and magnesium. according to Harder (42). After precipitating 15 ppm AI(OH)3 from a 3 ppm SjO, in solution. the residual silica was 0.8
ppm. whereas with 30 ppm aluminum hydroxide. no measurable silica remained.
Willey has given an excellent review of the extensive literature on the interaction of
silica and alumina in dilute solutions. The low levels of soluble silica reached (39)
depended on the particular solid aluminum silicate phase that was formed or
present. She studied the interaction at very low concentrations. generally less than
10 ppm, and found that only I ppm Si0 2 is required to initiate the precipitation of I
ppm of AI 203 from solution. and if more than about t ppm AI203 is in solution the
silica concentration becomes exceedingly low.
In further studies, Willey suspended separate mixtures of (I) microamorphous
silica ("silicic acid") and amorphous alumina, and (2) quartz and amorphous alumina in distilled water and 0.6 N NaCi solution as well as in seawater (which
behaved the same) at 4C. pH 7-8, for up to 38 days. The results can probably be
explained as follows.
The amorphous silica powder consists of aggregates of particles of colloidal size.
Consequently. during agitation of the suspension in water or salt solution. a small
nonreproducible fraction of the particles becomes detached and remains in colloidal
suspension. When salt is present. the colloidal particles are adsorbed at once by the
suspended alumina which does not disintegrate. Only soluble silica is left in solution.
However. in pure water. in the absence of coagulating effect of salt. coagulation is
less complete. Once alumina is transferred to the silica surface and silica to the alumina surface. both surfaces become equally negatively charged. and there is no
further tendency for mutual flocculation.
The solubility of amorphous silica was 82 ppm in perfect agreement with other
data (see Figure 1.4). but when alumina was present (0.04-0.10 ppm in solution),
enough was adsorbed on the silica to reduce the solubility to around 67 2 ppm.
The effect of soluble silica on the solubility of alumina was only slight. since the alu-
-.~
.;;.
.1.1
- I
.~
-'
--, of Silica
Removal and Deposition of Silica from Water,
ed to the
mina alone dissolved only to the extent of 0.06-0.3 ppm. some part of ~'hich could
have been colloidal.
Healy et al. (248) arrived at a similar conclusion in a study of the mutual or
heterocoagulation of mixed colloidal oxide dispersions. When two oxides with different isoelectric points are mixed at a pH midway between. they immediately coagulate. But if the coagulate is repeatedly aged. redispersed, and allowed to recoagulate, the coagulation time increases until finally the mixture forms a stable dispersion. This is because mutual transfer of oxides has occurred until all particle surfaces
become alike and bear the same charge.
.
Because of the great variation in experimental conditions. results of different
investigators are usually not comparable and generalizations are difficult to make.
Accordingly. all that can be done is to compare individual observations.
The effect of aluminum ion combining with soluble silica was found by Goto (249)
to be optimum at pH 8-9. To a solution initially containing 35 ppm Si(OH) aluminum ion was added as chloride or sulfate and then the pH raised to 8-9. Twenty
ppm AI reduced the soluble silica to 15 ppm. 50 ppm reduced it to ~ ppm, and 100
ppm to about 3 ppm. When each molecule of precipitated silica is accompanied by
one Al atom. then the molar concentrations of Si0 2 and Al remaining in solution
appear to be approximately related as follows:
rys
ie
monia to
'ace does
te ions in
id with a
Vohlberg
~ silica in
.hould be
mmonest
has to be
I 8.3 can
e has the
es of alur precipi1 was 0.8

emained.
action of
:hed (39)
irrned or
Ie
'an
itiou of t
ution the
norphous
hous aluer (which
ibably be
iidal size.
. a small
colloidal
ce by the
solution.
ulation is
a the aluere is no
lith other
solution).
:l:: 2 ppm.
cI
'\Iu-
M S IOt MAl = (0.1
81
0.05) x 10- 12
Colloidal silica can exist in water far below the equilibrium solubility of arnorphOUS silica. especially at low pH. Goto found that in water containing 40 ppm silica
present as colloidal particles, the addition of. I ppm Al as aluminum salt coagulated
90% of the silica, but only in the narrow pH range 4.1-4.7. There was essentially no
effect at higher or lower -pH, probably because below 4.1' the negative charge on
silica becomes vanishingly small. and above 4.7 the charge becomes too large to be
neutralized by such a small quantity of aluminum ion. Similarly. Okamoto. Okura,
and Goto (250a) found that the AI3+ ion precipitates colloidal silica only in the pH
range 4-5. It requires only I part AI3+ to precipitate 40 parts of Si0 2 On the other
hand. AP+ precipitates soluble silica in the pH range 5-11, but at least 4 parts Al
are required for I part Si0 2
From the widely diverse observations it is obvious that the alumina-silica system
is very complex. Under the right condition's alumina can remove silica from solution
down to a very low level. but this is difficult to accomplish under practical conditions.
Huang (250b) has made a detailed study of the removal of silica from dilute
aqueous solution by adsorption on gamma alumina, Adsorption isotherms and
kinetics were elucidated. Under suitable conditions the concentration of soluble
silica was reduced to the range of 2-4 x 10- M or 12-24 ppm SiO t ,
It is probably for this reason that lime and magnesia are commonly used for
removing silica from water. They flocculate colloidal silica along with other suspended or precipitated matter and combine with and adsorb soluble silica. A suitable
granular magnesia adsorbent for silica. made from magnesite. worked best at pH
82
~._.
8.5-9. according to Shemyakina (251). The water, previously limed to reduce silica
to 2-4 ppm, was passed through a I m deep bed of adsorbent on a filter. which
reduced silica to 0.5 ppm initially, and 1.5 ppm later when the adsorbent bed had
taken up 9% by weight of silica. However, the linear rate of flow was only 6 m hr
Chugunov (252) reported that the resulting silica level was as low as 0.3 ppm, but
pointed out that some magnesium then had to be removed from the water by ion
exchange. Other investigations of the use of magnesia as a silica precipitant or
adsorbent have been described by Nikolaev, Samusenko, and Tush (253), Schumann
(254). Tkachenko, Chernova, and Shuryshkina (255). and Straub (256).
Demineralization of boiler water with calcium under optimum conditions can
reduce the silica level to 0.4 ppm, according to Sramik (257). This involves preheating the water to 80C, adding lime, filtering. saturating with CO2 , but not below pH
9, and refiltering. The recovered CaC03 is chemically pure. The nature of the
deposits on turbine blades and effect on efficiency have been discussed by Kot and
Lobanov (258).
'In some low pressure plants (200 psi) water containing as much as 60 ppm Si0 2
can be fed directly to the boiler and treated in situ with sodium tripolyphosphate,
NaOH, sodium sulfite. and Na 2SO. (400 ppm) to maintain a pH of 10.5-10.8 (259).
r
'.
,
;
,{
..
I
Removal by Ion Exchange
r:
,!'
"
. For feedwater for high pressure stearn power plants. precipitation processes are used
only as a first step to reduce silica concentration to a few parts per million. Then ion
exchangers must be used to further remove silica to less than 1 ppm. In oncethrough boilers operating at supercritical pressure (3200 psi) and corresponding
temperature, where Si(OH}. becomes completely volatile, the silica content must be
kept as low as 0.01 ppm. The amount of silica carried mechanically is proportional
to concentration in the boiler water and varies with steam pressure (260).
Combinations of processes used for silica removal have been reviewed by Applebaum (261). Silica concentration is reduced to 2-3 ppm by a cold process (70 0 F)
using dolomitic lime (32% MgO). By operating hot (over 120F), only half as much
lime is needed. The most efficient is an activated MgO. of which only 12 ppm is
needed in a hot process to reduce silica from 5 to 3 ppm. Further reduction of silica
is accomplished by ion exchange on a strong-base resin. According to Stassart (262)
much of the silica can be removed by adsorption on Fe(OHh and the remainder
down to 0.3 ppm by a strong-base resin.
It is apparent that the lime or magnesia treatment reduces silica to 3 ppm under
rather simple process conditions. but is capable of reducing it to below 0.5 ppm if a
more complex process is used. If silica must be reduced eventually by ion-exchange
resin, it is likely that the more efficient but complex pretreatments are not justified.
Ion-exchange resins of the strong-base type adsorb only the soluble silica as silicate ions, but special wide-pored resins have been developed to permit also the
adsorption of colloidal silica (263).
The colloid is desorbed from the resin with acid. and the resin regenerated with
alkali. According to Ryabin, Novoselov, and Lazareva (264) after silica has been
,~
.,
--
..
:>fSilica
Removal and Deposition of Silica from Water_
ce silica
, \11'- ;,.h
oec . j
m hr".
ern, but
. by ion
.tant or
removed from water to a low level by a strong-base ion-exchange resin. further

reduction is achieved by passing it through a zirconium hydroxide-loaded
macroporous anion-exchange resin. A totally different type of exchange resin for
silica is a catechol-formaldehyde polymer in which the two phenolic groups in ortho
position can strongly adsorb sjlica by chelation (265).
Removal of colloidal silica by flocculation with cationic organic polymers is
involved in other aspects of water treatment. The chemistry of flocculation is
covered in Chapter 4.
rurnann
:>ns can
oreheat:low pH
of the
(ot and
Deposition of Silica from Water

The deposition of monomeric silica involves a very different mechanism from the
deposition of colloidal particles. Monomeric silica forms an impervious glass-like
film, whereas colloidal particles form a porous film, often white and opaque when
dried. In an intermediate range, where particles are smaller than about 50 A in
diameter, that is, approaching molecular dimensions, the coating is clear and the
pores in the close-packed mass of particles may be so small that only water or
certain ions can penetrate. This borderline region has been little explored.
Silica can be deposited molecularly from su persaturated aqueous solution.
Supersaturation can be brought about by one of the following processes: .
.rn Si0 2
osphate.
; (259).
He used
"hen ion
~-
ponmng
must be
ortional
. Apple; (70F)
:IS much
ppm is
of silica
irt (262)
mainder
i
~
r.
;..
i
f:
:.
..If.'
ted with
ia:
'~n
'"
1. Concentrating an undersaturated solution by evaporating water.
2. Cooling a hot saturated solution in water. '

3. Lowering the pH of an aqueous solution of a soluble silicate below about 10.7.
4. Generating Si(OH). in water by hydrolyzing a monomeric silicon compound such
as an ester, Si(OR)., hydride SiH., sullide SiS 2 halide SiCI. or even linely
divided elemental silicon.
Monomeric silica comes out of supersaturated solution in three ways:
I!
~,
f:
,
!
under
oprn if a
xchange
stilied.
1 as silialso the
11
83
"
+:
1. As a deposit on a solid surface: Si(OH). condenses with any preexisting solid surface that bears OH groups with which it can react. namely. SiOH, or any MOH
surface, where M is a metal that will form a silicate at the pH involved. Once a
receptive surface is covered by the reaction
I
I
o
+'
I
-M-OH
I
-M-OH
M-O
Si(OH)1
oI
I
r-.t-O
OH
""-/
Si
/""-
OH
the further deposition is silica on silica, thus building up a lilm.

2. As colloidal particles remaining in suspension: if an insufficient area of a receptive solid surface is available to accept silica rapidly. and if the concentration of
-_
....
The-Occurrence. Dissolution. and Deposition of Silica
84
>.
Si(OH). is greater than 200-300 ppm (depending on pH), polymerization occurs

with formation first of low polymers such as the cyclic tetramer; then these
further condense to form small three-dimensional polymers which are colloidal
particles.
3. As biogenic amorphous silica: by mechanisms still unknown. living organisms can
remove silica from extremely dilute solutions and deposit solid silica within
themselves in precisely controlled structures of intricate design, perfect almost to
molecular dimensions (see Chapter 7).
The mechanism of molecular deposition of SiO: from Si(OH). is apparently the
reverse of dissolution of solid silica. It involves a condensation reaction catalyzed by
hydroxyl ions and accelerated by the presence of salts. The process therefore occurs
principally above pH 7, since it is catalyzed by hydroxyl ion, but obviously not
above pH II where silica dissolves as silicate ion. Deposition is more rapid and
condensation and dehydration of the silica are more complete in hot solution.
The silica deposit, when laid down monomolecularly, is nonporous and probably
as impervious as vitreous silica. For example, such a film only 20-30 A thick
deposited on the surface of a nickel powder renders the metal insoluble in acid.
However, it must be emphasized that special conditions are required for this to
occur. The degree of supersaturation must be sufficient for deposition, to occur, but
must not be so great as to allow the formation of colloidal particles. or the process
becomes very inefficient (266).
Deposition of colloidal silica occurs by a process entirely different from the above.
In this case. deposits on solid surfaces are formed by either or both of the following
processes:
11
.f
,j
,'I
1. Alternate wetting of dilute sol and drying can build' up an adherent coating.
Once the particles dry on a surface they are irreversibly bonded. Hard films can
be built up. especially if each additional layer of silica is only a few particles
thick. Much of the siliceous deposit at the waterline around hot springs is formed
in this way.
2. Deposition of colloidal particles on a surface from a dilute sol may occur when
conditions of pH and salt concentration are close to those causing coagulation or
precipitation. Deposition occurs when the colloidal particles collides and combines with the solid silica surface. The concentration of colloid must be suitably
low because under these conditions a concentrated sol would be rapidly coagulated or gelled. and no coating obtained. This is somewhat analogous to
molecular deposition, in that the concentration of silica must not be so high that
the particles collide and adhere to each other rather than to the solid surface.
Deposition of colloid is greatly accelerated and the deposits are much more dense
and hard when soluble silica is deposited along with the colloidal particles. Some
hot-spring waters contain soluble silica in equilibrium with the colloidal silica. and
some soluble salts. When the solution cools. the colloidal particles are deposited on
solid surfaces at the same time the cooled solution becomes supersaturated with
Removal and Deposition of Silica from Water.
of Silica
occurs
en these
;01.
I
silica, which then is deposited on the layer of deposited colloidal particles, cementing
them together.
Most silica deposits are probably built up in this way. They may be hard and very
adherent, yet are microporous, since usually there is not enough molecular or soluble
silica present to fill the pores between the colloidal particles. In nature. almost any
imaginable set of conditions can occur at one time or another. Further deposition of
molecular silica can occur until the siliceous deposit becomes completely impervious,
This effect is seen in some opal and in the walls of geodes.
In the laboratory, air-drying a sol of silica particles 1.5-2.0 nm in diameter on a
surface gives a glass-clear layer of gel in which the pores are too small to admit
nitrogen molecules and the BET surface area is very low. By first growing the particles to 3-4 nm diameter and then drying the sol in the same manner, a similar glassclear gel is obtained, but the BET area is 800-900 m 2/g- 1 However. the first gel is
still porous to water molecules, and so is not equivalent to vitreous silica.
On the other hand, when silica is deposited molecularly, the resulting solid silica
contains little or no adsorbed water and few internal silanol groups. It'is very similar
. to vitreous silica or "fused quartz," as it is commonly but erroneously called.
:1
sms can
1 within
lmost to
:ntly the
lyzed by
e occurs
rsly not
pid and
.robably
A thick
in acid.
this to
.cur, but
process
Rate oj Deposition oj Monomeric Silica
e above.
0
)11
:>
coating.
ilrns can
particles
; formed
ur when
ation or
ld comsuitably
I coagugous to
.igh that
Ice.
0;
t
r
fG'
"
"
t
'~
f
~
j,
"
f,
0'
re dense
s. Some
ica, and
lsi ted on
'h
tee.
85
I
;;
"
.'I<
,
f,
u
~
l,
.,
l
!;
l-
At the outset it must be emphasized that regardless of the type of material on which
silica is. deposited, after more than a monomolecular layer of silica has been
adsorbed, further deposition of silica is always on a silica surface. It is obvious,
therefore, that at the beginning the substrate must be receptive to monomeric silica
at pH 8-10, where deposition is carried out. Hydrophobic surfaces are obviously not
receptive, and must be rendered hydrophilic by adsorption of a cationic surfactant or
polymer or other means. 'Negatively charged surfaces such' as anionic ion-exchange
films, carboxymethyl cellulose. or carboxylated surfaces on surface-oxidized
polymers are not receptive. but can be made so by the well-known methods used for
preparing surfaces for the deposition of metals. such as treatment with stannous
chloride solution. Such surfaces can also be treated with polybasic metal salts of iron
or aluminum. which are known to reverse the charge on negative surfaces (mordants).
Neutral hydrophilic surfaces such as cellulose are not very receptive. but can be
made so by treatment with conventional inorganic mordants. All insoluble metal
oxides and silicates including most refractory materials and glass appear to be receptive to silica after the traces of organic fatty acids that invariably contaminate such
surfaces are removed. As soon as the receptive surface is immersed in a solution of
supersaturated silica. a monolayer of silica is adsorbed. probably as silicate ions.
It is obvious that silica will be deposited from supersaturated solution onto a solid
surface at a rate that increases with degree of supersaturation. Since the condensation reaction is catalyzed by hydroxyl ions. deposition is always carried out above
pH 8 and it progresses faster at high pH. Also. the presence of a monovalent electrolyte such as sodium chloride will no doubt accelerate deposition as it docs dissolution, and for the same reasons.
86
The Occurrence. Dissolution. and Deposition or Silica
On the other hand, there are upper limits to all these factors which place an upper
practical limit on the rate of deposition on a given substrate. Thus if the concentration of monomeric silica is too high, it polymerizes with itself, forming silica particles or nuclei on which silica will also deposit. Since these particles have a very high
specific surface area, much sf the soluble silica thereafter is deposited on these
colloidal particles, as well as on the substrate.
The pH cannot exceed about II or all the silica will be dissolved as soluble silicate, but it should not drop below about 8, since the rate of deposition will be slow.
Also, if the electrolyte concentration is too high, for example, 0.2 N, adsorbed
hydrated metal ions will remain in the deposited silica, leaving micropores when
removed at low pH. However, a 0.2 N concentration of sodium salt accelerates the
process.
Although monosilicic acid, Si(OH)., is believed to be the material actually
deposited, it is possible to use "active silica" in the form of low molecular weight
'polysilicic acids (including extremely small colloidal particles) as a source of silica.
Such small particles are highly soluble and are in equilibrium with a concentration
of Si(OH). that is highly supersaturated with respect to larger particles or a flat surface.
Deposition of an impervious film of silica on a wide variety of surfaces has been
described in detail by Iler (266).
The active silica is defined as one that will depolymerize completely to soluble silicate in 100 min at 30C in an excess of 10- 2 N NaOH solution (pH 12). Such silica
is obtained when a dilute solution of sodium silicate (3.25 Si0 2 : 1.0 Na 20) is
deionized at ordinary temperature and contains monomeric' silica as well as particles
up to 10-20 A in diameter.
The rate of addition of active: silica to the reaction solution from which silica is
being deposited is preferably, but not necessarily, sufficiently slow for all of the silica
to be deposited on the substrate and not form colloid. This can be judged by determining the yield of silica on the substrate. However, in coating coarse powders or
other substrates of relatively low surface area, the silica yield is not as important as
long as the colloid formed can be separated from the substrate.
As an example, 400 g of powdered ferromagnetic nickel flake, cleaned by extraction with chloroform and alcoholic alkali, was suspended in 4124 g H 20 containing
71 g Na 2SO. and sodium silicate equivalent to 120 g Si0 2 and 37.5 g Na20 and
heated to 95C. Over a period of 3.5 hr 0.67 N H 2SO. was added to the well agitated mixture, and the pH dropped from 11.0 to 9.87. The metal powder contained
8.13% silica as a continuous film. corresponding to a 26% yield of silica. When compacted at 70.000 psi the billet had a resistance of more than 30 megohms. as compared to 30 ohms for the untreated powder. Also, the coated powder was much less
readily attacked by nitric acid.
Another method of operation is to put the substrate in a solution containing some
of the silicate and then adding sodium silicate and acid simultaneously to maintain
the pH around 10. When the same nickel flake was coated in this way the silica yield
was 80%. The coating thickness was estimated to be about 60 A.
.;;
\....
_..
,'
..,..
.:..,. .. -
of Silica
Removal and Deposition of Silica from WateL_
upper
nce-vra;a to
:ry high
in these
A convenient source of active silica is a 3% solution of silicic acid obtained by

passing sodium silicate solution through a column of sulfonic acid type ion-exchange
resin at such a rate as to collect an effluent with a pH less than 4.
Other materials coated in this manner were clays. asbestos fibers. aluminum flake
pigment. iron powder. and !l titanium dioxide pigment which showed tenfold
improvement in photodurability in an organic polymer. By using mordants. the individual fibers in cotton and nylon fabrics were coated with silica which amounted to
over 5% by weight.
The maximum rate at which active silica can be added to the system 'without
forming colloidal silica is expressed as follows:
in
ible silibe slow.

dsorbed
es when
ates the
actually
. weight
If silica.
ntration
flat sur-
_200A
87
(")"
where n = (T - 90)/10 and S = amount of Si0 2 added (g hr- I g-I of substrate). A

= specific surface area of substrate (rn" g " '), and T = temperature (OC). Thus at
90(, silica can be added at a rate of 5 grams per 1000 m2 hr
Extrapolated to
30(, the rate would be only 0.08 g per 1000 m 2 hr- I.
In depositing silica on colloidal silica nuclei to increase the size of the particles,
Mindick and Vassos (267) set a maximum rate of addition of silica' (molecular
weight less than 90,000) to avoid forming new nuclei by a formula that gives 5.0
grams silica per 1000 m 2 hr " '. In this case no sodium salt is present in the system, so
that the maximum rate is only half of what could be used when salt was present.
To determine more accurately the maximum rate of deposition at ordinary
temperature, lIer carried out the following experiment.
To 1 liter of solution containing 350 ppm monomeric silica at pH 9. at 22C. was
added a small amount of a concentrated silica sol of 8 nm particles (specific surface
area 350 m2 g-I) to give a concentration of 3.0 g I-I colloidal silica. At once the
monomer content was followed as it dropped over a period of 12 hr. In the first 12
min the concentration dropped from 350 to 250 ppm, or a rate of 500 ppm hr- I.
r
las been
ible sili:h silica
'a2O) is
)a,
s
silica is
he silica
y deter/ders or
rtant as
extrac-
rtaining
0 and
12
I~agi-
f.
"
Ii
"~.
.ntained
en com3S comuch less
l
(
19 some
t~
"
laintain
ca yield
;;
-,
i
i
~
'.
Thus 0.500 g was deposited on 1050 m 2 of silica surface. The rate was thus about 0.5
grams per 1000 m2 hr ",
In the absence of the colloidal nuclei the monomer level in the solution dropped
only from 350 to 320 in 2 hr, indicating only minor self-nucleation. The equilibrium
solubility of silica in the system was about 100 ppm. so the average supersaturation
was about 200 ppm or three-fold saturation.
When the supersaturation was only 50 ppm, of 1.5-fold saturation. the deposition
rate was 33 mg hr ", or 0.03 gram per 1000 rn" hr- I, which is below the maximum
because there was no measurable rate of self-nucleation even at two fold saturation .
The maximum rate determined experimentally. therefore. lies between 0.03 and 0.5
g, whereas that calculated from the above formula was 0.15 gram per 1000 m 2 hr ' '.
The maximum deposition rate can be put in terms of coating thickness deposited
per hour. Film thickness for I gram per 1000 m', based on a silica density of 2.2
...
88
~._-
\
cm -3, is 0.45 nm, or 4.5 A hr- I Thus at 90C, the maximum rate is 4.5'A hr and
at ordinary temperature is about 0.7 A br ", or I mm in 1600 years.
A silica coating was applied to particles of colloidal thoria by Barrett et al. (268)
by a simple heating process. A 5-10% deionized thoria sol was first added to a
strongly agitated 1-2% acidic sol of "active" silica. This coats the thoria particles
with a monolayer of silica. Then the pH of the mixture was suddenly raised to 10 to
stabilize the active silica which is converted to very small colloidal particles. Because
the silica-coated thoria particles are greater than 50 nm in diameter, silica dissolves
from the "active" silica particles and is deposited upon the thoria. The 'process is
completed by heating the sol mixture in an autoclave at 250C to obtain thoria
particles heavily coated with dense silica.
Also, a silica coating can be applied by the hot hydrolysis of a high ratio soluble
silicate. When sodium silicate with a ratio of 3.25 SiO~: I Na 20 is diluted from its
typical commodity strength of about 28.4% Si0 2 and 8.7% Na 20 to 2% Si0 2and
0.61% Na 20, the alkali concentration is not longer sufficient to keep at least some of
the silica from polymerizing. When such a dilute solution is heated to 80-100C, as
much as 20% of the silica is deposited on any receptive substrate surface, or
otherwise forms of colloidal particles. According to Azarian (269a) the presence of
sodium acetate is particularly benefical when apply a little coating in this manner to
bronze and other metal powders such as copper or aluminum. As discussed in a
following section, lithium polysilicate appears to deposit colloidal silica.
It should be mentioned that alumina can also be codeposited with silica as aluminosilicate ions in a silica matrix. Alexander (169b) patented a 'process for coating
particles up to 5 microns in size, including titania pigment with a skin from 3 to 50
nm thick composed of Si0 2 and Al 203 codeposited from sodium silicate and
aluminate solutions. The AI0 2 - is accompanied by Na + which can be ion exchanged
from the coating. This coating is much less soluble in water than pure silica. A very
similar process was later patented by Foss (269c) with an optional undercoat of
"sponge" alumina on the titania.
r
'
Silicification of Biogenic Materials
Our knowledge of life forms of the remote past is based on examination of

specimens preserved as silica pseudomorphs. Best known of these is petrified wood,
but of even greater fundamental importance are the fossilized microorganisms discovered by Barghoorn and Schopf, which are as much as 3 billion years old (270).
The latter were apparently coated with, then later impregnated with and enveloped
in, amorphous silica, which later was converted to a very fine-grained black chert
(submicroscopic quartz), which preserved the form of the filamentous algae and bacteria-like organisms. Small amounts of organic material are still present.
The most perfect replication of the organic forms is by silica, which is the one
mineral that is transported in solution in water and deposited in amorphous form.
All other minerals are deposited as crystals which, in most cases, are larger than the
detailed structure of the organism. Even after amorphous silica has crystallized in
,~
....
.~!
s:
~~
:)t
~
":t..
,t .
'.
..
Removal and Deposition of Silica from Water
n of Silica
89
situ to chert, the crystals are so small that even submicroscopic structures are
retained, visible only by electron microscopic techniques.
The unusually perfect preservation of the original structure of plant tissue is exemplitied in Figure 1.16 (271).
The natural process by which organic material is so faithfully reproduced as a
pseudomorph of silica is not yet understood and has not yet been duplicated in the
laboratory. It should be possible to generate silica gel within the spaces in plant
tissues which are normally" tilled with water, but the subsequent replacement of the
hr" and
at. >8)
lded to a
particles
j to 10 to
. Because
dissolves
orocess is
in thoria
o soluble
from its
Si0 2and
t some of
-OOC, as
rface, or
esence of
tanner to
ssed in a
as alumir coating
n
50
carerand
'(changed
a. A very
ercoat of
ration of
ed wood,
isms disild (270).
nveloped
ick chert
and bac; the one
JUS
form.
than the
rllized in
I
I
l
II
(
I
t
[
i.:!v
rEf!
Figure 1.16. Photom icrograph of a section of silicified wood-Pt(!rocaryoxl'/oll Know/toll

(65 x). (Courtesy or Elisabeth Wheeler. North Carolina State College. E. S. Barghoorn. Harvard University, and Richard Scott. U.S. Geological Survey.)
"~<~"":f~~;J
,
The Dccurrence, Dissolution, and Deposition of Silica
organic material with more silica would be difficult, and in nature is undoubtedly an
extremely slow process. The first stage of the process can be observed by placing
specimens of wood, for example, in hot mineral springs rich in silica, such as the hot
springs of Yellowstone Park, which contain up to 717 ppm of silica (272,273).
Silicification of wood is commonly associated with volcanic ash, which is a rich
source of readily available soluble silica (274). Correns (275) suggests that the silica
may be precipitated from alkaline natural waters by the carbon dioxide evolved during decomposition of the wood. In this way, silica would be deposited immediately
at the surface of the organic material, and as the organic portion dissolved 'away, it
would be replaced by silica. This presupposes that the silica initially formed is amorphous and porous, permitting diffusion of solution through the specimen: Since plant
tissues contain membranes that can be penetrated by soluble silicic acid but not by
colloidal particles of silica, Hellmers (276) believes that silicification occurs
immediately after the soluble silica is liberated by decomposition of silicate minerals
and before it can polymerize.
Barghoorn (277) has commented as follows on the mechanism of silicification:
Silicified wood, regardless of geologic age, contains unusual amounts of organic residues,
occasionally present to such an extent that the demineralized wood may be embedded, sectioned, and stained, much as living tissue.
However, in other cases, there is no cellulose remaining.

It seems likely that silicification took place at a time when degradation of the cell wall had
not yet passed the stage of the partial retention of a cellulosic structural residue. Thus, the
cellulosic framework of tissues was retained for sufficient time to allow preservation of structure before silicification. After"or during silicification, the remaining cellulose was lost from the
tissue, leaving a modified but coherent lignin residue.
Ii
II
I
The precipitation of minerals such as silica therefore fixes the structure in a

mineral form which retains a large measure of biological detail.
As pointed out by Correns (275), the liberation of acidic material, such as carbon
dioxide, by the decomposing vegetable matter may also lead to the formation of a
type of silica different from that of the original embedded matrix. It would be
expected that cellulose will decompose by hydrolysis and oxidation at a much faster
rate" than the lignin, in view of the known differences in chemical stability of these
materials. Thus the cellulose is likely to be replaced by silica before the lignin is
attacked.
The final stage in the formation of an organic-free dense fossil involves the final
filling in of the pores in the original porous silica deposit and the gradual conversion
of part or all of the specimen to crystalline silica. Because of the original variations
in the silica which replaced the different types of organic material, the final
crystallization will be varied and the pseudomorph will be visible even when it
contains few impurities to give it color. Ordinarily, iron is present, and the resulting
variations in color make the original organic structures plainly visible.
.,,
of Silica
.tedly an
pl:>r:ing
s t.
Jt
, ).
is a rich
he silica
ved duriediately
away, it
is amorice plant
t not by
occurs
ninerals
ion:
residues,
ded, sec-
wi,
.d
rhus, the
of strucfrom the
ire in a
; carbon
ion of a
ould be
.h faster
of these
lignin is
he final
iversion
riations
ie final
when it
esulting
Removal and Deposition of Silica from Watsr,
91
The silicification of various types of biogenic materials was reviewed' by Siever

and Scott (278). Possible mechanisms are discussed, but they believed that exact
duplication of the silicification process in the laboratory is impossible, because of the
time required. The youngest silicified wood is of the early Pleistocene age.
It is not only a matter of how rapidly silica is deposited, but also how rapidly the
organic material inside a partially silicified specimen decomposes in the absence of
microorganisms within the structure. Chemical degradation must occur before the
resulting space can be filled by further silica deposition. This fact, furthermore, precludes deposition of colloidal silica except initially in the open pores, since' colloidal
particles cannot pass through the cell walls. For this reason, silicification for the
most part involves diffusion of a supersaturated solution of soluble Si(OH)4 through
the structure. If the process occurs at ordinary temperature, the silica concentration
is not likely to be more than 200 ppm and the rate of deposition not more than 1
mm in 1600 years. Since rate of diffusion, even through micropores, is relatively
rapid, it means that silica deposition can continue to occur even in cavities to which
there is access only through a few pores. Thus dense, almost impervious masses of
silicified structures can be formed. It is difficult to v isualize how this could be
accelerated, say, a thousandfold, in the laboratory.
The most successful approach to duplicating fossilized wood has been made by
Leo and Barghoorn (279), who also presented a survey of the subject since the
attempts of Basil Valentine, the alchemist, in 1520. The wood specimen is boiled in
water until free of gas and then alternately immersed in separate sealed jars containing water and ethyl orthosilicate, stored at 70C.
Exposure time in each fluid may vary from a few days to a month and the
alternate immersions are continued for us to 1 year or more. Several times during
the ethyl silicate immersion vacuum is applied to remove water vapor from the wood
to facilitate further penetration by the ester. The ethyl silicate is replaced with fresh
liquid whenever it becomes viscous or cloudy. During the final cycle in the ester the
specimen is soaked in 0.004% HN0 3 to hydrolyze the residual ester in situ.
The silica-filled specimen still contains all the original organic matter and closely
resembles natural petrefaction of geologically young age. After organic matter has
been removed, as shown by a fragment not turning dark when it is place in
concentrated H 2S0 4, the silica Iithomorph is found to faithfully reproduce the
original organic structure. Unlike previous methods, this technique gives a strong
coherent lithomorph.
Since the organic matter can be removed by oxidizing agents it is obvious that the
lithomorph is highly porous. Presumably, this would be an ideal substrate for further
deposition of silica, perhaps colored with a little iron, to more closely approach the
appearance of a natural, highly petrified specimen.
Duplication of chert containing microorganisms is feasible in the laboratory
because diffusion distances are so small. Oehler and Schopf (280) made specimens
by embedding filamentous algae in silica gel and then autoclaving at 2-4 kilobars for
2-4 weeks at 150C. Under these conditons, the gel undergoes syneresis until completely solid and is converted to the microcrystalline state, as further described by
Oehler (l64b).
. The Oeeurrence, Dissolution. and Deposition of Silica
92
Rare of Deposition of Colloidal Silica

There are some situations, as in equipment handling hot geothermal brines, where
the cooled liquid deposits silica orders of magnitude faster than is possible by the
deposition of molecular silica. Such deposits invariably are hydrated. and although
often very hard, have a microporous structure. A high buildup rate is to be expected,
since particles corresponding to molecular weights of thousands (several nanometers
in diameter) are being deposited instead of single SiO, units. Also porosity, corresponding to the spaces between the colloidal particles, is to be expected. . .
There is one major difference in mechanism: deposition of colloidal particles
requires the presence of a potential coagulating agent, usually small concentrations
of polyvalent metal ions, although monovalent ions such as sodium have a similar
effect above about 0.3 N concentration. In the absence of flocculating ions, in neutral or alkaline solution, a colloidal particle of pure silica bears a negative charge
and so does the silica surface of the substrate. There is mutual repulsion so that the
collision rate is low. However, in this pH range metal ions are adsorbed on the silica
surfaces in some degree and upon collision, adhesion occurs. For deposition on a
surface to occur, the metal ion should not be present at such concentration as to coagulate the colloidal particles in suspension (Figure 1.17).
~.
.,.
~,
PARTICLES OF Si02
REARRANGEMENT
TO SMOOTHER SURFt.CE
MilI :.
I
ORIGINAL SURFACE
Figure 1.17. Flocculating action of calcium ion followed by spontaneous cementing effect
through dissolution and redeposition of soluble silica.
.
".
~~':~3..:7~
.. -
-- .:-
_0
1Il-
Removal and Deposition of Silica from WateL_
n of Silica
es,
.re
ile by the
although
expected,
.nometers
sity, corparticles
mtrations
a similar
s, In neuIe charge
J' that the
the silica
tion on a
1S to coa- .
f
I
ing effect
II
93
Deposition is likely to be unusually rapid when the colloidal particles are less than
5 nm in diameter. Such small particles are in equilibrium with a concentration of
monomer that is supersaturated with respect to a flat surface. Hence, as shown in
Figure 1.17, the surface of deposited silica rapidly fills in so that the radius of curvature is much greater than that of the colloidal particles. In effect, the surface tends
to be filled in and flattened out. This is an important factor in rapid desposition
because the small colloidal particles are then much more likely to adhere to the surface than to each other in suspension.
Also, the presence of small colloidal particles, especially in a hot sol that' is being
cooled, furnishes a high degree of supersaturation that causes rapid polymerization
of monomer at the moment of contact between particle and surface (Figure 1.17),
.thus increasing the rate of deposition beyond that initiated by the divalent cations.
As pointed out by lIer (281) in the slightly alkaline pH range, a concentration of
100 mM calcium ion is required to flocculate 4 nm particles (700 m 2j g- l ) whereas
for very large particles only abou t 10 mM is required. A flat surface corresponds to
the radius of curvature of a very large particle. Hence when 4 nm particles are in the
neighborhood of a relatively smooth surface, there is an intermediate calcium
concentration that will promote adhesion of particles to the surface, yet not cause
flocculation in solution.
It is probable that deposition of more than a monolayer of colloidal particles
larger than about 10 nm by the described local coagulation mechanism is unlikely to
occur. Much more monomeric silica would have to be deposited to smooth out the
surface. It is conceivable that by careful addition of monomeric silica to the sol to
maintain an optimum degree of supersaturation along with careful control of the
concentration of coagulent, continuous deposition could be maintained without coagulating the sol.
The importance of flocculating ions is borne out by Midkiff (282, 283) who found
that cooling water containing more than 300 ppm silica did not deposit a scale if cal. cium ions were first converted to soluble chelates: otherwise, a deposit of colloidal
silica. associated with calcium carbonate, was formed. At the concentration
involved, over half of the silica in solution must have been colloidal and the particles
quite small. The rate of deposition was over 100 times faster than would be possible
if monomeric silica alone were involved. Wohlberg and Bucholz (246) reported that
if the silica concentration exceeded about 240 ppm (at which point colloidal silica
would be expected to be nucleated). scale formation occurred when calcium was
present.
The deposits from hot deep-well brine near the Salton Sea in Cali fornia build up
very rapidly as the brine cools while going through pipes. The silica content is 400
ppm in a solution containing up to 15% NaCl as well as,a few percent of CaCl 2 and
KCI. The brine is slightly acidic. so there is no interaction of silica with calcium ion.
but iron. which is present at only 0.2%. is adsorbed on silica at this pH and is a
major component of the scale. More striking is that up to 20% copper and 6% silver
are found in the scale as sulfides. The deposit is amorphous to X-rays and consists of
a hydrated silica. classed as opal, but is actually a microporous silica gel. under the
coagulating influence of the metal ions. Since the brine contains 1-2 ppm H 2S, the
- _.-.
94
adsorbed metal ions eventually migrate and nucleate as fine sulfide crystals embedded in the silica.
The difference between depositing material molecularly and as particles has been
noted in other systems. Thus Howard and Parfitt noted that in depositing silica on
titania pigment either a layer, could be deposited as polysilicate ions by an
isothermal, pH-dependent process or colloidal silica particles could be deposited by
a coagulation mechanism (284a).
Silica is rapidly deposited on receptive surfaces from a hot lithium silicate solution
of 2 Si02 : I Li~O ratio. Sams (284b) describes the character of the coatings obtained
on glass from solutions of different ratios of silicate, from a solution containing
12.5% SrO, heated at 95C. The opaque white color of coating deposited during 1~
hr indicates that it is porous and that the silica was deposited as colloidal particles.
Even after only 60 sec the appearance of a hazy blue coating (after being washed and
dried) indicated that colloidal rather than monomeric silica was being deposited. It
was essential that the substrate be immersed in the solution as it is heated. Merely
drying the solution on a surface gave no adherent film. This behavior of 2: I lithium
silicate is associated with its unusual property of becoming insoluble and forming a
precipitate, apparently amorphous, when the solution is heated above about 48C,
yet redissolving slowly after the solution is cooled to ordinary temperature.
However. at 100C, the precipitate apparently disproportionates to insoluble silica,
probably colloidal in size. Further discussion of forming films from colloidal silica is
reserved for Chapter 4.
METHODS OF ANALYSIS
Various methods of analysis are involved in every aspect of silica chemistry, For
convenience, sources of information are assembled here, along with a few methods
particularly useful for research purposes.
1
,.
Atomic Absorption
,.
'::
if,
Analysis for silicon in the larger laboratories has been revolutionized by the atomic
adsorption method. Although equipment represents a large investment, the method
can be used for a wide variety of elements and, once samples have been prepared in
solution, permits dozens of samples to be run in a few hours. Usually the instrument
manufacturers can recommend suitable methods for preparing solutions for analysis.
Bowman and Wills (285) have recommended specific procedures for silicon.
Dissolution of solid samples and preparation of suitable solutions have been
described by Terashima (286). Dissolution of mineral samples in H3PO~ is a convenient method, according to Horton and Baines (287), especially since it eliminates
the background correction when the silicon is dissolved after alkali fusion. Spectral
interference of vanadium can be a problem (288). The method is ideal for determining total silicon.
of Silica
Methods of Analysis
embed-
Chemicall\lethods
]a~
:- .. -
95
A wide range of chemical methods and procedures is found in the treatise of

Kolthoff and Elving (289). They also give a summary of the chemistry and solubility
of silica. Preparation of solutions for analysis, the silicomolybdic acid yellow and
blue colorimetric methods including interferences, gravimetric procedures, and special procedures for biological materials' are discussed in concise detail.
Procedures especially suited to silicate rocks, minerals, and refractory silicates
and aluminosilicates have been described by Bennett and Reed (290). A history of
analytical methods was published by Andersson (291), and three new spectrophotometric procedures were developed. Available chemical methods listed by
Meites (292), in addition to the conventional gravimetric and colorimetric methods,
also include precipitation of the silicate ion as the cobalt salt, which is then
determined by chelometric titration, and as a nitrogen base salt which is titrated
with perchloric acid.
It has been my experience that for research purposes, in addition to the atomic
absorption method for total silica, the alkali titration of silica as SiF.2- is most useful for concentrations greater than 0.1 %, and the yellow and blue silicomolybdate
methods for concentrations down to I and 0.1 ppm, respectively.
.1
silica on
, by an
.sited by
solution
rbtained
ntainin,g
uring I ~
.articles,
.hed and
sited. It
Merely
lithium
rming a
It 48C,
.erature.
Ie silica,
silica is
Methods Involving Silicomolybdic Acid

The reaction of molybdic acid with monomeric Si(OH). to give the yellow
silicomolybdic acid is indispensable in investigating the behavior of soluble and
colloidal silica. The literature is too voluminous to cover here. Morozyuk (293)
made a chronological list of the literature to 1971.
This section deals with the chemistry of the reaction and gives some recommended
analytical procedures. Application of the reaction to determining the nature of polysilicic acids and colloidal particles is reserved for Chapter 3.
It is obvious that only Si(OH)., but not polymers thereof, can react directly with
acidified ammonium heptarnolybdate to form the yellow silicomolybdic acid, since
the latter molecule contains only one silicon atom:
try. For
nethods
; atomic
method
Jared in
trument
.nalysis.
silicon.
le been
; a conrninates
Spectral
:termin-
or
Since the molecular weight of ammonium molybdate is 1235.9. I g SrO, consumes

35.3 g of the ammonium molybdate.
Polysilicic acid de polymerizes slowly enough that it is possible to determine the
monomer in the presence of polymers by noting the rate of color development
!
I,
(294-297).
., ..
E~'
, It. ;j
.
.,
_._~
The-Occurrence. Dissolution, and Deposition of Silica
Although this reaction was discovered in 1898 by Jolles and Neurath (298) and
used for many years. it was only in 1952 that Strickland (299) showed that variations in the extinction coefficient under some conditions were due to the existence of
two forms of molybdic acid. alpha and beta. that react with silica to give yellow
silicomolybdic acids having, different extinction coefficients and absorption peaks.
The beta form is obtained at lower pH and is used in the "yellow" method. but
unless conditions are optim urn, it changes with time to the alpha form, which is less
colored but more stable. The beta form is the only one that is used for determining
monosilicic acid in the presence of polymers because it is formed at once. and its
color is more intense.
To eliminate the problem of beta changing slowly to alpha, Garrett and Walker.
(300) proposed measuring the color at 335 nm, where the alpha and beta forms have
the same absorption coefficient. They also studied the kinetics of formation of
silicomolybdic acids in very dilute molybdic acid solutions (0.0025 M) and concluded
the rate was proportional both to silica concentration and molybdate ion concentration; the alpha .forrn had a constant optical density between pH 2 and 4.5. Alcohol
catalyzes the color formation, especially when present at about 30 vol, %. even at
pH 5.
In contrast to the above. Andersson (30 I) reported that at a wavelength of 325
nrn, at pH 1.5. alpha silicomolybdate had a very low extinction coefficient as compared with the molybdic acid blanks, and for this reason he used 400 om. However,
his method involves a heating step to convert the beta to alpha form. and so is timeconsuming and inconvenient for studying silica polymerization. It is useful for
accurate determination of total silica with a standard deviation of less than 0.5%.
The Beta Silicomolybdate M ethod
This method was used long before Strickland's (299) discovery of the existence of
the alpha form. Thompson and Houlton (302) had used conditions that resulted in
the beta form and later Alexander (303) used it in his study of monosilicic
acid.
.
. Govett (304) determined the critical factors in obtaining the beta form:
!
j
I!
I. Adjust the stock ammonium molybdate solution to a pH of 7.5 with NaOH to
ensure that only MOO.2- ions are present.

2. Use an amount of molybdate in the reaction solution to give a 0.06 M concentration of MOO.2-.
3. After the reaction with silica there should still remain a 0.05 M concentration of
M00 4 2- ; that is. a fivefold excess should be used.
4. About 2.7-5.0 equivalents of H 2S0 4 should be added per mole of MoO/-.
Guignard and Hazebrouck (305) further examined this method and found that
over 3-4 hr the absorbance increased and then decreased as alpha was formed. In
20-50% alcohol. the beta form was more stable.
.i
-97
Methods of Analysis
of Silica
A Recommended Procedure
298) and
at v-riaste.
Jf
For most purposes I have found, it is possible to make up a dilute molybdic acid
reagent solution that is stable for a week. Thus to determine silica it is necessary
only to add the sample solutio~. Standards should be run each day.
e yellow
n peaks.
hod, but
ch is less
errnining
. and its
REAGENTS.
(A)
Add 41.0 011 95.5% H 2SO. to 800 ml water and dilute to 1 liter
(1.5 N) .
(B)
Walker
'ms have
at ion of
(C)
mcluded
ncentraAlcohol
even at
Dissolve 100 grams (NH.)6M0102. 4H 20 (mol. wt, 1235.9) in

900 ml H 20, add 47 ml concentrated NH.OH solution (28%
NH 3 ) , and dilute to 1 liter (0.566 M MOO.2- and 1.18 N NH.';'
ion).
To 500 011 H 20 add 200 ml solution A and 100 011 solution B
(800011 total). This is 0.0707 JI;[ with respect to MoO/-, 0.148 N
in NH.';' ion, and 0.375 N in SO/- and has a pH of about 1.2.
To 40 ml reagent mixture C add up to 10 ml of sample solution

containing not more than 2000 p.g Si0 2, and adjust the volume to 50 011. Measure
absorption at 410 nm wavelength.
PROCEDURE.
h of 325
as comIowever,
is time.eful for
.5
The number of H.;. ions added per MOO.2- ion is 5.3. which is slightly more than
recommended by Govett. If 2000 p.g of Si0 2 is present. it will consume 0.2 millimols
MoO/-. The mixture contains 40 x 0.0707, or 2.83 millimoles MOO.2-, so there is
a sevenfold excess.
This composition is compared with that of Govett, Alexander, and Kautsky et al.
(306) as follows:
tence of
suited in
cic acid.
Composition of Color-Forming Mixture
Authors
aOH to
Her
Alexander
Govett
Kautsky et al.
ncentra-
Maximum
mg Si0 2/ 50 01 I
Molar MoO/0.0566
0.0227
0.060
0.0566
5.3
4.4
3.3
6.5
2.0
1.0
2.0
1.5
ation of
Her found that with a H": M 00. 2- ratio of 5.3. the p H was 1.2 and monomer
reacted fully in 2 min. and the color was stable for 2 hr. At 3.7 ratio. the pH was 1.5
and the monomer reacted fully in I min. but the color began to fade in less than 100
min. At a ratio of 10.6. at a pH of 0.8. the monomer did not completely react in 100
min. The reaction rate appears to be proportional to the hydroxyl ion concentration.
even at this low pH.
md that
med. In
98
.::...'--
The-Occurrence, Dissolution. and Deposition of Silica
Interfering Substances
Iwasaki and Tarutani (307) found that in concentrated salt solutions, the
silicomolybdic colorimetric method gave low values. (Presumably the method can be
standardized using salt solution.)
Fluoride ion interferes if it is present before the molybdic acid is added (308). It
can be masked by Al H
Tannins, especially in natural waters, interfere with the yelIow silicomolybdate
method because of their yellow color. Thus 6.8 ppm of pyrocatechol tannins or 2.7
ppm of pyrogallol tannins give a color equal to 1,0 ppm of silica. Reduction of the
yellow to molybdenum blue by sulfite at low acidity (pH 2.5) and measurement of
light absorption at 620 nm avoid the problem, and at the same time elirnihate
interference by phosphate ion (309).
Traces of ferric iron may contribute to the yellow color and for this reason
Kenyon and Berwick (310) prefer to have tartaric acid present to form a less colored
complex with iron. In analyzing caustic liquors they added varying amounts of
sodium or potassium chloride, even though color is suppressed, because this permitted them to maintain a constant salt level when the alkali samples were neutralized
with hydrochloric acid.
Interference by phosphate ion is an especially common problem, Since the phosphate ion reacts like silica to form a yellow phosphomolybdic acid, its' interference
must be eliminated. Numerous techniques have been proposed. either for separating
the silica and phosphorus before analysis or preferentially reducing silicomolybdic
acid to molybdenum blue in the presence of the phosphomolybdic acid (311-313).
Snell and Snell (314) summarized the possible procedures: (a) precipitating and
removing phosphate as the calcium salt. (b) adjusting pH so only silica will form the
yellow color, (c) destroying the yellow phosphate complex with citric. oxalic, or tartaric acids, and (d) preferentially reducing the silicomolybdic acid to molybdenum
blue.
Molybdenum Blue Method
:; i
f t
'I
j I
:i'I I'
:I
:; I
" I
h
Ii;
~ I
'II
i:
,,
When the silica concentration is only a few parts per million, the absorbance of the
yellow complex is insufficient for accurate measurement. If the yellow complex is
reduced to molybdenum blue, and a reagent is used that will not reduce the residual
excess of molybdic acid, the much greater absorbance increases sensitivity perhaps
tenfold.
The best reducing agent, according to a study by Mullen and Riley (315). is a mixture of rrietol, sulfite. and oxalic acid which gives complete reduction in 90 min at
20C and stable color for 48 hr. Their method measured silica at a concentration of
0.4 J.Lg of SrO, in 20 ml of sample (0.02 ppm) with a standard deviation of I % and of
about 0.3% at concentrations up to 6 J.Lg (0.3 ppm). Possible interferences by all
common metals and anions were checked. eerie ion, fluoride, germanium, and vanadium gave serious interference; interference by phosphate was eliminated by the
oxalic acid. Their method was further developed by Yolk and Weintraub (3 J 6), expc-
of Silica
99
Methods of Analysis
cially for analyzing plant tissues. which were first ashed and fused with l'::lzC0 3 The
following reagent solutions are prepared in plastic bottles.
rn,
.re
d can be
REAGEl'TS.
(A)
(308). It
(B)
olybdate
1S or 2.7
>n of the
-rnent of
.lirnihate
(C)
reason
colored
ounts of
; permitrtralized
i
he phos.rference
parating
nolvbdic
I:
1}.
:ing and
form the
:. or tar'bdenum
(D)
(E)
PROCEDURE.
Dilute a 1-20 ml sample containing 10-50 J.Lg Si0 2 to 20 mJ. Add 3
ml solution A and let stand 10 0.5 min at 25C. Add 15 ml reducing solution E
and dilute to 50 mJ. Wait 3 hr and measure absorbance at 810 nm wavelength.
A similar method is described by Jarabin, Vajda. and Szarvas, except that the
color is measured at 660 nm (317). Another modification of the molybdenum blue
method is to develop the color in perchloric acid medium, by reduction with stannous ion and ascorbic acid (318), which eliminates interferences and gives a stable
color. Kahler, Betz, and Betz (309) and Milton (319) favor reduction with sulfite ion
for water analysis.
For Biological Samples
For analyzing biological materials the molybdenum blue method is invariably

used because of the very low concentrations of silica. For this purpose a method of
analyzing for traces of silica in the presence of iron. phosphorus. arsenic, and reducing substances was developed by Baumann (320).
REAGEl'TS.
:e of the
nplex is
residual
perhaps
s a mi:<-
) min at
'ation of
7cJ and of
;s by all
rd vana-
I by the
S}.
"c-
20 g I-I (NH~)dMo702~4H20; 60 ml I-I concentrated HCl

(36%).
20 g I-I 'S-amino-2-hydroxytoluene sulfate (metal); 12 g I-I
Na2S0~ (discard when colored).
100 g I-I oxalic acid.
9 N H 2S04 (250 mil-I 95% H2S0~).
Reducing solution: 100 ml solution B; 60 ml solution C: 120 ml
solution D; 20 ml H 20 (store refrigerated).
(A)
(B)
Acetic acid.
17.46 .grams NaHS0 44H zO + 23.71 grams Na2S0~.IOH20
made up to 100011 (2 M SO/-).
(C) 10% ammonium molybdate solution.
(D) 42 grams citric acid + 200112 N HCI made up to 100 m1.
(E) 0.20 gram l-amino-J-naphthol-ri-sulfonic acid dissolved in 100
ml solution with 2.4% Na 2SO . 7H 20 and 12% Na2S20~. Before
each use, 0.2 gram ascorbic acid is added per 10 011.
(F) 0.1 N KMnO~ solution. freshly prepared.
(G) 0.5 M K2C0 3 + 0.5 M Na ZC0 3 solution.
(H) 2 N HCI made by distilling HCI. titrated against solution G.
PROCEDURE.
In a 25 011 flask put 5 011 acetic acid. 10 - y 011 H20. and y 011 of
sample. and add 2 1111 of sulfate solution B. Add pcrrnangunate solution F to a violet
color and 1-2 ml of molybdate solution C. Heat 7 min in water bath at 60C. Cool 5
-100
,~~~i-~:-
..
. :!:
.;
The.Occurrence, Dissolution. and Deposition of Silica
min in water at room temperature. Add 5 ml citric acid solution D. Wait 20 min for
the phosphorous complex to be destroyed and add 0.5 ml of reducing solution E and,
after another 20 min, measure the extinction coefticient with light of 800 nm. As a
blank use a mixture of 5 ml acetic acid, 18 ml H 20, and 2 ml sulfate mixture B. The
color solution must be kept out of sunlight. Results by this method show that earlier
data on the silica content of blood, for example, were too high; by this method ox
blood contained only 2.2 ppm Si0 2, and this was present only as soluble Si(OH)4'
Proteins are removed from samples earlier by combustion or ultratiltration.'
A very small amount of silicon in the presence of a hundredfold amount of phosphorus was determined by Austin, Rinehart, and Ball (321a), who used a combination of H 2SO., preferred by King et a1. (321b), along with tartaric acid, preferred by
others (32Ic).
Methods of Concentrating Silica for Analysis
For samples containing less than 0.1 ppm soluble Si0 2 it may be necessary to
concentrate the silica before analysis. Some methods are as follows:
I. Add NaF and H2S0 4 to the sample in a lead still and distill SiF 4, up to 140C,
into H 2 0 (314).
2. Accumulate soluble silica as the silicate ion on a strong-base ion-exchange resin

and elutriate in more concentrated condition with base (322). This method was
used on samples containing 10 ppb silica.
3. Silicomolybdic acid can be concentrated by extraction with n-butvl alcohol
followed by reduction to molybdenum blue with ascorbic acid. The method is said
to be useful for determining silica in aluminum oxide (323).
4. Convert silica to SiF 6 2 - and absorb on ion-exchange resin. then elutriate. Useful
down to I ppb (324, 325).
5. Convert the silica to an amine salt of the silicornolybdenurn blue complex and
extract with chloroform. Especially useful in separation from metal salts (326).
The reaction product of laurylarnine with ethylene oxide was used.
6. Convert the silica to the Rhodamine B salt of silicornolybdic acid which is
extracted with isopropyl ether and measured at 590 nm wavelength. Arsenic and
phosphorus do not interfere in hundredfold excess over silicon (327).
7. Convert silica to catechol complex sail of an organic base and extract with
nitrobenzene ( 98).
To concentrate colloidal silica for analysis. coagulating procedures can be used:
I. Freeze the solution to coagulate the colloid so it can be filtered off (328).
2. Coagulate with polyvinyl alcohol at low pH (329). Gelatin has been used in the
past.
rf Silica
Methods of Analysis
min for
Depolymerizing Colloidal Silica Before Analysis
E ~--i ,
n.. .t
B. The
~
earlier
.hod ox
i(OH).
f phos-
rnbinarred by
101
Clear solutions of silica may contain polysilicic acids or small colloidal particles that
will not react completely with molybdic acid. Thus before determining total silica,
depolymerization to monomer is necessary.
Okura (296) recommended the following procedure: to 50 ml of the hot sample in
a platinum dish add 4 drops concentrated HzSO., 1 ml 10% ammonium molybdate
solution, and 20 mg NaF, in that order; cool and measure the color. On the other
hand, Tarutani (308) stated that F- ion interferes with the silicomolybdic method
and must be removed by cornplexing with boric acid or AP+. The difference
probably is that Okura added fluoride only after adding the molybdate. Shapiro
recommended a method of depolymerizing the silica with F- for the molybdate
method, rather than using alkali (330).
Govett (304) recommended that solid samples be fused with NaOH (3 g per 0.1 g
sample) in a nickel crucible for 10 min, leached into a plastic beaker, and acidified
with 1 N H 2SO. to pH 1.5. (This should be done quickly.) Aqueous samples should
likewise be boiled with solid NaOH in a nickel beaker and then diluted.
sary to
Standard Silica Solutions
:e ~- ''1
od . _.,;
alcohol
is said
Useful
ex and
(326).
hich is
tic and
:t with
Neutral solutions of silica in seawater containing about I ppm silica can lose silica
on standing in polyethylene bottles (316). but there was no loss at low pH. It was
thought that this could have been caused by adsorption of silica by the plastic at
neutral p'H, but it is more likely caused by aggregation and settling owing to traces
of metals such as aluminum in seawater. No such interaction occurs at low pH.
Solutions appear to be quite.stable at pH 12. but the pH may drop in storage owing
to absorption of atmospheric carbon dioxide. Solutions containing up to 80 ppm
should be stable in plastic at pH 2. Standard solutions can be prepared from pure
Na 2Si039H 20, but fresh material must be used since the water content can change
in storage.
The simplest procedure is to dissolve 1.00 gram of pure microamorphous silica
(so-called c.P. Silicic acid) that has just been heated to 800C in about 4 grams of
fused NaOH in a nickel crucible, cool. then add 20 ml water and heat until all is
. dissolved. dilute to I liter. and store in a cleaned. scaled plastic bottle. Then dilute
40.0 ml of this solution ( 1000 'ppm Si0 2 0.1 N alkali) by pouring it into stirred 600 ml 0.1 N H 2SO. and make up to I liter to give a stable 40 ppm standard
solution of Si0 2 Store in a polyethylene bottle that has been previously cleaned by
filling it with hot 5% NaOH solution. letting it stand a d3Y. then rinsing it with
water and 0.\ N H2S0~ solution.
Miscellaneous Colorimetric Methods
i r,
Snell and Snell (31,,0 recommended a simple colorimetric test de veloped by Berg and
Teitelbaum ill which 1 rnl of sample solution containing no more than 4 pg of silicon
":~~1
{
The.Dccurrence, Dissolution, and Deposition of Silica
102
(2 ppm) is mixed with 1 ml of 5% ferric chloride solution and 0.5 ml of a I % alcoholic solution of pyrrole and the mixture diluted to 10 ml. The color is compared
against standards. Sensitivity is 1 ppm Si02 The only interfering substance is selenium.
A turbidometric method based on the extreme insolubility of the quinine salt of
silicomolybdic acid was developed by Defasse (331). The reagent is a mixture of quinine sulfate, ammonium molybdate, H2S0~, and HNO~, and owing to the large mass
of precipitate' formed by a small amount of silica, the turbidity permits rapid
determination of silica down to 1 ppm in water as long as phosphorus is not present
at concentration greater than 1 ppm.
After converting silica to alpha-12 molybdosilicic acid, the latter can be titrated
with ferrous sulfate in the presence of EDTA, tartaric acid, and chloroacetic acid
buffer at pH 2.5. The end point is determined amperometrically with two platinum
electrodes (332).
Detection of Colloidal Silica on Surfaces

To detect whether paper or a textile material has been treated with colloidal silica,
Turner (333) sprayed the surface with a colorless. 1-2% solution in a hydrocarbon
solvent of a lower-alkyl amino-substituted triphenylmethane lactone. In contact with
the dry silica surface the silanol groups open the lactone ring, which converts' the
compound to a deep blue color. When the surface is then wetted with water or
alcohol, the color disappears, but returns when the surface is dried.
Rapid Titration of Total Silica as Fluosilicate

To determine silica in solutions containing more than about 0.1 % Si0 2, a convenient
and rapid method developed by Konig (334) is based on the conversion of Si0 2 at
ordinary temperature to H 2SiF. with excess HF; the excess is neutralized with
NaOH without decomposing the SiF.2- ion. Then in hot solution, SiF.2- can be
hydrolyzed quantitatively by titration with NaOH. The solution must be free of
CO 2 ,
Halfter (335) had already applied a similar but less versatile method for determining silica in soluble silicates. Another variation was adapted to determining silica in
fluosilicic acid (336).
REAGENTS.
,I
(A)
(B)
(C)
(D)
(E)
Indicator mixture: 0.2% bromothymol blue and 0.1 % phenolphthalein.

48% HF reagent grade.
Powdered NaF.
3.0 N NaOH standard solution.
Boiling distilled water.
"
.;,.,---
rSilica
Methods of Analysis
o alco-
PROCEDURE. (I) In a clear 500 ml wide-mouth plastic bottle place the sample, liquid
or solid, containing about 0.1-0.3 gram Si0 2 , and add water to give a total volume
of usually no more than about 20 ml.
(2) Add about 1.5 ml 48% HF, preferably dispensed from a plastic pipette using a
bulb or plastic syringe for suction (see Warning below).
(3) After stirring the mixture gently and letting it stand for a minute or so, add 3
grams of powdered NaF and stir until dissolved.
(4) Add about I ml of the indicator mixture and, if necessary, add concentrated
HCI dropwise to turn the solution yellow, avoiding excess.
.
(5) Add 3 N NaOH from a burette dropwise until the color changes from yellow
to blue-green.
(6) Add 200 ml boiling distilled water (which has been freed of CO 2 by boiling).
(7) Note burette volume and titrate dropwise with swirling or stirring until the
color changes to a deep blue.
npa-..d
is ~
salt of
of quie mass
rapid
iresent
itrated
ic acid
atinurn
silica,
carbon
ct with
rts the
ite- -r
-enient
;i0 2 at
j with
can be
ree of
103
NOTE. Preferably a size of sample should be taken to give a titration of 3-10 ml.
Silica content of sample is calculated on the basis that 1 ml 3 IV NaOH = 0.045
gram Si0 2
Stirring is most safely accomplished with a Teflon's-coated magnetic stirring bar.
Although less convenient, it probably would be just as effective to use NaF and
50% H2S04 instead of the 48% HF solution.
'.
WARNING. HF in any concentration is a dangerous reagent and rubber gloves
and face shield should be worn. For additional safety, the upper part of the pipette
and bulb or plastic syringe can be encased in an inverted plastic bag closed around
the pipette and manipulated through the bag, to avoid any possibility of contact of
HF with the fingers. The HF- reagent bottle should be set in a large plastic or metal
beaker to catch droppings.
Another method, described by Ackerman and Lange (337), depends on titrating
silica in 3 N HCI with NaF solution until the silica is all converted to SiF.2-, after
which the presence of excess F- ion is detected potentiometrically with a titanium
electrode. An automatic titrator is preferred, since the reaction is slow. Also, AI, Fe,
N0 3 -, SOl-, and P0 42 - all interfere.
erminlica in
Titration as the Silicomolybdic ACid
, phe-
A method not requiring measurement of color and permitting use of larger samples
was described by Funk and Frydrych (338). It involves stopping the reaction between
silica and molybdic acid by adding an- excess of He\, precipitating and recovering
the silicomolybdic acid as the insoluble salt of quinoline. dissolving this in standard
alkali. and back-titrating with standard acid to the mixed end points of cresol red
(pH 7.2-8.8) and thymol blue (pH 8.0-9.6).
- --"' ;
The..Qc<;;unence. Dissolution. and Deposition of Silica
104
REAGE:"TS.
32% HCI (d = 1.156).

.
20 ml quinoline in 900 ml of acid solution A. made to 1000 ml.
(C) 0.1 gram cresol red and 5.3 ml 0.1 N NaOH. diluted to 100 ml; 0.1
gram thymol blue dissolved in 20 ml ethanol plus 2.1 ml 0.1 N
NaOH. diluted to 100 mi. and the two indicators mixed.
(D) 0.5 N HC\.(E) 1.0 N NaOH.
(F) 70 grams (NH4)eM07024 .4H 20 dissolved to I liter.
(G) Molybdic acid reagent:30 ml solution F, 8.4 ml solution D. and
1.6 ml H 20 mixed to give 40 ml reagent for each determination. A
larger quantity can be made up for use on anyone day. A water
bath at 20C or other suitable temperature is needed for rate
measurements.
(A)
(B)
SAMPLE. Up to 10 ml volume containing up to 10 mg Si0 2 in the pH range of

about 1-7.
I!
I'
III'
I
I
I
if
I
I
,I
PROCEDURE. Place 40 ml reagent G in the thermostat at 20C and adjust the

sample to the same temperature before mixing. After the desired reaction time stop
the reaction by adding 25 ml of acid solution A. After 15 sec add 25 ml of solution B
from a burette. Cool the mixture to 10-15C and filter in a fritted glass crucible of
porosity G4; wash free of HCI. Disperse the precipitate in water: dissolve the residue
from the filter with 10 ml I N NaOH. and wash it into the precipitate suspension,
which dissolves. Back-titrate with solution Dusing 5 drops of reagent C.
One milliliter of I N NaOH consumed by the precipitate corresponds to 2.504 mg
Si0 2
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~ew
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Ii
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I
i
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of Silica
105
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'm\.
r
11 0.1 N
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.lution B
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~.5v ..ig
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256. F. G. Straub, Ill. Univ, Eng. Exp, Sin. Bull. Sa.. 364, 92 pp. (1946) [Chem. Abstr. 41,
5240a].
257. J. Srarnik, Milt Ver. Grosskesselbesitzer, 49, 275 (1957).
258. A. A. Kot and V. P. Lobanov. Trans. Wortd Power Can! sih, Vienna. /956 [Chem.
Abstr. 50, 13343b].
259. D. F. McDonald, Appita, 24 (2), 270 (197\).
260. A:A. Kot, Elektr. Stn . 22 (12).24 (1951).
26L S. B. Applebaum. Demineralization by Ion Exchange, Academic. New York. 1968.
\
-"
lf Silica
113
References
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264. A. I. Ryabin, A. A. Novoselov, and E. A. Lazareva, USSR Pat. 401.385 (CI Bolj. C
02b), October 12, 1973; Pat. Appl. 1,734.816. Jan. 4. 1972 [Chern. Abstr. 71, 9-54252z].
265. H. Baumann. Ger. Pat. 1,l..6I,867. B 65,735; (Bergwerksberbar.d G.M.B.H.). 1964.
str., SO,
266. R. K. Her, U.S. Pat. 2,885,336 (Du Pont), 1959.

267. M. Mindick and P. Vassos, U.S. Pat. 3,538,015 (Nalco Chemical Co.). 1970.
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268. W. T. Barrett, Arnold. M. G. Sanchez, G. Burnie, and M. C. Yanik. U.S. Pat: 3.097,175
(W. R. Grace & Co.). 1963.
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f CerroId, New
ace sci.,
274. K. J. Murata, Am. J. Sci., 238, 586-596 (1940).

275. C. W. Correns, Geochim. Cosmochim, Acta, 1,49-54 (1950).
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277. E. S. Barghoom. Bot. Mus. Leafl. Harv. Univ. 14, (l), 1 (1949).
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281. R. K. Her. J. Colloid Interface Sci. 53,476 (1975).

282. W. S. Midkiff, "Amorphous Silica in Cooling Waters." Annual Meeting. Cooling Tower
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istr., SO,
283. W. S. Midkiff and H. P. Foyt, "Silica Scale Technology and Water Conservation."
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284a. P. B. Howard and G. D. Parfitt, 49th Natl. Colloid Symp . Clarkson College of
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287. M. E. Hofton and S. Baines. Open Report GX/EX/43/72/C. British Steel Corp. 1975.7
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290. H. Bennett and R. A. Reed. Chemical, Methods of Silicate Analysis. Academic. New
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291. L. H. Andersson. Ark. Kem. 19 (21). 257 (1963).
--
_.~-
T..he Occurrence. Dissolution. and Deposition of Silica
114
292. Louis Meites, Handbook of Analytical Chemistry. 1st ed., McGraw-Hitl. New York.
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C. T, Snell. Colorimetric Methods of Analysis. 3rd ed. Vol. 2. Van Nostrand, New York, 1949, p. 692.
315. J. P. Mullen and J. P. Riley. Anal. Chlm . Acta. 12, 162 (1955).
316. R. J. Volk and R. L. Weintraub. Anal. Chem . 30, lOll (1958).
317. A. Jarabin, M. Vajda. and P. Szarvas, Acta Phys. Chint . Debrecina, 1910, (15/16).201.
318. L. H. Andersson, Ark. Kern .. 19,223 (1962).
319. R. Milton,J. App/. Chern. 1 (Suppl. 2), S-IJO (1951).
320. H. Baumann. Hoppe-Seyler's Z. Physiol. Chem .. 319. 33 (1960).
321a. J. H. Austin, R. W. Rinehart Sr., and E. Ball. Microchem, J., 17,670 (1972).
321b. E. J. King, B. D. neu, D. M. Yates, and D. Pickles. Analyst. 80.441 (1955).
321c. N. H. Furman. Ed. Scott's Standard Methods of Chemical Analysis. 6th ed. Vol. I. Van
Nostrand, New York. 1962. p. 962.
and
.\
j
!
322.
323.
324.
325.
326.
327.
O. I. Martynova, V. F. Fursenko, and A. S. Popov. Teploenerg., 6, 86 (1972).

Z. G. Szabo. E. E. Zapp, and S. Perczel, Mikrochim . Acta. 2. 167 (197.t);
R. Wick bold. Z. Anal. cs-.: 171.81 (1959).
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W. Sonnenschein. Z. Anal. Chern . 168. 18 (1959).
A. Gclkowska, Chern. Anal. Warsaw. 1~ (4), 803 (1969); 15 (1),59 (1970).
;
!:.
.
:
I
115
of Silica
References
;w York.
328. H. J. Thorner. Tech. Wiss. Abh, Osram Ges . 9, 241 (1967) [Chem. Abstr.. 69:797865j.
329. N. S. Tkachenko and A. V. Dobrzhanskii, Zavod. Lab . 35 (6). 666 (1969).
330. L. Shapiro,J. Res. U.S. Geol. Surv. 2 (3). 357 (1974).
331. C. Defasse, Trib. CIBEDEA U, 25 (342) 267 (1972).
332. D. Burne! and L. Malaprade, Ghim, Anal. Paris. 49 (5).253 (1967) [Chern. Abstr. 67,
7872lpj.
5,6995.
333. V. L. Turner. Jr. U.S. Pat. 3.032.401 (Du Pont). 1962.

334. H. Konig. Z. Anal. Chern. 196,401 (1963).
335. G. Halfter, Angew. Chem . 61,413 (1949).
336. S. M. Thomsen. Anal. Chern . 23,973 (1951).
337. G. Ackerman and J. Lange. Talanta, 17,693.701 (1970).
338. H. Funk and R. Frydrych, Nail. A cad. Sci., Nat, Res. COline. Pub!.. 1389,284 (1966).
941).
Ian Nos-
i), 201.
II. I. Van
- ---.
CHAPTER
-j
;i
'f
f
I
I
Vail's two-volume monograph on soluble silicates (1) after a quarter of a century is

still the primary source of technical and industrial information. It is pertinent to
review some of the advances made since then in the chemistry of soluble silicates,
from which silica colloids and gels are largely derived.
_
Silicate and polysilicate ions are still not well understood. The main distinction
between polysilicate ions and very small negatively charged colloidal silica particles
is probably one of terminology. In the past, solutions of alkali. metal silicates
obtained by dissolving sodium or potassium silicate glasses in water seemed to be
clearly distinct from sols of colloidal silica stabilized with a minor amount of alkali.
Silicate solutions were made by dissolving glasses with Si0 2 : Na 20 ratios less than
4: 1. Since these glasses with more silica and less alkali do not dissolve, silicate solutions of higher ratios were not available.
On the other hand, when it was learned how to make silica particles of different
sizes it was found that smaller particles could be stabilized as sols by adding more
alkali. Thus 5 mm particles were stabilized with a ratio of 25: 1. However. attempts
to obtain concentrated solutions with still smaller particles and lower ratios of 25: 1
to 4: I led to gelled mixtures when sodium hydroxide was used as the alkali. Then it
was found that such solutions could be made using other alkalis so that solutions
containing particles smaller than 5 nm, on down to molecular dimensions, were
obtained.
Solutions in this range are referred to here as "polysilicates,' with the understanding that these polyanions may at the same time be treated as very small charged
particles.
Further study of this question was simplified when it was recognized that the
sodium ion was unusual in its influence on the gelling behavior of the system. Solutions in this intermediate ratio range made with a potassium, lithium, or
tetramethylammonium base proved to be more stable in regard to thickening and
gelling. Other stabilizing cations were guanidinium and ethylenediamine copper.
Over the past 50 years there have been major changes in theories of the nature of
the silica in the conventional alkali silicate solutions with Si0 2 : Na 20 ratios from
2: 1 to 4: 1. The physical similarity of viscous. "stringy" solutions of soluble silicates
to solutions of linear organic polymers led in some cases to the supposition that vis116
l.
- .:...--Sodium and Potassium Silicates
117
cous silicate solutions must contain high molecular weight linear polymers. (This
was in spite of the obvious fact that concentrated solutions or syrups of low
molecular weight sugars are also very viscous.) Likewise, the rapid gelling of a silicate solution upon adding acid appeared to support the idea that the gelling
mechanism involved cross-linking of preexisting linear polymers, by analogy to
organic polymer systems. Thus developments in the theory of organic polymers,
improperly applied to soluble silicates, may have delayed a correct interpretation of
this inorganic system. Polymeric silicate species certainly occur in solution, but they
are not highly linear in form and the polymerization mechanism is entirely 'different
from that of any organic system.
SODIUl\l AND POTASSIUM SILICATES
.tury is
rent to
licates,
Manufacture
inction
articles
ilicates
i to be
alkali.
ss than
It has been known since the seventeenth century that sand and sodium or potassium
carbonate react at red heat to form a water-soluble glass called "water glass." As
noted by Vail (I), Johann Nepomuk von Fuchs was the first to investigate alkali silicates systematically and even before 1850 proposed their uses as adhesives, cements,
and fireproof paints. By 1855 water glass was being made commercially, both in
Europe and America.
Manufacture has generally been carried out in large open-hearth furnaces above
1300C by the following reactions:
.e
fferent
s more
tempts
if 25: 1
Then it
lutions
;, were
rstandharged
iat the
. Solu.m , or
ng and
;r.
ture of
s from
ilicates
1al
\
..
3 Si0 2 + Na 2SO.
+ - C
2
Except under unusual circumstances, the latter reaction using "soda ash" is always
-ernployed,
The manufacture of soluble silicates was reviewed by Williams (2). Improvements
in reaction furnaces have been proposed. Burke (3) discloses coating sand particles
with ,a mixture of sodium silicate and NaOH to give a Si0 2: Na20 ratio of 2.5: 1 to
4: 1 and heating the particles in suspension in a flame to more than 3500F, at which
temperature uniform particles of soluble glass an: formed. Other proposals are a
cyclone type furnace (4), a vertical column furnace in which reactants pass downward into a heated reactor and the product moves upward around the column as a
heat exchanger (5), anda submerged combustion furnace in which a 70CC reduction
in fuel cost and 80% reduction in size can be realized (6)~ Quantitative data on the
rate of dissolution of sand (quartz) in molten Na 2C0 3 or Si0 2-Na 20 glass have
become available. Terai, Sugac. and Hayarni (7) found that at atmospheric pressure
the reaction product at the Si0 2-mollen Na2C03 boundary is rnctasilicate, whereas
under vacuum the reaction rate is slower and mctasilicatc is not detected. Diffusion
118
I
i!
i.
F
I':i
-~-
of oxygen ions through the silicate boundary layers control the reaction rate. which
is not limited by the diffusion of sodium ions. Truhlarova and Veprek (8) found the
rate of dissolution of fused silica in molten SiOz-NazO had an activation energy of
29.8 kcal rnole " at 1050-1250C. At l200C. the rate depended on the diffusion
constant, which increased from 1.86 to 64.5 x 10- 8 ern" sec- 1 as Na.O content
increased from 22.5 to 50.8" wt, %. Kreider and Cooper (9) measured the rate at
which 1 mm quartz spheres dissolved in sodium silicate glass at 950C and concluded
it was diffusion controlled and the coefficient was 4.4 x 10 -8 em? sec:" when the Na 20
content was ~O%. Similar results were reported by Hlavac and Nadelrnynska (10).
Minor improvements in the clarity and purity of solutions continue to be made.
For example, Tauch found that if sodium silicate glass of 3.25 ratio is dissolved in
water in an autoclave to too high a concentration, the resulting solution becomes
turbid. By stopping at a concentration corresponding to 38Be and then vacuum
concentrating to 41Be, a clear concentrated product is obtained (11). To obtain a
clearer solution of sodium silicate, Rathmell disclosed adding TjO, to the glassbatch to give a concentration in the melt of 400-3000 ppm (12). Apparently the
presence of 4 moles of Ti0 2 per gram-atom of calcium prevents the later formation
of insoluble calcium silicates.
The use of sodium salts other than carbonate is still of limited interest. In 1941,
Iler and Tauch (13) studied the equilibrium
SiO:z(s) + 2 NaCI(g) + H:zO(g) = 2 HCI(g) + Na:zSi03(1)
and found K = [HCl]2[NaCI]-2 [H:zO]-l = +2.9 at \OOOe.
Calculations showed the impossibility of producing HCI at a practical concentration
while obtaining a reasonable conversion based on NaC!. The equilibrium is more
favorable under 1000 o e, but the reaction rate is very low. In 19i2, Hanf and Sole (14)
reexamined the reaction at lower temperatures down to 700C. and concluded that the
equilibrium constant was favorable to using the reaction for processing certain copper
ores containing silica.
Sodium sulfate reacts with sand even in an oxidizing atmosphere at 1400C if
reactants are spread in a very thin layer (0.5 mm). However, under reducing conditions (presumably CH 4 ) The reaction proceeds at 900C with production of
H:zS(15).
Sodium sulfate in a closed system reacts with silica at 700-900C as follows (16):
.~
When the cost of NaOH relative to Na 2CO a is favorable. silicate solutions with
SiO z: Na 20 ratios up to 2.0 or 2.5 can be made directly by autoclaving sand with
strong N aOH solution. According to Ordiales (17) if hydrated or microcrystalline
silicas such as opal. chalcedony, diatomite, or tripolite are available. it is possible to
produce a solution with ratio as high as 3.22. The system water-silica-sodium
monoxide has been examined by Morey and Hesselgesser (18) at pressures up to
2500 bars and 400C. The solid phases are Na 2SiO a NazSizOs. and quartz.
-<.
,.
iI
: Silicates
e, which
ound the
ne
"f
--
..;...---
119
Commercial Solutions
Properties and uses of soluble silicates have been summarized by Weldes and Lange
(19). Typical commercial (American) solutions are listed in Table 2.1. The key
diffusion
variables in silicate solutions are the following:
content
= rate at
I. The alkali metal.

2. The ratio of Si02 to alkali metal oxide expressed by either weight or molar ratio.
In the case of sodium silicate the two ratios are nearly identical.
mcluded
he Na 2 0
:10).
ie made.
.olved in
becomes
vacuum
obtain a
ie glassently the
irmation
3. The concentration of solids.
Sodium silicates are produced as glasses having Si0 2 : Na 20 molar ratios of

1.6-3.9. These are sold as lump or pulverized form, partly hydrated powders, and
concentrated solutions. Potassium silicate glasses have Si0 2 : K 2 0 molar ratios of
2.83-3.92 and are sold in pulverized, flake or solution form.
For the production of colloidal and finely divided silica powders the 3.25 ratio
sodium silicate solution is almost universally used.
The maximum practical silica concentration in commercial sodium silicate solutions is limited by the viscosity which must be low enough for the solutions to be
pumped under ordinary conditions. The higher the Si0 2 : Na 20 ratio, the lower the
maximum silica concentration in commercial products, as shown in Figure 2.1.
In 1941,
.nt,;
Table 2.1.
Solutions
In
is more
Sole (14)
Ithatthe
n copper
Alkali
Metal
Wt. Ratio
Si0 2:M 2O
Si0 2
(%)
Na 20
(%)
(lb/gal)
Sodium
3.75
3.25
3.25
3.22
2.87
2.58
2.50
2.40
2.20
2.00
2.00
1.90
1.80
1.60
25.3
29.9
28.4
27.7
32.0
32.1
26.5
33.2
29.2
29.4
36.0
28.5
24.1
31.5
6.75
9.22
8.7
8.6
11.1
12.5
10.6
13.85
13.3
14.7
18.0
15.0
13.4
19.7
11.0
11.8
11.6
11.5
12.4
12.6
11.7
13.0
12.5
12.8
14.1
12.7
12.0
14.0
2.50
2.20
2.10
20.8
8.3
9.05
12.5
10.5
10.5
11.5
~OOC
if
Ig condiction of
Ii
vs (16):
I
f
ons with
and with
'ystalline
issible to
-sodiu rn
cs up to
!
I
I
Il
I
I
i
i
I,
\
Composition of Typical American Commercial Alkali Metal Silicate
Potassium
19.9
26.3
Density
Viscosity
(centipoise)
220
830
160
100
1.250
780
60
2.100
400
70.000
60
7.000
40
7
1.050
':=;;.;;;:~~
--::-.,.-.__ .
.
120
....
en 40
..
...:r-
C)
iii
IZ
u
c::
20
0..
O""----J._ _-L.._ _
2.0
3.0
-'--_~'--
__'__ __'
4.0
5.0
MOLAR RATIO Si0 2/M 20
Figure 2.1. Maximum concentration of

SiO, for a pourable viscosity of silicate
solution versus molar SiO,: M,O ratio. 0,
M - Na; ., M "" Li.
Soluble Crystalline Sodium and Potassium Silicates

",-
Sodium metasilicate nonahydrate Na 2Si03 9 H 20 (m.p. 47C) is the only form made
chemically pure for use as a standard. For industrial uses, both anhydrous Na 2Si0 3
"and Na2Si03' 5H 2 0 are produced along with other more highly alkaline grades.
The following anhydrous crystalline forms, obtained from the melt, have a
SiO,: M 2 0 ratio of 1 or higher:
Silicate
Ii
I
J
I
Na 2Si0 3
N a 2Si 20 s
K2 S i0 3
K2 Si 2 0 s
K2S i.O g
1089
874
976
1045
770
There are numerous hydrates of meta- and disilicates, as listed by Vail (1), but
Na,Si0 3. 5H 20 (m.p. 72.2C) is the principal commercial product.
Properties of Solution
The properties of sodium silicate solutions at all ratios and concentrations have been
described in detail by Vail (1) in 1952. A very convenient summary of data on key
properties such as phase diagrams, pH, density, viscosity, and solubility has been
,
. i
.~
~:.
"
..,
.. _.
;ilicates
121
assembled by We1des and Lange (19). A few further observations are here noted as
follows. although a thorough literature search was not made.
The specific gravity of a silicate solution is used to determine concentration, if the
ratio is known. Otherwise, analysis for silica or alkali is required. Shtyrenkov et al.
(20) propose titrating the normality of the alkali, from which the molar ratio of
Si0 2 : Na 20 can be determined- as 55.16(d - I)N - 2.28 where d is specific gravity
and N is alkali normality.
Measurements have been made of certain physical properties of sodium silicate
solutions over a wide range of ratios and concentrations. Accurate pH data have
been published by Bacon and Wills (21), who used specially designed electrode cells.
Densities of the solutions were also reported and an empirical equation given:
d = 1 + aA
where d
A =
+ bA2 + cA
specific gravity, 20C/20C

wt, % Na 20 in the solution
and a, b, and c are constants that vary with the molar ratio of Si0 2 : Na 20 which,
however, covered only the range from 1.3 to 0.5.
Electrical conductivity was measured by Ukihashi (22) on solutions ranging in
Si0 2 : Na 2 0 ratio from 1.0 to 3.95 and concentrations from 10- 3 N to maximum viscosity.
The viscosity of 3.41 ratio sodium silicate solutions was measured by Grant and
Masson (23) over the concentration range of 0.005-0.3253 g ml " and the intrinsic
viscosity (specific viscosity divided by concentration) was found to be independent of
the shear rate. At a concentration of 0.325 g ml- 1 the intrinsic viscosity was 16 ml
g-l; at 0.02 g ml " it was 3.2 ml g-I, and at zero concentration the extrapolated
value was 3.1 ml g-l. Thisdemonstrated that the silicate ions were of low molecular
weight and lacked chainlike character even in dilute solution.
made
a/" .....
lave a
Fields of Use
I), bu t
I
I
I
i
~
e been
In key
s b-r-n
I
i
There are three major types of uses for soluble silicates, particularly sodium
silicates:
1. Cleaners and detergents that depend on controlled alkalinity are made generally
from silicates with molar SiO,: Na,O ratios less than 2.5. especially meta- and
orthosilicates.
2. Adhesive, binder. and dcflocculant applications. which depend on the presence of
polysilicatc ions. require silicates generally with ratios from 2.5 to 3.8. For
maximum adhesive strength the lower ratio types are used because they can be
obtained with a higher concentration of solids. For more water resistant bonds.
the higher ratios are needed.
--122
~"::l';"
.. ..... .....
..
..
-.
3. For the production of precipitated silicas, sols, and gels, sodium silicate of ratio
about 3.3 is usually used rather than lower ratios, since less acid is required for
neutralization of alkali per unit of silica, and this ratio is available at low cost
because such large volumes are produced. However, the 3.8 ratio may be used to
some further advantage if acid consumption is an important factor in cost.
For each particular application, specific grades of carefully selected ratio and
concentration (viscosity) are recommended by the manufacturers.
Trends in uses will no doubt change as organic binders and adhesives become
more expensive relative to sodium silicate. Over the last 40 years, starch replaced
much of the silicate adhesives used in making corrugated boxboard, but the trend
may be reversed. Resins used as binders in foundry molds and cores become less
economic with increasing raw material costs and the necessity to reduce atmospheric
pollution. Replacement by silicate apparently is becoming attractive as new means
of rapid set are devised (24). Fast setting by carbon dioxide, used in a limited way
for many years, may become universal (25). The use of silicate as a binder in cores
has posed problems not encountered with resins, which burn out easily. The addition
of amorphous silica along with silicate binder permits the development of a strong
cristobalite-rich bond at high temperature, which disintegrates when cooled below
200C, according to Yates (26).
Sodium silicates used as adhesives have Si0 2:Na 20 ratios in the range I to 4: 1.
A ratio of 3.3 is most commonly used on products of paper or asbestos. At ratios of
2 or less, adhesive bonds are weaker and very water sensitive. At ratios above 4.0
(polysilicates) the adhesive strength is less, although water resistance is better. Since
at a workable viscosity, the solids content increases with decreasing ratio. silicate of
ratio 2 and of high concentration is used in dense products such as grinding wheels,
where water is hard to remove and highest bond strength is needed.
As is discussed later, the silicate adhesive solution of ratio 3.3 may be thought of
as a solution of ratio 2 consisting of N a + and HSi0 3 - ions in which the remaining
silica is suspended as exceedingly small colloidal particles 1-2 nm in diameter. At
higher ratios, there is a decreasing proportion of ionic silica.
It is observed that when silicate solutions of increasing ratios are spread as uniform thin films on glass and dried, the films crack or craze beyond a certain ratio.
This assumes uniform film-forming and drying conditions, since lilm thickness,
rapidity of drying, and temperature can all influence the degree of crazing. The
greater the degree of crazing or micro-crack ing, the less strength the silicate exhibits
as an adhesive.
It is probable that crazing occurs when the volume of dried NaHSi0 3 is insufficient to till the spaces or pores between the spherical colloidal particles as they
become packed together upon drying. If the residual solid ionic silicate does not fill
, the pores, then the gel-like' network of particles shrinks. and cracks develop in the
film. Thus the greater the tendency to micro-crack. the lower the strength of the
dried film.
It is possible to calculate the relative volumes of NaHSi0 3 and colloid present in
dried silicates of different ratios. It will be assumed that NaHSi0 3 solution dries to
2:
t
f
j
I
!
i
.II/
I:
,I
'
:-
-- -=-.-.
123
icates
ratio
:d f"'"
its indicated composition, in which case its density is about 2.0 g em -3. "The silica
particles of about II A diameter contain 23% H 20 and 77% Si0 2 and have a density
of 1.72 (Chapter I). It is assumed that when the silicate is dried. the sodium ions are
coordinated with the oxygen atoms and silanol groups in the system and there is no
water bonded to the sodium ions. When a suspension of small spheres is dried, the
particles are randomly packed with a packing density about 50% by volume.
To meet the above postulated requirement that the pores must be filled to avoid
crazing, the final volume of dried NaHSi0 3 must equal that of the colloidal particles. This in turn requires, for 100 em? of dried adhesive, 85 grams of the colloid
(19.5 grams H 20 and 64.5 grams Si02~ and lOa grams of NaHSi0 3 (31 grams
Na20, 60 grams Si0 2, 9 grams H 20). This overall composition has a Si0 2: Na 20
weight ratio of 4.0: 1, or a molar ratio of 4.13. This is in agreement with the
observation that sodium or lithium silicate solutions of ratio higher than 4, generally
called "polysilicates" in commerce, do not dry to clear, continuous films as do solutions of lower ratio because micro-cracking occurs.
It should be pointed out that such a composition of 50 vol. % solids dried to an
extremely brittle state before the last of the water is removed. In considering the
behavior of fillers in plastics, for example, more than about 40SC by volume gives a
hard, relatively brittle mass. Likewise, less than 40% by volume of colloid in silicate
should give a less brittle film as the last of the water is removed. In this case, by
similar calculations it is found that this corresponds to a SiO:t:Na 20 ratio of 3.5.
Perhaps by coincidence this is near the common ratio used in adhesives.
It seems. therefore, that at least some of the behavior of soluble silicates with
ratios greater than 2 is consistent with the theory that the solutions consist of
N aHSi0 3 in .solution along with very small particles of colloidal silica with silanol
surfaces.
.ed to
, and
come
,laced
trend
e less
iheric
leans
I way
cores
Iition
trong
oelow
) 4: 1.
ios of
'e 4.0
Si
He
01
heels,
~ht
of
lining
-r. At
uniratio.
.ness,
. The
hibits
su ffithey
ot fill
n the
.r the
cnt in
ie~
THE NATURE OF SILICATE SOLUTIONS
The fundamental equilibria involved have in the past been listed as follows:
For the above equations at 25C, taking the ionization constant of water as 10-U:
[H"j [HSiOJ-j
[Si(OH).j
I 0 -~,~
or
[OH -j [Si(OH).j
[HSiOJ-j
I:
ii
It
~~~.. ~~
......
~ ..
~:~ ~
124
[H+] [SiOi-]
10-lZ.18
[HSiO;]
[H+] [SizO:-]
[HSizOi]
[H+] [HSizOl-]
[SizO:-]
[Si:zO~-]
[HSiO;]Z
10- u
10- 12.8
2200
or
or
or
[OH -] [HSiO;]
[SiOi-]
[OH-] [HSi:zOi]
[SizOZ-
[OH] [SizOi-]
1O- 1. z0
[HSizO:-]
The above constants were measured by Roller and Ervin (27) in a system involving calcium as the base. There is now some doubt whether disilicate ions are formed
in sodium silicate solution in accordance with the above equations. My observations
indicate that in the presence of colloidal particles and at very low sodium ion
concentration, only HSi03 - and Si0 3 z - are in equilibrium with Si(OH). and OHions. A I % sol of very small particles of colloidal silica was made by polymerizing
monosilicic acid made from ethyl silicate, for 24 hr at 25C, at pH 7.8. There was
some increase in pH as the specific surface area, determined by the Sears method
(28), dropped to 1040 m Z g-1 as the silica particles grew to about 2.6 nm in diameter.
To portions of this sol NaOH solution was added to adjust pH to various values
between 8.5 and 10.5. These sols were then aged at 25C while small samples were
taken repeatedly to measure the rate of color development with molybdic acid
reagent. After 2 hr aging, no further changes were noted in the reaction rates in the
different samples. The amounts of silica reacted at indicated times are shown in
Figure 2.2. After about 5 min, the slopes of all the curves are alike and correspond
to the rate of reaction of the colloidal particles with molybdic acid. As a matter of
interest, the rate of reaction was about 300 mg SiO z hr- 1 per 10 mg of total silica in
the sample, which had a total surface area of 10,400 m", The specific rate was 3 x
. 10- 5 g m -2 hr ".
By extrapolating the linear portions of curves in Figure 2.2 to zero time. the total
concentrations of soluble. that is, monomeric and ionic. silica in the original sol
samples were determined:
.,'
~.,."..
Monomeric and Ionic Si0 2

i
I
"
.~
m,H
pH of Sol
ppm
8.5
9.0
175
2.9
220
3.7
260
450
950
4.3
7.5
15.8
9.5
10.0
10.5
"-
- ---.
Silicates
125
105
1000
ii5
involvformed
500
10.0
.~
.a..
a..
vations
urn ion
d OHierizing
ere was
method
arneter,
values
es ,- 're
ic
J
s in the
own in
'._-
OL.....-_---'-_--'_ _...J...._ _...l...-_---J_ _- '
10
20
30
MINUTES
Figure 2.2. Reaction of molybdic acid with samples of a silica sol adjusted to various pH,
indicated on each curve.
'espond
atter of
.ilica in
'as 3 x
re total
nal sol
From Figure 1.l0b, line B, the equilibrium solubility of 2.6 nm particles at pH 8 is

indicated to be about 150 ppm or 2.5 mM; this is reasonably close to the value
extrapolated to pH 8 from the above data (see Figure 2.3).
Taking this value of 2.5 mM for the concentration of Si(OH)., and Roller's and
Ervin's equilibrium constants, it is possible to calculate the concentration of the
various species at equilibrium.
[HSiO;]
[SiO~- ]
[Si2 0 ; - ]
[HSi 20i]
[Si(OH).][Hj1
[HSiO~-][H-]-1 X
10- 9 . 8
10- 12.15
2200[HSiOjP
[Si20;-J[H-] x lO. u
Ca leuluted concentrations of Si(O H). HSi0 3 ". and Si0 32 - arc plotted cumulatively
for various pH values in Figure 2.3. Although the curves arc somewhat different at
--
~ ...
126
lr
20
<t
..J
:J
..J
~
I
10
0
(Ii
I.L.
0
.
lr
~
w
u
3
Cr-----l,';O::::=-------------l.~A
2
8
10
II
- -~
pH
Figure 2.3. Concentration of soluble silica species in equilibrium with 2.6 nm diameter silica
particles at pH 8.5-10.5: A, Si(OH). in equilibrium with 2.6 nm particles: B, calculated total
concentrations of Si(OH). and HSiO~ ": C, calculated total concentrations of Si(OH)., HSiO~-,
and SiOa2 - ; D, observed total soluble silica.
pH 9, it is clear that at pH 10.5, the total concentration of soluble silica can be

accounted for by Si(OH). and HSi0 3 - , with possibly a small amount of Si03 2 - .
Thus no other ionic species can be present in appreciable amounts.
According to the above equations, the disilicate ions Si 20$2- and HSi 20$ - should
also be present in much higher concentrations than HSi0 3 -. Since it is well known
that disilicic acid reacts completely with molybdic acid in less than 5 min, the total
silica reacting in 5 min should have been much higher than observed if the equations
relating to disilicate ions were applicable to the present system.
It is therefore concluded that Roller's and Ervin's (27) observations regarding the
formation of disilicate ions were valid only in the calcium silicate system in which
their studies were made. It would not be surprising to find that the divalent calcium
ion promotes the formation of complex disilicate ions in which Si-O-Ca linkages
are involved.
Theory
A concentrated solution of sodium or potassium silicate with Si0 2 : M 20 molar

ratios of I: I to 1:2 consists mainly of Si03 2 - and HSiO- ions. However, in solutions of higher ratios it is proposed that an increasing proportion of the silica forms
extremely small three-dimensional, internally condensed silicate polymer-ions or
charged particles. These are generally equiaxed or spheroidal in shape. The silicon
\
ltil
__
..,
licates
~-
..
127
atoms in the interior are linked only to other silicon atoms by oxygen atoms, but
each silicon atom on the exterior bears at least one OH group. These particles are in
solubility equilibrium with soluble silica monomer, SiC0 H)., which in turn is in equilibrium with monomeric silicate ions. The particles are also negatively charged by
partial ionization of the surface OH groups to SiO- anionic sites.
Si(OH).
+ OH-
= (HOhSiO-
(HO)3SiO-
+ OH-
= (HO)2SiOi-
+ H 20
+ H 20
4n - nx
2
where x is the ratio OH: Si that decreases as the degree of polymerization, n,
increases. Upon raising the pH, ionization occurs:
r silica
d total
Si0 3 -,
.hould
.nown
: total
ations
19 the
which
lcium
kages
molar
soluforms
-ns or
.ilir '.
where z is the number of charges on a polymer containing n silicon atoms.

Although it has long been known that polymeric silicate ions are present in such
silicate solutions, it has not previously been suggested that such polymeric species be
.considered as silica particles in solubility equilibrium with Si(OH).,' in 'accordance
with the Ostwald-Freundlich equation relating diminishing particle size to increasing
solubility. It is suggested that the equation may be at least approximately followed
even by spherical particles as small as 10-20 A in diameter, where a large fraction of
the silicon atoms are on the surface.
The existence of such small dense charged silica particles would appear improbable were it not for the fact- that particles of this type are known to exist as discrete
ions containing as few as eight silicon atoms. As discussed later in connection with
the structure of certain crystalline silicates, it is definitely possible for silica to form
a compact octameric structure (HOSiOI.5)s in which the silicon atoms are at the
eight corners of a cube, each being linked through oxygen atoms to three other
silicon atoms and each having one SiOH group which may ionize to give the polyion
(Si s020)8- (Figure 2.6). This unit is the beginning of a colloidal "particle" that is
about I nm in diameter. However it is only after it is surrounded' by further
condensation of monomer that it becomes a "silica particle" having a core of Si0 2.
From the various cyclic polysilicate ions that exist in small amounts in solution as
the Si0 2: Na 20 ratio exceeds 2: I, similar polycyclic oligomers appear as the first
three-dimensional particulate "colloid" species. These then serve as nuclei as still
larger colloid-ion species are formed at higher Si0 2: Na 20 ratios.
I n my earlier book (29), I suggested possible structures of polysilicate ions on the
assumption that the silicon might have a coordination number of six. Baker, Jue, and
Wills had earlier proposed that polysilicate ions might thus be analogous to isopolyor heteropolyacid anions (30). However, current evidence indicates that silicon still
has a coordination number of four toward oxygen in silicate ions, as will be further
128
discussed. Accordingly, the present theory does not involve 6-coordinated silicon in
any way.
The size of the polymeric or colloidal species in sodium silicate solutions can be
estimated from various available data according to the foregoing theory, and can
also be determined directly by several means including ultrafiltration, rate of reaction, and conversion to stable species which can be isolated.
According to Bacon and Wills (21) accurate pH values were measured on a silicate of Si0 2:Na20 molar ratio 3.36 and were reported at different concentrations of
Na 20 in solution. Since the ratio of Si0 2 to Na 20 was constant, the silica concentrations are also known. Using the foregoing theory it is possible to estimate the
particle size of the polymeric silica from its solubility, that is, from the concentration of Si(OH). present.
Referring to symbols defined in Table 2.2, and assuming that the only silicate ion
present is HSi0 3 - t
A = H +M'
S:
M+M'
MH
KI
10-4.2 (value listed earlier)
M'
M =
KIM'
H
KI
A-H
H
For solutions containing 0.7-0.10% Na20 the value of HI(A - H) is relatively

constant and averages 0.008. This also indicates that all the silica can be accounted
for as Si(OH). and HSi0 3 .: and that no disilicate is present. From this the
concentration of Si(OH). can be calculated:
M
10-.2
AI'
-
10-4.2
A-H
H
whence M is 10- 2. 1 or 0.0079 M, or 474 ppm as Si0 2.

This value remains relatively constant over a sevenfold range of concentration. It
is assumed that 474 ppm is the equilibrium solubility of the postulated colloidal
silica component in silicate of molar ratio 3.36. From the formulas in Chapter 1
relating particle diameter to solubility (Figure 1.10b), the solubility is that of silica
particles about II A in diameter. From equations relating size to molecular weight,
this corresponds to a molecular weight of 1.15 x 10- 21 d 3 X 6 X 1023 , or 920, or
about 15 silicon atoms per particle.
It is known that such polymeric species are present only when the molar ratio
exceeds about 2 Si0 2: Na 20. Hence in a solution of ratio 3.3, about (3.3 2.0)(3.3)-1, or 39%, of the silica is polymeric. whereas 61 % is mostly monomeric. If
the degree of polymerization of the higher molecular weight fraction is about 15,
::~
.... .=-...
Silicates
ilicon in
129

Table 2.2.
pH of Sodium Silicate Solutions"
5 C.
and can
of reac>n a sili-
uions of
ncentrarate the
ncentracate ion
elatively
.counted
this the
uion. It
:olIoidal
iapter I
of silica
\veight.
920. or
ar ratio
(3.3 reric, If
lout 15.
% NazO
0.7
0.35
0.25
0.15
0.10
0.226
0.113
0.0806
0.0484
0.0323
pH
M'
A-H
11.20
11.00
10.80
10.60
10040
0.00158
0.00100
0.00063
0.00040
0.00025
0.224
0.112
0.080
0.048
0.032
0.00705
0.00892
0.00788
0.00829
0.C-Q784
Average
Source.
0.380
0.190
0.1354
0.0813
0.0543
0.008
Data from Bacon and Wills (21).
a A = normality of total alkali in the solution; H = normality of OH - = lOU-PH:

S/ .. total silica concentration as moles SlO, per liter; R = molar .ratio of
. SiO z : NasO = 3.36; R = 2St! A and S/ .. 1.68 A; M' = normality of HSi0 3 - ;
M = molarity of Si(OH). = K I (A - H)/H. where K I = 10 -<.2.
then one can calculate the number-average and weight-average m.olecular weights,
which are 180 and 284. These values are at least of the same order of magnitude as
the number-average molecular weight 280 found by Her (63) by a cryoscopic
method, and the weight-average molecular weight 325 found by Debye and Nauman
(37) by light scattering. Aveston's (31) value of900 by equilibrium centrifugation is
probably higher because he measured the molecular weight in sodium chloride solutions. Extrapolation of his data at the lowest salt concentration (0.08 M) suggests a
molecular weight of about 600 for this Si0 2:Na20 ratio; in the absence of salt it
would be still lower.
The question might be raised why the polysilicate fraction should not consist of a
wide range of polyion or particle sizes. However, if this were the case, since the
smaller particles are more soluble than the larger, rapid redistribution of silica
would occur until all the charged particIeswere within a relatively uniform size
range.
Ultrafiltration is another method by which at least an approximate idea of
polymer size can be obtained. In an unpublished preliminary study, lIer used
ultrafilter membranes having poresof known diameters.
The silicate solution is somewhat diluted. aged. clarified. and ultrafiltered in a
rapidly stirred pressure cell at 50 psi. By following the concentration of SiO z and
Na 20 in the filtrate one can calculate by difference how much of the silicate is
. polymerized to a size that will not go through the pores. Also. it can be shown that .
Si(OH). and HSi0 3 - pass freely through the membrane so that the initial concentration of these species in the filtrate is the same as in the initial solution. The commercial sodium silicate solutions were diluted with an equl volume of water. aged
about a week. filtered through fine filter paper to remove traces of suspended matter, and then ultrafiltered.
., ..... -..
130
.
::
-~
..,.
--:
-.
With sodium silicate of 3.75 ratio the following observations were made:
Nominal Pore
Diameter of Membrane
(A)
-,
% of Silica too
-~
.1
Large to Pass
18
24
38
25
33
52
15
In another series of tests using a single type of membrane with 18 A pores, solutions
of different ratios were tested:
Molar Ratio
Si0 2:Na20
% of Silica too Large

to Pass Pores of 18 A Diameter
2.4
3.25
3.75
Si0 2 : K 20
3.9
1,-
~,
14
25
25
In a further study by Iler a 3.25 ratio sodium silicate solution was diluted to 6%
Si0 2 and diluted suddenly to 3% by addition to an equal volume of acid, giving a pH
of 2. Ultrafiltration showed that about half of the silica would not pass a 24 A filter.
Only 7% of the silica remained as monomer.
As will be shown later, esterification of such silicic acid with n-BuOH gave an
organosol that from the composition was calculated to consist of particles about 23
A in diameter. Apparently when the silicate was acidified the monomer added
rapidly to the colloidal nuclei already present. Since 14% of the silica had been particles of II A size they would grow by addition of monomer to a calculated size of
11 x (93/14)1/3 or 21 A diameter, which is in reasonable agreement with the size calculated from the organosol.
The main conclusion is that colloidal species are present in solutions of sodium silicates having Si0 2 : Na 20 ratios greater than 2: I and that at higher ratios a greater
proportion of the silica is present as polysilicate ions or particles generally smaller
than 30 nm diameter.
These observations are consistent with the foregoing theory that the particles are
in solubility equilibrium with Si(OH)4, which in turn is in equilibrium with HSiO J - .
Physical Studies
It is true that the results of some investigations in the past led to the conclusion that
dimeric species were present in sodium silicate solutions. Thus measurements of dif-
....-
... .=:...---
ilicates
utions
to 6%
: a.
filter.
.ve an
out 23
added
parti.ize of
re calsilireater
naller
11
es are
0 3- ,
n that
of "
131
The Nature or Silicate Solutions
fusion rates of silicate ions by J ander and J ahr (32) in 1940 and still earlier by
Jander and Heukeshoven (33) indicated Si03:- is the principal ion present above pH
13.6, but between 13.6 and 10.9 the main ion present is disilicate, Si:O/-; below pH
10.9 polymeric ions are also present, whereas below about 9.0 the silica exists mainly
as colloidal particles in equilibrium with Si(OH).
However, it is possible thatthe lower diffusion rate ascribed to Si 20s 2 - might be
due to HSi03 - hydrogen-bonded to water molecules, or to a loosely hydrogenbonded [03Si~~ Si0 3]2- complex and not to the formation of an oxygen-bonded
dimeric ion. In any case, the exact nature of the dimer ions in silicate solutions, if
present, remains to be determined.
Most investigators, especially since 1950, indicate that in aqueous 3.3: 1 ratio
sodium silicate solutions there are few dimer and trimer ions and the silica is distributed between monomer ions, HSi0 3- or SiO/-, and three-dimensional polymer
.ions or charged particles. There is some evidence that a minor amount of cyclic
tetramer ion may also be present.
Even in 1928, Harman (34) concluded from conductivity, transfer numbers,
activity coefficients, hydrolysis, osmotic activity, freezing point data, phase relations, and diffusion experiments that there are only two simple silicates, Na 2Si0 3
and NaHSi03, and that silicates in the Si0 2 : Na 20 ratio range of 2: 1 to 4: I become
increasingly "colloidal."
Viscosity studies by Main (35) led to the conclusion that above a ratio 'of2 Si0 2 : 1
Na 20 , colloidal aggregates of some type were present, along with simple silicate
ions. Hagg (36) reached similar conclusions from potentiometric measurements.
Nauman and Debye (37) carried out light scattering studies on carefully filtered
solutions of different Si0 2 : Na 2 0 ratios and measured the following molecular
- weights (expressed as anhydrous Si0 2 ) . They concluded that at ratios less than 2.0
. there are no polymers or particles, but at higher ratios increasing amounts are present.
Molar Ratio
Si0 2:Na 2 0
Average Mol. Wt.
0.48
1.0I
2.03
3.32
3.9
60
70
150
325
.400
In a potassium silicate solution of 3.8 molar ratio, Brady, Brown. and Huff (38a)
found an average molecular weight of 2000.
Using 29Si nrnr, Marsm an (38b) examined' solutions of sodium potassium and
tetraethylammonium silicate with molar ratios of base i Si or 4: I to 0.02: I. The
following species were detected: tetrafunctional branching groups. Si(OSi}4: trifunctional (HO)Si(OSi)3: middle groups, (HO)2Si(OSi)2: end groups. (HO)3Si(OSi): and
orthosilicate, (HO)3SiO -. These are in equilibrium. and equilibrium constants were
derived. With lower ratios of base to alkali. tctrafunctional groups predominate.
indicating the presence or colloidal particles.
132
.\
,!
. ,
Engelhardt et al. (38c) reviewed similar studies reported up to 1975 and made
more detailed measurements by which they identified different cyclic tetramers and
double-ring trimer (a prism-like hexarner). Many types of ions are in equilibrium
and as the ratio ofNa:Si falls below 1.0 (SiOz:NazO over 2.0), branching and crosslinking groups begin to predominate. This is in agreement with other types of evidence that as the SiOz:NazO ratio exceeds 2: 1, colloidal species begin to be present.
Infrared measurements can be used to identify simple silicate ions (absorption
band at 950 ern -1) and distinguish from polymeric species of molecular weight up to
10' (absorption at 1120 cm " ') (39).
In similar studies, Borisov and Ryzhenko (40) observed the absorption and reflection spectra (500-1700 em:") to vary with the SiO z:Na 20 ratio. In concentrated 1.5
ratio solution of (HOhSiO zz-, and (HO).{SiO),O:- the cyclic tetramer ion predominated, but disappeared when more alkali was added or when the solution was
diluted, No dimer or trimer was mentioned.
Dilution with attendant depolymerization probably explains why Greenberg (41)
concluded from a study of the literature and his own emf and conductance measurements that the data do not require postulating polymeric species even in solutions of
3 SiO z: Na-O ratio. However, careful measurements at different concentrations gave
valuable information as' to the variation of pK 1> the first ionization constant of
Si(OH), to HSi0 3 - , at different ionic strengths, the value being 9.85 at zero ionic
strength.
By chronopotentiometric and thermogravimetric methods, Franks and Mukherjee
(42) identified in a 2.5Si0 2:Na20 ratio melt the ions SiO:-, Si 20 7 ' - , and Si 30 1o aby their electroreduction potentials. However, there is no evidence that these ions
retain their identity when the glass dissolves in water.
Using a technique developed by Sillen and co-workers, Lagerstrom (43) studied
sodium silicate in 0.5 and 3.0 M solutions of sodium perchlorate to maintain
constant ionic strength, measuring the emf values with a hydrogen electrode. For
solutions corresponding to molar Si0 2: Na 20 ratios of 2: 1 to 2.8: 1 (1-0.7 negative
charges per Si atom), the data can be explained by assuming that three monomeric
species, Si(OH)" SiO(OHh -, Si0 2(OH)/-, and the tetramer Si,06(OH)..2- were
present. In 3 M NaCIO, solution some additional ions, Si 20 3(OH),2-, and
Si,Oa(OH):-, were postulated. Different SiO:NazO ratios were obtained by starting
with various proportions of colloidal silicic acid, NaOH, HClO., deaerated water,
and NaClO, solution with special precautions to exclude CO 2 , Equilibrium constants
were calculated for all species. As long as clear solutions (free from visible colloid)
were involved, equilibria were attained rapidly.
In solutions where there were less than 0.75 negative charges per silicon atom
(Si0 2:Na 20 = 2.67: I), the concentration of Si(OH), reached the approximate solubility of colloidal silica (120 ppm at 25C and 216 at 50 C). and colloidat species
were formed. Thus sodium silicates with ratios higher than 2.6 contained not only
monomeric ion species and tetra mer. but also higher polysilicates or very small
colloidal particles bearing negative charges.
Ingri (44a) carried out a similar series of pH titrations in a 0.5 M NaCI solution
with simiar results. and also gave further support to the existence of the tctrarner
-':
.~
- =-. ...
Silicates
made
ers -.,d
libi ,
j crossof evij
.resent.
orption
it up to
l reflecited 1.5
on preon was
:rg (41)
easuretions of
ns gave
tant of
'0 ionic
kherjee
;i 3 0 Il\8 .se
studied
iaintain
de. For
.egative
iomeric
:- were
-, and
starting
water,
.nstants
colloid)
n atom
te soluspecies
ot only
{ small
olution
.tr:
133
Si 4 0 s ( O H ) s 2 - . The following constants were reported:

log 3:.: at 25 "C
Si(OH)4 + OH- _ SiO(OH); + H 20
Si(OH)4 + 20H- _ Si0 2(OHH- + 2 H 20
4 Si(OH)4 + 20H- _ Si 40S(OHn- + 6 H 20
4.:9 == 0.05
5.:3 == 0.15
15.03 == 0.20
Following Ingri, Busey and Mesmer (44b) extended potentiometric studies tc 290C
in 1 m NaCl solutions at silica concentrations of 0.005-0.05 m. The equilibrium
quotients for the ionization of Si(OH)4 to SiO(OH)3 - and SiO:(OH)22- were
determined in. 0.1-5 m NaCI up to 300C. In the more concentrated (0.02 m)
solutions at around pH 8-10 some of the silica was present as the polyanion
Si 40 s(OH)s2-, but the amount of this form decreased at higher temperature.
A more detailed picture emerges from ultracentrifuge Sl udies of sodium silicate in
0.5-2 M NaCl solutions, by Aveston (31). He studied solutions in which each silicon
atom carried from 0.5 to 1.0 charges, corresponding to SiO:: Na.O ratios of 2: 1 to
4: 1. The data suggest that although the cyclic tetramer may be an important
component, there must exist a series of higher polymers in equilibrium. the average
molecular weight increasing first gradually and then more rapidly as the Si0 2 : Na 20
ratio is increased from 2: 1 to 4: 1. Converting the "hydroxyl number" (charges per
Si atom) to Si0 2:Na20 molar ratio. the following approximate average degrees of
polymerization, hence average molecular weights. were found in 0.5 ~l NaCI solution. The molecular weight increased with the strength of the solutio:::
Molar Ratio
Si0 2:Na20
2.0
2.2
2.6
3.1
4.0 (extrapolated)
Degree of
Polymerization
Mol. Wt.
(as Si0 2)
2.5
3
150
ISO
420
900
1600
15
27
In addition to monomers and tetramer, but no dimer or trimer. the polymers were
assumed to consist of units containing q silicon atoms with p charges to which
"monomer and hydroxyl ions are added stepwise: .
The authors did not assume any condensation of SiOH groups as polymerization
progresses. However. the equation might be rewritten on the assumption that the
particles contain anhydrous Si0 2 cores and a surface of Si(OH): with a certain portion of the hydroxyl groups ionized. Based on the maximum surface charge on larger
134
particles, about 40% of the SiOH groups on the surface are probably ionized. In this
case, there would be a decreasing fraction of the total silica bearing negative
charges, that is, the ratio of p/q would decrease with molecular weight once the
degree of polymerization reached about 10-12, above which all silicon atoms cannot
be on the surface of roughly .spherical particles.
For p = q = I:
log (31.1
[Si(OH)i]
=
[Si(OH).] [OH-]
4.72
This value com pares with 4.29 from Ingri's data (44a).
Electrical conductivity measurements on potassium silicate of SiO::: K:rO molar
ratios from 0.39 to 4.78 were made by Ivanov and Gur'eva (45). Anion mobilities
were determined and interpreted on the basis of the usual assumption that
(HO)2SiO:r:r- is in equilibrium with [(HO)2SiOSi(OH):r]:r- and (HO)JSiO-. Dissocia-
'-.!
tion constants of the silicate ion in dilute sodium silicate solution from 0 to 250C
were calculated from conductivity measurements by Ryzhenko (46).
The nature of silicate ions in molten Na 2SO.IOH 20 (m.p. 32.38 ClC) was extensively studied by Thilo and associates, who used the lowering of the melting point to
establish the number-average molecular weight of the silicate ions (47-49). The
degree of hydrolysis depended on the Si0 2 : Na 20 ratio and not on concentration. At
extreme dilutions the species Si(OH)., (HOhSi0 22 - , and (HOhSiO- are present. At
higher concentrations equilibria set in between these monomers and higher molecular
weight anions or particles.
At equilibrium, the average molecular weight of the silica varied inversely with
N a 20 content (SO).
Higher degrees. of polymerization were visualized as occurring stepwise. This
could, of course, also be interpreted as a change in particle size:
A general equation was developed and an equilibrium constant calculated for

Si0 2: Na 20 ratios from 2.0 to 3.34. However, the relation between these observations in molten Glauber's salt to the molecular weight distribution in water is not
known.
Another approach by Thilo and associates (51) was to precipitate silicates from
solution as the silver salts. Starting with Si0 2 : Na 20 ratios of 1 and 2. the degree of
polymerization of silica in the silver salt varied inversely with the silica concentration and content of neutral salt. It was suggested that the silver salt. containing one
silver atom per silicon atom, was a linear polymer, although no viscosity or
molecular weight measurements were made.
Effects of Diluting Silicate Solutions

Since the concentration of hydroxyl ions and pH are reduced when concentrated
alkali metal silicate solutions are greatly diluted, it is not surprising that hydrolysis
,,
1
j
.;
.'
'
.-r
----
Silicates
. In this
leg?+;ve
.ncc ~
, cannot
of silicate ions occurs and a large part of the silica is converted to higher polymeric
species or colloid along with a residual silicate of lower SiO z: Na.O ratio.
The electron microscope was used by McGarry and Hazel (52) to characterize the
colloidal particles in 3.45 SiO z : I KzO potassium silicate solutions which had been
diluted out from 10 to 0.03% SrO, in various ways. The samples were further diluted
to 0.015% SiOzjust before being examined. When diluted directly to 0.03%,89% of
the particles were from I to 5 nm in diameter. When diluted to 0.3SC silica and aged
for an hour and then diluted to 0.03%, the number-average diameter was 8 nm.
The results indicate that when the solution is aged at a concentration of 0.3% the
1-2 nm colloidal particles that were in the original 10% silicate act as nuclei upon
which the monomeric silica, liberated by hydrolysis of silicate ions. is deposited. On
the other hand, when the 10% solution is diluted directly to 0.03% SiO z or 5 x 10- 3
molar, the pH is 10.26 and all the silica passes into solution as Si(OH)4 and HSi0 3 ions, and even the original 1-2 nm polysilicate ions or particles slowly dissolve. As
seen in Chapter I, at pH .10.26 the total solubility of silica including Si(OH)4 and
HSi0 3 - is around 0.05%. The authors used pincyanol chloride to detect the presence
of colloid species. The dye micelles formed on the colloid by absorption shifted the
color from blue to red (600 to 500 nm).
The further polymerization of the colloidal species owing to the lower pH when a
3.3 SiO z: NajO silicate solution is diluted was also studied by Lehrman and
ShuJdener (53). They measured the amount of molybdate-reactive silicain solution
over a period of days and found that at a concentration of about 0.14% SiO z, the
amount of reactive silica, presumably monomeric species, decreased over a period of
2 days, although some further drop was noted over 1 week. The same occurred at
0.07% silica but not at 0.03%, where complete depolymerization occurred and all the
silica was molybdate-reactive within a few hours.
When 3.25 ratio sodium silicate solution is diluted to around 2st SjO, and heated
for 1 hr, there is disproportionation whereby colloidal particles grow in size, while
the SiO z : Na-O ratio of the so-called crystalloidal or dialyzable soluble silicate
approaches 2.6: 1 or 2.0: I, depending on dilution. It is my experience that during
this time the solution is supersaturated with respect to amorphous silica so that any
clean surface of glass or metal oxide becomes coated with a film of silica to a thickness of a few nanometers.
) molar
obilities
on that
iissocia-
extenpoint to
9). The
tion. At
sent. At
)leC",Jar
5
ely with
.e, This
ted for
.bserva-
135
r is not
es from
cgree of
icentra.ing one
isity or
Effect 01 Alkali AIetal Salts and Other Coagulants
The addition of a salt of a polyvalent metal to a solution of a soluble silicate results

in formation of a precipitate of a metal silicate. In this precipitate. silicate ions are
presumably linked together by the metal ions to form an insoluble network. On the
other hand. the addition of a salt of a monovalent metal. for example. sodium
chloride. to a solution of sodium silicate yields a precipitate that will redissolve if the
system is diluted with water.
The alkali metal silicate is salted out especially easily when the ratio of
Si0 2 : Na 20 is greater than 2: I. The fact that the precipitate can be dissolved in
water suggests that it may consist of polysilicatc ions linked together by coordina-
--
..
~.--~._
-~-
136
tion through sodium ions; such linkages would persist only in the presence of a large
excess of sodium ions.
Further details of the effects of a sodium salt such as the chloride or sulfate on a
solution of sodium silicate have been summarized by Vail (I). Thus sodium chloride
causes separation of a precipitate of sodium silicate which is more siliceous than the
original solution. In smaller amounts, sodium chloride and also the sulfate and carbonate increase the viscosity of sodium silicate solutions. It appears that the added
sodium salt coagulates the colloidal or high molecular weight polysilicate ions but
has less effect on the metasilicate ions.
The effect of salts on the equilibria in a silicate solution was studied by Pevzner et
al. (54) up to a NaCI concentration of 5 N, with silicon concentrations of 0.001-0.3
g-ion 1-1 in the pH range 10.2-14.0. Equilibrium was appraoched from lower and
higher pH. The dissociation constants (pK) for water at 25C in 0.5, 3, and 5 N salt
solutions are 13.7. 14.1, and 15.2, respectively. The tetrarneric silicate ion was
detected, as had also been reported by others (44). It is noteworthy that no dimer or
trimer was mentioned. The data are summarized in Tables 2.3 and 2.4.
The effect of salt on the degree of polymerization of the polysilicate ions in
aqueous potassium silicate was examined by Brady, Brown, and Huff (55), using the
light-scattering method. The molar ratio of Si0 2 : Na 20 was 3.8: I and in freshly
diluted solutions the weight-average molecular weight of the Si0 2 was about 2000.
When neutral salts were added, the apparent molecular weight increased in proportion to the fourth power of the salt concentration and in inverse proportion to the
square root of silica concentration. In alkaline solution, the molecular weight varied
with the temperature. The salt-induced polymerization at high pH was reversible
upon dilution, but the acid-induced polymerization at neutral or lower pH was irreversible.
It seems likely that. at high salt concentrations the. cations act as cross-links
between polyions through coordination with polysilicate oxygen atoms which replace
coordinated water on the cations. This would be reversed when water is added. On
the other hand, acid-induced polymerization leads to formation of siloxane
(Si-O-Si) bridges between the polysilicate ions which are not broken upon dilution.
Table 2.3. Composition and Stability of Silicare Ions at 25 C in 0.5.3.0. and 5.0 1"1 Aqueous
Sodium Chloride Solution
Logarithm or the Equilibrium
Constants in Solution with
Ionic Strengths
Equilibrium
Si(OH). + OH - ;:= Si(OHh - + H 20

Si(OH). + 2 OH ;:= Si0 2(OHh 2 - + 2 H 20
4Si(OH). + 2 OH-;= Si.O.(OH)S2- + 6 H 20
4Si(OH). + 4 OH-;= Si.O.(OH):- + 8 H 20
SOUTce.
Data by Pevzner et al. (54).
.;~~t1~:~
'-.---
(I)
(2)
(3)
(4)
0.5
1.0
5.0
4.3 == 0.1
5.3 == 0.1
15.1 == 0.3
4.6 == 0.1
6.0 == 0.1
11.0 ::!: 1.0
-25
5.6 ::!: 0.2

7.\ 0.1
12.0::!: 1.0
-27
i
I
1M'
ile Silicates
of a large
=..... ..-
))7
Table 2.4. Changes in Free Energy, Enthalpy. and Entropy for the
~
Formation of Silicate ions in 5.0 M Aqueous Sodium Chloride Solutions at
Ifa
I a
n chloride
s than the
e and carthe added
e ions but
25C
Pevzner et
Source. Data by Pevzner et al. (54).

The types of equilibria are indicated by the numbers given in Table 2.3.
0.001-0.3
lower and
d 5 N salt
~ ion was
) dimer or
:e ions in
using the
in freshly
lout 2000.
.n proporion to the
ght varied
re- 'ible
.ross-links
:h replace
idded. On
siloxane
dilution.
Aqueous
ibrium
. with
5.0
5.6 0.2
7.1 0.2
12.0 1.0
-27
Equilibrium"
-~G
I
2
3
(kcal g-ion "')
7.6 :: 0.3
9.7:: 0.3'
16.4 :: 1.5
-J.H (kcal g-ion ")
j.S (eu)
1.0 :: 0.5
1.5 :: 0.5
3::1
22 :: 3
28 3
45 :: 8
According to Prikhid'k o and Molchanov (56), the addition of alcohol or acetone

to a solution of sodium metasilicate causes the formation of two liquid layers, the
silicate accumulating in the lower layer. It seems probable that this is a simple
dehydration of the silicate solution, the organic solvent removing water from the silicate solution and being immiscible because of the "salting-out" effect of the ions in
the lower layer. Ordway (57) studied silicate of other ratios and concluded that
organic solvents always precipitate a liquid or a solid phase containing a higher ratio
of SiO z : Na.O than the original aqueous solution of silicate. This indicates that,
whereas the silicate separates from a fluid layer rich in organic solvent, the sodium
hydroxide is soluble in this organic layer and thus leaves a silica-rich aqueous phase.
Ammonium hydroxide is similar to alcohol in its effect. Sodium hydroxide is soluble in strong ammonium hydroxide or liquid ammonia. but sodium silicate is not;
a process of purification of sodium hydroxide from small amounts of sodium silicate
has been patented by Muskat and Ayres (58a) in which, at certain high concentrations of ammonia and water, the ammonia-rich layer dissolves the sodium
hydroxide, while the sodium silicate in the system accumulates in an immiscible
lower layer.
Effects of this type are apparently involved in a process for depositing silica coatings on glass from a solution of sodium silicate containing a critical amount of a
"clustering" or "coacervating" agent such as NH.OH, NazSO., or CHJOH at
ordinary temperature (58b).
Conversion to Silicic Acids
The nature of the silica in silicate ions in any alkaline solution cannot be determined
by a chemical measurement that involves any change in the concentration of silica or
alkali. electrolyte content, or temperature because these all shift the equilibrium
between monomeric and various polymeric ion species. However, if a sample is
simultaneously and instantaneously diluted and acidified to pH 2 at less than 30C.
the resulting silicic acid is sufficiently stable to permit characterization. The problem
is to ensure that acidification is so sudden that the various silica species do not have
time to polymerize or dcpolyrncrize as the pH is dropped from the usual region of
-- _
...
138
11-13 to 1.5-2.0. At the same time the silica must be diluted to a concentration of
1% or less to minimize polymerization even at this pH where the rate is at a
minimum. Also the temperature should be preferably at a-5C if the sample is to be
stored for more than a few minutes.
As will be discussed in detail in Chapter 3, this technique has been shown by
Alexander and others to al1o~ the formation of Si(OH). from N azSiOJ 9H:O. Saltfree solutions can be obtained by ion-exchange techniques. Since conditions have
been found for converting monomeric silicate ions to monosilicic acid, which is
extremely prone to polymerize, it is evident that higher polysilicates can likewise be
converted to the more stable polysilicic acids with even less difficulty.
By this means solutions of sodium metasilicate, Na:Si0 3 9H 20, especially when
previously mixed with excess alkali, are shown by molecular weight measurements
to contain monomeric ions, since only Si(OH). is obtained by sudden acidification
(59-61). Alexander (62) and Her (63) described making a 0.1 ,H solution of monosilicic acid, Si(OH)., by stirring finely crystalline N a 2SiO J 9H:O into a suspension
of a sulfonic acid type of ion-exchange resin in the hydrogen ion form at OC while
maintaining the pH at about 3.0 with 10- 3 N HC!. The degree of polymerization
was 1.1 by the freezing point method. Finely powdered Na.SiO. \vas also successfully used.
Similarly, Iler (64) found that a 3.3: 1.0 ratio solution of sodium silicate containing 12% Si0 2 could be added to the acid resin slurry to obtain silicic acid with a
number-average molecular weight of 200, as SiO:. A more dilute solution containing
2% silica gave product with molecular weight of 180 (63). This value compares with
325 found by Nauman and Debye (37) in a more dilute solution of sodium silicate
where the lower pH permits some further polymerization of the polysilicate ions.
Reaction with Molybdic ACid
The history and use of the silicomolybdate method for analyzing for soluble silica
has been discussed in Chapter 1. It is sufficient here to point out that molybdic acid
reacts only with monomeric silica. to form the yellow silicomolybdic acid. It is
fortunate that the reaction with molybdic acid occurs at pH 1-2, where silicic acid
polymerizes least rapidly. Thus polymeric silica must first depolyrnerize before it
can react; hence the higher the degree of polymerization. the longer the time
required for depolymerization and color development. This is reviewed in detail in
Chapter 3.
This method of characterization of soluble silicates is complicated by the fact that
a given type of silicate can give different results if not allowed to age under fixed
conditions of concentration and temperature until equilibrium has been established.
For example, samples of 3.25 ratio sodium silicate were diluted by Iler from a silica
concentration of 400 gl " to 200 and 100 gl-', and each was divided into two parts:
(a) aged at 30C for 6 hr, and (b) held at 100C for 6 hr, then cooled and aged at 30C
for 6 hr.
A 50 .ul sample of each relatively concentrated silicate solution was injected suddenly from the tip of a microsyringe reaching to within a few millimeters of a high
..:- ...
iilicates
:ion of
s at Ii
s tL
speed stirrer in 50 ml of the molybdic acid solution. Ionic species react in' less than
10 min, whereas most of the colloidal or polysilicate species require more than 20
min.
Owing to depolymerization upon dilution, the proportion of colloid or polysilicate
decreased from about 70% at a silica concentration of 400 g 1-1 to 45% at 100 g 1-1.
However, heating a solution at a given concentration and then cooling had little or
no permanent effect at these high concentrations, since equilibrium was reestablished
at 30C in a few hours. This conclusion was also reached by O'Connor (65), who
carried out similar experiments on concentrated silicates of different ratios.' He
found that solutions with Si0 2 : Na 20 ratios of 0.5-2.4 contain only a minor proportion of polysilicate ions, but there is a marked increase in polysilicate (or colloid)
content as the ratio increases from 2.4 to 2.8 and higher ratios. He proposes a rate
equation whereby the molybdic acid reaction rate constant can be correlated with
molecular weight as determined by light scattering. He showed that the distribution
of the ionic species depended mainly on concentration and that equilibrium was
reached quickly even when the solution was diluted from 400 g I-I to 20 g I-I of
Si0 2 and did not change further in 2 weeks at 25C.
Reaction rates of specific polysilicic acids with molybdic acid have also been
measured by Wieker and Hoebbel (66), whose data indicated the time required for
95% of the silica to react was about 1.5 min for monosilicic, 2.5 min for disilicic
(almost indistinguishable in a mixture), and 9.5 'min for the cubic octasilicic acid.
The authors later expressed the rates as reaction velocity constants, k n .l I , for higher
molecular weight species. The rate constant was approximately inversely proportional to the molecular weight of the polysilicic acid (67). From their data the
average degree of polymerization nh the number of silicon atoms per polysilicic acid
molecule, can be related to the reaction rate constant:
wn by
'. Salts have
rich is
vise be
, when
.ments
.cation
monoension
: while
zation
recesslntainwith a
aining
:s with
iiIi
1S.
: silica
ic acid
. It is
c acid
fore it
: time
tail in
ct that
. fixed
lished.
l silica
parts:
.30C
d suda1
139
Coudurier, (68b) further investigated these reactions and proved that mono- and
disilicic acids both react directly with molybdic acid, the latter only half as rapidly
as the former. Higher polymers all must depolymerize to the monomer before reaction can occur. In this wayan empirical relation between molecular weight of the
polymer and the rate of formation of silicomolybdic acid was worked out (see
Chapter 3).
Thilo, Wieker, and Stade (68a) standardized the molybdate reaction with silicate
species and calculated the characteristic reaction rate constants:
to
silicornolybdate in [. min and r 2 in 12

where '1 is the fraction of silica converted
min. Plotting -Iog( I - r) versus t. usually gives a linear section with a constant
slope between times 11 and 12 from which the constant can be calculated.
Certain anhydrous crystalline silicates known to contain SiO. 2 - ions, such as
NaH 2SiO.8H 20 (Na 2Si0 3 9H 20). Ca 2SiO . Li.SiO., and i\lgK 2SiO. all gave the
1.40
same constant, which was therefore characteristic. of monomeric silica. Other

crystals known to contain the disilicate ion such as Ca~Na2Si207 and N a.Si 20 7
served as standards for dimeric silica.
For monomer, k = 1.7 min:" and for dirner, k = 0.90 min-I. The constant for
cyclic tetramer was about half that-of the dimer, using (KH)4Si 4012 as the standard.
A solution of SiOz:NazO ratio of 2: 1 was shown to depolymerize with increasina
dilution. Thus in a solution 1.0 M in SiOz, the molybdate reaction curve was very
similar to that of cyclic tetrarner, However, upon dilution to 0.1 M it acted like
dimer and at 0.01 M had hydrolyzed to monomer.
~
Conversion to Esters ofSilicic Acids

Some indication of at least the maximum size of the silicate species in a solution of
sodium silicate of 3.3 ratio SiO z : NajO has been obtained from the nature of the corresponding silicic acid ester (69). Silicic acid of low molecular weight is so unstable
in aqueous solutions that any attempt to isolate it by evaporation of water, even at
ordinary temperature, results in rapid polymerization to a gel. The direct esterification of silicic acid therefore remained impractical until the discovery of Kirk (70) of
a method for transferring silicic acid of low molecular weight from aqueous solution
to solution in an alcohol. This transfer is accomplished by extraction of the acid with
a suitable polar organic solvent, simultaneously saturating the aqueous phase with
sodium chloride in order to salt the silicic acid into the organic phase. An alcohol
such as n.butyl alcohol is then added, and esterification is effected by azeotropic distillation of water from the alcohol solution (29).
The polysilicic ester, which is a tacky resin after the butanol is removed under
vacuum, typically contained around 25% carbon and 62% SiO z. The composition
can be expressed in terms of the molar ratios (C 4H9 )20 : Si0 2 =' 0.25 and H 20: SiO z
= 0.22.
Viscosity studies showed that polymer consisted of units of spherical rather than
elongated shape.. From the composition it can be calculated that the ratio of
hydroxyl plus butoxy groups to silicon is 0.95, which would be the OH:Si ratio in
the corresponding silicic acid. Referring to the formula in Chapter 1 relating particle
size to composition of surface-hydroxylated silica particles. OH: Si = 24.6cF-/l1.5d3,
the particle diameter is estimated to be 2.3 nm.
The monomeric and low molecular weight species in the original silicate had
polymerized onto the higher molecular weight polysilicate or colloid fraction. which
has been shown to consist of particles about 1.0-1.5 nm in diameter, so that the final
particle diameter in the ester is somewhat larger.
Conversion to Trimethylsilyl Derivatives ojSilicic Acids

,j
,,
i
~1
The various ion species which might be found in sodium silicate solutions can be
found in pure form only in certain crystalline silicates. Lentz (71) first announced in
1963 that the silica in selected minerals in which the ionic structure is known from
X-ray diffraction data can be converted to the corresponding trirnethylsilyl deriva-
-- ---: Silicates
~.
Other
-.r a, C': f)1
stant for
indard.
creasing
vas very
cted like
lution of
the corunstable
, even at
sterifica( (70) of
solution
reid with
ase with
alcohol
opic dis:d under
position
.o.sio,
her than
ratio' of
ratio in
particle
:; 11.5ef3.
:ate had
n. which
the final
; can be
unced in
. . . n from
Id
"1-
141
tives. Thus olivine. (MgFehSiO., contains monomeric silica which can be isolated as
[(CH3hSiO].Si. Hemimorphite, Zn.Si z0 1(OHh 2H zO. contains dimeric silica.
isolated as [(CH 3)SiOhSiOSi[SiO(CH 3hh. Similarly, natrolite, Naz(AlzSi301o)
2H zO, furnishes the linear trimer, and laumontite, CaAl zSi.0 1z4H zO, gives cyclic
rerramer, which is isolated as [(CH3hSiO]aSi.O.
Lentz then obtained the most direct and convincing evidence of the true nature of
the silica in sodium silicate solutions (72a) by developing a technique for converting
the silicate species to the corresponding organosilyl derivatives and isolating them by
distillation and gas chromatography. Conversions and yields were less than perfect
and the study was made on I M silicate solutions where some hydrolysis and
polymerization is known to occur, as compared with the concentrated solutions of
commerce. Also, it must be pointed out that since the technique involves the
transient formation of silicic acid, some polymerization may occur under the locally
acidic conditions to form dimer and trimer that may not be present in the original
alkali silicate.
The results showed that there is always less dimer than monomer and less trimer
than dimer, but a significant quantity of tetramer in the diluted solution with
SiO z: Na-O ratio of 2: 1. Colloidal species comprised an increasing fraction of the
total silica with increasing SiOz:NazO ratio. At 2: I ratio (Na.Si ratio of I) it
amounted to 45% of the silica and at 3.3: 1 ratio it was about 70%.
The colloidal species were converted to silyl derivatives having (CH3}3Si0o.s: SiO z
molar ratios of 1.32-1.05. Lentz concluded that these were spherical particles. on the
basis of which the diameter was deduced to be 10-15 A.
The fact that the solutions were somewhat dilute. containing only 6% by weight of
SiO z (l M), no doubt permitted some hydrolysis and polymerization to occur. As
shown by Thilo, Wieker, and Stade (68a) still further dilution results in depolyrnerization to dimer and then .monorner. In 1 M metasilicate solution (SiOz:NazO =
I: 1), 22% of the silica was colloidal, 10% was cyclic tetramer, 7% linear trimer, 12%
disilicate, and only 26% monomer. (Total recovery was 76%.) However. in
concentrated metasilicate solution and in N a zSi03 9H zO it has been shown that
under carefully regulated conditions. most of the silica is monomeric by reaction
with molybdic acid.
Glasser and Sharma (72b) compared different procedures for trirnethylsilylation
of the silica in sodium rnetasilicate solution (NazO:SiO z = 1: 1). The proportion of
polysilicate ions in solution decreased with dilution from 1 to 0.001 M, where only
monomer was found. Even in I M solution only a third of the silicate was
monomeric.
Conditions for reacting (CH 3hSiCI with minerals in various reaction solvents were
investigated by Gdtz and Masson (73). who found that a small amount of water
must be present. hexarnethyldisiloxane and isopropyl alcohol are beneficial, and conditions must be carefully controlled to minimize degradation or polymerization. to
obtain an optimum yield or the trirncthylsilyl derivative or the original silicate ion.
Subsequently it was found that sodium silicate was especially difficult to react
without polymerizing the silica species to some extent (74).
The structure of ions in numerous crystalline silicates has been further elucidated
142
by coverting the individual silicate ions directly to trirnethylsilyl derivatives. which

were identified after separation by thin-layer chromatography. This is possible if the
derivatives are soluble, that is, if the silicate ion exists as isolated units and not as
infinite chains or three-dimensional siloxane networks. Thus Wieker and Hoebbel
(66) showed that when Li:H 2SiO. solution is concentrated over H 2SO., the ions are
largely present as cyclic tetrasilicate. Also, crystalline N a 20 2eaO 3Si0 2 actually
. contains cyclohexasilicate ions and should be formulated Na.Ca.(Si.O u ) .
Similarly, these authors (75) coverted the following silicates to the corresponding
trimethylsilyl (T) derivatives which are used as standards for the identification of
individual silicic acids:
Crystal
Formula
Structure
N a2 H 2 SiO. H 20
CaSiO.
Na 6(Si 20 7 )
Na.Cd 2(Si30 lo)
Si.0 3C1 lo
(CaSi0 3)3
(KHSi03).
[(CH3)3N+]loSi7019xH20
[(CH3)3N+],Sia02o' 69H 20
[Cu(enh].Si a020 30H 20
T.SiO.
T.SiO.
T aS i207
T aS i30 10
T 1oSi.O I3
T 6S i309
T aS i.0 12
TIOSi7019
T aS ia0 20
T aSi,02o
Monomer
Monomer
Dimer
Linear trimer
Linear tetramer
Cyclic trimer
Cyclic trimer
Tricyclic heptamer
Cubic octamer
Cubic octarner
In this octamer, referred to as a "double-four-ring" structure there are eight silicon

atoms at the corners of a cube.
Silicates with Coordination Numbers Four and Six
t'
It has been previously theorized that in aqueous silicate solution silicon is coordinated with six oxygen atoms. Such views of Weyl (76) and Treadwell and Wieland
(77) were discussed by Iler (78). However, more recent spectroscopic studies of silicate solutions seem to indicate that the silica is 4-coordinated with oxygen and that
the Si(OH)62 - ion, for example, does not exist, at least in solution. Fortnum and
Edwards (79) concluded that Si(OH)i- was not present in solution because Raman
lines analogous to those of SiF.2-, PF6-, and Te(OH)6 were not found. The four low
intensity lines found at 448, 607, 777, and 935 cm -I suggested that the ion is
(HO)2Si0 22- since it is similar to (HO)2P02 ". which gives lines at 40 I. 511, 885, and
1050 em -I.
Similar conclusions were reached by Early et al. (80). who also noted the similarity of Raman spectra of (HOhSi0 22- and (H0>zS02' Using HzO and DzO, Freund
(81) examined silicate solutions with Raman-laser spectra and identified (HO)3SiO-,
(HO)2SiOl-, and (HO)3Si023-, the latter only at very high alkali concentrations.
Equilibrium was obtained rapidly and completely. There was no evidence for the
presence of dimer species.
"
"
'7'
~
",
."
1~3
ilicates
Solutions of Polysilicates
which
: if the
no.
oebbel
ns are
.tually
On the other hand, it is likely that most reactions of silica and silicates-in aqueous
solutions do involve a temporary expansion of the coordination number from 4 to 5
or 6. Also in certain crystalline silicates, the silicon atom is coordinated with six
oxygen atoms, for example, in thaumasite (82). This was also confirmed by Edge
and Taylor (83), who worked out the structure of this calcium silicate sulfate carbonate crystal and demonstrated the presence of Si(OH)e 2- ions.
It is in the hydrated metasilicate crystal that one might expect the silicon atom
most likely to be surrounded by six hydroxyl ions, but Jamieson and Glasser have
shown that this is not the case (84). In Na 2Si03 9H 20 they find by X-ray structure
analysis that silicon is surrounded by only four oxygen atoms. The sodium ions are
surrounded by six oxygen atoms and the more appropriate constitutional formu la is
Na2[(HO)2Si02]8H20. By similar procedures, Jost and Hilmer (85) found a similar
structure and concluded that isolated SiO. tetrahedra are linked through hydrogen
bonds into layers, separated by layers of sodium and water. The same formula was
arrived at by quite a different method. The nature of Na 2Si03.xH 20, where x is 9, 6.
or 5, was investigated by Thilo and Miedreich (86) by hydrolyzing the salt in wet
alcohol. From analysis of residue it was concluded that the salt should be formulated
as Na 2(HOhSi02yH 20, where y is 8, 5, or 4. A hydrated so-called "disilicate," is
formulated as Na(HO)3SiO, which has the same structure as Li(HOhP0 2, and is
actually monomeric.
From infrared spectra, Borisov and Ryzhenko (87) conclude that in 'solutions of
sodium metasilicate (Si0 2: Na 20 ratio of 1: 1) there are mainly ions of (HOhSiO/with some cyclic tetramer (HOMSi.O.)O.-, which increases in concentration with
increasing ratio, and also that silicon is coordinated with four oxygen atoms.
Thus, except in very rare instances, the silicate ions in solution or in crystals
appear to contain silicon with a coordination number of four.
inding
ion of
silic,..
SOLUTIONS OF POLYSILICATES
coorieland
of silid that
nand
.aman
.ir low
ion is
5. and
simi'reu nd
SiO-.
itions.
)r .'
For many years it was supposed that alkali silicate solutions with Si0 2: M 20 ratios
higher than 4: 1 could not be made. The corresponding glasses are not homogeneously soluble in water. Attempts to dissolve quartz or amorphous silica powders
in a minimum of NaOH solution to achieve the desired higher ratios were not successful. Liquid silicates with ratios higher than 4: I were sought for use in adhesives
because the lower alkali content was anticipated to furnish bonds that are more
water resistant. Also. in refractory compositions. loweralk ali was needed to raise
the softening point and improve refractory character.
As discussed at the beginning of this chapter. silicates with Si0 2: Na 20 ratios
of 4: I to about 25: I are usually referred to as "polysilicates." They do not have the
high content of sodium and silicate ions as do the conventional soluble silicates.
which have ratios less than 4: I. However. they contain much more alkali than
necessary to stabilize sols of smallest particle size manufactured and sold as colloids.
The borderline between a polysilicate solution and an "alkali-stabilized sol of
colloidal silica" can logically be drawn at the particle size of the silica below which
the increased solubility of the silica as Si(OH). at ordinary temperature causes the
144
particles to grow spontaneously unless more alkali is added. However," when particles less than 5 nm in size are stabilized against growth by adjusting the ratio to less
than 25: 1, an increasing and substantial fraction of the silica is converted to silicate
ions. Thus a "polysilicate" solution may be considered to be an equilibrium mixture
of ionic and negatively charged particles of colloidal silica of such extremely small
size that they can be classed also as polyanions.
Because lithium silicates are so different in behavior from sodium and potassium
.silicates, lithium polysilicate is discussed separately.
Sodium PoJysiJicate
The advantage of a binder having a Si0 2 : Na 20 ratio of 10: I, for example, is
demonstrated by the fact that such mixtures of an . alkali metal silicate and a
colloidal silica sol are proposed for making waterproof fireproof coating mixtures
even though the mixtures have a short shelf-life (88).
During the development of concentrated silica sols stabilized with NaOH around
1950, it was realized that the smaller the particle size, the more alkali and the lower
the Si0 2 : Na 20 ratio required for stabilization. However, in the ratio range of about
4: 1 to 25: 1 the concentrated com positions were generally found to be unstable, and
eventually gelled. When a 3.25 ratio sodium silicate solution was added to a
concentrated silica sol to reduce the Si0 2 : N a 20 ratio from 100: I to 5: 1, for
example, a gel immediately formed. However, lIer (89) found that by aging or
warming the mixture, a stable liquid was again obtained. Thus solutions with ratios
from 4.2: 1 to 6: 1 containing 10-30%Si02 could be prepared from sols originally
containing typically 5-25 nm particles. However, longer heating destabilizes the
mixture and an insoluble crystalline polysilicate or gel appears. the polysilicate solution is a clear, transparent fluid of low viscosity in which around half of the silica is
present as soluble or ionic silicate, as shown by its reactivity with the molybdic acid
reagent. Thus much of the silica that was introduced as colloid remains as such, but
the particle size is smaller owing to some depolymerization at equilibrium.
The unique nature of the product is shown by the fact that when it is mixed with a
silica sol containing an equal weight of 7 nm colloidal silica along with a sol containing an equal weight of colloidal silica as 100 nrn particles, there is formed a mixture
which, when cast as a film on glass, dries at 150C to clear, hard, adherent, waterresistant coating. The spaces between the 100 nm particles are filled by 7 nm panicles and the spaces between these by the still smaller colloidal com ponent of the
polysilicate and, in turn, the remaining spaces of molecular size by the soluble ionic
silicate species. Once dried, the sodium apparently is adsorbed on the extensive silica
surface so that no soluble silica remains and the film is impervious.
Instead of starting with a sol of preformed particles, Oken (90) claimed that by
starting with a low molecular weight solution of silicic acid, temporarily stable
liquids could be obtained with Si02:Na20 ratios in the range 4: 1 to 6: I, as in Iler's
com position, and also from 8: 1 to 40: I.
More recently, compositions with ratios higher than 4: I have been prepared by
heating an amorphous silica powder with 3.22 ratio sodium silicate to above 100~C ,
,.
j'
I
j
..
:.----
;ilicates
Lithium Silicates
partito less
sili
iixture
. small
to cause intumescence, and then the partly dried mass is further heated "to 315C,
after which the mass can be dissolved to give a polysilicate solution (91). The higher
temperature apparently partly dissolves the agglomerated silica powder, bringing
about its disaggregation. Probably the amorphous powder employed must consist of
ultimate silica particles of the same size range as in the sols em ployed in earlier
processes. According to a German patent, if waste silicic acid powder from the AIF 3
process is used, it is so lightly agglomerated that it can be dispersed by alkali alone
to give a solution of 4.3: I ratio of Si02 : Na 20 containing 13.7% Si0 2 (92).
assiurn
145
Potassium Polysilicate
ple, is
and a
ixtures
around
~ lower
~ about
le, and
j to a
: I, for
~ing or
Ir
c;
gin.... y
zes the
.e solusilica is
lie acid
ch, but
with a
ontainnixture
water1 partiof the
Ie ionic
e silica
It has not generally been recognized that in the polysilicate system, the potassium
ion behaves very differently from sodium. Although the coagulating effect of these
ions is generally similar in most colloid systems and even in collloidal silica at pH
7-10, the potassium loses its coagulating effect at higher pH but sodium does not.
(This is discussed in further detail in Chapter 4.)
When concentrated 3.25 ratio sodium silicate is mixed with an alkali-stabilized sol
containing 30% silica, coagulation and gelling occur at once, but they do not occur
if potassium silicate is added. This is apparently the basis for the disclosure of Waltersdorf (93). Thus stable mixtures of colloidal silica and potassium silicate can be
prepared with a silica concentration of 15-30 wt. %, with Si0 2 : K 2 0 molar ratios of
11: 1 to 24: 1. Although it is not so stated, such compositions are relatively stable
toward prolonged heating in comparison with similar sodium based mixtures, which
tend to crystallize.
Appreciation of this effect has led to the development of a number of practical
applications. Thus amorphous silicic acid powder is heated with 2.4: 1 ratio
potassium silicate solution to give a viscous solution that forms. a binder for a pigmented 'coating on asbestos-cement board (94). The final molar ratio of Si0 2 : K 2 0 is
5.7: 1. A composition with similar use is described by Yano (95).
Another unusual application of the compatibility of potassium silicate with
sodium-free colloidal silica is described by Shoup (96). By mixing concentrated
potassium silicate solution with a concentrated silica sol and adding an ester,
aldehyde, or amide which liberates acid as a homogeneous gelling agent, very strong,
dense, uniform silica gels can be made in cast shapes. When washed with acid to
. remove the potassium salt. these gels are so strong and coherent that they dry in the
shape in which they are cast. Because the silica is so concentrated, cracking is
minimized as the gel shrinks as it is dried. When fired at 900C it gives a strong
body with 70% by volume porosity. It can then be tired at 1400C and further
shrunk to an object of clear fused silica without losing its relative shape (97).
that by
stable
n Iler's
LITHIUM SILICATES
Ire
10
The lithium ion is very different from sodium or potassium in its behavior in silica
systems. The lithium ion rescrnbles these clements to some extent at ordinary
]46
,.
i.
temperature but above about 60 C it assumes some of the characteristics of calcium.

Thus, although a solution of lithium silicate can be made by dissolving amorphous
silica in LiOH solution at 20-40C, the silicate comes out of solution when heated.
The effect is reversible; it is remarkable to see the solution solidify to a white mass
when hot, then reliquefy to a clear homogeneous state after being cooled to 25C for
a few hours.
Ordway (57) in 1907 studied the properties of lithium silicate with molar ratios of
Si02 : Li 20 of 1: 1 to 2.3: 1 and noted the peculiar reversible insolubility when the
solution was heated and cooled. Even as late as 1952, Vail (1) stated that the possible concentrations and ranges of composition of lithium silicate were much more
restricted than in the case of sodium. In 1969, Weldes and Lange summarized the
properties of available aqueous lithium silicate systems (19).
It is apparently only since 1950 that it has been appreciated that stable solutions
of lithium silicates and polysilicates could be prepared with any desired Si0 2 : Li 20
ratio and that these have useful properties.
The difference from sodium is especially apparent in concentrated solutions with
molar ratios of Si0 2 : Li 2 0 from 4: 1 to 15: I or higher. These are clear and quite stable at 25C whereas, as previously discussed. most of the analogous sodium silicate
compositions either gel or crystallize. Furthermore, the properties of concentrated
sols of colloidal silica are appreciably different from those stabilized by sodium base,
especially in regard to much greater compatibility with water-miscible organic
solvents.
Lithium silicate solution cannot be made by dissolving the glass. so is prepared by
dissolving very finely divided amorphous silica in LiOH solution at 20-50C.
However, the reaction apparently proceeds more rapidly at 75-250C in an
autoclave, whereby one obtains a solution of LiSi0 3 plus a precipitate of higher ratio
silicates which dissolves when the solution is aged at 20-30C (98). A solution of 3.8
molar ratio can be prepared by adding 200 mesh silicon powder to a stirred 12%
solution of LiOH H 20, from which hydrogen is evolved, while the temperature is
held at 38-45C. The slightly viscous filtered soltuion contained 19% Si0 2 (99).
Another approach is to prepare a cation-exchange resin in lithium form and pass a
solution of sodium silicate through it to exchange sodium for lithium (100).
... ;c-
.~
<
I
1
I,
i
J
Lithium Polysilicates
. In 1954 it was discovered by lIer (101) that concentrated stable solutions containing
Si0 2 : Li 2 0 molar ratios from 4: 1 to 25: I could be obtained by adding LiOH to a
solution of polysilicic acid. to a suspension of silica gel. or to a silica sol free from
alkali metal or other cations. Since the mixtures thickened or immediately set to a
gel, this approach appeared useless until it was found that after a few hours or a day
or so at ordinary temperature. the mass spontaneously liquefied. When such mixtures were heated to 80- J OOC to accelerate liquefaction. they remained gelled. The
liquid compositions contained both ionic and colloidal silica.
"
.". =-.--icates
Lithium Silicates
num.
ihoi
Commercial solutions of lithium polysilicate are reported with the- following

properties (102):
I~i
at,
mass
C for
Polysilicate
os of
n the
iossimore
d the
Si0 2( %) .
Li20(%)
Molar ratio Si0 2 : Li20
Viscosity (cps)
Specific gravity
pH
Shelf-life at 75 F
(months)
with
e sta-
licate
rated
base,
ganic
ed by
50
n
all
ratio
of 3.8
12%
..
ure IS
(99).
lass a
20
2.1
4.8: 1
12
1.17
11
12
Type 85
20
1.2
8.5: 1
8
1.17
11
12
Since compositions of all Si0 2 : Li20 ratios from 4: 1 to 25: 1 are soluble and stable, this system offered lIer an opportunity to examine the relation between the silica
to alkali ratio and the nature of the colloid species pressent. Lithium polysilicate
solutions were made by mixing solutions of polysilicic acid, obtained by ion
exchange from 3.25 ratio sodium silicate, and lithium hydroxide and aging the mixtures at 25C for a week until clear liquids were obtained at equilibrium. The solutions contained 10% of Si0 2 and the Si0 2 : Li20 ratios ranged from 3: I to 10: 1.
These solutions were compared by measuring the rate of formation of the yellow
silicomolybdic acid when microsamples were suddenly mixed with molybdic acid
solution at low pH. For each sample. the percent of the total silica, P, which had
reacted at time t was noted at 2.5, 5. 10, 15, and 20 min at 25C. A solution of
sodium silicate of 3.3: 1.0 M ratio was also included and found to react in about the
same way as the lithium silicate
solution of corresponding... ratio.
.
.
It was assumed that the solutions all consisted, for the most part, of monomeric
silicate ions and higher molecular weight polysilicate ions in the form of very small
charged colloidal particles. Since the monomeric ions react with molybdate in about
2.5 min. the percent of monomeric silica. Pm. was noted in each case.
Then P - P trI' or p, was the percent silica in the polymeric state that had reacted
at time. i. This was found to follow the equation
log
lining
1 to a
. from
t to a
a day
i nuxj, Tht:
Type 48
100 - P
100
kt
(see Figure 2.4)
The values of k; the relative reaction rate. wen: plotted against (R - 2)-1 since
colloidal species are present only at a ratio greater than 2: I. This gave the relation
shown in Figure 2.5. Since. as has been elsewhere noted. the reaction rate is an
inverse function of particle size of the colloid. it is concluded that the size of the
colloid species must increase regularly and spontaneously in proportion to the degree
to which the ratio exceeds about 2:.1. This is at least true in the ratio range 3: I 10
10: I. A: higher ratios. the particle size is less closely related to ratio. since it is well
... =-- -j
.;
148
0.3
(\J
0.
J
Co
..
0.2
I
0
S!
(.?
..J
0.1
o,--~:....::r::
_ _-'-_ _.L-_----L_ _----L_ _-.I-.......J

20
10
30
MINUTES
Figure 2.4. Reaction of colloid species of silica in lithium polysilicate solutions of different
ratios of Si0 3 : Li 30 (indicated on curves) with molybdic acid reagent.
1.
1!
n
I'
I
i
known that at ratios higher than 25: 1. sols of different particle sizes can be stabilized at the same ratio without much. if any. difference in particle size.
Thus the polysilicate, solution spontaneously equilibrates to a mixture of
monomeric species and colloidal species. the size of which increases with increasing
ratio overZ: I.
Numerous procedures for manufacture have been suggested. Cuneo (103) prepared a lithium polysilicate from a 2.6% silica sol obtained from sodium silicate by
ion exchange. by adding LiOH to attain ratios of 2.5: I to 8: I and then concentrating the solution by vacuum evaporation to a silica content of 21 %. More
"crystalloidal." as opposed to colloidal. silica was said to be present because of the
nature of the starting sol which probably contained silica particles 1-2 nm in
diameter.
A lithium polysilicate solution of 3.5 M ratio can also be made by heating finely
divided amorphous silica with LiOH solution at a molar ratio of 1.5: I. separating
the precipitate that forms at elevated temperature. and letting it cool. whereupon it
liquefies to a polysilicate solution containing 23.4% Si0 2 Apparently the silicate
that separates from hot solution is of higher ratio than that which remains (104).
According to Patton and Cox (105). lithium silicates of molar ratios from 2: I to
6.3: I can be made in a similar manner at 75-150C by leaving the precipitate in
suspension and cooling to effect total solution. The polysilicate can also be made by
dissolving silicon powder in LiOH solution at 50-80C with Cu(OHh present as a
catalyst (106).
ilicates
Lithium Silicates
149
x
I
!<t
a:: 0.010
z
o
i=
u
<l:
w
a::
>
a::
0.005
0.5
( R-2f '
1.0
ifferent
Figure 2.5. Relative rates of reaction of colloid species in lithium polysilicates with molybdic
acid reagent versus (R - 2)-1, where R is the molar ratio of Si0 2 : Li 2 0 .
. st.
The presence of some lithium silicate in sodium or potassium silicate solutions is

apparently of some advantage (107, 108).
ure of
'easing
Uses for Lithium Silicates and Polysilicates
3) pre-
.ate by
entratMore
of the
nm in
find)'
irating
ipon it
silicate
(IOn
2: I to
tate in
ade by
1t .1" a
A major use of polysilicates is in anti-corrosion coatings containing finely divided

zinc, where the silica acts as an inorganic binder (109, 110). The addition of an
organosiliconate improves the water resistance of the coating (III). A similar composition is said to provide a binder for brake linings (112). For a simliar reason, a
minor amount of a styrene-acrylic copolymer emulsion may be added. which also
gives im proved adhesion to steel (113). Another additive to improve saltwater
resistance is a small percentage of barium hydroxide (114). Barium silicate is more
soluble than the calcium or strontium salt and liberates enough silicate ion into solution to inhibit the corrosion of aluminum by alkali. according to Dupre and Boornan
(115). The adhesion and weldability of zinc-rich primers bonded with lithium polysilicate were improved by substituting some di-iron phosphide or cadmium for some
of the zinc (J (6).
Some of the difficulties involved in using zinc-rich paints bonded with polysilicates
were reviewed by Wright (117). who pointed out that in storage. slow reaction of
zinc with the vehicle on aging reduced the quality of the final coating.
Several types of soluble silicates were evaluated. but a lithium polysilicate with
--
.f;;~-;.:::.:.
..
150
Si0 2 : Li 2 0 ratio about 5: 1 was satisfactory. using zinc dust of 2-3 micron particle
size. The advantage of lithium was mainly that the mixtures are more stable (118).
The binder properties are useful in other pigmented coatings such as clay-based
paints (119). The zinc-lithium silicate coatings can be applied by anodic electrodeposition on steel (120). In another-type of use, lithium polysilicate provides an intermediate bond between the fluorocarbon polymer coating and metal on antisticking
cook ware (121).
The precipitation of higher-ratio insoluble silicates from hot solution may be used
to deposit siliceous coatings on hydrophilic surfaces. Sams (122) discloses that silicarich coatings for optical or protective effects are deposited on surfaces such as glass
from 2: 1 ratio lithium silicate solution when the surface is immersed in the solution
as it is heated to 95C. Even after 10 sec, there is formed a colored film showing
light interference, which must be of the order of 0.3 microns in thickness. Solutions
with ratios from 1.3: 1 to 10.7: 1 may be used.
ORGANIC BASE SILICATES
I:
,I
Since silica dissolves above about pH 10.7-11.0, silicates can be prepared with
organic bases having dissociation constants greater than about 10- 3 , although some
silica will dissolve in aqueous solutions of weaker bases with constants as low 'as 10-
or 10- 5 (123-125). Merrill and Spencer (124) reported the preparation of a number
of water-soluble quaternary ammonium silicates by grinding silica gel with a solution of the free base. However, the compounds all appear to have a ratio of 2: 1
when expressed as SiO:z:(NR.hO by analogy with the alkali metal system.
The unusual behavior of the (CH 3).N+ ion in silica systems is probably due to its
inability to form coordinate bonds with the oxygen of SiOH groups as sodium does
at high concentration by exchanging one or more water molecules of the (HzO)sNa"
ion for silanol oxygens. Hence the quaternary ammonium ion cannot act as a coordinative crosslinking agent to promote precipitation and gelling. Furthermore. there
is some evidence that the quaternary ammonium ions are adsorbed on the surface of
the silica, thus interfering with the dissolution and deposition of silica that is
involved in particle growth.
In the case of the interaction of tetramethylammonium hydroxide with colloidal
silica, there is evidence that. unlike NaOH. this quaternary ammonium base does
not allow the colloidal and ionic species of silica to equilibrate readily. This is
probably because the (CH 3).N" ions are strongly adsorbed on the surface of the
colloidal particles and retard dissolution of Si(OH). This was described by Beard
(39). who examined mixtures of colloidal silicas with (CHJ).N"OH-(TMA) or
NaOH with equivalent molar SiO z: Na.O ratios from 0.5 to 3.25 by infrared
spectroscopy. This method does not require diluting the sample or otherwise 'disturbing the equilibrium. Silica concentrations were 13.3, 15. and 20 wt. %. Mixtures
were aged for up to 6 days to reach equilibrium.
Polymeric or colloidal species could be detected in sodium silicate solutions by an
absorption band at about 1120 em - I . At a ratio of 2.0 a peak at about 1025 cm - I is
assumed to be due to dirner, but is more likely HSi0 3 -. At a ratio of 0.67, where
o
SI
c:
c
t
s
s
r
licates
article
[8).
ba
.rodeinter.cking
: used
silicaglass
lution
owing
rtions
with
some
; 10-'
.rnber
solu'f '
to its
does
)e Na +
coorthere
Ice of
iat is
loidal
does
his is
Jf the
3eard
. . ) or
rar ed
.turb.tures
by an
1 -,
vhe.
lSI
silica must be present largely as Si0 32 - ions. the characteristic peak is at about 980
ern -1, whereas at a ratio of 1.0 it is not as sharp, suggesting the possible presence of
some HSi0 3-. With this interpretation, the results indicate that 3.25 or 3.0 ratio
concentrated sodium silicate solutions contain only colloid and HSi03-.
However, (CH 3),N+ silicate solutions differ from the sodium silicate solutions in
that even at 1.0 ratio, colloid still persists along with HSi0 3-. Likewise, in 3.3 ratio
solutions, there is much more colloid in the (CH 3),N+ based solutions than with
sodium base. The authors conclude that TMA cation "shifts the equilibrium to a
mixture of low and high species." It is likely that the colloid phase is stabilized by an
adsorbed monolayer of (CH 3),N+.
It will be noted that in these experiments the solutions were made from TMA
hydroxide and colloidal silica. It is possible that if TMA had been added to a dilute
solution of polysilicic acid of low molecular weight at a ratio of 3.3 and then vacuum
evaporated to 10% silica, solubility equilibrium would become established and the
distribution of silica species would be like that in sodium silicate solutions.
The tetramethylammonium salt, CH 3hN>s[Si s0 2oJ. was prepared and studied by
Hoebbel and Wieker (126a), who converted the polysilicate ion to the trimethylsilyl
derivative [CH3)3SiJs[Sia02o] characterized by analysis and mass spectroscopy. This
polysilicate ion is in effect a cube of Si0 2 indicating the possibility of small compact
particles existing in sodium silicate solutions of Si0 2: N a 20 ratio between 2: I and
4: 1. The copper-ammonium salt is discussed further in this chapter.
In crystalline organic base silicates, the size of the organic cation 'apparently controls the structure of the polysilicate anion. Hoebbel and Wieker (I26b) prepared a
crystalline tetra{n-butyl) ammonium silicate hydrate having the empirical composition 0.8 I N(n-C,Hgk Si0 2 26.5 H 20. The silica is present as two parallel fivemembered siloxane rings held together by five oxygen bridges. Each silicon bears
one ionizable OH group. However there are only four anionic charges on each fivemembered siloxane ring; possibly there is a proton, H 30+, at the center of each ring.
The corresponding N(t-CsH u ) , + silicate has a similar structure.
A series of organic nitrogen base silicates, formulated as (NRR'R"R"'hO
xSi0 2,yH 20, were patented in 1954 (127), where R, R', R", are H, alkyl, aryl,
aralkyl, hydroxylamine. and amino-substituted alkyl radicals, and R'" is any of the
aforementioned groups (other than H. alkyl, or R") or CH 2 groups forming part of
a heterocyclic ring structure which includes the nitrogen. The value x varied from 0.5
to 4.0. and y from 0 to 15. Typical examples' were (HOC 2H,),N+OH -,
CeHsN(CH3)3+0H-, and guanidines. A crystalline compound with analysis corresponding to the following formula was isolated:
Quaternary alkanolammonium bases are desirable for making solutions of silicate

free of alkali metals. since there is generally no amine odor and the compounds are
very water soluble. Wcldes patented a series of these materials along with a process
for making them using ethylene oxide as follows. in water solution (128):
...
152
.:.....--
When vacuum evaporated, the resulting syrup contained 39.3% SiO: and the composition corresponded to [(HOC2H.).N]20. 5.9Si0 2 8.3H 20 (129).
Another way of making this type of organic silicate is to add (HOC 2H.).N "OHto a solution of 3.75: 1.0 ratio sodium silicate and then remove the sodium by ion
exchange with (HOC 2H.).N+ ions on a cation-exchange resin. The mixture at first
gels, but then forms a viscous solution. An alternative is to prepare a dilute solution'
of ethanolamine and silica in this way and then form the quaternary ammonium salt
by reaction with ethylene oxide (130). Diethanol ammonium and morpholinium silicate and related salts have also been prepared (131).
Some of the available quaternary ammonium silicates have been listed by Weldes
and Lange (19), although the nature of the NR. + ion was not disclosed. Malar ratios
of Si0 2: (NR.)20 range from 1.2: 1 to 30: 1 and silica contents of the solutions from
10 to 45%. Hydrated amorphous powders are also listed with ratios of 15.6: I and
19.7: 1. These dissolve rapidly in water and are remarkably soluble in mixtures of
water and water-miscible organic solvents such as acetone and the lower alcohols.
The following suggests that even with a ratio as low as 7.5: 1 the composition may
be largely a colloidal solution rather than a soluble silicate. Wolter (132) first discovered that when enough tetramethylammonium hydroxide is present in a sodiumfree silica sol to have present four or five (CH 3).N+ ions per square nanometer of
silica surface, the sol can be dried to a gummy solid which can be redissolved in
water to the original sol state. In the sol of 1.6 nm particles the required
Si02:[(CH3).N]20 ratio was}.5: 1.
Guanidinium silicate has been prepared from the free base, readily prepared from
the carbonate and Ca(OHh and colloidal silica (133). The solutions had molar ratios
of Si0 2:G 20 of up to 3.1: 1.0 where G is guanidinium ion. The solution dries to a
clear water-soluble film: When alcohol is added, the salt is precipitated as an amorphous powder useful as a binder for refractory oxides (134, 135). The powder is stable and may be used for making up solutions which may be used as a binder in sand
cores, set by carbon dioxide, which are readily removed after casting metals. The
solution may be used to deposit silica when heated, owing to the slow decomposition
of the strong base. It is viscous and may be spun and heated to produce silica fiber.
According to Nakajima, Yamaguchi, and Tahara a mixture of guanidinium silicate
and sodium silicate is an especially useful binder for sand molds in metal casting,
since it can be set by carbon dioxide and gives excellent mold strength (136).
A variety of uses have been suggested for the quaternary ammonium silicates. As
shown by Weldes and Lange (19) these compositions supply silica as a binder which
loses most of its organic content at 300-400c. They may be used also to fill pores,
form coatings, and are of potential use for treating inorganic fibers, reinforcing
polymers, and as vehicles for coatings and paints for use at high tern perature. A
slowly dissolving tetraalkyl silicate acts as a setting agent in silicate-bonded cement
(137). Properties and suggested applications have been described for a series of quaternary ammonium silicates of undisclosed ion type, available under the trademark
QURAM:~ (138). Molar ratios of Si0 2 : (NR.hO range from 2.25 to 11.3, and silica
contents of liquids from 34 to 45%; a soluble powder contains 71 % SiO:.
., =-.-
Silicates
ie com-
Mixed Organic Base-Alkali Metal Base Silicates
-[+
by ion
at first
solution
urn salt
urn siliWeldes
.r ratios
ns from
5: I and
tures of
hols.
on may
irst dissodium.ieter of
olved in
'equired
ed from
ir
s
'ies tu a
n amor.r is stain sand
als, The
position
ca fiber.
silicate
casting,
ates. As
:r which
II pores,
rforcing
153
Double silicates of quaternary ammonium with Li, Na, or K silicates have been prepared. Hydroxy alkylammonium salt mixtures were described by WeIdes (139-141).
Sodium polysilicate solutions which are unstable in certain ratio ranges can be stabilized by adding quaternary ammonium base, even in small amounts. Of course large
amounts will reduce the Si02 : M 2 0 ratio (M being cation) to form soluble silicates,
but the effect of small amounts has not been explained. For example, solutions
containing 21.8% Si0 2 with Si0 2:Na20 ratios of 4: 1 to 12: I are stable ii the quaternary ammonium base N-hexamethylhexamethylenediammonium hydroxide is
present to give a mole ratio of Si02 to quaternary ammonium of only 850: I (142).
In a similar patent, Freyhold and Wehle (143) disclose that the Si0 2:(R.NhO
ratio may range from 35: I to 1000: 1. Possibly strong adsorption of relatively few
large organic cations on the surfaces of the colloidal particles serves to keep them
apart, preventing the aggregation that occurs when only sodium ions are present.
Organic bases, some of which are not as strong as the quaternary ammonium
type, when present along with an alkali metal hydroxide, have a different type of stabilizing effect on silica, namely, maintaining the colloid in the form of extremely
small particles. Yates (144) maintains silica sols with a specific surface area of
950-1800 m2 s" corresponding to particles only 2-3 nm in diameter with a
Si0 2:Na 20 ratio of 7: I to 20: 1 by having an organic base present with a basic
dissociation constant of at least 10- 2 at a concentration of 0.1-1.5 molal. This
includes bases such as morpholine or cyclohexylamine as well as tertiary and quaternary ammonium types. The small particle size is not maintained in the presence
of either the alkali metal hydroxide.or the organic base alone. The compositions are
prepared by adding the amine to a solution of sodium silicate and then removing
sodium to the desired degree with an ion-exchange resin. In the absence of the
amine, the specific surface area of the resulting colloidal silica spontaneously
decreases and the particles grow, but when amine is present it is adsorbed in proportion to the specific surface area of the silica and stabilizes the silica in the form of
extremely small particles or polyions.
That the effect is not that of pH or overall base strength alone is shown by Yates
in another case (145) where polyhydroxy organic compounds such as glycerol or
sugars, in conjunction with alkali metal base, have a similar effect of preventing
particle growth and maintaining stable particles of high specific surface area.
Adsorption of the polyhydroxy or alcohol-ether type compounds on the silica surface is probably involved, since calculations show that at least : one alcoholic
hydroxyl group must be present per square nanometer of silica surface.
iture, A
cement
of qua-
Other Organic Base Silicates
.dernark
.id silica
In the field of pharmaceuticals. an unusual type of organic base silicate is

methionine mcthylsulfonium silicate, which has the advantage of being nonhygro-
154
scopic and odorless (146). A wide variety of precipitated organic base silicates has
also been prepared for use as intermediates in making pharmaceuticals. In view of
the method of preparation and weak strength of some of the bases, it is possible that
the compounds are adsorbed on precipitated silicas of very high surface area (147).
Aluminosilicate is formed as a. stable sol when tetramethylammonium silicate and
tetramethylammonium aluminate solutions are mixed, whereas the sodium salts
immediately form precipitates unless the solutions are very dilute. When sodium
chloride is added to the sol, a gel or precipitate is formed which then develops zeolite
crystals, the size of which increases from 25 to 300 nm with NaCl: Al 20 3 ratios' from
0.1 to 1.0 (148).
Long-chain alkyl quaternary ammonium silicates are presumably formed when
cationic surfactants of this class are added to sodium silicate solutions and whipped
to form stable foams. Thus the silicate containing a gelling agent is foamed and set
to a lightweight gel (149). Similarly, a mixture of potassium silicate and colloidal
silica, which forms a very strong gel when acidified, is used as a binder for inorganic
fiber and expanded perlite. The mass is foamed with a long-chain quaternary ammonium salt before it sets to form a low-density thermal insulating material with a
density of 10-20 lb ft- 3 (150). Also, 3.25 ratio sodium silicate alone can be mixed
with perlite, foamed with hexadecyltrimethylammonium ion, and set with carbon
dioxide gas.
Reference also should be made here to the unique, highly siliceous crystalline
zeolite-like insoluble quaternary ammonium silicates from which the organic ions
can be removed, leaving' anhydrous, hydrophobic, microcrystalline Si0 2 of an
entirely new type discovered and described by Flanigen and Grose (see Chapter I,
refs. 71c, 71d).
"
COMPLEX METAL ION SILICATES

Werner complexes of metals such as cobalt with amines yield strong free bases
which can form silicates. Schwartz and Bausch (151) reacted Na 2Si0 3 with
[Co(NH3)~Cl}Cl to obtain Co(NH 3hCISi.O g and with [CO(NH 3)e}Cl to obtain
[Co(NH 3).Si3 0,]Si0 3, although there was no proof that silica was present both in
the anion and cation. The constitution of the silicate ions of ethylenediamine copper
silicate has been worked out by Hoebbel and Wieker (152a). In the compound having the empirical formula CuO 2en. 2Si0 2 7.4H 20, where en is NH 2C 2H.NH 2 , the
anion was shown to consist of a cube formed by two Si.O. rings, the corners of
which are linked by oxygen atoms. This probably corresponds to the smallest
"particle" of internally condensed silica that can be formed. It is a polysilicic acid
octamer which contains only one hydroxyl group per silicon atom and can be formulated [HOSiO I ~]8' The copper salt has the composition [Cu(en 2].[Si e0 2o ] 30H 20
(Figure 2.6). The compound was studied by paper chromatography, by the reactivity
with molybdate, and also by silylation to form the derivative [(CH3)3SiOSiOI' ~18'
which had also been made previously from the corresponding tetramethylammonium
silicate (126, 153). This octasilicic acid, which is called the "double-four-ring" silicic
acid, reacts with molbdic acid at a characteristic rate, 95% reacting in about 8.5
min.
r
I
~
.---
Silicates
155
.tes has
viev of
Jle
147).
ate and
n salts
sodium
zeolite
rs from
d when
.hipped
and set
olloidal
organic
ammowith a
. mixed
carbon
stalline
ric ions
of an
ip:
e bases
)3 with
obtain
both in
copper
rd havH 2 the
ners of
mallest
:ic acid
formu30H 2 0
activity
iO"s]a,
ionium
silicic
au' )
Figure 1.6. The double-four ring, or cubic

octasilicate ion, Sis0 2os-.
These authors (152b) later showed that the analogous cobaltic complex silicate
had a similar composition, [Co(en)3MH 2Si,02o], with 16-28 water molecules. Here
there are only three negative charges per ring of four silicons. There may be a
proton, H 30 -, at the center of each ring.
The ethylenediamine copper silicate was obtained in the form of a slightly different hydrate [Cu(en)2].[Si a0 2o] 38H 20 and the structure determined by' X-ray diffraction by Smolin, Shepelev, and Butikova (153), who confirmed the existence of
the anion lSi a0 2o]a- which is a "fourfold two-story ring." The anions and cations are
bound into a structure through hydrogen-bonded water molecules.
The precursor of the "double-four-ring" ion is probably the "single-four-ring"
cyclic tetramer ion which was found to be the anion in crystalline lead orthosiJicate,
Si0 22PbO. In the lead silicate glass, Gotz, Masson, and Castelliz (154) showed that
the silica is present as the orthosilicate ion, (SiO.)-, but as devitrification proceeds,
higher polymer species (Si 20 7 ) S - and (Si.o 12 )a- are formed until the product is
crystalline lead cyclic tetrasilicate, having the structu re Pb.(Si.0 12 )S- .
Yates called attention to the numerous metal polyamine silicate compositions that
can be formed with amines H 2N C"H 2,,(NH C"H2,,).rNH2, where n = 2-6 and x =
0-3. Metals include Cd2+, Cr 3+ , Fe2+, l-.!n 2 " , NiH, and Zn 2+ . The silicate solutions
are film-forming and give insoluble metal silicates when heated (155).
In another type of silicate solution containing metal cations which normally result
in water-insoluble .silicates. the metal ions are kept from reacting by cornplexing
them with chelating agents (156).ORGANIC CHELATE5 OF 51 LICO:"
It is not widely recognized that silicon can enter into chelate-type bond formation
with some oxygen- and nitrogen-containing organic compounds such that silicon is
coordinated with six of these polar atoms. The overall structure may be negatively
or positively charged and could possibly be neutral. depending on the organic
molecule involved. Such hcxacoordinatcd compou nds of silicon arc relatively
=-. ..
156
uncommon because of the strict requirements of spacing and orientation of the COordinating atoms.
One necessary structure is that in catechol, where adjacent hydroxyl groups are
held in planar relation by the unsaturated carbon ring and the oxygen-oxygen
distance is exactly that required. between oxygen atoms in octahedral coordination
with a silicon atom. If the ring is saturated, as in 1.2-cyclohexanediol, the hydroxyl
groups are not in the plane and are farther apart. Another structure is that found in
l-hydroxypyridine N-oxide, where again the ring is unsaturated and there are two
oxygen atoms attached to adjacent carbon and nitrogen atoms in a six-membered
ring. It also appears that two oxygen atoms or hydroxyl groups on adjacent carbon
atoms in other than a six-membered ring can chelate with silicon if they are held the
correct distance apart (see also Chapter 7).
Chelates of silicon have already been discussed in some detail in Chapter 1 in connection with the effects of organic compounds on the solubility of silica and also on
the rate of dissolution of silica. Further discussion will be limited to some of the
compounds that have been formed.
Catechol Derivatives
The hexacoordinate silicon dianions in pyridinium tris(o-phenylenedioxy)siliconate
have been examined by X-ray diffraction by Flynn and Boer (157).
The oxygen atoms are only slightly distorted from octahedral symmetry. The correct formulation is [CaHsNH]2%+[(CaH402)3Si]2-.
The reaction of silica with catechol, pyrocatechol. and 2,3-naphthalenediol has
been studied by several investigators (158-162), but Bartels and Erlenmeyer appear
to have been the only ones to use this reaction to characterize the rate of
depolymerization of silica (l63a). For example, monomeric silicic acid from ethyl
silicate in a standard solution of catechol in 0.8 N HCl reacted rapidly and could be
titrated to a constant pH of 8.5 with an equivalent amount of standard NaOH solution in a few minutes. An equivalent amount of silica gel required 2.5 hr, but ignited
gel reacted only slightly in 5 hr. The rate of reaction, followed by a constant pH titration, provides a way to estimate the relative degree of polymerization of silica or
possibly the specific surface area.
Baumann (163b) examined the relative stabilities of the six-coordinated silicon
complex anions of some catechol derivatives. He measured the equilibrium constant
K and also the pH at which 99% of the silicon in a solution containing 60 ppm silica
as monomer is complexed when the concentration of the agent is 0.1 M.
Agent X
Catechol
Dopamine
Adrenaline
pH
2.1 x 1011
2.4 x 1010
5.7 x 109
8.25
7.8
7.3
.""
- --.157
Silicates
re coor-
Baumann also examined the details of the reaction of silicic acid with catechol
(163c) as well as with a catechol-formaldehyde condensate which acted as a polyphenol (163d). The latter resin. when not too highly cross-linked. removes soluble
silica from slightly alkaline water.
uI:~
-oxygen
iination
ydroxyl
oundin
are two
mbered
carbon
aeld the
in conalso on
: of the
liconate
Iic
s
appear
rate of
methyl
ould be
H soluignited
pH tit.ilica or
silicon
onstant
m silica
Humic Acids
The presence of catechol-like materials such as tannic acid in decaying 'vegetable
matter and their solubilizing effect on silica has led to the interesting theory that aluminum ore, bauxite, occurs predominantly in the tropics because of the preferential
leaching of silica from clays under conditions of heavy rainfall and large quantities
of decomposing vegetation. On the other hand, in colder climates the residues are
more siliceous because alumina is more soluble in water with a lower pH and higher
carbonic acid content in the absence of vegetation (164).
Humic acid from decaying vegetation is believed to have a structure related to
fulvic acid, which has adjacent hydroxyl groups on an unsaturated six-membered
carbon ring and forms chelates with silicon (165). The soluble chelate with ammonium humate has been used to supply silicon as a nutrient to rice plants, which
require silicon in their structure (166).
The formation of humic acid in soil may involve oxidation of phenolic vegetable
substances such as tannins while adsorbed on silica. A solution of pyrogallol passed
rapidly over silica gel produces brown oxidation products. The silica surface plays a
role since it is inactivated by being heated to high temperature or by absorption of
AI, Ca, or Mg ions (167). The mechanism of the reaction was examined by
Zeichmann (168).
Pentacoordinated organosilicon derivatives of RSi(OHh, where R is a
hydrocarbon group. formed by reaction with catechol have been described by Frye
(169,170).
Other Organic Compounds
According to Muetterties and Wright. tropolone (T). 1,2-diketocycloheptane. can

form a cationic chelate with hexacoordinated silicon, T 3Si +CI-, in acid solution
(171). It can be crystallized from water but is unstable toward alkali.
A cationic silicon chelate is also formed with l-hydroxypyridine N-o:dde. Gardner
and Katrizky prepared 24 derivatives of this and the l-arnino analogue (172), and
Weiss and Harvey made salts with different anions (173, 174). However, as
described in Chapter I these chelates, which are apparently stable in water at low
pH, decompose rapidly at higher pH.
A polymer containing this N-oxide configuration. poly(2-vinylpyridine N-oxide),
appears to combine with rnonosilicic acid according to Holt and Nasrallah (175). but
this may involve hydrogen bonding.
-- ---158
Chelates of silicon with triethanolamine are classed as "atranes" by Veronk ov

(176). These are essentially esters with an additional R group attached to the silicon
atom which is coordinated with the nitrogen atom, as shown by the high dipole
moment infrared and nmr spectra: N(CzHsOhSi. R.
Hydroxy acids, such as tartaric, do not form complexes with silicon as they do
with the larger germanium atom, according to Clark and Waddams (177), who
examined a large number of mono- and poly hydroxy aliphatic acids. including those
derived from sugar.
HYDRATED CRYSTALLINE ALKALI METAL POLYSILICATES

There are certain crystalline silicates of Li, Na, and K in which the silicate ions are
polymeric and thus are not directly soluble in water. The conversion of some of these
to hydrated crystalline silicas has been discussed in Chapter I. Since some of these
can occur or can be formed in silicate solutions and represent different polysilicate
structures, some further discussion is justified.
Until Wegst and Wills isolated crystalline hydrated sodium "tetrasilicate" (178)
it was not realized that alkali silicates of higher SiO z : NajO ratio than 2: I could be
crystallized. Subsequent investigation (179a) showed that this water-insolu hie silicate
was better represented by the formula 13SiO z3NazOllH zO. It is probably similar
to or the same as the mineral kanemite later described by Johan and Maglione
(179b) and shown by Benke and Lagaly (179c) to have a layer structure in which the
sodium can be exchanged with a variety of organic cations. A simple synthesis and a
variety of properties and transformations to other sodium silicates and crystalline
hydrated silicas were described. The idealized formula is NaHSizOs3HzO.
McCulloch (180) discovered two more hydrated crystalline silicates of higher
ratios, 9.4: I and 11.1: 1. Also, he found another tetrasilicate different from the one
found by Wegst and Wills.
All the sodium ions in these sodium polysilicates were exchangeable for hydrogen
and other metal ions, as Wills discovered in the case of the "tetrasilicate" (181). He
was thus probably the first to synthesize a crystalline hydrated form of silica. A later
study by Her (182) showed that a microcrystalline sodium polysilicate hydrate having the formula 8SiO zNazO9HzO had an X-ray diffraction pattern similar to that
of McCulloch's compound 9.4SiO z NazOxHzO. and demonstrated that since the
crystals had ion-exchange properties, there could be varying degrees of substitution
of Na" for H+. Also, it was concluded that the cyrstals have a layerlike structure,
since sodium could be substituted by C16H33N(CH3)3 + ions, widening the interlayer
spacing from around 11.2 to 13.6 A. The interior surfaces of the silica layers could
even be esterified with n-butyl alcohol with little change in the spacing.
Mineralogists, apparently quite independently of the above publications, became
interested in silicates of this type with the annou ncement in 1967 by Eugster (183) of
the minerals magadiite and kenyaite from Lake Magadi in Kenya, having the composition 14 SiO z Na zO9H 2 0 and 22SiO z ' NazO 10H 2 0 . The corresponding acid,
-:'l':';.
.::
.....-.
"
...
-Silicates
ironkov.
: silicon
1 l
they do
7), who
19 those
.ons are
of these
of these
.silicate
;"(178)
ould be
silicate
similar
aglione
ric' '-e
is ah~ a
stalline
. higher
the one
.drogen
81). He
A later
ite havto that
nee the
titution
'ucture,
.erlayer
s could
became
183) of
re comg
'1,
Hydrated Crystalline Alkali Metal
:- ...
Polysilica~~_
159
6Si0 2 H 20, was claimed as the first known crystalline silica hydrate, indicating that
the mineralogists were not aware of the earlier investigations by McCulloch and
following workers. Magadiite was soon also discovered in California (184) and
Oregon (185).
In spite of the marked similarity in dehydration and ion-exchange properties to
the synthetic sodium polysilicate first made by McCulloch, magadiite differs in having a layer spacing of about 15.4-15.8 A instead of 11.2 A This is probably related
to the difference in Si0 2:Na 20 ratios of 14: 1 versus 8: 1. Conditions for the formation of magadiite were examined by Mariner and Surdam (186), who concluded that
the mineral must crystallize from a solution that is rich in silica and low in aluminum, since the brines of Lake Magadi range up to 1900 ppm Si0 2 but contain
only 1 ppm A1 203 Absence of alumina is undoubtedly of critical importance. .
The stability constants of both magadiite and kenyaite have been measured by
Bricker (187), who concluded that the minerals are stable in alkaline waters rich in
sodium and soluble silica. It appears that at pH 9 these crystalline sodium silicates
are actually less soluble in water than amorphous silica. The Gibbs molar free
energies of formation were also calculated as - 1,762.2 kcal for magadiite and
- 2,603.5 kcal for kenyaite.
Changes in the lattice spacing of magadiite when dehydrated and when Na + was
replaced by H+ were examined by Brindley (188). Lagaly and Beneke (189) further
examined the hydrogen form, or silica hydrate, which they formulated as
H 2Si 1402 9 5.4H 20, and found that it still retained water at 100C to the remarkable
extent of 14 Si0 2 : 1.5 H 20. The hydrogen form also absorbed various organic liquids
which became intercalated between the silica layers. For example, dimethyl sulfoxide
and various N-oxides and phosphine oxides gave different layer spacings with different arrangements of aromatic rings, A wide variety of heterocyclic nitrogen bases
of different ring sizes was examined and the I~yer spacings correlated with molecular
structure. Acid amides, urea and its derivatives, and alkyl amines received similar
attention.
Other workers (190a, 190b) studied rnagadiite in which sodium ions were
exchanged with long-chain and other quaternary ammonium ions, with special attention to the arrangement of the chains in the intercalated layers. A similar compound
had earlier been made by lIer (182) by replacing the sodium ion in McCulloch's
crystalline polysilicate with the cetyltrimethylarnmoniurn ion. Replacement of the
sodium in magadiite with other metal ions has not been examined, analogous to the
lithium, magnesium, copper, and nickel salts made by Iler (183) from McCulloch's
8: 1 ratio silicate.
It is now apparent that there can exist a series of similar polysilicate structures
depending on the ions present and conditions of formation. It is interesting that
m agadiite was synthesized by Lagaly and Beneke from a solution containing 27.4%
by weight of Si0 2 and 4.06 Na 20 with a molar ratio of Si0 2 : Na 20 of 7: lto obtain
a product with a ratio of 14: l , and under otherwise essentially identical conditions
Iler (182) used a ratio of 4.6: 1 to obtain McCulloch's product with a ratio of 8: I.
Ilcr also reported that starting with ratios of 5: I to 8: 1 a crystalline product with a
ratio about 20: 1 was obtained, but no X-ray pattern was reported.
-.
,..,.
160
Russian workers, Il'in et al. (191), have extended knowledge of this field by similarly preparing the following:
4-5Si0 2 Na 20. 30-60H 20
19.5Si02 Na 20 22H 20
12.5Si02 Na 2023H 20
These were apparently different from the previously reported crystalline sodium
polysilicates, but had similar ion-exchange properties. Systems containing Li + and
K + with different silica-alkali ratios were also studied. Crystalline silicates in the
lithium system can be expected, but my experience with the potassium system indicated that insoluble polysilicates did not form under conditions where the sodium
compounds were obtained.
Il'in et a1. (192) further examined the sodium silicate system and reported two
structural types of sodium polysilicates. One consists of rounded aggregates, 1-6
microns in size, of the general composition 9-l6Si0 2 Na 20 9-l2H 20. The second
type made at higher alkali ratio consisted of rectangular plates 2-6 microns across
with the general formula 8-l0Si0 2Na 2 0 9 - I I H 20. A third type,
2.5Si02 Na20 .xH 20, was reported also to be insoluble in water. Previously known
polysilicates appear to fall into one of the first two classes; except for the tetrasilicate, which was not reported. All the polysilicates were reported to have ionexchange properties like those of zeolites.
Mixtures or solutions with Si0 2:Na 20 ratios greater than 4: 1 are not necessary
for the formation of insoluble crystalline species, as indicated by Wegst and Wills
(178), who first made the "tetrasilicate." Apparently this species in one or more
crystalline forms can eventually crystallize out of cornrnercialvwater glass" solution
of 3.3: 1 ratio at 25C, as mentioned by McCulloch (180). What nucleates such
crystals is unknown, but on very rare occasions the whole contents of a container
partly filled with concentrated sodium silicate solution of this type has been known
to crystallize to a solid mass. This usually occurs after the solution has been aged for
several years and indicates the advisability of cleaning out storage tanks occasionally.
i.
.....
,
"
~!
-~ i
'f
I,
.1
&
f"
SILICATES CONVERTIBLE TO CRYSTALLINE FORMS OF (H 2Si 20 5 ) Z

Certain anhydrous crystalline silicates yield layerlike crystalline hydrated silicas with
the approximate formula (HzSi 20s)z. These are cited to illustrate the com plexity of
such apparently simple compounds.
Anhydrous crystalline K 2Si03 and KzSi z0 5 are hydrolyzed in methanol at 200C
to give two types of crystalline KHSi z0 5 With KOH present, crystalline (KHSi0 3 ).I
is obtained (193). The KHSi 20 s has a sheetlike silica structure from which the corresponding H 2Si z0 5 can be prepared (194), Similar crystalline silica hydrates can be
obtained by reacting acid with K zSi 20 5 , BaSi z0 5 , and beta-Na-Si.O, (195). From
Precipitation of Insoluble Silicates
licates
. simi-
odium
." and
in the
1 indiodium
:d two
.s, 1-6
second
across
type,
known
trasili'e ion;e~
I WiIls
. more
alution
s such
atainer
known
ged for
occa-
as with
.xity of
200C
ISi03 )%
he corcan be
f
=-..-
161
alpha-Na:Si 2 0 $ two sheetlike phyllosilicic acids. H2Si 2 0 $, were obtained, "depending

on whether a strong or a weak acid in methanol was used to exchange sodium ions.
Both silicas had structures similar to that of Li2Si 2 0 $, which proved impossible to
leach with acid, according to Le Bihan, Kalt, and Wey (194).
According to Hubert, Guth, and Wey (196), the beta-H 2Si 2 0 $ obtained by reacting beta-NajSi.O, gives a new'hydrated silica that gives a single DTA peak at 220C
where hydroxyl groups are lost. Still another form of H 2Si2 0 $ was obtained by
-extracting basic copper silicate with acid, having a two-dimensional (lepidoidal)
structure (197) of which the surface area was estimated by gas adsorption. .
Few if any of these various "disilicic acids," which are highly polymerized in two
dimensions, are identical. The relation of these to the previously discussed hydrated
crystalline silicas obtained from hydrated sodium polysilicates is not known. It is
evident that a large number of crystalline hydrated silicas may exist, some more stable than others, but all obtained from crystalline silicates by ion exchange. No
crystalline hydrate silica is likely to be formed directly in the silica-water system in
the absence of cations to bring about the organization of a regular polysilicate structure.
PRECIPITATION OF INSOLUBLE SILICATES
When a soluble silicate is mixed with solutions of salts of metals other. than the
alkali metal group, insoluble amorphous metal silicates are precipitated. However,
the nature of the precipitate can very widely, even with the same starting solutions,
depending on the intensity of agitation at the .point of mixing and whether one solution or the other is present locally in excess. The mechanism of formation of the
precipitate in the absence of mixing is visible in the making of the so-called
"chemical garden" in which crystals of metal salts are dropped into a relatively
concentrated solution of sodium silicate. The metal salt dissolves and at once a
mem brane is formed between the two solutions, consisting of amorphous metal silicate. However, since hydrogen and hydroxyl ions diffuse rapidly, silica gel is formed
on the silicate side and metal hydroxide on the metal-salt side. On the other hand,
when the two solutions are brought together in a zone of high shear, as by intensive
stirring, a more homogeneous, gelatinous amorphous metal silicate is precipitated.
In view of the fact that essentially all natural silicates are crystalline, it is of
. interest to consider why most synthetic silicates are amorphous when precipitated
from aqueous solution. In a crystalline metal silicate, metal ions and silicate ions of
uniform size and shape are arranged in a regular manner in a solid lattice or framework characteristic of the ionic sizes and charges. However. most solutions of soluble silicates contain not silicate ions of uniform size but. instead. a mixture of polysilicate ions, some containing up to 5-10 SiO: units each. Even in the case of
highly alkaline metasilicates which are known to contain monomeric silicate ions.
lowering the pH upon addition of a solution of a metal salt causes rapid polymerization to polysilicate ions. Since the polysilicatc ions are not of uniform size. they cannot arrange themselves along with the metal ions into a regular crystal lattice. Thus
.
., =-.---
162
.... ; .,.'
_.
.,
".;;'~~>.,
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.........
,~_.
!
when polysilicate ions combine with metal ions, the resulting insoluble precipitate is
almost always amorphous. In order to obtain a crystalline silicate, the polysilicate
ions must be depolymerized to smaller silicate ions of uniform size in order to rearrange themselves into a regular lattice.
Polymerization of basic metal ions is another factor which may interfere with
crystallization. When the metal salt is mixed with silicate, the increase in pH in the
environment of the metal ions at some point causes the formation of polymeric basic
metal ions or colloidal metal hydroxide, which likewise cannot fit into the silicate
crystal.
.
For these reasons, the precipitation of a metal silicate from aqueous solution at
ordinary temperature does not yield crystalline silicate, but instead usually results
in a colloidal mixture which may be visualized as an adsorption of metal ions on
gelatinous silica or as a mutual coagulation of the positively charged colloidal metal
hydroxide and negatively charged colloidal silica.
In dilute solutions, colloidal metal silicates are precipitated at a pH slightly below
that at which the metal hydroxide alone would be precipitated, according to Britton
(198, 199). This suggests that no definite compounds are formed and that the
hydroxides are precipitated along with silica by mutual coagulation.
From the above, it will be evident that "colloidal silicates" may vary from rather
homogeneous colloidal aggregates of extremely small' ultimate units of polysilicic
acids and metal hydroxide, to heterogeneous masses in which either 'silica or the
metal hydroxide is present as discrete colloidal units, held together by the other
component.
Vail (I) has extensively reviewed the practical aspects of precipitated metal silicates. In the case of magnesium silicates, which are used as adsorbents, decolorizing
agents, catalysts, and fillers in paints and also for treating stomach ulcers, the composition may be varied within wide limits. The strong tendency for magnesium
hydroxide to react with silica (even in the monomeric state) is shown by the fact that
the addition of 300 ppm Mg(OHh to water will reduce the soluble silica content
from 42 to 0.1 ppm.
In the case of precipitated calcium silicates made from commercial sodium silicate
at ordinary temperature (Si0 2 : Na 20 = 2.4: 1.0). there was no evidence of
crystallinity (200).
Precipitates from 3.3 ratio silicate (201) were found to consist of gels along with
excess Ca(OHh. Uses for soluble silicates, depending on the formation of insoluble
silicates. are extremely varied, ranging from surface coatings. pigments, adsorbents,
and fillers to use in cements and oil-well drilling muds. The precipitation of zinc
salts with sodium silicates at ordinary temperature appears to involve a mutual COJgulation of hydrated zinc oxide and silica, no crystalline compounds being formed
(202).
Wells (203) investigated the precipitation of a number of mctal salts with 3.2 ratio
silicate using insufficient silicate to react with the metal ions and found that by using
pairs of metal salts the relative ease of precipitation could be observed. The order of
precipitability, using mostly metal sulfates and starting with the most readily
-163
ilicates
Soluble Silicate Glasses
.tate is
precipitated metal, is copper, zinc, manganese, cadm iurn, lead, nickel, silver: magnesium, and calcium.
Under certain circumstances, where the metal hydroxide is formed in such a way
that it may be surrounded by hydrated silica, "metal silicate" sols, stabilized by
alkali, can be obtained. Vail states that those metal salts that are acid reacting, such
as FeCh, or acidified solutions of C 0 2 + , Zn 2 + , or Cu 2 + salts react with the silicate to
liberate colloidal silica, which then acts as a protective colloid, that is, forms a protective layer on the colloidal metal hydroxide. This being the case, it is not surprising
that high-ratio silicates favor the formation of such dispersions by supplying more
silica.
Precipitated metal silicates are difficult to characterize physically because, as Vail
points out, they are usually not homogeneous in composition. Upon the addition of
one solution to the other, it is obvious that, at the point of mixing, there is no control of the ratios of silicate and metal ions which are brought together: yet the composition of the precipitate as it is formed depends on the ratio of the components in
the reaction medium. Thus the composition of the first part of the precipitate which
is formed differs from that of the last. Homogeneous gels can be prepared by keeping the pH low, for example, until all the metal salt and silicate solution are mixed.
However, when the pH is then raised to gel the mass, it is still not truly homogeneous, since the silica is polymerizing continuously in such a mixture so that the
proportion of metal ions bound to the silica particles depends on how far' the silica
has polymerized before the pH is raised.
Metal silicates may crystallize in the amorphous mass after aging, especially if
components are present in suitable stoichiometric proportions. Also in some
instances, microcrystalline metal silicates may be formed immediately if the solutions of metal salt and silicate are brought together at high temperature or in very
dilute solution. It is unlikely, in any case, that macrocrystalline metal silicates
similar to those found in minerals will be formed, except at high tem perature under
pressure. However, when aluminum is present for form aluminosilicate ions, fairly
rapid crystallization of certain aluminosilicates such as the zeolites can occur at
iilir- ...
) rv.
e with
in the
:: basic
.ilicate
:ion at
results
ons on
metal
below
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at the
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100C.
For a further discussion of colloidal silicates, see references listed in the introduction, the chapter on colloidal silicates in Colloid Chemistry of Silica and Silicates
(29), and in Chapter 6, the section on polyvalent metal cations.
SOLUBLE SILICATE GLASSES
Since most soluble silicates are made by dissolving the corresponding sodium or
potassium silicate glasses, it seems appropriate to review some of the investigations
of glasses that have been made since Vail's comprehensive survey in 1952 (I).
However, it should be kept in mind that the structures occurring in these glasses
bear little or no relation to the nature of silica in the derived aqueous solutions
beyond the effect of the Si0 2 : Na 10 ratio.
.i
--
164
i
i
I
!I
~
"'------
A theory as to why silicate glasses do not readily devitrify involves the "presence of
small polymeric silica units of pentagonal symmetry which cannot fit into any
regular crystal lattice. Tilton (204) proposes that this "vitron" unit is built up of
pentagonal rings of SiO. tetrahedra, with the silicon atoms lying in a plane with all
Si-O-Si bond angles close 1{> 1800). As further tetrahedra are added, a stressed network cluster of 20 SiO: units is built up in such a way that further growth cannot
occur.
In sodium (or potassium) silicate glasses of SiO:: Na20 molar ratios of2: I to 4: 1
such "vitron" units, if actually present, might disperse without complete depolyrneri,
zation, giving the colloidal species known to exist in solution. However, since a 3.3: I
ratio solution appears to have the same properties whether made from glass or by
dissolving amorphous fine silica in alkali solution, it seems unlikely that the same
"vitrons" are formed spontaneously in solution. Possibly a detailed examination of
3.3 or 3.8 ratio solutions of sodium silicate made by the two methods might still reveal
a persistent difference.
The "vitron" theory is probably related to the later "iceberg" theory, namely, the
tendency of silica to form small immiscible clusters in melts of lower alkali content
(205). In sodium silicate glass with a SiO::Na 20 ratio of 7:1, the model predicts
collidal silica units or particles about 1.9 nm in diameter.
According to Tran (206), electron microscopic examination of sodium silicate
glasses shows two principal structural elements, the silica and 3Si0 2 Na 20 groups.
Masson has applied polymer theory to silicate melts to predict the distribution of
ionic species over the entire range of compositions up to the maximum polymerization allowed by the theory. Results were compared with experimental values for
polymer distribution determined by converting the ionic species in the glasses to trimethylsilyl derivatives (207-212).
Similar calculations of size distribution of ions in silicate melts were made by
Hess (213). Structural models of binary silicate melts have also been proposed by
Gaskell (214), who discussed experimental evidence for and against the validity of
the models.
PEROXY SILICATES
,.
e.:
The only mention by Vail (1) of peroxide structures in relation to silicates is the stabilizing effect of sodium silicate in combination with magnesium silicate in stabilizing peroxide bleaching baths, probably by adsorbing and inactivating traces of
catalytically active metals such as copper.
Rietz and Kopp (215) have found that dissolution of sodium metasilicate,
NazH2SiO~ 8H:O. in 30% H 20: gave crystalline NazSiOJ" 3H zO z . However,
this peroxide decomposes at room temperature via. the intermediate
Na:Si0 3 H 20 2 2H 20 to Na 2Si0 3 3H 20. which is dehydrated to Na zSi0 3 H 20,
which is stable up to 480C, then decomposes exothermally to (Na:SiOJ)r'
Hydrogen peroxide is useful as a blowing agent, along with MgO and paraforrnaldehyde, in making low density foams from a solution of sodium silicate (216).
\.
..
.
t
)
.icates
ice of
) a-'
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165
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J
J
1
1
]
-- =---Silicates
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,,~,
.:...)"j:....::,!.:.:~".;.~
-~.
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1
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,
r
..
'.
.....-
;ilicates
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'.
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74,408
Nauk.
~i~~T;:'::-:~
,:"
CHAPTER
From the time of Graham (1), who made an intensive study of sols and gels, many
attempts have been made to explain the behavior of silicic acid. When freshly made
by acidifying a soluble silicate or hydrolyzing the ester, silicic acid is not "colloidal,"
since it diffuses easily through parchment or animal membranes and has a molecular
weight by freezing point depression corresponding to monomer. Soon the molecular
units become larger and pass through membranes only slowly and then not at all (2).
This could be because the monomer or other small primary particles form
aggregates, or because the individual particles increase in size and decrease in
number.
Freundlich appeared to recognize these alternatives when he wrote:
Whether it is rather a matter of polysilicic acids. which give larger micellae. being formed
from simple silicic acid. or whether the crystalloid particles originally present already consist of
polysilicic acids. but are exceedingly fine amicrons which continually increase in size-cannot
yet be said with certainty.
In his terminology, a "micella" is a colloidal particle in which foreign substances

(ions, water) are present in its structure, that is. a porous aggregate. whereas the
"arnicron" is a discrete particle too small to be seen with the ultramicroscope. He
recognized that such particles in a colloidal solution could "consist of one very large
molecule," in other words. a single unit. not an aggregate.
Because the most obvious behavior of a silicic acid solution is that it increases in
viscosity and finally forms a gel. its polymerization was generally assumed to be an
aggregation process or a polymerization by which smaller molecular units linked
together into larger ones. The nucleation and growth of discrete particles prior to the
stage where aggregation begins have not been recognized by many workers. who
held to the idea that Si(OH). polymerized into siloxane chains which. then were
branched and cross-linked as in many organic polymers. Even now attempts are still
made to apply the idea of monomer functionality and condensation polymerization
theory of organic chemistry to the silica system. In fact, there is no relation or
analogy between silicic acid polymerized in an aqueous system and condensationtype organic polymers. [However. the behavior of silica in molten glasses is quite a
172
..
...
Is, many
11y made
illoidal, "
iolecular
rolecular
at all (2).
les form
crease In
formed
consist of
e-cannot
ng
rbstances
ereas the
cope. He
(ery large
creases in
; to be an
its linked
'ior to the
cers, who
hen were
.s are still
ierization
elation or
lens-vionis -, : a
173
different matter, and in that system the conventional polymer theory has been shown
by Masson (3) to be applicable.]
In 1925, Kruyt and Postma (4a) pointed out that there are two groups of silicic
acid sols. The first group has a pH of 4.5 or less, and the viscosity of the sol
increases with time. On the other hand, pure silica sols, having a pH of 7 or higher,
are relatively stable, the viscosity either remaining the same or decreasing with time.
This difference in behavior is explained as follows. The more alkaline sols bear a
negative charge and are thereby stabilized. However, the addition of soluble salts
lowers the charge of the particles and causes gelation or flocculation. On the acid
side, where there is essentially no charge, aggregation or flocculation occurs, causing
an increase in viscosity, and eventually gelation. Tourky (4b) also discussed the
structural differences between silicic acids in acidic and basic solutions; in acidic
solutions, fibrillar or network structures arise through the formation of oxygen
bridges between silicic acid units.
It was Carmen (4c) who first clearly stated that silicic acid polymerizes to discrete
particles which then aggregate into chains and networks.
The formation of silica gel can be regarded as taking place in two stages. In the first, initially
formed Si(OH). condenses to form colloidal particles. In dilute solution, a further slow
increase in particle size is the'only subsequent change, but at a concentration of about 1 percent
silica, these primary particles are able to condense together to give a very open but continuous
structure, extending throughout the medium, thus bestowing a certain degree.of rigidity upon
it. In both stages of polymerization, the mechanism is the same, that is, condensation to form
Si-O-Si links, but in the first stage, condensation leads to particles of massive silica, while in
the second, since it is not possible to fit two particles accurately together overa common face.
the number of Si-O-Si linkages between particles is fewer in number than those within the
particles themselves. They are merely sufficient to bind adjacent particles together, in a fixed
position relative to one another, and thereby lead to a rigid, highly porous. tangled network of
branching chains....
Thus three stages are actually recognized:
1. Polymerization of monomer to form particles.
2. Growth of particles.
3. Linking of particles together into branched chains, then networks, finally extending throughout the liquid medium, thickening it to a gel.
Since Carmen published this in 1940. further experimental data continue to confirm his point of view. There is general agreement that polymerization, that is, the
reactions that result in an increase in molecular weight of the silica. involves the
condensation of silanol groups:
-SiOH
+ HOSi-
-SiOSi-
+ H20
The term "polymerization" is used in its broadest sense, the mutual condensation of
Si(OH) to give molecularly coherent units of increasing size, whether these are
174
spherical particles of increasing diameter or aggregates of an increasing numb-er of

constituent particles. Formation and growth of spherical particles is one kind of
polymerization that takes place under certain conditions. Aggregation of particles to
form viscous sols and gels is another kind of polymerization occurring under other
conditions. Both types of polymerization may occur at once.
GENERAL THEORY OF POLYMERIZATION

The general theory of polymerization is first outlined. Then the details of each step
are reviewed and finally the more recent work of a number of investigators is discussed. Succeeding steps in polymerization from monomer to large particles and gels
or powders have been represented schematically by IIer (5) as in Figure 3.1. This
applies to aqueous systems, in which silica is somewhat soluble. Very little is known
about the polymerization when Si(OH)~ is formed in nonaqueous solutions.
The individual steps are as follows. Later each step is considered in detail in the
light of individual investigations.
(a) Monosilicic acid is soluble and stable in water at 25C for long periods of
time if the concentration is less than about 100 ppm as Si0 2 When a solution of
MOr-;OMER
,
I
DIMER
CYCLIC
I
pH< 7
PARTICLE
or
pH 7-10 WITH
SALTS PRESENT
I
'I
/A
4-
pH 7-10 WITH
SALTS ABSENT
C,'t,5nm
-,
i~nm
~~'0nm
#'OJ'I~
c$ ~30nm
/
-.
-~
--...
IDOnm
1
THREE -DIMENSIONAL
GEL NETWORKS
SOLS
Figure 3.1. Polymerization behavior of silica. In basic solution (B) particles in sol grow in size
with decrease in numbers; in acid solution or in presence of flocculating salts (A). particles
aggregate into three-dimensional networks and form gels.
=-....
General Theory of Polymerization
175
.~
..
,.,
monomer, Si(OH)., is formed at a concentration greater than about 100-200 ppm as

Si0 2 , that is, greater than the solubility of the solid phase of amorphous silica, and
in the absence of solid phase on which the soluble silica might be deposited, then the
monomer polymerizes by condensation to form dimer and higher molecular weight
species of silicic acid.
(b) The condensation polymerization involves an ionic mechanism. Above pH 2

the rate is proportional to the concentration of 0 H - ion and below 2 to the H + ion .
(c) Silicic acid has a strong tendency to polymerize in such a way that in the
polymer there is a maximum of siloxane (Si-O-Si) bonds and a minimum of
uncondensed SiOH groups. Thus at the earliest stage of polymerization, condensation quickly leads to ring structures, for example, the cyclic tetramer, followed by
addition of monomer to these and linking together of the cyclic polymers to larger
three-dimensional molecules. These condense internally to the most compact state
with SiOH groups remaining on the outside.
(d) The resulting spherical units are, in effect, the nuclei that develop into larger
particles. The solubility of these very small particles depends on the particle size,
that is, the radius of curvature of the surface. It also depends on the completeness of
the dehydration of the internal solid phase. If the latter is formed at ordinary
temperature it may contain uncondensed OH groups but if formed above 80C, and
especially above pH 7, it is almost anhydrous.
(e) Because small particles are more soluble than larger ones (Chapter 1) and
since not all the small three-dimensional particles are the same size, the particles
grow in average size and diminish in numbers as the smaller ones dissolve and the
silica is deposited upon the larger ones (Ostwald ripening). However, the higher solubility of smaller particles is pronounced only when the particle size is smaller than
about 5 nm and very pronounced when it is less than 3 nm. Hence above pH 7,
where the rate of dissolution and deposition of silica is .high, particle growth
continues at ordinary temperature until the particles are 5-10 nm in diameter, after
which growth is slow. However, at low pH, where the rate of polymerization and
de polymerization is slower, particle growth becomes negligible after a size of 2-4 nm
is reached. At higher temperatures, growth continues to larger sizes, especially above
pH 7. .
The very early formation of particles was also proposed by Vysotskii et al. (6),
who studied the early stages of polymerization and similarly stated that there are
two basic processes of particle growth of silica in the aqueous system:
I. Growth of particles .at the expense of silicic acid in the solution from the moment
of its preparation.
2. Further growth of larger particles by deposition of silicic acid dissolving from the
smaller particles. This is a slower process and may be negligible at low pH after
the monomer has been used up.
(I) Above pH 6 or 7, and up to 10.5, where silica begins to dissolve as silicate, the
silica particles are negatively charged and repel each other. Therefore they do not
collide, so that particle growth continues without aggregation. However, if salt is
.J
.j.,
4~._-::-,----:-"
:~?
176
present at a concentration greater than 0.2-0.3 N, as when sodium silicate is neutralized with acid, the charge repulsion is reduced and aggregation and gelling occur.
It is paradoxical that under some conditions, precipitation or gelling is prevented
by raising the temperature. In this pH range a sol of 2-3 % silica with a borderline
salt concentration of 0.2-0.3 IV gels if aged at ordinary temperature. However, if the
sol is first heated to 80-100 0 the particles grow in size and decrease in number so
that aggregation and gelling are greatly retarded or even prevented permanently.
(g) At low pH the silica particles bear very little ionic charge and thus can collide
and aggregate into chains and then gel networks. If the concentration of Si0 2 is
m ore than 1% such aggregation may beginas soon as the first small particles are
formed. However, at lower concentrations and at pH around 2, the monomer is
converted largely to discrete particles before they begin to aggregate. On the other
hand, at pH 5-6, monomer is converted rapidly to particles which simultaneously
aggregate and gel so that it is not possible to separate two processes. The rate of
aggregation increases rapidly with concentration so that in any case above 1% silica,
aggregation probably involves not only particles but also oligomers.
The process of aggregation and gelling in the silica system is unique because,
unlike other metal oxides, the solid phase remains completely amorphous and appreciably soluble in water and is generally in solubility equilibrium with the monomer.
It is essential to understand that while sol is being converted to gel. the growing
aggregates contain the same concentration of silica and water as in the surrounding
sol regions. These aggregates or "gel phase" cannot be seen because the density and
refractive index of the gel phase are the same as those of the remaining sol. Thus
before the sol solidifies only a slow increase in viscosity can be noted, with little
change in other properties, up to a point where the viscosity begins to increase
rapidly and solidification occurs at the "gel point." The most common way of determining the "gel point" is .to observe when the meniscus of-a sol in a container no
longer remains horizontal when the container is tilted.
It may be difficult to visualize how particles in a suspension can rearrange
themselves into three-dimensional networks without changing the silica concentration. In certain microscopic regions in the sol the particles arrange themselves in
chains, and these in turn branch and form networks. These can be isolated in sols
gelling at low pH by adding an inert miscible fluid such as water or alcohol. With a
twofold dilution, all the particles not attached to a three-dimensional network move
apart, but the rigid networks retain their structure and thus are more dense than the
medium, and so can be separated by centrifuging. In this way the percentage of
silica that has been converted to "gel phase" can be measured. Gelling occurs when
about half of the silica has entered the gel phase, which can be thought of as
spherical solidified regions in suspension which cause a rapid increase in viscosity
when the "volume fraction" reaches about 0.5.
After the gel network has been formed, the structure becomes stronger as the
necks between particles become thicker owing to solution and deposition of silica.
In this chapter, attention is concentrated on the details of the various processes of
polymerization Lip to the point of gel formation. The completion of gel formation
and subsequent changes in structure arc dealt with in Chapter 6.
.....
Monosilicic Acid
177
Overall Effect of pH on Gelling

Whether polysilicic acids or larger particles of colloidal silica are involved, the
general effects of pH are generally as indicated schematically in Figure 3.2. Curve
ABC represents the behavior of silica in the absence of salts. Sols have a maximum
temporary stability with longest gel time around pH 1.5-3, and a minimum stability
with rapid gelling around pH 5-6. Above about pH 7, no gel is formed since the
particles are charged and only particle growth occurs. Curve DEF represents the
general behavior when an electrolyte such as NaCI or Na 2SO. is present at a
concentration above about 0.2-0.3 N. The salt lowers the ionic charge on particles.
At low pH both sols gel, and salt has little effect. In the neutral region the pH of
minimum stability is higher (E) when salt is present.
MONOSILICIC ACID
Monomeric silicic acid, Si(OH). has never been isolated. It is a very weak acid and
exists only in dilute aqueous solution, since it polymerizes when it is concentrated. It
10
pH
Figure 3.2. The effect or pH on the gelling of silica sols. Curves .-I-C-sols in the absence of"
sodium salts: D-I-": in thc presence of sodium salts.
...
,::;:-...."i.
~..;,'
178
,;
.:
is the soluble form of silica that is in equilibrium with the solid phases. As described
in Chapter 1, it is a neutral highly hydrophilic, essentially nonionized substance that
cannot be isolated from water. In pure form, if it could be prevented from polyme.
rizing, it might be expected to be a clear liquid resembling glycerin. The basis for
this speculation is that a very low molecular weight polysilicic acid was isolated as a
clear viscous anhydrous liquid by Robinson (7), who found that it polymerized
immediately to clear, hard silica gel when exposed to a trace of atmospheric moisture. It was highly hygroscopic, and soluble in polar organic solvents such as
'alcohol, but insoluble in hydrocarbons. In view of its unique character, a brief
description of its preparation is justified.
To a violently agitated mixture of 83.2 grams tetraethylene glycol dimethyl ether,
52 ml H 2 0 , and 40 ml 20% H 2S O ., was added, in a thin stream, 125 ml of a solution
of sodium silicate containing 122 g 1-1 Si0 2 and 38 g 1-1 Na 20. After IO min, 50 g
anhydrous Na 2SO. was added and the mixture stirred, then allowed to stand. The
supernatant clear liquid layer of the ether contained silicic acid weighing 186 grams.
This was separated and at once subjected to vacuum distillation at ordinary
temperature to remove the water. Then the high-boiling ether was extracted with an
equal volume of benzene, leaving a viscous, water-clear, anhydrous polysilicic acid.
Sufficient H 2 SO. was present to make the liquid acidic, which gave it temporary
stability. It soon set to a clear hard gel, especiaIly when exposed to moisture or
warmed.
Monomer can be removed from solution by strong-base ion-exchange resin, presumably because it is ionized to HSi0 3 - by the OH - ions at the resin surface, and is
then adsorbed.
Preparation
The various methods of preparing monosilicic acid may be summarized as follows.
A saturated solution of monosilicic acid, Si(OH)., containing about 0.01 ~ Si0 2 , is
obtained when pure amorphous silica is equilibrated with water at room temperature. A more concentrated (supersaturated) solution can be obtained only indirectly
by liberating monosilicic acid from its compounds under carefully controlled conditions; at low temperature and low pH. dilute solutions remain supersaturated with
respect to amorphous silica for appreciable periods. For example, at pH 3 and OC,
solutions of monosilicic acid up to 0.1 M (0.6% Si0 2 ) can be prepared by spontaneous hydrolysis of monomeric silicon compounds, sich as silicon tetrachloride or
methyl orthosilicate, and also by reacting monomeric silicates. such as sodium or
magnesium orthosilicates or hydrated crystalline sodium metasilicatc, with dilute
acid.
Dissolving Silica
Jander and Heuk eshoven (8) reported that amorphous silica gel gives a true solution
of silica in water; later Jander and Jahr (9) found that the silica in solution had a diffusion coefficient of 0.53, indicating a molecular size about equivalent to Si(OH).
".
=-..--
Monosilicic Acid
i:
179
i
Subsequently Alexander, Heston, and Iler (10) verified that amorphous ~ilica
exhibits a definite equilibrium solubility in water, amounting to about 0.01-0.012%
Si0 2 in the saturated solution. Kitahara and Oshimo (II, 12) dissolved quartz under
high pressure at 400C to obtain a solution containing 350-400 ppm which was
quenched to obtain a solution of monomer at pH 6 which then polymerized. A 400
ppm solution of monomer was obtained by saturating water with silica gel at
95-100C (13). Egorova (14) reports that in the pH range 1.2-3.7 it remains
unpolymerized even after 2 he.
This appears to be a convenient way to make and store a 400 ppm solutiori of
monomer for polymerization or deposition studies at 25C, where the solubility of
gel is around 100-120 ppm.
Hydrolysis oj Monomeric Silicon Compounds
Dilute solutions of monomer can be obtained by hydrolysis of halides, esters, or acyl

derivatives such as silicon tetraacetate: SiCI. requires the later removal of HCl. Thus
Willstatter, Kraut, and Lobinger (15) led SiCI. vapor into water atOC while adding
silver oxide to maintain pH 3 and to precipitate the chloride. This method was also
investigated by Gruner and Eldd (16). The very rapid hydrolysis of tetraacetate gave
monosilicic acid, whereas (CH 3SOOhSiOSi(CH3COOh gave disilicic acid according
to Schott and Fischer (17). Using a cryoscopic method, they demonstrated 'that in
this system at 25C Si(OH). was most stable at pH 2.8 and the disilicic acid at 3.1.
The relative rates of polymerization of monomer and dimer, each at its most stable
pH, were compared at unspecified concentrations. The monomer was said to be
more stable than the dimer but this probably depends on the pH and the method of
preparation.
Ethyl orthosilicate has been -used to prepare silicic acid that, is not com pletely
monomeric because the two-phase hydrolysis is not instantaneous. Disilicic acid was
prepared from tetraethyl orthosilicate by the Brintzingers (18).
Methyl orthosilicate hydrolyzes rapidly t~ monomer. Brintzinger and Troemer
(19) obtained essentially monosilicic acid by hydrolyzing methyl orthosilicate in
0.001-0.01 Nl HC/. Weitz, Franck, and Schuchard (20) prepared monosilicic acid by
hydrolyzing tetrarnethyl silicate in 0.002 Nl HCI at room temperature, checking the
molecular weight by the freezing-point method. The methyl ester gives monomer
when hydrolyzed in about 10 sec in water at pH 3. Thus monosilicic acid can be
obtained as a 0.13 M solution (0.8% Si0 2 ) by hydrolyzing methyl orthosilicate in
\0-3 IV H2SO. or HClsolution at 25C, and it remains practically unchanged for
2-3 hr as described by Schwarz and Knau ff (21). They hydrolyzed the ester in an
apparatus from which the methanol and some water could be vacuum distilled and
the molecular weight of the silicic acid was determined by the freezing-point method.
After 24 hr. the molecular weight corresponded to that of dirner. but there was no
indication that it was more stable at this point.
At silica concentrations around 0.5-1 % Si0 2 it is impossible to preserve the
monomeric state at 25C, even at the pH of optimum stability. Five minutes after
the preparation of a 0.083 M solution of Si(Ol-!). (0.5% 5iO)2) at pH 2. some
disilicic acid is present (22).
..~'.'
\-.
180
Dissolving Monomeric Silicates in Acid
:I
"
II
Ii
,,
Monomeric crystalline silicates dissolve and are neutralized to liberate monosilicic

acid at about pH 2. Kraut (23) prepared monosilicic acid by dissolving sodium metasilicate hexahydrate in various acidic solutions at low temperature. He reported that
monosilicic acid is most stable at around pH 2-3. Weitz, Franck, and Schuchard
(20) demonstrated that when Na 2Si0 39H 20 was reacted with acetic acid it liberated
Si(OH). Also olivine (magnesium orthosilicate, Mg 2SiO.) dissolved in 1.0 N J:lCI to
give a practically 100% yield of monosilicic acid, the solution containing 0.04%
Si0 2 Thus monosilicic acid may be liberated from silicates which contain SiO.2 ions separated by cations, such as are present in anhydrous orthosilicates.
Alexander (24a) found that sodium metasilicate hydrolyzed to disilicate when
dissolved in water unless NaOH is added to form orthosilicate, Na.SiO . However,
if crystalline Na 2SiO.9H 20 and strong-acid H+ ion-exchange resin are added
simultaneously to a 10- 3 N solution of H 2SO. at OC to maintain pH 3, a 0.1 I'd
solution of monomer can be obtained.
Thilo, Wicker, and Stadt (24b) made monomer by dissolving Na.SiO. glass in
cold dilute acid. With glass of composition I Si0 2 : 1.5 Na 20, disilicic acid was
obtained. Contrary to Schott and Fischer (17), they found disilicic acid is much
more stable than the monomer and can be made reproducibly at higher concentrations.
Coudurier, Baudru, and Donnet (25) modified Alexander's method by maintaining
the pH at 2.5, and Okkerse (29) preferred 0.01 N HCl at pH 2 as the reaction
medium.
Silicic acid was prepared by Funk (26) by dissolving certain mineral orthosilicates
("monosilicates" in German) in a solution of HCI in anhydrous methanol. The calcium, barium, and magnesium chlorides were soluble in methanol and the resulting
monosilicic acid was much more stable than in water. Soluble minerals were beta
and gamma Ca-SrO, (dicalcium silicate); Ca 2 0 H ( H O S i 0 3 ) (dicalcium silicate alpha
hydrate); Ca 3 (HOSi0 3 ) 2 ' 2H 20 (synthetic aufwillite); BaOH(H 3SiO.) 4H 20;
Mg 2SiO. (synthetic forsterite); and Mg 3AI 2(SiO.)3 (garnet). The monosilicic acid
polymerizes and is precipitated when water is added. It would seem likely that it is
present at least partially as a methyl ester. Funk and Frydrych (27) prepared solutions in which 90% of the dissolved silica was Si(OH). at concentrations up to 1%.
by dissolving anhydrous Ca 2SiO. in dry methanolic HC!. Polymerization was very
rapid unless the solution was diluted at once to 0,1 % Si0 2 By adding acetone, the
CaCI 2 was precipitated, leaving a relatively pure solution of silicic acid (28).
Characteristics of Silicic Acid
.,
.
'
Since Si(OH). has never been isolated or even obtained in a concentrated solution
without considerable polymerization, very little is known about its physical or
chemical properties. Most measurements have therefore been made in very dilute
solutions .
.J
.,"
......::;.
:-._-
!;
a
Monosilicic Acid
181
Diffusion Constant
....
l-
This was measured in seawater by Wollast and Garrels (30) and found to be 1.0
0.05 X 10- 5 em? sec:".
It
Ionization Constants
:n
r,
id
~
.n
lS
:h
1-
The ionization constant of monosilicic acid has been evaluated in many ways. As
already discussed in Chapters 1 and 2, the pK a appears to be about 9.8 at i5C
determined by Roller and Ervin (31) in a system involving calcium oxide, silica, and
water. More recently, careful measurements by Marsh, Klein, and Vermeulen (32)
of the equilibrium between Si(OH). and HSi(OHh - over a range of pH led to a
value of pKa = 9.9.
Measurements on a system containing extremely pure silica by Schwartz and
Muller (33) give a still more precise value of pKa = 9.91 0.04. They hydrolyzed
extremely pure methyl orthosilicate in water in a system which rigorously excluded
atmospheric impurities, to obtain solutions containing from 12.4 to 155 ppm Si02.
The conductivity and pH were measured with precision at 25C using low frequency
alternating current. From the initial conductivities the value of the acidity constant
was calculated.
In 0.5 M NaCIO. solution Bilinski and Ingri (34a) found that rnonosilicic acid,
Si(OH)., had a first dissociation constant at 25C corresponding to pK a = 9.46
0.02.
The values of the ionization constants according to Scherban (34b) are as follows:
:s
119
[H+] [H3SiOi]
KI
ta
la
);
id
is
[H+]
K2
[H+] [HSi0 3-]
K3
[H2SiO~-]
b,
le
in
or
K.
[H2SiO~-]
[H 3SiOi]
J~y
2 x 10- 10
[H.SiO.]
[H+] [SiO-]
=
[HSiO~-]
2 x 10- 12
2 x 10- 12
2 x 10- 12
The increase in the first ionization constant of monosilicic acid with temperature
was measured by Seward (34c). The data were obtained in the presence of borax buffer at 0.1-0.6 M concentrations. The value of pK 1 ranged from 8.88 0.15 at 130C
to 10.0 0.2 at 350C.
The ionization behavior of Si(OH). and the formation of polysilicate ions in 1-5
M NaCI solutions at silica concentrations of 0.005-0.05 m have been measured with
precision by Busey and Mesmer (34d). They found negligible formation of any complexes between monomer and the sodium ion to form NaO(OH)J in solution. (The
cornplcxing behavior of polysilicic acid is of course quite different.)
182
Increase in Ionization Constant with Polymerization

The ionization constants of disilicicic and polysilicic acids, colloidal silicas, and gels
are pertinent to the polymerization of monomer and so are considered here.
The increasing acidity of silicic acid upon polymerization was reported by Belyakov et a1. (35). As the monomer polymerized. the pK a was determined by titration
and the degree of polymerization by the cryoscopic method. The maximum pK a was
reported as 10.7 for H 2 S i2 0 1 but then decreases to 6.5 for high polymers. However,
it is not known whether the decrease occurs upon the formation of ring compounds
with =Si(OHh groups or when three-dimensional particles with =SiOH groups on
their surfaces have been formed.
The most doubtful point is the reported pK" of 10.7 for disilicic acid. which would
mean it is a weaker acid than monosilicic acid, of which the pK" is 9.8. Analogy
with other inorganic acids would suggest that disilicic acid should be a stronger acid
than monomer. Unfortunately the dimer is difficult if not impossible to prepare and
keep in sufficiently pure state for strength measurements, although a solution in
which probably at least 50% of the silica was dimeric was prepared by Coudurier,
Baudru, and Donnet (36).
Another indication that polysilicic acid is a stronger acid than Si(O H). is
furnished by ion-exchange studies by Strazhesko and others (37, 38). The ionization
constants of acid centers on the polysilicic acid surface are at least two or three
orders of magnitude higher than the constant of monomeric Si(OH). Dugger et al.
(39a) estimated the acidity of the silanol groups on silica by measuring the ion
exchange of H + with 20 metal ions. By this means they showed that the first
hydrogen to leave the pure silanol surface must have a dissociation constant k" of
10-'-10- 5 This is much more acidic than 5i(OH) which has a k" of 10- 9. 8
The variation of pKa of the silica surface with degree of neutralization was found
to be as shown in Figure 3.3 by Strazhesk o et al. (39b), who carried out studies of
the mechanism of ion exchange on silica gel using Na ", Ca ", Cs", Ca 2 + , 5r2+, and
BaH, and also on gel in the form of divalent and trivalent metal salts.
Duffy and Ingram (39c) have been able to estimate the ionization constants of a
wide variety of acids from the electro-negativity of the constituent elements and also
from the Lewis basicity or "optical basicity" from spectroscopic data. Although this
has failed when applied to monosilicic acid it might give useful data for polysilicic
acids (39d).
Allen, Matijevic, and Meites (3ge) also developed an equation relating surface
change on particles of colloidal silica and pH which indicated that the pK" for the
surface entirely in the hydrogen form is 6.4 and completely in the sodium form is
9.6.
The acidity of silanol groups on the surface of silica or polysilicic acid has been
examined by Schindler and Kamber (40), who calculated the intrinsic acidity
constant, K l n l , from results of titrating silica gel at 25C in 0.\ M NaCIO~ solution:
;"
.i
log K i n l
-6.8
0.2
-~
183
Monosilicic Acid
w
u 10.0
i:'t
a:
::>
If)
9.0
If)
0-
::>
8.0
a:
:I:
7.0
If)
u,
6.0
:x:
0-
5.0
0.75
0.50
0.25
DEGREE OF NEUTRALIZATION
Figure 3.3 Relation between pK a of silanol groups on the surface of amorphous silica and the
degree of neutralization according to Strazhesko (39b).
With regard to the equation
+ H+
5SiOH
5SiO-
log K
log [H+]
+ log
a
I - a
where a is the degree of neutralization or the fraction of silanol groups that are
ionized at a given pH.
The intrinsic acidity constant K i n t is defined as equal to K when a approaches
zero. From the data they developed the following equation:
log K
where log KIM
= -
log K i n t
+ a 2)
. 0.039 + a
1.9(a
6.81. Then
+ a2 )
a
- log
0.039 + a
I - a
1.9(a
log [H +]
log K l n t
To obtain this equation it was necessary to take into account the silicate species in
solution at equilibrium. The following ionization constants for these species in 0.5 M
NaClO. solution at 25C were reported by Bilinski and Ingri (34a).
K, = Si(OH). = 10- 2 . 7
C\
-~I
- ~,~<,,:
.r-.:,-.'.'
.. . . . :;..
::t- x,
184
-.~
.~
.,.
This assumes the solubility of silica gel is 120 ppm.
':I;
[H+] [(HOhSiO-]
10- 9 . 46
Kt
[Si(OH).]
[H+]
[(HOhSiO~-]
. [(HO)3 SiO-J
O~-]
[H+]2 [(HO)6 Si.
10- 12.5 7
?}~
[Si(OH).]
[H+J [OH-]
II
10- 13 . 8
",~~i
K;
J:~
The total exchange capacity, C, defined as the maximum number of ionizable groups
under the conditions of titration, was found to be 2.43 OH groups nm -z in 0.1 N
N aCI0 4 solution. As a matter of interest, the authors report 3.4 OH nm -2 in I M
NaCIO. and 5.83 in 3 M NaCIO. solution.
This approach to the acidity of the silica surface is quite different from that of
Yates (41, 5). which was developed as a modification of the conventional equation
applicable to organic polyacids: .
pH
~ pK - k, log" aN -
k, log"
~~ - ~
where R is the ratio of the molar concentrations CSlo,/CNa:o (where Na-O is the titratable alkali), A is the specific surface area of silica in square meters per gram, and
a andN are the activity and normality of sodium salt in the system. Based on Bolt's
data (42), the constants were found to be pK = 12.08, k l = 0.74, k z ;; 3.47, and k 3
= 2430.
In this formula there is no assumption made as to the fraction of silanol groups
that are ionizable, but the number of charges per unit area can be calculated from
C N a : O and A. As an example, a point was taken on Schindler and Kamber's curve
for silica gel of specific surface area of 372 rn" g-I. At a = 0.1, log K was -8.3.
From their equations a pH of 7.35 was calculated.
Then taking the Yates equation with pH = 7.35 and A = 372, a value of R was
found to be 240 Si0 2 : Na-O. Thus for 60 x 240 grams of Si0 2 there are present 2 X
6 X 1023 Na" counterions and ionized OH groups. Then the number of ionized sites
per square nanometer is
12
1023
60 x 240
372 x
0.22
lOIS
Schindler assumed there are 2.43 ionizable OH groups nm -2 so a "" 0.22/2.43 =

0.09. This is very close to the value of 0.10 for the point originally selected. In other
words, the two approaches appear to lead to similar results.
:~.I ; -~
;~,::::.
..~.~
'
..;..,:.
:..
.;.;,
...
.:,~
._,
.,~~~-
-.;~
.:--:.~
Monosilicic Acid
185
The acid dissociation constant of the OH groups on polymeric silica has also been
shown to be about 10- 7 . 1 by an entirely different method. Hair and Hertl (43)
measured the frequency shift of the infrared absorption band of phenolic hydroxyl
groups when adsorbed on the surface of silica and compared these with the shifts of
phenol in the presence of alcohols of known acidity constants. Marshall et a!. (44)
concluded from a similar study that the pKa of some SiOH groups on the silica surface may be about 7.2.
Isoelectric Point
The isoelectric point (iep) of Si(OH), in solution in the absence of colloid or solid
phase has apparently not been measured but presumably it would be between pKa
and pKo, where these are the negative logarithms of the equilibrium constants for:
x;
Si(OH),
(HOhSiO-
Si(OH),
(HO)3Si"" + OH-
+ H+
The latter equation might also be written
Most measurements have involved solutions in which both Si(OH), and polymeric
silica or colloid or solid phase were present. An exception is the case where the
initial rate of polymerization of Si(OH), has been measured at different pH values.
Here the initial step is one of the following:
Si(OH),
+ -OSi(OH)3 = (HOhSiOSi(OH)3 + OH-
Si(OH),
+ +Si(OH)3 = (HO)3SiOSi(OH)3 + H +
. Presumably, then, the pH at which monomer reacts most slowly with itself to
form dimer might correspond to the iep of Si(OH). Okkerse (29) measured the rate
of disappearance of molybdate-reactive silica from solution and found it to be at a
minimum between pH 2 and 3. In a study by Goto (45) on the rate of disappearance
of monomer from a solution of 2400 ppm Si0 2 at 25C, a minimum at pH 2.0-2.2
was found.
CATlO;';IC SILlCO;';. The existence of a cationic form of monomeric silica is of
course implied in the assumption that Si(OH). has an iep, Colloidal particles of
silica have been shown to carry a positive charge at low pH. but direct proof that
silicon can exist as a cation has not been available. It is therefore interesting that in
very dilute solution (66 ppm) monomeric silica has been shown to react with HCI to
form the ion (H 20 3Si(OH)3+C!- according to Cherkinsk i and Knyaz'k ova (46). This
was determined by the difference in precise conductivity measurements of 0.0025 N
186
NaOH solution titrated with 0.005 N HCI, with and without the presence 'of 0.0011
M Si(OH). The chloride compound exists only in very dilute solution.
Point 01 Zero Charge

The point of zero charge (pzc) where the surface charge is zero and the isoelectric
point where the electrical mobility of silica particles is zero have been measured by
many methods. De Bassetti, Tschadek, and Helmy (47) measured the pzc for silica
gel by a calorimetric method, from which they concluded the value must be 'between
2.5 and 3. However, the data may not preclude a value as low as pH 2 since the heat
of neutralization becomes exceedingly small below pH 3.
In an extensive study of silica polymerization, De Boer, Linsen, and Okkerse (48)
found the iep to be between pH I and 1.5, and that condensation was slowest there,
as shown by several means including viscosity studies.
Vysotskii and Strazhesko (49) have pointed out that there has been relatively little
attention paid to the pzc or iep of silica in spite of the fact that in other colloid
systems they are key factors. These authors recalled the observation of Freundlich
(2) that whereas lyophobic colloids are least stable at the iep, the lyophilic colloid,
silica, appeared to be the most stable. This is not quite true because colloidal silica is
permanently stable when it is negatively charged at pH 9-10, but there is, as Freundlich recognized, a marked temporary stability maximum at the iep around pH 2
(see Figure 3.2).
Vysotskii and Strazhesko show that in the presence of a given acid such as
sulfuric, the iep is not only the point of minimum rate of gelling but also of syneresis
and is also the point at which gels of maximum strength and maximum specific surface area are obtained. All these characteristics result not only because the rate of
aggregation is at a minimum at the iep, but also because the rate of growth of the
ultimate particles from monomer is at a minimum, so that the ultimate particles are
smallest as they form the gel.
These authors noted the relation between the pH of slowest gelling and the pK a of
the acid used. Their data are plotted in Figures 3.4 and 3.5. Their pH values for
HN0 3, H 2SO., and H 2CrO. are similar to those reported by Iler (50), who also
reported a number of other very strong acids which gave maximum gel times at
about the same pH as for HCl and HN0 3 , for example. NH 2S03H, HCIO., and
CH(S03H)3' However, the point was not brought out that with weaker acids such as
acetic, although the sol may be most stable at pH 3.5, it is nevertheless far less stable than the sols made with stronger acids at pH 1.5-2.0.
Similar results were reported by Tai and Kiang (51). hydrochloric. sulfuric, and
nitric acid giving a maximum gel time at pH 2, phosphoric at 2.5, and acetic at 4.0.
It was proposed that the polymerization rate is. proportional to
The iep appears to be at about pH 1.5, according to ion-exchange studies by

Vysotskii and Strazhesko (52) and Kirichenk o and Vysotskii (53) of ion-exchange
,.
il
;...
20
Silica
en
c:::
.0011
;:)
:r
I
w
:i:
i=
10
..J
ectric
ed by
silica
tween
e heat
t.:>
e (48)
there,
little
olloid
ndlich
)lloid,
lica is
pH
Figure 3.4. Effect of pH on gel time at 25C of silicic acid sols of different concentrations
made from H2S0~ and sodium silicate: Curve 1: 1.09 M. 65.4 gl-I Si0 2. Curve 2: 1.33 M. 79.8
gl " SiOz. Curve 3: 1.78 M, 106.8 gl-I SiOz. [From Vysotsk ii and Strazhesko ('+9).]
-reun-
pH 2
.ch as
+5
ie:
ic sur'ate of
of the
!es are
en
JKa of
.es for
o also
nes at
'~, and
uch as
ss sta-
;:)
CHCI 3 COOH
<t
u,
o
a.
-5
c, and
at 4.0.
pH OF MAXIMUM GEL TIME:
Figure 3.5. Relation between the pH or slowest gelling rate and PA"'I of the acid used
trulizing the sodium silicate. [From Vysotsk ii and St ruzhcsk o (-1<)).]
lie,
:hange
[or
ncuIII7
II
188
sorption of rubidium ions from 0.1 N RbN0 3 solution on silica gels pretreated at
temperatures up to lOOOe. All curves in Figure 3.6 converge to this pH at zero
adsorption. This general approach is summarized by Klirnentova, Kirichenko, and
Vysotskii (54).
In summary, iep and pzc of silica have been variously reported to be from pH 0.5
to 3.7 according to a review of the literature on this point by Parks (55), who cited
12 references. However, a pH of around 2 0.5 appeared to be an average for
various types of silica ranging from purified ground quartz to colloidal silica. Some
variation may be expected, depending on whether the surface is crystalline or amorphous, possibly on particle size, and especially on the presence of impurities. The
question remains how the iep determined from maximum gel time or minimum rate
of disappearance of monomer relates to the polymerization mechanisms involved.
The relation between the isoelectric point of polysilicic acid and the stability of
sols, rate of gelling, and properties of resulting gels has been summarized by Klimentova, Kirichenko, and Vysotskii (54). This behavior can be summed up by saying that all the phenomena observed involve the formation and hydrolysis of
Si-O-Si bonds, and that the rates of these reactions depend on a catalytic effect
which is at a minimum at pH 1.5-2.0 in the presence of anions of strong acids and
the minimum becomes greater at higher pH in the presence of anions of weaker acids.
From the fact that the rate of disappearance of monomer by polymerization is
second order above pH 2 and third order below 2, Okkerse (29) concluded that an
anionic form of silica was involved above pH 2 and a cationic form below 2. Thus
the isoelectric point must be at pH 2. Similarly, De Boer, Linsen, and Okkerse (56)
considered that the isoelectric point is around pH 2, since the polymerization rate is
....
Q
><
cr:
~
w
::
~ 90
<t
::J
o(J)
cr:
W
c,
50
ow
::
<t
c::
<.:)
c::
o
2
5
pH
Figure 3.6. The isoelectric point. Adsorption of

rubidium ions versus pH on silica gels preheated to
various temperatures. Curves 1-5. temperatures 300.
500. 700. 900. and 1000C, respectively. [From
Kirichenk o and Vysotskii (53).]
=-. ..-
1
\I
Monosilicic Acid
189
a function of H+ and OH - on each side of this point. In further work (S7) they
found by electrophoresis studies that the iep was between pH 1.0 and 1.5 in a 0.5%
Si0 2 sol and at pH 2 when the sol was diluted to 0.26%. It was also shown that there
was a sharp minimum in the viscosity at pH 1.9.
Similar observations were made by Tai An-Pang (58), who related gel time to the
ionization constant of silica.
The significance of the iep of silica in the silica-water system involving Si(OH).
and polymerized or solid silica surfaces is still not clear, but the preponderance of
evidence suggests that for monomeric Si(OH). the iep may be between pH 2 and 3,
and for polymeric forms between 1.5 and 2.
Stability of Monomeric Silica

As long as the concentration of Si(OH). is below the equilibrium solubility of amorphous silica, usually assumed to be about 120 ppm for silica gel but around 70-80
ppm for vitreous silica, it has been assumed that monomer would remain, as such, in
water solution at 25C. However, such a solution is supersaturated with respect to
quartz and probably to other crystalline species (Chapter 1). There is also possibility
that a solution of monomer at a concentration of 100-150 ppm might nucleate a
particular less soluble polymeric species of lower solubility.
Such a case may be involved in the observations of Schwartz and Muller'(33), who
made a highly purified solution of silicic acid from methyl orthosilicate at concentrations up to 150 ppm. Initially, conductivity measurements indicated that the silica
was monomeric, but after half an hour the conductivity, at all concentrations, slowly
decreased to about half the original value. This happened even though in half the
samples the concentrations were less than the solubility of amorphous silica. It was
assumed that the monomer polymerized slowly at pH 7 to a polymer species that is
smaller than usual colloidal dimensions, since it passed through an ultrafiler, yet it
must be more insoluble than amorphous silica.
Unfortunately, this change was not followed by means of the molybdic acid
method to see whether it involved simple dimerization at pH 7, which might have
escaped the notice of previous investigators. However, if this were the case, and if
disilicic acid has a pK of -10.7 as reported by Belyakov et a!' (35), then the conductivity would have decreased by much more than 50%. (This is discussed later in
further detail.)
Q
Reactions of Monosilicic Acid
In view of the relatively neutral character of Si(OH), with its physical resemblance
to an organic polyol, it is not surprising that at pH 2, where it is not ionized, few if
any interactions with other substances have been observed. Its most obvious reaction
is self-polymerization to higher molecular weight polysilicic acids which are more
reactive. The interaction of polysilicic acids with other substances is considered later
in this chapter. However, there are a few reactions in which Si(OH). may take part.
190
These are interactions either with other acids to form anhydrides or with" a few
extremely weakly basic metal cations.
Phosphoric and Boric Acids

Silica has long been known to react with anhydrous H3PO~ but the wide variety of
possible compounds has not been investigated. The reaction is, in effect, a condensation, with water eliminated. For example, by heating amorphous silica with H3PO~
at a molar ratio of 1:2 for a week at 80-180C, silicon phosphate is formed. Excess
H3PO~ is removed with dioxane and the product is dried at IOOC. A 10% solution
can be made in water, giving a 2.7% concentration of silica (59a). Silicon phosphate
has long been known but this example of a water-soluble material is mentioned
because it probably hydrolyzes to Si(OH)~.
The reactions of boric acid with silica appear to parallel those of phosphoric acid
since in dilute solution there appears to be no interaction between the acids, but on
dehydration at high temperature, Si-O-B bonds are formed in the resulting mixedoxide glass. The Si-O-P and Si-O-B bonds are hydrolyzed in aqueous solution.
Sulfuric Acid
The issuance of a series of patents involving silicon salts of sulfuric acid is surprising
since it is unexpected that a reaction product of two of the oldest known chemicals
should have escaped attention for so long. However, the existence of silicon phosphate suggests that the sulfate might also exist. Blount (59b) has disclosed the compound "silicodihydrogen sulfate," SiO(HSO~), which was obtained by dehydrating
"dihydroxy silicon dihydrogen sulfate," (HO)2Si(HSO')2' with concentrated sulfuric
acid. It is claimed that these solid compounds are obtained 'by stirring powdered
N a 2Si0 3 5H 20 for several hours in an excess of concentrated H2S0~. Finally the
sulfate salt is hydrolyzed in water giving a white granular "silico-Iorrnic acid" or
"monosilanol," HSi(O)OH, and "rnonosilandiol." H 2Si(OH h(?). However, no
further information about properties or analysis is given. I f the products exhibited a
characteristic x-ray diffraction pattern or other identifying features their existence as
compounds would be less equivocal. If a crystalline character is retained the compounds might be clathrates with H2S0~ within the lattice or exist as a different crystal
structure, as in the case of the phosphates. On the other hand. if the powders are
amorphous then they may be microporous silica gels with pores filled with acid; if
anhydrous, internal surface groups of =SiOS0 3H may be present.
Iron and Uranium

Monomeric silica does not react with most metal ions in water at low pH where
can exist, since for reaction to occur it is probable that some hydrolysis to a
basic metal ion must first take place.
Si(OH)~
>
Monosilicic Acid
191
However, very few metal ions form basic ions at the pH of 2, where monomeric
Si(OH). is most stable. Iron and uranium are the only ones which have so far been
reported. Monomeric silica reacts with uranyl ion as follows, according to Porter
and Weber (60):
The equilibrium constant for monomer concentrations in the range 0.024-0.035 AI

is 0.01 0.001.
As evidence of some chemical combination, certain forms of natural hydrated
silica gels and also laboratory-prepared gels impregnated with uranyl salts have been
observed by Iler to fluoresce with a strong greenish yellow color under ultraviolet
light.
.
The other known reaction of monomer with a metal cation is the case of ferric
iron, reported by Weber and Stumm (61) and further examined by Porter and
Weber in regard to the effect of the degree of polymerization of silica. They
polymerized the silica at a concentration of 2280 ppm at pH 9-10 for various lengths
of time, conditions that are known to give very small spherical particles. With:
increasing polymerization of silica with formation of adjacent SiOH groups that can
combine with iron, at pH 2, the number of SiOH groups combined per iron ion
increases from one on the monomer to two or three as the particles become larger,
the radius of curvature larger, and the SiGH groups closer together. The following
equation suggested by the authors does not indicate the degree of polymerization of
silica, but only the number of SiOH groups that can react with Fe3+, liberating the
corresponding number of H + ions:
Following the absorption characteristics of the iron as it complexes, the following

values were obtained:
Mol. Wt.
D.P.
60
13000
26000
120000
1
217
434
2000
Calculated
Diameter (nm)
-log[Qn(Si)]
2.6
3.4
5.6
1.02
1.67
1.67
1.76
2.76
4.22
4.26
4.48
Qn = equilibrium constant
D.P. = degree of polymerization
In the stock solutions containing 2280 ppm of silica at pH 9-10 there must have
been an appreciable concentration of monomer in equilibrium with the polymer.
Based on the calculated particle sizes this would amount to at least 2.6, 2.2. and 1.7
.' ~:~~~.:
';.~
192
mM or 156, 132, and 102 ppm as monomer, which undoubtedly also combined with
the iron but was not taken into account.
The interaction of Si(OH)~ with ferric iron is evidenced by the fact that concentrations of 10-.-10- 3 M SiO:: in water catalyze the oxidation of Fe 2+ to Fe H Schenk
(62) has derived a quantitative relation between the rate of oxidation and the
concentration of monomeric silica. Below pH 3.5 a soluble complex between
Si(OH). and Fe3+ exists.
At pH 6-8, a ratio of 3 Si(OH). to 1 Fe3+ prevents precipitation of Fe(OH)3'
However, in the case of AIJ+, a fivefold excess of Si(OH). is required to prevent
precipitation.
Chromium
I
t'
..
:1
r;
:!
It is peculiar that in view of the similarities of AI3+ and Cr3+ in their precipitation
behavior as hydrous oxides these elements are widely different in their interaction
with silica. One reason is that the chromite ion is not formed as easily as the
aluminate ion, AlO:: -. The Cr3+ ion is much larger than AI3+ and cannot fit into the
SiO:: lattice to give stable anions like (SiAlO.) -.
Thus the Cr3+ ions show a peculiar inertness relative to monomeric, silica, in
marked contrast to the behavior of AP+. When amorphous silica was heated under
pressure with a mixture of Cr(OH)3 and AI(OH)3 for 2 days at 300C, only the alumina combined with silica (63). This behavior of chromium probably explains the
rarity of chromium silicate minerals.
Hexavalent chromium as H::CrO. appears to form a complex with Si(OH)~,
according to Iler (50). The chromate ion is unique among inorganic anions in that it
retards the polymerization of Si(OH)~ in the pH range from about 0.5 to 3.0. At pH
1.7, where Si(OH). is most stable, the increase in gel time of a I M silica sol was
linear with Cr03 : SiO:: ratio. It ranged from 69 hr with no Cr0 3 to 270 hr at a
Cr0 3 : SiO:: ratio of 0.75, and at higher ratios was then constant at 270 hr. The latter
is the gel time of a 0.5 M Si0 2sol in the absence of H::CrO.
Thus the system behaved as though H2CrO~ dimerized the silica quantitatively and
the excess had no further effect:
O-H--O--H-O
II
I"
HO-Si-O-Cr-O-Si-OH
O-H--O--H-O
It appears that this "dirner" then gelled at a rate as though the concentration of
silica was only half the original. Unfortunately, the gel obtained was not examined
to see if the CrO~::- ion was actually bound in the structure.
No compound such as silicon chromate has been reported, but evidently silicon
can be linked through oxygen to hexavalent chromium. A chromic acid ester of a
silanol group was made by Schmidt and Schrnidbaur (64), who prepared the tri-
.,
.",
Monosilicic Acid
193
rnethylsilyl ester:
o
(CH 3hSiOCrOSi(CH 3 ) 3
, !
Aluminum
As discussed in other chapters relating to the effect of aluminum ions. there is a
peculiar affinity between the oxides of aluminum and silicon. At this point only a
few observations regarding the interaction with monomeric Si(OH). are noted.
Aluminum oxide is far less soluble than silica in water at 25C. pH 5-8. as evidenced by early data by Okura, Goto, and Murai (65), shown in Figure 3.7.
Monomeric silica reacts with AP+ ions and is precipitated most effectively at pH
9, according to Goto (66). Thus with a solution containing initially 35 ppm
monomeric Si0 2 at pH 9. the addition of 20-100 ppm of Al as AP+ ions reduced the
silica concentration to a value C. such that A C = 300. where A and C are ppm of
AP- and Si0 2 respectively. However. this probably did not represent true equilibrium.
Over a long period of time monomeric silica. (SiOH) reacts with AP+ ion at
25C to form colloidal aluminum silicate of the halloysite composition:
By reacting soluble silica and alumina at various pH values for periods up to 4 years
and measuring the concentrations of residual Si(OH). and AP+. Hem et al. (67)
10
0::
t=
-l
0::
W
a.
d>
E
0,5
..J
<l:
02
01
pH
Figure 3.7.
Solubility or aluminum oxide in water versus pII [From Okura. GOlO. and Mur ai
"
(65) ).
",
':'
"
~:
..
19~
measured the following constants:

[AP+]Z [Si(OH).]Z
[H+]6
[Al(OH)iP [Si(OH).]Z [H]Z
The standard free energy of the colloidal aluminum silicate was - 897 1 kcal
rnole:".
Monomeric silica is strongly adsorbed onto the surface of hydrous aluminum
oxides. There is a reaction between Si(OH). and crystalline AI(OHh by which
several reaction layers of Si0 2 are built up, with simultaneous decrease in pH of the
suspension (68a). Formation of the first layer is rapid, but the second and third
layers form progressively much more slowly. It would seem that diffusion of AP+ Or
AIO2 - from the surface of the crystal must be involved. with the formation of a
silica-rich aluminosilicate. A relatively low content of aluminum ion in the SjO,
layer greatly reduces its solubility, thus explaining the deposition of Si0 2 from a
solution unsaturated with respect to pure amorphous silica.
Baumann (68b) found that when different amounts of aluminum ion were added
to a solution of monomer (420 ppm Si0 2 ) , more silica remained in the molybdate
reactive state than when no aluminum was present. With no aluminum' present, after
4 days there remained 130 ppm of molybdate-reactive silica as monomer in equilibrium with 290 ppm of relatively inactive high polymer. But when aluminum was
present in the AI: Si atomic ratio of 1: 7, there remained about 200 ppm of molybdate-reactive silica. It can be interpreted that the alumina had combined with silica
to form an aluminosilicate that later was decomposed by the strongly acidic molybdate reagent liberating additional active silica that appeared as monomer.
However, when the silica concentration was only 60 ppm. and thus below the solubility of amorphous silica, no polymerization occurs except when alumina is added.
In this case when the AI: Si ratio is 1: 1 to I: 10 the aluminum ion brings together
monomer to form a silica-rich complex in which some of the silica is also linked
together into a state that is later less molybdate-reactive. Baumann's extensive data
deserve detailed study.
The final reaction product at the alumina surface is halloysite. When a dilute
solution of monomeric silica is brought in contact with gamma alumina, it is
adsorbed at a rate strongly dependent on pH and area A. In a mediu m of constant
ionic strength (0.1 N NaC!) and at silica concentrations of 10- 3 - 10 - < M, Huang
(69a) found the initial adsorption to be rapid. When below pH 9 the rate is proportional to A Z [Si0zl U [H+]-o.5, whereas above pH 9 it is proportional to A 2 [Si0 2 JU
[H +]. Huang proposed that HSi0 3 - is the major reacting species.
It is possible that with a quaternary ammonium base and in the absence of metal
cations, aluminosilicate anions may remain in solution, for example,
(HOhSiOAI(OH)20Si(OH)J1-. Flanigcn (69b) reported that quaternary ammonium
silicate and aluminate remained in solution until a sodium salt was added.
In the case of pure alpha alumina, the writer has found that there is no interaction
with monomeric silica. Colloidal alpha alumina free from other forms of alumina or
-;
,.
-~
."
195
\I
AP+ ions has been prepared by treating the particles with 24% HF solution for 2~ hr
to remove all other types of alumina and silica impurities, and washing with water,
then NH.OH to remove all F- ions from the alumina surface (70a). At pH 7-8,
monomeric silica is not adsorbed, nor does it react with this form of alumina even
though the specific surface area.is 24 m 2 g-t. Presumably AP+ or polybasic Al ions
are required for reaction with Si(OH).
Divalent Cations
It is known that the ligand properties of deprotonated Si(OH). with a polyvalent
metal cation can lead to a stable complex such as [FeOSi(OHh]3+, as reported by
Weber and Stumm (61); however, much less is known about complexes of divalent
cations. Santschi and Schindler (70b) measured the stability of complexes involving
Ca2+ and Mg2+ at around pH 8-9 in 1 M sodium perchlorate solution at 25C.
Complex formation was weak and occurs only in the presence of excess salts. In
natural waters, such complexes are not formed.
CHARACfERIZATION OF SILICIC ACIDS

It is not possible to discuss all the techniques used for measuring or characterizing
silicic and polysilicic acids and small colloidal particles, but some of the methods,
especially applicable to following the polymerization, are reviewed.
Reaction with Molybdic Acid
The history and use of this reaction in analyzing for silica is discussed in detail in
Chapter 1 and its application in characterizing silicate ions in Chapter 2.
Further refinements and use of this indispensable reaction for studying the
polymerization of silica are now described. Most of these involve following the
course of polymerization by measuring the rate at which the monomer, or the
monomer and dimer, disappears. This in turn involves distinguishing monomer and
dimer, which react rapidly with molybdic acid. from higher polymers that react
more slowly. The method is particularly useful because, as described earlier, the
color-forming reaction is carried out at a 10:" pH where the polymerization or
depolymerization of silica is at a minimum. Hence samples taken from rapidly
polymerizing or depolymerizing solutions at higher or lower pH are "frozen" at the
moment they are added to the molybdic acid reagent. The monomer and dimer react
very quickly, whereas each higher polymeric species dcpolymerizes at a slower,
characteristic rate.
The structure of the silicornolybdic acid is such that within the molecule there is a
tetrahedron of four oxygen atoms in which only one silicon atom can fit (20, 24).
Thus only monosilicic acid. Si(OH). can react directly. All polymeric species must
first dcpolyrncrizc to monomer. The silicomolybdatc anion Sii\10 12 0 .o - apparently
has a compact structure similar to that established for basic aluminum chloride in
196
-.
Figure 3.8. Structure of silicomolybdic acid. All corners of octahedra are occupied by
oxygen atoms. A molybdenum atom is at the center of each octahedron. (see text).
which the polybasic aluminum ion is A 113 0 .(O H h .(H 20 )121 + , as established by
Johansson (71). The analogous structure for the silicomolybdate ion requires that all
the oxygen sites be filled by oxygen atoms (including those that in the aluminum
complex are filled by OH groups and coordinating water molecules): SiMo I2O:o- .
The structure of the silicomolybdate heteropolyion is shown in Figure 3.8. The
details of the sharing of the oxygen atoms (or ions) between the McO, octahedra
and the central SiO. tetrahedron have been described clearly by Cotton and
Wilkinson (72a).
Alpha and Bela Silicic Acids

Polymers of silica were classified first by Goto (45) into two types. "A" reacts
rapidly with molybdic acid and has a low degree of polymerization of less than four,
whereas "B" reacts more slowly with increasing molecular weight. It appears that
the difference is the size of the ultimate particles and thus the reaction ratevaries in
proportion to the specific surface area. Other workers have variously defined the
increasing degree of polymerization, as evidenced by decreasing rate of reaction with
molybdic acid, as alpha, beta, and gamma. Usually alpha is defined as silica that
reacts almost completely in less than 5 min. Beta reacts completely in 10-30 min.
:.....-.
Silica
197
and has been classed as an oligomer or oligosilicic acid by Baumann (72b)~ Gamma
then is the higher polymers that do not react after 10-30 min; it is often referred to
simply as "higher polymers."
Goto and Okura (72c) proposed that the monomer and dimer species which
reacted in 5 min be classed as type A. These could be removed from solution by a
strong-base anion-exchange resin. They recognized that there are different types of B
type polymer, since those formed in an acid medium depolymerized more rapidly
than those formed in a basic medium.
A method that is said to distinguish alpha and beta from gamma silicic acid was
developed by Nemodruk and Bezrogova (73a), who defined the gamma silicic acid as
that which did not react with molybdic acid reagent at 100C in 20 min, whereas
beta reacted com pletely.
Measurements of Reaction Rates
ied by
ed by
hat all
.iinurn
1-
L The
ihedra
;"1 and
reacts
, four,
's that
ries in
ed the
n with
a that
) r
Anum ber of investigators began to use the procedure developed by Alexander (24a)
to measure the rate of reaction of specific polysilicic acids with molybdic acid. This,
in effect, was a measurement of the rate of depolymerization in the colorimetric
reagent. It was hoped that once the reaction rates of individual polyacids were
known, the more complex reaction rate of a mixture of polymers could be
interpreted as a distribution of molecular weights.
The depolymerization of a particular species of silicic acid is a first-order reaction
so that the species can be characterized by a specific reaction rate constant.
Since in most solutions monomer is already present along with a higher polymer
or colloid, the following equations will hold:
. Cr
c,
Mo
Po
fraction of total silica reacted with silico-rnolybdate at time t

total silica in the system at t = 0
total monomer in system at t = 0
total polymer in system at t = 0
Cr
where k ; and k p are the reaction velocity constants for monomer and polymer. Taking a hypothetical case where 735 ppm of monomer is in equilibrium with 7265 ppm
of cubic octarner, or 9.2% of the silica is monomeric, with the known values k m =
1.5 and k p = 0.45, the color development curves are calculated from the equation. In
Figure 3.9, curve A is the curve that results when all the silica is monomeric. B is the
curve for the above mixture, and C is the curve for higher polymer alone. It will be
noted that the amount of monomer would be difficult to estimate from this plot.
However, by plotting the log of the fraction of silica not yet reacted at time t against
time. as in Figure 3.10, lines are obtained for A and C and. at longer times. also for
the mixture B. The linear part of B extrapolates at zero time to the fraction of
higher polymer (90.8%) in the mixture.
_
..
1.0
0
IU
<
W
a:
<
u
::;
iii 0.5
u,
0
Z
<
a:
u,
0.0
10
MINUTES
Figure 3.9. Reaction of silica with molybdic acid. Calculated curves: A. monomeric silica, B,
a mixture of 9.2% monomer and 90.8% cubic octarner; C. cubic octamer alone.
1
1.0
w
u 0.5
<
w
I-
a:
<
u
::;
Cii
-l
0.2
u,
0
Z
0
i= 0.1
u
<
a:
~I
u;
0.05
MINUTES
Figure 3.10. Reaction of silica with molybdic acid: A. monomer: B. 9.1 % monomer and
90.0% cubic octarner: C. cubic octarner alone.
198
:.... .
-~
199
: silica, B,
Because of rather low precision the method is of value only for distinguishing
monomer and very low polymers from relatively high polymers, not for following
the early stages of polymerization. However, Baumann (72b) studied the early stages
by stopping the reaction by adding citric acid and reducing the yellow complex to
the more sensitive molybdenum blue.
Alexander's method (24a) was used by Thilo (73b) and several other investigators
to characterize polysilicic acids by the rates of reaction with molybdic acid, each
having a characteristic reaction velocity constant k. Their procedure, in slightly
modified form for convenience, is given in detail in Chapter 1 as a recommended
procedure.
In some cases the polysilicic acid acid must be liberated from a crystalline silicate
in acid at 2C, or even in methanol-HCl, to obtain a solution stabilized long
enough to take a sample for the molybdate test. The reaction of molybdic acid with
disilicic or linear trisilicic 'acid is rapid because these depolymerize to monomer
within a few minutes at pH 3. Schwartz and Knauf (21) prepared the pure methyl
esters of these acids and found that by the time they had completely hydrolyzed in
water in 4 and 10 min, respectively, only monomer was present in solution.
The molybdic acid was somewhat modified by Coudurier, Baudru, and Donnet (36)
for their extensive study of polymerization of disilicic acid. Two solutions of molybdic
acid were used containing 4 and 6 g I-I ammonium molybdate, respectively, both at
pH 104. These contain 0.0235 and 0.0352 g-atorns 1-1 molybdenum. When they were
reacted with monomer at 25C the reaction rate constants were 2.1 min -I for the
more dilute and 2.6 min-I for the more concentrated solution. However, with higher
polymers the reaction rates were the same, thus indicating that the slow step is the
depolymerization to monomer:
polymer
orner and
k,
) Si(OH).
k,
) silicomolybdic acid
However, disilicic acid also reacted at different rates with the two different
concentrations of molybdic acid, indicating that it dissociates very rapidly to
monomer. Equations were developed on the basis that polymer must first
depolymerize before reaction. Using these equations, experimental data plotted as
logarithm of unreacted silica versus time can be resolved to give the relative proportions of monomer, dimer, and polymer.
The reaction rate of molybdic acid with specific polysilicate anions has been
measured after obtaining a solution of the free polysilicic acid by dissolving waterinsoluble, but acid-soluble, crystalline silicates of known crystal structure. Wieker
(74) applied this method to a number of calcium silicates. Four different types of
silicic acid were characterized by their rates of reaction with molybdic acid, by Funk
and Frydrich (75). However, they did not use the method of Alexander. Instead, the
reagent was more concentrated containing 0.28 g-atorns I-I Mo with a H"':Mo ratio
of 1.5. The high concentration of molybdic acid and the relatively low acidity
accounts for the rapid reaction of this reagent with monomer and also its promotion
of the de polymerization of polymers more than twice as fast as Alexander's reagent
(75). It will even gradually attack quartz. The reaction was followed not
200
colorirnetrically, but by precipitating the silicomolybdate as quinoline salt- and titrating the latter with base. Thus the method has the advantage of not requiring a spectrophotometer or colorimeter (for details see Chapter I).
As sources of the silicic acids, crystalline acid-soluble satls of monosilicic,
disilicic, and cyclic trio, tetra-, and hexasilicic acids were dissolved rapidly in rnethanolic HC I, in which the silicic acids are more rapidly dissolved yet are more stable
against further polymerization than in water. The liberated silicic acids were reacted
at once with molybdic acid reagent,at 20e.
For each silicic acid the reaction is first order and the constant is calculated:
-dC
dt
KC
or
where C is the fraction of unreacted silica at time t, and K is the rate constant (C =
LO at t = 0). Then k (sec- 1) = 0.693 (th)-\ where t h = half-life.
Reaction Rate Constants
Values of constants for silicic acids from known crystalline silicates are given in
Table 3.1. It is emphasized that these apply only when Funk and Frydrych's type of
reagent is used. The reaction rate decreases more rapidly than the increase in
number of siloxane bonds that must be hydrolyzed to depolymerize the polysilicic
acid to monomer. This is probably because of the greater stability of the ring structures as compared to corresponding chain polymers.
Since several investigators have used nearly the same molybdic acid reagent solution as used by Alexander (24), a number of values for the constants can be compared for monomer and polymers, excluding those of Funk-and Frydrych, who used
other reaction conditions. Each polysilicic acid in Table 3.2 was prepared from a
particular crystalline silicate known to contain that polysilicate anion, by dissolving
it under conditions that avoided changing the structure.
. The linear polysilicic acids hydrolyze rapidly to monomer according to O'Connor
(77), and the linear pentamer should have a rate constant of 0.66. that is, 90%
reacted in 3.5 min. It appears that in the case of all linear, cyclic, or polycyclic silicic
acids where all siloxane bonds are exposed to the solution, the rate of depo/ymeriza"
>.'
Table 3.1. Reaction Rate Constants of Silicic Acids with Funk and
Frydrych's Molybdic Acid Reagent
Starting Silicate
Dissolved
Ca~Si04
Ca 2Na 2Si 20 ,
CaJSiJO.
K4H 4Si,0I2
ce.st.o 11.6 H 20
Silicic Acid
Type
Si(OH)4
(HO)JSiOSi(OHh
[(HO)2SiO b
[(HOhSiOj.
[(HO)~SiOjd
Half-life
(sec)
5.5
23.5
36.0
83.0
360.0
0.12
0.032
0.019
0.0084
0.0018
7.2
1.9
1.14
0.50
0.1/
;.....- ..
ilica
rat-
Table 3.2.
201
Reaction Rate Constants of Silicic Acids with Alexander's Molybdic Acid'Reagent
ect-
ieie,
thaable
:ted
Silicic Acid
Degree of
Polymerization
Type of
Polymer
(Monomer
Dimer
Cyclic
5
6
Linear
Cyclic
Double 4-ring, cubic
r =
n in
ie of
e in
licic
rue-
Single chain
Double chain
High mol. wt.

High mol. wt.
Rate
Constant,
K (min-I)
Author
2.3
1.7
2.05 .
1.87
1.5
2.1
0.9
0.9
1.09
0.82
1.00
0.67
0.79,0.65
0.66
0.6
0.51
0.46
0.42
0.050
0.015
Alexander
Thilo et al.
Marsh et al.
O'Connor
Hoebbel et al.
Coudurier et al.
Alexander
Thilo et al.
O'Connor
Hcebbel et al.
Cordurier et al.
Thilo et al.
Hoebbel et al.
O'Connor
Hoebbel et al.
Wieker et al.
Hoebbel et al.
Hoebbel et al.
Wicker
Hoebbel et al.
.olu- .
.orn-
used
ma
ving
nnor
90%
ilicic
riza-
tion is so rapid that the rate of reaction with molybdate does not increase very
greatly with the degree of polymerization. However, with Frydrych's faster reacting
reagent, differences in depolymerization rates are more apparent.
Composition of Molybdic Acid Reagents
The compositions of the solution in which the color was actually developed are summarized in Table 3.3. One group of investigators used the Alexander composition
essentially unchanged. Others modified this for specific reasons. Except for the compositions of Funk and Frydrych and of Nemodruk, the reaction rate constants with
the various silicic acids are all about the same. The more concentrated reagents,
such as Iler's, permit the use of higher concentrations of silica. The indicated ratio
H ": Mo is not based on the H + ion concentration in the solution, but is the ratio of
acid to ammonium molybdenum used in making up the mixture. Actually, a ratio of
H ": M 0 of 0.86 is required to neutralize the N H. + ion.
Other Observations
The composition of silicomolybdic acid, determined by Khornchcnko et al. (78), corresponded to H .[SiM OIZO.O] 29H zO.
Complete conversion of silicornolybdic acid from the beta to the less intense
yellow alpha form was observed at a H +: MOO.2- of 1.66: 1.0 according to Mars
..,
...
.~."
.. ". :... """
._,
# . . .,~
"t
202
Table 3.3.
Composition of Molybdic Acid Reagents
Author
Alexander
Thilo et a!.
Marsh et al.
O'Connor
Coudurier et al.
Funk and Frydrych
Govett
lIer
Kautsky
Nemodruk
H+:Mo
Mo (g-atorns I-I)
4.4
4.4
0.0227
0.0227
4.4
4.4
(pH 1.4)
1.5
3.3
0.0227
0.0227
0.0235
0.28
0.0600
0.0566
0.0566
0.0226
5.3
6.5
2.2
Acid
H 2SO.
H 2SO..
HCl
HCl
HzSO.
HCl
H 2SO.
HzSO.
HzSO.
H 2SO.
H 2SO.
(79). It is for this reason that a H ": Mo ratio greater than 4 is generally used to
"
develop the beta form.
Sugars and other polyhydroxy organic compounds interfere with the reaction of
molybdic acid with monomeric silica. This is believed to be due to the formation of
stable complexes with the molybdic acid (80).
Goto and Okura (81) were the first to recognize that the depolymerization of
silicic acid is catalyzed by the presence of molybdic acid. Thus at pH 1-2 in the
presence of He 1 alone, polysilicic acid formed monomer only very slowly, as shown
by adding molybdic acid after 50 min. The rate of formation of silicomolybdate was
then the same as when molybdate was added at the start. However, it is not known
whether the molybdic acid 'is actually involved as a catalyst by direct interaction
with the polymer or whether it simply reduces the concentration of monomer in
solution to such a low level that an equilibrium between polymer and monomer is
displaced.
A peculiar phenomenon has been noted by IIer. When a small amount of NaF is
added to a polysilicic acid solution at pH 2 it converts an equivalent amount of the
silica to SiFez-, which, when molybdic acid is then added reacts us though it were
monomer. However, if the same amount of NaF is added with or after the addition
of molybdic acid reagent it does not depolyrnerize an equivalent amount of silica,
but instead acts as a catalyst for the depolymerization of polysilicic acids. When
NaF is added before the molybdic aeid so that it is converted to SiFez-, then when
the latter reacts with molybdic acid, the fluoride ion combines irreversibly with
molybdenum so that is is no longer free in the system. When added later, the
molybdic acid reacts with monomer as it is developed, but does not inactivate the
fluoride, which at the low pH is probably present as HF.
Separation of Silicic Acids

Although the rate of reaction of molybdic acid with individual polysilicic acid
species obtained from crystalline silicates can be measured. the results are of no
f Silica
.sed to
tion of
tion of
:ion of
in the
sh
.te '" ...s
known
-action
mer in
.mer is
NaF is
of the
.t were
ddition
. silica,
When
1 when
y with
er, the
ate the
c.. .
of no
203
value in studying the polymerization reaction unless it can be shown which polyacids
are actually present in the polymerizing mixture. For this reason, methods of
separating the oligomers or low molecular weight species are essential. A few examples follow.
Chromatography can be ,used, provided conditions are chosed to minimize
polymerization or depolymerization during the procedure. Wieker and Hoebbel (22)
found that by working rapidly, monomer, dimer, and higher species can be separated
by paper chromatography in 3-4 hr using dioxane containing (a) 1.6 g
I-ICCl 3COOH and 30 g 1-1 H 2 0 to separate monomer and lower polymers, or (b)
8.0 g I-I CCl 3COOH and 90 g L 1 H 20 to separate higher cyclic polymers. The paper
is dried and the separated spots are developed by spraying with 0.1 N NaOH and
aged wet for 10 min to depolymerize the silica, then with 2% ammonium molybdate
in 0.3 N Hel and aged wet horizontally for 30 min, then the yellow spots are
reduced to blue with 0.1 N ascorbic acid and bleached with ammonia gas to destroy
molybdenum blue, thus leaving the spots of blue silicomolybdate.
Low molecular weight silicic acids were separated by Baumann (82) with paper
chromatography using a mixture of isopropyl alcohol, water, and acetic acid as the
moving liquid and the molybdic acid reaction to locate the separate species.
Polysilicic acids of different molecular weights can be separated and molecular
weights estimated by gel chromatography on Sephadex columns, using 0.1 M NaCl
solution adjusted to pH 2 with HCl as the eluent. A blue dextran 2000 in 0.2% solution was used as a standard. Tarutani (83) made silicic acid at a concentration of 500
ppm by neutralizing the monomeric solution of sodium metasilicate with acid to pH
7. This solution was aged for various lengths of time and then acidified to pH 2 to
stop polymerization.
Polysilicic acids of low molecular weight have been isolated as trimethylsilyl esters
and separated by thin layer and gas chromatography by Hoebbel et al. (84). Specific
polysilicate ions known to exist in certain crystals were used to make the corresponding trimethylsilyl derivatives to use as standards. This method makes it
possible to separate these derivatives and characterize them further by gas
chromatography and mass spectroscopy. The sources of individual silicic acids and
their chromatographic constants are listed in Table 3.4. The derivatives were
separated, using a mixture of Merck alumina G and Merck silica gel G as adsorbent
and n-heptane as solvent. Programmed temperature chromatography was also-used
(84).
Particle Size and Surface Area by Titration
At a relatively early stage in the polymerization it is possible to characterize the

polymeric silica, or silica particles in terms of the specific area of the silica-water
interface. This is done by measuring the adsorption of hydroxyl ions in the pH range
4.00-9.00 (Beckman Typc E electrode) in a nearly saturated salt solution which
permits the surface charge denstiy to approach a maximum. This method was
developed by Sears (85) to determine the specific surface areas of colloidal particles
and gels. Then it was found that if carried out rapidly it could give reproducible
... ,.
-" ..,... -- ,,-- ...
::.~..:;l--..r
....- -~.
204
Table 3.4. Sources of Individual Silicic Acids and Chromatographic Constants of their
Trimethylsilyl Deriratires
Chromatographic
Constants
Source
Silicic Acid
Na2H2SiO.8H20
Ca 2SiO.
Si(OH).
Si(OH).
Pit
R,.
1.25
0.56
OH
I
(HO)3SiOSiOSi(OH)3
\f.
1.35
0.60
.,
.~
OH
o~
OHOH
I I
1.51
0.68
[(HOhSiOh (cyclic trimer)
0.71"
.0.31 "
[(HOhSiO]. (cyclic tetramer)

Tricycloheptasilicic acid
Cubic octasilicic acid
[HOSiOI.S]a
Cubic octasilicic acid
[HOSiOI.S]a
1.00
0.38
0.26
0.44
0.16
0.11
0.26
0.11
(HOhSiOSiOSiOSi(OHh
I I
OHOH
(CaSi0 3h
(pseudowollastonite)
(KHSi0 3).
[(CH3).N + ].o[Si 70 18]( aq)10[(CH 3).N +]a[Si a0 20 ] S -
" The constants for the "cyclic trimer," as compared to those of the cyclic tetramer, suggest
that it is more stable and less reactive even though the trimer ring should be under greater
strain
Source. Hoebbel et al. (84).
results on sols of particles only 3-4 nm in diameter with a specific surface approaching 1000 m 2 g-l.
However, in sols of such small particle size. there is an appreciable concentration
of monomer at equilibrium. Also, in alkaline sols at pH 9-10.5, there is an appreciable amount of ionic silica which is converted to monomer before the titration. Since
monomer reacts with base at pH 9 it is therefore necessary to correct the titration
for the effect of soluble silica in order to obtain a reliable value for the specific surface area of the polymer. The term "soluble silica" is used to include the ionic silica
and dimer which react with alkali-like monomer.
The soluble silica can, of course, be removed at pH 2 either by washing the silica
in a filter or ultrafilter or by centrifuging. Also the sample can be adjusted to pH 8
and let stand a few hours until the soluble silica has been polymerized upon the
colloidal material.
.;.. .J
. ~l,
:....---
ica
However. for colloids of extremely small particle size or dilute sols .....'here an
appreciable fraction of the silica is present as soluble silica. it is preferable to
determine the amount of monomer by suddenly acidifying a sample and determining
it by the molybdate method, after which the corresponding correction can be made.
205
Correction/or Soluble Silica
'Q
gest
ater
.ch-
.ion
ciance
.ion
surlica
lica
H8
thl'
In the Sears procedure, titration with 0.1 N NaOH is begun with a silica sample in
150 ml of solution containing 30 g NaCl at pH 4.0.
As a source of soluble silica a 0.1 % solution of Si0 2 from Na 2SiOJ 9H 20 in 0.1 N
NaOH was used. Different volumes (x ml) of this solution were added with rapid
stirring to 135 - x ml of water containing 1.25 ml 4 N HC!. Then 40 g NaCI was
added and the pH raised with 1.0 N NaOH to 3, and to 4.0 with 0.1 N NaOH, as
ra pidly as possible.
.
The mixture was immediately titrated with 0.1 N NaOH solution rapidly to pH
9.0 and the volume noted. Samples of the final solution were then analyzed by the
molybdate method to determine how much silica was still present as
monomer-dimer (reaction time 2-3 min). When no more than 200 ppm of monomer
was added at the beginning, essentially all of it remained, showing .that it had not
polymerized. Blank titrations were also run on x ml of 0.1 N NaOH containing no
silica. This blank titer was 0.3 m 1.
With samples ranging from 3.8 to 45 mg Si0 2 , a net titer of 0.135 0.005 ml 0.1
N NaOH mg " ' was observed. To convert the Si(OH)4 completely to HSi0 3 - would
require 0.166 ml mg- 1 Hence the soluble silica is 81.3% ionized at pH 9 in the NaCI
solution. [From this it can be calculated that in this 3.4 N NaCl solution, pK a for
Si(OH)4 is 8.37.] Then in titrating samples for surface area, for each 100 ppm soluble silica (15 mg) in the 150" ml of mixture being titrated, a correction of 2.08 ml 0.1
N NaOH should be substracted.
As an example in which this correction is significant, consider the surface titration
of a 4 nm sol containing 5% Si0 2 at pH 10 that has stood until the total soluble
silica (154 ppm) plus ionic silica is 439 ppm. Usually a 1.5 g sample of Si0 2 is used
for surface titration. Thus 30 g of sol is required and this contains 439 ppm of soluble silica. This will be diluted to 150 ml for titration, resulting in a concentration of
88 ppm of monomer. This then requires a titration correction of 1.83 ml 0.1 N
NaOH. The total titration volume is 25.9, which would give an uncorrected area of
734 rn' g-I. After substracting the correction, the surface area of the colloid is 686
m 2 g-I, a difference of 6.5%.
Determining the surface area of silica by the Sears method has been automated by
Meffert and Langenfeld (86a). They used a saturated solution of sodium chloride
containing suspended fine salt crystals which seemed to scour the silica off the surface of the glass electrode where it otherwise was deposited and gradually changed
the electrode characteristics. An automatic titrator was used so as not to exceed pH
9 at any time. Using the formula
'....: ;', :.
~
.,
206
specific surface area (rn" g-l)

ml 0.1 N NaOH required from pH 4.0 to 9.0 for 1.5 g SiO z
blank titer (ml)
Meffert found K = 25.2 when using a solution volume of 200 ml saturated NaCl
solution. This compares with K = 26.5 usually found with the Sears method using
150 ml of 200 g 1-1 NaCl. Vb is 1.3 ml for Meffert's and Langenfeld's method and
0.75 ml for Sears's.
Coagulation by Gelatin-Salt
','
As the ultimate particles of polysilicic acid begin to aggreate into chains and small
three-dimensional networks, the increase in size of the polymeric species can be
followed by an empirical procedure involving the precipitation of a complex of the
silicic acid with a given type of unflavored "edible gelatin" (86b). For a given sol the
method can be standardized by measuring the molecular weight by the freezing point
method.
The method is based on the fact that at pH 1.5-3.5, gelatin alone is coagulated
from dilute solution above a critical concentration of sodium chloride. This critical
salt concentration decreases with increasing molecular weight of the gelatin. When
polysilicic acid is present it hydrogen-bonds and cross-links a given type of gelatin,
thus in effect increasing its molecular weight. Then a lower salt concentration is
required for precipitation.
However, as the molecular weight of the polysilicic acid is increased, it soon
reached the point where, with the particular gelatin used, precipitation occurs even
without adding salt. To increase the range of the titration; a competitive low
molecular weight hydrogen-bonding agent is used, specifically the diethyl ether of
diethylene glycol (formerly known as diethyl Carbitol, or DEC). As shown in Figure
3.11, with increasing concentrations of DEC more salt is required in the system to
cause precipitation of the gelatin.
Since the tendency of silicic acid to be precipitated by gelatin increases as the
silicic acid polymerizes, all experiments are carried out near pH 2, where polymerization is least rapid. With a sol of a given age and at constant concentration of electrolyte, the precipitation characteristics are independent of pH in the range 1.5-3.5
and relatively independent of the concentrations of silicic acid and gelatin. When
other factors are held constant, precipitation occurs as the concentration of salt
exceeds a critical value. With the concentration of salt held constant, solubilization
of the precipitate occurs (or precipitation is inhibited) when the concentration of the
hydrogen-bonding agent exceeds a certain critical level. The coagulating effect of
salt is therefore offset by the solubilizing effect of the hydrogen-bonding agent on the
gelatin-silicic acid complex.
The general behavior of the system is exemplified in Figure 3. I I, which shows the
effects of concentration of sodium chloride, concentration of DEC, and the age of
the silicic acid solon the formation of a gelatin-silicic acid precipitate in a system
containing 0.5-2% gelatin and 1-5% Si0 2 at pH 2.5 and 27C. Each of the lines,
.v;
Silica
207
u
u
'0
....
1:lQ
NaCl
using
d and
10
U
d
Z
,,
small
In be
)f the
01 the
point
dated
-itica!
When
.latin,
.on is
SOOII
even
: low
ier of
'igure
ern to
s the
meri,elec5-3.5
Nhen
f salt
ation
if the
.ct of
n the
's the
ge of
'str
line,
,,
,
,,
,,
,
,,
,,
,,
,
,,
Figure 3.11 Precipitation of gelation-silica complex in the presence of a given concentration

of diethyl ether of diethylene glycol (DEC) occurs at concentrations of sodium chloride above
the indicated lines: A, gelatin without silicic acid; B, gelatin with low molecular weight polysilicic acid; C, D, E, with sols of intermediate ages and increasing sizes of microgel or
molecular weight: F, G, with sol approaching the gel stage. Scale on abscissa can be used as an
empirical measure of the degree of aggregation-polymerization of the silica. [From IIer and
Pinkney (98).]
representing a particular sol, is the borderline above which a precipitate is formed. It

will be noted that gelatin alone is salted out of water at pH 3 when the N aCl
concentration exceeds about 8 gj 100 ml. However, when DEC is present, a higher
salt concentration is required to cause precipitation, as shown by Line A of Figure
3.11. When silicic acid sols of increasing age are also present in the system, lines B
to G are obtained. An extrapolation of these lines to the DEC abscissa provides a
convenient scale for characterizing the state of polymerization of the polysilicic acid.
Before the effect of silicic acid in the system is discussed, the behavior of gelatin
alone should be considered. The hypothesis is advanced that gelatin molecules in
solution are associated with a sheath of water molecules, probably held by hydrogen
bonds. As salt is added, water is gradually removed from the gelatin molecules at an
increasing number of points. These dehydrated sites on different molecules then
associate with each other to form the cross-linked, gel network which is the
precipitate. Shorter gelatin molecules of lower molecular weight thus' require a
greater number of cross-links and therefore a higher concentration of salt for coagulation. The solubilizing effect of the hydrogen-bonding agent is visualized as follows.
When DEC, for example, is present in the system, the addition of salt brings about
partial removal of water from the sheath surrounding the gelatin molecules as
before, but these sites are immediately covered by adsorption of DEC molecules, so
208
,
IJ
j:
l:
,
~I,
that cross-linking of gelatin molecules through hydrogen bonding at these' sites is

prevented.
The effect of silica might be explained as follows. The polysilicic acid molecules
may adsorb or otherwise hold together a number of gelatin molecules through
hydrogen bonding. Furthermore, the larger polysilicic acid molecules can adsorb a
larger number of gelatin molecules and thus form a larger complex unit. However,
this larger unit then behaves the same way as a single gelatin molecule of higher
molecular weight, requiring less salt for precipitation. The mechanism of aggregation of the gelatin-silica complex is therefore the same as that of gelatin alone, as
indicated by the parallel slopes of the lines.
A titration procedure is as follows. A 10 ern" sample of a solution of silicic acid,
free from organic solvents and containing 4-6% Si0 2 at a pH of 1.5-2.5, is pipetted
into a I x 8 in. test tube. To this is added 2-3 cm' of an aqueous solution of dicthyl
ether of. diethylene glycol (diethyl Carbitol) containing 500 g I-I, the pH being
adjusted to 2.5 with HC\. To this is added 5 em? of a 2% solution of high grade edible gelatin. Sufficient diethyl Carbitol solution is used to prevent the formation of a
precipitate when the gelatin solution is added. This mixture' is then titrated with a
standard solution of NaCl containing 300 g I-I (previously adjusted to pH 2.5 with
HCl) until the solution becomes turbid. This is observed by holding the tube against
an aperture % in. in diameter illuminated from behind by a 60-watt lamp. The end
point is arbitrarily taken when the clear outline of the aperture can no longer be
discerned. This relatively crude method is satisfactory, since the end point is quite
sharp; the mixture usually changes from perfect transparency to extreme turbidity
within 0.2-0.3 em", The mixture is shaken vigorously for about 10 sec after each
addition of salt solution before the turbidity is observed. The turbid solution is then
cleared by adding another 1-2 ern" of diethyl Carbitol solution and again titrated to
the end point with NaCI solution. At each end point the total concentrations, in
grams per 100 ern", of NaCI and of diethyl Carbitol are calculated, with the total
volume at each end point taken into account. These values are plotted as in Figure
3.11.
The position of the lines obtained with sols of increasing molecular weight move
progressively to the right-that is, higher concentrations of diethyl Carbitol are
required to prevent precipitation. The intercept on the diethyl Carbitol axis therefore
served to indicate the relative molecular weight of the silicic acid.
In order to have an arbitrary scale with positive values, a function X was adopted
such that
where C = intercept on diethyl Carbitol axis. This "X value" then ranges from zero
for gelatin solutions alone (or for silicic acid sols of extremely low molecular weight)
to about 11 or 12 for silicic acid solutions which have polymerized to the gel stage
and which, therefore, contain material of high molecular weight.
In the case of polysilicic acid obtained by adding a 3.25 ratio sodium silicate solution to a rapidly agitated solution of acid to obtain a final pH of about 2. the relation between X value and the degree of polymerization as the silicic acid polymerizes
:~
,
.~
209
10
Z
u,
I-
o
o
a:
~
<
::>
o(/)
10
X - VALUE
Figure 3.12. Relation between "X value" and degree of polymerization, N determined cryroscopically.
is shown in Figure 3.12. In effect. the method indicates the degree of aggregation of
discrete particles of silica. In the present instance the initial discrete polysilicic acid
particles are about 2 nm in diameter. If one starts with particles 5 nm in diameter and
follows the aggregation process as the sol is being transformed to gel. the titration
procedure gives a series of lines similar to those of Figure 3.11. but ofa different slope.
MECHANISM OF CONDENSATION AND HYDROLYSIS
As discussed in connection with the isoelectric point of silica the rate of polymerization of monomer and formation of silica gel is at a minimum at around pH 2. It has
been assumed that since this is the isoelectric point of silica, the catalyst below pH 2
is the H+ ion which forms an active cationic complex. Also, above pH 2 the OHion is the catalyst in that active anionic silica is generated.
However, lIer (87) discovered that the pH at which the polymerization rate is at a
minimum is .strongly influenced by traces of fluoride ion, as little as 10- 4 M
concentration (1.9 ppm F) having a marked effect. Since traces of fluorine are difficult to avoid it was suspected that the catalytic effect of H + ion might depend
entirely on fluoride impurity. However. in view of the observations by various
workers on highly purified silica systems, it is now apparent that the effect of
fluorine is merely superimposed on the effect of H ion alone. The self-condensation
of monomer catalyzed by OH - ion is commonly written:
2 Si(OH)4
."
'.
"
~,
ih
..J'
'\
:u:;~~ .~
,..
4
210
Treadwell and Wieland (88) advanced the following hypothesis:
;1
In order to explain the mechanism of the polymerization of silicic acid, we would have to
start with the fact that the tetravalent silicon is still unsaturated coordinatively. Both of the
strongly defined secondary valences which are active in the fluoride complexes of silicon must
also playa role in the hydrated OXIde.
Iler (89) represented an intermediat-e 6-covalent stage shown in Figure 3.13, and
A. Weyl (90) postulated even more extensive complexes involving 6-coordinated
silicon.
There appears to be a basic difference in the polymerization mechanism below
and above pH 2. (See also foregoing section on the isoelectric point.) Above pH 2,
the rate of disappearance of monomer is a second order reaction; below 2 it is third
order. The order of the reaction has been explained by Okkerse (91) on the basis
that silicon increases its coordination number to 6, as a three-silicon intermediate is
formed below pH 2, shown at B in Figure 3.13.
/ ,I,
'HO
O--Si~OH
Figure 3.13. Possible intermediates in polymerization of silica: A, two-silicon anionic complcx involving OH - ion; B, three-silicon cationic complex involving H - ion [Ok kcrsc (29. 91)]:
C and D, suggested alternates to A: E, intermediate at silica surface.
211
Above pH 2 a proposed alternative to A involves only two silicon atoms, a's at C

in Figure 3.13. Another structure for the intermediate was suggested by Dalton (92).
shown at D. If one or both of the silicon atoms should be part of a polysilicic acid or
surface of a silica particle. only a coordination number of 5 might be involved. as at
E.
In any case it is supposed that when silicon becomes coordinated with five or six
oxygen atoms all the silicon-oxygen bonds are weakened so that rearrangements can
occur. This has been considered in considerable detail by Strelko (93). who proposed
.
the following rate equation for the pH range from 2 to 10:
where K D = M-[H+]/M, M and M- are the concentrations of Si(OH). and

HSi0 3 -. and C is the total concentration of Si0 2 Here
M-
=C- M
and
This equation corresponds to a maximum in the rate of polymerization somewhere

in the mid-pH range.~,,,,
A general theory of polycondensation equilibrium in silicic acid solutions was
proposed by Stober (94). From it he deduced the concentration of monomer in equilibrium with polymers of different degrees of condensation. Further data are needed
to check the validity of the complex equations that were developed.
Catalytic Effect of HF
Traces of fluoride ion have a marked catalytic effect at low pH where it is mainly
present as HF. Her (87) found that. whereas the polymerization reaction is catalyzed
above about pH 2 by hydroxyl ions as reported by others. at lower pH the polymerization is catalyzed by hydrogen fluoride. or more specifically the rate is proportional
to the concentrations of hydrogen ions and fluoride ions (Figure 3.14).
The value of the pH for optimum stability of silicic acid depends on what
impurities are present in the solution. Traces of aluminum ions and to a lesser
extent. iron. thorium. and beryllium ions tend to offset the effect of fluoride ion by
forming complex fluorides and thus retard polymerization in this pH range. Depending on the purity of the solution. the pH of optimum stability may range from I to
as high as 3-3.5. In silicic acid solutions free from aluminum impurity. as little as I
ppm of fluorine has a marked effect on the rate of polymerization in acid solu tion.
Iler advanced the hypothesis that the polymerization mechanism may involve the
temporary expansion of the coordination number of silicon from four to five or six,
just as in the case of OH- ion. It is not known whether the Hf'-catalyzcd reaction is
third order as in the H +-catalyzed reaction in the absence of fluoride below pH 2. or
I,
--
100
SODIU),l FLUORIDE -
r.lILLll.lOLAR CONC.
.~
0.7
,,
i.
en
c:
::J
:z:
10
I..J
W
C)
SOL-I.O r.lOLAR Si0 2

0.3 MILLIMOLAR AI 20 3
FROM COMMERCIAL SILICATE
1.0
pH
2.0
Figure 3.14. Effect of fluoride ion on gel time of silicic acid sols; line H represents effect of
hydroxyl ion (Iler). Below the iscelectric point. pH 2. the gelling rate (inverse of gel time) is
proportional to H' ion concentration and also to F- ion concentration. provided the
concentrations of AP- and Fe3 - impurities remain constant. Thus the catalyst is HF. [From
lIer (89).]
212
:..-.
213
whether it is second order and therefore analogous to the OH -catalyZed reaction

above pH 2. Strelko also recognized the possibility of alternate reaction mechanisms
but there are insufficient experimental data to make a choice.
Whereas lIer showed the effect of fluoride on rate of gelling which is the final
stage in polymerization, Tarutani (95) demonstrated that it accelerated the
polymerization of monomer which disappeared at a rate proportional to F- ion up
to 19 ppm fluorine in 3 N HCI. Fluoride had no effect at pH 7. Tai and Chen (96)
found that when silica gel was formed at low pH in the presence of fluoride ion, the
latter was held on the gel and none appeared in the syneresis liquid. In an alkaline
medium no fluoride ion was held.
The removal of F- ion by AI3+ can be estimated from the stability constant for
AIF,,_t + F = AIF", as measured by Agarwal and Moreno (97a). The values at
25C of K" for n = 1,2,3,4, were 6.69,5.35,3.68, and 2.75 (all less than O.04).
The equilibrium constant involving formation of SiF/- in the presence of excess
Si0 2 is as follows, according to Scherban (34b):
SiF~-
+ 2 H 20
[F-]6 [H+]4
[Sin-]
Si0 2
+ 6 F- + 4 H+
10- 17
POLYMERIZATION: pH 2-7
It is necessary to consider the polymerization of silica in solution below pH 7
separately from that above pH 7 for the following reasons:
.
I. It is only at low pH that the polymerization is sufficiently slow to allow the early
stages to be followed. Changes that occur in hours at pH 2 are completed in
minutes or seconds at pH 8-9.
2. The polymer units or particles formed at low pH bear no charge and unless the
silica concentration is very low, aggregation begins to occur soon after polymeric
particles are formed, not only because of the lack of charge on the particles, but
also because the particles are extremely small and cease to grow after they reach
a diameter of 2-3 nm. Since the rate of aggregation depends mainly on the
number of particles per unit volume and less on their size, aggregation occurs
even at very low silica concentrations.
:ct of
ne) is
j the
From
3. Above pH 7 particle growth continues up to a larger diameter, depending mainly

on the temperature, unless aggregation or gelling takes place when an electrolyte
is present in an amount approaching the critical coagulation concentration at the
pH of the sol.
It is therefore only at low pH that the progressive polymerization of monomer can be
followed and the initial formation of three-dimensional condensed silica polymers or
nuclei particles can be observed. The general observations of investigations are summarized here, but detailed discussions are included later.
214
Formation of Oligomers
By "cligorners" is generally meant the low molecular weight polysilicic acids from
trimer to perhaps octamer or dodecamer which react within 10-20 min with the
usual molybdic acid reagent. This includes linear, cyclic, and polycyclic polysilicic
acids. Their completely trimethylsilylated esters are generally distillable under high
vacuum and, except for monomer, are solids. No clear-cut distinction from
somewhat higher polymers appears to have been made. However, there may be good
reason for this. Once this degree of polymerization has been attained, further
increase in particle size of molecular weight occurs rapidly if monomer is still available or the overall silica concentration sufficiently high.
The peculiar polymerization behavior in this system appears to be explained by
the following:
1. Monomer, Si(OH)., has a pK a of about 9.9.
2. Dirner pKa is reported higher but is likely lower than that of monomer.
3. Higher polymerized species have a much lower pK a approaching 6.7 and hence
are more highly ionized than dimer or monomer.
This implies that the greater the number of siloxane linkages and the fewer OH
groups on a silicon atom, the stronger the acidity. Although the dimer was reported
as an exception in the acidity series, this seems doubtful.
Si(OH)4
<
=SiOSi(OHh
=SiQ
=SiO
=Si/
=Si/
'\Si(OHh < =SiO-SiOH

\
<
As previously mentioned, polymerization involves intermediate ionization to

=SiO- or to =Si+ below or above pH 2, respectively, but to simplify discussion only
==SiO- is used as the example.
It should be understood that in the following formulations the ions are represented
as anhydrous whereas they probably are associated with water in the form of
hydroxyl groups and in hydrogen-bonded forms. In the absence of specific
knowledge the anhydrous forms of the ions are used.
The key point is that condensation involves the reaction of an =SiO- ion with a
nonionized silanol group:
=SiO-
HOSi=
->
=SiOSi=
+ OH-
Then the following is evident:
I. At low pH where Si(OH)4 is ionized only to a very small degree and no polymeric
species is present, dimerization is slow.
.,
'Silica
215
2. Similarly, if dimer is a stronger acid than monomer, the main reaction-is with
ionized dimer:
fr,
.h the
silicic
," high
from
good
rrther
vaila-
(HO)3SiOSi(OH)20-
3.
4.
ed by
5.
hence
r OH
iorted
In to
1 only
.ented
'm of
iecific
6.
+ Si(OH).
(HOhSiOSi(OHhOSi(OH)3
+ OH-
However, the existence of linear trimer is transitory and concentration probably

remains low.
Owing to the ionization of dimer it can combine also with its own ionized species
to form linear tetramer.
Owing to the proximity of SiOH end groups in a given linear polymer, for
example, tetramer, and low concentration of monomer, ring closure is rapid.
Cyclic tetramer is mainly formed (84) since bond angles make ring closure of
linear trimer unlikely.
Once the cyclic species predominate, monomer and dimer react preferentially
with these more highly ionized species, increasing their molecular weight.
At the same time, the adjacent SiOH groups on the polymers condense wherever
further ring closures are possible, leading to more compact, three-dimensional
species, the precursors of colloidal particles.
The simple polysilicic acids can be represented by conventional formulas as in

Figure 3.15. As the, polymers become three-dimensional they can be shown instead
with spheres representing oxygen atoms arranged tetrahedrally about silicon atoms
which cannot be seen, as in Figures 3.16 and 3.17. In Figure 3.17 the symmetrical
structures of the double cyclic trimer and double cyclic tetramer (cubic octamer) are
shown as models of the smallest three-dimensional, fully condensed species.
However, these have never been isolated from polymerizing. solutions since they
would form only a small fraction of all the three-dimensional species that can be
formed by random combinations of monomer and various lower oligomers present.
After the three-dimensional species have been formed with their more highly
ionized silanol groups, the remaining monomer and dimer react preferentially with
them and through ring closure build up larger spheroidal particles as in Figure 3.17.
These roughly spherical polymers undergo further internal condensation and rearrangement to a more compact state. This change is rapid at pH above 7 and especially at elevated temperature, forming colloidal particles with a core of Si0 2 and a
surface of SiOH groups.
'lith a
Oligomers as Particles
meric
It has been generally known that when monomer polymerizes in alkaline solution
in the pH range 8-10 colloidal silica particles form quickly and grow spontaneously
to recognizable size. The possibility that three-dimensional or particulate polymers
of "subcolloidal" size form during the polymerization of monomer soon after cyclic
oligomers appear has not been generally recognized. However, particles about 20 A
in diameter corresponding to a degree of polymerization around 100 wert: shown to
::-#.- --,
...... __ ...
:-:-=-}':i,
o
o
o
HOSiOH
o
HOSiO- +
HO~iO~iOH + OHaH H
H H H
a
HaSiOH+
a
o 0 0
HOSiaSiOSiaH + OHa 0 0
H H
se
a a
HaSiOSi OH
H H
ao
o 0 a 0
HaSiOSiOSiOSiOH
+ ow
H H
H H
0
HOSiOHOSiOH
H H H H
H H
HOSiOSiaH
OW
H H H H
H H
H H
a 0
a a
HaSiaSiO- + HOSiOSiOH
Hot
a a
HOSiOSiOH
a 0
+
HaSiOSiOH
a 0
H20
H H
Figure 3.15. Conceivable steps in the polymerization of silica to cyclic species. However.
consideration of bond angles makes the formation of cyclic trimer much less likely than cyclic
tetramer. [From Iler (97b), permission of Plenum Press.]
Figure 3.16. Molecular models of silicic acids of Figure 3.15. Spheres represent oxygen
atoms; black dots, hydrogen atoms. Silicon atoms within oxygen tetrahedra are not visible.
Not all hydrogen and oxygen atoms are visible: (I) Si(OH ).: (2) (H OhO SiOSi(O H),: (3)
(OHh SiOSi(OHhOSi(OHh: (4) [(OHl,SiOh: (5) [(OH>,SiOj. The existence of cyclic trimer
is questionable. (From Iler (97b). by permission of Plenum Prcss.]
216
:~
polymerization: pH 2-7
217
B~
Figure 3.17. Models of (A) cyclic trisilicic, (B) cubic octasilicic acids, and (C) and (D) the
corresponding theoretical colloidal particles formed by condensing monomer to form closed
rings until the original species is completely surrounded by one layer of deposited silica bearing
silanol groups. When formed above pH 7 the inner silica contains few silanol groups. Different
kinds of incompletely condensed oligomers could form the cores of colloidal particles. There is
no evidence that A and B are specifically involved. Spheres. oxygen atoms; black dots.
hydrogen atoms. Silicon atoms are not visible. [From lIer (9ib) by permission of Plenum
Press.]
n cyclic
o\ygt:n
visible.
H),; (3)
: trimer
be present in polysilicic acid formed and aged at pH 2 (98). The possibility of

smaller spherical polymers with even lower degrees of polymerization was not
recognized until corresponding siloxane structures were shown to be formed by the
hydrolysis and polymerization of compounds of the type RSiCI 3. Scott (99) first
isolated the compound (CH 3SiOI . s)n, which sublimed without melting, and concluded the molecular weight was low but n was not determined.. A spherical siloxane
polymer was made by Olsson (100) in the form of the compound (C2HsSi)a0I2 or
(C 2HsSiO I . s)a. This molecule was reportedly so inert that it was not attacked by
refluxing nitric acid, aqua regia. bromine, perchloric acid, or 60% aqueous KOH.
Evidently the ethyl groups are so closely packed around the spherical core of silica
that only the very inert CH 3 ends are exposed at the surface of the molecule.
The corresponding siloxane (HSiO I . 5 )a was obtained as a crystalline compound
(m.p. 250C) by MUller, Kohne, and Sliwinski (10 I). If this were oxidized in dilute
solution it might yield the pure octasilicic acid.
When R is a bulky alkyl group, the condensation of RSi(OH)3 is forced into the
smallest possible three-dimensional unit, polycyclic tetramer, (RSiO I . s ). (102).
However, it is unlikely that this tetrahedral structure involving only four silicon
atoms can be formed by polymerization of monomer in water, since it was not
formed from RSi(OH)3 unless the R groups were bulky.
Further examples of small, generally spherical siloxanc structures of the type
(RSiO I ' 5 ) 1l were furnished by Barry et al. (103), who prepared the cubic octarner and
also a hexaprisrn 12-mer consisting of two parallel hexagonal rings linked together
through oxygen atoms. where R was methyl. ethyl. II-propyl, II-butyl, cyclohcxyl,
and phenyl. The phenyl group was sufficiently bulky to cause the formation of the
hexarncr in which two parallel trimer rings were linked together through oxygen
':..----
218
atoms. Thus from a structural standpoint corresponding polysilicic acids should be

capable of existing as the smallest possible "particles" of silica.
However, in water, condensation of Si(OH)., dimer, and trimer with cyclic
species, for example, tetra mer, must occur randomly. Thus it is not likely that any
regular three-dimensional fully internally condensed species such as cubic octasilicic
acid, (HOSiO ,.5 )s, will be formed in appreciable amount. Instead, less regular,
incompletely condensed three-dimensional oligomers must appear. Later, after
higher molecular weight polymers equivalent to very small particles have appeared,
the more soluble oligomers depolymerize or dissolve and the dissolved silica' is added
to the growing particles.
Nucleation Theory
It should be noted that in this system, polymerization, in terms of formation of

siloxane bonds, is a reversible process. The concentration of OH - ion that promotes
ionization and condensation equally promotes hydrolysis and depolymerization.
Thus each polymer species is in equilibrium with a certain concentration of
monomer in solution. Three-dimensional polymer units larger than the double-threering hexamer or similar species can be considered to be the core of a particle. A
polycyclic octamer or decamer is not actually a silica particle because there is no
anhydrous Si0 2 "core." As additional monomer condenses with SiOH groups on
these oligomers they also condense with themselves until the oligomer remains as an
anhydrous Si0 2 core surrounded by a layer of silica in which the silicon atoms retain
outwardly disposed silanol groups as shown in Figure 3.17.
In studying models it is found that when an oligomer such as octamer, or
decamer, is the starting point for further addition of monomer, the geometry is such
that by the time the original oligomer has become fully condensed to a nearly anhydrous "core" of Si0 2 surrounded by silicon atoms forming the outer hydroxylated
surface of the particle, the latter must contain 40-50 silicon atoms.
It is interesting that the formulas calculated for the composition and size of silica
particles in Chapter 1 give values in this range. Thus a 48-mer would have an OH: Si
ratio of 0.8-0.5 by calculation, whereas on the model it appears to be about 0.7. The
calculated hydroxylated diameter is 1.6 nm and from the model it appears to be
about 1.3 nm. The equivalent diameter of an anhydrous Si0 2 particle is 1.09 nm.
Even a "40-mer" particle is probably in solubility equilibrium with monomer and
should be large enough to follow the equation relating solubility and particle size, at
least approximately, although the surface energy must change somewhat as the
radius of curvature approaches atomic dimensions. Once such nuclei have been
formed, they grow by the addition of whatever monomer remains in solution and are
further supplied by dissolution of oligomers.
The theory of homogeneous nucleation has apparently not yet been developed on
a quantitative basis, but some relationships have been considered between degree of
supersaturation, interfacial energy of silica to water, and the critical size of nuclei.
A major difference between the silica-water system and other aqueous solutions
of inorganic compounds is that in the case of silica a catalyzed making and breaking
of siloxane bonds occurs. whereas no such requirement for a catalyst seems to be
f!.
,f Silica
uld be
C),
at any
rsilicic
egular,
after
-eared,
added
ion of
.motes
I.
ion of
-threecleo A
: is no
IpS on
; as an
retain
er, or
s such
anhyylated
. silica
)H:Si
7. The
to be
n.
~r
and
ize, at
IS the
been
ad are
on
ree of
lei.
utions
.ak
to ~_
led
219
involved in the nucleation and growth of molecular or ionic crystals, for example,
sugar or BaSO~. In most systems, heterogeneous nucleation is difficult to avoid
owing to the presence of minute impurities in suspension, but this is not the case
with silica. It is, of course, possible to supply particles with a large receptive surface
areas, such as a finely divided metal oxide or silica itself to a solution of monomer
and thus prevent self-nucleation. However, unless colloidal material is deliberately
added, a supersaturated solution of silica undergoes spontaneous homogeneous nucleation that seems to be unaffected by small amounts of foreign matter. The homogeneous nuclei are formed by condensation of monomeric Si(OH)~ when the
supersaturation ratio is sufficiently high.
The homogeneous nuclei are apparently in the same size range as those of ionic
materials, which, according to Walton (104), contain about 10-100 ions. In the case
of silica, 10-100 Si0 2 units corresponds to particles about 1-2 nm in diameter.
Experimentally, Nielsen (l05) found that with BaSO~ having an interfacial energy of
90 ergs cm -2, a supersaturation ratio of 21.5 was required for nucleation. If the
supersaturation ratio is the same function of interfacial energy as in the size-solubility equation, so that log R = kE, where R is the supersaturation ratio, then for
BaSO~, log 21.5 = k(90), whence k = 0.0148. Since the solubility of massive silica is
70 ppm and E is 48 ergs ern -2, log R = 0.0148(48) = 0.71, whence R = 5.12 and the
critical concentration for nucleation would be 5.12 x 70 or 358 ppm.
Marsh (32) followed the disappearance of monomer at pH 8 where therelatively
high concentration of hydroxyl ions permits dissolution-deposition to occur rapidly.
He observed that there was an induction period as though nuclei were being formed.
The period ranged from about I min at a monomer concentration of 697 ppm, to
1000 min at 359 ppm, indicating possibly that the critical supersaturation ratio may
be of the order of 5-10. This is within the range of R calculated above.
Dunning et al. (106a, 106p) have developed equations relating the rate of formation of nuclei to the supersaturation ratio and surface energy of the nuclei. Assuming
that nucleation became apparent when new nuclei appear at a rate of 100 ern -3 sec- 1
and taking the interfacial tension as 48 dynes em -1 and the solubility of massive
amorphous silica as 70 ppm, a supersaturation ratio of about 7 or a critical nucleation concentration of 500 ppm was calculated. This appears to be of a reasonable
magnitude (I06c).
Definitive data on nucleation of colloidal silica particles in brine solutions at pH
4.5-5.5 and 95C have been obtained by Makrides and associates in a study related
to the deposition of silica from hot geothermal waters (106d). Their work showed
conclusively that a solution of monosilicic acid requires an induction period for the
formation of nuclei that strongly depends on the degree of supersaturation. Under
these conditions appreciable time is required for the early stages of polymerization
to produce three-dimensional polymer particles of the type that can function as
nuclei. With a supersaturation ratio of 2-3. the nucleation time ranged from a few
minutes to several hours.
A theory of nucleation was developed. based on an interfacial surface energy of
the silica-water interface of about 45 ergs ern - I in good agreement with the values
obtained from solubility studies (Chapter I). Fluoride ion at 10-100 ppm accelerated
nucleation and particle growth.
II
'T
-,,':.-0",
0"-.- ,
" i
220
Particle Growth in Acidic Solution

Since the growth of amorphous silica particles involves the random aggregation of
SiO. tetrahedra, a model developed by Ordway is of interest (107). Thus on a growing sphere, Si(OH). will condense preferentially at a site where the silicon atom on
the surface bears only one OH group and is therefore the most acidic and readily
ionized. The model was built up to a "degree of polymerization" of 300 in the form
of a sphere free from voids. As soon as a certain concentration and surface area of
nuclei have been formed, the remaining monomer and dimer react preferentially
with the nuclei because of the greater acidity and degree of ionization of the polymer
surface. As the concentration of monomer and dimer decreases, the oligomers,
which have been in solubility equilibrium with the higher monomer concentration,
depolymerize and the dissolved silica adds to the growing nuclei.
As will be seen in experimental studies to be discussed later, the general course of
the polymerization to form high polymer is typified by the results of Weitz, Franck,
and Giller (l08). To make it possible to follow the polymerization, the initial
monomer concentration was 4000 ppm and the pH was 3 so that the changes were
relatively slow. The oligomer consisted of polymers which were low enough in
molecular weight to depolymerize and react with molybdate reagent, although the
reaction rate dropped as the average molecular weight increased. The concentration
of oligomers reached a maximum when about half the monomer 'had been
polymerized. At this point colloidal particles of higher molecular weight began to be
formed at the expense of oligorners, which then decreased in amount.
In the early stages of conversion of silica to particles, where the concentrations of
oligomers are decreasing, it is probable that once a certain concentration of nuclei
has been reached, they remain constant in number as they grow in size. When
oligomers have been consumed, the particles then grow in size at the expense of the
smaller particles, and thus decrease in number.
In acidic solution at 25C these changes can be followed only under conditions
where the solution is so dilute that the rate of aggregation is slow in spite of the lack
of charge stabilization. The low pH also minimizes siloxane bond formation upon
collision. However, aggregation inevitably occurs at low pH although only a viscous
suspension, rather than a gel, is formed in very dilute solutions. In any case, because
at low pH particles do not grow much larger than 2-3 nm in diameter and because
the minimum concentration for gelling varies inversely with particle size (Chapter 4),
gelling will occur even at a concentration of 1% Si0 2 or less.
In alkaline solution above pH 7, all these early stages of polymerization occur
very rapidly and particle growth by "Ostwald ripening" continues as the charged
particles remain as sol.
Depolymerization in Acidic Solution
A study of depolymerization of low polymers suggests that the degree of internal

condensation within three-dimensional polymers depends on the temperature at
which they were made or to which they have been heated. Even more importantly it
~._-
f Silica
iOI.
growern on
.eadily
; form
.rea of
ntially
ilyrner
omers,
'ation,
irse of
ranck,
initial
) were
igh in
gh the
ration
been
I to be
polymerization: pH 2-7
22J
depends on the pH since the rate of internal condensation within the three-dirnensional polymer units is controlled by the OH - ion concentration. Even at pH 2-3
there is a marked difference and at pH 8 the rate is many orders of magnitude
greater. As a result the rate at which polymer units of a given size depolymerize in
the molybdate reagent is much less when the polymer has been exposed to higher
temperature or to higher pH. .
Depolymerization of polysilicic acid was studied by Stade and Wieker (l09), who
prepared a solution of polysilicic acid containing a minimum of monomer by
dissolving (Li 2Si0 3)n powder in dilute acid at OC. Samples were then diluted to 12
ppm Si0 2 in water at pH 1.3-5.5 and the depolymerization to monomer followed at
different pH values and temperatures. The rate of depolymerization was followed by
removing samples periodically and analyzing for monomer in solution by the molybdate method of Alexander (24a). At the same time the rate at which the residual
polymer reacted with molybdate was also measured.
Figure 3.18 was drawn from data given by Stade and Wieker (109) and shows that
the half-life of the polymer at 12 ppm in water is at a maximum, that is, the rate of
depolymerization is at a mimurnun, at about pH 2.5. However, the effects of
/
1
or.
1\
\
nucrei
When
of the
(/)
0::
::::)
litions
elack
upon
iscous
ecause
ecause
ter 4),
occur
iarged
:c
0::
~ 10
oalL.
W
u,
-l
I
10
u,
-l
oCt
:c
ternal
He
ntly ,
pH
Figure 3.18. The effect of pilon the rate of dcpulyrncrization of silica at

12 ppm SiO~. (From Stade and Wicker (109).J
a to 65C diluted to
II
,-
-.
.~-'
............ r
222
temperature and pH are quite complex. It is probable that this is because ~\'O dif.
ferent reactions are going on simultaneously.
When polysilicic acid is formed at low pH at OC, polymer particles are formed,
but the inner SiOH groups are not all fully condensed. However, when such a sol is
warmed and/or the pH is raised. above 2, further internal condensation occurs. It is
therefore logical to expect that if the sol is diluted at OC, only depolymerization
will occur. However, if the temperature is raised, or if the pH is also raised, two
processes occur. The particle starts to depolymerize or dissolve, but also it condenses
internally with formation or more siloxane bonds that must later be broken to form
monomer for reaction with molybdic acid. Thus the reaction rate with molybdic acid
is greatly reduced.
Evidence for this is that the reaction velocity constant for the polymer made and
diluted at OC was 0.046 min-I, but when it was diluted at 25C the constant dropped to 0.03 min ? after 5 min. Additional evidence is that when depolyrnerization
was followed at OC where no internal changes occur in the polymer and only
depolymerization occurs, the rate of depolymerization in the range from 3 to 5 was
exactly proportional to the OH - ion concentration.
POLYMERIZATION BY AGGREGATION-GEL FORMATION

As already briefly described in the general theory of mechanisms and shown in
Figure 3.1, when silica particles are not charged, they link together into branched
chains to form three-dimensional network regions in the sol. These microgel regions
grow at the expense of the sol regions until the solid microgel occupies about half the
total volume, at which point the viscosity becomes infinite and the sol has reached
the "gel point."
A more detailed discussion of gel formation is reserved for a later chapter on
silica gels and powders. Meanwhile, to understand the role of aggregation in the
polymerization of polysilicic acid it is necessary to discuss the mechanism by which
the molecular weight of silica increases by aggregation of particles or small spherical
polymers.
Molecular Versus Particle Chains

In the silicic acid system, the formation of gel has usually been ascribed to the
condensation of Si(OH). into siloxane chains, then branching and cross-linking to
form a three-dimensional molecular network. Measurement of gel time has often
been used as an indication of rate of polymerization (90, 110-113).
Such a siloxane gel network might be obtained under conditions where
depolymerization is least likely to occur so that the condensation is irreversible and
siloxane bonds can not be hydrolyzed once they are formed. Thus Si(OH). made by
dissolving an anhydrous orthosilicate in anhydrous methanol-hydrochloric acid, or
by hydrolysis of methyl silicate with a theoretical amount of water in methanol, will
slowly form a gel. Owing to the insolubility of silica in the system (which is another
of Silica
Polymerization by Aggregation-i-GelFormatipn _
.wo dif-
way of saying that siloxane bonds are not readily broken) the condensation 'polymer
of siloxane chains cannot undergo rearrangement into particles. Even if some
extremely small particulate units were formed, they could not undergo Ostwald
ripening. Under these special conditions perhaps the polymerization of Si(OH).
might closely resemble the polymerization of a polyfunctional organic monomer and
may follow the corresponding theories which have been developed in organic
polymer chemistry.
However, the transformation of silica sols of relatively large discrete spherical
particles of known uniform size into firm homogeneous gels suggests that most, if
not all, silica gel networks may be made up to discrete particles rather than chains of
individual SiO. tetrahedra. Furthermore, it is becoming increasingly OO\10US that a
very early stage in the polymerization of Si(OH). involves the formation of cyclic
and then three-dimensional polycyclic polymer units that are, in effect, very small
Si0 2 particles bearing surface SiOH groups.
Also a study of the structure of even the finest-pore silica gels has led to the conclusion that they have a particulate structure. Vail (114) has pointed out that in silica
gel the particles grow in size, become more anisotropic, and coagulate by aggregation; that is, in the same volume of gel the individual particles may decrease in
number and increase in size. Signer and Egli (115) also concluded that the framework of silica gel was not made up of simple chains of Si-O-Si linkages. Even in the
case of silica gels made from 3.25 Si0 2 : Na 20 ratio sodium silicate. it is probable
that the network gel structure is composed initially of polysilicic acid uaits containing an average of 3-5 Si0 2 units each, since, as shown by Iler (116). tbe silicic acid
liberated from this silicate by acid is already polymerized at least to this degree.
On the basis of studies of the thermal aging of silica gels, Shapiro azd Kolthoff
(117) agreed with Elkins, Shull, and Roess (118) that the structure of silica gel could
best be visualized as being .made up of discrete particles. The latter authors estimated, from small angle X-ray scattering, that the average size of the primary particles, assumed to be spherical, in freshly prepared silica gel was around .:O-tO A.
for,
a sol is
rs, It is
rization
ed, two
ndenses
to form
die acid
ide and
it droprization
rd only
05 was
.own in
.anched
')
re,
half me
reached
pter on
I in the
y which
rherical
223
Mechanism of Interparticle Bonding
to the
king to
.s often
where
ble and
lade by
reid, or
10111
lnO~o.
The conversion of a sol of spherical particles to a uniform gel containing all the
liquid in the sol is not easily understood. When particles collide it is assumed that
adhesion can occur but in the case of silica particles there is reason to celieve that
the attachment is through the formation of Si-O-Si bonds. One reason fer thinking
so is that the same factors that promote polymerization of monomer and low
molecular weight silicic acids also promote the conversion of a sol oi colloidal silica
particles to a gel. Thus sols consisting of well-defined spherical particles form gel
least rapidly at about pH 2 and the process is accelerated by fluoride ices atlow pH.
One can only conclude that when particles collide, there are r.e:.:t::l.1 =SiOH
groups as well as =SiO- ionized groups on the surface of the particles which
condense to form Si-O-Si linkages by the same mechanism involved in the
polymerization of low molecular weight species. However, the presence of soluble
silica or monomer then plays a role of further cementing the particles together.
224
... ...
,
'0T'
o~
0101
OH
OH
OH
0",
0",
,,
,i
. ;
ow
catalyst
, ....----~
;
"'0 '
!-to
o~
"'0
1'40
0",
o ,.., T' 0
, 0",
Y', ...
...
",
"
i ,.
1
~'
~!
.i
'.~.
'!
:~
Figure 3.19. 'Bond formation between silica particles. With little or no charge repulsion. collision results in formation of interparticle siloxane bonds. catalyzed by base. Once bonded. the
panicles grow together.
...
Indeed it is even possible that the presence of Si(OH). at the point of contact
between colliding particles may playa role in promoting the formation of the initial
bond.
As shown in Chapter I. the solubility of silica at a negative radius of curvature is
less than that of massive silica. When two spherical particles come into contact there
is at that point an infinitely small negative radius of curvature and the solubility is
zero. Monomer will therefore be instantly deposited around that point (Figure 3.19).
\,
!
"
,"
Or
-,;:j
lica
polymerization by Aggregation-e-Gel Formation
225
Formation of Chains of Particles and Networks
olli-
th\:
tact
tial
e is
Jere
y is
9)
A silica sol of very small particle size which contains only 1% Si0 2, or about 0.5%
by volume of particles, will nevertheless solidify to a coherent gel containing all the
water of the sol. It is obvious that this can happen only if the particles can link
together into chains. As will be shown, these chains can develop into rods or
"fibers." It is therefore not surprising that there has been debate in the past whether
gels are made up of particles or have a fibrous structure or a solid structure full of
interconnecting pores like a very porous but uniform sponge. As is often the case in
such scientific arguments, each point of view may be essentially correct under
certain conditions. All such types of structures can be developed in the silica-water
system, depending on the original particle size and conditions of formation and
aging.
An electron microscopic study of fine-pored silica gel by Sugar and Guba (119)
revealed that the structure indeed was made up of a threadlike or fiberlike network,
but the fibers were made up of chains of spheres. The pore volume determined by
adsorption could be correlated with the observed size and spacing of the chains of
particles on the assumption that these were on the average cylindrical and that the
pore space was the complementary space of a skeleton built up of the network of
cylindrical elements.
The view that the structure of gel made from dilute hydrosol is better described as
"fibrillar matter" rather than as a series of independent particles was expresed by
Scott, Hockey, and Barby (120). The fact that the sol gelled at a concentration of
only 1-3% Si0 2 and was made at pH 3-7 by deionizing sodium silicate indicates that
the particles were less than 3 nm in size and that these must have chained together
into rather long chain segments between branch points. Evidently such particles
formed chains and coalesced into rods or fibers until they essentially lost their
particulate identity.
The aggregation of particles into chains was first explained by Usher (121) on the
basis that a single particle would preferentially aggregate with a neighboring pair of
particles to form a linear rather than triangular arrangement, since. the linear
arrangement requires the approaching particle to overcome the repulsive force of
only one of the particles of the pair. Rees (122) further analyzed the potential energy
contours around a pair of spheres in contact under different conditions of repulsion
and attraction. He showed that under conditions of high attraction, where presumably rapid coagulation occurs, compact three-dimensional aggregates occur, but
under conditions of low attraction chainlike aggregates arc formed. In the case of
silica. in the neutral pH range with coagulating salt present, a precipitate is formed;
when little or no salt is present chainlike structures art: formed leading to gel.
A study by Thomas and McCorkle (123) of the interaction of a linked pair of
spheres with a third approaching sphere showed that under certain conditions 'the
third particle "flocculates" or adds to the end of the pair and subsequent particles
add to the end rather than to the side of the growing chain. Applying the
Dcryaguin-Vcrwcy-Overbcek theory (124, 125). they developed equal-energy
contours around two spheres in contact. assuming certain zeta potentials and clcc-
.... y
:"{':'.,,:.~
... -f
..
".
.;
226
.
4
trolyte concentration. The contours show that a particle approaching" a pair or a

short chain of particles will have a greater probability of surmounting the charge
barrier if the approach is along the longitudinal axis. Thus the particle adds to the
end of the chain.
The question remains why silica sols will still form gels at pH 2, the isoelectric
point at which the charge' on the particles is presumably zero. It is true that gel
formation is slowest at this point, but this can be ascribed to the slowness with which
siloxane bonds are formed between particles at this pH. Nevertheless, silica particles
do chain together into a uniform gel structure at this pH and the structure is not any
different from that formed more rapidly at pH 3-5, for example. Also at the
isoelectric point no extreme retardation of gelling has been noted.
Since the formation of an Si-O-Si bond between two colliding particles requires
not only an SiOH group on one surface but also an ionized SiO- on the other surface, it appears that some ionization must occur even at the isoelectric point, pH 2.
But because the overall net charge is zero, there must also be present an equal
number of positive charges of the kind present at lower pH. However, the number of
both charged sites per unit area of silica surface must be exceedingly small, and
coverage sparse.
If this is so, then on a pair or on a chain of particles, one may speculate as to how
such sparse charges might be distributed. If such charges tended to be located at the
ends of chains as rather widely separated pairs with their accompanying counterions,
then this would explain why further particles would be added at the ends so that
chains would be formed.
.,t
Figure 3.20.
Computer projection of a chuinlik e aggregate by purely random aggregation of
uncharged particles which adhere rigidly together upon collision [According to D.N. Suther-
land (126:1).]
\.
227
on of Silica
Polymerization by Aggregation-Gel Forrnatiop__
. pair or a
the' "~rge
ide, ,the
Another mechanism by which aggregation of particles can result in a somewhat

fibrillar structure is proposed by Sutherland (126). He points out that directional
ionic forces have been previously thought necessary to account for chain formation.
However, his computer simulation of flocculation, which requires only that a rigid
bond be formed when particles and/or aggregates collide on a random basis, can
result in highly extended brandied chainlike aggregates. These consist not only of
short chains of single particles, but also of random multi-particle width as shown in
Figure 3.20. This may be the most reasonable explanation of how very small
uncharged polysilicic acid particles at pH 2 can still aggregate in such a open network, which can occupy and solidify the whole volume of a solution with less than
I % by volume of particles. However, the silica system differs from the simulated
flocculation in that, at least at a given low pH, only a certain small fraction of the
collisions result in formation of a rigid bond. Also on the periphery of a given growing network (microgel particle) there will be extended chains, between which unattached particles will be found, but these later attach themselves to the network so
that the concentration of silica within the microgel is the same as in the original sol
on a macroscopic basis.
A comprehensive review of computer simulation of colloidal systems has been prepared by Medalia (126b).
isoelectric
ue that gel
with which
ca particles
~ is not any
.lso at the
les requires
other suroint, pH 2.
it an equal
~ number of
small, and
~
:e as to how
cated at the
.ounterions.
nds so that
199regation of
D.N. Suther-
Partial Coalescence of Particles in Chains
An important step in the formation of a rigid gel is the strengthening of the interparticle bonds beyond the mere formation of a few siloxane bridges at the points of
contact, as shown in Figure 3.19.
When two silica particles unite in water, they grow together because the solubility
of silica in the crevice at the point of contact is less than that of the silica over the
surface of the particle. The neck joining the particles therefore increases in diameter,
until the difference in solubility becomes small. There is, of course, no true equilibrium, since the equilibrium condition would be represented when the two particles
became fused together, first into an oval and finally into-one large spherical particle.
The rate of thickening of the neck between the two particles will become very slow
after a certain point. This point can be estimated by the following reasoning:
As shown in Figure 1.8, the solubility, Sn, of a surface with a negative radius of
curvature is less than that of a -flat surface. Later in this chapter it is shown that
under given aging conditions very small discrete particles grow spontaneously until a
certain size is reached, after which growth becomes slow. Let this aged size correspond to a radius r a with a solubility of Sa' If two particles of radius R come into
.
contact as in Figure 3.21 the interparticle neck will grow to a radius r.,
Under the given conditions, the rate of growth of the neck will become very slow
when the effective negative radius oj curvature, r n, at the neck, is numerically
greater than a certain value. The solubility at the neck S; will be less than Stnt since
Sn/S/nt = exp(K/r,,) and r has a negative value.
,.~-~,--
-a~~kj
228
,,
I
I
'
.... _--""", "
Figure 3.21. Solubility at the negative radius of curvature of the neck between spheres is less
than elsewhere on the spheres: R. radius of spheres: rio positive radius of curvature of the neck:
r2. negative radius of curvature of the neck.
The effective radius,
T'"
in Figure 3.2\ is given by

2
(1)
where T" is the "effective radius of curvature," T 1 is the maximum positive radius of
curvature, and T 2 is the minimum (negative) radius of curvature.
For triangle ABC:
from which
2ri
and
-Tn
[T~
+ 4Rr n (r n
(r n
2)
ri -
2)]U
2R
+ 2r l
(2)
It seems logical to believe that if the growth of discrete particles becomes slow
when Sa - S, reaches a low value, then under the same aging conditions the neck
between two particles will likewise grow only slowly when Si - Sn reaches the same
low value. Thus
(3)
on of Silica
polymerization by Aggregation-Gel
Formati~_
229
Using the equation given later in this chapter for relating solubility to. particle
diameter:
S"
log S/
2r"
K
Sa
log - =
2ro
S/
and eliminating S/:

(4)
heres is less
of the neck:
(I)
~
radius of
(2)
ornes slow
i the neck
; the same
(3)
Therefore when a gel is formed under certain conditions the degree of coalescence
or neck growth can be estimated if one knows the size to which very small, separate,
and discrete particles will grow under these same conditions.
As an example, assume that at 25C at low pH, silicic acid particles will grow to a
radius, r a, of 2 nm, If this aged sol then is gelled and further aged under the same
conditions, the radius of the necks, r h can be estimated as follows:
Taking the formula developed later for 25C, where K = 0.918 and To = R = 2,
and substituting in equation 4,
.
IOo.918/2 r n =
2-
10.91814 =
0.304
whence r" = -0.89 and r 1 = 0.84 nm. Thus the neck diameter. 1.68 nrn, is 84% of
the original particle diameter. The particles are strongly coalesced.
On the other hand, if particles forming the gel are larger initially. for example, R
= 10 nrn, much less coalescence occurs when the gel is similarly aged. The values of
r a and r remain the same but the calculated neck radius becomes 2.2 nm. The neck
diameter of 4.4 nm is thus only 22% of the original particle diameter so the particles
are grown together to a much less extent.
In a gel, formed initially of discrete particles chained together, coalescence will
similarly convert the particulate chain structure into a fibrillar network, especially if
the particles are smaller than about 10 nm. As shown in Figure 3.22, the chain of
spherical particles (dashed lines) is thus converted into an irregular rod or fibril
(solid lines). If the particles are large as in one case in Figure 3.23. much less coalescence occurs under the same aging conditions where the smaller particles
approach a fibrillar shape.
The conversion of a particulate gel to one with a fibrillar structure of very high
specific surface area is represented two-dimensionally in Figure 3.24.
Although never demonstrated, the solubility of a freshly formed gel of very small
particles should be less than that of the sol particles from which it was formed. even
though there is little decrease in specific surface area. The solubility also should
decrease measurably during aging.
-----
~ ...
.......
""
\
,
I
,.,.
"\
/ r.'"
---.,."
,
J
{\
\
{/
\i
--...
,.
\
"
"
-,
..1
,i
' ............. _-
.1
[.
f. : ,:
{i
Figure 3.22. A chain of small particles is converted to a fiber or rod by the laws of solubility:
R. original diameter of spherical particles in a chain before formation of necks: R h final radius
of curvature of particles after neck growth: rio positive radius of curvature of neck: r2. negative
radius of curvature of neck; Rio radius of a rod formed by complete smoothing of chain (R, ..
O.82R).
.i
,---:-7 II
IOnm
2.2nm'I
". ~
.. -.1-----1----------
"
i~
~l
g .
~.
I'
j. .
i,.~.
~
r"I-
I;
~nm
'/J''
I
I
230
'~-j':_--
Figure 3.23. Gels of equal silica

concentration, However, smaller particles
develop greater coalescence and strength
and the structure becomes more fibrillar.
-,
231
polymerization by Aggregation-Gel Fcrmation,
..
olubility:
al radius
negative
in (R t =
Figure 3.24. Two-dimensional representation of

a dilute gel converted to "fibrils" by silica rearrangment.
Development of Microgel and Viscosity
silica
particles
str th
ibri.
. The difference between formation of microgel and formation of a precipitate is that

in a microgel region "the concentration of silica particles in the three-dimensional
network is the same as in the surrounding sol but in the floes or aggregates of a
precipitate the concentration is higher than in the surrounding liquid. In the rnic. rogel the refractive index is the same as in the surrounding sol so the microgel cannot be seen. Likewise the density is the same so the microgel does not settle out even
when-centrifuged. On the other hand in the precipitate the refractive index and
density are both higher so that the 'precipitate is visible and settles out. The difference is represented in two dimensions in Figure 3.25.
.
The initial step toward .Iormation of microgel is the aggregation ~f some of the
particles into short chains as shown in Figure 3.26. As the chain length is increased,
particles begin to be added to the sides as well as the ends of the chains. Thus a
region of branched chains is created. Free particles within this region are added to
the network which soon contains all the particles within its domain, forming a "microgel region" of what has been called "gel phase." Each region of gel phase
increases in size by addition of sol particles in the surrounding fluid region until gel
.:~.~
<
\i
..
GEL
Figure 3.25. Two-dimensional representation of the difference between a gel and a

precipitate.
PRECIPITATE
0
00
00
000
~<to
o~~g~
00
ogo aoo
~o
00 c::::::>
Figure 3.26. The gelling process involves formation of an increasing volume-fraction of the
sol being converted to microgcl (darker lines) with increasing viscosity until solidification
occurs. The three-dimensional process is repesentcd only in two dimensions.'
\.
Polymerization by Aggregation-s-Gel Formati.on
resenta:1 and a
233
phase occupies much of the total volume. At that point the gel regions grow together
into a continuous network of coherent gel.
Gel phase in invisible and the sol remains clear. Within the microgel regions the
refractive index is essentially the same as that of the surrounding fluid sol. The silica
concentration is the same and thus there is no difference in density so that the gel
phase does not settle out.
However, there is an increase in viscosity as the gel phase develops. The increase
is at first small but detectable. Also the presence of even a fraction of a percent of
gel phase can be detected by the rapid plugging of a filter through which the original
sol, free of rnicrogel, passed freely. Also when a sol is being washed or concentrated
by being circulated through an ultrafilter, the membrane becomes blinded rapidly if
even I % of the colloidal particles have been converted to microgel.
Isolating "Gel Phase" or "Microgel"

The following method is so simple that it is surprising it has not been used previously. A sample of sol that is in the process of gelling but has not reached the gel
point need only be diluted, for example, threefold, and centrifuged under a gravity
just insufficient to settle single particles. Since the microgel does not expand, it
retains its original specific gravity whereas the ungelled sol medium is diluted out
and has a lowered specific gravity. The gel phase is thus easily separated as a solid
cake. The proportion of the silica found in the cake is a measure of the fraction of
silica in the microgel at the moment of dilution.
In carrying out this test, it is best to use water containing the same pH and
concentration of salts (if any) as in the original sol. To ensure that no further gel
formation occurs during the centrifuging it may also be necessary to quickly adjust
the pH of the sample sol. to 1.5-2.0 with HCI or HN0 3 before the dilution. This stabilizes the system long enough for the test.
Effect of Electrolytes and Coagulants
In ofthc.:
lification
This discussion refers to homogeneous gels formed by uniform solidification of a sol.

Such gels are formed below about pH 6 whether or not a salt such as Na 2S0 4 is
present, and above pH 6 only if the salt concentration (sodium) is not too high. In
hot solution containing more than about 0.3 N salt, silica is precipitated rather than
gelled.
'.
Colloidal particles join into chains and thence into three-dimensional gel networks'
only if there are no forces present to cause particles to coagulate or come together
into aggregates which contain a higher concentration of silica than in the original
sol. Coagulants such as metal cations. especially polyvalent ones. or some organic
bases. especially cationic polymers, lead to precipitation rather than gelling.
Thus if a silica sol contains substantial amounts of salts and is neutral or alkaline,
a homogeneous gel is not obtained: instead. the silica usually appears as a white
precipitate, or in some cases as a white opaque gel owing to partial precipitation
before gel formation. Similar effects arc observed when small amounts of coagulants
:- ...
or flocculants are present as, for example, water-miscible organic liquids .polymers,
or surfactants.
Gel Density and Structure

Manegold (127) has considered what kinds and packings in regular network arrangements result when the "coordination number" of particles is varied, that is, the
number of particles linked to a given particle. In most densely packed gels, each
sphere is touched by 12 surrounding spheres, and the volume-fraction of spheres, S,
is 0.745. In a more open regular network, each sphere is connected to three others
(Le., a coordination number of 3) and S is only 0.05, as in Figure 3.27.
However, there is a tendency also for particles to form short chains in which the
coordination number is 2. Thus, along any series of particles forming a network, the
coordination numbers could be 3, 2, 2, 3, 2, 2, etc., in which case S = 0.0083. This
would correspond to a gel formed from a sol containing only 0.83% by volume, or
1.8% by weight of Si0 2, as in Figure 3.28. However, if the particles are small enough,
a silica sol can form a weak but continuous gel network at even 1% Si0 2 or less. In
this case, the coordination numbers may be 3, 2, 2, 2, 3. A model of such a very
open network in which the average coordination number is of this type is shown in
Figure 3.29.
! ;: ~ i
I'
"
, . ;.
. ..,--~~
~~,
..... :'
.~
.:
." . i-~;;... ;':;~:~~< . ;..:.:.~.-~<~::.(} ... ;..~-;':2.-:-":; .: , ..: .
".':'
: .:
I
Figure 3.27. Packing of spheres with
coordination number of three. [From Ilcr
. (89). by permission of Cornell University
Press. J
i .
.!
--
:......_-
lica
.ers,
.igethe
.ach
i, S,
hers
the
the
This
:, or
ugh,
Figure 3.28. Packing of spheres with

coordination numbers of 3, 2, 2. 3. Black
spheres touch three others.
In
very
n in
i.
with
ller
'sit ,.
'.
Figure 3.29.
Gel with particles with coordination numbers of 3. 2. 2. 2. 3.

235
236
r:
..
Increase in Viscosity
The question arises whether in the sol-phase regions when microgel is already
present, new aggregates continue to be developed initially as twins or triplet chains.
These could not contribute appreciably to viscosity until, through network formation, they enclose water in new microgel regions. Within any microgel network trapped particles, whether single or short chains, will soon join the network. Thus within
each microgel region the final gel structure is rapidly attained.
The viscosity during the process of gel formation increases in proportion to the
volume fraction of gel phase present. It will be .assumed that the diverse microgel
regions can be considered as having an average size which increases as the remaining
sol particles are added to the periphery of each microgel aggregate region. Once a
substantial volume fraction of the sol has been converted to suspended microgel
regions, the free single, doublet, or triplet particles then add to the periphery of each
microgel region, increasing its volume at the expense of the still fluid medium
without changing the silica concentration in either fluid or gel regions. We know that
this is so because at any point during the process of gel formation as evidenced by
the increasing viscosity, there is no large increase in turbidity and no gel phase can
be separated by centrifuging unless the sol is diluted.
The volume of microgel phase can be estimated from viscosity on the assumption
that the microgel regions are spherical in shape and of approximately uniform' size.
The volume fraction of microgel phase (which is also the fraction of silica immobilized in gel) can be calculated from the Mooney equation (128a):
. . 2.5C
In n, =
-...
1 - k 1C
where k, = 1.43 and n, is the ratioof the viscosity of the gelling sol to the viscosity
of the sol before the gelling process began, and C is the volume fraction of microgel
present. For convenience, values from this equation are plotted as log(n,. - 1) versus
log C in Figure 3.30.
As the volume fraction of microgel .approaches about 0.5, the viscosity rises
rapidly because the microgel particles approach random 'close packing. However,
since the microgel regions undoubtedlyvary in size. so that smaller gel fragments fit
between larger ones: actual solidification may not occur until the microgel volume
fraction. determined directly, is greaterthan 0.5.
As mentioned earlier. after an early stage the rate of increase in microgel may be
proportional to theamount already present. growth of each gel region being due to
addition of single. particles .or short chains. which have enough kinetic energy owing
to Brownian motion to collide with the microgel regions and add on. Then
de
dl
kC
-. Silica
Polymerization by Aggregation-Gel
~--_.
Form~t.!o_n
237
where t is time and C is volume of dispersed rnicrogel phase, and so

Ire.
:hains.
In
'orrna-
c trapwithin
to the
crogel
aining
)nce a
crogel
If each
edium
w that
:ed by
se can
nption
n size.
irnobi-
cosity
crogel
versus
rises
..
kt
where Co is the amount of microgel present at time zero.

To investigate the formation of microgel, a 15% silica sol of 6 nm particles was
deionized by Iler to pH 5.55 and aged at 30C. Samples were taken at different
times, diluted to 4% Si0 2, and deionized to pH 3.5 (to leave little or no charge on
particles), and the viscosity was determined. From this the volume percent of "dispersed phase" in the 4% sol was calculated from Figure 3.30 and then multiplied by
15/4 to find the volume fraction in the original sol before dilution.
Time (hrs)
Volume Fraction
C in 4% Sol
Volume Fraction
C in 15% Sol
0.048
0.062
0.090
0.120
0.140
0.165
0.200
0.212
0.240
0.18
0.233
0.338
0.450
0.525
0.619
0.790
0.795
0.90
k = 0.055
____0 _. __
I 2.5
3.5
4.0
4.5
5.0
5.1
5.4
When these data are plotted in accordance with the above equation. as in Figure
3.31, it is seen that the equation is followed up to 0.50 volume fraction of dispersed
phase. Above this point, the equations relating viscosity to volume of dispersed
phase are not valid. Also the gel network becomes so extensive that i~ is irreversibly
disturbed by dilution and measurement.
The activation energy for gelling varied with pH:
vever,
nts fit
olurne
lay be
Iue to
owing
pH
kcal mole-I
'4.0
5.5
7.0
15.0
14.5
11.9
Also. the use of a hydrophobic cation base (CHJ).NOH- instead of Na Ol-l ' at
pH 5.5 reduced the activation energy to about 8.0 kcal rnole " '. When this cation is
adsorbed on silica there is hydrophobic bonding between the silica particles and gel.
thus holding the surfaces 'together for longer times upon collision. and promoting
.
.
siloxane bond formation .. :;i
t
'",.,.;
:-._-
\
( n, -( )
(n, -I)
1.00
100
0.50
50
0.20
20
0.10
10
~';
jI
. i
..
0.05
0.02
"
0.01
0.01
0.02
. 0.05
0.10
0.50
0.20
1.00
C - VOLUME FRACTION OF SPHERES IN DISPERSION
Figure 3.30. Plot of the Mooney equation relating the volume-fraction of uniform spheres in
suspensions to viscosity.
-J
8
5
1.0
u,
o
z 0.5
o
;:::
"
~ .....
a:
~ 0.2
:E
:::>
-J
0.1
HOURS
Figure 3.31. The vol~~e-fractio~'o("dispersed phase" or microgel increases as a sol is

transformed lO gel. Sol: t 5% Si0 2 of 6 nm particles at pH 5.55 and 30C [Iler, unpublished.]
238
..
'"
~~:...~.-
...
:-.._-
Polymerization Above pH 7
239
Formation of Larger Particles by Coacervation

When the concentration of silica is low, generally under I %, and under certain conditions of pH and low salt concentration, the primary particles form small spherical
aggregates or secondary colloidal particles. In aqueous solution this is much more
likely to occur at ordinary temperature than in hot solution where growth of primary
particles with decrease in their numbers reduce the probability of aggregation.
. Such a mechanism must have been involved in the formation of 200 nm spheres in
a solution of pure silica sol prepared by hydrolyzing SrCl, and removing HCl by
electrodialysis, as reported by Radczewski and Richter (128b). The purified clear sol
contained about 0.5% SiOz and the pH was 6.8. Similarly, uniform porous spherical
silica particles up to I micron in diameter are formed by the aggregation of primary
particles less than 5 nm in size formed by the hydrolysis of ethyl silicate in a
water-alcohol-ammonia system as developed by Stober and Funk (128c) .
......:'~
. . . . ." , ' ,
.., .. '
','
. . . ',
,.
,_
POLYMERIZATION ABOVE pH 7
pheres in
In the foregoing section it has been described in detail how at low pH silica
polymerizes in stages to nuclei of silica which then increase in size to 2-3 nm. These
particles then aggregate into chains, forming higher molecular weight polymers.
Above pH 6-7 the behavior is entirely different. The ionization of polymer species is
much higheriso 'that"monomer polymerizes and decreases in concentration very
rapidly, even in a matter of minutes at 25C. At the same time, the particles grow
rapidly toa size that depends mainly on temperature., However, no aggregation or
chaining together of particles occurs because they are charged and mutually repel
each other:
All this is true provided the electrolyte concentration is low, as when silicic acid is
prepared by. hydrolyzing an 'ester or when the sodium' or potassium cation is
. .. :' :':"
removed frorna silicate solution to give pH 6-10. ,.
Only above' pH 7 can silica particles of suitable size be prepared and concentrated
'
, .. for industrial use,a;; discussed in Chapter 4:
,
Spontaneous Growth of Particles
.
* ",
a sol is
ished.]
- .
; .:.
.:.
Almost all the initial stages in thepolymerization or monomer to oligorners and threedimensional particles 1-2 nm in diameter, occur in only a few minutes at above pH 7.
Thereafter the polymerization involvesonly the increase in size and decrease in num. bers of silica particles. At the same time, the concentration of monomer in equilibrium with these particles decreases as the average particle diameter increases.
Under conditions where the relative rate or aggregation of silica particles is low;
the particles increase in size and decrease in numbers owing to "Ostwald ripening,"
a term' commonly applied to the coarsening or crystals in a precipitate such as
8aSO.; As described in Chapter I, small particles, especially smaller than about 5
' .l
'
.. ~ .
240
!
I
I
I
nm, are much more soluble than larger ones. According to available data, particles
of Si0 2 formed at 25C and not subsequently heated have the solubility of Curve B
in Figure 3.32, whereasparticlesmade by hot processing (80-100C) appear to
,
follow Curve A. ' , ';
The rate of growth depends on the distribution of particle sizes since the growth
occurs by the more soluble smaller particles dissolving and the silica being deposited
upon the larger ones. Generally, the distribution of particle sizes is not known but,
.with Gaussian distribution assumed, the increase in average particle size continues at
a given temperature until the size is so large that the difference in solubility of
, smaller, versus larger particles becomes negligible. The final size depends on the
temperature.
, ,:,:,'. ,_
The kinetics of Ostwald ripening has been examined mathematically by Sugimoto
(128d), who derived equations for the change in particle size, distribution with time.
lIer has found that with a fixed Si02 : Na 20 ratio the size, to which particles grow is
independent of the silica concentration. Silicic acid solution (3.7% Si0 2 ) was made
by passing silicic acid through a H+ ion-exchange resin, adjusted with NaOH to a
Si0 2:Na 20 ratio of 190: I and vacuum concentrated at 35C,to 7.7%. Samples were
diluted to lower silica concentrations and heated at lOOC for 48 hr and the particle
sizes then determined bysurface titration:
:: .....
% Si0 2 '
"
J
.'
Initial pH, : : Final pH"
Particle
Diameter (nm)
7.75 '
8.59 , .':
"
.,3.0 ~; -~" ' .: 8.91
1.0".:, /1; , 9.26
~.63
0.3
,
9.9 ,
9.9
9.66,
9.25
13.5 '
13.4
12.5
, 13.1,
II! ;,a given, ;~o~" ~i :;~-:~i~e'n' temperature, ' particle -size' appears to approach
asymptotically a final value that depends on the temperature, as shown in Curve A
'.' ,ofFigure,3.33. It might be supposed that particle growth would continue over long
periods of time until the specific surface area was reduced, to zero," However, this
does not occur. Sols of 15 nm particles have been stored at ordinary temperature at
pH 9-10 for more than 20 years with only minor increase in particle size.
Theoretically, if all the particles were exactly the same size, no growth would occur,
but such was not the case, since some particles were at least three times as large as
others. :,'
,-"~.,,.''':,
".
'
"
"
, Experience has shown that alkali-stabilized sols of silicic add polymerize during' a
few months 'at' 30Cuntil'thesurfacearea slowly drops to about 500m 2 g-I, corresponding to 5 nm: particles, after which there is little change.' At 90~C, the particles grow in a few days to around 7-8 nrn, after which spontaneous growth is very
:,,'"
'".;,
", - :."
,
,. :
slow.
I
r
\
Table 3.5 includesdata by Alexander and McWhorter (129) and Broge and lIer
, (130),' who 'studied the' particle growth 'during relatively long heating times at high
"-temperaiures"uri'der' superatrnospheric' pressure. The latter authorsfound that when
the alkali-stabilized sols were heated to above 300C, quartz crystals were produced
\.
"
i;
~.
__ .
f Silica
articles
urve It.
lea.
400
LOG 10
ss /s, =0.0191
E/d
growth
Josited
in but,
nues at
.lity of
on the
0
tn
A: Sj = 85 E = 53.5
E
c.
c. 300
I
B:Sj =70. E=48.0
'0
tn
I
>:J
iii
I-
::>
..J
gimoto
.1 time.
~row is
; made
H to a
:s were
iarticle
200
0
tn
100
2 3 4
d - PARTICLE DIAMETER NANOMETERS
Figure 3.32" . Effect oi'particle siz~ on solubility of amorphous silica in water at 25C: A,
particles heated at 8~-:loooC: B, particles formed at 25C but not heated [Iler, unpublished.]
: ,
, Table 3.5. Growth of Silica Particles by Heating a 4% Sol of Silicic Acid at

,pH 8-10
,_
\
, v.;
Mole Ratio
.....
Si02:Na20 ,':Time
pro~ch
urve A
.."
er long
sr, this
ture at
e size.
occur,
irge as
iring a
corpartiis very
idu
"
'-..-
. : -.:
..
;100.1 hr . 8 0
: ;-::'i~
~c ::,'.~.~~ ;.~. ::,,;:;:~;' ~.:;

.:
:.
78
6 hr
98
80 .'- ': 30 min
100
85'> '{3 hr :
160
: ' :,270
85 .<:. "'3.25 mfn
85
0.9 min
'. 250
.. ' 200
.: , 9 0 , ' 3.1 min
85
10 min
200
85
10 min
295
85
30 min
295
Very high"
3 hr
340
Very high"
6 hr" ... ~. ~'-" 340
'1,
td Her
tt high
t w' 1
'Temperature
,', ~. - i.(OC)
',Very high",. 3 hr
- ;....
--.
350
....
Specific Surface Area

, (m" g~l) .
600
510
420
406
350
,200
200
225
271
228
78
Estimated
Particle
Diameter
(mil)
5
6
7
7
8
IS
IS
IS
10
12
36
~
88
105
20
ISO
:J'CI'Traces 'of sodium ions remaining in the starting particles after deionization of
the sol before autoclaving resulted in a pH of about 8 in the /inal sol..
241
,
,
.,. .........
t;'
242
.
e
c:
Ir
~
w
:E
.:'
;~
o
w
..J
U
i=
a:
if 5
4
100
50
I
8 0
100
200
300
400
500
HOURS
Figure 3.33. Growth of silica particles at

pH 8.5: concentration of SiO:. 3%; SiO::
Na 20 . 102. (A) 90C; (8) 50C. [Iler,
unpublished.]
instead of stable colloids. Rule (131) found that if a so] consisting of particles from 8
. , to 15 mu in diameter is first thoroughly deionized and then autoclaved at 300-350C
under autogenous pressure, there. is insufficient alkali present to cause conversion to
quartz, yet traces of sodium and hydroxyl ions occluded in the original particles are
released during the growth process in amounts sufficient to raise the pH and stabilize the sol. In this manner, particles in the diameter range 88-150 m,u diameter were
produced, and such products could be concentrated to a stable sol containing more
. than 60% by weight of silica. It is pointed out by Biage and lIer (130), that if the
starting so] consists of discrete particles they grow as discrete spheres, but if they
start as aggregates or as a gel structure, the final sol particles are of irregular shape,
since they are formed by the densification of irregular aggregations.
particlegrowth Isnot proportional to concentration of OH- ion in the
,- -- 'The rate
pH range 8-10, but is only moderately influenced by it. Since the silica surface is a
poor buffer, the pH rises as Jhe particles g-row and specific surface area reduced.
Shown in Figure 3.34 is a sol starting with particles 3.5 nm in size made by deionizing a solution of sodium silicate and adjusting the Si0 2 : Na 20 ratio to various
values. When held at SO or 90C the particles grow very rapidly in the first 5 hr from
the 3.6 nm size they had reached at 25C. At 50C in 100 hr they grew to around 5
om and at 90~C to' 7-8 nrn, after which further growth was very slow when the pH
was 7-8, but continued somewhat further when more alkali was present to give a pH
Final Size of Particles Versus Temperature

- Obviously the rate of particle growth at a given tern peratu re becomes exceedingly
'slow when the difference in solubility of the smallest versus the largest particles has
i; , :..
_,
, .
become negligible.
.,,
. .1
.: - I
.
'.~
of
or8-10.
,;
~.
;,..._.
f Silica
icles at
; Si02:
. [Iler,
Polymerization Above pH 7
243
Thus at 90C, for example, the solubility of massive silica formed is ~bout 350
ppm, and the size above which growth is slow at 90C is about 8 nm. If we assume
growth occurs until all the particles are within the size range of == 10% or 7.2-8.8
nrn, then using the expression 101.03ID, the range of solubility isbetween 1.39 x 350
and 1.31 x 350, or 487 and 45~, that is, a solubility difference of 28 ppm.
At 30C the solubility of massive silica is 70 ppm (Si0 2 made at 85C) and
growth becomes slow at 3.5 nm diameter. A similar calculation, assuming the
expression lOu 2l u , gives for a == 10% spread in particle sizes a range in solubilities of
137-121, or a difference of 16 ppm.
.
It is therefore clear that the initial distribution of particle sizes about the mean in
the initial sol will have marked effect on the final size reached when the sol is aged
. at some higher temperature. Aggregation may occur when a 2-4% silicic acid sol is
made at pH 2-4 and then alkalized. At the low pH, and during the change of pH
. through the range around 5, colloidal aggregates or microgel are likely to be formed
unless the operation is conducted rapidly. The aggregates may then act as larger
particles or nuclei and the heat-aged sol will have a larger final particle size.
. For a quantitative study of spontaneous growth. data are needed on the particle
'rom g.
~50C
.ion to
les are
stabim .
.')
if the
f they
shape,
in the
ce is a
:i
Iuced.
:ionizarious
. from
lund 5
he pH
:a pH
...... :. 3
c- -::-,
es h"<;
'.
'0.
300
400
HOURS
Figure 3.3t
Rate of growth of silica particles at 50

,.
..
Cur~c :
jingly
...
.' 100 - 200.
,:.:0.
A
8
C
:;
'Temperature (OC)
.,
f)
E
F
., ..... - .
'
.. "
90
'90,'
90
50
50
50
500
.... -
e and 90 e and different pH

0
sio.. NazO
pH
97
186
470
97
186
470
8.8-9.7
7.9-9.7
7.1-8.1
8.8-9.0
7.9-11A
7.1-7.5
values:
1
~
POlymerization of Silica
size distribution in alkali-stabilized sols of particles 3-15 nm diameter. Eventually

such data may be obtained by stabilizing such sols at pH 2, diluted to around 1%
concentration, and measuring the size distribution by ultracentrifugation or liquid
chromatography.
VISCOSITY OF SOLS BEFORE AGGREGAnON BEGINS
: 1
This is of relatively minor importance in the overall view of silica behavior, yet must
be considered in interpreting viscosity data obtained during early stages of polymerization.
When silica first polymerizes to very small discrete particles at .low pH, the
increase in viscosity can be appreciable because so much water is associated with the
surface of the particles. As polymerization progresses with increase in particle size,
the viscosity' decreases, which may seem surprising. Thereafter the viscosity
.increases again when the particles begin to aggregate. This initial viscosity of the sol
of discrete particles must be taken into account in calculating the development of the
gel phase, which has already been discussed.
Viscosity of Sols of Very Small Particles at Low pH

At the point where most of the monomer has been converted to particles but where
these have not yet begun to aggregate, the viscosity of a sol may be calculated from
the volume fraction of the dispersed phase, which is defined as the silica particles
along with the water that adheres to the surface by hydrogen bonding.
As shown by Dalton and Iler (132), there is a monolayer of water molecules
hydrogen-bonded to the SiOH surface. From the standpoint of viscosity behavior
this layer acts as part of the dispersed phase.
Based on the formula for thecomposition of a particle developed in Chapter 1. the
formula for a particle of diameter d nm is
where the OH is presentassilanol groups on the surface of the particles. For each
OH there is' a hydrogen-bonded H 20 so that from the standpoint of viscosity
behavior, the composition of a particle of the dispersed phase is
where d is the diameter of an equivalent anhydrous Si0 2 particle in nanometers.

More simply, the formula may be written
From this formula the following can be estimated:
Viscosity of Sols Before Aggregation Begins
245
equivalent molecular weight as anhydrous (Si0 2 )z = 690 d 3
"
664.2d 2
weight ratio H 20: Si0 2
690d 3
0.963 d :'
volume of dispersed phase per gram of SiO z .;, 0.45 + 0.93d- 1

Knowing the silica content ofa sol, and the particle size one can calculate the
volume fraction of the dispersed phase. for example, 1 ml of a 2% SiO z sol of 1.5
nm particles contains 0.022 ml of dispersed phase. From the Mooney equation
(Figure 3.30) the value of n, - I is 0.055.
As an indication of the degree to which the viscosity of a sol at pH 1.5-3 can be
affected by particle size at different concentrations, typical calculated values are
shown in Figure 3.35.
It is obvious that a few percent of monomer in water would not contribute appreciably to viscosity, for example, any more than a small molecule like glycerol would.
It is probable that below a certain particle size, probably between I and 1.5 nrn, the
polymer no longer acts as a particle, but rather like liquid oligomers. Thus lIer (116)
found that the viscosity of polysilicic acidsolution containing 6.34% SiO z at pH 1.7,
derived from 3.25oratio sodium silicate, had a viscosity of 1.11 relative to the sodium
sulfate solution medium. This increased to l.15 as the degree of polymerization
(cryoscopic method) increased from o~ to 23, the latter corresponding to a 1.25 nm
in Figure .3.35, for the 6.34 g per 100 ml
particle of anhydrous SiO z As can be seen
.
..,
~
0.0
.'
-I
..
0,2
0"
c:
.:
0,1
,
0,05
2
-
PARTICLE DIAMETER NANOMETERS

0
Figure 3.35. Calculated decrease in viscosity of a sol of very small discrete particles owing to
" particle'growth:n;; relati~c viscosity: Concentration ofSi0 2 g perIOO,oml: A,'IS: B, 6.34: C.
2.0. L.large particles (sec text).
0
0 '
0 '
246
Polymerization or Silica
sol, the calculated value (solid line) for a 1.25 nm particle would be considerably
higher than this observed value, indicating that when particles are smaller than 2 nrn
diameter they do not have as much effect on viscosity as larger particles do. When
the particle size exceeds about 2 nm the contribution of such small silica particles to
viscosity is considerably greater than that of larger particles.
An indication of the type of situation that could arise if careful viscosity studies
were made in the initial stages of polymerization at low pH and at a concentration
where particle development occurred before aggregation began is shown in Figure
3.36. Here the logarithm of the reduced viscosity is plotted against the logarithm of
molecular weight, that is,"a Staudinger equation plot. The calculated values for the
viscosity of small discrete particles are shown as A. The values observed by Acker
(133a) for the aggregation stage are shown as B. There must be a transition region
as shown.
" .
To calculate the volume fraction of microgel in the course of a sol setting to a gel,
it is necessary to express the viscosity relative to that of the sol at zero time rather
than to the aqueous medium alone. Thus Acker (133a) presents data on a sol of
silicic acid made by neutralizing a 3.25 ratio sodium silicate solution at pH 1.5. It
contained 15% Si0 2 and gelled in 110 min. The initial viscosity was 5.4 cp. The
relative viscosity "at subsequent times can thus be expressed as the ratio of viscosity
at time 1 to that at time zero. Taking these values for TJtlTJo the Mooney equation can
be used to calculateC, the volume fraction of the dispersed phase (rnicrogel). This
interpretation of Acker's data is shown in Figure 3.37.
It is noted that after about 30 min. at which Acker reports a molecular weight by
light scattering ~f 14,000, there is ~.!it relation betwe~n log ~ and I. This relation
was observed with the J5% sot ~erete 6 nm particles (FIgure 3.31) whereby
the' large growing aggregates as a first-order
particles or small aggregates add
reaction. Acker similarly proposed that the larger molecular weight species bond
with the low molecular weight species, but assumed polymerization was linear based
to
~'--_-uo
-------
.s
-0
-
- ....
PARTICLE DIAMETER
nm,
c:
I
c:
;: 0.10.
"- - - t::-- .en
8
en
s
0.05
10
10
MOLECULAR WEIGHT AS Si0 2
Figure).36.' :Cha'nges in reduced viscosity of polysilicic acid sol due to particle growth and
aggregation: A/single particles. diameter in nanometers: B, aggregates, 'molecular weight in
daltons, [From Acker (1333).]
: Silica
247
Viscosity of Sols Before Aggregation Begins
lerably
:l2nm
0.5
...J
W
"
Cl
'des to
a:
0.2
:E
studies
tration
Figure
thm of
for the
Acker
region
LL.
0.1
i=
o.
<
a:
LL. 0.05
w-
--
:E
:::::>
...J
o a gel,
rather
_sol of
1.5. It
:p. The
iscosity
ion can
I}. This
.ight by
'el' '0
,hel_-,y
it-order
:s bond
r based
> 0.02
....
,0,01
;.'
o
..': ;.
20
40
60
80
100
MINUTES
Figure 3.37. Volume fraction of microgel versus age of sol during the process of gelling. [Calculated from data by Acker (133a).]
on viscosity behavior.. .However, as shown above, the viscosity can be equally well
accounted for on _the basis of growth of rnicrogel regions and the solidification to a
continuous gel network when the. microgel reached a' volume fraction of 0.5 under
.
. ,
,- these particularconditions. ' "
: _
. --"
-:
'
f.
Decrease in Viscosity on Conversion of Microgel to Sol
iwth and
veirl- in
When microgel is formed from extremely small particles at low concentration at Jow
pH, it may disperse and form a sol when the pH is raised above 7. This occurs only
if the salt concentration in the system is less than about 0.2-0.3 N, that is, the
critical coagulation' concentration. Otherwise the growing particles remain aggregated and become further cemented together as a precipitate.
When ~the pH is 'raised,there is particle growth as chain segments dissolve and
silica is deposited 'around branch points, eventually forming irregularly shaped,
separate particles. "At the same time the specific surface area of the silica is greatly
diminished.
, .Pfleger and Kautsky (133b) observed this phenomenon in silicic acid sols that had
been aged and developed .high viscosity as they approached the gel point a't low pH.
When the pH was raised to 8-9 the viscosity dropped to a low value as the sol was
.aged -fora month at room temperature. The particles thus formed at ordinary
temperature were not fully internallycondensed since they were porous enough to
still exchange H - for CuOH - ions. As described in Chapter 4, there is a commercial
248
process for making sols by washing the salt out of gel made from acid and sodium
silicate at low pH and then autoclaving the gel at pH 8-10.
THERMAL EFFECTS
,
"
i '
; ,
Energy ofActivation
In view of the different polymerization processes occurring simultaneously, it is
generally not possible to link a temperature coefficient to a specific reaction.
Flemming (134) observed that the temperature coefficients of polymerization were
different in acidic and slightly basic solution. This was verified by Hurd and co
workers (135-138), who found that the temperature coefficients were less in very
strongly acidic solutions than in weakly acidic solutions, namely, 9-11 versus 24 kcal
mole:". More recently, Penner (139) found that in the pH range from -0.441 to
0.863, where it is known that the reaction rate is proportional to the concentration of
H+ ion, the activation energy was about 9.5 kcal mole-', whereas at pH 4.64, where
the rate is proportional to OH- ion, it was 16.1 kcal mole';'. This strongly suggests
that two different mechanisms might be involved in these different pH regions.
Brady, Brown, and Huff (140) found that the activation energy of polymerization is
15.5 ::I:: 0.5 at pH 5.5, 9.6 ::I:: 0.3 at pH 8.5, and 14.6 ::I:: 0.5 at pH 10.5 in the presence
of potassium chloride.
,
,,
Coudurier, Badru, a'nd Donnet(36) obtained separate values for the energies of
activation er the condensation 'process (disappearance of monomer), 14.6 kcal
, mcle:", and of theaggregation pr'ocess,IS.I kcal mole:", at pH 4. ;
Bishop and Bear (141) followed the polyrnerlzation of monomeric silica at pH 8.5
at 25:-45C by measuring the decline in unreacted monomer using the molybdate
method. The initial rate constant, assuming a second-order reaction, showed a
peculiar variation with. ternperature; .'
j!":
"w
',i,"' ' " " ,
'",c':
- ; .. '
..
,:,
,.:; ,'" (OC) , '
',' 25
" , ,30
35
, 40
',45 '
.-
,., ...
~.
:'::;:Temperature'
<s, X
'J"
.::
._. ':
10',; r - : . " '
,(I molet-sec")
6
38::1:: 4
,,.~',57::1::
,23
38
52
::I::
::I::
::I::
3
6
7,
, Th~ drop iriactivatione~ergy,'in the, 25-35C region implied that. there was a
"preequilibrium" step in the polymerization. It is likely this involved the same type
of induction 'period observed by other workers under similar conditions at 25C and
the 'first step is; the' formation of some small polymeric species with which the
monomer' thenreacts preferentially.
,"
','
'.;
_.,:.
..-. :..; .-
,.:.-.
..
-i""
--
of Silica
sodium
Heat of Polymerization
Iy, it is
on were
and coin very
24 kcal
).441 to
ation of
~, where
iuggests
regions.
.ation is
iresence
rgies of.
.6
pH 8.5
Iybdate
owed a
:..,._-
249
Since solutions of silicic acid gel suddenly under certain circumstances, it might be
expected that a considerable heat of reaction might be involved. This is not the case.
Tourk.y (l42) found that when silicic acid was made from sodium silicate and acid
and polymerized in neutral solution. the heat of reaction, excluding the heat of neutralization ofthe acid by the base, was about 148 cal g-1 of Si02, corresponding to
8000 car mole:", In this case. the starting material was sodium 'metasilicate; hence
this probably represents the overall heat evolved in the transformation from monosilicic acid, to high molecular weight polymer.
': .
,
On the ather hand, Treadwell and Wieland (l43) found that during gelatinization
or a sol there was practically no thermal effect. no change in the refractive index,
and no change in electrical conductivity.' They concluded that the gelling process
cannot be a, normal change in liquid viscosity, since it did not cause a change in conductivity. The lack of a heat effect at the point wherethe viscosity increased rapidly
just before the solution gelled indicated to the authors that the polymerization of
silicic acid first goes from the molecularly dissolved oligomers to colloidal particles
of high molecular weight. Then, if these particles are not stabilized by sufficient
ionic charge, they forf!} themselves into ,"threads" or chains and by floc formation
occlude thedispersing medium (water) whereby .theviscosity is increased. At the
point of solidification or gelling, the solvent is completely occluded. :;
,
" ' However, in Treadwell, and Wieland's experiment, the' sol was made by elec"
trolysis on the alkaline side and we know now the 'particles were made larger than in
".: :.Tourky's sols" so that far fewer'siloxane (SiOSi) bonds 'were' formed during gelling,
and thus much less heat evolved.":_';','
.'_ _; -,:' '.~',',-,~ .'::
;, ..,. ' No accurate data exist for the heat evolved in the reaction in solution: . '
_,,.
'~'''.
. r .... ..,..
, >
~ '":' ; ~ '.., _~ _
,,- " : ::.,
'.;
_":
~,;. '.,
eSiOH
~-~.
:>. :.-:;.~..
":'.
t. '.
+ HOSiE
_~
'.
-t
'~.
'
.' ,
~.
:. .
eSi-:-O-:-Si~
-.
,~
-~
...
~ i-
__. ;
,," . .
_, _,,,
+ ~20.:
. ; ~ >-.: ". ~"-. ; ~ r..-";l~_"_:-.-)

. ' ,:'." ".'
: :'Howe~er, -the e~terit"of condensation in a silicic acid system has been followed by
":'"Tourky (144) by noting the-change in volume by a dilatorneter. ~A combination of
' ; ..>this techniquewith calorimetrymight permit an estimation of the heat of reaction if
one were to start with a solution of monosilicic acid.
.
~.'~'
,:
'
SUMMARIES OF INVESTIGATIONS ' , '
was a
ne type
C and
ich the
The foregoing description of the polymerization of silicic acid was based on a uniform interpretation of the data of about 20 investigators who studied polymerization
~ under different conditionsby different methods and interpreted their results in differentways.- From the following separate discussions of each investigation it will be
seen thai thedata are consistent with the view that at an early stage in the polymerization, the sllicic acid is converted to spheroidal particles about 1-2 nm (10-20 A) in
diameter. The data of severalearlier investigators confirm the most recent work that
. : ....: -:.
.. . ' . .
~....
.;
..-
.,,',
..1
150
shows clearly that nucleation plays a role in the formation of amorphous silica particles as it does in the formation of crystalline precipitates.
The amorphous particles' then grow' in size and decrease in numbers by the
phenomenon of Ostwald ripening. as has long been observed with very fine
crystalline particles. Under mosj conditions further increase in "molecular weight"
involves the chaining together of the particles into growing microgel networks until a
gel is formed. However, insalt-free alkaline solution. discrete particles continue to
"
grow; forming stable 'sols. ,': ,
The problem has been that the different processes have overlapped and so were
not easily recognized.
' ' .:
'" '
The lnvestigationsarediscussed in the or~er listed in Table 3.6.
:-_~
.J
,.
'"
.
-:
-'1
~
~?J
:~.:. J"~
'a;
--1
oj,
,f
,
"
.-.
Alexander' '. .,;,:,:,~ ;.', ""~:'

0': -',.
:..", 2-~=: ....~ .."._ ..
.~.i .. Alexander (24a) was the first .to follow the polymerization of monomer in the
absence of salts. At pH ,2, the number-average molecular weight increased linearly
with the square root of time. asreportedby Her (116).At pH 3.2 and 3.8 it increased
"in proportion to time. At pH4.36 it increased linearly with the square of the time, as
inasecond-orderreaction.. :~,.~>.~:;; :"'.'-.:1~~~~:>~, .. '-.
,a, ... <.~.,
However. at a given degree of polymerization of 3.5, the polymers formed at dir<
. ,:-;
...
"
..
:1
'0
Iler (116) studie~fthepoly;nerizatiori ~r~~ess at silica concentrations sufficiently high

, that the increaseinmolecular weight mainly involved the aggregation of small parti'cles. He prepared 2':6% 'sols' from 3.25 ratio sodium silicate by acidification at pH
.. , 1.7, where salts have negligible effect on polymerization. ",'
,
,
'
The degree,' of 'polymerization; calculated from the number-average molecular
weight. increased linearly with' the square root of the time. Also. the time required to
reach' a given deg~~e of 'polymerization was inversely proportional to thesquare of
the silica concentration.. Gelling occurred when the number-averagem.olecular
weightapproach'cci:a'-degree :ofpolymerization of 100' regardless' of the' silica
concentration. The viscosity increased rapidly after about 30 hr,: at which point the
relative viscosity indicated that the volume of the dispersed gel phase had increased
to occupy one-third of the total volume.
" These' observations" are -consistent with..the view that discrete silica "particles"
containing 10-20 silicon atoms were formed early in the process, as evidenced from
the low. constant viscosity which did not -begin to increase until the number-average
degree of polymerization reached about 16. Thereafter. aggregation proceeded until
the volume fraction of the microgel phase approached 0.50. Even at that point. half
the silica was still present as low molecular weight species. so that the num beraverage molecular weight was still low..-: , "
0;
:i
,f
':"
"
::
.
:
Iler
:~
Investigations at Low pH
':F' .,'
.. ~'! ,;
.t;.
.-c
:"1
: !'
\,
.:,
'-.
~i
.~
Silica
Summaries or Investigations
parti-
ferent pH values were not alike. The higher the pH at which they were formed, the
more slowly they reacted with molybdic acid:
.
'y "- ..
pH
fine
251
eight"
2.1 .
3.2
mtil a
iue to
3.8
were
Reaction Rate Constant

0.09
0.05
0.03
This is now interpreted to mean that the polymer particles initially formed were
internally more completely condensed and crosslinked at the higher pH. Polymerization involves three simultaneous process:s:
1. Reaction of monomer and dimer with themselves and higher polymers.
2. Ring closure and further condensation of silanol groups within the polymer, leading to particles.
.
3. Aggregation of particles into chains and microgel.

I
high
Because temperature can affect each of these mechanisms differently, it is not

possible to interpret the temperature- coefficient as an "energy of activation" since
two or more mechanisms operate simultaneously.
Some idea of the size of the discrete silica particles in the system is obtained as
follows. Alexander reported that when the 0.1 M solution of monomer at pH 2.2
was heated 30 min at 90C and cooled, the overall degree of polymerization (D.P.),
calculated from the number-average molecular weight, was 'only 2.4. This was
-because 40% _~of the silica was still monomeric. The remainder was polymeric
. (colloidal). The monomer was' present at a concentration of 2400 ppm, whereas the
solubility of massive amorphous silica is 'only 380 ppm at 90C. This can be
explained by assuming that the monomer was in equilibrium with small colloidal
":. particles. The. supersaturation ratio relative to massive silica was 6.3. For silica
formed at this temperature the ratio is 1OD.92IO. where D is the particle diameter in
nanometers. According to Figure 3.32, the particle diameter is!.3 nm.
partiIt
pH
ecular
red to
u<
ecular
silica
at the
eased
icles"
from
erage
until
, half
nber-
i
t
--'
-Schwarz and Knauff
-. -
. _Schwarz' arid Knauff (21), noted a strange ternporarily limited polymerization of

--. monomer. 'After about 150 hr at pH 3. 75 hr at pH 2. at a concentration of 0.8%
Si02 the number-average molecular weight became essentially constant at about
:-- 300 corresponding to a D.P. of 5 (Figure 3.38). The authors concluded that the
: system was stabilized by ring closures forming cyclic pentarners or hexarners.
.~ One can calculate the size of the particles, assuming the concentration of
. monomer corresponds to their solubility.
.
-- Let it be assumed that at this point there are n polymeric or colloidal particles of
'; diameter, l!. _nanometers having a solubility of S/) ppm of monomeric or soluble
. '.' ~- silica. From Chapter 1 itIs calculated that each particle contains 11.5 D3 silicon,
n the
iearly
eased
ne, as
,t c'
. . .&
0'
""
Ok
.... ;
,,,
.. ,.
. ...
,'.
-~-
',
.-
..". ,
':'. :" r.: ::, .::......~:.;':t:',:
~-
.,.,
~'.:'
.. _....
~,
."
.,
I.
,
.,
"
:.
"
Table 3.6.
....'
l,;"
'So~e InYesti~~tions of Polym'~rization of Siiica 1950-1975' ,

~~:
.,.~
, '.
:"p
",
,,t.
:'
._.
~ .o'
",
..,
Methods Employed
' .
;. Conditions .
Mol. Wt.
~. " . ~
',,',
I nvestigators
At LowpH .
lIer (116)
Alexander (24a)
Schwarz and Knauff (21)
Bechtold (145)
Goto (45)
Okkerse (29)
,
Audsley and Avestori (147)
Weitz, Franck, and Giller (148)
Bechtold, Vest, and
Plambeck (149)
Acker (133)
Hoebbel and Wieker (84)
...
_~ ..
__
~-~.'
-l.,
.'
Plambeck (149)
Acker(I--'
Hoebbe . .J Wicker (84)
Yes
No
15.0
6.0
3.5
1-9
5-6
Yes
Yes
0.05 N
No
3.0
0.6
x
x
1975
4-10
No
0.18
Greenberg and Sinclair (155)

Greenberg (156)
Goto (157)
1955
1958
1956
7-12
10-11
7-10
Yes
Yes
Tarutani (83)
Iler (Unpublished)
1970
7
8.5
Through Neutral pl/ Range

Merrill and Spencer (150)
Ashley and Innes (151)
Baumann (152)
Coudurier, Badru, and
Donner (36)
Marsh. Klein. and
Vermeulen (32)
1970
1973
1.5
1950
1952
1959
1971
4-9
x
x
Gel chara
(CH,),Si,
.vative
x
x
Polarized light
Above pH 7
Iler and Sears (158)

Richardson and Waddams (159)
Makrides et al. (106d)
0.05
1.0
9-10
1954
1977
7-9
5-6
x
1.5
0.2
x
x
x
30.0
No
Yes
0.15
0.5 (?)
x
x
Interferometery
Depolymerization
rate
Chromatography
Depolymerization
rate
Electron
microscopy
95C nucleation
':
..
,.,~
....ii;...
~.
-".-
254
350
5
300
....
250
:r
C)
UJ
-'
0
:E
200
150
100
0
50
100
150
200
HOURS
Figure 3.38. limited polymerization of monosilicic acid (0.8% SiO z) from hydrolyzed methyl
orthosilicate in different hydrolysis and aging media at 25C. Molecular weight: number
average as sio, Curve I. 10- 2 N HCI: Curve 2. 10 -~ N HCI: Curve 5. 10-' N HzSO.o [From
Schwarz and Knauff(21).]
atoms so that in 1 liter containing n particles there are 11.5 nD3 silicon atoms. In 1
liter there are also So ppm of monomeric Si0 2 or 1010 So silicon atoms. The total is
then 11.5 nD3 + 1019 So Si-atorns per liter. Since the total concentration is 8000
ppm. or 8 X 1022 atoms 1-1,
11.5 nD3 + 10111 So = 8
1022
The relation of solubility to diameter (Curve B. Figure 3.32) is
From the D.P. of 5.

111
10 So
+n =
1027
1.6 X 10 22
Solving the three equations gives D = 0.9 nm.

This particle size corresponds approximately to the diameter of the cubic octamer
and a monomer concentration of 735 ppm. Cubic octamer would be more stable
than the suggested cyclic species.
)fSilica
255
Bechtold
Bechtold (145) studied the polymerization of silicic acid made by removing sodium
from a solution of sodium silicate, leaving small amounts to adjust the pH. The
number-average molecular weight of the freshly made polysilicic acid was around
660, or a degree of polymerization of about II == 2. Thereafter, the molecular
weight increased over a period of days until the gel point was reached. Most rapid
gelling occurred at pH 5.05. An inflection in the pH titration was observed at pH
4.65. The molecular weight data were interpreted on the basis that S:(OH).
condenses with a functionality of slightly over 2.0, forming linear and then crosslinked siloxane polymers, eventually creating a gel. However, the intermediate
formation of particulate units, which then aggregate into chains, is now a preferable .
interpretation.
GOIO
methyl
number
[From
s. In
otal is
) 8000
Goto (45) measured the disappearance of monomer as it polymerized in a 0.24%

Si02 solution at pH 2.1 at 25C. Over a period of 60 days the monomer concentration dropped and the particle size increased, judging from the decreasing rate at
which the particles reacted with molybdate. Assuming that the monomer was in
solubility equilibrium with the particles, and using the formula' relating size and
solubility, the particle size was calculated, as shown in Table 3.7.
When the pH of the fresh solution was suddently adjusted to 8.8 the monomer
decreased to 20% of the original value in only I min. Assuming this is the solubility
of the resulting particles, the latter are calculated to be about 1.1 nm in size. This
particle growth at pH 8.8 was 3 x 10 times as rapid as at pH 2.
The relative rate of reaction with molybdic acid varied with the calculated particle
size. A log-log plot of the data showed the same slope as found by Her (Figure 1.15)
for the rate of dissolution of particles in this size range in 0.1 N NaOH solution.
This shows that the rate of depolymerization or dissolution in both systems depends
Table 3.7. Growth of Polymer from Monomer in Dilute Solution of Silicic Acid (0.24% Si0 2,
pH 2.1, 25C)
Age of Solution
time at 25C
-IS min
2.5 hr
4 days
9 days
20 days
60 days
Source.
Remaining as
Monomer (%)
Particle Size of
Polymer (nm)
(From Solubility)
Relative Rate
of Reaction with
Molybdic Acid
80
60
34
28
22
14
0.7
0.9
1.I
1.4
6
2
I
Calculated from data by Goto (45).
256
on the solubility of the particles. which in turn is an inverse log function of particle
diameter.
Okkerse
Okkerse (29) determined the apparent "order" of the polymerization by measuring
the rate of disappearance of monomer, at different silica concentrations and pH.
The equations for second and third order reactions are
Ci l = k 2 t + COl
Ct-Z = 2 k 3 t + C0 2
where k z and k 3 are the rate constants at a given pH and Ct and Co are the
concentrations of monomer at times t and zero. His values for the constants at different pH's are shown in Figure 3.39.
It is significant that the rate constant of the "third"-order reaction below pH 2 did
not change with silica concentration, but the constant for the "second" order reaction above pH 2 decreased when the silica concentration was less than about 0.06 M
(360 ppm). The authors pointed out that pH affects the rate, not by the direct
LOGlo k3
2.0
o
1.6
-I
1.2
pH
Figure 3.39. Rate of disappearance or monomer by polymerization at different low pl-l's and
Si0 2 concentrations. molar: Circles - 0.0128: Triangles - 0.0417: Squares - 0.0641 and
0.834: k 3 k 2 - polymerization rate constants below and above pH 2.2. [From Ok kerse (29).]
257
of Silica
particle
catalytic effect of H+ or OH-, but by their effect in generating positive or negative

ions on reacting species, which then react with nonionized species. However, this
does not explain why it was only in the case of the "second"-order reaction involving
negative ions above pH 2 that silica concentration had any effect.
The reason may be related to the phenomenon of the induction period noted at
low silica concentration, to be described later. The rate of disappearance of
monomer is very slow when the initial reaction can occur only with ionized
monomer or dimer. However, after some polymeric species with more acidic SiOH
groups have been formed, these ionize to a greater extent than monom.er and then
more rapid polymerization occurs, giving a higher rate constant. At low silica
concentrations, this stage is reached more slowly.
It was previously suggested by lIer (87) that polymerization below pH 2 was not
catalyzed by H+ ion, but by HF. However, Okkerse doubted that fluorine was
present in his system, since "no trace" of fluorine could be found in the sodium silicate used. Although Her noted that as little as 2 ppm of fluorine ion had an effect, it
now seems unlikely that this amount could be present in all the systems studied.
In a possibly related effect at low pH, Bogdanova (146) observed that below pH 3
the rate of depolymerization of polysilicic acid when greatly diluted is acid
catalyzed; that is, the rate increases with decreasing pH. The rate is independent of
the diluted Si0 2 concentration from 30 to 560 ppm at 20C. Traces of fluorine were
probably present since the polysilicic acid was derived from natural natrolite. As
shown by Iler, fluorine raises the pH of minimum polymerization rate from 2 to 3.
sasuring
mdpH.
are the
s at difH 2 did
er reac0.06M
e direct
Audsley and Aveston

Audsley and Aveston (147) made very careful measurements of molecular weight by
light scattering, ultracentrifugation, and viscosity, on a 2.19% solution of silicic acid
at pH 2.1 as it polymerized at 24.5C for 29 days. Since the sol was made on the
alkaline side and purified by ion exchange, the silica must have polymerized to small
spherical particles in the first day or so. Further polymerization during the next 28
days then involved aggregation. The viscosity and molecular weight data can be
interpreted in terms of the growing volume fraction of microgel and the size of the
microgel regions which corresponds to molecular weight. This is consistent with the
view of the authors that polysilicic acid does not exist in solution as an extended
chain.
.H's and
6.tI '''d
(2lj .
Figures 3.40 and 3.41, based on the investigators' data, show the increase in limiting viscosity n,P/C, from which the fraction of water immobilized within the
polymer or microgel was calculated. From the Mooney equation. viscosity increases
rapidly as the volume fraction of dispersed phase approaches 0.5, that is, where half
of the liquid volume is occupied by microgel. Then in their 2.19% silica sol. where
the overall molar ratio H 20: Si0 2 is 148: 1, gelling should occur when the ratio in
the gel phase reaches 74: I. From Figure 3.41 the weight-average molecular weight
at this ratio is about 4 x 107 On the other hand from Figure 3.40 at the gel point
the limiting viscosity is 0.75 and from the authors' curve (Ref. 147, Figure 7. not
reproduced here) this corresponds to a molecular weight of lOS, which is a reasonable agreement.
..
~'""~.:~",...
~- ~
,;-
-~
258
\,
..
1.00
GEL
0.50
u
.....
Q.
til
c:
...c:;;>;
0.20
u
(I)
0.10
Cl
E
~
0.05
::J
0.02
0.01
0
10
20
30
DAYS
Figure 3.40. Increase in limiting viscosity during aggregation polymerization: C. silica

concentration. 2.19%: pH. 2.1; temperature. 24.5C: n. p specific viscosity. [From Audsley and
Aveston (147).]
This molecular weight reflects the size of the microgel units as the gel point is
reached. A molecular weight of lOs corresponds to a microgel particle containing 1.7
X 10- 18 grams of Si0 2 Since the microgel contains 2.19% silica and has a density of
1.0 I g ern -3, the diameter of the average microgel particle is calculated to be about
0.27 microns.
The size of the initial silica particles can be estimated from the initial "hydration"
of the silica, reported as 1.8 H 20 per Si0 2 In the foregoing section on viscosity of
sols of very small particles, it was shown that the total bound water on discrete
particles (as silanol groups and hydrogen-bonded water) was related to particle size:
36.9(/2
3.21
H 2 0 : S i 02 = - - = - 11.5d3
d
where d is the particle diameter in nanometers.
From the hydration ratio of 1.8, dis 1.8 nm. The degree of polymerization is 11.5
d", or 65, corresponding to a molecular weight of 3900. This compares with 5000 by
direct measurement.
The limiting viscosity number, nsp/C, of the sol was related to weight-average
molecular weight, M w' of the aggregating polymer, by the relation
n sp
I. 74 x 10 -3 M u.'
U.:l~'
..;
.... - - -
of Silica
259
This and the remarkable linear increase in log of limiting viscosity with time cannot at present be explained in terms of a satisfactory theory of aggregation of particles into growing microgel regions. Obviously, such microgel particles are not uniform in size, as assumed above, but instead cover a range of sizes as shown by the
centrifugation study by the authors. Thus the mathematical implications are very
com plica ted.
.
Weitz, Franck, and Giller
-::. silica
Weitz, Franck and Giller (148) carried out one of the few studies at low pH in which
the polymerization of polysilicic acid was followed by measuring the decrease in
monomer while at the same time measuring the number-average molecular weight
and finally noting the time at which the monomer plus oligomer reacted completely
before any non-molybdate-reactive high polymer was formed. This was done at pH 3
and 20C in a solution containing 4000 ppm Si0 2
Their data were used to calculate the specific reaction rate constant of the
oligomer with molybdate by assuming that the time required to reach maximum
color was when 99% had reacted and by taking into account the amount of
monomer originally present. It is assumed that at anyone time the oligomer
molecules are all about the same size, since otherwise spontaneous particle growth
sley and
148
ooint is
ling 1.7
nsityof
e about
C) 100
en
...J
:E
"-
>1
50
...J
UJ
C)
ration"
osity of
Iiscrete
e size:
0::
:E
20
z
a
UJ
N
10
:J
ffi
:E
~
0::
UJ
is 11.5
iOOO by
~
::
I.L.
(/)
iverage
...J
:E
I
Id~
10
10-
10
Id
MOLECULAR WEIGHT AS
10
10
sro-
Figure 3.41. Immobilization of water in microgel as aggregation polymerization proceeds:

Si0 1 concentration. 1.19'J.: pl-l, 1.1; tern perutu rc, 24.5 C. [From Audsley and Aveston (147).1
Q
--
:...-._-
260
by "Ostwald ripening" would occur. The data are shown in Figure 3.4~ and are
interpreted as follows.
From the fraction. f of silicon that is present as monomer and the number-average
molecular weight. n one can estimate the average degree of polymerization of the
oligorners, P:
f + (1
- j)(P)-1
= 60n- 1
Thus when 43% of the silica is still monomeric and n is 118 then P is 7.3. Between
1.67 and 3.75 days P remained relatively constant between 8 and 11. Thus the
oligomers are in the range of octamers and dodecimers and their numbers increase
and then decrease. This relatively constant size also is indicated by the reaction rate
with molybdate which decreased only from 0.4 to 0.2. (Note that it is the inverse of
the rate that is shown in Figure 3.42.)
Oligomers decline when inert polymer begins to appear. The reaction rate with
molybdate decreases rapidly to 0.1 between 3.75 and 4.75 days. It is probably at this
stage that nucleation of colloidal particles begins. The oligomers dissolve and the
silica is deposited upon the nuclei. The nuclei grow and the concentration of
monomer in equilibrium decreases. The particle size can then be calculated from the
concentration of monomer. The proportion of monomer drops to 5% after 90 days.
which is 5% of 4000. or 200 ppm. This corresponds to the solubility of'2 om particles.
k- I
%
100
9
8
7
6
50
,
5
4
; .
3
2
a
0.2
0.5
1.0
20
50
10
20
50
DAYS
Figure 3.42. The relative proportions (%) of silica present .IS monomer. oligomer. and high
polymer (colloidal particles) as a 400 ppm solution of Si(OIl). polymerizes at :woC at pl l J: A.
monomer: B. oligomer: C "high polymer" or colloidal particles: D. reciprocal of the reaction
velocity constant. k, of oligomer with molybdic acid. [From Weitz. Franck. and Giller (I-lS).]
of Silica
261
2.0 ...--......-...,...-----,---'T-----r--....-------,
and are
e
m of the
~-a,
(/)
.....
o
o 1.5
I.IJ
Between
rhus the
increase
rion rate
nverse of
a::
ex
:c
(/)
1.0
"ate with
ly at this
and the
ation of
from the
90 days,
nm par-
----l_---L
l...---l..._....L.-
10
50
100
...l...-_...l...-
500
1000
.......I
5000
DEGREE OF POLYMERIZATION
Figure 3.43. Relation between the degree of polymerization and the ratio of shared oxygen to
silicon atoms: Circles. Hoebbel and Wicker (84): squares. Bechtold. Vest. and Plambeck (149):
solid line. theoretical relation for silica particles.
Bechtold, Vest, and Plambeck

Bechtold, Vest, and Plambeck (149) prepared polysilicic acids by hydrolyzing ethyl
silicate at low pH and then at various stages of polymerization the silanol groups
were esterified or "end capped" with trimethylsilyl groups. Products were
characterized by chemical analysis and measurement of molecular weight, from
which the proportion of shared oxygen (oxygen atom connecting two silicon atoms)
in the polysilicic acid was calculated. They showed that the polymer was not a linear
siloxane chain, which would have one shared oxygen per silicon atom. Instead they
found that after the degree of polymerization reached about IS the shared 0: Si
ratio increased only slowly and was in the region of 1.5.
This observation led to the postulate that the growing polymer consisted of a ribbon of three parallel siloxane chains. However, similar work later by Hoebbel and
Wieker (84) showed that at higher degrees of polymerization from 100 to 1000, the
ratio changes from 1.7 to 1.8. As shown in Figure 3.43 a composite plot of data of
both investigators indicates that the two sets of observations are reasonably compatible.
The results are consistent with the model that the silica consists of very small
spheres and that "polymerization" in the intermediate stage involves an increase in
size of these spheres. with decrease in their number. As shown in Chapter I. for surface-hydroxylated silica particles the ratio of shared 0: Si atoms is related [0 11, the
number ofSi atoms in a sphere:
and high
pH 3: A.
: rc~"'tion
(1-.
O:Si = 2.0 - 2.42n- 1 3 + 3.911- 2
2.09n- 1
The O:Si ratio according to this formula is shown as the solid line in Figure 3.43.
'.,.'"
,-'
.-'~ :~:-';';'-:"-'
--
-'-Polymerization of Silica
262
However, there is evidence that after a certain point the polymer does not consist of
single particles, but chains and networks of particles, as will be discussed in connection with Hoebbel and Wieker's work (84).
Acker
i ;
Acker (l33a) carried out a study of aggregation very similar to that of Audsley and
Aveston. The initial polysilicic acid had a molecular weight of 2000 and reached
about 3 x 10' at the gel point. The reduced viscosity, (71,. - l)/c, or [17], where 17,. is
the viscosity relative to water, was related to the weight-average molecular weight by
the formula
This is of similar form but very different in value from the equation found by
Audsley and Aveston, no doubt owing to the great difference in silica concentration.
The continued increase in gel strength after the gel point was shown to continue as
.
an extension of the viscosity before gelling.
Hoebbel and Wleker

Hoebbel and Wieker and co-workers (84) published a series of papers describing by
far the most intensive and thorough study of polymerization, simultaneously using
several methods of analysis and characterization to follow the process from the
earliest stages. Individual polymer species were isolated as trimethylsilyl derivatives
and characterized as to molecular weight and composition whence the characteristics
of the original silicic acid were calculated.
The earliest stages in the polymerization of monosilicic acid occur so rapidly that
it was necessary to study the reaction at -2 and even at -13C in order to follow
the formation and disappearance of low molecular weight species in 0.5 and 1.56 M
solutions. The use of ztSi-nmr spectroscopy was essential to clearly distinguish
monomer from dimer-trimer mixtures and from cyclic tetramer and higher cyclic
species. They observed the following negative displacements of the signal (ppm)
toward a higher field as measured on standard compounds of known structures:
Silicic Acid
Monomer
Dimer plus linear trimer
Cyclic tetramer
Higher cyclic
Branching groups-
Range
73.0-73.5
-82
90.4-91.5
91.8-92.6
99 - 101
Silicon linked through oxygen to three other silicons.
This was combined with improved methods of making trimethylsilyl derivatives of
263
.n of Silica
consist of
n c""nec-
these intermediates and clean separations by temperature-programmed gas

chromatography. As shown in Figure 3.44, the most significant conclusion was that
first there is a buildup of dimer, linear trimer followed by cyclic tetramer, and then
polycyclic polymers and three-dimensional polymers. The polycyclic compounds are
detected by the branching groups.
.
About 90% of the monomer had disappeared by the time the small cyclic
polymers had reached their peak. At pH I even at -15C the reactions went more
rapidly and higher polycyclic acids accumulated and then went on to higher
branched polymers.
The transformation of the latter, by further condensation with dimer, trimer, and
tetramer, to silica particles large enough to act as nuclei for particle growth, must
occur at some point. However, the mechanism, including internal rearrangements to
form a dense silica core, is not yet known. It probably involves breaking and reforming new siloxane bonds within the initial three-dimensional polymer in such a way as
to allow maximum formation of siloxane groups and elimination of silanol groups
with some shrinkage in particle size. However, the main effect will be to create more
SiOH and fewer Si(OH)z groups on the surface. The single silanol groups are more
highly ionized and thus condensation of additional monomer occurs much more
rapidly.
Once these nuclei have consumed all the smaller oligomer species, the resulting
colloidal particles remain in solubility equilibrium with monomer. However, if the
concentration is more than a few thousand parts per million (0.6% or 0.1 M SiO z)
the particles soon aggregate into strings or branched networks of microgel.
In earlier studies at 25C, Hoebbel and Wieker obtained basic data on the
polymerization of a 0.4 M solution of monosilicic acid (2.4% SiO z) at the most stable pH of 2.0 as the solution aged from 5 min to 24 days. Measurements were' also
dsleyand
::1 reached
there '1,. is
weight by
found by
entration.
mtinue as
cribing by
usly using
fr
the
lerivarives
acteristics
.pidly that
to follow
id 1.56 M
listinguish
her cyclic
aal (ppm)
res:
70
60
50
0'"
40
0~
30
en
20
10
40
80
120
160
200
240
280
320
360
400
MINUTES
Figure 3.4-t
va,
; of
Earliest stages in the polymerization of 0.501 monosilicic acid at - 2C and pH
2.0: A, monomer: B. probably cyclic trimer, may also be dimcr and linear trimer: C. cyclic
tetrarner; D. higher polysilicic acids. [Hocbbel and Wicker (84).1
. ':r"'.""::~-=t1'
."
. . . r..:...- :~.::~
~..,..
.",
:"~'
264
.:t
- -:-
:..
-
-:
..
2
..
ILl
I-
~
~
....
. -,
:>
-.~
::J
en
{
.C'
10
u,
20
ILl
,!
30
~ 40
.!
60
80
100
.,
10
20
30
40
50
60
MINUTES
Figure 3.45.
Reaction of polysilicic acids at various stages of polymerization with molybdic

2SC. A. polymerized for 5 minutes: B. I
hour; C.4 hours: D, I day: E, 3 days: F. 5 days: G, 8 days: H. 2.J days. For comparison: I monomer, 2 - dimer, 3 - three-dimensional polymers. 4 - same curve as D double: chain
polymer. [From Hoebbel and Wieker.1973 (84).]
acidr SfO, concentration - O.4m: pH -2: temp. -
'. i
made at 0.084 and 0.97 M concentration. The following data were presented: as the
polymerization progressed, the reactivity of silica to form yellow silicomolybdic acid
decreased. In each sample taken at different aging times, the percent of silica
remaining unreacted with molybdic acid was measured versus the reaction time up
to 80 min. For each age of silica sol, that is, stage of polymerization, the reaction
rate of the high molecular weight fraction was calculated as k H.\f min -I. Figu re 3.45
is based on Figure 1 of Hoebbe1 and Wieker (Ref. 84, 1973).
In 5 min, 40% of the silica had polymerized to dimer. By chromatography it was
shown that after I hr, perhaps 40% of the monomer and dimer had polymerized to
form cyclotetrasilicic acid as well as some hexarneric silicic acid and higher
polymeric acid. After 4 hr, about 50% of the polymers up to tetramer were
converted to cyc1opolysilicic acids with an average molybdate reaction rate constant
of 0.103 min - I .
As shown in Figure 3.46, there is a discontinuity in the relation between molecular
weight and the molybdic acid reaction rate constant that distinguishes oligomers
from higher polymers. As will be shown, this change occurs at the point where the
"high molecular weight," that is, colloidal, species begin to be the main constituent.
After 1 day, 15% of the polymers up to tetramer remained with a higher polymer
that had a reaction rate constant of 0.025 min - I and appeared in chromatograms as
. f
" I,
:- .. ~
Silica
olybdic
:5: B. I
265
a band. the position of which changed with molecular size. The molecular ~eight of
the polymeric species. as determined on the trimethylsilyl derivative. was 3440. corresponding to a degree of polymerization of about 52 silicon atoms per molecule or
equivalent to an anhydrous SiO z particle 1.65 nm in diameter.
Thereafter. as the solution aged 1-8 days. the polysilicic acids were converted to
trimethylsilyl ester species in which SiOH groups of the acids were converted to
SiOSi(CH 3)3 groups. After removal of volatile oligomer species by evaporation
and/or solvent extraction. the high molecular weight polysilicic acid derivatives were
analyzed for C, H, and Si, and the molecular weight in benzene determined by a
sensitive vapor pressure osmometer. The molecular weight of the polysilicic acid was
calculated from that of the trimethylsilyl ester and correlated with the rate constant
of the reaction with molybdic acid. From 8 days to the gel point at 42 days, the
molecular weight was estimated only from the molybdate reaction constant.
The authors showed the absence of polymers consisting of linear multiple chains
but left open the question of the nature of the high polymer species. It is here
proposed that in the I day old sol, when the degree of polymerization reached 52
silicon atoms per molecule, the polymer existed as spherical silica particles. In the
period of 1-8 days, these particles increased in size and decreased in numbers by
Ostwald ripening. Then between 8 and 42 days. the particles continued to increase in
size as they aggregated into chains and networks until gel was formed.
During the period of Ostwald ripening the molecular weight was estimated from
the rate constant of the reaction with molybdate. This constant decreased as the
In: 1-
ec
5
10
(3
..
as the
ic acid
. silica
me up
action
'e 3.45
it was
zed to
higher
. were
nstant
:t:
'N
(/)
u.. 10
0
:t:
I Day
-,
w
3:
a::
<l:
...J
,-" - -- .........,
"-
, \
10
=>
,
"
W
...J
Cubic Oclamer-0.52
Cyclic Hexamer-0.58
" Cyclic Telromer - 0.67
imer
0.9
Monomer- 1.7
10
ecular
omers
.re the
uent.
IlylT' ..r
irn,
0.001
0.01
0.1
10
Figure 3A6. Relation between molecu lar weight of (SiO z. :< HzO)" and rate constant of reaction with molybdic acid k ll M It may be significant that the cubic octarncr and cyclic hcxamcr,
which arc not on the linear plot. arc also not round in the course of aqueous polymerization of
monosilicic acid. [From Hoebbcl, Wicker ct ~II.. 1973 (84).J
266
..
..
"
particles grew in size. However, during the aggregation process the rate constant did
not decrease much further. When particles associate into chains, only a small part of
the surface area is lost at the points of contact.
Thus even though the effective molecular weight may have increased to millions as
the aggregates increased in size, .the molecular weight calculated from the molybdate
reaction constant corresponded only to the size of the particles making up the chains
and networks. Hence even though the molecular weight of the aggregates
approached infinity at the gel point, that of the equivalent constituent particles only
reached around 100,000, or a degree of polymerization of 1800.
The authors measured the molecular weight of the isolated trimethylsilyl derivatives of the high-polymer fraction during the first eight days of polymerization.
These were calculated from the formula
where x is the ratio of silyl groups to silicon atoms of the polysilicic acid and n is the
degree of polymerization as determined by osmometry.
The authors give evidence that all silanol groups were converted to trimethylsiloxy
groups. The molecular weight of the 'polysiltcic acid was calculated according to the
formula
Values for x and n at different polymerization times are shown in Table 3.8. The
number of shared oxygen atoms per silicon atom are calculated from x, As shown in
Table 3.8.
Values of n and x Calculated from Hoebbel and Wieker's Data
Molybdate
Reaction
Sol
Age
Constant.
(days) k H .., (min-I)
I
2
3
5
8
24
40"
I:'
25
8.5
7.6
3.2
2.1
0.76
X
X
X
X
X
X
/0-3
10- 3
10- 3
10- 3
10- 3
10- 3
Mol. Wt.
Reported
Silyl
Ester
Silicic
Acid
5.903
13.092
18.747
32.651
45.000
3.440
7.940
11.400
20.960
29,430
(80.000 C )
Observed
Corresponding
Degree of
Polymerization. n
52
122
175
325
460
( 1260 C )
( 1800C )
Calculated"
2 - 0.5x
OH:Si
O:Si
x
0.65
0.60
0.58
0.50
0.47
0.38
0.36
1.67
1.70
1.71
1.75
1.76
1.81
x
(from n)
0.82
0.70
0.6-t
0.56
0.51
0.39
0.36
Source. Hoebbel, Wieker, et a1. (84).

Extrapolated values.
a Assuming polymer is a spherical silica particle.
From the molybdate reaction constant. However. aggregation had begun and actual
molecular weight was much higher.
,-
-1:
Silica
it did
lrtr~
Ins as
bdate
hains
gates
. only
267
Figure 3.44, the ratio of shared oxygen to silicon atoms is a function of the degree of
polymerization and the values are reasonably in line with those of Bechtold, Vest,
and Plambeck (149).
According to the formulas developed in Chapter 1.
x = 2.15d- 1
1.53d- z + 0.36d- 3
where d is the equivalent diameter in nanometers of an anhydrous SrO, particle

containing n silicon atoms.
erivaition.
= 11.Stfl
d = 0.443n 1 / 3
or
Then
x = 4.8Sn- 1 / 3
7.80n- Z / 3
+ 4.2n- 1
is the
.iloxy
o the
.T
wnin
n)
Values for x were calculated for different values of n after the indicated numbers
.
of days of aging as shown in Table 3.8.
At the low degree of polymerization of 52, there is some discrepancy between the
o H: Si ratio of 0.83 calculated from the formula for a spherical particle and the
value 0.65 calculated from experimental data. However, in the discussion of nucleation theory it will be noted that. as shown in the model in Figure 3.17, at the stage
where the degree of polymerization is 48 (that is, a particle with a SiO z core has
been formed), the model shows a OH:Si ratio of0.66 rather than 0.8 from the formula for a spherical particle! This may be purely fortuitous but it seems to support
the view that the first particles of silica are formed with a nucleus of a three-dimensional octamer or decamer. (see Figure 3.17.)
Thereafter as the particles increase in size, their stoichiometry more closely
approaches that for a sphere, as postulated. Thus above a degree of polymerization
of 500 (particle size as anhydrous SiO z of 3.5 nrn), the composition of the polymer is
very close to that calculated for a spherical particle.
RATE OF POL'i:'tIERIZATION. The increase in degree of polymerization with time is
reasonably well represented by the equation
log
~
3000
3000 - n
0.01/
I
}
ictv
or dnfdt = 0.023(3000 - 11), where n is the degree of polymerization and t is time in

days up to about 8 days (Figure 3.46). At 8 days the degree of polymerization is
about 460 corresponding to a particle diameter of about 3.4 nm. Thereafter aggregation begins, and as it progresses. the microgel network continues to coarsen and
reacts more slowly with molybdate. The extrapolated limit of 11 = 3000 corresponds
to the size of discrete particles (6.4 nm) that would react at the same rate as the rnicrogel polymer docs: this size corresponds to a specific surface area of 400-500 m Z
-"~1
-~
268
g-1 which is reasonable for a gel. Also the size is about that at which the solubility of
silica drops to 100-120 ppm.
It is observed that the constant k H ." of the reaction rate of high polymer with
molybdate is close to being inversely proportional to the degree of polymerization, n,
The approximate relation is .
n
where n ranges from 121 to 1260.
It might be supposed that the reaction rate would be proportional to the surface
area of the silica, and also to the solubility difference between the very small particles and massive silica. It can be shown that by coincidence this difference varies
inversely with the square of the particle radius in this size range. Since the specific surface area varies inversely with radius, the rate should then vary inversely with cube of
the radius which is proportional to n, the degree of polymerization as observed above.
Investigations Through the Neutral pH Range
M erri// and Spencer

Merrill and Spencer (150) showed that in the presence of the electrolytes when a 3.3
ratio sodium silicate solution is neutralized with ammonium sulfate, the minimum
gel time is no longer about 5.5, as for salt-free sols, but moves to pH 7 and higher,
depending on the concentration (Figure 3.47). The gel time decreases, or the gelling
rate increases, not only with increasing silica concentration, but also the increasing
concentration of electrolyte- that accompanies the silica. (See Chapter 4, regarding
the effect of salts on the gelling of colloidal silica at different pH values.)
The very great decrease in gel time with increase in concentration at a given pH in
the range 7-9 is due to the great increase in coagulation effect as the electrolyte
concentration exceeds about 0.1-0.2 N, corresponding to silica concentrations here
of 1-2%.
Ashley and Innes

Ashley and Innes (151) in 1952 pointed out that the low viscosity of colloidal silica
at high concentrations clearly showed that the particles were spherical in shape,
since any other shape, chainlike or even acicular, would cause a much higher viscosity. The conclusion is that silica in some way polymerizes to dense particles of
more or less spherical shape, at least above neutrality.
Baumann
Baumann (152) studied polymerization under conditions where nucleation and
growth of particles could be followed. Wide ranges of concentrations and buffered
\
-:-. ..f Silica
ility of
5000
er w.
:ion, n.
::>
::E
~
..J
l partivaries
fie surcube of
ibove,
1.5 25
2000
3.5
(/)
I-
surface
269
1000
500
200
100
50
C)
20
10
5
2
4
10
pH
Figure 3.47. Gel time of sols from mixtures of sodium silicate and ammonium sulfate. Numbers on curves: % Si0 2 [Data by Merrill and Spencer (150).)
n a 3.3
nimum
Jig
gelling,
'easing
arding
pH in
trolyte
IS here
I silica
shape,
er visdes of
nand
Iffe" -l
pH were employed to follow the polymerization of monomeric silicic acid, the

concentration of which was followed by the molybdate method. Baumann (72b) also
followed the early stages of polymerization at pH 3 and 6. I by stopping the molybdate reaction in samples by adding citric acid and reducing. the yellow complex to
molybdenum blue for greater sensitivity.
In the alkaline pH range 5.8-9.0 the polymerization, which we now know consists
mainly of growth of very small spherical particles, showed an induction period, if the
concentration was low enough, after which monomer disappeared at an increasing
rate and then at a negligible rate as monomer concentration approached 150 ppm,
corresponding to the solubility of particles about 3 nm in diameter.
For Baumann's Figure I, the values were recalculated to obtain the amount of the
silica in excess of ISO ppm (the final value at longer times) that remained as
monomer at time t (minutes). This was then plotted against log t, as in Figure 3.48.
It is noted that the curves appear to have an inflection point at 50% remaining
monomer, at a time designated t l
When log t l is plotted against the reciprocal of the initial concentration of
polymerizable silica (parts per million in excess of 150). straight lines are obtained
as in Figure 3.49. In Figure 3.48 the shape of the curves strongly suggests that the
reaction rate is a function of monomer concentration times "polymer" concentration. The curves appear to be symmetrical about the point where half of the
monomer has disappeared.
The following relationship may be adduced: let C = fraction of polyrncrizable
.~-'
~ -,-:.
"'-"'-.
270
a::
l.LJ
:E
o
~
:E
100
l.LJ
.-1
lD
<l
N
a:l.LJ
:E
,
,-
:
:'
50
l.LJ
~
<l
l.LJ
a::
::J
l.LJ
l.LJ
a.
1000
100
10
TIME - MINUTES
Figure 3.48.
Unreacted monosilicic acid versus time in polymerizing solutions:
Curve
Silica
Concentration (ppm)
A
B
,
I
I
7.2
7.2
7.2
7.2
2020
1010
645
490
1550
1050
765
1012
600
435
pH
D
E
F
G
H
I
J
5.8
5.8
5.8
9.0
9.0
9.0
P .. polyrnerizable silica - (total - 150) ppm. [Data from Baumann (152).)
monomer at time I. Then Cis 0.5 at time t; Assuming
-dC
d log I
log
= kC(l - C)
1- C
= k log
C
Ii
From the data, k = 32 C-0.5.

The relation between I, and the initial concentration Co follows the empirical
f Silica
271
equation:
log II
29
+ 800C;! - 4.02
pH
,;. - -
where Co is the initial concentration of polymerizable SiO z.

It is likely that there is a similar relationship over the range of pH and concentration, since the data can be expressed by a single empirical equation except at high
concentration at pH 9, where no correction was made for the presence of Si0 3 - ions
which reduce the amount of polymerizable silica.
A possible explanation of the rate equation may be that a small portion of the
monomer polymerizes first to a three-dimensional nucleus such as polycyclic
. octamer or decamer, and that the main reaction is the addition of monomer to this
polymer, as will be discussed in relation to the work of Marsh, Klein, and Vermeulen (32). From solubility the final particle size is about 3 nm. If the initial nuclei
have an average diameter of around 1.5 nrn, then only (1.5/3.0)3 or 12.5% of the
silica initially is needed to serve as nuclei, after which the addition of monomer
proceeds by reaction with the particle surface until the monomer level approaches
the solubility of the particle.
Coudurier, Baudru, and Donnet
Coudurier, Baudru, and Donnet (36) made an extensive study of the polymerization
of "disilicic acid" in nearly neutral solution. By removing Na + from Na zSi0 3 9H zO
(f)
ILl
::J 200
5E
c::
ILl
:E
100
50
s
:E
ILl
...J
CD
<t
20
0:
10
ILl
:E
~
a..
u,
lJJ
u,
...J
u,
...J
<t
RECIPROCAL OF SILICA CONCENTRATION (PPMj'xI0
Figure 3.49. Relation between half-life of monomer and reciprocal of

polymerizablc silica at different pH"s. [Data from Baumann (152).)
concentration of
:'~:'-~'1
:.... ...
272
in solution at pH 2 they obtained more than 50% dimer plus monomer. but' since
both react so rapidly with molybdic acid both are called "monomer:'
Their data indicate that below pH 5-6 silicic acid first polymerizes to discrete
particles less than 4 nm in diameter (less than 50,000 molecular weight) and then if
the silica concentration is high enough, these particles aggregate by linking together
into chains which branch into three-dimensional networks, each of which is a
"polymer" molecule of much higher molecular weight according to light scattering.
Eventually all the discrete particles join the networks. which finally fill the aqueous
medium forming a gel.
The solution containing only 0.6% Si0 2 polymerizes rapidly to discrete particles
before the latter begin to aggregate (Figure 3.50). The concentration of "monomer"
decreases rapidly, whereas increasing amounts of oligomers and then higher
molecular weight polymers are found. Then the oligomers decrease as the polymers
become colloidal particles. The size of the colloidal particles must be less than 4 nrn,
judging from the concentration of monomer in solubility equilibrium. They increase
in size only slowly thereafter, as evidenced by the small decrease in their equilibrium
solubility, indicated by the monomer concentration.
The increase in molecular weight by light scattering is entirely due to aggregation
of the preformed primary colloidal Si02 particles into networks (Figure 3.51).
Donnet and co-workers recognized several early stages in the polymerization and
classified the corresponding polymers as oligomers. As shown in Table 3.9.'the reactions are 'only some of the possible ways in which oligomers are formed. Oligorner-I,
6000
----:------EQUILlBRIUM-----------
100
(f)
<:
(f)
::J
::E
a.
a.
<{
u
::3
:I:
3000
::I:
t.:)
50
Vi
l.LJ
a:;
<l:
...J
::::l
U
l.LJ
...J
5
HOURS -
10
15
20C
Figure 3.50. The relative proportions of "monomer:' oligomer and colloidal species at 6000
ppm of monomer as Si02 polymerizes at pH 5. Open circles. "monomer": squares. oligomer:
solid circles. polymer (nonreactive with molybdate). [Data from Coudurier, Budru, and Donnet
(36).]
,r Silica
It since
en 20 .....------.----,---.,...-----.
z
o
Iisc
then if
ogether
.h is a
ttering.
.queous
articles
iorner"
higher
ilymers
:14 nm,
ncrease
librium
egation
ion and
te reacarner-I,
273
15
10
20
30
40
HOURS
which includes cyclic tetrarner, is of such low molecular weight that it can still
depolymerize and react with molybdic acid at a relatively rapid rate. Still higher
molecular weight oligomer-Z de polymerizes to monomer only slowly, the rate
diminishing with the molecular (particle) size.
The effect of pH on the relative rate of disappearance of monomer and formation
of high polymer is shown in Figures 3.52 and 3.53.
At pH about 2 the initial disappearance of dimer is due to condensation with
itself, since they found the reaction is "second order," giving a linear plot of the
reciprocal of concentration of unreacted "monomer" versus time. On the other
hand, at pH 7.2, the reaction is "first order," the "monomer" adding to polymer
particles formed almost instantly after the pH was raised. In this case a plot of low
concentration of unreacted "monomer" versus time is linear with a negative slope.
From the curves it is apparent that the rate of disappearance of "monomer" and
of appearance of polymer decreases with change in pH from 1.2 to about 3, then
increases to pH 5 and 7.
Table 3.9.
Polymerization of Silicic Acid at pH 1-5-0Iigomer Species
Stages of Polymerization
Designation
Probable Structure
(I) 2 Si(OH). '" (HOhSiOSi(OHh
Dimer :
Monomer, dirner, some trimer
"Oligomer- I"
"Oligorner-I "
"Oligorner-Z"
Cyclic trimer (?)

Cyclic tetramer
3Dimensional polymers
(nuclei)
Particles 2-4 nm in size
H 20
(2) Si(OH). + dirner .. [(HOhSiOh
(3) Dimer + dimer '" [(HO)2Si-O].
(4) Trimer and tetramer plus
monomer
(5) Si(Of:I). + nuclei
"Oligomcr-J"
(mol.
. at 6000
.ligorner:
I Dt'-"ct
Figure 3.51. Molecular weight of polymer by

light scattering as monomer polymerizes at a
concentration of 6000 ppm Si0 2 at pH 5. [Data
from Coudurier, Badru, and Donner (36).]
OL..-----'=~-...L.-----'----'
W1. Jess
than
50.000)
(6) Oligorner-J + oligorncr-Z
Higher polymer
Aggregates of particles
(mol. W1. up to millions)
Refer 10 Coudurier, Baudru, and Donner (36)
--
~ ...
274
100
en
...J
.f
I.L
50
~~..i
U
0::
W
,I
.i
Q.
"f
;f
. t,
i
o
10
0.1
100
1000
HOURS
Figure 3.52. Effect of pH on course of polymerization at 6000 ppm SiO z: M. "monomer"; P.
polymer. [Data from Coudurier, Badru, and Donnet (36).)
Thus there are two entirely different mechanisms involved in the conversion of
monomer to polymer. Hydrogen ion must be the catalyst in this system below pH 3,
although with higher silica concentration this is true below about pH 2. Above pH 3,
the OH- ion is the catalyst for the addition of monomer or dimer to the growing
polymer. This addition is believed to be because the oligomer-2 particles have SiOH
surface groups that are more acidic and thus more highly ionized than those of
monomer or dimer. Thus monomer and dimer condense with these surface groups
. more rapidly than with lower molecular weight species.
The overall rate of disappearance of monomer-dimer (M) indicates that it reacts
simultaneously with itself. with oligorner-I (0 1) and with cligcrner-Z, which was
"
:3
>
-l
o
2
6
pH
10
Figure 3.53. Effect of pH on V. the

initial rate of disappearance of monomer
at 6000 ppm SiOz [Data from Coudurier,
Badru, and Donnct (36).)
275
later called S; (polymerized silica). At pH 4, the rate V was found to be

V
= K [Mp14 exp (0.135[0 1 + Sp])
The effect of temperature on the rate of disappearance of dimer was also

measured. In the above equation only K varied with temperature. The energy of
activation was 14.6 kcal mole- 1 at pH 4 for the process of polycondensation.
Aggregation of the silica particles referred to as oligomer-2, or Sp, begins at about
the time where the monomer or dimer has been mostly consumed and very little
oligorner-I remains (Figure 3.52). The rate of aggregation in anyone sample in the
pH range 1-6 follows the equation
: P.
of
I 3,
I 3,
in4
)H
. of
ups
lcts
was
the
.ner
-ier
where M w is the molecular weight of the aggregates at time t, and M o is the initial
molecular weight of the discrete particles. The size and number of the discrete particles remains constant in any particular sample below pH 6.
As shown in Figure 3.54, linear plots are observed except above pH 6, where it is
known that the particles grow by Ostwald ripening. Also the particles begin to have
an increasing ionic charge above this pH, sufficient to prevent collision and aggregation. At higher pH the increase in molecular weight is then identical with the
increase in particle size, since no aggregation-polymerization occurs. The curve of
Figure 3.54 at pH 6.3 is in a transition region where aggregation and particle growth
are both occurring.
It is of incidental interest that at pH 4, curves 1 and 4 of Figure 3.54 differ only in
silica concentration. The slope, which is the rate of increase in molecular weight, is
proportional to the square root of the silica concentration, and in this case to the
square root of the number of particles per unit volume.
Donnet and associates examined the solutions at the point where monomer-dimer
had been largely consumed using polarized light. This showed that at pH 5-6 the
polymer consisted of extremely small spherical particles, whereas below pH 5 the
polymer was apparently more anisotropic. The fact that the particles had begun to
link together into chains probably explains the observation.
The rate of aggregation was shown in general to be related to the total silica
concentration as follows:
The overall temperature coefficient indicated an energy of activation of 15.1 kcal

mole:" for the process of aggregation at pH 4.
Gels obtained from some of the polymerized sols were isolated and characterized.
The specific surface area of the gels by nitrogen adsorption was related to the pH of
the preparation as shown in Figure 3.55. However, it is known that gels with specific
..,
~_
...
276
6
i
"j
I
I
!
10
20
30
40
TIME AGED - MINUTES
Figure 3.54.
Molecular weight of polymer versus time.

Curve
pH
4
4
2
3
5
4
6.3
7
5
6
Temp. (0C)
Si0 2 (gl-I)
35
50
20
35
20
20
16
6
16
6
6
6
[Data from Courdurier, Badru. and Donnet (36).J

"'
surface areas higher than 800 m Z g-1 shrinkupon drying so that pores become too
small to admit entry of nitrogen molecules to the whole surface.
It is also known that the specific surface area of a gel is not much less than the
ultimate particles of which it is composed. The silica made at pH 5 with 800 m 2 g-I
corresponds to ultimate spherical particles about 3.5 nm in diameter, and by
extrapolation the particles of the silica made at pH 4 would be about 2.3 nm in
diameter. As will be seen from consideration of other investigations, this is close to
the size of particles made in a similar manner, but characterized by other means.
Marsh, Klein. and Vermeulen

Marsh, Klein. and Mermeulen (32) prepared a comprehensive review of the literature on polymerization kinetics and equilibria and conducted a detailed study to
establish the polymerization mechanism in the range of silica concentrations of
200-1800 ppm and pH 4-10 at 25C. Starting with Si(OH). solution prepared from
Na 2H zSi0 4xH zO by ion exchange at about pH 2.5. mixtures buffered with acetate
were made at various concentrations and pH values and the rates of polymerization
..
f Silica
;,..----
277
and disappearance of molybdate-reactive silica were measured. The "reactive silica"

was mainly Si(OH). and for convenience is referred to as "monomer:' Strong similarities in results can be noted between data presented here and in Figures 3.48-3.52,
both of which suggest nucleation and particle growth.
Valuable new data were developed, but the authors did not consider all the
implications of the fact that at least under the alkaline conditions studied, the
"polymerization" must have consisted of the nucleation and growth of dense amorphous particles of colloidal silica which were in solubility equilibrium with
monomer.
Fortunately in many of the experiments, the ionic strength and silica concentration were sufficiently low that little or no aggregation or gelling occurred so that
"polymerization" involved only nucleation and particle growth. The ionic strength
of the buffer was varied but not taken into account as a factor that could affect the
rate of polymerization.
Several interesting points can be deduced from the data on
polymerization at pH 8, which is shown in Figure 3.56. This confirms the earlier
observation of Baumann (152), who was apparently the first to observe that under
some conditions of pH and concentration there is an "induction period" during
which there is little or no polymerization of monomer. Marsh, Klein, and Vermeulen
also found that when the monomer solution, in the concentration range' of less than
500 ppm, is suddenly alkalinized from pH 2, where it is relatively stable, to pH
around 8, the monomer does not begin to disappear at once, but only after an indueINDUCTION PERIOD.
ne too
an the
m2 g-1
nd by
nm in
lose to
1S.
Iiteraidy to
JOS of
j from
zat.
Figure 3.55. Effect of pH onthe specific

surface area of silica gel. Dottcd line:
probable values if area had been
determined in solution to include smaller
polymeric species. [Data from Coudurier,
Badru, and Donnet (36).]
--
..~~
... ".
,1
~._-
278
.
Q
1.0
lJJ
N
a:
LU
~
0.9
Q..
z 0.8
::J
.l
<
u 0.7
:J
u;
4-
0.6
0.5
<
0::
4.
0.4
0.3
10
100
MINUTES
1000 10,000
Figure 3.56. Disappearance of monosilicic

acid versus time at different concentrutions of
359-697 ppm sio, Temperature. 25C: pH.
8.0. A-C. induction times at which polyme;i.
zation began: -H. times at which "nuclei"
may have appeared: I-L. points at which
monomer concentration became the controlling factor: -H. approxirnate inflection
points. [Data from Marsh. Klein, and Yermeulen (32). Circles: data by Ginsburg and
Sheidina (154) for 400 ppm concentration
interpolated between pH 7 and 9.J
lion period. The induction time increases enormously with only a relatively' small
I
I
j!
.1
I'
I
!
Iij;
,I.
;.
!
I
.1
decrease in total silica concentration. as can be seen at points A. B. and C in Figure

3.56. Then the monomer concentration drops at an increasing rate to points E-H.
suggesting that the initial formation of polymer is autocatalytic. Here also a small
decrease in the total silica concentration causes a large decrease in the rate. Based
on the relation between silica concentration and rate of the reaction. a "reaction
order" of 6 or 7 is indicated.
The authors concluded that polymerization of monomer involves a reaction
between Si(OH)4 and =SiO- ions, whether the latter are in solution as HSi03 - or
on a polymer as an ionized =SiO- group. This is the mechanism suggested by
Ashley and Innes (lSI). Marsh. Klein. and Vermeulen similarly explained the autocatalytic effect on the basis that the ionization constant of SiOH groups on the
polymer increased with the molecular size. and thus as more polymer formed and
grew in size the total concentration of SiO- ions in the system at a given pH also
increased by orders of magnitude. Thus the rate increased until there was an offsetting decrease in the concentration of Si(OH)4'
This may well be a valid explanation and is also consistent with the fact that the
rate of disappearance of monomer is approximately proportional to OH - Ion
concentration. which in turn determines the concentration of SiO- ions in the range
from 6 to 8. and thus the reaction rate in a given system.
NUCLEATION. One can also consider this induction phenomenon in terms of nucleation of colloidal particles in the 10-20 A size range, which then grow by further
deposition of silica from solution. The extreme effect of concentration on the induction period might be expected from nucleation theory. According to Nielsen (153).
.".
...
ilica
ilicic
ns of
PI1.
nericlei"
.hich
.trolction
Verand
arion
mall
gure
:-H,
m.
asea
ction
ction
;- or
j by
iutoI
the
and
also
:,.....
279
the apparent kinetic order of nucleation may be as high as 10. As shown in 'Figure
3.56, one may relate the times at the inflection points with the concentrations and it
will be seen that a plot of log time versus log concentration corresponds to a "reaction order" of 7 or 8. In this regard, the phenomenon resembles nucleation in other
systems. In Figure 3.56, points E-H probably represent the points after which no
additional nuclei are formed.' They then grow at the expense of monomer and
oligorners to points I-L, after which "Ostwald ripening" occurs and they are iifsolubility equilibrium with monomer as they grow.
PARTICLE GROWTH. The monomer concentrations after points I-L can be used to
calculate the size of the colloidal particles versus time. In the molybdate test, the
"unreactive fraction" corresponds to colloidal silica, and the "reactive fraction" is
monomer or "soluble silica." Using the graph of Figure 3.57 relating particle size
and solubility (taken from Figure 3.32) the calculated particle size versus time is
shown in Figure 3.58.
.
The linear relationship over such a wide range and the fact that the lines are
parallel over a certain range of size and silica concentrations indicate that the same
growth mechanism is involved at all four concentrations. It is also noted empirically
that for a given particle size, log time is a linear function of the reciprocal of the
silica concentration (Figure 3.59).
Ginsberg and Sheidina

Ginsberg and Sheidina (154) in a similar study gave some data similar to that of
Marsh, Klein, and Vermeulen, but observations were not reported for short enough
times to note the induction phenomenon. However, the final monomer concentration
in a 400 ppm solution at pH i was 120 ppm after 30 days at 25C, corresponding to
:::E
Q..
Q..
N
0
in
800
(J'J
::>
Tsett the
..
ion
ange
'
:I:
500
Q..
cc
0
:::E
u,
>~
200
:J
iii
::>
-l
nuc-
rther
.duc-
152
(J'J
100
2
5 6 7
PARTICLE DIAMETER nm.
Figure 3.57. Solubility as a function of the

particle size of amorphous silica formed at
25C. [Data from Chapter I.]
5 X 10 r------,r----r--...,---..,....----,
.
,
535
10
I
::I
-~
.: i
i
..
':'1(
I.
(f)
W
I-
--.j
'\
I
I
:;)
:i
10
.:
-:
10
: I
I
PARTICLE DIAMETER nm
2
ferlc
280
Figure 3.58. Time required at pH 7.

25C. for silica to polymerize to particles
of a given size. Silica concentrations indicated parts per million. [Data from
Marsh. Klein. and Vermeulen (32).] .
Figure 3.59. Time required at pH 7. 25C.

for silica to attain the indicated size versus
inverse of silica concentration (rpm). [Data
from Marsh. Klein. and Vermeulen (32).)
.. -
\...
"
281
the solubility of particles 3.7 nm in diameter. This compares with 3.5 mn

extrapolated from Figure 3.58.
Investigations Aboye pH 7
Greenberg and Sinclair
Greenberg and Sinclair (ISS) examined the polymerization of silica in the pH range
of 7-12 in mixed solutions of ammonium acetate and sodium metasilicate by means
of light scattering. Unfortunately, the pH and electrolyte concentration (sodium
acetate) were not controlled separately, so their effects could not be distinguished.
However, this is one of the few studies in which the main reaction involved growth of
porous microge/ particles 20-120 nm diameter containing water, by aggregation of
primary particles of the order of 3-4 nm diameter, followed by a secondary aggregation of the microgel particles to form a solid gel.
In the absence of salts in this pH range it is known that polymerization of
monomer at these concentrations forms particles about 2 nm in diameter in a few
minutes. However, in the presence of ~0.3 N ammonium acetate. which is above the
critical coagulation concentration for 2 nm SiO z particles. these particles then
aggregate.
Since the silica concentrations were generally less than I %, the sol did not form a
coherent gel. Instead the aggregates formed secondary, roughly spherical gel particles which grew in size to 150 nm and then these in turn coagulated. These aggregate
gel particles are highly porous and, as the authors emphasize. are in a "highly solvated state" since, of course, they- include much water. It was shown that up to a
diameter of 120 nm, the diameter of the secondary particles increased linearly with
time. The explanation might be that after a certain number of secondary particles
have been formed to act as nuclei early in the process, when most of the primary
particles are still nonaggregated, no additional aggregate nuclei are formed, so that
the rate of accretion will be proportional to the surface area of the growing particles
and the concentration of primary particles
where D is the diameter of the growing secondary particles and C is the concentration of primary particles. Early in the process, C will be nearly constant so that D =
k't, as observed. However, there is no way of knowing whether in fact only a small
part of the total silica had formed secondary particles by the time they reached 120
nm in diameter.
The kinetics of formation of primary aggregates and combination of these into
larger secondary aggregates remain to be determined.
\
Greenberg
to
Greenberg (156) also studied polymerization of silica in a mixture of sodium metasilicate and ammonium acetate which served as an acid to lower the pH below about
10.7 so that the silicic acid was liberated and polymerized. He followed polymerization by small changes in the refractive index of the solution which bear a significant
but not entirely understood relation to the condensation of SiOH groups to siloxane
(Si-O-Si) linkages. No polymerization occurred at pH 11.4 but rates were measured
at pH 10.0 and 10.8. It was concluded that the rate of disappearance of SiOH
groups in the system followed the first-order equation:
-dC
dt
kC
[OH-]
where C is the concentration of silanol groups, t is time, and k is a constant. In this

region the rate increases with decreasing pH, no doubt owing to increasing conver-sion of HSi03 - to Si(OH). which polymerizes. The rate is also proportional to the
concentration of uncondensed silanol groups.
Goto
Goto (157) was one of the first to examine the polymerization of silicic acid in the
absence of salts and in the pH range 7-10, where colloidal particles are formed and
no aggregation or gelling can occur as at lower pH. He used the equation
-dC
.;
! .
dt
= k(C-
S)3
to calculate the rate constant k, where C is concentration of monomer at time t, and

S is the solubility of "amorphous" silica. He found log k to be an increasing linear
function of the pH or log [OH-] such that
He also aged a silicic acid sol containing 2000 ppm Si0 2 for 6 days at different pH
values from 7 to 10 and then measured the rate at which the particles depolymerized
in I g 1- 1 Na 2C03 solution at pH 10.8. Particles formed at pH 7 depolyrnerized
faster and were thus concluded to be smaller than those formed at pH 10.
Tarutani
Tarutani (83) followed the decrease in monomer with time as it polymerized at pH 7
and 25C. The initial monomer concentration was 500 ppm:
.r Silica
Time aged
(hr)
rr,
about
nerizaiificant
iloxane
iasured
. SiOH
'I
In this
conver. to the
: in the
ed and
o
0.5
1
2
3
4
283
Monomer
Concentration
(ppm)
500
400
350
280
240
220
"
Fraction
of Total
1.0
0.8
0.7
0.56
0.48
0.44
From a log-log plot it is evident that there was a nucleation period of about 0.35 hr,
after which the fraction of silica present as polymer increased in proportion to 0.37
(I - 0.35)113, which would mean the rate of disappearance of monomer was inversely
proportional to the square of the amount of polymer that had formed.
By gel chromatography it was shown that after 1 hr as monomer decreased, particles of silica grew rapidly with no intermediate or low molecular weight polysilicic
acid present. This is consistent with the idea that once particles of a certain size are
formed by condensation of small species, further growth occurs by accretion and
condensation of monomer and "Ostwald ripening."
When the molecular weight (or particle size) distribution was revealed. by
chromatography after 2 and 48 hr, it was evident that after the longer time, larger
particles with a narrower size distribution were obtained.
Iler
and
: linear
: I,
ent pH
terized
nerized
It
pH 7
Iler has carried out a hitherto unpublished investigation of the rates at which
extremely small particles of colloidal silica depolymerize to monomer both directly
in the molybdic acid reagent and in dilute alkali in which the monomer is
determined on separate samples by reaction with molybdic acid. The size of the
particles was estimated from the specific surface area, which was determined by the
Sears alkali titration method corrected for monomer. The -measurernents were made
as the particles grew in size at pH 8.5 and also as they became aggregated at pH 5.9.
In Table 3.10, the aging conditions and the ultimate particle sizes are given. In
Figures 3.60 and 3.61 depolymerization rates at low and high pH are shown.
The initial sol made at pH 2.2 (Sample 1, Table 3.10) reacted very rapidly with
molybdic acid reagent. However, a mere 2 min exposure to pH 8.5 greatly reduced
the depolymerization rate in both reagents. which is evidence of rapid particle
growth.
The main difference between the alkaline and acidic depolymerization tests is that
in the alkaline test a small amount of low polymer is not easily detected because it is
soon overshadowed by dissolution of higher polymers.
In the test in acidic molybdate. only 4-8% of the silica is dissolved. Initially. the
molybdate reacts with any low molecular weight species that are present.
...
.._.
284
10
800
a: LlJ
w~
:Eo
Om
600
~g
:E:E
u,
OF:
400
en-
~~
l3 0
O~
a:<
Ai
200
~1IJ
:Ea:
1
1
0
0
10
20
30
40
50
60
MINUTES
Figure 3.60. Reaction of silica particles with molybdic acid at 27C. Total silica present: 10
mg. Slope of linear portion of curve is an inverse function of particle size: extrapolated intercept at zero time indicates amount of monomer and oligomers present. (See Table 3.10.)
The main effect of aging at pH 5.9 is to eliminate low molecular weight species
which are present in sols aged at pH 8.5. As shown in Table 3.10 and Figure 3.60,
the slopes of the lines are parallel before and after aging at pH 5.9, indicating no
change in size. Also, surface-titration measurement of specific surface area and
hence particle size shows a slight decrease, indicating the disappearance of some low
molecular weight material.
At pH 5.9, polysilicate ions, such as the cyclic species, probably aggregate with
the larger particles. This cannot occur at pH 8.5, since both species then bear a
similar high negative charge. Thus the dissolution rate at pH 12 gives a measure of
particle size, but is not sensitive to the presence of smaller particles unless special
attention is given to the very early stage of the test. On the other hand, the molybdic
80
u
z
,....
0
C\l
i=
a::w
~
:::>
..J
en
:I:
40
~ N
0 I
a. 0
w
0
60
20
0
0
MINUTES
Figure 3.61. Depolymerization of silica particles in dilute alkali. The slope of the lines in an
inverse function of particle diameter (See Table 3.10 and Figure 1.14.)
-.
-,
:;
285
Table 3.10. Comparison of Sols of Particles, first Grown in Size

at pH 8.5 and then Aggregated at pH 5.9'"
Time Aged
pH 8.5
at pH 5.9
(25C)
low Mol.
Wt. Species
(ppm)
0
2 min. 25e
2 min, 25e
1 hr. 25e
1 hr, 25e
1 hr,40 oe
1 hr.40 oe
1 hr, 60 0 e
1 hr.60 oe
0
0
1 hr
0
1 hr
0
1 hr
0
1 hr
High
410
250
410
250
380
225
370
210
~t
Sample
I
2
2A
3
3A
4
4A
5
SA
Particle
Diameter
(nm)
2.1
2.3
2.7
2.8
3.0
2.9
3.6
3.5
'" 1.0% SiO z finally stabilized at pH 2 before test.
acid test at low pH reflects the presence of low-polymer species and indicates the
nature of the silica on the surface of the particles which is first to dissolve.
l/er and Sears

lIer and Sears (158) also have examined the stability of sols in regard to spontaneous
particle growth. Growth of particles less than 5 nm in diameter in alkali-stabilized
solution at 25C is readily observed. However, the question remains .whether particles in the 10-20 nm range, for example. still continue to increase in size at a slow
rate. A rare opportunity to demonstrate the extremely slow growth of particles was
afforded by a sample stored for 20 years by Sears (158). This was a sol containing
30% SiOz and stabilized at a SiOz:NazO ratio of 100: 1. Electron micrographs made
initially and after 20 years show a small but definite increase in particle size. as
shown in Figure 3.62. As might be expected, particles initially smaller than 10 nm in
diameter decreased in number, whereas those around 20 increased greatly in
number. Analysis of the distribution curves showed the following:
Diameter (nm)
Number average
Weight average
Original Sol
13
17
Aged 20 years
at 20-30C
15
19
Richardson and Waddams
Richardson and Waddarns (159) measured the rate of disappearance of monomer as

it polymerizes at different pH. They found it to be most rapid at about pH 8.3 and
i
-j
:-._-
186
400
0
oct
::>
(f')
...
:r::
300
a:
LJ
0.
(f')
LJ
..J
U
200
i=
a:
~
100
o
10
20
30
PARTICLE DIAMETER NANOMETERS
Figure 3.61. Change in particle size in an alkali-stabilized sol aged at 20-30C for 20 years:
A, original sol: B, aged 20 years.
'
not greatly different in the pH range 7-9. However. below 7 and above 9, there is a
marked reduction in rate.
Monomer did not polymerize in 24 hr even at pH 8 at a concentration of 180
ppm. This means that no particle nuclei had been formed at this time. However. at a
concentration of 730 ppm nucleation did occur, and after 24 hr monomer concentration dropped to 144 ppm, showing particles had grown to a size with this equilibrium
solubility, namely. 3.0 nm in diameter. When the initial concentration was 1450 ppm
the monomer decreased to 124 ppm. corresponding to 3.75 nm particles.
These results are consistent with the assumption that as soon as polymerization
had proceeded to form 96 ppm of 48-mer nuclei. corresponding to 1.5 nm Si0 2
particles, then the rest of the silica was deposited on these nuclei when they grew,
until the concentration of monomer had dropped to the concentration corresponding
to the solubility of the final particles. Thus when nuclei at 96 ppm grow in size to
amount to 586 ppm, the diameter increases to (1.52) (586/96)113, or 2.78 nm:
Total Si0 2 concentration (ppm)
Final monomer (ppm)
Calculated particle diameter (nm)
(from solubility)
Silica forming particles (ppm)
Calculated particle diameter, starting
from 96 ppm of 48-mer nuclei
o.
730
1450
144
124
3.0
3.75
586
1326
2.78
3.64
In further tests lasting up to 14 days, Richardson and Waddams report that no

polymerization occurs at around pH 8, unless the monomer concentration is higher
...
Polysilicic Acids
:,..--
287
than 145 ppm SiO z They quote similar values of 150 and 160 ppm by other workers.
This appears to be the critical concentration above which oligomers begin to be
formed.
It is unlikely that small colloidal particles such as the 48-mer can be nucleated
unless the total silica concentration exceeds 300 ppm, since the equilibrium solubility
of the 48-mer (equivalent SiO, diameter of 1.52 nm) is about 290 ppm (see also
Figure 3.56).
M akrides et al.
Makrides and associates (l06d), whose work has already been mentioned in connection with the theory of nucleation, undertook the first study deliberately aimed at
.obtaining data on the nucleation phenomenon. They followed the same general
method used by Richardson and Waddams and many subsequent workers, wherein
the concentration of molybdate-reactive silica was followed by the molybdate
method as a solution of silicic acid was aged. It was perhaps fortunate that their
interest in data applicable to geothermal waters led them to work at 95C at pH
4.5-5.5 in solutions of sodium chloride. Under these conditions there was a definite
period during which the concentration of soluble silica remained constant even
though the. concentration was two to three times the solubility of amorphous silica
(around 350 ppm), followed by a relatively rapid drop when nuclei appeared. The
advantage was that in the hot solution no oligomers accumulated and the system
contained only soluble silica that reacted rapidly with molybdate, and colloidal
particles that were probably fully condensed internally and were not reactive. In
general, the curves relating soluble silica and time were of the same shape as those of
Coudurier, Badru, and Donnet (36) (Figure 3.52) and of Marsh. Klein. and Vermeulen (32) (Figure 3.56).
POLYSILICIC ACIDS
These are the inherently unstable polymeric species that are obtained when soluble
silicates are acidified at low pH. The term "polysilicic acid" is generally reserved for
those silicic acids that have been formed and partially polymerized in the pH range
1-4 and consist of ultimate silica particles generally smaller than 3-4 nm diameter, ..
which thereafter polymerize into chains and three-dimensional networks. Once a
polysilicic acid solution has been exposed to" alkaline conditions. it is rapidly
converted to colloidal silica particles larger than 4-5 nm diameter.
Thereafter. silica assumes different characteristics and can be stabilized as sols in
the pH range 8-10. Such sols of colloidal silica are the subject of Chapter 5.
The term polysilicic acid is justified. particularly by the fact that the silica has a
very high specific surface area and contains a high proportion of SiOH groups per
unit weight of silica. The term may be somewhat misleading in the sense that in the
low pH range where polysilicic acid is temporarily stable. the SiOH groups are
essentially nonionized. Nevertheless, these silanol groups form silicon-oxygen-metal
atom bonds with polybasic metal cations, as already described in the case of mono-
~'7"''''':
.:
.,r
-'~
288
-- Polymerization or Silica
silicic acid. However, polysilicic acids differ from the monomer in that they form
addition complexes with certain classes of polar organic molecules through
hydrogen-bond formation. Also, they can be isolated and esterified not only with
alcohols under dehydrating conditions, but also with trimethylsilanol, even in
aqueous solution.
The term "active" silica has sometimes been used in referring to polysilicic acid.
For example, a distinction has been made by Rule (160) between "active" silica and
other forms of polymeric or "colloidal" silica. "Active" silica is defined as "any
silica in molecular or colloidal aqueous solution, in such a state of polymerization
that when diluted with sodium hydroxide solution to a pH of 12. and concentration
of about 0.02 percent Si02 , at 30C, the silica will be depolymerized substantially
completely to monomer in not more than 100 minutes." The monomer is determined
by the molybdic acid method.
Preparation of PolysiJicic Acid

Solutions containing up to 12% Si0 2 can be prepared by adding a thin stream of
sodium silicate solution with Si0 2 : Na 20 ratio of 3.25: 1.0 into the vortex of a
violently stirred solution of H~O. kept at O-soC, stopping the addition when the
pH rises to about 1.7. A 6% solution can be made continuously by bringing together
solutions of sodium silicate and acid in a zone of intense turbulence and in such proportions that the mixture has a pH about 1.5-2.0.
Solutions free from the sodium salt can be obtained by hydrolyzing methyl or
ethyl silicate in water at pH 2 with a strong acid as a catalyst for hydrolysis and
temporary stabilizer for the silicic acid.
Aqueous solutions of polysilicic acid are' always unstable since even at low
concentration the polysilicic acid continues to polymerize. as has already been discussed in detail. Nevertheless, if the silica concentration is not too high the
polymerization can be followed so that the solution can be used at a reproducible
stage.:
Hydrogen-Bonded Complexes with Polar Organic Compounds

In the course of tanning research in 1949. Kirk (161) discovered that complexes were
formed between silicic acid and ethers or amides and that these could be salted out
of solution as viscous oils. or precipitates. Also, Kirk (162a) found 'that these polar
organic compounds were effective in inhibiting the reaction between silicic acid and
gelatin or hide substance. Since certain compounds that were found to be most effective in influencing the behavior of silicic acid were also found by Copley and Marvel
(163) to enter into association with molecules such as chloroform through the formation of a hydrogen bond, it was logical to suspect that the association complex with
silicic acid were likewise the results of hydrogen bonding. [For further information
on hydrogen bonding. refer to treatises by Pauling (162b). and Pimentel and
McClellan (162c).] The association of the polar compounds with the polysilicic acid
"'
Polysilicic Acids
289
probably involves an oriented adsorption, so that the surface activity of the compound is undoubtedly an important factor. However, since most of the compounds
studied are not "surface-active agents" in the usual sense of the term, they are here
referred to broadly as "hydrogen-bonding agents," for the sake of convenience.
A quantitative comparison of the association of polysilicic acid with various
classes of polar organic compounds has been reported by Her (164). The relative
degree of association was measured by noting the solubilizing effect of the organic
compounds on the precipitate obtained by mixing solutions of polysilicic acid and
gelatin, other factors being held constant. In the absence of gelatin, the association
of the polar organic compounds with polysilicic acid was demonstrated by the fact
that some of the silica-organic complexes could be salted 'out of the aqueous mixture. Liquid complexes were obtained from freshly prepared solutions of polysilicic
acid and polar organic compounds of low molecular weight. Solid precipitates were
formed from polysilicic acid of high molecular weight or from acid of low molecular
weight with organic compounds of high molecular weight. A titration procedure for
following the increase in molecular weight of polysilicic acid by formation of a
precipitate with gelatin has already been described.
Method of Comparing Hydrogen-Bonding Activity

As reported by Her (164), the observation that the precipitation of polysilicic acid by
gelatin was inhibited by hydrogen-bonding agents offered a convenient point at
which to begin experimentation. In preliminary qualitative tests, using a silicic acid
sol prepared from sodium silicate and sulfuric acid in a standardized manner at a
constant pH of about 2.5 and a constant concentration of salt, it was observed that
widely different amounts of different agents were needed to prevent the precipitation
of a gelatin-silica complex. To obtain a quantitative comparison of different polar
compounds it was necessary only to measure the minimum concentration required
for each compound to inhibit the formation of the gelatin-silicic acid precipitate, all
other factors remaining constant, particularly the characteristics of the silicic acid. It
was not always possible to reproduce exactly the preparation of a silicic acid sol:
since it was found that the absolute concentration of hydrogen-bonding agent
required to inhibit precipitation of the gelatin-silica complex varied severalfold as
the silica sol was aged for 24 hr, the following device was employed to give reproducible comparative values of hydrogen-bonding activity.
A particular hydrogen-bonding agent (HBA), dirnethoxytetraethylene glycol
(0 MTEG), was used as a standard against which the relative effectiveness of the
other organic compounds could be compared. Its relative effectiveness was arbitrarily assigned a value of 100. The relative effectiveness of each H BA was defined in
terms of the relative molar concentration required: 100 M HBA: AI. DMTEG. This
ratio was found to be independent of the age of the silica sol within :1::5%.
Many types of organic compounds do not have a solubilizing effect on the
precipitate. Compounds that are insoluble in water have no effect: also, highly
hydroxylated compounds such as ethylene glycol or sugar are inactive. Other compounds tend to coagulate the silica even in the absence of gelatin.
". :,...--
290
Temperature has a marked effect on hydrogen-bond formation. Few, if any. of the

phenomena here discussed will occur, for example. at 60C. The complexes are
increasingly stable as the temperature is lowered from 30 to 0 or 5C.
Structure versus Activity'

- The relative molar effectiveness of representative compounds of different classes is
shown in Table 3.11.
The compounds that solubilize the silica-gelatin precipitate can be divided into
two classes. (a) nonionic water-soluble compounds such as alcohols, ethers, ketones,
and amides, and (b) short-chain amines which are in the form of salts in the pH
range employed (1.5-3.0). In general it can be said that in any homologous series the
solubilizing activity increases with the size of hydrocarbon groups in the molecule to
the point where the members become immiscible with water or cause independent
precipitation of silicic acid and thereby become ineffective, With a given number of
carbon atoms in the molecules, the activity increases with decrease in the number of
hydrogen atoms attached to the polar oxygen or nitrogen atoms. Thus ethers are
more effective than the isomeric alcohols, and tertiary amines are more active than
the isomeric primary and secondary arnines.
The data in Table 3.11 suggest that in any given series the solubilizing action is in,
some way related to the ratio of the number of carbon atoms to polar atoms in the
molecule. Thus the solubilizing effect increases with the size of the hydrocarbon
groups. In general, nitrogen (amides) is a more effective polar group than oxygen
(ethers, ketones). The higher alcohols. glycols. ketones. and amides are ineffective,
probably' because they are too insoluble in water. On the other hand, the higher
amines, although soluble in water in the form of their salts. cannot be shown to have
a solubilizing action on the gelatin-silica complex because they precipitate silica,
probably in combination with some gelatin.
There appear to be two important factors that increase the affinity between the
polar organic molecule and the surface of the silica polymer, multiple bonding and
surface activity:
...
i
;
,
"
MULTIPLE BO:-:DING. It is obvious that when a molecule is adsorbed from solution

onto a silica surface through hydrogen bonds which are being continuously formed
and broken at ordinary temperature, if there are several such points of attachment
the probability of all the bonds being broken simultaneously becomes very low. This
was shown by lIer (164) in the case of the hydrogen bonding effectiveness of
polyethylene glycols.
Number of
Ether Groups
Molar
Effectiveness
Effectiveness
per Ether Group
I
2
3
5
8
15
31
49
103
229
15
15.5
16.3
20.6
28.7
\.
--
.. :...._Table 3.11. Relathe Effecti'eness of HydrogenBonding Agents
Compounds
Standard: dimethoxytetraethylcne glycol
Alcohols
Methanol
Ethanol
Isopropyl alcohol
,-Butyl alcohol
Glycols
Ethyleneglycol
Propylene glycol,
3-Methyl-I,2-butanediol
Hexamethyleneglycol
Ketones
Acetone
Methyl ethyl ketone
Amides .
Formamide
N.N-Dimethylformamide
N.N-Oiethylformamide
Acetamide
N.N-Dimethylacetamide
N,N-Diethylacetamide
N-Isobutylacetamide
U~
Tetramethylurea
Primary amines (as salts)

Methylamine
Cyclohexylarnine
2-Ethylhexylamine
m-Toluidine
Secondary amines (as salts)
Dimethylamine
Diethylamine
Piperidine
Dibutylarnine
Diarnylarnine
Tertiary arnines (as salts)
Trimethylamine
Pyridine
Quinoline
Cyclohexyldiethylarnine
Relative
Molar
Effectiveness
100
3
6
11
16
0
7
18
27
17
2S
0
2S
40
11
41
S4
22
7
44
0
2S
32
S8
0
19
. 38
65
70
14
42
66
117
291
';,..-_.
__ Polymerization or Silica
292
SURfACE ACTIVITY. Polar organic molecules tend to become concentrated at the

silica-water interface not only because of the hydrogen bonding of the polar groups
with the surface but also because- of the tendency toward micelle formation. or at
least the hydrophobic nature of the hydrocarbon portions of the molecule which
drive it from the water to th.e silica-water interface. which in turn is related to the
potential surface energy.
It. is observed from Table 3.12, that the "potential surface energy" (A) is proportional to the square root of the "hydrogen-bonding activity" (B) as measured by Our
empirical method. It will be noted that AB -D.5 is essentially constant except in the
cases of acetone and acetamide, for which lower values are obtained. This would
indicate that these two materials are more effective in their interaction with silicic
acid than would be predicted on the basis of the surface tension of their aqueous
solutions. It is thus probable that in measuring hydrogen-bonding activity we are
actually measuring a quantity which is a direct function of the surface activity. What
we have termed the "hydrogen-bonding effect" may amount to measuring the relative preferential adsorption of organic compounds from aqueous salt solution on the
surface of the molecular units of polysilicic acid or the gelatin-polysilicic acid complex..
According to Baumann (165), polysilicic acid combines with organic hydroxylated
compounds if the OH group has a dissociation constant greater than 10- 7 and especially with polyfunctional compounds if steric considerations permit the oxygen to
come into contact with the silica. This presumably refers to hydrogen bonding.
Liquid Hydrogen-Bonded Complexes-s-Coacervates

If the size of the silicic acid polymer is small enough and if the hydrogen-bonding
agent is of a type that can orient its polar groups toward the silica polymer. there is
then formed a molecular complex with a predominantly hydrocarbon surface. Such
Table 3.12.
Energy
Relation Between Hydrogen-Bonding Activity and Potential Surface
Compound
CH 3COOH
C 2H sCOOH
CH 30H
C2H sOH
C 3H1OH
C.H.OH
CH 3COOCH3
CH 3C(O)CH 3
HOCH sCH 2OH
CHsCONH s
Potential
Surface Energy. A
(cal mole:")
1710
2290
1240
1820
2430
2825
2340
2170
563
740
Hydrogen-Bonding
Activity. B
6
13
3
6
II
16
10
17
-lor less
II
AB-o.s
700
635
7J5
745
730
706
740
525 223
Polysilicic Acids
293
complexes separate as a second liquid phase when the aqueous solution is saturated
with sodium chloride.
Such a complex may be formed with such a simple molecule asr-butyl alcohol,
where the outer surface of the complex consists of the butyl groups. On the other
hand, if a linear polymer is flexible with polar groups located at intervals along its
length, and if the silica polymer is large enough, the surface can similarly be covered
with the adsorbed chain molecules with all polar groups turned toward the silica surface, so that the hydrocarbon groups are outwardly disposed. This can occur with
polyethylene oxide or with polyvinyl alcohol. However, the chains must not be so
long nor the silica polymer so small that the polymer cannot be accommodated on a
single silica particle or polymer. Otherwise. unadsorbed segments of the organic
molecule will bridge over to ether silica particles, causing coagulation. If factors are
such that the silica polymer becomes covered with such hydrogen-bonding
molecules, there is a phase separation and the coated silica polymer, if of low
enough molecular weight, will form a separate. oily, liquid phase.
In the case of polysilicic acid of very low molecular weight. such as cyclic
tetramer and similar oligomers no liquid phase can be salted out. It appears
necessary to let the silica polymerize to three-dimensional units or small particles
before it can be covered by oriented organic molecules to form a hydrophobic complex that will form a second phase. On the other hand. if the particles further
polymerize by aggregation to form microgel, then' only a -gelatinous emulsion is
formed.
Examples of liquid coacervates or complexes of polysilicic acid oligomers have
been disclosed in previous publications (89) and in the patent literature (I66-168),
from which the following examples are taken.
A complex formed with triethyl phosphate was prepared as follows: 900 grams of
a 15.5% solution of sodium silicate (Si02:~a20 ... 3.25: I by weight) was added to a
vigorously stirred solution of 214 grams of triethyl phosphate in 860.grams of 7%
sulfuric acid solution over a period of 10 min. To the resulting solution 450 grams
NaCI was added, and stirring continued for 1 hr. The mixture was allowed to stand
for 1 hr, and the solution of polysilicic acids in triethyl phosphate. which separated
as a lower layer, was drawn off and dried over anhydrous sodium sulfate. The yield
was 215 grams of clear, fluid, amber liquid which gelled in approximately 4 days at
room temperature. When the triethyl phosphate solution of polysilicic acids was
immediately dehydrated by heating under reduced pressure, it was stable for at least
several months at room temperature. The dry solution was miscible with several
times its volume of benzene and most other common organic solvents, but not with
water. A typical dry triethyi phos-phate solution of polysilicic acids contained 21.8%
SiO z, 30.0% carbon. 12.6% phosphorus, and 6.8% hydrogen. This corresponded
approximately to 2:!CC silica (SiO z), 74% triethyl phosphate. and 4% chemically
bound water. The bound water corresponded to about one OH group per silicon
atom in the polysilicic acid. This is consistent with silica particles of the order of I
nm diameter (see further discussion of interaction).
The complex with diethylene glycol diethyl ether was unusual in that it was only
partly miscible with an excess of the organic reagent. Thus there was a range of
compositions where two organic layers were salted out. a heavy one containing silica
.
i
I
.i
j
29~
settling to the bottom and a lighter one containing little silica appearing at the top,
By using silica sols containing 5-6 grams Si0 2 per lOO"ml. from 0.5 to 2 hr old at
pH 1.7 and at 25C, the data shown in Table 3.13 were obtained.
For a maximum yield of silica in the separate liquid coacervate phase.. a given
molecular weight of polymer requires either an optimum ratio of agent to silica or a
large excess of agent which, when salted out, can extract the complex from the
aqueous phase.
The complex of tetraethylurea was prepared as follows. To 500 parts of a silicic
acid solution prepared as above, aged for about 2 hr, were added 45 parts oi
tetraethylurea and 155 parts of sodium chloride. The mixture was stirred for 5 min
and then centrifuged. A layer lighter than the aqueous phase formed and collected at
the upper part of the solution; 43 parts of this liquid layer was recovered, to which
was added 12.5 parts of 95% alcohol. This resulting solution was analyzed and found
to contain 21.4% Si0 2 by weight. The liquid complex was soluble in alcohol and in
excess tetraethylurea, and as originally separated must have contained about 28%
Si02
Liquid complexes of polysilicic acid can be salted out of the aqueous phase with
the following compounds, containing the indicated content of Si0 2, as disclosed in
the Kirk patents: polyethylene oxides with terminal hydroxyl groups with degrees of
polymerization of 6-90 (mol. wt. 4000); monobutyl ether of ethylene glycol,
diethylene glycol, N-tetraethylurea, acetone (12%), diacetone alcohol (50%)~ npropyl alcohol (10%), isobutyl alcohol (23%), and r-butyl alcohol (12%). Many of
the compounds listed in Table 3.12 form liquid coacervates when added in optimum
amounts to polysilicic acid solution of optimum molecular weight and the mixture
saturated with sodium chloride. It happens that sodium chloride is one of the most
effective salting-out electrolytes because of its high solubility and ion characteristics.
Polyvinyl alcohol (169) forms a. coacervate with particles of colloidal silica much
larger than those in polysilicic acid. It is probable that no coacervate can be
obtained with polysilicic acid because the PVA chain is much too long to coat a
.: ,I
'-oj
\.
Table 3.13 Separation of Liquid Coacervate of Polysilicic Acid and Diethylene Glycol Diethyl
Ether (DEC)
.~!
Upper Layer
SiO,
SiO,
Recovered
(g 100 rnl ")
(%)
38.7
50.0
39.7
52
43
48
80
55
DEC Added
Sol Age
at 25C
o
o
0.5
1.0
1.0
1.0
2.0
(ml l ?
of sol)
87
Mil-I
of Sol
MIIof Sol
62
1.5
120
68
65
98
81
75
122
200
68
88
22
240
19.5
Lower Layer
89
0
79
If
~.
".
76
64
91
43.7
70
..i:
~
;<
.Ii~
J.'
.~
"
';,.. ...
Polysilicic Acids
295
figure 3.63. Silica surface covered with only

enough PYA to form a hydrophobic oriented
monolayer coating so that coacervation occurs.
[From Iler (169).)
single polymer particle. Another difference is that in the PYA-colloidal silica system
it is not necessary to add salt.
When certain ratios of colloidal silica and polyvinyl alcohol are present in aqueous
solution at pH 2-3, coacervation occur's with the separation of an oil-like viscous
phase containing up to 40% silica. The maximum yield of coacervate is obtained
when the ratio of Si02 : PYA in the coacervate is proportional to the particle
diameter such that there are 2.5 CH 2CHOH. chain segments per square nanometer
of silica surface. The coacervate, which still contains some water, appears to consist
of silica particles the surface of which is just covered with a monomolecular layer of
PYA; the PYA hydroxyl groups are oriented toward and hydrogen-bonded to the
SiOH groups on the silica surface, so that the hydrocarbon chains form a hydrophobic coating.
Figures 3.63 and 3.64 exemplify the critical nature of the ratio of hydrogen-bonding agent and silica surface to obtain a maximum yield of coacervate. Although in
this case colloidal particles of molecular weight of several 'millions are involved, the
same principle holds for much smaller polysilicic particles or "molecules" and
hydrogen-bonding molecules of limited size and number of polar groups. .
Figure 3.M. Excess PYA with chain segments bonded to silica surface with remainders of
chains extending into solution: no coacervation occurs. [From ller (169).J
__ Polymerization of Silica
~96
!comPlex ofsue Add with Amine Sail
The formation of a coacervate of polysilicic acid with a hydrochloride salt of an

amine poses the question as to how the association can occur (170). Since the
nitrogen atom in the amine salt does not possess a free pair of electrons, it is evident
that the association of this salt cannot involve the formation of a hydrogen bond
between the nitrogen atom and the hydrogen of polysilicic acid. In this complex, the
relationship of the components might be represented by the following scheme, in
which the electronegative chlorine, oxygen, and nitrogen atoms are associated
through hydrogen bonds:
I
I
-Si-O-H
a
I
-Si-O
6
I
c.a,
J;I-N ~CISHs
H!
-Si-O
CI-
C2Hs
The complex with low molecular weight polysilicic acid was a viscous liquid and
was made as follows: a solution of 3.25 SiO z : NazO sodium silicate containing 103 g
I-I SiO z was first prepared. Of this solution, 585 ml was added as a thin stream over
a 5 min period into 415 rnl 1.52 N HCI, which was being violently stirred at 20C, to
obtain a I M solution of silicic acid at pH 1.65. This was aged for I hr, and to 500
ml were added 250 ml 2 M diethylaniline HCI and 200 grams solid NaG. There
soon separated 80 ml of a heavy viscous, almost clear liquid, containing 25% SiO z,
35.2 grams diethylaniline, 1.91 % NaCl, and 8:77 grams HC!. Thus the molar ratio
of HCI to diethylaniline was 1.14, and of SiO z to diethylaniline 1.77. By difference,
the liquid contained 14.3% water. Diethylaniline hydrochloride alone in solution cannot be salted out.
Diethylaniline adsorbed as an oriented monolayer on silica occupies an area of
around 50 A2. If it is adsorbed as a monolayer on spherical silica particles. in two
experiments the ratio of amine to SiO z corresponded to particles about 1-2 nm in
diameter. This is about the size of freshly formed polysilicic acid particles as judged
from other studies. When the sol was aged 2 hr so that microgel began to be formed,
the coacervate was a paste containing emulsilied brine.
Interaction ofSilicic Acid with Phosphoric Acid ESler

A mixed ester of silicic and phosphoric acids appears to be developed after polysilicic acid is extracted as a coacervate from aqueous solution, saturated with salt,
into a trialkyl phosphate (171). When first obtained, the triethyl or tributyl phosphate can be dissolved away from silica by another solvent such as benzene.
However, when the coacervate is heated under vacuum to remove water, ester inter-
.
,.
i'
:- ...
297
change appears to occur and the surface of the silica polymer probably has the structLl" of an esterified mixed anhydride.
Et-O
.Et
Et
I I
H O=P-O H
I
I
I
0
0
I
I
I
0
0/1'0/1'0/1"0/1"
I
o
I
Si
Si
SiO
Si
The silica and phosphate can no longer be separated by solvents.

Colloids of silicophosphoric acid derivatives have not been further investigated,
but silicon phosphates have been studied. Jacoby (172) found that at atmospheric
pressure, melts of Si02 and P20S could be made in which 21 compounds were
detected. Physical properties of Si02 P20S and 3Si0 2 2P 20S were reported. Dissolution of some compounds of this type in water or alcohols would probably give
aqueous dispersions of colloidal silica. or mixed acid esters similar to that described
above.
COMBINATIONS WITH ORGANIC POLYMERS

More than a century ago, Graham (173) observed that silicic acid combines with
gelatin to form an insoluble precipitate. Later Mylius and Groschuff (174) observed
that silicic acid of very low molecular weight did not precipitate egg albumin. but as
soon as the silica polymerized to a small degree it coagulated the protein.
Lesley (175) found that gelatin and albumin were precipitated by silicic acid only
below pH 6. Since he believed that silica is negatively charged even down to pH 2,
and gelatin was likewise negatively charged, it appeared that the precipitation was
not a coagulation of oppositely charged colloids. He also showed that there was no
change in pH when the precipitate formed. These observation are consistent with the
modern view that the combination occurs by the formation of a multiplicity of
hydrogen bonds between the relatively large molecules of protein and polysilicic acid
such that a mixed network of these molecules if formed, leading to the separation of
the aggregates from the solution.
Now it is known that a number of classes of water-soluble polymers interact with
and are mutually coagulated by polysilicic acids and colloidal silicas. These include
polyethers (polyethylene oxides. methyl cellulose). polyamine salts (polyethylene
imine). polyalcohols (polyvinyl alcohol). polyvinylpyrrolidone. and proteins (gelatin.
albumin).
In the following discussions mainly polysilicic acids rather than colloidal silicas
an' "'onsidercd.
iI
I
,
i
I
I
198
Prevention of Hydrogen Bonding by Negative Charges on Silica
,
;
o'
It is now well known that it is only the uncharged neutral silanol groups on silica
particles or polymers that enter into hydrogen bonding with polar organic cornpounds. The effect of charge could not be studied in the case of polysilicic acids 0:
low molecular weight because the latter polymerized and gelled rapidly when the pH
was raised above 5, where the silica began to assume a negative charge.
The reason for the interaction of silicic acid with gelatin at low pH was supposed
by Bergman and Nelson (176) to be greater at pH 2.5 than at 7.5 because of the
greater positive charge on gelatin. It was assumed that silica still bore a negative
charge. However, Her (177) has shown that the interaction of silica with gelatin. as
well as with polyethers that could only engage in hydrogen bonding, was greauy
reduced when silica carried a higher negative charge. This was demonstrated usi:::.g
particles of colloidal silica which did not aggregate at an appreciable rate over the
netural pH range. Combination of the polymers with silica was greatly reduced by a
relatively small increase in pH, which increased the charge on silica. Also, the cornbination was greatly reduced, at a given pH, when the negative charge on silica
particles of a given size was raised by the introduction of anionic aluminosilicaie
sites.
The reason that polar organic molecules do not form hydrogen-bonded anaczments to negatively charged silica may simply be that the counter-cation (usually
Na" or NH.+) in the neighborhood of the SiO ion prevents access to that porticz
of the silica surface. It would not seem likelv that a molecule held to the surface bv
.
hydrogen bonding to uncharged SiOH groups could displace the counter-cation froz;
the neighborhood of a negative SiO- site.
It is for this reason that hydrogen-bonded complexes and coacervates are formed
mainly in the pH range 1-4, and especially 1.5-3.0~ Also, this explains why this ty;-:
of attachment does not occur with the surface of colloidal aluminosilicates such as
clays and zeolites. These materials combine with nonionic polar organic molecules.
including proteins, only if the aluminum has been extracted first from the silica surface by a strong acid, or if the mineral surface is coated with a film of relatively p~:e
silica.
I
f
Cationic Organic Compounds

It must be made clear that the foregoing discussion applies only to organic cc:::pounds which combine with silica by hydrogen bonding. Compounds that comaiz
cationic groups combine with silica at all pH values and especially with silica c:
which aluminosilicate sites have been implanted. This has also been demonstrated =:.
lIer (177) in regard to interaction of silica with organic molecules containing str0::.fbase cations such as quaternary ammonium ions. Also, certain proteins such as :11::.;mins which contain such cations will combine with silica bearing negative alurniz csilicate ions under conditions where gelatin will not react.
Thus the behavior or organic compounds with silicic acid may involve b,:-:::
hydrogen bonding as well as ionic bonding in the neutral pH range. However. at !,:-o.
I
I
~.P.
tion of Silica
299
pH (below 3-4) most interactions involve only hydrogen bonding if the silica is
relatively free from aluminosilicate.
ps
silica
'ganlc com.cic acids of
/herr the pH
supposed
ause of the
: a negative
I gelatin, as
was greatly
.rated using
ite over the
educed by a
0, the com- .
;e on silica
ninosilicate
1S
ded attachon (usually

hat portion
: surface by
car
from
are formed
lY this type
tes such as
molecules,
e silica suritively pure
ganic comrat contain

h silica on
nstrated by
ing strongch as albue alumino-
valve both
ver -t low
Miscellaneous Interactions with Organic Materials
Monolayers of 2- and 4-heptadecyl-pyridine l-oxide on an undersaturated solution

of monosilicic acid form solid films. This raises the question whether the monomer,
being collected and concentrated by the polar groups of the film,' may have
polymerized in spite of the fact that the solution is undersaturated with respect to
amorphous silica. Possibly the polymer particles become surrounded by the
monolayer film and isolated from contact with the water phase, since otherwise they
would dissolve. Alternatively, there may be formed polysilicic acid units of low
molecular weight stabilized by hydrogen bonding. The effect of organic molecules in
promoting polymerization of monomer at concentrations less than 100 ppm Si02
has not been further investigated (178).
Monolayers of polyvinylpyrrolidone (PVP) were made rigid when spread in water
containing polysilicic acid at a concentration of only 282 ppm Si0 2 The combination was said to result from hydrogen bonding between the carbonyl group of PVP
and the SiOH of silicic acid (179).
.
Polysilicic acid reacts with proteins and mucopolysaccharides but not cellulose
acetate, according to Holt and Went (180). At about pH 6 it reacts with a
monolayer film of laminarin, a linear polysaccharide of 20 units of beta-oglucopyranase linked through C 1 and C, atoms. Probably hydrogen bonding with
ether oxygens is involved, .
Emulsion polymerization of polysilicic acid to form small spheres or beads is also
possible through the use.of hydrogen bonding agents. In. one method an organosol is
first obtained in which the silica is then precipitated by further polymerization. In a
method described by Daiga and Cristanetti (181), 200 grams of silica is dissolved in
1700 grams 12% NaOH solution to produce sodium silicate. A separate mixture of
910 ml 12% aqueous H 2S0 4, 3.9 grams Na 2SiF., and 450 ml isopropyl alcohol is
prepared. To this the silicate solution is added rapidly with stirring, followed by 500
grams isopropyl alcohol. A second dispersed liquid phase of polysilicic acid in
alcohol is formed. After stirring for 3 hr silica beads are formed by gelling of the
droplets. Most of the principal impurities of iron, titanium, and aluminum in the
original silica are eliminated. In a similar process, Kummerle (182) mixes 16 grams
of Na 2SiF. as polymerization catalyst in 1140 grams 20% H~04 solution along with
108 grams n-butyl alcohol, adds 120 grams NaCl, and finally adds with intense
agitation 360 grams sodium silicate solution containing 6.32% Si0 2 and 1.75% Na.O
over a 7 min period. After 40 min porous silica gel beads about 1 micron in diameter
are recovered.
.
A different process involves first making a homogeneous solution containing low
molecular weight polysilicic acid, salt, and a selected hydrogen-bonding organic
agent. On standing, the silica polymerizes and the high molecular weight silicic acid
combines with the organic hydrogen bonder to form an insoluble liquid coacervate
300
which comes out of solution as droplets and then the droplets harden as the silica
gels before the droplets can coalesce. Thus transparent silica gel spheres 1-5 mic- ..
in size form spontaneously when 200 ml of a freshly made solution of polysilicic ....
containing 6% Si02, made by adding diluted 3.25 ratio sodium silicate to rapidly
stirred dilute H 2SO. solution to attain a final pH of 1.5-2.0, is mixed with 10 parts
of nonaethylene glycol and aged for 24 hr (183). The pH and concentrations of
sodium salt, silica, and hydrogen-bonding agent have to be optimized for each
organic agent, and agents must be found by trial and error (183).
Silicic acid has a definite effect on the properties of cellulose. The wet strength of
paper can be increased by impregnating it with a solution of low molecular weight
silicic acid. In view of the fact that colloidal silica, in which the particles are of a
molecular weight of the order of millions, does not confer wet strength to paper to
the same degree as freshly prepared solutions of silicic acid, it would appear that the
wet-strengthening action probably depends on the strength of the silica gel cementing the fiber junctions. Britt (184) developed a process based on saturating paper
with a dilute solution of sodium silicate admixed with sufficient ammonium phosphate to neutralize part or all of the alkali in the silicate (with evolution of
ammonia). This liberates the silicic acid directly in the paper, where it is insolubilized
by heating to 120-150C. Such treatment is especially useful on paper-towels, since
absorbency is not reduced. The sorption of sodium silicates and silica
.. sols by cellulose
fibers has been discussed by Merrill and Spencer (185).
Low molecular weight polysilicic acid is combined with tetrafluoroethylene-vinyl
acetate copolymer to give a hard scratch-resistant coating on clear plastic shep'"
(186). Additional compositions involving polysilicic acid with other polymers ~.
tetrafluoroethylene copolymers were also developed (187).
4
Interaction with Protelns-s-Tannlng

The phenomenon of hydrogen bonding plays a role in the reaction of silica with living tissues, and is further discussed in Chapter 7. Biological effects of silica have
stimulated numerous studies of the interaction of organic polymers with strong
hydrogen-bonding groups and silicic acid. Gonzales-Carrero and Moreno-Garcia
(I 88) pave discussed the interaction of silica with polymers of vinylpyrrolidine and of
vinyl pyridine N-oxide.
The strong interaction by hydrogen bonding between polysilicic acid and hide protein encouraged many attempts to develop a process for tanning leather. Vail (192)
summarized the history of silica tanning. In order to obtain good leather, it is
necessary to retard the polymerization of the silica until it has penetrated the leather
and also to retard its combination with the hide substance by having present either
(I) other tanning agents that will combine also with the protein in competition with
the silicic acid, or (2) organic agents that will temporarily combine with the silica to
make it less active. In the first category, polyphosphates, formaldehyde, sulfonic
acid derivatives, and salts of chromium, iron, or zircon~um have been employed. In
the second class, hydrogen-bonding agents such as amides, ketones, alcohols, or
ureas have been used. Combination tannages involving sulfite cellulose extract a~,
ation
or Silica
as the silica
1-5 microns
,Iy!
: acid
:e to rapidly
vith 10 parts
mtrations of
ed for each
t strength of
cular weight
eles are of a
to paper to
lear that the
gel cement-atlng paper
mium phoswolutlon of
insolu bilized
.owels, since
by cellulose
iylene-vinyl
astic sheets
lly' 's and
ica with liv. silica have

with strong
.eno-Garcia
idine and of
id hide pro. Vail (192)
.ather, it is
the leather
esent either
etition with
the silica to
Ie, sulfonic
nployed. In
.lcohols, or
ext -t and
301
silicic acid have been developed. However. because of the difficulty of chemical control and lack of outstanding advantages over other processes, silica tanning has not
been widely adopted.
Some of the most effective conditions for tanning were developed by Kirk (168),
who used organic hydrogen-bonding agents to retard the interaction and permit
good penetration of the hide with' a sufficiently high molecular weight silicic acid to
give good quality leather. Subsequent research along this line has been infrequent
(189-191).
Esterification ofPo/ysilicic Acid
This has already been discussed in connection with the characterization of soluble
silicates by conversion to the corresponding polysilicic acid (98). t-Butyl alcohol was
found to be the most practical hydrogen-bonding agent for isolation of the unstable
polysilicic acid as a liquid complex. The latter was then dehydrated by azeotropic
distillation, the tertiary alcohol being replaced by n-butyl alcohol during the
dehydration step and the n-butyl ester 'formed by continuing dehydration by
azeotropic distillation. The polymer dried from excess alcohol was a tacky, resinous
materiai soluble in many organic solvents. However, unless it was kept in solution it
gradually polymerized further to an insoluble state. The polysilicic .ester of higher
alcohols can be made by further ester interchange. The product could be incorporated into various resin and polymer systems, but no major uses were discovered.
In view of the increasing cost of hydrocarbons, the time may now be approaching
when the incorporation or essentially molecularly dispersed silica in organic polymer
systems should be further .examined.
Activated Silica Sols-Water Treatment

This particular form of silica must be discussed under the topic of polysilicic acid,
since it bears little relation to colloidal silica of commerce.
.Silicic acid from sodium silicate has long been used as a coagulant in water treatment, and the subject has been well summarized by Vail (192).
The term "activated" comes from the procedure developed by Baylis (193), by
which a solution of polysilicic acid made from soluble silicate at low pH was "activated" by an aging step at somewhat higher pH by which its effectiveness was much
improved. There is little doubt that this involved an aggregation-polymerization of
the 1-2 nm primary particles into very open microgel aggregates. In this form it was
much more effective in adsorbing or trapping suspended matter and forming a more
rapidly settling flocculent precipitate.
Okura and Goto (194) investigated the structure of "activated silica sols." They
used a rate of dissolution method to measure the relative specific surface area and
thus the relative size of the ultimate particles. They also measured the viscosity from
which the specific hydrodynamic volume was calculated. This is the volume of solu-
:......
302
tion immobilized per gram of silica as particles aggregate into gel networks. For this
a modified Einstein equation was used:
Relative viscosity = I
+ 0.0025CV
where V is the volume fraction of solution immobilized by 1 gram of silica and Cis
the concentration of silica in grams per liter.
Two types or sols were studied:
A. A salt-free silicic acid was made by passing a 1% SiO z solution (as 3.3 ratio
sodium silicate) through a column of hydrogen ion-exchange resin, then adjusting
the pH to 8-9.
B. A sol containing sodium sulfate (the "Baylis" sol) was made mixing a 3.3 ratio
(SiO z: NajO) sodium silicate solution containing 3% SiO z with sufficient volume
of 0.33 N H zS0 4 solution to obtain a 1.5% silica sol in which 85% of the alkali
was neutralized to give a pH of 8.5; Samples were aged at 25C for different
times and then diluted to 0.6% SiO z to avoid gelling.
...
From Figure 3.65 it is seen that the salt-free sol A maintains a very low hydrodynamic volume which corresponds to a suspension of discrete, nonaggregated SiO z
particles. In sol B the hydrodynamic volume rises owing to formation of gel
aggregates until the sol is diluted before it sets to a solid gel.
However, in both sols the ultimate particle size increases, as indicated by the
decrease in the rate at which sam pies dissolve in the acid-fluoride test solution. Also
it is noted that the decrease in dissolution rate of sol B, or the growth of particles,
I
K-,
80
<l:
~ 10'60
o
>:x:
I
I
.......~
E
/
~ ~40
7(
/
{33
ILl 0
g; >
I
>
:j
20
:
I,
0.8
0.6
I
I
t5
<,
0.4
<,
I
I
I
........
....... ,
.......
(f)
~ ~
...J
a::
g
:::>
<,
~ ~
c 0
0.20:
-r----!-----~--
0: 0
<,
ILl
!;x ::
I ....... --l
I
11
I
0.01
0.10
SOL AGE DAYS
.1
.,
1.00
Figure 3.65. Characterization of "activated" silica sols. Solid lines: sot A. 1% salt-free sol
made by removing sodium from sodium silicate by ion exchange and raising the pH to 5.
Dashed lines: sol 8. 1.5% Si0 2 made by acidifying sodium silicate solution to pH 8.5 and
diluting after 0.9 day. Sols aged at 25C. [From Okura and Goto {19~).l
1
I
7.-,.---
of Silica
in
s. For this
.1
and Cis
3.3 ratio
adjusting
3.3 ratio
volume
the alkali
. different
nt
hydrodyated Si0 2
on of gel
ed by the
tior Also
pa les,
~
z
303
continues at about the same rate in spite of the dilution. However, even-after a week
the particles are still less than 3 nm in diameter.
The difference between sols A and B is due to the presence of Na 2SO. in sol a,
which decreases the particle charge, permitting the particles to collide and aggregate.
Thus the "activated" sol contains silica particles of the order of 2 nm diameter, most
of which are linked together in' voluminous network gel aggregates. These are
essentially invisible because they have thesame refractive index as the rest of the sol.
Stumm, Huper, and Champlin (195) reviewed the interaction of polysilicic acid as
coagulants with other colloids. Polysilicic acids coagulate positive colloids at low
concentration, but in excess can reverse the charge and restabilize the system.
Specific interactions can outweigh electrostatic repulsion; thus negative polysilicate
ions can flocculate negative silver bromide sols.
Worldwide use of activated silica sols, new modifications involving use of Na 2SiF.
plus silicate, and new applications in sewage treatment have been summarized by
Middleton (196). Large-scale use in coagulating solids from water in Chicago has
been described by Vaughn (197).
In other studies, Slipchenko and Shelyakova (l98) found a rapid way to prepare
activated sols. At a silica concentration as low as 1.3% Si0 2, with a molar ratio of
Na 2SiF.: Na 20 of .5-0.6 and Si0 2 : F of 3.0-3.4, rapid polymerization occurs in 3-5
min to the stage where the sol can be diluted for use. If not diluted it gels in 12-20
min (198). The stability of "activated sols" was reviewed by Henry (199): The effect
of aging time before dilution has been explained by Heald and Coates (200). The
theory of the "activation" process and details of the preparation and use of activated
sols was described by Griffin (201). The theory and practice of activated silica sols
were also summarized by Lange and Spencer (202), who correlated the activity with
size and charge of the sol particles. Similar studies were reported by Goto and Yatsuyanage (203), who defined the "activated" sol as one in. which three-dimensional
structures of aggregated 'particles have been formed, but the gel point has not yet
been reached. In a "stabilized" .sol the aggregation-polymerization process has been
prevented entirely from the beginning or has been brought to a halt. A typical activated sol contains around 2% Si0 2 during its formation, in which it is aged about
halfway to the gel point, after which it is diluted out to give a 10 ppm dosage as a
coagulant in water.
Reaction of Polysilicic Acid With Metal Cations
The interaction of monosilicic acid with some metal ions has been discussed earlier
in this chapter. Polysilicic acid behaves in quite a different way, mainly because it is
more polyfunctional and can enter into chelate-like bonding with a metal atom, M:
"-.
-51-0
"'
M
"'S "-/'
/
alt-Iree sol
e pH to 5.
IH 0 " and
-1-0
:---.
304
..
The reaction of polysilicic acid with metal salts must be distinguished from the
reaction of a soluble silicate, such as sodium silicate with a metal salt, as described
in Chapter 2. In the latter case, metal silicates in which the silica is only slightly
polymerized may be obtained. On the other hand, polysilicic acid, being already
polymerized, combines with far less metal than corresponds to a metal silicate. It is
the nature of this combination that is discussed here.
When a solution of a metal salt is added to a solution of polysilicic acid, combina_.
tion occurs if the pH is above a critical value, which depends largely on the metal.
For example, Hazel, Schock, and Gordon (204) found with silicic acid prepared by
base exchange that, in the pH range 2~3, ferric ion reacted strongly, aluminum and
chromium less, in that order; barium, lanthanum, and copper did not react at this
pH.
The combination of the metal ion with the silicic acid may be regarded as an
adsoprtion of the metal hydroxide on the silica. Britton (205) has tabulated the pH
at which the silicates and the hydroxides precipitate from solutions of many metal
salts. Combination with silicic acid does not occur much below the pH at which the
metal hydroxide would be formed (either as a sol or as a precipitate) on prolonged
standing. This is perhaps not surprising, when it is recalled that silicic acid is an
extremely weak acid.
It is possible, therefore, that the combination between silicic acid and metal ion,
especially at low pH, may involve the association of polymeric units' both of silica
and of basic metal cations, so there are multiple points of attachment. Certainly on
the surface of silica, polybasic cations such as those of chromium or aluminum are
more strongly adsorbed than the single hydrated metal cations. Also, on the surface
of a metal oxide, polysilicic acid is adsorbed under conditions where monomer,
Si(OH)., does not react. That there is ionic reaction was shown by Hazel, Schock,
and Gordon (see above), who proved that hydrogen ion was liberated.
The combining capacity of silicic 'acid for metal ions decreases as the silica
polymerizes.
This phenomenon could conceivably be developed into a method of following the
decrease in available SiOH groups (or the surface area) as polymerization occurs.
Hazel, Schock, and Gordon found that by titrating freshly made ferric chloride solution from time to time with a sol of silicic acid as the latter polymerizes, the amount
of silica required to combine with a given amount of ferric ion increased with sol
age ..
The interaction of metal cations with colloidal silica is further discussed in
Chapter 4, and with silica surfaces in general in Chapter 6.
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151. K. D. Ashley and W.. B. Innes, Ind. Eng. Chem., 44. 2857 (l952).
152. H. Baumann, Kolloid Z . 162.28 (1959).
153. A. E. Nielsen. Kinetics of Precipitation, Mcmillan, New York. 1964, p, 18.
154. F. L. Ginsburg and L. D. Sheidina, Radiokhimiya, IS (3), 410 (l973).
155. S. A. Greenberg and D, Sinclair. J. Phys, Chem., 59435 (l955).
156. S. A. Greenberg,J. Polym, Sci., 27, 523 (1958).
157. K. Goto,J. Phys, Chem., 60. 1007 (l956).
158. G. W. Sears, personal communication.
159. E. Richardson and J. A. Waddams, Res. Corresp., 7, 543 (19S4).
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162a. J. S. Kirk. U.S. Pats. 2.276,314-2.276,315 (Du Pont), 1942.
162b. L. Pauling, The Nature of the Chemical Bond. 3rd ed. Cornell University Press, Ithaca,
N.Y. 1960.
162c. G. C. Pimentel, A. L. McClellan, The Hydrogen Bond, Freeman, San Francisco, 1960.
163. M. J. Copeley and C. S. Marvel, J. Am, Chern. Soc., 62, 3109 (1940).
164. R. K. lIer,J, Phys. Cbem., 56, 673 (l952).
165. H. Baumann, Beitr, Silikose-Forsch, Sonderb., 2. 317 (1956).
166. J. W. Robinson, U.S. Pat. 2,392,767 (Du Pont), 1946.
167. R. K. lIer and J. S. Kirk, U.S. Pat. 2,408,655 (Du Pont), 1946.
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1946.
169. R. K. lIer,J. Col/oid Interface s, 51, 388 (1975).
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Chern. Phys.
5th '72. Carl
..
CHAPTER
Colloidal
Silica-Concentrated Sols
DEFINITION OF COLLOIDAL SILICA AND HISTORICAL
DEVELOPMENT
"
i
i
tI
'":
The term "colloidal silica" here refers to stable dispersions or sols of discrete particles of amorphous silica. By arbitrary definition, the term excludes solutions of polysilicic acid in which the polymer molecules or particles are so small that they are not
stable. Such solutions, which are usually obtained by acidifying sodium silicate solutions or by hydrolyzing silicon esters or halides at ordinary temperatures, have been
discussed in Chapter 3 as precursors of colloidal particles.
Stable concentrated silica sols that do not gel or settle out for at least several
years became available. in the 1940s. after it was learned how to make uniform
colloidal particles larger than about 5 nm in diameter, stabilized with an optimum
amount of base.
When Vail (1) in 1925 and Treadwell and Wieland (2) in 1930 reviewed the status
of colloidal silica, only rarely could a silica sol containing more than 10% silica be
obtained; such sols were not- stable toward gelling. In 1933 the art was reviewed by
Griessbach-B), who reported that a 10% sol stabilized with ammonia was made by I.
G. Farbenindustries, A.G. In 1941 Bird (4) patented a process for removing the
alkali from a dilute solution of sodium silicate by a hydrogen ion-exchange resin,
adding back a small amount of alkali to stabilize the silica, and concentrating by
heating to boil off water. It is now evident that under these conditions silica particles
were grown to 5-10 nm in diameter. In 1945, White (5) patented a process of washing the salts out of silica gel made by acidifying a solution of sodium silicate,
impregnating it with an alkaline solution, and then heating until 'most of the gel is
peptized to a sol. These processes generally gave sols containing 15-20% solica, at
least temporarily stabilized against gelling or settling out. In 1951 Bechtold and
Snyder (6) developed the first process for making colloidal silica particles of uniform
and controlled size, and Rule (7) further defined the optimum concentrations of
alkali required for stabilization while limiting electrolyte impurities.
The history of the development and the state of the art in about 1954 was sum- '
marized by lIer (8). Further refinements by Alexander (9) in controlling particle size,
312
Growth and Stabilization or Discrete Pa.r.tjc!es
313
degree of aggregation, purity, and optimum concentration of stabilizidg alkali led to

stable sols of particles only 8 nm in diameter, yet containing more than 30% silica.
Stable, translucent, aqueous sols containing up to 50% by weight of Si0 2 have been
developed (10, ll) by making particles 20-25 nm in diameter and adding an
optimum amount of alkali for stabilization and sufficient salt to reduce the viscosity
without destroying stability.
.
Sols containing discrete particles -as.large as 300 nm or more in diameter, which'
settle out on standing, have been made by autoclaving wet silica gel with a base
under superatmospheric pressure and then breaking the lightly aggregated particles
apart in a colloid mill (l2a).
Thus in the past 30 years methods have been developed for making discrete silica
particles covering the whole range of colloidal size and stabilizing these as
concentrated commercial sols.
A broad review of "hydrosols" has been written by Napper and Hunter, including
their preparation and properties (12b).
GROWTH AND STABILIZATION OF DISCRETE PARTICLES
crete partins of polyley are not

Iicate soluha . been
ast several
:e uniform
1 optimum
the status
70 silica be
eviewed by
nade by I.
loving the
LOge resin,
.trating by
a particles
s of washTI silicate,
. the gel is
solica, at
.htold and
)f uniform
rations of
ws
rmrticle size,
As discussed in Chapter 3 (see Figure 3.1) silicic acid polymerizes to form discrete
particles in the pH range 7-10. No aggregation occurs if the concentration of electrolyte is generally less than 0.1-0.2 N, depending on silica concentration.
Because of the nonuniform distribution of particle sizes, especially when particles
are smaller than 10 nrn, spontaneous particle growth occurs. The particle size that is
attained strongly depends on the temperature. As shown in Table 3.5, at 50-100C
particles reach 4-8 nm in diameter, whereas at 350C in an autoclave they may
grow to 150 nm. This spontaneous growth is relatively independent of the silica
concentration. The size of particles produced by autoclaving aqueous sols is limited
at high temperature by the conversion of amorphous silica to crystalline quartz. Fyre
and McKay have shown that the rate of conversion under autogenous pressure at
330C is proportional to the square of the hydroxyl ion concentration (13). Oehler
(14) reported that after 4 weeks at 150C and 2000 bars microspheres of crystalline
tridymite 50 microns in diameter were formed.
Increasing Particle Size By Adding "Active" Silica
It was because of the small particle size of the colloidal silica made at ordinary
temperature that stable concentrated sols could not be obtained. Because higher
temperature was known to accelerate gelling, it seemed logical that sols should be
made and kept at ordinary temperature. Hence the ultimate particle size seldom
exceeded 2-3 nm. When a sol of this type was adjusted to pH 8-10 and vacuum
concentrated at 20-30C it gelled when the concentration reached about 10%. It was
not realized that it could be heated and evaporated at 100C to a stable concentration of 10-20% because at the higher temperature the particle size increased to
4-6 nm.
Colloidal Silica-Concentrated Sols
314
However, to obtain still more concentrated sols. even larger particle-sizes were
needed. This was 'first achieved by the further deposition of soluble silica on the
particles by adding silicic acid in the form of particles smaller than 5 nrn, generally
less than 2 nm in diameter or even smaller polymer species. These are "active" in
the sense that they are more soluble and dissolve in the presence of larger particles
or "nuclei" on which silica is deposited.
It was the process developed by Bechtold and Snyder (6) that first provided stable
concentrated colloidal silica sols of any desired particle size from 10 to 130 nm in
diameter. First a 3.5% solution of silicic acid is prepared by passing a solution of
sodium silicate through a bed of hydrogen ibn-exchange resin to remove sodium, and
then enough alkali is added to raise the pH to above the neutral point, using around
1% by weight of Na.O based on the silica. This part of the operation follows the
Bird process (4). However, instead of boiling down the solution directly, a portion is
heated to 100C, which converts the silica to particles at least 4-6 nm in diameter.
Then the rest of the alkalinized polysilicic acid solution in which the particles are
less than 3-4 nm in diameter is gradually added to the hot sol as it is concentrated
by evaporation. By carrying out this addition sufficiently slowly, all the incoming
silica is deposited on the original particles, which thus are grown at a uniform rate.
Water is usually simultaneously evaporated so that the total number of particles per
unit volume remains constant, but they grow in size as the sol becomes concentrated.
In the patent literature, the initial alkalinized sol containing the silica particles which
act as nuclei has been termed a "heel," used in the sense of a "residue" in a partly
filled container to which more liquid may be added.
In a modification of the Bechtold and Snyder process, Rule (7) started with a heel
of alkalinized sol but added a solution of polysilicic acid made by ion exchange to
which no alkali has been added. The silica particles were thus grown in a medium of
constant alkali content, so that stable concentrated sols were produced containing a
minimum of stabilizing alkali. Albrecht (15) patented the optimum rate of addition
of polysilicic acid in the Rule process for producing silica particles 45-100 nm in
diameter. By operating a similar process under superatmospheric pressure, particles
up to 150 nm in diameter have been produced (16).
Particles having a diameter of more than 100 nm have been prepared by Mindick
and Vossos (17) by adding silica of average molecular weight below 90,000 to a sol
heel having a pH of 7-11 and containing at least 0.1 % by weight of relatively uniform spherical silica particles with an average diameter of at least 30 nm. The rate
of addition of feed is maintained below a maximum according to the relation F, =
kS,C" where F, is the maximum feed rate at any time I, in grams of silica added per
milliliter of mixture per hour, k is a predetermined rate constant equal to about
0.005 for a constant volume process at 100C, S, is the specific surface area of the
particles at time I, in square meters per gram of silica, and C, is the concentration of
the silica in the mixture at time I, in grams per milliliter.
.
This method of increasing the size of silica particles is sometimes referred to as
the "buildup process." Colloidal particles in which only the ;urface of the particles
.~~ silica, whereas the interior is another insoluble material, can be made by
'''''" . . . ' >
ith suitable colloidal nuclei other than silica. using the buildup process.
Thus it is possible to produce sols having the dispersion and surface characteristics
-,
....
a,
...
-.
,'.
,;
:ntrated Sols
sizes were
lica on the
I, !
'ally
"active" in
er particles
of colloidal silica, yet with platelike or fibrous particles. by starting tslith colloidal
dispersions of platelike or fibrous colloidal silicate minerals, oxides, metals. or other
materials, according to a silica-coating process developed by I1~r (18). In growing
particles by this process "active" silica must not be added to the system more
rapidly than the available silica surface can take it up. Otherwise the solution
becomes so supersaturated that new small nuclei are formed and then the final sol is
not of uniform particle size. As shown In Chapter I, at 90C the maximum rate of .
addition without nucleation is about 10 grams active SiO z per 1000 m2 hr- 1 area of
silica surface. The theoretical increase in particle size depends on the "buildup
ratio," B,.:
'ided stable
130 nm in
solution of
odium, 'and
ing around
follows the
1 portion is
1 diameter.
articles are
.ncentrated
e incoming
iform rate.
articles per
ncentrated,
icles which
in a partly
wi' , heel
xch....ge to
medium of
mtaining a
)f addition
100 nm in
e, particles
Iy Mindick
00 to a sol
itively unit. The rate
ation F, =
added per
I to about
area of the
ntration of
erred to as
ie particles
Ie made by
.p : 'cess.
rae. .stics
315
where WCI is the amount of active silica added to the particles and W" is the weight
of silica initially present as nuclei. Obviously, the particle diameter will be increased
from the initial size d, to the final size d, in accordance with the following equation:
1 + B,.
A process by which 15% sol can be made directly by ion exchange was developed
by lIer and Wolter (19), whereby a heel of water or dilute sodium .silicate is heated
and stirred and then. wet, drained, regenerated hydrogen ion-exchange resin
(preferably of the weak acid type) and relatively concentrated sodium silicate solution are added simultaneously at such a rate as to maintain the pH at around 9.
Depending on temperature and relative amount and size of particles in the heel, the
rates of addition of resin and silicate can be regulated to increase the size of the
silica particles without further nucleation. A similar process is operated in a column
or fluidized. bed by which resin is continuously added at the top and withdrawn at
the bottom in counterflow to the silica sol (20).
In a study of the growth of silica particles by adding mon<?mer to a dispersion of
preformed nuclei. Bartholin and Guyot (21) studied the formation of nuclei when
low molecular weight silicic acid, made by ion exchange from sodium silicate, was
aged at pH 8. The very pure sodium silicate was made from ethyl orthosilicate. In
this case the 2.5% sol alkalinized to pH was stored at 4C to minimize spontaneous
particle growth and, because of the high concentration of small particles, promote
formation of microgel. When heated, the microgel aggregates condensed and shrank
to more or less dense spherical particles around 100 A diameter. However, it should
be noted that when the heating step from 4 t080C is slow (2 hr) the nuclei are much
more uniform in size than when the heating is rapid (10 min), as shown by the
greater uniformity of the final sol obtained by adding freshly made silicic acid solution also adjusted to pH 8.
316
While particles smaller than about 20 nm are being grown by this process, there is
some simultaneous spontaneous growth. This is important in making particles
smaller than 15 nm since even if no active silica is added, some growth of nuclei
would occur over the period of several hours normally required in the buildup
process.
The above remarks apply to systems where the silica is added as "active" silica
prepared as a separate solution, usually by.ion exchange. More rapid growth Occurs
when the silica is added directly as sodium silicate to a "heel" of nuclei from which
sodium ions are being constantly removed by hydrogen ion-exchange resin: as discussed later. In this case, 'the silica is initially present as monomer and oligomers
and thus no time is required to depolymerize higher polysilicic acids which are
invariably present when the silica is prepared first as a separate solution of "active"
silica.
Further variations in the "buildup" process are noted as follows; Albrecht further
defined the maximum concentration to which sols of different particle sizes may be
concentrated while the size is being increased by the deposition process (22) to 100
11m. By operating the growth process above 100C at steam pressures of 5-100 psi,
sols are obtained that can be concentrated to 55% SiO z according to Klosak (23).
The process should make particles of larger size than obtainable at 100C. Bartholin
and Guyot (21) studied particle growth in alkalinized solutions of pure silicic acid,
following the size of the growing spherical silica particles by light scattering. For an
increase in concentration when no further particle growth is desired, Reven and
Blake (24) propose boiling down a sol of 28-38% SiO z particles of 13-50 nm
diameter while adding a sol of the same composition until the concentration reaches
52% sio,
Irani made particles of very uniform size by the "buildup" process by starting
with a "heel" of water or. a sol of uniform small particle 'size at 6Q-150C and
adding silicate and hydrogen ion-exchange resin under prescribed conditions (25).
Another process variation (26) involves using a sol of "active" silica as it comes
from the ion exchange at pH 2.5-5.5 instead of making it alkaline before adding it
to the "heel sol" in the evaporation. However, it appears that the SiO z: NasO ratio
would continually increase during the process. Sippel (27) claims that by operating
in the above manner, feeding silicic acid to a "heel sol" of 8-20 nm in diameter, and
maintaining the pH at 8.5-9.5 by adding a solution of sodium silicate, which thus
maintains the SiOz : NazO ratio approximately constant, a sol of low turbidity is
produced. Starting with a "heel" of water and adding active silica is another way of
operating proposed by Weldes, Boyle, and Bobb (28). Specific conditions for making
nuclei and adding silicic acid to obtain particles over 50 nm in diameter are disclosed
by Cummings (29). Egbregt (30) proposed circulating a dilute sodium silicate solution through a column of hydrogen ion-exchange resin and adding more sodium silicate at a specified rate.
.
As pointed out in Chapter I, silica can be deposited on many different substrates.
SiO z, subsequent
Once the surface of a particle is covered with a monolayer
deposition is silica on silica in all cases. For example, particles of lead chromate can
be coated with an im pervious layer of silica (31). Also, as described previously, coating Ti0 2 pigment with SiO z is conducted on a large scale.
of
or Discrete Particles
trated Sols
Growth and Stabilization
s, there is
particles
of
~lei
: ~ul1dup
Methods of Making Particles Under 10 nm In Size
ve'tsilica
.
th occurs
om which
n, as disrligomers
vhich are
. "active"
,
1t further
.s may be
2) to 100
i-IOO psi,
isak (23).
Bartholin
licic acid,
g. For an
even and
3-50 nm
nr
hes
, starting
and
ons (25).
it comes
adding it
a20 ratio
operating
.eter, and
hich thus
rbidity is
er way of
r making
disclosed
:ate solu:lium sili-
;ooe
rbstrates,
bsequent
mate can
sly 'at-
317
Initial commercial sols were made with particles larger than about 8 nm so they
could be concentrated to at least 30% Si0 2 for economical shipment. Such sols are
extremely stable in regard to further growth of particles at ordinary temperature (see
Figure 3.52). Then it was realized that for some uses smaller particles were to be
preferred and such sols at lower silica concentrations were developed. However, the
problem arises that particles smaller than about 8 nm and certainly those smaller
than 5 nm grow spontaneously in storage with corresponding changes in properties.
Furthermore, since such sols are generally concentrated to at least 15%, those
smaller than 5 nm also may undergo a certain amount of aggregation in storage with
definite changes in use properties. A number of patents relate to the production and
stabilization of sols of this type.
The earliest salt-free sols of 5-8 nm particles were made by Alexander, who
defined thesilica concentration limits and alkali content for stabilization in terms of
particle size (9). The particle size was related to average specific surface area of
silica within the following limits:
Particles
, Diameter
Specific
Surface (m 2 g-l)
(nm)
600
350
4.6
7.9
Si0 2
(%)
Ratio
Si0 2 : Na20
15-20
20-200
15-34
34-340
A method of making a ;sol of 10% Si02 with particles about 3 nm in size, devised
by Her (32), involved starting with a sol less than 3 nm in size, adding sodium silicate in an amount not' exceeding 4% Si02 of added silica, so as not to exceed a
sodium ion concentration of 9.4 N, aging 10 min, and passing the sol through a
column of strong-acid ion-exchange resin in hydrogen form to recover a sol of pH
3.5, and repeating the process at ordinarytemperature.
To increase silica concentration without particle growth beyond 5-10 nm size. a
silicic acid solution is alkalinized with sodium silicate and then more silicic acid is
added while water is removed by vacuum distillation. Under these circumstances the
low temperature avoids excessive particle growth in spite of the addition of active
silica to the system (33). An earlier approach was to form the particles to the desired
size in dilute solution and then concentrate by evaporating water and adding more
dilute sol. Since the added particles are the same size as those in the evaporator, no
.
"buildup" occurs (34).
The use of ammonia as a stabilizer apparently minimizes particle growth. Weldes
and Derolf (35) claim that sols of particles size 2-3 nm are obtained in concentrations up to 12% when stabilized with both NaOH and NH.OH, the (NH.hO:Na 20
ratio being 25-150 and the SiO z : (NH.hO 2-8. Possibly the adsorption of NH 3 on
the silica surface reduces the rate of dissolution of silica so that growth is retarded.
Birkheimer (36) similarly claims stabilizing a sol with excess ammonia and then
boiling out the excess.
318
Particles estimated to be 1-3 nm in size were made by McNally and Rasenberg

(37) by deionizing sodium silicate solution with a weak-acid hydrogen ion-exchange
resin which had first been neutralized in suspension at pH 6-7. This presumably
prevented the formation of larger nuclei of silica that might be formed at lower pH
in contact with the resin. The Si0 2 : Na20 ratio of the sols was 4: I to 40: I and the
concentration 15-25% Si0 2 It is possible that in the absence of any larger nuclei,
the sol was unusually stable against spontaneous particle growth, although a
concentration as high as 25% suggests that in that case the particles must have been
larger than 3 nm.
Vossos claimed sols of particles less than 5 nm in size stabilized at pH 9-11
containing up to ~5'10 Si0 2. The. alkalinized dilute sol was vacuum concentrated at
less than 150F to minimize growth (38).
Reuter and Reven prepared particles 7.5 nm in diameter from a sol of 1-3 nrn
particles by heating at pH 8.7 and carrying out a "buildup" at 165F to get a 15%
sol (39).
Marotta (40) made 5-10 nm particles by adding silicic acid solution to a dilute
solution of sodium silicate over a period of hours at 25-50C, then more at
50-90C, and still more at 70-100C while evaporating water. This apparently
involved a combination of additional nucleation and particle buildup.
Other preparations of sols with particles under 5 nm in diameter and their stabilization have been discussed under the heading of polysilicates and silicates. Sols of
such small particles stabilized with relatively large amounts of base assume some of
the characteristics of soluble silicates or polysilicates rather than of colloidal silicas.
-,
Stabilization Against Particle Growth (Theory of Paul C. Yates)

As indicated in Chapter 3, polysilicates or sols of very small particles are stabilized
by having sufficient alkali in the system. Yates (41) proposed that alkali-stabilized
sols are stable not only against gelling, but also in the thermodynamic sense. He
pointed out that there are thermodynamic factors that prevent the spontaneous
growth of particles or their aggregation and stabilize the high interfacial solid-liquid
interface in the silica-water system. The main factor that counterbalances the free
energy change involved in loss of surface area in the silica-water system is the strong
adsorption of the continuous liquid phase or of stabilizing counterions or of other
adsorbed species at the surface of the dispersed phase, thus changing the free energy
of the interface.
The effect can most easily be understood by considering the changes in free energy
that occur during the following hypothetical, reversible, isothermal steps in the
three-component system Si0 2-H 20-NaOH starting with an alkali-stabilized sol:
1. Desorb NaOH from the surface of the colloidal particles: t1F1
2. Desorb water from the surface of the colloid; that is, the ftee energy of wetting
the surface: t1F 2
3. Decrease the surface area of the colloid to the minimum possible geometrical
area allowed by its density; that is, the free energy of the solid colloid: t1F3
.~
...
.;;.
itrated Sols
Growth and Stabilization or Discrete Part.!f!e~
Rosenberg
.-exchange
res -bly
lowe, pH
: I and the
~er nuclei,
4. Return solvent to the surface of the collapsed colloid of minimum area: ;j,F.
5. Return the NaOH to the system: AF,.
By definition,
AFt + AF,
lthough a
have been
pH 9~11
ntrated at
)f 1-3 nm
get a 15%
o a dilute
more at
.pparently
reir stabi:s. Sols of
e some of
11 silicas.
stabilized
stabilized
sense. He
mtaneous
lid-liquid
s the free
.he strong
. of other
ee energy
ee energy
ps-in the
:I sol:
319
free energy of adsorbed NaOH on colloid
AFz + AF2 + AF. = interfacial free energy of colloid in a
binary SiOz-HzO system

If
then the initial colloid system

of three components is at thermodynamic equilibrium.
I
In other words, if the free energy of adsorption of sodium hydroxide on the surface
of the colloid equals the free surface energy of the system in the absence of NaOH,
then the sol is thermodynamically stable.
Heretofore all colloid systems such as sols have been considered to be thermodynamically unstable.
In a silica sol the interfacial free energy of amorphous silica versus water is of the
order of 50 ergs em -z (Figure 3.32). The the decrease. in free surface energy
accompanying the loss of surface, assuming about 8 silicon atoms nm -z, amounts to
900 cal g-mole" of surface silicon atoms. If the colloidal particles are stabilized
thermodynamically, the counterbalancing free energy term must be of about this
magnitude. This stabilizing energy comes from the adsorption of OH- and the
counter Na+ ions on the colloid surface.
Yates calculated the amount of alkali necessary to stabilize silica particles against
.
growth as follows.
The free energy change connected with the ionization of surface groups depends
on the acid dissociation constant which, in turn, varies with the salt concentration
and the degree to which the ionization of surface groups has already occurred. The
free energy change under constant conditions will be
AF = a(-RTln K')
(I)
where a is the fraction of surface groups ionized and K' is the instantaneous value of
the dissociation constant at that particular value of a, other conditions being fixed,
and assuming a surface containing one mole of silanol groups.
As will be discussed in connection with the charge on particles, Yates derived a
formula for the value of K' as a function of pH, sodium ion concentration in solution, and a, the degree of dissociation of the surface.
pH
I-a
pK - n log - - - 0.74 10g(A Na+)

a
where K is the overall dissociation constant and (A Na")

sodium ion times the sodium ion normality.
IS
(2)
the activity of the
...
:".. ...
320
From titration data at a fixed concentration of Na" ion, a plot of -10g [( I _

a)/a] against pH gives a line of slope n and intercept pK. The value of n from the
experimental data is 3.47.
The corresponding expression involving K' is
I-a
pH .. pK' :- log - a
(3)
I-a
pK' - pK - (n - 1)log - - - 0.74 10g(A Na+)
a
(4)
where
From equations I and 4,

~F
1- a
- 2.3aRT [ -log K -(n - l)log -a- - 0.7410g(A Na+)J
(5)
It can be shown that,

2430
a ""
I;
rS
(6)
where r is the weight ratio of Si0 2 : Na 20 in the system and S is the specific surface
area of the silica in square meters per gram; Yates assumed the density of silica to
be 2.3 g ern -',
Substituting the numerical values for K, a and n gives
ilF =
I
j
I
3.38 x 10' [
rS
12.08 - 2.47 log
rS - 2430
]
- 0.74 10g(A Na+)
. 2430
(7)
which expresses the free energy change associated with moles of surface groups at
any level of ionization or salt content.
In order for a silica sol to lower its specific surface free energy by particle growth
or aggregation to form a sol of lower surface area, it is necessary to reverse the ionization and return the adsorbed ions to the intermicellar liquid. According to Yates
the free energy change will be 'YS, where 'Y is the value of the specific interfacial free
energy between the silica surface and water. The latter is a function of particle size
and thus of S.
Let the free energy change occurring when particles of diameter D lose AS em" of
surface be
(8)
"t
',n
'.........
,
..3
.'
ntrated Sols
Growth and Stabilization of Discrete Parti.!~s.
-log [(I n from the
A similar expression for a nat surface is
321
~Fo = -'Yo ~S
~Fo - ~Fo -
(3)
(4)
'Yo)~S.
(10)
This is the difference in free energy between a colloid of particle diameter D and the
same colloid if it had the free energy of a flat surface. This would be - R T
In(So/So), where So and So are the corresponding solubilities of the curved and flat
surfaces of silica.
Yates used the equation published by Her in 1955 (8):
So
In -
.s,
(5)
ho -
(9)
3.8
=
(11 )
where D is in millimicrons. This was based on an interfacial energy of 80 mg cm -2.

However, as shown in Chapter 1 (see also Figures 1.lOa and 3.32), the value is more
likely to be about 50 mg ern -2 so that the equation should probably be
2.4
So
In So
(6)
Then
fic surface
)f silica to
2.4
t:J.Fo - t:J.Fo = -RT D
(12)
From equations 8 and 10,

(7)
ha - 'Yo) t:J.S
RT
-2.4 -
(13)
RT
--
(14)
groups at
'Yo
de growth
;e the ionis to Yates
facial free
article size
= 'Yo
~Fo = -'Y~
+ 3.8
t:J.S
D~S
+ 2.4
RT
(15)
However, D can be related to S by taking into account the density of silica, assumed
by Yates to be 2.3 g ern-3:
(8)
2554
(16)
322
Then
2.4 RT
-AFo - "Y~S
2554
(\ 7)
Since at 25C. T == 298K, R == 1.987 cal deg- 1 mole ? and

-j,F0 == "Yo AS
+ 0.56S
(18)
-z.
Assuming "Yo .. SO mg cm
AS equals the area or 6 x 1023 surface silicon atoms.
Assuming 8 silicon atoms per square nanometer, the value of S is 7.5 X 108 ems,
Changing ergs to calories gives
-AFo == 50(2.39 X 10- 1 ) (7.5 X 108 )
- AF0
896
+ 0.565
(19)
+ 0.56S cal
Then -AFofrom equation 19 must equal AF from equation 7:

3.38 X 101
rS - 2430
2430
- 0.7410g(~ Nat)
(20)
3.38 x 10' (12.08 - 2.47 log [(rS - 2430)/2430] - 0.74 10g(A Na+)}
r ==
S(896 + 0.56S)
(21)
896
+ 0.565
rS
12.08 - 2.47 log
Rearranging gives
In the absence of foreign salts, the concentration of Na + can be calculated simply

from the concentration or silica. C., and the ratio r since
[SiOz]
,
... r
[NazO]
[Na-O] ==
[SiO z]
r
Since the sodium concentration in stable sols seldom exceeds 0.1 N, we may assume
the activity is about unity:
Na" ==
2C
r
where C is the molar concentration or StO, in the system:

r
3.38 x 108 (12.08 - 2.47 log [(rS - 2430)/2430] - 0.74 log(2C / r)}
5(896 + 0.56S)
(22)
.:~i?'w.
...
;..~
;:/
<~
:ntrated Sols
(17)
(18)
con atoms.
x 108 ern".
(19)
Growth and Stabilization of Discrete
Partiq~s
323
For specific examples, assuming values for Sand C, the following values of r were
calculated from the equation.
For a 15% sol of 4.5 nm particles (600 m 2 g-I) the calculated Si02:Na20 ratio is
47: l. For a 39% sol of 13.4 nm particles (200 m 2 g-l) the calculated ratio is 170: 1.
(Yates's earlier calculations gave 32: I and liS: 1.)
In commercial sols corresponding ratios of about 25: I and 100: I are actually
used for these particle sizes. As shown. in Chapter 2, particles of about 16 nm
diameter stabilized at 100: I ratio grow very little in 20 years. However, particles
4-5 nm in diameter in some cases undergo a slow 10-20% increase in diameter in a
year or so even though stabilized at 25: I ratio. However, lot-to-lot variations can
occur, probably because of variations in the initial particle size distribution.
The above formulas probably do not apply to particles much under 7-8 nm in
diameter' since the increasing solubility of the particles involves the presence of
appreciable concentrations of silicate ions which must be taken into account in the
stabilized systems. This would probably require more stabilizing alkali than the
present equations indicate, that is, lower values of r.
Stabilization Against Aggregation

(20)
(21)
ited simply
.ay assurne
.,/
, r,.
(22)
Concentrated silica sols are stabilized against interparticle siloxane bonding by

either (I) an ionic charge on particles so that particles are kept apart by charge
repulsion; or (2) an adsorbed, generally monomolecular, layer of inert material
which separates the silica surfaces to an extent that prevents direct contact of silanol
groups. This has been referred to as "steric" stabilization.
In the case of particles' of appreciable size, and especially. at low pH where
siloxane bond formation is .slow, spontaneous interparticle bonding is usually not
observed. Thus with particles more than 100 nm in diameter such bonding does not
appear to occur even in concentrated sols over the whole pH range unless the sol js
dried. With such large particles, even if some siloxane bonds are formed at the
points of contact, they are probably insufficient to withstand the mechanical strain
involved when a pair of such large particles collides with a third particle in the
course of Brownian motion.
Another form of instability in storage is sedimentation by gravity whereby a very
concentrated viscous layer is formed at the bottom of sols of large particles. In some
cases there appears to be a distinct liquid-liquid boundary suggesting that a
concentrated coacervate has been formed. Observation of a series of 30% sols stabilized at Si0 2 : Na 20 ratios around 100-200 showed that over a 20-year period sedimentation was pronounced only when the particle diameter was over about 70 nm.
Sols of smaller particles probably remained essentially homogeneous because of
convection currents since the storage temperature fluctuated between 20 and 30C.
The role of convection in the formation of stratified layers in silica suspensions has
been studied by Baruch-Weill (42).
'
There is one type of instability that is not encountered in this system, namely,
crystallization. As pointed out by Walton (4), the higher the degree of supersaturation the smaller the size of the critical nucleus, which may be so small as not to cor-
'";....----
324
respond to a particular crystalline phase. This solid phase then grows "With no
particular order to the structure. For simple compounds the ions or molecules can
rapidly rearrange to satisfy minimum energy requirements. In the case of silica the
energy difference between the amorphous and crystalline states is small and, further,
more, a high energy of activation is required to break siloxane bonds to permit the
rearrangement. No crystalline form of silica has ever been found in sols or gels even
after aging for 25 years at ordinary temperature;
Stabilization By Ionic Charge

An ionic charge on the particles in the presence of alkali is the chief mechanism of
stabilization in commercial sols. However, a completely satisfactory theory of stabilization has apparently not yet been developed. The basic principles of stabilization
'by the ionic double layer around particles were developed by Derjaguin and Landau
(44) and Verwey and Overbeek (45), hence the "OLVO" theory; it has been specifically applied to spherical particles (46a). An excellent summary of the forces affecting the stability of disperse systems was presented by Ottewill (46b).
Napper has written a summary of colloid stability (47), including the principles, of
both electrostatic and steric stabilization. A fundamental study of the van der Waals
forces between amorphous Si0 2 surfaces was carried out by Roweler (48), who
measured the attraction between two fused silica surfaces covered with thin films of
chromium metal in a high vacuum. However, it is difficult to translate these results
to an aqueous silica system. The Hamaker constant in many colloid systems has
been reviewed by Visser (49) including the Si0 2-H 20 system.
At least under some conditions the stability of silica sols is in complete. contradiction to the "0LVO" theory, as pointed out by Kitchener (50). Thus at pH 2, where
the charge on silica particles-is zero, the particles aggregate least rapidly and the sol
has highest temporary stability. However, it is only in alkaline solution where the
particles are highly charged that sols are permanently stable. Here the double layer
theory is more logically applicable.
Matijevic (51) has discussed the applicability of the "OVLO" theory to various
inorganic sols. In the case of silica sols, the nature of the electrolyte is of major
importance. Cations vary so enormously in their adsorption and formation of stable
complexes with the silica surface that the theory is of little practical value. The same
conclusion was reached by Webb, Bhatnagar, and \Villiams in regard to colloidal
Ti0 2 (52).
MAXIMUM CONCENTRATION OF SOLS. The problem of stabilizing sols becomes
acute at high silica concentrations, which are needed for economic shipment. No
appreciable change in properties should occur in .less than a year under ordinary
storage conditions.
.
Commercial sols are presumably stabilized at optimum pH and are concentrated
to the maximum concentration permitted by the particular particle size. It is likely
that in all cases the particles are concentrated u-ntil the atmospheres of stabilizing
counterions surrounding the particles begin to overlap so that a slightly higher
325
rtrated Sols
s with no
ecules can
~ si
the
concentration would lead to a marked rise in viscosity and long-term instability, that
is, gelling.
The concentrations and particle sizes of typical commercial sols are plotted as
curve A in Figure 4.1. Based on the density of amorphous SiO, of 2.2 g ml:", curves
Band C can be calculated, expressing the silica concentration as grams SiO, per 100
ml of sol and as volume
solid SiO, in milliliters per 100 ml of sol, respectively.
The latter volume percent divided by J 09 gives the "volume fraction," tP" of solid
silica in suspension.
Since all the sols are approximately at maximum practical concentration, the
particles plus their surrounding ion atmospheres are presumably at about equal
packing density. This maximum packing density is proportional to the volume
fraction of the dispersed phase tP" where the dispersed phase is defined as the
particle plus its ion atmosphere and d is particle diameter
d, furtheroerrnit the
. gels even
hanism of
y of stabiibilization
id Landau
en specifices affectnciples, of
der Waals
(48), who
.n films of
ese results
stems has
COl adic-
12, where
.nd the sol
where the
uble layer
to various
of major
1 of stable
The same
) colloidal
of
+ 2d a
2d
-;/(K tP,)113
tP.
tP,
= -
+ (K tP.)1/3 -
1- 0
Plotting tP,1I31d versus tP.lI~ from the data of curve C of Figure 4.1 results in the
linear plot of Figure 4.2. From this, du = 2.43 nm and K = 1.68.
For large particles, where the thickness of the ionic layer is much smaller than d,
tP, = II K = 0.6. This indicates the particles in such sols are packed somewhat more
closely than random packing. :
100
'"
en 75
0
Z
~
0:
~--A
50
~--c
I-
zw
u
25
icentrated
.t is likely
stabilizing
tly '1her
KtP~
where K is a constant, and d u is the thickness of the ion atmosphere or Gouy double
layer around the particle. Rearranging gives
LL
; becomes
ment. No
. ordinary
)3 =
d
(d
0
0
10
20
30
40
50
PARTICLE DIAMETER. (nm)
60
Figure 4.1. Maximum concentration

versus particle size in stable aqueous silica
sols at about pH 9.5. A, concentration
(wt. %); B, concentration (grams Si0 2 per
100 ml); C, volume fraction of Si0 2
(x 100).
326
The thickness. da of the Gouy double layer in a given system depends only on i
the ionic strength (53).
drr
= 3.05;5 A
Since it is calculated for the commercial sols that da averages about 24 A. the
mean ionic strength calculated from the .equation would be about 0.016 N for all the
sols. Actually. in a typical 15 nm sol containing about 500 gl-I of SiD:!> the usual
stabilizing ratio of SiO~:Na,O is about 100: I and the Na,O content is' 5 g I-lor
about 0.16 N. In such concentrated sols most of the sodium ions must lie very close
to the surface (in the Stern layer) leaving a concentration of the order of 0.016 N in
the outer double layer.
The amount of alkali required for stabilization is generally proportional to the
surface area of the silica particles in the sol. It amounts to roughly 1.0-1.5 molecules
NaOH nm -2 in most sols which may contain 10- 2 N salt impurities. However, if the
sol is nearly free from salt (less than 10- 5 N) then the concentration of stabilizing
NaOH can approach the theoretical value of 0.016 N giving a surface concentration
of 0.3 molecules NaOH nm -'.
Addition ofSalt to Lower Viscosity

In sols with particles larger than 10 nm in diameter which can be concentrated to
500-700 g I-a SiO,. the viscosity becomes very high. It can be lowered by a minor
reduction in the thickness of the double layer by adding a small amount of salt
without making the sol unstable. Atkins was the first to use this technique (54). He
disclosed stabilizing salt-free sols of particles in the range 15-40 nm in diameter with
alkali and adding a salt such as Na,SO. or NaCI to give a concentration of
0.01-0.04 N. This made it possible to concentrate the sols to considerably higher
1.0
0.5
III
-s.
0.05
n,
'P
1/3
s /d
0.10
Figure 4.2. Relationship between volume

fraction (4).) of siiica and particle diameter. d
(plotted as 4>.1/3/ d>, in stable silica sols of
maximum concentration.
.~
"of"
.,
.'-.;
.entrated Sols
Growth and Stabilization of Discrete Parti.l~s_
ls only on i,
silica concentrations without the excessive increase in viscosity which occurred when
no salt was added. Later Vossos and Mindick (55) added at least 0.003% by weight.
based on silica. of a metal-free ammonium or organic base salt of an anion of a very
weak acid. Thus NH.HC0 3 is added to reduce the viscosity of a concentrated sol
without introducing any impurities that would be nonvolatile when the silica was
dried. With the same objective of reducing the viscosity of a concentrated sol,
Marotta (56) claimed that a combination of 0.055-0.095 N NazSO. plus enough
sodium silicate to give a pH of 8.8-9.9 gave a stable sol but if NaOH is used to
.
adjust pH, gelling occurs..
24 A.
the
y for all the
2. the usual
sSg I~1 or
e very close
327
~0.016Nin
Sterle Stabilization
.onal to the
5 molecules
Never. if the
f stabilizing
The theory of steric stabilization of sols has been discussed by Smitham, Evans, and
Napper (57) and Bagchi (58). There have been some partly aqueous silica sols
developed that are stabilized solely by adsorption of nonionic molecules. A typical
example is the 35% sol of Luvisi (59) which is salt-free and adjusted to pH 3-4.5,
containing 30-90% of a monohydric alcohol. for example, isopropanol. At pH 4-4.5,
glyoxal apparently has a stabilizing effect on silicic acid sols and at the same time
promotes the insolubilization of water-soluble polymers such as gelatin or polyvinyl
alcohol (60). It is well known that silicic acid sols free from salt at low pH are more
stable in the presence of hydrogen-bonding agents such as lower polyether-alcohols;
no doubt. more concentrated sols of colloidal particles could be similarly stabilized.
However. maximum stability is attained when all water has been removed. Such
sols. generally referred to as organosols, are covered later in this chapter. A typical
process involves complete removal of cations and anions from a silica sol leaving the
pH between I and 7 and then partial or complete replacement of water with an
alcohol. ether. or ketone (6i).
Steric stabilization has been used in the case of very small particles to supplement
ionic stabilization. Thus Yates stabilized sols of very small particles with a combination of an inorganic or organic base with a water-soluble nonaromatic polyhydroxy
or hydroxy-ether compound, for example, polyvinyl alcohol (62). There is probably
also some steric stabilization when an organic base cation such as (CH 3).N+ is
present since; as Wolter (63) found, a silica sol of this type can be evaporated to a
dry powder that will spontaneously redisperse in water. Such sols also can be redispersed after freezing.
Steric stabilization by a monolayer of hydrogen-bonded water molecules (64)
must be involved in the case of sols which appear stable at least for several months
at low pH. Extremely low concentration of ionic impurities, other than the necessary
acid to maintain the low pH, is essential. Alkali tends to be buried within particles
and comes out slowly, raising the pH and causing gelling unless special precautions
are taken. Mindick and Reven (65) repeatedly deionize. age. and deionize the sol
with mixed cation- and anion-exchange resins until the pH does not rise above 3 during storage. It must be pointed out that traces of aluminum a;e present in all commercial silicates and may still be present as SiAIO. -H+ sites on the silica surface in
sufficient amounts to contribute to the stability at pH 3.
mcentration
zentrated to
by a minor
'f salt
lue \-4). He
ameter with
mtration of
"ably higher
aur
tween volume
de diameter, d
~ silica sols of
328
..
Porous Particles
The primary particles of colloidal silica are generally nonporous if formed or grown
in alkaline solution and especially if formed at elevated temperature. either above
60C in aqueous solution or condensed from the gas phase at very high temperature.
Fused silica (glass) has a density of about 2.20 g cm -3. If one measures the density
of colloidally subdivided amorphous -silica powders by im mersion in xylene and COr.
rects for the small content of surface OH groups. assuming the equivalent H 20 to
have a density of 1.0, the following densities have been observed:
Silica
Commercial sols
Commercial gel (large pore)
Condensed from vapor phase
Precipitated from hot solution
Density (g cm -3)
2.2-2.3
2.22
2.16
2.0
In all these powders the surface area determined by nitrogen adsorption is in

approximate agreement with the area calculated from the distribution of particle
sizes observed in electron micrographs, assuming a density of2.2 g crn ? (66). From
this it can be concluded that particles of this type have a porosity to nitrogen of less
than 5-10 vol. %.
On the other hand. silica sols can be made in which the discrete particles are quite
porous. They are formed generally at ordinary temperature in water by the uniform
aggregation of much smaller ultimate particles, less than 5 nm in size. Radczewski
and Richter (67) obtained porous 200 nm particles b~ hydrolyzing SiCl 4 and aging
the neutralized solution. "Stober, Fink, and Bohn made similar particles by hydrolyzing ethyl silicate in .:8 mixture of ammonia, water, and alcohol (68). The most
detailed study has been made of porous silica particles prepared by the dissolution of
powdered silicon metal in water. Balthis (69) discovered that fine silicon metal
powder, washed with dilute HF to remove the oxide film, will react with water with
evolution of hydrogen in the presence of an organic base catalyst to give clear dilute
sols of particles 8-15 nm in diameter that can then be concentrated by evaporation.
These particles were nonporous. Balthis then found that in the presence of ammonia
rather than an organic base, large particles were formed, up to 35 nm diameter.
Furthermore. the particles were shown to be porous. They depolymerized or
dissolved in dilute alkali at a more rapid rate than particles of the same diameter
that were known to be nonporous. The total surface area, measured by adsorption of
nitrogen (BET method) was two or three times the external area measured by
adsorption of methyl red dye from benzene solution.
McMillan then further studied the reaction and made particles larger than 100 nm
in diameter which were highly porous (70). By changing conditions during the reaction, the porosity of the inner and outer regions of the particles could be changed
and the size could be made to range from 100 to 500 nm. Spherical particles of very
uniform diameter could be obtained. A study of the particle structure. by measuring
.
\
-;
.-
entrated Sols
ed . 'own
ithei above
ernperature,
the 'density
ne and corent H20 to -
'ption is in
of particle
(66). From
ogen of less
es are quite
the ""'Iiform
Ra. ;wski
4 and aging
,y hydrolyz, The most
ssolution of
licon metal
I water with
clear dilute
vaporation.
)f ammonia
n diameter.
merized or
te diameter
Iscrption of
ieasured by
han 100 nm
ag the reacbe changed
icles of very
I m-vsuring
Growth and Stabilization or Discrete Particle~
329
the rate of depolymerization (dissolution) in alkali. indicated the constitaent primary

particles were 4 nm in diameter.
The freshly made particles obtained by reaction at 25-30C were highly porous to
nitrogen. the density being about 1.3 corresponding to a porosity of 40% by volume.
Spherical particles 200 nm in diameter with an external specific surface area of 15
m2 g-I resulted after the sol had been dried to a powder. However, before drying. the
internal surface area. measured by the adsorption of OH- ions. was 745 m 2 g-I, corresponding to ultimate or primary particles about 4 nm in diameter.
When a sol of such porous particles was heated at 90C, pH 9.8. the area
determined by nitrogen adsorption decreased to 22 m2 g-I, indicating that the
diameter of the internal pores had decreased so that nitrogen molecules could not
penetrate and thus could be adsorbed only on the outer surface. Ho~ever, microporosity still existed because the area determined by OH- ion adsorption was still 707
m2 g". By heating the sol for a longer time at pH 10, the pores could be further
closed and at least the surface became completely impervious. Some water and
alkali were no doubt trapped within.
Colloidal particles which are probably porous were made by Cummings (29) as a
milky sol when a solution of silicic acid was fed into a hot solution of sodium silicate
containing 0.35-0.4 N sodium ion. Until the sodium ion concentration is reduced by
dilution by the added silicic acid; the latter must be partially aggregated by the
sodium ions so that deposition of silica on small aggregates produces 'a sol of particles ranging from 20 to 250 nm in diameter.
Production of a sol of porous colloidal particles was observed by Iler when a solution of sodium silicate, Si02:Na20 = 3.25: 1.0, diluted to 4% Si02, was heated to
90C and then 60% of thealkali was slowly neutralized by adding H 2S0 4 , The high
temperature was necessary because when neutralization was conducted at 60C only
a soft translucent gel was obtained. The mechanism of the process appears to be as
follows.
In the initial 3.25 ratio sodium silicate solution about a third of the silica was
present as colloidal particles about 1-2 nm in diameter and the remainder as
HSi0 3 - ions. When part of the alkali was neutralized, the silica from the HSi03 ions was deposited on the colloidal particles which at the high temperature increased
in size to 3-;4 nm. At the same time, the sodium sulfate concentration was 0.3-0.4
N. which was above the critical coagulation concentration so that the highly charged
particles nevertheless aggregated into porous spheres 15-20 nm in diameter. The fact
that the spheres were made up of 4-5 nm dense silica particles was indicated by a
surface area of 600 m2 g-I as measured by adsorption of OH- ions before the
spheres were dried. After being dried the surface area by nitrogen adsorption was
only 160 m2 g-I corresponding to dense 17 nm spheres. The initial spherical
aggregates therefore shrank and the constituent ultimate particles became tightly
packed together, eliminating the internal porosity.
.
It is probable that if the initially formed wet particles had been acidified to pH 2
and washed with propanol before being dried, much of the internal porosity would
have been retained.
.
Several stages of aggregation of smaller silica particles into larger ones and these,
..
~._--
330
in turn, into even larger ones have been described by Greer (71). Stages-of particle
sizes 1.5, 10, 60, and 331 nm were described and an equation was given:
d - ar":'
where d is the diameter of the sphere at stage growth n, a is the diameter of the.units of
the initial growth stage, and r has a value of 6. If one assumes that a is 1.5 nm, then the
stages should occur at 9, 54, and 324 nm. Conditions for bringing about such aggrega_
tion were not disclosed.
Microporosity in colloidal particles may in some cases be demonstrated by low
angle X-ray diffraction. When the particle size determined in this way is much
smaller than the size calculated from the specific surface area by nitrogen adsorption
or observed in electron micrographs it means that the particles are made up of still
smaller discrete units so closely packed that the pores are not large enough to be
penetrated by nitrogen molecules (72). Most silica gels consist of primary particles
with intervening pores accessible to nitrogen. However, Lederer, Schurz, and Janzen
(73) reported that particles in their particular silica gels appeared to have some
"inner" area, because hydration corresponded to 0.15-0.26 gram H 20 per gram of
silica, which would indicate a high porosity.
Elongated Particles
An astounding observation of elongated or spindle-shaped silica particles has been
reported by Ogino and Kuronuma (74). This is the first time that discrete silica
. particles of colloidal size have been observed with a shape other than spherical. They
were formed by adding hydrogen ion-exchange resin slowly to a dilute solution of
sodium silicate (3.52 SiOz) at 40C until the pH dropped to 3, then adding ammonia
to raise the pH to 8-9 and heating I hr at 80C.
Particles With Non-Siliceous Cores

As long asthe surface of a colloidal particle consists of silica, its colloid properties
are the same as those of solid silica particles. As discussed in chapter I, silica can be
deposited on a wide variety of surfaces, as shown by lIer (18), To coat sol particles
carrying a positive charge, like Fe 20 z or 'Alz0 3, it is first necessary to reverse the
charge by adding the dilute sol into a dilute (10%) solution of sodium silicate under
conditions of intense agitation. It is also possible to reverse the charge with a chelating agent such as citrate before adding silicate. The surface is thus covered with a
negatively charged molecular layer of adsorbed silicate on which a layer of SiO z can
be applied. A sol of silica-clad thoria particles has been made by Barrett, Moises,
and Yanik (75). Stable sols of particles greater than 50 nm in diameter contained up
to 60% solids. The silica coating was about 50% by weight of the theria core. Silicacoated particles of thoria and urania are claimed by Fitch, Sanchez, and Vanil (76).
The kinetics of absorption of silica onto the surface of particles of thoria was
determined at 100-200C in an autoclave (77).
'"
'
..
.ntrated Sols
Methods of Making Sols
of particle
METHODS OF MAKING SOLS
ted by ,low
ly is much
adsorption
: up of still
ough"to be
ry particles
and Janzon
have some
er gram of
1 properties
ilica can be
01 particles
reverse the
icate under
th a chelatered with a
)f Si0 2 can
:11, Moises,
mtained up
.ore, Silica/anil (76).
th-
'1,
was
...
Many processes have been proposed and are employed for producing colloidal silica
from low-cost sodium silicate solutions. Sols have also been made from hydrolyzable
compounds such as ethyl silicate or silicon tetrachloride. To produce sols that are
stable at a reasonably high concentration, it is necessary to grow the particles to a
certain size under alkaline conditions -where the particles remain negatively charged
so they will not flocculate or gel. The particles should also be nonporous.
Colloidal silica is formed in nature when water is saturated with quartz at high
temperature and pressure and the solution is removed and cooled. Such sols contain
only a few tenths of a percent silica. but could be concentrated readily by ultrafiltration. The formation of colloidal silica in this manner was studied by Kitahara and
Oshima (78). who also examined the rate of dissolution of the particles when the sol
was diluted.
the.units of
rn, then the
ch aggrega-
:s has been
cr
silica
.rica., They
solution of
g ammonia
331
Neutralizing Soluble Silicates With Acids
...
When a dilute solution of sodium silicate is partially neutralized with acid to a pH of

8-9. a silica sol rather than a gel is obtained if the concentration of the resulting
sodium salt is less than about 0.3 N, and if the neutralization is carried out at elevated temperature, so that the particles grow as soon as they are formed to several
millimicrons in size. Thus a 3% silica sol may be made by partially neutralizing a
dilute solution of commercial silicate with acid. according to the conditions patented
by Alexander. Her. and Wolter (79). A sol of silica nuclei is first made by removing
sodium ion with an ion-exchange resin from a sodium silicate
. solution containing
2.2% Si0 2 until the weight ratio of Si02 to Na 20 is 85: 1. This dilute sol is then
heated at 100~C for about 10 min to form nuclei of desired size. Then dilute solutions of sodium silicate and sulfuric acid are added simultaneously while the mixture
is stirred vigorously at 95C over a period of 8 hr and the pH is maintained at about
9. The concentration of sodium ions must not exceed about 0.3 N or aggregation of
the particles will occur. Under these conditions. the silicic acid formed by the added
silicate and .acid is deposited upon the silica nuclei, so that particles of 37 nm size,
for example. are obtained.
In another patent, Alexander and Iler (80) describe the isolation of particles
formed in the above process by coagulating them with a metal ion such as calcium,
washing the precipitate free from sodium salt, and then peptizing the product to a
more concentrated silica sol by removing the calcium ions by ion exchange, for
example.
In making a sol by neutralizing a dilute solution of silicate with acid, it is essential
that the mixing be carried out so rapidly that none of the mixture remains in the pH
range of 5-6 for an appreciable time, since silicic acid gels almost instantly at this
pH. This requires that the acid and silicate be mixed with i~tense turbulence, with
either excess acid or excess silicate present to prevent local gelling. Even in the most
critical pH region, around neutrality, a mixing procedure patented by Armstrong
and Cummings (81) permits the formation of a uniform silicic acid solution at
.
--
332
":'.'. i I'
----
concentrations up to 20% Si0 2 , which even under the most adverse pH ~onditions
does not gel for a few minutes.
A different approach to making colloidal silica by reacting sodium silicate with
acid involves making an acidic sol and precipitating the sodium salt in a strongly
acidic medium. The polysilicic acid '!s temporarily stable at pH 2, and if the sodium
salt of the acid used for neutralizing the silicate is sufficiently insoluble, it can be
precipitated and separated. Once the sodium salt is separated from the acid sol, the
polysilicic acid can be alkalinized to grow colloidal particles and stabilize the
product, or can presumably be used for other processes of growing silica particles to
the desired size. Thus Teicher (82) neutralized sodium silicate with an acid to
produce an acidic sol containing a miscible organic liquid, such as an alcohol, which
precipitates the salt. An earlier process by White (83) precipitates the sodium sulfate
from a sol made from sodium silicate and sulfuric acid by adding acetone. Marcheguet and Gandon (84) instead use a material that will form an extremely insoluble sodium salt, such as the reaction product of sulfite ion and glyoxal, the sulfite
being the acid used for neturalizing the alkali in the silicate. By reacting sodium silicate with oxalic acid to obtain an acidic sol, sodium is precipitated as sodium
hydrogen oxalate, leaving about 0.13 N sodium ion in solution at 15C (85). The
remaining salt can then be removed by ion exchange (86).
.
:!
F
.;
.~
:;
.!
.
,
"
Electrodialysis
Colloidal silica has been made by various procedures involving electrodialysis

whereby sodium ions are removed from a solution of sodium silicate to produce sol.
These have been reviewed by Her (8), but in no case were stable products made.
Sanchez (87) and Her (88) patented processes of electrolyzing alkali metal silicate
solution to continuously remove alkali metal ions until a sol is obtained.
Electrodialysis may eventually replace ion exchange for making commercial sols
because alkali, oxygen, and hydrogen could be recovered and there is much less
waste water containing salts to be disposed of. In the Her process, there are three
compartments. In the anode compartment sulfuric acid solution is circulated around
a lead anode and in the cathode compartment where sodium hydroxide is generated,
the alkali is circulated around the steel cathode. These are located on opposite sides
of two parallel, closely spaced cation-exchange membranes between which the
process solution is rapidly circulated at 60-90C. The process solution is a silica sol
containing about 0.05 N Na 2S04 as a conducting or supporting electrolyte. A solution of sodium silicate is added to the entering process stream to raise the pH to 9.5.
The current density and rate of flow of the process stream are adjusted so as to
reduce the pH to no less than 8 as the stream leaves the cell. The liberated silica is
deposited on the silica particles which are thus grown to desired size. A.25% silica
sol of 15 nm particles can be prepared directly by this process. The electrolyte is
then removed by ion exchange, the pH adjusted for optimum sol stability, and the
sol concentrated to 30-50% silica.
'
There is essentially no consumption of acid except the small amount needed at the
start of each batch to neutralize a dilute solution of sodium silicate (0.5% Si0 2 ) to
pH 9 at 60-90C to form silica nuclei to start the process. A narrow uniform spac-
,,
~~
entrated Sols
conditions
ilk
with
a strongly
the sodium
~, it ,-can be
cid sol, the
:abilize the
particles to
an acid to
ohol, which
ium sulfate
tone. Marrely insoluthe sulfite
sodium silias sodium
: (85). The
Methods or Making Sols
333
ing between the membranes is required to minimize power cost and. avoid silica
deposition. Water is added to the anode compartment since it is slowly transported
to the cathode compartment, from which sodium hydroxide solution is constantly
withdrawn. Anolyte and catholyte are circulated from the corresponding electrode
compartments to separators for the removal of oxygen and hydrogen gases.
A process using a mercury cathode to remove sodium from sodium silicate is
patented by Vaquero (89). No supporting electrolyte is used so that as the alkali
becomes depleted the high electrical resistance of the sol increases the power
required. A three cell arrangement using ion-exchange membranes for making sols
by electrodialysis was discussed by Prajapati and Talpade (90). No supporting electrolyte was used. The final sol pH was 2-3.
A type of electrolytic process patented by Tripp (91) is used to dissolve an anode
of silicon metal in alcohol containing a metal salt catalyst such as copper sulfate to
produce a silica organosol.
In a study of transport of silica through membranes during electrodialysis, Boari
et at. (92) found that no transport or silica deposition occurred .unless the pH was
such that HSiO a- ions were present. This is consistent with the observation that it is
necessary to carry out electrodialysis at less than pH 9.5 (88) in order not to deposit
silica in the membrane.
Ion Exchange
:trodialysis
ro- ~ sol.
ucts lade.
etal silicate
aercial sols
much less
e are three
.ted around
generated,
posite sides
which the
a silica sol
'teo A solu-
: pH to 9.5.
:d so as to
.ed silica is
25% silica
ectrolyte is
ty, and the
eded at the
%: '2) to
for. .pac-
The pioneering work of Bird (4) by which sodium was removed from sodium silicate
by ion exchange, after which the sol was concentrated by evaporation at atmospheric
pressure, led to one of the earliest stable silica sols containing around 20% silica.
Further advances by Bechtold and Snyder (6) permitted control of particle size, and
other modifications, relating to permissible salt concentration and optimum alkali
content, by Alexander (9) and Atkins (10) led to the production of a series of
concentrated sols covering a wide range of particle sizes. Thus far, the silica sols
were made by passing relatively dilute sodium silicate solution through a bed of ionexchange resin to produce an acidic sol relatively free from sodium, which was then
stabilized and the particles grown as desired. An alternative approach was invented
by Wolter and lIer (93), in which th hydrogen ion-exchange resin and sodium silicate
were added to a weakly alkaline aqueous reaction medium in the pH range around
9, at elevated temperature. The silica particles grew continously under these conditions where they were stabilized against aggregation, so that relatively concentrated
sols in the range 10-15% silica were produced directly. An alternative procedure for
making a relatively concentrated 12% acidic sol of polysilicic acid has been patented
by Mindick and Reven (94), whereby the silicate solution is cooled and passed
through an ion exchanger so that the concentrated sol is formed at low temperature
to avoid gelling.
Many variations in the ion-exchange procedure have been proposed. Dirnberger
(95) showed that more concentrated sols can be made without' gelling by passing the
silicate solution upward through the ion-exchange resin bed, keeping the resin in
suspension. Other variations in the ion-exchange process have also been patented
(96).
-.
334
The last trace of electrolytes can be removed from silica sol produced by conventional means by heating and again passing it through a hydrogen ion resin to remove
alkali liberated from the particles. according to Mindick and Reven (65).
The use of a cation-exchange resin in ammonium form permits removal of sodium
from sodium silicate solution without exposing any part of the solution to low pH
where aggregation can occur. Wolter found that a 3.25 ratio silicate solution
containing up to 6% Si02 could be passed through a column of ammonium resin
without gelling. More silicate can be added to the alkaline effluent and the solution
again treated with ammonium resin (97).
For sols of very small particle size, Shannon (98) added sodium silicate to an
acidic suspension. of resin until the silica concentration reached 8 %. The sol was
removed and alkalinized with NaOH and NH a to have 1% Na and 3% NH a based
on the Si02
When making silicic acid by passing a solution of sodium silicate containing more
than 3-4% Si02 through a bed of hydrogen ion-exchange resin, silica gel is formed
within the pores of the conventional resin. This not only results in a loss of silica and
the need to clean the bed, but also causes the resin granules to disintegrate. According to Hoffman (99) a silicic acid effluent containing up to 6% Si02 can be made
without these. difficulties if one uses a macroreticular cation-exchange resin
(Amerlite IR.200) having pores about 10 nm in diameter, a porosity of 32%, and a
surface area by nitrogen adsorption of 42 m 2 g-I. The resin is treated with caustic
solution to remove small amounts of silica after each use and before regeneration.
Ion exchangers can be regenerated electrolytically according to Matejka (l00).
Instead of an ion-exchange resin, a cation-exchange membrane can be used to
remove sodium from a silicate solution into sulfuric acid (101). A hot sol of nuclei
particles is circulated rapidly through tubing of ion-exchange polymer which is
immersed in dilute sulfuric acid. Sodium silicate is added to the sol at a rate to
maintain the pH around 8-10 and the liberated silica is deposited on the sol particles, thus increasing their size. Some sulfate ions penetrate the membrane so that the
concentration of sodium sulfate in the sol slowly increases with time. The sol can be
purified and concentrated by ultrafiltration, but the sol concentration must be maintained so that the sodium in normality N does not exceed N = 0.26 - O.OOSC O.0012(T - 40), where C is grams of Si0 2 per 100 ml and T is the temperature in
degrees centigrade.
Peptizing Gels
As early as 1864, Thomas Graham reported that silica gel could be liquefied by a
trace of alkali, which he described as "peptization of the jelly." In 1922, Praetorius
and Wolf (102) produced silica sol from a gel by heating it in water at elevated
temperature and pressure. Neundlinger (103) prepared sols containing about 10%
silica by treating the gel first with ammonia and heating without evaporating water
until a sol was produced. Improved similar processes were invented by White (5) and
Trail (104).
., ....
':...,':f
7----
entrated Sols
Methodsof Making Sols
by conven1 to remove
A modification of the preparation of sol from gel is described by"Ahlberg and

Simpson (105), who formed the gel under alkaline conditions by incompletely neutralizing the alkali of a silicate such as sodium silicate with less than the equivalent
acid, then washing out the salts and heating the wet gel to peptize it. Much higher
conversion of gel to sol is claimed than when an acidic gelis first made. Characteristics of sols made by this process 'are not available, but probably sols 15-45 nm in
diameter were produced. A similar- process had been described by Legal (106).
Conversion of gel to sol in an autoclave to obtain a 30% ammonia-stabilized sol was
patented by Mertz (107). The effect of ultrasonic dispersion of silica gel was
examined by Bubyreva and Bindas (108).
1of sudium
tolow pH
te solution
mium resin
he solution
icate to' an
'he sol was
NH 3 based
335
Hydrolysis of Silicon Compounds
lining more
1 is formed
Ifsilica and
teo Accordto be made
ange resin
32%, and a
. . ith caustic
reration,
1
(100).
be ed to
)1 c. .uclei
:r which is
t a rate to
e sol partiso that the
: sol can be
st be main-
o.oose perature in
refied by a
Praetorius
at elevated
about 10%
iting water
lite (5) and
In 1944, Radczewski and Richter (67) reported that very pure silica sols prepared by
hydrolyzing silicon tetrachloride from which the acid has been removed to give a pH
of 6.8 formed spherical particles up to 200 nm in diameter, and that these appeared
to be spongelike under the electron microscope. More recently, Stober and Fink (68)
discovered that very uniform spherical silica particles of almost any desired size up
to 1 micron could be made by hydrolyzing a lower alkyl silicate in an alcohol
medium containing suitable amounts of water and ammonia. 'Subsequently,
Flachsbart and Stober (109, 110) were able to incorporate certain radioactive tracers
without affecting the growth of the silica particles during their formation, but it was
not certain whether the metals were homogeneously incorporated throughout the
spheres. Particle sizes from 50 to 900 nm in diameter were produced. It is likely that
the large spherical particles are actually spherical aggregates of much smaller particles, 10 nm or less in size, as described by Radczewski.
According to Brinsmead and Brown (111) a "silicic acid sol" containing 43% SiO z
was made by refluxing a mixture of ethyl silicate and isopropyl alcohol to which a
dilute aqueous solution of acid was slowly added to furnish a stoichiometric amount
of water for hydrolysis. There was no evidence that hydrolysis was complete, as
would be shown by complete miscibility with water, nor any indication that discrete
silica particles had been formed.
Sodium silicate can be hydrolyzed if sufficiently diluted. Thus a dilute solution of
high ratio sodium silicate can be hydrolyzed in an autoclave to form colloidal particles which coagulate to a precipitate if the sodium ion concentration is sufficiently
high. Schniirch and Koster (112) report that when a solution of sodium silicate with
a SiOz : NajO weight ratio of 3.89: I is diluted to 20 g 1-1 of SiO z and heated 1.5 hr
at 150C, 38% of the silica is precipitated as fine silica.
Dissolution of Elemental Silicon
If pulverized silicon metal is first treated to remove the oxide film with hydrofluoric
acid, it reacts rapidly with water in an alkaline medium, particularly ammonia, to
336
form colloidal silica which is stabilized by the alkali. This type of process has been
patented by Balthis (69); the process is accelerated by carrying out the reaction while
grinding the silicon (113).
Sols made from elemental silicon range from 8 to 35 nm in diameter. and under
some conditions up to 150 nm. The process and the nature of the product has been
discussed under the heading of "porous particles."
To make sols containing up to 50% Si0 2 by dissolving silicon. Bobb (114) claims
the use of an aqueous solution of an inorganic base (NaOH. KOH) to catalyze the
dissolution at 50-100C and stabilize the resulting sol. It is remarkable" that sols
made at 90-95C were said to be very viscous but when made at 98-IOOC were of
normal low viscosity. Particle sizes were between 15 and 45 nm. Also the sols were
unusual in that they did not form hard gels when acidified. but only soft coacervates,
These differences are unexplained. An alcosol is obtained when silicon is used an an
anode and dissolved by electrolysis in an alcohol-water mixture. Acid or a metal salt
is added to provide conductivity according to Tripp (91) or Chilton (115).
....
..
Dispersion of Pyrogenic Silica

,.-;
~
"'
Silica vaporizes only at very high temperature. around 2000C, but if a reducing
agent is present so as to form silicon monoxide, SiO. the sublimation temperature is
1700C. As the monoxide evaporates in an oxidizing atmosphere. the dioxide is
condensed in an extremely finely divided form. Ethyl silicate can be oxidized and the
resulting SiOz vapor condensed. The most common process involves the combustion
of silicon tetrachloride with natural gas, form ing hydrogen chloride and silicon
dioxide vapor, which condenses to a very voluminous powder. By controlling combustion conditions, presumably in a manner similar to that employed in making
carbon black. products of different ultimate particle sizes and degrees of coalescence
of the particles can be made. Another process involves vaporizing silica in an electric
arc and condensing the resulting vapors. Powders of this type are considered here
only because colloidal dispersions can be made from some of them. The processes
involved and the silica powders are discussed in Chapter 5.
Dispersion of silica to a sol of separate, discrete, ultimate particles is difficult
because the particles are coalesced to varying degrees. Also in many cases, the surface is partly anhydrous with only a few hydrophilic silanol groups. For these
reasons the properties of sols of this type are generally different from those made in
aqueous solution. They do not form strong gels and are of little use as an inorganic
binder.
The patent literature suggests that intense mechanical shearing forces, both on the
dry voluminous powder and on the subsequent suspension in water, are required to
attain reasonable dispersion in water or polar organic liquids. In water, wetting
agents are used to promote wetting of the hydrophilic siloxane surface areas and
alkali to promote surface hydration and dispersion (116, 117).'
A more stable dispersion is obtained by adding to the silicon tetrachloride a
certain amount of titanium or aluminum chloride to produce silica containing a
'I
I'
1
~
~
\.
.-~
~
~
,-!;
purification. Concentration, Prcscrvati~s_
centra ted Sols

.;,
ess has been

-acuon while
.1-
.='
r, anu under
uct has been
(114) claims
catalyze the
ole that; sols
OC were of
he sols were
coacervates.
IS used an an
a metal salt
.-
r a reducing
:nperature is
e dioxide is
.ized and the
co .. ustion
an. silicon
rolling coml~ in making
coalescence
n an electric
sidered here
he processes
s is difficult
ises, the surs, For these
lose made in
an inorganic
:..,.---
337
small amount of the metal oxide. Very stable concentrated sols containing 40-60%
solids are obtained (118). A silica produced by flame hydrolysis by Degussa, for
example. containing 1.3% aluminum oxide based on the silica (Aerosile MOX). is
sold particularly for making concentrated aqueous dispersions with ultimate particles in the range of 20-40 nm diameter. along with many smaller ones (119).
Flame-hydrolyzed silica with" specific surface areas in the range of 200-400 m2
g-I, under the name of Cab-O-SiI~, is dispersible in water at pH 9 with ammonia;
for example, to give sols up to 30% by weight of silica. provided the material is
passed through a homogenizer to break apart the three-dimensional network of ultimate particles. The resulting particles still consist mainly of chainlike aggregates
which increase the viscosity (120).
In general, the "fume" or "name hydrolysis" process does not yield silica that is
dispersible in water to give sols of discrete particles with the low viscosity at high
concentration that is characteristic of sols made by aqueous polymerization
processes. Nevertheless, with enough processing, pyrogenic silicas of ultimate
particle size of 10-25 nm can be disaggregated and dispersed to aquasols containing
up to 40% silica with suitable mechanical treatment and dispersing agents.
Extremely finely divided silica, composed of particles only 25-50 A in size and
having a specific surface area as high as 1000 mS g-1 has been made, according to
Spencer, Smith, and Cosman (121), by treating moist carbon black with
dimethyldichlorosilane and then burning away the organic materialin air at 500C"
The resulting silica, amounting to 4% of the original weight of the carbon black, was
an opalescent powder in the form of small spheres, about I mm in diameter, of
about the same size as the carbon black pellets. The specific surface area of the silica
was 1094 mS g-I, indicating an ultimate particle size of 2.5 nm. The material dispersed easily in water, with the particles forming chains up to 20 microns long, suggesting that they were partially hydrophobic.
Colloid milling of pyrogenic silica in water in the presence of boric acid or alkali
borate is disclosed by Clapsdale and Syracuse (122). A 30% sol can be prepared.
Some additional patents on making sols from pyrogenic silica mainly involve the use
of alkali stabilization with sodium silicate, sodium hydroxide, hydrazine,
hydroxylamine, or mixtures with pyrogenic metal oxides (123-125).
PURIFICATION, CONCENTRATION, PRESERVATIVES

Sols made by some processes contain salts or other materials that must be reduced
or removed before the sol is finally concentrated.
. both on the
: required to
iter, wetting
:e areas and
Ion Exchange
rachloride a
Special purification procedures to remove salts from the 'final concentrated sols
usually involve treatment with ion-exchange resins to remove soluble salts and then
stabilization with a minimum of base, including ammonia, to obtain a sol of
con: "ling a
338
maximum purity, according to Rule (7). The method has become so commonplace
as to require no further discussion. Sodium is difficult to remove after particles have
been formed; Schaefer and Gamage use an alkanolamine as the base during particle
growth (126a).
Dialysis And Electrodialysis
.~
'j
.41
Dialysis is the oldest purification procedure for removing soluble im purities from
sols. Once dilute silica sol had been by reacting acid and silicate, or by hydrolyzing a
material such as silicon tetrachloride, it was early recognized that purification
required removal of the electrolyte. Graham (126b), one of the earliest investigators
of silica sols, in 1861 used dialysis to remove the electrolytes from the silica and thus
prepared relatively pure colloidal silica. Since dialysis is relatively slow, it is not
much used on an industrial scale. A more rapid process, not requiring tubing or flat
membranes, has been proposed which involves passing the sol through a column or
bed filled with a swollen polymer gel with such a fine pore structure that soluble
salts, but not colloidal particles, can penetrate. The gel may be of regenerated cellulose or gelatin cross-linked with formaldehyde. The bed is regenerated by washing
out the salt (127).
More rapid purification can be effected by electrodialysis where a direct current
transports ions to the membranes. Improvements are constantly being made in
equipment (128), especially for desalting seawater. However, for purifying silica sols
the process has not replaced the use of ion-exchange columns, in which the investment is lower.
Washing Procedures
Methods that concentrate the sol particles but not the soluble components can be
used to purify the sol by rediluting the concentrated sol with pure water and repeating the process.
Sedimentation by gravity is generally too slow, but centrifuging permits
reasonably rapid concentration of silica particles larger than about 30-50 nm.
Alternatively, silica can be flocculated with divalent metal ions and the precipitate
washed free of soluble salts, then peptized by removing the flocculating ion.
Alexander and lIer (80) used ions such as Mg 2+ , Ca 2 + , and BaH and removed them
by ion exchange or, in the case of BaH, precipitation as the insoluble sulfate.
Concentration by ultrafiltration or electrodecanting can also be used as part of the
washing procedure.
Concentration
A variety of methods for concentrating sols are available but evaporation of water
has remained the most common industrial procedure. However, with rising cost of
power and steam, other known methods will no doubt be considered.
,i
"
.entrated Sols
purification. Concentration. Preservatives _
mmonplace
irticles have
-in.-tic1e
Evaporation of Water
rrities from
rdrolyzing a
purification
nvestigators
ica and thus
w, it is not
.bing or flat
1 column or
that soluble
:rated celluby washing
rect current
19 made in
g silica sols
I th- invest-
339
For stable sols such as colloidal silica, forced circulation evaporators have been
generally used. Special precautions must be taken not to permit the sol to become
too concentrated or to reach dryness at any point on the equipment walls and especially on the heat exchange surfaces. If this occurs, a layer of hard adherent silica is
built up. The problem becomes acute as the silica approaches the final high
concentration with increasing sol viscosity.
Evaporation has the advantage that high temperature often plays a significant role
in consolidating the structure of somwhat porous silica particles that were made at
lower temperature, and also in contributing to further growth in particle size.
Centrifugation
This is generally used for removing debris and clarifying silica sols but not for
concentrating them. Unless the particle size is greater than about 30 nrn, very high
speeds are required. Hence the method is not practiced for most commercial sols.
Ultrafiltration
Remarkable advances have been made in the last 20 years irr 'equipment and
membranes used in the process of ultrafiltration as shown in Figure 4.3. Basically,
the process removes water and small ions and solutes from a sol or colloidal suspension, which is thus concentrated without forming a filter cake or deposit on the
membrane filter..
FILTER'
ents can be
and repeatng
permits
30-50 nm.
. precipitate
ilating ion.
noved them
ate.
I
; part of the
ULTRAFILTER
STIR
.-. - -!-Jl.
.-
..-. c..~ ~ - ..
~ !'
- .e..
- -
- - ... . _
.+ _
- __
_e
:fo
. . . . . t . . ! : 4t:.:'_+.--- CONe .
_+.
on of water
sin' ost of
;!.-...
-.......
. . .~,
. - - - - -- SOL
- -.- +
.+.
~
Figure 4.3. Filter retains large particles

as a /ilter cake but passes colloidal particles (black) and salts. Ultrafilter retains
colloidal particles as a concentrated sol
but passes soluble salts.
..
340
~-_.
This technique is becoming increasingly important for purifying and concentrating

colloids with minimum consumption of energy. Thus a process described by lIer
(129) makes it possible to make colloidal silica by partly neutralizing a hot solution
of sodium silicate with acid at such dilution that the resulting particles are not coag.
ulated by the sodium salt. The sol (2-3% Si0 2) is cooled to 50C and concentrated
by ultrafiltration while salt is simultaneously washed out by adding water. To avoid
aggregation or formation of microgel, the water must be added at such a rate as to
keep the salt concentration below a certain normality N where
N ... 0.26 - 0.005C - 0.002 (T - 40)
j.
,
~;
and C is the concentration of silica in grams per 100 ml. The temperature, roc, is
gradually raised to 75C while the salt normality is reduced to below 0.15 Nand Cis
increased to 10. Ultrafiltration and washing are continued until a stable 30-40% sol is
obtained. Sols of particles smaller than 10 nm require that during the process, the salt
level be kept somewhat lower than with larger particles.
Reducing the pH of a silica sol to 2-4 before concentrating by ultrafiltering was
proposed by Chilton (130). However, such sols are unstable at high concentration
and especially at high temperature where ultrafiltration is much more rapid.
Improved membranes have been the key to recent advances in ultrafiltration. The
finest filter papers have pore diameters of as small as 1000 nm (l micron) whereas
ultrafilter membranes can be made with pore diameters from 1000 nm to as small as
2-3 nm. For many years "cellophane" or freshly formed films from collodion
(nitrocellulose) were used, but now a number of manufacturers supply strong, flexible, and durable membranes of remarkably uniform pore size yet with high porosity,
permitting rapid flow of water. Porous glass membranes have also been developed as
well as porous carbon. Porous ceramic with a microporous coating provides an
ultrafilter highly resistant to high temperature and chemical attack.
The development of membrane ultrafiltration for the chemical process industry
was described by Michaels (131). who reviewed the basic principles, equipment, and
types of applications. The useful ranges of available separation processes for
molecules and particles of different sizes were com pared by Porter and Michaels
(132). Available membranes were described with pores of uniform sizes of selected
diameters over the range 1-20 nm (10-200 A). A bibliography of applications has
been compiled (133). Equipment and information are available from a number of
manufacturers, representing a wide range of apparatus design and membrane
construction.
A better understanding of the basic principles of ultrafiltration has permitted the
development of much more efficient equipment and corresponding commerical
applications. A detailed consideration of the theory of ultrafiltration was published
by Porter (134), who dealt specifically with the problem of "concentration polarization." As shown in Figure 4.4, the movement of particles toward the membrane
results in the formation of a concentrated sol layer of high viscosity. This can reduce
the flux or rate of filtration to a small fraction of that of the liquid medium in the
absence of colloid. The resistance to flow is not due to plugging of pores, or even to
an actual solid layer (gel) of close-packed colloidal particles. In has been observed
entrated Sols
purification, Concentration, Preservatives
'ncentrating
bed by lIer
lot
rtion
e not coagoncentrated
:r. To avoid
a rate as to
ire, roc, is
; N and Cis
)-40% sol is
.ess, the salt
iltering was
ncentration
id.
ration. The
m) whereas
as small as
1 collodion
.ro: flexi~hl- _.osity,
eveloped as
irovides an
:ss industry
pment, and
ocesses for
d Michaels
of selected
cations has
number of
membrane
rmitted the
comrnerical
s published
in polarizamembrane
can reduce
fiurn in the
. or en to
m,
erved
341
MICROGEL
00000 0 0
0
o
0000
FLOWO~.o~O 00
0 CJRCULATION~
00
00 0 0
do
o 0..-<6
~o 0 0t9 OOo~
O&OOg6gg~ r?~ g&
----------------T---~(ME~BRANEl ! FLUX J (SLO~)!

H20
Ultrafiltration-concentration polarization and microgel. As dilute sol circulates

over membrane, sol is concentrated at membrane surface, and particles diffuse back to dilute
region. Microgel does not diffuse, remains at membrane.
Figure 4.4.
by Iler that the resistance is a direct function of the high viscosity of the
concentrated sol layer. When water above is flushed through the system, the particles diffuse away from the boundary layer and water passes at the original flux rate.
During operation the concentration of colloid becomes "polarized" in the sense that
it becomes more concentrated near the surface of the ultrafilter and less
concentrated farther away from it. This polarization is completely reversible.
To maintain a high flux the thickness and concentration of the colloid layer at the
filter surface must be minimized by creating high shearing forces in the liquid near
the surface. This is done by increasing the linear rate of flow of sol past the surface
and especially by turbulent flow, On small laboratory ultra filters with a horizontal
membrane, high turbulence is maintained by a mechanical stirrer located very close
to the membrane. Under otherwise constant conditions, the flux rate decreases
rapidly with increasing sol concentration. In general, increasing the pressure on an
ultrafilter is less important than minimizing concentration polarization.
Flux increases rapidly with increasing temperature. Hence, where possible,
process solutions should be ultra filtered at maximum feasible temperature.
LIMITATION ON SALT REMOVAL BY ULTRAFILTRATION. Ultrafiltration with
continued addition of water is an efficient way to remove salts down to a concentration of 0.03 N even from a concentrated silica sol. At these low levels there is a
tendency for the salt to remain associated with the charged surface of the colloidal
particles.. This may be a hitherto unrecognized phenomenon. at least in the
chemistry of colloidal silica, but it must have been noted during removal of salt from
other ionic colloids. It is suggested that in dilute sols where the charged particles are
far apart and there is a high concentration of sodium counterions around the particles, there is a tendency for sulfate ions to be concentrated as a secondary layer outside of the layer of sodium ions. As shown in Figure 4.5, around each silica particle
-:.---.
342
there is a boundary layer containing a preponderance of Na + ions. Immediately outside of this there must be a secondary layer that contains a greater number of negatively charged sulfate ions than of positive sodium ions. Thus there tends to be a
higher concentration of sulfate ions in the neighborhood of the particles than in the
intervening water, so that there is less sulfate in the filtrate.
The effect becomes marked in sols of small particles containing less than 20%
silica at pH 9. By measuring the concentrations of SO.2- in the ultrafiltrate and in the
sol the following typical observations were made.
To 6.5 liters of 9% Si0 2 sol of 6 nm particles at pH 9 containing 0.04 N sodium
sulfate, 10 liters of wash, water was added while removing filtrate to keep the sol at
constant volume. Calculations show that this should have reduced the salt content to
0.009 N, but actually it was 0.022 N. Simultaneous analyses verified that the
concentration of sulfate in the filtrate was less than in the sol during the operation.
In the final sol there were present 0.15 sulfate ions and 0.8 counter sodium ions per
square nanometer of silica surface. It is of course possible to further reduce the
sulfate content by continued washing. but this process soon becomes very inefficient.
EFFECT OF MICROGEL IN SILICA SOL. The most critical factor in using ultrafiltration to concentrate silica sols is the presence of microgel or silica aggregates which
are of the order of half a micron or more in size. Aggregates this large diffuse so
slowly in comparison with single particles that they are carried by the flux to the
membrane surface where they are deposited irreversibly as gel and reduce the flow of
water and ions. In a series of ultrafiltration tests on a 4% Si0 2 sol the flux was
Nat
0;
@
No..
N"
0
0.
0- 2
No"
+
Qa..
No
No+
~
+ No ..NO+~
No
+
N + No No t No
N +
Not
No
0
+ a 50N +
...- - - No
~
04
0 ".....
"No+
+
/
'"..
No
Not ;'
"
+
t
+@/\NONO+NO
No SO; No+ I
"No' + Q
+
f
Si02
r No ~ +
No
No :
I No+
No
T
0;
Figure 4.5. Salt retention by colloidal particles. Around a negatively charged silica particle
there is a layer of counter sodium cations. Outside of this there is a layer in which sulfate
anions are more concentrated than in bulk solution.
.,
...
_1
:entrated Sols
purification, Concentration, Preservatives
ediately out-
343
ber of negandr
be a
, thai, an the
.s than 20%
te and in the
Figure 4.6. Apparatus lor electrodeCONC.
h
SOL cantation:
ano d
e 'm dil
I ute aCIid; tree
4 N sodium
.p the sol at
t content to
ed that the
e operation.
rm ions per
reduce the
inefficient.
; ultrafiltragates which
e diffuse so
flux to the
the flow of
ie flux was
\
porous membranes or ultrafilter type barriers open at top and bottom; cathode in
dilute alkali; cation permeable. anion
impermeable membranes are located next
to each electrode..
reduced by 50% when only 0.5% of the silica was present as microgel and by 80%
when 1.5% was present. Thus as little as 200 ppm of silica in suspension caused an
immediate, serious reduction in flux.
Electrodecantation
When a current is passed through a low salt, dilute silica sol, electrophoresis occurs
and the negative particles move toward the anode. By setting up a series of
membrane barriers in the sol between ion-exchange membranes to isolate the sol
from electrolyte-filled electrode compartments, it is possible to concentrate the sol
as shown, in principle, in Figure 4.6 (135). The particles concentrate against the
sides of the membranes ra~ing the cathode, forming a dense liquid that sinks to the
bottom and is drawn off. For maximum efficiency the sol should be low in soluble
salts so that most of the current is carried by the particles and their eounterions.
Preservatives
.
ilica particle
Ihic~ -'Ilfate
Surprisingly, microorganisms often grow in concentrated silica sols; they may

appear as floating viscous masses, green, yellow, red, or brown particles in suspension, or whitish' fibrous aggregates. The presence of bacteria is often evidenced by
the smell of hydrogen sulfide and a dark color owing to precipitation of traces of
heavy metals. Algae can appear as green fibrous masses or brownish floes.
Preservatives are often added such as formaldehyde (t 36) or a polyhydric alcohol
along with pentachlorophenate (137). The polyhydric alcohol, such 'as ethylene
glycol, stabilizes the sol toward freezing. Other patented preservatives are 3,5dimethyltetrahydro-L'I.Sjz H-thiadiazine-2-thione along with f'ormaldehyde (138) or
25-200 ppm of sodium chlorite, NaCI0 2 (139).
For some unknown reason, sols stabilized with ammonia, even though at the same
pH as those stabilized with NaOH, do not support the growth of microorganisms.
344
CHARACfERIZING SOLS
..
It was only after methods were developed for. following the polymerization of silica
measuring the size of the particles. and defining their degree of aggregation. that
enough was learned about the behavior of colloidal silica to control the particle size
and predict behavior during processing. An understanding of the surface chemistry
of silica and the nature of the interaction between silica and water over a wide pH
range was necessary to achieve stabilization and particle growth without aggregation
and subsequent particle growth.
The most important characteristics of a silica sol are as follows:
Chemical analysis. Silica. stabilizing base, carbon including carbon dioxide.

organic carbon. soluble salts of alkali metals. total solids and non-siliceous ash,
metals including aluminum and iron.
Particle characteristics. Size and size distribution, porosity, degree of aggregation, specific surface area, rate of dissolution.
Physical characteristics. pH, density, viscosity, turbidity, refractive index, light
scattering, sedimentation rate by ultracentrifugation.
Chemical Analysis
I
,i
]
"
Silica content can be estimated approximately from density or refractive index or

determined by conventional analytical procedures (see Chapter 1). The amount of
stabilizing base is determined by titrations to a pH of about 3.5, or to 2.0 and correcting for, the 10- 2 N acid that is present. The old procedure for "non-siliceous
ash," which involved drying and heating the sample in a platinum dish, weighing the
residues, fuming off the silica with HF + H 2S0 4 , and again weighing, is still a useful
technique. This leaves a residue in which other elements can be easily determined by
atomic absorption. The weight ioss is silica.
Aluminum is of special interest because its presence indicates that the surface may
be modified with aluminosilicate groups which affect colloid behavior. Aluminum on
the silica surface can be determined by extracting the dried silica with hydrogen
chloride and analyzing for aluminum. The carbonate and organic matter are
important in that carbonate acts as an added electrolyte and may require a correction of the titration of base, and organic matter (usually due to low polymer
extracted from ion-exchange resin) can affect product behavior in some applications.
Analysis for total nitrogen and carbon reveals the possible presence of organic bases.
Particle characteristics are in some cases measured directly and in others inferred
from physical characteristics of the sol such as viscosity, turbidity, light scattering,
and sedimentation rate.
M easuring pH
The pH of a silica sol is one of its most important characteristics. Sol behavior may
vary greatly with only minor change in pH. For example, increasing the pH of only
'.,
'.
centrated Sols
Characterizing Sols
ior silica,
:gatlvll, that
particle size
ce chemistry
r a wide pH
aggregation
half a unit will double the rate of gelling at pH 4. or convert a sol to a solution of
sodium silicate at pH 10.5.
Measurements are ordinarily made with conventional alkali-resistant glass electrodes, although those specified for solutions high in sodium should be used when
measuring the pH in the presence of salt as in titrating specific surface area.
Bolt (140) pointed out that for greatest precision. pH measurements, particularly
in concentrated sols, require the use of a "gel bridge" to overcome the "sol
concentration effect" on the reference electrode.
345
Electrolyte Concentration
Jon dioxide,
.liceous ash,
of aggregaindex, light
A reasonably accurate indication of the salt content of a sol, without resorting to
chemical analysis, is to measure the electrical conductivity at about pH 4.5. At this

pH, the charge on the silica particles is negligible and conductivity is due chiefly to
the salt present. When an alkali-stabilized sol is involved, it is titrated with standard
acid to pH 4.5 and the resultant sodium salt subtracted from the total salt
concentration calculated from the conductivity. Alexander (9) gives the empirical
equation
N
.ve index or
: ar- -unt of
2.0 j coron-siliceous
veighing the
still a useful
termined by
surface may
uminum on
h hydrogen
matter are
re a correcIW polymer
pplications.
~anic bases.
ers inferred
: scattering,
hav;"r may
pf
only
8(L - 4.3
x 10- 5)
where L is the specific conductance of the sol diluted to 4% SiO:l at 25C and N is
the normality of equivalent Na2S0.
Particle Characteristics
Particle Size
If the silica content of the sol is more than 10-15 % the order of magnitude of the
particle size can be judged visually by the turbidity. If the particles are smaller than
about 7 nm in diameter the sol is almost as clear as water: from 10 to 30 nm there is

a characteristic opalescence or translucency when seen in bulk: above about 50 nm,
the appearance is white and milky. Particles larger than 100 nm settle on standing,
leaving a transparent upper layer after a few weeks or days.
A review of methods available for fine-particle characterization has been
presented by Kuhn (141).
The electron microscope provides a direct method for
determining dimensions of colloidal particles (Figure 4.7). With improved equipment, individual particles as small as only 1-2 nm can be discerned, but measuring
the diameter of particles smaller than 5 nm is diflicult. Alexander and Her (142) first
demonstrated that the particle size of colloidal silica measured by the electron
microscope correlated well with particle size determined by light scattering in solution, and also with the size calculated from the specific surface area of the dried
silica powder.
ELECTRON MICROSCOPY.
'7.--
346
.~
Figure 4.7.
Particles of colloidal silica about 20 nm in diameter.
i ,.-
!:,.
L
Ii
I;
,f
/,,r
'1
I~
Practically no sols are monodispersed, since the particles usually vary by at least a
few millimicrons in diameter. There are several ways of expressing 'the average
particle size. For example, the number-average particle diameter. d; is simply the
average diameter of a large number of particles. On the other hand, the size can be
expressed in terms of a particle which has the same weight as the average weight of
the particles. that is, the weight-average diameter. dlJ/' Likewise. the diameter may
be expressed as the diameter, d., of a particle which has a surface area equal to that
of the average surface area.of the particles.
The method of measuring and calculating d; and d. has been outlined in a patent
issued to Balthis (69). following the method described by Watson (143).
To distinguish discrete particles from permanent aggregates requires that the sol
be diluted so much that when the suspension dries. aggregation will not occur on the
grid. Greene et al. (144) describe the use of a positively charged layer of cytochrome
C on a carbon-coated grid" to adsorb negative particles.
For silica. a fresh 0.1 % solution of bovine albumin at pH 3 can be used. allowing
a thin film to dry on the carbon-coated screen. A drop of sample containing 0.1 %
Si0 2 is applied and immediately rinsed off. leaving a representative population of
adsorbed particles and aggregates, after which the screen is dried in air for examination.
Pertoft et a1. (145) increase the contrast of silica particles by applying a I % solution of uranium acetate at pH 4.6 and rinsing off the excess.
The specilic surface area, Se. expressed as square meters per gram. may be calculated from d s in millimicrons. taking the density of silica as 2.2 g em -3. which is the
density of amorphous. anhydrous, nonporous silica. as follows: '
Ad
I:
it
I
1
iI
103
density x d.
2720
.,. -:----Characterizing Sols
centra ted Sols
by at least a
the average
s simply the
: size can be
ge ight of
:an. st may
equal to that
I in a patent
that the sol

occur on the
.cytochrome
ed, allowing
aining 0.1 %
opulation of
r for exarni; a 1% soluay be calcuwhich is the
347
The specific surface area calculated from ds , assuming that the particles are dense, is
indicated by the symbol Ad'
An excellent discussion of the definition of particle size has been given by Bailey,
Beattie, and Booth (146), and a more recent and broader discussion of particle size
and shape is given by Underwood (147).
The particle size distribution itt a commerical colloidal silica (Ludox @) has been
determined by electron microscopy. by Dezelic et al, (148). A weight-average
diameter, dw , determined from the particle size distribution curve by electron
microscopy, was 20.0 nrn, for example, which agreed within the 5% limit of experimental error with the particle diameters calculated from light-scattering data.
A uniformity index, defined as the quotient of the number-average particle
diameter divided by the weight-average article diameter, may be determined by
methods described by Bailey, Beattie, and Booth (146).
LIGHT SCATTERING. A series of sols produced by Bechtold and Snyder (6) were
characterized by Alexander and lIer (142) by light scattering and the results correlated with particle size determined from electron micrographs. If it is assumed that
the silica consists of uniform spheres of density 2.2 g cm -3 and number-average
diameter, d", nm, then the theoretical molecular weight, M, in millions, is given by
the relation
log d" ... 0.333 log M + 1.054
However, a plot of actual log dw versus log M was best represented by the equation
., log d w
...
0.27 log M
1.15
The disagreement maybe due to differences in the distribution of particle sizes since
among these samples the ratio of the weight-average particle diameter to the
number-average diameter varied from 1.13 to 1.35.
Ludoxw colloidal silica, supplied as a sol of 15 nm particles with a molecular
weight of about 2.5 x 10', was used as a standard for the calibration of light-scattering photometers by Maron and Lou (149), who proposed an improved technique for
the calibration procedure. At about the same time, Trap and Hermans (150) used
Ludox" for calibrating scattering apparatus, having measured the absolute turbidity
by transmission measurements. Later Goring et al. (151) reported some difficulty
with reproducibility using different sam pies of colloidal silicas as standards, and also
found that erratic results were obtained when samples were diluted with distilled
water instead of a dilute salt solution. The latter phenomenon was further investigated by Dezelic and Kratohvil (152), who had noted the same phenomenon (148,
153) in an investigation of the change in the second virial coefficient with electrolyte
concentration. They verified that the light-scattering results were much more reproducible in the presence of at least 0.025 M NaCI solution. Oreenberg, Chang, and
larnutowski (154) recommended that light-scattering measurements be made in salt
solution with an ionic strength of 0.1 in order to suppress the influence of surface
charges.
-:... ....
348
Jennings and Jerrard (155) made a detailed comparison of the particle sizes of two
commercial silica sols by light-scattering electron microscopy and ultracentriju,
gation.
The effect of varying the refractive index of the liquid phase in colloidal silica on
light scattering has been studied by Bonnelycke and Dandliker (156), who found that
colloidal silica particles themselves do not absorb light by changing the refractive
index of the liquid phase, and showed that excess turbidity and scattering go to zero
concomitantly.
Claesson and Ohman (157) described an automatic recording 'light-scattering
instrument which was standardized with colloidal silica.
TURBIDITY, ABSORBANCE. As light is scattered, the transmitted light is diminished
as it passes through a sol. Transmittance and absorbance are related by the equation
100
A = log., -
,
~
where A is absorbance and T is percent transm ittance, defined as T = 10010 / / ,

where 10 is intensity of the incident light and I of the emerging light. As shown in
Figure 4.8a at low silica concentrations absorbance is proportional to silica
concentration and increases with particle size.
Absorbance using 400 nm wavelength light as in the figure does not provide a very
useful means of determining approximate particle size for particles less than 20 nrn
in diameter. With shorter wavelengths better sensitivity is attained. Absorbanc. \
provides a convenient way to observe changes in product quality including variations'
in particle size and presence of aggregates, larger particles, or debris.
The linear relation between absorbance and silica concentration persists only at
silica concentrations less than 5-10%. At higher concentrations sols reach a
1.0
E
c
PARTICLE DIAMETER, nm
0
0
62
LLI
CD
a: 0.5
0
30
fI)
CD
16
0
0
0.5
1.0
1.5
% Si02
(0)
Figure 4.8a.
sizes,
Absorbance of 400 nm light by silica sols of different concentrations and partie'

I.
.;
zentrated Sols
sizes of two
Itracentrifu-
~'.
-ve-
2.0
~-
dal s.oca on
J found that
re refractive
g go to zero
.....
E
c:
0
0
1.5
o
:'",
<l
IX)
It-scattering
349
Characterizing Sols
1.0
a::
s
IX)
<l
; diminished
he equation
0.5
10
20
30
% sio,
40
(bJ
= 100/0 / 1,
\.s shown in
rl to silica
rvide a very
than 20 nm
0\1: "lance
g vaations
ists only at
Is reach a
; an" .-article
Figure 4.8b. Absorbance of silica sol at 400 nm

wavelength showing a 'maximum is reached in
concentrated sols.
maximum turbidity and then become clearer at still higher concentrations, as shown
in Figure 4.8b. At first sight it is surprising to observe an almost clear concentrated
sol become more turbid as it is diluted. Absorbance is related to light scattering, and
scattering is a function of the average distance between silica-water interfaces. As long as particles are separated by several times their diameter, the critical distance is
the particle diameter. At a concentration of about 7 vol. % (about 15% by weight)
the distance between two particle surfaces is equal to one particle diameter. Hence at
higher concentrations the interface-to-interface distance becomes smaller than the
diameter, and scattering and absorbance decline. In a very concentrated sol the light,
in effect, passes through a. mass of silica interrupted by small regions of water which
cause the scattering and absorption.
Low Al'GLE X-RAY SCATTERING. Brill, Weyl, and Schmidt demonstrated the use
of low angle X-ray scattering for measuring the particle size distribution in relatively
dilute sols (158). Samples of colloidal silica of nominal particle size about 15 and 10
nm (Ludoxw HS and Ludoxs SM) were diluted to about 1% silica. Particle
diameters were measured at magnifications up to 32,000 by the electron microscope,
with an uncertainty of only about 1 nm. It was concluded that the X-ray and the
electron microscope determinations of the distributions of particle diameters in the
silica sam pIes agreed within ex perimental uncertainty. Sim ilar investigation of
Ludoxv HS is reported by Ja'nosi, Kratky, and Sekora (159), who examined solutions as dilute as 0.5% and found a particle diameter of around 18 nm.
By this technique both the particle diameter and the average distances of separation of the randomly spaced particles can be determined. Using particles ranging
from 10 to 50,000 nm in diameter, Dragsdore (160) showed that for smaller particles
a diffraction theory was applicable, whereas with large ones, the geometric optics of
a refraction and reflection theory was more useful.
This technique was used to determine particle size of silica sols, which were also
determined by electron microscopy and nitrogen adsorption. Lederer (73) reported
350
that there was almost complete agreement when the particle size distributioj, Was
taken into account. However, the conclusion that the particles contained an "inne,.
hydration" of 15-26% by weight of water based on Si02 surely must be in error I.
the particles were prepared, as stated, by the process by which Ludoxs colloidal
silica is made (161).
ULTRACENTRIFUGATION. By ultracentrifuging colloidal silica (Ludoxs), Hermans
and Ryke (162) report that a particle size distribution was observed in agreement
with data obtained from electron micrographs by Alexander and Her (142). Jennings
and Jerrard (155) measured the particle size of Ludoxf HS as well as Sytonr 2X
with an analytical ultracentrifuge, and also by means of the electron microscope and
by light scattering, and concluded either sol could be used as a calibration medium:
Particle Diameter (nm)
Sol
Ultracentrifuge
Electron Microscope
Light Scattering
17.4
14.2
19.9
14.5
19.5
14.2
Ludoxs HS
Syton@2X
Differences in the case of Ludox@ were attributed to a wider distribution of particle

sizes. The particle size distribution in sols Ludoxs HS and SM was examined by
Pertoft et al. (145) and some particles were found with extreme sizes of 8-25 and
5-15 nm, respectively.
SEPARATION OF PARTICLES BY SIZE. The classical method of separation is by centrifugation. Very high gravitational force is needed, corresponding to rotor speeds
greater than 10,000 rpm for particles smaller than about 30 nm diameter. Various
methods requiring less expensive equipment have been investigated. Some progress
has been made using chromatographic equipment, which is also expensive but more
generally available.
Burns and Chilton (163) patented a method based on gel-permeation chromatography, A dextran gel with 40-120 micron pores was used as column packing.
A silica averaging 6 million molecular weight (average 20 nm particles) was
separated into a range of molecular weight. Beads of porous glass were used as
column packing for exclusion chromotography of colloids by Coll, Fague, and
Robillard (164). In the case of silica under the conditions used, the double layer at
pH 9.5 was 6 nm thick so that the effective diameter was 12 nm larger than the
particle diameter and effective pore diameters in the beads 12 nm smaller than
actual size.
Hydrodynamic chromotography, in which sol particles of different sizes are distributed differently along a wall in streamline flow, has been used to separate
colloidal particles. Small (165) has described the technique and patented (166) its
utility for separating submicron sized particles. However, it probably will not be
applicable to very small colloidal particles. In connection with this techniqv -,
Stoisets, Poehlein, and Vanderhoff (167a) have proposed a mathematical mode.
~---
icentrated Sols
Characterizing Sols
tribution was
ied an "inner
be
rror if
ll
ox colloidal
Further developments in sedimentation field flow fractionation were-described by

Giddings and co-workers (167b, 167c).
A new method of separating latex particles by continuous electrophoresis may
become useful for colloidal silica. McCann et at. (168) found that under certain conditions of ionic charge and ionic strength, particles of different sizes migrate at different rates during electrophoresis, and they designed a separation device taking
advantage of the phenomenon.
Separation of organic polymers of different molecular weights by preferential coagulation and precipitation has long been known but apparently has . never been
applied to colloidal silica. Her (169) found evidence that silica particles of different
sizes require different critical concentrations of calcium ion to be flocculated. In a
narrow pH range around 8-9 it was demonstrated that 10 and 24 nm particles can
be separated by preferential precipitation of the larger particles.
1l), 'Hermans
in agreement
42). Jennings
s Syton~ 2X
croscope and
m medium:
t Scattering
19.5
14.2
of particle
examined by
of 8-25 and
10
on is by cenrotor speeds
eter. Various
irne progress
ive but more
SUBCOLLOioAL SPECIES. The characteristics of a silica sol can be affected markedly by the presence of relatively small amounts of so-called "active" silicas such
as monomer, Si(OH)4' low polysilicic acids, or in alkaline solutions, silicate ions.
These are all detectable by reacting the sol with molybdic acid and noting the rate of
formation and amount of the yellow silicomolybdic complex. Some authors arbitrarily define silica that react with molybdic acid within 3-5 min as type A, and that
which reacts more slowly as type B. A typical color development curve by Goto and
Okura (170) is shown in Figure 4.9, for a sol of small particle size which was diluted
about tenfold when added to molybdic acid reagent. In the original sol there would
be 100-200 ppm of monomeric silica in solubility equilibrium with the particles.
When it is diluted in the acid medium, further dissolution does not instantly occur,
so initially about 20 ppm of rapid-reacting silica monomer is found. The colloidal or
polymeric fraction (typ~ B) continues to depolymerize at a fixed rate giving a line of
constant slope which, according to the authors, gives the initial concentration of
monomer present when extrapolated to zero time. The rate of development of color
from type B silica, which is the rate of depolymerization, depends on the conditions
eation chromn packing.

rrticles) was
vere used as
Fague, and
uble layer at
ger than the
smaller than
.izes are disto separate

ted (166) its
will not be
s tP"hnique,
tic riodel.
351
40
....
W
0:
o:t
(,)
::;
til 20
~
10
MINUTES
Figure 4.9.
Reaction of colloidal silica with molybdic acid. [After Goto and Okura (170).J
.,
352
---Colloidal Silica-Concentrated Sols
under which the polymer or particles have been prepared. In another study. Goto
(171) suggests that the depolymerization is accelerated by molybdic acid and is pro,
portional to the total surface area presented by the colloidal silica particles. I.
similar studies. Baumann (172) stops the development of the yellow color by adding
citrate and then determines the silica by converting the yellow complex to
molybdenum blue. which gives a more precise measurement of the silica concen,
tration.
Colloidal solutions in which the particles are sufficiently small to be more soluble
than massive amorphous silica generally contain 110-150 ppm Si0 2 as monomer,
and if stabilized at about pH 9. also HSiO~ - ions.
The question has been raised whether at equilibrium at pH 9-10. there are polysilicate ions as well as HSiO~ - and Si(OH)4 present. Iler finds that in an aged sol,
the rate of reaction of silica particles with molybdic acid is not changed by removing
the colloid by centrifuging and rediluting with water, indicating that no polysilicates
are present. .
In sols where the particles are greater than 5 nm in diameter, and are relatively uniform with a normal distribution of sizes about an average value, determination of
the specific surface area provides a rapid and dependable method for estimating
average size. If, on the other hand, the sols contain particles varying widely in size,
such as is often the case with sols made from pyrogenic silicas or other redispersed
powders, the results may be misleading.
The relation between particle size determined from electron micrographs and the
specific area of the silica as determined by nitrogen adsorption at low temperature
(the BET method) was first worked out by Alexander and Iler (66), as previously
discussed.
In general, the particle diameter calculated from specific surface area is somewhat
smaller than the diameter that would be judged by eye from electron micrographs,
because smaller particles may remain unobserved yet contribute substantially to the
specific surface. Thus, for example, in an electron micrograph of 100 nm silica particles, 0:1 % of 5 nm silica would not appear to be particularly significant. but it would
increase the apparent specific surface area of the larger particles from 25 to 30 m2
g-l. Also the particles may have a surface roughness not seen in the electron micrographs.
The usual method of determining specific surface area is to acidify a sol to about
the neutral point, add an equal volume of r-butyl or n-propyl alcohol, and permit the
sol to gel and then air-dry. Under these conditions, the silica particles form an opennetwork gel with minimum points of contact between particles and thus minimum
loss of surface area upon drying. The dried powder is then heated" to 150C to drive
off physically adsorbed water and alcohol and the surface area determined by one of
several adsorption methods.
'
NITROGEN AOSORPTIO:-i. The BET method of nitrogen adsorption (173) is
most dependable and accurate and is further discussed in detail in Chapter 5. Rap._
.entrated Sols
Characterizing Sols
study, Goto
methOds for determining surface area by nitrogen adsorption involve 'Continuousnow equipment based on principles of gas phase chromatography (174).
APplicability of the flow method to silica was studied by Eberly (175). who reported
good agreement with the equilibrium isotherm method. Ettre and Cieplinski (176)
have surveyed the gas chromatographic methods and applications.
i and is pro-
Jar ~s. In
Ir by adding
complex to
ica ccncenlore soluble
; monomer,
re are polyaged sol,
ly removing
aclysilicates
in
latively unimination of
estimating
dely in size,
redispersed
.ld the
emperature
i previously
ph;
s somewhat
icrographs,
tially to the
silica partiJut it would
~5 to 30 m2
lectron mi01 to about
: permit the
m an opens minimum
C to drive
d by one of
17:' ;s the
er
~apid
353
ADSORPTION FROM SOLUTION. The adsorption of methyl red dye from an organic
solvent has been used as an alternative to nitrogen adsorption, but is more timeconsuming (177, 178). The dye is adsorbed only on a silica surface that is fully
hydroxylated, that is, has been generated in water and dried at moderate temperature. Adsorption of a fluorescent dye such as Rhodamine B was used by Kautsky
and Michel (179). When adsorbed as a cation, the dye fluoresced rose-red, but when
not ionized was bluish red. It might be useful for determining surface area of fully
hydroxylated silica as present in a sol since it can be adsorbed from water.
Unger and Vydra (180) used the adsorption of Zn(NH3).2+ or Zn(en)32+ from
aqueous solution on silica powders to determine surface area. Equilibrium is reached
after shaking the powder in the solution for 5 hr. The specific surface area is given
by the equation
A
= 480c + 6.6
where A is expressed in square meters per gram and c is millimoles Zn(en)32 +

adsorbed per gram of silica. Solution composition and conditions were as follows:
0.1 M Zn; 2.0 M NH.N0 3; 0.4 M NH 2C2H.NH 2; pH = 8.2; 20C; I gram Si0 2
shaken with 25 ml solution for 5 hr and the filtered solution analyzed for decrease in
"Zn.
A method employing radioactive hafnium could probably be developed, based on
the work of Stryker and Matijevic (l81).
TITRATION METHOD.. Adsorption of base on the surface of sol particles provides a
rapid estimate of the area of the silica-water interface. The sol rather than a dried
powder is used in the Sears (182) method of titrating the silica surface with alkali in
strong salt solution between pH 4.0 and 9.0. As discussed in Chapter 3, it provides
the simplest way to follow the change in the specific surface area and thus particle
size when the silica particle are smaller than 5-10 nm. However, it is equally useful
for larger particles, up to a micron or more in diameter, provided it can be shown
that the particles are not microporous by comparing results with the area
determined by nitrogen or water vapor adsorption, or from electron micrographs .
. The method is mainly of value for comparing relative surface areas of particle
sizes in a given system which can be standardized. Under these conditions results are
reproducible within =*:5%. Where there are variations in the types of silicas, differences from BET values may range up to =*: 10%.
The sol sample containing 1.50 grams Si0 2 is diluted with CO 2-free water at 25C
to a concentration of 2-3% Si0 2, acidified with HCI to about pH 3, and diluted to
135 ml volume. Then 30 g pure crystalline NaCI is added and the mixture stirred
rapidly. As soon as the salt is dissolved, the pH is adjusted to pH 4.00 with 0.1 N
,''II ':
I j
.'
't '
1','
::. !
.J, '.'.
354
; ;1,'
NaOH. A "high sodium" (Beckman Type E or equivalent) glass electrode is used

The mixture is rapidly titrated to pH 9.00 with 0.1 N NaOH and the volume noted
after the pH has remained at 9.00 :I:: 0.05 for about 1 min. (If the particles are not
porous. the end point is stable.)
Although there have been some past variations in the equation relating titration
volume to specific surface area. a series of tests by lIer on five well-aged sols
(50-420 m 2 g-I) made originally- at high temperature gave average values Cor':
responding to
: ; : ~ ,.
. :f:"
.
.:
A .. 26.4( VI - VII)
;:l i
.: I l.
, ;'1
;1
,',t . '
"
;:1; ,
~
!.! ' .
1
l :I
'fir
:
where A is square meters per gram determined by the BET method. VI the milliliters
NaOH required for 1.50 gram SiO::. and VII the titration blank in the absence of
silica. usually about 0.3 ml (compare equation in Chapter 3).
It is possible that sol particles may vary in their surface roughness. Also the areas
determined by nitrogen adsorption may depend to some extent on the method of
drying the sol. The method used above for determining A by nitrogen adsorption
involved deionizing the sol with mixed anion-cation exchange resins, adjusting the
pH to 2.0. and letting the sample evaporate at 25-40C until just gelled; the wet gel
was dispersed in at least a tenfold weight of n-propanol and air-dried, and samples
were then heated in air at ISO and 350C for 16 hr and the area determined by
nitrogen adsorption by the standard BET procedure. The BET values on duplicate
samples dried at the two temperatures varied less than :1::2%. When particles are
smaller than 7-8 nm in diameter, even the most careful techniques of gelling and 'drying silica may fail to prevent loss of surface area by particle-to-particle contact.
RATE OF DISSOLUTION OF PARTICLES. The relation between particle size and rate
of dissolution of silica particles has been reviewed in detail in Chapter 1.
It is logical to assume that the rate of depolymerization or dissolution of colloidal
silica particles would be proportional to the specific surface area. Thus different
solvents such as dilute hydrofluoric acid, molybdic acid, or dilute alkali. all of which
convert the monomeric silica permanently to other silicon com pounds. may
therefore be employed to measure surface area. The difficulty. however. is that the
types of silica particles studied have been so varied and ill-defined that this approach
has not been of any value until recently, when sols of uniform discrete solid particles
have become available. Even then the value of the method is in doubt unless one can
be sure that the samples of silica under study all have the same composition and
structure. Variables in the rate of dissolution per unit of surface area include the
following:
1. Degree of porosity or internal hydration in the form of uncondensed silanol

groups.
'
2. Amounts of impurities. especially aluminum in the case of particles dissolving in
alkali.
".
-:...--
3SS
ncentrated Sols
Characterizing Sols
rode is used.
/clurne noted
ire not
tic
3. Particle size, since solubility increases with decreasing size, especially when particles are smaller than 5 nm.
4. Nonuniform particles; smaller ones dissolve more rapidly.
ting titration
ell-aged sols
values cor-
Ionic Charge On Particles
:he milliliters
e absence of
.lso the areas

e method of
n adsorption
adjusting the
I; the wet gel
and samples
:termined by
on duplicate
particles are
:~
19 and
Ie contact.
size and rate
1 of
colloidal
different
al\ of which
ounds, may
~, is that the
lis approach
rlid particles
iless one can
position and
include the
The ionization of the silanol groups at the silica-water interface has been dealt with
in Chapter 3 in connection with the polymerization of silica. The isoelectric point
and point of zero charge of silica arc at about pH 2. The rate of condensation of
SiOH groups to siloxane bonds (Si-O-Si) as well as the rate of the reverse
hydrolysis reaction are at a minimum at this pH, because the reactions involve the
SiO- ion:
.
aSiOH
+ O-Sia - aSiOSia + OH-
Thus even though silica particles bear little or no charge at pH 2 and can collide, the
formation of Si-Q-Si bonds between particles and formation of gel is slow.
However, it is only above about pH 7 that a sufficient concentration of negative
ionic charges is developed on the surface of the particles to cause mutual repulsion,
thus stabilizing the sol against gelling. At intermediate pH's, gelling is most rapid.
Nature ofIonic Charge
As will be further discussed in Chapter 6, the negative charge on the surface of

amorphous silica can be represented in a number of ways. One view is that the silica
. structure is sufficiently open that a hydroxyl ion can occupy a space in the surface,
so that the coordination number of each adjacent silicon atom is increased by a fractional amount (see Figure 1.11). Another representation involves ionization of surface silanol groups:
.
1US
nsed silanol
dissolving in
=SiOH .. aSiO-
+ H+
In addition to the studies referred to in connection with the ionization of monoand polysilicic acids in Chapter 3, many more data are available on sols and gels.
Bryant (183) studied the effect of particle size and electrolyte concentration on the
pH titration curve of silica sols and interpreted results in terms of the theory of
polymeric electrolytes, taking into account the preferential adsorption of cations and
also that at high pH the particles dissolve as silicate. In the pH range from 3.5 to
10.5 hydroxyl ions are adsorbed by the silica surface in amounts increasing with pH,
as shown by Bolt (184) (see Figure 4.10). The concentration of anionic charges can
be expressed as milliequivalents of base per square meter of area, or as the number
of hydroxyl ions or charges per square millimicron. Bolt used a' commercial silica sol
with particles 15 nm in diameter, having a specific surface area of 180 rn" g " ' and
found the same values at concentrations from 3 to 30% silica. Heston, Her. and
356

II
10
e
ELECTROLYTE CONC.
pH
.
;
o
CI
c
o
10-"
0.001
0.004
0.01
0.04
0.1
0.4
I
4
N
N
N
N
N
N
N
N
NoCL
NoCL
NoCL
NoCL
NoCL
NoCl
NoCL
NoeL
2
0
0.1
0.2
0.3
me OH/gr.
,;. \
~
0.5
I
I
.;
0.5
0.4
sro,
1.0
OH nm- z
1.5
Figure 4.10. Charge density expressed as OH- ions on the surface of particles of colloidal
silica with a specific surface area of 180 m 2 g-I, in the presence of different concentrations of
sodium chloride. [Data by Bolt (184).]
Sears (185) showed that at a given pH, the number of charges per unit area of silica
surface is independent ,of particle size. Fundamental considerations of ionic charges
at the water interface with metal oxides and silica have been presented by Graharne
(186), Perram (187), Parks (188), Alien, Matijevie, and Mestes (189), Tadros and
Lyklema (190), Yates and Healy (191), and others. Vysotskii and Strazhesko (192)
have given special attention to the nature of the cation exchange or charged sites. A
site-binding model of the oxide-water interface was presented by Yates, Levine, and
Healy (19~), in which adsorbed counterions form interfacial ion pairs with discrete
charged surface groups. They also discussed the anomalous dissociation constants of
SiOH groups.
Silica is unique among colloids in its surface charge-pH and total double-layer
capacitance behavior, according to Yates and Healy (191). These factors are much
higher than on other colloids for which a suitable theory has been developed based
on the Nernst equation. Perram (187) proposed that the silica surface is coated with
a gel layer, providing a microporosity to ions but not to nitrogen or other molecules
when the .silica surface is dried. Yates and Healy reached similar conclusions based
on studies on precipitated (BDH) silica. They also corrected their potentiometric titration curves above pH 9 for the ionization of soluble silica. Similar studies had
also been made by Tadros and Lyklema (190) with the conclusion that negative
groups and cations must penetrate within the pores of a "gel layer," but the degree'
of penetration depends on the size of the cation.
I
!
.-~.
iT
':,..-_.
:entrated Sols
, of colloidal
entrations of
'ea of silica
nic charges
y Grahame
Fadros and
iesko (192)
.ed sites. A
.evine, and
.th discrete
onstants of
ouble-layer
j are much
)ped based
.oated with
, molecules
ions based
ometric titudies had
It negative
th-
'~gree
Characterizing Sols
357
As already discussed, colloidal silica particles made in different ways 'exhibit different degrees of microporosity. It is therefore not surprising that microporous silica
should act quite differently from nonporous particles of other inorganic colloids,
particularly those with crystalline surfaces. Properties must be measured on smooth,
nonporous surfaces to provide reproducible data that can be said to be characteristic
of the "the surface of amorphous silica:'
As shown also by Yates and Healy. if attempts are made to obtain nonporous
silica particles by heating to 800C, much of the surface is dehydroxylated to
siloxane groups. When this surface is then rehydroxylated there is no evidence that a
gel layer is formed again. However, on such heat-treated silica and on pyrogenic
silica particles, after hydration, the surface charge density in relation to pH is still
much higher than observed, for example, at the classical AgI-solution interface. It
was concluded that even on a "nonporous" surface of amorphous silica the charging
ions must be .able to penetrate the surface to some extent.
It has been suggested (Ref. 8, p. 246) that the silica surface is charged by hydroxyl
ions formed by the loss of protons from water molecules located in the spaces
between the oxygen atoms of the Si02 structure (Figure 1.11). Thus the negative
charge would lie just within the surface. If the surface resembles that of tridymite on
a local scale, as appears possible since it is consistent with 4.6 SiOH groups per
square nanometer, then there are depressions in which the counter cations could
remain close to the counterions.
.
As Tadros and Lyklema point out, the smaller univalent ions like Na" can most
readily follow the negative charge into the surface. They show that the large
(CHa).N+ countercation at a given pH allows the development of a much smaller
surface charge. It was also concluded by Her (169) that the peculiar ocagulating
behavior of the calcium ion differed from that of sodium because it remains farther
outside the outer silanol layer than sodium does. This creates a geometry that leads
to preferential coagulation of larger colloidal silica particles in the presence of
smaller ones. This does not occur with sodium ions.
The peculiarity of amorphous silica may be that at the solid-water interface the
negative charge can be developed somewhat within the surface rather than on the
surface so that more silica and less water. is involved in determining the average
value of the dielectric constant.
Since this chapter deals mainly with colloidal silica particles that have been made
by processes designed to make dense, nonporous particles, it is of interest to compare the surface charge density under a given condition with the silica powders that
have been studied. In Table 4.1 the chosen conditions are 0.1 M of uni-univalent
electrolyte such as NaCI, KCI, or KNO a at a pH of9.0.
The results of Bolt (184) (Figure 4.10) and Heston, lIer, and Sears (I85) on
nonporous silica particles are compared with those of Yates and Healy on precipitated silica (BDH) which is porous until heated to high temperature. It is evident
that the surface charge density on the sol particles is of the same order as that on the
precipitated powder that has been heated. The sol particles hal-e never been heated
over lOOC yet are dense because they were made by the slow deposition of
molecular silica. Unless particles are grown in this way, porosity will be present as
shown by the higher charge density. However, it appears that even these sol particles
358
Table 4.1. Comparison of Charge Density on Silica Surfaces under Fixed

Conditions
At pH 9
Authors
Silica
Yates, Healy
BDH
(500C)
(800C)
Bolt
Heston et al.
Ludox HS
Sol
Area Electrolyte
(m ' g-I) (0.1 N)
73
64
36
200
318
KNO,
KNO,
KNO ,
NaCI
Na+ o
MicroCharge
coulombs
Ions"
(per ern") (per nm ')
40.0
11.4
8.8
2.51
0.716
0.552
0.68
0.63
o Counterions only-no small anions other than HSiO, -; data slightly

extrapolated.
1 microcoulomb cm -I _ 0.0628 charges nm -I.
are not quite as dense as particles that have been heated to 800 0 e as evidenced by
the somewhat higher charge density of 0.63-0.68 versus 0.55.
Counterions and Double Layer
.,
,
The sodium or other counter cations in the water surrounding the charged silica
particles are not readily removed by filtration or centrifugation and remain on the
surface when the silica is dried. If the particles were not in constant "Brownian"
motion, the counterions (gegenions) such as sodium would- form a compact layer in
the water next to the adsorbed hydroxyl ions, but with the thermal agitation of the
particles, most of the counterions form a diffuse cloud around the particles called
the "Gouy layer," whereas those remaining at the surface are considered to be in the
"Stern layer." The thickness of the diffuse Gouy layer is defined as the distance
from the surface of the particle at which the potential is only 1/ e, or 0.37 of that at
infinity. The "zeta potential" is measured by electrophoretic effects and is
considered to be the potential between the "slipping plane" at the outer boundary of
the Stern layer, which moves with the particle, and the dispersion medium at an
infinite distance.
The adsorbed anions on the surface and the accompanying cloud of surrounding
cations form a "double layer." The distribution of ions, the thickness of the layer,
and the charge density have been clearly explained by Mysels (194) and reviewed in
detail by Graham (195). The charge density can be expressed as the number of
electronic charges (e.g., hydroxyl ions adsorbed on silica) per unit area: A complete
monolayer of average-sized ions would provide about 5 charges nm -2, but this
charge density is not attainable because of the mutual cha'rge repulsion. Even 1
charge nm -2 is a very high charge density on a stable colloid.
The charge on the particles and other factors governing colloidal stability and
related theories have been reviewed by Lyklema (196). The general theory has also
rcentrated Sols
Characterizing Sols
xed
been reviewed by Napper (197). Other excellent references are books -by Sheludko
(198) and Kruyt (l99).
The thickness of the diffuse double layer surrounding silica particles which bear
permanent negative anionic sites owing to the incorporation of tetracovalent alumina into the surface has been studied by Long and Ross (200), who used a commercial colloidal silica of this type, Ludoxs AM. They studied the overlap of the
diffuse double layers in relatively concentrated sols by measuring the electrophoretic
mobility at constant pH and electrolyte content over a series of concentrations of
silica. Although an increase in electrolyte concentration diminished the thickness of
the electric double layer, it also caused an increased adsorption of hydroxyl ions
which raised the surface potential so that the overall zeta potential which governs the
electrophoretic mobility remained relatively unchanged.
An unusual approach to studying the charge on silica particles was employed by
Deraska, Yaeger, and Hovorka (201). A Ludoxs colloidal silica having a particle
diameter o'f 15 nm was subjected to ultrasonic vibration; by placing electrodes at
nodes and loops they measured the colloidal vibration potential which increased with
silica concentration from zero to about 4% silica. The potential is presumably
generated by the motion of the charged particles with respect to the fixed electrode.
The velocity of sound in concentrated silica sols was measured by Younger et al.
(202) over a range of temperatures. The effect of temperature on the "hydration
hull" around the particle' is an important factor but no thermal anomalies were
observed as reported in other studies of quartz-water systems.
ge
.t
ml)
6
2
htly
evidenced by
ha
i silica
:m~,
. on the
"Brownian"
pact layer in
tation of the
rticles called
i to be in the
the distance
37 of that at
'ects and is
boundary of
edium at an
surrounding
of the layer,
[ reviewed in
: number of
A complete
\-2, but this
.ion. Even I
ita' "ty and
or) .is also
359
TYPES OF COUNTERIONS. In most patents relating to colloidal silica the stabilizing

bases include the hydroxides of potassium, lithium, sodium, and ammonium. The
sols are most commonly stabilized with sodium hydroxide, and then if other bases
are to be substituted, thesols are deionized in mixed anion-cation resin beds and
restabilized with the desired base. The ammonium-stabilized sols are employed
where pure silica is desired. The lower amines can be used in place of ammonia, but
are generally avoided because of odor (203).
Lithium appears to be unique among the alkali metal cations in its stabilizing
effect, according to Rule (7), in that water-miscible alcohols can be added without
gelling the .sol, as when sodium is used, and the resulting sols are then freezeresistant.
.
lIer (204) found that, unlike sodium hydroxide, lithium hydroxide can be added as
stabilizer in any amount without causing coagulation. Thus sols with Si0 2 : Li 20 ratios
of 4: I to 25: I are stable and compatible with water-miscible organic liquids and dry
to water-resistant films. (see Chapter 2, lithium polysilicates)
As has been discussed in Chapter 2 relating to lithium silicates and polysilicates,
the lithium ion is unique in that it is preferentially adsorbed at the silica interface
forming an impervious layer which retards the dissolution of silica at high pH (206).
Lower alkyl quaternary ammonium ions, particularly tetramethylammonium,
were found by Wolter (205) to provide such a degree of stabilization, by forming an
adsorbed layer of ions around the surface of the silica, that the sol can be dried to a
powder which will then spontaneously disperse to a sol in water. These sols are also
very resistant to freezing and compatible with water-miscible organic solvents such
w~ L:i
l' .
i \.
i
,i
:",..._-
360
i
!.
'
1
" 'i'
as acetone and alcohol. Long-chain amines or long-chain quaternary ammonium

ions. on the other hand. have a powerful flocculating effect on colloidal silica and
cannot be used as stabilizing agents in aqueous systems except by reversing the
charge.
"
.~, :
~
. t .s .
: \1
.~
i .j
e
.' .i
.
'
;.
. 1
!
EFFECT OF COUNTERION CONCENTRATION ON SURFACE CHARGE DENSITY.

It is
well recognized that in the presence of an electrolyte such as sodium chloride. a'
higher charge density is attained at a given pH. However. it may not be so obvious
that -in relatively concentrated sols stabilized with alkali. the concentration of the
sodium counterions must be included as "electrolyte" in the relation between surface
charge density and pH.
Bolt (184) carried out measurements in the presence of added NaCI. and Heston
ller, and Sears (185) made similar measurements in the absence of added salt but
considered the concentration of Na + counterions in the system. In the latter studv
the surface charge. in terms of adsorbed OH-, ions was expressed in terms of j. th;
fraction of the maximum possible charge density. taken to be 3.5 :l: 0.3 0 H - nm -z.
Bolt's data can be expressed in similar terms with the following results at pH 9:
~i>:;;
OH- Ions nrn"?

Counterion
Na" Normality
.. '.
NaCI
Normality
Heston et al.
0.001
,. '.
0.28
0.29
0.001
0.01.
0.42
0.44
0.01.
0.63
0.1
0.68
0.1
'I
.'
"
I,
Bolt
For concentrated sols of very small particles where a relatively high proportion of
sodium to silica is required to charge the surface. the concentration of sodium ions
can be so high that it reaches its "critical coagulation concentration" at the existing
pH so that the sol is unstable. imposing another limit on concentration for sols of
this type. '(Thus concentrated sols of very small particles stabilized in the SiO z : N a 20
ratio range of about 6-20 are unstable and gel.) This is characteristic of sodium ions
but not of lithium or potassium. With the latter ions, concentrated sols of solutions
can be made regardless of particle size, in which the silica particles may range from
the colloidal to the molecular dimensions of polysilicates. Lithium ions behave in a
unique way (206),
Viscosity
"
1
As pointed out by Kruyt (207) the viscosity of a sol depends on the volume fraction
of the "dispersed phase" in accordance with the Einstein equation
log, 71rl!'/ = I
+ 2.5eP
..
:-.--
centrated Sols
Characterizing Sols
ammonium
al silica and
'ev
19 the
where TI,.r/ is the relative viscosity or ratio of the viscosity of the dispersed system to
that of the dispersing medium, and tjJ is the volume fraction occupied by the dispersed uniform spherical particles. The Einstein equation was extended by Mooney
(208) to apply to a suspension of finite concentration:
361
~SI~Y.
It is
chloride, a
e so obvious
'ation of the
veen surface
log, TI,.~,
and Heston,
ded salt but
latter study,
rrns off, the
OH- nm- 2
"pH 9:
me fraction
I - 1.43 tjJ
Numerous other equations have been developed to even more accurately predict the
viscosity behavior of spheres in more concentrated suspensions, but these have
generally not been tested on sots. These include studies by Simha (209), Yand (210),
and Ford (211).
In 1965, Thomas (212) reviewed the extensive experimental data on the relative
viscosity of suspension of uniform spherical particles, and related the data to equations from previous theoretical analyses. He concluded that the following equation
best matched the data over the entire concentration range; for values of c less than
0.25, the exponential term can be dropped:
TI,,.,
oportion of
sodium ions
the existing
for sols of
SiOz:NazO
odium ions
of solutions
range from
behave in a
2.5 tjJ
-
= I + 2.5tjJ + 1O.05tjJ2 + 0.00273 exp( 16.6)
Lewis and Nielsen (213) have extended the theory to a consideration of the viscosity
of permanent aggregates of spheres ranging from doublets or triplets to clusters of
spheres composed of a large average number of spheres. This theory should more
properly correspond to silica sols in which not all the particles are individual
spheres, but in which some gel phase has begun to form and has then been stabilized.
It might also apply to sois containing aggregates such as those made from pyrogenic
silicas.
.
Fedors (214) took into account the maximum packing density of spheres in
suspension to develop an' equation for very high concentrations. The volume fraction
of random dense-packed spheres is 0.63.
Other studies of the viscosity of spheres in suspension have been made by Manley
and Mason (215) and Happel (216,), and the rheology of silica suspensions
(noncolloidal) has been described by Pivinskii (217) .
As represented in Figure 4.11, for a given concentration by weight of silica in a
sol, the volume fraction of the dispersed phase varies with (a) the volume of the ion
atmosphere in the double layer surrounding each particle, and (b) the porosity or
hydration of the particles. If the viscosity is measured at pH 2, where there is no
charge on the particles, then it can be used to deduce how much water is bound to
the surface of solid particles, or is held within spongy particles or aggregates, since
such water must be considered as part of the dispersed phase.
In a series of measurements by lIer and Dalton (64), on a series of sols of dense
particles smaller than 8 nm in diameter at pH 2, viscosity' data indicated that the
bound water corresponded to a layer one molecule in thickness. For particles larger
than 20 nm in diameter, this fixed hydration layer, which is only about 0.3 nm thick,
has little effect on the viscosity; however, with particles only 5 .om in size, a dif-
!
;.
(a)
(bl
(c)
(d)
(e)
,
..
]
ti! .
Figure 4.11. For sols or equal silica concentration, highly charged particles (0) give higher viscosity than slightly charged particles (b). Dense particles (c) give lower viscosity than porous
aggregates or smaller particles (d). Smal.1 particles, nonaggregated as in (e), also give lower viscosity than aggregates (d).
362
363
Characterizing Sols
ference of 0.6 nm increases .the effective diameter to 5.6 nm, which increases the
effective volume on the "dispersed phase" by 40%.
As for porous particles. which have already been discussed, viscosity is not a very
sensitive measure of porosity, especially if the pore volume is less than 10-20%. On
the other hand, viscosity at pH 2 is a sensitive measure of aggregation or presence of
microgel as has been dealt with in Chapter 3. In the case of particles smaller than
about 20 nm in diameter, the effect .of the hydration layer should be taken into
account. From the specific surface area, which does not change much as microgel is
formed, the average particle size can be estimated. From this the viscosity' of a sol of
nonaggregated particles of this size and concentration can be calculated. Then the
relative viscosity owing to the presence of microgel is taken as the ratio of the actual
sol viscosity to that calculated for the nonaggregated sol.
The relation of viscosity of concentrated sols to the thickness of the ionic double
layer has been considered in connection with the maximum practical concentrations
to which sols of different particle sizes can be concentrated. To characterize
concentrated commercial sols, it is useful to express the condition of the particles by
"the percent by weight of silica in the dispersed phase." If the dispersed phase
consists of large solid silica spheres, where the water bound to the surface is negligible in comparison with the weight of particle, the percent silica is close to 100%. For
smaller particles, where the bound water and silanol hydroxyl groups constitute an
appreciable fraction of the particle weight, the percent of silica is less than 100%.
But if particles are aggregated into suspended microgel masses, these aggregates
constitute the dispersed phase which encloses water. In this case, the percent of silica.
is much lower. (Alexander used the symbol S, but here the symbol c is used for
concentration of silica in the dispersed phase.) Viscosity provides a way of measuring the gel content of a sol, provided the measurement is made at pH 2. Details of
this procedure are described by Alexander (9). The silica sol is deionized and
adjusted to pH 2 with strong acid. A concentration of about 4% Si02 is convenient,
and the silica concentration must be accurately known. Viscosity measurements are
made on 10 ml samples at 30C in size 100 pipettes of the Ostwald type. The volume
fraction of the dispersed phase, q" is calculated from the Mooney equation (208) and
then, assuming a density of 2.2 g em -3 for amorphous silica, the percent Cd of silica
by weight in the dispersed phase is
Cd
: higher vishan porous

e lower vis-
O.00566c,
+ q,(1
- O.00566c,)
where c, is the total percent of weight of silica in the sol, and (P is the volume fraction of dispersed phase as determined by viscosity. Sols free from appreciable
amounts of gel phase have values of c less than 100%, generally around 70-80%,
owing to the water bound to the surface of the particles (64). If a sol has aged at low
pH and the viscosity has increased because of incipient gelling,
, the percent Cd will
fall below 50.
In the pH range around 3-4 where the surface of silica is only very slightly
charged the surface of commercial silica sols may exhibit a greater negative charge
Ii
\
364
Colloidal SilicaConcentrated Sols
owing to the presence of a few aluminosilicate sites. since aluminum is almost

always present as an impurity. At pH 2, these are destroyed. Greenberg,
Jarnutowski, and Chang (218) report that in silica sols at pH 2.8 the viscosity data
suggest that there is a water layer 15 A in thickness. corresponding to about five
molecular layers of water. This is the average distance from the surface of silica to
the surface of shear, suggesting that the surface is somewhat charged. At high pH,
the surrounding aqueous layer containing counterions becomes many times thicker
than this in dilute sols. In concentrated, alkali-stabilized sols, however. the coun,
terion atmosphere can be compressed so that the thickness calculated from viscosity
cannot be more than 20-30 A. This has already been discussed in connection with
the maximum practical concentrations of commercial sols of different particle sizes,
from which it was concluded the average minimum thickness of the double layer was
about 2.4 nm or 24 A.
It may be pointed out that to attain the highest possible concentration of colloidal
silica for use in certain applications, it is necessary to adjust the pH to 2 to eliminate
the double layer and also to use a mixture of two or three widely different particle
sizes as patented by IIer (219). By using 10 parts by weight of 100 nm particles and
6.24 parts of 7 nm particles the dried gel had a porosity of only 20% by volume.
.;
...
":
..;
AGGREGATION OF PARTICLES
. Definitions
It is sometimes not recognized that there is a basic difference between gelling and
coagulation or flocculation. Both involve colloidal particles linking together and
forming three-dimensional networks. But when a sol is gelled. it first becomes viscous and then develops rigidity. On the other hand, when a sol is coagulated or flocculated. a precipitate is formed. In a concentrated sol the precipitate may be too
voluminous to separate and wilt remain as a thixotropic mass, but in a dulute sol,
the precipitate will settle ou t. The difference is shown in Figure 4.12.
LaMer and Healy (220) have further defined the difference between the terms
"coagulation" and "flocculation," They proposed that the term "flocculation" be
used in the-special case of coagulation in which the final structure is promoted by
bridges of organic molecules or colloidal inorganic particles forming a loose threedimensional network having pores which permit easy filtration. Thus they preserve
the term "flocculate" in its original meaning of a loose. open structure. a floc, like a
tuft of wool. On the other hand, the term "coagulation" comes from the Latin
meaning "to drive together," and therefore is used for cases where the ultimate
particles are brought together in relatively dense aggregates or clusters which settle
compactly and therefore. in contrast, are difficult to remove by filtration. It is
obvious that there is no sharp distinction between the terms.
The world "aggregation" is used for all the ways in which coilloidal particles are
linked together. Thus aggregation includes the following:
'
I. Gelling, where the particles are linked together in branched chains that fill the
whole volume of sol so that there is no increase in the concentration of silica in
..
!""""'"
-.
.~
centrated Sols
365
m is almost
Greenberg,
isc " data
o about live
e of silica to
At high pH,
imes thicker
.r, the counom viscosity
nection with
article sizes,
ole layer was
(b)
(a)
of colloidal
to eliminate
rent particle
iarticles and
I
'olume,
g
's and
oge, ..er and
iecomes visited or flocmay be too
1 dulute sol,
n the terms
:ulation" be
romoted by
loose threeley preserve
1 floc, like a
n the Latin
he ultimate
which settle
.aticn. It is
oarticles are
thr ;1\ the

of
.ca in
(e)
Figure 4.12.
Silica gel versus precipitate. (a) sol; (b) gel. (c) flocculation and precipitation.
any macroscopic region in the medium. Instead, the overall medium becomes viscous and then is solidified by a coherent network of particles which, by capillary
action, retains the liquid.
2. Coagulation, where the particles come together into relatively close-packed
clumps in which the silica is more concentrated than in the original sol, so the
coagulum settles as a relatively dense precipitate.
3. Flocculation, where the particles are linked together by bridges of the flocculating
agent, which are sufficiently long that the aggregated structure remains open and
voluminous.
It is apparent that these differences will be noted mainly in dilute sols containing
only a few percent of silica. In concentrated mistures one can distinguish a gel,
which is rigid, but not between a coagulate and a flocculate.
...
.....
};.,.
';..,.---
......
".
4. Coacervation, a fourth type of aggregation, in which the silica particles.are Surrounded by an adsorbed layer of material which makes the particles less hydrophilic. but does not form bridges between particles. The particles aggregate as a
concentrated liquid phase immiscible with the aqueous phase.
A method of analyzing a sol containing aggregates has been described by Gruber
and Knell (221), who combined light scattering with viscosity measurements. The
dimensions and weight fractions of aggregates can be calculated.
Aggregation involves adhesion between colloidal particles, and a detailed
consideration of interparticle attraction and bonding has been written by Visser
(222) with 295 references. Special attention is given to immersed systems where
London-van der Waals force and electric double layer repulsion as well as ionic
attraction between surfaces of opposite charge are considered.
GeUing
i,
.:
.J
Aggregation and gelling have already been discussed in detail in Chapter 3 as one of
the mechanisms of polymerization in the case of extremely small "particles" of polysilicic acid. In this chapter only the conversion of sols of relatively uniform discrete
particles to gels is considered. The main discussion of gels is reserved for Chapter 5.
Most silica gels of the past have been formed from polysilicic acids or colloidal
silica particles so small, generally less than 5 nm in diameter, that the nature and
structure of the gel was long in doubt. Now that commercial sols of uniform known
size are available, the mechanism of gelling is much better understood.
Effect ofpH
-The basic step in gel formation is the collision of two silica particles with sufficiently
low charge on the surface that they come into contact so that siloxane bonds are
formed, holding the particles irreversibly together. Formation of this linkage
requires the catalytic action of hydroxyl ions (or, as interpreted by some, the
dehydration of .the surface of particles at higher pH). This is evidenced by the fact
that the rate of gel formation in the pH range 3-5 increases with pH and is proportional to the hydroxyl ion concentration.
Above pH 6, scarcity of hydroxyl ions is no longer the limiting factor on the rate
of gelling. Instead, the rate of aggregation decreases because of fewer collisions
between particles owing to the increasing charge on the particles, and thus decreases
with higher pH. Lines in Figure 4.13 schematically represent the increase in the
catalytic effects of hydroxyl ions with increasing pH, and the decrease in the number
of effective collisions between particles with increasing pH and particle charge. The
net result of these two effects is a maximum in rate of gelling at around pH 5. In the
range 8-10, sols are generally stable in the absence of salts.
,
There is also a region of temporary stability at about pH 1.5. Below pH 1.5,
traces of HF catalyze aggregation and gelling (223). In essentially all silicas, traces
of fluoride ions, even less than 1 ppm; are present so that the concentration of HF
:ntrated Sols
les are surless hydrore.'

as a
367
STABl.E-J
SOLS
I
f-----NEGATlVE-
SiOz
DISSOLVES
w
:E
by Gruber
merits. The
...J
W
a detailed
I by Visser
terns where
ell as ionic
I-
C)
>-
::::i
iIi
en
...J
en
10
12
14
Figure 4.13. Effects of pH in the colloidal silica-water system.
3 as one of
es" of polyrm discrete
Chapter 5.
or colloidal
nature and
'or, '<nown
increases with increasing acidity. The fluoride effect is influenced by the. aluminum
impurities present, since these inactivate some of the fluoride by forming complex
ions such as AIF.s- and other species (224). However, as discussed in Chapter 3, the
gelling rate increases as the pH falls below 3 even when fluorine is absent.
Once the siloxane bonds have formed between particles there is further deposition
of silica at the point of contact owing to the negative radius of curvature, as discussed in Chapter 3. This occurs rapidly above pH 5, and is slow at pH 1.5.
Effect ofParticle Size And Concentration

sufficiently
: bonds are
his linkage
some, the
by the fact
d is properon the rate
:r collisions
IS decreases
'ease in the
the number
charge. The
,H 5. In the
ow pH 1.5,
lic?- traces
iti;
f HF.
These two factors are interrelated, The rate of gelling apears to be proportional to
the total area of,silica surface present in a given volume of sol. Since the specific surface area of silica varies inversely with the particle diameter, sols having the same
ratio of concentration to particle diameter gel at about the same rate. Thus, under
equivalent conditions, a 10% sol of 10 nm particles might be expected to gel at the
same rate as a 20% sol of 20 nm particles.
With particles of a given size (14 nm) at 25C and in the presence of 0.1 N NaCI,
the relation between gel time and silica concentration is not simple. As shown in
Figure 4.14, the effect of silica concentration on gel time is not the same at various
pH values.
Electrolytes And Organic Liquids

Below pH 3.5. salts have little influence on the rate of gelling, whereas water-miscible organic liquids such as alcohol retard gelling. Above pH 15. where commercial
silica begins to bear a negative charge, the addition of salt reduces the overall net
repulsion effect and coagulation and gelling are greatly accelerated, as demonstrated
by Baxter and Bryant (225). The addition of salt to a dilute sol brings about coagu-
..
7..,.--
368
.,
100
.,
;
~
~
.i
en
:::>
pH
..
3.5
0::
0
J:
10
11.-........--'--"--........--'---'--..........---1-""----'
o
,
10
20
30
% SiO Z
40
50
Figure 4.14. Gel time versus concentration of 14 nm particles at various pH.
lation and precipitation, whereas in a concentrated sol coagulation is rapid and

indistinguishable from gelling. Thus when a salt is added to' a concentrated silica sol
at pH 9, the initial gel or precipitate may repeptize to sol if immediately diluted or
acidified, but even within a few seconds may become irreversibly gelled.
Water-miscible organic liquids have somewhat. the same destabilizing effect on
alkali-stabilized sols as added electrolyte, presumably because the dielectric constant
of the medium is reduced.
Temperature
As may be expected, since aggregation involves a kinetic phenomenon, the rate of
gelling increases with temperature. This is not always so in the case of flocculation,
where hydrogen bonding with organic molecules is involved, but in forming gels,
there is a marked temperature coefficient of the rate of formation of siloxane
bridges between particles. The activation energy of gelling has been measured in the
case of polysilicic acid, but there are few data on converting sols of known particle
sizes to gels. Below pH 2, where the reaction rate is proportional to hydrogen ion
concentration (HF catalysis), the activation energy is around 9~5 kcal mole " '. At pH
4.5, where the reaction is catalyzed by hydroxyl ion, it is 16.1 kcal rnole ", according
to Penner (226). A similar high value of 15.5 was measured by Brode. Brown. and
Hoff (227) at pH 5.5. At pH 8.S, they found a lower value of 9.6. whereas at pH
.entrated Sols
369
Aggregation or Particles
10.5 in the presence of potassium chloride it was 14.6 kcal mcle ", It ;s evident that
the temperature coefficient of the gelling rate must depend also on the changing ionization constants of the materials involved with increasing temperature. Earlier
studies of gelling mechanism have been summarized by Her (8).
In many investigations of gelling of very small particles of polysilicic acid,
measurements were confused by the fact that as the temperature was raised, the
particles increased in size. Significant data regarding the energy of activation of
aggregation can be obtained only when the particles have already been grown and
stabilized at a temperature higher than those involved in the experiments. Also the
energy of activation varies not only with the pH, which controls particle charge. but
also with the concentrations of silica and of electrolyte. It is therefore meaningless to
cite data for the energy of activation of gelling unless such variables are defined.
For a deionized sol of 14 nm particles (pH adjusted with NaOH) the activation
energies calculated from gel times at 23 and 60C were as follows:
sio, Concentration
s concentraIUS pH.
rapid and
ed silica sol
y diluted or
Ig effect on
ric constant
the rate of
loccu lation,
rming gels,
of siloxane
sured in the
,wn particle
Idrogen ion
le- 1 At pH
'. according
Br- \. and
-re, at pH
Activation Energy
(kcal mole:")
(%)
pH
20
30
20
30
5.5
5.5
10.7
3.0
16.4
11.9
3.0
7.6
The factors involved are obviously complex.
Theory ofStrength of Gels

Colloidal silica finds numerous uses because it dries irreversibly to insoluble silica.
Its usefulness as a stiffener and binder for inorganic fibers and powders depends on
the strength of the gel that "is formed around the points of contact between the
macroscopic materials being bonded.
This discussion is limited to gels formed from discrete particles of colloidal silica
larger than about 5 nm in diameter. No attempt is made here to review the
enormous volume of literature concerning gels made from the polysilicic acids
obtained by acidifying soluble alkali metal silicates. When polysilicic acids or particles smaller than about 5 nm are involved, the gelling process is far more complex,
involving internal condensation of silanol groups and cyclization to siloxane rings in
three dimensions leading to anhydrous SiO z particle nuclei.
The basic theory of gel formation from colloidal particles has been formulated by
Thomas and McCorkle (228), who show that the Verwey-Overbeek theory for the
interaction of two spherical double layers around adjacent spherical colloidal particles leads to isotropic flocculation. New particles can be attached more readily to
the ends of a chainlike floc where the repulsion energy barrier is at a minimum. It is
this type of aggregation that converts a sol to a gel at a certain point by forming an
infinite network of chains of particles throughout the sol volume. (See also Chapter 3.)
370
.;
I.
11
The stages by which sol is converted to dried gel are (a) solidification of sol to a
three-dimensional gel network of branched chains of silica particles in which the
liquid is retained by capillary forces; (b) strengthening of particle-particle bonds at
their points of contact by particle coalescence; (c) shrinkage of the three-dimensional
silica network as water evaporates; (d) development of stresses in the silica network
as three-dimensional shrinkage progresses; and (e) fracture of the dried silica gel into
fragments.
As shown in Figure 4.15, the shrinkage of silica gel is easily observed when a thin
layer of sol is dried on a smooth surface. At one stage, a clear, coherent gel film is
formed, and then as drying continues, this film shrinks with cracks forming in the
direction of drying, so there is left a fragile, fibrous, or hairlike residue of silica gel.
In the case of 100 nm particles, the ribbons may be up to I mm in width, and from
still larger particles, a relatively continuous soft film remains. As water evaporates
from a sol film of given silica concentration, a sol of smaller particle size gels at a
lower silica concentration and the gel thus shrinks more and cracks into smaller,
harder gel fragments. Thus there is a certain small distance over which a gel can
bridge as a coherent solid. Although a silica sol may not form a coherent continuous
film whendried alone; it can nevertheless act as a strong gel that can bridge the
distance between larger particles or fibers. Similarly, although a given sol may form
a fragile, nonadherent deposit when dried as a relatively thick layer on a test surface
such as glass, a very thin layer may dry to a continuous adherent film if the surface
is clean and hydrophilic so that the film remains spread out while being dried. If the
film is sufficiently thin, for example, I micron, when it has been concentrated almost
to the gel point, final drying is so rapid the particles are concentrated to a closepacked state before a gel can form and there. is no shrinkage or cracking; the silica
film is hard and adherent.
In alkaline sols small amounts of salts such as sodiumsulfate accelerate gelling as
the sol is dried. Since for strongest gel structure the sol must dry to the highest
possible silica concentration before gelling occurs, it is evident that in alkali-stabilized sols, electrolytes should be avoided. For example, Reuter (229) claims as a
binder a silica sol of small particles having a pH between 8.5 and 9, with a minimum
of electrolyte, so that its electrical conductivity is due only to the colloidal particles
and their stabilizing counterions and not to electrolyte impurities.
The role of the surface tension of water and surface roughness in the adhesion of
colloidal particles to a flat surface has been considered by Visser (222).
To obtain an adherent, hard film of silica on a surface is obviously difficult if a sol
of uniform particle size is used. Iler (219) takes advantage of the fact that when a sol
of 100 nm in diameter is dried as a thin film on a surface, it shrinks and cracks
much less than a sol of smaller particles, but the film is still soft; by adding a series
of progressively finer silica particles, a mixture is obtained that dries to a hard,
smooth, continuous film. The 100 nm sol alone gave a soft film in which the packing
volume of the silica was about 70%, but by mixing 74% of 100 nm particles. 11.9%
of 22 nm, 2.3% of 10 nrn, and 2.8% of 7 nrn, a hard film Was obtained in which the
silica packing density was 80.4%. Such a film does not craze or crack upon drying
because the spaces between the larger particles are filled by smaller ones, and the
mass cannot be com presssed further by the surface tension forces (Figure 4.16). The \
-:.... ...
ntrated Sols
of sol to a
which the
e 1 's at
mensional
371
(a)
:a network
ca ~el into
'hen a thin
gel film is
ling in "the
. silica gel.
, and from
evaporates
: gels at a
o smaller,
a gel can
(b)
iontlnuous
bridge the
may form
est surface
he surface
ied. If the
ted almost
o
lose; u, ..iliea
(e)
W
S
(d)
: gelling as
he highest
kali-stabiaims as a
minimum
.1 particles
dhesion of
ult if a sol
when a sol
nd cracks
19 a senes
o a hard,
ie packing
res, 11.9%
which the
'on drying
>,' I the
~.l.
The
Figure 4.15. Evaporating film of silica sol to gel and drying: schematic cross-section. (0) sol;
(b) concentrated sol-beginning of aggregation; (c) gel compressed by surface tension; (d)
fracturing of gel by shrinkage; (e) dried loose gel fragments. W, water surface; S. solid
substrate.
packing of spheres of three different sizes has been considered on a theoretical basis
'
by Dexter and Tanner (230).
Colloidal particles of uniform size are useful in making gels of uniform large
pores but the larger the particles, the weaker the gels. However, Yates found that by
adding a relatively small amount of soluble silicate to form silicic acid to reinforce
372
Figure 4.16. Strong, dense gel is formed from mixture of large and small particles.
the interparticle bonds, much stronger gels are obtained (231). Similarly, Sippel
(232) found that a strong gel of greater porosity can be made by using a sol containing particles of two different sizes, using 40% larger particles of diameter D and 60%
particles of 0.4-0.8 D. To some extent the low strength of gels made from larger
particles is partly offset by the fact that larger particles pack together better. Belotserkovskii (233) observes that in xerogels the effective pore diameter tends to remain
the same when the particle size in the originating 'sol is varied. Small particles tend
to bridge over, leaving pores as large as or larger than the particle diameter, and
larger particles (over 50-100 nm) become more closely packed, leaving pores smaller
than the particle diameter.
Very hard coatings can probably be made by applying the gel-forming liquid mixture of potassium silicate, colloidal silica, and setting agent developed by Shoup
(Chapter 2, Refs. 97, 98).
Coagulation
Although the same factors are involved in coagulation as in gelling, the two
phenomena appear much different. In gelling the sol appears to remain homogeneous and often stays essentially clear as it becomes viscous and sets to a firm gel.
On the other hand, during coagulation, by definition. particles become concentrated
in aggregates which have a higher refractive index than the medium. Hence coagulation can be followed by noting the increase in turbidity or decrease .in transmitted
light.
.
The difference in turbidity owing to the formation of doublets from single particles has been studied by Lichtenbelt, Ras, and Wiersema (234). Also. aggregation
has been followed by flow ultramicroscopy (235).
The subject of coagulation has been dealt with by Van Olphen and Mysels (236).
\. ~
trated Sols
373
Mechanism
Colloids have been classed as lyophilic or lyophobic, that is, "liquid-loving" or

"liquid-fearing," or, in the case of aqueous sols. as' "hydrophilic" or "hydrophobic."
The stability of hydrophobic sols depends mainly on the charge on the particles,
whereas with hydrophilic sols this is less important. since the particles are stabilized
by "solvation" or "hydration."
.
Silica is "hydrophilic." although under conditions where salts cause coagulation it
has been classed as "somewhat hydrophobic." The terms are not of much significance in relation to silica, except when organic flocculating agents are involved,
where their adsorption on the silica surface makes the surface definitely hydrophobic.
Coagulation has been considered to be the result of van der Waals attraction
which draws two particles together at the moment of collision, unless opposed by a
hydration barrier layer or by the electrostatic repulsion forces between the similarly
charged particles, or both. There are therefore two factors that retard coagulation-of
silica:
:icles.
ly, Sippel
II contain) and 60%
om larger
.er. Belotto "lain
.icl, .end
ieter, and
es smaller
quid mixby Shoup
the two
in homo1 firm gel.
icentrated
: coagulaansmitted
igle parti;gregation
Is (
).
1. The "hydration" of the surface of the particles by a layer of water molecules
hydrogen-bonded to the SiOH groups.

2. The negative ionic charge on the particles above about pH 3.5 andthe surrounding cloud of positive counter cations such as Na +, forming the "double layer,"
For most dilute silica sols around pH 2, where there is little ionic charge on the
particle. no coagulation by electrolyte is observed, presumably because of the hydration layer. However. Harding (237) has called attention to the fact that relatively
large colloidal silica particles 50-100 nm or more in diameter flocculate at low pH,
whereas small particles do not. It remains to be determined whether the flocculation
is due to the van der Waals attractive energy between the particles or to the formation of multiple hydrogen bonds between the silanol-covered surfaces over the area
of contact at collision.
.
In the pH range 7-10, silica sols are stable if electrolyte concentration is low, but
are coagulated when salts are added. There are generally considered to he two
mechanisms of aggregation:
1. Particle-to-particle attraction by van der Waals forces, described mathematically
by London and extended to colloidal particles by Hamaker (238).

2. Particle-to-particle "bridging" by the flocculating or coagulating agent.
In the first case the attraction leads to coagulation when the repulsion force
between particles. which bear similar ionic charges, is reduced by the addition of a
critical concentration of salt coagulant (c.c.c.), Most of the added salt remains in
solution so that the concentration remains essentially unchanged as flocculation
progresses. The very small fraction of the added salt ions which is adsorbed on the
flocculated particles and carried out of solution is usually ignored. In this case atten-
374 .
, i
,,
tion is usually concentrated on the properties of the dispersion medium rather than
on possible adsorption of ions on the flocculated particles.
On the other hand, when the aggregating agent is a polymer molecule or another
colloidal particle, most of the agent is adsorbed as part of the flocculated particles
until the c.c.c. is reached in the system, at which point only a small fraction of the
flocculating agent may actually be in solution. In this case, the amount of agent
required is directly related to the surface area of the particles being flocculated.
There are also, of course, intermediate situations, particularly when the agent is a
polyvalent ion or small polycation.
The distinction seems to be that if the flocculating agent is a large molecule or
particle and is predominantly adsorbed on the particles at the c.c.c., then the amount
adsorbed in the flocculate can be demonstrated. However, if the agent is a simple
salt such as sodium chloride which requires a large excess in solution at the c.c.c.,
then adsorption on the coagulate is not easy to measure and a possible bridging
mechanism by salt ions is difficult to demonstrate. Van der Waals forces are
assumed to be the source of attraction; in fact, the mechanism may merely involve
adsorbed ions such as Na" holding particles together at their ponts of contact.
The van der Waals forces are often referred to as "dispersion forces," a confusing
term because the forces involve attraction, not dispersion in the physical sense. Such
forces between silica surfaces have been investigated by Rouweler and Overbeek
(239). Similarly, Tabor and Winterton (240) measured the force between mica surfaces but concluded that water reduced the attraction by a factor of 10.
It is possible that dispersion forces play little or no role in the silica system. As
pointed out by Dumont and Watillon (241) silica is the most complicated oxide
system known since it shows a maximum stability at the point of zero charge, it has
a very low Hamaker constant so that the dispersion forces are very low, and at least
in certain pH ranges the aggregation involves chemical bonding. In a more detailed
study Depasse and Watillon (242) point out that one monolayer of water is enough
to screen dispersion forces between small colloidal silica particles (smaller than
25 nm).
Thus dispersion forces probably play no role except possibly in the case of particles larger than 100 nm.
The difference between silica and other oxides is emphasized by the fact that
oxides like Ti0 2 and A120~ are flocculated by salts and pH in a manner that can be.
satisfactorily explained by the OL VO theory whenever the zeta potential falls below
14 4 millivolts, according to Wiese and Healy (243).
j,
Coagulation By Electrolytes
"
I;,
,I
i'1
"
This subject has been investigated for half a century and the mechanism is not yet
fully understood. The lowering of the zeta potential by the addition of electrolytes
supported the idea that particles come together because the charge on particles is
reduced beyond a certain point where the presumed "van der Waals attraction"
between them could overcome the ionic repulsion. Jirgensons and Straumanis (53)
summarized the theories and calculations relating to the double layer advanced by
Gouy in 1910, Oebye and Hiickel in 1923, Burton (244), Hamaker (238), Deryagin
:1
'.~-
"
:entrated Sols
rather than
ec
'other
ted partlcles
iction of the
tnt of agent
flocculated.
ie agent is a
molecule or
the amount
t is a simple
at the c.c.c.,
ble bridging
s forces are
erely involve
.ntact,
, a confusing
I sense. Such
td Overbeek
en mica sursystem. As
~ic?
l oxide
:hal.. ,it has
and at least
lore detailed
ter is enough
smaller than
1
ease of partithe fact that

r that can be
11 falls below
sm is not yet
f electrolytes
n particles is
s attraction"
aumanis (53)
a,d 1ced by
18), .ryagin
375
(245), and Verwey and Overbeek (246, 247). In the case of lyophobic..colloids, the
calculations agree with experimental facts (see Ref. 248) but not in the case of silica.
Theories of the mechanisms by which cations are adsorbed on the silica surface are
reviewed in detail in Chapter 7.
AlJen and Matijevie (249-251) have examined the coagulation of colJoidal silica in
the pH range of 6-11, and find that the mechanism is different from that of
lyophobic colloids. The critical coagulation concentrations for different salts do not
correlate with changes in electrophoretic mobility or zeta potential. Harding (237)
has made similar observations, although he reports that larger silica particles, that
is, 50 nm instead of 12. behave in accordance with the double-layer theory. The
behavior of small silica particles. at least. therefore cannot be explained by the
conventional theory. AlJen and Matijevie (249) find that the cation of the coagulating salt ion exchanges with the silanol surface proton. The coagulating effect of a
variety of cations WQS correlated with the number of ion-equivalents that are
exchanged" rather than the valence of the ion. They propose that with every cation
adsorbed, the silica surface loses one silanol site for hydrogen bonding with water,
and in that sense is "dehydrated," and this increasing "lyophobic" character renders
the sol more sensitive to coagulation by electrolyte.
Direct "interparticle" bonding instead of "dehydration" is proposed as a
mechanism of coagulation of silica by Depasse and Watillon (242). They suggest
that at pH 7-11 and above certain critical concentrations of salts of all the alkali
metals. coagulation occurs because the particles become initially linked together .by
acid-base bonds. rather than Si-O-Si bonds since the fresh coagulate is peptized by
lowering the pH.
I
I
I
I
-Si-OH---O-Si"
(Once silaxane bonds, Si-O-Si.

. are formed they are not broken by acid.) However,
if the bond is as postulated. it is hard to understand why condensation would not occur
at once. since OH- ions are present as catalyst.
It was found that above pH 11. where the surface is covered with basic groups.
sodium andlithium salts continue to bring about coagulation but potassium. rubidium. and cesium salts do not. In this case they propose that since the particles. which
are fully covered with basic groups at this pH. would not be able to form acid-base
bonds. the sodium or lithium ion must be the interparticle bonding agent or "bridging factor." The remarkable difference in the coagulating effects of different monovalent ions was emphasized by Watillon (252). who pointed out that below pH 7 all
the ions Nar, K+, Rb", and Cs" exhibited about the same c.c.c . but above pH 10.
K+, Rb+, and Cs+ had no flocculating effect, whereas Nat and Li+ still did.
,
Monovalent Cations As Bridging Agents

Her proposes the somewhat different hypothesis that in all cases, flocculation is due
to interparticle bonding through the cations, but that above pH II. the larger
potassium, rubidium, and cesium ions at high concentration form a complete double
~-_.
376
layer of sufficient thickness around each particle to cause dispersion and prevent
aggregation. Sols stabilized with an excess of tetramethylammonium ions, which are
still larger, can even be dried to a powder without flocculation (63).
Although not recognized in the double-layer theory. the adsorbed cations of a
simple coagulating salt may be the "bridging factor" in the coagulation of silica.
similar to the somewhat larger isopolycations such as those of basic ferric or aluminum salts. If a bridging mechanism is involved. the amount of adsorbed or "ion.
exchanged" flocculating cation per unit surface area of silica should decrease with
increasing size of the silica particles. There is no apparent way to determine whether
the adsorbed cations in the flocculate are concentrated at the particle-to-particle
areas of contact, as might be expected if the cations form the bridges.
The hydration behavior of the sodium ion must be taken into account if it acts as
a bridging ion. The sodium ion in solution is surrounded by the oxygen atoms of six
water molecules of hydration. It is suggested that when a sodium ion is adsorbed on
the surface of a silica particle, one or more of the oxygen atoms of the water of
hydration can be displaced by the oxygens of the surface silanol groups (SiOH),
which thus become linked directly to sodium. The positive charge of the sodium ion
thus neutralizes the negative charge of the adjacent adsorbed hydroxyl ion which is
responsible for the surface charge and a neutral adsorption complex is formed. If
this can occur, then at high sodium ion concentrations above the "critical coagulation concentration" there is no reason why one or more of the water molecules still
linked to the outwardly disposed side of the sodium ion cannot be displaced by
. silanol groups on the surface of a second colliding particle (see Figure 4.17a). The
sodium ion may thus act as a bridge between two silica particles.
If this theory is correct, a coagulum can form as soon as there are enough ion\.
exchanged sodium or other oxygen-coordinating cations on the surface of each silica
particle to provide more than two points of contact with-other particles. Two points
would permit only chains of particles to form, not aggregates. With greater amounts
of sodium on the surface, each particle could have between three and six points of
contact with surrounding particles, forming progressively denser aggregates.
It must also be kept in mind that above pH 8.5-9.0, the silicate ions formed in
solution accompanied by their cations must be taken into account as though it were
an added salt or electrolyte. This has been discussed by Allen and Matijevic (249).
As pointed out by Depasse and Watillon (242) at pH above 11, only Na r and Li"
continue to act as bridging ions; the larger ions K+, Rb ", and CST do not. Presumably in the latter case the particles are fully covered with a layer of these
adsorbed cations covering corresponding negative charges in the silica surface.
At pH 7.5. Depasse and Warlus (253) reported that the tetramethylammonium
ion is a powerful coagulant as compared with guanidinium, ammonium, and sodium
ions. The corresponding c.c.c. values were about 0.01, 0.32, 1.0, and 2.2 M. The
(CH 3). N + ion is strongly adsorbed and causes coagulation at small concentrations
but the free base can act as a stabilizer at pH 9-10 since the adsorbed monolayer of
'cations provides steric stabilization (205). The fact that the "sodium ion can be coordinated with properly spaced oxygen atoms in diketones, but larger ions cannot, was
'pointed out by Garner (254). He suggested that on the surface of silica the difference
\
-:..,.- ..
entrated Sols
ind prevent
s, which are
'
atio ..:) of a
m of silica,
rric- or alued or "ioncrease with ..
ine whether
OH'
to-particle
if it acts as
toms of six
.dsorbed on
ie water of
ps (SiOH),
sodium ion
on which is
formed. If
al coagulalecules still
isplaced by
U7a). The
(II)
no. .ion. each silica

Two points
er amounts
x points of
:s.
formed in
ugh it were
ic (249).
a+ and Li+
) not. Pre:r of these
.ace.
immonium
md sodium
.2 M. The
centrations
inolayer of
10 be coorannot, was
: d:" 'rcnce
(b)
(c)
(a)
Figure 4.17a. Possible bonding between silica particles through coordination with flocculating
metal cations. (a) Hydroxyl ion transfers negative charge to water layer hydrogen-bonded to
silanol groups on particle surface; equivalent to adsorption of a hydroxyl ion; (b) hydrated
sodium ion is adsorbed at negative site forming neutral complex; (e) collision with uncharged
area of a second particle permits sodium ion to coordinate with oxygens of silanol and surfacebonded water, forming a coordination linkage between particles. Not~: circles represent oxygen
atoms. Colloidal particles are much larger relative to atoms represented here. A number of
sodium bridges may be formed.
377
~-_.
378
in adsorption of sodium versus potassium might be due to the presence of surface

cavities into which sodium can fit but potassium cannot.
The coagulation of commercial alkali-stabilized silica sols of different particle
sizes by Na" ion has been measured by lIer. The particles were nonporous. The
progress of aggregation was followed by centrifuging samples at speeds just Sufficient to cause the discrete particles to settle about I mm and measuring the amount
of aggregated silica sedimented from a 3-in. depth of sol. This was correlated with
the percent transmission of 400 nm light under fixed conditions. Particle sizes of 8,
15, and 25 nm in 0.24 and 0.30 N Na2S0. solution were aggregated at 25, 40, and
55C at a concentration of 12% Si02. The pH was about 9. The temperature coefficient of flocculation was much less between 25 and 40C than between 40 and 55C.
The corresponding calculated energies of activation were 4.7 kcal mole:" and 10.6
kcal mole", In all cases smaller particles were more sensitive to changes in electrolyte concentration and temperature than larger particles. At equal silica
concentrations at 55C, the rate of aggregation was directly proportional to the SUrface area of silica per unit volume of sol and is thus an inverse of particle diameter.
In general, sols in the usual size range of 5-25 nm cannot be processed without
causing some aggregation if the sodium salt concentration exceeds a certain level. It
is for this reason that in order to obtain discrete particles by hot neutralization of
3.25 ratio sodium silicate to pH 9, the corresponding silica concentration cannot be
more than 1-2%. lIer (101) gives an empirical formula relating the maximum normality of sodium ion, N, to the silica concentration C in grams per 100 ml and the
temperature, T, in degrees centigrade, so as to avoid aggregation at least over a
period ofa few hours necessary in a practical process:
N ... 0.26 - 0.D05C - 0.DOI2(T- 40)
. Coagulation by Divalent M eta/ Cations
As shown elsewhere, a characteristic of a divalent cation is that when it is adsorbed

on the surface of amorphous silica, only a single negative charge is neutralized, that
is, one hydrogen ion is released, at least in the first stage.
. At about pH 9 the divalent ion is adsorbed and acts as a positive charge site. Coagulation, of course, occurs long before the silica surface is saturated with divalent
ions because the divalent ion can act as a bridge by reacting with two particles at
their points of contact. For example, Tadros and Lyklema (255) studied the adsorption of calcium ions at various pH, and showed that for each Ca2+ ion adsorbed,
there was induced in the silica surface only 1 :::c 0.05 OH- ion in the pH range 8-9.
The calcium ions do not appear to form polymeric cationic species as do trivalent
metal ions such as AlH.
lIer (169) verified this behavior of calcium in studying the flocculation of silica
particles of different sizes. Somewhat similar behavior of the cobaltous ion has been
reported by Healy, James, and Cooper (256a), who found the charge on quartz
particles was reversed in the presence of 10- M Co2+ ion at pH 7.
There have been other studies relating to coagulation by divalent cations but no
reference to particle size. Thus McFadyen and Matijevic (256b) found that at pH
I:
\-
.,
entrated Sols
: of surface
ent
-ticle
orous. The
; just suffi:he amount
elated with
: sizes of 8, !S, 40, and
ture coeffiand 55C.
-I and 10.6
tes in elec[ual silica
to the surimeter.
ed without
tin level. It
.lization of
cannot be
imum norml and the
ast over a
s adsorbed
.lized, that
e site. Coh divalent

articles at
ie adsorpadsorbed,
"ange 8-9.
) trivalent
of silica
has been
on quartz
._-~-
379
...
5.2, colloidal particles of silica can be coagulated with a copper sulfate concentration
of only 10-3 yet at slightly higher pH hydrous copper hydroxide and silica are
coprecipitated. This confirms . that polybasic metal cations will coagulate and
precipitate colloidal silica at a pH only slightly less than the pH at which the hydrouS metal oxide or hydroxide is precipitated. If the pH is higher than this critical
point which depends on the metal ion, the silica is coagulated along with metal
hydroxide.
Coagulation by Polyvalent Cations-Basic Metal Salts

There appears to be a marked difference between coagulation by a divalent ion Ca H
or trivalent ions AIH or La H and by polyvalent basic polycations of trivalent
metals. The latter assume the characteristics of very small positively charged
colloidal particles and thus bear multiple charges and are adsorbed at the silica surface from such extremely dilute solutions that the adsorption is essentially irreversible.
Aggregation by a simple electrolye or salt is generally termed "coagulation,"
whereas aggregation by the addition of basic polyvalent metal salts is often referred
to as "flocculation:' Actually in dilute solutions of AIH and Fe H salt both
monomeric cations as well as polymeric multiply charged cations are present, the
latter often' being large enough to be identified as positively charged colloidal particles. For this reason coagulation by salts of polyvalent metals as well as by the corresponding colloids are considered together.
It is likely that coagulation of silica by monomeric or single cations, polycations,
or positively charged colloidal particles occurs through a bridging mechanism in the
sense that these positively' charged entities serve both to neutralize the negative
charges on the silica particles at their points of contact and remain in the precipitate.
However, their relative effectiveness depends on what fraction of the coagulating
species is adsorbed on the silica. particles at the critical coagulation concentration in
solution. Since the greater the size and number of positive charges in the coagulant
the higher the fraction adsorbed at equilibrium, the polymeric species are far more
effective than the monomer. Thus O'Melia and Stumm (257) point out that the
polymeric "hydroxo-ferric" complexes are adsorbed more strongly than the
monomeric trivalent metal ion, and function as coagulants at a much lower total
critical coagulation concentration (c.c.c.), than simple Fe H ions because they are
mostly adsorbed on the silica particles, with very little in solution, whereas only part
of the Fe H is adsorbed at the c.c.c. When most of the coagulant in the system is
adsorbed on the particles, the relationship between the c.c.c. and the total surface
area of the silica in the system becomes more obvious. They conclude that the
adsorbed polycation iron(III) species causes particle aggregation by acting as a
~~
These authors also made the unusual observation that silica is coagulated by iron
even when the latter is above its isoelectric point, and thus is negatively charged the
same as silica. They conclude that "specific chemical forces" must overcome the
electrostatic repulsive forces. Adsorption of such iron species on silica having the
same charge must involve formation of Si-O-Fe linkages. This supports the idea
ns -t no
rat
pH
.. --._-380
.. i
Colloidal Silica- Concentrated Sols
that formation of chemical bonds between silica particles through an. intermediate
bridging atom or particle may actually be the "attraction force" rather than the
assumed "van der Waals forces:' at least in the case of silica. Positive colloidal
particles act as bridges between negative silica particles. thus forming a three-dimen_
sional network according to Ruehrwein and Ward (258) and LaMer and Healy
(220). In this case, the coagulant is recognized as part of the precipitate. The ratedetermining step in coagulating silica particles with hydrolyzed aluminum ions has
been identified by Hahn and Stumm (259. 260). They postulate three distinct steps:
(a) formation of the coagulant polycation species through hydrolysis and polymer],
zation of aluminum(III), (b) destabilization of the dispersion by specific adsorption
of isopolycations, which reduces the surface potential on the colloid, a step termed
"adsorption coagulation." and (e) transport of colloid by Brownian motion Or
velocity gradient. Steps a and b are rapid, but step c is the slow, rate-determining
step. The coagulation rate was obtained as a product of the collision frequency and
the collision efficiency factor. They distinguished between "adsorption coagulation"
in the case of agglomeration of colloids with hydrolyzed metal ions, which are
adsorbed strongly on the colloid surface, and the "destabilization" with
nonhydrolyzed metal ions. where adsorption of these ions is significant relative to
the total number of ions present in solution.
However, as pointed out above. estimation of the number of adsorbed "bridging
ions" is difficult if only a very small fraction of the flocculating ions in the system is
adsorbed on the coagulate. that is, forming bridges. Their observations confirm the
great difference in coagulant effectiveness between monomeric species, but do not
rule out the possibility that cationic bridging can occur even with monomeric
cations.
..
Hahn and Stumm (259) observe that only a certain fraction of all collisions
between particles is observed to result in permanent agglomeration. It is possible
that when two particles bearing charges only at certain sites on their surfaces are
oriented so that the adsorbed, ion site on one particle is turned toward the ion site on
the other particle. the ion repulsion prevents close approach. and no agglomeration
occurs. But when orientation is such that a charged site approaches an uncharged
site. collision and union may occur (25 I). Sturn m and O' Melia make the im portant
point that flocculation is a stoichiometric reaction and review the phenomenon from
this point of view (261). Not only is stoichiometry involved, but also specific
chemical interactions between the flocculating ions and flocculated species. Stumm.
Huang, and Jenkins (262) concluded that the Verwey-Overbeek-Deryagin-Landau
(VODL or DLVO) theory neglects the role of specific interactions between the coagulating ion and the colloid surface.
Some coordination complexes of metals with aquo ligands are strongly bonded to
the surface of silica because the aquo group is exchanged for a silanol. Also the
.-,
OhSiO- surface group can displace Cl " in a complex such as trans-Co[(enhCl,]+.
Such adsorbed complex ions are much more stable toward hydrolysis than when in
solution (263).
'
Specific reaction to form metal-oxygen-silicon bonds must be involved in many
cases rather than simple ionic attraction. An analogous formation of Pb-O-AI
bonds occurs when positively charged Pb 2 + is strongly adsorbed on gamma alumina \ .
- ~
below the pZC where the alumina is also positively charged (264).
.centrated Sols
intermediate
her than the
Removal of colloidal and soluble silica by flocculation and adsorption on alumina

was optimum for the colloid at pH 4.5 but for the soluble form at pH 9 according to
Goto (265).
Extensive studies have been made by James and Healy (266a) of the adsorption of
polyvalent metal ions on silica. Fe3+. C~+. Ca H Co". La H and ThH were
adsorbed increasingly with rising 'pH, first neutralizing the charge on silica, then
nucleating the metal hydroxide on the silica surface. and finally covering the surface
with hydroxide.
It has been generally observed that in a mixture of a solution of a 'polyvalent
metal salt and polysilicic acid or colloidal silica at low pH. coprecipitation occurs as
the pH is raised to just below the pH at which the metal hydroxide is precipitated
from the metal salt solution when no silica is present. This relation has been put on a
quantitative basis by Schindler et al. (266b). who found a relation between the equilibrium constants for the adsorption of metal ions on silica and the equilibrium
constants for the formation of the hydroxides (see Chapter 6 for details).
Coagulation of silver 'halide by hydrolyzed aluminum salts was shown by
Matijevie, Kratohvil, and Sticles (267) to be inhibited by fluoride ion which formed
complex ions with aluminum. Similar reduction in coagulation effectiveness of other
metal cations such as Fe H and Th H on colloidal silica may be anticipated.
Iron(III) and uranyl ions are adsorbed on silica even at low pH (4.3 x 10- 2 M
HCIO.) according to Porter and Weber (268). Alumina adsorbed on silica. probably
as polybasic ions, permits attachment of fatty acids so that the silica particles
become sufficiently hydrophobic as to be isolated by "microflotation" (269, 270).
. Heterocoagulation of colloids bearing opposite charges is a very complex
phenomenon because the behavior depends on the relative sizes and concentration of
particles. manner of mixing, and changes occurring after mixing. As shown by Healy
et a1. (271). when colloidal silica and colloidal alumina are mixed. coagulation
occurs. When the coagulate is broken up by stirring it forms again but more slowly
until it will no longer coagulate, One or both oxides dissolve and are deposited upon
the other until all surfaces are alike. so that coagulation no longer occurs. This
mutual interaction was noted by Her (272) in a study of the solubility of silica which
was at first repressed after some of the surface had reacted with AIO z- ions but later
these ions became covered by deposition of silica.
Several factors involved in heterocoagulation of colloidal silicas with colloidal alumina were studied by Harding (273). The relative numbers of particles for optimum
coagulation depend on the relative particle sizes. High concentration of an indifferent electrolyte inhibits mutual coagulation. The effect of particle size has been
reported by Hogg, Healy. and Fuerstenau (274). A similar effect is reported by
Chernoberezhskii, Gollkova, and Girfanova (275) in a mixture of Si0 2 and Fe z0 3
sols at pH 3 which does not coagulate when the KCl concentration exceeds 10- 3 M.
This system was also studied by Madi et al. (276).
.
lloidal
three-dimen-
jVI
r and Healy
teo The rateurn" ions has
istinct steps:
id polymeric adsorption
step termed
1 motion or
-determining
equencyand
:oagulation"
t, which are
ition" with
.t relative to
ed "bridging
:he system is
confirm the
. but do not
rr omeric
III collisions
t is possible
surfaces are
e ion site on
glomeration
1 uncharged
.e important
menon from
ilso specific
ies. Stumm,
gin-Landau
veen the coy bonded to
)1. Also the
>[(en)zCl z]+ .
ran when in
'ed in many
If ",. -O-AI
ma rmina
381
Effect ofSilica Concentration and Other Factors.
Since flocculation involves the collision of particles, it is evident that the rate of flocculation depends more on the number of particles per unit of volume in solution than
on the weight concentration of silica. Thus at a given silica concentration of 1%,
:.----
\
382
there are 1000 times more particles in a sol of 10 nm than in one of l()()oonm. In addition, the smaller particles move with higher velocity (Brownian motion), affecting
the force of collision, which must be high enough to break through the ionic barrier.
No definitive work has yet been done to relate rates of coagulation by electrolytes
to particle size and concentration of silica. Also, no detailed study has been made of
the amount of coagulant in the coagulate.
Coagulation occurs when a sol is frozen. This is simply because the particles
become concentrated between growing ice crystals until they are squeezed together
and interparticle bonding occurs. Though it is possible to add an antifreeze like
glycol or alcohol, this is not ordinarily done in com mercial sols. Redispersion of the
particles also occurs if enough large countercations are present to cover the surface
of the particles so that they cannot come into direct contact (63). Buzagh and Rohrsetzer (277) pointed out that compaction of particles by freezing is similar to
concentrating them by withdrawing water through an ultrafilter membrane (278).
The possibility of redispersion depends on the nature of the film between the packed
particles.
Effect of Particle Size

-i!j
,I
"
"
"
According to the DLVO theory, the critical concentration of a coagulating ion

should be independent of the particle size of the coJloid, but Wiese and Healy (279)
have shown that by further refinement of the theory, taking into account both
primary and secondary minima, colloid stability increases with particle size and
reaches a maximum and then decreases. Such behavior has never been noted in the
case of colloidal silicas with particle sizes in the usual range of 5-100 nm.
Ottewill and Shaw (280) reported some variation in the c.c.c. of Ba2+ ion with
particle size of polystyrene latex (30-212 nm) but there was some argument whether
the effect was real (281). However, Kotera, Furusawa, and Kudo (282) reported a
similar effect in which the c.c.c, reached a maximum at a particle size of 758 nm.
Such size effects seem to involve the secondary minimum in the DLVO theory and
apply only to relatively large particles.
Frens (283) has noted that sols of metal particles can actually be fractionated
according to particle size by coagulation by electrolyte concentration. The results
are explained by the lower van der Waals attraction between small particles of
metal. Harding (237) further investigated this phenomenon in connection with
suspensions by pyrogenic silicas.
.
There are certain conditions in the case of colloidal silica where flocculation
depends directly on particle size. lIer (169) reported that in the case of flocculation
of colloidal silica particles of 4-130 nm diameter with Ca2+ in the pH range of
8-9.5, there' is a marked variation of the C.C.c. with particle size. However, to
observe this effect it is necessary to define the c.c.c. as the amount of calcium ion
still in solution, excluding that adsorbed on the silica surface.
By careful control of conditions, larger particles in a mixture can be preferentially
coagulated and separated from smaller ones. For coagulation, a critical number of
calcium ions must be adsorbed per square nanometer, of silica surface, independent
of particie size: but to attain this degree ofadsorption, a higher concentration ofcal-
l.,
~-_.
ntrated Sols
n. In addiI, affecting
'er.
ic:
:Iectrolytes
en made of
e particles
:d together freeze like
sian of the
.he surface
and Rohrsimilar to
ane (278).
the packed
.lating ion
lealy (279)
ount both
= size and
ite the
ion with
at whether
reported a
If 758 nm.
heoryand
to
actionated
'he results
articles of
.tion with
occulation
occulation
range of
iwever, to
ilcium ion
ferentially
lumber of
del
dent
ion
cal-
383
dum must be maintained in solution when the particles are smaller. On the silica
surface, which already contains negative charges, each adsorbed calcium ion
liberates only one hydrogen ion, creating one additional negative charge on the surface, so that each adsorbed calcium ion retains one positive charge (see also Ref.
255). On the more highly curved surface of smaller particles, each calcium ion,
adsorbed outside the particle surface, is repelled by its neighbors with a resultant
force away from the surface so that a higher concentration of calcium in solution is
required to maintain the critical concentration of adsorbed calcium for coagulation.
Coagulation is probably due to attraction between surfaces bearing a mosaic of positive and negative sites.
This behavior is probably restricted to large divalent and possibly polyvalent
cations since in the case of sodium ions there is no evidence that the concentration of
negative charges on the surface, at a given pH and sodium ion concentration, varies
with particle size. Other large cations have not been investigated in this way. The
critical coagulation concentrations for different particle sizes are shown in Figure
4.17b. Flocculation by the Ca2+ ion apparently does not lead to permanent siloxane
bonding between silica particles. The calcium ion, unlike the sodium ion, is large
enough to prevent direct contact between silica particles so that direct Si-O-Si
bonding does not occur. Thus Alexander and lIer found that silica particles can be
coagulated from dilute solution (80) and the coagulate can then later be redispersed
in water by removing the calcium ions.
The phenomenon of a calcium ion neutralizing only one charge on the silica surface, thus retaining one positive charge, has also been noted by Boehm and
Schneider (284), and the theory that particles can be attracted to each other by a
mosaic of positive and negative charges has been suggested by Goodman (285). The
cationic charges imposed. on the silica surface by adsorbed calcium ions is
demonstrated by the fact that the surface can then adsorb fatty acid anions, making
the surface hydrophobic. This phenomenon is used in a flotation process for removing silica from metal ore (286).
Partly Dehydrated Surface
There appear~ to be a significant difference between silica particles that have been
made in an aqueous medium and those made at high temperature, that is, pyrogenic
silica, when initially dispersed in water. Part of the surface of pyrogenic silica can
remain as a nonhydroxylated siloxane surface for some time so that only part of the
'surface is covered with ionizable SiOH groups. The difference has been clearly
demonstrated by Tschapek and Torres Sanchez (287), who showed that the
dehydrated silica acted as though it were hydrophobic. At low pH where there is
very little surface charge, the silica is flocculated by traces of salt.
For this reason sols made by suspending pyrogenic silica in water are more difficult to disperse until the surface hydration has been catalyzed with alkali.
As further evidence, Ru bio and Goldfarb (288) reported that in aqueous dispersions of pyrogenic silica such as Aerosil, the amount of quaternary ammonium ions
required for coagulation was much less than in the case of hydrated silicas; also the
sol was restabilized with much smaller excess of these organic cations.
i
~
"
--Colloidal Silica-Concentrated Sols
384
100
1 .
a:
<l:
..J
..J
10
z
0
fi
a:
IZ
au
Ii
. :;
u
c
u
8.5
. 9.5
pH
(bJ
Figure 4.17b. Critical coagulation concentrations of calcium versus pH for different particle
sizes of colloidal silica:
Curve
A
B
E (extrapolated)
Dashed (Allen and
Matijevie)
t.
Specific Surface
area
(m" g-I)
Particle
Diameter"
(nm)
540
404
215
114
0
210
5
7
13
24
:II;
13
'" Calculated from specific surface area.

:
..
,,
;.
Flocculation
,.
~1
i'
I'
Flocculation of a silica sol occurs with the addition of a polymeric or particulate

colloid, the micelle or particle of which is adsorbed simultaneously on the surfaces of
two different silica particles, thus linking them together. Such adsorption occurs
either because the agent is cationic and thus attracted to the negatively charged silica
surface, or because it contains electron donor groups such as the oxygen of a
polyether, and is held to the silica surface by hydrogen bonding. The latter does not
j:
\.
--
";...--
icentrated Sols
385
occur at high pH where the silica surface is highly charged, but onlt at low pH
where the surface consists of neutral silanol groups. Thus organic flocculating agents
are (0) cationic surfactants which form micelles, (b) cationic organic polymers, and
(e) nonionic water-soluble organic compounds, or polymers containing electrondonor groups such as ether, hydroxyl, or amide. These are summarized in Table 4.2
and the mechanisms are represented in Figures 4.18-4.20.
The mechanism by which silica particles are held together depends on the type of
flocculating agent:
., ~
ferent particle
1. If the agent is adsorbed on the surface and oriented so that hydrophobic areas are
produced, these areas on different particles come together to form a micelle. The
particles are held together by the' powerful surface tension forces around the
negative radius of curvature at the zone of contact, the so-called "hydrophobic
bond." It is also possible to consider this as the adsorption of two silica particles
on opposite sides of a surfactant micelle in solution. However, flocculation can
occur when the concentration of cationic surfactant is less than the critical
concentration for micelle formation in the absence of silica particles, suggesting
that the micelle is stabilized by being at the point of contact between solid particles
2. The second and more commonly recognized mechanism is where the organic
polymer or inorganic colloidal particle attaches itself to two different silica particles and acts as a bridge.
For a particular sol under given conditions, gradual addition of flocculating agent
first leads to flocculation of only a portion of the colloidal particles, and if more is
added, increasing amounts' are precipitated until no more single colloidal particles
are left in solution. Complete flocculation occurs only when there is enough
Table 4.2. Classes of Flocculating Agents
Type of Agent
Low molecular weight
Cationic surfactant
Nonionic surfactant
Basic metal salt
.' particulate
e surfaces of
rtion occurs
aarged silica
lXyr--'l of a
ter es not
High molecular weight

Cationic polymer
Nonionic polymer
Cationic inorganic
colloids
Example
Octadecyl trimethylammonium bromide
Nonionic detergents
Basic aluminum
chloride
Quaternary ammonium
substituted polyacrylates
Polyethylene oxide
Colloidal alumina
pH
Mechanism
Ionic attraction,
micelle formation
Hydrogen bonding,
micelle formation
Ionic attraction
4-10.5
Ionic attraction
3-9
Hydrogen bonding
Ionic attraction
<S
3-7
<3 (plus salt)

<7
.,.
-_.
386
(1)
(2)
(3)
Figure 4.18.. Flocculation of silica particles: Bridging by (I). cationic surfactant micelles (for
example, cetyltrimethylammonium ions); (2) cationic three-dimensional polymer molecules (for
example. cationic starch); (3) cationic linear polymers (for example. polyethylene imine.)
adsorbed flocculant to create bridges at an average of three points of contact per

particle. so as to form a three-dimensional network. Thereafter. more of the flocculant is adsorbed on the precipitate until the whole surface 'is covered. Depending on
the nature of the flocculant, further addition may result in redispersion of the particles. each of which is now surrounded by an adsorbed layer of "flocculant" and the
particles now have a positive charge.
\..__
rated Sols
+
+
+
Figure 4.19.
Flocculation of silica particles by colloidal particles of opposite ionic charge.
,,
,
'O-CH,
o~
o~
'9, It. It.0

Olt
o
II
CH,
0"'"0..10I
If 1-(0
--O:lfo
Ow \
OH CH,
H Ho
R-O: HO
OH CH,
celles (for
ecules (for
OH: 0
CH,
te.)
OH /CH,
OH : 0
ntact per
ie floccu.nding on
the 'rti a. .he
0lt. It
'0-
\
\
-" CH,
,
\
Figure 4.20. Flocculation and coacervation of silica particles at low pH by hydrogen bonding
to ethers, alcohols, and arnides.
387
388
It is therefore obvious that the term "flocculant" describes the action of the agent
only when a critical amount is present, since with further addition, the agent
becomes a stabilizing agent.
To prevent peptization in the presence of excess flocculating agent, Ruehrwein
and Ward (258) have shown that if the colloid is first coagulated so that the panicles
are in contact with each other before the polymer is introduced, then the polymer is
adsorbed around the points of contact, strengthening the bridges between particles.
However, the polymer does not become inserted between particles, and so does not
cause redispersion. On the other hand, if the particles are separated when the agent
is added, 'all surfaces can be surrounded and a sol is produced when an excess is
added.
A general model of floc structure has been proposerd by Sutherland (289), who
assumed that coagulation occurs with addition of single particles to doublets, triplets, and larger aggregates and also that aggregates can collide and become joined.
The theory of flocculate density and ease of filtration has been developed by Smellie
and LaMer (290).
Flocculation with Cationic Surfactants

The interaction of hydrophobic groups adsorbed on the surface of silica involves
hydrophobic bonding. Tanford (291) has described the effect in detail. Long-chain
amines, and particularly long-chain alkyl-substituted quaternary ammonium salts,
are powerful flocculating agents for colloidal silica. Thus Smith and Turnbull (292)
add a quaternary ammonium salt to cause a degree of flocculation so as to make the "
colloidal silica thixotropic when used as a binder in refractory powder slurries.
The course of adsorption of a surfactant on the surface of a colloidal particle has
been described by VoId and Sivararnakrishnan (293) in 'discussing micellar adsorption. The polar surface is covered by the adsorbed surfactant oriented on the surface
so that the exterior is hydrophobic. At a slightly higher concentration, additional
adsorption occurs on this primary sorbed layer to form a condensed double layer
over the surface, with the polar groups of the surfactant now oriented outward, thus
making the surface hydrophilic. They presented experimental evidence to show that
as more surfactant is added to the system, the concentration in solution decreases
past a certain point because of the sudden aggregation of the adsorbed material to
form the double layer of the surface micelles.
It is well known that hydrophobic particles adhere to each other in water once
they have established contact, so it is not surprising that silica particles rendered
hydrophobic even only on certain limited areas on the particles are flocculated. Thus
at low concentrations, ions such as dodecylammonium affect the zeta potential of
quartz particles in the same manner as sodium, but with higher concentrations there
is a critical point where the potential changes abruptly and the long-chain ammonium ion apparently associates into patches of ions on the interface, in much the
same way as micelles are formed in bulk solution (294).
'
The powerful flocculating action of small amounts of cetyltrimethylammonium
chloride in a silica sol is utilized by Alexander and Iler (295) to bring the silica parti- ,,~
c1es together under such conditions that they form sheet- or filmlike aggregates. An
-:..---
rated Sols
the agent
he agent
uehrwein
particles
olymer is
particles.
does not
.he agent
excess is
89), who
ets, tripe joined.
/ Smellie
389
electron micrograph of such planar aggregates is shown in Figure '4.21. The

mechanism by which such aggregates are formed is described in Figure 4.22. The
silica particles are held together by the micelles of the cationic surfactant. The
amount of surfactant required is only 5% of that theoretically needed to form a
.monolayer over the total silica surface. The micelles probably occupy the silica surface only at the points of contact between particles. This particular type of planar
flocculation is carried out in alkaline solution where the silica particles are negatively charged, and therefore repel each other, yet with sufficient force to overcome
the micellar bonds. Under these conditions the aggregate grows as a sheetlike layer
of particles only one particle thick, since particles can approach and attach
themselves to the growing sheet only around the edges of the sheet where ionic repulsion is least. Once the sheets or "planar aggregates" have been formed, more silica
involves
ng-chain
irn salts,
ull
(~92)
TI<.
he
:s.
-ticle has
. adsorpe surface
ddltional
ble layer
ard, thus
how that
lecreases
uerial to
.ter once
rendered
ed. Thus
ential of
ms there
1 ammonuch the
m 'urn
ca, ti-
.ates. An
Figure 4.21. Electron micrograph or sheetlike aggregates of colloidal silica formed in the
presence of a cationic surfactant...
390
'0-
- -- . --.
..
-..
--._. .......
-sr: .
:.
--.~
.,
I'
"
u.
i
!'.
if":
Figure 4.22. Mechanism of aggregation of silica particles into sheets. Particles can approach
the edges of a sheet of particles where the repulsion energy barrier is less than on the face. Coalescence between particles in sheet is shown in cross-section.
;:
"
i
I.
",
. :
I""
I; !:, ", '

.. .r . ;
.. ~ j , ,
ii
,
~.,.'
11"
I'.'
','
:; 1: :
-nj .., .
l!
:~n ~
is deposited on them, cementing the particles together and filling the spaces between
them, so that "an impervious flakelike particle of colloidal thickness is obtained.
The hydrophobic and hydrophilic nature of silica on which cetyltrimethylammonium ions are adsorbed has been studied by O'Connor and Sanders (296). When a
silica or clean glass surface is brought into contact with an aqueous solution of 10- 7
M cetyltrimethylammonium bromide, the silica surface is covered by adsorption of
the organic agent until a monolayer is formed. The surface at this point is hydrophobic. However, when more of the agent is present in the solution the surface does
not drain dry when pulled from the solution and, in fact, remains wet if the
concentration of the agent is greater than 10- 4 M. The critical micelle concentration
is around 10- 3 M, and so it is evident that at very low'concentrations, a single
monolayer of this agent is adsorbed on silica with the hydrophobic groups outwardly
disposed, giving a hydrophobic surface provided there is no additional agent in solution. If more agent is present, however, at a concentration of 10- 3 M, then a twofold
"
..
.ated Sols
approach
'ace. Coa-
between
ed.
/lamrno-
When a
of 10- 1
.ption of
s hydro'ace does
~t if the
1
mtration
a single
rtv ily
: in .IU. twofold
':.--_.
391
layer is formed, so that the outwardly disposed cations render the surface hydrophilic again and it remains wetted.
Colloidal silica flocculated through "hydrophobic bonding" between the hydrophobic spots on silica particles is characterized by the fact that the addition of a
watermiscible alcohol such as propanol redisperses the flocculate by "wetting" the
surface. The hydrophobic propyl groups are oriented toward the hydrophobic surface so that the outwardly disposed alcoholic hydroxyls render them hydrophilic.
When such silica is recovered and dried the alcohol evaporates leaving a fully hydrophobic surface.
For adsorption of a cationic surfactant on a colloidal particle, the particle must be
at least of a certain minimum size, as pointed out by Matijevic and Ottewill (297).
When there is only sufficient surfactant present to render the surface of the colloidal
particles hydrophobic, coagulation occurs; but when more is added to form a second
layer owing to van der Waals attraction between the hydrocarbon chains, the ionized
groups of the' second layer are then oriented toward the solution, and the particles
are separated and peptized with a reversed surface charge.
The nature of the "hydrophobic bond" in aqueous solutions between hydrophobic
molecular areas was recognized by Klotz (298), discussed in relation to proteins by
Scheraga (299), and further elaborated by Nemethy and Scheraga (300). Kauzmann
(301) defined hydrophobic bonding as the tendency of nonpolar groups to adhere to
one another in aqueous environments. This is similar to the formation of
intramolecular micelles analogous to those in aqueous solutions of detergents. A
. general discussionof hydrophobic bonding is presented by Kaufmann (302).
Studies show that long-chain quaternary ammonium ions, such as cetylpyridinium, are adsorbed on the,'silica surface at about the critical micelle concentration
(303). An alkyl ammonium ion occupies, about 33-45 A2 area of silica surface (304).
Actually at the silica surfacethese ions are adsorbed as dimers (305).
As a result of flocculation by a cationic surfactant such as cetyltrimethylammonium bromide, a silica sol can .be rendered highly thixotropic. which is a useful
property in some binder applications (306).
In studying flocculation of silica by cationic surfactants it is of interest that an
excess of the surfactant can be titrated with an anionic surfactant using bromophenol blue asan indicator (307).
Flocculation with Organic Polymers

The broad aspects of adsorption-flocculation reactions of macromolecules at the
solid-liquid interface have been reviewed by LaMer and Healy (220). For each
polymer-colloid system, maximum flocculation occurs over a narrow concentration
range of flocculant,
The initial stage where too little polymer is present to cause flocculation involves
adsorption of polymer upon particles, but with an insufficient number of molecules
to form bridges between all the particles. This can be a purely temporary situation,
since upon further agitation, at least in some instances, polymer is adsorbed
preferentially at the points of contact between particles, and thus some of the particles are flocculated, leaving the remainder dispersed. When excess polymer is
392
present. flocculation may occur through temporary formation of bridges linking

particles. but with further agitation. these bridges may be broken and the whole
particle surface covered with adsorbed polymer, so that redispersion occurs. The
ionic strength of the solution is also important, since this has a marked effect on the
coiling or uncoiling of linear ionic molecules, thus affecting their behavior in form.
ing bridges.
As the chain length of the flocculating polymer increases fivefold, the concentrs,
tion required for good flocculation of colloid may be decreased a hundredfold.
particularly in the range where the molecular weight of the polymer' is less than
1000. This is because with lower molecular weight. each polymer molecular cannot
bridge more than two particles. Beyond this chain length, the effect of molecular
weight becomes much less important. This suggests that for the flocculation of finely
divided silica suspensions the flocculating polymer must have a chain length suffi,
cient to form a bridge between the particles, and this factor is marked only when the
cationic polymer is present in sufficient amount to neutralize the charge on the silica
particles. Polymers of very high molecular weight tend to cause redispersal of the
flocculated material. (308).
.
Flocculation is dominated by the extent of adsorption of the polyelectrolyte leading to bridging between particles and not by electrostatic interaction. according to
LaMer (309), who presented a mathematical analysis of the steady-state kinetics of
flocculation and deflocculation. According to these considerations, flocculation is
not directly explainable by the DLVO theory. Electrostatic interaction, with which
the DLVO theory is mainly concerned, is not the primary factor in flocculation, but
specific chemical interactions between colloidal particles and flocculating agents. \.
The DLVO theory essentially neglects the role played by the adsorption of materials
from solution on the colloidal particles, and considers the materials added to solution only as having an ~influence on the properties of the aqueous medium and the
electrostatic and molecular forces between the colloidal particles. A general review
of the physical aspects of flocculation of colloids by polymers has been written by
Linke and Booth (310).
A broad review of the effects of macromolecular compounds in disperse systems
has been presented by Heller (311). He discusses the adsorption characteristics of
polymer .molecules which on the one hand, are adsorbed at the surface with a terminal segment only, with the remainder of the chain protruding from the surface
radially, and on the other hand, are adsorbed lying flat with all segments attached to
the surface. Both situations can occur, of course, depending on the nature of the
polymer and how much of an excess over the amount required to form a flat
monomolecular layer is present.
The various possible situations regarding the interaction of a polymer with silica
particles have been examined and described by Botham and Theis (JI2). They point
out that according to the bridging model, high molecular weight polymers flocculate
colloidal dispersions by bridging adjacent solid polymer segments if sufficient length
and number are available, and if there is free surface on the particles for bridge sites.
On the other hand, the flocculated system becomes dispersed if the surface becomes
so covered that there is insufficient free surface for bridging, Initially, bridges may'-,
be formed between particles. but there may be a redistribution reaction so that
.,.
...-
..'"
-:
-----ated Sols
linking
te whole
rrs 'ie
:t on the
in form-
localized excess concentrations of polymer forming bridges during initial stages are
redistributed uniformly over the particle surface. Also. if surface is available,
polymer chains tend to curl back and be absorbed on surface sites on a single
particle rather than remain as bridges between two particles.
"The interaction of silica and proteins through hydrogen bonding has been
reviewed by lIer (8) and more recently investigated by Kragh and Langston (313).
and Bergman and Nelson (314). Bridge formation is indicated by the results of
Kragh and Langston, who observed that flocculation occurs when only one-third of
the "maximum possible amount of gelatin is adsorbed on the silica surface. When
maximum gelatin is adsorbed. the thickness of the adsorbed layer is greater than a
monolayer and parts of the chain extend into the solution. They also demonstrate
that the polymeric flocculating agent is not adsorbed initially in monolayers, but
there is first formed a disordered structure with molecular chains projecting from the
particles, th~s permitting the formation of polymer bridges to be formed upon collision. However, when these links are disrupted by agitation, a slow rearrangement of
the surface layer occurs involving adsorption of the free chains, so that the surface is
completely covered with a layer of gelatin and no bridges can then be established
between particles. They emphasize that the effect of pH on flocculation is primarily
due to its influence on the configuration of the adsorbed layer of gelatin rather than
to its effect on the net charge of the silica particles. The gelatin chains may be
12,000 A long and particles may be flocculated by these chains through bridging,
even though they are 500 A apart. Under these conditions, flocculation occurs even
though there is a relatively high ionic charge on the particles. Bergman and Nelson
reported the unusual observation that globulin shows an intense affinity for silica,
far greater than that of albumin or gelatin, and proposed that this may be related to
the physiological effect of silica particles in tissues.
ricentraJredfold,
ess than
~ cannot
olecular
of finely
th suflivhen the
he silica
11 of the
fte leadrding to
retics of
lation is
h which
JOIl but
a. :s.
iatenals
to soluand the
I review"
itten by
systems
istics of
hatersurface
iched to
e of the
1 a flat
th silica
ey point
Jcculate
.t length
ge sites.
iec
-es
ay
so that
ges
393
-.
CATIONIC POLYMERS. .The relation between zeta potential and flocculation by a

polymer has been studied by Ries (315), who pointed out that as soon as a colloidal
particle is coated with polymer it bears the same charge as the polymer and is redispersed. Similar studies by Ries and Meyers (316) involved the use of microphoresis
and electron microscope observations of model colloids and polymeric flocculants.
Polyamine type flocculants appeared to extend out from the particle surface for a
distance of 20-300 A. Flocculation occurs simultaneously through charge neutralization and bridging of polymer chains from particle to particle; then excess polymer
reverses the potential and redispersion occurs. Adsorption of poly [(1,2.
dimethylvinylpyridinium) methylsulfate] on silica was similarly studied by Shyluk
(317). who concluded that the polymer chains lay flat along the surface when no
excess polymer was present.
The mechanism of adsorption of polymers containing quaternary ammonium ions
on silica at low pH is by no means clear. The point of zero charge of silica is about
pH 2, yet Derevyanko et al. (318) report that the adsorption of poly(2-methyl-5vinylpyridinium choride} is at a maximum at pH 2.9 and 'that a monolayer of
polymer was adsorbed on silica at pH 0.5 or 2.9.
During equilibrium adsorption of long-chain flexible macromolecules from dilute
solution onto a solid surface, only some chain segments are at the solid interface
394
I'
i:
Colloidal Silica-Concentrated SOls
while others are far out into the solution, according to Silberberg (319)."He discusses
the 'possibility that this concentrated layer of polymer at the surface may attract a
more extensive surface phase especially if the concentration is close to the critical
concentration for phase separation, that is, coacervation.
The theory of the structure of flocculated particles has been presented by Suther_
land (289). Floes may vary widely in density, which decreases as the particles tend to
aggregate into chains. Particle chains and expanded floes are likely to form irresps-,
tive of the nature of the flocculated system, and need not depend on polarization of
the particles.'
.
Gregory (320) concluded from his studies of the coagulation of latex particles that
flocculation and restabilization can be explained simply in terms of charge neu, .
tralization and charge reversal. It can only be concluded that the interaction with
latex particles is different from that with silica particles.
lIer (321) investigated the effect of the particle size of colloidal silica on the
1<
amount of cationic polymer required for flocculation and charge reversal. The'$~-~
polymer was poly[(m.ethyl acryloyl oxyethyl, diethyl, methyl ammonium) "'/.:,, . ~
methylsulfate] (322). For particles smaller than 500 A in diameter, the amount of
flocculant having a molecular chain length of 1500 A required to precipitate a unit
weight of silica is inversely proportional to the particle diameter, whereas for larger
particle sizes, it is inversely proportional to the square of the diameter. It appears
that with this particular 'flocculating agent, particles larger than 400 A in diameter
.require one or more polymer chains to form the bridge at contact points, whereas
with smaller particles, only a few segments of the chain are required at each bridging
point, and a single chain can extend from one contact point to another, thus linking
several silica particles together.
In this study a simple spot test was used to detect either excess silica or excess
polymer in the supernatant liquid after flocculation. It was based on adsorbing a
monolayer of the material in excess on a polished black glass plate and making its
presence or absence visible by applying a monolayer of 150 nm silica particles, which
gives a bright interference color in reflected light. I have since found that a cationic
polymer can be titrated in a 20:80 mixture of benzyl alcohol and water with a 0.02
N solution of sodium tetraphenylboron at about pH 4, using bromophenol blue as
indicator..Alternatively, sodium dodecylsulfate can be used instead of sodium tetraphenylboron. However, it is not possible to carry out the titration in the presence of
silica since these reagents remove the cationic polymer from the silica surface.
Polyethylene imine (PEl) is strongly adsorbed on the surface of silica. Lindquist.,.
and Stratton (323) have carried out flocculation studies using polymers ranging in
molecular weight from 1760 to 18,400. The silica was Ludoxe AM, an aluminatemodified sol which maintains a negative charge over the pH range 3-10. At most pH
values, PEl is completely and irreversibly adsorbed on the silica particles. The
critical flocculation concentration (c.f.c.) depended on the molecular weight of the
polymer above pH 9 if no salt was present. At the c.f.c. the silica particles still bear
a negative charge. Coagulation above pH 9 appears to be due to bridging of particles
by the polymer which bears only a low charge at that pH. A linear relationship with
negative slope was found between log c.f,c. and log of the cationic charge on the \-,'
PEL
.,.
rated Sols
:iiscusses
attract a
e ( :al
..~
cles'that
rge neuion with
on the
sal. The
roniurn)
rount of
te a unit
Jr larger
appears
iiameter
whereas
brjrl"'ing
) 11 ng
,r excess
orbing a
iking its
s, which
cationic
h a 0.02
blue as
m tetrasence of
indquist
nging in
irninatenost pH
'es, The
.t of the
till bear
oarticles
hir 'th
: o. . he
395
POLYMERS It is only at neutral or low pH, where the surface

bears little or no negative charge, that silica can be flocculated by a number of
polymers which are either nonionic or only weakly cationic in this pH range. Iler
(324) discussed this phenomenon and showed that when the silica surface is charged
by raising pH or by modifying it with aluminosilicate ions so that it remains charged
at low pH, interaction with these polymers is greatly reduced. The interaction with
silica appears to be due to hydrogen bonding between electron donor atoms in the
polymer and neutral silanol groups on the silica.
.
Silica interacts with laminarin, a linear polysaccharide consisting of 20 units of
beta-D-glucopyranose linked through C-I and C-3 atoms, at pH 5-6, according to
" Holt and Went (325). As will be mentioned in connection with coacervation, silica
also combines with polyvinyl alcohol at low pH. Polyethers are adsorbed onto silica
from water and the molecules lie flat along the silica surface (326). Studies of the
interaction of polyethers with silica in carbon tetrachloride, using infrared absorption, show hydrogen bonding between ether oxygen atoms and the hydrogen of surface silanol groups (327). Of special interest is the work of Rubio and Kitchener
(328), who studied the flocculation of aqueous suspensions of silica having different
types of surfaces, by high molecular weight polyethylene oxide (PEO). The polymer
is bound to the silanol groups by hydrogen bonding through ether oxygen atoms.
Also in the areas where the silica surface is hydrophobic, there appear-s to be hydrophobic bonding with the -CHzCH z- hydrocarbon chain. Like Iler (324), Rubio and
Kitchener concluded that ionization of the SiOH groups reduced the affinity for
nonionic compounds. This was interpreted as a "salting-out" effect. It can also be
visualized as being due to steric hindrance by the counter cation in solution near the
charge site as proposed by Her (324).
Polyacrylamide (PAA) is a widely used flocculant and. its interaction with silica
has received special attention. Kuz'kin et al. (329) reported that PAA flocculates
negative mineral particles below pH, 8 and effectiveness increases with molecular
weight. It has weak cationic properties at pH 1.2. Griot and Kitchener (330) showed
that hydrogen bonding was the mode of interaction of flocculation by this polymer.
The effect of polyacrylamide in neutral solution was most marked on pyrogenic
silica on the surface of which there is only a limited population of silanol groups.
The polymer forms hydrogen bonds with these groups as shown by the fact that coagulation is reversed by competitive low molecular weight hydrogen-bonding agents.
.It is remarkable that when the surface of the silica particles became fully hydrated,
no flocculation occurred with polyacrylamide. When the silica was again dehydrated
at 300C and redispersed, it could again be flocculated. The difference is so striking
that rehydration of the silica surface, as catalyzed by HF or OH- ions, can be
followed by the coagulation behavior. Hydrogen bonding apparently occurs only
with isolated silanol groups, but it is possible that hydrophobic bonding of the
hydrocarbon chain segments with the hydrophobic areas of siloxane surface also
plays a role. On the other hand, the polymer flocculates negatively charged allurninosilicates by an ionic mechanism since it is not inhibited by hydrogen-bonding
agents. A copolymer of acrylamide and a cationic monomer is a more effective coagulant for silica at pH 6-7.2. In this range both ionic and hydrogen bonding can
occur (331).
HYDROGEN-BONDING
, Sutherstend to
irrespecration of
7.----
,
396
LIME AND FATTY ACIDs. At high pH (over 11) silica adsorbs calcium iohs which in
turn adsorb stearate ions, making the silica hydrophobic enough to be removed from
iron ore by flotation. Starch at this pH is apparently adsorbed on the iron oxide preventing interaction with stearate so that iron remains in suspension, according to
Sorensen and Frommer (332).
Silica "slimes" can be flocculated by guar gum when calcium is present. Although
guar gum is presumable nonionic it combines in some manner, possibly by coordination through hydroxyl groups to silica particles on which calcium ions are .adsorbed
at high pH (333). Interaction of polyhydroxy compounds with calcium or strontium
atoms on the surface of silica at high pH might be worth investigating in view of the
known formation of strontium saccharate, which must involve coordination of sugar
hydroxyl oxygen atoms with the metal ion.
FLOCCULATION IN ORGANIC LIQUIDS. Ross and Schaeffer (334) have described the
behavior of different finely divided particles in organic liquids covering a range of
polarity of solids and liquids. The more highly polar the surface of the particle, the
more completely it is wetted by a polar liquid and the greater the deflocculation and
the more compact the sedimentation volume. On hydrophobic particles, small areas
or spots of hydrophilic surface greatly affect the behavior in liquid media. Thus a
hydrophobic solid in a nonpolar liquid. such as hydrocarbon, with no hydrophilic
spots gives a densely settled flocculate, but with a few hydrophilic spots to cause them
to chain together. the flocculate is much more voluminous. If a surfactant is added to
cover the hydrophilic spots and render them hydrophobic then the sedimentationvolume again decreases.
The addition of water to immiscible nonpolar liquids increases the sedimentation
volume of the solid of the .particles containing polar spots.because the water helps
form bridges. On the other hand, if partly hydrophobic particles are dispersed in
water, the sedimentation volume is high because of association between the hydrophobic spots on particles. This is reduced when a polar solvent such as dioxane is
added, which renders all of the surface water-wettable by adsorption of the polar
organic material at the hydrophobic areas. These factors are important to consider
when silica is used as a thickening agent.
In nonpolar liquids or oils thickened with silica certain additives cause a breakdowIl of the thickened gel or grease. The effect of polar compounds and of traces of
water in-the system have been studied by Wightman and Chessick (335).
t.
Coacervation
The term "coacervation" means the formation of a "liquid precipitate" by the

mutual coagulation of colloids. Coacervation actually involves coagulation, but with
the further provision that the bridges between particles or colloidal units are labile so
that they can exist in equilibrium. being formed and reestablished so that the
coagulum can continue to contract its network to the greatest possible extent. The
major liquid phase is thus excluded from the network of coagulating particles until
the coagulum is highly concentrated. yet fluid because the bridges or bonds between
(...
--
' '-
., :...--
397
ated Sols
Nhich in
colloidal particles are not permanent, but can constantly break and reform. The
classic example is the liquid phase that separates when concentrated solutions of
gelatin and gum arabic are mixed.
A wide range of hydrogen-bonded coacervates has been described by Iler (8).
These are formed when acidified colloidal silicas or polysilicic acids are mixed with
certain polar organic compounds that are miscible in water yet can be salted out of
solution, carrying the silica along with. them.
One of the best examples of a coacervate is the hydrogen-bonded association complex between the diethyl ether of diethylene glycol and polysilicic acid (8). When salt
is added to the mixture in acid solution, two organic layers separate from the brine,
the heavier phase containing about 40% silica but the upper phase containing only
about 1.5% (see Figure 4.20).
Coacervation apparently occurs only when the surface of the silica particles is
covered with an adsorbed layer of organic molecules in which the polar groups are
oriented toward the silanol surface by hydrogen bonding but sufficiently mobile to
rearrange until the outwardly disposed portions of the molecules consist mainly of
hydrophobic hydrocarbon segments. As a result the particles become somewhat
hydrophobic and separate as an oil-like coacervate phase. In the case of polyvinyl
alcohol (PVA) and colloidal silica, Her (336) has shown a coacervate forms at pH
3-5 only when there is just enough polymer present to cover the silica. surface. This
has been discussed in detail in Chapter 3. In view of the critical effect of electrolyte
on the flocculation of silver iodide sol by PYA described by Fleer (337), an analogous study with silica might be of interest. Fleer and Lyklema (338) reported that
PVA is adsorbed strongly on silica most strongly at pH 3 and is partly desorbed at
pH 8, indicating that hydrogen bonding is involved. The same observation was made
by Tadros (339), who extended his studies to mixtures of PV A and the cationic
surfactant cetyltrimethyhimmonium bromide (CTA Br). When the latter was
adsorbed on silica at pH 9.1, a bilayer was formed on the silica surface and the
adsorption of PVA was increased. Similarly at low pH when PV A was absorbed, the
adsorption of CTA + ions was' increased. It is probable that the hydrophobic cetyl
group and the hydrocarbon backbone of the PV A polymer became associated
through hydrophobic bonding. If this is the case then certain combinations of PVA
and CTA + should lead to formation of a coacervate over a wide pH range. Likewise
the adsorption of PV A may be greater on pyrogenic silica as in the case with
polyethylene oxide observed by Rubio and Kitchener (328).
ed from
.id
:-
.ding to
lthough
iordinadsorbed
rontiurn
of the
)f sugar
.bed the
ange of
.cle, the
ion and
.11 areas
Thus a
rophilic
se them
dded to
:nt;>:on
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:r helps
.rsed in
hydroxane is
e polar
onsider
breakaces of
Silica Spheres by Coacervation
by the
ut with
ibile so
tat the
11.
e
~s
\.. . 1
etween
If one of the components in a silica-organic coacervate is undergoing polymerization

just as the liquid coacervate droplets come out of the aqueous phase, the droplets
solidify into small spheres. When the organic material is burned out, porous silica
spheres .are obtained and under some conditions are very uniform in size. For
example, when a 6% solution of polysilicic acid at pH 2, made by adding a solution
of 3.3 ratio sodium silicate to' an excess of strongly agitated acid, is aged to an
optimum point and then mixed with a polyether such as nonaethylene glycol, or with
N,N-diethylaniline hydrochloride in proper proportions, a homogeneous solution is
398
lirst obtained. Then spheres of the organic com plex of silica are ~pontaneously
precipitated after further polymerization of the silica at ordinary temperature
(340-342).
Coacervation involving colloidal silica can also occur when an initialIy soluble
polar organic polymer is being further polymerized in solution at low pH where
hydrogen bonding can occur with the silica. Her and McQueston (343) observed the
formation of micron-sized liquid droplets of a coacervate formed when urea and
formaldehyde were polymerized in an acidic silica sol. The organic oligomers
apparently form a hydrogen-bonded coacervate containing silica or other hydrophilic colloidal particles. Under the right conditions, the droplets harden just as they
come out of solution, thus forming uniform spheres which can be from 0.5 to 20 microns in diameter. The organic polymer can be burned out leaving a silica powder in
the form of porous uniform spheres useful in chromatography.
. Aggregation Into Ordered Structures-Precious Opal

When colloidal particles are of extremely uniform size and shape they can come
together into a very uniform regularly packed state just as molecules can arrange
themselves in a crystal lattice. Indeed the result is a "crystal" made.up of colloidal
particles. However, because the lattice spacing is so large, the Bragg laws of
interference apply, not to X-rays, but to light waves which are much longer. The
result is that the ordered aggregates appear highly colored when viewed from certain
angles in reflected light.
Structures of this type formed from very uniform particles of colloidal silica
100-500 nm in diameter are found in nature as "precious .opal." Because of the very
curious nature of this phenomenon it is reviewed in some detail, including the analogousphenomenon involving uniform particles of other substances.
Opal Structure
The term "opal" broadly covers many types of hydrated amorphous silicas found in
nature ranging from the deposits within bamboo called tabasheer (344), to microscopic silica bodies within living tissues, to massive mineral deposits around hot
springs. It is amorphous in the sense that it does not give a sharp X-ray diffraction
pattern but in some varieties it has been shown to consist of submicroscopic
crystallites of cristobalite with water between the crystals. However, "precious opal"
showing brilliant irridescent colors is almost completely amorphous and is identified
as "Opal AU (345). It shows a diffuse diffraction band corresponding to a spacing of
4.1 A and does not show the endotherm in the differential thermal analysis curve at
1500 C that is characteristic of some other opaline silicas (346). Precious opal is
mined in several parts of the world orginialIy in Hungary but now mainly in
Australia, although smaller quantities are found elsewhere. '
The structure of precious opal was lirst described by J ones, Sanders, and Segnit
(347) and Sanders (348), who demonstrated that the structure consisted of spheres of
amorphous silica 150-350 nm in diameter showing an X-ray pattern devoid of any
...
399
rated Sols
:aneously
iperature
definite lines or peaks but only a broad band. Sanders showed through'electron micrographs the remarkable structure of uniformly packed arrays of the silica spheres
with material between the spheres of somewhat lower refractive index which gave
rise to the interference colors in reflected light. He showed that when the sphere size
was not uniform and thus the packing not regular, the resulting voids scattered light
giving the milky appearance of lower grade opals. When no color is seen, it is called
"potch." The role of water in opal was examined by Segnit, Stevens, and Jones (349)
by differential thermal analysis, infrared absorption, and nmr. Most opals contain
4-9% water but in precious opal less than 1% is lost at low humidity. From 20 to
70% of this water is held "chemically:', that is, as hydroxyl groups bound to the
silicon atoms on the internal surface, and the rest is in such small pores or in closed
pores that it is lost only very slowly at elevated temperature.
.
The genesis of precious opal requires three distinct processes: forming the uniform
particles, depositing them in a regular manner, and cementing them together. As will
be discussed later, aggregation into regular arrays may follow as a natural consequence of the extreme uniformity of spherical particles. The mechanism of formation in nature of uniform spheres 0.1-1.0 micron in size is unknown. Jones and
co-workers (350, 351) showed that certain minerals such as biotite are attacked by
acid and the soluble silica undergoes continuous reprecipitation to form colloidal
particles which aggregate into spherical particles. These could be transported as a
sol to the point of deposition. It was noted that abundant sulfates are found in the
environment of opal deposition. Particles may also be formed by thermal dissolution
and deposition of silica.
For the formation of precious opal Darragh et al. (352) point to three features
that are important, at least in the Australian fields: (a). an abundant supply of
readily soluble silica; (b) an arid climate restricting shallow.groundwaters to sharply
defined dams such as bentonite beds which prevent the formation from drying out,
thus retaining a solution typically containing up to 3% soluble sulfates and chlorides
and 80 ppm soluble silica; and (e) the presence of cavities, formed in various ways, in
which the silica particles can collect and arrange themselves. The authors state that
a silica sol of 10 nm particles will develop particles 150-200 nm in diameter upon
long aging but the conditions were not specified. The conditions for such aggregation
must be very specific because sols of 10 nm particles can be aged and gelled as well
as concentrated and flocculated under a wide variety of conditions without the
appearance of any large spheres. There is some evidence that the spheres may have
settled in a slightly viscous medium like a 0.1 % silica sol of small particles that are
flocculated by salts.
When first formed the opal structure was soft but then further silica penetrated
the pores. For maximum color the spaces between the spheres must not be fully
closed, for that leaves only a transparent mass. Instead the cementing action
probably involves deposition of more soluble silica in the form of a gel of extremely
small particles which thus hold water within the pores.
The banded structure of opal called twinning was investigated by Cole and
Monroe (353). They found that there are bands of hexagonal packing of the spheres
lying between bands of square packing, these bands being a few particles in width, as
shown in electron micrographs.
Y soluble
H where
erved the
urea and
iligomers
:r hydroit as they
to 20 milowder in -
an come
. arrange
colloidal
laws of
ger. The
n c.... tain
1al silica
. the very
~e analo-
found in
o microlund hot
ffraction
.rcsccpic
IUS opal"
dentified
pacing of
curve at
s opal is
rainly in
id " tnit
ph, ... of
d of any
.,
400
~-_.
The high water content but Jow porosity, as determined by nitrogen" adsorption,
suggests that the 200 nm spheres are in turn made up of densely packed smaller
particles IQ-20 nm in diameter, the surface of these being covered by a layer of
SiOH groups. The still smaller interstices between these small-particles would be
only 10-20 A in diameter and water within these would be strongly held. This structure, proposed by Jones and Segnit (354), was supported by electron micrographs,
dehydration curves, and infrared studies. Greer (355) concluded that the spheres
added to the structure by a screw dislocation mechanism as in crystal growth,
The diffraction of light by precious opal gave diffraction patterns which were
interpreted by analogy with X-ray diffraction theory. Sanders (356) found that the
spherical silica particles were arranged hexagonally in layers which were usually
stacked randomly. There are some parallel domains of ordered packing, usually
face-centered cubic.
Opal in which brilliant colors appear against a dark background are the most
valuable and probably the least understood. The effect is not entirely that of a dark
substrate but may also involve a phenomenon similar to that of a light trap like a
bundle of needles viewed from the points. There are no doubt other effects as well,
such as a dark material scattered through the matrix. For example. black opals were
examined by Mitsyuk et al. (357). The dark organic material in the pores was found
to resemble a hydrocarbon. After calcination the decolorized opal' increased in
density from 2.0 to 2.2 g cm -3 as organic matter and water were removed. The microstructure of opal has been described in further detail by Sanders and Darragh
(358). The uniform spheres in areas of uniform arrays are shown in Figure 4.23
(359). In this electron micrograph of an Australian opal, the unusual structure of the
spheres can be seen to be made up of still smaller particles arranged in layers about
a central core. In some opals many smooth concentric growth rings can be seen in
the particles. These are essentially all grown together into a relatively dense sphere
but are revealed by careful etching. It is surprising that the fracture often passes
through the centers of a layer of spheres rather than through the zone of contact
between them. In many specimens the fracture surface appears smooth with only a
series of dots showing the cavities between the original spheres which have grown
almost together.
The packing of the spheres is in uniform array in different zones of varying size,
the faulting being random. The faulting occurs in strips so that under the optical
microscope these are seen as fine parallel straight lines of specific uniform colors.
The attractiveness of an opal depends on the size and variety of the color areas
which in turn depend on the size and distribution of the faulting. The purity of color
and freedom from scattered white light depends on having the optimum small difference in average refractive index of a plane through the centers of the spheres and
a plane through the cavities between the spheres. If the difference is too small the
opal is almost transparent with minimum interference colors; if too large, white light
is scattered. These effects are most easily seen when a porous white mass of
synthetic opal structure is impregnated with liquids of different refractive indexes as
described by Her (360).
Sanders points out that the size of the spheres can be quickly estimated by eye. By
viewing the opal from various angles. the color of maximum wavelength (Am ax )
,.
~
.rated Sols
401
Isorption,
d smaller
of
would be
'his strucrographs,
e spheres
h.
rich were
I that the
e usually
~, usually
;).
the most
of a dark
"ap like a
s as well,
pals were
las found
~eased in
The mic- .
Darragh
~ur" 4.23
ue. .he
ers about
,e seen in
se sphere
en passes
f contact
th only a
ve grown
~
:~
;:.~
-~
-e
~-
'!:
st
'$
....,
i"'";'
,'..,_.
,.
.;: .
{
.~
,
,..
,.
"'~
/~
-."
, :'MICRON
;.. \e;.I_::
:.I.IQJ...,.,..
. .1M5--,-,~
Figure 4.23. Electron micrograph of opal structure lightly etched with HF. Fossil from
Cooper Pedy, Australia (I9,500x). [By courtesy of Dr. J. V. Sanders (359).]
ying size,
ie optical
m colors.
lor areas
( of color
.mall difheres and
small the
'hite light
mass of
ndexes as
y c_ By
th (Xm u )
is observed (violet to red increases from 300 to 700 nm). Then the particle diameter
is obtained by dividing by 2.5. Thus the particles in precious opal can range from
around 100 to 300 nm. The size is usually uniform in any. one specimen. All colors
can be seen only when the sphere size is about 300 nm. With still larger spheres
"second-order" colors can be seen, for example, cerise, which is both violet and red.
The shell structure of the spheres seems to be characteristic of some types of
opals. The particle size in the shell-like layers is 50 nm in some opals, and there can
be as many as five layers. In such cases, single 50 nm particles are often found in the
intervening cavities. In other opals the cross-section of the spheres show growth
rings, like tree rings, as though formed from much finer particles. Sanders and
Darragh state that in the laboratory dilute sots of 50 nm diameter can form 150 nm
particles by slow aggregation. Probably much smaller particles can also be deposited
around nuclei. This apparently occurs in cavities in the soil or rock, often left by
402
decayed organic matter, and the particles than settle or are concentrated by evap_
ortation of water. Then the phenomenon of phase separation and ordering, as
already discussed, must come into play". In the laboratory definite "crystals" have
been seen forming in the concentrated sol, growing upward from the upper surface
of the compact layer of settled particles and later being embedded in the growing
layer.
A study by Balakirev et aI. (361) led to essentially the same conclusions reached
by other workers.
.
General information on precious opal is available in several' monographs
(362-364).
, .
Other Ordered Aggregates

.
The spontaneous arrangement of uniforma colloidal particles into close-packed,

highly ordered arrays is essentialIy a form of crystallization in which the crystals are
made up of particles instead of molecules. Crystals of latex particles were described
by Alfrey et a1. (365). Particle sizes in the crystals were in the range from 100 to
1000 nm in diameter in different crystals, but in anyone crystal, the particles were
very uniform in size. Similar ordered arrangements have been noted in a number of
systems, especially where the particles are of the order of 100-300 nm in size so that
interference colors become obvious in reflected light. It was only in recent years that
it was recognized that the structure of precious opal was of a similar nature. Since
the way in which large particles of colloidal silica are formed in nature and deposited ~
in an ordered fashion is still largely a mystery, it is of interest to summarize some of".
what is known about the formation of uniform submicron particles, the forces that
lead to ordered aggregates, and examples in the laboratory and in nature of such
structures.
The general phenomenon of "crystallization" or highly ordered aggregation of
supermolecular" structural units has been considered by Luck, Klier, and Wesslau
(366), who presented observations of virus crystals and close-packed latex particles,
and developed the theory of interference colors in reflected light. Optical diffraction
was related to particle packing as observed under the microscope by using 2.68
micron spheres and 632.8 nm laser light by De Fontaine, Jackson, and Miller (367).
The theory of packing of spheres into orderly arrays has been considered by several
investigators (368-371).
Following the announcement of Alfrey et al. (365) of the formation of interference
colors in polystyrene latex the phenomenon has been studied by numerous workers.
Luck and others (366-372) attributed the colors to "Bragg reflections of visible light.
The formation of ordered regions in the presence of disordered regions was studied
by Krieger, Hiltner, and Papir (373), who found that long range repulsion owing to
anionic charges on the surface of the latex particles kept them apart until a certain
amount of electrolyte was added to permit closer approach, whereupon the
order-disorder transition occurred.
'
The long-distance interaction of dispersed particles of uniform size can lead t<.
"periodic colloid structure" (peS) in which the particles are far from touching each
other. Also, crowding can lead to such arrangements where there is some repulsion,
ated Sols
Aggregatio~
ly evapring, as
s"
'e
surtace
growing
according to a study by Eframov, Luk Ashenko, and Us'Yarov (374). A theory of the
shear yield stress in some crowded systems gave agreement with experimental data in
a polyacrylonitrile dispersion.
In a series of papers Hachisu, Kobayasi, and Kose (375-379) reviewed the literature and investigated the subject in further detail. The particles can form ordered
arrays without being in actual contact. In these arrays particles are all the same size
and other sizes are excluded. The phenomenon involves a phase transition when the
concentration exceeds a certain volume fraction, usually 0.5 % 0.1, whereby a second
more concentrated phase is formed within which the particles are in an ordered
arrangment. This is known as the Kirkwood-Alder transition (380-382) and is a
purely statistical effect that does not require an attractive potential for its explanation. It is inhibited when ionic repulsion forces exceed a low level. The transition can
occur in suspensions in aqueous and nonaqueous liquids. In aqueous systems it will
not occur e,ven when the particles are very uniform, unless the system is low in electrolytes.
A wide variety of iridescent colors in biological materials as well as inorganic
crystals have been identified as being due to similar diffraction interference
phenomena in uniformly ordered structures. Monroe and Monroe (383) mention'
opal, certain feldspars, potassium chloride crystals, mollusk shells, fossil brachiopod
shells, crystallized viruses, insects, and in their own study, the skin .of the indigo
snake. Greenewalt has shown that the colors in hummingbirds' wings are due to
ordered bubbles (384). Williams and Smith (385) studied a virus occurring as
brilliantly colored crystals making up 25% of the larva of the crane fly. This virus
was first described by Xeros (386) and according to Bowden and Smith (387) looks
exactly like precious opal. Iridescent opal is found in the base plates of teeth of
marine gastropods (limpets), described by Lowenstam (3~8a). There are spherical
granules 10-25 microns in diameter in the skin of the sea cucumber (Molpadia intermedia Holothuroidaey; each of which is made up of spheres of silica 100-190 nm
diameter mixed with particles of equal size of "ferritin," a calcium magnesium basic
iron phosphate. It is a coincidence that the silica particles are of about the same size
as those in precious opal (388b).
reached
rgraphs
packed,
itals are
escribed
100 to
les were
mber of
: so that
ars that
e. Since
:po..;ted
SOl
)f
ces that
of such
ition of
Nesslau
articles,
fraction
ng 2.68
.r (367).
several
-Ference
-orkers.
Ie light.
studied
wing to
certain
on the
ler
to
ng .:h
oulsion,
Formation
403
of Particles
QI Uniform Inorganic
Particles
Although uniform particles of certain types of latex and. virus particles were
recognized before 1950 there were few if any examples of inorganic particles of
similar uniformity and in the 100-500 nm size range necessary to show interference
colors. Isodispersed sols had been made of gold, silver, sulfur, silver chloride, and
barium sulfate, but not of silica (389). Early investigators had no hope of making
silica particles in this size range because they had no idea how to 'increase the
particle size. Freundlich (390) described the many attempts to obtain stable sols
more concentrated than 10% Si0 2 and was baffled that the addition of alkali, which
he knew should stabilize negatively charged particles, only caused gelling.
Silica particles of sufficiently large and uniform size to form uniform arrays
exhibiting brilliant interference colors were first made by Sears using the "build-up"
process of Bechtold and Snyder, and the colors were observed in a sol that had set-
404
tied for 2 years (360). Later Stober and Fink (68) discovered a process' using ethyl
silicate for making very uniform spheres in the diameter range of 0.05-2 microns.
Particles of this type can be settled in the same way to give colored strata.
Uniform particles of other materials in the same size range that should also
develop interference colors upon settling have been described by Matijevie et al.
(391), who developed methods for making uniform spheres of hydrous oxides of
Cr H , A13+, ZrH , and Cu", Also Catone and Matijevic (392) have made uniform
spheres of hydrated alumina in this size range. Similar particles of basic chromium
sulfate have been described by Bell and Matijevic (393). "Schiller layers" of tactoids
of beta-FeOOH showing brilliant colors, known for many years, have been investigated in detail by Watson, Cardell, and Heller (394). Her has made" blue-green
spheres of CrPO. xHzO which settle to a layer of uniform particles that appears red
in reflected light. No doubt many other types will be discovered.
Synthesis of Opal
The formation of brilliantly colored opal structures by settling sols was observed in
1953 by Sears and lIer and subsequent investigations were described in 1965 (360).
Solid masses with the appearance of precious opal were obtained by slowly drying
the original aqueous settled layer and impregnating the porous body with organic
matter having a refractive index close to that of amorphous silica. Gaskin and Darragh (395) patented synthetic opal-like material stabilized by impregnating the dried
porous body with a silica sol of very small particle size or with polymerizable
organic material such that the refractive index of the resulting cement is within
O.O I to 0.05 of that ofsilica.
This synthesis was announced in 1967 (396). Since then synthetic opals have
become available from Gilson of Switzerland (397). These have the appearance of
natural opal and many of the same properties, for example: hydrated, density 2.113,
refractive index 1.45, singly refractive, amorphous, hardness 6.15 mohs (398). The
synthetic black opal is said to be indistinguishable from the natural ones by visual
examination. Some difference in fluorescent properties was reported. The method of
manufacture is a trade secret of the manufacturing company, Gilem S. A.
More recently another material known as "Slocum Stone" has been developed by
John Slocum (399, 400). Specimens exhibiting brilliant interference colors of all
shades have been made with a wider range of background color than in any natural
opals. All types of opals can be simulated. However, in spite of the similarity the
material is not claimed to be a "synthetic opal" because it has a unique, characteristic appearance of its own and also because it does not have the composition of
opal. It is nonhydrated, nonporous, harder, and with higher density (2.4-2.5) and
higher refractive index (1.51). The colors appear to originate from interference films
dispersed throughout the matrix. The method of manufacture has not been revealed.
A composition claimed to have the appearance of opal but which is mainly
organic is claimed by Willcox (401), who dispersed particles of TlO, 0.05-0.1 micron
in diameter homogeneously through a colorless transparent organic polymer matrix,
the volume fraction of the TiO z being from 10- 4 to 10%.
-:
ued Sols
tg ethyl
Adsorption Of Silica Particles On Surfaces
405
ricrons.
lid also
C et al,
.ides of
miform
'omiurn
actoids
investie-green
.ars red
rved in
; (360).
drying
organic
rd Dare
cl";~d
:rh e
within
shave
mce of
2.113,
~).
The
visual
:hod of
ped by
of all
ratural
ity the
.harac-
tion of
5) and
e films
ealed.
mainly
nv
nal
.,
Colloidal .particles are attracted and held on planar surfaces, or are repelled by such
surfaces, by the same forces that cause attraction or repulsion between two colloidal
particles. Some of the basic principles have been reviewed by Jirgensons and Straumanis (Ref. 53, p. 10I.). The adsorption of colloidal silica on alumina and colloidal
alumina on silica was shown by Her,(402) to occur at about pH 4. Once the ionic
charge on the surface has been covered by a single layer of colloidal particles of
opposite charge, the covered surface then bears the charge of the adsorbed particles
and no further adsorption occurs.
Many separate layers of colloidal particles can be superimposed, one after the
other. When a clean hydrophilic silica surface such as glass, which bears a negative
charge, is brought into contact with a sol of colloidal alumina, a single layer of alumina particles is adsorbed on the glass, the net charge is reversed, and no more alumina is adsorbed. When the excess alumina is rinsed off, there remains a single
adsorbed monolayer of alumina particles. A layer of silica particles can then be
deposited by applying a solution of colloidal silica to the surface covered with alumina; there is adsorbed a layer of silica particles and the excess silica can be
rinsed off.
By repeating the process, a uniform multilayer may be built up of any desired
thickness (403). The alumina that is adsorbed may be a basic aluminum chloride
solution in which the particles are too small to be measured. Alternatively, a cationic
polymer may be adsorbed to form the positive layer over the silica, which is then
receptive to a layer of silica particles. Films can be formed having the thickness of a
quarter of the wavelength of visible light, that is, 150 nm. Since these films are
porous, the refractive index is approximately midway between that of air and of the
glass substrate, thus presenting ideal conditions for the development of interference
colors. Details of the technique and applications are described in a patent (404).
As applied, these adsorbed films are very soft and easily rubbed off, but may be
hardened by treatment with hydrolzyed ethyl silicate or tetra isopropyl titanate. The
films can also be strengthened by sintering at elevated temperature. Potential
applications include low reflective coatings, insulting layers on conducting surfaces,
conductive layers on nonconducting substrates, formation of oxide films on metals,
deposition of colloidal graphite to improve surface conductivity, or deposition of
solid lubricants. Alternating conducting and nonconducting layers could be laid
down for use in electronic devices.
The technique is useful for qualitatively detecting the presence of small quantities
of colloidal substances in solution. The key to the technique is the use of an indicator
sol of particles having a diameter of about one-quarter the wavelength of light,
which is readily observed when adsorbed as a monolayer of particles on a black glass
background. Thus, for example, low concentrations of cationic organic materials can
be detected by treating the black glass surface with these test solutions, rinsing or
drying the surface, and then applying a 100-200 nm silica sol used as an indicator,
rinsing off the excess, and again drying. The silica particles adhere wherever the
cationic substance from the test solution has been adsorbed on the glass, and the
silica film is readily observed by its interference color.
"
406
Small particles of colloidal silica can be detected in dilute solutions by this tech.
nique as shown in Figure 4.24. A positively charged layer such as colloidal alumina
or a cationic polymer solution is first deposited on the glass surface, the excess is
rinsed off, and the test solution of a negatively charged colloid such as silica is
applied to part of the surface and dried; the presence of the latter on the surface can
be detected by subsequently treating the whole surface with 100-200 nm silica particles which then adhere only to the positively charged surface if no negative colloid
has been adsorbed. The test procedures can be developed to detect less than 100 ppm
of negatively or positively charged colloidal substances; the smaller the particles. the
more sensitive the test. However. as also shown in Figure 4.24, the test solution of
large particles must be free from small ones.
The approximate particle size of a colloid can be judged from the difference in
color owing to the increase in the thickness of the overall multilayer where the
sample particles have been deposited.' Details of this method represented in Figure
4.25 have been described by Her (403).
In such work traces of adsorbed grease or other hydrophobing molecules must be
elminated. Weyl and Marboe (405) have pointed out the effect of adsorbed cations
on absorption of traces of fatty acids. Her has observed that when glass is acid
treated to remove cations it remains hydrophilic in laboratory air much longer than
after exposure to polyvalent cations or positively charged colloids, .which adsorb
fatty acids from the air within a few hours.
For thicker deposits of colloidal silica it is found that aggregates of limited size
(less than I micron) can be adsorbed on glass if coagulated and partly redispersed
with a slight excess of cationic surfactant or polymer. In this case the aggregates
carry a positive charge and are adsorbed to form one layer of aggregates.
Adhesion of a monolayer of dry silica particles to a glass surface can be achieved
by rubbing the surface with a powder consisting of discrete uniform particles of
hydrophilic colloidal silica around 100-300 nm in diameter (406). Apparently the
particles bond to the flat surface to a greater degree than to each other and thus a
sincle layer of particles adheres. In some cases a second layer can be formed by very
C2: "fully controlled rubbing.
\leasuring adhesion of particles to surfaces was described by Visser (407), who
used the known shearing force in water against the surface to dislodge particles. A
theory of adhesion or detachment of particles on a surface from a stream of sol was
Figure 4.24. Techniques for detecting small
colloidal particles: Left: large silica particles
A are adsorbed on an alumina-coated surface
forming a visible film at B. but not on the
area previously exposed to small silica partie
cles at C, which are invisible. Right: in a sol
containing a mixture of large and small particles of colloidal silica, the smaller ones dif
fuse. more rapidly to the alirnina-coated surface at D and exclude the slower moving
large particles E [ller (403)].
itrated Sols
this tech11 alumina

: e _ ;s is
.s silica is
urface can
.lica partive colloid
1 100 ppm
.ticles, the
elution of
ference in
where the
in Figure
:s must be
ed cations
ss is acid
,nger than
ch adsorb
nited size
:di~"p.rsed
.gg
ates
: achieved
irticles of
rently the
nd thus a
:d by very
407
Sols of Silica Particles with Modified Surfa.=:s_
Figure 4.25. A layer of small silica particles, and a second layer of alumina, shown as short
black rods, at A, increases the overall film thickness by II over the control, at B on surface of
black glass G [ller (403)].
developed by Gutowski (408). Adhesion of particles to various surfaces was

measured directly by a centrifuging procedure by Davies and Ranade (409).
SOLS OF SILICA PARTICLES WITH MODIFIED SURFACES

Once silica particles have been formed, the surface can be modified by the attachment of different atoms or groups to modify physical and chemical behavior. If the
silica surface is completely covered with a layer of alumina even as thin as one or
two molecules in thickness, for example. it then acts as though it were a solid alumina particle. bearing a positive charge and stable at low pH.
A monolayer of chemisorbed hydrocarbon groups makes the particle act as though
it were a large hydrocarbon molecule.
Negatively Charged Surfaces
Aluminosllicate Ions
\07), who
rticles. A
)f sol was
ting small
particles
:d surface
ot on the
fica partit: in a sol
nail partiones difrated surr.
ing
An important modification of the silica surface is with aluminate ions. As evidenced

by the exceedingly low solubility of aluminosilicate minerals, such as clays, there is a
strong specific interaction between the oxides of aluminum and silicon. The peculiar
relationship between aluminum and silicon is probably because both can, under
suitable circumstances, assume a coordination number of 4 or 6 toward oxygen, and
because both have approximately the same atomic diameter. Since the aluminate ion
AI(OH). - I is geometrically similar to Si(OH)., the ion can be inserted or exchanged
into the Si0 2 surface. thus creating an aluminosilicate site having a fixed negative
charge.
The anionic nature of aluminum, when substituted for silica in the 4-coordinated
state, was early recognized by Pauling in crystalline minerals (410) and soon
thereafter in alumina-silica cracking catalysts (411). The formation of the alumino-silicate anion by reaction of aluminate ion with the surface of silica is
408
represented as follows (412):
I
I
o
3 -O-Si-OH
o
I
"
. 1
. :
:1
. , .j . ;
I(r!
?r:.!
.,'
".
'--
I.
I
I
-O-Si-O-H
I
I
o
0
I
I
-O-Si-O-AI-OH
.+
I
I
o
0
I
I
-O-Si-O-H
I
o
I
. !
2 H 20
Milliken. Mills. and Oblad (413) showed that the anion is stable only in the
presence of a cation other than hydrogen. the free acid being unstable. and that
excess silica must be present. The pH is thus an important factor; only about 15%
alumina in silica was stabilized in the adsorbed anionic form at pH 6 when the stabilizing cation was ammonium. Below pH 3. in the hydrogen form. the aluminum
reverted to the 6-coordinate state.
This behavior of aluminum is used in modifying the surface of colloidal silica so
the particles will remain negatively charged down to pH 3 in contrast to very pure
silica, which is negatively charged by the adsorption of hydroxyl ions above pH 7 but
loses the charge in acid solution. Alexander and lIer (414) thus created a modified
silica sol that was stablein the neutral pH range where unmodified silica sol gels
rapidly. In a silica sol 'of 15 nm particles modified in this way with sodium
aluminate, "the incorporation of only 0.66% by weight of AI203 based on the silica
was required. This corresponds to only one aluminosilicate site for every 20 silanol
groups on the surface, but since the sites are probably uniformly distributed, they
are only about IS A apart. The difference between this type of modified silica sol
and an unmodified sol containing only the small amounts of aluminum present in
commercial products has been studied by Allen and Matijevie (250,251,415). The
increased stability over a wider pH range broadens the scope of practical uses (416,
417). Colloidal silica particles can also be covered with coatings from 3 to 25 nm
thick in which the atomic ratio of silicon to aluminum may range from I: I to 10: 1,
according to Alexander (418). Sols can also be made with particles that consist
entirely of aluminosilicate (419) but these are outside the scope of the present topic.
EFFECT ON PROPERTIES. The effect of introducing alurninosilicate ions into the
silica surface is shown by comparing the properties of the above aluminate modified
sol, Ludoxw AM (registered trademark of E. I. du Pont de Nemours & Co., Wilmington, Del.) and of the unmodified silica sol, Ludoxs HS, from which it was made.
Matijevie and co-workers showed that in the pH range 4-6 where silica. particles
bear very little charge. the modified particles retained substantial charge as shown
"
"
."
---. ....
trated Sols
ily in the
and that
bout 15%
n the stailuminum
I silica so
ver" pure
Pi but
modified
a sol gels
1 sodium
the silica
W silanol
ited, they
silica sol
iresent in
tiS). The
ises (4I6,
to 25 nm
to 10: I,
lt consist
1t topic.
into the
modified
r., Wilm'as made.
p
'des
as. Jwn
Sols of Silica Particles with Modified Surfaces_
409
by electrophoretic mobility. Also the polyvalent cation LaB coagulates the AM type
but not the HS.
I1er (324) prepared a series of sols modified with various amounts of aluminate.
One series was made from an unmodified sol of 22 nm particles (Ludoxs TM) and
another of 14 nm particles (Ludoxs HS). The coverage by aluminate ions ranged
from 1.8 to 25% of the total silanol groups on the surface (assuming 8 SiOH nm -2).
Stabilization as an aluminate ion in the particle surface requires that each aluminum
atom be surrounded by three oxygens linked to silicon, which means that no more
than 25% of the surface silicon sites can be replaced by aluminum atoms. This
assumes, of course, that the underlying silica surface is nonporous and not accessible
to reaction with AI(OH). - ions.
The coverage can be titrated with a cationic surfactant which is adsorbed more
strongly as more anionic sites are present at pH 3.5 (Figure 4.26).
With the,above series of modified sols, lIer demonstrated that with higher surface
charge, the particles became less reactive with hydrogen-bonding agents. Thus proteins, polyvinyl alcohol, and polyethlene glycols coagulate unmodified silica sols at
pH 3-5, whereas coagulation is inhibited as the silica surface is more highly charged
by aluminate.
.
The alumina-modified sol is much more stable toward gelling in the pH range
4-6, where unmodified sol gels most rapidly (Figure 4.27), and is less sensitive to
salt. .
Other Anions
Elements other than aluminum do not seem to form the same type of anionic sites
on the surface of silica. Shafer and Roy point out that Cr~+ cannot enter into a 4coordinated association with oxygen atoms as aluminum does (420). However,
Wagner (421) claims that stable sols can be obtained with pyrogenic silica formed by
burning SiCI. along with AICI;, or TiCI. It would appear that this might give a
negative surface charge with A1H but not with tetravalent Ti H Possibly the parti-
-I
~
1.5
10
.....
CD
1.0
w
u
~
0
0.5
-I
:E
0
0
10
20
30
% COVERAGE
Figure 4.26. Volume (ml) of a 1% solution of cetyltrimethylammonium bromide re~ired to coagulate 50 ml

of a 1% sol of 14 nm silica particles having the indicated
percentage of the surface covered by aluminosilicate
ions.
., :....-.
410
..
1000
ti
It')
N
Cfl
a::
100
::>
0
:I:
W
::E
t=
10
...J
Figure 4.27. Stability or aluminosilicate

modified silica sol (Ludox~ AM) versus
unmodified sol (Ludox@ HS). Ordinate, gel
time in hours at 25C. Abscissa, normality or
1.0 NaCI. Solid lines, Ludolt~ AM: dotted lines,
Ludox HS: pH indicated.
C)
0.001
.r
I
.!
Ii
'I.;
r,
;-
0.01
0.10
NORMALITY Noel
cles are simply coated with Al z0 3 or TiO z in which case they would be positively
charged at low.pH.
Iron would seem to be a likely candidate for forming a ferrosilicate anion but like
Cr. the atom may be too large. However. some peculiar action must occur because
the Fe H content in silica sols does not cause nearly as much brown color as when
present as Fe(OH),. Hazel. Gordon. and Schock (422) reported that when a silica sol
at pH 2.2 was mixed with a solution of ferric salt the color was discharged even after "the pH was raised.
. For the particle to retain a negative charge 'at low pH where the charge on pure
silica is negligible requires not only th~t the substituted atom have a valence ofless
than 4 but also that the metal have a strong affinity for silica at low pH and remain
4-coordinated with oxygen. This may restrict the substitution solely to aluminum.
The effect of boron' has apparently not been explored but the Si-O-B bond is
hydrolytically unstable.
I
Another type of negatively charged coated silica sol was described by Yates (423).
Colloidal phosphates of Ceo Hf, Sn, T~. or Zr are reacted with colloidal silica and
. adjusted' to pH 9 with a volatile basel The polyvalent metal ions in the complex
probably combine with the silica surface and the phosphate gives the colloid an
overall negative charge.
!
Positively Charged Particles
Polyvalent Metal Oxide Coatings

1
The negative charge on silica can be reversed by adsorbing an excess of positively

charged material on the surface. The ~eversal of charge on colloids has long been
known. but the first concentrated positively charged silica sol of this type was "-'
developed by Alexander and Bolt (424~, who defined the type of polyvalent metal
ated Sols
nosilicate
1) versus
linate, gel
rmalityof
tted lines,
ositively
but like
because
as when
.ilica sol
'er
~r
on pure
e of less
: remain
rrunurn.
bond is
es (423).
lica and
complex
Iloid an
Sols of Silica Particles with Modified Surfaces
411
oxide coating applied over the surface of the particles to provide maximum sol
stability. Coatings included oxides of tri- and tetravalent metals such as aluminum,
chromium, gallium, titanium, and zirconium. A preferred sol contained 26% silica
and 4% AlzO,; the positively charged particles were accompanied by chloride counterions. In making this product, the acidified silica sol was mixed with a basic metal
salt which contained extremely small colloidal particles of metal oxide which were
adsorbed on the silica surface. Mindick. and Reven made the basic metal salts in the
presence of the silica sol by mixing the sol with the metal salt and then removing
most of the anions of the metal salt by ion exchange' (425). Similarly, Ii titaniacoated sol was made by hydrolyzing an organic titanium compound in an acid-stabilized silica sol at a pH of less than 2 and heating the mixture to cause the titania to
be deposited on the surface of the particles (426, 427). Kovarik (428) claimed a
partial coating of metal oxide calculated as AlzO, by mixing Alz(OH)5CI with a
silica sol and removing Cl " with the bicarbonate form of an anion-exchange resin.
Basic aluminum acetate stabilized with boric acid can be used to avoid chloride
(429).
One characteristic of these sols is that they can be dried and repeptized. Since the
alumina-coated sols provide no soluble silica in solution and no silanol groups are
exposed at the surface of particles, no siloxane bonds are formed between particles
when the sol is dried to a powder. The counter chloride ions remains on the surface
and the powder can be redispersed to a sol in water at pH 3-5 (430). The stability of
these positive sols has been examined by Katsanis and Matijevic (431). At low pH
certain anions show a destabilizing effect, as might be expected from polyvalent
,anions. Destabilization by leaching of AIH from the surface was observed at very
low pH.
Numerous studies have been made of the interaction of polyvalent metal ions
. with the silica surface. The'development of Zr-O-Si bridges has been examined by
Nikolskii et a1. (432), who concluded that as the basic Zr ions polymerized they were
less reactive. Healy, cooper, and James (433) found that Fe H and CrH are adsorbed
on silica particles, giving them a positive charge. The chemistry of hydrolysis of
cations AI, Zr, Th, Cr has been summarized by Baes and Mesmer (434). Matijevie,
Janauer, and Kerker (435) have shown that it is the polymeric hydrolyzed species in
aluminum nitrate solution and not the single AIH ion that can cause charge reversal
in silver halide sols. The same is true in charge reversal of silica sols.
Polyvalent Organic Cations
ositively
ng
en
'pe .is
It metal
Although polyvalent organic cations, including cationic polymers, flocculate silica

when added to a negative sol, charge reversal occurs when an excess is present.
Redispersion occurs especially when the particles are large relative to' the chain
length of the polymer so that each particle may be coated with one or more polymer
molecules. When the silica particle is relatively small, the polymer chains are more
likely to bridge from one silica particle to another, preventing redispersion (321).
Redispersion can also occur when just enough cationic surfactant is added to a sol
to form a double layer around each particle which is thus surrounded by a spherical
micelle. Probably because of the relatively large amounts of organic material to
412
form each layer around silica particles, rela~ive to particle weight, no applications
for such positively charged sols have been developed,
,
I
Organic Modified Surfaces-Organosols
The silanol surface of silica particles limits [their dispersion in organic liquids to
lower alcohols, amides, and ketones. On the Qther
hand, adsorption of chemisorbed
I
molecules with outwardly disposed hydrocarbon groups makes silica particles quite
dispersible as organosols in a wide variety ef ~rganic liquids including hydrocarbons.
There are various ways of attaching organic groups to the silica surface as (a)
organic ions, (b) through Si-O-C linkages an~ silicic esters, or (c) by silicon-carbon
i
bonds as organosilicon groups.
Organic Ions
i~
Alkali-stabilized sols cannot be redispersed

water once they are dried, but if the
stabilizing sodium counterions are first replaced by tetramethylammonium ions, the
sol can then be dried to a powder which redissolves readily in lower alcohols to give
a sol. The monolayer of organic cations on ~he surface of the particles apparently
prevents the silica surfaces from coming into! contact when dried (205). By using a
quaternary ammonium ion containing a long-chain hydrocarbon group Iter (436)
found that the silica dispersed to a sol in organic solvents. Several patents relate to
making silica organophilic by adding an org~lDic amine or quaternary ammonium
compound in the presence of a water-immiscible organic liquid to cause the silica to
be transferred from the water to the organic phase. Hathaway (437) used as a
transfer agent RCONH (CH 2}.NH 2+IIH; R isla long-chain alkyl group and n is 1-4.
Vassos uses long-chain quaternary ammonium! ions (438). Kovarik and Vassos claim
a dried powder of this type (439).
I
Organic anions can be attached to the silicalsurface through metal cations. Thus a
silica sol coated with an oxide of trivalent AI, Fe, or Cr is further modified by
chemisorption of 2-ethyl hexyl phosphate to form a stable organosol (440).
Esterification
The surface of the silica particles may be mor~ permanently and stably modified by
converting some of the SiOH hydroxyl group~ to SiOR (alkoxy groups) by esterifying with alcohols. In some instances of silica dispersed in hydroxylic organic liquids,
it is not known whether the system was sufficiently
anhydrous to result in esterificaI
tion of the silica surface:

!
1
=SiOH + ROH - =~iOR + H 2 0

\
When a pyrogenic silica powder with a dehydrated silica surface was dispersed in
an alcohol, at least some degree of esterificatior no doubt was eventually attained.
Deliberate esterification of colloidal silica r.as first effected in the case of very
small particles of polysilicic acid, as discussed lin Chapters 2 and 3 (441). With such
rated Sols
Sols of Silica Particles with Modified Surfaces_
11ications
low molecular weight polysilicic acid, a relatively large proportion of buroxy groups
is incorporated into the product.
After colloidal silica particles of definite and uniform size became available, it was
possible to esterify the surface and show that the product indeed consists of a
monomolecular layer of oriented butoxy replacing some of the hydroxyl groups on
the silica surface so that the outer surface of the particle is essentially a layer of
hydrocarbon groups. This hydrocarbon surface may be aliphatic in nature, as when
an alcohol such as butyl is employed, or aromatic, as when benzyl is used. The
nature of the hydrocarbon surface affects the solubility and dispersibility of the
particles. Thus when silica particles 17 nm in diameter are esterified with benzyl
alcohol, a dry powder product is obtained that dissolves to a clear solution in benzene, but is not soluble in an aliphatic solvent such as kerosene. On the other hand,
when the same silica is esterified with an aliphatic branched-chain octadecyl alcohol,
the powder dissolves readily in kerosene (442).
Also it is possible to esterify the surface of the particles with glycol, so that
one end of each glycol molecule is attached to the silica surface through an
-SiOC- ester linkage, and the other end is at the outer surface of the particle as a
polar hydroxyl group. Such a colloid fO[J11s stable sols in polar organic solvents, but
not in hydrocarbons (443). On the other hand, the silica surface may be covered with
a layer of hydrocarbon groups if a glycol such as hexamethylene glycol is esterified
with the silica surface in such a way that both hydroxyl groups are turned in toward
and esterified with the surface. Aggregated silica powders esterified in this way are
patented by Broge (444) , but the principle also applies to silica sols. Excess of glycol
is avoided; the amount used is just sufficient to cover the silica surface when both
ends of the flexible molecule are attached to the surface. A hydrocarbon solvent is
used to remove water by azeotropic distillation. The surface is thus rendered
organophilic and hydrophobic, with a minimum of organic material, since the
hydrocarbon chains tend to lie flat along the surface, so the organophilic coating is
only a few angstroms in thickness.
These examples show that the nature of colloidal silica can be profoundly
modified by a monomolecular layer of a second material bound to the surface, and
that the colloidal properties are then largely determined by the properties of the surface layer.
Most complete reaction of hydroxyl groups on the silica surface is effected with
methanol. Broge (445) found that up to about 5.5 methoxy groups nm -2 can be
attached to the surface. Akabayashi, Yoshida, and Otsubo (446) have verified the
reaction of methanol with up to 95% of the silanol groups originally present on the
surface in an aquasol, which they assumed to be around 5-6 nm -2.
Conversion of an aquasol to an organosol is most simply effected by adding a high
boiling water-miscible polyol and boiling off the water. If the sol is first deionized
the silica remains dispersed and at the final high temperature of the boiling organic
liquid esterification proceeds rapidly as water is driven off (447-449).
lIer (450) reported that in the presence of excess glycol bnly one of the two
hydroxyl groups was esterified with the surface so that the outer surface consisted of
outwardly disposed alkyl hydroxyl groups and the sol was miscible in both water and
alcohols. However, it has since been observed that when just enough water is added
back to the system to provide only a monolayer on the surface of the particles
-;t
. .:~
\:
quids to
nisorbed
les quite
carbons.
:e as (a)
i-carbon
ut if the
ions, the
s to give
parently
. using a
.er (436)
rel"~
to
rn. .rn
silica to
.ed as a
n is 1-4.
os claim
., Thus a
lified by
jified by
esterify: liquids,
sterifica-
in
lin....
of very
'ith such
ier
~~:
1s
413
414
j
(about 8 H 20 nm -2) the sol is peculiarly unstable and gels. When ~ore water is
added the sol becomes more stable.
i
Similarly sols can be prepared in ether klycols which are polar enough to be miscible with the aqueous sol as water is e!vaporated. but an organosol forms in a
somewhat more volatile solvent. Stable s~ls containing up to 60% Si02 were made
with water-miscible alkoxyethanol. ROq2H40H where R is a lower alkyl group
(451). However, sols in ethylene glycol j monoethyl ether from which water was
removed at low temperature under vacuum were claimed not to contain esterified
silica (452). If so, then the stability must!b'be due to steric stablization by hydrogen
bonding of the silanol surface with the . ther and hydroxyl oxygen atoms. In an
earlier patent, this type of sol was heat+t to stabilize it, which probably effected
.
:
esterification (453).
. A silica powder redispersible to an organosol can be obtained by com pletely
esterifying the surface of colloidal particles before the sol is dried (442). The starting
sol must be free from ionic impurities andlis first transferred from water to a watermiscible polar organic liquid like n-propyl alcohol and then esterified by heating
under pressure or transferred to another alcohol and heated to complete the esterification, and dried. The nature of the orgapic coating determines the colloidal solubility of the powder in a particular organic solvent. A similar process was later
claimed by Mindick and Curtis (454) for ~aking an organic-dispersible powder.
Removal of salt from an aqueous sol at Ilow pH can be effected by dilution with a
water-miscible organic liquid like dimethylformamide or ethylene carbonate which
. precipitates the salt. Then the mixture is ~istil1ed under vacuum to obtain an anhydrous organosol. In the case of carbonate lesters hydrolysis probably provides alcoholic hydroxyl groups for esterification (4~S). Complete esterification of the surface
of the particles is not needed for stability if the dispersion medium is a strong
hydrogen-bonding agent. Sols of which less than half of the surface is esterified with
a water-miscible alcohol are stable in an excess of the alcohol (456).
Various methods have been used to dehydrate the esterification reaction mixture
and promote reaction. Azeotropic distillation is usually involved. Once the mixture
is anhydrous it is often heated under superatmospheric presure to accelerate the
reaction. Water may be removed from the system with a molecular sieve (457). The
silica may be in an emulsified mixture of water and immiscible solvent such as
mineral oil and cetyl-oleyl glycol ether and an emulsifying agent. This is dehydrated
in a climbing-film evaporator (458). Water can be removed by reaction with a ketal
according to Ryznar (459).
SHy/a/ion
A stillmore stable organophilic surface on silica particles is obtained by reacting the

surface with alkyl chlorosilanes, thus attaching organosilyl groups. For example, the
surface of colloidal silica was covered with trimethylsilyl groups by lIer (460), who
transferred silica from water to triethyl phosphate, dried the'sol, added trirnethylchlorosilane, then heated and removed excess reagent and solvent by vacuum
evaporation. The solid product was dispersible to form sols in benzene, ether, and
chloroform. but not in water.
415
trated Sols
: water is
Dispersions of silica particles completely hydrophobed with rnethylsilyl groups

covering the surface have been studied in propanol-water media by Benitez,
Contreras, and Goldfarb (461). It was observed that the particles have surface and
interfacial tensions similar to those of paraffin wax. Wetting of the powder occurred
in alcohol-water mixtures containing more than 15% propanol, 32% ethanol, and
50% methanol. The dispersion process does not appear to involve electrostatic repulsion but rather the interfacial free, energy which is closely related to wetting
behavior.
.
Silica particles in a sol can be rendered organophilic by reaction in a water-r-butyl
alcohol medium with mono or dimethylchlorosilanes according to lIer (462). The
surface-modified particles are transferred to an organic phase and dehydrated by
distillation.
Silica hydrosol of 3-5 nm particles emulsified with mineral oil was water-stripped
and reacted with polydimethylsiloxane oil to obtain a hydrophobic anti foam agent
b. sci.rms in a
'ere made
crl group
later was
esterified
hydrogen
ns. In an
, effected
rrnpletely
e starting
I a watery heating
e esterifiidaI soluwas later
-der.
:)0 with a
ite which
an "'1hyde. =0e surface
a strong
fied with
: mixture
: mixture
erate the
~57). The
such as
hydrated
h a ketal
cting the
n ple, the
SO), who
'imethylv~
1m
her, .nd
(463).
COMMERCIAL COLLOIDAL SILICAS
Because of the constantly changing developments and demands, new types of commercial silica sols become available and others disappear from the market. It is not
possible therefore, to predict which kinds will remain available in the future, but past
and current types are listed in Table 4.3, which includes some products that are no
longer available but may have been referred to in earlier technical publications.
Most of the sols contain particles 5-50 nm in diameter and with 30-50% by weight
of silica. Most are stabilized by alkali, either sodium hydroxide or ammonium, with
'pH between 8 and 10; a few are stabilized at low pH by special purification, by
replacing the water by polar organic solvent or by giving the particles a positive
charge with alumina. Commercial sols consist of discrete particles with very little
aggregation, since at high concentration any appreciable degree of aggregation
would greatly increase viscosity.
Dispersions can be made from certain grades of pyrogenic silica powders; these
are considered in Chapter 5. In powders with bulk densities less than about 5 lb ft- 2
the individual particles are so weakly linked that they can be dispersed at least to
aggregates of colloidal size in water at pH 9, by strong mechanical agitation or
shearing action. Powders of lowest bulk density and lowest specific surface area or
largest primary particle size can be dispersed most completely to sols. Since in many
references to applications it is not possible to distinguish between the sources of the
sols, the uses of sols of all types are considered in the following section.
USES OF COLLOIDAL SILICAS
In the following survey it is not possible to indicate the relative practical value or
importance of specific uses. It will mainly serve as a guide to the literature for those
engaged in application research. Only a small fraction of the issued patents related
' ,Ai"
.S~ ......, tt':T'.....A&
'4_
....,.....
.a.
Table 4.3.
Properties of Commercial Silica Sols Listed by Manufacturer
Q\
Stabilizer
Sol
(Manufacturer)
Ratio
SiOz:NazO
SiDz
LudoxllD (E. I. du Pont

de Nemours & Co.,
Wilmington, Del.)
Grade
(%)
HS-40
HS-30
TM
SM
40
30
50
30
40
30
35
30
30
xsLS
WP
(AS)C
AM"
Type
(%)
NazO
NazO
NazO
NazO
NH a
NazO
NazO
NH a
NazO
0.41
0.32
0.21
0.56
9S
9S
240
54
.'
0.10
0.62
300
0.13
230
130
pH
9.1
9.8
9.0
9.9
9.0
8.2
11.0
9.6
9.0
Particle
Diameter
(nrn)
Specific
Surface
(m! g-I)
Technical
Bulletin
12
12
230
230
130
360
130
130
130
210-230
210
EI0260 (1916)
E10260 (1916)
EI0260(1916)
E10260 (1916)
E10260 (1916)
EI0260 (1916)
E08913 (1916)
A82213 (1974)'
A21163
2~
1
21
12
21
13-14
IS
Positively charged sols-AlzOa coating
Nalcoags (Nalco
Chemical Co.,
Chicago, 111.)
l30Me
CL-X
30
46
Cl
0.9
1115
3261
EI36
1130
1030
1140
1050
1034A'
15
14.5
NazO
NaaO
0.8
0.01
30
30
40
50
34
30
NazO
NazO
NazO
NazO
0.65
0.40
0.40
0.35
CE-121
129
11
ee
3251
4.4
9.1
13-15
210
A85845 (1973)
E09550 (1976)
19
10.4
9.0
4
5
750
600
K-11I5
K-2326 (1975)
46
75
100
143
10.0
10.2
9.1
9.0
3.1
3.5
8
11-13
375
190-210
K-1030 (1976)
IS
200
17-25
16-20
16-25
120-116
135-190
K-1140 (1912)
K-1050 (1976)
K-I034 (1912)
Data sheet
(1914)
20
ISO
K-232S (1975)
9.3
20
150
K-2327 (1975)
35
I'
ISO
43J25
32?}
NH a
40
0.10
41001
, .'
.~
; .. 1. .. , . . . . . . . . . ,
;il i'I.~."'~ (C(~ ,,*.',. ;!':-tol':.,...." -~~, I~';; ,.:.; ,.l:;..t.I.;..;~~~i;N,;,t'I';;-fl~..t..-',~l...) 1'' '. . ~.-k~"
~
,; ...i ..~,. ,.~ ,...... .'
"'',I;
),
(1Y74)
\C-U.I
23251
( 43J25
2327J
( 41001
35
40
0.10
57
Na 20
0.10
1060
40004'
02149'"
02361"
50
50
30
30
Na 20
0.25
NH ,
AI2O,
0.03
1.8
215
830
1430
1440
2050
2034Ao
2046EC
1430 NH ,
15
30
30
40
50
34
46
30
Na 20
Na 20
Na 20
Na20 .'
Na 20
0.75
0.45
0.35
0.48
0.48
Snowtex@ (Nissan
Chern. Industries. Ltd.,
Tokyo, Japan:
200 Park Ave.
New York)
20
30
C
NP
Na 20
NatO
NatO
NatO
OP
20
30
20
20
20
Syton lOi (Monsanto, Ltd.

London, England)
W15
W30
W50
TIS
T30
X30
030
15
30
50
15
30
30
30
2600"
Nyacol~
(Nyacol, Inc.
Ashland. Mass.)
...
Not given
NH ,
0.2
0.35
0.6
0.2
0.04
Not given
Not given
Not given
Not given
Not given
Not given
Not given
20
150
K-2325
9.3
20
150
K-2327 (1975)
'75)
20
150
8.5
4.0
9.5
3.8
60
16-22
12-15
20
50
II
10.7
10.4
10.4
10
3.5
9.8
9.4
3-4
8
14
14
20
20
20
13-15
Data supplied
(1976)
9.5-10
9.5-10.5
8.5-9.0
9.0-10.0
3-4
10-20
10-20
10-20
10-20
10-20
Data received
(1977)
9.8-10.6
9.8-10.6
9.8-10.6
9.6-10.2
9.6-10.2
9.6-10.2
9.5-10.0
36
36
36
18
18
III
8.5
Data sheet
(1973)
K-I060 (1975)
210
150
"!
75
75
75
150
ISO
250
325
No. 53-3 (E)

M-E-2
( (975)
oIlo.
_-s.. _.
-- _
-.......- .&_....,.-....'"'.'
~Q,~ '._ ..-
.' .... 52
Table 4.3. (Continued)
00
Particle
Diameter
(nm)
Stabilizer
Sol
(Manufacturer)
Syton@ (Monsanto Co.
St. Louis, Mo.)
Grade
SiO,
(%)
C-30
C-40
C-50
200
240
250
30
40
50
30
40
45
Type
Ratio
SiOI:Na,O
(%)
pH
Sols no longer available

0.04
10.1
0.26
9.8
0.22
9.8
0.04
9.3
0.26
8.9
0.25
9.2
Not given
Not given
Not given
Not given
Not given
Not given
Specific
Surface
(rn ' g- I )
Technical
Bulletin
40
40
40
16
16
16
Sol contains O. I6% NH. and 0.08% Na,O occluded within particles.
o The value for SiO, includes 0.6% AI,O.
~I
.. An earlier type of AS differed in beingmore dilute, and of smaller particle size.

d Surface modified with aluminosilicate ions, 0.2% AI,O.
c 30% solids comprised of 26% SiO" 4% AI,O.
I Stabilizedwith ammonia (0.3%).
, Stabilized with acid only.
11 Stabilized with acid in aqueous alcohol.
, Dispersed in dimethylformam ide; pH at 50% dilution in H,O.
J Stabilized with ammonia.
It Dispersed-in oil (43%); fiber frictionizing.
, Dispersed in monoethyl ether of ethyleneglycol (available in 1970).
m Stabilized with 0.25% NH. (available in 1970).
n Positively charged sol (available in 1970).
o Stabilized by acid only.
P Stabilizer not disclosed.
, "
" ,r
,.
". '" ... 'l .
: . ,."
. I
419
to uses can be cited here. An extensive list was assembled in Monsanto Technical
Bulletin IC/SCS-237 (see Table 4.3) up to about 1967.
Colloidal silica found no consistent uses until concentrated, standardized, stable
sols become commercially available. In 1915, a dilute sol was produced by Schwerin
(464) by electrolyzing a solution of sodium silicate. In 1933, Griessbach (465) prepared a bibliography of the preparation and uses. A 10% sol stabilized with
ammonia was available at that time from I. G. Farbenindustries, A.G. Many of the
uses anticipated then have now been realized: application to paper and textiles, as a
rubber filler, and in ceramics and refractories. In 1945, White (5) of 'Monsanto
Chemical Company patented a process for converting alkaline silica gel to a relatively stable, 20% sol of heterogeneous particle size by autoclaving. In 1941, Bird (4)
of National Aluminate Co., and in 1951, Bechtold and Snyder (6) of E. I. du Pont
de Nemours & Co. patented processes for removing sodium from sodium silicate
solution by ion exchange and growing particles to a desired size while concentrating
the sol by evaporation, thus producing stable transparent sols containing 30% silica
as uniform particles 10-15 nm in diameter. Since that time, the scope of uses of
colloidal silica has grown, and the following types of applications are listed according to the purpose the silica serves:
...
..
(:;
:.0
ell '_
...
en
Q,
1. Making silica gels having surface area, pore size, and mechanical strength
determined by the particle size of the colloidal silica, for example, catalyst bases
and adsorbents.
2. Stiffening and binding fibrous and granular materials by incorporating sol and
drying to a rigid gel structure, for example, precision casting molds, molded
refractory products, arid high-temperature insulating materials.
3. Increasing the friction of surfaces ("invisible sand"), for example," railway
tracks, waxed floorscand textile fibers.
4. Anti-sticking, anti-blocking, antistatic effect on organic films.
5. Antisoiling treatments by: providing an ultrasmooth, oleophobic surface on
porous materials by filling micropores to exclude dirt particles, for example,
textiles, paper, and painted surfaces.
6. Providing hydrophilic, oleophobic surfaces by virtue of the highly polar SiOH
groups of the silica surface, for example, lithographic plates.
7. Increasing or reducing adhesion between surfaces, depending on the substrate
and method of application, for example, surfaces of organic films, glass, and
metals.
8. As a component of (a) thin refractory electrically insulating films on conducting '
surfaces, for example, laminations in transformer cores, or (b) conducting films
on insulating materials, for example, graphite coatings on paper.
9. Cross-linking, stiffening, and reinforcing polymers through association of
polymer chains with interspersed colloidal silica particles, for example, leather,
latex-foam products, elastomers.
10. Polishing agent for silicon wafers.
II. Modifying surfactant properties: flocculating, coagulating, dispersing, stablizing, emulsifying, suspensions; anti foam properties.
Colloidal Silica-Ccncentratea Sots
420
12.
13.
14.
15.
16.
Modifying viscosity: thickening. gelling.

Adsorbed coatings on surfaces; optical effects.
Photography; component in multilayer film systems.
Use in biological research; culture media, centrifuging medium.
Source of chemically reactive silica.
Making Catalysts, Gels, Adsorbents
"j
I
,I
The obvious advantages of starting with colloidal silica instead of sodium silicate are
the ease of incorporation with other catalyst components, the minimum washing
required to remove unwanted salts, and the wider, more uniform pore structure
obtained by forming the gel from relatively large. uniform colloidal particles. The
advantage of a catalyst base of colloidal "silica spheres in a densely packed arrange.
ment is that at elevated temperature, the mass cannot readily contract further and
collapse or sinter, and the uniform pores between the uniformly packed uniform
particles provide a constant surface area and high degree of catalytic activity (467).
The advantage of starting with colloidal silica to obtain a uniform distribution of
catalytic components in a gel catalyst is discussed by Maatman and, Prater (466). It
is difficult to attain uniform distribution by impregnating a preformed gel with a
solution of catalyst. The silica sol containing metal salts can be spray-dried Or
freeze-dried to give small spherical gel particles which can be further compacted as
desired (467). Sol can be converted to a fine powder by dispersing the sol in a partly
water-miscible organic solvent, gelling the silica, and distilling off the liquids (468).
After a catalyst has been deposited on particulate silica, silicic acid can be
deposited and dried to improve the strength (469). StileS. McClellan. and Sowards
have disclosed some typical uses of colloid in making catalyst base (470). Pre
sumably the catalytic activity of particles of colloidal silica added to diesel fuel
accounts for its prevention of fouling (471).
The formation of porous microspheres for use in chromatographic columns was
described earlier in connection with coacervation (343). A chromatographic column
packing of another type has been made by using the multilayering technique. For
most efficient separations a packing is needed in which there is a maximum area and
volume of porous adsorbent with minimum thickness. This was accomplished by
Kirkland. who deposited several layers of silica particles onto the surface of glass
beads to form a uniform porous film into which diffusion is rapid; yet there is no
porosity in the center from which diffusion is slow (472). A coated bead of this type
is shown in Figure 4.28. Structure and uses of the packing have been described in
several papers (473. 474).
Inorganic Binder, Stiffener
One of the earliest proposed uses for colloidal silica produced from sodium silicate
by ion exhange is in ceramic cements to improve strength (475). In this type of use
'7..-_.
rated Sols
licate are
washing
structure
des. The
arrange-ther and
uniform
f (467).bution of
(466). It
el with a
-dried or
pacted as
-tty
s (406).
1Q
can be
Sowards
70). Preiesel fuel
irnns was
c column
ique. For
area and
dished by
e of glass
iere is no
. this type
scribed in
m _ zate
/pe of use
421
Figure 4.28. Packing for chromatographic column: glass microbeads coated with a porous
layer of colloidal silica. Left: dp , diameter of microbead; d p/30, thickness of coating. Right:
electron micrograph of coating.
. -v .
colloidal silica acts as an adhesive binder or stiffener at ordinary temperature

because it is converted to a solid gel. Its effectiveness is in direct proportion to the
strength of the gel, the theory of which has been discussed earlier in this chapter.
In some cases the silica is used for its high chemical activity. Thus when glass
powder is coated with colloidal silica it can be molded. When heated. silica dissolves
in the glass so that a solid sintered body is obtained (476). The strength of colloidal
silica as a binder is apparently enhanced by transferring it toan alcohol and producing a mixture with ethyl silicate (477. 478). Where colloidal silicia is to be used as a
binder for a silica powder, stronger bonds are formed below the devitrification
temperature when boric acid (1':5%) is added to the silica sol to lower the sintering
temperature (479). Combinations of colloidal silica and polyvalent metal hydrogen
phosphates give strong bonds when heated, probably because some-combination of
silica and phosphate ion occurs. However, the phosphate usually reduces strength at
high temperature.
Improved bond strength in ceramic bodies is attained with mixtures of monoaluminum phosphate and colloidal silica when used with finely divided refractory
powders of zircon, zirconia, or alumina (480). The reaction of P,Oa with silica at
relatively low temperature develops high bond strength in refractory compositions;
thus silica sol may be mixed with ammonium phosphate or other PzOa precursors at
relatively low pH and used in minimalquantities as a binder in refractories (481, 482).
According to Lee, the binding properties of colloidal silica are improved by adding a
soluble quaternary ammonium silicate such 'as tetramethylammonium silicate which
is sufficiently alkaline to interact with the colloidal silica and coalesce it in a cement
structu re (483).
A typical use of colloidal silica as a binder for refractory particles to make a
refractory ceramic was described by Reuter (484), who described a castable mixture
422
of colloidal silica and pulverized refractory grain along with a gelling. agent to set the
mixture. Maziliauskus (485) reviewed the uses of colloidal silica in ceramics a"
developed by 1958. A strong ceramic bond is formed at relatively low temperature.
Very high strength gels have been made by Shoup from mixtures of potassium sili-cate and colloidal silica as described under potassium polysilicate in Chapter 2
Refs. 97 and 98. Such compositions may have high binder strength in cases wh~r;
the residual potassium salt is permissible.
Molded Refractory Bodies

'Refractory bodies of various types have been made from silica alone or by using
silica as a binder for ceramic particles. Bergna (486) describes making transparent
,
blocks .similar to "fused silica" by hot pressing pure silica powder, made by spray_. ,:.;"
drying colloidal silica, at 12OOC and 2000 psi for 5 min.
~
Spray-dried purified colloidal silica has been compacted and sintered by Bergna
and Simko to produce an opaque, amorphous silica body, similar to "fused quartz"
but having up to twice the transverse rupture strength because of the presence of
cylindrical or tunnellike pores which act as "crack-stoppers" (487). This novel structure is obtained through the compaction of the 1 micron spherical gel particles so as
to leave macropores between them, before the mass is fired. Within the spherical
particles the ultimate colloidal silica particles sinter completely to a nonporous
state, whereas between the spherical particles there remain macropores forming an
interconnecting, three-dimensional network of channels, which are not completel
collapsed during sintering. The body has a density of 91-99% of theoretical. If th~-.,
temperature is raised to the point where these pores also collapse and 100% of
theoretical density is attained, the strength of the bodydrops to that of conventional
fused silica.
Pure silica molded bodies can be made by sintering strong, dense silica gel made
from a mixture of potassium silicate and sodium silicate, as described by Shoup
(Chapter 2, Ref. 96).
A mullite bonded refractory was made by mixing colloidal silica and basic aluminum chloride in proportions to form mullite and using this as a binder for mullite
powderto form a mullite refractory body at 1300C (489). Refractory bodies of sillimanite have been bonded with a mixture of colloidal silica and basic aluminum
chloride acting as a binder for sillimanite powder, fired at 1300-1400C (488).
Although not strictly a ceramic, cold-molded metal bodies with thermal conductivity can be made from metal powders using colloidal silica and latex as the binder
(490). When colloidal silica is mixed with refractory powder and cast into a mold,
the ceramic particles settle and segregate. Also, as the mass is dried, the colloid
migrates to the surface with the water and the interior is robbed of binder. For these
reasons it is usually 'necessary to gel the silica in place or to at least develop
thixotropy to prevent the migration. This is accomplished either by adjusting the pH
to the range where gelling will occur in a known time or by adding a delayed gellinagent such as a silicofluoride which slowly releases HF. Another approach is to ad,
powdered alkali metal silicate glass which slowly dissolves and causes gelling (491). .~-
urated Sols
to set the
ramics as
en
~.
ssium sili'hapter 2,
ses where
Binders for Fibers
. by using
ansparent
by spray>y Bergna
d quartz"
.esence of
ivel strucicles so as
spherical
ionporous
mning an
or -tely
cal; the
100% of
iventional
423
An inorganic binder for inorganic fibers is made by dispersing clay in colloidal

silica, then acidifying to pH 3.5 and adding an aluminum salt such as aluminum formate. Glass fiber insulating block bonded with this composition retains excellent
strength at elevated temperature (492). A mixture of colloidal silica and polyvinyl
alcohol is patented as a binder in fiber glass insulating material which retains its
bonded character even after the polyvinyl alcohol has been burned out (493). The
colloidal silica can be attracted to the inorganic fibrous material by incorporating
positively charged starch into the colloidal silica, thus providing an improved bonding mixture for asbestos or aluminosilicate fibers (494). Fire-resistant reflective insulating material is made by binding fibrous potassium titanate with a mixture of latex
and colloidal silica (495).
Colloidal silica is used as he binder in highly refractory aluminosilicate fibers
(496). To maintain even distribution of the binder, a thickener such as an acrylic
polymer is used (497). Moore mixed colloidal silica with various types of latex which
is coagulated after the binder has been applied to the fibers (498). The stiffness and
strength of organic fiber sheets or papers can also be improved with colloidal silica
(499-502). In paperboard used for corrugating, stiffness is improved by impregnating with colloidal silica (503). From I to 5% colloidal silica in certain paper pulps
gives improvement in strength, stiffness, stability, etc. (504). Properties of polyimide
fiber laminates and sheets are improved by impregnation with colloidal silica.
Leather is plumped and firmed after absorbing colloidal silica (505).
_&
gel made
by Shoup
basic aluor mullite
es of sillialuminum
:8).
II conduc:he binder
o a mold,
he colloid
For these
t develop
ng the pH
ed cY~lling
I
is
rg
add
(4~1).
Refractory Coatings
.
:
-,
~
A major use of colloidal silica, as indicated by the number of pertinet patents, is

in coatings to resist the "erosive effects of molten steel on the "stool" or base of the
mold in which ingots are cast,' The coating prolongs the life of the base and aids
removal of the cooled ingot (506)~ In stool-coating compositions of pulverized amorphous silica glass and colloidal silica, evolution of hydrogen from metal
contaminants poses a problem that is solved by adding certain water-soluble dyestuffs (507). 'These inhibitors also prevent the evolution of hydrogen from suspensions of finely divided metals such as zinc in a binder medium of colloidal silica. The
compositions are concentrated slurries of a carefully sized refractory powder in a
concentrated silica sol usually 10-50 nm in particle diameter. The composition must
be such that when it is sprayed on a hot stool it instantly solidifies and dehydrates so
as to leave a dense coherent coating (508). For greater strength, Snyder claimed the
use of silicic acid of low molecular weight (less than 90,000) (509). A stabilizer to
prevent settling of the refractory grain in the sol binder is benefincial according to
Pollard, who claimed the use of "Xanthomonas" hydrophilic colloid sold as
"Kelzan" as a thickener (510). Additional compositions were; claimed by Kearfott
and Baer (511). Further complex formulations are described by Rusher (512), who
used a thickener, anti-gassing agent, adhesion promoter, wetting agent, and other
typical refinements in this highly specialized type of product.
.,.
424
~--
Molds Jor Casting Metals

Colloidal silica has long been used in the investment casting industry. An important
use of colloidal silica is as a binder in refractory molds prepared for precision invest_
ment casting, which was one of the applications visualized in 1945 when colloidal
silica first become available. Collins patented a plastic mixture for making a refrac_
tory mold comprising a refractory filler and aqueous colloidal silica, along with a
small amount of gel-promoting agent (513). Cloherty and Emblem (514) discussed
this use of silica sols. Reuter patented the basic idea of using colloidal silica as a
binder in such compositions by adding a controlled amount of electrolyte to catalyze
the setting of the silica sol to gel (515).
A combination of colloidal silica with an organic polymer binder for making
precision investment casting shell molds is patented by Emblem, Mountford, and
Morely (516).
Technical papers on the use of silica sols in making molds have been presented by
Emblem (517, 518).
Patents have been issued covering spraying the wax pattern with silica sol and acid
(519), coating with a concentrated acidic alcohol-water sol (520), using a dye in the
coating slurry that indicates when the coating has dried (521), and use of aluminacoated silica sol (522). A rapid buildup of the ceramic mold around the wax pattern has been accomplished by Beyer, Moore, and Rusher by a process that does not require drying after
each spray-coating or dip. Two suspensions of ceramic powder such as zircon are
prepared, one in a concentrated, alkali-stabilized sol of colloidal silica, another in
positively charged, alumina-coated colloidal silica. The pattern is dipped or sprayed
alternately with the mixtures, each of which coagulates and gels the other (523). The
.positively charged slurry may be stabilized with a complexing agent such as citric
acid (524). Other approaches involve alternate dips in ceramic slurries of colloidal
silica, or of sodium silicate, and a basic aluminum salt as coagulant (525) or a
polycationic setting agent (526). Cores for foundry molds can be made with colloidal
silica as a binder for foundry sand and silica flour, along with gelling and wetting
agents (527).
~;
Miscellaneous
,
"
Some types of plaster, for example, gypsum, can be made up with water containing colloidal silica to give cast bodies of superior strength (528, 529). However,
experience has shown that colloidal silica cannot be added to calcium-containing
cement mixtures that are too alkaline, because the silica is gelled by the calcium at
high pH. In Portland cement it causes swelling and cracking (530), but the sand or ,
fiber to be used can be coated with colloidal silica to prevent migration of harmful
impurities or solutes into the cement (531).
Low density fireproof thermal insulation is bonded with colloidal silica. One type
is a moldable foam of soluble silicate and colloidal silica foamed with a cationic
surfactant. The foam type may include a polyalkylsiloxane for improved water
resistance. Another is expanded perlite bonded with soluble silicate and colloidal
'~-
425
silica, especially useful as a replacement for asbestos insulation oft steel pipes
(532-534). A strong lightweight body is obtained by adding ammonia to a 45% silica
sol to obtain a soft gel, after which perlite is stirred in before it is dried (535).
Diamond powder is bonded into larger granules by silica to form abransive particles. The diamond powder suspended in 30% silica sol is poured into agitated 2ethyl-I-hexanol, followed by butanol, whereby silica granules with embedded diamond particles are obtained. The particles are sintered at 500C to harden them
(536).
Frictionizing Effects
The high friction observed between surfaces of sandpaper can be duplicated on an
invisible scale on various surfaces with colloidal silica. One of the early large-scale
applications of colloidal silica was in floor wax to make it less slippery (537, 538).
Powers and Harrison (539) applied colloidal silica to loose fibers before spinning to
reduce slippage and improve tensile strength.
Fibers
containHowever,
ontaining
alcium at
e sand or
fharmful
One type
1 c
-nic
-ed water
colloidal
Numerous patents have been issued on specific compositions or conditions for applying colloidal silica to textile to improve friction properties (539-551). Colloidal silica
. is coated with a cationic quaternary ammonium type of surfactant before application
to textiles for good frictionizing (552). Because of its frictionizing effects, silica is
also an aid in processing wool (553, 544).
Another use for a silica coating on an organic fiber is. where the latter is to be
pyrolyzed to form a new chemical structure, but where in the intervening period the
fiber must be supported mechanically as it goes through a plastic state. Barnett and
Zager coated pclyacrylonitrile.fibers with colloidal silica to serve as a support while
the fiber was converted to self-supporting cross-linked state by being heated (555).
Textiles are made more snagproof by improving fiber friction (556). Pyrogenic silica
is dispersed in water with a surfactant for application to textiles (557). Slippage of
glass fibers Is prevented and colors are simultaneously bonded to the surface by the
application of colored metal oxides along with colloidal silica and heating to bond
the coating. To prevent knots in nylon fishnets from slipping, colloidal silica is
mixed with CH 3[H 2N(CH2),]Si(OEt)2 and water and applied to the knots (559).
Paper
The need for greater friction between bags piled in a truck is obvious to the driver
who sees his load sliding to one side. Wilson increased the friction by treating the
surface of the paper containers with colloidal silica, after which the containers
remained as loaded, with no slipping (560). When it came to apply colloidal silica to
the paper going into the containers, the problem arose as to how to readily test the
paper for silica. Turner used a colorless lactone compound which he sprayed on the
paper; it turned blue only if silica was present (561). This is the same type of reac-
426
CoUoidal Silica-Concentrated Sols
tion that made possible the "no carbon paper" duplicating system develdped by the
National Cash Register Co. (562). The colorless lactone dye does not turn blue in I
contact with cellulose, but in contact with the surface of colloidal silica particles or ',
clay particles in hydrogen ion form, a deep blue color develops. The colorless lactone
"may also be used to develop invisible printing of colloidal silica on the surface of
paper. The addition of some fine clay to the sol along with antifoam and wetting
agents improves the frictionizing effect when applied to kraft paper (563). Tbe Use of
larger, 60 nm particles, was patented by Vossos (564). Formulations of. colloidal
silica with polyethylene glycol dioleate, glycerol, and glutaraldehyde gave superior
antislip effects (565). To act as a thickener and keep more of the silica on the Surface, aqueous colloidal silica is thickened by dispersing in it a low density silica
powder (566). The general application and performance of such antislip coatings was
reviewed by Fletcher (567).
Steel Rails
. i
Colloidal silica improves traction of locomotives especially where oil films are
present on the rails. Formulations for application to rails involve colloidal silica in a
water-miscible organic solvent along with wetting agents (568).
Other Surfaces,
Sliding parts of a keyboard musical instrument can be treated with colloidal silica to
give a better "footing" against slipperiness (572). The surface of polyethylene
terephthalate drafting film is improved with respect to reception of pencil and ink by
application of colloidal silica (573). In the same way polyolefin or polyolefin coated
paper is made ink-receptive by applying colloidal silica along with an acid-soluble
film-forming material (574).
AntisoiJing Surfaces
A film of. colloidal silica on the surface of fibers, as in carpets, greatly reduces the
pickup of dirt and leaves a cleaner appearance after vacuuming. It has been postulated that the silica forms a smooth adherent film to which soil particles do not
cling, especially because it fills crevices in the fiber surface that would otherwise be
filled with dark particles of dirt. Similar effects are reported on painted surfaces,
plastic fabrics, window shades, and wallpaper (575). This type of use for colloidal
silica was patented by Cogovan and Frederici (576). The advantage of using two
hydrous colloidal metal oxides together is claimed by Florio and Rainard (577).
Soluble aluminum phosphate is claimed to improve the' adhesion of the silica to the
fiber (578).
The theory of filling submicroscopic surface irregularities with colloidal silica, as
on painted surfaces, has been described by Rusher and Yates (579). To reduce soiling of a hydrophilic surface such as upholstery fabric by making it both hydrophobic
and soil resistant, a polydirnethylsiloxane oil is incorporated with colloidal silica
rated Sols
Uses or Colloidal Silicas
ed by the
using a metallic soap emulsifier, and applied to the cloth and cured (580). An
improved sol for soil-resistant finishes on fabrics is obtained by acidifying colloidal
silica and adding a small proportion of aluminum formate to make the silica
substantive to the fibers (581). To reduce static as well as improve soil resistance, a
combination of colloidal silica and a colloidal clay such as montmorillonite may be
used (582).
Even metal surfaces can be made resistant to soiling by adhesion of carbon black.
Metal strips of venetian blends are coated with silica, heated to 250F, and buffed
with talc (583). A rapid carpet cleaner is composed of colloidal silica and dIatomaceous earth (584). Water- and soil-repellent finishes for fabrics involve treatment with colloidal silica and Volan~ methacrylate-chromic chloride (trademark
registered by E. I. du Pont de Nemours & Co.) along with I,I-dehydroperfluorooctanol resin, polyethylene glycol, glyoxal, and acetate buffer in mixed alcohols.
After curing at 150C the fabric is highly soil resistant (585). As an antisoiling treatment for nylon that also acts an an antistat, positively charged alumina-coated silica
particles are preferred (586). The principles of the use of silica as an antistat have
been discussed by Ferch (587).
.
n bl.. ~ in
rti .. or
;s lactone
urface of
J:wetting
~e use of
colloidal
superior
. the"surity silica
rings was'
;rj
~
.Ji5
.1
.''''!''"
;~
.~
....
'"
1.'
~
:~
..
.~
ilms are
ilica in a
427
Hydrophilizing Surfaces
/et.......ene
id ink by
n coated
f-soluble
luces the
n postui do not
.rwise be
surfaces,
colloidal
sing two
-d (577).
:a to the
silica, as
uc
'it-opnonic
lal silica
Silica is one of the few materials in nature that is fully water-wettable. It becomes
hydrophobic only when covered with soap-forming polyvalent metal ions or organic
bases. The universal wettability of the sands of the seashore attests to the natural
hydrophilic character of silica.
A water-wettable surface is important in the lithographic.printing art, where printing surfaces holding theoil-ink must be hydrophobic and ink-wettable, but the nonprinting water-wettable surfaces must be very resistant to encroachment by the oilink, and permanently hydrophilic. A variety of patents has been issued in this field.
Transfer of oil-printing is prevented by a spray of colloidal silica (588). The hydrophilic nature of "planographic" paper printing plates is preserved or renewed by
colloidal silica (589, 590). A new type of lithographic printing plate is patented by
Marron (591), in which a hydrophilic film of colloidal silica contains dispersed inkreceptive material which is released to the surface by pressure or heat to form printing areas. A similar effect is involved in planographic offset masters (592).
An appreciation of the value of hydrous oxide colloids for wetting hydrophobic
surfaces with water is shown by Kenney (593), who claims that certain aqueous
particulate colloids can wet any known hydrophobic surfaces. without chemical
change. However, I have found that wetting by a silica sol occurs on certain hydrophobic surfaces only at low pH and with an optimum particle size of silica. After the
surface has been wetted by sol, rinsed, and dried, the area is rewettable only because
there remains an adsorbed monolayer of silica particles bonded to the surface. The
type of bonding depends on the type of hydrophobic surface. For example, a metal
surface, hydrophobic because of an adsorbed film of fatty acids (grease) is made
hydrophilic by the silica replacing some of the fatty acid and bonding to the oxide
surface film until the area is well populated by silica. This occurs mainly at neutral
-:...---
428
or low pH and is accelerated by the presence of water-miscible organic ~olvents such

as alcohol to help remove the fatty acid.
On the other hand, organic polymer films such as polyester or polyamide are
hydrophobic because the polar groups are normally turned inward, away from the
surface to permit mutual hydrogen bonding. When a silica sol is applied at pH 2-4,
the amide linkages or amino-end groups, if any, turn outward to the surface to
hydrogen-bond with the silica. In the' case of polyester, colloidal alumina is a better
wetting agent since it reacts with the carboxyl end groups. In the surface of polytetrafluoroethylene, it must be the carboxyl end groups of the fluorocarboxylic
surfactant commonly used in emulsion polymerization that permit wetting with
colloidal oxides. Grot (594) claims that to obtain a porous hydrophilic membrane of .
polytetrafluoroethylene, colloidal silica is incorporated into the polymer surface so
as to provide ionic conductivity through the pores.
Modifying Adhesion
Colloidal silica can be applied to surfaces either to increase the adhesion to other
materials, in effect by roughening the surface if the silica is adherent, or to decrease
adhesion by holding otherwise "sticky" surfaces apart.
.
Increasing Adhesion
i:
If silica particles are anchored to or embedded in a surface, the submicroscopic

roughness and polarity of the surface are increased and adhesion of a second
material is generally improved; on the other hand, if the silica is present as a loose,
friable coating, or is applied as a mixture with a silicone or fluorocarbon polymer,
adhesion is reduced.
Silica particles are embedded into the surface of polyethylene film to improve the
adhesion of coatings of thermoplastic polymers (595). A fluorocarbon polymer surface is made cementable by coating it with the mixture of dispersed polytetrafluoroethylene and colloidal silica, and heating the surface to over 500C for a few
minutes (596). On glassine paper used to separate uncured sheets of rubber, adhesion
is needed on one surface but not on the other. One side of the paper is treated with
0.04-0.6 Ib of colloidal silica per 1000 ft 2 so that rubber sheeting will stick only to
the treated surface when stored as a roll (597).
A film of polyethylene is strongly adherent if heated against paper coated with
colloidal silica (598).
A coating composition of polytetrafluoroethylene contains alkali metal silicate
and colloidal silica to improve adhesion and electrical insulating properties on metal
surfaces (599).
The adhesion of colored coatings on glass fibers is improved by first treating the
fiber with conoidal silica and heating to just below the fusion temperature (600).
Colloidal silica is also added to adhesives (601). Colloidal silica plus a contactpressure type of binding resin may be used for laminating cellulosic fabrics (602).
.
.
-Uses of Colloidal Silicas
ntrated Sols
vents such
an.
are
, from the
at pH 2-4,
surface to
is a better
:e of polycarboxylic
tting with
mbrane of
surface so
n to other
o decrease
,..
:i
:~
, ,'"
,"'Z
icrc, ..opic
a second
IS a loose,
, polymer,
iprove the
yrner sur/tetrafluofor a few
. adhesion
eared with
:k only to
.ated with
al silicate
.on metal
eating the
He (600).
set-
~ C
(60~J'
....
429
Colloidal silica along with oxalic acid is applied and "burned" into 'he surface of
iron and steel before a chemical coating of oxalate or phosphate is formed. The
initial product of the oxalate and silica reaction probably is pyrolyzed to form areas
of tightly bound silica and iron silicate which then anchors the chemical coating
(603). A silica coating on metal to provide increased adhesion to organic polymers is
made by mixing colloidal silica' with a dilute solution of a carboxylic polymer as
ammonium salt at pH 6.5 and applying it as a film to ferrous metal. After drying,
the organic polymer minimizes crazing of the silica coating. Alginic acid may be
used (604). Chromic acid is used to form a rust-preventing film on the surface of
zinc or galvanized iron. An improved film with better rust protection and adhesion
of paint is obtained when colloidal silica is present in the 'H 2CrO. solution (605). It is
probable that the chromic acid produces a mixture of hydrous F~OJ and Cr20~ in
which the silica is coagulated and embedded. Adhesion of polytetraCluorethylene to
metal cookware is improved by including colloidal silica in a primer coat (606). In
polyester fiberglass laminate adhesion between resin and glass can be improved by
mixing colloidal silica with the conventional unsaturated alkylaminosiline finishing
agent so that the"surface is covered with colloidal silica particles which are also
coated with polymer-reactive surface groups (607). Elmes claims that on fiber glass
tire cord, incorporation, of colloidal silica into a resorcinol-formaldehyde plus
,poly[butadiene-styrene-2-vinylpyridine] finish gives stronger adhesion to natural
rubber-SBR blends (608). A fourfold improvement in adhesion of polyester tire cord
to natural rubber-SBR blends is reported by Sakata and Tanaka (609) when the
cord is pretreated with a chlorophenol and silica is dispersed in the rubber formulation before it is vulcanized.
Incorporation of 2.6% colloidal silica into a polyolefin resin before polymerization, followed by etching-to expose silica at the surface ofa molded body, allows the
polymer to be electroplated (610).
-
Decreasing Adhesion
It may seem unexpected that whereas silica can increase the adhesion to surfaces, it
also can reduce adhesion between similar surfaces. The well-known addition of small
amounts of dry, low-density silica powders to prevent caking of granular material is
considered in Chapter S. Considered here are uses in which sols are applied to
various materials to reduce adhesion.
Fine glass beads are made free-flowing by treating the surface with a mixture of
aqueous colloidal silica and a long-chain alkyl quaternary ammonium salt along
with isopropyl alcohol (611).
In the pharmaceuticals field, colloidal silica is listed as an official ingredient in
Hungary (612). It makes it possible to dispense numerous drugs in dispersed solid
form.
When iron ore is reduced in a fluidized bed it tends to stick together before reduction is complete. A silica film on the particles overcomes the problem (613).
Small particles of silica on the surface of a polyester film act as spacers, preventing sticking and blocking. In this case silica may be deposited from reacting vapors
.
~--
j::: .
430
r,
. l
of SiCI. and H 20 (614). Blocking does not occur in cellophane if th"e surface is
treated with a dispersion of pyrogenic silica in an aqueous solution of polyethylene
imine or soluble stage of melamine formaldehyde .resin (615). It is possible that an
anti-sticking effect explains why colloidal silica in the coolants used in metal-cutting
prevents welding of the chip and improves surface smoothness as claimed by Breton
(616).
Coating Compositions
f
. i
.'
,
"
',i
. ,.
.;
Organic coating compositions with improved adhesion, hardness, durability, and

electrical properties are obtained by adding colloidal silica to organic polymer
dispersions (617-623).
Inorganic coatings may employ silica as the main component or as a binder in the
composition. In coatings mainly consisting of silica the problem is to prevent
shrinkage and crazing. This has been discussed in connection with the strength of
gels. It is almost impossible to produce a thick silica coating that is not porous. By
starting with pulverized "fused silica" glass of graded sizes to obtain closepacking,
and suspending this in a minimum amount of a concentrated sol of colloidal silica
also consisting of several particle sizes for dense packing (219), a dried body of
maximum hardness and minimum porosity is obtained which shows minimum
shrinkage during subsequent sintering at lOOOC or more.
The film-forming properties of colloidal silica are improved by dispersing
microfibrous materials in the sol to minimize crazing. Barbaras (624) claimed the
use of chrysotite asbestos which, in short-fibered form, can be dispersed colloidally
in alkali-stabilized silica sols. Crazing is also minimized and film strength improved
by adding certain water-soluble polymers, although many polymers are deleterious.
Gelatin (625), polymerizable cyclic sulfonium zwitterions (626), and a non-gelling
flocculating agent such as a linear hydrocarbon polymer with a quaternary imidazole
in side chains (627) have been claimed as useful.
Crazing is also minimized if the coating is built up slowly by spraying the solon a
gently heated surface (628).
Inorganic paint for asbestos board can be made with silica as a binder. Hard,
weather-resistant paint is made with a combination of colloidal silica, lithium
hydroxide and potassium silicate or alkali metal phosphate, clay, and pigment, and
baked on in the presence of steam (629). Collidal silica stabilized with tetraethanol
ammonium silicate was used as a binder for iron oxide and clay pigments (630). A
heat proof coating for asbestos or metals consisted of colloidal silica and magnesium
hydrogen phosphate (631) and was hardened at 200C.
On steel surfaces being hot worked, a coating of finely powdered chromium metal
bonded with colloidal silica prevented scaling when the metal was hot rolled at
1090C (632). When steel. zinc, or aluminum are dipped "in an acidic silica sol
containing sugar, an invisible film of silica is deposited which after suitable heating
improves resistance to chemical attack (633). A coating of colloidal silica acts as a
stop-off on steel in galvanizing (634).
-.
i
-,
.",.
~_
..-
entrated Sols
: surface is
olyetl.vlene
.bl, .it an
etal-cutting
I by Breton
431
When hot metal is quenched in water the cooling rate is high but 1f silica sol is
used, the quenching rate is much slower. Thus, in tempering steel, the cooling rate
can be controlled by varying the silica concentration. The effect is no doubt due to
the formation of an insulating coating of silica on the hot metal surface (635).
A corrosion-resistant coating on steel is applied as a mixture of colloidal silica,
trivalent and hexavalent chromium compounds, and an alkali metal cation in
specified ratios (636), and cured. . .
A very thin insulation layer can be placed between metal conducting layers in
str~tified multilevel conductors.
Silica sol is applied to a lower conductor layer and
.
spun to leave a film 10 nm thick. This is repeated several times so that any pinholes
will be staggered. An upper conductor is applied over this pinhole-free layer. Windows can be left in the silica film if conduction is required between them (637).
Insulating coatings are required on the magnetic steel sheets in laminated
transformer cores. Robinson (638, 639) invented coating compositions in which
colloidal silica is the binder for a refractory material such as magnesium oxide.
Another coating for the same use is made of colloidal silica and ammonium phosphate, the latter furnishing pzO. to react with the silica and bond it to the steel (640).
A pure silica coating is applied to steel by adding gelatin as a temporary binder to
colloidal silica in the proportion of 1.5-3 parts of gelatin per 8 parts of silica. This
composition, applied as a film, can be heated to decompose the gelatin and leave a
pure silica coating on glass or metals. Improved adherence of oxide coating on
metals is noted if the surface is first covered with a film of colloidal silica, and then
the metal heated in air to develop the film which forms under and through the
porous silica layer to give an impervious, adherent finish that reduces further oxidation at high temperature and improves corrosion resistance (641). A decorative
finish is obtained on metal objects by first anodizing the surface in an alkaline solution containing colloidal'silica to form a very thin invisible insulating film in certain
areas, forming a pattern, and then applying over this a bright nickel plate which
brings out the previously invisible pattern (642).
Corrosion-resistant coatings may involve later heating the applied polymer to fuse
or convert it to the impervious state. By first coating metal with a phenolic resin and
colloidal silica mixture, polyolefins can then be fused to the surface (643). Quaternary ammonium polysilicate (Qurame 200) mixed with acrylic-ethylene
copolymer and ethylamine is baked on steel at 300C and heated at 800C in a
reducing atmosphere to develop a black adherent glossy coating with good insulating
properties (644).
A fluorocarbon coating can be applied to metal or pottery along with methyl
cellulose and colloidal silica to give adhesion (645). Such coatings for cook ware
usually involve colloidal silica or polysilicate to obtain good adhesion (646-648).
Conductive electrical coatings to be used at elevated temperature generally involve
graphite bonded with colloidal silica. Smith-J ohannsen uses about equal parts of
silica and graphite to produce a conductive film on paper or asbestos sheet through
which an electric current is passed to generate as much as 20 watts of heat per
square inch. The surface resistance is from 10 to 1000 ohms per square (649). He
subsequently found that by drying this coating at 350F, sodium silicate adhesive
can be applied to attach an asbestos covering without changing the resistance (650).
.
ibility, and
ic polymer
inder in the
to prevent
strength of
porous. By
isepacking,
oidal silica
ed body of
minimum
d., . ising
.lairned the
colloidally
1 improved
leleterious.
non-gelling
, imidazole
he solon a
der. Hard,
ia, lithium
~ment, and
etraethanol
ts (630). A
nagnesium
iiurn metal
t rolled at
~ silica sol
ole '.ting
a ac... as a
-;~
;~
~
.',
432
The dyeing and printing of glass fiber textiles involves the use of col1~idal silica in
the coating either as a precoat (651) or included in the organosilane binder for the
pigment (652).
In multiple coatings on paper, a coating of colloidal silica can act as a storage
layer for reactive compounds. Thus in a pressure-sensitive coating, a base layer silica
retains copper and nickel salts which react and develop color when the
microcapsules containing dithiooxamide in the upper layer are broken by pressure
(653).
Coatings on Ships, Tanks
.': .~
.
~
~
~~.,
,
,-
I'
"
r L, :
~ ~: 1 ,;
.' ,.r ,".J.

....
t -.:;
!
': ,
A special type of coating for steel is used where exposure to crude oil and seawater is
encountered, as in oil tankers. This involves an inorganic paint containing zinc
powder which gives cathodic protection against localized corrosion. This has already
been discussed in connection with the uses of lithium silicates in Chapter 2. Some
further points are as follows.
In zinc-rich paints some early patents indicate the importance of a silica
component. Colloidal silica was reacted with finely divided zinc to form a colloidal
zinc silicate in which the excess zinc metal was suspended (654). A water-insoluble
binder for zinc-containing coatings was produced by mixing alkali-stabilized
colloidal silica with lithium hydroxide in suitable proportions (655). Evolution of gas
from mixtures of colloidal silica with zinc powder is prevented by adding an indigoid
compounds (656).' Another formulation involves quaternary ammonium polysilicate
solution milled with lead oxide as the binder for zinc (657). Some of the problems
stem from the impurities in the zinc powder which promote reaction with the
medium (658). Adhesion .of paints of this type of steel is improved by adding up to
2% of a styrene-acrylic resin dispersion (659).
An anti-fouling -paint for ships, containing tributyltin oxide, is bonded with
colloidal silica and resin dispersion, the silica being made organophilic by the addition of a cationic surfactant (660).
-Reinforcing Organic Polymers
The strengthening or reinforcing effects of colloidal silica in organic polymers, films,

and fibers are so varied that they are not categorized. Silica has been incorporated
into polyolefins (661), thermoplastic organic polymers (662), potyamides (663), and
other types (664). Reinforcement of silicone polymers with silica in various forms is
a highly specialized technology beyond the present scope of consideration.
Copolymerization of colloidal silica and a soluble silicate polyester gives a strong
water-impermeable mass (665). Reinforcement of rubber by incorporating silica
powders is covered in Chapter 5. Aqueous sols are used in the rubber industry
mainly for stiffening open-cell foamed rubber. The silica d~posited on the walls of
the pores apparently has a frictionizing effect, making the foam less easily
compressed and thus increasing load bearing capacity (666-668). A pickup of only
3% Si0 2 increases compression resistance by 90% (669). Superior results were
...
~---
urated Sols
al silica in
ler r"., the
obtained with a metal-free sol of particles only 1-3 nm diameter as corhpared with 8
nm diameter (670).
polyvinyl alcohol films can be stiffened and insolubilized in water after incorporation of colloidal silica (671-673). Hard PVA molding material is made from a mixture of the polymer solution and colloidal silica, with glycerol as plasticizer. The
heat-pressed sheet was strong, stiff, and impact resistant (674).
a storage
ayer silica
when the
y pressure
433
polishing Agent for Silicon Wafers
eawater is
ining zinc
as already
~ 2. Some
f a silica
colloidal
<insoluble
-stabilized .
ion of gas
n indigoid
oly ":cate
prl..~.ems
In the electronics industry wafers cut from single crystals of silicon are polished to
extreme smoothness using colloidal silica as a polishing medium at high pH. Even
the finest conventional abrasive powders are much too coarse. Details are described
by Walsh and Herzog (675). An improved sol is claimed by Sears, who stabilized the
silica particles against dissolution by alkali by applying a partial coating of aluminosilicate anionic groups, thus making it possible to operate at a pH of II or more for
a more rapid rate of polishing (676). .
, . Very pure silica particles, 10-20 nm in diameter, are formed by hydrolyzing
(C 2H,O),Si in a butanol-water-ammonium system. The precipitated silica is dried
and dispersed at pH 11 with (CH,),NOH for polishing (this base probably tends to
repress the dissolution of silica at high pH) (677). Silica partiles less than 100 nm in
size in a slurry at pH 10 thickened with a water-soluble cellulose derivative are disclosed by Tredinnick, Gambale, and Dupree (678). A suspension of microfine
precipitated silica in a solution of quaternary ammonium silicate at pH 10 can also
be used for polishing (679).
.
with the
ling up to
.'
Surfactant Effects .
ided with
the add i-
ers, films,
orporated
:663), and
s forms is
deration.
; a strong
.ing silica
. industry
e walls of
ess
sily
ip 0, only
ults were
The chemistry of the flocculating action of silica has been thoroughly reviewed by
Okura, Goto, and Murai (680). Problems of coagulation in water treatment are
further discussed by Goto and Yotsuyanagi (681). Although commercial colloidal
silica has flocculating action, silicic acid 'polymerized from a mixture of sodium silicate and acid is far cheaper and, provided it is made under controlled conditions,
probably more effective. The use 0. such activated silica sols for flocculation has
been discussed in Chapter 3.
Dispersing Effects
Dispersing and suspending effects, particularly in the manufacture of emulsion
polymers, continue to be of interest. Colloidal silica is used as a dispersing agent in
the manufacture of certain organic copolymers, thus avoiding the use of organic
surfactants or dispersants which lower the surface tension of the dispersion. High
surface tension is advantageous in coating applications by dipping or flow-coat
methods (682). Emulsion polymerization of styrene or acrylic monomers using
colloidal silica as a suspending agent avoids the use of organic surfactants which
detract from the heat stability of the polymer (683).
434
When colloidal silica is partly coated with adsorbed cationic organic molecules it
provides a very stable emulsifying agent for oil in water emulsions. Presumably, tr uncoated silica area of the particle remains at the water boundary while the:
organophilic area (adsorbed micelles) is in the oil phase. A wide range of such
cationic materials has been listed and their use in emulsion polymerization or
organic manomers described (684).
Micro-encapsulation involves stabilizing an emulsion by forming strong films
around each droplet. This can be done with a combination of colloidal silica and
gelatin as described by Brockett (685). Further study of the interaction of colloidal
silica with cationic polymers or with cationic surfactants in oil or polymer emulsions
and dispersions in water appears worthwhile. particularly from the standpoint of
highly stabilized interfaces.
Detergents can be improved by addition of silica. In removing oil from metal Surfaces it is likely the colloidal silica is adsorbed on the oxide film on steel and helps
displace the fatty acids. Thus slightly acidic silica sol in alcohol or other water-miscible solvent degreases metals (686). Colloidal silica can replace phosphate in
detergents if formed from sodium silicate and an anionic detergent-forming acid
(687).
Particles of colloidal silicates of polyvalent metals, for example, clay and asbestos.
adsorb colloidal silica. Addition of colloidal silica improves dispersion and lowers
viscosity of dispersions of asbestos in water without introducing strong alkali such as
sodium silicate (688. 689).
Antifoaming Effects
The mechanism of "inorganic fillers" in antifoarning-effects of silicone fluids has
been studied by Povich (690). He measured the marked increase in effectiveness of
the fluids as more silica was added. Silica did not lower the spreading pressure.
absorb enough impurities, or change viscosity sufficiently to explain the effect.
Aqueous silica sol can be used by emulsifying it in oil, stripping out water. and
reacting it with polysiloxane to make the silica hydrophobic (691). Instead of silicone oil, a water-insoluble oxyethylene-oxypropylene addition polymer can be used.
in which colloidal silica is added, along with an emulsifier (692).
It is speculated that the antifoam effect occurs when a large hydrophobic particle
occurs in the wall of a bubble. Owing to the low adhesion of water to the surface of
the particle it acts much like a "hole" so that the film is ruptured. Kinetics of foam
destruction has been investigated by Gleim, Khentov, and Bashikov (693a) and the
mechanisms of antifoaming action was studied by Kulkarni, Goddard, and Kanner
(693b).
Modifying Viscosity-Gelling
Where liquids are to be thickened, voluminous silica powders rather tha. .
concentrated sols are generally employed. Just as silica, made nonpolar with a "
hydrophobing agent, aggregates in water to a thick mass, so does a hydrophilic silica
\..
~-
ited Sols
ecules it
,40
;"
bly the
.
lik
of such
.tion of
-i!!
~
~:. .
.'
...
,:;"
.0
g films
ica and
olIoidal
iulsions
loint of
..
$
;"-:
~
.~
~~
"'-
":.--;0.
.1-
..
<
435
aggregate in nonpolar liquids to a gel. Trace amounts of water help "cement" the
hydrophilic silica particles together into a three-dimensional network in the oil. The
mechanism of gel breakdown by certain additives has been examined by Wightman
and Chessick (694). Colloidal silica thickness the sulfuric acid electrolyte in storage
batteries (695). Pyrogenic silica powder is used as a thickener in polyester resins,
oils, epoxy cements, plastisols, and sealants (696).
An unusual clectroviscous effect is observed when silica particles are dispersed
with a nonionic (polyethylene oxide type) surfactant in a napthenic liquid. Current is
generated when the liquid is stirred between electrodes, and conversely the viscosity
of the mixture increases when a current is passed (697).
.;<
:tal sur.d helps
?
.,
-.-,
.er-mis-
..
hate in
ng acid
"i.
""
1)
sbestos,
lowers
such as
4".
".~}
.~:.
,.
-
.'
ids has
.ness of
~essure,
effect.
er, and
.of sm.e used,
oarticle
'face of
If foam
lOd the
Kanner
r' ,
wii., a
c silica
MisceUaneous Optical Effects, Color, Photography
-.. -
The colors of precious opal has already been discussed in connection with ordered
aggregation and the interference colors of uniform layers of particles described
under adsorption of particles on surfaces.
Numerous patents have been issued on antireflection coatings in which silica in
various forms is deposited as a thin, adherent layer, generally on the surface of glass
or plastic sheets and lenses. Coating with a "low-hydrated oxide of silica" was
described in 1945 (698). Films of colloidal silica .are deposited in various way
(699-704).
A film- of colloidalsillca on glass redues glare when of the right thickness (70S).
.As has already been described, Her developed a method of building up multilayers of
uniform colloidal particles. on surfaces to any desired thickness (403, 404). Land
claimed an antireflecting layer composed of two eighth-wave layers, one of colloidal
silica, the other of a fluorinated polymer of refractive index 1.3-1.45 (706). Moisture
changes the optical properties of porous silica films due to condensation in pores
(707). Other antireflecting layers consist of multiple films of Ti02 and Si02 or SiO z,
s-o, and
(708, 709).
A "black mirror" transparent to. infrared is made by depositing layers of nickel
(10-15 nm) and Si0 2 (80-90 nm); it is used to absorb solar energy (710). On the
other hand, films on glass that are highly reflective can be made by depositing Ti0 2
and Si02 (711). Films thicker than 1 micron tend to crack and peel off glass unless
they are applied to polished substrates and contain porous layers (712). The thickness of thin films as well as refractive index can be determined by ellipcometry as
described by Vedan et at. (713). To produce interference colors in paints, a mica pigment is coated with Ti02 and Si0 2 of the correct thickness (714). A coating inside
electric light bulbs to diffuse light without adsorption is formed with colloidal silica
(715, 716), which may also be used to bond a phosphor to the inner surface of a
lamp bulb (717). A light diffusing coating on glass may be applied by spraying
colloidal silica at 100-400C (718). Even skin can be delustered. Makeup cosmetics
containing 3-7% colIoidal silica eliminates the need for powder'(719).
Photographic and diazo-type papers are coated with colloidal silica (720-723). In
Polaroidw photographic film colloidal silica plays an essential role in the receiving
layer to which the image is transferred and in which the black silver positive image is
z-o,
436
developed. Details are disclosed in a series of eight patents to Landet at (724). The
advantage of incorporating into the image-yielding layer of colloidal silica a silanic
compound containing at least one compound containing silicon-hydrogen bonds to
aid in the reduction of silver is patented by Gray (725).
Other uses in photography involve silica-hardened gelatin surfaces on X-ray film
(726). colloidal silica-modified silver halide emulsions for higher sensitivity (727).
and silica-polyvinyl alcohol as a replacement for gelatin in image-receiving layers
(728).
Use In Biological Research-Density Gradient

. Colloidal silica has found use as a high-density medium for separating biological
materials by centrifugation. Pertoft (729) reported the use of a mixture of colloidal
silica (Ludoxe HS) with polyethylene glycol of molecular weight 3000-3700 in a tris
buffer solution at pH 7.5 as a density gradient solution in centrifuging and purifying
a virus. This general method was described by Pertoft and Laurent (730). Intact
chloroplasts were also separated in Ludoxs solutions by Lyttleton (731).
Morgenthaler et a1. (732. 733) used Ludox~ AM. the aluminate-modified sol that is
stable in neutral medium and has less tendency to form hydrogen-bonded complexes
with some porteins. Polyethylene glycols had an effect in the system. probably
because of the competitive hydrogen-bonding effects of the other groups.
In separating blood cells in a colloidal silica medium some structural changes
were observed (734). Addition of polyvinylpyrrolidone (PYP). as a competitive
hydrogen-bonding agent for the silica surface apparently prevents interaction with the
cells (735).
In the original search for a isopycnotic cushioning solution for density gradient
media in centrifuging. Mateyko and Kopak found colloidal silica to be the only
suitable material (736). Almost a quarter century later it was still apparently a useful medium (737a). However. there was still a need for a dense colloid that shows
less interaction with biological substances over a wider pH range and not containing
free polymer. This need apparently was fulfilled by Percolle (737b). a specifically
formulated combination of colloidal silica (Ludoxs HS, particle diameter of 17 nm)
and polyvinylpyrrolidone in which the surface of the particles is covered with an
adsorbed monolayercoating of the polymer. It is likely that a suitable molecular
weight. optimum ratio of polymer to area of silica surface. and a pH of 8.8 are all
necessary to achieve such stability in a concentrated sol that it can be sterilized by
autoclaving (737c-737e).
,
Experiments by Wolff and Pertoft (737f) showed that PYP is not displaced from
the silica surface by polyethylene glycol of molecular weight 4000, which is known
also to be strongly bound to 'the silica surface. Another interesting
property is that
,
this composition is much less subject to gelling or coagulating in the presence of
salts than unmodified silica and bears a low or masked ionic charge (737b).
The use of silica gel as a culture medium is described in Chapter 7 since such gels
are made from other sources of silica as well as colloidal silicas.
.
'.
~---
rted Sols
Uses or Colloidal Silicas
~4).
Source of Chemically Reactive Silica
The
437
\ sil , 'c
one,
CoIloidal silica is much more chemicaIlyreactive than the most finely pulverized
sand, not only because the specific surface area is several hundred times greater, but
also because amorphous silica is 10 times as soluble in water as crystalline quartz.
,0
"ay film
f ."(727),
~ layers
SolubleSilicates
~,
Silica rapidly depolyrnerizes in the presence of strong alkali. Thus colloidal silica
can be converted to a solution of sodium polysilicate containing from 4.2 to 6.0
moles of silica per mole of sodium oxide (738)' or lithium polysilicate and lithiumstabilized sols with 4-25 moles of silica oxide per mole of lithium oxide (739). These
compositions cannot be obtained by dissolving a sodium or lithium silicate glass, nor
by dissolving sand in the alkali because of the peculiar fact that lithium silicate is not
soluble in hot water. For lower ratio silicates the advantage of starting with colloidal
silica is only a matter of convenience because of the rapid reaction rate.
alogical
olloidal
n a tris
irifying
. Intact
(731 ).
that is
nplexes
.obably
:hal&e>C:s
petitive
vith the
radient
ie only
I a use:' shows
taining
:ifically
17 nm)
vith an
ilecular
are all
ized by
d from
known
is that
ence of
ch gels
'.
,
......
Silica Bodies
Because very small particles sinter at relatively low temperature, various kinds of
silica objects can be made most easily from colloidal silica. Thus porous expanded
silica spheres are made by mixing powdered fused silica and colloidal silica which
contains hydroxyl surface groups, and forming granules which are passed through a
zone of 2000C. The released water forms voids within the granules (740). A
somewhat similar process using only colloidal silica is claimed by Walsh for making
hollow Si02 spheres (741). Quartz fibers are more easily spun from rods of pulverized quartz bonded with colloidal silica (742).
For making synthetic.quartz crystals, colloidal silica could be used as a source of
soluble silica under autoclave conditions at high temperature (743). In making clear
hot-pressed silica glass bodies.. the water evolved from particles of colloidal silica
acts as a catalyst permitting the formation of fully sintered bodies (744). The
clearest glass had the highest residual content of OH groups.
The general reactivity of amorphous silica has been considered by Okkerse and
DeBoer (745). To lower the sintering temperature of silica powders for hot pressing,
Iler incorporated boric oxide uniformly through an amorphous silica powder (746).
To eliminate water from silica powder before consolidating, it can be heated in
chlorine gas at 600-1000C (747). A film of pure silica around a glass fiber of higher
coefficient of therm al expansion increases the tensile strength by exerting a
compression on the glass when cooled (748).
Glass Compositions
Homogeneous glasses can be made by admixing the other ~omponents intimately
with colloidal silica (749). The chemical reactivity of colloidal silica plays a role in
colored or conductive coatings on glass or refractory materials in which a vitrified
bond is developed without damaging the substrate (558, 750).
438
Forming Solid Silicates-Cements
'
..
The oldest known reaction of amorphous silica is that in Roman cement where lime ~
was mixed with sand and colloidally subdivided silica of volcanic origin mined at
Pozzuoti, Italy, and the Greek island of Santorini. This was the basis of the
extremely impervious cement linings used in cisterns throughout the Mediterranean
area and in construction throughout the Roman Empire without which some of the
vast domes could never have been built (751). Sand and lime along donot form such
cement.
The reaction between Ca(OH)2 and Si0 2 has been studied for many years. The
stability of the specific calcium silicate-carbonate compound scawtite,
6CaSiOaCaCOaxH 20 (752), is shown by the fact that lIer found crystals 5 mm long,
first thought to be quartz, which had grown on the inside walls of a soft-glass bottle in
which a 30% silica sol of 14 nm particles at pH around 9.5 had been stored for 20
years. The loose bottle cap had presumably admitted atmospheric carbon dioxide. In
scawtite the silica exists as cyclohexasilicate anions. The reaction of lime and silica
has been studied by Greenberg (753, 754) and Assarsson (755); the formation and
properties calcium silicate in Portland cement have been and are being continually
investigated because of the obvious practical implications.
of
Other Reactions and Uses

Mullite can be made below its fusion point from colloidal silica and basic aluminun
chloride (756). Hydration of tricalcium aluminate is accelerated by low levels of>
colloidal silica (757).
Reaction of colloidal silica to form magnesium silicate is retarded by small
amounts of alumina and depends on the rate of dissolution of silica (758). Also,
magnesium hydroxide reduced the solubility of silica" and retarded reaction of
colloidal silica and magnesium salts (759). '
Formation of claylike minerals is extremely slow if not impossible from sand, but
will proceed under favorable conditions from colloidal or amorphous silica. Synthesis
of montmorillonite in an autoclave at 300C, is disclosed by Granquist (760). Hectorite, a colloidal magnesium silicate in the form of molecularly thin ribbonlike
crystals, was synthesized from silica gel (probably better from silica sol) by Granquist
and Pollack (761).
When lime-bonded insulating materials are being made, inclusion of colloidal
silica increases the strength when sand or diatomaceous earth are the major
components (762, 763).
The high reactivity of colloidal silica is shown by the reaction with phosphoric
acid (764). However, phosphoric alone is adsorbed on the silica surface, retarding
the reaction unless a stronger acid, H 2S0 4 , is added (765). Flame-dried silica reacts
with CH aAICl 2 to give methylchlorosilanes (766).
Platinum and tungsten metals are hardened by incorporating colloidal silica into
the hydrous oxide before reduction or adsorbing silica on the surface of the finel;
divided metal before compacting and sintering (767, 768).
.~
1
,1
1
I
1
1
!
1
l
f
l
I
1
:entrated Sols
439
References
COLLOIDAL SILICATES
w. ,; lime
in mined at
,asis of the
:diterranean
some of the
,t form such
.
years. The
: scawtite,
5 mm long.
ass bottle in
ored for 20
,dioxide. In
e and silica
marion and
continually
: a'
~inum
w,
els of
d by small
758). Also.
reaction of
n sand. but
i. Synthesis
(760). Hec-
ribbonlike
{Granquist
)f colloidal
the major
phosphoric
:. retarding
.ilica reacts
I silica into
f r 'inely
Although colloidal silicates were included in the earlier book by lIer (8), the literature has grown too voluminous for consideration here. A survey of surface and
colloid chemistry of clays by Swartzen-Allen and Matijevic (769) is an excellent
reference.
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744. G. G. McCarthy. R. Roy. and J. M. McKay. J. Am. Ceram, Soc. (Dis.). 54, 637 (1971).
745. C. Okkerse and J. H. De Boer. in J. H. De Boer, Ed. Reactivity ofSolids,. Elsevier. New
York. 1961.
746. R. K. Iler, U.S. Pat. 3.761.936 (Du Pont). 1973.
747. T. H. Elmer and M. E. Nordberg. U.S. Pat. 3.459,522 (Corning Glass Co.). 1969.
748. D. A. Krohn and A. R. Cooper.J. Am. Ceram, Soc. 52, (12).661 (1969).
749. R. Roy.J. Am. Ceram, Soc. 52, 344 (1969).
750. M. S. Tarnopol, U.S. Pat: 2.694.649 (Pittsburgh Plate Glass ce.i 1954.
751. "Cement." Encyclopaedia Britannica. 14th ed., The Encyclopaedia Britannica Co.,
Chicago. Vol. 5, 110; also "Rome." Vol. 19. p. 465:
752. W. Wicker and U. Hahn. Z. Chem . 13 (5). 195 (1973).
753. S. A. Greenberg. J. Phys, Chem . 61, 373 (1957).
754. S. A. Greenberg,J. Phys, Chem., 65, 12 (1961).
755.. G. O. As~arsson.J. Phys. Chem, 61, 473 (1957); 62, 223 (1958).
756. R. E. Albert. U.S. Pat. 3.615.778 (Du Pont). 1971.
757. J. G. M. De Jong, H. N. Stein. and J. M. Stevels,}. App/. Chem . 19, (1).25 (1969).
758. H. G. Srnirnova, A. D. Dushina, and V. B. Aleskovskii, Izv, Akad, Nauk, SSSR. Neorg.
Maler. 2, 284 (1966).
759. N. Hast. Ark. Kem. 9,343 (1956).
760. W. T. Granquist. U.S. Pat. 3.252.757 (National Lead Co.), 1966.
761. W. T. Granquist and S. S. Pollack. Proc, NaIl. ConI. Clays, Clay Miner. 8, 150(1960).
762. F. l. Shea. Jr., H. l. Hsu. and J. M. Steebels, J. Appl. Chem . 119, 125 (1969).
763. F. l. Shea. Jr. et al., U.S. Pat. 2.698.256, (Great Lakes Carbon Corp.), 1954.
764. H. Makart, Helv. Chim, Acta. SO, 399 (1967).
765. B. M. Mitsyuk, Zh. Neorg, Khim . 17 (4), 903 (1972).
ned Sols
References
461
766. R. C. Anderson and G. J. Sleddon, Chern. Ind. London. 1960, 1335. .

767. J. S. Streicher. U.S. Pat. 2.752.665 (J. T. Baker & Co.). 1956.
..
weden.
768. A. P. MacCragh. A. S. Patil. and G. E. Ashby. U.S. Pat. 3.713.816 (W. R. Grace ce.i
1973.
,': Anal.
769. S. L. Swartzen-Allen and E. Matijevic, Chern. Rev. 74, 385 (974).
nkton in
ion, Vol.
), 1959.
(1971).
ier, New
--.
ica Co.
-,
, Neorg.
:1960).
CHAPTER 5
Silica Gels and Powders
1
DEFINITIONS
The forms of silica considered here are solids having specific surface areas of more
than about 5 m t g-1. The state of subdivision ranges from large, solid masses to
submicroscopic particles, and the degree of hydration from almost anhydrous SiO z
to soft gelatinous masses containing 100 parts of water per part of silica. The cornmon feature of gels and powders is that they consist of ultimatesilica particles of
colloidal size, ranging from 1 to 100 nm in diameter.
Silica gel may be described as a coherent, rigid three-dimensional network of
contiguous particles of colloidal silica. The formation of silica gel by polymerfzatio:
of silicic acid has been discussed in detail in Chapter 3 and by aggregation of parti-'
cIes of colloidal silica in Chapter 4.
Silica powder may ecnsist of small granules of silica -gel or of coherent aggregates
of submicron .particles that are linked together in extremely weak networks.
Theoretically, a silica powder might consist of separate, discrete silica particles, but
when the particle diameter is less than 100 nm, the particles spontaneously adhere
together in loose aggregates. It is only when the discrete particles are much larger,
that is, 5-50 microns (5000-50,000 nm), that the cohesive forces become so low that
the particles do not attract each other and are very "dusty," that is, small enough to
form a "smoke" when shaken in air.
There are silicas which are borderline between gels and powders. When the bonds
between the ultimate colloidal particles are very weak, and can be readily broken by
mechanical means, the silica can be classed as a powder that is not a gel. On the
other hand, when the colloidal particles form a strong, coherent structure, the silica
is classed as a gel even though' the size of the gel granules may be as small as a few
microns.
.
Figure 5.1 schematically represents the variables of particle size, packing density,
porosity, and interparticle coalescence or aggregate strength.
,
Types of Gels
Silica gel is formed in a liquid medium, usually aqueous. The terms alcogel and
aquagel are gels in which the pores are filled with the corresponding liquid, that is,
462
., -:...--463
Definitions
A
S,...----.......,
SIZE
COALESCENCE .
Eo-------,
"~
~
of more
lasses to
ous Si02
"he comrticles of
twork of
eri7Qtion
01
:ti:gregates
etworks.
icles, but
y adhere
h larger.
low that
nough to
he bonds
token by
. On the
:he silica
as a few
density,
')gel and
, that is,
r ,.
PACKING
,,,
:.~
~.
'a
ce.
Figure 5.1. . Silica gels and powders. Schematic representation of cross-sections of different
structural variations: A, small particles. close-packed, low coalescence; B,' small particles,
open-packed, low coalescence; C, large particles. close-packed, low coalescence; D, large particles. close-packed. low coalescence; E. large particles. close-packed, highly coalesced; F. large
. particles. open-packed highly coalesced. Coalescence is the degree to which two particles are
bonded or grown together.
;Of
"_.
.~.~
"i~
.';'
;.~
v~
gel from which tbeIiquid medium has been

alcohol or water. A xi,ogel is
removed. the structurebeing compressed and the porosity reduced to at least some
degree by the surface tension forces as the liquid is removed. 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. Specifically. this is done
by heating the liquid-filled gel. usually an alcogel, in an autoclave to above the
critical point of the liquid so that there is no liquid-vapor interface. and releasing the
vapor.
Porous glass is essentially aspecial form of silica gel.
Types of Powders
Silica powders can be classified according to the way in which they have been made,
which usually confers'special characteristics.
Pulverized gels. Made by grinding or micronizing xerogels. Ultimate gel structures remain unchanged.
Spheroidal gels. Made by subdividing the precursor silicic acid or colloidal sol
into fine droplets before gelling. Gel structure is similar to massive gels formed under
the same conditions. The droplets may be suspended in air and dried or may be sus-
I .
..
.
...
464
..
!
::
"Ii
.:
."
,f
. '!
.,
-:.---
pended in an immiscible liquid in which the droplets solidify. The droplets mayalsc be
formed in the aqueous phase by coacervation of colloidal silica with an organic agent
to form droplets which are then solidified.
_
Precipitated silica. Formed when the ultimate silica particles are coagulated as
loose aggregates in the aqueous medium, recovered, washed, and dried. Coagulation
may be effected by high salt concentration or other coagulants such as ammonia,
water-miscible solvents, or certain types of organic materials. When the ultimate
particles are larger than 5-10 nm they may be only weakly joined together and if in
an open-packed condition subsequently they can easily be broken apart and dispersed, for example, in oils .or rubber.
..
Aerosils or pyrogenic silica. Powders made by condensing silica from the vapor
phase at elevated temperature. The silica vapor is produced by (a) direct volatilization of Si02, (b) reduction of Si0 2to volatile SiO which is reoxidized, (c) oxidation
of volatile silicon compounds such as chloride or esters, or (d) vapor phase
hydrolysis of SiF.
Phyllosilicas (Ieaflike) or lepidoidal (scalelike) silicas. Less well known and iIIdefined, but generally consisting of particles with a laminary or sheetlike shape.
These are of several types, depending on how they are made, as described in Chapter 1.
.
.
.
Organophilic silicas. Made from all the foregoing types of powders by covering
the surface with a monomolecular chemisorbed layer of organic groups attached to
the surface atoms through Si-C, Si-O-C, Si-O-N+-C, Si-O-M-O-C types of
linkages (M is a polyvalent metal cation).
Aluminoslllcate anions. May be implanted into the silica surface to provide a
stronger anionic surface with greater cation exchange capacity and acidic catalyst
~~~..
Current literature relating to various aspects of finely divided silicas is growing

rapidly, usually in connection with particular applications or areas of technology.
Various aspects of silica gels and powders have been summarized, often in detail, in
reviews by various authors (I-lOc).
In spite of the; great volume of literature, it appears that the diverse aspects of the
subject have not yet been brought together into one convenient source of information.
PHYSICAL CHARACfERIZATION
Most of the methods of characterization apply equally to gels and powders. Von
Buzagh (IOd) in 1937 clearly identified the variables that must be taken into account
to define an aggregate structure:
I. The size and shape of the primary particles.
,
2. The spatial distribution of the particles, including the order and density of packing (see Figure 5.1).
3. The strength of the bond between particles (coalescence).
./
.,.
..
-:..,-_.
! Powders
Physical Characterization
ly also be
nic aaent
He further pointed out that the size of the particles determines the specific surface
area; also, for a given density of packing, the size of the particles determines the size
of the pores or "intermicellar spaces" throughout the aggregate or gel.
465
ulated as
agulation
mmonla,
Ultimate Particle Size
ultimate
and if in
and dis-
Methods have been covered in detail in Chapter 4 relating to colloidalparticles in

silica sols, which in many cases were dried to a gel or powder before being
characterized, The same methods therefore are applicable in the present instance.
.he vapor
'olatilizaoxidation
Electron Micrographs
Even in dense gels, in which the ultimate particles are closely packed together, it is
possible to discern the ultimate particles in a thin section of a gel fragment. By using
techniques developed .for carbon black by Cohan and Watson (11), the apparent
. particle diameter can be measured in those cases where the particles are lying in
such a way that the silhouettes present more than a semicircle of cross-section. After
measuring several hundred particles, the average particle diameters can be calculated as d,u the number-average diameter, and as d., the surface-average diameter,
which is the diameter of a particle having a specific surface area equal to the average
calculated for all the measured particles:
or phase
and illce shape.
:l
in Chapcovering
tached to
tyoes of
provide a
= catalyst
'0
; growing
:hnology.
detail, in
cts of the
of infor-
Iers. Von
o account
-
::J.
.~
'!i
-x-
'0"
...
where n, is the number of particles in the ith range of sizes, the mean diameter of
each being dh and k is the number of size ranges.
The specific surface area, Sc, can be calculated from d, on the assumption that the
particles are dense amorphous silica with a specific gravity of 2.2. Thus S; equals
2720/ d, where Sc is expressed in square meters per gram and d, is in millimicrons,
Medalia and Heckman (12,13) describe a method for determing the sizes of both
the ultimate particle and the aggregates in carbon blacks which should be equally
applicable to silica powders. The procedure gives particles per aggregate, a measure
of bulkiness which corresponds to porosity as well as ultimate particle size. A
similar study of the porosity of a meso-porous silica gel was presented by Havard
and Wilson (14). The silica was considered as a surface area standard (Gasil I) and
its surface area described by Everett et al. (15) was 286.1 :!:: 3.5 m 2 g-l. Havard and
Wilson obtained electron micrographs of remarkably high resolution from which the
average particle diameter of 8.8 nm was calculated. Then an' anamoly developed: in
the case of particles this small, which should correspond to a specific surface area of
about 2750/d, where d is diameter in millimicrons, and assuming the particle density
to be 2.2 g cm- I , the specific surface area should. be about 2750/8.8 or 312 m 2 g-l.
Actually, 286 mS g-I was measured. The difference is explained by the fact that
around each point of contact between spherical particles there is an area or annular
crevice too small to be penetrated by nitrogen molecules during the measurement of
specific surface area, the diameter of the nitrogen molecule being 0.4 nm. For larger
particles, the specific surface area, calculated from particle size in electron micrographs, is in better agreement with the area measured by adsorption methods (see
Chapter 4, Ref. 142).

The specific surface area is most dependably measured by the widely accepted
method of adsorption of nitrogen or other gases and vapors. However, methods
involving adsorption of specific ions or molecules from solution, either aqueous or
organic, may require less equipment or prove to be more convenient, especially for
- routine use.
In all cases the key question is whether the ultimate silica particles are sufficiently
separated so that the pores between them are accessible to the adsorbed ions or
molecules and so that the silica surface can become covered with at least a single
layer of adsorbed material. There are numerous instances, as in microporous gels,
where water molecules or OH- ions can penetrate where nitrogen 'or other large
molecules cannot. It will Be assumed that the pores of the solids on which surface
areas are being determined are such that the surface is generally accessible to the
material being adsorbed.
Other properties, which are a function of surface area, can also be measured but
are not widely used. Various techniques available up to 1954 were surveyed by Moll
(16), including all the types of solids on which the methods were used, along with
about 150 references.' Methods for nitrogen adsorption developed to 1953 were
reviewed by Joy (17).-A symposium was held on the general subject in 1969 (18),
especially reviewing all aspects of the BET method.
By ADSORPTION OF GASES AND VAP~RS. A large number of summaries and
reviews are available on this subject, which has been the main topic in numerous
symposia (1-8, 18, 19).
Standards for specific surface area have been established. One is a hydroxylated
silica powder free from pores, "Fransil EF" (20) with a surface area of 38.7 mS g-I.
Subsequently, a worldwide search for suitable standards settled upon two carbon
blacks and two silica powders. The latter are designated as TK-800 with an area of
165.8 :: 2.1 m2 g-I and Gasil I with an area of 286.2 :: 3.5 (21).
Of course it was long ago necessary to establish the area covered by one nitrogen
molecule by measuring adsorption on a nonporous surface of accurately measured
geometric area. Uniform crystals or glass spheres measured microscopically have
been used. A typical example is the work of Dietz and Turner (22a) who used E
glass fibers of uniform, accurately measured diameter. 'Resulting values were:
nitrogen, 16.2 A2; argon, 13.8 A2; and krypton, 20.2 A2 at 77.4K. Similar values had
earlier been established by other methods. McClellan and Harnsberger (22b) recommended the following values: nitrogen (-195C), 16.2 A2; argon (-195C, -183C),
..,. -:---
ph)"Sh....
: fact that ~
or - "'uJar:~'
rre..... u of ~;:
For larger';
~~n micro- ,.~
:thods (see
accepted
" methods
tqueous or
lecially for
..:.~"
~.
;.
.~
~
m(ficiently .~
ed ions or:'.::
.st a single;'
orous gels
, '~.
nher large {
ich surface <,~
;ible to the:~ .
asi, J but .'

ed by Moll
along with 'if
1953 were {
1969 (18), ',~.
naries and
numerous
467
.....\ Characterization
id Powders
13. A'; krypton (-195C), 20.2 t\2; benzene (20C), 43.0 A2; and n-butane (OC)
8
'~~~~gen
has been 'by far the' most widely employed adsorbate at -196C. In
similar facilities, argon and krypton can also be used and suitable values for atomic
etOss-sectional areas are known (23). The advantage of krypton for penetrating
lIer pores was shown by Vezina and Berube (24).
sm; general survey of th: a~sorption.of nitrogen on. solids and the va~ious methods
of interpreting the data IS included 10 a broad review of porous solids by Broek',.....
- .. ...' .
. .. . ..
horr (25). 'The BET (Brunauer, Emmett, Teller) (26-28) method of-calculating specific sur(; ce area from an adsorption' isotherm has been mainly applied to nitrogen as the
a~sorbate at -196C. Innes (29) developed a rapid automatic technique for measuring the Isothertn. Lippens and Hermans described suitable apparatus in detail (30,
31). Also, commercial equipment has been developed using the static equilibrium
method, which does not require calibration and gives surface area by automatic
digital readout (e.g., Micrcrneritics, Inc.).
.
'.
.
. In spite of alternative equations to describe the isotherm, the BET equation has
retained. its utility. for many years. Subsequent proposed schemes are' useful for
certain situations but the BET equation is still widely used. The BET equation is
p '.
voCPo - p)
.1
(c - l)p
VmC
vmcpo
--+
where Va is the moles of gas adsorbed per gram of adsorbent when the gas pressure is
p, v"' is the monolayer capacity of the surface, that is, the number of moles of gas
per gram of adsorbent re9uired to form a monomolecular. layer, Po is the saturation
gas pressure at the temperature used.rand C is a constant. When plV(Po - p) is plotted as ordinate versus plpo as abscissa a line is obtained with slope (c - 1)/vmc and
intercept on the ordinate equal to l/vmc. The constant c is a function of the heat of
adsorption and depends on the chemical nature of the surface.
From vm , calculated from the experimental data using the above equation, the
area is determined from the equation
'droxylated
8.7 m2 g-I.
.wo carbon
an area of
ne nitrogen
I measured
ically have
tho used E
ilues were:
. v: shad
~2b/:...;com..
, -183C),
where SSET is the specific surface area in square meters per gram, as determined by
this method, am is the molecular cross-sectional area of one gas molecule in square
angstroms, and N is 6 X 1023 The value of am for nitrogen may vary on different
surfaces, but is commonly assumed to be about 16.3 A for oxide surfaces.
To compare different solids, it is convenient to use a term v., the "reduced
pressure," which is defined as v.. = vIvo. where Vo. is the volume of gas adsorbed at
p/Po = 0.4. Carruthers et a1. (20) compared the adsorption of nitrogen on four types
of silica powders plotting vlvmversus v. (where V m is the monolayer value from the
BET equation) and found direct proportionality.
The BET method gives the same results whether or not the surface of the silica is
hydroxylated or dehydrated. On 19 specimens with widely different stages of
468
dehydration of the surface. the effect on the measured surface area was less than 5%
(32). Lowen and Broge (33) showed that as an initially fully hydroxylated powder
was dehydrated. along with some loss of surface owing to sintering there was a
marked decrease in the constant c in the BET equation. which corresponded to a
lower energy of adsorption:
Dehydration .
Temperature (OC)
Surface Area
(m2 g-l)
120
620
810
182
170
141
SiOH
. Groups (nm -2)
10
3
2
Constant
c
104
53
45
Upon rehydrating the surface the value of c returned to about 100 while the surface
area remained unchanged. The effect of surface hydroxylation on nitrogen adsorption also has been examined at various temperatures by Koberstein and Voll (34).
Microporous materials might be thought to be unsuitable for area determination
by the BET method. However. Brunauer (35) pointed out that since small pores fill
at a lower partial pressure than larger ones, there is a compensating effect so that by
coincidence the method still gives a true value for the specific surface area provided
there are no pores with radii smaller than about 12 A.
The Harkins and Jura (36) absolute method of calculating specific surface area
from adsorption data apparently gives more consistent results than the BET method
when different adsorbates are used on different kinds of solids. It is based on an
em pirical equation:
log -
Po
== B -
v~
where A and B are constants. V o is the volume of gas adsorbed, and p/Po is the
partial pressure of the adsorbate.
Plotting log p/Po versus V;2 a straight line of slope s is obtained. From this, the
area is calculated
i
I
II
==
where S is specific surface area in square meters per gram and k is a constant for the
particular adsorbate determined by the "absolute" method" (39). Some values of k
are as follows:
Vapor
Nitrogen
Butane
Water
Temperature (OC)
-195.8
0
25
4.04
13.6
3.83
.'.;:
,"---- 0
....
7..,--
Powders
.han 5%
powder
: v
J
ed to a
nstant
c
104
..
'"
469
Many workers subsequently verified agreement between the Harkins'and Jura and
the BET methods of calculating surface area from adsorption data. According to
Dreving et al. (37) the BET equation is obeyed on silica gels at p/Po from 0.035 to
0.33, and the Harkins and Jura equation is obeyed from 0.075 to 0.58.
The t-plot method of plotting the amount of nitrogen adsorbed versus the thickness of the adsorbed nitrogen film on a flat, nonporous surface was proposed by
Shull (38). Cranston and Inkley (39) assembled available data and published a com- .
posite r-plot which they and others have used widely in characterizing porous solids.
De Boer et al. (Ref. 4, p. 32) extensively studied the application of the method to
numerous solids free from micropores, using the equation
53
45
I ...
surface
adsorp34).
ination
ores fill
that by
rovided
Vm
where I
Va
Vm
= thickness of adsorbed nitrogen film (A)

=
=
volume of nitrogen adsorbed

volume of nitrogen adsorbed to form a monomolecular layer
The surface area, Sit is calculated from the equation
:e area
S, .. 15.47
.nerbod
: c.
3.54 ..!.
(for N z)
Va
is the
lis, the
where I is taken from a table or equation relating I to p/Po, based on extensive

experimental data. The .area, Sit is in square meters per gram and Va is in cubic
centimeters of nitrogen gas at STP adsorbed per gram of solid.
Details and examples are given in a series of papers by De Boer et at. (40-42) and
summarized by Broekhoff and Linsen (Ref. 4, p, 23).
To calculate I from p/Po, Dollimore and Heal (43) examined 36 samples of silica
and alumina and concluded that the formula given by De Boer should be recommended:
. I
. [-5
= 3.54
]1/3
lnp/po
where I is in Angstroms.
for the
es of k
Various investigators have tried to improve upon the original I-curv.e of Cranston
and Inkley, mainly by trying to ensure that no pores are present in the adsorbent.
Girgis (44) developed a different type of r-curve and corresponding equation but the
values must be used with a special equation.
,
I -
6.15 - 2.25 In
~n
:')
+ 10.5~.)
470
:: ' .
i .
I,
I
! .
i
j .
j.. ':'
I:
:'
j
f~;
I
::,'
~ - I'~ ;
!.
1 ;~
-, .
The r-plot for nonporous but very finely divided voluminous silica shows deviation
from the standard r-curve, This is believed by De Boer et al. to be due to adsorption
at points of contact of the very small particles. They developed an adsorption equation taking into account the packing geometry of the particles.
The method is useful for materials in which there is no capillary condensation
below p/Po 0.7-0.8. The equation is applicable up to at least p/Po 0.3. A t~eoretical
equation for the r-eurve not requiring any adjustable constants was proposed by
Ternan (46). Based on thermodynamics. and taking into account dispersion forces
using the Lennard-Jones potential. the equation related relative pressure to film
thickness in reasonable agreement with experimental data.
The difficulty with the r-method is that it is necessary to know VIII. the arnoum
adsorbed as a monolayer. that is, the surface area. Thus its use should be confined to
isotherms where the BET method gives an unequivocal value for the B-point or
monolayer capacity. However. Brunauer pointed out that the surface area of
microporous materials can usually be dependably measured by the BET method
(47). Hence the presence of micropores need not eliminate the use of the I-method.
Some r-curves for water on surfaces on which there are different heats of adsorption have been published by Hagymassy, Brunauer, and Mikhail (48). For use on a
given surface the curve should be selected to match the heat of adsorption of water
on that surface.
The "a, method" 0/ Sing (49) plots a, versus x where a, - xfx, x is the amount
of gas adsorbed. and x, is the amount adsorbed at a selected relative pressure
(standard state). Usually by definition, a, is taken as 1.0 at p/Po == 0.4. This
pressure is selected because only monolayer coverage and micropore filling. occur
below this point and hysteresis loops owing to capillary filling effects occur at higher
pressure.
.
Surface area is calculated from the slope of the linear portion of the plot, after
determining the "standard slope" using a nonporous standard powder of known
specific surface area. This method was compared with the BET method on a wide
range of porous and nonporous silicas by Bhambhani et al. (50). In the absence of
micropores there was excellent agreement of surface areas.
Kiselev's method is based on thermodynamic consideration of the complete hysteresis loop of adsorption-desorption and involves the surface tension of the liquid
adsorbate (6, 51, 52). However, it is useful only for adsorbents with mesopores and
necessitates determining the whole isotherm.
Kaganer's method (53) uses an equation that applies especially in the range of
p/Po from 10- 5 to 3 x 10- 2 :
log v. - log v. - D
~Og :~.
where D = 2.3kR2T2. The specific surface area is calculated from VIII' which is
obtained by plotting the data using the above equation and extrapolating to (log
Polp) = O.
The Frenkel-Halsey-Hill method (54-56) can be used at high relative pressures
'.
;
~.
..
...
~---
~~
d Powders
deviation
idsorption
tio }a-
physical Characterization
471
where the adsorbed film is several molecular layers in thickness. The rsotherm can
be described by the following equation:
.
densation
heoretical
".
iposed by
ion forces
e to film
where s is based on the decrease in surface forces with distance. Pierce (57) showed
that for nitrogen the equation holds beyond the first molecular layer and that for
p/Po above 0.3 the isotherm is
e amount
1.305
mfined to
t-point
or
: area of
r method
nethod.
)f adsorp use on a
I of water
e amount
pressure
OA This
inb.. cur
at higher
ilot, after
of known
m a wide
bsence of
plete hysthe liquid

rores and
range of
which is
g t n (log
pressures
P
k
-In - po
(v/vm)S
logpo/p
where V m is the ~olume of nitrogen adsorbed at the monolayer stage, v is the volume
adsorbed at pressure P. and Po is the saturated vapor pressure. Since in this case
.nitrogen is being adsorbed on nitrogen. the adsorption is independent of the
substrate.
.
A continuousflow technique of measuring surface area by adsorption of nitrogen
or other adsorbate from an inert gas stream is now widely used. It was described by'
Nelsen and Eggertsen (58) and confirmed by Lee and Stross (59). Many improvements have been made and compact commercial instruments are available (e.g.
Quantachrome Corp.). Details are further described by Ettre and Cieplinski (60). A
known mixture. for example. 20% N s and 80% He, is passed over a previously
degassed sample at room' temperature and then through a thermal conductivity
detector. When the sample is" suddenly cooled in liquid nitrogen it absorbs nitrogen
but quickly reaches saturation. This causes a temporarydecrease in the nitrogen
content of the stream which is shown as an inverted peak by the continuous
recorder. When the sample is warmed suddenly to room temperature nitrogen is
evolved, giving a peak in the opposite direction. Peak area and/or heights are
obtained on standard samples of known area (determined by the regular BET
method) and serve for calibration. Usually the desorption peak is used. Commercial
instruments give the integrated area under the peak and direct area readout.
Gaziev, Yanovskii, and Brazhnikov (61) pointed out that the method ignores
variations in heat of adsorption which corresponds to variations in the c value of the
BET method. Reviews of the method appeared in 1972 (62. 63). Pommier. Juillet,
and Teichner demonstrated that very small areas could be determined. Lowell (65)
used krypton instead of nitrogen to measure specific surface areas as low as 0.019 m 2
g-I. Payne. Sing. and Turk (66) compared argon and nitrogen on hydroxylated
silicas and found that the area covered per argon molecule is 18.2 A2, assuming the
value for. nitrogen is 16.2 A2. For microporous solids nitrogen was preferred.
Other gases and vapors may be used. especially where liquid air temperatures are
inconvenient Methanol has been used at ordinary temperature to measure area and
pore properties (67). At p/Po 0.1 the surface area is 145a m 2 g-I where a is millimoles adsorbed per gram. or about 4 CHaOH molecules nm- s FUTan at 23C and
butane and lsobutane at OC gave monolayer coverages of 42. 54. and 53 As per
OIl
-_...
if
"
J
472
molecule, respectively (68). Ammonia at its boiling point gave "ariable mOlecular J
coverages depending on the nature of the silica surface (69). Nitrogen mono)" . , 1
(NO) was adsorbed at temperatures from 181 to 293K as the magnetic susce],. :
bility was measured (70). When benzene was adsorbed at p/ Po 0.214, a monolayer
was present on silica from which area could be calculated (71). The adsorption
isotherms for different gels varying in area, pore size, and surface hydroxylat,ion .1
were calculated from basic prlnciples by Kiselev ( 7 2 ) . '
Water vapor is a useful adsorbate provided the surface is fully hydroxylated, With
silicas that are rendered hydrophobic by surface treatments or that have been J
dehydrated above about 300C, the adsorption of water is useful for determining
_1
only the hydrophilic area. However, for gels and powders formed in water and dried
i
at moderate temperature, the adsorption isotherm for water give~ a dependable
i
i
j
measure of specific surface area. Water adsorption on silica was studied, for
example, by Gans, Brooks, and Boyd (73) and Kantro, Brunauer, and Wise (74),
~
1
who found that the surface area could be calculated using the BET equation.
~
Adsorption was measured by weight increase as the sample absorbed moisture for 7 '~
1f
days at 25C from solutions of known vapor pressures 0 f water. Vapor pressures
ranged from 0.07 to 0.33. The method is slow but requires only simple laboratory
~
glassware, Adsorption on gels of widely varied structures was examined by Beli
, yakova, Dzhigit, and Kiselev (75), who reported that one'H,O occupied an area o f ;
25 ).., in the monolayer.
.;
'Carbon tetrachloride adsorption was measured at 28C with a microbalance giv~
ing a linear BET plot from which the specific area agreed with that by nitrog
~
adsorption. There was no chemical interaction (76). Carbon dioxide at the tempera _
ture of - 7SoC can be used in the same equipment as employed for nitrogen at
- 196C and gives the same results within 10% (77). .
With the now method using butane in carbon dioxide, the butane desorbed can be
recovered and the volume measured after adsorbing the carbon dioxide in alkali
solution (78).
.
Adsorption/rom solution has already been mentioned in Chapter 4 relating to the
specific surface area of colloidal silica. These and other methods have also been
applied to silica powders and gels. Adsorbates include organic compounds from
organic and aqueous solutions as well as organic and inorganic cations and the OHion from water. Polar compounds in nonpolar (hydrocarbon) solvents are adsorbed
on the polar SiOH surface. Adsorption on the dehydrated siloxane surface is not as
well understood. However, there is evidence that in water, the siloxane surface is
hydrophobic. It adsorbs only hydrophobic materials or groups.
Surface areas of hydrophilic (hydroxylated) silicas have been measured by adsorption of nitrophenol from water or benzene (79) and phenol from decane or carbon
tetrachloride (80, 81). The system must be anhydrous and the solvents dried by
molecular sieves. The phenol may be determined by bromine titration or
interferometer. Stearic acid is adsorbed from anhydrous methanol and determined
by difference by potentiometric titration with alkali. Tlie data given indicate that
each stearic acid molecule covers only 20.6 A2 (82).
\
Adsorption of Zn(en)i'" on silica gels and powders was already mentioned in'Chapter 4 and can be used to determine surface areas of silica powders free from
1
!
't
and Powders
le molecular
'n monoxide
:tic
~epti
1 monolaYer
: adsorption
I~roxylation
vlated. With'
; have been
determining
er and dried
dependable
studied, for
I Wise (74),
r equation.
iisture for 7
>r pressures
: laboratory
led by Bel: an area of
ialance givby ..;trogen
Ie . peranitrogen at
~bed
can be
le in alkali
ating to the
: also been
.unds from
d the OHe adsorbed
:e is not as
surface is
byadsorpor carbon
s dried by
:ration or
letermined
Iicate that
ntic, .d in
free from
.>
473
micropores, according to Unger and Vy~ra (83). Th~ dec:ease in zinc cbntent .of the
tuticn in the pH range 6-9, determined by a ntration procedure, provides a
. :easure of surface area within about ::3%. Coverage is about 1.26 molecules nm- s,
.or 79 ASper molecule.
.
Adsorption of dyes on powders has long been used to estimate areas since the
nalysis requires only colorimetry. Methylene blue has been studied by a number of
~nvestigators and factors influencing the adsorption have been explored (84, 85).
Giles, D'Silva, and Trivedi (86, 87) compared a series of cationic dye~ including
methylene blue and crystal violet as adsorbates on various powders from solutions in
p_nitro'phenol or water and correlated results with areas determined by the BET
method using nitrogen and krypton as well as electron micrographs.
Adsorption of cationic surfactants (cationic soaps) on silica has been studied by
Ter_Minassian-Sarage (88) and by Bijsterbosch (89), who have shown that either a
monolayer or a bi-Iayer may be formed. Similar complexities may exist with some
micelle-forming dyes, and special conditions would have to be worked out for each
adsorbate to eliminate confusion. Also, the adsorption of these ionic species is
affected by pH and by aluminosilicate ion impurities on the silica surface. Use of
cationic dyes and surfactants is generally restricted to rapid comparison of surface
areas of a series of silica powders of the same type.
Nonionic dyes such as methyl red are useful for determining the hydroxylated surface area of silicas, especially those of which the surface has been partly
dehydroxylated or rendered organophilic.Lowen and Broge (33) used the method of
Shapiro and Kolthoff (90) Involving physical adsorption of methyl red dye from benzene solution onto the polar silica surface. In parallel experiments, the silanol groups
were reacted with (CH,),SiCI and the number of chernisorbed (CH,),SiO groups
related to the number of SiOH groups remaining on the surface after dehydration at'
a series of elevated temperatures. It is clear that with fully hydroxylated silicas free
from micropores, surface area can be measured with either reagent (Figure 5.2).
Each methyl red molecule covers 116 A' and each (CH,),Si group 45 As.
Adsorption of monomolecular Hf(OH)4 from neutral solution onto silica was
proposed by Stryker and Matijevic (91) as a way to determine specific surface area,
using radiolabeled hafnium. Murphy, Posner, and Quirk (92) reported that attempts
to repeat the method failed. There followed an interchange of notes which left the
question unresolved (93).
Phenyl trichlorosilane, C.HsSiCI" reacts quantitatively with dry silica gels and the
amount irreversibly reacted with the silanol surface permits estimation of surface
area. There are 2.16 phenyl groups anchored to the surface per square nanometer
(3.6 micromoles m-') (94).:
Titration with alkali in salt solution between pH 4.5 and 9.0 is a very useful, rapid
method for determining the area of hydroxylated silica. The OH- ions are small
enough to penetrate pores not accessible even to nitrogen. Details of this Sears titration method are given in Chapters 3 and 4. When gels or powders are involved, equilibrium is rather slowly reached at the final end point at pH 9. Meffert and Langenfeld have studied titration of silica powders (95) using an automatic titrator to reach
the end point. The need for a high salt concentration to permit titration of surface
within fine pores has been accounted for by Abendroth (96).
~---
474
0.8
.~ 2.5
1.0
1.2
1.4
1.6
1.8
2.0
. Ii
..
:
SiOH
PER om2
Figure 5.2. Relationship between silanol groups per square' nanometer, temperature or
dehydration, and adsorption of (A) trimethylsilyl groups and (8) methyl red molecules.
;.:
, .
!"
!.: .
Chromatographic methods using adsorption from the liquid phase have been
developed. When a large enough sample of silica is available it can be packed into a
column 2 mm in diameter. The length of tile chromatographed colored zone of
methyl red in benzene is measured and related to specific surface area (97). Adsorption' of C1-C. alcohols from various concentrations in benzene was measured by _
Hoffmanet a1. (98), frcmwhich the surface areas covered by the physically
adsorbed molecules on silica were calculated as follows:
:.,'
Alcohol
Methanol
"Ethanol
I-Propanol
2-Propanol
l-Butanol
Molecular Area (J\2)

19.9
25.5
30.2
30.8
34.4
Hoffman et al. then used the liquid chromatographic system of CH~OH-H20-silica

developed by Frenkel et al, (99) and determined the surface area of the silica which
agreed with the BET method using nitrogen adsorption. It was concluded that the
lower alcohol-benzene system offers a simple method for measuring surface area
requiring little equipment or skill.
Another procedure for measuring hydroxylated surface areas uses octadecyl
alcohol as adsorbate which is determined by gas chromatography. Serpinet et al,
(100) used this method to check the accuracy of the flow method using nitrogen
. adsorption.
'
\
This method has been used to follow the adsorption of

liquids and vapors on silica. As benzene penetrates micropores, the interaction with
DIELECTRIC MEASUREMENTS.
.....
i Powders
475
Physical Charactcrization
the surface changes the dielectric isotherm. Changes in behavior after" heating the
silica were also observed (101). In earlier studies, McIntosh, Rideal, and Snelgrove
(102) had noted discontinuity of the slope of the curve relating electrical capacity of
silica versus the amount of water adsorbed. For relative humidity under 40%,
Kurosaki (103) found the adsorption of water follows the BET equation, but
dielectric capacity and loss show discontinuities related to changes in the freedom of
rotation of molecules on the silica surface..
The dielectric constant of a given type of silica powder is related to the SiOH surface groups and therefore to specific surface area. Pyrogenic silicas, low in silanol
groupS, have a lower constant (104).
irature'
or
s.
ave been
ed into a
zone of
Adsorpsu
by
hys,.....lly
IO-silica
ca which
that the
lce area
ctadecyl
et et al.
nitrogen
Jf
ion with
'ph
-;;...
THERMAL EFFECTS. . Numerous measurements of heats of adsorption on silicas of

known areas have been reported, but there are many factors affecting the results and
the equipment is complex. Harkins and Jura (lOS) developed an absolute method in
which the sample powder is equilibrated with water vapor isothermally until the surface is coated with a film of water and then it is immersed in water in a highly sensi, tive calorimeter. The liberated heat in ergs per gram divided by the total surface
.' energy of water (118 ergs cm-I) gives the specific surface area. The method can be
. used only with limited types of silica. The heats of immersion of various powders,
including silica, have also been related to surface area by Okuda (106).
One of the complications is the higher heat of adsorption in very fine micropores
(107) which, of course, can be 'used to characterize the porosity of gels of known
area. Another important variable is the state of hydration of the silica surface which
can cause a threefold difference in heats of immersion in benzene or cyclohexane (108).
.
A heal of immersion in. water of 160 ::f:: 3 ergs em -2 was found on hydroxylated
silicas of specific surface areas in the range from 8 to .150 m 2 g-1 free from
. micro pores. Taylor and Hockey (109) reported the value to be constant in this range
provided the surface 'properties were similar. In all cases the surface had been
dehydrated at elevated temperature as the silica was sintered for various times at
700-1040C to reduce the surface area and then rehydroxylated to 4.71 OH groups
nm -2. Thus, at least theoretically. the surface area of silica after suitable preparation
of the surface could be determined by measuring the heat of immersion in water.
" MERCURY PENETRATION. The pressure, p, required to force mercury into a pore
is inversely related to its diameter, and the volume of mercury, v, which penetrates
at that pressure measures the volume and thus the "length" of the pore. From this
the internal area of the pore can be calculated. However, in practice, the pores are
widely different in size and the surface area is determined by an integral;
s =-
I'
CT.COS 8
lllmaz
11 0
p dv
'
where CT and 8 are respectively the surface tension and the contact angle of mercury
. with the pore wall, and Vo and V maz are the volumes of mercury penetrating the
---476
pores at 1 atm pressure and maximum pressure, respectively. The method is

generally applicable only when S is less than 100 mS g-1 (110).
The resistance of a packed powder to the flow of a gas can be used
under certain circumstances to measure particle size or specific surface area.
Methods of .this type are described by Arnell (111) and Deryagin, Fridlyand, and':
Krylova (112). Such procedures are probably now seldom used since the rapid flow>.
method of nitrogen adsorption has become available.
.
PERMEABILITY.
",
THE HYDROXYL CONTENT. The amount of "bound water" in silica, after complete
surface hydration and drying under vacuum at less than 100C, is a direct measure
of surface area. In the case of nonmicroporous silicas, the area determined in this
way agrees with the BET area by nitrogen adsorption. According to Zhuravlev and .
KiseJev (113) when the surface OH content is measured by deuterium exchange, it .1:.~
corresponded to 5.0 OH groups nm- I on more than 40 different amorphous si1icas.:~;~':,
In the case of microporous or so-called lepidoidal and hydrated silicic acids, the OH ~r:
content is a measure of "surface" in the sense that it measures all silicon atoms that " ':;;.
are not completely linked through oxygen atoms to surrounding silicon atoms.
'
For many colloidal and precipitated silicas, Tiwari et al. (114) found that differential thermal analysis (DTA) peaks, which are proportional to the number of
SiOH groups that are dehydrated, can be closely correlated to the BET surface
areas. The OH coverage per unit surface (BET) area is independent of particle size
or pore size as long as micropores are absent.
Low Angle X-Ray Scattering
"
The us~ of this technique for determining the size of ultimate silica particles was
reviewed in Chapter 4-.Early studies by Shull, Elkin, and Roess (115) correlated diffraction data with other structural features of silica gel. Also Bastick and Faivre (116)
found that the dimensions of the "micellar surface" of siJica gels calculated from diffraction data correlated with surface area as determined by nitrogen adsorption.
Shull found average particle diameters in different gels (2.9-8.8 nm) were in
agreement with measured specific surface areas, assuming dense spherical particles
were linked' into the three-dimensional gel network with little loss of area at the
points of contact. Correction of the scattering curve for scattering aside from silica,
and measurements of ultimate particle diameter in silica gels were described by
Kakudo et al. (117). The particle diameter of Ludoxll> HS colloidal silica was
determined by Tamagusuku and Shuin to be 15.5 nm (118). On pyrogenic silicas
good agreement with particle size from electron micrographs was obtained by
Bradaczek (119), that is, 8.2 versus 8.9 nm diameter.
As discussed later, gel structure can also be elucidated by this technique.
Aggregate Size-Powder Particles, Gel Granules
In powders and gels the ultimate of primary particles are always aggregated into
what have been variously called "secondary particles," "clusters," or "aggregate
nd Powders
method
IS
an be used
face area.
.yand, and
rapid flow
. complete
:t measure
led in this
ravlevand
change, it
)US silicas..
ls, the OH
items that
ms.
I that dif
lumber of
T surface
.rticle size
ticles was
elated dif.ivre(116)
from difIsorption.
were in
particles
ea at the
om silica,
cribed by
ilica was
iic silicas
ained by
-,
ated into
iggregate
477
particles." They will be referred to simply as "aggregates." The "ultimate particles"

will generally be assumed to be nonporous although in a few special cases may
contain micropores less than 5 nm in size as described in Chapter 4. In the
aggregates t~e ultimate pa~ticles are linked together by siloxane bonds and are not
'
dispersible without mechanical rupture...
Silica powders consisting of discrete nonporous particles or granules larger than
half a micron or so in diameter, such as made by grinding massive silica, are outside
the scope of this book. Discrete particles of silica coated with large organic cations
or covered with alumina and chloride anions, which can be dried to powders that
spontaneously' disperse in water, or discrete silica particles covered with chemisorbed
alkoxy or organosilyl groups and dried to colloidal powders spontaneously redis.
persible in organic solvents, have been reviewed in Chapter 4.
. It is interesting to visualize the extremely small size of the ultimate particles. If a
small granule of typical.silica gel lmm in diameter were enlarged or magnified to a
diameter of 50 m, then the ultimate silica particles of which it is made would be
about I mm in diameter!
.. Aggregate size can be measured by a number of conventional methods including
screening. Screens are now available in mesh sizes down to microns. In the case of
._ some pyrogenic silicas, otherwise referred to as "silica smoke" or "white soot," the
linkage between the ultimate particles are extremely weak and thus the aggregates
are so fragile that the measured screen size changes as the powder is subjected to the
mechanical action of the screen. On the other hand, the aggregates of precipitated
silicas and especially of dried silica gels are sufficiently coherent to give reproducible
measurements.
.Wet methods may be used in which the powder is suspended in a liquid, usually
water with a surfactant to, overcome flocculation of aggregates, Aggregate size can
then be determined by diluting out the suspension and measuring aggregate sizes by
optical microscopy.
."
Various sedimentation and elutriation methods are available but these are of value
only after standardization for given type of powder or gel with constant aggregate
density. The same applies to measurement of permeability jo a stream of air or
liquid. The external surface area of porous aggregates, which is an indirect measure
of aggregate, size, can be measured by "ambient pressure perrneametric" measurements. Gas is forced through a bed of powder and the flow rate and pressure drop
are measured. The apparatus that is used for the flow method of measuring surface
area by nitrogen adsorption (Quantasorb from Quantochrome Corporation) can be
adapted to this measurement.
A complete bibliography up to 1950 to the foregoing techniques is found in
Chemical Engineer's Handbook (120). For research purposes wet or dry screening is
generally the simplest available method. However, Van den Hul and Lyklema have
considered the broad question of ultimate particle sizes versus aggregate size (121)
and examined various techniques, especially "negative adsorption." This approach
' .
may prove practical for gels of certain pore sizes.
Negative adsorption is a rather contradictory term referring to the phenomenon
by which, in a suspension of the adsorbent in a solution, one component is more
highly concentrated and the other less concentrated within one or two molecular
diameters of the surface than in the bulk liquid. Thus, for example, in a suspension
.
iI
_ _ e.
I
478
Silica Gels and Po.....ders
of silica with a negative surface charge in water. anions are expelled from the
immediate surface and especially from narrow pores. In comparing six methods of
determining the surface area of silica. among other finely divided solids. Lyklema
and Van den Hul (122) included the negative adsorption method. With a silica
powder of a specific area of 56 m'g-I by the BET method, the negative adsorption
method gave 34.5 m J g-I.
Pore Characterization
".1
.'j
..
Measurement and definition of porosity is possible only with aggregates that are ':
mechanically strong enough not to be affected by the method of test. For example,
in characterizing porosity by measuring the penetration by mercury under pressure,
conventional catalyst gels are not affected but-with aerogels or precipitated silicas
the structure . would be collapsed and the results meaningless. On the other hand ,
measuring the pore size by filling the pores with liquid nitrogen is far less destructive, and analysis by low angle X-ray scattering is obviously nondestructive.
The structure of aggregates and gels has been described in Chapter 3 and also
there is some discussion in Chapter 4 of gels formed from discrete colloidal particles.
The volume of literature on this subject is enormous, especially relating' to silica gelbased catalysts and more recently silica packings for chromatographic columns.
Several comprehensive reviews and discussions are available (1-6). Unger (6) has
given an especially clear and concise description of the nature and characterization
of pores in silica.
.
A monograph on pore structures was published by Linsen and Van den Heuvel
(123) with a review of methods of measurements.
The following structural variables characterize pores:
I, Specific surface area (m t g-}). This includes the total surface of the solid phase.
.Except for extremely small aggregates that are submicron in size. the external
. area is negligible in comparison with the area of the pore wall surfaces. Methods
of measurement have been discussed in a previous section.
2. Specific pore volume (v p , ml g-I) is the total volume of pores per gram of solid.
This is usually determined by measuring the volume of a liquid required to fill the
pores but not the spaces between aggregates.
3. Average pore diameter (d,.. A).
4. Pore size distribution in terms of a distribution function I:J. vp / I:J.dp - J(dp ) .
5. Degree to which entrance to larger pores is restricted by smaller pores ("bottlenecks" or "ink-bottle" pores).
.
These parameters are usually derived from one or more types of experimental data:
1. Gas or vapor adsorption 'isotherms whereby the quantity of adsorbate Xu is

measured as nearly as possible over the range of partial pressures p/Po 0-1.0.
d Powders
from the
ethods of
2. Mercury penetration whereby the volume of mercury forced into pores is
479
measured as a function of pressure. The pores must be completely nonwetted by

the penetrating liquid and mercury is the only suitable liquid available at ordinary
temperature.
3. Low angle X-ray scattering provides a measurement of distance between
solid-gas interfaces; that is, pore diameter (and particle diameter).
L. .na
h a silica
dsorption
4. Electron microscopy is useful for confirming the mathematical models used in

-,
- that are
example,
pressure,
ed silicas
rer hand,
i destrucand also
particles .
ilica gelcolumns.
r (6) has
eri- ..tion
n Heuvel
interpreting adsorption or penetration data.

5. Permeability to gases is in some cases a measurable function of average pore size.
6. Exclusion of ions or molecules of known size can be used to measure pore size
under suitable circumstances.
7. Volume of imbibed liquid provides a measure of pore volume, if measured under
suitably controlled conditions.
Because adsorption characteristics change with pore size, it is convenient to classify
porosity by the terms submicro-, micro-, meso- (intermediate), and macropores.
This terminology was proposed and later modified by Dubinin (10, 124) who defined
the terms as follows: : Diameter (A)
Micropores
Mesopores
Macropores
;
....~~ .
. 10-12 to 26-28
30-32 to 2000-4000
- 2000-4000
ParticleSize and Packing:

-
id phase.
external
Methods
of solid.
-0 fill the
("bottle':
\1 data:
te.
1.0.
is
.~--.
The structure of silica gels remained for many years a matter of debate. The gel
structure was often visualized as a cross-linked network of molecular "chains" of
polysilicic acid similar to organic gels. However, in 1926, Freundlich suspected and,
in 1940, Carmen clearly proposed that silica gel was made up of ultimate spherical
particles.
.
Before it was discovered how to make uniform silica particles larger than 5-10 nm
in diameter, the only silica gels were those made by acidifying sodium silicate or
hydrolyzing silicic esters. Even with the electron microscope it was difficult to
discern the structure of such gels. However, there is no longer any doubt that silica
gels and powders are primarily formed from "corpuscular" or "globular" discrete
particles as discussed by Her (2), Kiselev (3), Vysotskii (in ref. (5 and Unger (6). A
technique for preparing thin sections of very fine gel structures was developed by
Sugar and Guba (125) permitting magnification of lOs-fold, by which it was seen
that the structure indeed consisted of fiber like threads made sp of a chain of globules. From measurements of the pore size and particle diameter, a specific surface
area and average pore size was calculated which compared satisfactorily with values
obtained by nitrogen adsorption. Carbon replicas of silica gel structures were used
Silica Gels and Po';ders~ ~~.... .'
480
for electron micrograph studies of various silicas by Leont'ev and Lltk'Yanovich-(126a).

The chaining together of spherical silica particles into a gel structure has been dis:cussed in detail in Chapter 3. Now the effects of particle size and particle packing On
porosity will be considered.
A typical pore in a dense silica gel is shown in Figure 5.3a. Here the silica spheres
are in cubic packing and the pore volume is 48% of the total volume. Since the 52%
by volume of silica has a density of 2.2 g cm- a, the specific porosity is 0.42.cm a g-l.
As long ago as 1954, Kiselev (126b) calculated the surface area, pore volumes and
sizes, and coordination number of the average particle as the packing density of
spherical particles was varied. As seen in Figure 5.3b, when the geometry of packing
remains the same, then the pore diameter decreases with particle diameter. On the
other hand, by changing the packing particles of a constant size, the pore diameter
can be changed. Also, both packing and particle size can be changed simultaneously
to maintain a constant pore diameter.
.From the experimental standpoint all silica gels and precipitates tend to be
compressed by the shrinkage forces of the surface tension of water as water dries out
of the pores. Unless special precautions are taken to strengthen the structure and
:"
I
.... -- ..... ... <,
,I'
"
'<
I
I
,
I
"
.,- ---- --... .J.
,;.
..,
.I'
...
"
,
I
,;
\
\
\
\
'
-"
... ....
...
,
\
"........
"'>-tt~.
,;.1'"
i
i
;
I
(a)
Figure 5.3a.
Model or an "elementary pore" in a regular 6-coordination sphere packing.
'.
d Powders
'Yanovich
b
dislacking on
481
COORDINATION
NUMBER
VOLUME
SOLID PORES
ca spheres
the 52%
em! g-I.
lumes and
density of
Jf packing
er. On the
: diameter
ltaneously
PORE
VOL
-I
12
745
25.5
OJ55
52
48
0.42
95
8.6
3-2-3
1.3
98.7
35
0.83
99.17
54
end to be
r dries out
.cture and
fbJ
Figure S.3b. The size of the ultimate particles and the coordination number (number of particles touching each particle) control the pore volume and average pore diameter. (Drawing is
schematic; actual structure is three-dimensional.)
. .
.
reduce the surface-tensionforces, the wet precipitate or gel is strongly compacted to
about the same coordination number 5-6. In this case the pore diameter is proportional to the particle size and varies inversely with specific surface area. For
example, Unger (6) gives the following associated values:
,
\
\
Micropores
Mesopores
Macropores
packmg.
Pore Diameter (A)

(Dubinin)
Specific Surface
Area (m! g-I)
(Unger)
. <20
20-2000
>2000
>500
500-10
<10
However, this relation does not always exist; some very low density aerogels can
have both a large pore diameter as well as a high specific surface area.
The relation of particle size and packing to the pore characteristics has been
considered in terms of several models. Mason (127) considered random packing of
spheres. since certainly in silica gels the packing is not regular (except in opals as
discussed in Chapter 4). He considered the pore as a tetrahedral subunit formed by
joining the centers of neighboring spheres which do not necessarily touch each other.
482
Table 5.1.
Characteristics or Bodies or Packed Spberes or Radius R
Type or
.. Packing
Hexagonal
(close packed)
Tetragonal
(body centered)
Hexagonal
(primitive)
'Cubic
(primitive)
Tetragonal
~l
....
.,
Porosity
(em' poresl
cm ? body)
Density"
or Body
(g em-I)
Radius or
Sphere
Inscribed
in Cavities
Radius or
Circle
Inscribed
in Throats
12
0.260
1.63
O.225R
O.lSSR
Coordination
Number
0.414R
10
0.302
1.54
O.291R
0.395
1.33
0.527R
0.476
1.15
0.732R
O.414R
0.666
0.73
I.00R
0.732R
l'
'.~
'-~
~
0.26SR
O.IS5R
0.414R
O.ISSR
Source. Avery and Ramsay (129).

Assuming sphere (silica) density of 2.~ g cm-'.
The pores are thus "defined by the coordinates of the centers of the spheres, The
properties of the pores. were evaluated by computer. According to Mason, the
random packing of 'spheres gives a volume density of 0.63 which is about halfway
between 0.52 for open packing (cubic) and 0.72 for close packing.(hexagonal).
Particle packing has been studied experimentaJIy by starting with very fine silica
powders of uniform particle size in a voluminous state of low. bulk density where
each particle touches only two, three, or four others. When this is mechanically
compressed there are more and more interparticle contacts.
The absorption characteristics and geometry of packed spherical particles have
been calculated by Dollimore and Heal (128). Using coordination numbers of 4, 6,
and 8, equations were developed to calculate the amount of adsorbate at different
partial pressures.
Thecharacteristics of different modes of packing uniform spheres have also been
calculated by Avery and Ramsay (129), and values are given in Table 5.1. Although
in actual gels no such regularity is likely, nevertheless from the porosity of a gel one
can approximate the coordination number, n, The density of the gel permits an estimate of the pore diameter if the average' particle diameter is known. This presupposes that the ultimate particles in a gel are all of uniform size and this is generally
true unless special means are taken to have two particle sizes present.
Alternative packing arrangements with fraction of solids, q, (where 1 - q, is fraction of porosity) calculated for different coordination numbers, have been considered
by Meissner, Michaels. and Kaiser (130), who cited earlier similar considerations by
Heesch and Laves (131) and Manegold, Hoffman. and Soff (132). Meissner
proposed a general equation
i
0
;>
{
. .\
= 2 exp(2.4<1
.,.
~-_.
d Powders'
483
POROSITY
3
crJ/cm OF BODY
PORE RADIUS
Rl "of
Cirere
1.0 xR
R a PARTICLE RADIUS
Inscribed
in Throats
1.0
O.lSSR
O.26SR
O.ISSR
0.5 xR
0.414R
O.ISSR
0.414R
0.05
O.132R
OxR
....
o
2
eres, The
ason, the
t halfway
I}.
'inesrlica
ity where
.hanically
cles have
s of 4, 6,
different
also been
Although
a gel one
san estis presupgenerally
10
12
COORDINATION NUMBER
.#
:.
Figure 5.4. Calculated ~ariation or"A, volume porosity (em' of pores per em" of body); B,
radius of pores at throats; C, radius of pores in cavities with varying coordination number of
spheres forming a three-dimensional gel-type network. [Dashed line from the equation of
.
Meissner, Michaels. and Kais~.r (130).]
. for whieh calculated values are.shown in Figure 5.4. The fractional volume porosity
is I - ,p.'
.
To more closely simulate actual gel structures, the studies of random close packing of spheres is pertinent. Scott reports that loose random packing of uniform
spheres gives' a volume packing density of 0.60 and dense random packing gives 0.64
(133). Results were discussed by Bernal, Mason, and' Knight (134, 135). The effect of random sphere packing on capillary properties has been described by Mason (127).
Loss ofSurface Area by Particle Packing

'/J is frae-
msidered
ations by
Meissner
Avery and Ramsay (l29) prepared Si02 (also Zr02) particles about 4 nm in
diameter as a voluminous powder by a vapor condensation method and compacted
this in stages up to 100 tons in. -2. In the original fluffy powder- it was not possible to
determine any definite "pores" but at the point beyond where a coherent body was
obtained, the approximate relation between pressure and the coordination number of
silica particles was as follows:
.,
--_ ..
484
.;.
Pressure
(tons in. -Z)
Surface
(mZ g-l)
Coordination
Number
0
10
50
100
636
522
373
219
3
5.6
9.8
Porosity
(ern! pores cm- J body)
:- ~
J -,
,j.
0.51
0.33
0.204
It is noted that it is easy to compress particles to a state of approximating cubic

packing where the body has about 50% by volume of pores. However, at 100 tons
in. -z the porosity drops to 0.204. which is even less than that of perfect close-packed
spheres, which is 0.255. Under this pressure some of the particles may have become
flattened together in which case the formulas are not applicable.
The specific surface area of the compressed powder was predicted by an approxt,
mate equation assumed by the authors to be
; i;
.! '."
. .,
. .
.-
.;
':
::.
~ ,
j,
where S is the accessible specific surface area in square meters per gram of a compact of spheres of radius R in nanometers, n is the number of contacts of each
sphere with other spheres. d is the assumed diameter of the nitrogen molecule 0.375
nm, and So is the specific surface area of the original separate spheres. For discrete
spheres the specific surface So - 2750/2R m Zg-I, where R is in nanometers. Substituting in the above equation,"
SR Z
I, '
1375R
128.9n = 0
Calculation of the ultimate sphere size, R, is thus possible from data of specific
surface area and of specific pore volume from which the coordination number can be
estimated. Taking the indicated values for Sand n, R and So are calculated using
the above equation:
'
'I
R (calc.)
(nm)
So (calc.)
(rn! g-I).
5.6
9.8
1.91
1.95
719
705
S (measured)
(m~g-l)
t
5~2
3 3
However. this equation ~ay not be valid for such small particles because it was
assumed that the nitrogen molecule is of negligible size relative \0 the silica particles.
A more exact expression for the loss of available surface area when two spheres of
radium R are in contact is given in Figure 5.5.
,.,
id Powders
~_.~
485
.,
Figure 5.5. Area lost to nitrogen adsorption at the

point of contact between spherical particles: R,
radius of sphere in nanometers; a, radius of nitrogen
molecule, 0.177 nm; b, radius of inaccesible circular
area.
ting cubic
t 100 tons
se-packed
Ie become
1
b2 _ a(2R + a)
I
I
Approximate area lost per contact per particle _

rb 2 Fraction of area of sphere lost per contact _
a(2R + a)/4R 2. A slightly more accurate value is
O.SaR/(R + a)2 but this is less convenient in solving
for R.
I
I
I
~2b---1
approxi.
Then in a body of uniformly aggregated spheres the resulting surface area S. is a
fraction of the surface area. So before the spheres came together:
S ... So
of a corns of each
zule 0.375
Ir rete
s. Substi- ..
)f specific
ier can be
ited using
\1
_ n _Q<_2R_+_Q_}\
4R2)
-~
When the variation of S with n is known. the value of R can be calculated from the
above equation by substituting for So:
2750
SO" -
2R
where Q and R are in nanometers, According to Broekhoff and Linsen (Ref. 4. p. 24)
the diameter of the nitrogen molecule should be taken as 3.54 A so that Q is 0.177
nm. The equation becomes:
SRI - 1375.2R2 + 121.7nR - 1O.76n ... 0
The pore volume PUt in cubic centimeters per gram of Si0 2 can be converted to
porosity. PI. by the equation
PI ...
ise it was
particles.
spheres of
PII
Pu + 0.455
where PI is cubic centimeters of pores per cubic centimeter of the silica body. From
this the average coordination number can be found from curve A of Figure 5.4. Then
taking the data for surface area S and the coordination number n, the value of R,
the particle radius. can be calculated from the above cubic equation. Then So is calculated from 2750/2R.
From the data of Avery and Ramsay:
~-_.
,::-.
.",.;
'
OJ
Silica Gels and Powd' ,,~,
486
ell
Pressure
(tons in. -')
Area (avg.)
(m' g-l)
Coordination Number,
n
0
10
50
636
522
373
5.6
Calculated Calculated
R (nm)
So (m' g-l)
2.02
2.10
9.8
;"
680
655
These values are reasonable in view of the 636 m' g-1 measured on the
uncompressed powder which must have a very low coordination number, indicating
that many particles may be held to the network by only one point of contact.
A useful form of the equation is as follows:
L, == n
0.0885
0.0075
R'
where L, is the fraction of the total sphere area lost when each sphere of radius R
nm is touched by n surrounding spheres. Based on further considerations by De Boer
et al. (45) a somewhat more accurate equation is
R
L, = 0.0885n - - - (R + 0.177)'
In this case, to calculate R, knowing the measured area Sand n, the equation to be '.
solved is
S _ '1375 (R +. 0.177)' - 0.885nR(R
R(R + 0.177)'
+ 0.177)'
Barby (8) has made similar calculations.

These calculations do not apply when the spheres become so closely packed that
the pores are so small that one nitrogen molecule is large enough to fill the width of
a pore. Hence in the more highly compressed silicas the surface area measured by
nitrogen is much too small. This has been discussed by Dollimore and Heal (136),
who showed that the true area in such a case may be 3.63 times the apparent area,
and also that adsorption data using nitrogen can never show a pore diameter smaller
than 1.4 nm and even pores that appear to be 2.0 nm diameter by nitrogen adsorption are more nearly 1.0 nm. This probably explains why the pore diameters
reported for compressed silica with a particle diameter of 4 nm are twice as large as
that calculated from the packing geometry.
Loss of surface area when spheres are brought into contact has also been observed
by compressing a silica aerogel and measuring changes ia the adsorption isotherm.
This cannot be done with silica gels dried from water since such structures have
already been compressed by surface tension forces during drying. On the other hand, '--
..
and Powders
Calculated
(rn 2 g-I)
5'0
':..---
487
Cbarac;teristics of Compressed Aerogel
Table 5.2.
Figure
5.6
Curve
Symbol
680
. 655
Compaction
(kg em-I)
2.38
1.28
0.40
906
858
660
o.
red on the
r, indicating
.act, .
Pore Volume
(em- g-I)
Specific
Surface
(m 2 g-I)
B
C
2.000
10,000
Source.
Nicolaon and Teichner (137).
'.
of radius R
by De Boer
ua.,
.1 to
be
. ,,:,,";
"'~
packed that
the width of
neasured by
Heal (136)
parent area.
.eter smaller
'gen adsorpe diameters
e as large as
sen observed
m isotherm.
lct'-~s have
0\
hand.
:4
~
. .
highly porous aerogels are made without collapse of the structure so that wide pores
and very large pore volume can be attained with small particles of high specific surface area.
Nicolaon and Tcichner' (137)
nitrogen adsorption isotherms on an
. measured
...
original aerogel and also after mechanical compression and compaction as shown in
Table 5.2 and Figure 5.6. The original aerogel was an extremely light solid. 100 em!
weighing only 5 grams{v~" - 8 ern! g-I). However, when filled with liquid nitrogen.
which was then evaporated, the liquid surface tension caused the structure to shrink
and reduced vp to 2.38 cm' g-I. After the powder was mechanically compressed
(under vacuum) the other curves of Figure 5.6 were obtained.
Iler used the foregoing cubic equation to calculate the ultimate particle radius R
of the aerogel, with results shown in Table 5.3. Rather surprisingly. the calculated
specific surface area corresponding to separate particles is much higher than
measured on the sampleonly compressed by removal of liquid nitrogen. The relative
consistent values for R 'ranged only from 1.00 to 1.08 nm and corresponded to an
average area of 1315 ni2 g-I.
, "These studies are convincing evidence that the properties of silica gels can be
explained in terms of three-dimensional aggregates of nonporous amorphous silica
spheres of various sizes and packing densities even in the case of particles only 20 A
in diameter.
-, ...I.~-.
Table 5.3.
Calculation or Ultimate Particle Size or Compressed Aerogel
Pore
Volume
(em! g-I)
Porosity
(cm S
cm-~ gel)
Coordination
Number,
2.38
1.28
0.4
0.84
0.74
0.47
")i
Average
R
(calc.)
(nm)
' Sa
(calc.)
(m S g-I)
3.35
3.7
6.2 '
906
858
660
1.06
1.08
1.00
1297
1273
' 1375
1315
,,/
."
Measured
Area
(m S g-I)
,.,
---Silica Gels and Powders
488
1500
en
C)
1000
a::
~
N
C)
500
OL.--------.. . . .
\ l.
~:
~t
".
.~ . .
; .:! ;,; ..
0.5
--l
0.977
PI Po
Figure 5.6. Nitrogen adsorption and desorption isotherms of aerogel. A, not compacted; B,
after compaction at 2000 kg cm -2: C, after compaction at 10.000 kg cm -2. [Nicolaon and
Teichner (137).]
1'I/
Characterizing Pores by Adsorption Isotherms
..
Sing (8) has presented an exceptionally clear and concise description of adsorption
isotherms and methods for their interpretation in terms of pore size distribution. As
shown in Figure 5.7, an adsorbate vapor such as nitrogen or water is adsorbed in a
porous gel or powder in increasing amounts as the relative vapor pressure, p/Po, is
increased, Po being the saturated vapor pressure of the liquid.
Starting at zero pressure (A) a typical adsorption isotherm exhibits several stages:
first, an increasing fraction of the surface is covered by adsorbed molecules (8). At a
certain point around C the surface becomes covered with a single layer of molecules.
At this stage those pores with diameters only two or three times the diameter of the
adsorbate molecules will also be filled. At higher vapor pressure (D) larger pores
begin to be tilled. When p nears Po, (E) liquid fills all pores and gives a measure of
the porevotume. At first it wasthought that pore diameter could be calculated from
the Kelvin equation (138) based on the theory that liquid remains in pores even when
the vapor pressure is lower than that of the massive liquid phase, since the vapor
pressure of the liquid in the pores is lowered because of surface-tension effects in
.small capillaries. Kelvin's equation (138) relates the vapor pressure, p, at which
489
d Powders
vaporwill condense in a cylindrical capillary, to radius ric:

-
...,;
-2 tTV cos fJ
R T(2.303 )Iog P/ Po
.,
wheretT ... surface tension of liquid nitrogen at its boiling point (-195.8C) ... 8.85
ergs cm- 2
8 angle of wetting, taken as zero so that cos fJ ... I
V molar volume of liquid nitrogen ... "34.7 ems
R - gas constant ... 8.314 x 10' ergs deg- 1 mole:"
T ... absolute temperature ... 77K
.~.
For nitrogen the equation simplifies to

4.146
rll -
.pacted; D,
:or
md
logpo/p
where ric is the capillary radius which fills at a partial pressure of p/Po. However, this
. is substantially true only for larger capillaries. When the diameter of a capillary
approaches molecular dimensions it is necessary to take into account the fact that
when p/Po exceeds about 0.2-0.3, even a flat surface becomes covered with a
monomolecular layer of adsorbate. For example, at p/Po ... 0.93 the layer is four
/
dsorption
ution. As
.rbed in a
:. p/Po. is
aJ stages:
(8). At a
rolecules.
ter of the
ger pores
easure of
ited from
yen when
he vapor
effl""ts in
at
..:h
,
Figure 5.7. Stages in adsorption of vapor and filling of pores with liquid with increasing
partial pressure. [Her (2). by permission of Cornell University Press.]
490
molecules thick (14 A). The Kelvin equation indicates the additional amount of
adsorbate over and above that which condenses on a flat surface at a given pip
Hence if t is the thickness of the adsorbed layer on a nat surface, the pore radius,
that is filled at.plpo is then
Tp -
+ Til
As shown in A . in Figure 5.8, after pores are filled and the pressure is again
reduced, the isotherm often follows a different course because a somewhat lower
pressure is required to evaporate the liquid. This "hysteresis loop" occurs because in
most gel structures there are pore cavities which are larger in diameter than the
openings leading into them. As a pore is emptied, the pressure is controlled by the
smaller diameter of the opening which retains a liquid meniscus as the inner larger
cavity is emptied.
A different situation exists if all the pores are so small that they are no larger than' 1
only a few times the diameter of the adsorbate molecule, for example, 20 A diameter
1
pores with nitrogen molecules 3.54 A in diameter. As shown in B in Figure 5.8, thei
pores may become filled even at low pressure. In this case it is difficult to determine _~
the point corresponding to a monolayer.
"Persorption" was a term coined by McBain (139) for adsorption in pores only
:l
one or two molecular diameters wide. More recently, pores generally less than 20 A
j
in diameter have been designated as "micropores." In such pores, the heat of 11
adsorption is higher than on planar surfaces, and pores can become filled even belo. j..
the pressure where a monomolecular layer is formed on a plane surface. Some silk. __;
gels, even those having large pores, have a certain volume of very small pores (140).
These may occur as the crevices between colloidal particles making up the gel, as
postulated by Carman-(141). Adsorption of alcohol vapors on random-packed glass
spheres, with capillary condensation in the crevices at the points of contact of the
spheres, has been studied by Shereskefsky and Russel (142). This is essentially a
large-scale model of the probable structure of certain silica gels, particularly those
made by drying down sols of uniform colloidal silica particles. On the other hand,
"
B
::I 400
cl
a:
C)
a:
Nl&J
za.
200
UO
Ul&J
a:
0
.....- ,....-
en
0
cl
0.5
1.0
P/Po
0.5
1.0
Figure 5.8. Representative nitrogen adsorption isotherms of A, mesoporous gel with 36

radius pores; B, microporous gel with 10 A radius pores. [ller (2), by permission of Corne.
University Press.]
.,
:i Powders
"".---
491
mount of
ven p/Po.
-ar'
rp,
. is again
rat lower
ecause in
than the
ed by the'
ier larger
0.5
PI Po
rger than
diameter
e 5.8, the
letermine
ores only
han 20 A
heat of
'en helow
m 'ica
~es (140).
Ie gel, as
ced glass
ct of the
:ntially a
rly those
ier hand,
ritlIf"
"I)
A
ell
/.0
Figure 5.9. Hypothetical nitrogen adsorption isotherms of

three porous solids having the same specific pore volume of
cylindrical uniform pores of three different sizes. Pore
diameters arc in angstroms.
such small pores may also occur in large numbers in the case of gels made of very
small particles which are densely packed. Thus close-packed particles of 1-2 millimicrons diameter would inevitably form gels which would be full of pores of almost
molecular dimensions.
According to Coelingh (143) and Brunauer (144), it is possible to subdivide silica
gels into four groups, depending on pore radius:
1. Gels with pores of molecular dimensions (less than 2 nm diameter) exhibiting
persorption, but no capillary condensation.
2. Gels with pores of about 2 nm diameter, showing hysteresis for water but not
large molecules and strong capillary adsorption at p/Po in the range 0.5-0.8.
3. Gels with pores 3-10 tim in diameter (micropores), exhibiting hysteresis for large
molecules and capillary adsorption only at higher values of p/Po.
4. Gel~ with pores larger tha~ 10' nm in diameter which show capillary adsorption
only when p/ Po approaches unity (aerogels and pyrogenic silicas).
Bering, Dubinin, and Serpinsky (145) class pores less than 3 nm in diameter as
"micropores" and from 3 to 200 nm diameter as "intermediate pores."
If it were possible to bore parallel cylindrical holes through solid silica, a series of
samples with holes of different sizes could be made while keeping a constant pore
volume per gram of silica. Then the adsorption isotherms should appear as in Figure
5.9. Since all the pores are the same size they would all fill at once when a certain
vapor pressure is reached. Also, since the pores are of uniform size, no hysteresis
should be observed. With very large pores, essentially infinite in size compared to a
water molecule, pores are filled only at p/Po = 1.0.
This idealized situation, of course, does not occur in actual silica gels where the
pores consist of the irregular spaces between the randomly arranged ultimate
spherical particles. As practical examples, Figure 5.10 shows water vapor adsorption
isotherms and the pore size distribution curves for a series of typical silica gels, each
of a relatively uniform pore size, as discussed by Kiselev (146). Pore volumes were
.j"j
it;, ,: ,
":...---
492
0
"'0
l
l
-;
C)
....
LLI
90
70
~'
60
LLI
..I ' ,
a:
0
c
40
30
,I
.,
'
:~,'J.
, .'
"::'1
:
.,
.j.. . .
"l -,
0
CD
CD
0.02
.....
80
::E
a:
LLI
<l
<t
0.03
C)
..J
<l
'S
3
0.04
0
0
0.01
0
0
so
100
ISO 200
250 ~ A
!SO
J+-"""':"'"-""r"'-~-"---:-----'
30
.t. '.
t ': ~ " (
:
;T~-t
20
20
10
10
0.4 0.8
0.4 0.8
0.4 0.8
0.4 0.8
0.4 0.8
0.4 0.8
PIP.
Figure 5.10. Adsorption isotherms or water on various silica gels and corresponding pore size
distribution curves. Peak pore diameters given in angstroms. [Kiselev (146).]
essentially the same in gels 2 and 3 and in 4 and 5 as 'shown by about the same
amounts of water required to fill the pores. Thus for gels 2 and 3, 50 millimoles H,O
per gram of gel equals 0.9 em" of H 20 per gram. The areas under the pore size distribution curves for the same samples, 2 and 3, are about equal and also amount to
the same value of 0.9 em" g-l. These isotherms are representative of the range of
silica gels that are commonly made.
!.
.; .,:
'Pore Volume
r::
I.
,I
;i :
',; 1- '
:\
: ,-.
';-
~ ,~
:~
..
:
,:
The pore volume is indicated by the volume of liquid nitrogen required to fill the
pores as the pressure approaches pfpo = 1. The volume of liquid = 1.55 x 1O~3 V"
where V, is the gas volume at STP. As shown in Figure 5.10. the volume adsorbed
is clearly indicated at the end of the curve. This is true as long as the specimen has a
. certain rigidity and form, that is, occupies a definite volume and has' a measurable
density. However, in the case of very fragile aerogels or loose, easily compressed
powders. the isotherm continues upward with no measurable break as bulk liquid
'
nitrogen begins to condense.
To determine the total pore volume. Lard and Brown (147) recommended a flow
method whereby a nitrogen-helium mixture containing 96.7% nitrogen is equilibrated with the sample at liquid nitrogen temperature, T.hen the sample is warmed
.,
id Powders
~---
493
to 25C and the volume of evolved nitrogen gas is measured. Only simple volumetric
apparatus is needed. Presumably. for very wide-pored material a mixture containing
99% or more nitrogen would be used to ensure pore filling.
The oil absorption test. long used to evaluate carbon blacks and pigments. can
give an indication of pore volume. A nonvolatile liquid that readily penetrates the
pores in silica. is used. Using the term "oil" in this sense. for example. glycol. the
amount of "oil" absorbed by a silica powder is an indirect measure of porosity. As .
the oil is mixed with the silica. the mass remains pulverulent until the pores are
filled. at which point the mass loses its friable nature and can be molded "into a single
mass held together by the surface tension of a thin film of liquid on the outer surface
of the porous aggregates (148). However. with finely divided aggregates the space
between the aggregates also is filled with oil. and the volume of oil needed to make a
coherent mass about equals the volume of the gel aggregates plus the pore volume.
assuming aggregates of uniform size.
10
pore Size and Size Distribution

!O
10
:ize
the same
oles H 20
: size dismount to
range of
o fill the
10- 2 V"
adsorbed
len has a
.asurable
npressed
lk liquid
:d
'w
.s equiliwarmed
These characteristics can be estimated in several ways from desorption isotherms.

Broekhoff and Linsen have reviewed this subject in some detail (149): In addition to
the laborious process of accurately measuring the adsorption isotherm, most
methods involve separate calculations for a large number of intervals of the
isotherm. However. with greatly improved control and read-out capabilities for getting the data and computer programs to calculate pore size, the labor has been
greatly reduced.
.
Two. types of commercial apparatus are available, one using a. vacuum system as
in the original BET method (Micrcmeritics) and another the flow system
(Quantachrome). An isotherm with 10-15 points can be ~determined in a few hours
and surface area and pore size distribution quickly obtained (150. 151).
Various mathematical approaches to calculation of pore size distribution have
evolved during the past century.
The r-plot is involved in most of the methods for the reason that on a relatively
flat surface in the absence of pores. adsorption occurs and "the adsorbed film
becomes several molecular layers thick before the vapor pressure reaches pjpo .. 1.0
for the bulk liquid. Obviously, in the multilayer film the properties of the nitrogen
are not the same as in the bulk. As already pointed out, determination of pore size
requires not only the Kelvin equation to calculate the size of pores that fill with bulk
liquid- nitrogen but also the thickness of the adsorbed film on the inner surface of
pores that are not filled.
To obtain experimental data on film thickness the silica must be free of
micropores. Harris and Sing (152) examined a number of such silicas of low surface
area (less than 12 m 2 g-l) and published an average isotherm in terms of vjv m versus.
p/Po. However. since then numerous workers have made suitable nonporous silicas
for more accurate determination of r-values. Very uniform large pores in silica with
no micropores were prepared by Bebris, Kiselev, and Nikitin (153). by heating the
pyrogenic "Aerosil" in steam at 750C. giving a silica with an area about 70-80 m 2
g-l with pores about 400 A in diameter. Generally accepted values of t for various
",
-:...--
. '. !. ~
; I
494
Silica Gels and POWders
values of P/PO. using nitrogen, are based on data by Lippens, Linsen, and De Boer
(154) and De Boer, Linsen, and Osind (ISS).
Table 5.4 lists typical r-values versus p/Po. and the following equation represents
the average of most of the available data at p/Po greater than 0.3:
".
~l
4.58
1=-----[- Jog(P/Po)]l"
I
L
Many workers contributed to the development of methods for calculating pore
size distribution from the adsorption isotherm, as described by Broekhoff and
Linsen (156). The original approach and general equation developed by Barret ,
Joyner, and Halenda (IS7) was followed up by Pierce (158) and later by Cranston
and Inkley. The subsequent evolution of the subject has been described in detail by
Gregg and Sing (7).
.:
...
. ",
'.
~.
".!
.~:
~I
... '.1
::'
.;:,:
"
.
:
. i ".
'
'
''0'
1. A volume of liquid nitrogen a VlIq is evaporated from pores. forming a gas

volume a V" usually expressed as cubic centimeters at STP per gram of
adsorbent.
',
I
;
.!
<.. ,
:~
...
.,;.~
'1,"
..
CRANSTON AND INKLEY METHOD. Cranston and Inkley (39) used the known thick.ness, I, of the film of nitrogen on the inner walls of the pores. along with the
diameter of pores filled by nitrogen according to the Kelvin equation. to develop a
procedure for calculating the volume and size of pores from the desorption or
adsorption isotherm. Use is made of the portion of the isotherm for p/Po above 0.3
where at least a monomolecular layer of nitrogen is adsorbed.
It is a stepwise procedure which, though simple, involves several calculations at
each step. The desorption isotherm consists of a series of experimental points at each
of which the adsorbed volume of gas is measured at a given pressure. Starting at
. p/Po ... 1.0 with fuJI pores, the pressure is reduced stepwise and the adsorbed volume
noted at each step. (This applies to desorption, but the calculations are the same if
the adsorption isotherm is used.) As pressure is reduced from a value of pJ/po to
P'l/ Po. the following are true:
:....
".
Table 5.4. Film Thickness oC Nitrogen Adsorbed on

Nonporous SurCace at -195C verses Partial Pressure oC
Nitrogen
pIp.
0.3
0.4
0.5
0.56
0.6
Source,
(A)
plpo
I (A)
plpo
t (A)
5.6
6.2
6.8
7.2
7.5
0.66
0.70
0.76
0.80
0.86
8.0
8.5
9.2
9.9
11.2
0.90
0.93
0.96
0.98
0.99
12.7
14.4
17.3
22.1
27.8
Lippens. Linsen, and De Boer (154).
',-
~_
....
ld Powders
De Boer
495
II
t,--ItII
rer ... ~nts
II
'I
II
ating pore
khoff and
>y Barret,
Cranston
I
detail by
iwn thick: with the

develop a
irption or
above 0.3
:Iations at
Its ~t each
.ta. . at
ed volume
ie same if
f pdPo to
ing a gas
gram of
.i:
..
. 2'2-4
:;
-NEW
~l
SURFACE~,
I
Figure 5.11. An idealized adsorbent with cylindrical pores shown in cross-section with
nitrogen adsorbed at pressure PI and P2. A, pressurePI: all pores of radius less than r, are filled
with liquid. The adsorbed film thickness is II and the Kelvin radius filled by the surface tension
effect is r",. B, Q lowerpressure P2: more pores are empty; those with radius less than r remain
filled. The adsorbed film thickness, ' 2, is less than II. The Kelvin radius n; is also smaller than
''''. L is the total length of pores emptied as pressu re was reduced. (sec text)
2. A volume AVll q of liquid nitrogen has emptied from the pores with radii between
VI and V2 , leaving a film of nitrogen on the walls of thickness ' 2
3. In pores emptied in previous steps, the nitrogen film thickness on the walls is
reduced from II to ' 2
For the uninitiated, Figure 5.11 may be helpful. This represents a cross-section of
a sample with idealized cylindrical pores of different sizes, showing the decrease in
thickness of the film of nitrogen on the walls of empty capillaries from 11 to ' 2 , and
also the decrease in liquid nitrogen that is desorbed, leaving more empty pores, when
the pressure is reduced from PI in A to P2 in B.
In A of Figure S.ll, there is one partly filled pore with diameter 2r" in which the
liquid nitrogen is just in equilibrium with the vapor at pressure PI' Similarly, in B,
.,
"f
496
the pore with diameter 2r2 contains liquid nitrogen in equilibrium at pressilre pz. In
these pores. the radius r; - t + 'Iu where z, is the radius calculated from the Kelvin
equation for the pressure.
Calculations are based on the following equations. Let L equal total length of
emptied pores with radii in the range from
to
the average being rp Then the
total volume of liquid nitrogen evaporated. Vllq is
'1 '2.
'
. .'
where A is area of adsorbed film remaining in the pores that have emptied.
The mean volume of pores of radius rp is
~:
t,
Elimination of L leads to
'~'':
:
"
",:
.. !;J!
i ' , ..
'
.. ~ ,
...
.':
'"
i .
Since
--,'.
;"1
I:U
where z, is from the Kelvin equation. then
The volume of gas evolved. measured at pressure p atm and at TO K. corresponds

to a liquid volume
v.; . =
V,
[2...-]
2.37T
ern"
The area A of the internal surface of the pores. assumed to be cylindrical. is
"
where Vp is in cubic centimeters and rp is in angstroms.

Using desorption data. calculations start at p/Po nearest l.O,where the pores are
essentially full of liquid nitrogen. Cranston and Inkley have described the steps in
calculating the volume and areas of pores that are emptied. However, the following
detailed description is helpful.
.,
-... ---
and Powders
ssure P2' In
. th- Kelvin
Calculations are made for each pressure step, starting with full pores and p/Po
nearest 1.0. For each step the following values are calculated:
~.
II length of
fl' Then the
497
;/1 - average of the two Kelvin radii 'II. and '111 in angstroms at PI and P2' respectively, where r, is calculated from the Kelvin equation:
4.146
'11 -
logpo/p
2. 11 and 12 , the film thicknesses in angstroms at PI and P2' from I ... 4.583/(log
PO/p)ll3 (or taken fr?m tables).
3. ;p, the average pore diameter:
1.
4. I ... 11 - 12, in angstroms.
.~
..~
5. A Vllq - volume in cubic centimeters of liquid nitrogen desorbed per gram of

adsorbent. AV"q - (1.55 x lO-')A V" where A V, is the volume, in cubic
centimeters, of gaseous nitrogen evolved, corrected to STP.
6. ,The volume of liquid nitrogen, in cubic centimeters, lost by thinning of films on
.. . pore walls - (At) (L A). L A is the area, in square meters, of the walls of all
. pores emptied in all previous steps (or AA in the first step). This volume - (AI)
., (L: A ) (10- 4) cma, since At is in angstroms and L: A is in square meters..
7. AA. - 2(AV"q) (;p) (104) , in square meters.
. 8. Obtain L: A by sum~ing up all AA\ from previous steps.
':." ..
orresponds
11, is
e pores are
he steps in
ef
wing
It is this operation that makes the stepwise procedure necessary.

This set of calculations is jnade for each step in turn at lower pressures and the
results tabulated.
The cumulative pore volume, Ve, starting from p/Po - 0.3 up to a higher value of
p/Po, is simply the sum of the A VlI q values in the intervening steps. This is usually
plotted as.ve versus log 'p'
_
The cumulative surface area, A e , is the total of AA values for all steps. If no
micropores are present, A e usually amounts to 85-100% of the BET value. Since the
latter is obtained in a lower p [p; range of 0-0.3, such agreement indicates that
micropores are absent.
Cranston and Inkley concluded that for many silica gels the method should be
applied in reverse, starting from p/Po ... 0.3 and following steps along the adsorption
isotherm.
.
A further discussion of the Cranston and Inkley method and some useful graphs.
have been given by Hougen (159). However, it is not easy to translate a set of equations into actual calculations, which is why the above steps have been given in detail.
Pore size distribution can be estimated from the r-plot, according to Broekhoff
and De Boer (160).
j.:
498
Silica Gels and Powder'

s . _
,1
r
t
MICROPORES. Special problems arise in the measurement and description of

extremely small pores. It is impossible to review the large volume of literature
appearing in the past decade, but the following is an attempt to describe certain
aspects, with examples.
According to Brunauer, it is generally agreed that "the mechanism of adsorption
of molecules in micropores is not well understood" (35). Sing (161) concluded in
1976 'that "no reliable method has been developed for the determination of
micropore size distribution." However, it is clear that in micropores the adsorption
differs radically from that on wide pores and on open surfaces arid that the
molecules in the pores are subject to the attraction of the surrounding solid and are ,
in effect, under high compression. Dubinin (124) has discussed the theory of adsorp_
tion under such conditions. It involves the concept of adsorption into a "volume"
rather than on an area of surface.
The surface area of microporous materials cannot be determined if the micropore
radius 'is less than 12 A according to Okkerse (162). He used the term "subml,
cropore" in the same sense that others, including Iler, use "micropore," He Summarized the use of other equations that have been developed for smaller pores.
Micropores can be detected by examining r-plots of adsorption isotherms, as
clearly summarized by Broekhoff and Linsen (i63). If the linear plot of Vo versus t
deviates downward toward the r-axis, the presence of micropores is' indicated. Plots
similar to those reported by Mikhail (164) are shown in Figure 5.12 for two silica gels
of similar specific surface areas and thus lines of nearly the same slope. Gel A is
microporous and dense, and the I-plot begins to deviate downward toward the r-axis
at about p/Po - 0.1. Gel B is a mesoporous, low density type in which the r-plot
deviates upward at around p/Po - 0.5 as wide pores begin to fill. In such gels with
uniform pores, it is easy to show that micropores are present. However, in many gels
most of the surface area is in mesopores with only a smallportion in micropores and
deviation from a linear r-plot is difficult to detect. A mixture of mesoporous and
microporous materials was examined by Mieville (165a), and by the r-plot method,
10% of microporous material could be detected in the mixture.
0.8
0.6
rC)
. !
'"u:E
0.4
1...1
>
"
"
0.2
0.6
I
0.9P/PO
0.8
I
I
0.0
0
t (A)
10 12 14
Figure 5.12. Typical r-plots of two silica powders of about the same specific surface area: A,
microporous; S, macroporous. V L , volume of
liquid N z adsorbed (em" g-I); I, thickness of
adsorbed N z film.
..
:\
'-....
.,.
.d Powders
~-_.
.iptlcn of
literature
Je
'.ain
499
:~
.~
'j
~
~~
.,.
~
.dsorption
icluded in
nation of
.dsorption
that the
i and are,
>f adsorp"volume" .
-'~-:
;'f
Figure 5.13. Typical a. plots: A, wide-pored gel

,with unrestricted monolayer-multilayer adsorption but no capillary adsorption; B, condensation
in mesopores where curve deviates from A; C,
micropore adsorption; micropore volume filled at
Vp a. - x/x., where x, - amount adsorbed at
p/p~ - 0.40 and x - amount adsorbed at other
pressures.
.i
1-
-::t
.:~
-~
..'"
'.
.J
_ \'!f,
'.!.
nicropore
"subrniHe sumes.
terms, as
"0 versus I
ted. Plots
silica gels
Gel A is
the r-axis
th, plot
gels with
nany gels
pores and
.rous and
: method,
.lica pow: area: A,

oluroe of
:~
of
:.~
',.
:;~
The a. plot of Sing (8) shows the presence of mesopores by deviation from
linearity at higher a. values from the a. axis. Micropores are evidenced by deviation
toward the a. axis at lower a. values. Extrapolation of the linear portion to the x
axis gives the micropore volume. (See Figure 5.13.) This was further examined in
connection with a wide variety of silicas, and deviations were explained by
Bhambhani in terms of micropores and mesopores (SO).
'
.
Data on adsorption of nitrogen in microporous silica compacts were obtained by
Ramsay and Avery (I 65b). They plotted their data using the DKR equation (165c):
P)'
'.::
. In -x . = - ' D ~RT In
.....
:' .-:
Xm
'
Po
'
Pyrogenic silica powder of 3-4 nm particle size was compressed to pore volumes of
0.22-0.11 em" g-l (silica packing densities of 67-80%) forming pores 22-12 A in
diameter. The plots gave decreasing slopes showing the change from volume filling
to monolayer coverage (where a monolayer fills the pores). In this study, the C value
of the BET plot started from 73 for the uncompacted powder and increased from 184
to more than 1000 as pores decreased from 22 to 12 A in size.
THE "MODELLESS PORE" (MP) METHOD. Brunauer, Mikhail, and Bodor (166)
developed a method of characterizing pore size distribution even in part of the
micropore (MP) range.
By the Cranston-Inkley method, involving the r-curve and the Kelvin equation,
pore structure curves can be calculated for pores with radius from 10 to ISO A.
However, the results depend on the assumption of cylindrical pores. Since the pores
are not cylindrical, the calculated pore size distribution does not represent the real
situation, especially in small pores.
In the "modelless method," the term "hydraulic radius," 'h~ is introduced where
Jll:~
.. -----
i/i
;: ! ' ~
d.~ I ~
~. t i
...
500
_~ j -,;
for which V is the volume of the pore system and S is the surface of th~ pore wall. It
applies to pores of any shape. The values of V and S are calculated from adsorption
or desorption isotherms. When desorption occurs and a group of pores empty, a
multilayer of nitrogen molecules remains on the walls at pressure p. The empty pore
space is called the "core." It is the volume desorbed as pressure is reduced from Po
to p.
The method differs from that of Cranston and Inkley also in that instead of the
Kelvin equation. the equation of Kiselev is used:
".,
"1
. :':""
',1
.;
'.lq,-
. ,"'1
;1~
"
JI
,~
.1
y.
!. 'I ,
.- : i
!
'
;
. ,!i
,I
:!
"y
'j
tis
eo
~IJ.
da
,j
.
i
~.
';" :I
,:
.f
"
;;
;' r -~ ;
where v is the surface tension, tis is the surface that disappears as a pore is filled, ~IJ.
is the change in chemical potential. and da is the number of liquid molecules taken
up by the pore. (The Kelvin equation is a special case of the above equation applica,
ble to cylindrical pores.) It turns out that -AIJ. - -RTln(Plpo).
Integrating gives '
.. :,!]
,;
:
s .. _I
';"
"Y
,:
I.
I:'
I'
I',.
I .~ .
I!:. :;:ii
I,.; ,,:
,,!
, . ~
.
"
Ii
I
,. ~
. !
-RTln
s.Po da
where ala is the number of molecules adsorbed at the beginning of the hysteresis loop
and a, is the number adsorbed at saturation.
This equation is integrated graphically in steps:
1. Lower plpo from 1.0 to 0.95 bydesorbing a l moles.

2. Volume of cores created = {all (molar volume) of adsorbate .. 34.6a l em' for
nitrogen.
,"
3. SI .. surface area of cores-
"i:i
I
I :1
-I
"Y
;' !: '
i
a.
"
,,'
,.,',
fa.
0\
-RTln -p da
Po
This is integrated graphically.

4. rIa - Volume of new cores {step 2)/surface area of cores (step 3).
! '
:;
-.: 1
Then in the subsequent nth step where
all
moles are desorbed:
1. Lower plpo frolT1 p'.Ilpo to P,.-I/PO'

2. Volume of cores created - 34.00,. em'. However, of this volume desorbed, a
certain volume, VII~ comes from the pore walls of the previously formed cores.
This volume, VII~ is calculated using the r-curve to determine -At, the decrease in
thickness of the liquid film on total area of cores produced thus far multiplied by
that area. This correction is a key step.
3. Then all - VII' gives the volume of new cores produced.
:I Powders
:e wall. It
dsorotion
en ,a
1ptypore
i from PD
~
ad of the
filled, Ap.
les taken
I applica-
'esis loop
ern!
for
SOl
4. SII' the surface area of new cores is then determined by graphical Wttegration as
before.
This suffices to show the difference between this "corrected modelless" method and
. the Cranston-Inkley method. For detailed description and examples of calculations
reference must be made to the original paper.
Often the "modelless" method gives a smaller peak pore radius than obtained by
the Cranston and Inkley method. In an example with pore radii in the range 5-10 A,
the desorption isotherm gave a peak value of about 6 A by this method and 10 A by
the Cranston-Inkley method. Hanna et a1. (167) obtained remarkable agreement of
pore sizes using nitrogen or oxygen at two different temperatures on widely different
.silica gels. In some cases the silicas contained both micro- and mesopores.
PORE SIZE STANDARD. Use of the "rnodelless" method on Gasil (I), a mesoporous
silica consisting of spheres with an average 4.38 nm radius packed with a coordination number of 4, has been described by Havard and Wilson (168). This is one of the
SCI/IUPAC/NPL standards for surface area and can be used also as a standard for
pore size determinations and for calibrating the BET apparatus over the full
pressure range.
The MP method was demonstrated by Mikhail, Brunauer, and Bodor (164) to be
applicable to micropores and the "corrected modelless method" to large pores.
When applied to gel with both micro- and mesopores, the method gave a cumulative
area of pore surfaces agreeing with the BET value. This indicates that, in spite of
arguments to the contrary, the BET method can be depended on to give reliable surface areas even on microporous silicas.
Pore structure analysis of five silica gels by Hagymassey and Brunauer (169) is
typical of many similar evaluations of the method. In this paper, water vapor and
nitrogen were compared as adsorbents and results were reasonably in agreement,
with peak diameters -of 4.1 and 4.6 At respectively. However, for adsorbents that
have any hydrophobic surface, nitrogen should be used.
SUPERMICROPORES. This is a term suggested by Dubinin (170) for pores with
diameters from 1.3 to 30.0 nm. The different pore types are as follows
Name
Micropores
Supermicropores
Mesopores
orbed, a
ed cores.
crease in
ipli"ri by
Radius (A)
<6-7
6-7 to 15-16
> 15-16
The basis for this suggestion is that micropore analysis can be used for supermicropores and mesopores but not for the micropores, as defined.
The MP method has been criticized (171) and rebuttal given (47).
ULTRAMICROPORES OR SUBMICROPORES. These have been defined as those with
radius less than 3 A. It is the mechanism by which these are filled that has been a
...
-~
.. ---_.
::s*,.......
:~':s
Silica Gels and Powders,., . ~
502
.;,;
main point of discussion. Obviously, if the smallest known gas molecule (He) cannot
penetrate the pore, it does not exist, as far as the experiments can tell. The lower
limit at which pores can be detected simply depends on the size of the adsorbate
molecule used.
However, the main point is that when a molecule enters a pore that is less than
twice as wide as the molecular diameter, the van der Waals forces are very strong
and the heat of adsorption is higher than on a plane surface. Thus the situation differs from that where only multilayer and capillary absorption (pore filling) OCcur.
According to Dollimore and Heal (136), pores that appear to be 7-10 A in
diameter by the conventional calculations from the nitrogen adsorption isotherm are
actually only 4-5 A in diameter. Submicropores in silica gel prepared from sol particles only 10 A in diameter are so small that even krypton cannot enter. It is known
that monosilicic acid rapidly polymerizes to particles of about this size at low pH.
Dollimore and Heal (172) prepared such gel by freeze-drying a I % solution of monosilicic acid. Since the evaporating and freezing removed much water, the pH of the
system at the gel point was at 1-2. which is the point of slowest particle growth. The
silica might be called "porous" because the "pores" were penetrated by helium
(only). Helium also penetrates fused silica! In the normal sense such silica is not
porous.
"
"
.r .
;:
:.i
t ;.
,, '
"
THE ISOSTERIC HEAT OF ADSORPTION. The value of the heat of adsorption is

abnormally high in micropores. Sing and Ramakrishna (173) found that by careful
choice of adsorbates and application of the a, method of analysis, it is possible to
distinguish between capillary adsorption and adsorption on high-energy sites. They
showed that from p/Po 0.01 to 0.2 the isosteric heat of adsorption of nitrogen on
silica free of mesopores remains essentially constant at 2.0 kcal mole:". On
mesoporous gel it drops from 2.3 to 2.0 .and on microporous gel from 2.7 to 2.0. The
isosteric heat q" is calculated from the adsorption isotherm by the
Clausius-Clapeyron equation,
Microporosity can be simply characterized by plotting q, versus p/Po from the
nitrogen adsorption isotherm.
Calorimetric studies of microporosity were made by Cancela et al., who measured
the heat liberated during the adsorption of benzene on silica. They verified that the
energy of adscrptlon is highest in micropores and measured the area still open to
adsorption of nitrogen at various stages of adsorption of benzene (174).
Microporosity has been characterized by Dubinin (10) by the equation
o
a = W
v*
$
(
'." -
{!:;y. 2]
- exp BT2 log\jj
where a is the amount adsorbed, T is the absolute temperature, Wo is the' limiting

volume of the micro pores, v* is the molecular volume of the substance adsorbed,
and B is constant that is a characteristic of the size of the rnicropores, Where two
pore sizes are present, a is expressed as the sum of two similar expressions with different Woand B' variables.
)
\"
"~
..
..,
; and Powders
(He) cannot
I. The lower
le .. '-'lrbate
~-
..
S03
At constant temperature the equation reduces to

log a- C - D
: is less than
: very strong
iituation difg) occur.
: 7-10 A in
isotherm are
im sol partiIt is known
: at low pH..
on of monoie pH of the
growth. The
J by helium
silica is not
dsorption is
It by careful
i possible to
, s;
They
nit, ,,~en on
mole-I. On
1 to 2.0. The
m by the
Po from the
measured
led that the
nill open to
10
the limiting
e adsorbed,
Where two
lOS ,:t.h dif-
~Og
:J'
where C and D can be calculated from the adsorption isotherm and converted to
values of Wo and B. Dubinin used the method to characterize silica gel with
micropores in the diameter range of 20-40 A. It was still in the trial stage (7).
DIFFERENT SIZED ADSORBATES. These can be used with the r-plot to reveal the distribution of micropore sizes. Mikhail and Shebl (175) used water. methanol, propanol. benzene, hexane. and carbon tetrachloride. Marked differences were observed
relating to pore size as well as degree of surface hydroxylation. Most of these
molecules are not suited to measuring the areas of silicas containing fine pores (176).
Bartell and Bower (177) carried out earlier studies with these vapors at 25, 40. and
45C. Using the free surface energy method of Fu and Bartell (178). the areas
determined with the different vapors were generally consistent and in agreement with
the values by nitrogen adsorption.
Water can be used to measure the area' of materials containing micropores into
which the larger nitrogen molecules cannot penetrate. The MP. or "corrected
modelless" method of analysis was used in this case for data obtained on hydrated
calcium silicate by Bodor, Skalny, and Brunauer (179).
TOTAL ADSORPTION CAPACITY FOR MOLECULES OF DIFFERENT SIZES. At relative
pressures near saturation this is another way to measure micropore characteristics
(180). Differences in volumes adsorbed indicate the volume and size of pores that
'cannot be penetrated bY' a given larger molecule of adsorbate in comparison with
"complete" pore penetration which can be defined as the volume penetrated by the
smallest molecule used, such as water.
When micropores are so small as to exclude methanol or benzene molecules, they
can still absorb water. This is no doubt the explanation of this type of behavior by a
silica gel prepared from silicic acid and dehydrated at low temperature as described
by Vysotskii and Polyakov (181).
A novel "preadsorption" approach was developed by Gregg and Langford (182)
for determining micropores in the presence of mesopores in carbon. They first
adsorbed nonane which penetrated micropores at 77K. then pumped it off at
ambient temperature. The micropores remain filled. Then the BET area was
determined by nitrogen as usual and found to agree with the geometric area from
electron micrographs. This "preadsorption" method of determining micropores will,
no doubt, be applied to silica but some more highly polar adsorbate such as decanol
may have to be used to block the micropores.
Low ANGLE X-RAY SCATTERING. Ritter and Erich (183) lpplied the method and
compared .results with those from adsorption studies. The method was compared
with the results of mercury porosimetry by Longman et al. (184). Earlier evaluations
I
I
or
~-_.
S04
of this method were described by Porai-Koshits et a1. (185), PoroP (186a), and
Imelik, Teichner, and Carteret (186b).
'
MERCURY PENETRATION METHOD. Mercury does not wet the surface of silica and higher pressure is required to force the liquid into a small pore. Washburn (187) :
developed the equation
.':
p ..
20' cos 8
where p .. equilibrium pressure, (J == surface tension of mercu.ry (480 dyne ern -I),
8 == contact angle between mercury and the wall (140), and T p IS pore radius. From
this, prp .. 70,000 when p is expressed in atmospheres and T p in angstroms. Pores of
100 A radius are penetrated by mercury above 700 atms. Very high pressures are
therefore needed to penetrate micropores.
.: ~
One problem is that if the silica gel is not very strong, the structure collapses by
the external pressure of mercury before pores are penetrated. It is for this reason
that the nitrogen adsorption isotherm method is preferred for research purposes.
Nevertheless, for strong bodies like industrial catalyst gels, the mercury penetration
method is far more rapid not only in execution, but also in converting results to pore
size distribution curves.
.
Commercial mercury porosirneters are available and the development of the technique has been described (188, 189). DeWit -and Scholten (190) have compared
results versus the nitrogen adsorption methods. They conclude that the mercury
penetration method is open to doubt for pores smaller than 10 nm diameter (SO A
radius). In the case of compressed "Aerosil" powder the pore radius by the mercury
method peaked at around 70 A, whereas by nitrogen adsorption the peaks were at 75
and 90 At calculated by different methods. Discrepancy may be due to the curved
meniscus of mercury.with a radius of 40 A, having a surface tension 50% lower than
for a flat surface. According' to Zweitering (191) agreement between the methods is
excellent for larger pores around 30 nm diameter. A detailed description of the
operation of a commercial mercury porosimeter (or penetrometer) and recommended corrections and method of calculation of pore size have been given by Frevel
and Kressley (192). These authors also presented theoretical porisimetry curves for
various packings of uniform spheres.
Miscellaneous Effects in Micropores

THE DIELECfRIC ISOTHERM (25C I Mc sec:"). The isotherms observed as benzene was adsorbed on silica showed a curved region at low pJpo values where adsorption occurred in micropores, then a linear relation at higher pressures (193).
t
GEL PERMEATION CHROMATOGRAPHY. There is a rather cumbersome method of

measuring pore size by using the silica as the column packing and determining the" .
penetration by molecules or polymers of different sizes (184) as long as absorption
effects do not interfere.
d Powders
36a), and
,.
-..
silk.. and
urn (187)
ie em-I),
us. From
Pores of
sures are
lapses by
is reason
purposes.
50S
ION EXCLUSION. The pores in silica gels immersed in electrolyte solutions tend to
exclude the ions. This has been used to compare the sizes of ions using a fixed silica
gel of known pore diameter. Maatman et al. have published extensively; only typical
papers are cited (194). Presumably, the pore size of a silica unknown might be
determined by using ions of known size. (See also negative adsorption)
THE MOSSBAUER EFFECT. The spectra of ions in small pores can be used to note
differences in pore size. Goldanskii et al. (195) reported that the temperature
dependence of the spectra varied markedly with pore size because the spectra-giving
S 1+ ions were restricted in their vibrations in small pores.
"
Nature of Silica Surface

The chemistry of the silica surface is dealt with in Chapter 6. However, a full
characterization of silica gels and powders requires methods for determining at least
the physical properties of the surfaces in the pores.
netration
:s to pore
TYPES OF SURFACES.
the techom pared

m ry
er lJ~ A
mercury
ere at 75
e curved
wer than
ethods is
n of the
recomly Frevel
irves for
1. A fully hydroxylated surface in which the surface structure terminates in silanol

(SiOH) groups. This is readily wettable by water and water-soluble organic
molecules. All silicas dried from water at less than 150C are of this type.
2. A siloxane surface which consists mainly of oxygen atoms, each bonded to
adjacent silicon atoms. Usually a low fraction' of isolated or paired SiOH groups
is also present. Pyrogenic silicas condensed from the vapor state are of this type.
Also, hydroxylated silicas which have been dehydrated at around lOOOC develop
a siloxane surface by removal of water from adjacent silanol groups.
3. An organic surface formed by chemical or physical attachment of organic
molecules or radicals. The nature of the resulting surface may be one of the
following:
(a) Hydrophobic and highly organophilic behavior when the outwardly disposed
. group'are hydrocarbon.
These can be categorized:
(b) Hydrophilic and oleophobic when the attached organic groups contain many
outwardly disposed C-OH or other highly polar atoms..
(c) Both hydrophobic and oleo phobic when the surface groups are fluorocarbon.
as ben. adsorp-
ethod of
nins the
SOl.
This is a rapidly expanding field of investigation in connection with the development of packings for chromatographic columns. At this point only a 'few of the
characterization techniques developed in the past can be mentioned.
The hydroxylated surface can be evaluated in several ways,,as discussed at some
length by Barby (196).
HEAT OF ADSORPTION. The nitrogen adsorption isotherm varies with the degree of
hydroxylation of the silica surface, as shown by changes in the value of C in the BET
II
.,.
~---
S06 .
equation. This can be used as an approximate measure of the relative proportions of

siloxane and silanol groups on a partly hydrated surface. The data of Lowen and
Broge (33) suggested that
.
C ... 30 + 7.4h
where h is the number of silanol groups per square nanometer of surface.
The value of C also dropped to about 22 when the surface was covered with 1_
butoxy groups by esterification of some of the underlying silanol groups. The
remaining silanol groups were covered by the larger butyl groups and were not
exposed to the nitrogen. The C value is similarly affected when the silanol surface is
covered with trimethylsiJoxy groups by reaction with trimethylchlorosilane.
ADSORPTION OF METHYL RED DYE. Measurement of the adsorption of certain
dyes from benzene gives an indication of the degree of hydroxylation of the silica
surface, provided the structure is sufficiently porous as t6 be fully accessible to the
dye molecules. This is the case with powders and gels with relatively large pores
but not with dense silica gels. The method has been described by Lowen and Brege
O~
INFRARED ABSORPTION. This is the most generally applicable and widely studied
procedure for examining surface silanols. The method is enhanced when combined
with hydrogen-deuterium exchange in H 20-D:O. This is more fully discussed in
Chapter 6 and also has been summarized by Barby (196). The method provides
information about the .nature and association of the hydroxyl groups. Also, the
nature of binding of organic molecules to the surface -can often be determined.
However, only semiquantitative data can be obtained in most cases.
1
1
I
CHEMICAL ANALYSIS: After the removal of volatile or soluble compounds,

chemical analysis does not necessarily prove that the residual organic content is uniformly bound as a monomolecular layer on the surface. However, absence of
exposed silanol surface is indicative of surface coverage. Measurement of the
adsorption. isotherms before and after removing the organic matter under conditions
that do not change the silica structure provides useful data. If a known percentage of
bound organic matter was present as a layer of molecular thickness, the specific surface areas along with the volume and diameter of pores of the residual silica permits
calculation of the thickness of the layer.
Organic matter can usually be removed by soaking in 70% HNOa and heating
slowly to 400C in air to complete the oxidation. Most silicas are not physically
changed by this treatment.
.
Aggregate Strength-Interparticle Bonding

The development of bonds between the individual particles in silica aggregates and
gels has been described in Chapter 3 (See Figure 3.19). The formation of inter-
.,.
~-_.
507
Figure 5.14. Formation of interparticle "necks." Top,

solution and redeposition process rearrangement of silica;
bottom, deposition process of additional silica. Dashed
lines: original silica spheres before reinforcement.
particle "necks" can occur by two processes as shown in Figures 5.14 and 5.15. The
first is by the solution and redeposition process described in Chapter 3. The second
is by the deposition of additional silica from supersaturated solution, a deliberate
process which requires careful control and has been used only in a few instances. In
either case, the particles are bonded together to a degree that has been defined. as the
"coalescence factor." The ways in which this can be accomplished will be described
later; here, methods of measuring the degree of coalescence will be reviewed.
...... ;
..
Electron Micrographs, .
nnpounds,
tent is uniabsence of
ent of the
These can show the actual appearance of the interparticle bonding, especially if the
particle diameter is greater than 15-20 nm. This is the case with certain powders but
generally not so with conventional gels.
conditions
centage of
oeciflc surca permits
nd heating
physically
Figure 5.1S. Determining the coalescence factor by partial

dissolution: T p and rp' - different degrees of reinforcement;
r - radius of neck between particles; r p - r" - radius of
dispersed particles.
egates and
1
of inter-
":.,.,-_.
Silica Gels and Powders .~.
508
-~
If the particle diameter, d, can be measured, the theoretical surface area, Set for>3;
spheres can be calculated from the relation
;:,;._.
11-
..~ ..~
S,4 - 2750
where S, is in square meters per gram and d is in nanometers. When the particles are "~':.l".
strongly coalesced, surface area is lost at the areas of contact so that the area'
measured by nitrogen adsorption, SN' is less than St:. The ratio Sc:SN can serve as an
arbitrary measure of the degree of coalescence if the coordination number (packing
arrangement) of the structure remains the same. The latter is established when the
aggregates are formed.
Partial Dissolution Method
This is applicable to low density silica powders with specific surface areas' in the
range 60-400 m2 g-I, Alexander, Iler, and Wolter (19~) disclosed details or' a
procedure by which 1 gram of silica particles is suspended in 100 ml of water at
sooe and the pH maintained at 11.0-11.5 by continuous addition of 1 N NaOH
solution. Turbidity of the suspension is measured frequently by the transmission of
400 nm wavelength light through 1 em thickness of sample. At the same time the
amount of dissolved monomeric silica is measured on 0.1 ml samples by the
silica-molybdate method. Total silica in the suspension is measured by adding
NaOH to make it 0.5 N and heating 2 hr in an alkali resistant (stainless steel) ,
container' and analyzing by the same method.
When percentage of silica dissolved is plotted versus percent light transmission, an
inflection point is observed. This indicates the average amount of silica that must be
dissolved away to permit .the ultimate particles in the aggregates to become dispersed, As can be seen in Figure 5.15, two conjoined spheres of radius r p will not fall
apart as silica is uniformly dissolved from the surface until the thickness of the layer
dissolved away is equal to the radius across the neck, r. The coalescence factor, C,
in this case can conventiently be defined as the fraction of the total silica that has
dissolved when the rate of dispersion of particles from the aggregate reaches a
maximum.
For example, when C ... 0.5, then r" was 20% of the particle radius; when C ... 0.75, r
was 37%.
The method was applied to a precipitate of silica particles about 12 nm in radius.
This precipitate had a coalescence of C = 0.47, from which r ,,/!,p = 0.19 and r tl = 2.3
nm. Additional silica was deposited on the original suspension to the extent of 2 parts
of added silica to lof original silica, which should increase the particle radius by 3 113
ld Powders
ea, Se, for
rticles are
the area
erve as an
. (packing
when the
las in the
tails of a
. water at
TV NaOH
aission of
time the
s by the
y adding
ess steel)
issiou, an
must be
orne disII not fall
the layer
actor, C,
that has
eaches a
t
509
or to 17.5 nm (16.5 calculated from surface area). A sample then had a measure coalescence of C = 0.69 so that rll/rp - 0.32 and r = 5.3 nrn, Deposition of silica was
continued until 4 parts had been deposited per part of original silica and the particle
radius and coalescence again determined. The data are summarized as follows:
Neck Radius
Particle Radius
.
rp
12
16.5
20.5
~rp
r ll
sr;
Arn/Arp
4.5
7.5
2.3
5.3
7.8
3.0
5.5
0.67
0.73
It is seen that the incr.ease in particle radius is of the same magnitude as the increase
in neck radius. However, the latter should have increased more, rather than less,
rapidly than particle radius. Possibly deposition of silica is more rapid on the open
surface of the particle than in the crevice at the neck.
Another typical application was to follow the sinteringof relatively large colloidal
silica spheres with a radius of 50 nm when heated for I hr in air at elevated temperature.
Temperature, Coalescence,
r(OC)
200
300
400
600
. 800 .
1000
r n (nm)
0.06
0.11
0.17
0.28
0.43
'0.53
2
3.8
6.0
10.4
17.1
22.2
Constant
0.025(T - 150)/rn
0.65
1.00
~1.05
1.09
0.95
0.96
As noted above, for some unexplained reason, the radius of the neck increases in
proportion to T - I SO.
M echanlcalStrength ofthe Aggregate .
: 0.75, r
:1 radius.
rll
= 2.3
f2 parts
.s ~
"'1/3
Another way of comparing the coalescence of particles in gel structures having the
same particle size and packing arrangement is by measuring the mechanical
strength. Meissner, Michaels, and Kaiser (130) have developed equations for the
strength of aggregates of spherical particles with a given coordination number, n,
and a given binding force between spheres. Using a general equation relating coordination number to the volume fraction of solid in the body, the following equation
was developed:
,
Crushing strength
PD
-2
K q, exp (7.2r/
"".
----Silica Gels and Powders
510
i
i
"
'j
JI
,i
!
,l
I
, ,J
,
where P - crushing load

D - diameter of agglomerate
q, - fraction of total volume occupied by spheres
K - a constant which is a function of the diameter of the spherical particles
and the bond strength between two particles. It emphasizes the very
rapid decrease in strength with more open packing. all other factors
. remainingccnstant.
.!
Porosity
(cm
of gel)
3/cm-3
0.260
0.30
0.5
0.6
;.
"
o
b
Strength Relative
100
71
12
Regular close packing.

Open packing.
The equation adequately described the variation in strength of agglomerates of finely

divided zinc oxides with volume porosities of 0.5-0.7.
SILICA GELS'
This section is restricted to silica gels and does not include aluminosilicate gels and
catalysts. Some aspects of aluminosilicate surfaces are discussed in Chapter 6.
The theory of the formation and structure of silica gels formed by the polymerization of silicic acids has been discussed in Chapter 3 and similar aspects of gels made
from sols of discrete colloidal particles dealt with in Chapter 4. Characterization or
gels has been described in the foregoing section. Described here are methods of making gels and the factors and process variables that affect and control gel properties
and uses. .
The background and history of silica gels can be obtained from a number of surveys and reviews published over the last half-century, starting with Wolf and Praetorius in 1928 (198). Vail summarized the history. manufacture. and use of commercial gels in 1952 (199). The particle theory of gel structure and behavior was
described by lIer in 1955 (2). A review by Neimark covered mainly Russian work to
1953 (200). At about the same time a survey by Romos and Vega (201) was
published. .,
Two decades later there appeared a new series of reviews. Kiselev discussed the
structure and behavior of silica gels during drying (202). In Japan, Kondo (203)
reviewed the chemical and physical properties of silica gel iIi 1972. A similar review
by Neimark and Sheinfain (204) appeared in Russia in 1973. Also. a most useful
survey is that of Barby (8).
Since 1970, research activity and publication have been stimulated by the growing
Silica Gels
.d Powders
need for specially structured gels for use in chromatographic columns so Jmportant
for chemical analysis and process controls.
The mechanism of formation of silica gel from silica particles has been described
in Chapter 4. Gels from colloidal silica along with those from sodium silicate and
other sources are included in the further discussion of factors controlling gel characteristics. "'
""-
I particles .
: the very
cr" factors
--.,$
"0&
"
,
,
s of finely
: gels and
. 6.
Iymeriza~els made
ization of
s of makiroperties
er of surd Praetoof comivior was

1 work to
201) was
ussed the
ido (203)
ar review
ist : 'ful
: growing
SI1
.. '.
~
Sources of Silica Gel

From Soluble Silicates and Minerals
Sodium silicate has been and probably always will be the cheapest source of reIa'tively pure silicic acid from which silica gel can be made. However, certain natural
colloidal aluminosilicates including some clays can be attacked by acid leaving a
residue of a porous, hydrated silica which in some instances can be formed into a gel
(205). Such a source of silica may become m~re important if clays become a source
of aluminum. Also, certain orthosilicate minerals easily attacked by acid may prove
advantageous in making silica gel. For example. Flanigen and Grose (206) found
that highly porous gels with area of 600-900 mt g-I and very fine pores can be made
from a fibrous calcium silicate. wollastonite. by dissolving the mineral in acid and
gelling in acid solution. ,
'_, _
Murata and Schlecht (207) have summarized the action of acids on the various
silicate minerals as follows. Those silicates that contain silicate radicals of low
molecular weight. or have 'continuous silicon-oxygen frameworks incorporating a
sufficient number of iron .or aluminum' atoms (which are removed by acids). yield
gelatinous silicas. On the-'other hand. minerals having siloxane structures of large
dimensions. such as Si9~' chains. Si4 0 u double chains. and SitO. sheets. are not
gelatinized. but yield insoluble silica pseudomorphs. Glaucosil, silica separated from
glauconite which has a micalike sheet structure. has a specific surface of 82 mt g-I.
according to Brunauer (208). If the structures of aluminosilicates contain more than
two aluminum atoms for every three silicon atoms, then acid attacks the network at
enough points to break it down into "islands" of siloxane fragments which yield
gelatinous silica. according to Murata and Schlecht.
- Patrick and McGavack (209) were instrumental in developing silica gels of
practical importance as adsorberits. Strong coherent gels which could be heated to
red heat without disintegration or loss of adsorptive power were produced by mixing
rather strong solutions of 3.3 ratio sodium silicate with excess hydrochloric acid. letting the gel form. then washing and drying it slowly. In the years 1920 to 1950. a great
many procedures for acidifying and gellingsolutions of soluble silicates, increasing the
mechanical strength, reducing shrinkage. and increasing porosity had been devised. as
summarized by Vail (199). Slow drying is essential in order to keep the gel lumps from
shattering because of greater shrinkage of the exterior portions. I-ligh concentration of
silica (up to IS g per 100 ml) in the gelling solution gives gels which are dense but
mechanically strong. The relation between the conditions of preparation of silica gel
--_ ..
...
'
"
.
,
~'
1
I
;:
f: .::
.s"
l:
,~
!,. .
i
iI;
I'
I,,.
::
.
.i: ~
,:
, i, ~
512
from acid and silicate and the final properties of the product has beenJ'eviewed by .
Wolf and Beyer (210). The main point is that washing with hot water increases the size
of the ultimate particles and decreases the surface area. Exposure to pH above 7 has a
similar effect. If water in the gel is replaced with an organic liquid having, a low'er SUr.
face tension, the gel shrinks less during drying. leaving larger pores.
Acids used most commonly in commercial manufacture are H 2S04, HCI. and CO 2
in that order. To obtain the hardest and strongest gels, the gel is usually formed at
low pH and at ordinary or even lower temperature. This keeps the ultimate particles
very small, after which the pore structure and component particle size are'coarsened
and the gel further hardened by subsequent treatments.
To produce gel of maximum hardness, the silicate is diluted as little as possible
when mixed with the acid and, in this case, gels very quickly. For example, a silica
sol containing 13-17% SiO s was made by mixing streams of sodium silicate solution
and acid in proportions to reach pH 6~10.5. It was sprayed the instant of mixing and
the droplets gelled in less than a second while in suspension in air and fell into water
to age (211).
New recipes for particular types of gels are continually being devised. For
example, Winyall and Acker (215) obtain a wide-pored gel with an area of less than
320 m2 g-1 and a pore volume of I ern" g-1, by making a hydrogel from acid and silicate mixed to give a pH of 9.8-10.4. It is aged up to 50 min, then acidified to pH
2-3 for up to 5 hr, then aged up to 4 hr at pH 8 and washed and dried. It is probable
that high pH permits growth and coalescence of the ultimate particles giving the
desired structure, after which the acid treatment is needed to remove the occluded
sodium ions. These probably leave micropores which are closed by aging at pH 8.
Many similar, apparently arbitrary, and complex procedures can be explained on the
basis of the presently known chemistry of the system.
, Another approach is, to use a compound which releases acid slowly. The compound NasSiF. has long been used in certain formulations but water-dispersible
aldehydes, amides, and esters also have their special uses. Concentrated glyoxal
(30%) solution (6.5 parts) mixed with a concentrated (36 Be) sodium silicate solution (100 parts) reacted and set in a day to an extremely hard gel which was washed
with 4 N H 2S04 and water and dried. The delayed neutralizing action permitted the
neutralizer to be mixed homogeneously with the silicate so that the silica
polymerized at a very high concentration and thus produced a very strong gel (212).
Similarly, when a very dense silica gel was to be formed in pores as in concrete for
waterproofing, esters such as glycerol or glycol acetates were mixed into the
concentrated silicate solution before application to cause it to gel in place in 2 hr
(213). A combination of H 202 and paraformaldehyde added to a solution of sodium
silicate causes it to foam and solidify to a lightweight insulating gel structure (214).
RATE OF GEL FORMATION. The time required to gel the type of silicic acid sol
made from acid and silicate' has been studied for many years. The gel time is
assumed to be the inverse of the rate of polymerization or gel formation. In a series
of papers by Hurd and associates practically all the factors influencing the gel time
of silicic acid sols made from acid and 3.3 Si0 2:Na20 silicate were reported (216a).
Reference should also be made to the studies of Sen and Ghosh (216b), who
.nd Powders
eviewed by
ises the size
"as a
1low .... Sur-
>0\
.Land CO 2
formed a t l
te particles - it
,-:.;
: coarsened'i
"-
as possible
ile, a silica
te solution
nixing and
into water
:.
vised. For
Ifless than
id and silified to pH
s probable
giving the
e occluded
~ Go
{ 8.
ned (111 the
513
Silica Gels
'~'
developed equations relating gel time to pH, concentration temperature'using different acids. The gel time reaches a maximum at around pH 2, as has been discussed
in Chapter 3. In the pH range of around 3-5, the gel time varies directly with
concentration of H+ ion (inversely to OH-). In. the pH region 4-9 there is a
minimum gel time around neutrality as shown in Figure 5.16, based mainly on data
by Merrill and Spencer (217). It will be noted that owing to the concentration of
sodium ions, which is proportional to silica concentration, the most rapid gelling
occurs around pH 7-8, whereas in the absence of salts, colloidal silica gels most
rapidly at pH 5-6 (see Chapter 4). Different acids bring about most rapid gelling at
slightly different pH values.
Heald, Coates, and Edwards (218) found that the further addition of salts
accelerate gelling at pH 7-8, those of calcium being very effective.
At a fixed silica concentration, silicic acid sols made from sodium silicates of
higher Si02 : Na 20 ratios gelled more slowly, probably because of the lower sodium
ion concentration.
The effects of monovalent electrolytes on gel time have been reviewed by
Mookerjee and Niyogi (219), who reported results on silicic acid sols at pH 2.7
where the salt effect is less marked, whereas most previous work was done at higher
pH. The effects of cations to accelerate gelling increased in the order Li", Na", and
K+ and of anions in the order NO~-, CI-, Br-, and 1-. For some unexplained reason
I - had about fivefold the effect of NO~ -. The effects were directly proportional to
1000
500
The comdispersible
ed glyoxal
.cate soluas washed

mitted the
the silica
gel (212).
ncrete for
into the
ce in 2 hr
of sodium
~e (214).
:; acid sol
:1 time is
n a series
e g~' time
ed '" 'a),
6b), who
f3
!::
Z
~
100
50
::E
..I
10
7
pH
Figure 5.16. Gel time or sols made from 3.25 SiO J: NaJO and H~04 at 25C varying with
pH. Silica concentrations: curve I, I %; curve 2, 1.5%; curve 3, 2.5%; curve 4, 3.5%, curve 5.
6.0%. [Data for curves 1-4 from Merrill and Spencer (217); for curve 5, from Her
(unpublished).}
':.---
514
salt concentration and there was no evidence of a "critical
coagulation~concentra_
tion."
Early stages of polymerization and gel formation from 3.3 SiO,: Na,O at pH 1.7
were studied by Her (220), who showed that the polymerization rate and gel time
were inversely proportional to the square of the silica concentration. Vysotskii and
Strazhesko (221) made careful measurements of gel times for this type of silicic sol
at 1-2% SiO, concentrations over the pH range 0-4 and likewise found a sharp
maximum gel time at pH 1.7 that was also exactly the inverse of the square of the
silica concentration. It is sometimes convenient to be able to make a sol that will gel
in a reproducible time. The gel time is least sensitive to pH changes at the pH were
the gel time is at a minimum (see below). This pH changes with silica concentration.
The following data are for sols made at 25C by adding one volume of 3.25 ratio
sodium silicate to one volume of intensively stirred dilute H,S04 of such strength
that the pH rises toz. Thus for a 2% Si0 2 sol the silicate solution must contain 4%
Si0 2 Then the pH is raised to the final value by adding I N NaOH very carefully
with intense agitation:
I.i
%SiO z
pH
0.5
1.0
1.5
2.0
3.0
4.0
6.9
II
I
I:
7.3
7.7
8.05
8.35
8.7
Gel Time (mins.)

Minimum
260
53
1.0.5
3.3
0.5
0.15
The gel point does not indicate completion of formation of the gel structure. It is
only the point where the growing solid microgel regions that are suspended in the sol
approach 50% by volume so that viscosity rises sharply (see discussion of gel
mechanism in Chapter 3). The remaining sol regions still continue to solidify and
this takes at least as long again as the gel time. During this period, the gel begins to
shrink as the network tends to contract and exude water. This syneresis goes on for a
period several times as long as the gel time. Vysotskii and Strazhesko (221) showed
that the same process of particle aggregation goes on during syneresis as during gelling, the proof being that the pH affects the rate of syneresis just as it does the rate of
gelling and is at a minimum at pH 1.7.
From Colloidal Silica

Gel formation from colloidal silica has been discussed in Chapter 4. Colloidal silica
now available as concentrated sols of various particle sizes will no doubt play an
~
increasingly important role in gel manufacture.
Reaction of soluble silicate with acid has long been the common method of manufacturing gels. However, there are certain limitations which are recognized. For
example, it is not possible to grow the silica particles to a larger size before gelling.
\.
concentrs,
at . 1.7
d gel'time
sotskli and
f silicic sol
:d a sharp
rare of the
rat will gel
e pH'were
centration,
3.25 ratio
h strength
ontain 4%
f carefully
SIS
silica Gels
nd Powders
;:"..
-.~.
.~
.. ~
~&
. .,.
~~
.r!
..p".~
;j'
,~,
-.%
+.
if
."'.j
.-
~.~
,~
.....
~~.
.',
~~~
"
'~
~7l
.f
~
~
'"
..
"
.'
~,,~
<
..
At low pH were the silicic acid is stable long enough to cast the gel ints a desired
form, the ultimate particles remain less than 2-3 nm in diameter. At pH 4-10,
ex'cept at low silica concentrations, the sodium salt causes very rapid precipitation or
gelling so that growth of discrete particles before gelling is impossible. The particle
diameter in the final gel is 3-7 nm (222). Thus when sodium silicate is used at make
gel, any further decrease in surface area or increase in pore diameter must be done
by subsequent treatment of the gel such. as heating in water or at high temperature in
steam. Washing out the salt is a slow process and results in a large volume of waste
water. To avoid the washing process, sodium silicate solution can first be passed
through a hydrogen ion exchanger and if carried out at lo~ temperature can furnish
a 12% silicic acid sol (223). Unless this is converted to larger colloidal particles, this
gives the same fine-particle, fine-pored gel as the silicate acid process.
As shown in Chapter 4, hot ion exchange or electrodialysis of a more concentrated
solution of. sodium silicate produces colloidal silica of a predetermined larger
particle size at a concentration of at least 12-15% Si0 2, from which the minor
amount of residual sodium can be removed by further ion exchange. By varying the
concentration and size of silica particles in the sol to be gelled, it is possible to make
a gel with predetermined pore size, pore volume, and specific surface area.
One difference between gels made from stabilized colloidal silica and gels from
silicic acid is that the commercial colloids are made in hot, slightly alkaline conditions that remove water and micropores from the interior of the particles. On the
other hand, the particles made by polymerization of silicic acid, usually below pH 7
and at less than 80C, and often in the presence of sodium salts, may be
microporous. This point has been discussed by Vysotskii et a1. (221), who suggest
that the pores may be accessible to water but not large molecules.
,
From Hydrolysis ofSilicon'Compounds

ture, It is
in the sol
on of gel
lidify and
begins to
s on for a
I) showed
Iring gellhe rate of
idaI silica
t play an
'1Uof
izeo. "or
'e gelling.
The preparation of silica gel from SiCI. of silicic esters is ordinarily too expensive
except where extremely pure silica is required. Very dense gels have been prepared,
according to Lenher (224), by hydrolyzing SiCI. and squeezing the washed gel under
a pressure of 272,700 kg in. -2; the water content of the resulting white powder was
12.3..,.12.9%, corresponding to 2 Si02 : H 20. The ultimate particles in this gel were
probably less than I millimicron in size and under this pressure must have been completely close-packed and coalesced. Schwarz and Richter (225) prepared gel by
hydrolyzing SiCI. at OC and dehydrating the gel with liquid ammonia to obtain
products corresponding to Si0 2 : H 20. More recently, Bartell and Donahue (226)
prepared silca gel by hydrolyzing SiCI. vapors in water, drying by heating the gel
gradually to 75C, and finally to 280C for 4 hr, and then washing and reheating to
280C four times. The gel had a specific surface area of 455 m 2 g-1 (corresponding
to ultimate particles 6 nm in diameter). The average capillary diameter was 8.2 nm.
Formation of silica gel has been observed in electron microscope studies by
Radczewski and Richter (227). Silica sols prepared by the ~hydrolysis of silicon
tetrachloride and purified by electrodialysis initially contained particles less than 10
nm in diameter. On standing at pH 6.8, spongelike aggregates were observed to be
formed from the individual particles. The polymeric silicas which were so obtained
"
: c-:
..
.
;'
"
.'"
I:
Ii
'
516
<,
were examined carefully by X-ray diffraction and also by electron diffe-action, but
there was no indication of crystallinity, the silica showing instead the broad
interference bands ~haracteristic of silica glass. It is probable that gels of the finest
possible microporestructure can be made most readily by hydrolyzing a monomeric
silicon compound such as SiCI. rapidly at low temperature and low pH (see section
below on submicroporous gels).
Silica gel with wide pores has been made by hydrolyzing ethyl silicate to a pol- "~
. yethoxysilane (PES) in alcohol using limited water and an acid catalyst, then adding "
hydrocarbon such as hexane, and finally adding ammonia with fast stirririg to effect
emulsion polymerization. Unger and Sharf (228) developed this _method for making
porous silica gel in the form of microbeads for use in chromatographic columns.
Pore diameters from 116 to 160 A can be obtained at a constant surface area of 420
m 2 g-I simply by using PES at progressive stages of polymerization where the
molecular weight is in the range 75-2000. The pore volumes can be varied from 0.5
to 2.0 cm' g-I. By adding hexane before gelling, pore volume can be increased to
more than 3.0 cm' g-I, but 'the additional pores are in the macropore range up to
1000 or even 3000 A in diameter. . The remarkable thing about this type of silica is that the pores do not collapse
upon drying as do gels made from sodium silicate and acid. It is conceivable that in
the series made with increasing molecular weights of PES, the lowest molecular
weight PES gives the widest pores because at constant silica concentration a
stronger gel structure is formed from smaller ultimate particles. It thus shrinks less
under the surface tension forces during drying. The specific surface areas of the gels
, are all alike; that is, the size of the ultimate particles forming the gel network
remains the same, only the packing density changes. If the wet gels had been washed
with alcohol and ether until anhydrous and converted to aerogels, the pore volumes
and diameters would have probably all been alike.
It is probable that pure silica gels of almost any known type can be made via
SiCI., (C 2HsO).Si, or other volatile, hydrolyzable silicon compounds. In research on
any phenomenon involving the surface or colloid chemistry of silica made from
other sources, comparative specimens should be made from one of the above pure
sources to ensure that some variable trace impurity like sodium or aluminum is not
affecting results.
I
I,
i
Factors Controlling Gel Characteristics

The final characteristics of a finished, dried gel are determined by the physical and
chemical conditions at every step or the process of preparation:
1. The size of the primary silica particles at the moment they aggregate into the gel
i
I.
!
I
~
network.
2. The concentration of the primary particles in solution and thus the compactness
of the gel network.
.
3. The pH, salt concentration, temperature, and time during which the gel is aged or
.nd Powders
silica Gels
action. but
the broad
r t ":nest
monvmeric
'see section
otherwise treated while in the wet state (this includes the possible step ~or replacing water with a water-miscible liquid like alcohol).
4. Mechanical pressure or shearing forces applied to the gel before or during drying.
5. Conditions of ternperature. pressure. pH and salt content, and surface tension of
the liquid medium as it is being evaporated from the pores of the gel.
6. Temperature. time. and type of atmosphere in which the gel is heated after being
dried.
.
eto a polhen adding

19 to effect
for making
c columns.
irea of 420
where the
d from 0.5
icreased to
ange up to
,~t
.~
~.
c_.~i
,'t
.ysical and
.1tO
the gel
tness
is aged or
The particulate theory of gel formation was described by lIer (2) in 1955. Kiselev
and Lygin (229) verified by electron microscope studies that as silicic acid
polymerized. particles up to 5-10 nm in size can be formed as a sol and this size
retained in the gel structure.
:~
-3i
....,
ot collapse
~
ible that in
Z
.~
molecular
.::
ntration a
]
hrinks less
""
of the gels. .,,'<::
,'i<
:1
york,.. .'
.en washed
re volumes'
: made via
esearch on
lade from
ibove pure
rum is not
517
Size ofPrimary Particles_pH Effect

When the diameter of colloidal particles in a sol is larger than about 5 nm as in
commercial colloidal silicas. which range in size from 5 to 60 nm, gels of corresponding surface areas from 550 to SO m' g-l can be prepared from them directly.
The pH has only minor effect on the resulting gel area. However. when gel is made
from silicic acid generated by acidifying sodium silicate or hydrolyzing a silicon
halide or ester. the initial particles are only about 1-2 nm in size because they are
usually formed atlow pH. The size to which they grow as the gel is formed, washed,
and dried increases with pH above about 6. Here pH is the single most important
factor in determining the final surface area of the gel.
'
, As discussed in Chapter 3~ polysilicic acids of low molecular weight are formed
first. These evidently can- pass through an 'ultrafilter, Sen and Ghosh (23)
demonstrated this point by determining when a cellophane ultrafilter would no
longer permit silica to pass through. At pH 2.3 with a freshly made 3% SiO, sol
from acid and silicate. they found that 94% of the silica passed through for 216 hr of
the total 264 hr required for gelling. that is. for 82% of the gel time. As soon as
aggregation began the filter was quickly plugged. An increase in turbidity indicates
the growth of aggregates in this acid system where the primary particles are too
small to scatter much light.
Starting with silicic acid, gelling at pH 2-6. higher pH results in the growth of
larger primary particles before the gel is formed. This results in a gel of lower
specific surface area after drying at 110C. Thus in a 1947 study of silica gels made
at initial SiO z concentration of 4% at various pH values. Plank and Drake (231)
observed the following surface areas:
pH
Specific Surface
Area (rn" g-l)
2.7
656
5.3
413
404
354
8.7
11.0
518
As the pH increased, the calculated particle diameters increased from 4.2\0 7.7 nm
while the pore diameters increased from 6.4 to 13.8 nm. It was also of interest tha;
when the silica was gelled in a more concentrated solution (higher packing density)
the density of the final dried gel was less, presumably because the stronger strueture~
collapsed less upon drying.
.
There have since been many similar observations. In such series of gels, not only
is the surface area at a maximum when the gel is prepared at low pH, but also, since
the surface is covered with SiOH groups. the "bound water" content is correspond;
ingly high. A typical study is reported by Cuha and Gupta (232). who made gels with
different densities by preparing them at different pH values. Previously, Sing and
Madeley (233) made gels at different pH values and reported surface areas and
water contents:
pH
Surface Area
Found (m' g-l)
H,O
(%)
Surface Area
Calc. (m' g-l)
3.7
4.0
4.63
5.76
592
578
505
335
6.5
5.0
4.2
3.2
785
60S
508
387
The water content is about proportional to the surface area. Assuming all the water
. is present as SiOH groups on the surface. calculation gives the above values for Sur.
face area assuming 5 OH groups per nm",
A few similar studies will be mentioned. Outoumaand Ukihashi (234) measured
particle size in sols from 3.,22 ratio sodium silicate gelling at. pH 3.25. 3.53, and 4.05.
The initial particle size by .light scattering was 10-20 A and these grew to 40-50 A.
then formed aggregates 'up to 1200 A in size as visible gelling began. Gartner and
Griessbach (235) made similar sols at pH 3-6 and showed that the average pore
radius of the gels ranged progressively from 10 to 70 A. with a similar decrease in
specific surface area. This again shows the larger size of primary particles with
higher pH.
.
Okkerse and De Boer (236) carried out a more detailed study which in retrospect
confirms that pH mainly affects the size to which the particles grow before they
form the gel. The concentration of silica is only a secondary factor because the
specific surface area and pore size of the gel are determined by the size of the
primary particles which reach about the same packing density. regardless of
concentration. after the gel shrinks in drying. According to their observations
(Figure 5.17) particle size increased rapidly from pH 4 to 8. as evidenced by the
marked drop in specific surface from 800 m' g-1 (3-4 nm diameter) to 200 m' g-1
(14 nm). When the particles are smaller than about 5 nrn, shrinkage forces in the
very small diameter pores during drying can com press the particles into random
close packing (60% by volume of SiO, or a porosity of 0.3 cm\ g-I).
At pH 5-6. with a slightly larger particle size such as 6 nrn, the pores are larger
and the compressive forces weaker so they cannot collapse the structure nearly as
.. -..--silica Gels
md Powders
!t07.7nm,
ntee-st that
ng '" ~ity),
r structures
(II
I
519
(2) - - - - - - - - - - . ,
: _I
mitt. m 0
(3) .
Yp
cm3 g- 1
0.7
10' sOO
0.6
Irr 600
:l~, not only

t also, since
:orrespond.;
de gels with
I, Sing and
: areas and
.,.'-'(.;
..
0.5
tOz 4OQ
0.4
10'
0.3
200
.~
..wtt_
-::::.,.
"~~.
5~
6
pH
'~
;..e.
8.10
. Figure 5.17. Effect of the pH at which

sodium silicate and acid are reacted to
producesilicic acid (5% Si0 2) : (1) gel time
(min); (2) specific surface (m" g-l); (3) pore
volume (em' g-l). [Based on data by
Okkerse and De Boer (236).]
~f
-::
~.~;
""
~
;;0.-.
,"",
~4
::t"
.',
~,.:
n the water
ues "or sur-
) measured
3, and 4.05.
040-50 A,
lartner and
'erage pore
decrease in
rticles with
".
-."'
completely. Thus a more open gel is obtained with a pore volume of 0.8 em! g-I,
corresponding to a silica sphere packing density of only 36% by volume.
At still higher pH and larger particle sizes the gel strength decreases because the
degree of coalescence is less and the gels are weaker so tha] the gel shrinks further
and the pore volume is lower.
It must be emphasized that the relations are observed only if the gels are washed
and dried with no further aging or heat treatment in the wet state after the gel has
been formed. . ;
,
Shein fain and Neimark (237) have reviewed this now generally accepted theory
that silica first forms small particles which then join together to form the gel network. Of special interest are th.eir extensive series of gels in which the surface areas
and pore volumes are varied independently. These were made with surface areas of
100-800 mi g-1 and anyone of these can be made with pore volumes from 0.45 to
about 1.7 m t g-l. In the case of 650 m t g-I, pore volumes of 0.35-2.37 em' g-1 can
be produced. To do thisrequires not only the proper conditions of gel formation but
washing at controlled pH and drying under specified conditions.
Wet Gel Strength

retrospect
iefore they
iecause the
size of the
~ardless of
bservations
ced by' the
200 m t g-1
'rces in the
to random
;a 'arger
e 1'. ,'ly as
The strength of gels made from colloidal silica as distinct from silicic acid has been
discussed in Chapter 4. We now consider the spontaneous strengthening of the interparticle bonds when the particles link together. However, this refers to the hydrogel
after it has reached the gel point and then aged at least an equal length of time, but
not subjected to any special heat-aging step. This strength of the wet gel may bear
little relation to the properties of the subsequently dried gel since many further
changes in structure, for example, shrinkage, may have occurred.
It is well known that sols of polysilicic acid in which the silica particles or polymer
units are only 20-30 A in diameter can form gels with silica concentrations as low as
0.5-1.0% by weight, yet conventional silica sols of cornmercexwith particles 50-300
A diameter, will not form gels at such low concentrations. One reason is that the
rate of gel formation is so extremely slow that such gels are seldom observed.
Silica Gels and Powders ..;
520
Another is that when such dilute sols form a gel. the structure is S'O weak and
tenuous that it tends to collapse to a voluminous precipitate.
.
Obviously. with smaller particles at a given silica concentration. there are many .
more particles per unit volume and a much finer network is formed. But, more
important. the total number of siloxane bonds holding the network together is mUch
greater. Consider. for example, a gel formed from particles of diameter d
nanometers at a concentration Cd grams of silica per liter: the volume concentration
in cubic centimeters of Si0 2 per liter, is Cd/2.2, where 2.2 is the specific gravity or
colloidal silica.
.
. Since the volume of a single particle is
t
1("
tJ3
10- 21 em'
the number, N, of particles per liter is
. C
. 0.87 X 1021 ~
tJ3
.'
.. i
..!
...
'
'.' ~
.:
.'.
i .
To estimate the number of siloxane bonds that can be developed between particles
of a given diameter. d, in neutral or acid solution, it is necessary to refer to the
geometry of two particles in contact. At the point of contact, not only do the Surface-silanol groups condense, forming siloxane bonds, but also the annular crevice'
around the point of contact becomes filled until the negative radius ofcurvature, r, is
5-10 A (Figure 5.18). In solutions of monosilicic acid prepared by deionizing or suddenly acidifying dilute .scdium silicate solution to pH 2; ther is relatively rapid'
formation of particles of this radius of curvature, so that the equilibrium solubility
drops to below 200 ppm. The same supersaturation causes deposition of silica. or
brings about a local redistribution, to create a neck of diameter M between the
particles as soon as they are joined by a few siloxane bonds.
The strength of the bond between particles will be proportional to the area of the
contact. M2. The gel strength, for example, in tension, is proportional to the areas of
all the necks across a section of gel, which in turn depend on the number of necks
per section area, which in turn depends on the silica concentration.
I
:
.!
;
.,
Figure 5.18. Coalescence of particles

forming strong interparticle bonds.
\...........-.
... ----nd Powders
521
Silica Gels
weak and
Calculating the value of M in nanometers for particles of radius R, 'and neck of

negative radius of curvature r, it can be shown from geometry that
:a
any
But, more
ier is much
Iiameter d
centration,
: gravity of -
(r+ R)' -
M -
.'
--~
t~ +~1
-2(:!::
R'
2(r2 + OR)1/2
Let T be proportional to the tensile strength of the gel. which in turn' is proportional to the number of particle chains intersecting a given cross-section of gel, and
the area of contact between particles in a chain. The number of particle chains will
be proportional to N2/3.
T = K N2/3M2
where K is a constant
Sinced ~'2R
T
:n particles
efer to the
lo the surlar -vice
atu, .. r, is
ing or sudvely rapid
I solubility
f silica, or
etween the
irea of the
ie areas of
r of necks
C~f3
T = K'C 2 / 3
T
+ (r 2 + 2rR)I/2]2
K' - [:"'r
R2
2
[r +
lR2
r __
r (r 2 + rR)I/2]
_
R
R2
where K' and K" are new constants,

and/is the function in brackets
K"C~/3 feR)
Ifit is assumed r = I nm.then

T = K"C2/3' [_1 + ~ __
I (1 + 2R)I/2]
d
R2 - R
R2
T .. K" C~/3ft(R)
where/1(R) is the new function in brackets
If it is assumed r = 3 nrn, which may occur on prolonged aging of the gel or at higher
pH, then
-9 + -3 - -3 (9 + 6R )1/2]
1R2
T =
p,
.ds. -
. .les
K'C~/3fz(R)
R2
where.fa(R) is the new function
Values offl(R) for r = 1.0and for heR) wherer = 3.0 are given in Table 5.5.
For sols made at low pH at ordinary temperature, experience indicates that r is
around 1 nm. If made at neutral or alkaline pH, further coalescence develops and r
may be 3 nm. For a given condition (pH, temperature) of gel formation the above
equation should predict the combinations of concentration and particle size that will
., -...,--522
Silica Gels and PowdcrsTable 5.5. Values orf(R) from which Relathe Gel
Strength at a Gben Silica Concentration may be
Calculated
Assuming
r .. 3 11
heR)
Assuming
r .. 1
11 (R)
I
2
3
5
7.5
0.268
0.191
0.151
0.107
0.080
0.046
0.025
0.016
IS
30
50
..
0.31
0.27 (See Fig. 5.1)
0.211 .
0.168
0.108
0.064
0.043
41 r .. 1 may be expected for gels formed at pH 1-3 at

25C.
II r .. 3 is more likely for gels after longer aging at
25C, or at higher pH.
give gels of equal strength. For example, if a 2% sol of particles of 1 nm radius

forms a gel of a certain strength. then one should be able to calculate what
concentration of particles of 7.5 nm radius will be required to produce a gel of equal
strength. .
Taking r ... 1 and finding values ofj{R) for corresponding R from Table 5.5,
C~'3(O.08)
... 22 / 3(0.27)
CIS = 12.5%
Under similar room temperature gelling conditions, around pH 3, calculations show

the following should give gels of about equal strength:
Particle
Radius
(nm)
Required Si0 2
Concentration
1
3
2
4.8
(%)
Her confirmed this by making sols of these concentrations and particle sizes,
adjusted to pH 3 at a constant N a 2S04 concentration of o.~o N and placing the sols
in containers of equal size. All the sols gelled after 2-3 days. After 5 days they all
"rang" with the same audible frequency when the jars were struck, showing that all "-...
had about the same .,modulus. Equal strength was shown by the fact that a glass rod
..
'
.,
.wders
7"...--
Silica Gels
.
523
-
-.
5 mm in diameter required 275 :I:: 59 grams of force to penetrate each of the gels to
a depth of I em.
The strength of a silicic acid hydrogel of fixed silica concentration was at a sharp
maximum when formed at pH 1.7, according to Vysotskii and Strazhesko (238a).
This is to be expected since particle growth is at a minimum at this point, so that the
smallest particles yield the strongest gels, all else being equal.
MINIMUM CONCENTRATION FOR GEL FORMATION. It is observed that a sol made
from freshly acidified sodium silicate, in which the ultimate particles are only about
1-2 nm in radius,
form a weak gel when adjusted to pH 5.5 at a concentration
as low as 0.5 wt. %, or about 0.25 vol. %. Based on the foregoing theory of equal gel
strength, one might expect the following minimum silica concentrations that will
permit the formation of gel from 3.25 ratio sodium silicate at pH 5-6.
will
Concentration
Particle Radius
(nm)
1
3
5
7.5
'adius
what
e"
Vol. %
Wt. %
0.25
0.6
0.9
0.5
1.3
2.0
2.2
4.8
Three salt-free sols of colloidal particles with 3, 5, and 7.5 nm radii were prepared
by Iler, all at 0.6.vol. % SiO, and adjusted to pH 5.5. The one with 3 nm radius
gelled in 5 days, the larger ones not even in 10 days.
Particle Size and Packing Density in Dried Gels
show
The final particle size and the way in which particles are linked together obviously
determine the physical characteristics of the gel, particularly its adsorptive
properties. These variables have been discussed in Chapter 3 and also under the
topic of characterization earlier in this chapter.
Silica concentration at the time the gel is formed is not an important factor in
determining properties of the dried gel provided the wet gel structure has not been
further reinforced before drying.
sizes,
e sols
::y '.
at
.s r~d
Okkerse (162) has shown clearly that silicic acid gels can be made with particles of
different sizes (i.e., different surface areas) by varying the pH. However, when made
from particles of a given size, the gels dry to the same final area and pore volume
regardless of the silica concentration in the sol and wet gel (1.2-5.0% SiO,).
The explanation seems to be that for a given particle size, the gels shrink to about
the same packing density upon drying regardless of different silica concentration in
~
.
the wet gel as formed.
However, in gels formed" at various pH and then well washed and dried, there is a
peculiar relation between pH and pore volume. From interpolation of Okkerse's
data the relations have been plotted in Figure 5.19.
.. -..--Silica Gels and Powders
514
. ~.
1.0
I.
':0,
pH
o -1---rI
pH 5.2
o 0-;'
01-"
o 3-~"''''
--4---
O'---...&....-......L.--..I...-_....L...._---!_-.l
200
400
600
800
1000
SPECIFIC SURFACE AREA M2 G-'
i ,.
,
...
:
., I
::1
I
~.
''\!
,.:1
i
Figure 5.19. Relation between pore volume and surface area (BET method) or washed and
dried gels made from sodium silicate and acid at various pH. Dashed line: possible true area.
[Okkersc data (162).]
The decreasing pore volume with increasing particle size (smaller area) from pH
10 to pH 6 can be explained on the basis that the coalescence factor or width of the
interparticle necks is greater with smaller particles, so that the gel is mechanically
stronger and more resistant to shrinkage. (For example, with large particles, spontaneous coalescence is so slight that they approach SO vol. .% packing with a pore'
volume of 0.45 em" g-I jtist as shown in the figure for very low surface area.)
However, gels with smaller particles have pores with smaller radii. At 600 m2 g-I
and a pore volume of 0.8 em" g-I, the particles are only about 3.5 nm in diameter
and the pore radius is no larger. than about 20 A. At some point in this region the
compressive forces of the surface tension of water drying from the pores becomes
enormous. The particles become randomly close-packed, with porosity 40% by
volume or 0.30 ems g-I. This is the pore volume actually observed because the
slightly finer pores formed below pH about 5.5 are collapsed upon drying.
The higher packing density in xerogels formed from ultimate particles of larger
size has been noted by Dobruskin et al (23gb). The larger particles bond to
each other less strongly and so can move and arrange themselves into a more compact structure during drying.
There still remains the increase in pore volume that occurs at still lower pH.
There is little doubt that gels formed at pH lower than 5 actually contain smaller
particles. However, this is not reflected by the BET surface area that remains at
about 800-850 m 2 g-I for gels formed at lower pH. This may 'be explained by the
loss .of measurable BET area around the points of contact of progressively smaller
particles (see earlier section on characterization). Thus the true area of the gel may
continue to increase, but this cannot be measured by nitrogen adsorption. However,
the increasing pore volume of gels made at lower pH is real but not easy to explain.
Silica Gels
d Powders
525
It must be that as the particle diameter decreases further from 3.5 to '1-2 nm, the
greater coalescence and increase in crushing strength more than offsets the increasing forces of surface tension as the pores become smaller. Even at pH 3.4, Okkerse
measured a pore radius of only 10 A. In fact, the water in such pores no longer has
its normal properties and the surface tension may be less than supposed because of
the strong molecular attraction of the pore walls.
In any event, it is interesting to know that to produce a microporous gel a very
low pH of 10 N Hel produces the highest pore volume ofO.S em' g-a.
"
:l!
,0;
:..:
:,...:
-ashed and
true area.
MIXED PARTICLE SIZES. A mixture of different sizes of particles gives a gel with
.wider pores, for example, higher porosity and lower bulk density. Sippel (238c)
found that a mixture of 60% of 12 nm particles and 40% of 25 nm particles gave a
gel density less than that of either sol alone. It seems logical that particles of a single
uniform size would pack more uniformly to a higher density than a mixture in which
each interferes with the other. However, it must be kept in mind that if the two sizes
differ by more than eight- or tenfold in diameter, the smaller ones can fit between
the larger, and then the overall packing density is higher than with either one alone
and the porosity is less.
"
.,~
.,''f'
-: ~
from pH
ltb -f the
ha. .lly
es, spon.h a pore
ce area.)
o m2 g-1
diameter
egion the
becomes
40% by
ause the
of larger
bond to
ore comwer pH.
I smaller
mains at
d by the
, smaller
g'
lay
10. _ ,er,
explain.
.,.
Increased Porosity with Removable Fillers

. There is voluminous literature, especially patents, on adding inert materials before
the gel is formed, which can later be removed to provide greater porosity. Such
materials include water-soluble salts, acid-soluble powders, organic matter than be
burned out, and metal compounds removable with acid or ammonia. A few of these
. have played a significant 'role in catalysts and have been described by Vail (199).
It might be supposed that water-soluble organic polymers would be especially useful for introducing greater porosity or at least a network of fine channels that would
.improve the rate of diffusion o'f reactants into a catalyst gel. However, the matter is
not so simple. Many polymers do not readily form molecularly homogeneous solutions with either soluble silicates or colloidal silica. Phase separation seems to take
place on a micro scale, especially during gelling, and the usual effect, after removing
the polymer' from the dried gel, is either to leave more or less isolated cavities or to
interrupt the gel structure in such a way as to greatly weaken it.
However, there appear to be, for example, certain polyelectrolytes, which improve
the strength properties of silica gel. in the dried state before it is fired. Also, in
certain cases, the objective of providing a double-pore system in gel appears to have
been attained. A patented Japanese gel (239) is described as an inorganic aggregate
in the form of granules interconnected with a sintered inorganic binder, with
microholes between the granules. The microholes are left after burning out an
organic hole-forming material.
According to Montgomery and Parsons (240) an increased-volume of pores from
20 to 10,000 A in radius is formed when 30% or more of a water-soluble polymer
like polyvinyl alcohol or polyethylene glycol is suitably incorporated into silica gel
and later removed by. oxidation. In this case, a washed aqueous gel was first formed
---526
and then blended intimately with the aqueous polymer solution before it twas dried
and heated slowly in air to burn out the organic matter.
Forming and Shaping Gel Particles
iI,
t
,i
:.
For many applications silica gel is needed in pelleted or granular form. Instead of
the common process of pelleting or extruding pulverized gel with a binder, silica can
be gelled in spherical form by (a) forming small droplets of sol in the porcess of
spray drying or (b) spraying droplets into an immiscible liquid and gelling by
chemical action or heating. Another procedure for making spheres only a few microns in size involves coacervation whereby the partly polymerized or colloidal silica
combines with a water-soluble organic compound to form a liquid complex which
comes out of solution as droplets which then solidify. Gel flakes can be formed by
freezing an aqueous sol or gel. Ice crystals are formed between which the silica is
concentrated and compressed. The resulting shape of the gel particles depends on the
size and shape of the ice crystals. By drying in thin layers, gel can be obtained as ribbons. Many of these techniques developed in the past have been described by Vail
(199) but numerous new procedures have been developed..
Spray drying a solution of silicic acid made from sodium silicate by hydrogen ion
exchange was patented by Bailie (241). Another process patented by Winyall, Ellicott, and Acker (242) makes a sol by partly neutralizing a solution of sodium silicate
at pH 9.6-10.9 and then acidifying before spray drying. This procedure probably
first produces colloidal particles around 3-4 nm in size at the high pH, then liberates
more silicic acid of low molecular weight at low pH which acts as a binder to reinforce the gel structure so that a high surface area (965 m 2.g- l ) and a high pore
volume (0.75 em" g-I) are retained. The ultimate particles remain in a relatively
open-packed condition, the silica occupying only 38% of the gel volume.
In a patent to Bergna (243) a. deionized sol of colloidal silica is spray-dried to
obtain micron-sized gel spheres, the specific surface area of which is determined by
the particle size of the sol.
Emulsion polymerization or dispersing droplets of sol in an immiscible liquid
before forming the gel is the subject of numerous patents as reviewed by Vail (244).
In a typical process, droplets of an acidified solution of sodium silicate are formed
mechanically and fall through an oil as they solidify and thence into a lower layer of
water to wash out the salts. LePage, Beau and Duchene (245) leave a small amount
of alkali in the silica beads formed in this way so that during drying the alkali promotes growth and coalescence of the ultimate particles, and a pore volume of 0.9
ern! g-I is retained with a surface area of 310 m 2 g-.I after being calcined at 600C
for I hr.
Spheres of different sizes can be obtained by varying the droplet size of the silicic
acid sol in an immiscible liquid before it gels. For small spheres a silicic acid sol
made frorri acid and sodium silicate can' be pH-adjusted so that it will gel in a
predictable time. The sol is emulsified in an oil with an emulsifying agent until the
droplets harden. As an alternative, the polysilicic acid at low pH with added salt can
be extracted into a liquid organic hydrogen-bonding agent, as described in Chapter
.~.
--lfO
Powders
:to:.
Silica Gels
527
~~
"
..
"
las dried
,.~
, ,. .
..:....
'.
. ..
'
'-"i
.~
siead of
ilica can
ircess of
lling' by
ew mica
tal silica
.x which
.med by
silica is
.s on the
j as ribby Vail
igen ion
.n, EJIisilicate
ro..... bly
ibl. :s
to rein~h pore
:latively
fried to
ined by
liquid
I (244).
formed
ayer of
imount
ali pro: of 0.9
600C
: silicic
cid sol
el in a
1t;- "'e
ali - .n
'hapter
..
... (
.':-Z:
',-
..
..;
~f~
-:
"
,.
....
4. The liquid complex can then be emulsified back into the aqueous phase until the
... droplets gel. This can be accelerated by raising the pH to 5.
Drexel (246) emulsified a solution of silicic acid made by ion exchange into nbutyl alcohol previously saturated with water. Ammonia was added to raise the pH
sufficiently to gel the aqueous sol droplets. The suspension was then heated to
. ' strengthen the gel. .
:.. ...: ',;';'
Gring (247) sprayed a solution of. sodium silicate into oil saturated with sulfur
. ,'dioxide, which gelled the droplets. Ritter (248) made an emulsion of sodium silicate
in perchlorethylene and added H 2S04 to raise the pH to 6 to form the gel as fine
beads. Schwartz (249) mixed solutions of sodium silicate and ammonium acetate in
a nozzle which directed the droplets of the gelling mixture into oil to harden. Moehl
made a solution of silicic acid of which droplets were then introduced into hot oil
with ammonia present to cause gelling (250a)..
A different system developed by' Kummerle (250b) uses n-butyl alcohol and
sodium chloride to extract the silicic acid from acidified sodium silicate solution into
a liquid hydrogen-bonded complex at low pH which is dispersed to droplets which
. polymerize to gel "beads" when catalyzed by F- ion.
, -, Spherical particles can be made from silicon esters. A method 'of Kohlschutter
and Mihm (251) is to partly hydrolyze ethyl or methyl silicate in alcohol with a little
less than the theoretical amount of water using hydrochloric acid as a catalyst. The
polyethoxysiloxane is an oil which forms an emulsion in more water-alcohol and
solidifies to gel beads 0.2-0.5 mm in diameter with a pore diameter of 20 A. Unger
.. and Scharf (252) examined the effects of varying the molecular weight of the pol. ~,yethoxysiloxane from 700 to 2000, using a basic catalyst to complete the hydrolysis
, and gelling of the emulsion droplets, and adding a liquid hydrocarbon to dilute the
droplets to achieve a lower gel density (253). The methodproduces spheres from 1
micron to I mm in size with pore volumes ranging from 0.3 to 4.2 em' g-l and pore
diameters from 20 to 800 A.
In a somewhat similar process, ethyl silicate is emulsified in water with strong
acid as the catalyst and heated to 90C; then salt is added whereupon silica spheres
are formed (254a). In another variation of the process, Thomas (254b) prepared
partially hydrolyzed ethyl silicate, dispersed it in water and hexane, and added
triethylamine to gel the droplets. The 50-500 micron beads had a specific surface
area of 500-700 ~2/g-1.
.
The formation of gel spheres by coacervation with hydrogen-bonding com pounds
has been discussed in Chapter 4. Depending on the particle size of the silica, which
can range from 10-20 A particles of polysilicic acid to 200 nm colloidal particles,
gels of almost all possible combinations of specific surface area, pore volume, and
pore diameter can be made. A method by Kummerle (255) involved adding to a
stirred dilute (1.8% Si02) solution of sodium silicate about 10% of n-hexyl ether of
diethylene glycol, then adding H 2S04 to drop the pH to 6.7. After 20 min stirring, 10
micron particles of dense silica gel were obtained. This polyether is a hydrogenbonding agent and is strongly adsorbed by silica at low pH. ~
Freezing a sol concentrates the silica until the particles are forced into contact. A
gel forms quickly unless the pH is about 2-3, where gelling occurs more slowly, as
shown by Hazel et al. (256), who studied this phenomenon in some detail. Because of
.. ---_.
528
the leallike shapes of gel particles produced under some freezing condittons, it has
been called "Iepidoidal silica." This type of gel was extensively studied by LOUer_
. moser and Langenscheid (257) and Kautsky(258). Hinz, Ruttloff, and Teufel
examined the surface area and pore properties of gels obtained by freezing (259) and
. the structure was described by Kolosentsev, Belotserkovskii. and Plachenou (260).
Dollimore and Shingles (261) prepared dilute silicic acid from sodium silicate by ion
exchange, then froze the solution to obtain a microporous gel.
. Preferred conditions for making flaky gel were patented by Wulf (262). The effect
. of freezing temperature on the pore volume has been examined (263). Butcher and
Simpson (264) patented freeze drying a silicic acid made by ion exchange, after "stabilizing" it with ammonium hydroxide. The higher pH probably permitted gr~wth of
particles before gelling so the surface area of the gel platelets was 450 ,m 2 g-1 (about
60 A particles) and the pore diameter 70 A.
Freezing an aqueous precipitated gel after it has been formed compacts the gel
granules, squeezes out water, and permits filtration and recovery of a product
containing less water (265). Changes in properties of hydrogels after freezing have
been studied by adsorption isotherms (266). According to Halberstadt. et a1. (267),
electron microscope study shows that the gel structure after freezing bears no relation to that before freezing. The general subject of freezing and thawing of colloids
has been considered by Vol'kin, Ponomorev, and Zoltavin (268).
Certain drying conditions produce gel particles of particular shapes. As a thin
layer of gel dries, the shrinkage causes it to crack usually into scales or ribbons. A
fibrous form of gel 5-25 microns wide and several inches long is obtained by drying
a film of concentrated silica solon an inert surface. The gel cracks into parallel ribbons especially when drying progresses along the surface in one direction (269).
"Microballoons" or discrete hollow spherical particles are formed when water solutions of Si02 are spray-dried with a small amount of gas-former such as ammonium
carbonate to innate the droplets (270).
Wet Gel Treatments

Once the gel structure has been formed it can be further modified in the wet state by
treatments to (a) strengthen the structure without greatly affecting the pore structure-sometimes referred to as "gel reinforcement" (see Chapter 4 discussion of
strength of gels-or (b) enlarge the pore size and reduce the surface area by a
process of dissolution and redeposition of silica, coarsening the gel texture.
The processes were described by Iler (2). More recent investigations have confirmed the' particulate or "globular" structure of silica as it is transformed into gel
and the further transformation and rearrangement of this type of structure as it is
wet-aged and heated, dried, and calcined. These steps have been well summarized by
Vysotskii, Golinskaya, Kolychev, Strelko, Strazhesko, Sheinfain, and Niemark in
these excellent chapters covering various aspects of the formation and aging of silica
gels (5).
Though heating gel in water in an autoclave is mentioned here, it is covered in
greater detail in the section on hydrothermal treatments.
\ ."
.,
~
"
;.
id Powders
ms, it has
Jy , otternd
fel
(259) and
lOU (260).
a~e by ion
The effect
tcher and
ifter "stagrowth of
t- 1 (about'
tsthegel
product
zing have
a1. (267).
s no relaIf colloids
l\s a thin
ibbons. A
by J-ying
ral.'ibon (269).
ater solunmonium
t state by
ire strucussion of
rea by a
lave conI into gel
'e as it is
arized by
ernark in
~ of silica
-~~
J'-
Silica Gels
529
Gel Reinforcement
..
This can be done in three general ways: (I) deposition of additional silica on the gel
structure; (2) addition of "active silica" or polysilicic acid to a sol (particles larger
than 5 nm or so) at the time of gelling; or (3) heat-aging wet gel to a limited extent
to increase coalescence of the particles. DEPOSITION OF AODITIONAL SILICA. If a gel is broken up after it is formed so that
particles are in suspension, it can be strengthened by the deposition of more silica
from supersaturated solution. Alexander. nero and Wolter (271) describe a process
whereby "active" silica or silicic acid of low molecular weight can be released into
the suspension. which is maintained at pH 9-10.5 and at 95C. at such a rate that
the added silica is deposited uniformly within the gel structure. It is obvious that this
is not applicable to macroscopic gels. The process is described further in connection'
with the manufacture of precipitated silica powders.
ADDITION OF ACTIVE SILICA BEFORE GELLING. Reinforcement can in some cases
be effected by the presence of active silica at the time the gel is formed. Gels made
by gelling sols of colloidal silica with particles in the range 5-100 nm in diameter are
progressively weaker with increasing particle size. For use as a binder or as catalysts
or adsorbent. the strength can be greatly increased by having a certain amount of
silicic acid present during gel formation. In effect, the silicic acid forms strong gel
bridges between the colloidal particles. Thus the colloidal particles form a rigidly
__ interconnected, porous. three-dimensional network with the low molecular weight
silicic acid polymerized upon it as a strong, dense gel cement. ' '.
Yates (272) patented the process for making gels of this type which contain large.
very uniform pores yet are strong and hard. Porosity is about 50% by volume indicating that in the dried gel the particles are approximately cubic-packed. A typical
gel was made by mixing a 55.1% sol of colloidal silica of 112 om particles with 90
grams of a solution of sodium polysilicate containing 50 grams of SiD, and 11.1
grams of Na,D, and acidifying with 50% aqueous acetic acid to about pH 7. The
mixture gelled in around 2 min, then was aged for 10 hr. washed, and vacuum-dried.
After being heated at 600C. the specific surface was 26 m S g-l, the median pore
diameter was 60 nrn, and the transverse rupture strength was 2000 psi.
When this gel was heated at 1100C for I hr it shrank until it reached 98% of
theoretical density and the transverse rupture strength increased to 5000 psi.
Sodium polysilicate, rather than the more common 3.25: I ratio of SiD,: N a,03'
was used because the latter is incompatible with the colloidal silica, causing gelling
even before acidification..' Sirnilar . gelled bodies have been described by Shoup
(Cahpter 2. Ref. 96), who found that potassium silicate of any ratio is' compatible
with concentrated colloidal silica.
AGING WET GEL. Reinforcement is most commonly carried out without much
change of the gel structure by heat-aging the wet gel to an optimum degree. When
carried further the aging process coarsens the structure. Depending on the character
, of the initial gel and the temperature, time. and pH of aging, the gel structure can go
532
Without reinforcement by heat aging the gel dries to hard dense granules, but
when prepared as described, it is obtained as soft pellets readily dispersible to particles of colloidal dimensions. A typical product had an oil absorption of 4.54 cm 3 g-I ....
which corresponds to a volume porosity of 0.91 cm 3 cm -3, or an average coordina_ .
tion number about 3. The pore diameter was about 27 nm and ultimate particles
were about 9 nm in diameter. Based on the degree of coalescence, the neck diameter
was about 2 nm.
As discussed in connection with measuring the coalescence factor it seems anoms,
lous that the very low mechanical strength of the dried product is accounted for by .
the fact that the wet gel WQS strengthened so as to shrink less during drying.
ADDITIONAL FACTORS IN HEAT AGING. Heating gel in water or salt solutions at
80-100Cgenerally brings about reinforcement but does not modify the pore struc,
ture.Okkerse and de Boer (275) heated a series of gels for 1-4 days at 800C in
water, acids, and potassium chloride solutions and found that if the gel. had a
specific surface area greater than about 200 m 2 g-I, then it underwent a decrease in
area with little change in pore volume. Obviously, the pores increased in size. There
was little effect at pH 2, but in netural or alkaline solution, especially in the presence
of salt, the gel texture was markedly coarsened. For example, surface area decreased
from 752 to 452 m 2 g-Iwhile pore radius increased from 13 to 22 A but pore volume
remained at 0.50 em" g-l..
It is of interest that at 80C there was no effect unless the gel hacta surface area
greater than 200 m 2 g-I. It is no coincidence that in the case of a silica sol, heating
at 80C does not cause particle growth unless the specific surface area is greater
than about 200-300 m 2 g-I~
Prolonged aging of silica gel with an initial surface area of 920 m 2 g-I, in water at
pH 6.8 at room temperature, was carried out by Shein fain, Stas, and Neimark
(276). Surface area .dropped from 725 to 420 rn" g-I while pore radius increased
from 9 to 43 A. However, t~e porosity also increased from 0.31 to 0.90 ern" g-I. The
structure was thus strengthened so that shrinkage upon drying was reduced.
However, the reinforcement was much more striking when samples were first
washed with acetic acid and then dried. Since the surface tension of acetic acid is
only one-third that of water, the reinforced gel had a much higher pore volume of
2.36 ern" g-I, which is quite a low density gel.
Soaking gel in dilute ammonium hydroxide solutions at 50-85C resulted in
drastic coarsening of the gel texture. Girgis (277) reported that even soaking gel at
pH 10-11 for I day at 20C caused the surface area to drop from 650 to 467 m 2 g-1
with corresponding increase in pore radius.
Data on the effect of ammonia concentration on the rate of decrease in area (430
to 126 m 2 g-l) and increase in pore diameter (85 to 397 A) have been disclosed by
Jenkins and Schwartz (278). Similar effects of pH, salts, acids, and alkalis on the
aging process have been reported by a number of investigators (279-284).
It should be pointed out that gels containing polyvalent metal ions, particularly
aluminum (i.e., aluminosilicate gels) are less susceptible to changes when wet-aged
because the metal oxides reduce the solubility of silica. Thus Acker (285) added
2-6% of metal salts to obtain a fine-pored gel of high adsorption capacity for water
.,
silica Gels
and Powders
'anules, but
ale t" partl,

.5-.
' g-l
e coordinate particles
:~. diameter
rns anoma-
nted for by
g.
.olutions
at
pore strucat 80C in

gel. had a
decrease in
size. There
ie presence
l decreased
ore volume
irface area
01 ~ating
is,
ater
in water at
! Neimark
; increased
l ' g-l. The
; reduced.
were first
:tic acid is
volume of
'esulted in
cing gel at
167 m2 g-l
area (430
sclosed by
.lis on the
articularly
... 'lged
85) . .ded
for water
......
...
-...--533
at low humidity. Similarly, Preston, Veltman, and Hubbard (186) obtained

improved water-absorbing capacity by soaking silica gel in aluminum formate solution before drying.
. .:
It might be thought that since silica does not dissolve at low pH, acids would have
no effect on wet aging other than to adjust pH. However, Sheinfain et al. (287)
found that treating the gel with strong acids, HCI, HNO" or concentrated H 2S04
before drying, increases the pore volume of the dried gel without lowering the surface area. This can only be because the acid promotes coalescence between particles
without particle growth and coarsening of the texture. On the other nand, 8 N
H2S0 4 caused a drop in area from 700 to 300 m 2 g-l and at the same time increased
the pore volume. The difference may be that silica is actually more soluble in 8 N
H2S 0 4 than in the. other acids. and the observed difference is only a matter of the
degree of modification of gel structure. In any case, strong acids (pH below 2) pro- .
mote heat-aging of silica gel, but unlike alkali as a promoter, cannot dissolve the gel
if added to excess.
_,
In all the foregoing discussions, it is seen that aging and thermal treatments result
in a one-way process: loss of specific surface area and increase in pore size. The pore
size can be enlarged also' by dissolving away some of the silica. Neimark and
Slinyakova (279) report that treating gel with 0.5 N KOH or dilute HF can enlarge
pores from 7 to 37 A or 37 to 47 A. If silica were dissolved away evenly from all the
surface, there should be an increase in specific surface. However, it is probable that
regions of lower radius ~urvature will dissolve more rapidly so that the specific
area may actually decrease.
Heat aging in water above 100C under pressure in an autoclave brings about far
greater structural changes than can be attained at 100C. If the system is neutral or
alkaline the gel retains Its form and porosity, but surface. area decreases and pores
become very large. If the'medium is alkaline the gel may become dispersed to a sol
(see Chapter 4, refs. I Q2-108). The effects of water as well as steam on silica gels are
. reviewed in detail later in this chapter.
Drying and Shrinkage-Xerogels

In 1911, Zsigmondy (288) visualized that gel is made up of very fine grains
separated by what are in effect very fine capillary tubes and showed how this view
harmonizes with the phenomena observed in dehydrating and rehydrating Si0 2 gels.
. For instance, the diminution of vapor tension of the water is a direct consequence of
the fineness of the capillary. .'
Since the gel consists of a three-dimensional network of particles or short chains
of particles linked rigidly together and since the silica particles themselves are
essentially inelastic, it is apparent that, as the gel dries and shrinks owing to the surface tension of the water in the pores, the network must fold or crumple (289, 290).
. The cause of collapse of an aggregate during drying has been discussed in detail by
Bikerman (291). The final gel structure will depend on the structure of the gel originally formed in solution, but it will be a contracted and distorted version of the
latter.
.
~---
., J
,
i
I.
S34
_However, a most important point in connection with silica gel is tha"t, as the strue,
ture shrinks, a certain number of the particle-to-particle bonds throughout the strue,
ture must break, since the silica particles are essentially inelastic. If the structure of -,
gel is rather compact and the mass is brittle, it is likely to shatter. If the packing
density is low and the gel soft and gelatinous because the chains of very small part],..
. cles are slightly flexible (even as glass fibers are flexible), then the gel will shrink
considerably without cracking because there is always enough of the network left at
anyone moment to hold the mass together.
However, the shrinkage of silica gel is essentially irreversible. It is probable that
as certain bonds break, the portions of the network thus released come into contac~
with other members and new contacts and bonds are formed. In this manner, the
packing density is increased and the pore diameters are diminished .
.This shrinkage during the drying process proceeds until the mechanical strength of "z r .~
the gel can withstand the pressure exerted upon the structure by
the surface tension: ~ b.."
.
of the liquid around the boundary of the gel. As shown by Barkas (290), the
..no
compressive force on the gel increases with smaller-diameter capillaries. This
compression is akin to the force that tends' to pull plates of glass together when
standing in liquid, as described by Bikerman (291). The force between the plates
varies inversely with the distance between the plates. Bikerman shows that, when any
wet. mass of powdered' material' is dried, "the capillary forces press the grains
together, provided the surface of the solid is wetted with a liquid having essentially
zero contact angle (see Figure 5.21). : .
Figure 5.21. The forces that cause silica gel to shrink during drying resemble those that cause
wet plates of glass to draw together. [ller (2), by permission, or"Cornell University Press.)
.....
.<
.4"
id Powders
the struc: the struc~
.ru
of
Silica Gels
535
COLUMN
OF GEL~
. ALCOHOL
ATMOSPHERE
ie packing
nail parti-
ALCOHOL VAP. PRESS. - PO/2
........._------
~i1l
shrink
ork left at
------
aable that,
to contact
anner, the
I
I
itrength of
.ce tension
(290), the
.ries. This
ther when
the plates
when any
the grains
essentially
. I
I
I
8 KILOMETERS
RISE OF LIQUID
I N GEL
I
I
.-:
ALCOHOL VAP.
PRESS.- Po
LIQUID ALCOHOL
Figure 5.22. The height to which a liquid (alcohol) would rise in gel capillaries indicates the
compression to which the gel is subjected when the liquid is evaporated from the pores (see
:
text). [ller (2), by permissio~ ~r Cornell University Press.]
.;,.
r
e ttl
ruse
'ress.]
Alexander and Johnson (292) also point out that the liquid in the capillary, having
a reduced vapor pressure and being under tension, transmits this tension to the
capillaries. For example, Foster (293) found that, in capillaries about 1.5 nm in
diameter, alcohols are adsorbed at a relative pressure of around 0.5. This is
equivalent to a capillary rise to such a height that the pressure of a column of vapor
of equal height is only half that at the base of the column (see Figure 5.22). This
height, calculated from the formula for capillary rise (using the surface tension of
alcohol), is of the order of 8 krn, corresponding to a hydrostatic pressure of 10,000
psi. This means that, if one were to erect a very high column of a dry, solid silica gel
in a tube immerse the lower end in the liquid. and place the apparatus in a closed
system filled only with the vapors, the liquid would rise to a height of 8 km. (At this
height the pressure of the vapor would be only about half the value at the base. for
the same reason that atmospheric pressure diminishes with height.) In order to
withdraw liquid alcohol from a piece of such gel, a "suction? of 10.000 psi would
have to be exerted. In this way it can be seen that. if the liquid is permitted to evaporate from a piece of gel having 1.5 nm pores. the mass is subjected to very high
compression of this order of magnitude. However, for gels having larger capillaries.
.,
~--
ii
I!
!i
.!.l
. :.1
I
,
I
for example, 15 nm in diameter, the compressive force is only of" the order or
2000 psi.
It is for this reason that. in the case of very coarse gels or precipitates containing
particles larger than about 20-30 nrn, where the spaces or pores are also. of this
order of magnitude, the dried products are not strongly compressed but are light and
friable.. - .. ' --" - .--'- . -- . ..
The changes in structure as gels are dried have been examined in detail by Manegold and Huertel (294), who relate the resulting internal strains to the "mud-crack_
ing" during drying. The gel is compressed by the surface tension forces. ihe spherical
primary particles are packed more closely together, and their coordination number
is increased. The relations between pore volume, sphere packing density, and coordination number have been calculated by Kiselev (l26b) and related to pore diameter.
The particles are assumed to be of a given small size (the order of 3 nm diameter).
and as the coordination number increases upon compression from 3.2 to 7. the surface subsequently available to nitrogen adsorption decreases from around 900 to 300
m2 g-l.
It is not generally appreciated that the larger the dimensions of a single gel mass,
the greater the compression and shrinkage. Imelik (295) pointed to an experiment by
Foster and Thorp (296) in which a single piece of gel was divided into two parts.
Part I was cut into 3-5 em cubes and part II was crushed into small pieces, and both
were dried the same way. The pore volume of I was 0.39, but that of II was 0.50,
showing that there was less shrinkage.
Low density gels' are obtained only when shrinkage is avoided as the liquid phase
is removed. This can be accomplished in five ways:
1. Strengthening the gel by reinforcement. increasing the strength of the interparticle bonds, thus opposing the shrinkage forces.
2. Reducing the surface tension forces by enlarging the pore diameter by an aging or
hydrothermal process.
3. Replacing the water with a polar liquid of lower surface tension, for example,
water by alcohol.
4. Heating the liquid-filled gel under pressure to above the critical point where no
liquid-vapor boundary exists and releasing the vapor, that is. the "aerogel
process."
5. Making the surface of the silica hydrophobic.
Methods I and 2 have been discussed with regard to heat aging.
Drying from Low Surface Tension Liquids

Instead of drying silica gels from water, other liquids of lower surface tension are
sometimes employed. Behrman (297) dehydrated silica gel from ammonia. Teter
(298) washed a silica-alumina gel with methanol and dried it in an autoclave.
Kearby (299) produced a pulverulent low density, finely divided gel by treating
precipitated gel with water-miscible organic liquids such as alcohols or ketones and
o.
nd Powders
e order of
C<J
ling
Iso of this
e light and
. by Manenud-crack, -
e spherical
>n number
.nd coord i: diameter.
diameter),
7, the sur900 to 300
~
gel mass.
eriment by
two parts.
;. and both
was 0.50,
~uj-'
-ihase
the intern aging or

. example,
where no
: "aerogel
ension are
nia. Teter
au' 'lave.
y t ling
:tones and
silica Gels
537
then drying at atmospheric pressure. Archibald (300) employed a sirhilar process,

except that the gel, wet with organic liquid, was heated under pressure between 100
psi and the critical point, and the liquid vaporized. Pierce and Kimberlin (30 I) pre.pared adsorbent gels by mixing the silica hydrogel with n-butanol and distilling out
water as azeotrope until the gel particles would no longer agglomerate. Gel particles
. were made by suspending droplets of sol in butanol which abstracted water and
-, promoted gelling...
Solvent drying was proposed. particularly for dehydrating silica gel beads or
peIlets. Thus See and Bailie (302) produced catalyst beads of high strength by gelling
droplets of sol in an immiscible fluid medium and then washed the gel with organic
liquids such as alcohols to abstract water before drying. Neimark and Sheinfain
(303) demonstrated with acetic acid and alcohols that both die surface tension of the
..
liquid and the wetting of the pore surface played a role.
Simply washing 95% of the water out of the gel with a water-miscible solvent
. leaves the pores full of a liquid with a much-lower surface tension than water so that
upon drying the gel structure is less compressed. This leaves a weaker gel that is
more easily dispersed as a thickening agent in oils and resins (304a).
Esterification or other methods of hydrophobing the surface of the gel while still
in the organic liquid further reduces the interfacial adhesion of liquid to solid and
further minimizes gel shrinkage during drying.
A polar liquid that wets the silica surface is essential. For example. if water in the
pores of the gel were replaced in turn by acetone and then bexane,' the water later
liberated by dehydration of the silanol surface at high temperature remains in the
'. pores while the hydrocarbon remains outside and shrinkage still occurs. However, if
.'. :- the surface is first hydrophobed so the pores remain full of hydrocarbon, it can be
dried with less shrinkage: Sirianni and Puddington (304b) added ammonium oleate
. and a high boiling, easily'oxidized oil to wet gel and heated to drive off water, leaving 60% by weight of organic matter in the pores which was driven out up to 500C.
. The resulting low density pellets had a density of only 0.04 g cm -2 and were easily
dispersed to a fluffy powder like an aerogel.
Drying Without Shrinkage-Aerogels

. According to Kistler, an aerogel is a gel in which the liquid phase has been replaced
by a gaseous phase in such a way as to avoid the shrinkage which would occur if the
gel had been dried directly from a liquid. Thus it would seem that an aerogel could
be identified as a gel that shrinks and loses pore volume when wetted with a liquid
and dried. It would have to be a liquid such as n-propyl alcohol that (a) wets the surface of the pores; (b) has a very low surface tension; and (c) evaporates at ordinary
temperature. There are ways of making an aerogel according to this definition
without using Kistler's process, for example, some "estersils."
Kistler (305) prepared silica aerogels by replacing most of the water in the gel
with alcohol, _heat~ng the gel in an autoclave above the critical temperature of
alcohol so that there was no meniscus between the liquid and gas phases. and venting
:-,---
538
:1
t;
!,1.
,,-
I;
I,
I _
I
l.
the vapors. In this way. liquid phase was removed without subjecting- the gel strue,
ture to the compressive forces owing to the surface tension of the liquid-gas
-._interface. The fact that the aerogel structure closely resem bles the structure of the wet gel
originally formed was demonstrated by Marshall (306). who gelled silicic acid in
alcohol-water solutions at different silica concentrations and converted the gels to
aerogels. In Table 5.6 it is evident that the density of the aerogel is directly prope-,
tional to the concentration of silica in- the alcohol which was gelled..The packing
density of silica particles in the aerogel is thus close to that in the originally formed
gel. Aerogel containing as little silica as 0.02 g em -3 was made by Kistler: it was a
very light. transparent, slightly opalescent solid.
o
The method of manufacture on a commercial scale, including a discussion of the
problem of heating and cooling a product which is a good thermal insulator. has
been described by White (307) - and others (308). Harvey (309) has studied the
adsorption of nitrogen, butane, and water on a silica aerogel having a specific Surface area of 710 m2 g-I, a particle diameter (ultimate) of 2.5 nrn, and a wide range
of capillary sizes with most of the pore volume in capillaries 40 nm in diameter:
When water was sorbed, it caused a coalescence of the ultimate particles in the gel
and a shrinking of the gel with loss of pore volume. It is concluded that the surface
properties of the aerogel are similar to those of other silica gels, but the volume and
size of pores are greatly different. Also, Johnson and Ries (310) found that largepore SiOI aerogel contracted on treatment with water and dried to form a smallpore xerogel structure with an insignificant change in surface area. The surface areas
. before and after collapse were 796 and 813 m 2 g-l. respectively. while the pore
volume decreased from 3.90 to 0.66 ern" g-l. and the pore diameters were reduced
from 20 to 3.2 nm.
.
:
The effects of sintering and grinding an aerogel. in comparison with a xerogel,
have been noted by Van Nordstrand, Kreger, and Ries (311). who utilized low
temperature nitrogen adsorption isotherms to follow the changes in gel structure.
Sintering in vacuo caused a proportionate decrease in adsorption at all pressures.
The aerogel loses its largest pores first. Grinding the aerogel apparently breaks up
the structure enough to make large micropores or voids between gel fragments with
I1 .
1
,
!
Table 5.6.
Comparison of Densities of Alcogel and Aerogel
% SiO a in Alcosol
Aerogel: Apparent Density

Ratio
Wt.%
g 100 rnl" (a)
3.89
5.66
5.93
6.20
7.25
3.1
4.5
4.75
5.0
5.8
Source.
Marshall (306).
Ib
ft- a
2.2
3.10
3.20
3.50
4.45
g 100 ml " (b)
alb
3.5
5.0
5.1
5:6
7.1
0.88
0.90
0.93
0.89
0.82
" -:...--
nd Powders
: gel struc1iC1"id-gas
,
the wet gel
cic acid in
t~e gels to
tly properne packing
Illy formed
er; it was a
sion of the
ulator, has
uudied the
pecific surwide range
1 diameter.
; in the gel
the surface
'olume and
that largen a smallrf? areas'
e L pore
re ~educed
a xerogel,
tilized low
structure.
pressures.
breaks up
ments with
539
sitica Gels
"-~
the result that. as p/Po approaches 1.0, the amount of nitrogen adsorbed increases
indefinitely, so that it is not possible to assign a definite pore volume.
For use as a thermal insulator, White and Wilson (312) patented aerogels of high
transparency. The gel must be very pure, containing less than 0.01 % metal impurity
so as to avoid particle growth during processing.
Other modifications of the aerogel process include adding urea to an acidic sol in
". ethanol-water to decompose to ammonia to produce a neutral product (313).
Instead of using alchohol under pressure, an aerogel can be made by heating an
aquagel with cresol to boil out all the water, then boiling out the cresol. Apparently,
at this high temperature the interfacial surface tension is so low that there is little gel
.~ .shrinkage. The residual cresol, probably chemisorbed, is removed by heating in air
: -t0800C(314)."'--;:.
. An organophilic aerogel with. improved dispersibility .in organic materials was
claimed-by"Taulli (315). who heated the aerogel under pressure with alcohol vapor
which may have covered the surface with ethoxy groups. although the nature of the
organic content of the product was not clear. Transparent silica aerogels of very low
' . j :densities in the range of 0.18-0.35 g cm-Sgave an excellent response to the
.: Cerenkov effect for high energy particles of a proton accelerator according to
~'; Teichner et al. (316). Such low densities were achieved by hydrolyzing ethyl silicate
in alcohol with a minimum of water and removing the vapor above the critical point.
Some transparent aerogels were obtained with an area of 1000 m 2 g-1 (corresponding toa particle diameter of only 20-30.A). a pore volume of 18 em! g-I, and a
".
density of 0.05 g cm- s. A mixture of 10% by volume of methyl orthosilicate,
Si(OCH s)., in methanol. with acetic acid at a concentration of 0.175 N. along with 4
moles of water per moleof the methyl ester. was heated in an autoclave to 250C
(critical temperature of .CHsOH is 242C). The vapors were removed under vacuum
.. and the aerogel cooledunder nitrogen. The process using lower alcohols from
methyl to butyl is patented (317).
.
...'. . In a series of papers, Nicolaonand Teichner (318) have described the methods of
preparation, the transformation of hydrogels to alcogels, the mechanical and
thermal stability, and the chemical structure of aerogels. An aerogel is probably the
lightest (lowest density) coherent solid that can be made.
Hydrothermal Treatments
. This section is concerned with wet gels that have never been dried as well as dried
gels that are subjected further to the action of water.
.. Strictly speaking, any aging or heating step involving silica gel and. water in any
form could be called a "hydrothermal" treatment. However. by custom. the term
. generally means that the gel is exposed to water or water vapor at a temperature
higher than the normal boiling point of 100C. It may involve heating the gel in a
stream of moist air, but more commonly involves an autoclaving process in which
_the gel is held in water or steam at over 100C at superatmospheric pressure.
. In 1952, Ries (319) described the marked difference when silica gel was heated in
..
540
..
i
!
~J
'7....--
steam instead of in air or vacuum. The sintering occurs in two different ways,
depending on whether water vapor is present or not .
. .In steam. sintering or loss of surface can occur by a movement of the amorphous
silica from the surface of wider capillaries to fill in the smaller capillaries or pores
so that the average pore size is increased. Steam is one of the principal factor~
responsible for deteriorating cracking catalysts, particularly under pressure. In
steam there is 'minimum change in pore volume. the external shape of the gel
granules is not much affected, and instead there is a coarsening of the structure, so
that the pore size increases as the surface area diminishes. This indicates that in the
presence of steam the silica is more mobile and moves along the surface to fill in the
pores of smallest size. resulting in a further enlargement of the larger pores without
any general collapse of the gel framework. In comparing silica gel catalysts modified
by alumina and magnesia. the silica-magnesia gels are more resistant to steamsintering and have thus found greater favor in recent years.
Sintering of the second type occurs in air or vacuum at high temperature; as will
be discussed. This type of sintering has an effect on gel structure quite different from
sintering in the presence of water vapor. In vacuum. the gel structure collapses. and
surface is diminished. but those pores that remain do not change in size.
Weyl (320) visualized the type of sintering in steam in some further detail:
At a temperature which makes material transport possible, the system lowers its surface
energy by decreasing its surface area. Those parts of each individual grain which protrude into
a void are carried away so that the grain becomes more rounded. The material is used to till
existing gaps. This process decreases the surface area and rounds out both the individual partldes and the existing voids, : .',
.,.I
:!
I
II
,ii
r
f,
11"
!.l
1:1
t !
if
!~
;,
I!
II
,.
"
,
l
,
:
It is 'pointed outthat this process can. increase the mechanical strength of mass
by widening the areas of contact between constituent parts, but there is no obvious
reason why it should cause the mass to contract. According to this picture, once a
capillary begins to be filled in, complete filling should occur rapidly as the diameter
diminishes, and other large capillaries will grow accordingly.
The mechanism of alteration of silica gel structure when silica gel is heated in
water in an autoclave has been observed and summarized by Kiselev et al. (321)
along the following lines,
The solubility of fine particles (globules) forming the gel framework is greater
than that of large particles. Silica thus dissolves from the fine particles and is
deposited first in the regions around the particle contacts where there is a negative
radius of curvature. Below 200C this is the main process, along with deposition of
silica on the surfaces of the larger particles. There is only a moderate decrease in
specific surface area. At 200-300C where silica is much more soluble, the reaction
. goes much faster. There can be a tenfold increase in particle size and corresponding
decrease in area, but nevertheless the structure of the silica skeleton remains corpuscular.The network becomes much coarser and the members of the framework
increase in diameter as the finer branches in the original network disappear. At
higher temperature, presumably above the critical point. there is irregular particle
growth and large nonporous masses appear within the greatly coarsened skeleton.
.. -...-_.
; and Powders
Silica Gels .
Terent ways,
Liquid or Vapor Phase
e Co
There is a difference whether the silica is in the vapor or liquid phase when undergoing hydrothermal treatment. According to Chertov, Dzhambaeva, and Niemark
(322) if the gel is in the vapor, then after being dried the pore volume is greater than
that of the untreated control. If it is submerged in liquid water the pore volume is
decreased. No explanation was given, but one would guess that the water-immersed
'sample must have undergone some shrinkage as it later was dried, whereas the
sample in the vapor did not shrink because its pores were not filled with water.
phous
or pores,
cipal factors
pressure. In
e' of the gel
structure, so
es that in the'
: to fill in the
ores without
IStS modified
ot to steam-
~ies
-,'
541
:-
..
HEATING IN STEAM.' The same authors measured the rate of change of surface area
when the gel was heated in the vapor phase (steam). It is expressed as - dS/dl kS" where S is in square meters per gram and I is in hours. The values of the
constant, n, are given by the equation .
iture; as will
ifferent from
ollapses, and
n .. 9(I - 0.00222 1)
where T is the temperature (OC) and

tail:
. (-33,220,
. k .. 101D.2 exp \: . T )
ers its surface

protrudeinto
is ..-:d to fill
:ih
,I parti-
th of a mass
; no obvious
.ture, once a
the diameter
is heated in
et al. (321)
k is greater
Icles and is
s a negative
!eposition of
decrease in
the reaction
'rresponding
ains corpusframework
sar -ar. At
ll~
article
skeleton.
The energy of activation is 66 kcal mole-I.

. Silica powders can be converted to gels (323). An Aerosil powder was ground in
water to obtain a thick, paste and dried and treated as follows:
,.
-.'
(ern" g-l)
Average
Pore Diameter
(A)
1.32
1.22
1.17
300
375
530
Pore Volume
Treatment
Dried 140C
Heated in air 4 hr 940C
Heated in steam 6 hr 800C
192
128
89
Pores were not uniform except after heating in steam. The change in pores by heat. ing at 500C in superheated steam was examined by Robinson and Ross (324), who
observed that in air at 500C, a gel of 660 m 2 g-I area changed only to 600 m2 g-I
after IS hr, but to 335 m 2 g-1 in steam. The pore volume does not change and as a
result the pore diameter is increased from 25 to 45 A. However, there is evidence
that steam treatment may introduce some pores smaller than 10 A (see discussion of
micropores below).
.Silica' gel catalysts are steam-treated under pressure in: the range 200-4S0C and
then heated in air up to 500C to produce a strong structure that will withstand the
internal stresses of wetting and drying which otherwise would cause the gel to shatter
is use.. Many patents were issued on this in the 19505 (325. 326a).
fir'
----
542
Simply drying in superheated steam appears to strengthen the structure so that a

low density gel is produced. Jenkins and Schwarz (326b) made a hydrogel containing
7% Si02 that set in 25 sec in a 1.1 n salt solution at pH 10.8. It was aged I hr at
70F and cut up, the residual sodium base was exchanged out with ammonium
sulfate, then the gel was washed and dried in steam 4 hr at 250 F, then heated in air
at 400F. This gel had a density of only 0.16 g cm- 3
Additional examples make it clear beyond doubt that when gels are heated in
steam at less than about 700C the size and shape of the gel particles or granules
.remain unchanged while the inner structure undergoes drastic coarsening with great
decrease in surface area and enlargement of pore size, but no change in pore volume.
The kinetics of structural changes as silica gels are heated in steam at atmospheric
pressure at temperatures in the range 478-863C has been examined by Schlaffer,
Adams, and Wilson (327). In the case of an aluminosilicate gel. the rate of loss of
surface area S with time t was-described by the equation
-dS
--dt
kS"
where k and n are constants for a particular aging condition. However, for silica
after the area had declined to about half the original value, the further decline was
more rapid-than indicated by the equation. Data are given for changes in area and
pore volume for different types of silica gels. In general, the surface area did not
drop more than 10-20% in 10 hr unless the temperature exceeded 600C.
. If the initial gel contains only micropores and there are no impurities present,
steam can close the pores to produce impervious silica glass. For example, when a
film of silicon acetate (tetraacetoxysilane) is applied from acetone onto a silicon
wafer, it hydrolyzes in air to form a thin layer of extremely fine-pored silica gel.
.When heated to 800C in steam an impervious coating of Si02 is produced (328).
Kiselev et al. (329) confirm that hydrothermal treatment at 250C, 50 bars, does
not change the pore volume (1.1 ern! g-l)eventl)ough the surface area decreases
from 300 to 2 m2 g-1 and the pore diameter increases from 100 to 16,000 A. No
change in pore volume after hydrothermal "aging" was also reported by Bohlen,
Buehlmann, and Guyer (330). The treatment provided a catalyst carrier that was not
further affected during use at high temperature in reactions involving steam.
Buehlmann (331) hydrothermaJIy treated three gels with small. medium, and large
pores in steam up to 176C and in all cases noted that the pore volume remained
constant; that is, there was no shrinkage.
Autoclaving a silicic acid gel made at low pH, at 90-215C for 2-400 hr, results
in gels that subsequently shrink less on drying. The products have surface areas
ranging froni 421 to 48 m2 g- land pore volumes from 0.76 to 1.96 em! g-l. The
changes involve an increase in the size of the ultimate particles forming the gel struc. "ture and in the pore diameter (332).
Starting with commercial colloidal silicas, Hill (333) gelled relatively concentrated
sols of silica particles 7 and IS nm in diameter, then autoclaved the gels in water for
............
.
\'-..0"
d Powders
Silica Gels
a day or so at 180-190C. The product of lowest density had a specific sbrface area
of 119 m 2 g-1 (23 nm particles) and a pore volume of 1.14 em! g-1 corresponding to
a porosity of 0.71 em! cm- a of gel, or a coordination number of around 4. In some
cases a small amount of ammonium fluorosilicate was added to promote gelling, but
it also promoted reduction of surface area.
so that a
ontaining
;d
. at
.: r
nmonium
ued in air
."
heated in
granules
vith great
e volume.
nospheric
5chlaffer, .
of loss of
543
HEATING IN THE LIQUID PHASE. The effect of immersion in water when silica gel is
heated was very clearly demonstrated by De Boer and Vleeskens (334). A pure silica
gel made from SiCl. and thus free from alkali was dried and heated in air and
another sample in water in an autoclave for 6 hr:
-rc
In Air
In Water
Temperature
_ (OC)
Area
(m2 g-l)
Pore Volume
(ern" g-l)
Area
(m2 g-l)
Pore Volume
(em" g-l)
. As Dried
230
450
650
890
530
0.965
530
80
0.965
0.92
498
477
439
- 0.89
0.85
0.705
.-
for silica
:cline was
area and
a did not
i
pi esent,
e, when a
a silicon
silica gel.
(328).
iars, does
decreases
)0 A.. No
{ Bohlen,
.t was not
g steam.
and large
remained
ir, results
Ice areas
g-l. The
gel struc-
cer 'lted
w.
for
In' air at greater than 600C the ge-l begins to shrink rapidly and pore volume
decreases. In 6hr at 450 and 650C. there is little further change in area or porosity
after 96 hr. However, at 890C, the changes continue as volume diffusion occurs; in
effect, the silica slowly "flows" together. In water, the smaller particles dissolve and
the silica further increases the size of the larger ones, but there is not much change
in the dimensions of the gel. Pore volume remains almost unchanged.
Fully hydroxylated wide pores are obtained by
autocIaving the gel in water, drying and heating to 900-1000C for 6-10 hr, and
then rehydroxylating the surface by soaking in water and drying below 150C (335).
However, if heated above 1000C, micropores are developed. (This might be due to
formation of "microcrystals of cristobalite which undergo a volume change causing
microcracks upon cooling.)
On the other hand Gorelik, Zhuravlev, and Kiselev (336) state that maximum
microporosity was developed when a gel with an area of 210 m 2 g-I, free of
micropores, was treated hydrothermally at 130-150C. Further experiments (337)
indicated that the ultrapores formed on Aerosil were finer (penetrated by H 20 but
not N 2 or CH:sOH) than on a silica- xerogel, Both had about the same surface area.
The micropores are apparently within a thin layer of polysilicic acid deposited on the
dense silica surface. This probably came out of solution on cooling and was
deposited at less than 100C. Otherwise, it would not be micropcrous. Furthermore,
although the pH was not mentioned, it is likely that the pH of the xerogel suspension
was slightly higher and thus resulted in somewhat wider pores in the coating.
DEVELOPMENT OF MICROPORES.'
EFFECTS OF ADDITIVES, IMPURITI ES. The presence of much alumina, as ih alumino.

silicate catalysts, reduces the physical changes during heating at 478-863C in steam.".
at atmospheric pressure (337). In the case of pure silica, it is the diffusion of silica in
the presence of steam that converts microscopic clusters of small silica particles to a
solid mass as though undergoing localized fusion. This causes a decrease in pore
volume that occurs above 700C. When alumina is present the mobility of silica is
reduced in somewhat the same manner as alumina reduces the solubility of silica.
Schlaffer, Morgan, and Wilson (338) and Adams and Voge (339) made ~xtensi\'e
studies of the' structural changes in aluminosilicate gels caused above 700C in
steam. The localized nature of the collapse of particle clusters to a solid mass was
demonstrated under the optical microscope by dyeing the heated catalyst with
methyl. red from benzene. Theoriginal catalyst was uniformly red, but the aged
catalysts showed colorless regions where collapse to impervious masses had occurred.
.
.
Absorbed alkali (Nat) impurity remaining in the gel contribute greatly to the
'structuralchangesduring hydrothermal 'treatment. Akshinskaya -ct at (340) report
that well-washed gel undergoes less change at 275C. The effect of autoclaving silica
gel in water for 4 hr up to 360C was investigated. The pore diameter of avery pure
silica gel autoclaved at 270C increased from 9 to 150 nm while the pore volume
decreased only from 0.94 to 0.87 em! g-l. At 360C the pore diameter increased to
1250 nm and the pore volumedecreased to 0.63 em! g-l. Heating the gel in air for 6
hr at 900C had about the same effect as autoclaving in water for 4 fr at 295C, giv. . .{
ing a po~e diameter of 180 nm-. ~'"
Silica gels arc sometimes autoclaved in water under mildly alkaline conditions
(ammonia) to develop high strength and wide pores in the range of 100-1000 A
diameter (341). It is interesting that in hydrothermal treatments it was noted that
very pure gels underwent more rapid changes than did some commercial gels. This is
no doubt due to the AI20 , up' to 1000 ppm, commonly found in commercial sodium
silicate (321) which remained in the gel.
.,
.j
. -j
Heating in Air, Vacuum

-
As silica gel is heated to progressively higher temperatures water is lost from pores
and then by dehydration of surface silanol groups. The hydration-dehydration of the
surface is considered in Chapter 6. Here only the changes in the physical structure
are considered. _ .
The first stage up to 300C mainly evolves loss ofmaterial (water)from the pores,
and is often referred to as "activation" since afterward the gel has a higher adsorption capacity for vapors. An important factor is the effect of the water held on the
surface (presumably as silanol groups). If a' sample of silica gel is suddenly heated to
a high temperature, the evolved water has a marked catalytic effect so that the sur-face is greatly reduced. However, if heating is gradual, to permit more complete
escape of water before the sintering temperature is reached, sintering and loss of surface area is less marked. The main effect" of a vacuum is to remove any evolved
Ii
.~
-,
~;
.,.
Powders
aluminoin j:t,,:am
r s... in
icles to a
: in pore
i silica is
of silica.
extensive
'OOC in
nass was
yst with
the aged
had ocY to the
) report
ing silica
'ery pure
: volume
'eased to
air for 6
i-c, givim,
.ns
-1000 A
ned that
. This is
I sodium
m pores
of the
)0
.tructure
pores,
adsorp1 on the
.eated to
the sur.ornplete
ie
S'
eV~.
ur-
ed
~--
SilicaGels
'-
54S
water vapor quickly so it will have less effect as shown by Gallard-Hasid~ Jones, and
Imelik. (342).
From 150 to around 600C there is little, if any; change in surface area or pore
structure. However, stronger bonds develop at the contacts or "necks" between the
ultimate particles; that is, there is an increase in the coalescence factor.
At still higher temperatures the specific surface area decreases, the gel shrinks,
and the pore volume also necessarily decreases, but the size of the remaining pores
usually remains about the same. This is difficult to understand.
Kiselev (3, 343a) said that in vacuum the surface area and pore volume decrease
proportionally to each other and the ultimate spherical particles flow together; that
'is, there is volume diffusion. Patrick, Freyer, and Rush (343b) showed that the
capillaries in silica gel began to close when the gel was heated to 700C. Milligan
and Hachford (344) made a careful study of the effect of elevated temperatures on
silica gel having a surface area of 380 m! g-l. Samples were heated 2 hr at temperatures from 200 to 1000C. In no case did X-rays reveal any crystallization.
Temperatures up to 500C had no effect on surface area or pore structure. Slight
sintering occurred at 650C, and more rapid loss of surface took place at higher
temperatures, but the pore diameter remained constant at about 5.6 nm. Van Nordstrand, Kreger, and Ries (345) and also Bastick (346) have shown that in commercial silica gel having a pore diameter of about 2 nm, as well as silica-alumina
xerogel, having a pore diameter of about 4 nm, there is no change in average pore
size as sintering progresses. It appears that pores are destroyed in some manner as
the silica is converted from the porous to the nonporous state without the size of the
remaining pores undergoing any change.
"Even in sintering a voluminous aerogel where shrinkage was 83% by volume,
Teichner and Nicolaon found that the average pore diameter, d p , which is the ratio
of specific pore volume to specific surface area, changed only by a modest amount
(316).
.
Temperature
(OC)
Semi g-l)
Vp(cm' g-l)
dp(A)
300
500
700
900
1004
800
477
162
1,48
1.26
0.9
0.3
14.8
15.8
18.9
18.5
In similar studies, silica gel heated from 100 to 1000C showed no change in pore
diameter which remained at 22 A, whereas the surface area decreased from 618 to
341 m2 g-l, according to Kohlschiitter and Kampf (347). The density measured in
"helium changed only from 2. I 8 to 2.22 g cm -, and the structure remained arnor phous by X-ray diffraction. The pore volume dropped from 0.57 to 0.33 em! g-1 so
that the density of the gel increased from 0.98 to 0.79 g cm-i , corresponding to a
volume shrinkage of 19% or a linear shrinkage of 6.8%.
Much of the sintering data is not reproducible because it is now known that many
546

to
of the gels studied contained unknown, but no doubt significant, amounts of

impurities. One explanation for the foregoing phenomenon, whereby some pores
disappear leaving others of the 'same size unchanged is that there could be localized
impurities such as a sodium ion here and there which promote sintering in its neigh_
borhood.
.
.
However, this now appears unlikely. Ion-free silica was prepared by Goodman
. and Gregg (348) for a careful study of sintering silica free from impurities. The gel
was made by hydrolyzing tetraethyl silicate (tetraethoxysilane). The .micropore
diameter remained constant at 6.0 :!: 0.3 A from 200 to soooe, whereas the surface
area and pore volume decreased in a similar manner, their ratio remaining constant,
The surface area dropped from about 700 to 450 m Z g-1 as the gel shrank in three
dimensions.
It is therefore a well substantiated fact that when silica gel is sintered it shrinks;
.
:.
,
~ ~ i:
, ...
,. ...
the pore volume decreases in proportion to the decrease in surface area and the
pores that remain do not change in size. It is as though portions of the gel shrank
completely to dense solid silica while the remainder underwent no change.
Another peculiarity is that as the temperature is increased stepwise, a further fraction of the gel shrinks to density and the surface area quickly drops to a lower level
and remains there at the new temperature. De Boer (349) called attention to this
fact, saying that for each higher step in temperature, up to about 700C in 6 hr, the
specific surface area drops to a certain value, after which it changes very slowly. In
other words, there is rapid loss of surface down to a certain value at a given
temperature, beyond which further change is slow. Possibly this behavior involves
shrinkage of the gel structure in certain localized microscopic regions to zero . \,'1
porosity, that is, to solid SiO z glass. If these regions were distributed as a network,
"t
the overall gel volume would contract and surface and pore volume would be lost,
but the remaining regions would stay unchanged with their original pore diameter.
.:
An explanation of the mechanism is based on the assumption that the tendency of
adjacent particles to flow or sinter together is opposed by the internal tensions
created when a solid network starts to shrink in three dimensions simultaneously.
But if in a local spot two particles begin to flow together and one breaks loose from
its other neighbors, then the two will sinter more rapidly. This upsets the local
balance of' forces so in that region extensive localized sintering to a solid mass
occurs. At each higher temperature a new set of localized ruptures and further
sintering occurs.
.",
.~
Sintering Uniform Structure

If all particles in a gel are of very uniform size and they are packed in a uniform
manner, sintering will only occur suddenly as a given temperature is reached and the
pores are all eliminated at the same time. Her has observed such a phenomenon in
uniformly close-packed silica spheres 200 nm in diameter (see section in Chapter 4
on synthetic opal). This white opaque gel shrinks quickly as a certain temperature is
reached (IOOO-1200C, depending on Na-t- content) and is converted to clear
nonporous SiO z glass far below its normal softening point.
\.:
.. -....-...
Silica Gels
id Powders
547
It also appears that in such uniform gel structures the sintering terrrperature is
lower for smaller pores. Thus at a given temperature, once a group of particles start
to coalesce the pores between them become smaller and the rate of pore closure
accelerates until closure is complete..
.'
.- Comparison of conventional dense, small-pored silica gels with an aerogel of open
porous structure indicates that at a given temperature under vacuum-sintering conditions the wide-pored structure is the more stable. It is suggested by Ries (319) that
, the solid surfaces of the "pores" are so widely separated that their approach and
"fusion" on heating is slow. Wolf and Beyer (350) also have shown that low gel
. density, indicative of fewer particle contacts, that is, a lower coordination number,
minimizes shrinkage and loss of surface area at high temperature. They dried two
portions of the same gel, part I from a low surface tension liquid (acetic acid) and
part II from water: .
. '.
nounts of
om "ores
e I~ .ized
1 its neigh- .
Goodman
s, The gel
micropore
he surface
; constant.
k in three'
it shrinks;
a and the
~el
shrank
-
-.
rther fracower level

on to this
16 hr, the'
slowly. In
.t a given
r' lives
s 1 ... .lero
. network,
ld be lost,
..;
_~
Gels having only uniform micropores sinter completely to theoretical density at rela, tively low temperature. Malanchuk and Stuart (351) reported that a gel with 10 A
pores sintered at 'unusually low temperature:
.. -
- . ' -'
Temperature (OC)
ameter,
:ndencyof
I tensions
taneously.
oose from
the local
olid mass
Id further
1 uniform
:d and the
imenon in
Chapter 4
ICC
're is
tc .ear
".
~;:
Surface Area (m S g-l) .
-', 25
'. ;.... 800
900-1000
700
500
Production of molded articles of pure vitreous silica involves two problems: (a)
. forming a type of gel that does not crack on being dried, and (b) consolidating the
washed and dried gel body at high temperature before devitrification occurs. Shoup
et al. (see Refs. 96 and 97 of Chapter 2) solved the problem by using a compatible
solution of soluble silicate (potassium) and colloidal silica of high silica content.
When formed in a mold with a homogeneous acidifying agent (formamide) the gel
was exceedingly strong because of high silica content and very fine pore structure.
After being washed with acid to remove the alkali metal, the molded gel body was
dried and sintered at 1350C. Consolidation was rapid with uniform three-dimensional shrinkage of the gel to a final shaped article of clear fused silica.
Alkali Metals, Impurities, and Crystallization .

At some temperature above 1000"C, devitrification may begin by nucleation of
crystals of cristobalite. This is strongly catalyzed by traces of impurities, especially
...
548
.;.
,i
;1
:.1
"
:----
alkali metals (sodium). On the other hand. if the silica gel is very puree it does not
devitrify even in 5 hr at 1400C. according to Goodman and Gregg (348). Actually,
there are interatomic bonding changes within the SiO, itself even at moderate
temperatures although the gel remains amorphous in the sense that no X-ray diffrac_
; tion pattern of any crystalline form can be found. Fraissard and Imelik (352) concluded from infrared absorption studies that there were small organized domains
with structures resembling either quartz or tridymite or cristobalite. Aerogels show
the quartz structure and xerogels the tridymite but both change to cristobalite-type
bonding above 600-800C. The temperature at which the surface area drops rapidly
to zero is greatly influenced even by traces of alkali impurities. Ries (319) found that
an aerogel made by condensation from the vapor phase and thus very low in sodium
and alkaline impurities approached zero area only above II OOC. A commercial silica
gel dropped to zero at about 1040C, and an aerogel known to be made by a process
involving sodium sulfate reached the point of zero area at about 900C.
. The allowable concentrations of sodium in silica gel catalysts are so low that
chemical methods of analysis may not be sufficiently sensitive. Acitivation analysis
..by neutron flux converts sodium to a radioactive isotope so that 3 ppm can be
determined with a standard deviation of 0.2 ppm (353).
Silica gel structure is destroyed and the amorphous silica crystallizes at quite low
temperature when 5 mole % of the alkali metal oxides is present. Lithium promotes
crystallization to quartz. and sodium to cristobalite, at only 700C. Potassium acts
almost as rapidly at 700C (354). The surface area of such alkali-containing gel
drops almost to zero at 650-700C (355). When the gel is taken at an intermediate
stage as it shrinks. and is treated with acid. washed. and dried. it contains very wide
pores. 300-1200 A diameter. Also there are micropores which are probably left after
the sodium is extracted {rom the thin glassy layer on the.surface, Any surface area
from 70 to 6 m' g-1 can be obtained by cooling the sample at the right point.
The rate of conversion of amorphous to crystalline silica is strongly influenced by
the presence of various materials which may serve as crystal nuclei and also by
materials which labilize Si-O-Si bonds, thus making the silica structure more
mobile. For example. it was noted by Milliken. Mills, and Oblad (356) that with 2%
Al,03, a gel which had been heated to 1160C gave a much stronger pattern of
cristobalite than silica gel containing no alumina. On the other hand, with still more
alumina, the cristobalite pattern became weaker. The most significant point is that
small amounts of alumina greatly strengthen the cristobalite pattern in silica after
the gel is heated to high temperature. These authors stated that, since cristobalite
has the same structure as potassium aluminate without the potassium ions present,
the influence of silica on the crystal habit of alumina is probably very great.
Likewise, the aluminate structure affects the orientation of the silicon tetrahedra
. adjoining the aluminate structure, so that at the interface well-defined cristobalite
rings probably exist. This crystallizing influence or "cristobalite nucleus" probably
extends only a few molecules deep into the silica particle. These cristobalite nuclei
thus may act as seeds for the crystal growth observed when'catalysts of low alumina
content are heated to 1150C.
Mougey, Rossetti, and Imelik (357) and Godon-Renou et at. (358) observed that
when alkali is adsorbed on silica gel it makes considerable difference whether the gel
1
"
.~
...~
. '8
,~
-
~,--.
.,
~-_.
id Powders
t does not
. Actually,
rr,
"ate
ay ditfrac(352) coni -dcmalns
>gels show
ralite-type
IPS rapidly
found that
in sodium
rcial silica'
, a process
) low that
-n analysis
im can be
: quite low
promotes
ssium acts
.aining gel
:er"- -diate
Vt.
vide
y left after
rface area
lt.
luenced by
id also by
ture more
It with 2%
pattern of
still more
lint is that
silica after
:ristobalite
1S present,
ery great.
tetrahedra
:ristobalite
, probably
ilite nuclei
walumina
Silica Gels
549
is then heated in vacuum or in air. With 1.5 x 10-' g-ions of Nar a~sorbed per
gram of silica, heating in vacuum to only 150C reduced the surface area from 695
to 380 m2 g-I but in air the area dropped to 175 m2 g-I. It seems likely that the
alkali held less waterwhen under vacuum s~ that the effect was not as great. With
this amount of either Na + or K+ present, most of the surface was lost and
crystallization to cristobalite occurred at only 8QO-S50C.
" A very unusual explosion phenomenon was described by Kondo, Fujiwara, and
Muroya (359). who heated a silica gel. containing about 500 ppm of. adsorbed
sodium ions. rather rapidly to 800-10OOC. The gel initially shrank so that pores
closed. and then suddenly exploded or expanded. much as popcorn does and for the
same reason. The original gel had a BET area of 700 m2 g-I, a pore volume of 0.40
em' g-I, and a water content of about 6% bound as surface SiOH groups. With the
right amount of sodium adsorbed on the silica surface, the gel granules become
sealed off at around SOOC. before all the water has evolved and the mass acts as an
extremely viscous liquid which then foams up with the internal pressure of the
liberated steam. With too little sodium. the viscosity is too high and an impervious
skin is not formed. With too much sodium the viscosity is too low and the steam
escapes before pressure can build up..
Boric oxide lowers the sintering temperature of silica and will no doubt accelerate
loss of surface of gels-athigh temperature. However. it has the effect of delaying
devitrification since crystallization of cristobalite occurs less readily in Si0 2- B20a
glass (360). Lithium is a strong "mineralizer." by which is meant that it promotes
crystallization of amorphous silica. according to De Boer (361). In large amount
. (20%) LiCl converts amorphous silica powder to quartz in 2 hr at 700C according
to Bassett. Boucher. and Zettlemoyer (362). The effect of sodium ion is to promote
the making and breaking; of Si-O-Si bonds. which increases the mobility of the
structural elements. Avery low sodium concentration is effective, but when present
.in very small amounts if can influence only the region around each sodium atom.
. Hence sintering and structural. effects occur only in localized zones leading to a
. heterogeneous structure (363a). !
Thesintering and devitrification of silica gel can probably be reduced by the same
methods by which these changes can be retarded in high silica glasses. Elmer and
Nordberg (3,63b) have shown that nitriding porous glass at 500-IOOOC in an
atmosphere of ammonia reduces devitrification. Elmer and Meissner (363c) incorporate carbon into porous glass as furfural which is polymerized and pyrolyzed to
carbon in the absence of air at high temperature. This dehydroxylates the silica surface, thus removing the water that promotes softening of the silica at high temperature.
Special Gel Structures

Submicroporous Gels-s-Impervious Silica
""
;en .. that
her the gel.
"
In contrast to the preceding methods of making larger pores there is also some
interest in making pores as small as possible. Gels of this type have pore radius less
..,
S50
"
;
:
~ i
;,
:=;;
1':
i
l(l,1
j~
"
,:11
rl!
:'.
'! "
,
;.:
i '
,i
I
II,
,.
;-i;
'
", ,
,
,'
!,
~--
Silica Gels and PO\Vders_

:
than 3 A. In such a pore each nitrogen or other molecule smallenohgh to enter'

s
essentially surrounded by pore walls and is very strongly held by the van der Waa:
forces (364, 365), hence the term "persorption." Smaller pores admit H 20 but no~
N" and still smaller ones only He. Discontinuities in the solid structure which ar
even smaller may exist, but cannot be called pores since there is no atom smal~ -. .
'
, .
enough to penetrate them.
Submicroporous silicas are obtained in two ways: (I) by starting with a solid sili
. cate glass or' crystal, usually somewhat hydrated, and removing the cations without
disintegrating or dissolving the structure; or (2) starting with discrete, extremely
small (diameter 10-20 A) silica particles and compressing them together into a
densely packed state. The compression results either from surface tension forces
while drying from a liquid or freezing to squeeze particles together with ice crystals
or simply from high mechanical pressure.
.. .
'
Several examples of "hydrated amorphous silicas," described in Chapter I, are in
fact silica gels in which the pores are so small that the contained water has a very
low vapor pressure. Such gels are formed when a solution of polysilicic acid of low
molecular weight, like the cubic octamer described in Chapter 3, is evaporated at
low pH. If the pH, after concentration to the gel stage, is around 2, the particles
remain unaggregated .and dry to a dense mass which is powerfully compacted by the
surface tension as the water dries from the extremely small pores .(see Chapter I,
110, III). The submicroporous silica of Dollimore and Heal (172) was obtained only
. when this optimum amount of residual acid was present.
Submicroporous gel is obtained only when the initially formed silicic acid particles
are not permitted to aggregate beyond the stage of forming short chains, before \
being concentrated and dried to the solid state. If aggregation occurs in solution, the
pores in the aggregates .are carried through into the dried gel. However, if the gel is
subjected to extremelyhigh pressure to squeeze out water, as reported by Lenher
(366), then the particles can be forced into a close-packed state. The gel described by
Lenher was made from silicic, acid generated by hydrolysis of SiCI. and probably
consisted of particles only about 10-15 A in diameter. These particles may have corresponded approximately to the cubic octamer (see Chapter 3) and when closepacked would create such small pores that water could not easily escape. In any
case; the dried composition corresponded to (HSiOl.ll)n after having been compacted
.at a pressure of more than 106 kg cm -'.
Silica compacts with pores of molecular size were prepared by Ramsay and Avery
(367) by compressing silica powders. At highest compression, only micropores were
reported, but submicropores were probably also present.
Submicroporous silicas contain pores in the same size range as the zeolites, but
they are not as uniform in size. However, with care to start with particles of silicic
acid of uniform size, it may be possible to produce more uniform pores than in
the past.
Impervious silica may be formed if the particle diameter is as small as 10-15 A
(172). If the particles are closely packed, only submicropdres are present and these
remain filled with strongly held water molecules. Attempts to strengthen such films
by including minor amounts of water-soluble organic polymers usually result only in \..._.'~
f
interfering with close packing and making the film weaker. The practical problem is
that silicic acid sols of such low molecular weight or particle size are not stable even
:;.c
"-
....
,iff',
nd Powders
to enter is
de- Waals
~ not
20
which are
.tom small
solid sili.ns without
extremely
her "into a
sion forces
ce crystals,
er 1, are in
has a very
acid of low
.porated at
ie particles
cted by the
Chapter 1,
tained only
id :
~ticles
in~
-efore
alution, the
if the gel is
by Lenher
escribed by
d probably
y have cor/hen closepe. In any
compacted
and Avery
.pores were
eolites, but
es of silicic
res than in
10-15 A
t and these
films
.s
SUI _ .nly in
problem is
stable even
IS
SSt
Silica GelS
when concentrated at pH 2 where aggregation is slowest. Impervious silica is

obtained only when the freshly made solution is dried rapidly as a thin film or
concentrated by freezing, which produces solid silica as a pseudomorphs of the
spaces between the ice crystals.
Submicroporous silicas are often known by different names depending on how
they are obtained and may not be recognized as belonging to the same class. The
pores may account for up to 50% .by volume of the silica mass and yet have
diameters only large enough to accommodate small molecules. For example, by
reacting solid alkali metal metasilicate, dried to less than 6 moles of water, with
concentrated HzSO., Blount (368) obtained what he termed "silico-dihydrogen
sulfate," SiO (HSO.)z and similar compositions. When mixed with water it yields
"silico-formic" acid, which can also be classed as a submicro- or microporous silica
. gel. He has disclosed numerous analogous "compounds:' These may have a simple
stoichiometric composition by chance and because of the strong association of
components can, in a sense, be classed as "compounds:' .
Some "lepidoidal" silicas described in Chapter 1 (so-called because of the physical
shape of the powder particles) belong to this class, as do many forms of so-called
"hydrated silicas" obtained by freezing solutions of silicic acid of low molecular
weight.
According to Akshinskaya et al. (369). silica gels that contain ultrapores as well
as rnesopores lose their ultrapores when heated in air at 800C or in steam at 750C.
.Porous Glass .
A highly porous form of nearly pure silica can be made with pores in the same size
ranges as many silica gels, At present one type, Vycor~ 7930, is commercially
available. First, a homogeneous borosilicate glass is made at high temperature. Then
the glass is held at a lower temperature at which two immiscible liquid phases begin
to separate. By careful control 'of composition, the amounts of the two phases can be
obtained in a suitable ratio so that they begin to separate as mutually interpenetrating networks. As the two phases become coarser in structure with time, the system
can be solidified at any stage to stop the process. The boron-rich glass phase is
dissolved out in strong acid leaving a silica-rich highly porous glass (371). It is not
usually referred to as "silica gel" since that term normally indicates a porous silica
that has been formed by gelling a silica sol and thus consists of a network of
contiguous particles.'
Vycor@ 7930 consists of 96.3% sto, 2.95% s.o, 0.04% RzOa) and RO z. The
density is 1.5 g cm -a, void space 28%, average pore diameter 4 nrn, specific surface
area 200 m Z g-l, and modulus of rupture 6000 psi. The structure as, revealed in
electron micrographs is shown in' a summary paper by Elmer and Nordberg et a1.
(372). A bibliography is also given.
Specific Adsorbents
The preparation of "specific adsorbents" having a special affinity for certain
molecules was first described by Dickey (373) and also discussed by Pauling (374).
S52
These materials were silica gels which preferentially adsorbed a t>articular dyestuff
in the series methyl. ethyl, n-propyl. and a-butyl orange:
\
-t::
j
; '.
.! i
where R is one of the alkyl groups mentioned. Bernhard (375) verified Dickey's
observations. The silica gel is first prepared from sodium silicate and acid in the
presence of the particular dyestuff to be adsorbed. It is then air-dried, pulverized,
and extracted with methanol for several days to remove all of the 'extractable dyestuff. The gel made in the presence of a given dyestuff had a greater adsorptive
power for that particular dye than a control gel made in the absence of dye. The
adsorption of the dye on the silica apparently depends on cationic centers in the dye
molecule, such as the dialkylammonium group, and the specificity of the gels has
been shown to depend on the constitution on the diaJkyl amino group.
Under the conditions of gelling and drying which were employed, the polymerization of the silica apparently leads to the formation of a silica gel surface with a configuration which is molded around the dye molecule originally present. so that the
surface thereafter exhibits specific adsorptive power for a molecule of that type. This
implies that the particles making up this type of gel structure have to be of
molecular dimensions. . .
. The separation of optical antipodes of camphorsulfonic acid and of mandelic acid
has been reportedly achieved by means of specially prepared silica gel, according to
Curti and Colombo (376). The gel was prepared by adjusting the pH of 30 ml sodium silicate (of specific gravity 1.4 and having a ratio of NazO:SiOz of 3.34,\
which 2 grams of o-camphorsulfonic acid has been dissolved) to 4 and diluting with
250 ml of water. The acid was then extracted with methanol. and a mixture of OLcamphorsulfonic 'acid was chromatographed on this gel. The eluate showed a levorotatory activity, indicating that the gel adsorbed the D-camphorsulfonic acid. Some
separation of nt-mandelic acid by a similar method was claimed.
The experimental difficulty with silica gels of this type is that in aqueous suspension they continue to undergo rearrangement of structure, with loss of specific surface area. Also, unless the gel is carefully analyzed for the organic compound
present during its formation, there remains some doubt as to whether the agent is
completely extracted prior to the test for selectivity. However, in this case it would
seem to be relatively certain that the optical activity of the eluate was not due to any
organic residue left in the gel. since the eluate exhibited levorotatory activity,
whereas the dextrorotatory compound was initially used in the preparation of
the gel.
Dickey (377) carried out further work on gels made to specifically adsorb methyl
orange. In forming the gel in the presence of the dye, it was essential the pH,
temperature. and salt content all be low. Some of the dye could not be extracted
from the dried gel. This raises the question whether the specific adsorption later
observed was due to residual dye molecules. Haldeman and Emmett (378) examined
specific adsorbtive silicas after aging for a year at room temperature and found
specificity slowly decreased.
Work by Beckett and Anderson (379, 380) using quinine appeared to confirm the
.
; Powders
Silica Gels
. dyestuff
Dickey's
id in the
.lverized,
ible dyeIsorptive
dye. The
1 the dye
gels has
ymerizah a conthat the
'pe, This
o be of
elic acid
rding to
;0 .. ' of
3.. in
ing 'with
e of DL-
.Ievoro1. Some
suspeniiic surnpound
agent is
t would
e to any
activity,
.tion of
methyl
he pH,
.tractcd
>n later
arnined
un Ie
..
irm the
'
."
'
-;...._ ....
553
phenomenon of specific adsorption. Since 1957, a few studies, in Europe d'nd Russia,
continued to be published. Positive results in Poland were observed with silicas
precipitated with picolines, pyridine, quinoline, and acridine (381). However, the
possibility was raised by Vysotskii, Divnich, and Polyakov (382) that the dye which
remains in nonextractable form is not near the surface but within the silica and cannot contribute to specific adsorption. It was concluded the specificity is "footprinted" into the structure of the surface of the primary silica particles as the gel is
dried in contact with the "forming agent," which is then removed (383).
An unusual claim by Patrikeev (384) is that silica gel subjected to surface orientation in the presence' of certain microorganisms later accelerated the growth of that
and certain other organisms. (It might be difficult to prove that some beneficial
organic matter was not adsorbed and carried over.).
Successful demonstrations of silica gels specifically adapted to adsorb various
'types of molecules continue to be" described: hormones (385); a wide variety of
organic bases and their isomers (386, 387); and even enzymes (388). '
An improved method of making specific adsorbents was described by Kanibolotskii et al. (389). Not only sols and gels but also aerogels can .be used as the
source of silica. Also, the "imprinted" gels retain specificity even after being heated
to 250C (390). The adsorption of propyl orange on a gel prepared with this dye
present and then removed was 20-30 times greater than on a control gel. Reviews of
thls subject have' been published from time to time (391-394). The nature of the
'''impreSsion'' or ..footprint" lett on the silica surface by the molecule which is to be
, specifically adsorbed bas been investigated. Bartels (395) concluded from X-ray diffraction studies that silica formed by polymerizing silicic acid in the presence of
1,1 O-phenanthroline (which.was later removed) had a "geometrically restricted 2dimensional structure" 'that. can adsorb the' printing molecule specifically. However,
a two-dimensionalstructure is formed when silica polymerizes in the presence of
many organic bases; that is', Ilakelike particles are formed. The specificity is thus not
, necessariy related to the shape, but rather to the nature of the surface. Also,
, Kanabolotskiietal, (396) concluded that, in some cases, the adsorbent which proved
to be highly specific did not differ in texture from ordinary gels. '
Bartels (387) concluded from studies involving a number of organic bases that the
"footprint" consisted of a "2-dimensional arrangement of signs. ":
.
By comparing' adsorption of different molecules resembling the "printing"
molecule, conclusions can be reached about steric factors in 'specific adsorption
(397). There is the possibility thatthe printing molecules which cannot be removed
by solvents are not buried within silica as Vysotskii, Divnich, and Polykov (382) supposed, but are bound through stable Si-C bonds. Strelko, Kanabolotskii, and
.Vysotskii (398) later found that when silica gels dry in the presence of organic matter, the shrinking of the gel ruptures Si-O-Si bonds, leaving free radicals' which can
create Si-C bonds .. This may seem' surprising until it is remembered that silica
covered with Si-R groups, where R is a hydrocarbon group, can be made simply by
grinding silica in' a hydrocarbon. However, even if the "f60tprint" consists of
chemically bonded molecules, it seems unlikely that these could exert such a specific
attraction for only their ownkind.
In summary. the phenomenon of specific adsorption on gels made in the presence
.,
--_.
554
of 'the material to be adsorbed is a real phenomenon, but little is known about the
"footprints."
PRECIPITATED SILICA POWDERS

Consideration is given here only to silica powders that consist of aggregates of ultimate particles of colloidal dimensions that have not at any point existed as macro,
scopic gel during the preparation. This is a purely arbitrary distinction, but serves to
separate the voluminous literature on silica gel in massive, granular, or pulverized
form, from that on all the other types of fine silica powders made by precipitation
from the gas phase and from solution. '- .
Broadly speaking, precipitated silica powders differ from gels that have been pulverized in having a more open structure, that is, a higher specific pore volume. Both
consist of aggregates of particles of colloidal size, but generally the structure of gels
, has been compressed as it was dried.' Aerogels are an exception and, when pulverized, may be difficult to distinguish from some precipitated silicas but, nevertheless, have been included under gels. ' , .
-The terminology is questionable in the case of silica particles larger than about 50
nmwhich, when concentrated and dried from water below pH 7, gives a relatively
soft cake not readily classified as a gel or a powder. Alexander (399) observed that if
no salts or smaller particles are present, the coalescence factor is less than 5%.
~
. l
. SiJici Precipitated from Sodium Silicate Solution

. There is a close relaiion between formation of silica' gel and of precipitate. In
precipitation, the silica concentration is lower and the particles are brought together
into aggregates by forces of coagulation. In the absence of a coagulant, silica is not
precipitatedfrom solution at any pH.
As shown in Chapters' 3 and 4, in acidic solution silicic acid polymerizes to
extremely small particles which chain together to form a network of gel throughout
the water. At low concentrations, this may collect into weak gelatinous masses, but
otherwise fills the whole volume. In alkaline solution silica polymerizes to discrete
colloidal particles which grow in size to larger than 4-5 nm and remain as a stable
sol. If a solution of silicic acid free from salts is suddenly made alkaline to pH 7-8
with ammonia or dilute sodium hydroxide, a thin gel may first form, or the solution
may thicken, but it soon thins out again as the fine gel network disintegrates and
larger colloidal particles are' formed. If the concentration is above some critical
value, the gel may remain and coarsen in structure, but no precipitation occurs.
Barby (400) has defined "precipitated silica" as "a dry silica with no long or short
distance characteristic structure." This is based on the fact that in a gel each particle
bears a certain average geometric relationship to the surrounding particles; that is,
'all parts of a gel are similar in structure. This is probably not true of a precipitate.
However, the silicas now to be considered are categorized on the basis of the process
'
..
and Powders
n about the
{--'
- ..l.
s:
555
by which they were made, with no attempt to define their structjlre except as
apparent from their properties. According to Weiser (401) the only difference
between a precipitate and a gel is that a precipitate encloses only part of the liquid in
which it is formed. .
~ 1':.
,~j
.~
ates of ultl-.
:l as macro.ut serves to
~ pulverized
recipitation
about 50
a relatively
.rved that if
15%.
cipitate, In
.ht together
silica is not
'rnerizes to
throughout
nasses, but.
to discrete
as a stable
to pH 7-8 .
he solution
:grates and
me critical
xurs.
ng or short
.ch particle
es: that is.
)n. 'tate.
the I'l0cesS
I ' .....
.: Silica Coagulated with Sodium Ions

,
-e been pulilume Both

:ture of gels
when pult. neverthe10
......
,,- ..
When silica particles are present in hot suspension at pH 9-10, they arc: coagulated
when the concentration of sodium ion exceeds about 0.3 N.
In a solution .of sodium silicate with the commonly used ratio 3.3 Si0 2 :Nai it
.happens that the sodium ion normality is 0.1 C, where C is the silica concentration in
grams per 100 ml. .
These simple facts are the basis of many precipitation processes for silica. They all
involve neutralizing sodium silicate solution with an acid so that colloidal particles
will grow in weakly alkaline solu tion and be flocculated by the sodium ions of the
resulting soluble sodium salt. However. there is the further factor' of reinforcement
or strengthening of the aggregate structure that must also be taken into account.
For uses where silica is to be dispersed in a polymer to give reinforcement or in a
liquid to thicken it. precipitated silicas must be made so as to be easily disintegrated
and dispersed to single ultimate particles or very small clusters of colloidal dimensions. As made. the precipitated aggregates must be relatively large so as to be easily
washed and dried. However, the structure within the aggregates must be open. and
highly porous, so that when subjected to compression and shearing forces; that is,
when being milled into rubber. the structure can be easily crushed and broken down
to colloidal dimensions: ~ If the ultimate silica particles are close-packed. as in
aerogels, conventional mechanical forces cannot break them apart, at least not to
. fragments much smaller.than 500 nm.: .
.
The shrinkage forces during drying have been discussed in the foregoing section
on gels. The same forces operate while precipitates are being dried. To obtain a
mechanically dispersible fine silica, the aggregates forming the precipitate must not
be excessively compressed by surface tension forces. even locally on a microscopic
scale. In this case, the requirements hi a precipitate to be dried from water are as
follows:
. ' ..
, 1. Ultimate particles .should be larger than about 15 nm in diameter, more commonly 20-30 nm.
2. The particles should be coalesced or reinforced to such degree that the aggregate
structure will not collapse during drying.
The lower limit of ultimate particle size is simply because smaller particles are
accompanied by smaller pores. With smaller pores. the aggregates must be more
highly reinforced or coalesced to withstand the shrinkage. forces. However. with
excessive reinforcement, the structure becomes too strong and is not easily dispersed
by milling. In the case of 10-15 om particles, if the precipitate is dried from a liquid
with lower surface tension than that of water. then the aggregates need not be so
.. .
..,.
--
. ~~ .
.. :. ~
, ~ .. ~
, 'i
. ..
. -'~
strongly reinforced and the product remains dispersible. However, 'even when
washed and dried from propanol, precipitates with specific surface areas much
greater than 300 m2 g-1 (particles smaller than about 10 nm diameter) still shrink
excessively and are not readily dispersible as useful fillers.
Most of the precipitation processes have simply involved partial neutralization of
a sodium silicate solution in the presence of a 'soluble salt to cause coagulation \;::-.
Purely empirical procedures are described in dozens of patents, but the three funda:-- : . mental steps in the formation of useful products were not generally upderstood.
These were first appreciated and disclosed in patents but not in the scientific literature.
-As represented in Figure 5.23, the three basic steps are similar to those involved in
formation of gels but take place under different conditions:
;
j
..
!-
S56
",
'":...--
'
1. Forming and growing colloidal particles.

.2. Coagulating particles into aggregates forming a suspended precipitate.
3. Reinforcing the aggregates.
His remarkable that' precipitated silicas of such widely different structures and
properties can be made simply by mixing acid and sodium silicate in different ways
. at suitable times and temperatures. It requires knowledge of the reaction conditions
in hot soluti~~, t.hat lead to the following results:
. --
of particles.
1. Nucleation
.
..
2. Growth of particles to desired size.
3. Coagulation to form aggregates by control of pH and Na + ion concentration.
4. Reinforcement of theaggregate structure to the desired degree without further
nucleation.
~" '.
o
'1
': ~! ~
': -,
i
.(
.
"
: i-,
,
I::
. _
. To obtain a' final product with larger ultimate particles, before the particles are
aggregated, it may be desirable to increase their size beyond that reached by spontaneous Ostwald ripening which is around 5 nm at 25C and 10 nm at 80-100C.
Ways of growing discrete particles have been described in Chapter 4 and the
procedure when making silica from acid and sodium silicate was particularly discussed (402):- This or another equivalent procedure is needed as an intermediate step
prior to aggregation and structural reinforcement if the final product is to have a
,particle size much larger than 12-15 nm.
Coagulation may also be brought about by adding small amounts of polyvalent
metal salt; for example, calcium, or by temporarily lowering the pH to a point of
;" minimum stability of the sol, for example, to a pH between 5 and' 8. However,
aggregation at a pH between 8 and 11 is usually brought about by carrying out the
- process in the presence of sodium salt formed from the silicate..
-..: Once the aggregates of particles of desired size are produced, usually in the form
of a flocculent precipitate, "active silica" is added to the suspension to reinforce the
: aggregates. "Active silica" is defined by Rule (403) as any silica in molecular or
colloidal aqueous solution in such a state of polymerization that, when diluted with
'-..
..
md Powders
"
1
..~
':..-_.
precipitated Silica Powders
55'
-~
" ;
..
even when
lre~" much
st.
rink
Silica Sols
"-
.,:~
. .:<.{
"---
alization of
.oagulation,
hree funda-:
e e- e
S e ee
Coagulate
~"
-.
(lower charge)
-~
mderstood.
itific Iitera-
-"i
"
,-
involved in
:.
Sodium Silicate
..
..
Coagulated Silica
Slurry
ictures and
ferent ways
1 conditions
acid
Accretion by adding
'''active'' silica
Slurry of Reinforced, Reticulated Silica

Figure 5.23.- Process of reinforcing silica aggregates; spheres represent silica particles. [ller
- (2). by permission of Cornell University Press.]
,ration.
out further
articles are
:d by spon- 80-IOOC.
4 and the
cularly disiediate step
; to have a
polyvalent
a point of
, However,
ing out the
n the form
'e the
olec'...r or
:iluted with
.in
sodium hydroxide to a pH of about 12 and a SiOz concentration of about 0.2% by

weight at 30C. in _the absence of cations other than sodium. the silica will
de polymerize to monomer -in not more than 10 min. The amount of monomer
formed at any given time is determined by the formation of silicomolybdic acid
which is determined colorimetrically.
Active silica is prepared by adding dilute solutions of sodium silicate and acid
directly to the suspension of the silica aggregates in such proportions as to liberate
the active silica while maintaining the suspension in an alkaline condition at more
than 60C.. In the presence of hydroxyl ion as catalyst. the active silica that is added
to the system accretes to the surface of the silica aggregates. The pH of the suspension during this process is between 8 and 11.
The amount of "reinforcement" of the silica aggregate is characterized by the
"buildup ratio," which is defined as the final weight of silica in the system. divided
by the weight of the aggregated silica in the suspension at the beginning of the reaction. Thus with a buildup ratio of 3: I. an aggregate of 5 millimicron particles will be
converted to a "reinforced" _aggregate structure consisting of reticulated particles
about 7 millimicrons in diameter. A buildup ratio of less than 4: I is usually preferred. since it is ordinarily not desirable to cement together the ultimate silica particles
in the aggregate to suchan extent that they cannot later be'broken apart when the
final 'product is milled into rubber. for example.
In the reinforcement step the acid and silicate should be added at such a controlled rate that the liberated "active" or low molecular weight silica polymerizes on
.,
558
the suspended silica and does not form new particles. This is determined by follow.
ing the specific surface area of the silica in the system, an increase indicating that
the active silica is being added too rapidly and that new nuclei are being formed. A
typical addition rate is 10 grams active silica per hour per 1000 m S of silica surface
in the suspension.
1\1'
~ 1
-'
,I
SEPARATELY CONTROLLED PARTICLE. FORMATION AND AGGREGATE REINFORCE_

MENT. A process of this type was first described by Alexander, Her, and Wolter
(271). Since it has been described only in patents, details are given here. .
First, a sol of 5-7 nm particles was made as follows: 425 parts of a sodium silicate
solution containing 2.39 grams SiOs per 100 rnl, having a molar SiOs:NasO ratio of
-3.25, was heated to 35C and stirred intensively while 162 parts of 2.4% HsSO. solution was added uniformy over a period of 30 min to neutralize about 80% of the
alkali and bring the pH down to 9.7 :f:: -0.2 measured at 25C. This clear sol was
heated to 95C in IS min to grow the particles to a diameter of 5-7 nm. The alkali
released from tbe diminishing silica surface increased the pH of the sol to 10.1.
Then 85.4 parts of a solution of. sodium silicate (13.22 g SiOs per 100 cm 3 ) and
about 95 parts of acid solution (4.65% HsSO.) were added slowly and
simultaneously to the rapidly stirred solution over a 2 hr period. These proportions
maintained the pH at 10.3 :f:: 0.2. The temperature was kept at 95C.. The sodium
ion concentration increased to about 0.27 N and the alkali was about 80% neutralized. During this operation the silia was precipitated and the rest of the silica
deposited upon the precipitate. Then about 32 parts of the acid solution was added
over 20 min to reduce the pH to 5.
After aging the solution at 90C for 4 hr, samples of silica were filtered off and
dried. The specific surface area of the silica was 335 mS g-l.and the coalescence factor was 45%; tests' showed'that the aggregates consisted ofultimate, nonporous, 10
nm particles.
The main product was filtered off, after adding 0.2% cetyltrimethylammonium
bromide based on SiOs to improve flocculation, then washed with acetone and drid
at ordinary temperature. This powder was light and soft with a surface area of 335
m2 g-l, had a linseed oil absorption of 476 ml per 100 grams, a bulk density of 0.12
g ern -3, and was readily dispersible in oil. From the oil absorption test it can be concluded that the specific pore volume is at least 2 em" g-I and in that respect exceeds
some commercial aerogels.
A more practical precipitated silica of lower surface area that can be dried from
- water, yet retains an open structure with easy dispersibility, is described in detail in
another patent to Alexander et aI. (271). The main difference from the above is that
the initial sol was made in a more concentrated solution: 123 part of sodium silicate
solution containing 3.71 grams SiOs per 100 em! was heated to 90C, and 10.1 parts
13% H 2SO. solution was added in 30 min. Then added simultaneously over a 2 hr
period were 119 parts of sodium silicate solution containing 8 grams SiOs per 100
ern" and III parts 3.11 % HzSO. solution. At the end of the r~action more acid was
added to reduce the pH to 7. To the product slurry, 3 parts of 1% cetyltrimethylammonium bromide solution was added to aid filtration. The recovered wet silica was
washed to remove salt, the pH adjusted to 8, and the silica dried at 110C. This
.,
:d Powders
by followati"~ that
.or. 1. A
ca surface
:INFORCE-
id Wolter
m silicate
o ratio of
$04 solu)% of the
ir sol was
rhe"alkali
0.1.
em") and
iwly and
oportions
ie sodium
80% neuthe silica
'a~ ided
d off and
:ence facorous, 10
nmonium
"and drid
ea of 335
ty of 0.12
n be con:t exceeds
.ied from
detail 'in
ve is that
n silicate
0.1 parts
er a 2 hr
2 per 100
acid was
et
un-
iilic .:as
C. This
.;:}
.. 1-
~_
....
SS9
product had a surface area of 132 m 2 g-I, oil absorption of 207 ern! pet' 100 grams,
bulk density 0.22 g cm- 3 , ultimate particles about 20 nm in diameter, and a coaiescence factor of 60%. It was an outstanding reinforcing agent in rubber. The oil
absorption indicates a specific pore volume of about 1.0 em! g-l.
"" ".: Alternate sources of the primary silica particles can be used, of course, but are
generally more expensive than those made from sodium silicate in the first part of
the process. However, to avoid sodium in the product, colloidal silica of suitable
particle size from other sources might be flocculated and precipitated, that is, with
ammonium nitrate adjusted to pH 9-10 with ammonium hydroxide, and' reinforced
with sodium-free silicic acid made by ion exchange from silicate.
, For each type of precipitated silica there is an optimum degree"of reinforcement
for maximum dispersibility. Obviously, the reinforcement should not be carried
farther than necessary to prevent collapse of the aggregate structure during drying.
Another modification of the process used CO, as the acid. In this case, CO 2 was
fed into a solution of .3.25 ratio silicate containing 3.5% Si02 with a sodium normality of 0.35 at 95C for 40 min until the CO,: Na,O ratio was 1.2 and the pH was
10. It is interesting that under these conditions 16 nm particles were produced as a
sol. The sodium ion concentration required to cause coagulation is not quite
constant, but increases somewhat with particle size. Coagulation and reinforcement
were then effected by continuing COl addition along with the addition of sodium silicate solution to a buildup ratio of 4: 1. The product consisted of highly coalesced
particles about 26 nm in diameter measured by electron micrographs, with a coalescence factor of 70% and a BET area of 60 m 2 g-l. It was easily milled into rubber
and gave outstanding tensile and tear strengths and high modulus.
The method of isolating the reinforced silica aggregates is important. When the
specific surface area of the final product is less than about 700 m' g-I, the silica may
be recovered by filtration and drying the water out the filter cake. On the other
hand, when the specific' surface area of the producr is greater than about 200 m 2 g-I,
it is preferred to displace the ",ater by a liquid such as an alcohol or ketone, so that
the structure is not so strongly collapsed or densified during drying. A process for
making dispersible' silica with a higher surface area has been described by
Alexander, Broge, and lIer (273).
A somewhat similar process for making bulky adsorbent silica gel was patented
by Marotta (404), who first generated microgel from acid and silicate below pH 6
and below" 50C, . and then reinforced this by adding more silicate and acid at
70-95C. A high surface area of 300-600 m' g-1 was maintained along with high
porosity and low density (0.5-1.0 ern! g-t, 3-7 lb ft-3). Further modifications and
improvements in this general approach have been described in several patents and
publications (405-412). "
There is some suggestion that instead of operating in hot solution, somewhat
similar results may be obtained at ordinary temperature by pausing after partly neutralizing the sodium silicate solution to give the particles time to form, aggregate,
and coalesce. Thus Wason and Van der Heem (413) claim a~ silica having a surface
area of 100 in.' g-1 and oil absorption of 170 ern" per 100 em" by acidifying a solu"tion of sodium silicate at ordinary temperature to the onset of precipitation and then
letting it age 15 min before completing neutralization to pH 5.8. A similar idea is
.,
~--
~H
f
",'
disclosed by Denner, Baudru, and Coudurier (414), who stop acid addition when the
ratio of SiOz:NazO is in the range 5.5-7.0, and then proceed at a rate prescribed by
a formula. A precipitated silica is obtained with a surface area of 100-600 m Z g-I
which does not change on drying.
In still another instance. a precipated silica having low density properties similar
to an aerogel and very stable toward sintering at up to 1000C was described by
Aboutboul, Kreekler, and Kirch (415). A solution of sodium silicate containing 10.8%
SiOz and 1.08 N in alkali was cooled to SoC. and 40% of the alkali was slowly neutralized in 1 hr with 12.75% HzSO. The silicate had a ratio of SiO,: Na,O of 3.25
and thus the acid was sufficient at this point to raise the ratio to 5.4. Thus most of
. the silica must have been converted to the colloidal state. The neutralization was
then completed in another 45 min to obtain the silica as a precipitate. In this way
-. formation of massive gel was avoided. The particles were then grown and internally
'consolidated by heating for 3 hr at 95C, washed with water, then with concentrated
NH.NO, solution to ion-exchange out residual sodium, then with acetone to remove
free water to less than I%, and the acetone was then removed by distillation. The
powder had a surface area of 268 m t g-I, pore volume of 2.52 em! g-I. and average
pore diameter of 365 A, and it remained unchanged after 3 hr at 983C.
This has been discussed in detail because -it appears to be a way to making wide-pored. low density silica that is an alternative to neutralization in hot solution, and
can be carried out at higher silica concentration.
Particle growth and coagulation only. without a special reinforcing step, give a
fine soft powder provided the ultimate particles are so large that the accompanying
pores are also large enough for the shrinkage forces during drying to be too weak to
.cornpact the mass. Thus in an earlier patent by Alexander, Her, and Wolter (416),
colloidal particles were grown to 37 nm in diameter, by reacting silicate and acid in
hot solution while keeping die sodium ion concentration between 0.2 and 0.27 at pH
9.5-10.3. The particles were then coagulated by adding sufficient dilute calcium
chloride solution, filtered off, washed, and dried. The soft powder was dispersible in
rubber but was not as good a reinforcing agent as when the particles were first
formed into suitably reinforced aggregates before being dried.
Coagulation by Adding Sodium or Ammonium Salts
':
There are many patents disclosing combinations of acids with additional sodium
salts, or ammonium salts that act both as acids and salts. Often there is additional
free ammonia. When the reactions occur at ordinary temperature there seems little
doubt that the precipitates consist of microscopic particles of microporous silica
gels. These are of little use as dispersible fillers, but find many other applications.
When the reactions are carried out in hot solutions quite different products are
-formed and. in this case,some readily dispersible materials appear to be obtained.
: Arsem and Wright (417) produced finely divided silica by reacting sodium silicate
with ammonium chloride, boiling the mixture to form "silicic acid" (whereby
ammonia was evolved), and filtering and drying the resulting product. The product
-'contained 15% of combined water when dried at 100C, indicating that it must have
been fine microporous silica gel. "Heuser (418) made a precipitated silica gel having
~'--
-~
; and Powders
ion when the

>resrribed by
l-t.
11 g-I
'
...
erties similar
described by
aining 10.8%
) slowly neu~a20 of 3.25
~hus most of
ilization was
In this way
nd internally
::oncentrated
ie to remove
illation. The
and average
laking wideiolution, and.
step, give a
:co~- "1anying
tc
eak to
Volter (416),
: and acid in
:i 0.27 at pH
lute calcium
lispersible in
:s were first
mal sodium
is additional
: seems little
iorous silica
applications.
xoducts are
obtained.
Hum silicate
I" (whereby
n -rcduct
it f. ~t have
a gel having
.,
~-_.
561
large pores, so that it will absorb 100% or more of its weight of water from air saturated with moisture, by reacting sodium silicate and an ammonium salt under
, specified conditions at ordinary temperature. The silica gel particles are spherical
and range from 0.5 to 5 microns, with a bulk density of 10-15 lb ft-'.
Silica may also be obtained as a precipitate instead of a gel by reacting sodium
silicate with a sodium salt such as sodium sulfate, then acidifying the gel and washing. The gel made in this way (419) was obtained as a mass of granules, each of
which is like a sponge containing ultramicroscopic pores. A similar pr~cess operated
in hot solution was disclosed by Wason (420). The use of sodium bicarbonate for this
purpose is patented by Craig and Kirkham (421).
Simultaneous neutralization of sodium silicate and precipitation of silica with
ammonium salt is characteristic of another group of processes. Acker and Sanchez
(422) made a 5% sol of silica in ammonia bypassing a solution of sodium silicate
through an, ammonium "ion-exchange resin, ,then, coagulated the silica with a
concentrated .ammonium salt solution at pH 8-9.5 and heat-aged it 4 hr. This
produced a high purity precipitated silica with an area of 414 m l g-I, pore volume of
, 1.46 em! g~I,cand pore diameter of 141 A.. ,
The effect of NH.CI and NaCI in coagulating silicic acid and influencing reinforcing properties in rubber has been investigated by Dering et a1. (423). Coarse
agglomerated silica of particle size 100 microns, pore volume 1.75cm' g-I, and area
43 m t g-1 was made by Acker and Winyall (424) by neutralizing concentrated
sodium silicate solution; they added rather concentrated ammonia, acetic acid, and
ammonium acetate in specified amounts in succession and heated the mixture to
90C for 1 hr, then washed with ammonium carbonate solution to remove adsorbed
.sodlum,"
't
,;,,':';;'
.~~.
In another modification (425) concentrated ammonia was added .as a coacervating

agent for the silicateand then the silicate was partly neutralized to pH 10.6-11.2 and
precipitated, filtered and washed with acid, washed, dried, and pulverized. In this
case, there was 'no'aging or. heating period, which probably explains the high surface
area of 449 m t g-I. The particles (probably porous microgel) are 50-75 nm in size
and the pore volume 2.4 em! g-I, which explains the low bulk density of only 0.06
g cm-'.
This exemplifies the possibility of forming porous microgel particles which
themselves are of colloidal dimensions that do not shrink on drying. However, it is
reasonably certain' that in some cases the rnicrogel particles retain microporosity
during drying, thus giving a dual pore system.
Under certain conditions, however, the micropores may be closed or reduced in
size so that the BET nitrogen adsorption method measures only the exterior surface
of the microgel particles. Such a product may thus have a low specific area especially when the process is conducted hot and the precipitate aged at high pH, as done
by Acker and Winyall (424). '
Coagulation with Calcium, Polyvalent Metal Ions

This is the basis of an important class of precipitated silicas. Boss (426) described
the development of two siliceous products which assumed commercial importance as
I,
iI
562
Silica Gels and POwder{;'::

-:-'
~....
,,~;-.
~'
"
1"
reinforcing fillers in elastomers and plastics. The first, Silenes, is a very finely divided'I
'calcium silicate made by precipitating a 3.3 ratio sodium silicate with calcium chloride .:.
, under very carefully controlled conditions.' Boss pointed out that the somewhat
alkaline -ultimate particles, 35 millimicrons in diameter, tended to form aggregates
, , upon being dried, making it difficult to disperse the product in rubber. Coating the .. '.'
individual particles to prevent aggregation was out of the question because of the Cost
.
of applying enough organic material to cover the surface even with a monomolecular '.,
, layer. However. the problem was solved by the use of an unidentified additi.ve.Follo w_
ing this development. a wet process was then devised, for producing a slightly
hydrated. finely divided silica. of relatively low alkalinity and with excellent dispersion'
characteristics. This product, Hi-Sils, has a particle size of 25 millimicrons. Newer,
im proved versions of still smaller particle size have since been developed. According
to Allen (427) a superior silica filler is made by precipitating calcium silicate, treating
this with NH.CI to form CaCI,. and steaming out the ammonia. Streams of 3.3 ratio
sodium silicate solution and CaClrNaCI solution are mixed through a centrifugal
pump, NH.CI added, and the mixture boiled 4 hr to remove NH 3 , then digested with
HCI at 30C for 16 hr, filtered, washed, and dried. It is the alkaline boiling step at
which the final silica structure is established.
. ,
,,<
"
.l] ;.
".'
;'1
"
I: i
. Coagulation with Organic M aterials '

Coagulation in the soluble silicate-acid system can occur in different ways with dif.ferent added materials:'
I. Water-miscible solvents such as acetone at high pH coagulate sodium silicate,
precipitating it as a splid or semiliquid coacervate, which can be reacted with
acid.
2. Organic cationic compounds that are polymeric or are surface-active by having
large hydrocarbon groups attached can coagulate silicate ions and silica particles
over a wide pH range.
3. Polar organic compounds that are polymeric, for example, polyethylene oxide,
combine with silica at low pH through hydrogen bonding, forming precipitates.
4. Low molecular weight, water-soluble polar' compounds, for example, propanol
triethyl phosphate. and dirnethylforrnamide, combine with silica at low pH and
are precipitated by adding soluble salts.
'
In all cases, if the pH is less than about II. the silica polymerizes to form finely
divided silica which can be separated from the coagulant. ,
As SILICA. In acid solution colloidal particles of silica are flocculated by polymeric
hydrogen-bonding agents. A wide range of polymers including polyvinyl alcohol
have been mixed with the aqueous medium before or after, precipitation to obtain
fine silica from solution at low pH (428). Long-chain aliphatic amines coagulate
colloidal silica to give a soft powder (429). Cationic surfactants are adsorbed on the
, silica surface and, promote coagulation. This was used by Chiola, Ritsko, and
, -:...--d Powders .
.Iy divided
n ct-I'lride
SOl.
aat
iggregates
eating the
)f"the cost
molecular
e. Follow.
a slightly
Iispersion
s. Newer,
\ccording
:, treating
f 3.3 ratio
entrifugal
ested with
19 step at
Vanderpool (430) to recover fine, pure silica from the aqueous hydrcilysis or ethyl
silicate with ammonia. The product bulk density was about 0.1 g em -3.
The precipitation of silica in acid solution as a coacervate of fine liquid droplets
has been described in Chapter 4. Silica used in chromatographic columns can be
made this way (431, 432).
A sheetlike precipitated silica obtained by flocculating colloidal silica with a longchain quaternary ammonium base has already been described (433).
.~
:.'
with dif-
silicate,
cted with
563
As SILICATE BEFORE NEUTRALIZATION.. In a typical process, invented by Moyer

(434), sodium silicate solution was poured into methanol to produce a suspension of
finely divided spherical particles of sodium silicate. These were then neutralized by
reaction with acid. In this way, globular particles or silica gel about 1-2 microns in
diameter, free from sharp edges, were obtained. In another approach to making
small particles of silica gel, Kanhofer (435) mixed an alkylene polyamine with the
sodium silicate before reaction with acid. Silica gel particles from 5 to 20 microns of
unusually low density were obtained. It is probable that the polyamine acted as a
. flocculating agent and minimized gel shrinkage.
In another somewhat related process an agent that coagulates sodium silicate
solution, such as alcohol, NaCI, or NH3, is added in a quantity just sufficient to
develop turbidity by a "clustering effect" not a precipitate. According to Baker and
Austin (436), when this is suddenly acidified, silica is precipitated as particles 11-22
nrn in size with surface area 69-301 m' g-l. A product of this general type is claimed
to be an outstanding reinforcing filler in rubber.
ly having
particles
ne oxide,
iitates.
propanol
, pH and
'm finely
olymeric
l alcohol
:0 obtain
:03' -Iate
ed
'he
sko, and
Silica Precipitated rro~.~luoride Solution

.. :
Coagulation by fluoride ion at low pH is a unique phenomenon apparently unrelated
to coagulation by cations. One theory is that the SiOH surface becomes at least
partly converted to SiF groups and becomes hydrophobic. Such particles then are
flocculated by hydrophobic bonding.
There are a number of processes which involve the precipitation or silica in the
presence of fluoride ions. For example, Gewecke (437) passed silicon tetrafluoride
vapors into hot sodium carbonate solution to obtain a finely divided silica
precipitate. Alsfeld (438) prepared a highly voluminous, finely divided hydrated
silica from sodium silicate by reaction with ammonium fluoride in ammonium
hydroxide solution. Svendsen (439) covered a process for making finely divided silica
from siliceous residues by heating the silica or silicates with ammonium fluoride to
form vapors, presumably containing silicon diaminotetrafluoride, which were then
hydrolyzed in water. A product containing only 2% water and having a density or
10-14 Ib (t- 3 is plastic and will form a coherent mass which hardens on calcining. It
is transparent in oils but opaque in water and is characterized as "alpha silica." On
the other hand, by hydrolyzing the vapors at relatively low temperature in
ammoniacal solution, a more highly hydrated product is obtained which retains 7%
water at 1l0C and even 5% at 250C. In this case, the air-dried product has a
.. ----564
~,
"
f
,.
.r.
:q:
. :' fl"
:
._,.
Silica Gels and Powder~
density of 30-40 lb ft -3, and the index of refraction is lower than that of amorphous
silica, presumably because it is hydrated.
These products are probably similar to those first described by Schwarz and Liede
(440). They reported that, by hydrolyzing silicon tetrafluoride in boiling water
opaque, nongelatinous scales were formed, which, after dialyzing for 8 days:
.contained 95% water and differed little from the product obtained by hydrolyzing
SiF4 at OC as far as its appearance or rate of dehydration is concerned. However,
the chemical reactivity of the two products is entirely different. The firs! product
(called "beta silica"), made in boiling water, is made up of larger primary particles
and in solution gives a more highly polymerized polysilicate. Hydrolysis of silicon
tetrachloride at 100C gave a product showing all the properties of the "alpha"
product, which was obtained by hydrolyzing silicon tetrafluoride at OC. A related'
product called "silica fluff" was described by Jacobson (441). This material. formed
. by the hydrolysis of silicon 'tetrafluoride vapor in water, is an extremely fluffy
material, having a bulk density of only 0.0248, and is so light that it flows like water.
Its index ofrefraciion is 1.45, corresponding closely to amorphous silica. The particles
consist of microscopic flakes and contain 92.86% Si0 2 and 7.44 % water.
Nickerson and Burkert (442) hydrolyzed a 15-25% solution of H 2S iF. with
ammonia at pH 6-8 to obtain fine silica by a continuous process. According to a
similar patent to Borsos (443). silica is obtained as 30 micron hydrated particles.
Silica Precipitated from" Organic Liquids
.;
'
~
~ ,;
'r i .;
. i
:,
Silica of low bulk density,O.016 g cm- 3, and area of 300 Il}2 g-1 useful as a rubber
filler is made by precipitating silica from alcohol, generated from ethyl silicate (444).
Thus 6.8 ml of (C 2H.O)4 Si and 20 ml of concentrated NH 40H are reacted in 280 ml
of alcohol. The process is closely related to one developed by Stober (445) for making sols.
Silica Precipitated from Colloidal Silica Sols
!i
"
,.
"
I
I,. _
:
j
In all the foregoing methods, silicic acid has been polymerized more or less in the
same system in which it was then precipitated. It is. of course, possible to start with
a previously prepared sol of silica of any colloidal size and precipitate it by flocculation or coagulation to produce a dry product. However, unless special precautions
and procedures are used, the precipitate dries and shrinks to hard gel, especially if
the utlimate particles are smaller than 25-50 nm. To obtain a soft dispersible
powder either the gel must be reinforced or the surface made at least partly hydrophobic to minimize shrinkage. Flocculation or coagulation with long-chain organic
base cations has already been discussed. These tend to give voluminous flakelike
aggregates for the reasons discussed in Chapter 4 (Figure 4.21).
.,.
~---
d Powders
morphcus
silica Precipitated from Vapor: Pyrogenic Silica
an,
ede
ng water,
. 8 days,
'drolyzing
However,
t product
. particles
of silicon
: "alpha" .
A related
I, formed
ely fluffy
ke water.
: particles .
.. :.:
. ,r
liFe with
ding to a
ides.
~"
".'';''
S6S
The condensation of anyhdrous SiOz vapor probably involves different mechanism

and kinetics than the condensation of Si(OH)., which is probably formed when SiCl.
or Si(OCzH.). are hydrolyzed in a flame containing water vapor. Amelin (446)
. pointed out that ala flame temperature of 1270 0K the vapor pressure of SiOz is only
. 10-1 torr, so that there is very high-supersaturation resulting in large numbers of
small nuclei from I to 10 nm in size.
.
Ulrich (447) has further considered the factors governing particle size as
condensed from vapor and concluded that the initially formed, very small particles
assume the translational velocities of large gas molecules and that final particle size
is determined by collision and coalescence. The logarithm of final size is proportional to logarithm of growth time. This also explains why there is an increase in .
particle size with increase in silica concentration. This suggests that the final particles are likely to have a microporous structure. However, since the primary particles
. are only 10-20 A in diameter, and are closely packed, the internal pores of the final'
particles are usually impervious to nitrogen adsorption and detectable only by water
adsorption.
Barby has presented electron micrographs of silica condensed from different
vapors and compared their properties (8). The density of the particles is 2.2 g em-',
which is that of fused silica, that is, amorphous. Even though the particles are
condensed at temperatures where crystalline forms are stable, it is useless to speculate about their "crystal structure" since they no doubt have the same structure as
silica glass which also results from quenching. X-ray diffraction patterns indicate a
glassy or amorphous state.
a rubber
He (444). '
in 280 ml
for mak-
ess in the
.tart with
flocculaecautions
ecially if
spersible
y hydro1 organic
fl?' "'like
Vaporized Si0 2
Silica can be vaporized directly at extremely high temperature in a plasma jet
(448-450). When condensed in the absence of hydrogen, the powder is nonthixotropic when dispersed in an oil such as dibutyl phthalate. It was recognized that
SiOH groups on the surface of the particles are necessary to hold the particles
: together in a thixotropic network by hydrogen bonding in a relatively nonpolar liquid.
As pointed out in Chapter 4, discrete silica particles with a fully esterified surface'
free from exposed SiOH groups disperse perfectly even in hdrocarbon solvents at
high concentration with little increase in viscosity. The completely anhydrous SiOz
surface is organophilic and hydrophobic and if dispersed in water at pH 2 (to retard
sur face hydration) will, no doubt, develop some thixotropy through hydrophobic
bonding, as noted with other partly hydrophobic silica powders. An apparatus using
nitrogen as the plasma gas for vaporizing silica was patented by Houseman (451).
As described by Barby (8) inclusion of any material in the plasma gas stream
that can generate SiOH groups on the silica surface then makes the silica thixotropic
in oils. Everest, Sayee, and Shelton (452) pointed out that when the plasma
contained hydrogen or ammonia, there was some reduction, presumably to SiO,
~-_.
which is more volatile, and when this was reoxidized a product with'a very high surface area was obtained.
Oxidation olSiO Vapor
Although at very high temperature (around 2000C), silica vaporizes and the vapors
condense the finely divided silica. vaporization can be effected at much lower
temperature by having a reducing agent present so as to form SiO. which has a
sublimation point of about 1700C. Upon oxidation of the monoxide. the dioxide is
regenerated and condenses as a "fume." Potter (456) made a fine silica by bloWing I .
the monoxide vapors through a heated chamber along with an oxidizing gas. Von
.;,"
Stroh (457) patented the use of such SiO, as a rubber filler. Also, Reik and Byrns of
Permanente .(458) patented a process for making fine silica via the monoxide route,
using temperatures of only 1250-1450C.
When hydrocarbons are used as the "stabilizing liquid" in the plasma burner. even
the coarser silica particles in the feed are reduced to SiO vapor. according to Kugler.
-,."
Sins, and Silberger (453), who disclosed a burner design. A "fluid convection" electrode was described by Korman et al. (454). The so-called "arc-silicas." which
appear to be simply volatilized. are probably at least partly converted to SiO by the
carbon vapor of the arc and then reoxidized. A series of products sold as Arc Silicas~
are described as 2-3 micron clusters of 15 nm particles (455).
A process of sweeping SiO, vapor out of an arc furnace in" which sand and coke
are rea~ted and oxidizing it to SiO, of 8-28 om particle size was patented by Biegler. ~
Neugebauer. and Kempers (459). In another process (460) the sand and coke were '.
vaporized from the furnace at lSOQ-2500C. the gas mixture of CO and SiO was.
mixed with steam and. air to cool it to 3S0-400C, and the condensed silica was
separated by centrifugation. This intermediate silica was then heat treated at
200-700C in a fluidized bed. The product consisted of silica particles 5-150 nm in
size and 50-300 m' g-1 in area. with a bulk density of only 15-30 g 1-1.
A most peculiar form of fine. silica has been described by Nemetschek and Hofman (461). SiO is made by reacting Si and SiO z in a tube in vacuum at 1200C.
Between the reaction mixture and the SiO which condenses nearby. there forms after
.48 hr a mass of hollow tubes or fibers of amorphous SiD, 30-70 nm in diameter with
wall thickness of only 6-~S nm. This material eventually plugs the tube.
Oxidation and Hydrolysis 01 SiCl. Vapor
Silicon tetrachloride vapor can be either oxidized or hydrolyzed at high temperature.
SiCI. can be burned in-oxygen to yield SiO z and Clz (462). Presumably CI, could be "
recycled to make more SiCI. from lump silicon which burns in chlorine gas as easily
as coal burns in a stove.' However. simpler equipment can be used when SiCI. is
mixed with CH. and burned to produce fine SiO z and HGJ. Presumably. the latter.
could be oxidized to Cl, for recycling if economics permit.
The flame hydrolysis process was patented in 1942 by Kloepfner (463) and the \._.:.
..,.
and Powders
ery high Sur-
.
d.the vapors
much lowerwhich has a
:-te dioxide is
. by blowing
ng gas. Von
md Byrns of
oxide route,
burner, even
g to Kugler,
ection" eleccas," which
I SiO by the
; Arc Silicas
id and coke
It 'iegler,
c\.....: were
nd SiO was
j silica was
treated at
i-150 nm in
:k and Hofat 1200C.

forms after
arneter with
-_...
567
reactions studied by Wagner and Brunner (464) and Bode. Feach, a~d Fratzscher
(465). Some properties of the silica powder were reviewed by Loftman (466). who
described the industrial process. White and Duffy (467) stated that in America SiCI.
is burned in a mixture of HI and O 2 by the Godfrey L. Cabot Corporation using a
process that was developed in 1940 by Deutsche Gold-und-Silber Scheideanstalt
Vormals Roessler (Degussa). The SiCl 4 is made by chlorinating SiC .
An apparatus in which a number 'of finely divided metal oxides can be prepared
from the anhydrous chlorides (Ti, AI, Si, Fe. Zr) is described by Cuer.. Long, and
Teichner (468). The oxides can be produced as uniform particles from 10 nm to 60
microns in diameter. The use of CH4 instead of HI as the fuel was investigated by
Nikolina (469), who found that with a flame temperature of 793C the silica had a
surface area of 112 ml g-l. Bittner et al. (470) patented certain specific concentrations of reacting vapors and flow rates to the burner to obtain a high concentration
of HCI with low Cl, content to facilitate acid recovery. A cooled plug-burner to
obtain good gas premixing permits a flame temperature of 1000-1200C,to be used
while obtaining a silica of high surface area (471). On the other hand, Rum, Yun,
and Jang (472) reported that the highest area product of 160 ml g-l was obtained at
only 690C and that during post-treatment to remove HCI, the silica began to
,"crystallize" about 500C.
" The silicas made by this process are commonly known by their trademarks,
Cabosil~ in America (473) and Aerosil~ in Europe (474). Their structure has been
discussed in some detail by Barby (8), particularly in reference to the surface area
that is lost at the points of contact between the ultimate spherical particles. It was
concluded that the initially condensed particles are only about I nm in diameter and
." that these are so closely packed (high coordination number) that only a small
amount of nitrogen canpenetrate the micropores between. them. Thus the "secondary" particles are the ones that determine surface area and are commonly identified
in electron micrographs. They are the "primary" particles in the voluminous
aggregate structure and have a low coordination number of about 3. Barby's conclusions were based on studies by Gens and Keil discussed by Broekhoff and Linsen
(475).
. Extremely porous spheres of silica consisting of aggregated 25 A particles with an
area of 980 m 2 g-l was obtained by Spencer, Smith, and Cosman (476) by adsorbing
moisture on spherical pellets of carbon black, exposing the pellets to (CH)2 SiCI2
vapor at 25C, then burning out the carbon at 500C.
0
0'
Oxidation and Hydrolysis ofSilicon Ester Vapors
emperature.
:1 2 could be
tas as easily
len SiC}, is
I, the latter
S3}
the
Some finely divided silica similar to that made from SiC}. has been made from time
to time from silicon esters, especially when very high purity was desired since the
ester is easier to obtain in an extremely pure state. Gass, Juillet, and Teichner (477)
have examined the hydrolysis of butyl and methyl silicate vapors with moist nitrogen
at 950C and obtained silicas of 100 nm particle diameter. Wide variation in particle
size is, of course, possible by varying combustion conditions.
-:,.-_.
~i1ica Gels and Powders
H'ydrolysis ofSiF. Vapors
,".
f'
t'"'
Probably one of the most important developments has been the production of fine
silica powder suitable as fillers from SiF. vapor. This is a much more complicated
system than the hydrolysis of SiCl. because HF, unlike HCl, can attack the silica ,
reversing the process and forming H 2SiF. and SiF. Potentially, the large volume of
by-product SiF. from the phosphate fertilizer industry might be used for making
silica. Another practical point is that processes that use sodium silicate C,9nsume
acid and alkali and make by-product Na 2SO., which can be a disposal problem. On
the other hand, in the SiF. process the HF could theoretically be recycled to attack
sand, with no large volume by-products. Unfortunately, matters are not so simple;
recovery and concentration of HF will probably always involve consumption of
secondary chemicals, expensive equipment, and occupational hazards.
Numerous patents have been issued relating to this process involving many details
of the hydrolysis recovery and recycling steps, making it difficult to determine
which, if any, have proved to be of practical use (478-480). Heller, White, and Gunn
(481) proposed a process for reacting HF with crystalline Si02 (sand) at 120-180C
to make SiF., mixing this with oxygen and methane, burning the product in a
cooled-wall reactor, and recovering the Si02 According to Tomita (482) fluffy silica
in fiber form is obtained if steam and SiF. are allowed to react at the walls of a reactor at SOQ-800C. The fibers are typically 5 mm long and 0.5 micron in diameter,
and the mass has a density of 8 g I-I. According to "a patent application by Flemmert
(483), fine Si02 and HF are obtained from SiF. and H 20 and H 2 burned under
specified conditions. Driscoll (484) states that silica is manufactured by injecting
SiF. into a flame in a combustion chamber that he describes; the surface area of the
product is in direct proportion to the concentration of SiF. in the reaction gases.
In Sweden, a fine silica, FluosiJ<~ (485), is manufactured by reacting SiF4 with H 2
and O 2 at 1600-2200C by a process covered by several patents.
According to Smirnova et al..(486) thermodynamic calculations show that with
excess H 20 present, hydrolysis of SiF. to Si0 2 and HF can proceed to 99% conversion below 900C. The silica must be removed from the hot gas at high temperature
using ceramic filters and the HF removed from the silica by blowing air and steam
through it at 600C. Takagi and Suwa (487) reported the reaction to proceed in a
similar range of SOO-900C with H 20: SiF. ratios of 4-10. The activation energy is 13
kcal mole " and the surface area of the silica varied from 250 to 50 m2g- 1 with
increasing H 20: SiF. ratio.
The overall recovery of K2SiF. and its conversion to SiF. with excess H 2S04 was
described by Zaitsev et al. (488). Also, methods for converting SiF 4 to pure Si0 2
SiC, and Si3N 4 were outlined.
::~:
<
'1
";
NATURALLY OCCURRING SILICA POWDERS

These materials "are generally outside the scope of this book although, in some cases,
the powders have a fairly high specific surface area and at least fractions may be of
colloidal particle size. A few are mentioned as examples.
~,
Microcrystalline Hydrated Silicas
Powders
~
.
~/'-
"
Ie
1 \.
iplicated
ie silica,
>fume of
making
consume
lem. On
o attack
I simple;
ption of
y details
etermine
rd Gunn
)-180C
ret in a
fry silica
fa reaciameter,
lemmert
d ,. 1er
,nj" .1g
:a of the
sese
with Hz
tat with
converperature
d steam
eed in a
rgy is 13
~-1 with
:;0. was
re
sio,
~'"
' . ~.~
'--1
:.;
.,,:
-'!l'
569
Silica glass. formed by fusing high grade quartz sand. is ball-rnilled'to produce a
fine powder, GP-31, of which 99% is finer than 30 Slm and 21 % less than I Slm.
_ ~_..:..Obviously, a sol of colloidal amorphous silica could be made from the fines fractions
(489). As a filler in epoxy resin, it greatly reduces the thermal expansion.
Quartz particles of colloidal size can be obtained from Southern lJlinois tripoli, a
finely divided microcrystalline silica mineral (490). The mineral is "amorphous" in
the sense that the particles do not have the angular shapes of crystals. The
microcrystalIineparticles average 1-10 microns in size and were apparently derived
originally from skeletons of marine organisms. It is widely used as a low cost
extender and filler (491).
'
. An amorphous finely' divided silica having some of the characteristics of silica
aerogel occurs in Japan. It was formed by the action of natural HzSO. solution on
volcanic silicates. The amorphous character is confirmed by absence of X-ray pattern, high surface area, and solubility in 2N NaOH at lOOoe (492).
Diatomaceous earth or diatomite is a naturally occurring form of fine silica of
great Industrial importance, which,in regard to specific surface and particle size,
approaches the colloidal state, Commercial products contain particles only a few
microns in diameter, but have a characteristic finely porous skeletal structure which
.glves a specific surface area of about 20 m t g-l (493). The silica content is as high as
94%. This silica is composed of the skeletal shells of many varieties af microscopic
aquatic, single-celled algae, disklike or elongated in shape. These algae, known as '
diatoms, usually consist of single cells surrounded by two half-cell walls or valves of
transparent silica' a fcw millionths of an inch thick and made up of patterns of
chambers and lacelike partitions of extreme beauty and complexity. In live
organisms and recently form ed deposits the silica is amorphous but most of the
.- natural deposits are millions of years old and microcrystalline (see Figure 7.2).
Very finely divided aitlorphous silica containing a small amount .of carbon can be
produced by controlled' incineration of rice hulls. It is reported to be a reinforcing
filler for rubber competitive with thermal carbon blacks (494).
There is a highly siliceous alteration product of volcanic ash that is so reactive
with lime that it formed the basis of the cement used throughout the Roman empire.
I examined a sample from' the original deposit at PozzuoJi near Naples, Italy and
found it to .be a very .finely divided amorphous silica powder with a specific surface
area greater than 100 m Z g-l. This matter has been discussed in chapter 4 with
regard to the use of colloidal silica in cements.
It appears that most amorphous forms of silica that are generated in nature'
eventually crystallize to microcrystalline quartz, probably in less than a million
years, thus becoming much less soluble and reactive.
MICROCRYSTALLINE HYDRATED SILICAS
.e :
Iy
'':S.
of
Powders of this type have invariably been made from hydrated crystalline salts of
metals, mainly alkali metals or metal complexes. by removing the cations with acid.
These crystalline polysilicates have been discussed in Chapter 2 and the crystalline
I
;
570

. ' ..
".
. ..-. 'i
'
:.
". -~~
-.':
.....
:"
;"
.'
.' .-; ,.Figure 5.24. Crystalline hydrated silica. [ller (495).]
hydrated silicas in Chapter 1. Thus far they have not been much investigated and
have been of no practical interest.
When dehydrated, the crystals are subrnicroporous, being penetrated by water and
small ions. They have a layerlike structure which, in some types, expands and
contracts during ion exchange or hydration-dehydration like the layerlike clays. The
layer structures thus differ from the zeolitetype aluminosilicates, which have a rigid,
three-dimensional lattice. The unusual, extremely thin silica sheets from a synthetic
sodium polysilicate are shown in Figure 5.24 (495).
HYDROPHOBIC-ORGANOPHILIC SILICA POWDERS'

This discussion is limited to silica powders which have been surface-modified by
chemisorbed molecules that profoundly change the adsorption characteristics or
"..
Hydrophobic-Organophilic Silica Powders__
Powders
.
-
-.,
.~
..
",.
,.::.":..i
"
.',
571
dispersibility of the particles in liquid systems. Details of the surfa~e chemistry

involved are covered in Chapter 6.
Interest in hydrophobic-organophilic dispersible silicas was stimulated about midcentury by several apparent needs: (I) a non-black reinforcing rubber-filler for white
sidewall tires; (2) a thickener for oil to make lubricating grease superior to the commonly used calcium soaps; and (3) an efficient reinforcing filler for silicone rubber
then under development. Furthermore, several of the present processes for making
fine silicas were under development and surface modifications were being considered
simultaneously. '.
For various reasons, some of the hydrophobic silicas. are no longer made but
others as well as newer ones are now manufactured. However, as the cost of
hydrocarbons and the derived carbon blacks increases, there may eventually be a
renewed interest in hydrophobic silica as a partial, if not complete, replacement for
the large tonnage of carbon black now used as an essential component in rubber
tires. The problem in the past has been that investigation of organic surface treatments was not coupled with a broad investigation of particle size, degree of reticulation of the particles, and optimum coalescence for reinforcing use. Furthermore, it is
probable that different degrees of surface coverage with optimum types of organic
groups are required for each kind of elastomer.
In more recent times interest in surface-modified silicas has increased in connection with adsorbents and column packings for gas and liquid phase chromatography.
There are five types of surface modifications that have received attention:
L,. -
. .'
....
- ~
....
'.
_.~
l.!,dsorbed organic cations or polycations.
' -..
2. Adsorbed polyvalent metal ions with attached organic acid groups (metal soaps).
3. Surface silanol groups, esterified with alcohols to cover the surface with SiOR
. ' groups.:,4. Polymeric organic coatings of various types.
.
.
5. Surface silanol groups reacted with organosilicon intermediates to produce a surface of Si-O-SiR a or similar multiply bonded (SiO)zSiR z groups.
ated and
-ater and
mds and
.ays. The
e a rigid.
synthetic
'.
iified by
'istics or
It is only the last type of surface modification that has proved to be the most
widely useful, probably because of the simplicity of application and stability of the
, resulting surface.However, all approaches are reviewed briefly.
Adsorbed Organic Cations

The adsorption of organic cations, such as long-chain substituted ammonium ions,
on the surface of silica is employed in the flotation of silica from ores (496). For
example, when dodecylamine hydrochloride is. added to a suspension of finely
ground limestone containing silica, the dodecylammonium ion forms an adsorbed
layer on the silica, which thus becomes hydrophobic and floats with the froth as air
is bubbled through the mixture.
The long-chain "organic cations meet all the requirements for strong adsorption-the polar end of the molecule is positively charged and in neutral or alkaline
..
"
~-_.
sn
"
"
;'.. !
Silica Gels and Powders -
solution is attracted to the negatively charged silica surface, while at th~ same time :"._"
the hydrophobic hydrocarbon chains of the molecule tend to escape from the Water; ',,; .
and associate with each other' in the adsorbed monolayer.' Numerous processes 'J~"
employing this general principle have been patented. Thus polyethylene polyanions ""-,
mixed with long-chain acids form compounds used in this way (497). Finely divided
silica coated with organic nitrogen compounds such as long-chain amines and quatemaryammonlum compounds has been patented by lIer (498).
In using fine silica as athickener for oil to make a grease the addition .of a longchain amine (499) or quaternary ammonium cations (500. SOl) improves stability in
the presence of water. ,- -,-;:,
'A long-chain quaternary ammonium cation salt that is soluble in oil can be used"
to keep silica organophilic and hydrophobic when milled into the oil to make a
grease. Remes. Martinek. and Froncziak (502) claimed the use of the carbamate
salt: '
.'
,,>
..... - ~ -
"
ill: ji'
;t;
: 'J
. i
;'.
I
!:
"
"
where R's are hydrogen and hydrocarbon groups of 1-16 carbon atoms. at least one
of the R's on N being of the long-chain type. There is no doubt that there are many
combinations of long-chain ammonium ion salts which could be used to coat the surface of silica to make it hydrophobic. However. there are two drawbacks: the
molecular weight of this type of compound is so high that on fine silicas of 200-300
m% g-I surface area the surface-modified product has a very high content of relatively expensive organic material. The latter, furthermore, is not very stable thermally. Uses for silicas rendered hydrophobic in this way appear to remain limited.
--.,
"
i ;.
'
.
';
Adsorbed Polyvalent Metal Cations with Organic Anions
j,
!:
Stabilization of silica-thickened grease with basic aluminum 'stearate probably"

involves adsorption of the aluminum on the silica with the fatty acid anions attached
(503). Silica fillers for elastomers are improved by rendering the surface organophiJic with basic chromium complexes of the type
4+
/Cr
~O
I,
R-C
"
'j
" ' "O-H
"0/
"
Cr
'
where RCOO- is methacrylate or oleate (504). It is probable that other

organophilizing coatings of the metal-carboxylate type could be developed.
... ---d Powders
HydrophObic-OrganophiJic Silica .Powder~ _
.arne time
the Water
pi . iSes
olyaitions
ly divided
and qua-
Surface Esterification
)f a long:ability in
n be used
I make a
arbamate
least one
are many
t the surthe
2~.
300
~ of rela.ble thermited.
IC'
probably
attached
organo-
A class of hydrophobic gels and powders claimed in a patent to lIer (50S) involve the
chemical attachment of a monomolecular layer of primary or secondary alkoxy
groupS eontaining 2-18 carbon atoms to the silica surface. Since the surface is
covered by Si-OR groups analogous to the linkages in silicic esters, the products are
called estersils. The most complete.coating is applied by heating the silica with
alcohol in the absence of free water for I hr at 190C in the case of primary
alcohols, or up to 275C with secondary alcohols. For partial coatings much simpler
treatments are effective. The structure of the silica is unchanged by the esterification
of the surface, but the product becomes organophilic and hydrophobic. When a
sample of estersil is heated in oxygen at 500C to remove the coating and rehumidified over water and redried, the resulting silica cannot be distinguished from the
starting material.
For straight-chain alcohols such as a-butyl alcohol, about three ester groups are
required to cover 1 nm", This corresponds to an area covered by each butyl group of
about 30-35 At. The OR groups are chemically bound and cannot be desorbed
under high vacuum at 150C. Complete coverage of the surface is indicated by the
fact that the product will no longer adsorb methyl red dye from benzene solution,
whereas the original hydrophilic silica, with a silanol surface. adsorbs a
monomolecular layer. Estersils have been prepared from a wide variety of siliceous
materials, including aerogels, fine powders, and finely divided or fibrous silicate
minerals, after acid treatment...
The particular estersil of greatest potential use was made by first preparing a
silica sol of about 8 nm particles, gelling it at pH 5.5, reinforcing the gel structure by
further heating it 'at pH 5.5, reinforcing the gel structure by further heating or
deposition of some silica;' transferring this to n-butyl alcohol by azeotropic distillation until all water was removed, and then heating in an autoclave to complete esterification of the. surface until it was completely covered with butoxy groups and no
SiOH groups remained exposed. The dried product was an extremely soft low
density powder similar to an aerogel except that it was completely hydrophobic and
organophilic, with a specific surface area of 275-325 m t g-1 and completely dispersible in silicone elastomers, oils, inks, etc. The process is described in some detail by
Ballard et al. (506). By heating above the consolute temperature of water and nbutyl alcohol and evaporating while fractionally distilling off water, shrinkage of the
gel was avoided (507a).
.
A partly hydrophobic and organophilic silica can be made very simply by a
process patented by Goebel (507b). Fine silica powder is dehydrated and the surface
dehydroxylated to an optimum degree by heating it for 1.5 hr in air at 470-530C.
The BET area was 297 mt g-:1 but the resulting specific hydroxylated area was 184
m' g-l. When' this powder 'was cooled and refluxed at 118C in butanol at
atmospheric pressure. or even when simply exposed to butanol vapor in a closed
week, esterification occurred and the surface became about half
container for
covered with attached butoxy groups.
The n-butoxy groups on the fully esterified surface are remarkably stable (samples
it
her
573
----574
of discarded powder which had been buried in the earth for a year were *il1 dry and
dusty when uncovered on a rainy day). As a grease thickener this product proved to
have outstanding resistance to degradation by water when used in mining equipment.
However, for uses where prolonged exposure to water at high temperature is
involved, the ester type coating could not compete with one or methylsilyl groups,
which cannot be hydrolyzed..
A variety of ester groups have been explored, some of which were discussed in
Chapter 4 in connection with organosols. There are many types or SiO~ groups,
such as where R is nitroalkyl, chloroalkyl, or alkoxyalkyl (508); R contains an acidic
substituent such as mercapto, phenolic, sulfonic, phosphonic, or carbamic (509); R
contains fluorocarbon groups, for example, OCH2(CF2)IIX, where X = H or F and
n = 1-17 (510); ORN+ and ORS+, where Nand S are in the form of "onium" ions
(511); OROH groups, where R is a divalent hydrocarbon group, for example, glycol
(512); unsaturated groups (513); and amino groups (514).
Broge discovered that more methoxy groups than any other type could be packed
onto the surface (up to 5.8 nm -2) under sufficiently high temperature and pressure
under anhydrous conditions to' obtain a hydrophobic surface (515). The methoxy
estersils have subsequently received the attention or several investigators. Chertov et
al. used diazomethane as an esterifying agent (516). Baverez and Bastick found that
when the silica surface was first partly dehydroxylated at high temperature, CH,OH
reacted both with remaining SiOH groups and also appeared to open up SiOSi surfacegroups (517).
Kitahara and Asano (518) investigated the silica-methanol system up to high
temperatures and pressures and found up to 5 methoxy groups nm -2 esterified to the
surface. They also made similar studies with higher alcohols.
Pyrogenic silica can begiven an esterified surface by treatment with (C.H,O).Si
vapor at up to 300C out of contact with air using some dry ammonia as catalyst (519).
Reference should also be made to Chapters 4 and 7 regarding esterification of
colloidal silica and silica surfaces.
Organosilicon Coatings
.
An early approach to hydrophobic silica was to mix sodium methyl siliconate with
sodium silicate before acidification (520). Gels containing varying proportions of
CH 2=CH-Si groups were prepared and absorptive properties studied by Slinyakova
and Kurennaya (521). Silicone oil can be adsorbed on the silica surface and reacted
. with heat (522, 523). A monolayer coating of methylsilyl groups was applied to finely
divided silica by reaction with (CH3)2SiCI2 vapor (524) or aminosilanes (525).
Aerogels formed with organosilicon intermediates present are hydrophobic and do not
shrink when placed in water and dried, but do so when alcohol, which wets the pores,
is used (526). A coating of organosilicon polymer can be applied to silica (527.528). A
hydrophobic coating can be applied to silica in aqueous suspension by reaction with
CH,Si(OH), formed from the ethyl ester or the sodium salt (529). A silicone grease
.,\
...
nd Powders
till dry and

t proved to
eqt, ~:nt.
oerature is
lyl groups,
iscussed in
)R groups,
s an acidic
ic (509); R
{ or F and
iium" ions'
.ple, glycol
be packed
I.d pressure
e methoxy
Chertov et
found that
e, CHaOH.
SiOSi sur- .
lp
6-
ifie.
'-_.
high
the
CcH.O)cSi
a as catafication of .'
mate with
ortions of
.linyakova
td reacted
dto finely
nes (525).
md do not
the pores,
:7,528). A
cti
Nith
me c,;.ease
Hydrophobic-Organophilic Silica Powders_ _
'.
r
575
was made be replacing the water of silica gel with a water-miscible sol~ent and then
with a dimethylsiloxane type of silicone oil (530).
Numerous variations of processes for hydrophobing pyrogenic silicas by treatment
with organosilicon vapors' have been described. Alkylchlorosilanes along with
ammonia react with surface SiOH groups, as shown long ago by Kistler, who so
treated aerogels (531).. However, this probably leaves chloride residues in the
product. More recent patents cover methods of hydrophobing that leave no
unwanted residues. Pyrogenic silica can be hydrophobized by treatment with a
silizane such as RaSiNH(SiRaNH)nSiRa, where R is a Ct., alkyl group and n is 0-3.
Actually, (CHa)aSiNHSi(CHa)a, hexamethyldisilazine, is commonly used (532, 533).
It reacts with SiOH groups to give SiOSi(CHa)a on the surface and NH a. The reaction goes to completion, that is, until the silica surface is covered, in a few minutes
at ordinary temperature (534).
Another approach is to react the silica surface with HSiCla and then react the SiH
'. surface groups with ethylene or butadiene to attach alkyl groups to the surface (535).
'~.
Bueche and Oliver contacted vapors of an organophilizing silane with the freshly
made silica at 150-500C as it cooled (536). Treatment of silica with vapors of
(CHa)aSiO(CHa) and related compounds with I % of an amine catalyst such as
butylamine can be continued in a closed container for 2 weeks at ordinary temperature to obtain good surface coverage. The product is used in polysiloxane elastomers
as a reinforcing filler (537).
A thermally stable monolayer of C,H,Si a on silica was studied by Unger, Berg,
and Gallei (538). The reaction of C,H,SiCl a gave a surface of C,H,Si(CI)==, and
then the CI was hydrolyzed off. The size of pores in silica could be estimated by noting the degree to which smaller pores were blocked off by this reagent. Many similar
modifications' of silica: surfaces have been carried out in connection with
chromatographic column packings; these are summarized l~ter.
Silicas with a surface of organic surface groups have properties quite different
from those of the unmodified materials. Burwell (539) reviewed studies of silica surfaces covered with different kinds of organic groups; for example, amino groups
adsorbed copper by coordination and also adsorbed SOa and COa, as might be
anticipated for a basic amine surface. Various other types of organic groups can be
attached through carbon chainsto silicon atoms on the surface. Groups that have
. catalytic effects in homogeneous solution retain the effect when held outwardly disposed on a silica surface. Burwell says, "The silica surface provides a convenient
pegboard to which a number of different groups can be attached and it will prove
widely useful in heterogenizing homogeneous catalysts and in preparing new types of
catalysts."
Organic Polymer Coatings
Organic polymer coatings were developed by Puddington and Sirianni. Silicas were
made organophilic with polymers of polystyrene, linseed oil, and alkyd resin (540,
541). A polymer coating of the reaction product of a polyisocyanate and a polyol
..
~--
576
(glycerin) on the silicon surface was claimed by Weldes (542). A hy~rophobic

polymer of valcraldehyde is formed on the surface of silica when heated with the
aldehyde at 200C at 35 psig for 4 hr according toAcker, Sanchez. and Kramm
(543). Reaction of the surface with a carbodiimide such as cyclohexyl carbodiimide ,
C.HllN=C=NC.H u , gives an organophilic surface (544) which is probably an
isourea. Heating silica with furfural under pressure at 250C for 4 hr results in
deposition of an organophilic surface filin according to Acker (545).
.1
I:
'-'1
,!
"I"
.. !
.,
I
h:[1
r
:!
.:
SILICA GELS WITH ION-EXCHANGE SURFACES

The pure silica surface is so weakly acidic that there is only a minor degree of
exchange of monovalent cations for hydrogen ions of the SiOH surface groups in
neutral solution. Also. ion exchange involving polyvalent metal ions is complicated
by the formation of covalent bonds between the metal atoms and the oxygen atoms
of the SiOH surface groups so that reversible exchange is impeded or impossible, as"
when ions such as Cu 2 + or Co2+ are adsorbed .
,The surface is converted to a much more acidic condition with cation-exchange
capacity of the order of one cationic charge per square nanometer by treating the gel
or powder with NaAI02 solution at pH 9-10. Aluminosilicate sites are formed in
which the aluminum atom is coordinated with four oxygen atoms, as is silicon, leaving a negative charge:
,,~J
.-O-Si-OH
.~
,!
--_t
NaAIO t
-O-AI-'OH Nam
.\
,'}
The ion-exchange arid catalytic properties of the aluminosilicate sites in H + form

are further considered in Chapter 6. So-called "synthetic zeolites"-gels made by
reacting sodium silicate and aluminate-left in the sodium form were used for water
but are unstable at low pH and are not generally useful for cation exchange.
More stable silica-based exchangers fall into two classes: inorganic surface modifications and organosilicon modifications where the surface is covered with organic
ion-exchange groups held on the surface through carbon-silicon bonds.
Inorganic Ion-Exchange Sites
When thoria or zirconia is adsorbed on the silica surface, probably as polybasic.

cations or extremely small positively charged colloidal oxide particles, the surface
becomes positively charged and can act as an anion exchanger. This surface in turn
adsorbs phosphate ions irreversibly and these surface anions then can act as
exchange sites for cations:
-,
..
..,.~."':.
nd Powders
ydrophobic
--
..i.
:;.
:d \V;th the
ld
nm
'bodiimide,
-obably an
results in
., c;-
.",.
~~
.
._,..,
- ...;
- ;:--
'"'
degree of
groups in
omplicated
..
~---
Silica Gels with Ion-Exchange Surfaces
__
577
The actual surface structure is, of course, more complex than represented. A silicabased cation exchanger of this type could be used to separate metal ions such as
Ag2+, Cu'+, Fe'+, Ca2+, according to Kautsky and Wesslau (546). Ion-exchange surfaces of this type have been described by Yates (547), who prepared colloidal phosphates of Ti H , ZrH , Sn H , HfH , and Ce'+ and adsorbed them. on the silica surface.
The advantage of making an exchanger with a silica base rather than entirely of the
polyvalent metal phosphate is that silica is easier to form into the wide-pored structure of high surface area needed for efficient performance.
Silica is the base for an ammonium molybdophosphate exchanger which can be
used for recovering cesium ions from acid solution (548, 549). Kaletka and Konecny
also use silica gel as a support for insoluble nickel, copper, cadmium, or zinc hexacyanoferrates, which act as cation exchangers. They can remove traces of cesium
ions even from strong nitric acid solution. Exchange capacities of the different compounds were measured (550)..- .
/gen atoms
iossible, as
Organic-Linked Ion':'Ex~hange Sites
-'.
i-exchange
:ing the gel
formed in
licon, leav-
H+ form
s made by
I for water
e.
ice modifith organic
polybasic
he surface
ice in turn
an act as
.It now appears .that almost any type of ionic or chelating organic group can be
attached to the surface of open-pored silica gel or powder to obtain 'useful exchange
. properties. Unger (6) has summarized the various ways in which Si-C bonds can be
formed on the surface of porous silica. These are discussed further in Chapter 7. At
this point consideration is given only to specific ion exchangers of this type.
Egorov et at. (551) grafted styrene, acrylic acid, vinylpyridine, and vinylphosphinic acid to the surface of silica by gas phase irradiation with X-rays and fast
electrons, and then ionicgroups were introduced by sulfonation, chloromethylation,
and amination. The capacity was 1-2 meq g-l.
.
Unger and Berg (5~2) treated silica gel with C.HaSiCI, and then sulfonated the
phenyl group to obtain a sulfonic type cation exchanger with a capacity of 0.46 meq
g-l. Unger, Berg, and Nyamah have further described the properties and uses of
these silica-base ion-exchange powders in chromatography (553, 554a). To make an
anion exchanger, porous silica of 600 m' g-1 area is refluxed with (3-chloropropyl)trichlorosilane in xylene and dried, and the 3-chloro groups on the silica surface reacted with dibutylamine in toluene at 140C. The product has an exchange
capacity of 0.5 meq g-1 (554b). Silica gel containing amino groups absorb dry CO,
from air but moisture must be present to adsorb HzS and SO, (554c). Aminopropyl
groups are also applied to the silica surface by reaction with (3-aminopropyl)triethoxysilane (555a). For use as a chelating type of adsorbent for copper,
the amino group is reacted with p-nitrobenzoyl chloride, then the NO, group
reduced to NH, with dithionate. The p-aminobenzyl group is then diazotized and
reacted with 8-hydrooxyquinoline, the chelating agent. The exchanger is dark red
and absorbs heavy metal cations down to extremely low concentrations,
An exchanger said to be a "silicon lactate" may actually by lactic acid esterified
onto the surface of silica: SiOCH(CH,)COOH. The silica gel or powder is first
heated to 230C to dehydrate it and then with lactic acid in an autoclave at 150C.
The cation exchange capacity is 0.6 meq g-1 (556).
..
~-_.
578
_ Another way to create ion-exchange sites is by reaction of the surface with

_CI2Si(CH,) CH 2CH2CN. thus forming
coating of SiO Si(CI)CH,CH 2CH 2CN
hydrolyzable to COOH groups (555b). The claim is repeated that the hydroxyl groups
of citric cr lactic acid vapors can esterify SiOH groups leaving attached
COOH groups. However. the stability of such coatings seems doubtful unless used
.for ion exchange in nonaqueous chromatographic systems.
..,
;-
"';
s
-~f
,.
i'
e,
-<:.'
COMMERCIAL SILICA GELS AND POWDERS
1.1,
lola:
......
ppc
Ltd
F',~ -
~.
(Ge
De
(G.
USES' OF SILICA' GEtS AND POWDERS
. 1
,.
."
The long-established uses of silica gels and powders were surveyed by Vail in 1952
(557). The largest uses cfsllica gels in granular or pelleted form appear to be as a
adsorbent or desiccant.
. . .
catalyst base and as
Based on the scientific, patent; and manufacturers' literature, the uses of silica
gels and powders can be grouped according to the following functions:
an
.:,
Reinforcing, stiffening. and hardening organic solids.

. Reducing adhesion between solid surfaces..
Increasing adhesion of adhesives.
Increasing viscosity and thixotropy in liquids.
Creating various optical effects.
Surfactant effects.
Hydrophobing effects.
Absorbent.
Catalyst base.
Source of reactive silica..
Cloud seeding.
Chromatographic column packing,
){t
0'
Pc
(5
FI
Si
(f
P
~
J
(
.
id Powders
rface with
H2r ''' 2CN
IXyl,
JUpS
attached
mless used
Usesof Silica Gels and Powders ,
:---
579
Kress (558) has summarized the major fields of use and Teicher (55~) has listed
specific silica aerogels and xerogels and their uses. No attempt is made here to
review all the literature on catalysts or adsorbents or in anyone of the listed areas.
Instead. some of the mechanisms of action are discussed and a few technically
.
. interesting points note~:_ ..., . __ .. __. _, _ . ' . . .' '.
.,
, ...,
--_.
"
Table 5.7. (Continued)

;.
Manufacturer
Product
Surface "
Oil
Area
Absorption
(g g-I)
BET (m' g-I)
Bulk
Density"
(g I-I)
Remarks
X erogels (Hydrogels); Aerogels
Davison Chern.
Div.
(W. R. Grace
Corp)
(USA)
1977
12 Grades, particle sizes
44
81
407-408
,923-950
720-760
700
'"0.43
600
720-760
700
590
750
735
0.70
72
74
80
161, 162
166
200 Series
300 Series
600
,I
!.
i
675
340
320
340
175
220
270-320
250
, ~ 95
0.6
2.2
2.0
2.6
I.S5
2.3
3.0-3.1
2.5
1.8
9
.4
8
112
5.6
7-9
240
112
80-112
160-190
335
2-4
3.7-7
20
Aggregate
Particle
Size
(microns)
"
2.7
2.2
1.9
1.9
1.75
1.8
1.75
1.8
1.75
320
320
2.05
2.05
G-604
320
2.05
176 .
176
176
176
176
G-900
625
0.8
400
G-910
700
0.9
400
G-130
G-300
G-310
G-600
G-601
G-602
G-603
. j
580
r
Surface
Treated
Yes
No
l'
275
300
300
300
200
225
200
225
200
325
325
G-IOO
G-5OO
G-510b
G-520b
G-530b
G-550b
,:'
Sileron
"
I
(
0.40
460
176
255
Glidden
Pigments
(USA)
Particle Sizes (microns)
Syloid
Grades
60,AL-l
Pore Volume (cm' g-I)
Grades
Nos. 01 to
Davison Technical Bulletin
Granular "
gels
2.1
2.1
96
160
3
3
4.2
160
192
5
5
208
192
208
112
192
5
6
5
x
x
x
x
4.7
6.5
7.1
10.1
12.0 .
8.S
9.0
x
x
x
x
-_
------
fable 5.7. (Continued)
--~----------------------------Product
Manufacturer
narks
- -
cal Bulletin -
M~nsanto Chem.
Co. (USA)
Santocel
C
260
54
270
FR-C
350
~ .
3~
68
350
. Aerosil
. 120:1: 30
R-972
170:1:: 30
..
MOX-170
. 80:1:: IS
MOX-SO
MOX-60
60 :I: 15
COK-84
150:1:: 25
OX-50
50:1:: 10
TT-600
200:1:: 50
2491-380
380:1:: 40
2491
300:1:: 30
Aerosil C
200 ~ 25
Aerosil UC 200 :I: 2S
CabosiJ
;200:1:: 2S
M-5
.:
200:1:: 25
MS-7
:-.
MS-75
::.: 255 :!: 15
,."
325:1:: 15
HS-5
EH-5
325:1: 40
5-17
400:1:: 20
Fluosil
200U
220 :!: 25
300U
300 :I: 25
200U
100:1:: 20
300C
300 :!: 30
H
190 :l:: 25
2S0C
260 :l:: 25
250CNG
240 :t: 25
43
Deg ussa
(Germany)
..
.40
:es (microns)
9
4
s
.6
-9
4
-4'
7-7
. Godfrey L.
Cabot Corp.
(USA)
:0
Surface
Treated
Yes
No
x
x
NynasPetroleum
(Sweden)
x
x
x
x
x
x
Oil
Surface
Absorption
Area
(g g-')
. BE~ (m' g-')
Bulk
Density"
(g 1-')
Remarks
. SilicasPrecipitatedfrom Sodium SilicateSolution
particle sizes
ne (em' g-')
70
... -
280
280
280
UO
280
32-48
40-56
40-80
56-100
56-100
40-56
40-56.
40-56
40-56
125
40-56
Monsanto Dev, Data Sheet

Dee. 21. 1950
Degussa Bulletin '301-0366

Hydrophobic (Bull. 3002)
MOX - mixed oxide containing 0.3-1.3% AlaO,
14 :!: 2% AI,O,
C ~ compressed
UC - uncompressed
37
60-80
60-80
37
3-7
60-80
40 :!: 10
40:1:: 10
100:1:: 20
100 :!: 20
100 :I:: 20
100 :1::20
80:1:: 15
U - uncompressed
C - compressed
Hydrophobic; 90% sro,
Nonglossygrade
160 g 1-' - 10 1b ft-'.

Approx, 10-20% loss of weight on lgnition,
x.
x
x
x
x
581
..
--_ ...
582
Reinforcing and Other Effects in Organic Solids
In Rubber
i
I
.. I
I
The reinforcing filler used inlargest volume is carbon black. There is already a move
toward partial or complete replacement by silica as evidenced by development of
fine silica that gives the same properties in vulcanized rubber. One example of such a
silica has a specific surface area of 60 m t g-l and an oil absorption of 1.8 ern! g-l
and therefore has a very open reticulated structure that is easily dispersed 'by milling.
This makes it possible to make tough durable rubber products in colors other than
black (560). A typical analysis shows the presence of 1.7% NaCI and 0.8% CaO,
in.dicating that it probably is a precipitated silica coagulated with calcium chloride.
The particle size of 40 nm is larger than the 22 nm particles of silica heretofore
made for reinforcing filler (561). This may explain the improved dynamic properties
of the rubber .and faster cure because of lower adsorption of vulcanizing accelerator.
Because of the possible increasing importance of silica reinforcing fillers, some of
the past literature will be discussed in further detail especially since much of the
information has not been generally available except in patents.
Around 1959, papers by Wagner and Sellers (562) and Bachman et at. (563)
comprehensively reviewed the reinforcing effects of silicas of different types.
Properties were listed for 27 precipitated, pyrogenic, and aerogel silicas then available, along with an extensive bibliography. It was shown that the amount of "bound
rubber". on a filler indicates its reinforcing effect. The filler is milled into the rubber
with no other additives and heated at different temperatures, and the soluble rubber
then extracted with solvent. Bound rubber forms during milling by a free-radical
mechanism.
.
Gessler and Rehner (564) and De Francesco et aI. (565) examined the effect of
dehydrating the silica surface and of organic surface coatings on rubber reinforcement.
;
A survey of the reinforcing mechanisms and effects of a wide range of fillers on
physical properties of elastomers, with 47 references, was published by Smith (566a).
The effects of substituting part of the carbon black with silica in natural rubber were
examined by Salvador (566b). Complete substitution gave poorer properties but with
15 SiO t:35 C there was enhancement of elongation and tear and heat aging, but
lower modulus and rebound.
"Estersils, surface-esterified silicas, were specially studied as fillers and patented
by lIer (567). These could be dispersed into various elastomers even though the
particles were as small as 5-7 nm in diameter. Various particle sizes and degrees of
reticulation or packing densities of ultimate particles in the aggregates were prepared and reinforcing properties compared with and without a hydrophobic and
organophilic surface coating of butoxy groups.
Table 5.8 summarizes data from the patent. Tests were made in natural rubber at
a loading of 60 parts by weight of filler per 100 parts of rubber using 3% sulfur and
an optimum amount of accelerators benzothiazyl disulfide and thiuram M and
optimum cure time. usually for highest tear strength.
II
0-;;
o ....
.., (;>
..,
...
....
50
0.
."
Q.
...n
'"
584
With each type of silica, comparison of the material with a nonesterified hydrophilic surface. and with the corresponding esterified (n-butyl) surface shows that ir
cases A-C, esterification increased the resulting tensile and tear strengths. with the \. .
smallest particle size having the greatest effect. A and B are similar in structure and
reinforcing effects. The esterified silica of C gave higher values for tensile and tear
strengths and hardness, yet has a lower modulus than vulcanizate made with EPC
Black. D is an easily dispersed filler of low "structure" or reticulation as evidenced
.;
by the decrease in bulk density when compressed at 3-1500 psi. Dispersion results in
a very low modulus like that obtained with nonreticulated discrete nonaggregated
esterified particles (see Table 5.9). A sample reinforced with EPC carbon black was
included for comparison.
In E, a silica aerogel gives markedly better rubber properties after esterification
with n-butyl alcohol. In F, there is demonstration that esterification with increasing
chain length of primary alcohols does not greatly change reinforcing properties
which again are much superior to the unesterified silica.
.. i
In G and H, the particles are colloidal fibers with esterified silica surfaces. Most
remarkable is the effect of the anisometric shape; that is, highly elongated particles,
resulting in a very high modulus. In fact, all the recorded properties obtained with
esterified acid-treated attapulgite clay' are similar to those obtained with EPC
carbon black. In parallel work confirming the foregoing results, additional tests and
observations were made. A range of silica particle sizes, reticulation, or chaining of
structure and degree of coverage of the hydrophobic silanol surface with n-butyl
ester groups was tested in natural rubber using optimum accelerator levels and vulcanization time. Esterification reduced the amount of accelerators required.
, \... -'
The effect of the degree of esterification or, conversely, the proportion of the surface that is hydrophilic and polar, on reinforcing properties was determined as
follows: a silica powder was selected having a structure such that it was fully dis- .
persed when milled into rubber. When dried from acetone it was fully hydrophilic.' .
When refluxed with n-butyl alcohol it was only partly surface esterified. After being
milled into rubber the polar surfaces consisted of unesterified silanol groups and the
"bare" spots developed when the reticulated particles were broken apart. In another
sample, the surface of the reticulated silica was fully esterified by autoclaving with
butanol; then after milling into rubber, the only polar surfaces were the "bare" spots
where particles were broken apart. Finally, in a fourth sample, by ball-milling some
of the foregoing esterified reticulated silica in butyl alcohol and reautoclaving, the
resulting particles developed very little polar surface even after dispersion in the
rubber.
As shown in Table 5.9, it is clear that the polar or hydrophilic areas on the particles (which correspond to the oxidized areas on carbon blacks) stiffen the stock. This
is entirely analogous to thickening oil to a grease with this type of silica. With good
dispersion and fixed particle size, esterification has no effect on tensile or tear
strengths. However. since the hardness and modulus were least with fully esterified
particles. the elongation was greater so that the true tensilestrength on the cross-section at break (proportional to T x E) was highest on fully esterified p a r t i c l e s . ,
To completely eliminate polar surface groups and reticulation of particles, sols of \ ..... '
uniform silica particles were converted to organosols by esterification in the sol state
.,.
'":..--
I Powders
d hydro's t""t in
Table 5.9. Reinforcing Rubber with Fine Silica-Effect of Replacing SiOH with-SiOBu on
SiJia Surface
wi.
ole
:tureand
and tear
'i~h EPC
videnced
esults in
gregated
lack was
.ification
creasing
roperties
ss. Most
iarticles,
led with
th EPC
ests and.
.ining of
n-butyf
an-' 'JI- .
the' surlined as lily dis.ophilic.
er being
and the
another
ng with
e" spots
19 some
ing, the
I in the
e parti- ,
ik. This
th good
or tear
terified
oss-secSet..
of
01 state
Silica Filler
".
Nonesterified ,
Partly esterified before
dispersion
Fully esterified before
, dispersion . _ '. '
Fully esterified, ballmilled, reesterified
Nonreticulated, fully :
.esterified .
Particle Diameter
58S
T
E
-Tensile . Elongation
(psi)
(%)
'
TxE Modulus Hardness

(x 10-') (300%)
(Shore)
Tear
(lb in.-I)
2830
4500
-490
670
1.4
3.0
1625 .
1325
89
'87
190
700
4900
730
3.6
1060
78.5
700
"~ 4900
760
3.7
840
71.5
700
740
815
800 :
3.0
3.3
4.0
540
450
575
56
650
870
865
nm
Area (m' g-I)
25
17
10
110
160
' 275
4000
4400
5000
6~
72
, .as described in Chapter 4. As shown in Tabl~ 5.9, decreasing particle size results in
,. greater tensile strength and elongation at break. along with a low modulus yet high'
tear strength. With most kinds of fillers (which usually contain some polar surface) .
such very fine particles usually result in very hard vulcanizates and high modulus -;
owing to association of.the filler particles through their polar surfaces.
.The resulting piciureof reinforcement is that tensile and tear strength and general
toughness are greatly increased when very small filler particles 5-10 nm in diameter
are completely dispersed as' separate and discrete particles within the silica matrix.
For good dispersion such small particles must probably be hydrophobic. When polar
Or hydrophilic areas are present on the filler particles, they tend to chain together
through association of these areas which are not wetted by the hydrocarbon
, elastomer matrix. This stiffe~s the structure, that is, increases the modulus and
hardness.
'
", .
Whether or not a silica filler could eventually replace carbon black in tire treads
where most of the carbon black is consumed depends on developing adequate wear
resistance. If a hydrophobic silica .is needed, it depends on whether, the lower cost
esterified surface, in comparison with the organosilyl type, is sufficiently stable during use. Optimizing a filler for maximum tread wear-resistance is complex; it
involves developing an optimum combination of high modulus, which minimizes the
- abrasive lateral sliding of the tread against the pavement as the rubber is deformed
arid spread under' pressure,' and high abrasion resistance which is related to high
tensile and tear strengths. Conceivably this could be accomplished by a combination
of hydrophobic and hydrophilic silicas of different particle sizes.
.,
;;
----
In Silicone Elastomers
-- -- - .
Fine silica is apparently an indis'pensabTe-componeriCof silicone elastomers. It is
likely that the type of silica required has become highly specialized, but no informa_
tion is available. In an early patent to Bueche (568) a surface-esterified silica was
used as a cross-linking agent in organopolysiloxane elastomer. According to Kidwell
(569) "Valron" Estersil (570) was much superior
a pyrogenic silica of similar
particle size for reinforcing methyl-phenyl-vinyl-polysiloxane elastomer g~ving a vul.
canizate with a tensile strength of up to 1300 psi (443 kg cm- 2) and 880% elongation
at break.
As reported by Zelikin et a1. (571), hydrophobic pyrogenic silicas were used as
reinforcing fillers in silicone rubber giving a tensile strength of 71 kg ern-2 and 460%
elongation at break. However, the reinforcement of this type of elastomer is now
probably considerably advanced by new techniques of introducing particulate silica
with optimum characteristics.
.
"'l
to
','
"
.,
In Various Organic Polymers

~
. 1:'
. ;i
. !'
t :! H
;
;'I~
:!,
~l;:
;..\r ~
. 1: 1 /
.';
.!l
li!
"I: :
. i
j:. :', !
I .. i
t:
!.
,.
Silicone-coated silica gave superior reinforcement in trinuorochloroethylene-vinyl

copolymer (572). Olefins were copolymerized with silica coated with unsaturated ali- ~
phatic hydrocarbon groups (573). By incorporatingestersil into polyethylene the tear .
strength transverse to the machine direction was increased 50% without loss of other: .
properties (574). A methyl-esterified silica was milled into polyethylene molding .
powder giving no 'visible undispersed particles at 10% loading. Similar dispersion \,
was obtained inpolymethyl methacrylate (575). Silica surface modified (esterified) with diethylene glycol ~JlS inorcmiscible and compatible with polyester resins and
can be used as filler in' furniture finishes (576). , -.
Fiberlike Si02 made by oxidizing SiO reinforced a polyurethane gum cross-linked,
with,'-I,5-naphthalene diisocyanate to give a 'material with tensile strength of 7000 .
psi, a modulus of 1900 psi, and an elongation of 700% at break (577).
. ,.
In the last decade there seem to be fewer references concerning reinforcing
polymers with silica. It is difficult to say whether this is because the subject has been
'extensively investigated with disappointing results or because suitable new types of
silicas have not been available for testing in various polymers. For further advances,
a cooperative effort may be required to provide experimental silicas representing a
wide range of particle sizes, structures, and surface characteristics for evaluation in
the most important polymers.
A very different application is in making a microporous polymer. By incorporating silica into monomer used to make ion-exchange resins, extra porosity is obtained
.~
by later dissolving out the silica with dilute HF (578).
.
~
Silica has been introduced as ethyl silicate in the monomer precursor mix of
polyester resins (579). The water liberated during condensation polymerization, for
example, in making poly(ethylene succinate), 'hydrolyzes the ester, liberating silica
essentially as a copolymer. This should give extremely fine pores if the silica were
removed. .
.
In cellulose acetate membranes for reverse osmosis Stana and Calderwood (580)
':1'
~.
ld Powders
Usesof Silica Gels and Powders
587
.$
ne, 't is
) informasilica was
to'Kidwell
of similar
ling a vul-
elongation
e used as
and 460%
er is now
.late silica
found that membranes containing about 0.6% of silica particles

nm in size
performed well without change for 56 days whereas without silica the throughput
dropped 50% in 17 days. A silica content of 50 vol. % gave a fivefold higher
throughput when cellulose acetate of low permeability was used (581).
. A rubber-coated fabric that is highly resistant to passage of liquid water but easily
.passes water vapor can be made by coating fabric with latex mixed with hydrophobic
silica aero-gel to provide the porosity ,(582).
Ice is reinforced by hydrophilic silica. Nayar, Lenel, and Ansell (583).found that
when 0.5-1 % by volume of uniformly dispersed silica particles was present in icc, the
rate of creep under pressure was 10-30 times slower than in pure ice..
Polyethylene oxide glycols are converted from a waxlike state to firm solid by
inclusion of fine silica which hydrogen bonds with the ether groups and cross-links
the polymer. This effect is used in forming the walls of encapsulated materials (584).
Reducing Adhesion
lene-vinyl
irated aliie the tear
is of other
: r 'ding
dis,
.ion
esterified)
~esins and
oss-linked
h of 7000
einforcing
~ has been
/ types of
advances,
:senting a
luation in
corporat; obtained
lr mix of
ation, for
:ing silica
ili< 'ere
ood (580)
Antiblocking or preventing adhesion between layers of sticky materials has long

been achieved with talc or starch powders, but the extremely small size of some
silica powders and their low refractive index make them more effective and less visible. Anticaking of powders or granules which tend to flow together or recrystallize
in storage is also prevented by silica which is nontoxic and generally inert. Stickiness
or surface tack is a very similar problem. as is the tendency of freshly applied colors
or inks to offset. Apparently. the fine silica aggregates adhere to the surface and
absorb traces of liquid phase or sink into the plastic surface increasing the hardness
or viscosity, giving a "drying" effect. Also, in grinding powders a small amount of
fine silica in the batch forms a thin film on the freshly formed surfaces, holding them
. from contact and rewelding when again subject to impact.
A coating of silica' aerogel. in a silicone oil. dispersed in water with an organosilane triol, on the paper liner of a baking pan prevents adhesion of baked
goods (585).
An antiblocking effect in polymer films can apparently be attained by adding fine
silica to the mixed monomers before polymerization. Hoppe and Behn claim that
around 0.5% silica based on polymer gives a 50% reduction in adhesion (586). The
nature of the film containing silica was examined by scanning electron microscope
and it was found that the polymer around the particle protuberances was less soluble. Film separation was observed by Newton's rings in reflected light (587).
There are many uses involving anticaking. Typical is the use of pyrogenic silica to
keep antiperspirant powders from caking in propellant spray' cans (588) and medi'
cinal dusts to be dispersed above flocks of birds (589).
Increasing Adhesion
There are instances where adhesion can be increased rather than reduced, that is,
where silica particles are present not as weak aggregates but as dispersed particles
S88
within a liquid adhesive that hardens in contact with a solid surface." The' particles
are beneficial if they are strongly adsorbed .at the solid boundary and, in effect ,
increase the area to which the adhesive is bonding. Thus 10% of pyrogenic silica in
butyl cyanoacrylate liquid improves strength and adhesion when this adhesive
polymerizes and bonds to skin in surgery (590). This type of silica is used as a
thickener in components of epoxy adhesives where it may also improve adhesion to
some surfaces.
'
Increasing Viscosity, Thixotropy
..
It is sometimes not realized that dispersion of substantial proportions of discrete,

fully disaggregated particles in a liquid does not appreciably increase the viscosity
and does not develop any thixotropy. Thus organosols containing 20-30% Si02 are
quite fluid. It is only when particles of colloidal size form a network through the
liquid that these thickening effects are observed.
Young and Chessick (591) described the effects of hydrophilic and hydrophobic
particles in thickening polar and nonpolar liquids, but did not develop a complete
picture of the system. Wightman and Chessick (592) examined the effect of polar
(hydrophilic) silicas in thickening nonpolar (hydrocarbon) liquids after adding minor
. amounts of water and n-heptyl derivatives including the acid, chloride, aldehyde,
amine, and alcohol. The sedimentation volumes of a hydrophilic fine silica in decane
in the presence of these additives showed that alcohol and amine prevented interparticle bridging and thus settling to lowest volume.
..
.~
-"'?
Mechanism
The overall behavior of silica cannot be understood until the following variables are
considered in turn:
1.
2.
3.
4.
5.
Size of ultimate particles.

D.egree to ~hich particles are dispersed-to separate particles or aggregates.
Size of aggregates..
Relative energy of particle-particle contacts versus particle surface-liquid.
Adsorption of additives on particles.
Different surfaces are shown in the different combinations in Figure 5.25. The
silica originally consists of two classes of particles: single discrete particles and
macroaggregates. In each case the surface is in three conditions:
Ii
1. Unmodified silanol surface: hydrophilic.

2. Partly organophilic, for example, partial esterification.
3. Completely organophilic, for example, the surface covered with hydrocarbon
groups...
!
-;
..,.
~---
id Powders
e particles
in ..ffect,
ic ~
t in
i adhesive
used as a'
dhesion to
I?\RTICLES
589
POLAR
Hydrophilic
SURFACE
POLAR - NON-POLAR NON-POLAR'
r-------..,
Hydro-Organo-philic
Organophilic
Single
Large
Aggregates
r discrete,
: viscosity
) SiO z are
rough the
Small
Aggregates
(after
-milling)
..
drophobic
complete
t of polar
ing minor
aldehyde,
in decane
ter' 'nter-
iables are
ites.
d.
5.25. The
icles and
roc, Jon
Figure 5.25. Surfaces of single particles, large aggregates, and small aggregates. each shown
as hydrophilic, partly organcphilic, and completely organophilic (before milling). Hydrophilic
surface- thin lines; organophilic surface-s-heavy 'lines; bare. hydrophilic spots after milling-wavy lines.
,
'
~..
. .-.
-. -
'
The third class of particles is formed when macroaggregates are broken apart by
milling, creating bare, hydrophilic spots on smaller aggregates.
The behavior of all these types of particles in water. alcohol (butanol). and
hydrocarbon (hexane) is i1Iustrated in Figure 5.26 and Can be described briefly as
of the surface of each particle is not wetted by the liquid, the nonwetfollows. If
ted areas of two different particles adhere to each other.
Thus in water, hydrophobic nonpolar areas adhere by hydrophobic bonding.
In oil, hydrophilic polar areas adhere by hydrogen bonding.
In alcohol. which wets both surfaces. particles do not adhere to each other. The
hydrophilic areas are wetted by adsorption of the OH ends of alcohol molecules. The
hydrophobic areas are wetted by the hydrocarbon groups of alcohol (or other
molecules with polar and nonpolar segments).
As shown in Figure 5.26, a network of particles forms in water if particles have
hydrophobic or partly hydrophobic surfaces. A network forms in oil if particles have
hydrophilic or partly hydrophilic surfaces. The network is most voluminous when
'. particles have both hydrophilic and hydrophobic areas on the particles. No network
. forms in alcohol and viscosity depends only on the volume fraction of the liquid
occupied by the aggregates. Since no network is formed, there is little thixotropy.
This is an oversimplified picture since the degree of wetting of the hydrophilic and
hydrophobic surfaces depends on the alcohol or other polar-nonpolar substances
present....:
The term "wetting" simply implies a low interfacial energy between the liquid and
the solid surface.
all
.:
.,
590
LIQUID
POLAR
(WATER)
TYPE OF
SILICA
fQLAB
..
Discrete
0000 0
o 00 0
POLAR - NON-POLAR
(ALCOHOL)
NOtrPOLAR
(HEXANE)
000
000
o 0
0
Small
Aggreg.
PARTLY
fQ1.AB
Discrete
Smoll
Aggreg.
..
lllQti::
f.QL.AB
Discrete
:0"
_.
i.
I!
....
o
o
00
0
0 00 0
00 0 0 0 0
0
00 0 00
Small.
Aggreg: .
Figure 5.26. Viscosity and thixotropy effects of different types of silica in different liquids.
Discrete particles: hydrophilic, partly hydrophobic, and completely hydrophobic. Small milled
aggregates: originally hydrophilic, partly hydrophilic, and completely hydrophobic, now with
additional hydrophilic spots.
When the whole surface of a particle is not wetted, the particles adhere together in
dense clumps. On the other hand, when only certain spots on each particle.are not
wetted, the particles adhere together only at these spots and thus Corm more open
networks.
Maximum network formation occurs in oil (hexane) when the only nonwetted
areas on hydrophobic particles are the "bare" spots that were formed by fracture
when open, h~ghly porous aggregates were milled and broken apart into smaller
aggregates.
Maximum network formation and thixotropy occur when small three-dimensional
aggregates link together into a still larger three-dimensional aggregate which extends
through the liquid medium (Figure 5.27). Aggregates link together through the polar
spots on particles in oil, or through hydrophobic spots in water. Such linkages
involving hydrogen bonding or hydrophobic bonding, respectively, are readily
broken by shearing forces and readily reestablished when the mass is at rest. Thus a
high degree of thixotropy is established. Different aspects of silica thickeners in
various liquid media as affected by secondary additives are discussed in typical
papers (593-596). The performance specifically of pyrogenic silica (Aerosil) is the
subject of investigations by Rupprecht and Liebl (597) and Kaspar et a1. (598); in
some cases surfactants were added.
..
d Powders
~--
591
LubricQting Grease
)
)
A few expired patents on the use of hydrophobic fine silica as a thickener to convert
lubricating oil into grease are here discussed since some of the information has not
otherwise appeared in the technical literature.
_ Hydrogels of silica were milled into oil with an oleophilic surfactant such as a
long-chain quaternary amrnonlum compound, dimethyldioctadecylammonium
chloride, or metal soaps, Clays were used but the process also applied t~ fine silica
(599). This was only one of many patents relating to grease thickeners made from
bentonite-type clays (600). Surface-esterified reinforced low density silica (estersil) was patented as a grease
thickener in hydrocarbon oils (601) and in silicone oils (602). Silica surface-coated
with both butoxy ester groups and silicone oil improved long term stability of the
grease (603). Braendle (604) found that addition of some polar hydrogen-bonding
compound like tricresyl phosphate greatly improved the adhesion of estersil grease
to steel under prolonged wet conditions, kept it from hardening, and stopped corrosion..
The properties of estersil greases were described by Meyer and Braendle (60S),
who reported them free from abrasive wear and less subject to change at high
temperature than metal-soap greases.
nt liquids.
iall milled
no- with
.gether in
e are not
ore open
onwetted
fracture
I smaller
tensional
1 extends
the polar
linkages
: readily
:. Thus a
:eners in
1 typical
it) is the
(59\; in
Figure 5.27. Maximum thickening effect and thixotropy are produced by small aggregates
linking together through nonwetted spots into an extensive three-dimensional gel network
throughout the liquid medium. Black areas of contact between small aggregates indicate (a)
. polar or hydrogen bonds when the hydrophobic aggregates are milled into oil. or (b) hydrophobic area when aggregates that are partly hydrophobic are mechanically dispersed in water.
.,
592
According to more recent Russian work, a butoxy type of estersil improved the
oxidation stability of grease (606).
It was during the development of these particulate grease thickeners that a better
understanding was gained of the thixotropic effects of fine particles and aggregates
of particles in liquids.
'"
'
To make silica organophilic in grease. Fronczak (607) patented CZ-C II alkylene
carbonate as an additive. The compound is probably adsorbed on the silica and may
even react with SiOH to form an ester-type coating.
Silica was coated with a phenol-formaldehyde resin from acetone solution and
cured and found to impart good shear stability when used as a grease thickener (608).
Greases thickened with silica are prevented from gelling on aging by adding diols
as 2-methyl-2.4-pentanediol or 2-ethyl-I.3-hexanediol according to Blattenberger
(609). These diols undoubtedly are strongly adsorbed on the silica surface through
double hydrogen bonds.
The' economics of grease thickening changed in the 1950s and the greater
availability of lithium stearate as a water resistant grease thickener, among other
factors, reduced interest in this use of hydrophobic silicas.
,
I
"
Paints, Coatings. Inks
II
.'
:.
'
The thickening and thixotropic .effects in these classes of products attained with
silica are too numerous to cite. Usually several effects are attained, namely. flatting
or lower gloss, prevention of settling of pigment in storage. stabilization of emulsion,
as well as dripless application. However. no information is available as to relative
use of silicas versus otherithickeners in these products. Flatting seems to be the
effect in paints and finishes most commonly mentioned in manufacturers' bulletins.
In inks, viscosity control is usually featured.
,
Pharmaceuticals and Cosmetics '
A general survey of the use of pyrogenic silica in pharmaceuticals and cosmetics has
been published by Ferch (610). The transparency of highly porous, high surface area
silica permitted the development of transparent toothpastes containing silica and a
hydrophilic organic polymer thickener, along with glycerin, oil, detergent, and flavoring material (611, 612). Various combinations of dentifrices and anti-tartar
agents are included in other compositions (613, 614).
Other than thickening effects,the use of silica in cosmetics to remove oil from the
skin is mentioned under use as an-adsorbent.
, to
~.
.." !
Miscellaneous Compositions
The electrostatic clutch involves the electroviscous effect of silica dispersed in oil.
For example, fine silica and glycerol monooleate dispersed in oil fills the thin space
.,
Powders
Usesof Silica Gels and Powders
ved the
l
r
;regates
.Ikylene
nd may
on and
thick19 diols
1 berger
hrough
..!
greater
g other
:~
,.;.
:d with
na' . 'g
.ul:
.,
.elative
be the
.lletins.
om the
593
between two clutch plates, as described by Martinek and Klass (61S)~ The plates
move freely past each other except when a 2000 volt, three-phase alternating potential
is applied to them. This causes the silica to thicken the oil to a gel which transmits
torque from one plate to the other. A 'similar electroviscous liquid is described in
detail in another patent (616). Parameters of the system were studied by Klass (617).
The phenomenon is explained by the interactions between polarized double layers
and between the layers and the particles.
The effect of temperature on the electrorheology was examined by Shul'man and
Matsepuro (618). Additional patented compositions have been described (619,620).
Large crystals can be grown in a silica gel medium which cannot be grown in
water. The gel structure prevents convection and permits even diffusion of the
components. Such growth of single crystals of neodymium-doped calcium tartrate
tetrahydrate was described by Rubin (621) and of cuprous oxide by Brenner (622).
These and other crystals were grown by Henisch, Dennis, and Hanoka (623), who
also studied the effect of irradiation on nucleation rate. Growth of HgCl z2H zO was
studied in some detail by Kurz (624); calcium oxalate by Bisaillon and Tawashi
(625). An apparatus to supply the gel from two sides with reactants was described by
Armington and O'Connor (626).
The subject of crystal growth in gels was reviewed by Kachi (627).
Alkyl nitrates, hydrazine, and other rocket fuels are thickened to agel or greaselike state with a voluminous silica gel (628). ;',
, -To inject acid to the desired point in an oil well, the acid is thickened with silica.
On dilution with water once it is in place the mixture liquefies and the acid becomes
,'. active (629). Silica can also be used to thicken acid in lead storage batteries.
The addition .of silica as a thickener in foam -enhances its fire-fighting properties
(630).
' ., ,
-:
Optical
ics has
ce area
and a
nd fla-tartar
~---
Effe~ts~Flatting
Dyes often have such high color intensity that they must be diluted out in a
transparent". medium for greatest color effect. This is especially true of some
, fluorescent dyes. 'Rhodamine is adsorbed on powdered silica gel so that a few
percent gives intense fluorescent color (631).
Another way, to improve very insoluble organic pigments is to nucleate the
crystals to obtain them in more finely divided form without grinding. Thus phthalocyanine is synthesized in the presence of very finely divided silica which is coated by
the pigment. The product is about two-thirds silica and this permits development of
the full hue of the organic compound which is thus spread out (632).
Delustering and anti-gloss effects in paints, plastics, and printing inks probably
represent one of the largest 'uses for silica powders, judging from manufacturers'
literature. The numerous grades of xerogel powders listed in Table 5.7 appear
mainly to provide various degrees of flatting in different types of finishes.
"
,.
...
~-_.
- ~
594
Surfactant Effects
Stabilizing Emulsions
"
"
Particles with both hydrophilic and organophilic areas obviously will collect at the
oil-water interface. This stabilizes the boundary to an even greater degree than a
surfactant alone. Though not usually used specifically as an emulsifying agent, Surface-treated silicas often stabilize emulsion systems, as in paints, where the silica
may also play other roles.
Hydrophilic Surface
t['
Polyamide fiber can be made hydrophilic by treatment with a I % suspension of a

highly porous, "finely 'divided silica gel with a surface area of 400 m 2 g-1 and pores
10-20 nm diameter. The silica forms an adherent gel film that improves washability
and cleanability (633).
"
Antifoam .Agent
'
;:.
.. .' ....
;"~
.:;
"":!
The mechanism by which bubbles in foam arc broken by at least partly hydrophobic
silica particles is discussed in Chapter 4. Finely divided silica aggregates, made sufficiently hydrophobic to be suspendable in a hydrocarbon or silicone oil, probably
should retain some hydrophilic areas to be held at the bubble surface. The silica is
treated with a silicone oil and heated to 245C to react it with the surface, then suspended in an oil (634). A surfactant in the oil may be included (635).
",il
t.:,
1 ""
Hydrophobing Effects
! "
.....
Hydrophobing or water-repellent effects can be produced with hydrophobic silicas

that are so finely divided as to form a very thin adsorbed layer on normally
hydrophic surfaces. This effect is, of course, involved in the anti-caking action of
hydrophobic silicas in moist powders.
A basic patent (636) on this use of estersils claims application to many kinds of
materials including paper and fabrics which are made highly water-repellent by an
invisible adsorbed film of hydrophobic colloidal particles.
Dye-marker powders used at sea may consist of hydrophobic silica containing dye
particles which thus dissolve near the surface rather than after sinking (637).
"Dry" Water
An extreme example of hydrophobing is a patent on dry powdered water made by
coating finely ground ice particles with hydrophobic silica (638). When the powder is
warmed to ordinary temperature it remains as a "dry" free-flowing white powder
which under the microscope can be seen to consist of individual spherical droplets of
d Powders
ect at the
e~ than a
gent, surthe silica
,.
S9S
clear liquid water, each coated with an almost invisible film of silica. When
mechanically worked, the powder collapses to liquid water, but if undisturbed in a
closed container to prevent evaporation it is stable for several weeks. 'Aqueous solutions can be made in powdered form in this way if free from wetting agents.
Concentrated hydrogen peroxide (20-70% H 20 ,) can be similarly converted to a
stable powder form by vibrating the liquid with the silica powder (639).
Absorbent
sion of a
md pores
ashability
lrophobic
ade suffiprobably
e ~! --a is
the JS-
lic silicas
normally
action of
kinds of
:nt by an
ining dye
made by
lowder is
: J: ier
opr, ..of
The largest use as an absorbent is probably as a desiccant in packaged products subject to corrosion or deterioration by moisture. Some miscellaneous observations are
as follows.
Insecticidal activity of fine silica is discussed in Chapter 7. The oily or waxlike,
: components that prevent loss of moisture through the insect cuticle are absorbed by
silica and the insect dies from dehydration. The mechanism is described by Ebeling
(640). A hydrophobic estersil is especially effective (641).
Spot cleaners consist of a cleaning solvent in which silica is suspended. The silica
remains on the surface of the fabric and when the solvent evaporates from the surface the soil is carried into the silica which is later brushed off.
, '. ' Absorbent for oil spills is a use in which synthetic hydrophobic silicas may playa
, role. However, a hydrophobic low cost expanded perlite, made hydrophobic by treatment with sodium methyl silanolate in water,' is used to absorb floating oil. For'
some reason the presence of aluminum powder is said to improve the efficiency of
the hydrophobing reaction (642).
..':. .
. Concentrated ozone can be obtained by absorption of the gas on silica gel at -117
: to 20C (643).'
:'~ ..
. ...
Polysaccharides are, preferentially adsorbed on silica surfaces coated with polyaromatic molecules according to Kennedy, Barker, and White (644). It is surprising
~. that a hydrocarbon surface should have any special affinity for such highly hydrophilic molecules. Siliceous porous materials coated with adsorbed 1,3-diaminobenzene adsorb glycogen and branched polysaccharides but not neutral or charged
monosaccharides.
.
Uranium, zirconium, and niobium ions or oxy ions are adsorbed by silica from
. nitric acid solution down to pH 0 and niobium even for 10M acid. A weak oxalic
acid solution removes the adsorbed metals (645). Zirconium can be separated from
hafnium on silica gel (646).
Color tests can be made several times more sensitive by carrying them out on the
surface of powdered silica gel; for example, dithizone with Hg2+ and K4Fe(CN).
with UO,2+ (647).
Glycerol can be selectively adsorbed on silica gel from waste fermentation liquors
. (648). The gel pores were probably very fine.
Antioxidants of the polyhydroxy aromatic type can be adsorbed on fine silica of
the rubber-filler type and dispersed in polyethylene. It proved to be as good an
antioxidant as carbon black yet the film was clear (649).
.,
~---
S96
Silica Gets and Powders
Cosmetics may include silica as an adsorbent of natural oils. Greasy'scalps can be

. treated with a suspension of silica in water to absorb the oil and cure the condition
(650). Cosmetics containing pyrogenic silica are invisible. keep the face from lOoking
oily, and can be washed off with only warm water (651). .
Catalysts
Only a few miscellaneous items will be mentioned.
Aerogels
Teichner et al. (316) have prepared catalysts of very high specific surface area
(around 600. m 2 g-I). Such a silica-supported NiO-AI~O, catalyst oxidized
isobutylene to acetone and methylacrolein without formation of CO or CO, even at
305C.
.
I:
~:
'
Base for Mitochondria
'!t:
t.:
!;
~-
l:
'
Enzymes have been adsorbed on the surface of silica and found to retain activity, but
the finding that mitochondria (particles from living cells bearing complex enzyme
systems) can be similarly immobilized may open up whole new areas in biochemistry
(6S2a). Other membrane-contained particles or organelles can similarly be bound,
for example, chloroplasts and liver microsomes. The silica surface must first be
rendered organophilic by treatment with alkylsilyl groups. Then these biological
moieties adhere as a monolayer provided the temperature is around 27C, but
desorb at SoC. The nature of this effect is not understood, but 'one may speculate
that since hydrogen 'bonds become much stronger at SoC. water somehow displaces
.. the particles which must be held by hydrophobic bonds. Such bonds have since been.
, employed to anchor enzymes (6S2b).
Spillover'
.;
" ,
fl
1
I
It has been proved that in a silica-supported platinum hydrogenation catalyst. covering the silica surface with methylsilyl groups did not have much effect on its hydrogenation activity (653). It is known that hydrogen molecules are split to hydrogen
atoms on the platinum and the hydrogen atoms can then migrate or "spill over"
onto the surrounding oxide surface. Teichneret a1. (6S3) have proved that on alumina hydrogen atoms migrate from a basket containing platinum catalyst embedded
in the alumina. After the basket is withdrawn, these hydrogen atoms then activate
sites on alumina so that hydrogenation of ethylene and benzene can occur. However,
Kung, Booksc and Burwell (654) find no such activation of the silica surface. Covering the silica 'surface with {CHa)3SiO groups reduces spillover. but the catalytic
-:
activity is unchanged and resides solely on the platinum.
.:;'."
Powders
>s can be
Reactive Silica
cnd'rion
10. 19
:.!
.ce area
ixidized .
even at
/ity, but
enzyme
.emistry
b d,
firs, be .
ological
'C, but
>eculate
isplaces
ce been
0' cover-
hydroydrogen
II over"
on aluI bedded
activate
owever,
Coverat
ic
o
00
S97
The high surface area and rate of dissolution of amorphous silica permits reactions
at much lower temperatures than required with pulverized crystalline silica. The
high chemical reactivity of colloidal silicas thas been reviewed in Chapter 4.
Transparent fused silica can be formed at 2000 psi and 1200<;: from silica powder of
15 nm ultimate particles. whereas 2000C is required for blown or cast material .
(655).:
It is remarkable that fine amorphous silica reacts with ammonia at only 550C to
form Si 2N20 and at 1250 to' give SiaN. This raises the question whether a whole
. new series of silicon oxynltride refractories could be made by hot-pressing (656).
Oxygen-deficient silica glass that does not readily devitrify is made by reacting
powdered boron with amorphous silica (657). Rare earth oxides can be formed in
intimate combination with silica prior to forming glass by hydrolyzing SiCI. vapor
in an aqueous solution of rare earth salt, then drying and fusing to obtain fluorescent
glass (658).
' ,
Amorphous fine silica is so reactive that it can be used to make synthetic clays.
Hectorite, a magnesium bentonite.' is useful for making electrical insulation after
conversion to the silver form (659). Kaolin forms hydrothermally at 200-300C
. using silica gel as the source of silica (660)..
High purity silicon carbide as a light yellow powder is made from SiCI.
hydrolyzed to silica gel in a sugar solution and heating in inert atmosphere at
-1800C for 4 hr (661). .. - -. One to two percent pyrogenic silica added to Portland cement improves its
properties owing to its high reactivity (662).
Zinc ion reacts in aqueous solution with wide-pored silica gel to form zinc silicate
until about seven layers-are formed. Small pore diameter limits the stratification of
the silicate layer so that reaction is less complete (663).
0
. CloudSeeding
......
Zettlemoyer, Chessick, and Teheurekdjian (664) discovered that for the nucleation
of ice crystals, the first step in the formation of raindrops in a cloud, silica particles
30-1000 nm in diameter are active provided the surface consists of a mosaic of
hydrophilic spots on an otherwise hydrophobic surface. About 20-30% of the surface
should be hydrophobic. The interactions of water vapor with oxide surfaces have
been elucidated through heat of immersion. colorimetry, dielectric dispersion
measurements, and reflectance infrared spectroscopy (665).
The theory and practice of cloud seeding has been summarized by Boucher (666).
Apparently the nucleating effect can be attained to some extent by partly dehydrating the silica surface at moderately high temperature, but even better by partly.
covering the hydroxylated surface with chemisorbed hydrophobic organic groups or
~
organosilyl groups.
This use may some day become of practical importance if it can complete economically with silver iodide...
---598
Chromatographic Column Packings

Silica can be used in three ways as packings:
. 1. As an adsorbing surface of silanol groups or through other polar, nonpolar, or

ion-exchanging organic groups attached to the surface.
2. As a sponge to hold a static liquiiJ phase ~hich is the active adsorbent.
3. As a microporous packing of uniform pore size into which smaller molecules can
diffuse rapidly, slightly larger ones more slowly or not at all, that is, size exclusion .chromatography for determining molecular weight distribution of polymers.
"
I. . . . .
i!;
.'
...
" .i
i:
,./
. I
,' .. "
I.,
, t:', " .:.

".
i .
[ ,.
..
,I
f' r.:
I
I
I.
'
Each of these requires silicas of special structural characteristics, but in general the
following applies. '.
The powder particles should be spherical to permit uniform packing; of uniform
size to ensure uniform flow across a column cross-section; of a size, usually in the
range of 5-50 microns, to obtain maximum efficiency within the limits of practical
pressure drop through the column; and with a uniform porosity and optimum structure for the particular type of use.
.
In some uses, sharpest separations are obtained with particles that are solid in the
center but superficially porous. The porous layer holds a stationary 'liquid phase of"
absorbent into which the molecules being separated can equilibrate rapidly without
being delayed by diffusion into the centers of the packing particles.
.'.The literature on this subject has grown enormously since 1960 and the types of
special silicas developed for packings have multiplied beyond the possibility of
review.
.', .. .
The structural variables of silica column packings have been summarized by
Unger (6), including pore characteristics, surface area, and surface modifications.
He also has described a procedure for making prous silica microspheres of controlled pore size (667), by hy<Irolyzing ethyl orthosilicate in an emulsion system.
Another type of porous microspheres for use in chromatography is made by the
coacervation process of lIer and McQueston (668). In this case a particular size of
uniform colloidal particles can be used to give a desired uniform pore size. Use of
chromatographic column packings of this type has been described by Kirkland, who
also patented this use (669). The porous spheres are of uniform size in the range of
5-10 microns in diameter made up of uniform dense silica particles of much smaller.
size (670). The chromatographic performance has been described (671, 672). The
effect of pore size on chromatographic behavior has been examined by Kiselev et al.
(673,674).
Superficially porous microspheres can be made by depositing layers of colloidal
, particles on glass beads to build up a uniform porous coating that holds a liquid
phase as the stationary adsorbent. Kirkland and associates have described their
performance (675-678). Wide-pore microspheres are used for "size exclusion" or
"gel permeation" chromatography. Such materials are the subject of typical papers
(679-683) relating to their preparation and use in separating soluble polymers of'
high molecular weights. The pore diameters are in the range of 200-1500 A..
--:Is and Powders
'_ ..
'
" nonpolar, or
mt,
molecules can
is. size excluof polymers.
in general the
Ig; of uniform
usually in the
ts of practical
ptimum struc.re 'solid in the
iquid phase of'
ipidly without
d '. 'ypes of
poseiollity of
mmarized by
nodifications.
heres of con1 system.
i made by the
ticular size of
e size. Use of
(irkland. who
1 the range of
much smaller
71. 672). The
Kiselev et al.
's of colloidal
iolds a liquid
escribed their
exclusion" or
:yr: "1 papers
: p,lers or
20Q..:.1500 A.
References
S99
Generally the relation between pore diameter and specific sbrface area is
approximately in the range DA - 15000-10000, where D is diameter in angstroms
and A is in m' g-1 (680).
The silica surface is modified by monomolecular chemisorbed coatings in varlousways to change chromatographic performance. Some surface modifications with ionexchange properties have already been discussed. Esterification of the surface silanol
groupS with alcohols bearing various substituent groups has' been used in numerous'
cases, beginning with Kirkland (684). who evaluated n-butyl esterified silica. Here
the surface bond is through Si-O-C. Esterification of the surface has been carried
out with polyethylene glycol' (685). various aliphatic alcohols (686). and 3
hydroxypropionitrile (687). . . _.
"Attachment of organic groups to the surface by direct Si-C bonds generally gives
a coating more stable toward hydrolysis. Various polar and ion-exchanging groups
may be attached to the hydrocarbon group linked to silicon so that a wide variety of
surface modifications are feasible (see earlier section in this chapter on silica with
Ion-exchange surfaces). Typical work along this line has been' reported by Unger and
. others. Coatings consist of groups such as -C.H., -CH, (688); -CH,OH. -CH,CN.
~ "'CH(OH)CH(OH)-.. -CH,CH=CH,~-(<;H,)aC.H.CH,CI (689); -_ and
-CH 2C.H.NO,. -CHaC.H.NH a -CH,C.H.SO.H (690).
., .
Brust. Sebestian. and Halasz (691) modified the surface with organic groups
linked through Si-N-C bonds with functional groups in an attached aliphatic chain
such as -COOH. ...SOaH-NHa. -CN. or ~NOa. The SiOH surface is first reacted
with SOCia which converts it to SiCI. which then reacts with amines.
Another approach is to adsorb metal ions Oil the silica surface which can form
coordination complexes' with organic materials to be separated. Kunzru and Frei
(692) adsorbed cadmium ions Oil the silica surface to enhance separation of aromatic
amines.
..' .
'
..': It should also be possible to coat silica with relatively stable nonionizable bonds
formed between eOOH groups and Cr H ions adsorbed on the surface, especially in
.-the case of long-chain aliphatic acids. Terminal polar end groups could be employed
to modify surface polarity. and the hydrophobic bonding between parallel
hydrocarbon chains attached side-by-side to the hydrated, Cr,Oa-covered surface stabilizes the coating.
-. A novel type of ion-exchange surface was created by Kirkland (693). who adsorbed
alternate layers of oppositely charged particles' on the surface of glass microbeads.
On the clean glass surface a monolayer of 0.1-0.5 micron particles of strong-base
ion-exchange resin is first adsorbed. Then a layer of colloidal silica 0.0 I5 micron
particles is adsorbed on the resin layer. and the process repeated to build up a
porous film with anion-exchange sites in an efficient form for chromatographic use.
o'
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.. ---Silica Gels and Powder$:---:
600
,4 .'
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.
-;
I"
,,. ,!.,
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>
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.
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.;
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..',.'
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.'
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--
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......
"
,.
;
j.
...
"
_.v_
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,j
~
<
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.,
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-.~
..-....
'. Rererenccs
715
or decemJC by Atser
: is
nschucssel
."
eoncentra-
"';,',-
. . . . . . ".,
".z: . \'17.J:A"H~keY.Clie;;;.: Inti.' L~~don.
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,.
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.:""'.
, , ~.i-,~ Y. " 28.:~'M. N: piooite~indS.N.Gitlin). Phy.!. Cht;':'.~ 75, 3322 (1971').
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'~
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R~ Zi~-n.!r~:a~,.B._G~. H~lm,cS.a~di A~~sate~:_~.Phys. Chtm., 60, 1157(1956).<
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38. C.Okkerse,Ref.ll,p.2SI. ,
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,'~
;:
~4'"
,,_ '
'4
' ....
;:,.' .. , ,.' ",~'.. ':
~_ "",;".
-:
~.'
. ...;
_.,; . :~~"
.'
.f,: "~~ri::~~~~P~:~::~~~~~: ~e~:~:~~~~;~y~~~~;!;~'6~:~~1:IS:l;~

,
"
.:.
.'
- ,'
...
,:,
_"r." ,
"
_'.
;.
' . . _...
..
41. R. K. lIer, personal

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_, ; -,
,,' ',' .-'. . . '_':
'.
' '.
'.
.'
' , . 1 ,. . .'
. _.,
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(19~)...,~ ~~'ii:~':":~"',~.'~:':::',,- -:'.'-"":~,-':-"".";"
~~
."~
i," in J. F.
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.'.-' .
':...,..
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., " .,,:,
',.1..
'",,- .
8"'~
::::..
.':.i'
"'"
- . . . .-.48.
": ..'{
._IJ
, . . , .
'
oJ..
..
'
..
J. Mo.rimotQ
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.,f_
~-.;-..
~:_..
'.
.'
'.
..,
.
ry ofSilica';~_ ,,~:.
~--.
)r decemC by At-
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..:~,~.:
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., .
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_.~
~.~.
(,',!''''".'
'!
".
-,.~..
'-'.
,'
~. ' . '
;',
'~i
.;
.!
_l~-
'.".#
~ -.
_.-.
'-
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.' ..
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" - , . - '
. "'.
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f
p
~7"
t - .. _ . ~, . ~
. _ .. _ . . . . . ~
.
~ ~_ ~
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.. -
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'
..:J.
'
... J.
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"',.
";'.
.\11":,
'
~\
_,
, .~O:~
\V..~K: ..L,~~~~.~.~.~,E.}~.
.'
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W.Noll,
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~.
'.
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...
,.
".
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.
"
..,
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...
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..
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1
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..
..
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---~
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-...-..
CHAPTER, '. 7'

.
.. -
Silica in. Biology

.. :
,
.. < ~
<
,..:
INTRODUCTION
;' :1.
.
:
...
'
Since the survey by Her in 1955 (1) of silica in living organisms a brief survey of the
relation of silicon to life has been written by Hunter and Aberg (2). Also there have
. appeared a short monograph 'by Mohn (3) and a book by Voronkov, Zelchan, and
Lukevitz (4a). Mohn summarized mainly the literature of the last quarter-century,
including a brief review of silica chemistry as related to biology and extensive experiments on the uptake of silica by rats when various forms of it were added to the diet.
Voronkov and associates presented an exhaustive survey of the occurrence of silica
in nature, its possible role in the origin of life, distribution in all types of living
organisms, toxicity, and therapeutic uses of new organic derivatives of silica and
silicon, accompanied by more than 5000 references.
,
A summary of the literature of silica biogeochemistry was presented by Leo and
Barghoorn (4b), who discussed the cyclical movements of silica, including passage
through the biosphere. "
In this chapter some of ~these aspects are reviewed briefly. Attention is
concentrated on the chemistry of soluble and colloidal silica in relation to interaction
with biochemicals and biocolloids.
In many biological studies, data are given in terms of "silicon" rather than
"silica." Since there is little evidence that silicon occurs in any biosystem in any
form other than in coordination with oxygen, data are referred to here in terms of
"silica" or sio,
The fossilization of life forms has already been described in Chapter I since there
is no biochemical involvement of silica.
ORIGIN OF LIFE
Even though silicon is one of the most abundant elements. it has been considered to
be nonessential in most living organisms, whereas carbon, which is far less plentiful,
is the primary element upon which all life depends.
However, it .has been suggested that compounds of silicon originally may have
played an important, perhaps necessary, part in the origin of life. As pointed out by
For an excellent survey see G. Bendz and I. Llndqvist, Eds .. Biochemistry or Silicon and Related
Problems. Nobel Foundation Symposium 40. Plenum Press. New Yurko London. 1978.
730
Earliest Life Forms
.
.-:;
,,.1
731
Gamow (5), the transition between nonliving and living matter may have been very
gradual. Oparin (6) has postulated that life first began through the association of
simple, naturally occurring carbon compounds with inorganic colloids. Bernal (7)
has speculated on the possible role that colloidal silicates played in catalyzing the
formation of complex organic molecules from simple ones. He presumes that the
original atmosphere prior to the appearance of life must have consisted of hydrides
such as methane, ammonia, hydrogen sulfide, and water vapor. As shown by Miller
(8) amino acids can be formed from methane, nitrogen, and water vapor under the
influence of electrical discharges, so that a wide variety of organic compounds may
have been present in the ancient seas. 'Bernal suggests that a concentration of simple
organic molecules might have been brought about by adsorption on colloidal clays,
. ~ which have an enormous surface area and an affinity for organic matter. He points
out that small molecules attached to the surface of clay are not held at random, but
. are in definite positions relative not only to the clay but to each other, and are thus
held in a position so that they can interact to form more complex compounds, espec" cially if energy is supplied in the form of light. The formation of asymmetric
..- molecules which are- characteristic of compounds occurring in living organisms
might have first occurred, according to Bernal, through preferential adsorption of a
,: pair of asymmetric molecules on the surface of quartz, which is the only common
-_ mineral possessing an asymmetric structure.
It must be recognized that, even though complex organic molecules might have
been formed originally through the agency of such inorganic catalysts, this was only
the first step out of hundreds or thousands of reactions which must have occurred
subsequently in order to produce the first true "living" organism, that is, one having
.the power io 'reproduce itself; To say that this first step was the "origin of life" is
like' saying that the first removal of a' piece of iron ore from the ground was the
.
origin of the automobile:-~~;. .' "
" The role of silica in prebiotic 'evolution was reviewed by Janet (9), and its role in
the evolution of life has been. further considered by Sedlak (10) and Vysotskii,
Danilcv, and Strelko (11): If th.e colloidal silicates first furnished a molecular pattern in the origin of life, the pattern was no longer needed once a highly ordered
"living" arrangement of organic matter was established. However, if the hypothesis
is correct, the crystal pattern of the silicate should have left some imprint upon the
structure of living matter. For example, there should be some relationship between
the molecular structure of biological materials such as proteins and the atomic spacings characteristic of the surfaces of colloidal silicates such as bentonite,
paligorskite, or kaolinite.
-YoronkowZelcban, and Lukevits (4a) have summarized all the beliefs and
hypotheses of the last 2000 years on this subject, including the possibilities of other
life forms in the universe based on Si-Si, Si-N, or Si-C polymers.
EARLIEST LIFE FORMS

By far ~h'~;oldest fossil remains of living organisms are the blue-green algae embedded in chert (microcrystalline silica), discovered by Barghoorn and Tyler (12) and
., -...,_...
Silica in Biology
.,
:\
Figure 7.1. Colloidal.silica adsorbed on an alga membrane. .>
further studied by many others (13-17). These microscopic life forms were obviously
closely associated with soluble and colloidal silica since they must originally have
been embedded in silica gel. These organisms lived 3.5 billion years ago, probably
only 1 billion years after the earth was formed and long before the Metazoan life
forms proliferated 0.6 billion years ago. It was during the intervening 3 billion years
that the blue-green algae are thought to have converted the original reducing
atmosphere to an oxidizing one by producing oxygen by photosynthesis. It is now
thought that photolysis of water in the upper atmosphere, with loss of hydrogen into
space, could not have provided much of the oxygen during this Precambrian period
( 18).
There is as yet no evidence that silica is necessary to the metabolism of blue-green

algae, but at least one type observed by Her grows readily inconcentrated 30% sols
of colloidal silica. Well washed cell membranes are found to have absorbed colloidal
silica as shown in Figure?I.
,,_ .
.,
I
in Biology
-....-..

. . "i"
;.
733
Oehler and Schopf have experimented with fossilizing algae in sili~a gel (19).
Algae were suspended in concentrated colloidal silica, gelled, and autoclaved at sufficiently high temperature to convert the gel to microcrystalline quartz. The result
was a chert-like mass containing embedded algae similar to the ancient fossils.
,
1-
..
BIOLOGICAL DISINTEGRATION"OF ROCKS
-....
:.~; :~l
...
~
":
1.
obviously
rally have
probably
azoan life
lion years
reducing
It is now
regen into
ian period
.'
~.. ~
""
:' ..,
. Although most' of the- secondary minerals such as the clays can be formed from the
primary silicate rocks by means of purely inorganic reactions in the presence of
water, this weathering process may nevertheless be catalyzed by organic agents.'
Jacks (20) has reviewed the work of a group of Russian scientists, who believe that
the weathering of rocks may in many cases involve biological attack. Polynov (21)
believed that many of the unstable minerals now found on the surface of the earth
" would have long ago disappeared if they were not being continuously synthesized by
',living organisms. Aidinyan (22) reported that on rocks on which lichens were growing there was a colloidal mineral weathering product having a SiD,: R,O, (iron and
aluminum oxides) ratio identical to that in the ash of the lichen, indicating that the
" colloidal mineral was of biological origin. Glazovskaya (23) concluded that algae
.and diatoms were powerfulweathering agents and produced amorphous silica and
synthesized aluminosilicates such" as beidellite and montmorillonite. Yarilova (24)
found that lichens excreted acids which ate into solid rock and could split plagioclase
. crystals into smaller particles: Some of the clay minerals of the nontronite-beidellite
type appeared to be synthesized in the tissues of the vegetation. Bolyshev (25)
believed that blue-green algae decomposed soil minerals and brought silica and aluminaInto solution and that the silica was thus made available for utilization by
certain diatoms which accompanied the algae. Aleksandrov and Zak (26) isolated a
bacillus (B. siliceus) which decomposed insoluble, potash-containing aluminosilicates
and made potassium available to plants; inoculation of soil fertilized with nitrogen
and phosphorus but low in soluble potash increased grain yields (wheat, maize) by
50-100%. In laboratory studies, Oberlies and Pohlmann (27) found that polished
feldspar specimens were attacked by various bacteria as in corresponding studies on
glass (28). A variety of microbes and minerals were included in extensive studies by
Kutuzova (29), who found the pH of the media was reduced in some cases to pH 2,
decomposing aluminosilicates. Even quartz released SiD, to Sarcina. The various
types of bacteria that attack silicates have been reviewed by Voronkov, Zelchan, and
Lukevits (4a).
,
-'-"
....-
ASSOCIATION WITH PRIMITIVE ORGANISMS
rlue-green
: 30% sols
i colloidal
Whether or not microorganisms contain silica or have silica adsorbed on the exterior
as in Figure 7.1 is difficult to determine by chemical analysis. Separation of the
cellular organisms from contaminants such as colloidal clays is also a problem which
...;
Silica in Biology
734
casts doubt on the significance of the reported silica content of the "ash. e~pecial1y
in many earlier studies before the electron microscope became available:
. .
It
'-.
. ,
Viruses
Silica is reported to be an essential component even in a virus. Faust and Adams

(30) isolated a crystalline virus consisting of polyhedral particles from lepidopterous
larvae (Bombyx mori, etc.) and found that it contained silicon,' corresponding to
0.2-0.6% SiO,. as an integral part of the protein matrix. .
'
. Bacteria" "
With certain soil bacteria. the uptake of silicon as soluble silica in a culture medium
is followed by the excretion of phosphorus. Factors that accelerated and inhibited
this exchange were studied by Heinen (31). In theabsence of glucose. silicon was lost
in the presence of excess phosphate: Particulate fractions isolated from the bacterial
membranes were involved in the metabolism of silicon (32). Many more details were
given by Heinen in 14 papers between 1960 and 1967.
The' essential role of silica in the metabolism of certain bacteria and the interaction of bacteria and silica gels and minerals have been extensively investigated, especially in Russia, and have been summarized by Voronkov, Zelchan, and Lukevits
'(4a).'
'.
"
.
.
Fungi and Lichens . '

.....
The mere fact that fungi absorb silica when soluble silicates are added to the culture
may prove only that the resulting'collcidal silica is adsorbed on the surface of the
cells. However. the fact that in the absence of phosphorous oxygen accelerates the
uptake of silicon suggests that silicon may playa role in the metabolism (4a).
Lichens, a symbiotic combination of fungi and algae, have probably existed from
earliest times and, as previously mentioned. are probably responsible for much of
the conversion of rock to soil. The algae are photosynthetic and supply energy in the
form of carbohydrates while the fungi attack the rock supplying mineral nutrients.
In view of the highly entangled structures and close association with the mineral silicates, chemical analyses for silica content must be viewed with suspicion, but ash
contents of 10-20% silica are reported. Reports of quartz being attacked by lichen
could not be confirmed (4a).
Algae and Diatoms
Out of the thousands of types of algae, one group, the diatoms, constitute the class
Diatomaceae or Bacillariophyceae, which absorb soluble silica from water even at
'-
.,.
Association with PrimitiveOrganisms
; Biology
'.
specially
.
.
Adams
ipterous
iding to
nedium
ihibited
vas lost
acterial
ils were
interac:1, espe-
"
.~
ukevits
culture
: of the
ites the
d from
:uch of
'in the
trients.
ral siliiut ash
lichen
e ' ,;
wenat
,.
--_ ...
735
extremely low concentrations and metabolize and deposit it as an externai skeleton.

According to Calvert (33) there are more than 10,000 varieties of diatoms, some living in fresh water, some in salt water. Nearly all varieties are alike, in that their
walls are impregnated with silica. These plants are single-celled organisms consisting
of two parts with the edge of one pari fitting inside the other like the two halves of a
. pillbox. In addition to secreting the siliceous skeleton, each cell accumulates a
droplet of oil, and it is suspected that this oil, together with other hydrocarbons
formed by the decomposition of the organic matter of the diatom, might have been
responsible for the formation of a great part of our petroleum resources. Deposits of
diatomaceous mud as large as 400 miles long and 100 miles wide have been found
off. the coast of Africa. The organic shales from which petroleum is obtained are
believed to have been formed from thedead bodies of these organisms which were
deposited on the bottom of ancient oceans. Photographs of some of the beautiful
forms of the microscopic skeletons of diatoms are shown by Calvert.
Seawater contains only 2-14 ppm of Si02 and is far below saturation with respect
to amorphous silica (34). Part or this is suspended fragments of siliceous organisms
. (35). Siever has pointed out that the major mechanism for the precipitation of silica
on the surface of the earth is biochemical (36). The various organisms responsible
.' for silica deposition were reviewed by Voronkov, Zelchan, and Lukevits (4a). The
microcrystalline quartz minerals jasper and chalcedony are probably transformation
products of very early diatomite deposits. About two-thirds of the deposited silica is
from diatoms and the remainder from radiolaria and sponges.
A certain. minimum concentration of silica in solution is essential to the growth of
. each kind of diatom. Increasing silica content from 3.5 to 8.3 ppm doubles the rate
of growth of one type of diatoms of which the dry weight of the cells is 4-22% SiOs
(37). However, some species which contain only 0.4% Si02 C!ln obtain enough silica
for growth from ordinary: glassware. Lewin found that colloidal silica will not support growth until it depolymerizes to soluble silica. Navicula pelllculosa requires 35
ppm for maximum growth rate (38). Growth rate in seawater falls off as the silica
content is reduced by overpopulation (diatom bloom) (39). Diatoms can reduce silica
concentration in water down to less than 0.08 ppm, and when cell concentration is
, high, an inhibitor is given off which retards silica uptake (40). The half-saturation of
silica uptake varies with different species, ranging from 0.05 to 0.2 ppm SiOs (41a).
Apparently below. a concentration of about 0.06 ppm, Si0 2 is not available to these
. organisms' (41b). When silicon becomes depleted, cells become coated with a
gelatinous capsule of polyuronide of glucuronic residues (42).
A monograph by Lewin and Lewin (43a) summarized what was known of the subject in 1962, and Voronkov, Zelchan, and Lukevits (4a) listed references up to 1975.
A monograph on the biochemistry and physiology of diatoms (43b) appeared in
1977.
.
,
The siliceous skeleton 9f diatoms is a marvel of complex design extending to
molecular dimensions. Electron micrographs showing the fine structure of some
diatoms are shown in Figure 7.2. It will be noted that the geometrical regularity of
. the structure is characteristic not only of the larger portion of the skeleton, which
can be .observed by the optical microscope, but is continued down to the smallest
, -....,--
-----
Silica in Biology
.r
!
,j
"
'~
" ..
Figur,7.2. 'Electron micrograph of the silica skeleton of a diatom. [Iler {l):by permission of
Cornell University Press.]
~.
.:
..
.-
units visible at a magnification of 100,OOOx. The silica is tightly enclosed in organic

material and is not exposed directly to the surrounding water. The silica is thus
obviously deposited from" within the tissues in well defined patterns (44). A review of
the silicification: process has' been prepared by Darley (45). The skeleton is a
microporous ' silica' .gel that exhibits ion-selective properties. The properties of
the silica isolated from freshly killed cells by dissolution of organic matter in 70%
HN03 are very different from those of diatomaceous earth which has undergone
densification and even crystallization on a submicroscopic scale. The freshly isolated
silica was observed by Iler to have a specific surface area, by nitrogen adsorption, of
more than 100 m2 g-I and if not dried, has further microporosity accounting for the
selective ion-exchange properties. The area of diatomaceous earth;;housands of
years old is much lower since the silica has become microcrystalline (46a).
Electron micrographs at very 'high magnification by Pankratz reveal two kinds of
structures in acid-cleaned silica from a radiolarian. According to Hurd (46b). who
prepared the specimens, Figure"7. 3 shows silica as 500 A thick lam ina separated by
open channels.i The darker silica appears to consist of aggregated ultimate particles
about 200 A in diameter. This would correspond to a specific surface area of 140 m 2
g-I. Figure 7.4 shows an apparently continuous matrix of silica (darker material)
. full of round pores or' holes 20-500 A in 'diameter.
The question is whether in the living cell the open spaces in the silicaare occupied
by living tissues or only an aqueous phase. The mechanism by which silica is
deposited in predetermined form "is unknown. Observation of the early stages of frustule formation in a diatom have been described by Dawson (46c).
- A
......-ica in Biology
r'~iJ~
737
A peculiar dark green alga. found by lIer growing in concentrated c~lIoidal silica
at pH 9-10. was described by Kingsbury (47) as being unusually small; the cells were
around I micron wide and 2 microns long. Iler has observed algae of this type in
which the cells are enclosed in a tubular casing or skin. from which fibrils extended
out all around to a total width of 3 microns. A section of the sheath. bearing
adsorbed silica, was shown in Figure 7.1. A supply of nitrate and phosphate greatly
accelerated growth.
The extraordinary occurrence of quartz crystals 100 nm in size in the cell wall of
the microorganism Chlorochytridian tuberculatum was described by Brandenberger
and Frey-Wyssling(48). It is extremely unlikely that quartz crystals of such small
size could have been present as a contaminant and it can only be concluded that the
crystals were formed in situ. The question arises as to why the siliceous skeletons or
decomposed diatoms do not redissolve in the seawater, which is greatly undersaturated. Jorgenson found that the skeletons of freshly killed diatoms dissolved in water
(49), but as shown by Lewin (SO) and discussed in Chapter I, the rate of dissolution
is very slow when traces of aluminum and iron are present.
. Metabolism involving silica has been studied in diatoms by measuring the effects
of silica-deficient growth conditions. Lewin found that silica is not taken up by
washed. ceUs until 'supplied. with ~ sulf~r compound. Cadmium inhibited uptake.
.}
.\
permission of
di
rganic
ilica is thus
A review of
.eleton is a
roperties of
itter in 70%
i undergone
shly isolated
lsorption, or
iting for ,the
iousands of
'.. :;
.. : ..
'.
...
.,'
:.
"
.wo kinds or
. (46b). who
eparated by
ate particles
ea of 140 m2
er material)
Ire occupied
ch "ica is
age ...3 frus-
figure 7.3. Biogenic silica. 'acid cleaned. from a radiolarian showing silica lamina made up of
ultimate particles aboui 200 A in diameter. [Courtesy' of Hurd and Pankratz (46b).]
..
'";...---
Silica' in Biology
738
':
c:
area
"
'
Figure 7.4. A different

or silica shown in Figure 7.3, where the silica is a continuous
matrix full of rounded por~s (lighter areas) 20-500 A in diameter. [Courtesy or Hurd and Pan..'" ,:-:"':1<.'., ". '.> ,-0. ' . . . . " . '
.
kratz (46b).]
TI'
...
..~:
~'
,-.
possibly by sequestering the" sulfur compound. The uptake is also an aerobic process'
.(51). Relation between uptakes of IlSi0 2 and uC0 2 indicated that during uptake of
silica more carbon went to amino acids but when uptake of Si0 2 ceased, the carbon
went to form sugars (52).,' In a study by Azam, Hemmingsen, an Volcani (53) the
. ingested 'I1Si02 first accumulated in the cytoplasm, almost certainly indicating that
silicic aid was is some chemically combined state. It was not in equilibrium with the'
external aqueous medium and was concentrated more than 30-fold in the cytoplasm.
Uptake was inhibited by inhibitors of metabolism such as 2,4-dinitrophenol. Energy
is required for the uptake and deposition of silica as evidenced by the consumption
of nucleoside triphosphate (54).
The critical role of silica in the early stages of development of diatoms, algae. and
plants is suggested by abnormalities in the development of Cyclotella cryptica (55.
56). As also observed by Azam, Hernminsen, and Volcani. germanic acid is an
inhibitor for silicic acid in diatoms.
The compound 2.3-cis.lrans-3,4-dihydroxyproline was identified in the cell walls
of diatoms (57). The question whether this could be related to the mechanism o:
'. i,
. silica metabolism and transport is a matter of specuJation(58).
, 'The concentration of silica in algae of many types and a review of the literature on
Association with Primitive Organisms"
n Biology
..,
"
.,
739
diatoms was presented by Voronkov, Zelchan, and Lukevits (4a). Silica was found
to stimulate TMP kinase and DNA polymerase in C. fuslformis according to
Sullivan and Volcani (59). The details of silicic acid requirements for these enzymes
were investigated by Sullivan (60). Apparently silica plays a very fundamental role
in the metabolism of algae. In the absence of silica, the entire cell becomes disorganized and cannot keep on dividing according to Reimann (61). It is possible that
silica plays a role in the ON A of algae as it may do in higher organisms.
Sponges
entlnuous
and Pan- "
: process
ptake of
: carbon _
(53) the
.ing that
with the
:oplasm.
. Energy
umption
The silica from sponges is also the source of some silica minerals. The silica content
of sponges varies widely from 1 to 90% (4a). The hard, rigid sponges are reported to
have skeletons consisting 'of crystalline spicules of "cubic opal" or silicic acid of
cubic symmetry.The glass sponges are very rich in silica; the needle sponges consist
of "cubic opal" cemented by protein material known as spongin, and the four-ray
sponges contain "tetrahedral opal."The strong, tough mineral flint. from which
arrowheads were made, is believed to have been derived from the siliceous spicules
" of fossil sponges (62). The SiOz may only be "crystalline" in appearance.
-Sponges may absorb so much silica as to lower the silica content of the water of
inland seas. Votintsev (63) reports that the water of Lake Baikal contains less SiOz
(2-4 mg 1-1) than its tributary river (7-10 mg ]-1) because of the presence of siliceous sponges. The silica" content of the sponges was about 30% of the dry organic
material, and the dead remains formed a typical siliceous sediment on the bottom of
the lake. The silica is generally amorphous in spite of the particle shapes suggesting
possible crystals. One sponge, Geodia gibberosa, contains S5 micron spherules with
a solid glassy core covered, with small projections 3.5 microns long which were
proposed for use in chromatographic columns (64). In some sponges the amorphous
silica is embedded in a protein (65). The size of the spicules increased with decrease
in number as the silicate content of the growth medium was increased, while growing
.
freshwater sponges (66).
The flint boulders embedded at certain levels in chalk strata in England were
apparently formed by the gradual syneresis of sponge skeletons. Each skeleton
gradually shrank and turned into a rounded boulder. This is a remarkable example
of the decrease in surface area even with only a very small decrease in interfacial
" surface energy over a period of 80 million years. Within the boulders trapped
belemnites, oysters, and other debris have been noted by Iler.
.
gae, and
fica (55,
id is an
:11 walls
nis . ')f
\--~_.-:
ature on
-,
Gastropods, Sea Cucumbers, Limpets
The teeth of the limpet P. vulgata were shown to consist of 80 nm fibers rich in SiOz
probably bonded together by Fe Z0 3 (67). In the sea cucumber (Mo/padia, intermedia, Holothurioidea) it is interesting that silica occurs in granules in the skin in
the form of spheres 100-190 nm in diameter mixed with spherical particles of "ferritin" of the same size. "The latter is a calcium-magnesium-basic iron phosphate
(68). The biological role of the silica is unknown, but since the ferritin may serve as
\I
740
---_.
Silica in Biology
a reservoir of iron for the organism perhaps the silica is also kept as a reserve supply. This suggests that silica may play an unusual metabolic role in this organism (69).
PLANTS
It appears that although silica may not be necessary to the healthy growth of most
plants, it nevertheless often seems to have secondary effects. For example, some
plants employ silica for building certain parts of the skeletal structure; others take
up silica from the soil even though the silica has no apparent useful function. The
question of the nutritional value of silica is confused by the fact that in some plants
.. the presence of silica seems to enhance resistance to fungus disease, making the
plants appear healthier. Also, on some soils, the addition of soluble silicates
increases plant growth indirectly by liberating phosphate ions adsorbed on the soil,
thus increasing the total amount of available phosphate. The need for silicon in
plants has not been demonstrated except in a few isolated instances; it is not easy to
remove all traces of silicon from artificial growth media (70). Sprecher (71) believed
that silica has an important biological' function in. stimulating plants to greater
growth and probably plays a role in maintaining a ."physiological equilibrium" in
the nutritive
.
. solutions in the soil.
.
" It is usually difficult to prove that silicon is essential to plant growth, but at least
in the case of beets (Bela vulgaris), silicon appears to be an indispensable element
for growth, according to Raleigh (72). The importance of silica in the physiology of
. -, rice . and barley; has been emphasized by Okawa -,<73). For example it was .::
,demonstrated that the silica is useful to the young plants as a nutrient. Silica is also
necessary in order that the rice plants may open and, in general, appears to be
necessary for normai growth, especially in forming the' ears. For some unexplained
reason, young barley plants appear to be protected from injury, by cold if colloidal
silicic acid is present in the .culture solution. Lipman (74) added sunflowers to the list ,'.
of plants which appear to require silica; the yield of seed was increased in the ', ..
presence of silica. The possibility that silicon might be taken up as a substitute for .. ;~
boron is suggested by the observations of Das and Montiramani (75). Gram (mung
bean) plants which showed yellowing were found to be richer in silica and lower in
boron than healthy plants. .
,
..
However, the difficulty of determining whether silica is directly affecting the plant
itself or. is merely modifying. the environment is ,typified in the investigation by
Onodera and Kageshima (76a) of the effect of colloidal silica on rice. The addition
of colloidal silica to rice grown in nutrient solution appeared to make the plant more
tolerant of potassium. However, it is equally possible that the silica acted as an Ion"
adsorbent and therefore kept the potassium ions out of solution .and away from the
plants. ',.
. .:'
~
The pollen of certain plants. such as Lychnis alba. has 0.8% silicon (about 2%
Si0 2) apparently concentrated in the outer structures to improve resistance to decay
.. or weathering (76b).,
'
.,..
In many plants soluble silica appears to be taken into the plant merely as an Inerts-:
component in the water and then deposited wherever it is concentrated as water
r:
l.
1 in
Biology
Plants
eserve supinism (69).
.',
th of most
iple, some
ithers take
ction. The
orne plants
laking the
e silicates
In the soil,
silicon in
lot easy to
I) believed
to greater,
brium" in
......
'-::~
.."
--:
iexplained
the plant
gation by
e addition
Jant more
as an ion
. from the
about 2%
: to decay
.s a, _.~lert '
as water
, It is generally observed that silica' deposited within plant tissues is amorphous.

'Nevertheless, several cases of crystalline silica have been reported although there is
no way of knowing whether these might have been due to mechanical inclusions of
dust.' Umemoto (77) claims that
low temperature plasma method of obtaining
plant ash is essential to avoid thermal effects. (This avoids the possible hazards of
using powerful oxidants.) Although silica was primarily amorphous Umemoto
reported that it was mixed with small amounts of alpha quartz. Lanning (78) and
Sterling (79) definitely report quartz in various plants.
Silica deposits in plants occur most commonly in the form of particles of characteristic shapes (phytoliths). The shapes are characteristic of a given plant and vary
enormously between different species (80). In grass the silica content may be 2% and
cause death of calves from silica calculi in the urinary tract if salt is not added to
their diet to make them drink more water (81). The phytoliths pass through the intestinal tract and accumulate in' the soil (82). The phytoliths are opal-like (hydrated
, amorphous silica) and occur' in the tissues of grasses in a three-dimensional distribution (83) in such away 'as suggestsilica is excluded from the cells and is deposited
essentially as silica get in'-spaces between cells (84-86). The silica is transported as
Si(OH). and then concentrated and gelled as water evaporates from the leaves (87). It
, , is not surprising that the edges of leaves of sorghum wheat and corn are most highly
',' silicified, -because silica is found most highly concentrated where water is lost most
rapidly (88). The structure of silica in several plants has been shown to consist of a
., dense gel with pores 1-10 nm diameter full of water; the silica is completely amorphous (89). The pattern of distribu tion has been studied by examining the spodograms
or ashed images (90) of leaves. The pattern varied even with different species of wheat.
Lanning compared the index of refraction and X-ray pattern of the silica and concluded it was biogenetic opal since it was amorphous and not very porous (91). It is
peculiar that on the same soil under identical conditions different plants accumulate
very different amounts of different elements. Analyses of dry matter by Cooper,
Paden, and Mitchell (92) were as follows as percent by weight of element
,ut at least'
Ie element
'siol,,~y of
Ie
was
licais also
ears to be
evaporates from the leaves. In other cases, the deposition of silica is r~stricted to
certain characteristic regions and excluded from other regions. For example, as it is
, concentrated and converted to colloidal form it cannot pass cell mern branes and so
remains where it is concentrated. Finally, in some plants the silica must enter into
the plant metabolism since it is transported and deposited in very precise forms, as
in the case of the hollow stinging needles or nettles.
Nature of Silica Deposits in Plants
f colloidal
to the list'
sed in the
stitute for
am (mung
j lower in
741
..
to
. Element
,.,Si
Ca '
'.
Al
P
N
Cotton
Wheat '
0.08
1.21
0.08
0.41
2.42
1.00
0.13
0.10
0.11
0.53
----
742
Silica in Biology
The difference in silica content can surely not be explained by the' diff~rence in the
amount of water transpired. Holzapfel and Engel showed that the uptake and
'deposition of silica in wheat could be influenced by experimental conditions (93a).
Streagthening Plant Parts

Though the deposition of silica as phytoliths does not necessarily benefit the plant.
silica that is distributed precisely through the structure. especially in stems, plays a
definite strengthening and stiffening role. This is a general effect in many common
plant tissues, including "the stems of grasses and grains. the hulls or shells of certain
nuts. bamboo, certain species of wood. and the spines and stinging hairs of some
plants such as -nettles, Silica-hardened tips of hairs or spines on some plants provide
protection against herbivores (93b).
-
"Equisetum
The Equlsetum genus (horsetail) contains so much silica it was used in the kitchen
as "scouring rush."Pioneers used it to clean the teeth. According to Frison (94)
these plants were used for" centuries as abrasives, one type being 'employed for
polishing wood and another for household utensils.
,Silica in E. aTve~eis deposited aslong fibers within the epidermal membrane and
is also exuded as wormlike projections until the surface is covered with opaline silica
" (95). Silica probably occurs" in the epidermis in organic combination with the
cellulosic material of the: cell, wall. according to _Viehoever and Prusky (96). This
conclusion was reacheden.the basis of the observation that the epidermal tissue
"remaining after disSolying" away cellulose in cuprammonium hydroxide solution
consisted of a combination of silica with organic matter. When treated with HF. it.
"became soft and thengave a positivetcst for cellulose. Also it showed considerable
resistance to attack by cellulose-destroying bacteria. Details of the deposition and distribution of silica were described by Kaufmann et al. (97a-e). who also reviewed the
literature on silica in Equisetum (97b).It was found that the silica is deposited suddenly at a certain stage .in cell -differentiation. The distribution of silica in perennial
scouring rush (Equisetum hyemale var. affine) was examined by the scanning electron
microscope along with the electron microprobe. which reveals the silicon concentration at each point in the structure. Silica is deposited only after the cell wall has been
fully elongated but not in those sections of the stem that are still growing. This is true
-also in oats and rice plants.:
.
The above-mentioned microfibrous silica in Equisetum arvense described by
Laroche (95) may be formed by the same process by which silica gel is excreted
within cells from the inner surface of the membranes in Avina sativa. As shown in
electron micrographs by Kaufman et a1. (97c). the silica appears to be extruded as
fibers around 120 A in diameter and 120 A apart. from the inner surface of the walls of special "silica cells." As the mass of parallel fibers grows away from the
membrane surface it seems to undergo syneresis like most freshly formed silica gels.
, -
.. --.-Biology
Plants
ein the
However, because of the oriented structure there is shrinkage in only two 'tiirections
and the fibers are drawn together into parallel bundles or rods about 600 A in
diameter. In the micrograph the dried: silica is disrupted but in the living cell the
silica forms a lining within the cell in which therods project from the surface like a
. pile carpet. ':"~ :;.";- . ..
The silica, having been formed by polymerization at ordinary temperature,
probably consists of close-packed ultimate particles of SiOI with surfaces of SiOH
groups and with water held tightly in the micropores between these small particles as
.in microporous silica gels formed in the laboratory. If suitably dried, such gel should
have a specific surface area of more than 400-600 m l g-l. _ .
,
The fibers n.tay be formed by biochemical concentration and release of Si(OH). on
the outer side ,of the cell membrane. This may then diffuse through closely spaced,
sieve-like holes 120 A in diameter in the membrane and polymerize continuously at
each hole at the inner surface of the membrane.
Kaufman suggested (97d) that silica polymerization is inhibited in regions where
the hormone gibberellic acid causes a lowering of the pH from 6.5 to 5.0 or less, as
noted in elongating cells, for example (97e). It may be significant that such a drop in
pH would stabilize thetropolone-type chelates of silicon and thus inhibit release of
monomer (seeWeiss, in ~ef. 127).'
.. ,
.ke
Sl1'1d
na,
e plant,
plays a
ammon
certain
If some
provide
citchen
on (94)
/ed for
Bamboo
me and
e s'" 'a
ith ..e
). This
~ tissue
olution
HF, it
ierable
nd diszed the
:d sudrennial
lectron
centrais been
is true
Jed by
.creted
own in
ded as
ewalls
m
'a gc.s.
743
; .: . ~_. :
'The ha~dness and stiffness 'of bamboO-can be partly ascribed to silica in the fiber
structure. However, such excesses of silica are taken up that masses of silica gel are
often found in the hollow .stems.' This gelatinous material containing some organic
matter, known as tabasheer {also tabashir and tabaschir), used to be employed in the
Orient as a medicine. According to' Frison (94)'this material has, been known from
antiquity in China' and India arid was reported by .odorico' Porto, a fourteenth. century contemporary of Marco Polo. Interest in this curious substance seems to be
revived periodically. It was studied by European chemists in the latter part of the
nineteenth century, then essentially forgotten until Rakusin (98), in 1926, reviewed
what was known about it. A year later, Wolter (99), studied the peculiar physical
properties of this gel, but since then it has received little attention and has not been
examined by modern techniques. According to Rakusin, tabasheer was also known
as bamboo sugar because of its sweet taste. Evidently the silica gel also contains
sugars or other 'organic material from the plant juices. The inorganic part of
tabasheer is 99.9% Si02 Presumably because of its purity, tabasheer was patented
for use in making cracking catalysts (100) in the East Indies.
As long ago as' 1791~ tabasheer was studied by Macie (IOI), who prepared sodium
silicate from it.A century later, the physical properties were studied by Cohn (102)
and van Bemmelen (t03). According to Cohn, the pore volume of the gel is 0.75 ml
g-I. The transparent homogeneous pieces are amorphous, and the pores cannot be
seen under the optical microscope. However, the porous mass imbibes different
liquids giving a glass-clear solid; in the course
the absorption, the mass appears
fluorescent. By coloring the mass with various materials, Cohn prepared synthetic
of
..
.... ~.j'
~-_.
Silica in Biology
744
opals and onyx. Cohn stated. "Neither in the vegetable nor animal kingdom ~s there
an odder material than tabashir." Wolter (99) investigated tabasheer which was in
the form of glasslike pieces weighing 3-15 grams. This material in some respects
"resemblesthe opal obtained by drying silica gel very slowly. The refractive index of
tabasheer is about 1.18. By putting it in various liquids. the refractive index can be
. changed. Calcined tabasheer takes up about 166%' of its weight of water. The
specific gravity of calcined tabasheer is 0:54. and the silica skeleton occupies 25.7%
,. of the volume. It has about the same adsorptive capacity for various liquids as commercial silica 'gel. Tabasheer is present in an astonishingly porous form in the plant.
It takes up iodine solution. methylene blue. or phenol very readily. More recently
the properties' of tabasheer were examined by Jones. Milne. and Sanders (104). who
found it to consist of an opal-like silica gel consisting of clusters of 10 nm silica
:", particles:
Grasses
.-
.'
Many orthegra~ses. reeds, and straws owe their weather resistance (e.g. thatching
of roofs) to heavy impregnation with silica (94). Rice hulls are very high in silica.
The shiny epidermis of rattan. used for furniture. is impregnated with silica.
Both the straw and grain of wheat contain silica. The silica content ofthe straw
ranges from 2 to 3% and makes up about half of the total ash. The upper half of the
stalk contains twice as much silica as the lower part. Also, the grain contains from
0.07 to 0.025%, according to Ccppenet and co-workers (l05).'The silica content of
wheat at various stages of growth was studied byChene (106).
'
A consequence of the silica content of grain is that beer is essentially a saturated
solution of silica: accordingto Stone and Gray (107, 108) assays of 14 types of beer
showed ~IOO ppm Si02which came almost entirely 'from the malt husk, The
grasses such as oats and wheat are strengthened by deposition of silica in specialized
epidermal cells (109).
"- : 1
'
.
Spiny Plants
.
.'
...
Certain plants secrete almost pure silica. particularly in spines or spicules. For
example. according to Noguera (1I0). two South American plants. Melinis minutiflora and Pappophorum silicosum.: form readily: detachable spicules containing
75-84% Si02 The dried flowers- contain 7.S and 10% Si02 respectively.
Nettles are reported to have silica in the barbs. Dried nettle plant (stems and
leaves) contained 3.3% by weight of StO, (111). Figure 7.S shows two of the barbs at
lowmagniflcation. In transmitted light, the tip is glass-cleat and. when fresh. filled
with liquid containing a few bubbles. According to Strasburger et al. (1I2a) the tip
of the. tube is siliceous. and the base (bulb) contains calcium. The liquid contents of
the tip are released when the tip penetrates the skin and breaks off. The liquid is
highly poisonous and contains a proteinaceous toxin. Some tropical nettles are not
only painful but dangerous. inducing cramps.
"
"
'-.
745
Plants
Biology
res,
..
is there
1 was in
.;:
- ",; ~~
.s
index of
( can be
:er. The
..'I'!
:-
....
,
.....
w
.
~
..
,:-,~ '
".,.
.,' I.:
s 25.7%
as cornIe plant.
recently
14), who
m silica
-' ' .-
....... f
,'".
....
.- _ f
. ,
..
..
'
~:-:~. ;. ~~ -,
;-,.
....
....,
"
.
,..~
".
. :. -.
:-'-
.;'~~,~".;.
\.
.' .
. -:-"
latching
n silica.
straw
If of the
ns from
~e
lte
')f
.turated
of beer
ik. The
cialized
Figure 7.5. Photomicrograph of the stinging hair of nettle. [ller (I) by permission of Cornell
University Press.]
."
.~.
When the leaves touch the skin lightly, the fragile barbs penetrate the skin, but
.when the contact is sudden and hard, the barbs tend to break off before the skin is
penetrated. This idea lsexpressed in an old rhyme (contributed by Mr. F. C.
Carlson, Wilmington, Del.):
es. For
minutiitaining
ms and
'arbs at
1, filled
the tip
.ents of
iquid is
are -ot
--
Nettles
Grasp it with a touch that's gentle,
And it stings you for your pains,
Grasp it as a man of mettle,
And it soft as silk remains.
Anon.
Without silica, nettles do not develop the ability to sting. Barber and Shone (112b)
described experiments in. which the nettle Urticaria dioica was grown in a culture
solution nominally free of silica. The leaves showed little stinging ability. Then a
solution of silica was added to the culture medium and in 2 weeks the stinging hairs
..
"
.. -
~--
Silica in Biology
746
had become effective, presumably because they had become stiff by the deposition of
silica.
In the stiff hairs covering the stems of some types of poppy plants the silica fills
the. space between closely packed fibers of cellulose (113). According to Tingey and
Pillemer (114) sharp plant hairs or tichomes protect plants by impaling insects.
Obviously such hairs or needles as in nettles and thistles protect plants against being
eaten by animals. This role of silica in barbs may be universal, but has been actually
proved only in a few cases.
";;'
Job's Tears
The seeds of this plant (Coix lacryma L.), hard, brilliant, and neatly spotted, are
used for beads. The epidermis is so heavily impregnated with silica that opal can be
scratched with it, according to Frison (94).
Palms
The leaves of the palmyra palm of India, used for centuries as writing paper, contain
beautiful siliceous concretions. The endocarp of the ivory nut contains a layer of
elongated cells assembled in palisade-like formation, each cell having a funnelshaped lumen filled with silica. Frison developed a method for preparing specimens
for optical examination so that the beautifully formed spines of silica, each covered
with still finer spines. could be readily observed by microscopists. Siliceous concretions also appear in the endocarp of the coconut and in coco fiber, bass fiber, and
Manila hemp;
:
Wood
',~
l
.. ~- i
'
.{
:.','il
r.
1.
j:
',
-,
I"
1
, .According to Frison (94) siliceous concretions' in the form' of dense silica particles
within the cells often occur in tropical woods and contribute to blunting of saws and
other tools. Up to 3.18% by weight ofSi02 has been found in some types; more than
50 varieties of tropical woods (e.g. teak) contain more than 0.5% silica. However,
no trace of silica has been found in wood from the temperate zones. Certain tropical
woods have a high resistance to marine borers (teredo). It has been conclusively
demonstrated that this resistance is due to the presence of silica particles: wood
containing more than 0.5% of silica is practically immune. Amos (115) has listed 400
siliceous timbers (more than 0.05% SiO z) belonging to 32 families. in regard to Si02
content. resistance to borers, and working properties.
Amos and Dadswell (116) have investigated the occurrence of silica in the wood of
the Australian turpentine (Syncarpia laurifolla Ten.), which has a worldwide reputation for resistance to the marine borer. It was shown that the resistance to the borer
was related to the silica content (0.59% Si02) . since timber from this same species
grown in' Hawaii, having a content of only.0.09% Si02 , exhibited low resistance to
the borer. It has been suggested that the silica particles in the wood damaged the
minute cutting teeth of the borers, but these authors believe that the silica may act
. .:
.,
I
in Biology
position of
sil
fills
"ingeyand
19 insects.
iinst being
actually
:n
ott ed, are' '

pal can be
r, contain
layer of
a funnel-
specimens
h covered
IS
concre-
lib
and
particles
saws and
nore than
However,
n tropical
iclusively
es: wood
listed 400
d to Si0 2
: wood of
e reputathe borer
e species
stance to
ag the
may act
--_ ..
Plants
747
as a poison, since it is soluble in very weak alkali and would therefore ~ass into solution in the alimentary tract of the organism.
~. '
.~.
..
- .~
'~'.".
..-
.~'
_Mechanism or Absorption, Movement, And Deposition or Silica
:' In view of the solubility of silica in water and the relatively large volumes of water
drawn 'up into plants and transpired, it is remarkable that all plants are not highly
-.silicified. Frey-Wyssling (117) believes that the secretion of silica in plants should be
considered as merely a separation 'of nonassimilable material taken in with the
transpiration stream. This point of view explains the accretion of silica within hollow
....', sterns," as in. the case of bamboo, but does not explain the formation of specific,
highly silicified elements of plant structure such as the stinging hairs of nettles.
-: However, as Frey-WyssIing points out, .in most plants silica is deposited in
peripheral tissues and along conducting vessels, and in this regard resembles the
separation of calcium sal~s which are taken in inadvertently and are deposited in
some plants in much the same w a y . . ~.'.
. :, The mechanism by which silica is brought into solution by the roots of rye and
sunflower was examined by Whittenberger (lIS), who found that, with 450 ppm of
silica in the culture solution, the plants accumulated silica primarily in the roots. In
view of the fact that silica is soluble to the extent of only about 100 ppm, it is now
evident that much of this accumulation must have been due to the filtering out of
colloidal 'silica on the root membranes. However, at less than 150 ppm (correspond. ing approximately to a true solution of amorphous silica), silica accumulated only in
the shoots and leaves, indicating that 'soluble silica moved along with the transpiration stream. When clay was 'used as the source of silica, it was shown that the roots
secreted a substance '~hich brought silica into solution. ;This was demonstrated by
separating the clay from the roots by a colloidion membrane; under these conditions,
no silica was' absorbed, It was concluded that under natural conditions silica is
probably absorbed by plants' principally as soluble silicic acid and that soluble silicates are formed by the decomposition of complex silicates. This study emphasizes
the role which plants serve in weathering of rocks and building of soil. Holzapfel
believed silica was solubilized by certain sugars (119). However, there are certain
catechol-like compounds that solubilize silica which are also likely to be involved
(120) (see Chapters 1 and 3).
Amos and Dadswell (116) postulate that in plants which absorb silica the protoplasmic surface of the root hair is basic in character and has a preponderance of
hydroxyl groups which are exchanged for silicate ions. Those plants with root hairs
more acidic in character probably have an ion activity which produces the situation
favorable to the adsorption of cations. It is pointed out that other plants may have
plasma membranes containing more nearly equal numbers of acidic and basic
groups. which would therefore take up anions and cations in similar amounts.
. The amount of silica in solution is reduced by the addition of metal salts. Thus
spraying a rice plant and soil with copper sulfate solution reduced the amount of
silica deposited in the leaves (l21). This effect is undoubtedly due to the formation
of insoluble copper silicate. which thus rendered the silica unavailable.
l'
!f
{
1.:
J:
..
::
l' . :\
I.
I::
Very little is known about the occurrence of silicon compounds, 'othe'r than free
silica, in plants. Malfitano and Catoire (122) reported that the most highly purified
potato and corn starches yielded an ash containing SiO" suggesting that the silica
might be present in a form chemically combined with the starch.
Engel (123) has studied the nature of silica in rye straw and deomonstrated that
organic complexes of silica are present. With hot water or methanol, after pretreatment with a methanol-benzene mixture, labile organic compounds of silica' can be
obtained from the straw; these compounds are easily transformed into the inorganic,
insoluble polymeric condition. of ~ Sip,. A small amount of ether-soluble
organic-silica complex was also obtained in which galactose was found to be present
in the ratio of 2 moles of Si02 per mole of sugar. Whether 'the silica complex in the
ether extract also consisted of fatty components and phosphoric acid, along with a
small amount of a pentose associated in a more tightly bound manner, could not be
determined. After further growth, rye straw contains another silica complex in which
. the ratio of SiOz to galactose is 1: 1. It appears that the silicic acid combines with
the sugar components as well as other components in the physiological structure.
About 18% of the silica in the rye straw. structure must be combined with the framework cellulose, becausetbis amount of silica. is separated when the cellulose is
dissolved in cuprammonium solution~. . ._"
.. Engel (123) points out that, since the deposition of silica at specific sites in the
plant is apparently well controlled, it must enter into certain metabolic processes,
and therefore organic compounds of silica must be involved. .
In a low-silica medium, wheat plants can actually lose silica from the above. ground tissues, showing that it can be carried downward to the roots by the circulation within the plant (124). '.. ; ; ' .
..
To reduce the silica c~ri:tent of quack grass. and make it more palatable. leaves
were sprayed with glyphosphate (125). The silica content of forage reduces digestibility; this has been confirmed by experiments in which soluble silicate was added
(126).
The first pure silicon compound identified in a plant was isolated and identified by
Weiss and Herzog as a silicon chelate of thujaplicine, an isopropyl tropoJone in the
conifer Thuja plicata (l27)(see also silicon metabolism discussed below).
Relation
Silica in Biology
748
or Soluble Silica To Soil Fertility
Although silica is apparently not essential to the growth of most plants. it has been
shown repeatedly that the addition of soluble silicate to soil or culture solutions had
a beneficial effect when there was a deficiency of available phosphorus. It now seems
clear that .this is not because the plant utilizes silicate instead of phosphate ion. as
first believed. but rather because silicate ion is able to displace phosphate ion from
the surface of soil or colloidal material. thus increasing the ayailability of the small
amount of phosphorus which is still present.
For example, Sreenivasan reviewed the available information on the role of silicon'
in plant nutrition and concluded that silicate in the soil facilitates the uptake of . -
.,
Plants
:a in Biology
:r than free
hly nurilied
it \
silica
..
"
strated that
er pretreat- ...
.lica can be
: inorganic,
her-soluble
) be present
iplex in the
long with a
ould not be
ex in which
rbines with.
I structure.
the framecellulose is
sites in the
processes,
the 'I)ove.he cula.ble, leaves
ces digestiwas added
lenti lied by
lone in the
it has been
utions had
now seems
ate ion, as
e ion from
r the small
icon
upc..lCe of
: 0
~-_.
..! .
- ,.-
749
phosphorus. In other investigations by this author (128), it was shewn that soluble
silica (or silicate ion) is adsorbed by certain components of the soil, particularly
clays. The relation between the concentration and retention of silicate is logarithmic,
, "indicating absorption. It .was demonstrated that alumina and iron oxide gels
. adsorbed silicate in somewhat the same manner as soils, forming an adsorption com; plex from which silicate is not readily removed by washing. It was further shown
. . : that, when" soil is treated with. soluble silicate, phosphate ion is less strongly
, adsorbed. Silica gel does not adsorb phosphate ion. It therefore seems clear that the
addition of silicate may have a nutritional effect because it displacesphosphate ion
.' " from the adsorbed condition on the soil. thus making phosphate more available to
; the plant. It has also been shown by Bastisse (129) that phosphate ion can be
liberated from the adsorbed state on certain soils by the addition of soluble silica.
. .: This is especially true 9f lateritic soils which adsorb phosphate ion rapidly, so that it
, '-becomes. unavailable. to the-plants because of the formation of insoluble iron and
aluminum phosphates. In soils of this type. the addition of silicate displaced the
',:-'; ~ . adsorbed phosphate ion. with the result that corn yields were doubled or tripled in '
. . : silicate-modified alkaline media and increased up to fivefold in neutral media. There
. : was also a marked increase in the plant content of SiOI PSOl. and iron. The dis-placement of phosphate.ions from certain soils by silicate was also demonstrated by
adsorption isotherms by Laws (130). Treatment of the soil by sodium and potassium
,
silicates decreased the capacity of the soil to adsorb phosphate from solution. It
- appears that silicate masked the active adsorption centers of the colloid and was held
'. .r. more strongly than the phosphate ion. thus tending to prevent the adsorption of
..
.~; ".~.
phosphate...
.' ,,_,-,
'~'_:~:i":
'.
"
In a study of the displacement of anions from soil by soluble silicate, Toth (131)
,,' ' .. showed that phosphate ion: was released from the absorbed state only in slightly
;. alkaline media, so thal displacement-is by hydroxyl or silicate ions rather than silicic'
, .acid. At about pH 7.; soluble silica is essentially nonionized and has little tendency to
displace phosphate ion. Definite increases in yield of barley and Sudan grass were
noted when calcium or magnesium silicate was added to soil, these materials being
, apparently sufficiently alkaline to furnish some silicate ions. There was marked
absorption of silica by rape. barley. and Sudan grass when grown in silieated soils.
> Other. observations regarding the effect of silica on the nutrition of plants are as
follows. In the water culture of barley, soluble silicate caused a significant increase
in' dry weight of the plants.if insu(ficie~t phosphorus was present (132). Leaf
development was retarded by phosphate deficiency and hastened by the addition of
silicate. In the presence of sufficient phosphorus, silicate had little effect. Silica gives
an increase in yield of certain crops, particularly legumes and cruciferous plants,
only when there is a deficiency 'in phosphoric acid, according to Lemmermann and
Wiessman (133). However. the beneficial effect of silica was muchless when there:
was a deficiency of potash or of nitrogen. These authors (134) do not believe that
silica modified the plant functioning, but instead has a solubilizing action on phosphate compounds.
,,' '
. '.
Duchon (135) concluded that the favorable action of colloidalsilica on crop yields
,in sand cultures with .lnsufficient phosphoric acid fertilization is due mainly to
.,
7..---
750
.,
. ~J
: .,
..
r ..
,.
Silica in Biology
physical properties of the colloid, improving the physical condition of the-sand, and
permitting better utilization of. the phosphorus which is present. Hampl (136)
reached a similar conclusion. ' .r: . ~
The amount of soluble silica available to plants in soil moisture is greatly affected
by the chemical composition. Free oxides or iron or alumina absorb and insolubilize
the silica. Oats take up silica at a rate that depends directly on the amount of silica
in solution in the soil and the total .silica increases with the amount of water
transpired. In the oat plant, silica thus plays a' passive role from a biochemical
standpoint (137).
Organic acids which form chelates with Fe3+ or AIH apparently release silicic acid
from combination with these elements in soil or conversely remove these elements
from the surface of the silica, perrnlttlng it to dissolve. Uptake of silica is promoted
by lowering soil pH (138). Soil can be fertilized with silica solubilized as a complex
with ammonium humate, which is.analogous to the catecholate complex (139).. , . ..
,Phosphate ion can be displaced. from soils and clay, minerals such as montmorillonite, according to Reifenberg and Buchwald (140), the effect being least at
, pH 7.5. However, silicate can displace phosphate especially at higher pH.
The extraction of silica' by plants from soil consisting entirely of the inert rocks basalt, rhyolite, and quartz diorite was' studied by Lovering and Engel (141) using
plants like Equisetum,'known to' accumulate silica. Demineralized water was used
and recycled. From the' amount of silica taken up it is calculated that it equalled I
acre-It of basalt in 5000 years. There was evidence that at least part of the silica
taken up was present as a complex with an aromatic ring type of compound.
According to Erhart (142) plants playa role in the formation of clays. In soils
poor in Ca and Mg, the plants contain'Al and Si in the proportions of kaolin, and
dead tissues release prekaolinite, which then crystallizes to clay. This appears to be
substantiated by Peinemariii and Ferreiro (143), who reported that in upper soil
levelsthe fine amorphous.silica and clay fractions are generated by plants by forma.
'tlon of phytoliths arid prekaolin."
, The availability of silica maybe relatively high in soils high in humus. There is
reported to be an area in Germany where soil contains silicic acid in combination
with the tannin-like components of humus which is stable at pH 9-10 (144). Rice
plants take up. more silica from the growth medium when poly (2-vinylpyridine
oxide) is present (145). This is a material which reportedly reduces the toxicity of
colloidal or polysilicic acid. The nature of the complex formed, if any, is not understood (Chapter I) unless it is only a pH effect.
Beneficial and Protective Effects of Silica
';
. i
I
, t
.
;~
There is a convincing- body of evidence that the presence of silica in certain plants
increases resistance to' fungus diseases. Luridie (146) concluded that silica is not
essential as a plant food, but believed that it is deposited ih the epidermis and
provides protection against fungus diseases such as rust.
The function of silica' in cereals has been investigated by Germar (147), especially
..
Plants
plants
\ is not
nis and
pec._ y
~---
7St
with reference to resistance to mildew. Rye, barley, and wheat wer~ grown in
purified quartz sand and supplied with colloidal silica at different rates, along with
suitable fertilizers. Silica caused an increase in the dry plant weight when there was a
deficiency of potassium oxide. Silica is deposited in the epidermis of the leaves and
also forms the siliceous bodies which together make up a siliceous skeleton of the
- plant. A deficiency of nitrogen and an excess of potash favor the accumulation of
silica, but the phosphorus supply is without influence. Germar investigated the effect
of silica in the leaves -and concluded that Si02 does not affect the mechanical
-strength of the leaf. However, cereals which are well supplied with silica are more
resistant to mildew infections, apparently because the deposition of Si02 in the epi dermis makes the latter more resistant to attack by the enzyme secreted by the
.. fungus hyphae. Resistance to fungi which enter through the stomata is not increased
by the presence of silica.
.
The importance of silicic acid in increasing the resistance of plants to powdery
mildew fungi was demonstrated by Wagner' (148). In water cultures, a deficiency of
silica produced growth depression in rice, oats, barley, maize, cucumbers, tobacco,
bush beans, and. tomatoes. Plants deficient in silica apparently require greater
amounts of water for a given growth. Silicic acid favors an accumulation and better
utilization of calcium, phosphorus, potassium, and magnesium in the plant. It was
not possible to substitute phosphoric acid for silicic acid in plant metabolism, and
silica was regarded as essential to these plants. In laboratory experiments, the
amount of mildew infection was inversely related to the available silica. Sommer
(149) concluded that, in the case of millet grown in solution culture, silica increased
.. the yield of seed and rendered the seeds immune to infection by fungi.
The effect of silicic acid on the resisitance of rice to rice-blast (a fungus infection)
was studied by Yosii (150)'. It was determined that the resistance of the rice plant to
this disease was proportional to the concentration of silica in the culture medium
and in the rice plant. However, the resistance was not connected with the toughness
of the leaf blade, measured by-a needle-puncture method. The toughness of the leaf
was not related to the silica content, and, in fact, the leaves were less tough when
grown in the presence of silica. Thus it was established that the presence of silica
protected the plant against this disease, but the mechanism of the protection could
not be traced to any toughening effect, and the mechanism of the protection is stilI
obscure. Further study by Ishizuka and Hayakawa (151) of the effect of silica in the
resistance of rice to disease revealed that magnesium was necessary in order to
obtain the beneficial effect with silica. It was demonstrated that in the absence of
magnesium the plant did not take up silica. Only when magnesium was present did
the plant absorb silica, .which then could be found in the leaves and provided
resistance to the fungus (Piricularia oryzae).
.The beneficial effects of silica were reviewed by Sticher and Bach (lSi) and Ponnaiya (153) including mobilizing nutrients from soil and improving resistance to
insect and fungal attack. No relation between SiOI content of wheat plants and
resistance to Hessian fly or disease was noted by Lanning (154), but in some
sorghum varieties a direct correlation was observed (ISS). In pot experiments on
barley fertilization with silica gel and its application as a dust to plants reduced
.,
5~,.-...
.,
-----
. r1
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751
Silica in Biology
infection with mildew (156). Numerous workers report beneficial effectfof silica on
.rice. Leaves were harder and stiffer as silica content of leaves increased from 0.3 to
13%. and there was evidence that deposition of silica was controlled by metabolic
activity (157). The resistance to helminthosporia (158) as well as to the stem borer
(159) was increased. Other benefits include greater resistance to brown spot (123).
: In rye as well as cucumber. tomato. beans. and tobacco Engel (123) reported that
deficiency of silica made plants more sensitive to wintering and to mildew. Some
investigations of the effects of silica in rice plants suggest that it may playnot only a
beneficial but possibly an essential role. Okamoto (160) found that soluble silica in
the nutrient medium increased the rate of growth and the final dry weight, as well as
the size of plant parts and grains.
For a complete survey of the significance of silica in plants, reference should be
made to the dozens of references cited by Voronkov, Zelchan, and Lukevits (4a).
.t
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The silica content of insects is highly variable, certain types such as Spanish fly
containing up to 15% and certain Homoptera up to 88% in the ash. However, 1-2%
is most common (3). Again the question is how much of the silica could have been
present as adhering soil or in the gut. Nevertheless silica apparently is truly within
certain tissues as a hardener, as in the mandibles (161).
Silica interacts 'with certain- insects in a physical way, not related to any
biochemical process within the insect, that makes it an insecticide. As any old hen
knows, she can control her lice by sitting in the dust, fluffing out.her feathers, and
working the dust into theskin. Perhaps the powdering of seventeenth-century wigs
served a similar purpose! ./ . . .
Finely divided solids'of high specific surface area act as contact insecticides
because they absorb lipids (oils) from the insect cuticle so that the body is rapidly
dehydrated. Hydrophobic silica was more potent than hydrophilic powders. The
dusts are most effective at low humidity, but a desiccant alone, such as CaCl z which
is not oleophilic, has no insecticidal action (162). Silica aerogel, which is somewhat
organophilic because of the process by which it is made, controlled weevils in grain
at a concentration of 0.05% (163). At 60 Ib silica per 1000 bushels of wheat a pyrogenic silica ("Cab-O-SiI") gave longer protection against grain borers than did
chemical insecticides (164).
.
Fine alumina dust is also insecticidal. When larvae crawl over wet dust there is no
effect because moisture is present. However, the skin has lost its oily protection by
adsorption on the alumina and the insect dries out and dies quickly when placed in
dry air (165). A combination of aerogel and ammonium fluorosilicate was especially
effective for controlling mites on caged reptiles (166). Silica gel insecticides killed
DDT-resistant mosquitoes (167); boric acid-modified silica aerogel was effective
against cockroaches. and it was lethal even when their mouths were waxed shut so
they could not eat it (168, 169).
The necessary characteristics of an optimum insecticidal powder were studied by
I.
.,
Mammals: Man
n Biology
. silica on
im 0.3 to
net
'ic
em borer
(123).
rfed that
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. silica in
IS well as
753
Ebeling (170). who found the powder must have a high specific surfac! area accessible through pores larger than 2 nm in diameter and with a high absorptive capacity
.for wax. which, when removed from the insect cuticle, caused it to dry out rapidly
and die. A silica suspension containing an adhesive is useful for spraying chicken
coops for Mallophaga and mites (171).
. '. Tarshish (I72) has reviewed the action of inert dusts as a insecticide, especially on
. ~.' cockroaches. .
..
'.. :
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The few data that areavailable have been assembled by Voronkov. Zelchan, and
,_ Lukevits (4a). In some cases it is not possible to decide whether the reported amount
of silica is greater than could have been present as Si(OH). in solution in the body
:; fluids. Thus if the organism consisted of 50% water and 10% ash and the water were
., saturated with amorphous silica. the silica in the ash would be 0.05%. Generally, the
. silica is no lower than 0.1-0.2% based on ash. Skin. feathers, intestines. etc., which
~,"~can .be exposed to contact with materials from outside. are all higher in silica. For
example. feathers may contain up to 77% silica in the ash. strongly suggesting the
.' possibility of physical adsorption of colloidal silica or silicates. Also. earlier data
. ~"may indicate a falsely high silica level because of interference by phosphorus in the
.
.'silicomolybdate test. ..."..
-', ':.; .Nevertheless there are some instances. as in blood, eggs, and internal organs,
where up to I % silica is found in the ash. which cannot be explained by either
" physical occlusion or concentration of soluble silica. The essential role of silica in
, developing chickens will ~e mentioned along with its role in mammals.
houldbe
(4a).
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, It has often been assumed that in higher life forms, that is, animals. the element
silicon is not essential. However, Holzapfel (173, 174) showed that silica is present in
trace amounts in most animals and thus might have some definite function.
Animals invariably take ina certain amount of silica in water but. unlike plants
can also excrete silica in solution so that no accumulation in the body need occur.
. Taken orally silica is almost certainly innocuous. Rabbits have been fed 2 grams of
, silica gel per day for 30 weeks with no ill effects (175). Magnesium silicate, whichis
, easily attacked by acid, liberating silica, is used in internal medicine.
. Whether or not the ingestion of silica gel could be beneficial under some circumstances .is a matter ofdebate. Tabasheer, the silica gel found inside 'bamboo (94),
.was once believed to be of value in treating asthma and tuberculosis (98), and it is
conceivable that there might have been some practical basis for the treatment. as has
,been the case with other primitive medications. .
'
In Europe around 1920 there was some interest in silicic acid as a therapeutic
,agent for tuberculosis. For example, Gonnermann (176) pointed out that the herbs
.......-754
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Silica in Biology
used by country folk of middle Europe for the cure of tuberculosis we~e unusually
rich in silica. The ash from various animal tissues was analyzed and found to
contain, generally, 2-10% Si02, suggesting that silica was of some physiological
. . importance. However, it should be kept in mind that the ash content of tissues is
very low, so that the actual silica content is extremely small. The silica content of
the pancreas was believed by Kahle (177) to vary with different types of diseases. In
the case of tuberculosis, the pancreas contains less silicic acid than normal, whereas
cases of cancer reveal more silicic acid than normal, provided there has been no
operation. In the event of operative interference. the silica content was less than
normal. During pregnancy, the fetus is. believed to withdraw silica from the pancreas
of the mother. thus accounting for increased susceptibility to tuberculosis at this
time. It was claimed that experimental tuberculosis in guinea pigs could be inhibited
" by the administration of silicic acid. To some extent. silicic acid was prepared and
, sold for therapeutic use as in pulmonary tuberculosis. The methods of characterization that were avilable in 1921 do not make' it possible to describe accurately the
nature of the sols which were used (178). However, Kadisch (179) did not find any
beneficial results from the use of silicic acid therapy in 14 cases of open pulmonary
tuberculosis. and it appears that there is no longer .any interest in the type of treatment. . :. .....;, " .~:~,>.: , - "
The data on thesilica content of mammals collected by Voronkov, -Zelchan, and
Lukevits (4a) are subject to the same doubts as mentioned in the preceding section.
Animal parts exposed directly to material from outside the body such as hair.
stomach, skin, and intestines show silica contents in ash ranging up to 15%.
However, internal organs and blood more commonly contain 0.1-1.0%. Again the
significance of the concentration in the ash cannot be judged without knowing the
percentage of ash in thesample. In living tissues and fluids 10-100 ppm on a wet
basis is very common. Since this is less than the solubility of amorphous silica in
saline solution at physiological pH, it is not certain how much. if any, of the silica is
bound up with biochemical components.
The large volume of data on silica in man and mammals has been generated in
connection with the problem of silicosis. Some odd observations have been made,
such as the fact that the silica content of blood is higher in' the morning than the
evening and increases with old age. Obviously, accumulation of siliceous dusts in the
lungs increases with age. On the other hand. the silica content of the arterial walls is
high, 190 ppm, in babies, but only half that in middle-aged adults (180).
In human serum the silica concentration is' about 7.9 ppm regardless of sex or age
(181). Austin (127) reported that in red blood cells the SiO, content ranged up to 92
ppm, of which '42 ppm was bound. In whole blood Gohr and Boenniger (182)
reported 16 ppm. and it reached 20ppm'in cases of silicosis. However, according to
, Chvapil (127) the silica content in serumdepends more on the degree of current
exposure than on the extent of silicotic lesions. In other tests on hundreds of people
the average was 8.3 :f: 2.4 ppm in whole blood (183, 184), and there was no correlation
with sex, age, occupation,' or pulmcnaryconditicn. However. the level increased when
silicon compounds were specifically administered. It might seem. then, that silica
, levels would vary somewhat in different countries and geographical environments.
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Biology
Mammals: Man
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Sauer et al. (185) confirmed that in test animals the silica content of tiss~es was inde pendent of silica concentration in the diet. In rats the silica content of muscles
increasedwith age and then declined in old age.lt was increased by caffeine (186).
Silica in blood varied inversely with the level in muscle.
From these diverse results it is obvious that past analytical methods have given
misleading high results. The work of Baumann shows that the concentration of silica
in blood is much lower than previously assumed and that it is present almost entirely
as" free, soluble monosilicic acid (187). In, animals Baumann found that the
concentration of silica in the red cells is the same as in plasma and in both cases is
present as monomer since it passes an ultrafilter. In whole cattle blood the normal
concentration is 1.9 :f: .0.5 ppm. In man it is 0.4-0.5 ppm but when 50 mg of soluble
silica is given in drinking water it is all excreted in the urine in 10 hr; the concentra, tion in urine ranges from' iOOto 600 ppm at its peak. depending 01) urine volume.
,and it is still all monomeric. Incidently silicic acid polymerizes at the same rate in
. 'urine as in water. The elimination rate is constant when measured as micrograms
per minute. regardless of urine volume and the rate is proportional to the amount
not yet excreted. The concentration in blood reaches 2-3 ppm. If 300 mg of soluble
.silica is given. it reaches 6 ppm. The ratio of micrograms per minute excreted to
plasma concentration in parts per million is about 100: 1. This is because the kidney
excretes silica from the' plasma water. along, with all other dissolved materials of
molecular' weight under '70.000. by ultrafiltration through membranes of the
': glomeruli to produce "primary urine." Then in a second 'step in the tubules there are
biologically active membranes that reabsorb 99% of the water by an unknown
"active" process. leaving behind in the final concentrated urine all the materials for
which no specific reabsorption process exists. Thus the silica is excreted in a far
more concentrated state than it is.in the plasma (187b).
.
Japanese investigators "found that the high silica content 'of drinking water correlated directly with mortality owing to vascular injuries to the central nervous system ..
The silica content of organs was higher. in cases of atherosclerosis. especially in the
aorta where the concentration increased with age (188). On the other hand, Loeper
.andPolet (189)' concluded that although all bovine and human arteries contained
silica, the silica content was higher in normal arteries than in atheromatous
(degenerated) ones. Also, in cases of calcification of the arteries the silica content of
blood was low. Kvorning found 120-150 ppm in undried human aorta tissue (190).
On the other hand, in a highly calcified aorta the silica concentration was only 50
ppm. although this could be due to the high content of calcium salts. The silica
concentration in 'the organic portion could be quite high.
.
The lower silica content in atheromatous arteries induced by high cholesterol diet
led to experiments to learn whether administration of soluble silicon compounds
could prevent the disease in rats. Loeper and Loeper (191) found that administration
of sodium silicate intravenously or lysine silicate orally reduced the development of
atheromas from. 100 to 40%. and monomethyl. trisilanol salicylate given
, intravenouslyreduced it to 11 % . '
~
" According to Charnot and Peres (192) silicon metabolism is controlled by steroid
and thyroid hormones and the changes in silicon content with age could be due to
'.,,''
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756
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decline in hormonal activity. A continuing 9 year study of silicon in th~ animal body
, by Charnot and Peres (127) led to the following conclusions: aging is accompanied
by a decrease in silicon in the'soft tissues of the female and augments silicon in calcified tissues of both sexes. Silicon plays a role in a hormonal balance system. A
complex of NaOSiCH a(OH)2 and sodium orthohydroxybenzoate reduces the
abnormal 'mineral 'deposits in ovariectomized rats and improves the Ca-Mg
:'imbalances' caused by hormonal changes of ovariectomy or aging.'
, In human optic nerves the silica content increased with age, especially after 60
'
years (l93a).,
Silica is also involved in the aging process in senile dementia and in the identical
, . ~ype of deterioration that occurs in the brain in younger people as Alzheimer's
, , , 'disease. Austin (127) described characteristic microscopic bodies or "plaques" as
" .. well as other' bodies (corpora amy/acea) that appear in the midst of certain
': deteriorating brain cells. These bodies contain a remarkably high concentration of '
, .' silicon-in some regions up to 1-2% by weight.
,
'--. It had' been 'otherwise reported (l93b) that four times the normal amount of
alumirium is present in the nuclei of neurons in such diseased brains but the increase
in silicon now appears to be. far more significant. The aluminum may simply be '
. adsorbed on the silica in view of the great affinity between silica and alumina. The
,,highly localized silicon in plaques may only be the result of polymetization of silicic
'acid released from the debris of the deteriorating surrounding tissues in which a very
, low concentration of silicon may be bound when the brain is in the normal state (see
: following section). ".
'
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Silica in Biology
.#
Essential Role of
I'
I
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Silica in Mammals
..
Although silicon has' long been known to be present, and probably essential, in
certain lower organisms and plants, it has been very difficult to determine whether at
least trace amounts' are essential in mammals. Since traces of silica are present in all
natural foods, water, and airborne dust, there was no way to provide a completely
silica-free environment until synthetic diet, filtered air, pure water, and all-plastic
utensils and equipment could be made available.
Earlier data on silica contents of living tissues were found to be grossly higher
than now found when completely glass-free apparatus is used along with silica-free
reagents. The level in most tissues is as low as 1-2 ppm. However, it is definitely
higher (100 ppm) in connective tissues and in regions of active calcification reaches
0.5% where young bories are being developed.
Faure (194) reported that 'denser, harder bones were developed i~ rabbits fed 3
grams per day for 3 months. The Si02 level in bones was tenfold higher than in con, trois. The Ca: P ratio was constant and silica appeared to be involved in early stages
of bone development.' However, prolonged administration of silica caused bone
inflammation. Schwarz and associates (195-197)develope'd new refined techniques
for determining the requirements of trace elements in animals and discovered that \
silicon is essential. About the same time, Carlisle also found this to be true in chicks ,-._,
(198, 199).
.
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Mammals: Man
in Biology
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757
Schwarz (200) and Carlisle (20 1) -found that the developing bone structures in
embryos were deformed when silicon was absent. All this suggests that silica is
important in skeletal and connective tissues in one way or another. Carlisle (127)
reported that silicon is necessary as a nucleating agent, probably in the form of cal_' . cium silicate. for the subsequent' deposition of calcium fluorophosphate. Schwarz .
- . reported that silicon is essential in connective tissue and is bound in mucopolysac,charides in an esterlikelinkage, although this aspect remains controversial. Pectin '
. contains 0.5% bound SiOI' Some hyaluronic and chondroitin sulfates and the pro, teins in connective tissues contain bound silica. Both animals and plants' use silica as .
': a cross-linking agent in connective tissues (202).
. ," Silicon in drinking water [as soluble Si(OH).] correlated to a limited extent with
statistically lower death rates in different communities. In general, high concentra: tions of dissolved solids reduced the probability of cardiovascular-renal diseases
(203). On.the other hand, in England, a similar study seemed to indicate that high
calcium in drinking water (tea?) had an effect opposite to that of silicon, which was
positively correlated with mortality (204a). The relation of silica content of the body
: ,
to age and health remains unknown in view of the conflicting available reports.
;" Austin's findings, discussed in the foregoing section, indicate that silicon may be
,;l, .' ...., an essential element in trace amounts in the brain. It is found that, although there is
- n o overall increase in silicon content with age, silicon appears to be.concentrated in
microscopic bodies in, the brains of cadavers of persons who died form senile
..... ..
dementia, or younger. persons .dying from, Alzheimer's disease, where similar
deterioration of the brain hasoccurred. This suggests that the silicon was liberated
from specific sites and was concentrated in certain by-products of the deterioration.
Austin summarized ~is:findings (127) previously described in a series of papers
(204b.c). There was no evidence that overall silicon was present in unusual amounts
. or played any role in thedegeneration..
"Granules containing silicon also appear in the mitochondria of normal rat liver.
kidney, and spleen according ,to Mehard and Volcani (204d). The granules, 25-75
nm in diameter. contain small electron-opaque granules 5-10 nm in size that are
high in silicon content as well as phosphorus. The function of silicon is not known
but it is possibly a component of enzymes. '
; '.
:d
.,..-j
Toxicity of Silica
.
In view of the universal presence of at least some soluble silica in natural waters, it is
not surprising that it is considered harmless in food and drink. Monomeric Si{OH).
penetrates all body liquids and, tissues at concentrations less than its solubility
(0.01 %) and is readily excreted (187a. 205). In human blood, in both corpuscles and
plasma. the silica concentration is 1 ppm and in bovine blood 2.2 ppm.
. ' At least in small amounts. the ingestion of amorphous silica powders appears to
be completely harmless since it dissolves to give only monomer. It is a safe additive
in foods and its use is permitted as an anti-caking agent (206) in amounts up to 2%.
In tissue cultures of rabbit spleen and lung, no effect was noted over 6 months,
when 65 ppm of silicic acid was present. It was apparently added as an oligomer, but
..
.1
758
':...-_.
Silica in Biology
probably it quickly depolymerized to monomer under these ccnditioas (207, 208).

Earlier similar experiments at 9-21 ppm Si02 also showed no effects. It is not
known if monosilicic acid reached an equilibrium concentration within the tissue
.."cells.
.The nontoxic behavior of Si(OH)4 and its elimination were demonstrated by
Scheel, Fleischer, and Klemperer (209). Saturated solutions of monosilicic acid at
38C were shown to contain 170 ppm SiO, at equilibrium with respect to colloidal
amorphous silica. Rats to which silica gel or silica sol was administered excreted 184
ppm in the urine, indicating that silica is excreted as monomer. The silica caused the
water intake and urine volume to double or treble, and this diuretic effect was the
, only symptom of toxicity shown by the rats. [Is it possible that a saturated solution
of Si(OH 4 is a safe diuretic?]
An excessive uptake insoluble silica by cattle, unaccompanied by enough' water to
remove-if from-the system,-can lead, to stones or calculi in the urinary tract (210,
211), especially if concentration' in the urine exceeds 70-80 ppm (212). Similarly,
"dogs fed on a diet high in silicate bulking constituents developed siliceous stones in
-the kidneys. bladders, and urethras (213).
Rats fed on a high silica diet for various periods eventually excreted essentially all '
of it. much in the urine (214). From analyses of the amount excreted, it was concluded by Minova (215) that silicais 20 times more soluble in the organism than in
saline solution. Much of this silica must be combined in one way or another in the
tissues. Rats fed heavily with silica gel develop nodules in the intestines, according to
,Desai, Burkman. and Salisbury (216). Formation of calculi (urolithiasis) can be
reduced by giving salt to make the animals drink more water and flush silica from
the system (217). Feeding tests on sheep showed the relation between silica
concentration and urine -volume (218). A high silica content in blood and urine is
symptomatic in cattlesuffering from chronic vesical hematuria. Silica itself is not
the cause of the difficulty, which is apparently the result of some toxic organic compound in hay, possibly saponins (219). The biochemical action of monosilicic acid
was surveyed by Kersten and Staudinger in 1956 (220).
When silica enters the body in any other way than by ingestion, some type of
toxicity almost invariably results and silica is deposited in various parts of the body,
as in the following typical examples.
Finely divided silica, calcium silicate, and sodium silicate were given to dogs to
inhale as aerosols. The silica was retained completely in the lungs. The silicates
liberated soluble silica, which pervaded the body and was found especially in the
liver and urine, the calcium silicate taking longest to be excreted (221). Inhalation
eventually led to silicosis.
Pregnant rats injected intravenously with a suspension of pyrogenic silica (Aerosil)
all aborted completely (222).
,
It is not surprising that continued intravenous injection of colloidal silica into rabbits led to high silica levels in liver, spleen, heart, lungs, and kidneys and killed the
animals (223).' When silica particles were made organophiIic by esterification with "
alcohols or alkylsilanols, there was no immediate reaction as with unmodified silica,
but after several days the toxic effects of silica appeared (224).
,
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a in Biology
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Mammals: Man
759
(207, 208),
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From the thousands of rats and rabbits that have met their doom 'Over the years
. by having all imaginable forms of silica injected into the bloodstream, there has
come mainly one obvious conclusion: silica injected this way is deposited throughout
the circulatory system and damages liver, lungs, spleen, and kidneys. Nothing very
profound seems to have been learned from this completely unnatural way of introducing silica into the animal body except that a rabbit can safely dissolve and excrete up to 5 mg of silica per week when injected as a silica sol (225). When injected'
into the renal artery it causes fibrosis and the animal develops hypertension (226).
Subcutaneous or intraperitoneal injection and inhalation appear 'to be more
natural ways of introducing silica to study the interaction with various kinds' o~
tissues.. -_,
,-' .
-. . ...
It is well known by primitive ,tribes that by rubbing certain soils into cuts in the
skin, .permanent decorative scars can be produced. As discussed by Shelly and
Hurley (227), when a person is subjected to injuries in which silica becomes embed- ,.
ded in the tissues, nodules of silica granuloma may develop as long as 10 years later."
This hardening effect resembles. the fibrosis of lung tissues. Sarcomas may also
develop later (228). .Innumerable studies involving intraperitoneal injections have
been, reported. Inhalation is, of course, the most common route by which silica
exerts a serious toxic effect. Thousands of inhalation tests have been made in the
_.
investigation of silicosis. '.'
Microfibrous silica is probably produced when' chrysotile asbestos reacts with
stomach acids. Asbestos in food was implicated in stomach cancer. A statistical
study by Merliss (229) indicates that rice that has been treated with talc that
contains some asbestos is the cause of a high incidence of stomach cancer in Japan
where such rice is commonly consumed. The talc is held to the surface of the rice
grains by glucose to;~elp .preserve the flavor. This i~ a practice limited to the
Japanese. Pure talc appears harmless.
.
A unique type of toxicity occurs when a high concentration of organophilic hydrophobic silica particles is inhaled, This material has some of the characteristics of an
antifoam agent and probably causes collapse of lung membranes in much the same
way. The result is a prompt fatal pulmonary edema. Yet when this powder is
injected intraperitoneally it is essentially inert, although the identical silica powder
without the hydrophobic monolayer of hydrocarbon groups causes severe peritonitis. '
On the other hand, when the same uncoated powder was .inhaled, there was eventual
lung damage but no rapid pulmonary edema (230).
.
When hydrated silica gel was injected intraperitoneally into rats, the gel dispersed
to give polysilicic acid of 1 nm particle size which entered the blood and passed
through the glomerular capillaries of the kidney, but at the site of resorption
polymerized and damaged the kidneys (231).
Cytotoxicity
The basic difference between silica dusts and those of other' materials like clay, coal,
and silicon carbide, is that when the latter reach the lungs the particles are engulfed
by macrophages and carried through the lymphatic system to the lymph nodes of the
.".
---_.
")
760
Silica in Biology
lungs, where they are rejected. On the other hand, when a silica particle- is taken in
by a macrophage it kills the cell and silica is not removed. The evidence for this has
"been shown in many in vitro as well as in vivo studies, although the mechanism of
" the toxic action has long been a matter of debate.
The measurement of dust toxicity in vitro involves the use of macrophages in
tissue cultures, noting the effects of dust particles on oxygen uptake, glucose
consumption, etc. (232). Marks and Nagelschmidt used this method to compare the
. toxicity of a variety of dust particles. -Silica was much more toxic t~an other
powders tested (233). "
In cultures of macrcphages, the tridymite crystal form of silica caused a decrease
in oxygen uptake and production of lactic acid whereas amorphous silica did not.
When tridymite was coated with amorphous silica or AI 20" it became inactive. On
the other hand, tridymite had no effect on polymorphonuclear leucocytes and several
other cell cultures "(234); Comolli and Perin suggest that silica exerts its toxicaetion
at the site of protein synthesis (235).
".
In vitro cultures indicated that the mechanism by which silica promoted silicosis
was that the quarti particles" inactivated the macrophages, thus permitting more
rapid bacterial growth (236). In another" study the toxic effect of silica on
: macrophages was used to minimize the foreign body reaction to skin grafts which
are normally rejected through attack by macrophages (237). It seems clear that one
.. im mediate effect of silica in the form of 0.1-1.0 micron quartz particles is that the
particles are taken into macrophage cells and kill these cells by reacting with the
membrane of lysosomes, releasing "lysosomal enzymes which not only kill the
macrophage, but are released into surrounding tissues and may result in fibrosis.
The action of silica on the lysosome membrane is to make it permeable, probably by
tearing the membrane as it is adsorbed around a silica "particle, so that the enzymes
escape (236, 238). Another' indication that silica interferes with an animal's immuni. zation mechanism was described by Zisman, Hirsch, and Allison (239). Mice were
infected with herpes simplex virus and then either an anti-macrophage serum or a
suspension of 2 micron quartz particles was injected." Both materials greatly
increased the" mortality, and it' was concluded that silica inactivated the
macrophages. "
The surface of crystalline quartz, treated to remove the amorphous silica surface
layer, differed from. untreated quartz in reaction with macrophages. The purified
quartz at once interacted and increased acid phosphatase activity but untreated
quartz did not (240a).
Tests on all forms of silica as particles a micron or so in size were made in regard
to hemolytic activity by Stalder and Stober (240b), who showed that all forms
except stishovite were quite active. The decreasing order of activities was tridymite,
quartz, cristcbalite, vitreous (amorphous) silica, and coesite. Quartz and tridymite
were much alike and the others only moderately less effective. This seemed to
establish a direct relation between hemolytic activity and silicotic activity of the surfaces of these types of silica. Stalder (240c) went on to show 'that all the silicogenic
powders exert their specific cytotoxic effects by injuring biological membranes. The
o. strong tendency of membranes to be attracted to the silica surface disrupted
"
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in Biology
Mammals: Man
is taken in
'or this has
iha
1 of
., lysosornes, releasing acid hydrolases, and disrupted macrophages. 'Tbe'silica surface

appears specifically to attract membrane lipids which change the shape of the lipid
micelles and thus destroy permselectivity of ions so that osmotic swelling occurs,
followed by lysis of the cells.
, ..
More specifically, it might be ,$uggested that the powerful attraction of the
membrane to the silica surface may be due to the presence of phosphatidyl choline.
This type of compound is a component of membranes of most higher organisms and
is characterized by having a grouping containing a quaternary ammonium ion.
Recent studies have shown the strong attraction of the silica surface forthese strongbase cations:
, ' .
aphages in _
e; glucose .
pare the
.han other
m;
a decrease
:a did not.
active. On
md several
ixic action
ed silicosis
:ting more
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ir that one
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robably by .
e enzymes
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re purified
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: in regard
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tridyrnite,
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of the sursilicogenic
oar The
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761
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.(diglyceride)
.
" I
0The idea that the lytic acti.on of silica .particles on membranes is due to strong
interaction with membrane trimethylammonium ions has been supported by Depasse
(240d).
.
... . . , '. ' .
Silica in Biochemical Combinations'

The known ways in which silicon can enter into .combinations with organic
molecules is quite .llmited. As discussed later in this chapter there is little evidence
,. that organosilicon compounds with direct carbon-silicon bonds can be synthesized in
, , living cells. Also 'no nit~~ogen--silicon linkages are formed. Even the formation of
silicon-oxygen-carbon: bonds requires very specific configurations of oxygen and
carbon atoms in the organic molecule, as in catechols or tropclones, so that chelate
rings can be formed. Such compounds are discussed inChapter 1 and 3. with special
reference to the publications Weiss and of Baumann..
..
'
.Certainly hydrogen bonding may be involved if the silicic acid is polymerized at
least to some degree, but in most'living tissues where silicon is being metabolized or
transported, nothing is known about the monomeric or polymeric state of the silica.
" . In view of the reported 'occurrence of silica in many kinds of biological tissues. it
.. seems likely that other types of bonding remain to be discovered. '.
Some of the earliest efforts to isolate silicon compounds from living tissues were
made by Holzapfel (241). who investigated the molecular association of higher
alcohols with silicic acid, found 530 ppm SiOs in ox blood. and summarized investigations of esterification of .silica with cholesterol in lung tissues. Tissues were wetashed with a I: 5 mixture of concentrated HsOs and HN0 3 at 100C.'and the silica
was insolubilized by repeated wetting with concentrated HCI and evaporating to dry.. ness and washed free of H 3PO. impurity on a filter. Holzapfel concluded that. in the
human and animal tissues' examined, silicic acid is in combination with lipoid
substances and cholesterol (242, 243). Galactose is the only carbohydrate component
present in combination
with silicon.
.
.
.
of
.,'tl~
".
762
i':;
--.---
.~
Silica in Biology
..'l...
-f: ~-.
.-
The possibility that silica can exist in combined form in certain fats ~as shown by
Klein and Nienburg (244). The orthoesters of silicic acid were formed with alpha
monostearin, yielding the orthosilicate C...H lII4O I.Si. The melting points of these
glyceride orthosilicic esters, as well as solubility relationships, closely resembled
., those of the original glycerides. The compounds appear to be fairly stable toward'
hydrolysis and, because of their lipoid nature, may. be readily adsorbed by tissues.
Another lipoid-soluble silicon compound is the ethyl ester of silicyl recinoleic add,
as described by Kaufmann (245). This compound is a clear oil, is insoluble in water,
resists hydrolysis, and is very soluble in organic solvents.
Combination with Polysaccharides
",
Chemically the' silica is bound.in tissues with glycosaminoglycans and polyuronides

(246). About 800 ppm SiO:a was found 'bound to purified hyaluronic acid, chondroitin 4-sulfate, and heparin sulfate. This corresponds to only one Si02 per 200
repeating units of polymer. Silica is also reported bound in pectin and alginic acid. It
is not dialyzable or reactive with molybdic acid; it is stable against autoclaving with
8 M urea, and against acids and bases. It is separated only by strong alkali. It is
probably present as esterlike linkages of Si-O-C, but surely must be in some well
protected configuration of surrounding oxygen atoms, as in a chelate, for such
stability to exist. It is not known whether the silica is present in monomeric or low
..
polymeric form.
.
,.
. . The combination of polysilicic acid at pH 6 with a film of laminarin (poly-I,3 ..
glucopyranosejmaking it rigid was reported by' Holt and Went (247). One might
r
suppose that this polyhydroxy polyether would form hydrogen bonds with silicic acid
below pH 6, but since the combination occurred at pH 6, it is possible that some'":
!
<
spontaneous chelation Qr~ esterification had occurred.
The interaction of polysilicic acids with polysaccharides appears to be an open r: ~ ,~.;
field for investigation. There may be some common factor, as further evidenced by
the finding that in the serum of silicotic 'patients there is an increase in mucoproteins
and protein-bound hexoses, along with higher level of silica (248). Some association
of polysaccharides with silica has' probably existed since life began because in a
primitive organism such as the diatom, when silica is deficient the cells become
coated with a polyuronide of glucuronic residues (42), and no doubt the micro porous
silica skeleton is interpenetrated by this polymer.
,;
"
Combination with Proteins

It has long been known that leather is tanned with polysilicic acid and albumin is
coagulated with colloidal silica, The nature of such interactions involving hydrogen
bonding has been discussed in Chapters 3 and 4. Interaction with protein monolayers
on water has thrown' further light on the nature of the association.
Clark, Holt, and Went (249) carried out some remarkable investigations of the
effect of silicic acid and polysilicic acid in aqueous solution of monomolecular layers
of albumin and nylon on the surface of the solution. In these studies, the effect of
Mammals: Man
n Biology
.hown by
.th
;al!)ha
se
esernbled
of
toward
, iissues.
'eic acid.
in water.
j.
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d. chon-"
per 200
: acid. It
-ing with
ali. It is
irne well
for such
c or low
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re
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nt
.icic acid
iat some
an open
meed by
iproteins
.ociation
lise in a
become
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ydrogen
nolayers
s of the
ir I rs
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763
monosilicic acid or polysilicic acid is observed as it is adsorbed on the tlndcrsidc of

the monomolecular organic layers. thus stiffening them so that the compressibility of
the monomolecular protein or organic polymer layer is modified. Most important, it
was observed that monosilicic acid is not adsorbed at all. The silica must be
polymerized before it is adsorbed on the protein monolayer. In this instance. the
polymer chains become less compressible and there is good evidence, based on the
pH effect during aging. that the adsorbed polysilicic acid under the surface of the
film. undergoes polymerization. forming a layer of silica gel. perhaps only a few
angstroms thick. which stiffens the film and prevents its subsequent compression. In
the case of nylon 66/6 and 10/6, monomolecular layers are readily formed. and
these interact with polysilicic acid between pH 2 and 9 and are particularly stiffened
or tanned between pH 4.5 and 6.5. which is the known point for maximum polymerization rate of silica to form gel. '. ' '. ,
Polysilicic acid apparently can make mluti-point attachments to the protein. If the
protein molecule is coiled in solution and not fully unfolded and spread on the surface before silica is added. it cross-links the protein and prevents further unfolding.
._ When gelatin monolayers on polysilicic acid solution are compressed, the-CH I '. groups of proline rings are pushed away from the surface bringing peptide groups
.. closer together and these are then cross-linked by the polysilicic acid and the film
becomes rigid .. Monolayers of synthetic polyamides (nylons) were .also similarly
.
"tanned" (250. 25 I). .
Bovine albumin was adsorbed on quartz and amorphous silica powders at a
maximum around pH 6 and was in equilibrium with that adsorbed (252). However,
Her (253) found that the pH. below which enough albumin was adsorbed to cause
flocculation of colloidal silica.depended on the salt concentration. With no NaCI
present it was pH 4.4. but in 0.1 N solution was 6.2. It was also noted that when the
surface of the silica wasonly 5% covered with aluminosilicate anions, no coagulation
occurred in 0.1 N NaCI solution above pH 5.5. Thus colloidal aluminosilicates
(clays) which bear a higher anionic charge than pure silica does in neutral solution,
are less reactive with some proteins.. . .'
Although polysilicic acid combines with a monolayer of trypsin at pH 3.5-7, the
film is not tanned (247). The interaction and mutual coagulation of gelatin with
polysilicic acids has been discussed in detail in Chapter 3. Subsequently Bergman
and Nelson (254) compared the behavior of polysilicic acid sols at pH 2.5 and 7.5
without realizing that the sol at low ph consisted of 2-3 nm particles in colloidal
aggregates; at 7.5 the particles were probably twice as large and separate and
discrete. The larger and fewer particles at pH 7.5 explain why less gelatin is coagulated with a given amount of silica. As shown by Iler (253). there are two ways in
which proteins are adsorbed on silica. Those that bear strong-base cationic groups
are strongly adsorbed in neutral solution to negative sites on the silica surface at pH
6-7. However, proteins like gelatin are bound to silica mainly by hydrogen bonding,
and this occurs only on the nonionized SiOH surface. Hence hydrogen bonding is
strongest in the pH range 2-5 and then decreases at higher pH as the silica surface
becomes progressively charged. Aluminosilicate anionic sites do not form hydrogen
bonds, but strongly bind organic strong-base cationic groups.
- - ....
764
Silica in Biology
Lipoproteins can be removed from human sera with colloidal silica. Other types of
proteins were unaffected and the sera became more stable in storage (255).
Denaturation 0/ Proteins, Coagulation 0/ Blood

When certain proteins are adsorbed on glass or silica surfaces they are denatured
and, when recovered, have undergone irreversible changes in structure. It is thought
that the reaction to -silica that is injected into the peritoneum of test animals is due
to such denaturation. Runner and Isler (256) noted that globulins were especially
strongly adsorbed on the surface of silica and when desorbed were found to be denatured. Scheel, Fleisher, and Klemperer concluded from silica interaction with proteins that the toxic action was due to denaturation (257).
One would expect that the smaller the silica particle and thus the greater the surface' area, the greater the denaturing effect. However, Lundgren and Swensson (258)
found that with a given amount of silica the effect increased as increasing sizes of
particles (10, 14, 60 nm) were compared. Also, the toxicity of a supersaturated solution of monosilicic acid was found by Glomme et al. (259) to increase as it
polymerized. Thus below a certain low molecular weight or particle size, polysilicic
acid does not denature protein, whereas larger size causes greater denaturation.
. However, above a certain size the decreasing surface area per gram of silica then
results in decreasing activity. Thus when particles larger than 10 nm are compared in
.regard to toxicity by intravenous injection, the toxicity decreases with increasing size
.
simply because lesssurface area is present (260).
Charache and MacLeod found that hemolysis of red cells (erythrocytes) was not
caused by monosilicic acid but soon began when silica had polymerized to a large
enough particle size. Thus a 0.2% solution of monomer polymerized sufficiently to
become active at pH 7.4" in 20 min (261).' With concentrations of monomer of
0.125%, hemolysis began. only after 5 hr. Harley and Margolis (262) found that
hemolysis did not occur with 4 .or 3 nm silica particles, but did occur with 5 nm
particles and with increasing effectiveness at still larger particle sizes (5.5, 7, and
30 nm).
The effect of silica was described by Margolis as due to the adsorption and
denaturation of a globular protein, the Hageman factor (263). The denaturing effect
was found to increase with increasing size of colloidal silica particles that were
added to the system. The proposed mechanism was that on sufficiently large particles or on nat surfaces of silica, the protein molecule was stretched out of shape by
adsorption forces as it formed a monolayer on the surface. When the silica particles
were very small, the molecular segments of the protein could become attached to different particles without the segment being stretched. Figure 7.6 is similar to one by
Margolis to explain the effects involved. When protein is adsorbed on a larger silica
particle or a coherent aggregate of smaller particles. the chain is stretched and
certain internal hydrogen bonds which hold the protein molecule in a specific configuration are broken. On small single particles no such stretching occurs (264-266).
The activity per gram of silica reaches a peak at 20-30 nm particle diameter.
However, the activity per unit area of silica rises rapidly as the diameter increases
..,
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Biology
Mammals: Man
765
types of
Figure 7.6. Mechanism of denaturation of proteins by silica proposed by Margolis (26). A,

silicic acid particles only 2-3 nm in diamter are
too small to separate the molecular coils of prof. '
tein and cause disruption of structure; S, a single
.
small colloidal, particle 5-10 nm in diameter
BE,
causes limited disruption of protein; C. a silica
~ @~ ~. particle larger than 20-30 nm in diameter causes
~ ,~ .
' severe disruption; D, aggregated or gelled small
, ; ... "
. ' particles extending in chains more than 10 nm
.' ". ,
, long can distort and rupture protein configuration when hydrogen bonding occurs along the
c
F
,
chain; E, an aggregate or gel of 5-10 nm parti~~
... cles causes less disruption because the surface is
~J less continuous than in C; F. a protein coil with
.
. . adhering particles of silicic acid as in tanning.
natured
thought
s is due
pecially
ie denaith prothe surm (258)
sizes of
ed solu.e as it
~.
.t
a large
ently to
uner of
nd that
h 5 nm
7, and
on and
g effect
st were
e partirape by
articles
I to difone by
:r silica
ed and
'ic con'-266).
1m
cre.._~s
_"
"-J
from 3 to 10'nm and more slowly up to 100 nm. In the case of silica' gel. a compact
aggregate of 3 nm particles apparently provides a sufficiently extended surface to be
.an active denaturant. However. with a gel of 30 nm particles. each separate particle
acts as a denaturation' site. In each case the activity per gram of silica is.low because
only the outer surface of the gel granule is effective. It is interesting that when the
erythrocytes are first exposed to 3 nm particles. they apparently become coated so
that then they are not denatured by larger particles. '
Micelles of free fatty acid in the blood stream. being weakly acidic like silica. can
also denature .the Hageman factor and cause blood clotting according to Margolis
,r
:
r
'
.
.,
_(267).
lysilicic
nation.
ca then
iared in
ing size
was
Ther~ must besoment,ajor 'differences either in the energy of adsorption of silica
on the erythrocyte or, in' mechanical strength. depending on the source animal.
Arienzo and Bresciano (268) reported that the number of micrograms, of a given
type of SiOI required to induce hemolysis of 10' cells varied from 0.104 in rat. 0.173
in man. 0.33 in rabbit. '0.63 hi hen. I.] 7 in ox. 4,8 in horse. to 80.0 in frog. with
values for other animals falling in between.
An observation by Holt and Went (269) suggests how silica particles smaller than
5 nm, and therefore innocuous. may become toxic in a biological system by a type of
polymerization that is promoted within the system. They observed that a monolayerof protein (insulin) on the liquid surface of a very dilute silicic acid sol absorbs parti. des from solution and then when the film is compressed these particles are brought
together so they can polymerize. They observe that this polymerization is most rapid
between pH 5.4 and 6.1, which is the pH for most rapid gelling of silica sols in
general. This means that although polysilicic acid of particles less than 5' nm in size
may be innocuous in a biological system. they nevertheless may be brought together
into large aggregates by the above mechanism, especially if membranes collapse.
These large aggregates would then be active in denaturing proteln.
When erythrocytes were centrifuged in collodial silica (14 nm particles) as the suspending medium, the surface of the cells was wrinkled with a granular texture, no
..
~--
Silica in Biology
766
II
I
doubt owing to distortion by the adsorption of colloidal particles (270). Browtt has
observed that lipids are adsorbed from the erythrocyte surface by silica (271).
Depasse and Warlus (272) suggest that the strong bonding of silica to the surface of
erythrocytes is due to the presence of quaternary ammonium ions in the membrane.
Not all proteins adsorbed in silica are denatured. At least gamma globulins that
.are adsorbed on powdered quartz retain their antigenic specificity. Pernis, Clerici,
and Ghezzi (273) concluded that this shows that 'the.immunological reactions of silicosis could not be due to antibody production against serum proteins altered by
quartz. However, other types of proteins are definitely denatured and may be the
cause of the reactions.
.
Combination With Specific Compounds, Enzymes

The surface of quartz catalyzes the air oxidation of d/-proline to hydroxyproline,
indicating that some type of'activated, oriented, and specific adsorption may be
involved (274). It is therefore noteworthy that the hydroxyproline excreted in the
miners wishsillcosls was 31% higher than in normal individuals. The total
urine
hydroxyproline in blood and urine served as an index of fibrosis activity (275).
Sugars differ in their tendency to combine with silica. Holzapfel (173, 276) found
that galactose was adsorbed on quartz and reacted with phenylhydraz6ne and
formed osazones, butarabinosc did not. The amount of adsorbed galactose was
twice that of lactose and four times that' of glucose.
Enzymes can be adsorbed on silica and still retain activity. Bovine trypsin
adsorbed on 14 nm particles of colloidal silica, then insolubilized with glutaraldehyde, retained 80% of its ester-ase activity and 17% of its proteolytic activity. The
coated particles can, be .isolat~d by centrifuging and later redispersed (277). The
enzyme was adsorbed from a.O..l M borate buffer solution at pH 8.5 and formed a
monomolecular layer of thc"4 nm diameter enzyme molecules around the 14 nm
silica spheres, which could be seen With the electron microscope. Once the coating
has been formed, it is cross-linked with glutaraldchyde and does not come off.
An enzyme can also be attached to the surface of a voluminous pyrogenic silica
powder. by reaction with aminopropyl sHyl groups previously chemlsorbed on the
surface. An activator' may simultaneously be applied. Reynolds and Miller have
patented a recoverable trypsin of this type (278).
.
Enzyme inhibition by silicic acid oligomers may be due either to the active site
being oriented toward the silica surface, or to denaturation of the molecule by the
Margolis mechanism. Glucose-6-phosphatase of rat-liver microsomes is inhibited by
100-250 ppm of oligosilicic acids, but some other phosphatases, dehydrogenases,
and oxidases are not (279). Some enzymes are inhibited by silicic acid or gelatinous
silica and some are not. King et at. (280) reported that those inhibited are
acetylcholinesterase, succinic dehydrogenase, esterase and hyaluronidase; those that
are not are amylase, pancreatic lipase, pepsin, alkaline and acid phosphatases,
trypsin, and urease.
.
Monosilicicacid has no effect on enzymes according to Rowsell and Leonard
(281). The monomer penetrated liver cells yet caused no interference with vital
or
j.
Biology
wn has
(271 ).
fac
irane.
ns that
Clerici,
of siliired by
be the
"1"
-;...--
Mammals: Man
767
enzymes and had no blocking effect on cell membranes which remained normally
permeable to ions and small molecules such as acetate or urea.
Enzymes can be coupled to the surface of a very open-pored silica gel to obtain a
.relatlvely stable fixed enzymatic catalyst (282). Porous silica with a pore diameter of
51 nm was used as a carrier to the surface of which the enzyme B. subtilic protease
. was attached. a bifunctional diazonium salt, was reacted with the surface of the
silica, followed by reaction of enzyme with the other end of the diazonium molecule.
, The silica-supported enzyme hydrolyzed casein and had a half-life of more than 7
months whereas that of enzyme simply adsorbed on the silica was 2.5 months.
Vitamin C (ascorbic acid) is stabilized when adsorbed on silica gel at pH 6.5
(283). It does not appear to be adsorbed by hydrogen bonding in view of the rela,tively high pH but may possibly be held by a chelation reaction with silanol surface
, .: groups since it possesses the typical pair of hydroxyl groups on adjacent doublebonded carbon atoms; these characterize. catechol" which is a powerful chelating
agent for silicon. If indeed both hydroxyls were condensed with a surface silicon .
atom it would tend to stabilize the double bond against oxidation. Apparently, the
possibility of a water-soluble anionic chelate of silicon has not been examined in the
case of vitamin C.
"
The orientation' of crystals of low peptides and amino acids when grown on quartz
surfaces indicatesthe epitaxial matching which may have played a role, in prebiotic
.
evolution ( 2 8 4 ) . '
Combination in Phosphorus Compounds: Nucleic Acids, DNA, RNA

The exchange of Si(OH). for H.PO. in ribonucleic acids is difficult to imagine in
view of the stability of DN~, but Schwarz and Baronetsky report that in hydrolysis
studies in which phosphoric acid was liberated, the reaction was accelerated in the
presence of Si(OH). They showed there was an exchange of silicic acid with phosphoric in the ribonucleic acid (285). The interaction of silicic acid with DPN and
even ATP was indicated by Kersten and Staudinger (286); doubt was later thrown
on this observation by a reported artifact caused by the incidental presence of bacteria.
Some interaction with ribonucleic acid (RNA) was also indicated in experiments
by Kikuth and Schlipkoter, who found that when silica sol was administered.
intratracheally to rats, silica alone caused limited nodular fibrosis, but when
administered with RNA, the effects were much more severe, with development of a
heavy fibrous collagen network (287). Trypsin also augmented the effect of silica
~88~'
'
Monomeric silica is more toxic to isolated mitochondria than is polysilicic acid,

according to Hauger, Krisch, and Staudinger (289). The monomer caused swelling of
rat liver mitochondria and inhibited oxidative posphorylation. Since it is monosilicic
acid that is involved it seems likely that interaction with a nucleic acid has occurred.
As discussed later in connection with silicosis, the presence of quartz particles in
the lungs or peritoneum leads to the formation of an unusual layer-lattice type of a
Silica in Biology
768
crystalline ferro-ferri-phosphosilicate. The relation of this hitherto bnknown and

most peculiar kind o~ compound to toxicity or disease is not known (127, 290).
. The presence of soluble silica has an effect on the metabolism of phosphate. At a
concentration of 100 ppm, oligosilicic acids lowered the P: 0 quotient of rat liver
mitochondria in vitro, inhibiting assimilation of phosphate by 30% (291). When rats
.. were fed high levels or"silica for' 3 months, inclusions formed in the kidney tubules
where silica combined in some way with purine or pyrimidine bases (292). Voronkov
et al. propose that silicic acid replaces phosphoric significantly in DNA and RNA so
that the Si: P ratio may be 1: 20 to 1: 45. Orthosilicic acid may form ester bonds
with OH groups of carbohydrate moieties (293). According to Schwarz (2~4, 295) 1
. ppm of Si(OH). catalyzed the hydrolysis of ribonucleic acid and silicic acid is
exchanged for HaPO . Monosilicic acid also damages cell respiration through
interaction with DPN (liver homogenate) and also reacts with ATP (adenosine
triphosphate) (285~ 286).
Mutations, Atheroscle~osis, Cancer
,j
Since it appears that Si(OH). can exchange to an appreciable extent with HaPO. in
nucleic acids it follows that at 'certain points along the DNA chain there must be
links that are' different from the remainder in regard to stability. The two types of
linkages are represented as follows:
deoxyribose
1
,0
ii
-::'
"
'O-='P-O- .
~.,'
, :i
.'"
I
I.
HO-Si-OH
.1
deoxyribose
; :
deoxyribose
deoxyribose
The phosphate or silicate groups are located on the outside of the double helix so
that at least from a steric standpoint exchange could occur. However, once inserted
in the chain, the silicate linkage must be different from phosphate in stability, especially since the SiOH group is much less likely to be ionized. There is no way to
predict whether the silica makes the DNA more or less stable.
There are obviously some similarities between the development of fibrotic tissue in
silicotic lungs and the development of atherosclerotic plaques in arteries. In both
cases there is loss of elasticity and abnormal proliferation of one type of tissue. Also
there is development of necrotic tissue. As pointed out by Benditt (296) the plaques
were previously thought to consist of fibroblasts but have now been identified as
smooth muscle cells. The growth of the plaque appears to involve a "mutation" that
leads to proliferation of smooth muscle cells which thicken the artery wall and lead
to necrosis within the plaque mass. Benditt cites possible agents of mutation as
chemical mutagens, viruses, and ionizing radiations.
Possibly another factor might be involved: the development of atherosclerosis has
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Biology
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Mammals: Man
769
in some studies been related to the silicon content of blood. Silicon has been shown
to be a very minor but apparently real component in nucleic acids (DNA. RNA). If
- . it should turn out that this silica influences the possibility of "mutation". then a connection between silica levels and atherosclerosis would be established:
" '.,' Possible evidence that the presence of silica could be beneficial is' furnished by
..- Loeper and Loeper (297). who found that in atherosclerosis there was an increase in
.:.. calcium and a significant decrease in silica in the artery wall. Also. De Franciscis
:and Oliviero (298) examined the effects of soluble silica in the drinking water (61
. ppm) of rats with normal and elevated blood cholesterol levels. The high-cholesterol
rats showed iower cholesterol levels when on the high-silica drinking water. and also
.less fatty infiltration of the liver than in controls. According to Charnot, Desmaris. Delecraz, and Peres (299) the presence of sodium silicate in drinking water had a
'. sparing effect 0'0 the accumulation of calcium. etc. in atheromas. As will be discussed under organosilicon compounds. 'some of these compounds, appear to be '
metabolized and may furnish silica which prevents atherosclerosis in rabbits on a
'.-'
high cholesterol diet (300).-' ,:.. .'- ,, A similar role of silica in' the-cancer problem is .also conceivable; that is. a change
in silica level in old age may influence the probability of mutation. Limited studies
of silica in tissues and fluids 'of cancer patients have been summarized by Voronkov,
Zelchan, and Lukevits (4a). In neurosarcomas the silica content of the tumor is
lower than elsewhere. In the pancreatic fluids the silica content is higher in the case
of cancer.but goes back to normal after surgery. In cancer patients the silica
. " content of urine is 2.5-17 times less' than normal. Such observations are said to
. :'". provide early diagnosis ofcancer. Tumor of the bladder increases the silica content
~ : ofurine. The 'blood of cancer patients also' co~tains higher amounts of silica.
" .The' protective action of' siJica' in cases of cancer is suggested by the claim that
cancer seldom begins in silica '(or' magnesium) rich regions but frequently in calciumrich regions since calcium, is an "antagonist of silicon." Voronkcv, Zelchan, and
..
Lukevits (4a) even postulate that cancer is more frequent in higher organisms
because less silica is present as a result of evolutionary processes. However. there are
, many other factors involved in the incidence of cancer and it is doubtful if it could
., be broadly related to the amount of silica in food or drinking water in a particular
region. Also. some of theforegoing information goes back over a period of 50 years.
when analytical results for silica may be subject to some doubt.
, In view o'f the reported presence of silica in DNA and RNA. and the above
reported changes in silica levels in cancer patients. some further investigation of
silica as a possible factor in cancer is probably justified. The development of cancer
in animals on abnormally low and abnormally high intakes of monosilicic acid
migh~ p~?vi~efurther insight.' .
'
,
. Silicosis-Pneumoconiosis-Fibrinogenesis .
"
osis lias
.The. most common way human beings absorb silica in dangerous quantities is
through the lungs. 'although there has been some suggestion that there can be a dele-
~---
Silica in Biol~gy
770
.
terious effect of colloidal silica in open wounds. However, continued exposure of the
latter sort is very improbable,and it is silicosis of the lungs that is normally
enountered, ,Historically~ it is of interest ,that in the early 1800s in England,
industrial workers in factories preparing finely ground flint or silica for pottery were
, so susceptible to silicosis that it was, common for the women to expect to marry
consecutively three or" four husbands, owing to their rapid demise. The problem of
silicosis in industry resulted in'strict governmental controls to minimize worker
exposure. Incidence of the disease has been greatly diminished in most countries.
The enormous and still. growing volume of research and publications on silicosis
and related chemistry is impossible to review here. However, some of the chemical
aspects are considered and some of the leading theories. summarized. According to
Voronkov, Zelchan, and Lukevits (4a) there have been more than 50 theories
advanced to-explain the mechanism of action of the silica, and they cite hundreds of
references.
- Brief reviews of the subject have be~n written by Butenandt (301), Brown (302),
Garcia (303), Thomas and Stober (304a), Thomas, Embrodt, and Scoedel (304b),
Hofmann (305), and Soffge (306). Holt's monograph in 1955 with 657 references and
Heppleston's publications and monograph in, 1973ar: discussed later in detail.
.
~.
J':.
'
Mechanism ofSilicosis
The way iIi which finely divided quartz dust in the lungs brings about silicosis has
long been a matter of debate. The fact is that crystalline quartz particles about a
micron in size, unlike many other dusts even of the hardest materials like SiC (307),
, bring about structural changes in the lungs involving fibrosis, hardening of the
tissues, and loss of lung capacity and greatly increase the probability of tuberculosis.
'. "
There have been two types of theories:
1. Earlier. sol~ble silica was thought 'to playa role. One possibility was that mono-
silicic acid. entered into DNA or RNA leading to modification of enzyme

systems. The more prevalent idea was that quartz dissolved to soluble monomeric
silica. This in itself. was harmless but polymerized to polysilicic acid. which is
. generally known to be a protein denaturant and a destroyer of cell membranes,
that is, it is cytotoxic. .'
2. According' to current theory. it is the clean surface of particles of crystalline
silica, usually quartz. that is the sole initiating cause of silicosis.
Confusion existed for a long time because of the false assumption that the proteindenaturing and cytotoxic effects of silica must lead to the development of fibrous
tissue in the silicotic lung. On the contrary, strong cytotoxic activity seems to be
almost the reverse of fibrotic activity in the sense that the most active cytotoxic
forms of silica, such as polysilicic acid and amorphous and-colloidal silica, are' the
least active in causing fibrosis. It is now the prevailing view that it is quartz in the
form of inhaled particles 0.05-5 microns in size that produces typical silicosis or
pneumoconiosis characterized by the development of massive fibrosis of the lungs.
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More specifically, the living macrophage or phagocytes, which are the lung's
defense against foreign matter, engulf the quartz particles. There the quartz surface
. acts as a specific heterogeneous catalyst to generate a "factor," possibly a modified
enzyme, which, when later released from the dead macrophage, stimulates fibroblasts to produce an excess of hydroxyproline. This leads to the formation of an
abnormal amount of fibrotic tissue.
At the risk of confusing the reader. the various earlier theories and many related
observations are also reviewed in order to give an appreciation of the enormous
effort that has been expended in the past on this complex problem. At the same time
this presents an opportunity to describe many incidental but interesting observations
that have been recorded.
The volume of literature on this subject is so enormous that it is possible to make
reference here only to more recent.reviews. Some summaries of the theories regard..
ing silicosis which appeared since 1955 are as follows.
Schepers presented an extraordinarily clear survey of the history of research on
silicosis, discussing SO of the main theories (308). which were classified as chemical,
physiological, and biological. He emphasized that after the first particle-protoplasm
interaction and the destruction of phagocytes, many further changes continue to
occur once necrotic tissues are present. Much of the silica may be removed but biological changes continue with development of fibrotic tissues and large amounts of
pulmonary lipids so that the lungs may increase thirty-fold in dried weight, of which
.
.less than 5% may be silica.
.He concluded that the solubility theory was not applicable. Instead the chemical
properties of the surface of the silica particles directly involved them in reaction with
tissues. Physical theories were generally judged inadequate. Although there may be
some correlation between specific surface area, or adsorption. capacity for albumin
and pathogenicity, exceptions can generally be found. An explanation of how a silica
particle ki1ls a phagocyte is far from an explanation of the biochemical interactions
involved in the development of a silicotic lesion.
.
Stober surveyed the history of silicosis and the three main theories involving (1)
solubility of silica, (2) surface interactions of silica, and (3) immune reactions resulting from the presence of silica. He then presented a summary of extensive tests made
with particles of all known forms of silica in which surface properties and dissolution
characteristics were correlated with their biological reactions (309). He pointed out
that the simple solubility theory cannot be correct. The fact is that if one arranges the various forms of silica in order of increasing solubility (crystalline silicas, opal,
fine-particle amorphous silica, and colloidal silica) the fibrogenic activity decreases
whereas the toxicity to tissues increases.
As for the "surface" theory, the soluble silica is considered to be incidental and it
is the surface or phase boundary of
quartz particle that changes the organic
molecules. One general idea is that the regular spacings of the atoms on the surface
of the crystal lattice act as a matrix on which matching spacings between polar
groups in protein molecules can be adsorbed and then modified.~The immune reaction theory attempts to explain further steps in the development of silicotic lesions
and does not conflict with the other theories.
..
772
---_.
-~.1;-.
Silica in Biology
'
It was the high dissolution rate of stishovite along with complete inabtivity from a
biological standpoint that seemed finally to eliminate the solubility theory. This
form of silica is similar to alpha alumina, in which the metal atom is coordinated
with six oxygen atoms. The major difference in surface properties is the fact that
stishovite has twice as many SiOH groups per unit area of surface and the surface
does not adsorb PYPNO, which is strongly adsorbed on the other -modifications.
However, the rather high silicotic activity of quartz among the other modifications
was not explained.
.
Heppleston (310, 311) in 1972 reviewed the main theories of the fibrogenic action
of silica likewise classified as (1) solubility, (2) surface, and (3) immunological. The
immunological theory is of secondary importance because it does not explain the
primary action of silica in stimulating proliferation of connective tissue. The solubility theory was left by default, but was still inadequate because neither the known
surface structures of the different modifications of silica nor their characteristic
adsorption of albumin or gamma globulin could be correlated with their relative biological activity. However Stober (312) showed that all crystalline forms except stishovite are relatively active.
Heppleston pointed out that the cytotoxic effects of silica particles on phagocytes
had not been definitely correlated with fibrinogenicity and silicosis. In this he raised
the key question that is finally being resolved. He cited evidence' (127, 310) that
quartz interacts with macrophage cell constituents to produce some agent that
stimulates collagen formation, that is, fibrosis. The link between cell damage and
fibrosis is nonlipid in nature and a galactan may be involved. In any event, some Hfactor (hydroxyproline factor) is believed to be released which stimulates collagen
production in the fibroblasts. Since silicotic tissues contain excess lipid, it is possible
that once the process .is started, these lipids alone may promote continuation of
fibrogenesis.
Heppleston (313) 'reported the remarkable observation that pathogen-free rats
ii.e., no phagocytes) did not develop the typical silicotic nodules that appear in
standard rats even when silica was inhaled. This strongly supports the idea that
phagocytes are specifically involved in the development of fibrosis. Weller et al,
(314) claimed that in pathogen-free rats silica caused pathological effects, but the
silica was injected intraperitoneally and the results cannot be compared with effects
in the lungs where typical fibrosis develops.
Heppleston clearly demonstrated the course of events by incubating macrophages
with quartz particles, then disintegrating them and centrifuging out the quartz and
cell debris to obtain a solution containing the factor causing fibrosis. When the latter
was applied to a separate culture of fibroblasts, there was marked stimulation of the
production of hydroxyproline, which is a characteristic component of connective or
fibrotic tissue. He showed that it was necessary to culture the macrophage with
quartz particles; addition of quartz to disintegrated macrophage did not produce the
factor. Merely killing the macrophages with excess quartz. (cytotoxic effect) did not
produce the fibrosis factor (127).
.
Heppleston et al. also demonstrated another type of effect in which the epithelial
cells in the lungs respond to excess quartz dust by producing massive amounts of
........
, "1:,"
n Biology
11
Mammals: Man
773
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phospholipids (specifically the dipalmitoyl type) which engulf the quart~ particles,
keeping them from the macrophages. In this case, no fibrosis develops (127,315).
Allison (127) found evidence that within macrophage, the lysosomal membranes
containing phospholipids become hydrogen-bonded through the oxygen atoms of
phosphate ester groups to the uniformly arranged SiOH groups on the quartz surface. Under these conditions the fibrogenic factor-possibly an abnormal or
modified enzyme-is synthesized and accumulates in the cell until the latter is killed.
lIer (127) summarized what was known about hydrogen-bonding between polar
organic compounds and the surface of amorphous silica. The reason for the unique
high activity of the quartz surface is not known. However, it is conceivable that the
regular arrangement of SiOH groups on the crystalline surface of quartz may permit
more complete hydrogen bonding of a membrane than the more randomly spaced
SiOH groups on amorphous silica. The surface characteristics of quartz certainly
differ from those of amorphous silica as shown by the fact that the quartz surface
adsorbs monomeric silica from solution whereas the amorphous surface does not
(see Chapter 1).
Summerton et a1. (316) proposed that it was a protein component rather than a
phospholipid that was adsorbed because only a polymeric protein could form a large
number of cooperative bonds and be so strongly adsorbed. However, they did not
consider the strong hydrophobic bonding between the long alkyl groups of the
adjacent adsorbed phospholipid molecules that can also stabilize the adsorbed layer.
The following steps in the mechanism whereby quartz particles cause fibrosis were
suggested by Allison (317-319) and summarized by Summerton et al. (316) with
minor modifications:
1. The quartz particle in "an alveolus is covered by hydrogen-bonded organic
polymer material, for example, proteins.
2. The coated particle is phagocytosed by a macrophage (taken into a white cell).
3. Within the macrophage a lysosome and its enzymes remove the coating from the
particle.
4. The unmasked particle hydrogen-bonds to certain components from the inner
surface of the lysosome membrane which releases enzymes into the protoplasm,
which then cause death and dissolution of the macrophage.
However, it was then found by Heppleston and Styles (320a) that it was not the
death of the macrophage that was important. Instead, the damage was done while
the macrophage was still living with quartz particles within the cells. The quartz surface somehow damaged the lysosomes in such a way as to produce a new factor,
possibly an enzyme. When this was released from the dead macrophage it stimulated
fibroblasts to produce more hydroxyproline that is associated ~ith the formation of
fibrotic tissues. Possibly this is supported by the observation by Marasas and Harrington (320b) that the surface of quartz catalyzes the air oxidation of dl-proline to
hydroxyproline.
TIi
774
Silica in Biology
Amorphous versus Crystalline Silica and Particle Size

Under actual working conditions silicosis involving fibrosis of the lungs is .not caused
by amorphous silica dust, but rather by quartz dust. However, in innumerable
studies, the effects of particle size were not clearly separated from differences in
crystallinity.
A careful comparison was made' by King et al. (321) of the effects of quartz,
cristobalite, tridymite, and fused silica glass, all of the same particle size (generally
1-4 microns) and specific surface area. The dust was injected as a suspension into
the lungs of rats and the progress of silicosis then followed. All the silicas caused
pulmonary fibrosis. However, the effects of amorphous (fused) silica were least
severe. Quartz and cristobalite were about alike in causing typical symptoms of silicosis. However, tridymite was very potent, causing much more rapid and severe
symptoms. This same order of fibrogenic activity was reported by Inglebrecht and
Nagelschmidt (322). Stober (323a) concluded that for particles of equal size there is
still a moderate difference between amorphous silica glass and quartz in causing silicosis under experimental conditions. This view was supported by in vitro studies by
Baumann and Rasche (323b), who demonstrated the remarkable difference in biological activities of the clean crystalline surface of quartz and the same powder on
which an amorphous layer of silica had been deposited. The crystalline surface was
toxic to a cell culture of canine alveolar phage whereas the amorphous surface was
essentially inert. Three particle sizes were used, 0.6, 1.2, and 2.0 microns, and the
amorphous layer on the crystalline surface was only three or four molecular layers in
thickness.
From a practical standpoint there are very few conditions under which amorphous
silica (glass) dust could be encountered in the dangerous 1-4 micron size range.
Almost all amorphous silica dusts consist of particles at least two. orders of magnitude smaller than this. On the other hand, almost all silica dusts in the 1-4 micron
range encountered in industry are crystalline-usually quartz.
Thus it is possible to state that from a practical standpoint, amorphous silicas
generally do not cause silicosis. Also, it appears that even w.hen allowance is made
for differences in particle size, the quartz surface (and especially tridymite) is more
fibrogenic than amorphous silica.
As shown by Schepers (324) and Klosterkdtter (325), pyrogenic submicron amorphous silica powder, typically made up of aggregates of ultimate particles of
colloidal size, does not cause silicosis.. Extended inhalation tests on rats and rabbits
caused irritation and bronchial difficulties, but no fibrosis occurred and the animals
returned to normal when the test was completed. Precipitated amorphous silica was
likewise not fibrogenic (326).
The really hazardous particles are those of solid crystalline silica, in any form
(except stishovite) in the 5.0-0.5 microns size range. Still smaller crystalline particles
from 0.05 to 0.5 microns in size may be even more dangerous but they apparently
have not been tested in the lungs. It is possible that the reported much higher
silicotic activity of coesite (less than 0.5 microns) than that of quartz (1-3 microns}
was simply due to the smaller particle size (327a).
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Even the finest amorphous silica powders can cause temporary nodular forms of
pneumoconiosis; for the pyrogenic Aerosil a maximum level in air in working areas
was recommended to be 1 mg m-:-' (327b).
Susceptibility 10 Silicosis
Susceptibility to silicosis was found to be greatly enchanced by smoking and drinking alcohol, which shortened life by 6-7 years, whereas abstainers under identical
conditions lived more than 12 years longer (328). Reducing dust concentration by
50% doubled the life span. Individual susceptibility is no doubt a widely variable factor but one that is difficult to isolate. Development of lung cancer is not a result of
silicosis and silica is not carcinogenic. However, silicosis increases the susceptibility
of smokers to cancer because elimination of the carcinogenic tabacco smoke compounds from the lungs is impaired (329).
An Unusual Compound in Silicotic Tissues

An unusal crystalline inorganic compound formed when quartz remains in animal
tissues, discovered by Weiss (290), has already been mentioned. In 76 lungs from
victims of silicosis, but not in 11 lungs from nonsilicotic cadavers, Weiss (127) found
a crystalline hydrated iron phosphatosilicate. The compound-is unknown in nature
except where synthesized in the lungs or in the intraperitoneal cavities of rats in
which finely ground quartz has been deposited. It is synthesized in vivo in 6-18
weeks. The composition is represented by the formula:
iorphous
:e range.
of mag4 micron
IS
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is made
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1S)
mi
77S
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The M + cations are exchangeable; also the water can be replaced by small polar
organic molecules. This may be related to the calcium-magnesium-basic iron phosphate found associated with silica in the sea cucumber (69).
Whether this compound plays any role in the biological effects of quartz is not
known. It may be only a by-product formed in the living system simply because all
the components happen to be maintained in solution at the specific concentrations
with which this particular inorganic crystalline phase is in equilibrium.
Solubility Theory
It now appears that the solubility theory cannot account for the development of
typical silicosis which involves fibrosis. However, polysilicic acids and colloidal
silicas certainly have other toxic effects in tissues and on living cells. Much of the
work originally directed toward silicosis and based on the solubility theory failed to
explain the mechanism of fibrosis and silicosis but nevertheless provided much of
what we now know about the other effects of silica.
In his monograph on pneumoconiosis, Holt (330) assembled many important
facts, for exam ple, (I) polysilicic acids or colloidal silica denature proteins and are
Silica in Biology
776
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cytotoxic; (2) monomolecular film tests prove that protein monolayets strongly
adsorb polysilicic acid and are thereby permanently changed and cross-linked; and
(3) protein monolayers on water can concentrate silicic acid by adsorption and promote polymerization when the overall silica concentration is otherwise too low for
silica to polymerize.
'
The solubility theory assumed that polysilicic acids or colloidal particles must be
present in tissues in order to cause damage. Soluble or monomeric Si(OH). is inert
at low temperature. However. these polymeric silicas are not formed by polymerization until the concentration of soluble silica exceeds the solubility of amorphous
silica. which is well.over 100 ppm Si02 Yet quartz is soluble only to the extent of
around 10 ppm. One way to account for the formation of polysilicic acid and
, colloidal particles from relatively insoluble quartz is that the soluble silica is first
concentrated by biological processes. As listed under (3) above. Holt argued that
silica could be concentrated at- membranes and there polymerized. Another possibility of spontaneous concentration is as follows: in an experiment by Iler a solution
of monosilicic acid. unsaturated with respect to amorphous silica. was aged in a neutral solution containing a low concentration of cetyltrimethylammonium bromide.
Silica was precipitated in combination with surfactant. It appears that a micelleforming cation can attract and concentrate monomeric silica so that it polymerizes
to particles which are protected from dissolution by a surrounding layer of cations.
that is. within a micelle. It is thus conceivable that within living cells. cationic groups
might similarly collect silica and bring about polymerization to the point where the
polymer is large enough to denature protein. '
Another way to account for the formation of polysilicic acid and colloidal silica
from quartz particles is that the particles contain an unusually soluble Fraction when
freshly formed. Accordingly. Holt proposed an "extended solubility theory." which
postulated that silica dust particles can initially produce a supersaturated solution of
sflica which then polymerizes. Both Holt (331) and Soffge (306) emphasized the
dissolution of silica- followed bypolymerization, The silica particles are collected and
concentrated by phagoeytes, creating higher local concentrations. Collagen is
adsorbed and cross-linked by the silicic acid in a manner similar to silica tanning.
This type of theory was long ago supported by Kettle (332), who demonstrated
that when silica powder in a collodion bag. from which only soluble silica could
escape, was implanted into the flank of a rabbit an inflammatory reaction was prosuch reaction occurred when the bag contained no silica.
voked.
Faber (333) was one of the first to propose that the dissolved silica polymerized to
polysilicic acid which was the active agent. Another type of observation supporting
the solubility theory was that when quartz particles smaller than 2 microns were
introduced into the animal system (i.e., rabbit's ears) silica was deposited in liver,
lungs. spleen, and bone marrow. This certainly suggests that soluble silica was
present throughout the living system.
An objection to Holt's "extended solubility theory" was that it gave no explanation as to why particles of submicron quartz were more toxic than particles of the
more soluble types of silica. However, Jager pointed out that the disturbed layer on
the surface of quartz was unusually soluble and proposed that it furnished
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monomeric silica which could diffuse away, polymerize, and form toxic polysilicic
acids (334). Freshly pulverized quartz has a higher surface energy than other types
and thus very smal1 particles or sharp corners and edges could supply a relatively
higher concentration of monomer for a longer time than other silica modifications
that are more soluble. The latter would rapidly lose such regions of higher solubility.
As discussed in Chapter l, the interfacial surface energy of the quartz-water surface
is probably around 416 ergs cm- 2, in contrast with around SO ergs cm- 2 for amorphous silica. In accordance with the Thompson-Gibbs effect, quartz particles with
very small radii of curvature (either particles of small diameter or sharp corners and
edges) should be more soluble than amorphous particles with the same radius. lIer
(1) calculated that with a radius of curvature of 1.5 nm the solubility of the quartz
surface would be of the order of .000 ppm.
Stober and Arnold (335) demonstrated that finely ground quartz, because of the
above effect, can dissolve in water to give a monomer concentration of 80 ppm even
when only a limited concentration of quartz powder is in suspension. At the surface
~f a particle embedded in tissues the concentration of dissolving monomer could
become even higher and thus could polymerize to harmful polysilicic acid or even
diffuse through adjacent membranes and then form polymer.
The observation by Gothe, Lidstrom, and Swensson (336) that freshly drycrushed
quartz is more active than wet-ground quartz of the same particle size might be
explained by the presence of sharper corners and edges which produce more soluble
silica. During wet grinding the points ef high surface energy would be rounded off by
the. solution-deposition mechanism. The activity was judged by the increased
hydroxyproline content of lungs which parallels fibrosis. However, another explanation is that during wet. grinding, the quartz surface becomes covered with an
adsorbed layer of amorphous silica and is thus less active. ;
Other apparent support for the solubility theory by silicosis came from several
sources. The less soluble types of silica were less harmful. Thus the deposition of
soluble aluminum ions on the silica surface reduces solubility as well as toxicity
(337-340). Also, aluminosilicate minerals such as clays, which are even less soluble
than quartz, do not cause silicosis. The report that silicotic lung tissues contained
esters of silicic acid, for example, cholesterol (341), seemed also to support the idea
that soluble silica must be involved.
The solubility theory was not "wrong," in that it was based on many valid
observations and explained many of the cytotoxic and other harmful effects that can
occur in the animal system when silica is introduced by unnatural means. However.
there was a false but persistent belief that these effects must result in the fibrosis that
is characteristic of silicosis.
Soluble silica does not cause silicosis. The crystalline form of silica, stishovite,
dissolves in water to give a concentration of soluble silica much more concentrated
than from quartz (309). If soluble silica is the active agent, then stishovite should be
even more toxic than quartz. Instead. it is harmless.
. Amorphous finely divided silica does not cause silicosis. . In animals, inhalation
causes only bronchitis or interstitial pneumonia, but no silicosis. Yet this type of
silica easily produces a saturated solution of monomer in water. It is true that very
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l micel1elymerizes
f cations,
ic groups
vhere the
dal ca
ion when
'," which
ilution of
sized the
ected and
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mingo
onstrated
ca could
was proerized to
:pporting
ons were
in liver,
.lica was
explanaes of the
la~
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urn., .ed
777
778
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Silica in Biology
large amounts of this type of silica cause bonelike fibrosis. whether injected into
lungs. under the skin, or into the body cavity. but this effect appears different from
the silicosis induced by quartz.
If soluble silica were produced by quartz it should be found in the lungs. Wheatly
(342) was unable to find any form of amorphous silica in lungs into which quartz
had been injected. Also, he found no polysiJicic acids in aqueous extracts of quartz.
The idea that silicosis is generated by silica dissolving from freshly formed quartz
particles was found to be incorrect by King et al. (343), who removed the highly
soluble silica from quartz particles before they were tested in the animal lungs. The
soluble layer was removed by alkali so that the powder then showed the true solubility of quartz (about 10 ppm); the powder was still an active fibrogen (HF treated
powders were even more toxic, possibly because adsorbed fluorine cannot be
removed by washing with water but can be replaced by OH- only by washing with
base).
. Policard, Collet, and Rey' (344) concluded from a study of a culture of embryonic
myocardial cells of chicken that there was no effect from adding either very fine
quartz particles or amorphous silica. He believed that the particles have to be within
cells so that the surface is in contact with cytoplasm to cause toxicity. as when silica
is taken into phagocytes. Thus soluble silica is apparently not involved. Much of the
support for the solubility theory came from observations of toxicity of' polysiJicic
"acids in tests on other than in lungs. Using intraperitoneal injections. Paterson and
Wheatley (345) stated categorically that the resulting so-called "silicosis" was caused
by silicic acid dissolved from the surface of quartz and that only monomeric or
oligomeric silicic acids (molybdate-reactive) were toxic. This is true in
intraperitoneal tests, and there is no question that polysilicic acids can denature pro':'
tein and cause inflammatory-reactions. However. the development of true silicosis.
that is. fibrosis of the lungs, from inhaled silica particles seems to be an additional
effect. involvingdifferent o"t additional mechanisms.
It is the surface of particles of quartz that causes silicosis, provided the particles
are in a certain size range. As summarized by Stober (346). "It appears unlikely that
the release-of silicic acid from the surface of a particle has anything to do with the
chemical mechanism that causes the development of silicosis."
Silica Antagonists 'to Prevent Silicosis
. i
I :
I
, I
Since it is the surface of solid silica that attracts and disrupts cell membranes and
causes silicosis. any covering or chemical modification of the surface to reduce the
adsorption of components of cell membranes, especially phosphatidyl choline. will
also prevent the initiation of silicosis. This has been accomplished in three general
ways:
1. The addition of a water-soluble biologically inert organic polymer. such as
poly(vinylpyridine N-oxide) (PVPNO) that is adsorbed on the silica surface even

more strongly than membrane components.
2. The addition of a source of soluble alumina which is adsorbed on the silica surface and changes its chemical properties, making it less fibrogenic.
iology
Mammals: Man
d into
: frC'''''
" material
3. Covering the silica surface in advance with a chemisorbed layer. of any
that is not fibrogenic or that makes it generally inert such as a monolayer of alkyl
groups.
779
heatly
l~artz
irtz,
quartz
highly
s. The
: solureated
.ot be
~ with
ryonic
y fine
within
, silica
of the
'silicic
In and
iaused
ric .
ue '. ...
'e proicosis,
itional
rticles
ly that
.th the
PVPNO. Starting in 1958, compounds were found that offset the development of
silicotic tissues in animal tissues treated with silicogenic forms of silica. An undisclosed compound 48/80, an organic base, was found effective by Marks et al.
(347-349) but too toxic for use in man. They also reported that certain phenazines
. and a histamine-releasing agent neutralized silica toxicity. The compound 48/80
may simply coat the silica surface. Some protection was observed by polymyxin B
and by hexylamine.
Later, Schlipkdter et al. (350-353) and Beck, Bruch,' and Brockhaus reported that
PVPNO was an effective antagonist and this material has continued under investigation. It apparently was effective subcutaneously, even 30 days after silica was
injected intratracheally.
It may be coincidental that the monomeric I-hydroxypyridine Noxide is unique in
forming a chelate with silicon (Chapter 1). Such a bond cannot be formed with
PVPNO except after biological oxidation of the polymer to the I-hydroxy derivative.
It is strange that this polymer is essentially the only material that has been intensively studied as an antagonist of silica for almost 20 years. It is probably the unique
combination of two strongly electronegative atoms, -NO, that accounts for its
strong interaction, probably by hydrogen bonding, with SiOH groups, as shown in
the following structure:
I
I
CH;.
1 :.
~
<,
CH-C
1
CH-CH .
"
:.:
N=O: H 0, SI
t
0:
; CH=CH
H
Si
I
,CH-CH"
:
CH-C/
N=O : HOI Si
I.
'CH=CH/
!
H 0: Si.
CHz
es and
.ce the
e, will
.eneral
ich as
ee "
~a
sur-
The only other polymer that has been included in some studies was polyvinylpyrrolidone), PVP, used as a blood plasma substitute. It is also adsorbed on the silica
. surface but is generally a less effective antagonist for silica, possibly because it is less
.strongly adsorbed. .
The effect of PVPNO is apparently systemic. Thus Klosterkotter (354a) found
that subcutaneous injections protected the liver and other organs from the damaging
effect of intraperitoneal injections of silica. Marchiso and Comolli (354b)
demonstrated that PVPNO protected macrophages in vitro from injury by silica.
Mohn (354c) reported that colloidal silica injected intravenously into rats damaged
the liver but was antagonized by PVPNO of molecular weight around 13,500. In the
same experiments it was found that polyvinylpyrrolidone, was also an antagonist but
was much less effective, requiring ten times the dose of PVPNO, which was only 10
mg per rat. The PVP also intensified kidney lesions.
780
Silica in Biology
.
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By electromicrographs in which PVPNO was tritium-labeled and located by

development of silver particles, Fromme, Stober, and Strecker (354d) showed that in
rat granulomas the PVPNO was associated with the tridymite particles that were
present.
In cultures of phagosomes PVPNO delayed or prevented the escape of the toxic
lysosomal enzymes which are liberated when silica dust is added (355). It appears
that the PVPNO is taken into the cell andthere combines with silica (probably by
coating the particle) and prevents the silica from absorbing and denaturing proteins.
Thus lysosomal membranes remained intact and enzymes were not released to kill
the macrophage from within.
There is evidence that after silica has caused harmful effects PVPNO may help
restore healthy conditions. It decreased liver granulomas after they had been formed
in rats by intrasplenal injection of silica (356). The antagonistic effects of PVPNO
against silica have been demonstrated also in a reverse way by observing the oppos. ing effect where silica is used deliberately to suppress graft rejections by destroying
macrophages, Skin grafts on rat tails are rejected by the action of macrophages but
are more permanent when silica is injected intraperitoneally to destroy the
macrophages. Injection of PVPNO completely prevented this immunosuppressive
effect of silica (357). In a similar manner, bone marrow grafts are normally rejected,
but intravenous injection of 5 micron silica particles given in advance to destroy
macrophages reduced the rejection. Also in this case when PVPNO was injected in
advance of the silica, the latter then had no effect (358).
The toxic effects of inhaled silica were reduced by intratracheal administration of
PVPNO (mol. wt. 40,000-80,000) which, however, caused hemorrhages and bronchitis (359, 360). Also, PVPNO stimulated the removal of silica dust as well as
protected lung macrophagesagainst destruction by silica, and all silica-induced
damage disappeared after" a year of treatment. A molecular weight of
50,000-150,000 was more effective than 2000 (361, 362). The elimination of Ti0 2 a
nonsilicogenic powder, from the lungs was not promoted by PVPNO (363). The incidence of silicosis in rats induced by intratracheal injection into lungs was reduced to
less than one-third even as long as 140 days after the silica was deposited (364). The
antitubercular agent, isoniazid. given along with PVPNO was very effective in animals infected with a combination of tubercular bacteria and silica (365).
The slow damaging effect of chrysotlle asbestos in the lungs or in vitro was not
inhibited by PVPNO (366). Possibly in this case the extremely sharp fibers (around
250 A diameter) mechanically penetrate membranes regardless of whether the surface is coated with PVPNO. The therapeutic effects of PVPNO were reviewed in
1971 by Barhad, Rotaru, and Lazarescu (367) with 45 references (see discussion of
asbestosis below).
MECHANISM OF ACTION OF PVPNO. There is some evidence that PVPNO serves a
double role of being adsorbed both 0!1 the silica surface and also on cell membranes.
by which the latter are strengthened (368). By this means PVPNO also affords protection against other toxic agents (369). In contrast, polyvinylpyrrolidone does not
protect cell membranes, so it is probably less effective in preventing silicotic
symptoms because it is adsorbed only on the silica.
io\ogy
ed by
that :.,
t w..
: toxic
ppears
bly by
oteins.
to kill
y help
ormed
IPNO
JppOSroying
.es but
'y the
ressive
iected,
estroy
cted in
tior " r
br. _
veIl as
iduced
:ht of
~i02' a
.e inci.ced to
~). The
in ani-
as not
iround
. Mammals: Man
781
It is the N-oxide group that is involved since a number of polymers,"all with this
grouping, were all active in inhibiting lysis of macrophages by silica (370). Both
PVPNO and PVP reduced the hemolytic activity of silica, the effect being inversely
proportional to molecular weight (371). There is little doubt that the adsorption of
these polymers on silica is due to hydrogen bonding, since the same inverse relation
of bonding and molecular weight is commonly observed in hydrogen bonding of
polyethers and other polar polymers to silica.
Holt and associates, in a series of studies from 1966 to 1969,' investigated the
mechanism of interaction between PVPNO and silica. Ultraviolet absorption studies
showed that there are strong hydrogen bonds between the N-oxide and SiOH groups
(372). Comparison of isomers showed that the poly(2-vinylpyridine oxide), but not
the' 4-vinyl isomer, was a silica antagonist in cultures of macrophages (373). It can
be seen that in the case of the 2-vinyl isomer, the polyvinyl hydrocarbon chain can
lie closer to the silica surface to which the N-oxide groups are attached, than in the
case of the 4-vinyl polymer. Substitution of alkyl groups on the pyridine ring
.
reduced antagonist activity, probably by stefic hindrance.
There was no relation between the isomer's effectiveness as a silica antagonist and
its tendency to precipitate silica. It was observed that the 4-vinyl isomer, but not the
2-vinyl isomer, appeared to be cross-linked on standing with "monosilicic acid."
However, it 'is now apparent that cross-linking was due not to monosilicic acid but
instead to slow formation of an oligomer since it occurred only when the Si02
concentration was 600 ppm, at which monomer polymerizes, and not at 300 ppm, at
which polymerization is very slow (373, 374).
If proof were needed that the PVPNO is associated with silica in tissues, it was
supplied by Fromme, Stober, and Strecker (375), who used radio-labeled PVPNO
along with electron micrographs to show that the PVPNO:was concentrated around
the silica particles (it mayhave also have been present on cell membranes but in this
.
case would be too much spread out to have been detected).
One factor to be considered.in the therapeutic use of PVPNO is that it is not excreted and is deposited in tissues, that is, the reticuloendothelial system (phagocytes)
(376).
In 1963, Schlipkoter reviewed all the known substances that act as inhibitors in
the silicotic 'process, with 91 references (377). Voronkov, Zelchan, and Lukevits cite
39 references to investigations of PVPNO (4a).
ie surNed in
sion of
BETA-AMINOPROPIO,NITRILE. Reports by Stalder and Strecker (378), as well as by

Levene, Bye, and Saffloti (379), indicated that this compound had an inhibitory
effect on silicotic fibrosis. However, no further work has been noted.
erves a
NONIONIC SURFACTANT. The compound C.HnC.H.O(CH2CH20).CH2CH20H

was claimed by Gabor et a1. (380) to act as an inhibitor of silicosis when inhaled by
rats. Since experience shows that polyethers of this type are strongly' adsorbed by the
silica surface, its action may be similar to that of PVPNO. ~
iranes,
is pro-
.es
ilic'CJ~lc
STEROID HORMONES. The report 9Y Kazantseva and Aretinskii (381) that hydrocortisone inhibited the development of silicosis in rats suggests that the adsorption of
steroids from Ringer's solution onto the silica surface might justify study.
--,...
~! -.
782
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Silica in Biology
EFFECT OF ALUMINA IN SILICOSIS. As mentioned in connection with the s01ubility

theory of silicosis, Haldane (337) early in this century recognized that alumina had
an antagonistic or preventive effect on the development' of silicosis. While the solubility theory was in vogue, this seemed to be logical since it was known that when
alumina was mixed with silica. much less soluble silica appeared in solution. Now
the "surface" theory requires a further explantion.
It has been obvious for many years that clay dusts and other aluminosilicates do
not cause silicosis. Therefore. when alumina is administered along with silica there
must be some combination of the oxides on the surfaces to create harmless surfaces
of aluminosilicates. This type of exchange has been dealt with in earlier chapters. As
shown from lIer's work in Chapter 4. the creation of aluminosilicate sites on the surface of silica generally reduces the tendency of proteins to be absorbed from neutral
solution.
However. it is still not clear why a negatively charged surface of an alumincsilicate should not exert an even more powerful attraction for the cationic groups of
choline on cell membranes than does pure silica. Itcan only be assumed that both
ionic attraction and hydrogen bonding are necessary. As shown by Her (253) the aluminosilicate ions prevent hydrogen bonding. It is on this basis, then, that a relatively
low concentration of alumina must reduce the destructive attraction of the silica surface for cell membranes.
The inhalation of aerosols of aluminum hydroxide suspensions or other nonirritating aluminum-containing solutions prevents silicosis following inhalation of silicotic
silica (382). Also aluminum metal dust or amorphous hydrated or colloidal alumina
may be used (383, 384). Schepers showed that soluble silica had no harmful effect
and that soluble silica remaining in solution (2 ppm) in a mixture of suspended silica
and alumina, was physiologically inert (385a). These are only typical of the many
references to alumina as an antagonist to inhaled silica. Zinc supplement in the diet
inhibited progress of silicosis in test animals. According to Chvapil (127. 385b), zinc
inhibits various functions of rnacrophages and thus may reduce the production of the
substance that stimulates fibrosis.
Iron oxide has no antagonist effect against silica (386).
COATED SILICAS. These are of no practical significance in preventing silicosis,
because the coating must be applied before inhalation. As described elsewhere (e.g.,
Chapter 4) the surface of finely divided silica can be reacted with alcohols oralkylchlorosilanes and thus covered with a molecular layer of organic matter. In the
animal body these coatings temporarily prevent silicotic reactions, but eventually
metabolic processes appear to remove the coatings. after which the particle acts in
its usual way (387, 388a).
Asbestosis-Microaciculosis
The effect when microscopic needlelike particles, generally less than 5 microns long,
are inhaled is entirely different from that of inhaled silica. It is now recognized that
.,
---..
Biology
Silicon Metabolism
ilubility
ina L."\d
he ~ ..it when
n. Now
cancer of the lung, especially the lining of the chest cavity, can be c;used particularly in cigarette smokers 25-30 years after exposure to asbestos dust. Since the
asbestos minerals-chrysotile,crocidolite, amosite, etc.-are all silicates it might be
thought that loss of the metal cations leaving needlelike pseudomorphs of silica
might be the causative agent. However, according to Selikoff this cannot be so since
nonsiliceous needlelike particles of alumina or glass can cause similar effects, at .
least in test animals where this type of cancer develops more rapidly (127). Also the
effect of asbestos is not inhibited by PVPNO, which is effective against silica (366).
Since this disease appears to be due to mechanical damage to tissues and is not
related to the chemical nature of the microacicular dust particles, it is proposed that
a broader and more descriptive term than "asbestosis" should be used, such as
"microacicu losis."
iates do
ca there
surfaces
ters. As
the surneutral
783
rinosilioups of
.at both
the alu.latively
.ica sur-
nirritatsilicotic
rlu . 1a
J I t..:t
ed silica
e many
the diet
;b), zinc
n of the
.ilicosis,
re (e.g.,
.hols or
'. In the
entually
: acts in
~,
ns
zed ..rat
Beneficial Effects Of Silica

Besides the necessity of trace amounts of silica essential to animal life, silica appears
to produce some useful effects.
Its effect of reducing tissue rejection in grafts on animals has been mentioned. The
converse is, of course, that it must also reduce immunity to disease. .
Vail (388b) reported that "powdered hydrated Na 20:3Si02 has been added to cattle feed for many years to make up for natural deficiencies which affect the growth
of livestock and to limber the joints of older cattle."
When amorphous silica (0.1-1 micron) was applied to wounds on rabbits, it
promoted healing without causing a foreign body granuloma (389). According to
Grundmann (390a)' colloidal silica helps heal wounds by resorption of toxins and
promotes development of connective tissues.
The presence of silica seems to lower cholesterol levels in blood and its abnormally low level in atherosclerotic arteries, as already discussed, suggests it may be of
some benefit to the circulatory system.
SILICON .METABOLISM
Nothing is really known about how silicon is taken up and utilized in various ways in
living organisms. Low levels of silicon as Si(OH). must permeate most aqueous
regions in living organisms. It can undoubtedly diffuse wherever water or glycerin
can penetrate. Probably it cannot pass the lipophilic barriers of membranes.
However, for silicon to be specifically transported, concentrated, and deposited, it
seems logical to suppose that chelate-type compounds are involved. Weiss and
Herzog (127) find that in plants the cationic silicon complexes of tropolone derivatives are formed in the pH region 4.0-6.8. Such a complex might be translocated
and concentrated and then the silicic acid liberated and deposited if the pH were
slightly raised to 7. The energy involved in transport, concentration, and release may
be quite small. It would mainly involve the reactions required to change the pH
Silica in Biology
784
I
I
! I
I i
. !
( ~
(!
slightly in a localized region. As soon as the local SiO z concentration exceeds

100-200 ppm, especially in the presence of quaternary ammonium ions (of phospholipids, for example) polymerization to solid silica can then occur.
In animals it is possible that silicon metabolism involves another type of chelate
(i.e., catechol-type anionic complexes). In this case, according to Baumann (390b),
the chelate is stable only above pH 7 and liberates silicic acid below this pH. No
chelates of silicon have been isolated from animal tissues. However, the presence of
a variety of molecules with catechol-like structure such as catecholamines makes. it
possible that compounds of this type could be involved in animals. Such chelates
have been discussed in Cha pters I and 2.
The way in which silica is nucleated at specific sites in the organism is a matter of
speculation. To form solid silica particles in suspension in water requires a highly
supersaturated solution of monomer. However, if an organic surface adsorbs a
monolayer of silicic acid which polymerizes' toa film- of silica, silica deposition will
continue at that site from a solution that is only slightly supersaturated in that
region. In the case of diatoms, from a study of the composition of cell walls of
several species, Heckey et a1. (390c) proposed that silicic acid may be taken up on a
highly hydroxylated cell surface of a protein rich in serine and threonine. This protein layer is supported on the polysaccharides of the cell wall. The hydroxyl groups
of these amino acid segments could form a surface in which the close-packed OH
groups could form a template with a special affinity for silicic acid. The adjacent
silicic acid molecules could then polymerize to give a surface of hydrated silica on
which further deposition could occur.
SILICA GEL AS A CULTURE; MEDIUM

. -
i'
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,l
The use of silica sols.as a medium for density gradient in the centrifugal separation
of cells and other biological moieties has been dealt with in Chapter 4. Another use
for silica in biological research is as a gel-substrate culture medium. It can be
sterilized by autoc1aving and, when necessary, could be made in very pure form free
from other inorganic or organic contaminants.
The preparation of silica gel plates for the cultivation of certain types of bacteria
has been described by Muller and Holm (391). A silicic acid sol is made by adding a
solution of sodium silicate to hydrochloric acid buffered at about pH 4.5. The gel is
permitted to set in Petri dishes, washed, soaked in nutrient solution, and then
autoc1aved. For a purer medium, the intermediate sol may be dialyzed before it is
permitted to set to gel (392). An improved procedure for incorporating nutrients
directly into the acid, forming the gel under sterile conditions and eliminating
dialysis, was developed by Sterges (393). A simplified method (394) is described as
follows. Seven hundred milliliters of 0.5 N Hel is mixed with 300 ml of the mineral
nutrient solution to be employed. To 1 volume of 0.5 N sodium silicate is added 1
volume of lime water, and to this 1 volume of the acid nutrient is added. The mixture is poured into Petri dishes, aged 2 hr, and placed in an oven at 100C for 1 hr.
The use of tetramethyl ester of orthosilicic acid is advocated by Ingelman and co-
Biology
Organosilicon Compounds
785
.
exceeds
.hcsnho-
-.
workers (395, 396). Pure silica sols for this purpose have been prepared by ion
exchange, then sterilized in the sol form and stored for use. Additon of the nutrient
solution effects gelling (397). The use of silica gel as a culture medium has also been
advocated by Singh (398) and Temple (399). Commercially available solutions of
colloidal silica should greatly simplify the preparation of silica gel media. Details of
a reproducible method of preparing, from a commercial sol, culture media containing various types of nutrient solutions have been described by Kingsbury and Barghoorn (400). Pramer has described detailed conditions for preparing salt-free gels
by passing a solution of pure crystalline sodium silicate through an ion exchanger to
remove sodium and converting this to a gel culture medium (40Ia). Purification of
commercial colloidal silica for making up defined growth media and conditions
required for gelling were described by Buhagiar (401b).
, chelate
! (390b),
pfl,No
sence of
nakes it
chelates
latter of .
a highly
[sorbs a
tion will
in that
walls of
up on a
'his proI groups
ked OH
adjacent
silica on
ORGANOSILICON COMPOUNDS
paration
ther use
can be
arm free
bacteria
idding a
he gel is
nd then
'ore it is
iutrients
ninating
ribed as
mineral
added 1
'he mixfor -r.
anc;o-
I
I
There is no evidence in either the animal, vegetable, or mineral worlds of the natural
occurrence of any organosilicon compound, that is, a compound in which an organic
radical is linked to a silicon atom through a carbon-silicon bond. A possible exception is the report by Heinen (402) that the organism Proteus mirabilis can synthesize
a variety of organic ester and amide derivations of. silicic acid containing Si:-O-C
and Si-N-C bonds and also some with Si-C bonds. Although it is difficult to
imagine such a biochemical reaction as -SiOH + H-C - -SiC- + HIO, it would be
no less remarkable than the common biochemical transformations through
photosynthesis that result in CO 2 + 4 H 2 .. CH. + 2 H 20 and formation of C-C
bonds..
..
In the past century: thousands of compounds with Si-C bonds have been
synthesized and have been tested in limited numbers for possible biochemical effects.
Especially in Russia, compounds of this type have been widely investigated, according to Voronkov (403, 127). A striking example is the ciass of l-arylsilatranes, which
are highly toxic. As Voronkov points out, in the wrong hands they could serve as a
subtle poison, being undetectable by the victim even in drinking water since they are
colorless, odorless, tasteless, and so potent that trace residues in the victim would be
hard to detect. The basic structure of silatranes is simply silicic acid esterified with
all three OH groups of N(CIH.OH)3' with an organic group. such as an aryl, linked
to the fourth silicon bond as a Si-C linkage. The p-chlorophenyl derivative is used as
a rodenticide because the compound is rapidly inactivated after death and the corpse
is nontoxic to other animals. In the case of p-CH3C.H.Si(OC2H.)3N the approximate lethal dose for mice is 0.2 ppm (mg kg-I).
According to Voronkov numerous organic derivatives of silicon are finding uses in
medicine, for example, "mival" and "migugen," compounds of undisclosed structures, which are claimed to be powerful anti-cancer drugs. Compounds of the class
XYZSi(CHI)3NRR' are said to be antibiotics. Others stimulate development of connective tissue, promote hair growth, prevent hair loss, and improve metabolism of
fats. However, these are all in the early stage of development. According to
Silica in Biology
786
Voronkov, Grigalinovich, and Zelchan (404a) some silicon compounds injected into
rats caused dystrophic changes in cells of Walker carcinoma and induced collagen
formation.
Fessenden et a1. (404b) has shown that organosilicon compounds undergo biological oxidation in the organism even to the point of breaking the Si-C bond:
-SiH .; -SiOH - -SiOSi-SiCH s - -SiCH 20H

-SiC,H , - -SiC.H,OH
-Si(CH2)IICHS - -SiOSi-
It is therefore difficult to say that any specific physiological effect is due to the
particular structure that is introduced into the organism. As mentioned earlier in
connection with atherosclerosis, the compound sodium monomethyl trisilanol 0hydroxybenzoate appears to prevent this disease in rats on a high cholesterol diet
(300).
Large numbers of compounds of silicon are being evaluated and there is no doubt
that out of these will come many new pharmaceuticals. The remarkable discovery
(127) that 2,6-cis-diphenylhexamethylcyclotetrasiloxane has exactly the same
hormonal effect as an estrogen, in spite of no obvious molecular similarity, indicates
that other surprises may be in store. Voronkov's silatranes (127) and Wannagat's
summary (127) of silicon-nitrogen "silopharma" materials, of which over 10,000 have
been described, represent only a beginning.
,I
!
! ;
ANALYTICAL PROBLEMS
i :
In addition to the analytical methods described at the end of Chapter I, special mention should be made of the problems that existed and still exist to some extent in
determining traces of silica in biological specimens.
Bertrand (405) pointed out that the siJicomolybdate method of determining silicon
might give, in the presence of phosphorus, a phosphomolybdate which would make
the 'silica analysis appear too high: Conversely, it is also possible that, unless suitable
precautions are taken, the common colorimetric procedure for determining phosphorus by the phosphomolybdic acid method may also include silicon. For this
reason,' it is likely that silicon has sometimes in the past been reported as phosphorus. Isaacs (406) developed a method for determining silicon in the presence of
phosphorus. This was examined by Foulger (407), and it was shown that the method
proposed by Isaacs, if properly followed, permitted the determination of silicon in
the presence of phosphates. In fact, the values for silicon appeared to be somewhat
low by this method, if much phosphorus was present, because the phosphates inhibit
the reduction of the siliccmolybdate; but within the limits of.phosphate concentration found in ash from animal tissue, the retarding action of phosphate can be
removed by slightly increasing the activity of the system before adding the reducing
agent.
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col11~en
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annagat's
,000 have
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References
787
Gohr and Scholl (408) state that the microdetermination of traces or silica in biological 'tissues is one of the most difficult problems in analytical chemistry. The
gravimetric method of determining the loss in weight of SiF4 when the ash from the
specimen is fumed off with HF and H 2SO. gives high and inexact results. The usual
colorimetric method was reported not to be specific for silicon in the presence of
phosphorus and is inaccurate in the presence of iron; both P and Fe are usually
present. These authors describe an improved technique for separating phosphoric'
acid from the silica and for determining the latter by the silicomolybdic acid method
after reduction to molybdenum blue. By the recommended procedure, as little as 2
micrograms of silica can be detected, and only a 2 gram sample is required.
There are modifications of the above procedure which do not require the complete
separation of phosphorus from silica, but depend on the preferential reduction of
silicomolybdic acid to molybdenum blue in the presence of phosphomolybdic acid.
In general, it is emphasized that dependable results rely on careful avoidance of
contamination of the sample with silica from glassware, elimination of interference
by phosphorus, and maximum sensitivity in making the colorimetric measurement
(409-411). Baumann described a preferred technique for analysis of silica in blood
and other biological materials (see Chapter 1, Ref. 320).
Special procedures for eliminating interference by phosphorus in biological samples analyzed by the molybdate method were developed by McGavack, Leslie, and
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To determine whether silicon was present as an organic complex Holt and Yates
(414) added soluble silica as isotopic I1Si to tissue culture and also injected it into the
peritoneal cavity of a rat and later isolated alcohol-soluble compounds containing
alSi from the tissue. However, they pointed out that the extracted material might
consist of micelles of organic-coated silicic acid polymers. Most of the IlSi in tissues
remained insoluble.
.cial menextent in
CONCLUSION
ng silicon
uld make
.s suitable
ing phosFor this
as phos"esence of
Ie method
silicon in
The number of elements found to be essential to life appears to be gradually increasing as experimental techniques are refined. The possibility cannot be denied that all
the elements may be required for life to develop. Life, and finally intelligence, may
have been the ultimate purpose of the creation of the universe. Life may be another
form of infinity-an infinity of chemical and electronic complexity.
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378. K. Stalder and F. J. Strecker, Beitr, Silikose-Forsch, Sonderb.; 6, 161 (1965).
379. C. I. Levene, I. Bye, and U. Saffioti, Br. J. Exp, Pathol., 49, 152 (1968).
.
800
----Silica in Biology
,
380. S. Gabor, E. Zugravu, et al., Igiena, 21 (6), 329 (1972) [Chem. Abstr.; 79, 1414Iq].
381. S. V. Kazantseva and B. V. Aretinskii, Tr. Tsentr, Nauchn.slssled, Proekt-Konstr. Profllakt, Pneumokonlozov, Tekh. Bezopasn, (S), ISS (1971) [Chem. Abstr.; 78, 143915y].
382. H. Daniel, J. C. Martin, and L. LeBouffant, in W. H. Walton, Ed., Inhaled Panicles,
Vol. 3, Proc.Lnt, Symp. 3rd, 1970, Unwin Bros., 1971.
383. O. A. Sander, in F. A. Patty Ed., Industrial Hygiene and Toxicology, Vol. I, 2nd rev. ed.,
Interscience, New York 1958.
384. G. W. H. Schepers, 9th Conf, Mcintyre Res. Found. Toronto, 1958.
385a. G. W. H. Schepers, Toxicol. Appl, Pharmacol.,3, 188 (1961).
385b. M. Chvapil, in S. D. Lee, Ed., Biochemical Effects of Environmental Pollutants, Ann
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386. T. A. Kuchelkova, Bor'ba Silikozom Adad, Nauk SSSR Sb, Stat., 7, 272 (1967) [Chem.
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387. W. Klosterkbtter, Arch. Hyg. Bakteriol.; 152 (I), 7 (1968) [Chem. Abstr.; 69, 21753m].
. 388a. I. S. Ostrovskaya and A. N. Timchenko, Bor'Ba Silikozom, 9, 206 (1974).
388b. J. G. vsn, see Chapter 2, Ref. I, Vol. 2, p. 597; hrsey Bull Dairy World, SS, 1642, 1652
(1936), Rural New Yorker, 96, 284 (1937).
389. K. W. Jdtten and W. Klosterkdtter, Die Medizinsche, 1076, 1093 (1956) [Chem. Abstr.;
SO,I7103h].
390a. G. Grundmann, Zentralbl. Chir. 75 158 (1950); Chem. Zentralbl.l, 2375 (1950) [Chem.
Abstr 48, 824d; 11444a).
390b. H. Baumann, Beitr, Silikose-Forsch. Sonderk. 4, 43 (1960).
390c. R. E. Hccky, K. Mopper, P. Kilham, and E. T. Degens, Mar. Bioi., 19,323 (1973).
391. D. Muller and F. Holm, Z.!ntralbl Bakterlol. Parasitenkd., Part.II, lOS, 131 (1942).
392. W. Olszewski and H. K~hlcr, Bas-u, Wasserfach, 85.483 (1942).
393. A. J. Stergcs,J. Bacteriol.; 43, 317 (1942).
394. A. J. Sterges, J. Bacteriol. 44, 138 (1942).
395. B. Ingleman and I. Jullander, Nature, 156,572 (1945).
396. B. Ingleman and H. Lauren, J. Bacteriol., 53, 364 (1947).
397. .A. S. Taylor,J.
Gen. Microbiol., 4, 345-237 (1950).
.
398. B. N. Singh Nature, 157,302 (1946).
399. K. L. Temple,}. Bacteriol., 57, 383 (1949).
400. J. M. Kingsbury and E. S. Barghoorn, Appl. Mtcrobiol.; 2 (I) (1954).
401a. D. Pramer, Appl, Microblol.; 5, 392 (1957).
401b. R. W. M. Buhagiar, J. Gen Microbiol., 1(1977).
402. W. Heinen, Arch. Microbiol., 37, 199 (1960); 41,229 (1962); 45, 145, 162, 172(1963); 52,
49,69 (1965); Arch. Blochem, Biophys. 110, 137 (1966); 111,236 (1966); 120~ 86,93, 101
(1967).
403. M. G. Yorcnkov, Chem, Br., 9, 411 (1973).
404a. M. G. Voronkov, G. A. Grigalinovich, and G. Zelchan Dokl. Akad. Nauk SSSR, 200
(4),967 (1971).
404b. R. J. Fessenden et ai., J. Med. Chem., 7, 561, 695, (1964); 8, 604 (1965); 9, 262 (1966);
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-. .
n Biology
lq].
istr "roji_
H:..
Panicles,
.
id rev. ed.
'ants, Ann
n. Health
.,
References
405.
406.
407.
408.
409.
410.
411.
412.
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L. Isaacs, Bull. Soc. Chim, Bioi., 6, 157(1924).
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P. Ohlmeyer and V. Olpp, Z. Physiol. Chem., 281. 203-207 (1944).
H. L. Kahler et al., Ind. Eng. Chem, Anal. Ed., 13,536 (1941).
.
S. Gajatto, Studi Sassarest, 22, 259 (1944).
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414. P. F. Holt and D. M. Yates, Blochem, J., 54, 300 (1953).
i7) [Chem.
1753m].
1642, 1652
m. Abstr.
;0) [Chem.
3).'-
142).
.
(1963); 52.
36,93, 101
SSSR,2oo
!62
66);
-....-...
-.-
.,
._-~.
Author Index
Italic page numbers indicate reference pages.
.'<
Aabrust, P., 457

Aarons, R., 455
Abayashi, H., 693, 725
Abba, C. G., 168, 457
Abd-EI-Moneium, I. 676, 722
Abendroth, R. P., 473. 602. 662. 667. 720
Aberg, B., 730, .787
Abernathy, M., 794
Ablyaev, Sh. A 729
Aboutboul, H. A. 560, 612
Abress, M. S. 456
Acker. E. G. 246. 247. 252, 262, 309. 412. 512,
526. 532. 561. 576, 606. 607. 608. 613. 616
Ackerman, G. "103, I IS
Adams, C. R., 542, 544, 610
'Adams, J. R., 734, 788
Adams, N. M., 457 "
Adams, P. B. 788
Adrian, P., 698, 726
~
Agarwal, R. D., 213, 3.08 ,"
Agzamkhodzhaev, A. A., 634, 645, 716. 717
Ahlberg, J. E., 335, 442
.
Ahmed, A., 695, 726
Ahmed, S. M., 661, 720
Ahrland, S., 673, 675, 676, 720
Aidinyan, P. 1< 733. 788
Akabayashi, H. 413, 452
Akai, S. 791 "
Akatsu, E., 675. 722
Akiya, S., 793
Akoshima, A., 725, 726
Akshinskaya. N. V, 544, 551, 610. 6//
Albert. R. E., 453, 460
Albon, C., 457
Albrecht, W. L. 314, 316, 439. 452
Alder, B. J . ~03, 450
Aldfinger, K.~H 628, 715
Aleksandrov, G. A., 459
Aleksandrov, V. G., 733, 788
Alerseeva, J. P., 620
AleskovskH, V. B., 57.110, 460.7/0.721.723.
727
i';
Alexander. A. E 535, 6/)8

Alexander, G. B. 1.2.40,41,43.47,51,54,88,
96,97,107.109. 113. 114. 138,166. 179.180,
197, 199,200. '221,240.250,252,305.309.
312.317.331.333.338,345,347,350.363,
383,388.408,410,43~44~
441.
443.44~
451. 452. 508, 529, 530, 554, 558, 559, 560,

605. 608. 612. 613. 616. 618
Alexanian, C., 30, 108
Alfrey, T., Jr. 402, 449
Alim-Marvasti, F 74, 111
Allen. E. M., 562. 613
Allen, E. T., 90, 113
Allen, L. H., 182.306. 356.375.376.408,444.
446
Allen. L. S. 439
Allen, W. S., 457
Alling, R. D., 617'
Allingham, M. M. 687. 724
Allison, A. C. 760, 773. 795. 797. 799
Alois, F. J . 309
Alsfeld, Max. 563. 613
Aleamcra, L. 70 I, 726
.Amalgamated Oxides (Company), 168
Amelin, A. G., 565, 613
Amicon Corporation (Company), 340, 443
Ammon, R. 794
Amos. G. L. 746. 747. 791
Anatskii, F. I., 74, I I I "
Andelman, J. B. 676, 722
Anders. G. Y. 165
Anderson. G. M. 32, 108
Anderson, J. H., 634, 716
Anderson, J. T., 459
Anderson, P 552, 661
Anderson, R. C., 461
Andersson, L. H. 95. 96, 99, 1/3. I J4
Andre, J . 611
Andreev, V. I., 451
Angell. C.1..., 692. 725
Angier, D. J. 613
An-Pang, Tai. 189.306
803
, ..... -_.
Author Index
804
Ansell, G. S., 587,617
Antonini, J. F., 637, 716
Antoshenko, E. I., 109. I/O
AntweiJer, H., 799
Appleman, D. E., 17,82, 106. //2
Archibald, R. c., 537, 609
Arehart-Treichel, J., 793
Aretinskii, B. V., 781, 796. 800
Arienzo, R., 765, 794. 796
Aristov, B. G., 652, 718
Aristova, V. G., 616
Armington, A. F., 593, 619
Armistead, C. G., 633, 656,716. 7/7. 719
Armstrong, J. E., 331, 441
Arnell, J. C., 476, 603
Arnold, M., 30, 52, 108. 777, 798
Arsem, W. C., 560, 612
Asano, T., 61, II I. 574, 615. 692, 725
Ashby, G. E., 461
Ashley, K. D., 252, 268, 310
Assarsson, G. 0., 438, 460
ASTM (American Society for Testing
Materials), 604
Astrand, L., 12, 105
Atkins, R. C., 326, 333, 439. 440
Atyaksheva, L. F.~ 619, 714, 729
Audsley, A., 252, 253, 257-259, 262, 310
Austin, J. F., 166. 563, 613
Austin, J. H., roo, 114, 754, 756, 7$1, 794
Avakov, V. A., 109
Avery, R. G., 482, 483, 485, 499, 550,603.604,
6/1
Aveston, J., 129, 133, 166, 252,257-259,262,
310
.
-:'
Axelson. J. W., 110
~~::
Ayres, F. D., 137, 166
Azam, F., 738, 789
Azarian, M. V., 88, II 3
Azrak, R. B., 692, 725
Babkin, r, Y.,699, 702, 726. 727
Bach, R., 75, 111, 169.751,792
Bachman, J. H., 6/5, 617
Back, 0., 460
Bacon, F. R., 75, /10. II 1
Bacon, L. R., 121, 128, 129, 165
Badollet, M. S., 724
Baer, C. E., 423, 453
Baer, C. E., Jr., 454
Baes, C. F., Jr., 411, 451
Bagchi, P., 327,440
Bagmut, N. N., 449
Bailey, C. B., 794
Bailey, J. T., 347, 443
Bailie, J. C., 526, 537, 607. 609
Bainbridge, J. P., Jr., 455
Baines, S., 94, II3
Baker, C. L., 127, 166. /70. 563,45/J

Baker, F. S., 652, 718
Bakyrdzhiev, I., 644, 717
Balakirev, V. G., 402, 449
Balk, ~., 723
Ball, B., 681, 724
Ball, E., 100, 114
Ballard, C. C., 573, 615, 689, 724
Ballou, E. V., II 0, JlJ
Balthis, J. H., 66, 69, II I, 328, 336, 346, 441
Banford, J. A., 618
.
Baran, A. A., 632, 716
Barbaras, G. D., 430, 456
Barber, D. A., 745, 791
Barby, D., 225, 309, 486, 505, 506, 554, 600,
605,612, 61j, 624, 637, 714
Barclay, R. W., 309
Barghoom, E. S., 52,53,88,90,91,109, 113.
730, 731, 785, 788, 800
Barhad, B., 780, 799
Barkas, W. W., 534, 608
Barker, S. A., 595, 619
Barnes, W. R., 613
Barnett, I., 42S, 454
Baronetsky, E., 767, 768, 796
Barr, T., 448
Barrett, E. P., 494, 604
Barrett, J. W., 439
Barrett, W. T., 88, I/J. 330, 441
Barry, A. J., 103, 308. 616
Barsukova, Z. S., 1II
Bartell, F. E., 503, SIS, 605,606,617.650,657,
689, 718, 719, 724
Bartels, H., 553, 61 I, 612
Bartholin, M., 315, 316, 439
Baruch-Wcill, M., 323, 440
Bashikov, M. M., 458
Basila, M. R., 723, 727
. Bassctt, D. R., 549, 61 I. 652, 702. 718. 727
Bastik, J., 403, 475, 545, 602. 610. 615, 630,
632,649, 71~ 71~ 725
Bastissc, E. M., 749, 791
Bataafschc Petrol. Maats (Company), 615, _
618, 791
Baudru, B., 167, 180, 182, 199, 248, 253.
271-274,276,277,287,305.306.560. 612
Baucr, G., 654, 689, 692, 719. 724. 725, 726
Bauer, J., 453. 454
Bauer, J. M., 112
Baumann, H., 38-43, 52, 57, 65,73,75,77,99,
106. 109-1
114. 156, 157, 169. /70.
194, 197, 199, 203, 252, 253, 268, 269, 270,
271,292,307, 31U, 353, 444. 755, 761, 774,
794. 797, 800
Bausch, H., 154, 169
Baverez, M., 615. 630,632, 716. 725
Baxter, S., 367, 445
n. us.
..
or Index
346,441
554,600,
109,113,
-....---
Author Index
80S
Baylis, J. R., 301, 302,311

Bear, J. L, 248, 309
Beard, W. C., 150, /66
Beattie, W. H., 347, 443
Beau, R~, 526, 607, 620
Beaven. C. H. J. 604
Bebris, N. K 493. 604. 609'
Bechtold. M. F 66, JJ t, 252. 255. 261, 267,
310, 3JJ, 312.314,333,347,403,419,439
Beck. E. G., 779. 798
Becker, A 6/2
Beckett, A. H., 552, 66/
Beckwith. R. 5., 38, /09
Bedford. J. A., /07, 126
Beg. M. V . //0
Behn, R., 587.6/8
Behrman. A.S. 536. 609
Bektesh, L 5. 62/
Bell, A 4Q4. 450
Belotserkovskii. G. M 372. 445, 528, 607
Belyakov, V. N. 182. 189.306
Belyakova, L D. 472, 602, 624.625. 636, 691,
714, 7/6~ 725
Benditt, E. P. 768. 796
Bendz, G 308 '

Beneke. K. /07, 158, 159. 170
Benesi, a, A., 603, 728
.650,657,
Benitez. R. 415. 452

Bennett. B., 457, 458
Bennett. H 95. JJ3 '
Benson. R. E. 698. 723
Bentley. R. A., 38. ,/09
Benton, D. P. 672. 72/
...~.:
Berekoven, B., 6/9
Berezhskil, Y. M. e., 446 ....
Berg, H., 4$7
.'.
.
Berg, K. 575, 577. 602, 6/6, 697, 726
Berger. E 4.58
.
Bergman, I.. 38, 73, 76, 77. /09, / / /, / /2. 298,
310,393,448, 763, 795
Bergna, H. E.. 307, 422, 4.52, 453,526,607,6/9
Bering, B. P. 491, 604, 626, 7/5
Berkheimer"E. R. 317. 440
Bermudez, V. M., 630, 635. 640, 7/6
Bernal, J. D., 3. /04. 483,604. 731, 788
Bernard, H. W., 721
Bernhard, S. A., 552, 66/
Bertrand, G., 786, 801
Berube, Y., 467, 600
Berwick. H. A., 98, /14
Best, P., 726
Best, W. V., 620
Beyer. H., 512, 547, 606. 610. 723
Beyer, J. N., 424, 454
Beyers, P. D., 798
Beyersdorfer, P. 165
Bezncgcva, V. E., 6/0
,
oJ
'18, 727
f15,630,
/},615.
.253,
560,612
725, 726
75,77,99,
169. 170.
269,270,
761,774,
"
Bezrodnykh, A. A., 799

Bezrogova, E. V., 197,307
Bhambhani, M. R~. 470, 601
Bhatnagar, P. D., 324, 440
Bickley. Fr., /05
Bidaud, A. F. 6/6
Biddle, J., 449
Biegler, H. /67, 566, 614
Bigelow, W. C., 790, 7~/
Bijsterbosch. B. H., 473, 602, 682, 684-686, 724
Bikerman, J. J., 533, 534, 608, 629; 715
Bilinski, H.~ 181, 183,305
Bindas, B. P. 335, 442
Binh.Dinh.Ngoc, 729
Birbeek, M. 795, 799
Bird, P. G., 312, 333. 419. 439
Bisaillon,S. 593, 619
Bishop, A. D Jr., 248. 309
Bittner, F., 567. 614
Blackgood, M. R. D 442
Blackman. L. C. F. 680. 686. 724
Blake, D. G., 316, 439
Blake, R. K., 456
Blattenberger, J. W. 592, 6/8
Bliznakova, G., 649, 7/8
Bloemke, R. E 45.5
Blomfield, G. A. 723
Bloom, G. 795
Bloom, H. J7/
Bloom, S. M 4.59
Blount. D. H. 190,307, 551. 61/
Blum. A. Y., 728
Blumberg, A. A., 76, 77. //2
Boari, G 333, 44/
Bobb, J. S. 5., /68, 316, 336. 439. 441, 442
Bock. R. 59, //0
Boekris, J. O. M. /7/, 7/5

Bode. R., S67, 614
Bodor, E. E 499. 501. 503, 604. 605
Boehm. B., 454
Boehm, H. P., 57, //0,383,447.602.623,635,
636.639,667,669. 713. 714, 720. 723
. Boenniger, W 754. 793
Boer. F. P 169
Bogdanov, Y. A. 13. /05, 788
Bogdanova, V. I. 257.310
Bogdanskaya, N. I.. 799 '
Bogel. V. 723
Bohlen, B. 542. 605, 6/0
Bohn, E. 16, /06. 328.441, 725
Boksanyi, L.. 624. 696, 7/5
Bolctcva, L. T . 691. 725
Bolt. G. H 184. 306,~345. 355-358. 360,410,
443,444,45/,660.661.664,683,720
Bolyos, A., 447
Bolyshev, N. N. 733. 788
Bondarenko, A. V. 712. 728
. ---_.
Author Index
806
Bonetzkaya, A. K., 655, 7/9
Bonnelyeke, E., 348, 443

Bonnier, J. M . 728
Booman, K. A., /68
iI
'- I
fto. ,'
li.
JllJJ.
tij ;
~:j.~ 1
:'
i.
I:
;1 :
'
-[I, .
~
-.,
]\ :
,
,I-tI
-~
;
--I
- I
Booth. C. 347, 443

Booth. R. E. 392, 448
Borcskov, G. K. 605. 722
Borisov, M. V. 132. 143. /66. /67
Borokov, V. Y 721
Bcrsos, A.. 564, 6/3
Boss. A. E. 561.562. 6/3
Botham, R. A. 392, 448. 709, 727
Bott, L. L. 455
Bcttinga, Y 37. 109
Boucher. E. A. 549. 597. 6//. 620. 652. 702.
7/8. 727
Boulton. L. H 603. 7/9
Bourne, K. H., 718
Boweott, J. E. L. 707, 727. 795
Bowden. F. C. 403. 450
Bower, J. E. 503, 605
Bowman, J. A. 94. 1/3
Boyd, G. E. 472. 602
Boylan, F. J., 6/9. 694, 715
Boyle, F. A. 316. 439. 441
Boyle, T. W 649.- 7/8
Bradaczek, H. 476. 603 Bradford, E. R 449
Bradstreet. S. W 453
Brady, A. P. 131. 136, 166. 248,309
Brady, E. L. 12. 105
. Braendle, R. 0., 591. 617. 618
Bragg, Law. 398
Brakhaus, A., 60, liD
Brandenberger. E. 737. 789
Brannock. W. W. 14. 79. 105. 111
Brasen, W. R. 311
Brazhnikov, V. V 471. 602
Breiger, H., 798
Brenchley, W. E., 79/
Brenner. W. 593, 6/8
Bresciano, A., 765. 796
Bresler,
E., 682. 707, 724. 727
Breton. E. J., 430, 456
Brichard, R., 7/7
Bricker, O. P., 21, lOS, 107. 159, 170
Brijs, B., 61/ .
Brill, O. L., 349, 443
Brindley, G. W., 21. /07. 159, /70
Brinsmead, K. H., 335. 442
Brintzinger, H., 179, 305
Brintzinger, W., 179,305
Britt, K. W., 300,31/
Britton, H. T. 5 . 162, /7/. 304,31/
Brockett, B. W. 426, 434, 455. 458
Brockhaus, A. 779, 798
Brode, A. P. 227. 368, 4~5
s,
Brodt, R., 456

,
Broekhoff, J. C. P., 485, 493, 494, 497, 498,
567, 600. 604. 611. 6/4
Brege, E. C., 5 I. 109. 240, 242, 309. 413, 443.
444. 452. 460. 468, 506, 530, 559, 574.601.
_ 608. 615. 631.689,692,693, 702, 715. 724.
725
Brohn, H. 718
Brooks, B. I., 596, 619
Brooks, U.S. 472, 602
Brotikovskii, O. I., 674, 712
Brown, A. G. 131. 136, 166. 227. 248, 309. 368,
445
Brown, E. A., 766, 796
Brown, H. V. 770, 797
Brown, R. L., 453
Brown. S. M. 492, 604
Brown, W. B. 335, 441
Briichner, -R 1.1
Bruck, J., 779. 798
Brunauer, Emmett. Teller (BET). 467
Brunauer,S. /05,462.468;472.490,499,50I,
0
503,511,600.601.602.604. 605. 606. 642,

645, 646, 650, 717. 718
Brunner, H 567. 6/4. 619
Brusset, H., 44/
Brust. O. E., 599, 621
Bryant. K. C., 355, 367, 444. 445
Brzezinski,S. 619
Bubyreva, N. 5. 335, 442
Bucholz, J. R. 80, 93. 1/2. 1/3
Buchwald, S. J., 750. 792
Bueche, A. M . 575. 586, 6/6. 617
Buehlmann, M. R., 542, 610
Bugosh, J., 455
Buhagiar, R. W. M. 785, 800
Bullitt, O. H., 456
Bunger, P. 456
Burgess, T. E., 625, 7/5
Burhans. R. W 608
Burke, O. W. Jr., 117, /65. 607.612
Burkett. G. M . 564, 6/3
Burkman, A., 758, 794
Burnel, D. 115
Burnham, C. W., 32. J08
Burnie, G.. 113
Burns, A. C., 566,6/4
Burns, G. P. 350, 443
Bursh, T. P. 641,644, 7/7
Burton, E. F. 374, 446
Burushkina, T. N., 617
Burwell, R. L., Jr., 446,575.596,619,670,674,
721. 722. 726 ~
Burzynski, A. J., 607
Busey, R. H., 133, /66.181,306
Butcher, H. J., 528, 607
Butenandt, A., 770, 797
0
rIndex
',498,
;3,
'4, 6(JJ,
'5, 724,
J9,368,
)9,501,
16,642,
70,674,
Author Index
Butikova, I. K., ISS, 169
Butler, C., II, 797
Butuzov, V. P., 449
Buurman, P., 109
Buzagh, A., 382, 447
Bye, 1., 781, 799
Cabot, Godfrey L. (Company), 614
Cabot Corporation (Company), 442
Caillat, R., 723
Calba, J., 675, 722
Calderwood, A. 5.,586,617
Calteka, R., 577,616, 674, 675, 676, 722
Calvert, R., 735, 788
Calvert, S. E., 13, 105
Cambar, R., 797
Cameron, E. N., 104
Campbell, L. E., 169
Campbell, M., 794
. Campbell, R. A". 453
Cannings, F. R., 728
Cantow, H. J., 717
Cardell, R. R., Jr., 404, 450
Carlisle, E. M., 756, 793
Carman, P. C., 173,305, 479,490,604, 623,
714 .
Caroselli, R. F., 455, 456
Carr, R. M., 16,26, 106
Carret, G., 113
Carroll, B., 667; 673, 720
Carruthers, J. D., 467, 600
Carter, W.-K., 452
Carteret, Y., 504, 605
.:....~
Cartwright, J., 38, 109
-, .
Case, J. M., 455
..
Caseley, J. C., 791
.
Cassell, E. A., 447, 451, 668,671,675; 721
Castelliz, L. M., 155, 169
Castle, J. E., 698, 713
Catoire, M., 748, 791
Catone, D. L., 4Q4,'450
Cengarie, L., 692, 725
Chakrabarti, V. K., 610.
Challis, A. J., 455
Chambard, P., 311
Champlin, R. L., 303,311
Chang, T. N., 58, 110, 347, 364, 443, 445
Chao, E. C. T., 16, 106
Chapman, 1. D., 723
Charaehe, P., 764, 795
Charles, R. J., 52, 109
Charnot, Y., 7SS, 756, 769, 793, 797
Chase, C. E., 445
Chavannes, 1. L. B., 451
Chavey, A., 793
Chen, N. Y., 20, 107
Chen, Y. 5.,213,308
807
Chene, M., 791
.
"
Cherkinskii, Y. 5.,42,43, 109. 185,306
Chernoberezhskii, Y. M., 387, 447
Chernova, L. A., 82, 112
Chertov, V. M., 541, 574, 610, 615, 633,640,
716, 720
Cheslova, V. 5., 639, 642, 644, 651,717
Chessiek, J. J., 110, 396,435, 448, 458, 588,
597,618,620, 650, 718, 720
Chilton, H. T. J., 336, 340, 350, 442, 443
Chiola, V., 562, 613
Cho, J. 5., 441
Christian, G., 790
Christian, J. B., 618
Christman, L. J., 615
Christopher, C. A., 619
Chuang, S. Y., 712,728
Chugunov, V. 5., 82, 112
Chuiko, A., 617, 692, 697 725. 726, 718
Chukhlantsev, V. G., 528, 607. 608
Chukin, G. D., 713
Chung, C. W., 799
Chvapil, M., 782, 797. 800
Cieplinski, E. W., 353,444.471,601
Claesson, 5., 348, 443
Clapsdale, L. G., 337, 442
Clark, B. R., 603, 719
Clark, E. R., 158, 170
Clark, S. G., 762, 795
Clark-Monks, C., 652,719
Cleriei, E., 766, 796
Cloherty, D. J., 424, 453
Cloud, P. E., Jr., 788
Coates, K. B.; 303, 311, 513, 606
Cochran, C. N., 7, 105
Coelingh, M. B., 490, 604
Coes, L., Jr., 16, 106
Coffey, W. D., 458
Cogavan, E. J., 426, 455
Cohan, L. H., 465, 600
Cohn, F. J., 743, 791
Cole, S. u., 399, 449
Coleman, M. F., 603, 719
Coli, H., 350, 443
Collet, A., 778, 794, 798
Collette, A., 60, III
Collins, P. F., 424, 453
Colombo, U., 552, 661
Colom-Pastor, J. F., 453
Comolli, R., 760. 779, 795, 798
Conell, a., 758, 794
Conrad, F. J., 610
Conrad, V. H., 715
,
Contrelas, 5.,415,452,701,726
Coombs, r., 789
Cooper, A. R., 118, 165, 460
Cooper, H. P., 741, 790
.,
-...-Author Index
808
Cooper, R., 378,41 1,446.451.669,670,674,
675, 721
Copeley, M. J., 288,3/0
Coppenet, ,M., 744, 79/
Cornet, D~, 722
Cornier, G., 632, 7/6
Corning Biological Products (Company), 72/
Correns, C. W., 90, 113
Corte's, J., 701, 726
Cosman, A. F., 337, 442. 567, 6/4
Cotton, F. A., 196, 307
Coudurier, M., 139, /67. 180, 182, 199,248
253,271,272,273,274,276,277,287,305.
306. 560,6/2
Coupland, D., 791
Cox, J. B., 148, 168
Cox, J. J., Jr., 457
Coyle, T. D., I, 2
Craig, T. J. t, 561, 611
. Crampton, C. F., 790
Crang, R. E., 790
Cranston, R. W., 469, 494, 496, 497, 499-501,
60/
Cristanetti, M., 299, 3/1
Crombie, D. W., 798
Cromwell, W. E., 458
Crooks, L. L, 455
Crosfield, J., and Sons (Company), 169. 612
Crowningshield, R., 450
Cudkowic, G., 799
Cuer, P., 567, 6/4
Cuha, D., S 18, 606
Cull, N. L., 456
..
Cullen, J. M., 687,724
Cummings, W., 316, 329, 4J9 :;
Cummings, W. P., 331, 44/ "
Cummings, W. W., J06
Cuneo, F. L., 148, 168
Cupery, M. E., 456. 457
Curthoys, G., 635, 638, 653, 658, 7/7. 7/8
Curti, R., 552, 661
Curtis, T. C., 414, 452
Cutting, P. A.,. 472, 600-602
Cypres, R., 6/0
Cyrot, Mme., 607
",.
Dadswell, H. E., 746, 747, 791

Daimon, N., 620
Dake, H. C., 104
Dalang, F., 672, 720. 72/
Dalton, R. L., 211, 244, J08. J09. 361,441,628,
715
Daly, J. W., 789
Damm, K.,630, 715
Damon, J. P. 728
Dandlicker, W. B., 348. 443
Daniel, H., 800

Danielli, J. F., 715
Danilov, V. I., 731, 788
Darley, W. M., 736, 789
Darragh, P. J., 399, 400, 404, 449. 450
Das, S. C., 740, 790
Daudt, W. H., 308
Davies, C. N., 797
"Davies, R., 407, 451
Davis, J. A., 665, 720
Davis, J. M. G., 799
Davis, K. M. C., 656, 7/9
Davydov, V. Y., 543, 6/0. 6//. 631,632,
634,635, 715-717. 7/9

Davydov, Y. P.,676, 722
Dawson, P. A., 736, 789
Day, R. E., 600
DeBoer, J. H., 29, 107. 186, 188, J06. 437,
460.469,470,486,494,497,518,519,
532,543,546,549,60/. 604. 607. 608.

6/0.6//.629,634,636,640, 715. 7/6
De Bruyn, P. L, 108
Debus, E., 456
De Bussetti, S. G., 186, 306
Debye, P., 129, 131, 138, /66
Debye and Hucke1 theory, 374
.
Defasse, C., llS
De Fontaine, D., 402, 449
De Francesco, A. J., 582, 617
De Franeiseis, P., 769, 797
De Grotenhuis, T. A., 617
Degussa, see Deutsche Gold und
Silber Anstalt
Degussa (Company), 442. 6/2-6/4
De Jong, J. G. M., 460
De Keyser, W. L., 74,1//.6/0
Demidova, N. A., 728
Dempcy, D. F., 453. 456
Dempster, P. B., 30, 108
Dennis, J., 593, 6/9
Denny, J. J., 56, /10
Depasse, J., 374, 376, 446. 761. 766, 795. 796
Deraska, J., 359, 445
Derevyanko, L. A., 393. 448
Dering, N. A., 561, 6/2
Derolf, M. R., 317, 440
Deryagin, B. V., 225, 324, 374, 440. 446.
450. 476. 603
Desai, C. H. 758, 794
Descter, A. R., 371, 445
Desmaris-Delecraz, D., 769, 797
De Stefano, J. J. 620
Deuehar, J. A., 7/9. 756 ~
Deutshe Gold u. Silver. Arnst., 442
Devel,H., 676, 721
Devi, A., 723
Devide, Z., 44J
,
vuthcr Index
1,45U
u, 632,
306,437,
8, 519,
7, 608,
5, 7/6
----
Author Index
809
De Vos, L., 789

De Vries, A. J., 610
De Vries, E. R., 456
DeWit, L. A., 504, 605
Deyrup, A. J., 718
Delelic!, Gj., 347, 443
Diaga, V. R., 299, 3/ /
Dibbs, H. P., 671,72/
Dick. A. B. (Company). 459
Dick, R. 447, 720
Dickey. F. H. 551.552,661
Dienert, F. 74. II t. //4
Diety. V. R., 466, 600. 638. 7 J6
Dillarstone, A. 455
Di Maio. V., 454
Dios-Cancela, G., 475. 502, 603, 605
Dirnberger, L. A., 333, 44J
Dithmar, K., 455, 457
Divnich, L. G., 553, 66/
Dixon, J. K., 448
.
Dmitrevskii, G. E., 45,57, /09, / JO
Doban, R. C., 456
Dobay, D. G., 650, 689, 7J8. 724
Dobruskin, V. Kh., 524, 607
Dobrzhanskii, A. V., J15
Dobychin, D. P:, 602
Dohr, M., 6/9
Dolezal, J., 616, 674, 712
Doigner, R., 798
Dollimore, D., 482, 486, 502, 550, 60/, 603,
604, 607. 608
Domicone, K. J., 308.

Donahue, D. J., 515, 606. 657, 7J9
Donnet, J. B. 167, 180. 182,199,248,253,
271-277,287,305,306,560,6/2, 713, 729
632.716
Doremus. R. H.,74,
Dorokhova, E. N., 307
Dorosh, A. K., /05

Dove, L. D. 454
Dow Chemical Company, 458
. Doyle, C.. F., 692, 725
Drake, L. C., 517, 605, 606
Drcving, V. P., 469, 60/
Drexel, R. E., 452. 527, 607
Driscoll, R. E., 568, 6/4
Drogosz, F. B., 79/
Drogsdore, R. D., 349, 443
Drost-Hausen, W., 445, 628, 7/5
Druckrey, H., 794
D'Silva, A. P., 473, 602
Dubinin, M. M., 479, 491, 501,60/.603-605.
626,652, 7/5, 7/8
Ducet, G., 79/
Duchene. J., 526,607
Duchon. E., 749, 792
Duel. H., 725
Duffy, G. D., 567, 6/4
ut.
i6, 795. 796
0,446,
Duffy, J. A., 182,306

"
Dugger, D. L., 182,306
Dumas, J. R., 618
Dumont, F., 374, 446
Dunning, W. J., 219, 308
DuPont de Nemours (Company), 168. 6/7
Dupre, J., /68
Dupree, P. M., 433, 458
Dushina, A. P., 57, JJO. 460, 672-674, 72/, 722
Dzhalilov, A. T., 448
Dzhambaeva, D. B., 541, 609: 6/0, 7/6
Dzhigit, O. M., 472, 602, 636, 653, 714. 7/6,
7/8. 7J9
Dzis'ko, V. A., 639. 642. 644, 65 I, 7/7

Eadington, P., 604
Eakins, W. J., 726
Early, J. E., 142, 167
Ebeling, W., 595. 6/9, 753. 793
Eberly, P. E., Jr., 353, 444
Eckart, R., 727
Edge. R. A., 143. /67
Edlin, F. E., 453
Edwards. J. E. 513, 606
Edwards, J. 0., 142, 167
Eframov, I. F., 403, 450
Egbregt, J., 316, 440
Eger, W., 799
Egerov, P. P., 459

Eggertsen, F. T., 444. 471, 60/
Egli, H., 223, 309
Egorov, E. V., 577. 6/6
Egorov, M. M., /08,642, 7/7-7/9
Egorova, E. N., 179. 305
Ehrhart, L. A., 794
Einbrodt, J. H., 799
Einstein equation, 361
Eirich, F. R., 703, 727
Eitel, W., I, 2, 791
EI-Akkad, T., 605
Eldridge, J. M., 723
Elker. A. L., 655, 7/9
Elkin, P. B., 223,309, 476, 603
Elkington, P. K., 7/8
Elliott, J. R., 6/5
Ellis, B., 652, 719
Elmer, T. H., 31, 41, 43,65, /09, 460. 549,
551, 6JJ, 7/7, 723
Elmes, O. C., 429, 456
Elod, J . 179,305
EI'tekova, Y. A., 620. 654, 7/9
Elton, G. A. H., 672, 681, 721. 724
Elving, P. J., 1,2; 95.1/3
Elwood, P. C. 794
Emblem, H. G. 424, 453. 454
Embrodt, H. J., 770, 797
Emmett, P. n., 444. 467, 552. 60/. 661
.. -_..
!.
J
~~
I
I
I
(. I
i
I
I
I
.' II
I
II
I
!I
.,
:i
. I
I
810
Engel, C. 750, 791

Engel, W., 742, 748. 790. 791. 796
Engelhardt, E. R. J/I. 4S7
Engelhardt. G., 132. 166
Engelson, G. E., 6/4
Ephraim. F., 3, /04
Erdel, G. 716
.Eremin, N, I., 166. 728
Erhart, H., 750, 791
Erich, L. C. 503, 605 "
Erkelens, J., 631. 71S
Erlenmeyer, H., 6/1. 6/2
Ermatov, 713, 71J. 719
Ervin. G., 48, lOS. 124-126. /6S. 181, J05
Erwin, W. R., 697. 716
Eschrick, H. 675, 72/
Ettre, L. S., 353, 444. 471, 601
Eugster, H. P. 20, 21, /07. 158, /70
Evans, C. D., 60J
~
Evans, R., 327, 440
Everest. D. A. 565. 6/J
Everett, D. H., 465. 600
Eyles, W. C., 449
Faber, O. M., 776, 798
Fague, G. R. 350. 44J
Faivre, R. 476, 60J
Falivene, P. J 4SS
Fanger, G. 0 . 6/7
Farkas, M., 458
Farrow. J. E., 457. 4S8
Faure. Ch . 756, 79J
'".
Fauss. R.,,630, 7/5
Faust, R. M., 734. 788
Fawcett. F. S., J II
Feach, H., 567, 6/4
Feder, H. M. 104. lOS
Fedkina, L. G., 796
Fedors, R. F., 361, 44S. 461
Fedotov, Y. Y. 449
Fejes, D., 601
Feldt, C. A., 440.
Ferch, H. 427, 45S. 592,6/8
Ferreiro, E. A. 750, 790. 791
Ferris, A. P., 718
Ferruti, Po. 799
Fery, No. 713
Fessenden, R. J., 786, 800
Fikar, E., 458
FiJimonov, V. N., 717
Fink, A., 239, J09. 328, 335,404, 441
Fink, H., 619
Fink, P., 717. 713
Fisch, K., 619
Fischer, E., 179, 30S
Fisher. J. R., 460
Author Index
"
Fisher, S., 1/4
Flanigen, E. M., 18, 106. 154, 194.307.
5 11.606
Flaschbart, H. 335, 441
Fleener, F. L., 104
Aeer. G. J., 397, 449
Flehmig, W. 79. 112
Fleischer, E. 258. 794
Flelscher, E., 764, 795
Flemmert, G. t., 568, 6/4
Flemming, W. 248, 309
Fletcher, C. H., 426. 455
Fletcher, K., 797
Aood, E. A. 478, 603
Florio. P. A., 426, 455
Fl3rke, O. W., 16, 106
Flynn, J. J., 169
Fontana, B. J., 727
Ford, T. F., 36 I, 445
Forman. S. A. 758, 794
Forni. t., 718
Forsman, W. C., 709, 727
Forsyth, M. W., 168
Fortnum, D. 142. 167
Foss, W. M., 88, JJJ
Foster, A. G. 535, 536, 608. 609
Foster. L. M . 7, 105
Fotiev, A. Y. /70
Fouealt, G., 60, II /
Foulger, J. H., / /4, 786, 801
Fournier, R. 0 . 7, 3 I, 32. 45, 52, /05. /09
Fowkes, F. ,M., 625, 7/5 .
Fowler. R. H., 3, 104
Foyt, H. P., 93. / /3
Fraissard, J . 548, 6/0. 713
Franck. H. G. 220.252,259,308. 310
Franck. H., /66. 179. 180, J05
Franks. E., 132. 166
Fratzscher, H., 567, 6/4
Frazier, S. E., /07, 696, 726
Frederici, E. D. 426. 455
Frederick, J. E. 459
Freeman. E., 667,673, 710
Frei, R. W. 599, 611
French. C. M. 675, 676. 711
Frenkel, E. No. 603
Frenkel. J. 470. 601
Frens, G., 382. 447 ."
Freund. E., 142. 167
Freundlich, H . 186.304.308. 403.450. 479
Frevel, L. K. 504, 605
Frey, S. S., 457
Frey. Wyssling. A.. 737, 74"1, 789. 791
Freyhold, H. Y. 153. /68. 169
Fricke, R . I, 1
Fridlyand, R. 476; 603
,
~
Index
'-
109
Author Index
811
Friedberg, K. D., 74, // I

Garrett, H. E., 96, //4
"
Fripiat, J. J., 630, 633, 635, 636, 652, 691,
Gartner, K., 518. 607
693, 715-718, 713, 715
Gaskell, D. R., 164, 171
Frison. E. 743. 746, 790
Gaskin, A. J., 404, 449, 450
Frissard, J. 716
Gass, J. L., 567, 614
Frolov, I. I. 610
Gastuche, M. C., 717
Frolova, N. N. 799
Gaw, W. J., 649, 7/8
Frolova, N. P 459
Gaziev, G. A., 471,602
Fromme, H. G. 781, 799
Gebura, S; E., 616
Frommer, D. W., 396. 448, 714
Gees, R., 31, 79, /12
Frommer, M. A., 603
Geffcken, W. G., 458
Fronczak. E. T., 572, 592, 615, 618
Geishin, P. A., 718
Frondel, C., 16,22, /06, /07
. Gendre, P., 797
Freyer, J. C. W., 545, 610
Gentili, R., 725'
Frydrych, R., 103, us. 180, 199,200,305,307 Gentles, R. P., 452
Frye, C. L., 157, /70
Georgiev, R., 794
Fu. Y., 503, 605
Germar, B., 750, 792
Fuerstenau, D. W., 381, 447, 660,681,688,
Germer, L. H., 798
710,714
Gerost, H., 721
Fujita, T. 451 .
Gerow, S. A., 169. 454
Fujiwara. F., 549, 6//, 641, 717
Gerritsen, T., 459
Fuks, J. G., 618
Gessler, A. M., 582, 617
Funk, H., 103, //5, /66, 170, 180, 199.200.
Geus, J. W., 567
305,307
.
Gewecke, F., 563, 613
Funnell, N. A., 611
Ghezzi, I., 766, 796
Furman, N. H., /14
Ghosh, B. N., 512, 516, 606
Fursenko, V. F., 12, /05, 114
Gibb, J. G., 108
Furst, B., 447, 710 ..
Gibbs. M., 459
Furukawa, H., 672-675, 71/
Giddings. J. C., 351, 444
Furusawa, K., 382, 447
Gieskes, J. M 29, 108
Fyfe, W. S., 16,26, /06, 313.439
Gilem, S. A. (Company). 404, 450
Giles. C. H. 473 .. 601
Gabor, S.t 781, 800
.
Gilkey. J. W. 308
Gabrielyan, N. A., 448
Giller, M . 220. 252. 259.308. 310
Gage. J. C. 798
Gillson, J. L. 615
Gajatto, S., 801
Gilson, P . Jr. see Gilem, S. A., Company
Galinskaya, V. I., 178, 305, 6/2
Ginsburg, F. L. 279,310
Gallard-Hasid, Mme . 545, 6/0
Girfanova, T. F., 381.447
Gallei, E., 575,601, 616, 695, 716
Girgis, B. S. 469. 532, 601, 608
Gamage, L. P., 338, 442
Gitlin. S. N. 628. 715
Gamble, R. J., 433, 458
Glarnm, A. C., 308
Gamow, G., 731, 788
Glasrock Prods. (Company). 615
Ganculi, N. C.,. 608
Glass, R. W. 654. 719
Gandon, L., 332, 440, 441, 606
Glasser. L. S. D., 141. 143. 167
Ganguli, N. C. 603
Glazovskaya, M. A., 733. 788
Ganichenko, L. G., /08, 655, 719
Gleim. V. G. 468
Gans, D. M., 472, 601
Glernser, 0., 12. 105
Ganyuk, L. N., 712, 723, 728
Gloates, R. J . 715
Garcia, M., 770, 797
Glomme, J. 764. 795
Garcia, S. F., 310
Goddard. E. D., 434, 458
Gardes, G. E. E., 609
Goddin, A. H., 619
Gardner, G., 455
Godon-Renou, J. 548, 610
Gardner, J. N., 60, /lO, 157, 170
Goebel, M. T . 573,~615, 693. 725, 726
Gardner, LV., 30, 108
Goertsema, A.. 719
Garner, W. E., 376. 446
Gohr, H., 114, 754, 787, 793, 801
Garrels. R. M. 105, 181,305
Gdkcek, C. 692. 715
;a;
J.479
-_.
.. --_.
812
Author Index
Goldanskil, V. I. 505. 605. 674. 722

Goldfarb. J . 383.415. 444. 452
Goldfinger. G. 715
Gollkova, E. V., 381, 446. 447
Golkowska, A. 114
Gonnermann, M., 753, 793
Gone, F., 799
Gonzales-Carrero, J., 300.311
-,
Good. F., 646, 717 .
Good. W. D., 105
Goodman. J. F., 383, 447, 546, 548, 610
Gordon. M., 304,
410. 451
Gordon. R. 0., 788
Gorelik, R. L., 543, 610
Goring. D. A. R. 347. 443
Gorshkov, V. I., 165
Gorksi, C. H., 718
Gorum, L. A., 618
Gosheh, N. S., 790
Gosslain, P., 602
Gothe, C. J., 777, 798
Goto, K., 11,31,43,48,66,67,69,81,109. ut.
112. 185, 193, 196, 197, 252, 253, 255, 282,
301-303,306. 307, 310~
351.352,381,
433. 444. 446. 458
Gottfried, W., 457
Gotz, J . 141. 155.167. 169
Gouy theory, 374
Govett, G. J. So. 96, 97, 101, 114
Grace, W; R., Company, 537. 609
Graham, D. 358, 444
Graham, Thomas, 172,297,304.310. 338,442
Grahame, D. e.t 356, 444
....
Granquist, W. T., 438, 460 :
Gransden, J. F., 456
~ ..
Grant, R., 121. 165
Grassi, R., 790
Gray. P. Po, 744. 791
Gray, R. s., 736, 759
Grebenschikova, O. G., 611
Grebenshchikova, V. I., 676, 722
Green. J. H., 712, 728
Greenberg, S. A., 1,2,6,44,58,67,68. 105.
/JO. tt t. 132,166,253,281,3/0,347,364,
438, 443. 445. 460, 667, 673. 720
Greene. a. S. s., 346, 443
Greenewalt, C. H., 403, 450
Greenland. D. r., 704, 708, 727
Greenwood, R., /06
Greer. R. T., 330,400, 441. 449
Gregg, S. J., 494, 503, 546, 548, 600. 60S, 6/0
Gregory, J., 394, 448
Grenthe, 1.. 720
Grib, J., 792
Griessbach, R., 312, 419, 439. 452. 518, 607
Griffen. R. H. 619
su,
,,
I
i
,
\I
i I!
:i
: ,I
I
."
i
I
i
t
su,
Griffin. A. E., 303. 3//

"
Griffin, G. J. L.. 6/8
Griffiths. Do Mo. 655. 7/9
Grigalinovich, Go A. 786. 800
Gring. J. 1... 527, 607
Griot, 0., 395. 448, 662. 708. 720. 727
Grohman. K 620
Grames. W 602
Gromov, V. V., 729
Groschuff, E., 166. 297.3/0
Grose. R. W.. 18. /06. 154, 5 II. 606
Gross. A., 725
Gross, H. 26, 107
Gross. P., 798
Grosse-Breuckmann, E. 792
Grot, W. G., 428, 456
Gruber, Eo. 366, 445
Gruenspan, M., 799
Grundmann, G., 783, 800
Gruner, E., 179.305
Guadin, A. M., 688, 724
Guba, F. 225, 309, 479. 603
Gude, A. J., 20, 107
Guerillot, J., 791
Guignard, J . 96, 1/4
Guillard, a. R. L., 460
Guillemin, C. i., 620
Gummerman, o., 457
Gunn, E. F., 568, 614
Gupta, J., 518, 606
Gur'eva, T. G. 134, 166
Gusel'nik, Y. Y., 449
Guth, J. t., 161, l7t
Gutowski, W., 407, 45/
Guyer. Ao, 542, 605, 610
Guyot, A. 315. 316, 439 .
Guzy, J. K . 797
Gye, W. E., 793. 794
Haacks, a., 797

Haag. I. L., 453
Haas, u. Co. 457
Haber, F. 622, 7/4
Hachford, H. H., Jr., 545, 610
Hachisu, S., 403, 450
Hackerman, N., 625, 7/5
Haedicke, u., 723
Hagg. G., 131, /66
Hagymassey, J., Jr., 470, 501, 60J~ 605
Hahn. H. H., 380. 446
Hahn. u., 460
Hair, Mo. 185.306.623.648.649,65 1,652.654,
660.695,696. 71 I, 1/4. 7/8-720. 723. 726
Halasz, I., 620
Halberstadt, E. S., 528. 608
Haldane, J. S. 782. 798
. ---thor Index
I
,
I
,!
,
'27
t
.!
I
II.
'.
605
.652,654,
723. 726
Author Index
Haldeman, R. G., 552. 66/
Halenda, P. P., 494, 604
Halfter, G. 102, //5
Halicki, P. J., 789
HaUer, G. L,446
Haller, W., 24, /07
Halsey, G. D., 470, 60/
Hamaker, H. C 373, 374, 446
Hamaker constant, 324
Hamann, K., 723
Hambleton, F. H. 716. 723
Harnett, L. P., 728
Hamori, E., 709, 727
Hampl, J., 792
Handreck, K. A., 790. 792
Hanf, N. W., 118, /65
Hanke, W. 636, 7/6 .
Hanna, K. M. 50 I, 605
Hanoka, J. I., 593, 6/9
Hansen, O. H., 789
Happel, J., 361. 445
Harano, Y., 725
Harder. H., 42, 79, 80, /05. //2
Harding, R. D. '373, 375. 381, 382, 446. 447
Harington, J. S. 773, 795-797. 799
Harkins. W. D. 468, 469. 475, 60/. 603. 689,
724
Harley. J. D., 764, 795. 796
Harman. R. W., //4, 131. /66
Harnsberger, H. F., 466, 600
Harriot, P. 6/7
Harris, M. R. 493, 600, 6f)4
Harrison. C. V., 797. 798~;
Harrison. D. H., 425, 454 Harrison. J. H., 454:.'
Harrison, J. S. 797 .
Harrop, R., 680, 686, 724
Harshfeld, J. J. 455
Hart, P., D'A.. 795
Harth, H., 6/8
Harvey, D~ R., 60, //0, 157, /70
Harvey, E. N., Jr., 538. 609
Harvey. W. W. 308
Hasegawa, M. 7/9
Hast, N., //0. 460
Hathaway. B. J., 674, 722
Hathaway, F. S., 412, 45/
Hauger, R., 767. 796
Hauser, E. A., 1,2.309,712, 728
Havard, D. C. 600. 605
Havas, J., 457
Hawkins.. W. L 6/9
Hayakawa, Y. 751, 792
Hayami, R., 117, /65
Hayano, K., 458
Hayek, M., 394. 448
813
Haynes. R . 796
Haywood. F. W., 453

Hazel. J. F., 135, /66,304.3//,410.45/.458,
527.607
Hazelbrouek, G. 96. //4
Heal. G. R. 482, 486. 502. 550. 60/. 603-605.
608
Heald, I. A., 303, 3/ t, 513, 606
Healey, F. H. / /0
Healy, T. W.. 64, 81,
//2,356-358,369,
374, 378. 380-382, 391. 411, '444-447. 45 I.
660, 664, 665, 669, 670, 671, 673-676. 7/5.
tu.
720-722. 728
Heany, J. A . 459
Heard, H. C. i08
Hechtman, J. F. 456
Heckman, F. A., 465, 600
Heeky, R. E., 784, 800
Hedberg, M. C., 686, 724
Heeren. E. 799
Heesch. H . 482. 604
Heffelfinger. C. J., 456
Hegelson, H. C., 32, /08
Heine, W., 797
Heinen. W. 734, 785.788,.800
Heinz, F. / /4
Heitmann, H. G. 12, 32. /05
Helgeson. H. C. 7, /05
Helgesson, C. I. 452
Heller, G. 568. 6/4
Heller. W. 392,404,448. 450
Hellinckx; E. 633. 7/6
Hellrners, J. H., 90, //3
Helmcke, J. G. 789
Helmy, A. K., 186,306
Hem. J. D . 193.307
Hemmingsen. B. B., 738. 789
Henisch,~H. K., 593, 608. 6/9
Henkel et Cie., /69
Henniske, H. W. 106
Henry, C. R . 303,3//
Hensley, A. L., 636, 7/6
Heppleston, A. G. 770, 772, 773, 797 ~
Herkenhoff, E. C. 447. 724
Hermans, J. J . 347, 350, 443
Hermans, M. E. A. 467,60/
Hermans, f. H., 600. 608
Hermes, M. E. 3//
Herrera-Huertas, M. 675, 72/
Hertl, W., 185,306,651,652, .654,660,695,
697, 7/8-720. 723. 726
Herzberg, W. J., 697, 726
Herzog, A. 748, '79/
Herzog, A. H., 433, 458
Hess, P. C., 164,./7/
Hess, R., /69
.,.
---Author Index
814
Hesselgesser, J. M., 118, /65

Heston, W. M., 43, 47, /09,356,357,359,360,
444
Heston, W. M., Jr., 179, J05
Hetherington, G., 5, /04
Hcukeshoven, W., 131, /66, 178, J05
Heuser, R. V., 560, 6/1
Hcydemann, A., /06
Heyer, W., 11J
Hichwa1t, C. A., 6/9
Hierl, G., 674, 711. 714
Hill, J. M., 6/7
Hill, T., 542, 6/0
Hill, T. L., 470, 60/
Hilmer,
143, /67
Hiltner, P. A., 402, 450
Himmelmann, W., 459
Hindea, S. G., 7/7. 717
Hinderson, J. H., 31, i08
Hingston, F. J.;J07
Hinz, W., I, 1, 528, 601
Hirai, N., 66, 1//
Hirowatari, T., 1//. 715
Hirsch, M. S., 760, 795
Hlavac, J., 118, /65
Hochstrasser, G., 637, 1/6
Hockey, J. A., 225, J09, 475, 60J, 624, 635, 640,
646,647,656, 7/5-7/9. 72J
Hoebbel, D., 142, 151, 154, ISS, /67-/69,203,
W.,
204,252,261,263-266, J05. J07

Hoekstra, W. G., 793
Hoene, R., 723
Hoenig. S., 797
Heesch (Company), 6/2 .
Hoff, R., 368, 445
Hoffman, G. W., 334, 442
Hoffman, R., 482, 604
Hoffman, R. L., 474, 603
Hofman, U., 24, /07,566, 602.6/4, 770,797
Hofton, M. E., 94, 1/3
Hogan, J. P., 456
Hogg, R., 381, 447
Hohl, H., 446~ 669, 720. 72/
Holker, K., 457
Holm, F., 784, 800
Holmes, B. G., 7/5
Holmes, S. T., 606
Holmquist, C. E., 795
Holmquist, S. B., /65
Holt, B. D., //4
Holt, P. F., 34, /08, 157, /70. 299,3/0.3//.
395, 448. 707, 727, 762, 765, 770, 775, 776,
. 781, 787, 795. 796. 798. 799. 80/
Holten, C. L. M., 720
Holzapfel, L., 742,753,761,766,790.79/.793,
795. 796. 798 .
Hood, H. P., 6/ /.
"
Hoover, C. L., 16, /06
Hoover, W. G., 450
Hopfe, V., 602
Hoppe, L., 587, 6/8
Horikoshi, H., 695, 725. 726
Horning, S. C., 445
Horst, F., 457
Hostetler, R. E., 706, 721
Hougen, O. A., 497,604
Houlton, H. G., 96, //4
House, L. R., 21, /07. /70
Houseman, J., 6/3
Hovorka, F., 359, 445
Howard, G. J., 448, 709, 727
Howard, J. P., 675, 676, 12/
Howard, P. B., 94, / JJ
Howard, R. N., 454
Hower, J., /07. 726
Hsing, H. H.;700, 726
Hsu, H. L., 460
Huang, C. P., 81, 1/2, 194,307,380,446,664,
720
Huanga, W. H., /07
Hubbard, S. S., 533, 608
Hubbard, W.N., /04. /05
Hubert, Y., 161, /7/
Hue, A., 789
Huckstadt, H., 459
Hudon, F. A., 6/6
Hudson, G. A., 75, / / /
Huertl, M., 536, 608
Huettenrauch, F., 6/8
Huff, H., 131, 136, /66, 248,309
. Hughes, R. E., 709, 727
Hughes, R. L., 620
Hulett, G., 50, /09
Hunter, E. A., /68
Hunter, M. J., 730, 787
Hunter, R. G~, 313, 439
Huntsberger, J. R., 456
Huper, H., 303, 3/ /
Huque, M. M., 443
Hurd, C. B., J08. 309, 512, 606
Hurd, D. C., 29, /08. //0. 736-738, 789
Hurley, H. J., 759, 794
Hurst, H. 792
Hutchinson. G. E., 790
HUttig, G. F. I, 2
Hwang, S. 790
Ibbitson, D. A., 656, 7/9
Ikeda, C. K., 456
Ikeno, S., 723
Iler, R. K., 1,2, 13,20,43,47,51,54,56,59,60,
67,77,79,80,86,93,97, /05./07, /09. lJO.
I
J
1I
J
a
~
.. --_.
ir Index
,I
I
I
I1-,
i
16,664,
Author Index
/ /2. / /3, 118, 124, 129, 130, 138, 142, 144,
146, 147, 158, 159, /65-/68. /70, 174, 179,
186, 192,202,207,209-213,216,217,223,
234, 237, 238, 240-242, 244, 250, 252, 253,
283,285,289,290,295,298,305-3/0,312,
315, 317, 329-333, 338, 340, 345, 347, 350,
351, 356, 357, 359, 360, 361, 364, 366, 370,
371,378,381-383,388,393-395,397,398,
400,404-409,412.414,415.438.439-442.
444,445,447-449,45/-454.456-458.460.479.
487. 489, 490, 508, 510, 513, 514, 517. 523,
528,530;.531. 546, 557-560, 562, 570, 572,
573, 582, 583, 598, 599. 605. 606. 608. 6/2.
6/3.6/5.6/6-620,622,628,631,636,646.
647,667,673,681,689-691. 7/4. 7/5. 720.
724. 725. 727. 730, 736. 737. 739. 745. 763,
773, 776, 782. 787. 79/. 795
Il'in, B. V. 7/8
Il'in, V. G., 158, /70
llIigen, A., 6/4
Illinois Minerals (Company), 6/5
Imelik, B., 504, 536, 545, 548, 605. 608. 6/0.
638, 7/6
Ingelbreeht, I. M. 774, 797
Ingleman, G., 784, 800
Ingram, M. D., 182, 306
Ingri, N., 132, 134, /66, 181, 183,305
Inkley, F. A., 469, 494, 496, 497, 499-501, 60/
Innes, W. B. 252. 268.3/0,467. 60/
Irani, F. A. 316. 439
Irey, B. N., 306
Iribarnegaray, J. E. 3/0
lrnich, R. /7/
Irwin. D. A., 56. //0 .
Isaacs. L.. 114. 786. 80/ ..';:
Ishihara, T., 458
Ishizuka, Y., 751, 792
Ish-Shalom, M., 603
Isler. K. M. 764. 795
lsohata, S., /68
Ivanov. N. K., 134, /66
lvanova, I. D., / / /
Iwasaki, I" 98, / /4
Iwata, Y;, 456
lzawa, T., 620
Jack. K. H. 5. /04
Jacks. G. V. 733, 788
Jackson, K. A., 402. 449
Jackson. M. L.. 31, /08
Jackson. P. R., 457
Jackson. R. P. 457
Jacobs, A. W., 798
Jacobson. C. A., 23. /07. 564, 6/3
Jacobson. H. W., 673, 674, 72/
Jacoby, W. R., 297,3/0
81S
Jager, R., 776, 798

Jahoda, E., 459
Jahr, K. F., 131. /66, 178, 305
- James. D. M. 794. 798
James. R. 0 . 378, 381.411,446.45/.665,669.
670,671.673-676. 7/5. 720-722
Jamieson, P. B., 143. /67
Janauer, G. E., 411. 45/
Jander, G. 131. /66. 178,305
Janet. J . 731.788
Jang, H. 0 . 567,6/4
Ja'nosi, A 349, 443
Janzen, K. H., 330. 44/
Jarabin, A. 99, //4
Jarnutowski, R. 347, 364, 443. 445
Jayne, D. W., 615
Jeffs. D. G. 728 "
Jekabsons, J., 6/0
Jelinek, A. G. 453
Jenkins, E. E. 532. 542, 608, 6/0
Jenkins, S. R., 380, 446. 720
Jennings, B. R., 348. 350, 443
Jephcott, C. M., 56, / /0
Jepson, W. P., 728
Jerrard, H. G., 348, 350, 443 .
Jewett, H. A., 455
Jewitt, C. L., 455
Jimenez-Torres, N. V. 799
Jirgensons, B. 405, 440
Jiru, P., 7/8
Johan, Z., 158, /70
Johansson, G., 196,307. 668, 72/
Johns-MansvilleHlcmpany), 6/5
Johnson. J.' H., 56,"//0
Johnson. M. F. L. 538,609
Jolles, H. 96, //4
Jones, B. F. 170
Jones, D. C., 655, 656, 7/9
Jones, H., 545, 6JO
Jones. J. B., 398-400, 449
Jones, L. H. P., 449. 744,790. 79/. 792
Jones, M. M., 14, /05
Jones, P., 640, 7/7
Jorgenson, E. G., 737. 789
Jorgesen, S. S . 31, 43, 44. /09
Josh. V., 6/0
Jest, K. H., 143, /67
Jost, L.. 79J
Jdtten, K. W., 800
Joy, A. S., 466, 600
Joyner, L. G., 494, 604
Judge, J. S., 76, //2
Jue, L. R., 127, /66. J70
Juillet, F., 471,567,602.6/4
Jullander, I., 800
Jura, G., 468, 469, 475, 601. 603
Author Index
816
1
I
:~
. ~
!
Kachi, S. 593. 6/9

Kadisch, E 754, 791
Kaganer, M. G., 470, 60/. 605
Kagel. R. 0., 7/8
Kageshirna, J., 740, 790
Kahane, E., 79/
Kahle, H., 754, 791
Kahler, H. L., 114, 80/
Kainaraskii, I. 5., 18, 106
Kaiser, R., 482, 509, 604
Kakudo, M., 476, 601
Kalatsei, E. A., 674, 722
Kalokerinos, A., 449
Kalousek, G. L., /7/
Kalt. A., 20, /07. 161,170
Kamakin, N. M., 602
Kamb, B., 18, /06
Kamber, H. R., 182, 184,106. 660, 720
Kilmpf, G., 545, 610. 726
Kanabolotskii, V. A., 553, 6//. 6/2. 677, 722
Kane, P. F., 624, 7/5
Kanhofer, E. R., 563, 6/1
Kanner, B. 434, 458
Kano, T., 725
Kantro, D. L., /05. 472, 602, 642,645,646. 7/7
Kao, Y-K. T., 787, 801
Kapitonova, N. V., 60/
Kargin, V. A., /7/
Karle, I. L., 789
Karsten, G., 791
Kasai, N., 60J
Kaskin, I. G., 728
Kasparov, A. A., 799
Kasper, H., 590, 6/8
Kastner, M., 29, /08
Kato, A., 614
.
Katritzky, A. R., 60,
157, /70
uo.
,i
.
.
Kats, S. A., /7/

Katsanis, E. P., 411, 45/
Katzenmayer, W., 676, 722
Kaufman, P. B., 742, 743, 790. 79/
Kaufmann, H. P., 762 795
Kautsky, H., 21, 97, /07, /14. J7/. 247, J09.
353,444. 528,577,607, 6/6. 638, 7/6
Kauzmann, W., 391, 447. 448
Kavanagh, B. V., 81, // 2. 447. 728
Kaverinski, V. A., 673, 722
Kawaguchi, K., 672-675, 72/
Kayama, 1., 11,43,105. 109
Kaymenskaya, N. P., 602
Kazantseva, S. V., 781, 800
Kazlauskas. R., 602
Kearby, K. K. 536, 609
Kearfott, J. B., 423, 45J
Keat, P. P. 16, /06
Keeler, R. F., 794'
Keene. J. B., 29, /08
Keller. H. 456
Kellum, G. E. 630, 7/5
Kel'tsev, N. V., 721
Kelvin, 495, 497, 499, 500
Kelvin, Lord (Thompson, J.), 488. 490, 604
Kempers, H., 566, 614
Kenna, B. T., 6/0
Kennedy, G. C., 12, 32, 105, /08
Kennedy, J. F., 595,6/9
Kenney, J. T. 427, 456
Kenney, M. E., /07, 726
Kenyon, O. A., 98, //4
Kerker, M., 411, 451
Kersten, W., 758, 767, 794. 796
Kessaissia, Z., 7/9
Kessel. R. W. I., 795
Kesztus, J., 447
Kettle, E. H., 776, 798
Khaskin, I. G., 695, 726
Khentov, V. Ya., 458
Khodakova, G. S., /08. 602
Khokhlova, T. D., 620
Khomchenko, G. B., 201, 307
Khopina, V. V., 719
Kiang. L., 186, 106
Kibota, Y., 603
Kidwell, A. S., 586, 6/7
Kiel, A. M., 567
Kikuchi, K., 670, 72/
Kikuth, W., 767, 796
Kilham, S. S., 789
Killman, E., 710, 727
Kimberlin, C. N., 537, 609
Kimura, M., 60J
Kindl, G., 656, 7/9
KincH, P.O., 729
King, D. R. 792
King, D. T., 34. /08. /09
King, E. J., 100, /14. 766, 774, 778, 787,
796798. 80/
Kingsbury, J. M., 737, 785, 789. 800
Kingsford, C. L., 454
Kira'ly, J. 602
Kirby, J. E., 6/5
Kirch, W., 560, 612
Kirchgassner, H., 6/8
Kirichenko, L. F. /70. 186,188,306.666,720
Kirk, E., 791
Kirk, J. S. 140, /67. 288. 301., 3/0. 3//. 449.
659
Kirkham, A., 561. 6/2

Kirkland, J. J., 420, 452. 598, 599,613. 620.
621. 727
Kirkwood, J. G., 403. 450
Kirkwood-Alder transition, 403
Kiselev, A. V., 472, 476, 480, 491, 492, 493,
500, 5 10, 516, 517, 536, 540, 542, 543, 545,
-..-...
Author Index
Index
I, 6fJ"
817
598,60/. 602. 603. 604. 606. 609. 6/0. 6/1.

620.623,624,631,632,634,646,648.649,
652, 653, 654, 691, 699, 702, 714. 7/5. 7/6.
7/7. 7/8. 7/9. 723. 725. 726. 736
Kiselev, V. F. /08.60/.655.712,7/7-7/9.728.
729
Kistler. S. 5 . 537. 575. 609. 6/6
Kitahara, 5 . 7. 32. 51. 61, 62. /05. /08. /09.
/11. 179,305.331.44/.574,6/5.691.692.
724, 725
Kirchener, J. A . 4,/04. 324, 395. 397. 440. 448,
647. 662, 673. 674. 704. 708. 7/8. 720. 722.
727
Kittaka, 5., 629. 7/5
Klass. D. L. 593. 6/8 '
Klein. G. 762. 795
Klein. J. M. 6/6 "
Klein. 5 . 181.253,276,278-280.287.305
Klemperer, F. W. 758. 764, 794. 795
Klenke. E. F. 459
Klier. M., 402. 449. 450. 627. 7/5
Klimentova, Y. P. 188. 306
Kloepfer. H., 442. 566, 6/4
Klosak, E. J. 317, 439
Klosterkbtter, W. 77, 111. 774, 779. 798-800
Klotz. I. M. 391. 447
Klunker, F., 6/7
Klyatskina, I. K. 795
Knake, E. 794
Knauff, K. G. 179, 199, 25 I, 253, 254. 305
Knell. W. L. 366, 445 "
Knight. K. R. 483, 604
Knoezinger, H. 718
Knoll, A. H. 52. /09
Knyazeva, N. N. 166
"
Knzaz'kova, I. 5.,42.43. /09. 185.306
Kobayashi. H. 607
Kobayashi. Y. 403, 450
" Koberstein. E., 468, 601
Kobyshev, G. I., 676. 722
Koelling, J. G. 698, 726
Koepp, R. L. "457
Koerner. G:, 6/9
Koerner, 0., 46. 107
Kogishi, 5 . 458
Kohler. H. 800
Kohlschlltter, H. H. 527,545, 607. 6/0. 668
675. 676, 696, 721-723. 726
Kohn, H. W. 728
Kohne, R., 217, 308
Kolb, K. E. 698. 726
Kolosentsev, S. D. 528. 607
Kolthoff, I. M. 1.2.95,113.223,309.444.473
602. 650. 669, 674, 718. 72/
Kol'tsov, S. I., 669, 710, 7/6. 72/. 723. 727
Koltun, M, 459
Kolychev, V. I., 305
\ ...
'.
"I
!
87,
l,
I
I
I
;66,720
JJ. 449.
3.620.
2, 4 _,"
43,545,
"
Komarova, L. A., / /2
Komissarenkov, A. A., 72/
Komovskii, A. F., 17/
Kondo. 5., 510. 549, 606. 6/1. 629, 640, 641.
7/5. 7/7
Kondrasheva, A. L. 72/
Konecny, C. 577, 6/6
Konig. H. 102. //5
Koninklijkc Zwavclzuur Fabrieken
(Company), 6/2
Kontorovich, S. I., 606
Koopmans, M., 30, /08
Kopak, J. J . 436. 460
Kopeiken, V. A., 37. /09
Kopp, H. 164, 17/
Korenmann, I. M. 619
Korman. 5 . 566. 613
Korclev, A.Y. 725
Kose. A. 403, 450
Koshi, K. /08. 795
Koster, A. 335, 442
Kot, A. A., 82. / /2
Kotera, A. 382, 447
Kotov, A. G. 729
Kovarik. J. F. 411, 412, 45/ ,
Kovats. E. 5 . 620. 624, 696, 7/5
Kozawa, A. 674, 72/
Kragh. K. M. 393. 448
Kramm, D.oE. 576. 6/6
Krase, H. 457
Krasil'nikov, K. G. /08. 601, 655. 712.
7/7-7/9. 728
Krasnoschekov, E. N.,307
Kratky, 0 . 349. 443
Kratohvil, J. P. 347. 443. 445. 447
Krauskopf, K. B. 41. 109
Krauss, H. L. 674, 722. 724
Kraut. H. /66.179,180.305
Kreckler, J. H. 560, 612
Kreger, W: E., 538, 545, 609. 6/0
Kreider, K. G. 118. /65
Kress, W. 579, 6/7
Kressley, L. J . 504, 605
Krieble, R. H., 6/5
Krieger, I. M., 402, 450
Krisch, K., 767. 796
Krishnakumari, M. L., 792
Krohn. D. A. 460
Kruger, G., 166
Kruglikova, N. 5 . 720
Kruner, N. 793
Kruyt, H. R., 173,305.359,360,445.450.600
Krylova, T. N., 459 ~
Krylova, V., 476, 603
Kubelkova, L. K 718
Kubitschek. H. E. 449
Kuchelkova, T. A., 800
818
Kuchen, W., 169

Kudo, K., 382, 447
Kugler, T., 566, 61J
Kuhn, A. T., 442
Kuhn, W. E., 345, 443, 444. 449. 599
Kukhtina, A. P., 793
Kukolev, G. V., 1,2
Kulividze, W. I., 717
KUlkarni, R. D., 434, 458
Kum, K. A., 113
Kumar,S., 611
Kummerle, H. F., 299,31/. 527,607
Kunath, D., 693, 725
Kunawicz, J., 640, 717
Kung. H. H., 596, 619
Kunin, R., 113, 114
Kunowski, H., 602
Kunzru, 0.,599, 621
Kurennaya, L. I., 574, 615
Kuronuma, I., 330, 441
Kurosaki, 5., 475, 603
Kurz, P. F., 593, 619
Kutuzova, R. 5., 733, 788
Kuz'kin, S. F., 395, 448
Kuznetsov, B. V., 610
Kvitkovskii, L. N., 719
Kvlividze, V. 1.,632,716
Kvorning, S. A., 793
Kyrs, M., 676, 722
..
La Croix, J. D., 790

Lagaly, G., 21, /07. 158, 159, 170, 448
Lagerstrom, G., 31, 44, /09,132, 166
La Heu, D. W., 792
Lai, R., 459
Lakhanpal, M. L., 715
Lambert, R., 725
La Mer, V. K., 364, 380, 388, 391, 392,445.
447,448
Lamina, J., 793
Lampatzer, K.,456
Land, E. H., 435, 436, 459
Landau, L., "324, 440
Lang, J., 620
Lange, J., 103, 115
Lange, K. R., 119, 121, 146, 152,165,303,31/,
630, 695, 716, 726
Langenfeld, A., 205, 308. 473, 602
Langenscheid, F., 528, 607
Langford, J. F., 503, 605
Langmuir, I., 622, 714
Langston, W. G., 393, 448
Lanning, F. C., 741, 751, 790. 792
Lanzet, M., 459
Lard, E. W., 492, 604
Laroche, J., 742, 790
Larrabee, G. B., 624 7/5
Author Index
,
Lasater, J. A., 715
Lasierre, R., 311
Laskowski, J., 647, 718
Laufer,S., 615. 616
Langner, R., 618
Laurell, H., 800
Laurent, T. C., 436, 459. 460
Laves, F., 482, 604
La vrov, L. 5., 448 "
Lavrova, K. A., 606
Lawrence, M., 110. 361,445
Laws, W. D., 749, 791
Lawson, D. 5., 29, 108
Lazarescu, I., 780, 799
Lazareva, E. A., 82, /13
Leal, 0., 726
. Leban, M. I., //0, /11
Le Bihan, M.-T., 20, 107, 161, 170
Le Bot, J., 715
Le Bouffant, L., 800
Leckie, J. 0., 620, 665
Leclat, P., 796
Lederer, L., 330, 349, 441
Le Done, D., 619
Lee, C. F., 471,601
Lee, L. H., 689, 726
Lee, P. L., 719
Lee, S. D., 800
Lee, W. M., /69. 421, 453
Leechman, F., 449
Leftin, H. P., 728
Legal, C. C., 335, 442
Lehman, R. L., 76: 77, 1/2. 135, 166, 606
Leitrneier, H., 79, JI2
Leko, V. K., 76, 112
Lemmermann, 0., 749, 792
Lenel, F. V., 587, 617
Lenher, V., 5 IS, 550, 606. 611
Lenz, C. W., 140, "141, /67
Leo, R. R., 91, 113. 730, 788
Leonard, R. A., 766, 796
Leont'ev, E. A., 480, 603
Le Page, M., 526, 607, 6/0, 610
Leptien, E. E., 455
Le Rat, B., 441
Lesley, W. H~, 297,310
Leslie, J. G., 787, 80/
Leuchs, H., 169
Levene, C. I., 781, 799
Levine,S., 356, 444, 664, 665, 720
Levitsky", M., 456
Lewin, J. C., 56, I/O, 735, 737, 789
Lewis, C. E., 674, 722
Lewis, G. L., 459
Lewis, T. B., 361.. 445
Li, Cassian, 448
Liardon, 0., 624, 696, 7/5
1
.
j
I
J
..
hor Index
\,
Author Index
I
I
{
1
56.606'
I
1
--819
Lichtenbelt, J. W., Th., 372, 446

'Lukomskaya, Z. T., /09. / /8
Liddecoat, R. T., Jr., 450
Luk'Vanovich, V. M., 480, 60J
Lidstrom L, 30, /08. 777, 798
Lumley, G. 1.,452
Liebau, F., 20, /06. /7/
Lundgren, K. D., 764, 79S. 797
Liebl, H., 448. 590, 6/8
.Lundie, M., 750, 792
Liede, 0., /07. 564, 6/J
Luvisi, G. W., 326,440. 45S
LieOinder" M., 57, JJO. 636,7/6. 72S
Lygin, V. 1.,516,517,606,645,648,653,
Likhaeheva, O. A., 60/
7/7-7/9,723, 726
Linall-Kiesseling. K.,460
Lyklema, J., 356-358,378,397,444.446.449.
Lind, J. C., J07
477,478, 60J, 628, 660, 664.667, 673,
Lindenthal, J. W., 460
7/S.720
Lindquist, G. M., 394, 448. 727
Lyon, R. J. P., /OS
Lindqvist, I., J08. 4S9. 796
Lyttleton, J. W., 436, 4S9
Lindsay, H~, 799
Lyubtsev, R. I., 4S/
Linford, ~. B., 448 '
Linke, W. F., 392, 448
Maatman, R. W., 306, 420, 4S2,50S, 605, 669,
Linke, Y., 792
676, 7/9-722
'
Linsen, B. G. 186. J88.306,308,478,485,493.
McAtee, J. L, 2J, /07. /70
494,498.567.600.60/. 60J. 604. 6/4,631, , ' McBain. J. W. 490. 604
McBride, R. T. 4S6
7/4. 7/S
Linton, H. R., 440
'McCafferty, E. 620, 702, 727
Lipatov, Y. 5" 727
McCann. G. D., 351,444
Lipman. C. B. 740. 790
McCarthy. G. G., 460
Lippens, B. C. 467, 494,60/. 604
McCarthy, J. J. 4SJ
Lipsett, S. G., 458
McClellan. A. L. 288, 3/0~ 466, 600
Lisitsyn, A. P., 13, /05. 788
" McClellan, W. R. 420, 4S2
List. G. R. 603
McConnell. B. L. 306
Litkovets, A. K., 713, 728
McConnell, D. G., 60J
Little. L. H. 648, 7/8. 723
McConnell. P., 448. 709, 727
Liverovskaya, N. V. 7/6
McCorkle, K. H. 225, J09, 369, 445
Lobanov, V. P., 82. JJ2 .:
McCormack, R. W. /70. 792
Lobinger, K., J79. JOS
MacCragh, A.. P. 46/
Loeb, A. L. 309, 324, 4-!0:.
McCullagh. K~ G., 794
Loeper, J. and J., 755, 769, 79J. 796
McCulloch, L., 20, /07. J58, 159, /70
Loftman, K. A., 442, 567. 6/4
MacDiarmid, J. R.,4SJ
Long, J., 567, 6/4
.
McDQnald, D. F., JJ2
Long, R. D., 359, 445
McDonald, L, 458
Longman, G. W., 503, 605
McDonald, R. 5., 7/7
Lopenski, S. A., 459
McDowell, M. J., 456
Lorentz. G. M. R., J07
McFadyen, P., 378, 446. 450
Lethe, Th., 616
McGahan, J., 44J
Lottermoser, A., 528, 607
McGarry, M. A. 135, /66
Lotzova, E., 799
McGavack, T, H., 787,80/
Lou, R. L. H., 347, 44J
McGavick, J., 511, 606
Lovering, T. 5. 750, 792
. Mcintosh, R., 475, 603
Low, M. J. D., 7/9. 723. 72S. 728
Mcintyre, J. W., 456
Lowell,S., 471,602
McKay, D. 5.,313,439
, Lowen, W. K., 44J. 444. 468,506,601,631,
McKay, J. M.,460
689,702, 7/S. 724
Mackenzie, F. T. 31,79. /05. JJ2
Lowenstam, H. A. 403, 450. 789
McLean.5., 459
Lowenstein, W., 728
MacLeod, C., 764, 795
Lubimova, O. I., 729
McMahon, W. M., 168, 457
Luck, W., 402, 449. 450
McManus, J. C., ~728
Lukashenko, G. M. 403, 450
McMillan, D.,. 328,44/
Lukes, F., 4 5 9 .
McNally, P. H., 68, JJI, 318, 440
Lukevitz, E. Ya., 730, 731. 733-735, 739,
McNicol, B. D., 669 , 675, 721
752-754, 769, 770, 781,788
McQueston, H. J., 398.449,598, 6JJ. 620
.,
---Author Index
820
McWhorter, J. R., 240, 309. 440. 6/5. 724
Macie, J. L, 743, 79/
Madden, J. E., 620
Madi, I., 381, 447
Madieley, J. D., 5IS, 606, 634, 7/6
Madsen, B. M., 16, /06
Maglione, G. F., 158, 170
Maher, P. K.., 1,2'
Main, V. R., 131, /66
Majumder, S. K.., 792 '
Makart, H., 460
Makeev, O. V., 793
Makeeva, E. D., 691, 725
Makrides, A. C., 219, 253, 287,308
Malanchuk, M., 547, 6/0
Malaprade, L., /15
Malato, M., 794
Malfitano, G., 748, 79/
Malygin, A. A., 72/. 723. 724
Man, C. Y. /68
'
Manegold, E., 234, 309, 482, 536, 604. 608
Mangravite, F. G., Jr., 447. 451
Mank, V. V., 632, 7/6 '
Manley, R. St. J.,' 361, 445
Marasas, L. W., 773, 796. 797
Marboe, E. C., 3, 57, 104. 1/0.406,450,688,
724
Marchand, R., 620
Marchegut, H. G. L., 332, 44/. 606
Marchisio, M. A., 779, 795. 798. 799
Marcie, L, 799
' ...
Margolis, J., 764, 765, 795. 796
Margolis, L., 788
. '-:
Margrove, J. L., /04. /05 ,
Mariner, R. H., 159, 170 .'0
Markova, V., 669, 673, 72/
Marks, J., 760, 779, 794. 795. 798
Maron, S. H., 347, 443 '
Maroto, A. J. G~, 662, 720. 72/
Marotta, A. J., 309
Marotta,R., 318,327,440. 442, 559, 6/2
Marron, T. V., 427, 455
Mars, E., 20I, 307
Marsden, M. P. F., 459
Marsh, A. R., III, 181,219, 253, 276, 278-280,
287,305
Marsh, H., 605
Marshall, K.., 185,306,655,656,660,7/9.720
Marshall, M. D.;: 454, 538, 609
Marsman, H. C., 131, 166
Martin, J. C., 800
Martin, M., 794
Martin, R. E., 607
Martinek, T. W., 572, 593, 615. 618
Martinez-Martinez, F. J., 453
Martynova, L. G., 109. 110
Martynova, O. I., 12, 105. 1/4
0
'
'Marvel, C. 5., 288, 3/0
Marx, G., 602. 723
Maser, M. D., 788
Maskell, E. J., 79/
Mason, J., 483, 604
Mason, S. G., 361, 445, 481-483, 603
Masson, C. R., 121, 141, 155, 164, 165.
169. /71. 173,304
Mastrianni, V., 457
Matayo, D. R., 655, 719
Matejka, Z., 334, 442
Mateyko, G. M., 436, 460
Matijevic, E., 182,306.309. 324,353,356,370,
375, 376, 378, 391, 404, 408, 411, 439, 440.
444-447. 450. 451. 461.473, 602. 668, 671,
675, 721
Matrecon (Company), 615
Matsepuro, A. D., 593, 6/8
Matsushima, K.., 108
Matsuzawa, T.., 695, 725. 726
Matyash, I. V., 449
May, G., 790
Mayer, E. F., 608 .
Mazabrard, A. R., 6/9
Maziliauskus, 5., 422, 453
Meadus, F. W., 6/8
Medalia, A. I., 227,309. 465, 600
Meffert, A., 205, 206, 308, 473, 602
Mehaffey, R. J., 6/9
Mehard, C. W., 757, 794
Meier, W. M., /69.307
Meiller, F., 616
.
, Meir-Ewart, H., 442
Meissner, H. E., 549, 6//
Meissner, H. P., 482, 509, 604
Meites, L., 95, /14, 182, 306
Melanson, B., 443
Mellor, W., 788
Mende, W. C., 6/9
Mengel, W., /69
Mercer, R. 5., 453
Merki, C., 44/
Merkushev, O. M., 448
Merliss, R. R., 759, 794
Merrill, R. C., ISO, /68,252,268,300,310,
31/,513,606
Mertens, G., 693, 727
Mertz, G., 335, 442
Mesmer, R. E., 133, /66. 181,306,411,451
Messing, R. A., 796
Messinger,S., 448
Mestes, L., 356, 444
Meye, W., 7/8
Meyer, D. E., 625, 7/5
Meyer, G. C., 591, 6/8
Meyer, K., 723
Meyer, R., 459
0167.
.,. -.,..--
Author Index
dex
57.
,
!
70,
'40.
71,
I
I,
I
0,
51
821
Meyer, W. C., 60, III

. Monet, G. P., 442
"
Monroe, E. A., 399, 403, 449. 450
Meyers, B. L., 393, 448
Meyers, C. B., 167
Montaguer, 5., 7/5
Meyers, M. N., 444
Montenyohl, V. 1.,442
Micale, F. J., 600
Montgomery, D. 5., 525, 607
Michaels, A. 5., 340, 443
Montiramani, D. P., 740, 790
Michalski, R. J., 443
Mookerjee, S. L., 503, 606
Michel, D., 719
Mooney, M., 236, 238, 246,309,361,445
Michel, R., 353, 444, 638, 7/6
Moore, E. P., 423, 424,451. 453. 454
Moore, G. E., 567, 6/4
Michels, A. 5.,482,509, 604
Moore, R. C., 793
Michon, R., 794
Micks, D. W., 792
Morachevsky, Y. U.,42, 109. 305
Morariu, V. V., 7/5. 720
Middleton, A. B., 303,3/ I
Mordovskoy, G. G., 799
Midkiff, W. 5., 93, 113
Morely, C. W., 424, 453 .
Miedreich, W., 143, 167
Moreno, E. C., 213,308
Mieville, R. L., 498, 604
Moreno-Garcia, F., 300, 31I
Migunova, L. T., 307
Morey, G. W., 7, 14,31,32,52,105.108. 118,
Migurov, E. A., 719
165
Mihm, U., 527, 607
Morgan, C. Z., 544, 610
Mikhail, R. Sh., 470, 498, 499, 501, 503, 60/.
Morgenthaler, J. J., 436, 459
604.605. 718
Morimoto, T., 630, 715. 719. 791
Mikhailov, A. 5., 37, 109
Morozov, Y. L.,616
Miller, C. E., 402, 449
Morozyuk, I. G., 95, //4
Miller, J. D., 106
Miller, J. P., 170
Morris, T. G., 798
Miller, J. R., 619
Morrison, E. 0., 792
Miller, R. E., 766, 796
Morrow, B. A., 723
Miller, S. L., 731, 788
Morterra, C., 728
. Moser, H. M., 603 .
Milligan, W.O., 545, 610
Milliken, T. H., Jr., 408,451,548,610. 727
Motohashi, N., 793
Mills, G. A., 408, 451, 548, 610. 717. 727
Mougey, C., 548, 610
Moulson, A. J., 6, 104
Mills, G. 5., 656, 719
Mills, R., 715, 720
Moulton, H. R., 458. 459
:-. :
Mountford, G. A., 714, 729
Milne, A. A., 449, 744, 791 -;,'.
Milne, D. B., 793 .
Mountford, N. D. G., 424, 453
Moyer, E. F., 563, 613
Milsson, O. I. H., 452
M uetterties, E. L., 157, 170
Milton, C. L., 445
Mukherjee, A., 132, 166
Milton, R., 99, 1/4
Mullen, J. P., 98, //4
Mindick, M., 87, 113,314,327,333,334,411,
Muller, D., 784, 800
414,439-44/.451.452.606
Muller, R., 308
Minones, T. J., 310
_..
Muller, W. D., 181,189,305
Minova, K. F., 758, 794 .
Munari, 5., 692, 725
Mironov, V. E., 166
Murai, M., 67, III, 193,307,433,458
Misawa, T., 793 .
Muranova, G. A., 459
Mitchell, J. H., 741, 790
Murata, K. J., 14, 79, 105. 112. 113,511,606
Mitchell, S. A., 600. 716
Muroya,M., 549, 611, 629, 640, 641, 715. 7/7
Mitsynk, B. M., 58.105.110.167,400,449.460
Murphy, P. J., 473, 602
Miyamoto, T., 727
Miyata, K., 725
Murray, J., 728
Muskat, I. E., 137, 166
Moehl, R. W., 527, 607
Muttik, G. G., 714. 718
Mohn, G., 730, 779, 787. 794. 799
Moises, S. G., 330, 441
Myles, T. A., 453
Mylius, F., 166,297, 3"10
Mokronosova, K. A. 798
Mysels, K. J., 358, 372, 444. 446
Molchanov, V. 5., 137, 166
Moll, W. L. H., 466, 600
Momii, T., 724
.
Naccacche, C., 7/7
Nadelmynska, H., 118, /65
Monaco, L., 795
-.... --
821
Nag, a Bo. 6/ /
Nagel, M. 7/9
Nagelschmidt, G. 760. 774. 795. 797. 798
Nagi, Y. 455
Naidu, S. R.,603. 608
Nakajima, M., 152, /69
Nakajima, T 789
Nakazato, H. 79/
Naono, H., 630,715. 719
Napper, D. W 313, 324,327,359,439. 440.
445
Nardell, E., Jl2
Nash. T., 797
Nashed, S., 7/8
Nasrallah, E. T. 157, .170.3/0. 799
National Lead (Company), 6/8
Nauman, R. V., 129, 131, 138, 166
. Nauroth, P., 6/2
Naveau, H., 723
Nayar, H. S. 587, 617
Neal, J. T., 170
Nebera, V. P., 448
Nechtsehein, J., 658, 720
Neimark, I. E., 5 10, 519, 530, 532, 533, 537,
541,6056/0. 695, 720, 722. 726
Nelson, E. S., 298,3/0, 393, 448, 763, 795
Nelson, F. M., 444. 471, 60/
Nemetny, G., 391, 447
Nemetschek, Th;, 24, 107, 556, 6/4
Nemodruk, A. A., 197,307
Nepomuk von Fuks, J., lJ7 r
Netting, D. I., 457 .
.
Neugebauer, W., 566, 6/4
Neundlinger, N., 334, 442
Neurath, F. Z., 96, J14
.'
Newell, W. J., 454. 620
Newton, R. C., /08
Nicholas, K. E. L., 165
Nichols, O. 5., 455
Nichols, R. F., 6/7
Nickerson, J. D., 564,6/3
Nickerson, R. F., 443. 453. 454. 456. 609
Nicki, J., 608
Nicolaon, G. A., 486. 488, 539, 545, 604. 609
Nicoll, F. H., 458
Nielsen, A. E., 78, Jl2, 219, 278, 308. 3/0
Nielsen, L. E., 361, 445
Nienberg, H., 762, 795
.
Nikitin, Yu. 5.,493,604. 609. 6/0. sit. 610
Nikitina, N. Z., 6/4
Nikolaev, A. F., 448
Nikolaev, A. L., 7/9
Nikolaev, A. V., 82, III
Nikolaeva, No, 691, 725
Nikolics, K., 456
Nikolina, V. Y., 567, 614
Nikorskii, B. P., 411,45/.6/9
Author Index
'
Nilsson, 0., 459. 796
Nishimura, So, 70 I, 715. 716
Nitsche, S., 6/6
Niyogi, S. K., 513, 606
Noble, R. D., 453
Noguera, G. E., 79/
Nohejl, T. C., 455
Nolinov, I. I., 728
Noll, W., 630, 7/5
Nooner, D. W., 788
.
Nordberg. M. E., 31,41,45,65, /09,460,549,
551, 6J1. 7/7. 723
Nettle, M. C., 794
Novikova, V. N., 654, 7/9
Novoselov, A. A., 82, lJ3
Novotny, M., 61/
Novy, L. E., 457. 458
Nyamah, D., 577, 6/6. 621
Nynas-Petroleum, A. B. (Company), 6/4
Obba, U., 606
Oberlies, F., 733, 788
Oblad, A. G., 408,45/,548,610, 717
O'Connor, D. J., 390, 447, 686, 724
O'Connor, J. J., 593, 619
O'Connor, T. L., 67, Ill, 139,/67, 200,307
Odler, I., 605 .
Oehler, J. H., 45, 91, 109. us. 313,439. 733,
788
Ogenko, V. M., 728
Ogino, K. 330, 44/
Ogura, H 0' 729
Ohlmeyer, P., 801
Ohman, J., 348, 443
Ohsawa, K., /68
Okada, H., 456
Okamoto, Y., 752, 791
Okawa, K., 740, 790
Oken, A., 144, 167
Okkerse, C., 31,46,47, /09,180,185,186,188,
210,252,305.306.308,437,460,498,518,
S 19, 523-525, 532, 604. 607. 608.. 624, 637,
~,
i
,
l
640, 7/01
Okomoto, G., 81, / /2
Okuda. 5., 475, 603
Okura, T., 11,43, 67, 81, 101, /05. /09. Ill.
in. 1/4. 193, 197,202,301,302,307. 3J1.
351,433,444. 458
Oliver, C. 5., 575, 616
Oliver, J., 448
Oliviero, G., 769, 797
Olpp, V., 801
Olson, C. M., 442
Olson; F. A., 107
Olsson, K. 217, 308
Olzewski, Wo, 800
O'Melia. C. R., 379, 380, 446
.., -:...-r Index
Author Index
Onodera, I., 740, 790
Oparin, A. 1.,731, 788
Opie, J. W., 448
Ordiales, E. 1I8. 165
Ordway, F., 25, 107. 220, 308
Ordway, J. M., 137, 146, 166
Or6, J., 788 .
O'Shea, B. J., 453
Oshima, F., 179,305,331.44/
. Osind, T. J., 494, 604
Osinga, Th. J., 601
Oster, G., 449
Ostrovskaya, I. S., 800
Ostwald-Freundlich effect, 5I
Otsubo, Y., 413, 452
Ottewill, R. H., 324, 381, 391, 440, 447
Otto, W., 107
Outouma, H., 518, 607
Outridge, L., 655. 719
Ovcharenko, F. D., 606
Overbeck, J. Th. G., 108, 225, 309, 324, 374,
375, 440. 443. 446
Ozeroya, L. V., 799
,0,549,
0,307
9. 733,
:6, 188,
8, 518,
~, 637,
'J. 1//.
7. 3//.
}
:
Paasche, E., 789

Pabst. A. 20. 107
Paden. W. R., 741, 790
Pader, M., 618
Pakunov, J., 459
Pancratz, H. S., 736-738, 789
Pankhurst, K. G. A., 715
Papir, Y. S., 402, 450
Parfitt, G. D., 94, 113, 465; 600
Pariiskii, G. B., 729
Park, Y. D 792
Parks; G. A . 188,306, 356, 444. 660, 720
Parry, E. P., 728 .
Parry, W. D., 790
Parsons, B. I., 525, 607
Passino, R., 441
Paterson, M. S., 30, 73. /08. // I, 778, 798
Patil, A. S., 461. 613
Patrick, W. A., 511, 545, 606, 610. 646, 7/7
Patrikeev, V. V., 553, 61 I
Patton, R. "H., 148, 168
Patton, R. L., 18, 106
Patty, F. A., 800
Paudert, R 728
Pauling, L., 288,310,407,451,551,6//
Pavelchek, E. K., 74, I I I
Pavlic, G. E., 617 .
Payne, C. C., 455. 456
Payne, D. A., 471, 602
Payne. J., 455
Pe, J., 789
Pearlman, M. B., 457
Pearsall, N. N., 795
823
Pearson. L. L., 606

"
Pearson. R. G., 446. 721
Pecchiai, L., 796
Peglar, R. J., 723. 728
Peinemann, N., 750, 790, 792
Pelts, C. R., 454
Pence, R. J., 793
Penner, S. S., 248, 309, 368, 445
Perezel, S., 114
Peres. G., 755, 756, 769, 793. 797
.
Peri, J. B., 716
Perin, A., 760, 795
Pernis, B., 766, 796
Perolin Company, 452
Perram, J. W., 356, 444, 664, 720
Perry, J. H., 603
Perry, S. G. 620
Persson, B. S. S., 452
Pertoft. H., 346, 350, 436, 443. 459. 460. 736
Perveev, A. F., 459
Peschel. G. 628, 715
Peter, H. 794
Petering, L. B., 790. 791
Peterson, L. E., 448
Peterson, R. E., 459
Peterson, W. H., 615
Pethica, B. A., 635, 640, 646, 647, 717. 718
Pevzner, I. Z. 136, 166. 728
Pfeifer, H. 719
Pfleger, H. 97, 107. 114, 247,309
Pforr, G. 723
Philadelphia Quartz Company, 169
Pickles. D., //4
Pierce, C., 471, 494. 601.604
Pierce, J. A., 537,609
Pillemer, E. A., 746. 791
Pimentel, G. C., 288,310
Pinkney, P. S., 167,207, J08. 451
Piret, S. L., 110
Piryutko, M. M., 42, /09. 305
Pitkethly, R. C., 728
.
Pitrot, A., 6 I 9
Pittsburgh Plate Glass (Company), 613
Pivinskii, Yu. E., 361, 445
Plachenou, T. G.,' 528, 607
Plachinda, A. S. 605
Plaisted, A. C., 606
Plakhotnik, V. N.,45, 109
Plambeck. L., Jr., 252,261,267,310
Plank, C. J., 517, 606
Pleith, K., 603
Pliskin, W. A. 76, 77, //2
Plooster, M. N., 628, 715
Plum. H., 457
Pluta, L. J;, 452
Poehlein, G. W., 350, 444 .
Pohle, W., 7/7
..,
j
.,.
:'
-----
Author Index
824
.'
"'i
Pohlman, S. L., 107

Pohlmann, G., 733, 788
Polak, F., 619
Polet, C., 755, 793
Policard, A., 778, 794. 798
Polikarova, R.. 649, 718
Pollack, S. 5., 438, 460
PoUard, L., 423, 453
Polyakov, M.S., 451
Polyakov, M. V., 503, 553, 605, 6/1
Poly nov, B. B., 733, 788
Polzer, W~ L., 307
Po matti, R. C., 309
Pommier, B., 471,602
Ponnaiya, B. W. X., 751, 790, 792
Ponomorev, E. I., 528, 608
Popov, A. 5., 12, 105. 1/4
Popova, S. V., 16, 106
Porai-Koshits, E. A., 504, 605
Pore, J., 31/
Porod, G., 504, 605
Porter, M. C., 340, 443
Porter, R. A., 191,307,387,447
Poskus, D., 602
Posner, A. M., 473, 602
Postma, J., 173,305
Pott, G. T., 669, 675, 721
Potter, C., 460
Potter, H. N., 566, 613
Povick, M. J., 434, 458
Power, W. H., 441
Powers, D. H., 425, 454. 456
PPG Industries (Company), 617 ~
Praetorius, M., 334, 442, 510, 605
Prajapati, M. N., 333, 44/
....
Pramer, D., 800
Prater, C. D., 420, 452
Preece, R. E., 454 .
Prener, J. 5., 620
Prenzlow, C. J., 603
Preston, L., 533, 608
Preston, W. J., 452
Price, C. A., 459. 460
Price, E. W., 6, 44, 105
Prigogine, M., 652, 718
Prijs, B., 6/2
Prikhid'ko, N. E., 137, 166
Proda n, L., 798
Proust, J. E., 683, 724
Pruett, R. D., 457
Prusky, S. C., 742, 790. 792
Puchkov, Y. G., 6/4
Puddington, I. E., 4/2,537,575,609.6/6.6/8
Pullukat, T. J., 676, 722
Purdy, W. J., 793. 794
Pure Oil (Company), 6/8
Puri, B. R., 7/5

Pytkcwiez, R. M., 14,31,105
"
Quirk, J. P., 473, 602

Rabe, J. R., 729
Rabin, E. A., 105, 788
Rachkovskii, R. R., 723
Rackow, B., 723
Radc:zewski, O. E., 239, 309, 328, 335, 44/,
575, 606
Raggon, F. C., I/O

Rahman, Q., 110
Raibmann, B., 59, /10. 791
Raikhlin, N. T., 799
Raiklin, I. M., 796
Rainard, L. W., 426, 455
Rainone, N. J., 459
Rakhlevskaya, M. N., 656, 719
Rakusin, M. A., 743, 790
Raleigh, G. J., 740, 790
Ralph, B. J., 712, 728
Ramakrishna, V. R., 502, 605
Ramamurthy, P., 723
Rambler, M., 788
Ramsay, J. D. F., 482, 483, 485, 499, 550, 603.
604,61/
Ranade, M. B., 407, 451

Rand, B., 605
Ras, H. J. M. C., 372, 446
Rasche, B., 774, 797
Rassln, E. H., 454
Rath, E. H., 457
Rath, P., 107
Rathmell, R. K., 118, 165
Ratinov, V. B., 74, III
Raupach, M., 307
Ranter, R., 458
Ravey, J. C., 449
Rayner, J. H., 620
Read, A. D., 673, 674, 722
Reardon. E. M., 460
Rechter, H. L., 453
Reed, R. A., 95, 113
Rees, A. L. G., 225, 309
Reeve, R., 38, 109
Rehner, J., Jr., 582, 6/7
Reider, M. J., 454
Reierson, D. A. 793
Reifenberg, A., 750, 792
Reiff, G., 59, 110. 169
Reik, R., 566, 6/4
Reimann, B. E., 739, 789
Reimsehuessel, H. K., 714, 729
Reis, H. E., Jr., 548
Reise; R., 21, 97, /07, / /4
,
Index
Author Index
441,
jO,603,
---_.
Remers, N. A., 455

Remes, N. R., 572, 615
Renge, P., 451
Reuter, G. L., 6/8
Reuter, R., 318, 370, 421, 424, 439, 440, 441,
445, 453, 454
Reven, L. E., 316, 318, 327, 331, 334, 439, 440,
441, 451, 606
Rey, L., 778, 798
Reynolds, J. H., 766, 796
Rhee, K. H., 723
Rice, S. A., 3, 104
Richardson, E., 59, lJO, 253, 285, 307, 310
Richmond, R. C., 634, 716
Richter, H., 106,239,309,328,335,441, SIS,
606
.
Riddeford, A. C., 715
Rideal, E. K., 475, 603
Ridgewell, G. L., 306, 710
Rieck, G. D., 30, /08
Ries, H. E., Jr., 393, 448, 538, 539, 545, 547,
609,610
Rietz, G., 164, 17/
Rigterink, M. D 460
Riley, J. P. 98, 114
, Rinehart. R. W., Sr., 100, 114
Ringe, P., 610
Rios, A., 799
Ritchie, P. D., 30, 108
Ritsko, J. E., 562. 613
Ritter. H. L., 503, 605
Ritter, H. S., 527, 607
Robb, L. E., 617
Roberson, C. E., 307
Robert, L., 655, 719
Roberts, B. F., 604 .
Roberts, J. P. 6, 104
Robillard, K. A. 350, 443
Robinson, E., 541,609
Robinson, J. C., 431, 457
Robinson, J. M. 459
Robinson, J. W., 104, 178,305.310
Robeck, OK., 77, III
Robson, W. D., 56, lJO
Rochester, C. H., 306. 655, 656, 719. 710
Roess, L. C., 223, 309
Roev, L. M., 717
Rohrsetzer, S., 382, 447
o.
Roka, L., 795
Roller, P. S., 48,105, 124, 125, 126. 165, 181,
305
Romig, O. E., 457
Romos, R. deC., 5 10, 606
Roney, B. H., 619
Ronquist, G., 459. 796
Rooney. T. D. 170
825
Rootare, H. M., 603
Roquerol, J . 605
Rosen, J. J., 790
Rosenberg, N. W., 68, 1/1, 318. 440
Rosenheim, A., 59, 110, 791
Ross, L C., 475, 603
Ross, R. A., 541, 609, 654, 718, 719
Ross, S., 359, 396, 445. 448
Rossetti, J. F., 548, 610
Rossi, C., 692. 715
Rossman, G. R., 403, 450, 789
Rotoru, G., 780, 799 .
Rouquerol, F., 605
Rouschet, P. G., 649,7/8. 728
Rouweler, G. C. J., 374, 446
Row, R. D., 104
Rowe, 'J. J., 7, 14,31,32,45,52,105. 106. 108.
109
Roweler, G. C. J., 324, 440
Rowsell, E. V. 766, 796
Roy, R., 106, 409, 451, 460
Roy, W., 616
Rozen, R. B., 728
Rozen, Y. B., 160
Rozsa, P., 458
Rozzel, T. C., 676, 722
Rubank, S. C., 306
Rubin, B. F., 593, 618
Rubio,J., 383,395,397,447,448. 704,708.727
Ruehrwein, R. A., 380, 388, 446
Rule, J. M., 242,288,309,310,312,314,339,
359,439,453.. 556,612
Rum, C., 567, 6/4
Runggas, F., 457
Runham, N. W., 738
Rupprecht. H. 448, 590, 618, 656, 719. 724
Rush, R. I., 545, 610
Rusher, R. L., 423, 424, 426,453,454.455,456.
457
Russel, E. R., 490, 604
Ruttenberg, F. W., 723
Ruttloff, H., 528, 607
Riittner, J. R., 764, 795
Ruzicka, Z., 602
Ryabin, A. I., 82, lJ3
Ryabinina, T. L. 620
Ryerson, L. H., 602
Ryke, A. M. 350, 443
Ryss, 1. G., 45, 109
Ryzhenko, B. N., 132, 134, 143. 166. 167
Ryznar, J, W., 414.452.455, 458
o
Sabake, H., 795

Sabatier, G., 32, 108
Sacks, T. J., 444 .
Saffioti, U., 781, 799
826
,.
"
St. John, D. 5., 615, 724

Sakabe, H., 30, lOB "
Sakata, M., 456
Saleck, W., 459
Salisbury, R., 758, 794
Salomka, K. A., 728
Salvador, A., 582,617
Sammet, K., 792,
Sams, R. H., 94, 1/3, 16B
Samusenko, A. P., 82, /12
Sanchez. M. G., 1/3,332, 441, 561, 576, 612.
6/6
Sanchez de Alaiz, M. J., 799
Sandell, E. B., I, 2
Sander, O. A., BOO
Sanders, J. P., 390, 447
Sanders, J. V., 398-401, 449, 686, 724,744,791
Sane, R., /67San Pedrero, P.,3/0
Santschi, P. H., 195,307
Sanyal, P.,307
Sapienza, M. S., 443
Sasaki, B., 75, 11/
Sasaki, K., /6B
Sasamoto, K., 792
Sauer, F., 755, 793
Sauer, H. I., 794
Saukel, H., 687, 694, 724. 725
Sawai, H., /69
Sayee, I. G., 565, 6/3
Scanlon, J. J., 619
,
Schaefer, D. P~, 338, 442. 451. 455
Schaeffer, H. M., 396, 448 :. ' ~
Scharf, B., 516, 527, 606. 607
Schaupp, K., 454
.::.
Schay, G., 602
Scheel, L. D., 758, 764, 794. 795
Schench, H., 79/
Schendel, G., 59, 110. 79/
Schenk, J. E., 192,307,669,675, 72/. 722
Schepalin, K.' L, 723
Schepers, G. W. H., 77 J, 774, 782, 794. 797.
BOO
Scheraga, H. A., 391, 447

Scherban, J. D., 305
Schick-Kalb, J., 4.52. 620
Schindler, P. W., 182, 184, 195,306,307. 381,
44,7, 660, 672, 674, 720
Schlaffer, W. G., 542, 544, 6/0
Schlatter, R., 455
Schlecht, W. G., 5 II, 606
Schlipkdter, H. W., 60, //0,767,779,781,796.
798. 799
Schmal; D., 794
Schrneiss, U., 6/8
Schmidbaur, H., 192, 307
Schmidt, D. L., 456
Author Index
Schmidt, E., 796
"
Schmidt, M., 192, 307
Schmidt, P. W., 349, 443
Schmidt, R., 790
Schmitz, F. T., 6/9
Schnabel, W., 729
Schnaidman. I. M., 796
Schneider, M., 57 1/0,383,447,667,720.723
Schneider, R. H., /67
Schniirch, R., 335, 442
Schober, P., 454
Schock, R. V., Jr., 304, 311, 410,45/
Schofield, P. J., 712, 728
Scholl, 0., 1/4, 787, 80/
Scholten, J. J. F., 504, 605
Schopf, J. W., 88, 9Ji 1/3, 733, 788,
Schott, G., 179,30.5
Schuchard, M., 1/4, 179, 180,305
Schueller, K., 603
Schumacher, D. F., 455
, Schumann, E., 82, / J2
Schutt, B., /67
Schutte, D., 6/9
'Schurz, J., 330, 44/
Schwab, G. M., 790
Schwartz. A. B., 527, 532, 54~, 607-6/0
Schwarz, K., 756, 757, 793, 794. 795
Schwarz, R., 28, /06. /07. 154, /68. /69. 179,
181, 189, 199,251,253,254,305,564,6/3,
767, 768, 796
Schwarz, V. R., 515,606
Schwerin, B., 419, 4.52
Scoedel, W., 770, )97
Scott, B., 225, 309
Scott, D. W., 217, 308
Scott, G. D., 483, 604
Scott, R., 89
Scott, R. A., 91, / /3
Sears, G. W., Jr., 124, /6.5. /68,203,205,253,
285,308.3/0, 353, 356, 360,403,404,444.
453. 458
Sebestian, I., 599, 620. 62/
Secord, R. N., 6/4
Sedlack, W., 731, 788
Sedova, I. V., 307
Sec, M. J., 537, 609
Segnit, E. R., 398-400, 449
Segura, M. A., /68
Seifert, H., 796
Sekora, 0., 349, 443
Self, J. M. 459, 483
Selikoff, I. J., 783
Sellers, J. W., 582, '6/5, 617
Semenov, G. I., 793
Sernpels, R. E., 649, 7/8. 728
Sen, K. C., 512, 516. 606
Sen, S. P., 603. 608
.ndex
),,723
. 179,
.6'
,253,
,444,
Author Index
Senez, M., 443
Serpinet, J., 424, 603
Serpinsky, V. V., 491,604,626, 715
Serratosa, J. M., 725
Seward, T. M., 181,306
Seymour, R. B.-, 456. 458
Shabynina, N. K., 798
Schaeffer, V. E., 455
Shafer, M. W" 409, 451
Shannon, R. F., 334, 442, 454
Shapiro, I., 223, 309. 444.473,602,631,650,
715. 718. 723
Shapiro, L, 101, Jl5
Sharma, S. K., 141, 167
Sharp, S. S., 619
Shartsis, L., 110
Sharygin, L. M., 528, 607. 608. 72J
Shaw, C., 452
Shaw, H., 613
Shaw. J. N., 382, 447
Shay, C. W., 445
Shcherbakova; K. D., 702, 727
Shea, F. L., 460 .
Shebl, F. A., 503, 605
Sheer, C., 613
.
Sheidina, L D., 279, 310
Sheinfain, R. Yu., 510, 519, 530-533, 537,
606-609. 720
Shell, T., 453
Shelly, W. B., 759, 794
Shelton, B., 565, 613
Sheludko, A. 359, 445
.
Shelyakova, E. M. 303, 3J1 ~,
Shemyakina, O. N., 82, Jl2 .
Shengeliya, K. Y. 7J7
.'
Shepelev, Y. F. 155. 169
Sheppard. R. A., 20. 107
Shereskefsky, J. L. 490, 604
Shevets, D. I., 713, 728
Shigeyasu, A., 792
Shima, I., 108
Shimada, M., 452
Shimano, M., 168.456
Shimazaki, M., 701, 726
Shimizu, M., 728
Shingles, T. 528, 605, 607
Shnaidman, I. M. 799 _
Shock. S. P., 446
Shoemaker. E. M., 16, 106
Shoup, R. D., 145, 146, /67. 168,372,422,547
Shscherbakova, K. D., 7/4
Shtyrenkov, E. V., 121, /65
Shuin, T., 476, 603
Shuldner, H. L., 135, 166
Shull, C. G., 2.23, 309, 469. 476, 601, 603
Shul'man, Z. P., 593, 618
Shuryshkina, G. K., 82, Jl2
827
Shvets, V. A., 722
"
Shyluk, W. P., 393, 448
Siegel, S. M., /70
Siever. R., 13,32,91, 105. 108. JlJ, 735, 789
Siffert, B., J07
Signer, R., 26. 107, 223, J09
Silberberg. A., 394.448 .
Silberger, J., 566, 61J .
Sillen, L. G., 132
Simha, R., 361. 445
Simko, F. A., Jr., 408, 422, 451-454, 457. 458
Simmler, W., 107. 308
Simmons, D. 454
Simmons, R. L., 799
Simon, A. /07
Simon, E. M . 790
Simon. H. 107
Simon, I., 728
Simpson. E. A., 335, 442, 528, 607, 692, 725 .
Simpson, J., J06. 720
Simpson, V. P., 168
Sinclair, D., 253. 281, JIO
Sing, K. S. W., 465, 470, 471, 488, 493, 494.
498. 499. 502, 518. 600-602, 604-606, 652,
718
Singer, N., 725
Singh. B. N., 785, 800
Sippel, R. J., 316, 373, 4J9. 4.45. 525,607
Sirianni. A. F., 537, 575,609. 612, 616. 618
Sivararnakrishnan, N. H., 388, 447
Skalkeas, B. G. 454
Skalny, J., 503, 605
Skinner, B. J., 17; 106
Skinner, S., 110
Skryshevskii, A. F., 105
Slaughter, J., J08
Sleddon, G. J., 461
Sleex, M., 635, 7/7
-Slinyakova, I. B. 530. 533. 574, 608. 615
Slipchenko, V. A., 303. JJI
Sliwinski, S., 217,308
Slocum. J. 404, 450
Slovetskaya, K. I.. 702. 727
Small, H. 350. 443
Smellie, R. H., 388, 447
Smirnova, H. G., 460
. Smirnova, M. F., 57. /10
Smlrnova, Z. G., 568, 6/4
Smit, W. 664, 720
Smith. A. F., 449
Smith, A. L., 308
Smith. D. A. 582, 6/7
Smith, D. R., /68 ~
Smith. E., 338. 447. 448. 455
Smith, F. A., 20, /07
Smith, G. S., 79/
Smith, G. W., 673, 674. 72/
---_.
828
Smith, H. B., 456

Smith, J., 793
Smith, K., 403, 450
Smith, M. D., 308
Smith, V. E., 789
Smith, W. R., 337. 442,567, 6/4
Smitham, J. B. 327, 440
Smith-Johannsen, R 431, 457
Smithson, F., 106. 790
Smolin, Y. I., ISS, 169
Snelgrove, J. A. 475, 603
Snell, C. T . 98. 1/4
Snell, F. D. 98, I J4
Snell, F. D. and C. T. 101
Snoeyink, A., 624, 7 J4
Snyder, L. R., 624, 643, 645, 652, 7/4. 7/7.
727 '
Snyder, O. E., 66, / / 1, 312, 314. 333, 347,403.
419.439
Snyder, W. T. 423, 453
serr, K., 482. 604
Soffge, K. H. 770. 776, 797
Sokolova, R. S., 459
Sol bakken, A., 602 '
Sole, M. J., 118, 165
Solomonova, I. N., 726
SoItiuskii, N. M. 306
Sommer, A. L. 751. 792
Soni, S. L. 790
Sonnenschein. W I J4
Sorensen, R. T., 396; 448. 688, 724
Sortwell, E. T. 453
Sosman, R. B. I, 2, IS. 16.106
Sowards, D. M. 420. 452',
Sowman, H. G. 454
"
Spalink, F. 165
Spencer, R. W. 150,168,252.268; 269.300,
303,310.311. 513,606
Spencer, W. B., 337, 442, 567, 6/4
Spitsyn, V. I.. 729 '
Spittle. J. H., 309
Sprecher, A., 740, 790
Springer. R. A. 655. 719
Spychalski, R.,46. 109
Squibb, E. R. and Sons (Company), 618
Sramik, J . 82. ll2
Sreenivasan, A., 748, 791
Srinivasan. R. 459
Stacy, B. D. 801
Stade, H. 139, 141, 167. /70.221,307.308
Stadt, H., 180, 305
Stalder, K., 760, 78 I, 795, 799
Stana, R. R., 586. 617
Stanley. L. N., 459
Stanton, J. H. 306, 675, 676, 720
Starer-Mendes, H., 720
Starodubtsev, S. V~. 728
Author Index
..
Stas, O. P., 532, 608

Stassart, Mo, 82, us
Staudinger. H., 767, 796
Staudinger, J. J., 758, 794
Stavrinou, S. C. 76, 77, 112
Steck. R. E., 168
Steebels, J. M., 460
Stein. H. N., 460
Stenger, V. A., 669, 674, 721
Stephan, W. 795
Sterges, A. J., 784. 800
Sterling, C., 74 I, 790
Stettler. L. E., 718
Stevels, J. M., 460
Stevens. T. J., 399, 449
Stich, W. K. /68
Stlcher, H., 75, lll, 751, 792
Stickels, J., 445, 447
Stiles, A. B., 420, 452
Stinson, J. R. 796
Stischov, S. M., 16, 106
Stober, W., 1,2, 16,30,31,33,34,36,37,41,
52,57,63,64, 77, /06. /08. 109.21 1,239,
308. 309, 328, 335,404, 44/. 442. 564,613,'
624, 636, 64 I, 654, 689, 69 I .692, 694, 696,
7/5-717. 719. 724-726. 760. 770-772. 774.
777, 778, 781. 795. 798. 799
Stoisets, It F., 350, 444
Stone, F. S., 600
Stone, I.. 744, 79/
Stone, M. G. T., 745. 79/
Storks, K. H., 798
Storrow, R. R. 456
Stossel, E., 452
Strachan. M. N., 454
Strasburger, E., 79/
Stratton, R. A., 394, 448. 727
Straub, F. G., 82, ll2
Straube, B., 452. 620
Straumanis, M. Eo. 374, 405. 440
Strauss, C. Mo, 77, //2
Strazhesko, D. N., 182, 183, 186. 187.305.306.
356, 444. 5 14, 523, 600. 606. 607. 6/2.
723
Strecker, F. J., 781, 794. 799
'
Streicher, J. S. 461
Strelko, V. V. 63, II 1,211.213,305. 306. 308.
553.6/2.6/7,637.677, 712, 7/6. 722. 728.
731, 788
Stremouskii, R. A., 617
Strickland, J. D. H., 96, I J4
Strickler, Ao, 444
Strolle, C. H., 456. 457
Stross, F. H., 471, 601. 615
Struckman. Co; 42, 109
Strufe, R., /69
Stryker, L. J. 353, 444, 473. 602
no.
.,.
Index
----
Author Index
Stuart, E. B., 547, 6/0
Stubbings, W. V., 448
Stumm, W., 191, 195,303,307. 3/0, 379, 380,
446,664,669,672, 720. 72/
37, 41,
,239,
~, 6/3,
~, 696,
774,
'5.306.
i.r.
6.308.
2.728.
Sturm, L., 6/8

Styles, J. A., 773, 797
Suchard, M., /66
Sueiu, I., 798
Sud, R. K., 7/J
Suess, W., 6/8
Sugai, I., I 17, /65, 225, 309, 479, 603
Sugimoto, T., 240, 309
Sugiura, M., 704, 727
Suite, K., 66, / / /
Sukhinina, L. A., 448
Suleek, Z., 674, 722
Sullivan, C. W., 789 .
Summerton, J., 773, 797 .
Sun, G. C., 453
. Sundman, J. A., 792
Sutherland, D. N., 226, 227, 309, 388, 394, 447
Suwa, M., 568, 6/4
Suzdalev, I. P., 605, 674, 722
Suzuki, K., /68. 457
Svendsen, S. S., 563, 6/3
Swan, J. W., 706, 727
Swartzen-Allen, S. L., 439, 46/
Swensson, A., 264, 777, 795, 797. 798
Swidam, R. C., 159, /70
Syers, J. K., 31, /08
Symons, N. K.,457
Syracuse, M. G., 337, 442
Sysoev, E. A., 60/, 712, 7/8, 728
Sytnik, L. V., 602
Szabo, Z. G., 114, 447
Szarvas, P., 99, //4
Tabak, G., 7/9
Tabor, D., 374, 446
Tabouriech, F. P. M., 606
Tachika, J., ,729
Tadros, E., 378, 446, 667, 673, 720
Tadros, Th. F., 356, 357, 397, 444. 449, 664,
705, 706, 720. 727
Tagieva, M. M., 729
Tahara, M., 152, /69
Tai, A-P., 186,213,306.308
Takagi, J., 568, 6/4
Takahashi, H., 691, 725
Takahashi, M., 79/
Takano, K., 450. 452
Taki, K., 66, / / /
Takigawa, K., 606
Talalay, J. A., 458
TaUberg, K., 675, 72/
Talpade, C. R., 333, 44/
Tamagusuku, 5.,476, 603
829
Tamele, M. W., 451. 727
..
Tamura, H., 456
Tanaka, A., 792
Tanaka, M., /68.456
Tanako, J., 6/4
Tanford, C., 388, 447
Taniguchi, K., 673, 674, 722
Tanner, D. W., 371,445
Tao, S. J., 712, 728
Tarasevich, Y. I., 606
Tarnpol, M. S., 460
Tarshish, I. B., 753, 792. 793
Tarutani, T., 98, 101, //4, 203, 213, 253, 282,
307.308
Taueh, E. J., 118, /65

Taulli, T. A., 539, 609
Tawashi, R., 593, 6/9
Taylor, A. H., 635, 7/8
Taylor, A. S., 800
Taylor, H. F. W., 143, /67
Taylor, J. A. G., 475,603,635,646,647, 7/7,
718
Taylor, L. J., 6/7
Teheurckdjian, N., 597, 620
Teicher, H. 332. 44/, 579,6/7
Teichner, S. J., 471, 486, 488, 504, 539, 545,
567, 602. 605. 609. 6/4. 6/9
Teller, E., 467. 601
Temple, K. L., 785, 800
Terai, R., 117. /65
Terashima, S., 94. /13
Teravanti, T. 44/
Terenin, A. N.; 727
Ter-Minassian-Seraga, L., 448, 473, 602.
682-684. 724
Ternan, M., 470, 601
Terrell, B. C., 449
Tertykh, V. A., 723. 726. 728
Teter, J. W., 536, 609
Teufel, A., 528, 607
Theile, M., 19, /06
Theis, C., 392, 448, 709, 727
Theissen, P. A., 46, /07
Thereault, J. R., 442
.
Theyer, F., 29, /08
Thilo, E., 134, 139, 141, 143, /66. /67, 180, 199.
305. 307
Thoma, K., 448. 724

Thomas, C. L., 407, 45/
Thomas, D. G., 361, 445
Thomas, I. L., 22S, 309, 369, 445
Thomas, I. M., 527, 607
Thomas, J., 6/5 ~
Thomas. J. R., 727
Thomas, K., 689, 692, 724, 770, 797
Thomas. W., 698, 726
Thompson, A. C., 45/
--_.
Author Index
830
Thompson. C. B. 454
Thompson-Gibbs effect. 5 I
Thompson. J. (Lord Kelvin). 488. 490. 604
Thompson. K. D. 674. 722
Thompson. T. G., 96, / /4
Thompson, W. K., 632, 7/6
Thomsen, S. M., //5.458
Thomson-Houston, Francaise (Company).
6/6
Thorington. L., 459
Thorner, H. J., //5
Thorp, J. M., 536, 603.605.609,639,717. 7/9
Tilton, L. W., 164, /71
Timchenko, A. N., 800
Tingey, W. M., 746, 79/
Tiwari, R. N., 476, 603. 608
Tjok, P. B., 446
Tkachenko, N. S., / 15
Tkachenko; V. K., 82. //2
Toigskaya, M. S., 799
Tomita, T., 568, 6/4
Torres-Sanchez, R. M., 383, 447, 662. 663,720
Toth, S. J., 749, 79/
Tolir~y, A. R., 173,249,305.309.310
Tozyldo, A. J., 439. 441
Trail, H. 5., 334, 442
Tran, T. L., /7/

Trap, H. J. L., 347, 443
Treadwell, W..D., 142, /67; 210, 249, 308. 309,
312,439
Trebilcock, J. W., 724
Tredinnick, B. C., 433, 458
Tripp, T. G., 333, 336, 44/
Trivedi, A. S., 473, 602
Troemer, B., 179, 305
Trouton, F. T., 651, 7/8
Truhlarova, M., 118, /65
Tschapek, M., 186,306,383,447,662,663,
720.790
Tschermak, G. 19, /06

TselJinskaya, T~ F., 602
Tsinober, L. I., 449
Tsutsumi, K., 691, 722. 725
Turk, D. H., 471,60/. 602
Turnbull, J. 5., 388, 447
Turner, M. J., 308
Turner, N. H., 466, 600, 638, 716
Turner, V. L., 102, //5, 425, 455
Tuseev, S. E., 729
Tush. K. N., 82, /12
Tyler, A. J., 656, 716. 7/8. 7/9
Tyler, S. A., 5 I, /09, 731, 788
Uci, I., 475. 603

Uiklein, M., 620
Ukhova, T. V. 723
Ukihashi, H., 121, /65, 518, 607 "

Ullmann, E., 448. 724
Ulrich, G. D., 565, 6/J
Umemoto, K., 741, 790
Underwood, E. E., 347, 443
Unger, K., 353, 444. 452, 473, 478, 481,516,
527, 575, 577, 598, 600. 602. 606. 607. 6/6.
620. 695,.698, 700, 726
Unilever (Company), 456. 612. 6/8
Unkauf, H. C., 759
Urbain, H., //3
Urquhart, N. 5., 79/
Usher, F. L., 225, 309
Us'Yarov, O. G., 403, 450
Utsugi, H., 6/5, 695, 701, 725. 726
Uytterhoeven, J. B., /69, 307, 611, 630, 633,
635, 650, 715-718. 723-725
Vail, J. G., //3, 116, 117, 146, 162, 164, /65,
223,300,301,309.311,312,439.510,511,
525,526,578,605, 6/6. 6/7. 783, 800
Vajda, M., 99, / /4

Valentine, Basil, 91
Van Assche, J. B., 650, 7/8
Van Bernmelen, J. M., 19, /06,743, 791
Van Cauwelaert, F. H., 650, 7/8
Vand, V., 361,445
Van den Heuvel, A., 478, 603
Van den Hul, G. G., 477, 478, 603
Van der Heem, P., 559, 6/2
VanderhofC, J. W., 350, 444. 449
Van der Plas, L., /09
Vanderpool, C. D.; 563, 6/3
Van der Waals, J. D., 550, 6/ /
Van der Walls forces, 324, 550, 6/ /
Van Dongen, R. H., 611
Van Haaren, M., 457
Van Lier, J. A., 30, 31. 36, 48,49,75.77,79,
/08
Van Nerstrand, R. A., 538, 545, 609. 610

Van Olphen, H., 372, 446
Van Oosterwyck-Gastuche, M., /07 .
Van Tongelen, M., 630, 7/5, 723
Vaquero, M. G., 333, 44/
Vasak, M., 674, 722
Vassos, P., 87, 113
Vatamanyuk, V. I., 6/7
Vaughn, J. C., 303,3/ /
Veach, F., 608
Vedan, K., 435, 459
Vega, M. N., 510, 606
Veltman, L., 533, 608
Yeprekv O.; 118, /65 ~
Veremchuk, M. K., 7/9
Vermeulen. T., 181,253,276,278-280,287,305
Verwey, E. J. W. 225, 309, 324, 375, 440. 446
---_.
idex
il6,
5!6.
133,
/65,
5II,
Author Index
Vessey, C. A., 457
Vest, R. D., 252,261,267,3/0. 31l. 457
Vezina,S., 600
Vicarini, M. A., 609
Viehoever, A., 742, 790. 792
Viray, M.S., 793
Vishnevskaya, A. A., 639, 642, 644, 651, 7/7
Visser, J., 324, 366, 370, 406, 440. 445. 45/
Viswanatham. P. N., / /0
Vivian. H. E. //0, 361, 445
Vlacil, F., 59, / /0
Vleeskens, J. M., 543, 6/0. 629,634,636,640,
7/5. 7/6
Voge, H. H., 544, 6/0
VogeU, W 97, //4
Vogler. D. L., /07
Voitlinder, J. /07. /70
Voicani, B. E., 738, 757, 789. 794
VoId, R. D., 388. 447
Volk, R. J., 98, //4
Vol'kin, V. V., 528.608
Volkov, A. V., 645, 7/7
Vclkova, A. N., 710, 72/. 723. 727
VolI, M., 468, 60/
Von Bonin, W., /7/
Von Buzagh, A., 464, 600
Von Glahn. W. H., 459
Von Stroh. G. 566, 6/3
Vorob'eva, R. G., 620
Voronkov, M. G. 158. /70, 730-731,733-735,
739, 752-754, 769, 770, 781. 785, 786, 788.
796.800
,79,
Vossos, P. H., 314, 318, 327, 412, 426, 439. 440.

. 45/. 452. 454-458
Vctintsev, K. K., 739. 789
Vovchenko, G. D., 7/9
Vukasovich, M.S., 6/9
Vydra, F., 353, 444, 473, 602, 669. 673-675,
72/. 722
Vysotskli, Z. Z., /05, 175, 186-188,305.306,
356, 444. 479, 503, 514, 5 I5, 523, 553,
605607.6/2.66/.662, 712, 720. 728,731,
788
Waddams, J. A., 30, /08, 158, /70, 253, 285,
3/0
,3e
44,
Wadsworth, M. E., 44/

Wagner, E., 409, 442. 45/. 567. 6/4
Wagner, F., 751, 792
Wagner, G. H., 6/6
Wagner. H. B., 6/7
Wagner, M. P., 582, 6/5. 6/7
Wagstaff. F. E. 620
Wahl, B., 790
Wainer, E., 608
Wainwright, T. E. 450
831
Wakatsuki, T., 672, 675, 72/
-.
Wake, M., 452
Waksmundzki, A., 6//. 6/2. 620
Walker, A. J., 96, JJ4
Walker, J. C. G., 788
Walles, E. W., 456
455
Walsh, J.
Walsh, K. A., 796
Walsh, R. J . 433, 437. 458. 460
Waltendorf, W. J., 145. /67
Walther. J. V., 7, /05
Walton, A. G., 26, 54. 78, /07. / /0.219, J08,
5.;
323,440
Walton, W. H., 799. 800
Wandenbulcke, F., 74. / JJ. /14
Wannagat, U. 786
Ward, D. W., 380, 388.446
Ward. J. W., 642, 7/7
Warington, K., 79/
Warlus, J., 376, 446, 760, 796
Warren, D. /65
Wartman, J., 676. 721
Washburn, E. W., 3, /04. 504, 605
Wason, S. K., 559, 561, 6/1
Wasserberg, G. J., /08
Watase, T., 603
Watillon, .A., 374-376, 446
Watson, J. H. L., 346, 404,443.450.465,600
Way, A. P., 455
Webb, J. L., 789
Webb, J. T., 324, 440
.
Weber, W.J.,Jr. 19I,195,307,38I,447,624,
675, 71/. 711
.
.
Wegst, W F., 158. /70
Wehle, V., 153, /68. /69
Weidman, V. W., /69
Weidman, V. W., 454
Weil, W. A., 57, / /0
Weill, D. F., 37, /09
Weintraub, R. L., 98, / /4
Weis, P. L., /04
Weise, C. H., /05.' 472,602, 642, 645,646,
7/7
Weise, P. B., 609
Weiser, H. B., 555, 600. 6/2
Weiser, R. 5., 795
Weiss, A., 17,59,60, /06. /07. / /0, 157, /69;
/70. 448. 743, 748, 761, 775, 781, 796
Weiss, H. G., 631, 7/5
Weisz, R. 0., 6/7
Weitz, E., / /4. /66, 179, 180, 220, 252, 259,
O
305.308. 3/0
Weldes, H. H., 119, 121, 146, 151-153, /65.
/68. /69. 316,439-44/.457,576,6/6
Weller, W., 772, 797
Wells, A. F. 16, /06
.. ---..
Author Index
832
Williams. R. C. 403. 450. 620"
Wells, H. W., 789
Wills. J. B., 94. 113
Wells, R. C., 162, 17/
Wills, J. H., 121. 127-129, 158, /65. 166. 170.
Welsh, T. H., 6/6
458
Weitier, J . 456
Willstatter. R 179.305
Wendlandt. H. G., 12, /05
Wilson. B. H . /04
Went, C. W., 299. JI/, 395, 448, 762. 765.
Wilson. I. V 425, 455
795. 796
Wilson. J. N S42, 544.6/0
Weres, 0., 3, /04
Wilson. R. 465. 600, 605
Werner, D. 789
Wilson. W. 5., 539, 609
Werner. E. R., /68
Winkler, H., 656, 7/9
Werner, L. C. 459
Winslow, W. M., 6/8
Wesslau. H., 402, 449, 450. 577. 6/6
Winter, K., 727
Wey. R 20. /07. 161, 170. 17/
Winterton. R. H. 5., 374, 446
Weyl. C. G., 349. 44J
Winyall, M. E., 452, 512, 526. 561,606. 607.
Weyl. W. A., 3, /04. 142. /67,210 J08. 309,
613
406. 450, 540, 609. 688. 724
Wirth. D. G. Jr., 613
Whalen. J. W. 603. 642; 717
Wining. G. 630, 634. 716. 726
Wheatley. K. H 30, 108. 778. 798
Wise, S. S. 104. /05
Wheeler, E., 89
Wistuba, H 723
White, C. A., 595.6/9
Witkop, .B 789
White, D. E. 14. 79. /05. //2
Wittich, E. K. H., 107. 170
White, E. W., 608
Wittman. A., J. 2
White, J. F., 312, 332, 334,419.439.44/.538,
Witzel, F. 308
539.609
Wodtcke, F., /66. /71
White. J. W., 568, 6/4
Wohlberg, C., SO, 93, 1/2
White, L. J . 567. 614
Wojicicki, A. 167
White. P., 795
Wolf. D. R., 617
White, T. E. 699, 726
Wolf, E., 723
Whiting, F., 758, 794
Wolf. F., SJO. 547, 606. 610. 723
Whittenberger, R. T., 747. 79/
Wolf, K., 334,442,510,605
Wiberg. E., 107, J08
Wolf. P., 447. 720
Wickbold, R. 1/4
:
Wolf, R. F., 616. 617
Wiekersham. K.. A., 634. 716
Wolfcrseder. E. 448
Wiegel. E., 74, 1//
Wolff, D. A . 436, 460
Wicker. W. 139, 141. 142, lSI, 154, ISS,
Wolfgang, K., 169
/67-/69, J80. 199,203,221,-252.261,
Wolfson, L. I., 443
263-266, 307. 308. 460
Wolinsky. L. E., 456
Wieland, W.,142. /67,210,308.309,312,439
Wollast, R., 74, J/I. 181,305
Wiersema, P. H., 3,09, 324, 372,440, 446
Wolter, F. J., 152.169,315.327,331.333,334;
Wiese, G-. R., 8 (, 1/Z. 374, 382, 446. 447, 624,
359,376.439-442. 445, 508. 529. 558, 560.
659,665,668.671,674,676. 7/5. 710-722
605. 608. 612
Wiesner. W. 6/8
Wolter. H., 743. 744, 791
Wiessman, H., 749, 792
Woodward. A. I . 4J5
Wiggell, J. B., 726
Woolf. J. B. 605. 7/9
Wightman, J. P., 396, 435, 448. 458,588,6/8,
Worth. G., 793
.655, 7/9
Worthy. W 6/9
Wignall, G. D., 605
Wright, C. M . 157. 170
Wikstrom. S. A., 788
Wright, J. G. E. 560, 6/2"
Wilbur, B. C. 458
Wright. M. G. B. 149. 168. 457
Wilcox. N. D . 616
Wright, W. H. 457
Wiljes, J., /67
Wrischer, M.,.443
Wilkinson, G., 196,307
Wulf, G 52S; 607
Willcox. 0., 404, 450
Wyart, J . 32, 108
Willey, J. D., 10.20,31.38,45.58,79,80./05.
Wyatt, 1.. 797
1/2
Wydeven, T., JlO. III
Williams, D. G., 324. 440
Wynn, P. D., 792
Williams, J. R., 117, /65
----Index
5.
6.607.
333,334,
;58, 560,
Author Index
Yadrintsev, N. S., /65
Yaeger, E., 359, 445
Yakobovich, I. A., 448
Yakunin, Y. P., /65
Yamaguchi, A., 152, /69
Yamaoka, K., 6/5
Yang, J. F., 444
Yankovskaya, G. F., 306, 632, 7/6
Yano, T., 145, /67
Yanovskii, M. I., 471, 602
Yarilova, E. A., 733, 788
Yarnto, D., 602
Yates, D. E., 64, 81, tu. iu, 356-358, 444.
447, 664, 665, 7/5, 720, 728
Yates, D. M., /U, 787, 80/
Yates, P. C., 122, 153, 155, /65, /69. 184,306.
318,327,372,410,426,440. 44/,445. 45/,
453, 455. 459, 477, 529, 608. 6/6. 724
Yatsuyanage, T., 303,3/ /
Yaushev, V. M., /65
Yeager, J. L., 6/3
Yen, F. F., 60, / / /
Yonekura, A., / l I, 724
Yoshida, A., 4 J3, 452. 725
Yoshino, T., 7/8
Yosii, H., 751,792
Yotsuyanagi, T., 433 458
Young, D. A., Jr., 450
Young, G. J., uo, 588, 618, 641, 644, 7/7
Younger, P. R., 359, 445
833
Youngs, R. W., 452. 458 .

Yun, C. G., 567, 6U
Zager, S. E., 425, 454

Zaidi, S. H., l/O
Zaitsev, V. A., 568, 6/4
Zak, G. A., 733, 788
Zaki, M. R., 676, 722
Zapp, E. E., l/4
Zatsendina, T. I., 6/8
Zeichmann, W., 157, /70
Zelchan, G.I., 730, 731,733-735,739,752-754,
769, 770, 780, 781, 786, 788,800
.
Zelikin, M. B., 586, 602. 6/7
Zettlemoyer, A. C., uo, 549,597, 6l/,620,
627,650,652,700, 702, 7/5, 7/8. 726. 72.7
Zhdanov, S. P., 636, 638, 651, 7/6. 7/8
Zhuravlev, L. T., 476,543,603,6/0,631,634,
635,7/5-7/7
Zimmerman, G. 0., 445
Zimmerman, J. R., 7/5
Zisman, B., 760, 795
Zlatkis, A., 788
Zolin, S. N., 448
Zolotarev, E. M., 459
Zoltai, G., 458
Zoltavin, V. L., 528, 608
Zsigmondy, R., 533, 608
Zugravu, E., 800
.,
-.....---
Subject Index
In this index the word "silica" is to be inferred. Thus "Precipitation" indicates "Precipitation of
silica". "Adsorption of XX" infers "Adsorption of XX on silica". etc. Unless otherwise stated
the medium or solvent is assumed to be water.
Abortion in' rats. by intravenous silica. 758
Absorbance. sols. effect of particle size. 348.
349
Absorption of silica in plants. 747
Acetone: adsorption on silica. 653
, coagulates soluble silicate. 137
Acetyl acetone. adsorption on silica. 649
Acid. strong solutions. adsorption of ions
from. 670
Acid. thickened with silica. 593
Acidity. intrinsic. of silica surface. 183
. Acids. organic, see individual names
.Acid strength of silica surface. 660
Activated silica sols. characterization. 30 1.302
Activation energy: adsorption of wateron
surface. 630
of gelling. 237
of polymerization. 248
Active oxygen on surface. 7:
Active silica. definition. 86
Active sites on surface. 712
Adhesion: increasing with colloidal silica. 587
of particles to surfaces. 406
reducing with silica on surfaces. 587
Ad hesives, use of silicates in. 121. 122
Adsorbent. specific. 551
Adsorbent uses of silica. 595
Adsorption:' amino- and quaternary
ammonium polymers on silica. 703
by hydrogen bonding. on silica. 657. 658
from salt solutions on silica. 659
from solution. surface area by. 353
ions. forces involved. 665
Adsorption (cont'd)
isotherm. automatic recorder. 650
isotherms. nitrogen. gel structure effect.
489492
pore characterization by. '478. 488
low molecular weight materials on silica. 648
metal ions on silica:
order of. 672
summaries. surveys. 672
tabulation of. 673
of particles. 710. See also Deposition of
particles
on hydrophobic silica surface. 699
organic polymers on silica. 704
Physical. of non-ionic materials on silica.
648
polybasic cations. irreversible on silica. 669
polymers from:
aqueous solution on silica. 704
non-aqueous solvents on silica. 709
polyvalent metal cations on silica. 667-67]
potential. specific. 664
quaternary ammonium ions on silica.
682-686
salts from organic solvents on silica. 657
silica on metal hydroxides. 79
site-binding theory. 664
.
univalent cations on silica. 666
vapors on silica. 648
water: from alcohols on silica. 657
on dehydrated silica. stepwise. 65 I
on hydrophobic silica. 700
Adsorptive capacity of tabasheer gel. 744
835
Ii
. ----836
Subject Index
Aerogel: compressing. effect on properties.

487.488
control of weevils in grain. 752
definition. 537
dried without shrinkage. 537
from ethyl silicate. 539
natural, Japan, 569
ultimate particle size. 487
..Aerosil", 464. See also Pyrogenic silica
Aggregate size, determination 0(, 476, 477
Aggregates of particles: ordered structure.Iike
opal. 402
.
role in viscosity. thixotrophy in sols. 591
stages in size of. 329
strength of. '506-509
viscosity effect in sols. 363, 364
Aggregation of particles: forming gel. 225
mechanism of. 364-366
observed by coagulation with gelatin-salt,
207
polymerization by. 222
stabilization against, 323
stages of. 329
to ordered structure. 398
see also Flocculation and Coagulation
Aging. human: decrease in silicon content in
tissues. 756
senile dementia. 756 .
Aging gel: effect on curvature of surface in
pores. 644;
wet, reinforcement by;529
Albumin: bovine, interaction with silica, 763
interaction with silica. 393
. Alcogel: conversion to aerogel, 538
definition. 462
Alcohol: coagulates silicate solution, 137
consumption. of. enhances silicosis, 775
Alcohol; methyl. solubility of silica in, 61
Alcohols: adsorption of water from. by silica.
657
branched chain. surface area covered by.691
esterification of silica surface. 689
surface area covered per alkoxy group. 689
Algae: blue green. earliest life form. 731
colloidal silica. growing in colloidal silica,
343
growth in concentrated silica sols, 732. 737
in chert. made in laboratory. 9 I
silica particles adsorbed on membranes of.
732
see Diatoms
Algicides, see Preservatives
in
Aliphatic (fatty) acids. adsorption ~n silica.

656
Alkali. titration with. for surface area
measurement. 473
Alkali metal ions. adsorption on silica. 666
Alkaline earth cations. adsorption on silica.
667
Alkoxy groups on silica surface, 689
Alpha-s method (or determining surface area
470
Alpha-s plot. detection of micro pores. 499
Alpha silicic acid, definition. 196
Alumina: alpha. monosilicic acid not adsorbed
on. 80
code posited with silica. 88
dust. as an insecticide. 752
inhibitor of silicosis. 782
particles, silica coated. 330
reaction with silica: equilibrium constant.
193
review, 80
solubility: in presence of slliea in water. 81
versus pH. 193
Aluminate-modified silica sols. properties. 410
Aluminosilieate: fibers binder for. 423
ions: on silica powders. 464
on silica sol particles. 407, 409
tetramethyl ammonium. soluble. 154, 194
Aluminosilicate ions: on silica sol particles.
reduces H-bonding, 395
Aluminosilicatc ions on silica surface: acid
forms of. 711
adsorbs basic proteins. 763
exchange sites. 576
hydrophobed by organic cations. 687
structure of. 408
titration of. with CETAB. 409
AluminosiJicate surface. nature of. 711
Aluminosilicic acid. see Aluminosilicate iOJ1S
Aluminum. corrosion of, inhibited by barium
silicate. 149
Aluminum chloride. basic. flocculating agent
for silica. 385
Aluminum ions: adsorption on silica. 668
reaction with monosilicic acid. 193
reduce effect of fluoride in silica
polymerization, 211
reduce solubility of silica. 13. 56
reverse charge on silica. 411. 671
Aluminum oxide coating on silica sol particles.
411
Aluminum retards dissolution of silica. 7S
.,
Index
666
silica.
.e area,
499
sorbed
istant,
ater, 81
jes.410
I
\
;4, 194
ticles.
: acid
87
,I
ate ions
. barium
19 agent
.668
:a. 75
Subject Index
-...-...
837
Aluminum salts. coagulation of silica by, 381 Anti-caking agent. for powders."587
Aluminum silicate. free energy, 194
in food, 757
Alzheimer's disease. silica in plaques in brain, .Anti-cancer drugs. organo-silicon compounds.
756
785
Ambient pyrite. movement through quartzite, Anti-corrosion effect of soluble polysilicates
149
52
Antifoam agent. silica use in. 415, 594
Amicrons (small particles), 172
Amine salts, hydrogen bonding with silica;296 Antifoaming agent. theory of action. 434
Anti-gloss. effect of silica in paint~, 593
Amines: adsorption on silica. 650
lower. adsorption from solution on silica, . Antimony adsorbed from strong nitric acid on
667
.
silica, 671
Aminopropionitrile (beta). reported inhibitor Anti-oxidants adsorbed on silica. 595
Anti-reflecting films with colloidal silica. 435
of silicosis. 781
Aminopropyl silyl groups on surface, anchors Antistat effect of alumina-coated colloidal
enzyme, 766
silica. 427
Ammonia: inhibits growth of silica particles, Anti-sticking. s~~ Adhesion
317
Aquagel. definition. 462
preservative in silica sols, 343
Area. see Surface area
on silica. 649
Areas of molecules. atoms. see Molecules
surface area measured by. 472
Argon: atomic area. 466
Ammonium: counterions in silica sol, 359
interaction with hydroxylated surface. 653
hydroxide coagulates soluble silica, 137
Arteries. silica in. 754. 755
salt. role in making silica powder. 560
l-Arylsilatranes, extreme toxleity of. 785
Amorphous silica: entropy of solution. 45
Asbestos cement. polysilicate in. 145
Asbestos: chrysotile: conversion to fibrous
forms of. 25
silica, 659
heat of solution. 45
source of hydrated crystalline silica. 20
hydrated.'properties. 26
coating of silica on, 87
inflammatory, non-flbrogenic, 774, 776
Asbestosis. unlike silicosis, 782
non-silicotic. 777
Atheromas. reduc~d by silicon compounds,
particle size versus solubility, 55
solubility. effect of pH. 47
755
Atherosclerosis. similarities to fibrosis. 768
solubility. equilibrium, 40, 41
Atomic absorption. analytical method for
spheres, formation of, 25
.X-Ray diffraction. 22
silicon. 95
Analysis: biological specimens. problems in,
Atranes, chelates of R-Si compounds with
99. 786
triethanolamine. 158
colorimetric methods. 10\
Aufwillite. source of monosilicic acid. 180
concentrating silica for, 100
Aystralian turpentine wood. silica content
detection of silica on paper surface. 102
resists borers. 746
methods of. 94. 786
Autoclaving. see Hydrothermal treatment
molybdenum blue method, 98
A vlna saliva silica extruded as fibers in cells.
. silicomolybdate method: reagent
742
compositions. 97
recommended proced ure, 97
Bacillus siliceus; attacks aluminosilicate
standard solution of monomeric silica. \0 I
minerals. 733
titration. as fluosilicic acid, hydrolized, 102 Bacteria: silica in. 734
silicon exchange for phosphorus. 734
as silicomolybdic acid. 103
Bactericide. see Preservatives
Aniline. diethyl, 296
Bamboo. silica in hollow stern, 743
Animals. silica content of. 14. 753
Barium ions. adsorption on silica. 667
Anion exchanger based on silica, 577
Barium silicate: corrosion inhibitor for
Anodizing metal in colloidal silica. 431
aluminum. 149
. Anti-blocking agent for plastic film. 587
838
.;
SUbject Index
Barium silicate fcont'd)

monosilicic acid from. 180
Barley: mildew on. reduced by silica dust. 752
silica requirement. 740. 749
Bases. nitrogen, adsorption on silica. 659
Basic metal salts. see Polyvalent metal cations
Bauxite, origin of. 14
Beans (Mung. gram) silica requirement. 740
Beets. requirement of silica. 740
Beneficial effects of silica: in mammals. 783
on plants. 750
.
Benzene: adsorption of silica, 472. 653. 656.
657
molecular area. 467
Beryllium ions: reduce effect of fluoride on
polymerization. 211
retard dissolution'of silica. 75
reverse charge on silica. 671
Beta silicic acid. definition. 196
BET method: Brunauer, Emmett and Teller,
467
surface area measurement. 467
Binders. use of: polysilicate in. 149
soluble silicate in. 121
Biochemical combinations with silica. 761
Biogenic silica. types of. 29
Biogeochemistry. silica in, 730
Biological disintegration of rocks. 733
Biological samples. analysis for silica. 99
Biology. silica in. 730
."~;'
Birds. silica content. 753 .';'
Blocking of plastic film. prevention of. 429
Blood. coagulation by silica. 76~ :
Body Iluids, penetration by monomeric silica.
757
Bonding. interparticle. 223. 224. 227. 506-508
effect on .gel strength. 506-508
Borers in wood. resisted by silica. 746
Boric acid: lowers sintering temperature. 421
reaction with monosilicic acid. 190
wi,th silica as cockroachlcide, 752
Boric oxide: delays devitriflcation, 549
in quartz fibers. 638
Boron. relation to uptake of silica by plants.
740
Boron-oxygen silicon bond. 410
Bound water. on surface of sol particles. effect
on viscosity. 361
Brachiopod shells. iridescent colors of. 403
Brain. silicon may be essential in. 757
Brake lining. use of polysilicates, 149
Bridging by monovalent cations. role in
coagulatlon, 375
Bridging ions. at high pH, 376 "

Bridging mechanism. coagulation by. 373
BrOnsted acid type of site of aluminosilicic
acid. 711
Brownian motion in double layer. 358
MBuild-up" process. set Particle growth
Butane adsorption. for measuring surface
area. 471
Butyl alcohol: normal. esterified with silanol
surface. 30 I. 690
tertiary: adsorption of silica. 649. 653
extraction of silicic acid by. 30 I
"Cabosil", see Pyrogenic silica
Caesium versus sodium. roli in coagulation,
375
Calcium. adsorption mechanism versus
sodium. 357
Calcium ions: adsorption. on colloidal silica.
size effect. 382
on silica. 667
. charge density on silica. effect on. 357
coagulant for precipitating s~Hca. 561
coagulation effect on particles. 378
deposition of silica .role in. 92
fatty acid combination with. separating
silica from iron ore. 396
Calcium silicate, source of monosilicic acid.
180
Calcium sodium silicate, 140. 142, 143
Calculi. urinary. from excessive silica intake.
658. 741
Cancer: associated with 10Yl silicon levels. 769
of lung caused by asbestos. not silica. 783
of stomach. from asbestos on rice. 759
role of silica. no evidence for. 769.
Carbon dioxide: .adsorptlon, for measuring
surface area. 472
occurrence in quartz crystals. 3
Carbon fibers. silica coating on polyacrylamide before pyrolysis. 425
Carbon tetrachloride, interaction with
hydroxylated surface. 653. 656
carpets. antisoil treatment with silica, 426
Casting molds. of silica. 424
Catalysts, silica based. 596
Catecholamines, possible silicon chelates in
mammals, 784
Catechol: bauxite from clay in presence of, 14
chelate with silicon, 12. 59, 75, 156
dissolution rate of silica, effect on, 75
-formaldehyde polymer for removing silica
from water, 83
(
(
(
(
(
(
(
(
(
(
(
c
c
c
c
c
c
c
c
c
1_
I
I
..
Subject Index
376
rlation by. 373
)f r' -inosilicic
: layer. 358
1icle growth
~uring surface
:rified with siIanol
lica, 649, 653
id by, 301
ilica
,Ii in coagulation,
anism versus
on colloidal silica,
effect on, 357

ng silica, 561
rticles, 378
in, 92
vitI- separating
,re, ,
. mcnosilicic acid,
40, 142, 143
essive silica intake,

11.
silicon levels, 769
.os, not silica, 783

os on rice, 759
:e for, 769.
-n, for measuring
-stals, 3
19 on polyacryl-
olysis, 425
raction with
face, 653, 656
t with silica, 426
24
)
silicon chelates in
,y ir -resence of, 14
59.
156
., effect on, 75
for removing silica
-----
Subject Index,
Catechol (cont'd)
solubility of silica, effect on, 59
Cation exchanger based on silica, 576
Cationic dyes, adsorption on silica, 687
Cationic polymers, adsorption on silica, 706.
See auo Polymers, cationic, 393
Cationic silicon, evidence for, 185
Cationic surfactant: flocculation of silica by,
388
titration with anionic surfactant. 391
with PVA. adsorption on 'silica, 397
Quaternary ammonium ions, 684
Cattle, urinary calculi, from excessive silica
intake, 758
Cattle feed, addition of sodium silicate, 783
CCC, 373
Cellulose, strength improvement by polysilicie
, acid,300
Cement, Portland, effect of silica in, 597
Cement, Roman, lime with reactive silica, 438,
569 ,
Centrifugation: concentrating colloidal silica
by, 339
density medium for separating bio fractions,
. 436
purifleation of sol by, 338
Ceramic molds for casting metal, 424
Cerium Phosphate coating on colloidal silica,
410
CETAB, see Cetyl trimethyfammonium
bromide .
i.e.
Cetyl pyridinium ion, adscrption on silica, 391,
Cetyl trimethyl ammonium bromide,
adsorption on silica, 681
sheetlike silica obtained with, 389
titration of aluminosilicate ions, 409
Chains: molecular siloxane, polymer, 223
of silica particles, 173, 223, 226
Chalcedony: biogenic, 29
from diatoms, 735
Characterization of silicic acids, 195
Charge, see Double layer
Charge density: comparative data, 358
counterion concentration, 360
pH, effect of, 661
porosity of silica, effect on, 357
silica surface, 356 .
sodium chloride, effect of, 356
see a/so Surface charge, 661
Charge reversal on silica: by polyvalent metal
ions, 671
by Th, Zr, Be, Zn, Fe, and Al ions, 671
Charge on surface, prevents H-bonding, 65S
839
Charge within surface, 357
"
Chelates of silicon, 58, 75, 155, 748, 783
cationic, 157
in plants, 748
tropolone, 157
Chelation with surface, role in adsorption of
metal ions, 669
Chert: biogenic, 29
containing algea, synthetic, 91
earliest fossils, 731
Chickens, silicon essential in embryo, 756
Chlorine, dehydroxylation of surface by, hot,
641
Chlorochytrldon lubercu/alumcontaining
quartz crystals, 737
Chlorosilanes, reaction with surface silanol
groups. 696-699
Cholesterol: associated with silica, 761
Cholesterol in blood. reduced by silica. 769, 783
Choline, phosphatidyl, in membrane,
. . . .adsorbed on silica, 761
.Chromate ion. adsorption on silica, 671
Chromatography: column packings of silica,
420,598
hydrodynamic, separating silica particles by
size. 350
separation of polysilicic acids, 203, 205
. Chromium (chromic acid), reaction with
monosilicic acid. 192, 193
Chromium: complex ion on silica surface, 5.72
complex of carboxylic acid on silica surface,
.
688
methacrylato complex on silica surface, 572
Chromium (ous) ions adsorbed on silica, 668
Chromi'um oxide on silica surface, 411
Chromium powder, coating on steel, bonded
with silica, 430
Chrysotile asbestos, see Asbestos
Clarity of silicate solution. 118
Clausius Ciapyron equation, 502
Clays: coated with silica. 87
colloidal silica binder, 423
formation, role of plants, 750
origin of life, possible role in, 73 I
soluble silica. source of, 13
synthesis from reactive silica, 597
Cleaners, use of silicates in, 121
2-Chloropy~idine, aclsorption on silica, 649
Cloud seeding, hydrophobic silica powder,
597, 702
Coacervation: definition of, 396
emulsion polymerization, role in, 299
growth of large particles, 239
c:
, .."
..
\
Subject Index
.!
i
I
.;j
Coacervation (COni'(/)
of silica with: diethyl aniline(N.N) salt. 397
H-bonding agents. 387
nonaethylene glycol. 397
polyether, 294
polyvinyl alcohol. 295. 397
urea- formaldehyde polymer. 398 .
silicate solution bysalts, solvents. 137
Coagulants: effect in silicate solution, 135
effect on gelling. 233
organic. in precipitating powder. 562
Coagulation: definition. 364
particle size separation by, 351
polysilicic acid by gelatin-salt, 206,
turbidity effect on sol, 373
usually unaffected by particle size. 382
see a/so Flocculation
Coagulation by: calcium ion for size
separation. 382
divalent metal cations (Ca 2.>.. 378
electrolytes. 374
freezing. 382
metal ions, polyvalent. 379, 381
monovalent cations, 375
sodium ions. energy of activation, 378
tetra methyl ammonium ions. 376
Coagulation mechanism. 373
monovalent cation bridging, 375
role of: ion exchange. 375,
specific chemical forces,380
Coalescence between particles. 227-23"1
effect on gel strength. 230
in gels. 506-509
measured by partial dissolution. 508
Coating: black. on metal. silica and organic
polymer. 431
codeposition of alumina with silica. 88
hydrophobic. on silica. 679
Coating of" silica: hard. from colloidal silica.
372
on asbestos; clays. iron powder. pigments.

87
on nickel particles. 86
on thoria particles. 88
rate of deposition. 87
Coating on silica for chromatographic base.
599
Cobalt: complex ions adsorbed on silica. 670
com plex silicate. 154
Coco fiber. silica in. 746
Coesite, stability range. 16
Colloid. detection by pinacyanol chloride.
- 135
Colloidal alumina. flocculating alent. 385

Colloidal graphite. film bonded with silica. 405
Colloidal silica: in soluble silicates. 127. 128
absorbance (light). 348
algae in. 737
antifreeze for. "382
characterization of. 344
chemical analysis. 345
commercial types. 415-417
compatibility with potassium silicate. 145
concentrating. methods for. 338
concentration. maxium stable. 316. 325
definition. 312
deposition rate of. 93
electrolyte concentration. measurement.
345
electron micrography of. 346
films. drying of. 371
films of. 430
gel from. 334. 514
history of. 317
light scattering by. 347
making. see Colloidal silica preparation
manufacture. see Colloidal silica
preparation
particle characteristics. 345
particles. charge on. 355
density of. 328
porous. 328.
smallest. 217
particle size under 10 nm, 317
pH measurement. 344
preparation: by electrodialysis. 332
by ion exchange. 333
by peptizing gel. 334
from hydrolizable silicon compounds.
335
from pyrogenic silica powder, 336
from silicon metal. 335
from soluble silicate and acid. 331
preservative for. 337
processes for making. commercial. 316
processes for preparation. 331
purification. 337
reaction with silicic acid. 351
stabilization against aggregation. gelling.
323
stabilization by ilkali. 323
surface area measurement. 352
thermodynamic stability. 318
ultracentrifuging of. 350
uses of. 415-439
see also Sols
..
,
Subject Index
ildex
5
405
12f'
145
325
ent,
jon
nds,
16
ling.
~._.,
----
.1
Conoidal silica. use for: adhesion. decreasing.

429
increasing. 428
adsorbent gel. 420
antisoihreatment for surfaces. 426 .
binder: foundry molds. 424
inorganic. ceramic. 420
catalyst base. as gel. 420
coatings: inorganic. protective. 432
organic. improving. 430. 431
density gradient in centrifuging
biochemicals. 436
friction. increasing on paper. floors. 424
hydrophilizing surfaces. 427
optical effects. 435
photographic products. 435
polishing agent for silicon wafers. 433
. reactive form of silica. 437
reinforcing filler in polymers. rubber. 432
surfactant effects. 433
viscosity. increasing. of liquids. 434
wettability, increasing. of surface by
water. 427
Colloidal silica. viscosity of. 360
.
Colloidal suspensions. formation of second
- concentrated phase. 403
Color effects with colloidal silica. 398. 435
Colorimetric methods of analysis for silica. 101
Color indicator for silica surface. 425.426.687
Color in opals. 399
"
Colors. iridescent in natural solids. 403
Color test for silica on paper. 425
Color tests. increased sensitivity on silica gel.
595
Commercial gels and powders. 578
Commercial types of colloidal silicas. 415-417
Concentrating colloidal silica. 338-342
by centrifugation. 339
by electrodecantation, 343
by evaporation. 338
by ultrafiltration. 339
Concentrating silica for analysis. 100
Concentration of silica: effect on flocculation.
381
effect on gel time. 368
gelling. effect on. 367
Concentration of silica sols. practical
maximum. 325
Concentration on monomer. effect on rate of
polymerization. 256. 270. 271. 278.
280
Concentration polarization in ultrafilter. 341
Condensation. a form of polymerization. 173
841
Condensation polymerization of ~i1ica. 173.

175.209
Conductive (electrical) coatings. 405
silica binder. 431
Conductivity ofsilicate solutions. 121. 132. 134
Cooking ware. antisticking coating. 429
Coolant for metal cutting. improved with
silica. 430
Coordination number: of packed spheres. 480
of silicon: hexa, 142
in silicate ions. 142. 143
penta, 157
Coordination of metal ion with surface oxygen
atoms. 664
Copper complex ions: silicate of. 154
with acetylacetone, adsorbed on silica. 670 - .-. -.'. -"
with diphenyl picryl-hydrazide. adsorption
on silica. 670
Copper in silica deposited from hydrothermal
waters. 93
ion-exchange on crystalline hydrated silica.
24. 159
Corn (maize). silica in leaves. 741
Corpora amylacea, see Plaques
Corrosion resistant coatings containing silica.
431
Cosmetics. use of silica in. 435. 592
Cotton: coating of silica on. 87
silica vontent, 742 '
Counter ions: concentration of. effect on
charge density. 360
in double layer. 358. 359 .
prevents H-bonding with silica surface. 298.
658"
Cranston and Inkley method. pore size
distribution. 494
Cristobalite: formed from gel. 548
relation to amorphous silica. 22
solubility of. 32
stability range. thermal. 15
surface. hydroxyl groups on. 637
Critical coagulation concentration (ccc), 373
calcium versus particle size. 384 .
Critical flocculation concentration. versus
surface dehydrcxylation, 663
Critical micelle concentration (erne) of cetyl
trirnethyl ammonium ions. 390
Croix lacryma L. se1! Job's Tears
Cryroscopic method. molecular weight of
silicic acid; 252
Crystal violet lactone. indicator for silica on
surfaces. 687
Crystalline: hydrated silica. 19.570
-....--
842
Crystalline (COnl'd)
silica, necessary for silicosis, 774
silicas, anhydrous. 15
Crystallization. of amorphous silica, 26. See
also Devitrification
. Crystals, growth of. in silica gel, 593
Culture medium: preparation of gel from
colloidal silica. 78S
silica gel. 436, 784
Curvature of surface: dehydration. effect on,
643 ..
.
positive or negative, in gel pores, 644
solubility, effect on. 50
C-value, BET equation, significance. 506
Cyclohexane: adsorbed on microporous gel.
657
adsorption on silica. 653
Cyclohexyl silicate. hydrolysis of. 26
Cytotoxicity of silica: injures membranes. 760
unique.7S9
see also. Hemolysis
De boer method. surface area measurement.
469
Deflocculants, use of silicate in. 121
Dehydrated. 662 ' .
see also Dehydroxylated
Dehydrated silic~. flocculation of. 662
surface. hydrophobic. 62 .:
Dehydration of: insects by sili~a dust. 752
organosol. methods for. ~ 14
surface. 637. 645
by chlorine. 641
.
effect of pore diameter. 642-645
of radius of curvature of surface. 643
on adsorption. 650
flocculation promoted. 395
free energy of, 9
heat of. 645
of quartz. 641
temperature effect. 635
Dehydroxylated surface: effect on adsorption
of vapors (water), 650
properties of. 661
Dehydroxylaticn, see Dehydration
Dehydroxylation of: silica. effect on
adsorption of polymers, 708
surface: effect on critical concentration of
salt for flocculation. 663
reaction with hydrocarbons, 693
versus temperature. 635
Delustering, silica for, 593
Subject Index
Denaturation of proteins: by eclloidal silica.
prevention of, 437
by silica. glass, 764
Dense. 549
Density gradient medium for centrifugation
separations. 436
Density of silica. refractive index. relation to,
19
Density of silicate solutions. 119-12~
Deoxy ribose. silicon replacing phosphorus.
768
Depolymerization of silica: catalyzed by
molybdic acid. 202
hydrolysis mechanism. 209. 222
in alkali. effect of particle size. 283. 284
in silicate solution. ISO
pH. effect of. 221
Deposition of silica: as colloidal particles.
83.93
biogenic. 84
calcium, role in. 92
from geothermal solutions. 93.
from hot lithium silicate solution. ISO
from hot sodium silicate solution. 88
in living cells. mechanism unknown. 736
in living organisms. 3
in plants. mechanism. 747
in power plant equipment. 12
on silica gel, 529 .
particles on surfaces. 83, 710
processes for. 83
ra~e of. 87. 314
reaction involved, 5
role of monomer. 85
Deryagin-landau-Yerwey-Overbeek theory
(DlYO or YODL). 380
Detection. colloidal silica on paper. 425
Detection, collcidal substances by interference
film method. 405
Detergents, usc of silicates in. 121
Deuterium exchange. determination of
hydroxyl, silanol groups. 476. 634
Devitrification: effect of impurities. 547
inhibited by nitriding silica,' 549
promotors, 549
Dextran. molecular weight standard. 203
Dialysis, purification ~y, 338
Diamond powder bonded with silica, 425
Diatomaceous earth. natural occurrence, 569
Diatoms: classes Diatomaceae, Bacillariophyceae, 734
distribution. deposition, 735
"
Index
Subject Index
ilica,
tion
rn to,
irus,
.j
-,
84
i
I
'. l
I
:s,
!
!
'36
)ry
renee
>34
S
, SI'
)-
\~...
-....-843
Dissociation constant, of silicic acid, 10, 49,

Diatoms (cont'd)
18J. See a/so Ionization constant
germanium, inhibitor for silicon uptake, 730
Dissolution of aggregates, determining
silica concentration required for, 735
coalescence between particles, 508
silica removal from water, 13
Dissolution of sand, making silicate, I 17
silica uptake from water, 735
Dissolution of silica, 3, 62-76
skeleton, electron micrograph, 736
by hydroOuoric acid, 76
source of chert, Oint, organic shales,
crushed powders, 73
petroleum, 735 ,
from clays, promoted by roots, 747
summaries, monograph, 735
of structure, 64
effect
, Diborane, reaction with silanol groups, 630
for determination of surface area, 354
Dielectric: effects in adsorption on silica gel,
mechanism of, 62
.657
particle size effect, 65
isotherm: characterization of gels, 504
pH effect, 65
detection of micro pores, 504
rate
of, 36, 62, 77
pore size effect, 504
retardants,
75
methods, surface 'area measurement, 475
salt effect, 74
Diethyl aniline-(N,N) hydrochloride:
very smal! particles, 69, 72
coacervation of silica by, 397
Diuretic effect of soluble silica, 758
complex with silica surface, 296
Divalent metal cations, coagulating effect, 378
Diethyl "Carbitol," see Diethyl ether of
diethylene glycol
DLVO, theory, 380. See a/so DeryaginDiethyl carbonate, salt removal by diluting sol
Landau-Verwey-Overbeck
with,4l4
DNA, silicon exchange with phosphorus, 767
Diethyl ether, adsorption on silica, 649, 653
Double layer: counter ions of, 359
Diethyl ether ~f diethylene glycol: coacervadescription of, 358
ionic, 664
tion of silica with, 293, 397
thickness, 359
H-bonded complex with silica, 293
. Drugs: adsorption on silica, 656
in gelatin-salt-silica system; 206
in solid form, 429
Diethyl stilbestrol, see Estrogen
"Dry
water", stabiiized with hydrophobic
Diethyl trimethyl ammonium'lons, adsorption
silica, 594
on silica, 684 t:'
DTA, hydroxyl group, determination by, 476
Differential thermal analysis, see DTA
Dye, cationic, adsorption on silica, 687
Diffraction of light in opal, 400 :
Diketocycloheptane (1,2), chelate with silicon, Dye adsorption: on specific adsorbent, 52
surface area measurement, ~73
15.7 Dye markers (on sea), usc of silica, 594
Dimethoxy tetraethylene glycol,' H-bonding
agent, 289
Dimethyl acetamide, adsorption on siiica, 658 Einstein equation for viscosity, 361
Dimethyl formamide, salt removal by diluting Electrical conductivity of silica surface, 629
sol with, 4 14
Electric light bulbs, diffusing coating, silica in,
Dimethyl zinc, reaction with silanol groups,
435
Electrodecantation, concentrating sol by, 343
636
Dioxane, adsorption on silica, 653
Electrodialysis: colloidal silica made by, 332
purification of sols by, 338
Diseases, see specific disease, e.g, Silicosos
Disilicate ions on silicate solution, 126
Electrolyte concentration, in colloidal silica,
Disilicic acid from hemimorphite, 141
345
Electrolytes:
coagulation of silica by, 374
Dispersibility of particles from 'aggregates
effect on gelling, 233, 367
(gel), 531
effect on solubility of silica, 44, 45
Dispersion: forces in silica system, minimum
role in, 374. See a/so Van der Waals Electron microscopy: diatom, radiolarian
skeletons, 735, 736
forces
measuring particle size of silica, 345, 465
of silica, pyrogenic, 36
----
844
Electron microscopy (cont'd)
of silicate solutions, dilute, 135
of sols, 345
pore characterization by, 479, 507
Electrorheology, temperature effect, 593
Electrostatic clutch; use of silica in, 592
Elongated particles of silica, 330
Emulsion polymerization: of silica to gel, 526
of silicic acid, 299
organic, silica dispersing agent for. 433
Emulsion stabilization with silica, 594
Energy of activation: for coagulation by
sodium ion, 378
for gelling, 237
for polymerization of silica, 248
for sintering silica gel in steam, 541
Enthalpy: of formation of silicate ions, 137
of silica, 6
Entropy: of formation of: silicas. 7
silicate ions, 137
of solution, amorphous silica, 45
of water in silica, 629
Enzymes: adsorbed on silicaremain active, 767
bound to silica through diazonium salt, 767
list of, inhibited by polysilicic acid, 766
silicon in structure, 766
Epitaxial matching of crystalline peptides,
amino acids, on quartz, 767
Equation: BET method, 467
Clausius-clapyron, 502
Kelvin (Lord), 489, 500
Mooney, viscosity ofsuspensions, 361
Poisson-Boltzmann, 664
~
Equilibrium constants of silicate ions. 136
, Erythrocytes, see Red blood cells
Esterification of: polysilicic acid with n-butyl
alcohol, 30 I
silica surface, 689
dehydroxylated, with unsaturated
hydrocarbon. 689
in micro pores. 694
making organosol, 412
partly dehydroxylated, 693
reaction conditions for, 691
with methanol, 692
with substituted alcohols, 695
silicic acid from silicate solution. 140
Estersil, esterified silica powder. 582
Estrogen activity of piphenyl hexamethyl
cyclotetrasiloxane 2.6,-cis ","mer,
787
Ether, destroys self bonding between silanol
groups, 653
Subject Index
Ethyl acetate, adsorption on silica, '653
Ethyl amine, adsorption on silica, 649
Ethylene diamine complexes with metal ions,
adsorption of, 669
Ethylene glycol, preservative. 343
Ethylene oxide, use in making quaternary
alkylammonium silicate, 151
Ethyl orthosilicate, hydrolysis, 179, 261
Ethyl silicate: conversion to gel. 539 .
for making spherical silica powders, 404
see also Ethyl orthosilicate
Evaporation, concentration of sols. 339
Excretion "of soluble silica by mammals, 755
Exploding gel, low density foam, 549
Feldspar, iridescent colors in. 403
Ferric: chloride, hydrolysis and polymeriza. tion of, 306
ion: interaction with silica sol, 410
reaction with monosilicic acid, 1I
see also Iron
Ferritin. iron phosphate complex. in sea
cucumber, 403
Fiber laminates. stiffened with colloidal silica.
423
Fibers: natural. silica content, 746
of silica: by drying sol, 24
extruded from cell walls. 742
from SiFc, mechanism, 24
reduced slippage in spinning, 425
Fibrillar network of particles. 229
Fibrogenesis, characteristic of silicoses,
769-778
Fibrosis. similarity to atherosclerosis, 768
Field flow fractionation of particle sizes. 351
Fillers: for rubber. plastic, 582
Fillers in gel. removable. to increase porosity.
525
Film thickness, of adsorbed nitrogen, 494
Films: drying of colloidal silica, 370
of adsorbed particles. hardening of. 405
of silica, preventing crazing (cracking on
drying). 430
Fish, silica content. unknown, 753 .
Flakelike silica. 21
Flatting agent. silica use as. 593
Flint: boulders from fossil sponges. 29. 739
from sponges, mechanism. 52
origin. 3
Flocculant, see Flocculation agent
Flocculation: agent: stabilization of sol by
excess. 388
types of, 385
"
ct Index
\
i
111~
lary
404
~
s.755
ierlza-
silica.
68
., 351
osity,
)4
05
g on
739
'y
I
j
---_.
Subject Index
Flocculation (cont'd)
by cationic polymers. 393
by cationic surfactants, 388
by lime and fatty acid. 396
by polymer: effect of chain length. 392
mechanism of. 394
ccllcidal silica. 384
definition. 364
dehydrated silica particles. 383. 662
effect of: anionic charge on surface. 395
silica concentration. 381
in organic liquids. 396
mechanism. 386. 387
promoted by surface dehydration of silica.
395
role of stoichiometry. 380
sol. purification by. 338
versus precipitation. 365
see also Coagulation
Floor wax. antislip .with colloidal silica. 425
Flotation. of ores. use of cationic surfactants,
686. See a/sa Microflotatlon
Fluidized beds. silica improves now in. 429
Fluorescent colors, silica. use in. 593
Fluoride: accelerates nucleation of colloidal
. particles. 219
coagulating ion in making silica powder. 563
ion. effect on polymerization of silica. 209.
212
.
peculiar effects in reaction of silica with
molybdic acid. 202
Fluosilicate: ammonium. with aerogel as
insecticide. 752
titration method for silica, 102
Fluosilicic acid from silica, 12
Foam. fire-fighting. thickened with silica. 593
Forces involved in ion adsorption, 665"
Formaldehyde. preservative in colloidal silica.
337. 343
Forsterite, source of monosilicic acid. 180
Fractionation of particle sizes in sols. 351
Free energy: change with particle size. 9
different forms of silica. 6
formation of: aluminum silicate. 194
silicate ions. 137
Free radicals on surface of silica. 712
Freezing. coagulation of sol by. 382
Freezing point method. see Cryroscopic
method
Freezing sols to obtain silica powder. 23
Frankel-Halsey-H ill method, surface area
measurement. 470
Fuels thickened with silica. 593
845
Fungi. possible role of silica in metabolism.
734
Fungus disease. resistance of plants to. role
of silica. 750
Furan, adsorption on silica. surface area
measurement. 471
Furnace for making soluble silicate glass. 117
"Fused Silica" bodies from silic.a powder. 597
Galactose: adsorbed on quartz. 766
combination with silica. 748. 761
Galvanizing stop-off with silica. 430
Gamma globulin. on quartz. retain antigenic
activity. 766
Garnet. monosilicic acid from. 180
Gastropods. silica in. 739
Gel: aging wet. 529
cast shapes from potassium silicate and
colloidal silica. 145
characteristics. factors controlling. 5 I6
coalescence of particles in. 507
colloidal silica by dispersing. 335
commercial types. 578
definition. 462
dense. from mixed particle sizes. 372
density. particle packing. 234
. deposition of silica on. 529
dlsperslbilityalter drying improved by wet
. strengthening. 531
dispersion to sol. 334
dried. particle: packing density in. 523
size in. 523
exploding to low density. 549
film. hard. from mixed particle size. 372
films. cracking on drying. 370
formation. 225
from sol. 176. 226
minimum concentration for. 523
rate of. 512
stages in. 370
form of. shaping. 526
freezing to obtain particles. 527
from colloidal silica. 514 .
from hydrolized silicon compounds. 5 15
from silicates and minerals. 5 II
from soluble silicates. 122
heating in: air. 544
steam. 544
vacuum. 544
water. 543
-history of. 510
hydrothermal treatment of. 541
846
Gel (cont'e/)
impurities, effect on divitrification, 547
ion-exchanger, based on, 577
open pores, base for enzymes, 767
ozone adsorbed in, 714
particles by freezing sol, 527
permeation chromatography: pore size
distribution by, 504
silica. use in, 598
Gel phase: definition of, 231
volume fraction of, in sol, 236
see also Microgel
Gel point, definition of, 222
pores: micro, development by hydrothermal
treatment, 543
submicro, impervious, 549
volume of, 492.
wide, 516
primary particle size, pH effects on, 517
pulverized, 463
relnforeement: by wet heat aging. 532
effects of impurities. 532
methods of. 529
wit h active silica, 529
shrinkage on drying, 533-537
reduction of. 531, 537
. by hydrophobing, 536
by wet reinforcement, 531
silica: as culture medium,' 784
reviews on, 464
...
sintering, effect of impurities, 544
..
sources of. 5 II
.specific adsorbent, 55 I
spheres, formation of, 526
spheroidal. from silicic acid. 463
strength: theory of, 369
wet, 519
theory of. 520-522
structure: effect on nitrogen adsorption
isotherm, 489-492
.
sphere packing theory, 480-483
surface area. effect of pH during
preparation, 277
tabasheer in bamboo,.743
time: effect of: aluminosilicate anions. 410
pH and concentration of silica, 368.
513. 519
of silica sols. 177, 187.212.252.269.367
types of, 462
uniform structure. sintering of, 546
uses of. 578 ~
versus precipitate, 232, 365
wet treatments of, 528
Subject Index
Gelatin. interaction with silica, )OS. 393. 431
Gelling: prevents migration of silica binder,
422
Gelling rate. effect of: acid anion, 187
of coagulants, 233 .
electrolytes. 233, 367
organic liquids. 367
particle size. 367
pH, 177. 187, 269, 277, 367
silica concentration, 367
see also Gel, time
Gelling sols: activation energy of, 237, 369
alkali silicate glass, promoter. 422
catalysis by hydrophobic cations. 237
following progress of, 237
silicofluoride promoter. 422
temperature effect. 237.368
Geminal hydroxyl groups on silica surface,
633.640
Germanium. inhibitor for silicon in diatom.738
Giberellin, inhibits silica deposition in plant
stems, 743
Gillespite, source of hydrated crystalline
silica. 20
Glass: homogeneous, made from colloidal
silica. 437
Glass. porous. type of gel, 463. 551
Glass: beads. free-flowing, silica coated. 429
Glasses. silicate. soluble, 119
Glass fibers: anti-slip effe~t of colloidal silica.
425
coated with silica, higher strength. 437
Globulin. interaction with silica, 393
Gluco-pyranose (beta-De), H-bonding
polymer, 395
Glycerol, adsorbed from water on silica. 595
Glycine. retards dissolution of quartz, 59
Glycol, silica surface esterified with. 691
Glycosaminoglycans, association with silica.762
Gouy-Chapman theory, 664
"Gouy"layer at charged surface. 358
Granuloma containing silica in scars, 759
Graphite. silica binder in coatlngs, 431
Grasses. silica in stems, 744
Grease. thickened with silica. 591
esterified silica. 574
Grignard reagent. reaction with silanol groups.
630
Growth or particles. see Particle growth
Guanidinium silicate, 152
Guar gum. flocculates silica "slime". 396
Gypsum. silica. reinforced by. 424
-----
ndex
Subject Index
431
Hafnium: hydroxide. adsorption on silica.

area measurement. 473
phosphate on silica. develops negative
charge. 410
separation from zirconium on silica. 595
Hageman factor. denaturation by silica. 764
Halloysite, formation from monosilicic acid.
193. 194
Harkins and Jura method. surface area
measurement, 468
Healing of wounds. promoted by amorphous
silica. 783
,
Heat: aging wet gel to strengthen. 528
Heat content of water on silica surface. 629
Heat of adsorption: micropore detection. 502
nitrogen on silica. 505
ozone on silica. 714.
Heat of formation of silica. 6
hydroxylation of siloxane surface. 646
Heat of immersion: effect of surface
esterification. 70I
relation to PZC. 660
surface area measurement by. 475
Heat of polymerization of silica. 249
Heat of solution of amorphous silica. 45
Heat of wetting. silica surface by polar liquids.
646.648
Hectorite clay, synthetic. from silica. 597
Hemimorphlte, .disillcie acid- from. 141
Hemolysis: activity of silica, mechanism.
760-766
of red blood cells. 764
Hemp fibers. silica in. 746
Heptadecyl-pyridine l-oxide, monolayer.
" interaction with monosilicic acid. 299
Herpes simplex virus. mortality from.
increased by silica. 760
Hessian fly. see Sorghum
Heterocoagulation by colloid of opposite
charge. 381
Hexyl alcohol. adsorption on silica. 655
History of colloidal silica. 312
Hormone activity (estrogen) of substituted
cyclic tetrasiloxane, 786
Horsetail (plant). 742
Human organs. silica in. 754
Humate. ammonium. complex with silica in
soil. 750
Humic acids. chelates with silicon. 157
Hummingbirds. iridescent colors in feathers.
403
Hydrated amorphous silica: bound water.
theory of. 28
er,
e.
m.738
lOt
l29
lica,
595
.ca,
ups
"
847
Hydrated amorphous silica (cont'ei)

dehydration of. 27
from hydrolysis of silicic ester. 26
solubility of. 46
types of. 26
vapor pressure from. 27
Hydration of silica surface, free energy of. 9.
See also Hydroxylation
Hydrocarbon gases. adsorption on silica. 652.
656
Hydrocortisone reported inhibitor of silicosis.
781
Hydrofluoric acid. rate of dissolution of silica
in. 76
Hydrogen. ionized. on silica gel. 7 1 3
Hydrogen-bending; activity. 289
factors affecting. 658
in biochemical phenomena. 761
inhibition by surface charge. 409. 657. 658
multiple attachment to surface. 648
nature of. 648
organic complexes with polysilicic acid. 289
polymers. to silica surface. 395
. prevented by: ccunterions, 658
surface charge. 658
relative effectiveness. 658
strength of. 653
structure versus activity. 290. 291
surface activity; relation to. 292
water to silanolsurface, 628
Hydrogen evolution from metal particles in
Hydrogen fluoride. polymerization of silicic.
catalysis by. 211
Hydrogen peroxide. in crystalline sodium
silicate. 164
Hydrolysis of: ester groups on surface. 694
silica. rate of. 37. See also Depolymerization
silicon compounds to gel. 5 15
Hydrophilic coatings on silica. 679
Hydrophilizing surfaces with colloidal silica.
594
Hydr.ophobic bonding: nature of. 391
. role in adsorption of organic Ions, 666
Hydrophobic coating on silica. 679
alkoxy groups. 689
cationic surfactant; 686
gels. powders. surface esterified. 689
organic cations. 681
sol particles. role in viscosity. 590
Hydrophobic silica: adsorption of vapors on. 699
powder. toxicity in inhalation. 759
sols. organosols, 373
848
Hydrophobic surfaces. by coating with hydrophobic silica particles. S94

Hydrophobicity of: dehydrated silica surface.
662
glass. by adsorbed fatty acids. 688
Hydrosols, see also Colloidal silica
Hydrothermal: silica dissolved under pressure.
12-IS
treatment of gel. 539541
Hydrothermal conditions: amorphous silica.
solubility. 45
particle growth. 241-244
quartz solubility. 32
Hydroxylation of surface. 625-627
Hydroxylated silica surface: ionization of. 659
state of water on. 627
Hydroxylation of dehydrated silica surface.
646
Hydroxyl groups: characterizing by infra red
. adsorption. 634
Hydroxyl groups. internal. in silica. 632
Hydroxyl groups on surface: dchydroxylation.
effect of pore radius. 643
deuterium exchange with. 476-477
geminal, 633
infra red adsorption. 634. 639
per square nanometer. 8. 627. 631-634
theoretical number. 636
types of. 626. 634. 639.
versus heat of immersion. 647
versus temperature. 635
Hydroxyl ion. adsorption on sili~a versus p H,
356.661
Hydroxyproline. high in urine of'silicctics, 766
l-Hydroxypyridine N-oxide. cationic chelate
with silicon. 157
IEP. isoelectrle point. 660
Immersion, heat of. 647
Impervious gel. 549
lmpueities, effect on solubility of silica. 56
Indicator. color. for silanol surface. 687
Induction period for nucleation. 277. 287
Inert gas. adsorption. 653
Infinity. Life as a form of. 787
Infrared adsorption: by hydroxyl groups. 639
characterizing by hydroxyl groups. 634
.detection of water on surface. 630
hydroxyl groups. detection. 506
Ingestion of amorphous silica. harmless. 757
Inhalation of hydrophobic silic, toxic. 7.59
Inhalation of silica. effects of. 758
Subject Index
Inhibitors. preventing hydrogen-evolurion
from metals. 423
Inhibitors of silicosis. PVPNO. alumina. 779
I nk-receptive surface on polyolefin film. with
silica. 426
Inks. thickening wit h silica. 592
Insecticide: fluosilicate and silica. 752
powder, use of silica as. 59S
role of silica as. 752
Insect mandibles. hardened with silica. 752
Insects. silica. toxicity to. 752
Insulation. thermal. 424
Interfacial energy. 54
silica-water. 9
Interference colors in opals. 399
Internal hydroxyl groups. 632
Intestines. nodular silica in. 758
Intraperitoneal injection of silica. damaged
kidneys. 759
Intravenous silica. pyrogenic. causes
abortions. 758
Intrinsic acidity. 183
.
Investment casting. molds for. 424
lonexchange: colloidal silica by. 333
in polysilicates, 159. 160
purification of sol by. 337
role in coagulation. 375
surface coatings: on silica powder. 576
on glass microbeads, 599
Ionexchanger, based on silica gel. powder. 576
Jon exclusion. pore characterization by. 479.
505
Ionic charge: nature of. 355
on particles. 355
stabilization of sols. 325
see also Charge and Surface charge
Ionization: constant: decrease with
polymerization. 182
of silicic acid. 181
of the silica surface (silanol groups). 659
Ion pair. see Surface complex
Ions: adsorption: effect of hydrophobic
bonding. 666
on silica. forces involved. 665
Ions. specifically bound. 666
Iron. ferric ions: adsorption on silica. 668
offsetting effect of fluoride ions, 211
reverse charge on silica. 671
Iron. reaction with monosilicic acid. 190-192
Iron. role in nucleation of quartz. 79
Iron. silico-phosp hate complex crystals in
silicotic tissues. 775
.,
-...--
Iron. see also Ferric

Iron ore. silica. separation with calcium and
fatty acid ions, 396
Iron oxide particles. silica coated. 330
Iron phosphate complex (ferritin) with silica
. in sea cucumber, 739
Iron salts, coagulation by. 381
Irradiation o~ silica surface. 713
Isobutane adsorption. surface area
measurement. 471
Isoelectrlc point (iep), 185
. definition. 660
Isosteric heat of adsorption. see Heat of
- adsorption
119
'ith
Job's tears. silica in hard epidermis. 746
:d
,576
n9.
Kanager's method. surface area measurement.

470
Kaolin. synthetic. from silica. 597
Karl Fisher reagent, to distinguish water from
silanol, 630
Kelvin (lord) equation. 489. 500
Kelvin radius (pore). 495
"Kelzan" thickener for sols. 423
Kenyaite, crystalline polysilicate, 158
Kieselguhr. diatomite. 29
Kinetics of particle growth. Ostwald ripening.
240
. Kirkwood-Alder transition. In suspensions.
403
Kiselev's method. surface area measurement.
470
Krypton. atomic area. 466. 467
Lactone dye, silica on paper. detection of.
425. 426. 687
Laminarin, combination with silica. 762
Lanthanum ions adsorbed on silica. 671
Lateritic soil. silica increases fertility. 749
Latex. colloidal silica mixturp, binder for
metal powder. 422
Laumontite, source of cyclic tetrasilicic acid.
59
141
)8
I
1-1'
'.
"-
in
849
Subject Index
dex
Lauric acid. adsorption on silica. 656

Lead: ion. adsorption on alumina. 669
silicate. source of cyclic tetrasilicic acid.
ISS
Leaflike silica. see Phyllosilica and Lepidoidal
silica
Leather, plumped with colloidal silica. 423
Lepidoidal, types of. 21. See also Leaflike
Leucosite, see Phagocyte. Macrophage, and

White blood cell
Lewis acid site of aluminosilicic acid. 711
Lichens: associated with mineral silicates. 734
rocks attacked by. 733
Life: all elements possibly essential. 787
form based on silicon. 731
infinity, a form of. 787
origin of, 730
ultimate purpose of universe, 787
Light scattering: aggregation of particles
followed by. 366
polymerization of silicic acid. followed by,
252.273
silica particles, molecular weight by, 347
sodium silicate solutions. molecular weight
by. 131
standard for, IS nm sol. 347
Lime and fatty acid. flocculation of silica. 396
Limiting viscosity during aggregation.
increase. 258
Linoleic acid. adsorption on silica. 656
Lipids. adsorption by silica. 752
Lipoids, associated with silica. 761
Lithium: aluminum d-n-butyl amide. reagent
for silanol groups. 630
chloride. adsorption on silica from acetone.
657
counterions surrounding silica particle. 359
hydroxide. silica solubility. effect on. 58
ion: similarlry to calcium ion above 60C. 146
unique counterion, 360
nitrate. adsorption on silica from acetone-.
657
promotes devitrification of amorphous
silica. 549
silicate: comparable with water-miscible
liquids. 146
deposition of silica from solution. 94
insolubility in hot solution. 1.46
properties. 142. 144. 145. 147, 153
solution. particle size of colloidal fraction.
147
Living tissues. solubility of silica in. 60
London-Hamaker forces. 373
Lost-wax process. casting molds for. 424
Low angle X-Ray scattering. see X-Ray
Lubricating grease. 'thickened with silica. 591
Lyophilic (hydrophilic) sols. coagulation of.
373
Lyophobic (hydrophobic) sols. coagulation of.
373
..
----
850
,-
Macrophage: inactivated by ingested quartz

particles. 760
role in silicosis. 772
see also Phagocyte. Leucosite, 01U1 White
blood cell
Macropores. definition. 479. 481
Magadiite: crystalline sodium polysilicate, 158
source of hydrated crystalline silica. 20 "
Magnesium: essential for silica uptake by rice
plant. 751 '
hydrogen phosphate and colloidal silica.
heatproof coating. 430
ions. adsorption on silica. 667
silicate: monoslliclc acid from. 180
precipitated. 162
Magnetic susceptibility of ions adsorbed on
silica. 670
Mammals: silica content. 753
silicon essential in. 753. 756
Manufacture of soluble silicates. 117
Marine borers in wood. prevented by silica.
746
Mechanism: coagulation of silica. 373
denaturation of proteins by silica. 765
depolymerization of silica. 210
dissolution of sand in molten silicate glass.
118
insecticidal action of silica powders. 752
interparticle bonding in gel formation. 223
polymerization of silica. 174-177
precipitation of silica. 78. 554
silicosis. initiation of. 770
viscosity. thixotropy increase with silica. 588
Medicinal value. of tatasheer, 744
Melanophlogite. unique natural crystalline
silica. 17
Membranes. cell. destruction by silica
particles. 764-766
Mercury occluded in quartz crystal. 3
Mercury penetration method: pore
characterization by. 479. 504
surface area measurement by. 475
Micropores, definitions. 479. 481. 50 I
Metabolism of silicon: in mammals. possible
catechol-like chelates, 784
in plants. chelate with tropolone, 783
Metal: ethylene diamine complex ions.
adsorption on silica. 669 .
oxides. spherical particles of. 404
salts, silica uptake by plants reduced by. 747
Metal bodies. molded. bonded with silica. 422
Metal cations: adsorbed on silica. tabulation
of. 381. 673
Subject Index
Metal cations (cont'd)
,
coordination with surface silanols, 664
polysiJic:ic acid. reaction with. 303
polyvalent, attach organic anions to silica
surface. 572
Metalsilicates, precipitation. effect of pH. 162
Meteor Crater. occurrence of stlshovite,
coesite, 16
Methanol. adsorption on silica. 653
Methionine methylsulfonium silicate food
supplement. 153
Methods of making silica sols. 331
Methyl bromide. adsorption on silica. 650
Methyl chlorosilanes, reacrion with silanol
surface. 696
Methyl cyanide. adsorption on silica. 653
Methyl esterified silica surface. 574. 692
Methyl nitrite. adsorption on silica. 653
Methyl orthosilicate, hydrolysis to monosilicic
acid. 179. 189
Methyl Red. adsorption on hydroxylated
surface. 473. 506
Mica pigment. silica coated. 435
Micelles of cationic surfactant on silica
surface. 681
Microaclculcsis, see Asbestosis

Microbeads, glass. porous coating on. 421
Microcrystalline hydrated silica powders. 569
Microencapsulatlon, use of colloidal silica.
434
Microfibrous silica from asbestos. 759
Microflotation of silica. 381
Microgel: conversion to sol particles. 247. 315
formation of. 227
increase in. during gelling process. 247
sol of microporous particles. gelled. 281
ultrafiltration of sol containing, 342
viscosity of sol increased by. 231. 232
volume fraction of. in sol. 238
water content of. 259
Micropores: definition. 479. 481. 50 I
detection by: alpha-s plot. 499
dielectric isotherm. 504. 657
gel permeation chromatography. 504
Mossbauer effects. 505
t-plot, 498
developed by hydrothermal treatment ofgel.
543. 632
~
effects in. 504
esterification in. 694
size. estimated from different adsorbates.
503
Microporous silica. types of. 22
.,
t Index
sili",~
H.162
" ,
650
1001
1.
653
3
osilicic
.ed
42. ,
rs.569
lica,
n.31S
47
281
504
of gel.
8S1
Subject Index
Microspheres of silica. porous. 420 .
use in chromatography, 598
Mildew on cereal plants, silica improves
resistance to, 75 I
Mitochondria: adsorbed on silica. 596
silicon in structure of. 757
Modeless pore method. size distribution by.
499501
Molds, foundry, use of silicate in, 122
Molecular weight: light scattering method.
252,273
silica: cryroscopic method, 252
particle diameter, relation to. 246, 347
particle size by rate of depolymerization,
252
ultracentrifugation, 252
sodium silicate solutions, 129. 131, 1~8
Molecules: adsorbed, areas covered by,
. 466-474"
.
size range, adsorption of, to detect
micropores, 503
Mollosc shells, iridescent colors of, 403
Molpadia lntermedi Holothurldea, see Sea
cucumber
Molten salts, solubility of silica in, 62
"Molybdenum blue, analytical method. 98
Molybdic acid: beta to alpha, conversion, 96
Molybdic acid, rate of reaction: with silicic
acids, 195,200, ZOI, 264, 266, 283
with colloidal silica, '351
with silicate solution; :125, 135, 138, 139,
141, 148, 149
Molybdic acid method, silica determination
in presence of phosphorus. 786
Molybdic acid reagent, 201, 202
Monomer, see Monosilicic acid
Monomeric silicate, see Orthosilicate
. Monosilicic acid: adsorption on quartz, 38
adsorption on strong-base ionexchange
resin, II
.
alpha alumina. no adsorption on, 80
animals, inert in. 755
body fluids, tissues. penetration by, 757
characteristics of. II
deposition. rate versus p H, 85
dissolving amorphous silica in hot water.
178
diuretic effect. 758
enzymes, no effect on. 767
hydrolysis of silicon compounds. 179
kidneys concentrate and excrete, 755
non-toxic. 758
olivine, source fer, 141
Monosilicic acid (cont'd)

orthosilicate minerals. source of. 180
phosphoric acid. reaction with. 190
plants and animals, essential to. 14
polymerization rate. versus pH. 188. 256.
285
polymerization studies. 177-304
preparation methods. 10-14
properties. 10-14
proteins, no reaction with. 763

reactions, inorganic. 189
reaction with: alumina, 193
boric acid, 190
chromium compounds. 192
iron. 190-'192
sulfuric acid, 190
uranium, 190-191
"soluble" silica, 4
stability, factors affecting. 189
structure, 10
toxic to mitochondria, 767
Mooney equation for viscosity, versus
concentration, 236. 361
Mordenite, source of hydrated crystalline
silica. 20
Morpho!inium silicate. 152
Mossbauer effect, detection of micropores, 505
Mucopolysaccharides, interaction with silica,
299,
.
Multilayers of eolloldal particles on surfaces.
404, 711
Mutations, possible role of silica in, 768
2-3,Naphthalenediol, chelate with silicon, 156
Natrolite, source of linear trisilicic acid. 141
Natural waters, silica content. 13
Nature, soluble silica in. 13
a-Butane, molecular area. 467
Neck radius, between particles. 509
Negative adsorption, aggregate size
determined by. 477. See also Ion
exclusion
Nerves. optic silica content increased with age.
756
Nettles: silica i~ stinging hairs, 745
silica requirement for growth of stinging
hairs, 745
Network of particl~s, forming gel. 176. 225
Neutron bombardment of silica, 713
Nickel flake, coated with silica, 86
Niobium ions, adsorbed on silica. 595. 671
Nitric acid; 'solubility of silica in. 43
.Nitrides of silicon, from silica, 597
I
.,
-----
152
Subject Index
Opal (cont'(/)
ordered aggregates of spheres, 398
simulation by "Slocum Stone". 404
steps in formation. 399
structure. 398
banded twinning. 399
synthesis of. 404
synthetic. by Gilson. 404
ultimate particles. concentric structure of.
400
water. role in. 398
Opalescent dispersion of titanium dioxide, 404
Optical effects. silica. use for. 593
Ordered structure in aggregates. 398
Organic base 'silicates, 150
Organic cations: hydrophobic coatings on
silica. 571. 680
polyvalent. reversal of charge on silica. 411 .
Organic compounds. effect on solubility of
silica. 58
Organic groups attached to silica surface. 599
. through metal atoms. 688
Organic ion exchange sites on silica powder,
577
Organic liquids. effect on gelling. 367
Organic polymers: adsorption on silica, 704
coatings on silica powder. 575
combinations with polysilicic acid. 297
effect of salt on adsorption on silica, 708
Organic surfaces. hydrophobic. wettable by
Organisms, primitive. containing silica. 733
Organophilic coating on silica. 505
Organophilic silica. definition. 464
Organosilicon: coatings on silica surface, 695
compounds. 785
Oats. absorption of silica from soil. 750
compounds. possible synthesis by Proteus
mirabilis, 785
Octasillcate ion. cubic. 155
pharmaceuticals. 785
Octodecyl trimethylammonium bromide. 385
surface coatings. 574
Oil absorption test. measurement of pore
Organosol:
compatability with solvents.
volume. 493
depends
on surface groups, 413
Oil in quartz crystals. 3
dehydration. see dehydration of organosol
Oil spills. adsorbent for ~ 595
silylation of silica particles, 414 .
Oleic acid. adsorption on silica. 656
surface esterified: particles. 413
Oligomers, polysilicic acids, II, 214, 215. 260,
surface esterified with octadecyl (branched)
263,273
alcohol. 413 ~
as particles (nuclei). 215
with benzyl alcohol. 413
definition. II
with butyl alcohol, 413
Olivine. source of monosilicic acid, 141
Opal: color indicates size of silica spheres, 400
with glycol. 413
types
of, 413
electron micrograph, 40 I
natural structures, similar to, 403
Origin of life, possible role of silica, 370
Nitriding silica reduces devitrification, 549

Nitro alkanes. adsorption on silica. 656
Nitrobenzene. adsorption on silica. 656
Nitrogen: adsorption, surface area of silica
dried from sols. 352
.molecular area of. 466, 467
monoxide adsorption for measuring silica
surface. 472
, Nitrogen organic bases" adsorption on silica,
659. See a/so Organic base
Nitrophenol adsorption, surface area
measurement, 472
NM R. characterization of surface groups. 633
NM R-nuclear magnetic resonance: of water
on silica surface. 629
of silicic acids using Z9Si. 263
see also PMR
n-Octanol, esterified with silica surface. 695
Nodules. silica. in intestines. 758
Nonaethylene glycol. coacervation of silica
with. 397
Nonionic: adsorption. 657. See also Hydrogen
bonding
surface reactions, tabulation of, 676, 677
N-oxides, effect on silica solubility. 60
Nucleation: induction period, 277. 287
of icc crystals. hydrophobic silica. 702
.of quartz, 78
role in precipitating silica, 78 ~
theories, review of. 218
Nuclei. formation from silica oligomers, 217
Nucleic acid. silica interaction with. 7_67
Nucleic acids. silicon replacement of
phosphorus. 767
Nylon, coating of silica on, 87
'""
..... ---
'ndex
Subject Index
Orthosilicic acid, see Mcnoslliele acid
Ostwald-Freundlich equation, 5 I
"Ostwald ripening". 175-220, 223, 239, 240,
265, 275, 556
Oxides, hydrous, metal, spherical particles,
404
Ozone, adsorption on silica. 595. 712
. of,
,404
Paint: inorganic, colloidal silica binder, 430

thickened with silica, 592
Palms, silica in leaves, 746
Pancreas. silica in. 754
Paper: colloidal silica antislip, 425
corrugated, stiffened with colloidal silica.
. 423
n
.411
of
.599
der,
704 ..
'08
by
'33
.695
'eus
0501
hed)
detection of colloidal silica on surface. 102

indicator for silica on. 687
strengthened with potysilicic acid, 300
Particle, ionic charge on. 355
Particle growth: acidic solution, 220
commercial processes, 314
deposition of soluble silica, 314
effect of pH, temperature, 241
inhibited by ammonia, 317
kinetics, 240
limited, .10
rate by silica. addition, 314
silica, "173, 279, 313
spontaneous, by "Ostwald ripening", 239
stabilization against. 318 .
storage 20 years, 285. 286
temperature effect, 313
see also "Ostwald Ripening"
Particles: aggregates, effect on viscosity of
sols, 363
colloidal silica; chains of, 173, 223
deposition on surfaces, 93
interaction with organic polymers. 392..
porous, 281
.
properties modified by aluminosilicate
sites, 409
coordination number in gels, 234
detection of small ones among large, 406
diameter. silica, relation to molecular
weight. 347
large: by coacervation. 239
from microgel, 315
multilayers on surfaces, 405
non siliceous, coated with silica, 314 .
oligomers of silicic acid, 215
packing: coordination number. 234, 479
in gels and powders, 479
853
Particles (cont'd)
porosity. calculated from sol viscosity, 363
primary in gel. pH effect on size, 517
silica: bonding between. 223
characteristics of, 345
. composition versus size, 244
non-siliceous cores, 330
positively charged with alumina coating,
410
types, effect on viscosity. 362
smallest colloidal silica, 217
stabilization against growth. 318
surface: modification in sol. 407
modified with metal phosphates. 410
Particle size: average from surface area, 465
change in free energy, 9
effect on: coagulation. 382
dissolution rate, 65
gelling, 361
hydroxyl groups per nm 1 8
maximum concentration in sols, 325
solubility, 49, 239. 241, 279
viscosity, 245
estimation from film color. 406, 407
final. versus temperature, 242
flocculation by calcium ion, mechanism. 3'83
hydroxyl to silicon ratio, 8
number average. 465
. quartz. narrow range causes silicosis. 174
role in protein denaturation. 765
separation. 350
silicon atoms per particle, 7
sols. 313, 345
ultimate. 465
by x-ray scaltering,476
in gels and powders. 479
versus: particle composition, 7, 244
reaction rate with molybdic acid, 283. 284
Pentachlorphenol, preservative. 343 .
Peptizing gelto colloidal silica, 334
"Percell", density gradient medium for
centrifugation. 436
Periodic colloid structure. 402
Permeability. aggregate size determination,
417
Permeability method, surface area
. measurement. 476
Peroxide surface on silica. 713
Peroxysilicates, 164
Petrifaction. 88
Petrified wood, 89
Petroleum, derived from diatoms. 735
.,
854
---_.
Subject Index
Pigment, coating of silica on. 77

Phosphorus interference, eliminatio'" of. in
Pinacyanol chloride. for detection of colloidal
silicomolybdate method. 787
silica, 135.
Photographic papers and films. use ofsilica in.
Piricularia oryzae, rice fungus. 75 I .
435
pH: colloidal silica. measurement. 344
Phylloidal silica. 20, 464
effect: on adsorption of hydroxyl ion on
Phytoiiths in plants. 741
silica, 661
Plankton. forming insoluble silica. 13
of adsorption of metal ions, 672
Plants: extraction of silica from rocks (basalt).
on adsorption of quaternary ammonium
750
ions, 683
mechanism of deposition of silica, 747
on combination of metal cations with
nature of silica deposits in. 741
polysilicic acid. 304
parts. stiffened with silica, 142
on dissolution rate of silica. 65
silica content. 3. 14. 740-752
on gelling, 177, 188.367,519
silica deposition in. pH controlled. 143
on particle growth. 241, 243
silicon chelate found in. 748. 783
Plaques, silicon containing, in deteriorating
on particle size in gels, 517
. brain, 156
on polymerization rate, 256, 270, 274
Plutonium ions adsorbed on silica, 668
on pore volume of gel. 519
PM R. s~~~rot.c:>n magnetic resonance
on precipitation of metal silicates, 162
Pneumoconiosis, $~t Silicosis
on rehydration of surface. 663
. Point of zero charge (pzq, of silica, 186,660
on silica deposition in plants, 743
Poison. silicon-based, arylsilatranes, 785
on silica interaction with proteins, 763
Poisson-Boltzmann, equations, 664
on solubility of silica, 47
Polishing agent colloidal silica. for silicon
on surface area of gel. 518, 519
wafers, 433
on surface charge density. 661
Pollen. sllica content. 140
high. inhibits flocculation by potassium
Polyacrylamide. H-bonding polymer. 395
ions, 666
of sodlum silicate solution. 12i. 125. 132
Polyethylene glycols, adsorption on silica
Phagocyte, see Macrophage
from solvents, 710
Polyethylene imine. flocculation agent. 394
Phagocyte-free rats immune to silicosis. 772
Polyethylene oxide: adsorption on silica. 704.
Pharmaceuticals, use of silica. in. 592. 656
705
-Phases of silica. 15 .
Phase transformations of silica, 16 ;
flocculating agent~ 385
Phenol adsorption. surface area measurement,
H-bondins 'po!y~~r~.387, ~.9.5
Polymeric
species of silica in silicate solution,
472
132
Phenols, adsorption on silica. 656
Polymerization of silica, 172
Phenyl chlorosilanes, reaction with silanol
above pH 7.239,281
surface. 697
at pH 2-7,2.13,251
Phenyl trichlor silane reaction, surface area
by aggregation, 222, 275, 276
measurement. 473
definition, 173
Phosphate. adsorbed on soil (lateritic)
degree of, versus silicon-shared oxygens,
displaced by silicate ions. 749
Phosphates of metals. coatings on silica
261
effect of aluminum iron, thorium,
particles. 410
beryllium, 211
Phosphor. silica binder for, 435
effect of fluoride, 209, 212
Phosphoric acid: reaction with monosilicic
acid. 190
effect of pH, 177,257,285
reduction in solubility of silica. 58
pH and concentration. 2S6, 270, 274,278.
Phosphoric oxide and silica binder in coatings.
280
421,431
energy of activation, 248
Phosphorus in DNA, possible replacement by
formula,S
silicon, 768
heat of. 249
.,
---ass
et Index
Subject Index
of, in
Polyvinyl alcohol (con,'d)

Polymerization of silica (cont'd)
in silicate solutions, 133, 141
coacervation with colloidal silica, 295, 296
H-bonding polymer, 387. 395
limited state, 255
Polyvinylpyrollidine: competitive H-bonding
mechanism. 209
agent. 436
rate of. 267, 270
refractive index changes, 283
interaction with silica, 436
prevents denaturation of proteins by.silica,
steps in. 216
.
.summaries of investigations. 249, 252. 253
437
theory of. 174
Poly(2-vinylpyridine N-oxide) complex with
Polymers: cationic. flocculation of silica by,
silica. 157
'393
Popcorn type of exploding gel, 549
P.ore: characteristics, 478 .
Polymers, organic: flocculation of silica by,
391 .
filling by liquid. 489
Polymers, organic, reinforcement with silica, . " surface curvature: negative. 644
positive, 644
432, 586
Polymers. silica: distribution of species during Pore size: distribution, 493
"Cranston and Inkley method, 494
polymerization, 260. 262, 263. 270.
mercury penetration. determinaticn by, 504.
272. 274.287
end-capped by trimethyl silyl groups. 252.
M.P. method, 499, .501
x-ray
scattering method. 503
261. 265
effect on: dielectric isotherm. 509
growth from monomer. 255
surface dehydration, 642
Polysaccharides, combination with silica. 762
Pclysilicates, crystalline. 158
standard for. 50 I
ion exchange in. 159. 160
Pore volume in gel, 492
made from reactive silica. 437
coordination number and size of particles.
sodium. 144
481
Polysilicate solutions: colloidal silica in. 116,
pH effect. 519
128, 144
Porosimeter, mercury. 504
Porosity. effect on charge density. 356
commercial. 147
definition. "143
Porosity of gel, increase by removable fillers.
particle size in, 116, 128, 140, 141. 144. 147
525
uses. 149
. .
.
Porous colloidal particles. 281
Polysilicic acid: chromatographic separation
Porous glass, 551
Portland cement. effect of silica in, 424
.
by molecular weight. 203, 205
Positively
charged silica particles, 410
coagulation by gelatin-salt; 206
Potassium: chloride crystals. iridescent colors
combinations with organic polymers, 297
in. 403
'definition, II, 287
hydrogen disilicate, source of hydrated ...
hydrogen-bonded complexes. 28.8 .
crystalline silica. 20
inhibits some enzymes (listed). 766
ion. does not flocculate silica at high pH, 666
preparation from sodium silicate, 288
silicate, compatability with colloidal silica,
reaction with metal cations, 303
145, 422
trimethyl s!lyl derivatives. 203
silicate, manufacture, types of, 117. 134,
see also Silicic Acid
135. 145, 153, 158 .
Polystyrene latex. interference colors. 402
Polyuronides, association with silica. 762
titanate fibers, silica binder for, 423
Polyvalent metal cations: adsorption on silica,
versus sodium. role in coagulation, 375
667
Potential surface energy and hydrogen
coagulation of silica by, 379
bonding, 292
Polyvalent metal oxide coatings on silica. 410 Potentiometric studies on silicate solutions,
Polyvinyl alcohol: cationic surfactant: co133
Powder, silica: by coagulating silicic acid with
adsorption on silica. 704, 706
joint coagulation of silica. 397
salt, 560
.ilic
basalt),
)
'47
743
~ating
86,660
85
con
395-"ica
.394
a,704,
lution,
ens,
~,
278,
Subject Index
Protein (con,'d)
Powder. silica lcon,'d)

denaturation by silica, preventing, 437
eharaeierizaticn of. 464
denaturation, mechanism, 765
coagulation ~y calcium, polyvalent ions,
interaction with silica. 393
561
coated with organic polymer. 575
. Proton magnetic resonance (PM R), 635
commercial types. 578
Pulmonary edema. inhalation of hydrophobic
.
silica. 759
aefinition. 462
esterified surface. 573. 574
Purification of colloidal silica. 337
Purification of silica by emulsion
from colloidal silica. 565
from crystalline polysilicates. 569
polymerization of monomer. 299"
hydrophobic. organophilic, 570
Purification of sol: by di'llysis, 338
by electrodialysis, 338
ion-exchanger based on. 577
by ion exchange, '337
microcrystalline. hydrated. 569
by washing, 338
naturally. occurring. 568 .
Purine bases, combined with silica, 768
particle formation before aggregation.
PVA, see Polyvinyl alcohol
558
PVP. polyvinylpyrrolidone. 779
precipitated by coagulation by sodium
PVPNO. poly(vinyl pyridlne-Neexlde),
ion. ~55
778-781
precipitated from acid and soluble
Pyridine. adsorption on silica, 649
silicate. 554, 555
Pyridine l-oxide, 2-. 4- heptadecyl monolayer,
precipitated from organic liquids. 564
reinforced precipitate. 557, 560 .
interaction with monomer, 299
reinforcing aggregates before drying,
Pyrimidine bases. combined with silica, 768
Pyrite, ambient, set Ambient pyrite
557-560
reviews. 464
_
Pyrocetechol, chelate with silicon, 156
surface esterified with butyl alcohol, 573 Pyrogenic silica. 25, 662
surface modifications. 571
colloidal silica from, 336
surface modified with. ion exchange
flocculation promoted, 383
internal hydroxyl groups, 633
groups, 576 .
mechanism of formation. 565
surface modified with organosiliCon
...
groups. 574
set also Dehydroxylated surface
types of. 463 .
Pyrrole, adsorption on silica. 649
PZC (point of zero charge). 660
uses of. 578
relation to heat of immersion, 660
Powder. silica glass, pulverized. 569
Pozzuoli (Roman) cement from active silica,
Quartz: amorphous silica, thermodynamic
438,569
functions, 7
Precipitated silica, definition, 464
colloid a' silica conversion to, 313
Precipitated silica powders, 554
Quartz crystals: from reactive silica, 437
Precipitate versus'gel, 232, 365
inclusions, 3
Precipitation: insoluble silicates, mechanism,
161 .
in living cells, 737
mechanisms, 78
in plants, 741
versus flocculation, 365
nucleation, 78
Precision investment cating, molds for, 424
in presence of metal hydroxides, 79.
Preservatives {or colloidal silica, 337, 343
Quartz, entropy of, 6
Pressure, effect on silica solubility, 14, 58
Quartz fibers: containing boric oxide, 638
"Printing" molecule on specific adsorbent gel,
from colloidal silica, 438
553
Quartz, heat of formation, 6'
Printing on film, improving ink reception, 426
in vivo, crystalline ferr-ferri-phosphosilicare
Proline oxidation to hydroxyproline, catalysis
generated from, 768
by quarts, 766
macrophages inactivated by, 760
Protein: adsorption on silica, 707
monosilicic acid, adsorption on, 34
silicosis, mechanism of. 773
combination with silica, 763
,
j
.~
. -_..
Index
Subject Index
robie
r.
!
,
1
ayer,
768
cat
Quartz (cont'd)
. solubility: hydrothermal conditions, 32
equilibrium, 39
Quartz surface: coverage with PVPNO, 779
dehydration of, 641
.
reacts with macrophages, 760
source of asymmetric organic molecules,
731
Quartz spheroliths, 79
Quaternary ammonium: aluminosllicate, 194
cationic polymers, 393
ions: adsorption on silica versus pH, 685
silica surface, coverage by, 685
silicate, 131, 142, 150; 151
in baked organic coating, 431
Quinoline, insoluble salt of silicomolybdate,
103
"
Rabbit, 753. See also Mammals
Radiolarian, electron micrograph of skeleton,
737, 738
Radictracers, use in adsorption studies, 664
Radius of curvature: of neck between particles,
solubility, 227
of surface, effect on solubility, 50
Rain, seeding clouds with silica, 597
Rat, silicon essential in young, 756
in mammals, 753
:"
Rate of: deposition of silica",;.s3-94, 315
dissolution of silica, 62-76, 508
gelling, 237, 367-369, 513
polymerization, 267, 270, 271
reaction, silicic acid molybdic acid, 197,200,
201 "
Ratio: Si0 2:M 20, of silicate solutions, 119
Reactions with silanol groups, tabulation of,
677"
Reactive"silica, uses of, 597
Red blood cells: different animals, interaction
with silica, 765
silica in, 754
Reduced pressure, definition of, 467
Reduced viscosity versus molecular weight,
262
Refractive index: change during
polymerization, 283
Refractive index of silicas versus density, 19
Rehydration of surface, 637-645
mechanism, 645
Rehydroxylation of surface, rapid at pH 10,
663
Reinforcement of rubber, organic polymers,
582
857
Reinforcing silica: gel, 529
precipitate, 557
Removal, silica from water, 78
by ion exchange, 83
by metal hydroxides, 79
Reptiles and amphibians, silica content (no
date),753
Resorcinol, surface ofsilica esterified with, 691
Retardants of dissolution of silica, 75
Reversal of charge, see Charge reversal
Reviews of: hydrccols, 313
" silica chemistry, I
surface chemistry, 623
surface structure.. 624
Rice blast (fungus) silica improves resistance
to, 751
diseases. repressed by silica uptake, 752
hulls, source of silica powder, 569
silica requirement, 740, 750
Rocks, biological disintegration of, 733"
Rodenticide, p-chlorophenyl silatrane, 785
Roman cement: lime and active silica, 438, 569
made from reactive silica, 438, 569
Roots, promote dissolution of silica from clay,
747
Rubber, reinforcement of with silica, 582 .
Rubber sheet, glassive separators, silica
treated, 428
Rubidium: ions, adsorption on silica at low
pH, ~88
versus sodium, role in coagulation Qfsilica,
375
.
Rust (plant disease), silica increases resistance
to, 750
Rye straw, organic complex of silica in, 748
Salt: concentration, maximum allowable
in sol, 340
effect on adsorption of polymers on silica,
708
making silicate from, with sand and steam,
118
removal. limit in ultrafiltration, 341
solutions. adsorption on silica; from, 659
Sand: dissolution: for silicate, 118
mechanism. 118
molds. use of organic base silicates, 152
silicate from, with salt and steam, 118
Sarcina, obtains silica from quartz, 733
Scar tissue, by rubbing soil into cuts, 759
Schiller layers, colors in, 404
Screening. aggregate size determination, 477
Sea-cucumber, silica granules in, 403, 739
858
Sears method, surface area measurement, 473
Seawater, silica in, 13
Sedimentation, aggregate size determination,
477
Senile dementia, see Alzheimer'sdisease
"Sephadex", column packing in gel
chromatography, 203
Serum. silica in. 754
Sewage treatment with activated silica. 303
Shared oxygens, between silicon atoms, 261,
267
Sheet-like: aggregates of silica. mechanism of
formation. 390
silica: formed by cationic surfactant, 24
particles, see also Lepidoldat, 21
Ships, anticorrosion paint for. 432
Shrinkage of gel on drying, 370, 533
Silanes, organo, commercial for surface
modifications, 698
Silanol: definition. 2
groups: deuterium exchange on. 634
distinguishing from adsorbed water, 629
ionization of. 659
isolated, 652
on surface. acid strength of, 660
per nmz, 631. 633. 634
PMR distinguishes from water. 635
reactions with. 677-679
reactions with. tabulation of, 677
reagents for, 630
~
types of, infra-red adsorption, 639
see also Hydroxyl
.'
Silanol number. definition. 625
Silanol surface: energy of, 645
heat of wetting. 646.
Silatranes, silicon chelated and esterified with
triethanol amine, 785
Silica: anhydrous crystalline. 15
anti-cancer effect, 769
bodies molded Crom amorphous powder,
422
colloidal, definition, II
definition, usage. 2
fiber forms, 23,24, 225. 229, 742
foamed,424
from frozen sols. 23
from silicon monoxide, 24
from SiF. hydrolysis. 23
fused objects from, potassium silicate and
colloidal silica, 145
gel, see Gel
hydrated crystalline, 19
in biochemical combinations, 761
Subject Index
Silica (cont'd)
,
in DNA, RNA, 768
phosphoric acid' mixed ester, 297
Silica M, 21
Silica O. 18
Silica phases, 15
precipitated. from soluble silicate, 122
properties, see under specific subject: e.g.,
Entropy. Solubility, etc.
ribbon form, 23
scale-like, 23
sheet form. 23
similarity to water. 3
sp~eres,see Spheres of silica
surface coated with metal oxides unique
among oxides, 374, 665
water system, 4
Silica powder: see Powder
Silica W. fibrous. 17.24
Silica X, 18
Sllicalite, hydrophobic zeclitic silica, 18
Silicate: anhydrous crystalline, 139 .
Silicate, crystalline. conversion to: crystalline
hydrated silicic acids, 160
mono. di, silicic acids. 140
Silicate. cubic octasilicate ion. ISS
cyclic tetra ion. ISS
Silicate, guanidinlum, 152
hydrated crystalline alkal! metal. 158
insoluble, precipitation of. 161
Silicate glass: soluble, 117
species in. 132
Silicate ions: composition and stability, 136
displace phosphate from soil, 749
enthalpy of formation, 137
entropy of formation. 137
free energy of formation, 137
Silicate melts. polymerization in, theory, 164
metal. insoluble, mechanism of
precipitation. 161
methionine methyl sulfonium, 153
morphalinium, 152
of complex metal ions, 154. ISS
peroxy, 164
poly, layer-like. 158
potassium. 117. 134, 135. 153, 158
quaternary ammonium, 131, 142, 150,
151. 153
~
Silicate, sodium. 117. 132. 133, 138. 140, 141,
143, ISO, 158
-calcium, 140, 142
commercial solution, slow crystallization,
160
r
i
Subject Index
Index
e.g.,
Je
lline
~-
..
36
164
,
41,,_,
n,
.:
Silicate (cont'tI)
from sand, salt and steam, 118
in sodium perchlorate solution. i 32 . kenyaite, 158
magadiite, 20, 158
Silicate, soluble. 116
American commercial. 119 .'
commercial. properties and uses, 119
crystalline. 120
drying. 122
films fro~. 122
from microcrystalline silicas. I 18
glasses. ,119
manufacture. 117. 118
reviews. 116. 117
systems, H20. Si02. Na20. 118
uses. 121. 149
Silicate solution: absorption spectra. 1-32
activity coefficients. 131
characterization by conversion to silicic
acid. 140
characterized by ultrafiltration. 129, 130
clarity of. 118
coacervating. 137
coagulation by ammonium hydroxide, 137
coagulation by salts, 135
coagulation by water miscible organic
liquids. 136
.colloidal particles in. 127,' '128, 132
conductivity, 121, 132. 134
conversion to silicic acid, 137
conversion to silicic acid esters, :140
coordination ,number of silicon, 142. 143
density, 119, 121
deposition of silica from. 135, 137
diffusion experiments, 131 .
disilieate ions in, 126
effect of: coagulants. US
dilution, 134
sodium chloride on polymerization,
136
equilibria in, 123
freezing point data, 131
hydrolysis, 131
light scattering in. 131
molecular weight, 129, 131, 138
nature of, 123
osmotic activity, 131
phase relations. 131 .
pH of, 121, 125, 132
polymeric species present, 132
polymerization in. 133, 139, 141
potentiometric measurements, 131
859
Silicate solution (cont'tI)
, properties, 120
ratio: Si02:M 20. 119
reaction with molybdic acid. 125. 135, 138
139. 141. 148. 149
stabilization of small particles, 153
transfer number. 131
trimethyl silyl derivatives of ionic species,
139
ultracentrifuge studies on. 133

viscosity, 119. 121
Silicate. tetra alkoxy (ester) combustion
hydrolysis to PYJ;ogenic silica,.56?
tetramethyl ammonium. 18. 131. 142, ISO,
151
Silicic acid. alpha: beta. definition. 196
characteristics, 180
crystalline, from crystalline silicates, 160
definition, 196
esters of carbohydrates, 768
from silicate solution, 131, 140. 160
ionization constant, II. 49. 181
models of types of. 216
oligomers, 11.214.215.260,263,273
polymer distribution. 137, 260, 262, 263,
270, 272. 287
rate of reaction with molybdic acid, 197,
200. 201: 264. 266, 268. 283
reaction with molybdic acid, 195, 200
trimethyl sHyl derivatives of. 137,203,204
see a/so Monosilicic acid and Polysilicic
acid
Silicification: in laboratory, 91
mechanism, 90
of biogenic materials, 88
of wood, 89
review. 91
Silicofluoride ion, equilibrium constant. 213.
See Fluosilicate
Silicomolybdate, analysis method
interferences, 99
Silicomolybdic acid. 195
analysis method, 45
structure. composition, 196. 20 I
Silicon, cationic state below pH 2, 185
Silicon. chelates, ISS'
with catechol, 156
with tropolones, 157, 748, 783
see a/so Chelates of silicon
Silicon compounds. hydrolysis to: colloidal
silica, 335
gel, SIS
.,
--_...
860
Subject Index
Silicon elastomer, reinforcement with silica,

,
Silylation of (cont'd)
586
sol particles. methyl silyl, 414
Silicon, essential in mammals. 756
Sing's alpha-s method. surface area
Silicon esters. source of pyrogenic silicas, 567
measurement. 470
Silicon. in biology, 730. See Silica
. Sintering gel in: air or vacuum, 540 .
Silicon in deoxgribase (RNA). 768
steam. 540
. effect of impurities. 544
Silicon metal. colloidal silica from. 335
energy'of activation, 541
Silicon monoxide. oxidation: to silica powder.
of uniform structure. 546
566
Site-binding theory. 664
to tubular silica fibers. 24
Size of particles. see Particle size
Silicon nitride, oxynltride, from silica. 597
Slime of silica. flocculation by guargom, 396
Silicon oxyhydride, 24
Silicon tetraacetate, hydrolysis to monosilicic Snake. indigo, color in skin. 403
Soda ash. sodium silicate glass manufacture.
acid, 179
117
.
Silicon tetrochloride: source of gel. 5IS
Sodium:
adsorption
mechanism. versus
source of pyrogenic silica. 566
calcium. 357
Silicon tetrafluoride. hydrolysis to pyrogenic
.
silica. 568
chloride. effect on surface charge. 356
chlorite. preservative in colloidal silica, 343
Silicon wafers. colloidal silica polishing agent'
disilicate crystalline. source of hydrated
for. 433
crystalline silica, 20
.
Silicophosphate, iron. calcium magnesium
crystals in silicotic lungs, 775
dodecyl sulfate, titrant for cationic polymer.
394
.
Sllicophosphorie acid. ester of. 297
hydroxide. purification of. with ammonia,
Silicosis: alumina as inhibitor. 782
characterized by fibrosis. 770
137
(fibrosis) factor formed by quartz in
inside silica particles. 632
macrophage. 773
iodide. adsorption on silica from acetone.
generated only by 5 to 0.5 micron quartz
657
Sodium ion: bridging effect in 'flocculation.
particles, inhaled. 774
377
history and summaries, 769
inhibitors, 781
coagulant for silica. 555
critical concentration for coagulating silica.
mechanism. theories of. 770
378
prevention by silica antagonists. 778
flocculating silica, 666
promoted by smoking. drinking, 775
Sodium metasilicate: conversion to
solubility theory review of. invalidity,
monosilicic acid, 180
775-778
Silicotic miners, urine high in hydroxyproline,
tetrahydrate source ot hydrated crystalline
silica. 20
776
Sodium perchlorate solution. sodium silicate
Silicotic tissues, unusual crystalline iron
siliccphosphate, 775
in. 132
Sillimanite powder. silica binder for. 422
polysilicate solution. 144
Siloxane: derivative, estrogen activity. 786
salt. flocculation of precipitated silica, 560
network, gel formation, 222
silicate. 117. 132. 133. 138. 140, 141. 143.
surface: energy of, 645
150, 158.331: 511.554-562
heat of wetting, 646
addition to cattle feed, 783
nature of, 505
hydrogen peroxide complex. 164
Siloxane-silanol surface, heat of immersion;
molten sodium sulfate decahydrate,
647
dissolved in. 134
Silver holide emulsions, silica modified, 436
neutralization. colloidal silica by, 331
Silver silicate, precipitated from silicate
precipitation of silver silicate from. 134
solution, 163
Sodium sulfate. for making silicate. 118
Silylation of: silicic acids (trimethylsilyl), 137. Sodium sulfate decahydrate, molten. sodium
203,204
silicate in. 134
i
I
.0
.,
~ex
396
are,
343
d
lymer,
\.
me,
on.
.ilica,
alline
licate
1.560
143.
.-.
33.,
13<+8
odium
1.
--
... -
Subject Index
Sodium versus potassium. coagulating ions for'
silica, 378
Soil, liberation of phosphate by silicate ions.
740. 748
Soil fertility. role of silica. 7. 48
Sols: characterization of. 344
from: micro gel, 247
soluble silicate. 122.
in organic liquids, see Organosol
methods of making. 331
modification with aluminate ions. 410
stability during processing. 340
see also Colloidal silica. Polysilielc-aeid,
ana Silicic acid
Solubility: decrease with particle size. 55
Solubility. effect of: catechol. 59
electrolytes. 44
. impurities. 56
organic compounds. 58
particle size. 49
pH. 42
polyhydroxy compounds. 59
N-oxide,59
.
organic bases. 60
.pressure, 58
Solubility equilibrium. 41
theory.35 erroneous data. 52
hydrated amorphous silica: 46
Solubility in: alcohols. 61:.
living tissues, 60
.-.'
molten salts. 62 .
nitric acid. 43
organisms. twenty-fold that in water. 758
Solubility of: amorphous silica, effect of:
pressure, 14
temperature and pressure, 45
neck between particles. 228
quartz. 30. 31
silicas. forms of. 31
Solubility theory of silicosis. not valid,
775-778
Solubility' versus particlesize, 241. 279
Soluble silica: correction tor. in titrating
surface area, 205
definition of. monosilicic acid. 10
nature, occurrence in, 13
silicosis not caused by. 777
Soluble silicates. see Silicate. soluble
Solution. see Dissolution
Solution. silicate. see Silicate solution
Sorghum: silica increases resistance to Hessian
fly, 751
1'1
Sorghum (cont'cJ)
-.
silica in leaves. 74
Spanish fly. silica content, 752
Specific adsorbent gel, 55 I
Specific adsorption potential of metal ions
(coordination tendency). 664
Specific chemical forces, role in coagulation.
379
Specific gravity, see Density
Specific surface area, see Surface area. specific
Spheres: in suspension, viscosity of, 361
(micro). silica. by emulsion polymerization.
300
of gel. formation. 526
of siJica by coacervation. 397
Spheres, packing 0(: in gel structures. 234-236.
480-483
in ordered structures, 402
Spheres. uniform: of hydrated chromium
phosphate, 404
of metal oxides. 403-404
Spillover effect, absent on silica catalyst. 596
Spiny plants, siiica in spines. 744
Spleen cultures, soluble silica harmless in. 757
Sponges: silica. removal from water by. 13.739
source of flint. 3, 52. 739
Spot cleaners. silica usc in, 595
Spray-dried silica. hot pressed. strong silica
bodies from. 422
Spray-drying. gel microspheres formed by. 526
Stabilization of sols by ionic charge. 325
organic compounds. 327
steric, 327
Stability. thermodynamic. of colloidal silica,
318
Stability of sols during processing, 340
maximum salt concentration, 340
Standard solution of silica. 101
Steam, gel sintering in, 539-541
Stearic acid adsorption, surface area .
measurement. 472
Steel. coating on, with silica. 429
"Stern" layer. 358. 660.664
Stishovite: docs not cause silicosls, 777
hemolytically inactive. 760
solubility. 34
stability range. 16.
Stoichiometry of flocculation. 380
Stomach cancer. see Cancer
Stool coating (ingot molds) silica coatings for.
423
Straw stiffened by silica, 744
Strengthening. see Reinforcement
'"
----
861
Strength of gel, measurement of, 509
Strontium ions, adsorption on silica, 667
Subcolloidal species, silica, determination of,
195
Su bmicropores, definition, 50 I .
Submicroporous silica gcl,-549
Sugars, interfere with formation of
siJieomolybdatc, 202
Sulfide ion, role in deposition of silica from
hydrothermal brine, 93
Sulfonic acid ion exchanger based on silica,
577
Sulfuric acid, reaction with monosilieic acid,
190
Summaries: of investigations of
polymerization, 249287
on silicosis, 770
Sunflowers, silica requirement, 740
. Supermicropcres, definition, SO 1
Supersaturation, critical degree of, for
nucleation, 219
Surface: active oxygen on, 712
"active" sites, 712
adhesion of particles to;405-406
adsorption of metal ions on, tabulation of,
672
alumina, silica acid sites, 711
aluminosilicate, 687
Surface.area: by adsorption fr0l!' solution,
353, 472, of various gases, 471
by alkali adsorption, 473::'
alpha-s method of Sing, 470
BET method, 467
continuous flow method, 471
De Boer method, 469
dielectric methods, 474
Frenkel-Halsey-Hill method, 470
gas adsorption, 466
Harkins and Jura method, 468
Kanager's method, 470
Kisilev's method, 470
liquid chromatographic methods, 474
mercury penetration method, 415
nitrogen adsorption, 352
permeability method, 476
rate of dissolution, 354
Sears method, 353,473
thermal effects, ~15
titration with alkali, correction for
soluble silica, 205
t-plot method, 469
Surface area, gel: effect of pH, 518, 519
particle packing, loss by, 483-488
Subject Index
Surface area, gel (cont'e/)
relation to pore volume. 524

Surface area, polysilicic acids, as particles, 203
specific, of colloidal silica, 352, 466
standards, 466
titration method (Scars), 353
Surface characterization by N MR. 632
Surface charge: aluminosilicate ions. 407
counter ions. 359
density versus pH. 661
ionization, 659
reduces hydrogen bonding. 298, 409, 657,
658
reversal by polyvalent organic cations, 411
titration of, 409
see also Charge
Surface, ehemisorbed organic groups on, 599
chemistry, reviews, surveys, 623
coated with hydrophobic organic cations, 681
complex with metal ions, 664
Surface coverage: by quaternary ammonium
ions, 685
with alkoxy groups, 689
Surface, cristobalite, hydroxyl groups on, 637
Surface crystallinity of silica necessary for
silicosis, 774
Surface. curvature of: effect on dehydration,
643. See also Curvature of surface
Surface, definition of. 625
Surface, dehydraticn, 637-645
effect on adsorption, 650
promotes esterification, 693
promotes flocculation of particles, 383, 395
reaction with unsaturated hydrocarbon, 693
versus temperature, 635
see also Dehydroxylation
Surface. detection of silica. 102
electrical conductivity, 629
Surface energies, types of silica surface, 645
Surface energy: increase with specific surface
area, 646
role in nucleation. 219
see also Interfacial energy. 54
Surface ester groups: hydrolysis of; 694
thermal stability of, 695
Surface esterification: of powder..573
reaction conditions f~r, 691
esters with alcohols, 689
Surface, gel theory of adsorption, 665
Surface, heat of: adsorption on, 505
wetting, 646
wetting by polar liquids, 648
hydrophobic coatings on, 679
.. ----ndex
20,)
57,
411
599
Ins, 681
ium
,637
>r
.ion,
'ace
,395
1,693
645
.rfaee
Subject Index
Surface, heat of (cont'd)
hydroxylated: strength of interaction with
adsorbates, 653
structure of, 625
hydroxylation,
heat of, 646
,
.. .
2
hydroxyl groups: per nm " 631
theoretical eoncentration, 636
types .er, 626
ion exchange groups on powder, 577
ionization, equations for silanol groups on,
183, 184
Surface modifications of: powders, 571
s(),l particlC$, 407
Surface, modified: by esterification, various
orgamc IlroupS, 694
Surface, modified with ehromlum complex
with organic acids, 688
with organosilicon groups, 695
Surface, quartz, dehydration of, 641
Surface, radius of curvature, effect on
solubility, 50
reactions. non-ionic, tabulation of, 676,
677
rehvdration of, 637-645
....esidual valences". 622. 6~3
Surface, silica: acidity of, 183..660
adsorption of positively charged particles
on, 710
denaturation of proteins. by, 765
modified with metal phosphates, 410
nature of, 624
Surface. silica, uniform, non-porous, 653
silica, unique among oxides, 665
silanes, commercial for reaction with, 698
silanol groups, reactions with, 630
siloxane, definition of, 505
sol particles, modified with organic
materials, 412
structure, review, 624
Surface tension, role in gel shrinkage, 536
Surface types: energy.of, 645
on silica, 505
Surface, underlying silica, 624
Surface, water adsorbed on: AMR of, 629
distinguishing from silanol groups, 629
entropy of, 629
'
heat content, 629
Surface, wetting of, 646
Surfactant: cationic, adsorption, surface area
measurement, 473
effects of silica, 594
non ionic (polyether), inhibitor of silicosis.
781
803
Surveys of: adsorption of metal iOns on the
silica surface, 672
silica chemistry, 2
silicosis, 770
Syncarpia laurifolia, Ten., see Australian
turpentine tree
Syneresis of sponge skeleton to flint boulder,
739
Synthesis of opal, 404
System, water-silica-sodium monoxide, 118
Tabasheer, silica gel in bamboo, 743

Tanning leather with silicic acid, 300, 762
research, 288
Tartaric acid, no complex with silica, 158
Temperature, effect on: final particle size, 242,
243 "
gelling, 368
particle growth, 241, 242
Temperature, subterranean estimated from
dissolved silica, 14
Tempering steel, quenching in colloidal silica.
431
Tetra alkyl silicate, combustion hydrolysis to
pyrogenic silica" 567
Tetra butyl ammonium silicate, 151
Tetraethyl ammonium silicate, 131
Tetraethyl urea, complex with silicic acid, 294
Tetrahydrofuran, adsorption on silica, 653
Tetra hydroxyethyl ammonium silicate, 152
Tetramerie silicic acid, cyclic, from
laumontite, 141
Tetramethyl ammonium: aluminosilicate,
-, soluble, 154
counterions, 359
ion, catalyst for gelling, 237
ions: coagulating effect on silica, 376
may reverse charge on silica, 671
silicate, 131, 142, ISO, 151,421
Tetraphenyl boron anion, titrant for cationic
polymers, 394
Tetra propyl ammonium silicate, 18
"Tetrasilicatc", sodium, crystalline, 158
Textiles: fiberglass, printing on, colloidal silica
binder, 432
treatment with colloidal silica, 425
Th'eory of: antifoaming agents, 434
gel strength! 369
nucleation, 219
silicosis mechanism, 770
site-binding, of adsorption, 664
viscosity, thixotropy, increased with silica,
589
~..
.,
-_...
Subject Index
Thermal: expansion of water near silanol

surface, 628
insulation of silica, 424
methods, surface area measurement, 475
see also Heat, 475
Thermodynamics, silica-water, system, 6
Thermodynamic stability, colloidal silica, 318
Thermogravimetric method, used on silicate
glass, 132
Thickener in polymer dispersions, 435
Thickening agent for liquids, 588
Thixotropy: increasing with silica, 588
. theory of development with silica, 589
Thomas equation for spheres in suspension,
361
Thompson-Gibbs effect, see OstwaldFreundlich,SI
Theria, silica coating on, 8&
Thorium: ions: adsorbed on silica, 668
reverse charge on silica, 671
offsetting effect of fluoride, 211
oxide on silica surface, 411
oxide particles, silica coated, 330
phosphate cation exchange sites on silica,
576
Thujaplicata (conifer) chelate of silicon in, 748
Tissue graft rejection, reduced by silica, 783
Titanium dioxide: silica coating on particles
of, 87, 330
suspension, opalescent, 404
Titanium dioxide coating, on silica particles,
411
Titanium phosphate coating on silica, 410
Titration method (Sears) surface area by, 353
Tobacco, smoking, enhances silicosis, 775
Toluene, adsorption on silica, 656
Toxicity: cytotoxicity; 761
extreme of p-tolyl silatrane, 785
of silica, 757 .
t-plot, detection of micropores, 498
t-plot method, surface area measurement, 469,
470
Traction of locomotives, improving with
silica, 426
Transformer laminations, silica coating on,
431
Tridymite: crystals, effect on macrophages,
760
from colloidal silica, 313
solubility in water, 33
stability range, thermal, 15
Triethanol amine: conversion to substauted

silatranes. 785
Triethanol amine, formation of atranes, 158
Triethyl phosphate: complex with, 293
silylation of silica particles in, 414
Triisobutyl aluminum, reaction with silanol
groups, 636
Trimethyl silyl derivatives of polysilicic acids.
203
Trimethyl silyl groups, modification of
particle surface, 414. See a/so Silicic
acids, trimethyl silyl derivatives of
Tripoli powder, microcrystalline silica, 569
Trisilicic acid, linear, from natrolite, 141
Tropalone: chelate with silicon, 157
isopropyl, chelate with silicon in plant, 748
Trypsin: association with silica, 763
bovine, remains active bound on silica, 766
Turbidity, absorbance of colloidal silica, 348
coagulation increases, 372
Ultracentrifuge studies of colloidal silica, 350
silicate solutions, 133
Ultrafiltration: micrcgel, plugging effect, 342
of sodium silicate solution, 129, 130
of sols, concentration by, 340
rate, effect of sol concentration, 341
salt removal by, limit of, 341
Ultramicropores, see Submicropores
_Ultrasonic vibration, effect on double layer,
359
Uniform spherical inorganic particles,
formation of, 403
Univalent cations, adsorption of, on silica, 666
Unsaturated hydrocarbons, reaction with
dehydroxylated surface, 693
Uranium: adsorbed on silica from acid, 595
oxide particles, silica 'coated, 330
reaction .....ith monosilicic acid, 10,90, 191
Uranyl ion. adsorption on silica surface, 668
Urea-formaldehyde polymer, coacervation
with silica, 398
Urinary: calculi from excessive intake of silica,
658
tract of cattle, silica calculi in, 741
Urine: excretion of silica in, 758
from silicosis patients, high in
hydroxyproline, 766
Urticaria dioica, see Nettles
Uses of: colloidal silica, see Colloidal silica,
uses
I
f.
4
I
I
---Index
Subject Index
.uted
'.
Uses of (cont't!)
gels and powders. 578'
soluble silicates. 121. 149
,.
anol
acids.
Silicic
:s of
569
II
It. 748
a. 766
a.348
:a.350
:t.342
<.
ayer,
:a.666
:th
,595
), 191
e,668
ion
'silica,
iIiv.
"-
l.
. Valences. residual. on surface. 623

Van der Waals force. 373. 374. 647
factor in adhesion of water to surface. 647
Vaporized silica. pyrogenic powder. 565'
Vesical heaturia, in cattle. high silica. 758
2-Vinyl pyridine oxide. effect on silica uptake
by rice plants, 750
Vinyl pyrrolidone (and -N-oxide), H-bonding
with silica, 300
Virus crystals, iridescent colors in, 403
Viruses, silicon essential to, 734
Viscosity: equations for spheres in suspension,
361
increase during gelling, 236
Mooney equation for, 236, 238
silicate solutions. 119, 121
Viscosity: sol. 360
aggregation effect in, 588
microgel, increase due to. 23'1, 232
particle size effect. 245
salt effect, 326
surface bound water, effect of. 36'1
types of particles. effects of, 362
spheres in suspension, 361
versus molecular weight of silica, 246
Vitamin C, stabilized on sillca gel, 767
Yitron, units in glass, 164
Volatility of silica in steam, 12
Volcanic ash, role in silicification: and
petrifaction, 90
Wallpaper, antisoil treatment, 426
Water: adhesion to surface, factors involved.
647
adsorbed, distinguishing from silanol
groups, 629
adsorption: for measuring surface area. 472
from alcohols onto silica, 657
on dehydrated surface, 65 I
on hydrophobic silica surface. 700
on quartz surface, 642
as dry powder, 594
boiler feed, silica content. 12
content in solid amorphous silica.
equilibrium, 633
diffusion into solid amorphous silica, 633
drinking, silica in, 757
105
Water (cont't!)
entropy of, on silica surface. 629
Water, ionization constant versus
temperature, 49
Water on hydroxylated surface, state of. 627,
628
on silica surface. N MR of, 629
heat content of. 629
silica removal from. 78
similarity to silica. 3
solubility in amorphous solid silica. 5
thermal expansion of. near silanol surface,
628
trapped, 632. See also Hydroxyl groups,
internal
treatment. with activated silica sols. 30 I
undercooled structure of, 3
Water-glass. 117. See also Sodium silicate
Wax. aritislip on floors; 425
Weathering of rocks by algae, lichens. 733
Weevils. in grain, control by silica dust. 752
Wetting: hydrophobic surfaces by colloidal
silica. 427
of silica surface by water, 646
Wetting angle on adsorbed CETAB on silica.
681
Wet treatments of silica gel. 528
Wheat, silica in leaves. 741, 744
White blood cell, see Leucocite, Phagocyte,
and Macrophage
Window shades. antisoil treatment. 426
Wood: immunity to marine borers. by silica,
746
species. silica content of. 746
tropical, silica particles in. resist borers, 7!t6
Xanthomonas colloid. thickener for colloidal
silica. 423
Xerogel, definition. properties, 463, 533
X-Ray, low angle scattering: particle size by,
476
pore characterization by, 479. 503
"X-value" definition. 208
.,
"
I
~
1\
.1
.j
Yates theory of thermodynamic stability of

colloidal silica, 319
Zinc: metal paints. bonded with silica. 430
retards dissolution of silica. 75
-rich anticorrosion primer paints, 149, 432
.,
;t
l
.,
866
Zinc-arnmine complexes. adsorption on silica.
. 670
Zinc (en)i-. ionic area of. 473
Zinc (en)i- adsorption. surface area by. 472
Zinc ions reverse charge on silica. 671
Zinc silicate. 162
----Subject Index
-.
Zinc silicate icont'd)
from silica. 597
Zirconium: ions adsorbed on silica. 595. 671
ions reverse charge on silica. 671
oxide coating on silica particles. 411
phosphate coating on silica particles. 410
. ......-".,:-.- -......:.:.. _
~_-:-
..
-_.
:..-
'
._-..J_... __"..
.!
About the author

RALPH K. ILER is currently a consultant and a member of the Advisory
Board of the Journal of Colloid and Interface Science. He received his B.Se.
and Ph.D. degrees in' chemical engi...
.
neering from the University of Toronto,
and worked' for Canadian industries,
Ltd. in Montreat and the Tire Division of .
J.' ..:
U.S. "Rubber Company at Detroit, Michigan. From 1937 to 1974, Dr. lIer con- '.
ducted research in various capacities
for E.1. duPont de Nemours and Company. He is responsible for approxi, mately 100 U.S. patents, and is the au.. thor of over 25 scientific publications'
. and THE COLLOID CHEMISTRY OF
SILICA AND SILICATES.
.~
'
-,
.,
.~
. :.:' ;....
'.'
".
~..
~t~<
,
. .l
- - ..
-~
.....
--
, ..
.'
"-_.-.'_.
- "....
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.'

Chemistry of Silica - Ralph Iler

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W~{!.~.~.:.

' . ,' . '

Solubility, Polymerization, Colloid and

To my wife, Mary, with gratitude for her never-ending

Previous Books and Reviews of Silica Chemistry

. 1 The Occurrence, Dissolution, and Deposition of Silica

The Silica-Water System

Solubility of Cristobalite and Tridymite

Removal of Silica from Water

Sodium and Potassium Silicates

Silicates with Coordination Numbers Four and Six

General Theory of Polymerization

Reaction with Molybdic Acid

and Giller; Bechtold, Vest, and Plambeck; Acker: H~ebbel

Colloidai Silica~Concentrated Sols

Definition of Colloidal Silica and Historical Development

Source of Chemically Reactive Silica

5 Silica Gels and Powders

Characterizing Pores by Adsorption h'Jtherms

Particle size and packing, Loss of SUrface area by particle

Electron micrographs, Specific sur(:II,;C area, Low angle X-ray

Pore volume, Pore size and size dislt'ibution, Miscellaneous

Electron micrographs, Partial diss,'lltlion method, Mechanical

" " _..._ - -_._ -... -

. -'~.-"--, ....... - - - -.. -

" ' - " - -~-_... _. __.. - ,---

Drying and Shrinkage-Xerogels

Reinforcing and Other Effects in Organic Solids

6 The Surface Chemistry of Silica

Reviews and Summaries

Active Sites, Free Radicals, Active Oxygen, Ozone

Silicosis-Pneum oconiosis- Fibrinogenesis

THE CHEMISTRY OF SILICA

Numerous outlines or surveys of the chemistry of silica. especially the water-silica

lb. R. Brilchner, "Properties and Structure of Vitreous Silica:' J. Non-Cryst, Solids. 5,

3. E. A. Hauser, Silicic Science, Van Nostrand. Princeton. N.J., 1955.

1 I. P. K. Maher. Kirk-Othrner Encyclopedia of Chemical Technology. 2nd ed.. Vol. 18.

10. T. D. Coyle. Kirk-Othmer Encyclopedia of Chemical Technology. 2nd ed . Vol. 18.

7. W. Stober~ Kolloid Z. 147, 131 (1956).

6. W. E~tel. Silicates Science. Vols. I-VI. Academic. New York. 1964-1975.

8. S: (Greenberg.J. Chem, Educ. 36, 218 (1959).

The Occurrence, Dissolution,

THE SILICA-WATER SYSTEM

The Occurrence. Dissolution. and Deposition of Silica

For massive amorphous silica, the equilibrium concentration of Si(OH). at 25C

The Silica-Water System

phous silica consist of extremely small particles of amorphous silica. or porous

[Sill+mOzlI-clIZlzl+zmlz-p,(OH)IlZHm-p,] + 2pm HzO

where n = number of silicon atoms in a polysilicic acid molecule or particle or

The: Occurrence. Dissolution. and Deposition of Silica

Thermodynamics of the System

The heat of formation of silica by the reaction

Alpha quartz (q)

- 1220 (~Fq - AFcs 200C)

for the overall equilibrium

and Deposition of Silica

irmed, These. in turn,

'or alpha quartz, and

Relating Particle Size and Composition

.rphous solid silica

w ... weight of one anhydrous Si0 2 particle (grams)

weight of one surface hydroxylatcd particle

The Occurrence. Dissolution. and Deposition of Silica

taneous changes are unlikely to occur.