Journal of Non-Crystalline Solids 121 (1990) 397-403 397

North-Holland

THE BASE-CATALYZED HYDROLYSIS AND CONDENSATION REACTIONS OF DILUTE

AND CONCENTRATED TEOS SOLUTIONS *

Michael T. HARRIS, Ronald R. BRUNSON and Charles H. BYERS

Chemical Technology Division, Oak Ridge National Laboratory 1, Oak Ridge, Tennessee 37831, USA

The synthesis of submicron silica particles by the hydrolysis and condensation of dilute and concentrated solutions of
tetraethyiorthosilicate (TEOS) has been studied in low molecular weight alcohols (C1-C4). A base (ammonia) was used to
catalyze the reaction. Raman spectroscopy, gas chromatography and the molybdate method were used to establish the
hydrolysis and condensation kinetics. Dynamic and classical light-scattering techniques were employed to monitor particle
growth and particle number concentration kinetics, and particle size distribution. The effects of solvent and TEOS
concentration on the degree of monodispersity of the particles are discussed. Further, the chemical and particle growth data
were used to test theories of homogeneous nucleation and aggregative growth, which have been proposed as mechanisms that
govern the growth of submicron monodisperse silica particles by TEOS hydrolysis.

1. Introduction independent of the initial TEOS concentration.

Tetraethylorthosilicate (TEOS) has been studied
extensively in recent years because of its potential
as a model and precursor material for the synthe-
sis of submicron monodisperse oxide particles.
Monodisperse silica powders are especially im-
portant as base materials in the production of
composite ceramics and as support materials for
chromatographic packing.
The method of Stober et al. [1] is used to
synthesize submicron monodisperse silica par-
tieles. Their method utilizes the base-catalyzed-hy-
drolysis of TEOS in various low molecular weight
alcohols. By varying the solvent and the con-
centration of the morphological catalyst (NH3, i.e.
O H - ) and water, particles are formed from less
than 0.05 to 2 ~m in diameter. An interesting
feature of the Stober-Fink-Bohn method is the
formation of monodisperse silica particles during
the hydrolysis of dilute and concentrated TEOS
solutions. Further, the ultimate particle size is
* Research sponsored by the Office of Basic Energy Sciences,
U.S. Department of Energy under contract DE-AC05-
84OR21400 with Martin Marietta Energy Systems, Inc.
Operated by Martin Marietta Energy Systems, Inc.
Two mechanisms, homogeneous nucleation and
aggregative growth [2], have primarily been pro-
posed to explain the formation of monodisperse
silica particles by the Stober-Fink-Bohn method.
It is the purpose of this study to provide experi-
mental data on the hydrolysis and condensation
reactions and particle growth kinetics which will
hopefully help to elucidate our understanding of
the formation of monodisperse silica particles by
base-catalyzed hydrolysis of TEOS.
2. Experimental
Methanol, ethanol, 1-propanol, 2-propanol, and
1-butanol were used as solvents and were of ana-
lyrical reagent quality. The TEOS (Fisher Scien-
tific Co.) was the purified grade. Distilled water
was used in all studies. The ammonia (Mallick-
rodt, Inc.) was analytical grade.
In each experiment, separate solutions of am-
monia-water-alcohol and TEOS-alcohol were
prepared to minimize localized reactions zones
during the mixing of the reactants. After mixing,
the concentration of water and ammonia was 6.0M
and 0.7M, respectively, for all the experiments.

0022-3093/90/$03.50 © 1990 - Elsevier Science Publishers B.V. (North-Holland)

398 M.T. Harris et al. / Dilute and concentrated T E O S solutions

Initial TEOS concentrations were 0.05M for dilute
solutions and 1.0M for concentrated solutions.
The chemical analysis included gas chromatog-
raphy, the molybdate method for soluble silica
determination, and Raman spectroscopy. A Tracor
550 Gas Chromatograph equipped with a flame-
ionization unit was used to follow the production
of ethanol. The glass chromatographic column was
packed with 1% SP1000 on 80/100 Carbopac C
and was operated at 130 ° C.
The molybdate method was used to monitor
the total soluble silica (TS) (i.e., unreacted TEOS
plus monomeric and some dimeric silicic acid) in
the reaction medium. The method was adapted
from the procedure given by Makrides et al. [3].
Raman spectroscopy was performed during the
hydrolysis of concentrated TEOS solutions in
ethanol. Before running Raman spectroscopic
analysis, acetic anhydride was added to a sample
of the reaction medium. The acetic anhydride
reduced the rate of hydrolysis by neutralizing the
[ O H - ] ions and flocculated the submicron par-
ticles for easy filtration through a 0.22 ~m Duro-
pore filter. Raman spectra were obtained in a
standard quartz spectrophotometer cell with the
use of a Spex 1404 spectrometer that was con-
trolled by a Compudrive microprocessor. The
sample was excited with the 488 nm line of a
Spectra-Physics 165-06 argon ion laser and a power
setting of 400 mW. The scattered light was col-
lected at 90 o without a polarizer analyzer and was
detected by a photomultiplier/photon counter
(EMI No. 9863B350) device. The photomulti-
p l i e r / p h o t o n counter was connected to an IBM
PC-AT computer which housed a multichannel
analyzer board for data acquisition and display.
The characteristic peak at 790 cm-1 was used to
follow the TEOS concentration.
Classical and dynamic light scattering measure-
ments were used to determine the intensity aver-
age particle size, the weight-averaged particle size
distribution, and the particle number concentra-
tion. All samples were diluted such that the par-
ticles were at least 20 diameters apart, thus mini-
mizing multiple scattering and particle-particle
interactions. Classical-light scattering (CLS) mea-
surements were obtained by measuring the trans-
mittance of a 400 nm light source passing through
a dilute solution of colloidal particles. Those mea-
surements were carried out in a Perkin-Elmer
Model 200 spectrometer. The method of calculat-
ing particle number concentration from CLS
methods is discussed by Hulst [4]. The dynamic-
light scattering (DLS) spectrometer used here has
been described in previous publications [5,6].
3. Theory
3.1. Chemistry and reaction kinetics
Understanding the mechanisms which control
the formation of monodisperse silica by the base-
catalyzed hydolysis of TEOS requires an initial
investigation of the chemical behavior of the hy-
drolysis and condensation reactions. The overall
hydrolysis and condensation reactions are given as
follows:
Si(OC2H5)4 + 4 H 2 0 OH- )Si(OH)4 + 4C2HsOH,
(1)
OH-
Si(OH)4 ~ SiO 2 $ + 2H20. (2)
Schmidt et al. [7] and Byers et al. [6] have pro-
posed a mechanism for the base-catalyzed hydrol-
ysis of TEOS where TEOS reacts with hydroxide
ions and water to form a transition state complex
which decomposes to form monosubstituted silane,
alcohol, and hydroxide ions. Initially, the O H -
attacks the TEOS molecule by a nucleophilic reac-
tion mechanism. Since nucleophilic attack is sensi-
tive to the steric effects of the substitutes and the
electron density around the silicon atom, the fewer
bulky and highly basic alkoxy groups surrounding
the silicon atom, the more rapid the attack by the
O H - . Thus, the controlling step will involve the
removal of the first alkoxy group and the mono-
meric partially hydrolyzed products will hydrolyze
at a faster rate, tending to produce monomeric
silicic acid [8,9]. Using the above mechanism and
assuming that condensation occurs between com-
pletely hydrolyzed species, the resulting rate ex-
pression for the hydrolysis reaction is
d[TEOS]
dt k~ [H20] I o n - ] [TEOS ] . (3)
 M.T. Harris et al. / Dilute and concentrated TEOS solutions
When ammonia is used as the base and the ioniza-
tion reaction of ammonia with water is consid-
ered, eq. (3) becomes
d[TEOS]
dt k~ [H20]"5[NH3 ]°'5[TEOS].
Iler [10] has proposed a mechanism for the con-
densation of silicic acid which also involves a
nucleophilic attack on the silicon by the hydroxide
ion. Thus, the rate of condensation should be
proportional to the concentration of base catalyst.
In contrast, eq. (2) suggests that the dissolution
reaction should be proportional to [H20] 2. There-
fore, the rate equation for the silicic acid (eq. (2);
[OH-] = constant) is
d[Si(On)4]
at = k~ [H20]"5[NH3]°5[TEOS]
- kc[Si(OH)4 ] + kDSp[H20] 2,
where Sp is the total surface area of the silica
particles. This equation is expected to be applica-
ble if the condensation of silicic acid primarily
yields nuclei. However, if the silicic acid is pre-
cipitating on the surface of the particle, if [OH-]
is constant, and if the rate of reaction is surface-
reaction controlled, it is expected that the k c
should be proportional to the total surface area of
the silica particles. Therefore, eq. (5) becomes
d[Si(OH),]
at k~q [H20]"5[NH3 ]°5[TEOS]
- k~Sp[Si(OH),] + kDSp[H20] 2,
or, considering the fact that k D / k ~ = [Si(OH)4le
= K[SiO2] ,
d[Si(On)4]
dt k~ [H20]l5[NH3 ]°5[TEOS]
- k~Sp [Si(OH)4]
. 2 • [NH3] °'9. Table 1 lists the values of k~, the 'ab-
+ kDSp[H20 ] [S,O2] ,
where k ~ = k ~ K and [Si(OH)4]e is the equi-
librium concentration of silicic acid. Equations
5-7 can be written in terms of the experimentally
determined [TS] by noting that [TS] = [TEOS] +
[Si(OH)4].
399
3.2. Controlled homogeneous nucleation and
aggregative growth
The theory of controlled homogeneous nuclea-
(4) tion involves slowly increasing the concentration
of a precipitable material, [Si(OH)4 ] and other
silica species, to attain a degree of supersaturation
at which nucleation becomes appreciable. Since
the generation of precipitable material is slow, the
formation of nuclei accompanied by the relief of
supersaturation is restricted to a relatively short
period, and few new nuclei are formed after this
initial outburst. Subsequently, the nuclei grow by
the addition of monomer to its surface [11]. In this
mechanism, the final number of particles is essen-
tially the same as the number of particles that are
produced during the short nucleation period.
Aggregative growth [2], which is based on the
electric double layer theory, assumes that very
(5) small ( - 1-5 nm) nuclei, because of their colloidal
instability, rapidly coagulate to form larger, more
stable spherical particles. As nucleation proceeds,
the very small nuclei preferentially attach to the
larger particles rather than aggregate with other
primary nuclei. Thus, the formation of monodis-
perse spherical particles is achieved by the con-
trolled aggregation of these nuclei.
4. R e s u l t s a n d d i s c u s s i o n
4.1. Hydrolysis and condensation reactions
The concentration of TEOS in the reaction
(6)
medium is computed from the experimentally de-
termined ethanol concentrations. In dilute and
concentrated solutions, these data exhibited pseu-
do-first order kinetics with respect to the TEOS
concentration for the hydrolysis reaction. Previous
studies [6,12] have shown that this pseudo-first
order rate constant, kr~, varies with [H20] 1"5 and
(7)
solute' rate constant, for the hydrolysis of TEOS
in each of the solvents. These data show that the
rate of hydrolysis in the solvents decreases at
1-butanol > methanol > 1-propanol > ethanol-2-
propanol. The effect of solvent on the rate of
hydrolysis has been observed by other investiga-
400 M.T. Harris et a L / Dilute and concentrated TEOS solutions

I I I I I I I I I I a n d 6.0M H 2 0 in m e t h a n o l , e t h a n o l , 1 - p r o p a n o l ,
1.000 ~] METHANOL --
A 2-PROPANOL --. 2 - p r o p a n o l , a n d 1-butanol. S i m i l a r to the rate of
~7 1 -BUTANOL
0.800 ~k~ 0 1 -PROPANOL -- hydrolysis, the rate o f c o n d e n s a t i o n d e c r e a s e d as
~" 0 ETHANOL --
1-butanol > methanol > 1-propanol > ethanol >
0.600
v 2 - p r o p a n o l . This is expected, since b o t h the hy-
o.,,oo drolysis a n d c o n d e n s a t i o n r e a c t i o n s involve a sim-
ilar r e a c t i o n m e c h a n i s m , i.e., the n u c l e o p h i l i c at-
0.200
tack on the silicon b y the h y d r o x i d e ion.
I n a d d i t i o n to the h y d r o l y s i s rate c o n s t a n t s ,
0
0 2 4 6 8 10 103 table 1 c o n t a i n s the rate c o n s t a n t s (i.e., k c, k ~ ,
TIME (s) k D a n d k ~ ) for the c o n d e n s a t i o n a n d d i s s o l u t i o n
Fig. 1. Total soluble silica: TEOS hydrolysis in various al- r e a c t i o n s w h e n eqs. (5), (6), o r (7) a r e used. T h e
cohols (1.0M TEOS, 0.7M NH4OH, 6.0M H20 ). total surface area, Sp = 4 N ~ f f z, was d e t e r m i n e d
f r o m the i n t e n s i t y a v e r a g e d p a r t i c l e radius, ~, a n d
the p a r t i c l e n u m b e r c o n c e n t r a t i o n , N, m e a s u r e -
m e n t s that were o b t a i n e d f r o m light s c a t t e r i n g
t o t s [13,14]. T h e relative rates o f the h y d r o l y s i s measurements. The condensation and dissolution
r e a c t i o n in 1 - b u t a n o l , 1 - p r o p a n o l , e t h a n o l a n d rate constants, which r e q u i r e Sp, were o n l y c o m -
2 - p r o p a n o l h a v e b e e n e x p l a i n e d in terms o f h y d r o - p u t e d for e t h a n o l (dilute a n d c o n c e n t r a t e d solu-
gen b o n d i n g a n d steric effects [6]. T h e u n e x p e c t e d tions) a n d 1 - p r o p a n o l (dilute solutions) b e c a u s e of
faster rate of h y d r o l y s i s in m e t h a n o l requires fur- flocculation, which resulted in e r r o n e o u s p a r t i c l e
ther i n v e s t i g a t i o n to d e t e r m i n e if this p h e n o m e n o n size m e a s u r e m e n t s for the o t h e r solvent systems.
is d u e to alcoholysis o r a l t e r a t i o n s in the b a s i c i t y T h e d a t a clearly show a large difference b e t w e e n
( c a u s e d b y h y d r o g e n b o n d i n g [15]) of the r e a c t i o n the c o n d e n s a t i o n rate c o n s t a n t , k c (eq. (5)), for
medium. the 1 M a n d 0.05M T E O S solutions. O n the o t h e r
F i g u r e 1 shows the c o n d e n s a t i o n kinetics for h a n d , k ~ (eq. (6)) was a p p r o x i m a t e l y equal for
the h y d r y l o s i s of 1 M T E O S with 0.7M N H 4 O H the h y d r o l y s i s of the 1M a n d 0.05M T E O S solu-

Table 1
Summary of results for TEOS hydrolysis in various alcohols
Solvent [TEOS] k~I a) Eq. kC k~- k D b) k• c) r2
(mol/l) (rain - 1) (rain - 1cm)
methanol 1.0 0.0036
ethanol 0.05 5 0.0015 1.4×10 -8 0.998
ethanol 1.0 0.0025 5 0.0119 6.0 >(10-7 0.975
ethanol 0.05 6 0.00029 4.7×10 .8 0.995
ethanol 1.0 0.0025 6 0.00031 7.8×10 .7 0.980
ethanol 0.05 7 0.00021 8.0>(10 -7 0.997
ethanol 1.0 7 0.00023 8.8>(10 -7 0.992
1-propanol 0.05 0.0031 6 0.00039 4.2×10 -8 0.980
1-propanol 0.05 0.0031 7 0.00056 1.2>(10 .6 0.989
1-propanol 1.0 0.0030
2-propanol 0.05 0.0018
2-propanol 1.0 0.0019
1-butanol 0.05 0.0058
1-butanol 1.0 0.0057
a) min- 1 (mol/l)- 2.4.
b) min - 1 cm(mol/1)- 1.
c) rain- l cm(mol/1)- 2.
 M.T. Harris et aL / Dilute and concentrated T E O S solutions 401

X I0 -2
6
I
4.2. Particle size, size distribution, and particle
number concentration

4
\ E1 EXPERIMENTAL [TS]
A THEORETICAL [SI(OH)4 ]
O EXPERIMENTAL [SI(OH)4 ]
THEORETICAL [TS]
Figure 3 shows the intensity-averaged particle

o
E 3
\ \ ElN o l I THEORETICAL [TEOS] size and particle number concentration for the
hydrolysis of 1M TEOS in ethanol with initial
[ H 2 0 ] = 6.0M and [NH4OH ] = 0.7M. The figure
•~ El\ shows that the initial particle radius starts at ap-
proximately 0.05 rtm and continues to grow to a
1
final particle radius of 0.135 t~m. Thermodynamic
consideration suggests that the initial particle size
0
I I l I ~ "~ "" l " "~'--- -L .iJ __ 1 I (i.e., nuclei) should have been 0.001 to 0.005 I~m.
0 40 80 120 160 200 240 It requires about 10 s to obtain particle size mea-
TIME (rain)
surements by dynamic light scattering. Therefore,
Fig. 2. TEOS hydrolysis in ethanol (0.05M TEOS, 0.7M as suggested by the aggregative growth mecha-
NH4OH, 6.0M H20 ).
nism, the very small nanometer size nuclei rapidly
aggregate to form the larger more stable colloids.

tions in ethanol. This suggests that primarily the 10 12

condensation reaction involves the addition of 2O
1 I I I I I I I I I I I I I
monomeric silicic acid to the surface of the par- 18
16
ticles rather than the continuous formation of new
E 14
nuclei. u
12
When eq. (6) was used to fit the experimental o
data, the dissolution rate constant, k o , varied by 1o
68 ~/°''q-'°~ °"''' ° ~ °
an order of magnitude between the 1M and 0.05M z
TEOS in ethanol solutions. However, when eq. (7)
2
, f
is employed, k[~ did not vary for the 1M and 0
0.05M TEOS. This indicated that the equilibrium PARTICLE NUMBER CONCENTRATION,
concentration of silicic acid increased with the ETHANOL
concentration of silica in solution.
Figure 2 shows the fit by eq. (7) of the experi-
0.27 I
0.25 /I:] a,~.O --
mental ITS] and [Si(OH)4 ], and the theoretical 0.25
oo
oj o
[TEOS] data for the hydrolysis of 0.05M TEOS in o.21 d
ethanol. The data are adequately described by eq. 0.19 7
(7). It is interesting to note that the [Si(OH)4 ] 0.17 ~o
0.15
( - 0 . 0 1 tool/l) was greater than the equilibrium
0.13
concentration, [Si(OH)4]e = 0.003 mol/1 through 0.11
a great portion of the reaction. This was observed
0.09 1~ 1-
in the dilute and concentrated solutions and in all o.o7 I I I [ I I I I I I I I I
of the solvents. Therefore, it is expected that 0 20 40 60 80 1O0 120 140
TIME ~rnin)
nucleation occurs over most of the reaction; al-
though, the greater portion of the silicic acid pre- PARTICLE DIAMETER,
ETHANOL
cipitates on the surface of the particle. The very
small nuclei ( 1 - 5 nm) preferentially deposit on the Fig. 3. TEOS hydrolysis in ethanol: particle size and number
larger particles in solution. concentration (1M TEOS, 0.7M N H 4 O H , 6.0M H 2 0 ).
402 M.T. Harris et aL / Dilute and concentrated TEOS solutions

I I I I I I I I I I I I i I I I I It is also observed from fig. 4 that the particles

1.; - -
CONT~N: I M TEOS are larger and there is a wider particle size distri-
F- • "l~,~ EXP.: 1 M TEOS
m ' ' O " CONTIN: 0.05 ~d TEOS
: : EXP.: 0.05 _M TEOS
bution for the 1M TEOS sample than for the

0.8
~,. ?/"% 0.05M TEOS sample. Transmission electron mi-
croscopy has shown that this occurs in all of the

,.~ O.E i '?' \ solvent systems except 1-butanol where the par-
ticle size was essentially the same but the size
~ 0.4 distribution broadened as the initial TEOS con-
centration increased. Further, the particle size dis-
No tribution in all the solvents is about the same;
thus, the solvent has little effect on the degree of
0,03
monodispersity for the reaction conditions of this
0.05 0.07 0.09 0.11 0.13 0.15 0.17 0.19 0.21

r, PARTICLE RADIUS (,~rn)

study. This was also observed by Stober et al. [1].
Fig. 4. TEOS hydrolysis in ethanol: particle size distribution
The particle size tended to increase with the
(0.7M NH4OH, 6.0M H20 ). molecular weight of the alcohol. This was possibly
due to the chemical and viscous effects, and in-
creasing organophogicity of the particles as the
alkyl chain of the alcohol increases. D a t a obtained
The particle number concentration, which is by Tan et al. [17] indicated little effect of solvent
weighted towards the larger particles, increases on particle size at temperatures < 40 ° C, but a
until it attains a final particle number concentra- slight increase in particle size with increasing
tion of 1 × 1013/cm3 at - 20 min. The final par- molecular weight of the solvent at higher tempera-
ticle number concentration is attained in the dilute tures.
and concentrated TEOS solutions at - 2 0 min.
The long period over which the particle number
concentration increases and the high supersatura- 5. Conclusions
tion levels favors the aggregative growth mecha-
nism. This study has shown that the rate of hydroly-
To check the particle number concentration sis and condensation are affected in a similar
obtained from light scattering, it was assumed that manner by the solvent type. The effects are attri-
all of the TEOS was converted to silica, and that buted to hydrogen bonding and steric effects.
the density of silica was 2 g / c m 3. The final par- Condensation and dissolution data are best mod-
ticle number concentration for an ultimate particle eled by the addition of monomeric silicic acid to
radius of 0.135 ~tm was approximately 3 × the surface of the growing particles and the dis-
1012/cm3. These two particle number concentra- solution reaction occurring at the surface of the
tions are in fairly good agreement. particle. The conversion of silicic acid to nuclei is
The discrepancy between the particle number also occurring and is the predominate mechanism
concentrations that were reported above is most for the removal of silicic acid during the early
probably due to the particle size distribution (PSD) stages of the reaction. However, during most of
that exists in the sample. This is shown in fig. 4 the reaction, the silicic acid is primarily removed
where the PSD are computed from the analysis of by m o n o m e r addition to the particle surface. A
dynamic light scattering results by C O N T I N [16] complete model of this process must take into
and are obtained from transmission electron mi- account silicic acid removal by nuclei formation
crographs (TEM). The light scattering and T E M and monomer addition.
PSDs are in good agreement. Further develop- The monodispersity of the silica particles is
ments will entail modifying the computer code to affected very little by the alcohol solvents (C~ to
handle PSDs when computing the particle number (]4). However, particle size tends to increase with
concentration. increasing molecular weight of the alcohol solvent.
 M.T. Harris et al. / Dilute and concentrated T E O S solutions
The authors express their gratitude to Mike
Burgess for his careful efforts in performing the
experiments in this program.
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