Colloids and Surfaces A: Physicochemical and Engineering Aspects, IO (1993) 239-251 239

Elsevier Science Publishers B.V., Amsterdam

Hydrolysis and polycondensation of ethyl silicates.

1. Effect of pH and catalyst on the hydrolysis and
polycondensation of tetraethoxysilane (TEOS)

J. CihlZ
Technical University of Brno, Technickci 2,616 69 Brno, Czechoslovakia

(Received 5 June 1992; accepted 15 September 1992)

Abstract

The effect of pH and of catalysts on the course of the hydrolysis and condensation of tetraethoxysilane (TEOS) in
water-ethanol solution was studied with the aid of chromatography, potentiometry and gelation tests. Strong acids (HCI,
HCIO,, HNO,, H,SO,, p-toluenesulphonic acid), weak acids (Cl,CCOOH, (COOH),, ClCH,COOH, CH,COOH,
HCOOH) and LiOH were used as catalysts. The rate of hydrolysis depended on the pH of the solution and not on the
chemical structure of the catalyst. The hydrolysis was both acid and base catalysed and its rate was at a minimum
at pH 7.0.
The rate of condensation of the reaction products of the hydrolysis of TEOS (water-ethanol solutions of ethoxyhy-
droxysiloxanes) was at a minimum at a pH of about 2.0. The condensation was both acid and base catalysed and was
markedly accelerated by both HF and H, P04.

Keywords: Condensation; hydrolysis; kinetics; pH; tetraethoxysilane.

Introduction

Reactions of tetraethoxysilane (TEOS) with -Si-OEt + Hz 0

water have recently attracted considerable atten- I
tion from the point of view of the sol-gel processes I
hydrolysis oi TEOS
applied in the preparation of glass ceramics. The . -Si-OH + EtOH (1)
esterificalion
data obtained have also led to a better understand- I
ing of the physicochemical processes taking place
during the reactions of TEOS with water, which
I I
eventually lead to the formation of SiOz gels [l].
-Si-OEt + HO-Si-
If the transformation of TEOS into silica gel
I I
takes place in a water-ethanol medium, the process
can be described schematically at the level of the alcohol condensation
I I
. -Si-O-Si- + EtOH (2)
functional groups by means of Eqns (l)-(3): alcoholysis
I I

0921-7751/93/$06.00 0 1993 - Elsevier Science Publishers B.V. All rights reserved.

240
I I
-Si-OH + HO-Si-
I I
I I
water condensation
k -Si-O-Si- + HZ0
hydrolysis of sdoxane
I I
The alcohol or water hydrolysis and (poly)con-
densation reactions presented above are included
in the fundamental reactions that bring about the
conversion of TEOS to silica gel. In the course of
this conversion a wide range of intermediates is
formed which belong to the category of ethoxysi-
lanes, ethoxysiloxanes or ethoxyhydroxysiloxanes
[2-4]. Their structures and molecular weights
determine the properties of the intermediates (SiOl
~01s) or final products (SiOZ gels). Thus the rates
of hydrolysis and polycondensation determine the
structure and instantaneous properties of the pro-
ducts of the TEOS-water reaction. These rates
depend on the reaction conditions, especially on
the pH of the reaction solution. The dependence
of condensation rate (or of gelation time) on pH
has been investigated thoroughly for water solu-
tions of silicic acid and the results have been
summarized in the familiar Iler graph [S].
It follows from this graph that the condensation
rate in solutions of strong acids is at a maximum
for pH ranging from 6 to 7, and at a minimum for
the pH ranging from 1.5 to 2.0. In the alkaline
region the condensation rate of silicic acid falls
sharply and at pH above 11 it is not condensation
that takes place but a reverse reaction (depolymeri-
zation or hydrolysis of Si-0-Si bonds). It is logical
to assume that an analogous dependence of con-
densation rate on the pH of the solution also holds
for the reaction solution of TEOS [l]. However,
the results obtained from an examination of the
effect of pH on the condensation rate of water-al-
cohol solutions of TEOS [S-S] do not agree with
Iler’s conclusions [S]. This discrepancy may be
due to the complex mechanism of the TEOS
reaction with water, which includes not only con-
densation in the presence of silane groups but also
condensation in the presence of Si-OEt groups
J. Cihlbf/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
and the preceding formation of silanol groups by
hydrolysis. The other very important factor is the
water-ethanol medium in which the pH of the
TEOS reaction solutions was measured.
(3) On the basis of the above data from the literature
the following aims have been set for the present
work:
(1) to elaborate a method of measuring the pH
of the reaction products of TEOS hydrolysis and
polycondensation;
(2) to study the effect of pH on TEOS hydrolysis
and polycondensation;
(3) to study the effects of acid and base catalysts
on TEOS hydrolysis and polycondensation.
Experimental
Materials
Prior to application, the tetraethoxysilane
(TEOS pure, Alfa) was purified by vacuum distilla-
tion. The theoretical content of SiOZ was 28.5 wt%
and the Si02 content established by analysis was
28.5 wt%.
Ethanol (EtOH) and isopropanol (i-PrOH)
(pure, Lachema), desiccated over calcium and then
distilled, were used as solvents. The substances
(pure, Alfa) used as acid catalysts of the
TEOS reactions with water were HCl, HNO,,
HISOs, HClO,, p-toluenesulphonic acid (PTSA),
(COOH), , Cl,CCOOH, ClCH, COOH, HF,
CHJCOOH, HCOOH, H3 PO4 and HCl/LiCl
solution. The base catalyst LiOH was also used.
Techniques and methods
Reaction of TEOS with water
The reaction of TEOS with water (hydrolysis)
took place in a stirred laboratory batch reactor at
a constant temperature of 25°C for a period of
2-5 h. Reaction conditions, i.e. initial concen-
tration of TEOS (c&~~), initial concentration of
water (c&o), the type (acid HA or base B) and
concentration (cuA or cg) of the catalysts, the SiO,
J. CihW/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251 241

concentration and the dissociation constant pk,, .O

are given in Table 1.

Study of hydrolysis kinetics by gas

chromatography
The content of low molecular weight reaction
components (H,O and EtOH) in the reaction
solutions was determined on a Chrom 5 gas chro-
matograph (Laboratorni pfistroje) equipped with .O
a thermal conductivity detector and a stainless
steel column (2500 x 3 mm*) filled with Porapak IO0 200 300
Temperature of ln~ectton Chamber TC]
QS. The carrier gas was hydrogen or helium, with
a flow rate of 25 ml min- ‘. During the hydrolysis Fig. 1. Dependence of water and ethanol contents in the
of TEOS, samples of the reaction solutions were reaction solutions containing the hydrolysed TEOS on the
temperature of the chromatograph injection chamber.
removed and injected into the column. The water
(ethanol) content of the samples was evaluated by
the absolute calibration method [9]. The temper- in the temperature range lOO-200°C. It is only at
atures of the column and of the injection chamber higher temperatures that the contents of the two
were maintained at 140°C. The temperature of the components increase. Thus it can be assumed that
injection chamber was selected by plotting the at an injection chamber temperature of 140°C
dependence of the content of water and ethanol in there is only evaporation of water and ethanol
the reaction solutions on the injection chamber from the reaction solutions. The functional groups
temperature. It follows from the graph (Fig. 1) that (SiOH and SiOEt) bonded in the products of the
the contents of water and ethanol remain constant TEOS-water reaction were markedly liable to

TABLE I

Reaction conditions of TEOS hydrolysis and condensation

Reaction Catalyst cHA or cn CRos csioz c&o PKHA

no. HA or B (mol I-‘) (mol I-‘) (mol I-‘) (mol I-‘)

1 HCI 0.01 2.14 2.14 4.4 -7.0

2 H,SOb 0.01 2.14 2.14 4.4 -3.0
3 HNO, 0.01 2.14 2.14 4.4 -1.8
4 HClO, 0.01 2.14 2.14 4.4 > - 7.0
5 PTSA 0.01 2.14 2.14 4.3 ZO
6 CI,CCOOH 0.05 2.14 2.14 4.3 0.89
7 (COOH), 0.05 2.14 2.14 4.3 1.25
8 H,PO, 0.1 2.14 2.14 4.3 2.12
9 HF 0.1 2.13 2.13 4.4 3.17
10 CICH,COOH 0.1 2.13 2.13 4.4 3.17
II CH,COOH 0.15 2.13 2.13 4.3 4.16
12 HCOOH 0.24 2.17 2.17 4.4 3.75
13 HCI 0.04 2.14 2.14 4.3
14 HCl/LiCl 1~10-3/9*10-3 2.0 2.0 4.2
15 HCl/LiCl 4. 1O-4/96* IO-“ 2.0 2.0 4.2
16 HCl/LiCl 4 * lo-4/99 * 10-d 2.0 2.0 4.2
I7 HCl/LiCl 5. lo-5/995* lo-5 2.0 2.0 4.2
18 LiOH 0.01 2.19 2.19 4.4
242
undergo hydrolysis or condensation only at injec-
tion chamber temperatures exceeding 200°C.
Water concentration values at the beginning of
the reaction (c&o) and during the reaction (c&o)
were used to evaluate the water conversion x&o
and the hydrolysis rate constant kH. The conver-
sion of water (as a percentage) was calculated by
using the relationship
c&o - c&o
xL,cJ =
c&o
The initial hydrolysis rate t$ (mol l- ’ sp ‘) was
calculated from the time dependence of the concen-
tration of water in the reaction mixture by numeri-
cal differentiation
0; = dcu*o
( dt 1t=o
with subsequent calculation of the initial rate con-
stant of the hydrolysis kH (1 mall’ SiOZ SK’)
where
cSi02 = c&OS = 4CgiOEt
0
cSiOEt
being the initial concentration of SiOEt.
Polycondensation of hydrolytic products of TEOS
The reaction solutions obtained by TEOS
hydrolysis were kept in closed bottles at a temper-
ature of 25°C. At regular weekly intervals the
solutions were checked for their water and ethanol
contents, viscosity and pH (or pH’). The gelation
time t, was established from the viscosity vs time
plot. The condensation rate constant kK (1 mol-’
Si02 s ‘) was calculated from t, by means of the
relationship
kK= ’ (8)
f(f - 2)c0 4
where c&os is the initial concentration of TEOS
(mol SiO, l- ’ ) and f is the functionality of TEOS.
The value f = 2.05, reported by Bechtold et al. [3],
has also been confirmed by our kinetic studies.
J. CihlS/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
Determining the pH value
The pH values of solutions of hydrolysed TEOS
or of water-ethanol solutions of the acids were
measured with a pH meter equipped with glass
and calomel electrodes. The pH meter was cal-
ibrated in the range from 1.68 to 9.2 with the aid
of aqueous standards.
Determining phophorus bonded in SiOz gel
(4) The sample of SiOZ gel produced by TEOS
hydrolysis and condensation in the presence of
H,P04 was extracted five times with anhydrous
ethanol. Phosphorus was determined by means of
analytical microscopy (Jeol JXA 840 A).
Results
(5)
pH of water-ethanol solutions of hydrolysed TEOS
The measurement of pH in non-aqueous media
is related to the choice of a standard condition
(6) that would hold for both aqueous and non-aqueous
media. The acidity scale conceived in this way (the
so-called absolute acidity scale) assumes the poten-
tial of the standard hydrogen electrode to be zero,
(7)
independent of the solvent in which the measure-
ment takes place, or, in other words, it assumes
the activity of dissociated particles (hydrogen ions)
to be independent of the solvent [lo]. The activity
of hydrogen ions in an arbitrary medium or the
value of pa, is given by the relationships
aH = mHYH,sYH,m (9)
paH = -log aH (10)
where mH is the molality of hydrogen ions, yH,s is
the so-called salt effect and yH,,, is the medium
effect. The value of yu,$ can be determined by
means of the Debye-Hiickel equation [lo]. Deter-
mining the value of yu,m has, however, met with
difficulties that have not yet been overcome and
which are connected with determining the solva-
tion energy of the hydrogen ion [l 11. Thus the
absolute acidity scale, which holds for all solvents,
cannot be applied. In amphiprotic solvents, which
J. C~hi~~/Colla~dsSurfaces A: Physicochem. Erg. Aspeets 70 (1993) 239-251 243

include not only water but also aliphatic alcohols,
it is possible to use a cell made up of a glass and
a reference (e.g. calomel) electrode [12] for the
measurement of pH. To calibrate this cell, standard
buffers of the same solvent composition as the
solution to be measured can be used. The measure-
ment procedure is practically the same as for the
measurement of pH in water solutions. Under
optimum conditions (when the composition and
acidity of the solution measured are close to the
composition and acidity of the standard) the value
pH* is obtained, which is approximately equal to
paf (i.e. the activity of hydrogen ions in non-
aqueous media).
Between the pH* and the pH of water-alcohol
solutions, the following relationship holds:
pH*=pH-6
where pH* characterizes the activity of hydrogen
ions, referred to standard conditions in a solvent
of the same composition as the solution measured,
pH corresponds to the value obtained from an
instrument calibrated with aqueous buffers, and 6
represents the correction parameter. The parameter
6 includes the so-called diffusion potential E, and
the medium effect yu_, according to the relationship
6 = &I - log YH.m
For water-ethanol solutions of HCl, the depen-
dence of 6 on the EtOH content in the solution
was evaluated [ 131. The results are given in Table 2.
Within the range O-80 wt% EtOH in the solution
the value of pH differs little from that of pH* since
the two components of 6 (diffusion potential and
medium effect) compensate each other [14]. For
higher concentrations of EtOH the difference
between pH and pH* increases and for pure EtOH
6 is -2.36 units of pH.
The working value of pH* in water-ethanol
solutions, which is an expression of the activity of
the hydrogen ions, can thus be obtained by
subtracting 6, which corresponds to the ethanol
content in the solution, from the pH value obtained
with the aid of a pH meter calibrated with use of
aqueous standards.
The effect of water content on the pH of water-
ethanol solutions of HCl is apparent from Fig. 2.
The pH of ethanol-water solutions with a con-
stant HCl concentration (cHc, = 1.5. lo-’ mall-‘)
(11)
rise steeply over the concentration range
O-15 vol.% HZ0 and it reaches a maximum value
in the concentration range 15530 vol.% H, 0. With
increasing water content the pH rises slightly and
with a water content exceeding 60 vol.% it remains
constant. This pH value practically corresponds to
the Vahe -loge,,, (1.8 pH unit).
In the ethanol/water/hydrolysed TEOS solution
with an HCl concentration of 1.5. 1O-2 mol l-l the
behaviour of the pH over the water content ranges
(12)
O-l 5 vol.% H, 0 and 60-100 vol.% H,O is practi-

TABLE 2

Dependence of 6 on ethanol content in water-alcohol solutions

EtOH content 6
(wt%) (pH units)

I
A TEOS/EfOH/H,O/tUI - H,O/HCI
0 0 0.5 - A EtOH/H~O/HCI - H,O/HCI
20 - 0.02 . TEOSIEfGti/H,O/HCI H,O
35 0.10
50 0.2 1 L4 -
65 0.24 0 20 40 60 80
80 water conrent Iv01 %J
0.11
90 - 0.40 Fig. 2. Dependence of pH on water content in water-ethanol
100 - 2.36 solutions of HCl.
-
244
tally the same as in the preceding case. From Fig. 2
it is further apparent that the dependence of pH
on the water content is the same as in the preceding
cases if water is added to hydrolysed TEOS up to
a concentration of 15 vol.%. With the water con-
centration in the solutions under investigation
ranging from 10 to 15 vol.% H2 0 the pH was
practically constant, having a value which, after
deducting 0.1 pH unit, corresponded to -log cuci.
The pH value of a water-ethanol solution of TEOS
hydrolysate containing 12.5 vol.% H, 0 reduced by
0.1 pH unit was designated as the pH’. Similar
results were also obtained for other strong acids
(HClO,, HNO,, HzS04 and PTSA).
The relationship between the water content and
the activity of hydrogen ions in water-ethanol
solutions of I-ICI (expressed with the aid of pH*
or with the aid of Eqn (11)) can be seen in Fig. 3.
In water-ethanol solutions of ethanol/water/hy-
drolysed TEOS with a constant HCl concentration,
pH* is almost constant over the whole concen-
tration range of cH,o and is approximately equal
to -log cHcI. The same also holds for hydrolysed
TEOS with a water content of up to 20 wt%. Thus
the pH’ also represents an approximate expression
for the activity of hydrogen ions in solutions of
hydrolysed TEOS containing strong acids.
The dependence of pH on the water content in
Fig. 3. Dependence of pH* on water content in water-ethanol
solutions of HCI.
J. CihkifjColloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
a solution of TEOS hydrolysed in the presence
of oxalic acid is given in Fig. 4. In the EtOH/H,O/
hydrolysed TEOS solution which had a constant
concentration of oxalic acid (cuA = 5.1 lo-’ l
mol l- ‘), the pH decreased continuously with
increasing water content, the minimum value being
reached when the water content was above
70 vol.%. If, instead of an aqueous solution of
(COOH),, water was added to the TEOS hydroly-
sate, the two relationships were identical up to a
water content of 20 vol.%. Similar relationships
between the pH and the water content were also
obtained for TEOS solutions hydrolysed in the
presence of other weak acids (H,PO,, HF,
Cl, CCOOH, CICHz COOH, CH, COOH and
HCOOH).
The pH’ values of water-ethanol solutions of
TEOS hydrolysates containing weak acids given
in Table 4 need not, in contrast to strong acids,
reflect the activities of hydrogen ions in the solu-
tions since they can also include the effect of the
water-ethanol medium on the dissociation con-
stants of the weak acids.
Hydrolysis of TEOS
Figure 5 gives the values of time vs water
concentration in the course of a TEOS hydrolysis
catalysed by strong acids (HCl, HNO,, HClO, or
1.0Iv 0 TEOSlEtOHIH,O/~COOHJ, - H,O/(COOHfa
0 TEOSIEtOH/H,O/lCOOH~~ . H,O
0 20 40 b0 80
water ctmmt peaI XI
Fig. 4. Dependence of pH on water content in water-ethanol
solutions of (COOH),.
J. Cihl6f/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
c) PTSA
l H,SO,
S
f~ HNO,
0 HCIO.
0 20 40 60 80
Reactton Ttme fm!nl
Fig. 5. Dependence of water concentration on reaction time
during hydrolysis of TEOS catalysed by strong acids.
PTSA) with a concentration of 0.01 mol 1-l.The
concentration of water dropped abruptly about
10 min after the beginning of the reaction. The
subsequent decrease was slow and after 2.5 h at
the most the hydrolysis was practically over
(Fig. 5). The HzO/TEOS molar ratio was 2.0 (for
reaction conditions see Table 1) and this theo-
retically provided for complete reaction of all the
water in the reaction solution. However, the
hydrolysis of TEOS was never complete, and the
con~ntration at the “end” of the hydrolysis
(ci!&) ranged from 0.27 to 0.97 mol 1-l (Table 3).
This corresponded to a maximum water conver-
sion ~$6 of 78-94%. The rate constant values, k,,
for the hydrolysis catalysed with strong acids lay
within the narrow interval from 7.2 * 10m3 to
1.0*10-21 mol-’ SiO, s-l. The constant k, for
the hydrolysis catalysed with PTSA was up to two
thirds lower (kn = 3.0. 10e3 1mol-’ SiOZ s-l) as
a result of the smaller dissociation constant pKHA
of the above acid. With the decreasing dissociation
constant of the catalysts used there was a marked
decrease in the value of the hydrolysis constants
and an increase in the time necessary to obtain
maximum conversion of water (c$!$). The value of
kH for the hydrolysis catalysed with trichloroacetic
acid and oxalic acid at a concentration of
0.05 mall-’ was 1.5. 10e3 1mol-’ SiOZ s-l and
1.0 * lop3 1mol-’ SiO, SK’ respectively (Table 3,
245
Fig. 6). Maximum water conversion values of 87%
or 89% were obtained in 72 h and 192 h respec-
tively. Weak acids (chloroacetic, formic and acetic
acids) proved to have little effect as catalysts of the
hydrolysis even at concentrations from 0.1 to
0.24 mol 1- ’ (Fig. 7). The hydrolysis took a very
long time and the rate constants of the hydrolysis
were low (kH = 2.4. lop5 1mol-’ SiO, s-l,
2.8 * 10e5 1mol-” SiO, s-‘, or 1.0. 10V6 1 mol-’
SiOZ s-l for chloroacetic, formic or acetic acids
respectively). In spite of that, the maximum conver-
100
sion of water reached values from 86% to 89%.
The TEOS hydrolysis catalysed with H3P04 and
HF was sufficiently fast (kH = 1.2 - low3 1mol-’
SiO, s-l and 6.7. 10m41mall’ SiOZ s-i respec-
tively), but with the low degree of hydrolysis
obtained (x;$ = 46% and 70% respectively) the
hydrolysates were liable to gelation. The effect of
pH’ on the speed of TEOS hydrolysis can be seen
in Fig. 8 and Tables 3 and 4. HCI and LiOH,
concentration 0.01 mol l- ‘, and HCl/LiCl solu-
tions with a total concentration of HCl + LiCl=
0.01 mol l- ’ were used as catalysts. For pH’ 2.0
the value of the hydrolysis constant was
7.6. 10m3 1 mol-’ SiOZ s-l. With increasing pH’,
k, decreased to as little as 2.0 - lop6 1 mol-’
SiO, s- ’ (at pH’ 4.3). At about pH’ 7.0 the rate of
hydrolysis was negligible. The value of kH increased
again to 6.0. IO-‘1 mol-’ SiOZ s-l at pH’8.8.
condensation of TEOS
The polycondensation which follows the hydro-
lysis of TEOS is characterized by gelation times,
t,, and condensation rate constants, kK, given in
Table 4. The values of kK for reactions catalysed
with strong acids lay within a narrow interval from
1.1 * lo-’ to 1.4. low7 1mol-’ SiOt s-l. Similar
values of kK were also found for TEOS hydrolysates
containing trichloroacetic acid and oxalic acid
(1.5. 10e7 1mol-’ SiO, s-l and 1.2. lo-’ 1 mol-’
SiOZ s-l respectively). In the solutions with weak
acids (chloroacetic, acetic, formic acids) the rate
of condensation was two to three times faster
(2.2 * 10-7-4.4* 1O-7 1mall’ SiOl s-l). These
differences were related to the pH of the reaction
246 .l. CihtciF/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251

TABLE 3

Kinetic parameters of TEOS hydrolysis

Catalyst ku rS:“o log kn

HAorB (1 mol-’ Si02 s-l) (mall-t) (%) (s)

HCl 7.6 * lo-3 0.27 94 4.3. IO3 -2.1

H,SO, 8.0. 1O-3 0.64 85 6.6 - 10’ -2.1
HNO, 7.2~ lO-3 0.35 92 8.8 +IO3 -2.1
HCIO, 1.0. lo-* 0.97 78 1.2. IO3 -2.0
PTSA 3.0. Io-3 0.80 82 6.5 * lo3 -2.5
Cl, CCOOH 1.5. 1o-3 0.58 87 2.6 * 10s -2.8
(COW, 1.0. 1o-3 OS0 89 6.9 * IO5 -3.0
H3PO4 1.2.10-s 1.32 70 7.1 . 103 -2.9
HF 6.7 * 1o-4 2.38 46 8.8 * 10’ -3.2
ClCH,COOH 2.4. 1O-5 0.60 86 5.2 * 10s -4.6
CH,COOH 1.0. 1o-6 0.58 87 1.7 1106 -6.0
HCOOH 2.8.10-s 0.50 89 1.7 * 10s -4.6
HCl 3.3. lo-2 0.40 90 4.0 * lo3 -1.5
HCl/LiCl 1.1 * lo-2 0.90 80 6.0 * 10s -3.0
HCl/LiCl 1.4. lo-4 I .20 73 2.1 - 105 -3.9
HCl/LiCl 3.9. Io-6 1.10 7.5 6.0 +IO6 - 5.4
HCl/LiCl 2.0. lo-6 1.00 77 6.5 * IO6 -5.1
LiOH 6.O*lO-5 0.60 86 4.7 * IO6 -4.2

0 t&PO, @ CICH,COOH
0 ICOOH),
b HF 0 HCOOH
s 0 0,CCOOH 0 CH,COOH

Reaction Time paws]

Fig. 7. Dependence of water concentration on reaction time

Fig. 6. Dependence of water concentration on reaction time
during hydrolysis of TEOS catalysed by trichloroacetic acid
and oxalic acid.
solutions. The dependence of kK on pH’ within the
pH’ range 1.5-4.5, given in Fig. 9, has confirmed
that the rate of condensation is the lowest for pH’
about 2.0. It can be seen at the same time that the
dependence of the condensation constant on pH
under the given conditions (1 vol.% H,O in TEOS
reaction solution) was directly measurable up to
about pH’ 4.5 (see Fig. 9). Above this pH’ value
during hydrolysis of TEOS catalysed by weak acids.
the rate of TEOS polycondensation was given by
the rate of hydrolysis, which was lower than that
of condensation. The effect of pH’ on kK over the
whole acid range of pH’ was therefore studied
using a two-stage method.
TEOS was hydrolysed at about pH’ 2.0 after
which the pH’ of the reaction solution was adjusted
with HCl solution or with LiOH to values ranging
from 0.1 to 7.8. In all the solutions examined, the
J. Cihl&/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251 241

TABLE 4

Kinetic parameters of TEOS condensation

Catalyst k log k PH PH’

HAorB (1 mot-’ SiO, s-l)

HCl 4.03 ’ IO’ 1.12. lo-’ -6.95 0.4 2.0

HzS0.s 3.42 * IO’ 1.33. 1o-7 -6.88 0.3 2.0
HNO, 4.32 * IO’ 1.05’ lo-’ - 6.98 0 2.0
HCIO, 3.33 * 10’ 1.37, lo-’ -6.86 0 2.0
PTSA 3.40 * 10’ 1.40. 1o-7 - 6.85 0.4 2.2
Cl,CCOOH 3.11 * 10’ 1.47.10-’ - 6.83 2.1 2.0
WOW, 3.84. 10’ l.19*lo-7 - 6.92 2.5 2.2
H3PO4 3.60 - 104 1.27. IO+ -3.90 2.2 2.1
HF 1.08 * 104 4.22. 1O-4 -3.37 3.7 3.1
ClCH,COOH 1.04 * IO’ 4.38. lO-7 -6.36 3.6 3.0
CH, COOH 2.05 * IO’ 2.22.10-7 -6.65 3.5 2.8
HCOOH 1.57 * 10’ 2.90-10-7 -6.54 3.5 3.1
HCl 5.70 * 10’ 1.58. 1o-7 - 6.80 0 1.4
HCl/LiCl 3.70 * 10’ 1.32*10-7 - 6.88 1.2 3.0
HCl/LiCl 3.00 * 10’ l.63*10-7 -6.79 I.5 3.4
HCl/LiCl 2.00 * 10’ 2.44.10-T -6.61 2.9 4.1
HCl/LiCl 1.63 * 10’ 3.OO~lo-7 -6.52 3.7 4.3
LiOH” 600 7.60-10-3 -2.12 8.8 8.8

aPrecipitation of SiOz.

o-o

-0 0

0 20 40 60 80 m
Rezctimlm @Q

Fig. 8. Dependence of water concentration on reaction time

and pH’ during TEOS hydrolysis.
water content was adjusted to 12.5 vol.%. The
dependence of log kK on pH’ is given in Fig. 10.
In comparison with preceding reaction solutions
with a low water content (about 1 vol.%) the k, in
solutions with 12.5 vol.% Hz0 increased by one to
two orders. The lowest value of kK was established
for the pH range 1-2.3. The dependence of log k,
Fig.9. Dependence of hydrolysis and ~ndensation rate con-
stants on pH’_
on pH within the range 2.3-7.8 could be described
by the equation log kK = - 7.14 + 0.73 pH’. This
equation held for both strong and weak acids.
Exceptions to this behaviour were found in the
polycondensation of TEOS catalysed with HF and
248 J. Cihkif/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251

.2 /
0
-3 .

8
*-4o /
\

-5- O\_/

4’
1
V’
I I.__, Tome
lhr]
0 I 2 3 4 5 6 7
PH
Fig. 12. Dependence of water con~ntration and pH of TEOS
Fig. 10. Dependence of condensation rate constant on pH’. hydrolysates containing weak acids on time.

Discussion
H, P04. Their values of k, were about three orders
higher than kK values for reactions catalysed with
pH of wuter-ethanol solutions of TEOS
the other acids at a comparable pH value. With
hydrolysates
the exception of the above acids (HF, H3P04)
the TEOS reaction solutions hydrolysed at the
The dependence of pH on water content in
HzO/TEOS molar ratio of two and a pH of about
water-ethanol solutions of HCl (or HiClOd, HNO,
2.0 are very stable (Table 4). A long-term investiga-
and HzSOs) agreed with the results reported by
tion of their pH’, pH and water contents revealed
Bates and Schwarzenbach [14]. Analogous rela-
that while the value of pH’ remained practically
tionships were also obtained for water-ethanol
constant, the value of pH in solutions with strong
solutions of hydrolysed TEOS (Fig. 2). Ethoxyhy-
acids increased (Fig. 11) and in solutions with weak
droxysiloxanes (i.e. products of TEOS hydrolysis
acids it decreased (Fig. 12). In both cases the water
and condensation) present in these solutions thus
content was slowly increasing and led to the above
had no significant effect on the value of pH. The
shift of the pH (see Figs 2 and 4).
potentiometric method of determining pH with the
aid of glass and calomel electrodes is also suitable
for water-ethanol solutions of TEOS. Even with
these solutions, the value of pH did not correspond
to the activity of H+ ions (see Introduction). Using
4 6D @J HCIO. . 1 the correction parameter 6 (which has been pub-
5
lished for water-ethanol solutions of- HCl [ 13]),
H

93
estimates were made of the activity of H+ ions (or
UI of pH*) in TEOS hydrolysates with a low water
2
content (about 1 vol.%). The values of pH*, pH
and -log cHA (HA = HCI, HC104, HzS04,
I
HNO,) usually did not differ by more than
I I t-O.1 unit.
0 2000 4000 6000
ii [hr) The results of determining the pH in water-etha-
Fig. 11. Dependence of water concentration and pH of TEOS nol solutions of TEOS hydrolysed in the presence
hydrolysates containing strong acids on time. of weak acids were also consistent with the results
J. CihlLiF/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
reported by Bates and Schwarzenba~h [14]-pH
was increased with increasing ethanol content in
the solution. However, its value reflected not only
the diffusion potential and the effect of the medium
on the H+ ions but also the effect of the medium on
the dissociation constant of a weak acid. For the
above reason neither the pH nor the pH’ of
water-ethanol solutions of weak acids is a general
expression of H’ ion activity. Their appearance in
the text is only for comparison with those of
water-ethanol solutions of strong acids.
Efect of pH and catalysts on TEOS hydrolysis
TEOS hydrolysis is an equilibrium reaction irre-
spective of the type of catalyst and pH’ of the
solution used (Figs 5-8, Table 3). The maximum
water conversion, ranging in the majority of cases
from 73% to 94%, shows that there is
0.27-0.97 mol H, 0 l- ’ remaining in the reaction
solution. The hydrolysis reaction products (ethoxy-
hydroxysiloxanes) thus contained 6-27% of un-
reacted SiOEt groups (if re-esterification of SiOEt
groups is excluded). The lower values of x;;&
established for the hydrolysis of TEOS catalysed
with HF and H3P0, (46% and 70% respectively)
were due to the fast gelation of the two hydroly-
sates. The hydrolysis rate did not depend on the
anion of the acid catalyst but on the activity of its
H+ ions in the reaction solution. The dependence
of ku on pH’ (Fig. 9) has shown that in the acid
region, k, decreases with increasing pH’. At pH’ 7
no measurable values of kH could be established.
(By extrapolating the dependence in Fig. 9 we
obtain a k,, value of lo-” 1 mall’ SiOZ s-i.) At
pH greater than 7 hydrolysis again occurred
(Table 4, LiOH). Thus there can be both acid and
base catalysis of TEOS hydrolysis. The behaviour
of the dependence of kH on pH’ confirmed experi-
mentally the behaviour assumed by Brinker [l].
From the viewpoint of controlled TEOS hydroly-
sis, the most suitable catalysts are strong acids
since they make it possible to set a defined pH’
value (within the range 1.5-4.0) and thus also the
rate of hydrolysis.
249
Effect a~~~ on TEOS condensation
The condensation rate constant was at its lowest
at pH’ around 2.0. For PI-I’ of the hydrolysates
above 2.0 the values of kK increased (see Table 4,
weak acids). This finding is not surprising, and it
is in agreement with the behaviour of water solu-
tions of silicic acid [15-171. The relative stability
of silicic acid solutions round pH 2.0 is explained
by its isoelectric point (zero mobility of silicic acid
particles) or by the point of zero charge at the
given pH [18]. This can also explain the stability
of ethoxyhydroxysiloxanes present in TEOS reac-
tion solutions which may be regarded as silicic
acids partially substituted by OEt groups. The
slow condensation of ethoxyhydroxysiloxanes
taking place in TEOS hydrolysates at about pH 2.0
was demonstrated not only by an increase in the
viscosity but also by an increase in the water
concentration in the hydrolysates and thus also by
the related changes in the pH values (Figs 11 and
12). The increase in the concentration of ethanol
in the hydrolysates was not very pronounced.
Although esterification of Si-OH groups according
to Eqn (1) cannot be excluded completely, it is
likely that the condensation takes place mainly in
accordance with Eqn (3). This same conclusion
was arrived at by Assink and Kay [19] in their
study of tetramethoxysilane condensation. The
condensation of TMOS according to Eqn (3) was
about six times faster than that according to
Eqn (2).
Increasing the water content in TEOS hydroly-
sates to 12.5 vol.% (at pH’ 2.0) increased the value
of kK by about one order (Figs 9 and 10).
The increasing water concentration in the
hydrolysate was accompanied by an increase in
the content of Si-OH groups in ethoxyhydroxysi-
loxanes according to Eqn (l), which favoured the
condensation according to Eqn (3), this being faster
than the condensation of SiOH with SiOEt groups.
This explanation assumes that the reaction accord-
ing to Eqn (3) is shifted to the extreme right, and
consequently the hydrolysis of siloxane (depoly-
250 J. Cihkif/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
merization) is not significant. This assumption
holds for pH around 2.0 [l].
In TEOS hydrolysates with HF and H,PO, the
condensation was roughly three orders faster than
in the other hydrolysates. This fact was not related
to the pH’ of the above solutions, which was
comparable with the pH’ of the other hydrolysates
containing weak acids. The behaviour of HF can
be explained by the catalytic action of F- ions
during the condensation reactions. The catalytic
action of F- ions during the condensation of water
solutions of silicic acid has been proved [20]. In
the case of H3P04 it could be assumed that
phosphoric acid participates in the formation of
cross bonds of the type
I pi I described by Iler [S]. In both types of solution the
-Si-O-P-O- Si- (13)
I I I
between adjaczt chains and thus accelerates gela-
tion. Compounds with Si-O-P bonds were in fact
prepared by the reaction of H3P04 with SiOl but
under different reaction conditions [2 11. On analy-
sis (by analytical electron microscopy) of a TEOS
hydrolysate gelated in the presence of H,PO, we
found that the specimen practically did not contain
any phosphorus. Theoretically there could have
been as much as 20 wt% of phosphorus. Although
this finding does not exclude the formation of
Si-O-P bonds by the condensation of Si-OH and
P-OH bonds, especially when we realize that
Si-O-P bonds are easily liable to hydrolysis [22],
the speeding up of the polycondensation of TEOS
hydrolysate owing to the formation of Si-O-P
bonds is not likely to be significant. More
acceptable seems to be the idea that H3P0, forms
non-chemically bonded bridges between adjacent
siloxane chains, e.g. hydrogen bridges (Eqn (14)) or
other donor-acceptor interactions:
H OH H
I I 1 I I (14)
_II si - en ___ 0 - p - 0 ___ He - si -
I II I
0 described by Iler [S]. The condensation of ethoxy-
These bridges can draw adjacent chains closer
to each other and sterically facilitate the condensa-
tion between Si-OH (or SiOEt) bonds. However,
this problem deserves further investigation.
In the Introduction an opinion was expressed
that the study of the dependence of the TEOS
condensation rate (at a TEOS/H20 molar ratio of
two) on pH is complicated by TEOS hydrolysis
and by determining the pH of hydrolysates with a
low water content. Figure 9 confirms that at
pH’ 4.5 the rate of condensation is given by the
hydrolysis rate. If first the hydrolysis is carried out
at pH around 2.0, when the condensation is at its
slowest, and only after that is the pH adjusted, it
is possible to arrive at a dependence of kK on pH’
as shown in Fig. 10. This dependence confirms that
water-ethanol solutions of ethoxyhydroxysilox-
anes (TEOS hydrolysates) behave in the acid region
in the same way as water solutions of silicic acid
condensation is at its slowest at pH around 2.0,
and its rate increases with both increasing and
decreasing pH. F- ions catalyse the condensation
in both cases.
Conclusion
The similarity in the acido-basic behaviour of
water-ethanol solutions of strong acids and of
water-ethanol solutions of TEOS hydrolysates
(ethoxyhydroxysiloxanes) has become the basis for
determining the pH’ of TEOS hydrolysates. This
made it possible to evaluate the dependence of
both the hydrolysis and condensation rates of
TEOS on the pH’ and the catalyst type. The
hydrolysis is an equilibrium reaction catalysed by
acids or bases. In the acidic region the hydrolysis
constant decreases with increasing pH’, with the
minimum value at pH’ around 7.0.
The dependence of the condensation rate of
water-ethanol solutions of ethoxyhydroxysilox-
anes on the pH’ is governed by the same relation-
ships as the dependence of condensation rate on
the pH of water solutions of silicic acid, as
hydroxysiloxanes is acid as well as base catalysed
and is slowest at a pH of about 2.0. The catalytic
action of F- ions and of phosphoric acid has also
been proved. The mechanism of accelerating the
J. Cih&/Colloids Surfaces A: Physicochem. Eng. Aspects 70 (1993) 239-251
condensation with the aid of H3P04 deserves
further investigation. Extending the validity of the
results obtained to another type of the initial Si
monomer would lead to their generalisation.
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