Journal of Non-Crystalline Solids 108 (1989) 249-259 249

North-Holland, A m s t e r d a m

H Y D R O L Y S I S - C O N D E N S A T I O N R E A C T I O N S IN T H E ACID S T E P O F A T W O - S T E P
SILICA S O L - G E L P R O C E S S , INVESTIGATED W I T H 29Si NMR AT - 7 5 °C

A.H. BOONSTRA and T.N.M. B E R N A R D S

Philips Research Laboratories, PO Box 80000, 5600 JA Eindhoven, The Netherlands

Received 23 May 1988

Revised manuscript received 21 December 1988

The relation between the hydrolysis time in the acid step a n d the gelation time in the basic step of a two-step sihca sol-gel
process was investigated using different HC1 concentrations in tetraethoxysilane (TEOS), ethanol and water mixtures with a
molar ratio of 1 : 4 : ( a +0.5), where a was in the range of 0.25 and 4. At values of a < 3 a m i n i m u m in gelation time was
followed by a m a x i m u m and subsequently by a gradual decrease; at a/> 3 a strong decrease in gelation time, followed by a
nearly constant value, was found as a function of the hydrolysis time. For all the mixtures, the hydrolysis times associated with
the minima in gelation time are found to be inversely proportional to the HC1 concentration.
The hydrolysis-condensation reactions in the acid step at 50 ° C were observed by 29Si N M R spectroscopy at - 7 5 ° C using
samples drawn from the hydrolysing mixtures and immediately quenched to temperatures below - 1 0 0 o C. At any desired
m o m e n t in the course of the hydrolysis, an accurate spectrum with a good signal-to-noise ratio can thus be obtained,
corresponding with a well-defined hydrolysis time.

1. Introduction titrations [17] etc. have been used, especially to

The synthesis of silica glass by a sol-gel pro-
cess has become an area of intense interest of
materials science. The features of this technique
are the homogeneity and purity of the gels and a
low sinter temperature, important in the manufac-
turing of material for the drawing of optical fibers
[1-3]. Fundamental understanding of the reaction
mechanisms in each of the various steps in the
sol-gel process is clearly vital for the progress in
this technology. A good approach to studying the
kinetics and the mechanism of the hydrolysis-
condensation reactions of alkoxysilanes was the
division of the sol-gel process in an acid step and
a basic step [4-8].
To investigate the dependence of the hydroly-
sis-condensation reactions on the reaction tem-
perature, the composition of the alkoxysilane, al-
cohol and water mixture and the presence of an
acidic or basic catalyst, a large number of tech-
niques, such as 1H and 29Si N M R spectroscopy
[5,6,9-13], gas-liquid chromatography [5,14], the
molybdenum chemical reaction [15,16], water
follow the condensation reaction. However, at the
temperatures normally used, the rate of the initial
hydrolysis of TMOS and of TEOS was found to
be very fast and therefore difficult to follow, ex-
cept under special conditions. The addition of
formamide to the mixture decreases the hydrolysis
rate drastically but may influence the reaction
mechanisms [18,19]. A decrease in hydrolysis rate
can also be obtained by reducing the HC1 con-
centration [20]. Harris et al. [21] found that the
hydrolysis of TMOS is remarkably slow in the pH
range of 3.5-4.0 at - 10 o C.
When investigating the hydrolysis reaction as a
function of time by means of 29Si N M R spec-
troscopy, a choice was usually made between a
prolonged measurement [9,16,19,22,23], resulting
in a spectrum with a good signal-to-noise ratio but
mean hydrolysis time, and a measurement during
a short period [10,13] giving a less accurate spec-
trum but a better defined hydrolysis time.
A possibility to obviate this problem is to fol-
low the hydrolysis reaction at such a low hydroly-
sis temperature that during the measurement the

0022-3093/89/$03.50 © Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
250 A.H. Boonstra, TN.M. Bernards / Two-step silica sol-gel process
changes are negligibly small. However, using the
results thus obtained to explain the hydrolysis at
much higher temperatures is very risky because of
the complexity of the sol-gel process. In such a
temperature range an equal temperature depen-
dence of all the hydrolysis and condensation reac-
tions of TEOS and its reaction products is not
probable. Therefore the following procedure is
used to investigate the hydrolysis at the desired
temperature.
F r o m the hydrolysing mixture, samples are
drawn at each desired m o m e n t and very rapidly
cooled to below - 100 ° C to quench the reactions.
A low temperature is maintained during the mea-
surements in order to reduce the reaction rate
drastically. In this way an accurate spectrum with
a good signal-to-noise ratio can be obtained at
each m o m e n t of the hydrolysis process.
2. Experimental
2.1. Sample preparation
The influence of the degree of hydrolysis in the
acid step on the gelation behaviour in the basic
step of a two-step silica process has been investi-
gated. In the TEOS, ethanol and water mixtures
with a final molar ratio of 1 : 4 : ( a + 0.5) a num-
ber of values of a were therefore selected in the
range of a = 0.25 and a = 4 where a is the acidic
water fraction and 0.5 the water fraction in the
basic step. The dependence of the gelation time in
the basic step on the hydrolysis time in the acid
step was measured at different HC1 concentrations
for several values of a in the TEOS, ethanol and
water mixture.
Both the hydrolysis and the gelation steps were
carried out at a constant temperature of 50 ° C.
The water fractions were diluted with an equal
weight of ethanol to avoid immiscibility during
the water addition in both steps [8,24,25]. For
values of a > 3, only half the amount of ethanol
was used to dilute the acid water fraction, to leave
enough ethanol for the T E O S - e t h a n o l mixture.
This mixture was warmed to 50°C. Then the
acidic water-ethanol mixture was added dropwise
in about 0.5 min to the well-stirred T E O S - e t h a n o l
mixture. The hydrolysis experiments were per-
formed for 2 h in which period several samples
were drawn. To each sample, vigorously stirred at
50 ° C, the specific amount of the basic ( N H 4 O H )
fraction was added and the gelation time was
determined. The amount of N H 4 O H in the basic
fraction was selected for each of the values of a,
so that a gelation time in the range between 15
min and 2 h was measured. For each sample, the
hydrolysis time (tH) was defined as the time inter-
val between the addition of the acid fraction and
the moment its basic fraction was added. The
gelation time (t G) was defined as the time interval
between the m o m e n t the basic fraction was added
and the moment when, tilting the tube, no more
fluidity of the sol was observed. This state was
always preceded by a short period of strongly
increasing viscosity. The inaccuracy in gelation
time was found to be less than 15 s [20]. We used
one bulk portion for the hydrolysis of each TEOS,
ethanol and water composition and subjected the
samples drawn from this bulk portion to the same
gelation procedure. In this way a series of experi-
ments that could be readily compared with one
another was obtained. However, a number of the
acid samples was not submitted to the gelation
procedure, but directly cooled to - 1 9 5 ° C to
quench the hydrolysis-condensation reactions, or
to - 1 1 5 ° C (melting ethanol) to prevent solidifi-
cation or immiscibility. These samples were used
for the 29Si N M R measurements at - 7 5 ° C.
2.2. Characterisation of gels
To investigate the effect of the hydrolysis time
on the parameters of dried gels, samples were
drawn in duplicate at typical hydrolysis times
from the TEOS, ethanol and water mixtures with
the final molar ratio of 1 : 4 : 2 . 5 and 1 : 4 : 3 . 5 ,
respectively. After the addition of the basic frac-
tion to the drawn samples, a constant amount of
the solutions was poured into test tubes whose
inside walls were coated with a two-component
silicone rubber as an anti-adhesive layer. After
gelation at 5 0 ° C in less than 45 min, the tubes
were kept at that temperature for about 3 h to
reduce the sol fraction.
Each of the series of test tubes was transferred
 A.H. Boonstra, T.N.M. Bernards / Two-step sifica sol-gel process 251

separately to an autoclave. The system was filled
with N 2 gas up to a pressure of 80 bar to climinate
temperature gradients during firing. The presence
of some N 2 gas also prevents boiling during
evaporation of the water and ethanol, still present
in the gels. The autoclave was heated at a linear
rate of 50 ° C / h to 300 ° C and kept for about 12 h
at that temperature. The system was then decom-
pressed to 1 bar in about 7 h and subsequently
cooled to room temperature.
The volume shrinkage, the density and the light
scattering were determined from the samples thus
prepared. The light transmission was measured by
a transmission measurement with a H e - N e laser
(632.8 nm) on cylindrical samples having a low
impurity concentration. Corrections were not made
for the relatively slight differences in diameter.
The samples were then evacuated at 7 5 ° C to
remove physisorbed compounds and next fired at
4 0 0 ° C in air for 16 h. The loss of weight as a
result of the combustion of chemisorbed groups
from the surface of the gel particles was de-
termined. The specific surface area of the samples
so dried was measured with the BET method using
krypton [26,27].
spectra of samples with or without Cr(acac)3. Pulse
times of 10 #s were used. The spectra with a good
signal-to-noise ratio, were recorded using 200
transients accumulated at 4 s intervals. A line
width of 2.0 Hz was obtained.
Because the hydrolysis-condensation reactions
are quenched very strongly at - 7 5 o C, the num-
ber of scans can be varied without affecting the
spectra.
3. Results
In fig. 1, the relation between the hydrolysis
time and the gelation time is given for the TEOS,
ethanol and water mixtures with a final molar
ratio of 1 : 4 : ( a + 0.5) for a = 1, 2, 3 and 4. For
all compositions, an HC1 concentration of 6.7
10-3 M in water was used in the acidic fraction,
but an N H 4 O H concentration in water of 2.0 M
(a = 1), 0.24 M ( a = 2), 0.12 M (a = 3) and 0.12
M ( a = 4) was used. These different N H 4 O H con-
centrations were chosen, because using the same
N H a O H concentration at increasing amounts of
water in the acidic step results in great differences

2.3. :9Si N M R measurements

Each of the cooled samples was inserted into

the magnet of a Nicolet NT-200 N M R spec-
trometer operating at 39.74 M H z and series of 29Si
N M R spectra were obtained from the samples,
,oI: I
/
/o
o o I

whose temperature was controlled at about io

A /o
- 7 5 ° C. At this low temperature no change in "~ 5 0
?
spectra was found even after 5 h. The temperature
of the samples was maintained at - 7 5 ° C by a N 2
stream, led through a helical cooler in a Dewar
1 30
0
: oLj.L/
~ ]I" ~ iF,.
~
•
~ Tr

vessel, kept at - 115 ° C with melting ethanol. A

constant amount of tetramethylsilane (TMS) was
added as an internal reference and special 12 m m 10
~.o ----+ + + m
o-o-o o o o o o -- -- o -- --
sample tubes with thin walls were used. The nega-
I i i i i i i i i i~
tive nuclear Overhauser effect (NOE) was sup- 10 30 50 70 90

pressed by gated decoupling. The addition of a
paramagnetic relaxation agent provides a relaxa-
tion path to dipolar relaxation and also suppresses
the NOE. Therefore small amounts of chromium-
triacetylacetonate (Cr(acac)3) were added to the
samples. N o further differences were found in
• tH (rain)
Fig. 1. T h e r e l a t i o n b e t w e e n the g e l a t i o n t i m e (tG) a n d the
hydrolysis time (tH) of TEOS, ethanol and water mixtures with
a f i n a l m o l a r r a t i o o f 1 : 4 : ( a + 0.5) w i t h a n [HCI] = 6.7 × 1 0 - 3
M in the a c i d s t e p a n d a n [ N H 4 O H ] o f 2.0 M f o r a = 1 (I), 0.24
M f o r a = 2 (II), 0.12 M for a = 3 (III) a n d 0.12 M for a = 4
(IV) in the b a s i c step.
252 A.H. Boonstra, T.N.M. Bernards / Two.step silica sol-gel process

0.25 'io
I/
/ 0.30 /
/ iv +//II
/ / / j/ I
0.20 / /~ / ,/o
/ / / ×5,"
/ '~ // / .///
/ "i 0.20 l i~ I
I I il
/
0.15

ffi,:o,,
'=_ /
~= II/i,
/o
/
/
I/ l 911 o

7= HI 0.10 //~/
/ / /
J f+.~.l
0.10
/ / / /+~////Iv
/o / / i/ / // /
/ / .I
/o/ / / + / / , ,/, ~ I
/ / / /
o.~o o.Ao o.~o 0.70 0.90
0.05 / // --- c (retool HCIII)
7 ,. ~/
io / i '// +//"6 Fig. 3. The hydrolysis rate per unit of water against the HCI
/ .~"/ concentration for values of the hydrolysis times associated with
the minima in gelation time, for TEOS, ethanol and water
0:1 013 015 017 0.9 mixtures with a final molar ratio of 1 : 4 : ( a + 0.5) for a = 1, 2,
3 and 4.
= c (mmol HCI/I)
Fig. 2. The relation between the hydrolysis rate and the HCI
concentration for values of the hydrolysis times, associated and t~ 1 for the values of the hydrolysis time
with the minima in gelation time, for TEOS, ethanol and water
associated with the minima in gelation time is
mixtures with a final molar ratio of 1 : 4 : ( a + 0.5) for a = 1, 2,
3 and 4.
shown in fig. 2. This relation was found to be
linear for all the amounts of water used in the acid
step (a). When the hydrolysis time per unit of
in gelation time. Lowering the N H 4 O H concentra- water is plotted against the HC1 concentration, the
tion leads to an increase in gelation time at the differences in slope of the lines are small (fig. 3).
same degree of hydrolysis [20]. The results found The samples dried in the autoclave were fairly
for the values of 0.25 < a < 1 are qualitatively in translucent, depending on the hydrolysis time.
agreement with those for a = 1. N o gelation was There were small amounts of white fluffy silica
found even after 104 min for values of a < 0.25. powder at the top of the tubes of the first two
The hydrolysis experiments were repeated using samples of each series. The results of the measure-
various HCI concentrations. The relation between ments of the volume shrinkage (S), density (d),
the HCI concentration of the hydrolysing mixture light transition ( T ) and specific surface area (A)

Table 1 Table 2
Physical properties of silica gels prepared from T E O S : Physical properties of silica gels prepared from T E O S :
ethanol : water = 1 : 4 : (2 + 0.5) ethanol : water = 1 : 4 : (3 + 0.5)

tH d S d(1 - S ) T A tH d S D(1 - S ) T A
(min) ( g / c m 3) ( g / c m 3) (%) (m2/g) (min) ( g / c m 3) ( g / c m 3) (%) (m2/g)

8 0.140 0.158 0.118 8.6 512 8 0.126 0.081 0.116 0.2 283
11 0.170 0.264 0.125 27.2 574 10 0.137 0.170 0.114 5.0 315
20 0.254 0.440 0.142 54.9 645 15 0.170 0.276 0.123 33.2 348
35 0.298 0.530 0.140 63.6 661 21 0.224 0.421 0.130 55.6 388
95 0.315 0.546 0.143 51.3 656 50 0.292 0.546 0.133 69.6 378
180 0.327 0.562 0.143 45.6 664 100 0.300 0.562 0.131 67.4 384
 A.H. Boonstra, T.N.M. Bernards / Two-step silica sol-gel process 253

as a f u n c t i o n o f the h y d r o l y s i s time are given in - 1 0 0 ° C , were i n v e s t i g a t e d after w a r m i n g up to

tables 1 a n d 2 for the s a m p l e s p r e p a r e d f r o m
T E O S , e t h a n o l a n d w a t e r m i x t u r e s with a m o l a r
c o m p o s i t i o n of 1 : 4 : (2 + 0.5) a n d 1 : 4 : (3 + 0.5),
respectively.
T h e samples, d r a w n after different h y d r o l y s i s
t i m e s a n d i m m e d i a t e l y q u e n c h e d to b e l o w
- 7 5 o C, b y m e a n s of 29Si N M R . T h e a b s o r p t i o n
s p e c t r a of the samples, q u e n c h e d at s o m e typical
h y d r o l y s i s times, a r e shown in figs. 4 - 6 for mix-
tures o f T E O S , e t h a n o l a n d w a t e r having a m o l a r
r a t i o of 1 : 4 : 1, 1 : 4 : 2 a n d 1 : 4 : 3, respectively.
T h e times a s s o c i a t e d with the m i n i m u m gelation

I
TEO5: ethonol: wot@r=l: 4:1
i 0 min 26 rnin
hydrolysis hydrolysis

~ , , , I . . . . . . . . I . . . . I I i i i I t ~ J i i

7 min 50 min
hydrolysis hydrolysis

12 min go min
h'ydrolysi$ hydrolysis

I . . . . I ' ' I . . . . ! . . . . I . . . . I ' r-m--]-I

-75 -~0 -85 -90 -95 -100 - 7 -= -80 -05 -90 -95 -1(;3
PPM PPM

Fig. 4. 29Si NMR spectra measured at - 75 o C of drawn samples of a hydrolysing mixture of TEOS, ethanol and water with a molar
ratio of 1:4: 1, quenched after different hydrolysis times.
254 A.H. Boonstra, T.N.M. Bernards / Two-step silica sol-gel process

time, some minutes before that minimum, halfway
between the minimum and maximum gelation
time, the maximum gelation time and a period
after that maximum were taken as typical hydroly-
sis times. However, a quantitative comparison be-
tween the spectra of one series is not possible
because of the poor miscibility of TMS with the
hydrolysing mixture, especially at short hydrolysis
times when large amounts of water are still pre-
sent. This problem can be solved by choosing a
more soluble internal reference or separately in-
troducing the reference into the sample tube in a
smaller tube.
The spectra of the samples were also measured

TEOS:
I
ethonol: woter=1: 4 : 2
0 min 30'min
hydrolysis hydrolysis

I I I I I I

12 min 55 min
hydrolysis hydrolysis

~iiiv
I135 min
1 8 min hydrolysis
hydrolysis

-75 40 -85 -90 -95 -100 -75 -80 -85 -90 -95 -10
PPM PPM

Fig. 5.29Si N M R spectra measured at - 75 o C of drawn samples of a hydro]ysing mixture of T E O S , ethanol and water with a molar
ratio of 1 : 4 : 2, quenched after different hydrolysis times.
 A.H. Boonstra, T.N.M. Bernards / Two-step silica sol-gel process 255

at 0 o C. T h e s a m p l e s were w a r m e d for that p u r - p p m with respect to the i n t e r n a l reference T M S .

p o s e from - 7 5 ° C to 0 ° C in 5 rain a n d im-
m e d i a t e l y o b s e r v e d at 0 ° C for 10 min. T h e s e
s p e c t r a are c o m p l e t e l y in a g r e e m e n t with r e c e n t l y
p u b l i s h e d results [22,28,29]. I n table 3 the 29Si
c h e m i c a l shifts at - 75 o C a n d at 0 o C are given in
A t 0 ° C the h y d r o l y s i s r e a c t i o n s are fast, even
d i m e r i s a t i o n takes p l a c e r a t h e r rapidly, b u t p l a i n l y
m o r e slowly t h a n the hydrolysis. The effect of the
m e a s u r i n g t e m p e r a t u r e is great, p a r t i c u l a r l y at
short h y d r o l y s i s times as shown in fig. 7 for a

i
TEOS," ethonol: wotQr=1~ 4, 3
0 min 14 min
hydro iys is hydro Iys is

7 min 24 min
hydrolysis hydrolysis

[ . . . . I . . . . I . . . . . . . . . ' . . . . .

11 mln 65 min
hydrolysis hydrolysis

'0" '-;s"' - g o ' " ' - L ' " ' - g o " 2 " s ' " _~,00 .... -,5' . . . . -80'. . . . -85"" '-go'" '-~'5' " '-,;0
PPM PPM

Fig. 6. 29Si NMR spectra measured at - 75 o C of drawn samples of a hydrolysing mixture of TEOS, ethanol and water with a molar
ratio of I : 4 : 3, quenched after different hydrolysis times.
 256 A.H. Boonstra, T.N.M. Bernards / Two-step sifica sol-gel process

mixture of TEOS, ethanol and water in the molar

TEOS: ethonoi: woter=i: 4:3 ratio of 1 : 4 : 3 with a hydrolysis time of 7 rain. At
7 min Hydrolysis
- 7 5 ° C only the peaks of TEOS at a shift of
T= -75 °C - 8 1 . 5 p p m and of Si(OEt)3OH at - 7 8 . 7 p p m
occur. At 0 ° C in addition to a small peak of

;, t I TEOS at - 8 2 . 1 ppm, those of Si(OEt)4_,(OH),

occur for n = 1 to 4 at - 7 8 . 8 , - 7 6 . 5 , - 7 4 . 5 and
- 7 2 . 7 ppm, respectively, as well as peaks of hy-
drolysed dimers at - 8 8 . 8 , - 8 6 . 0 , - 8 4 . 0 and
- 81.7 ppm.

I . . . . I . . . . I . . . . I . . . . I . . . . I . . . . I

4. Discussion

T= 0 °C
As shown in fig. 1 the relation between the
gelation time in the basic step and the hydrolysis
time in the acid step is different for values of
a ~ 2 and a > 2 in the mixtures of TEOS, ethanol
and water with the final molar ratio 1 : 4 : (a + 0.5)
and can have the following explanation.
At short hydrolysis times, the silanol concentra-
- 8 '5 . . . . --90 - g '5 . . . . --100 PPM
tions increase with hydrolysis time. Dimerisation
-7'0' ' ' '-7'5 . . . . -do . . . . ' . . . . '
of silanols starts at the same time. When almost
all the added water has been consumed in the acid
Fig. 7.29Si NMR spectra of a sample quenched after a hydrol-
step, which is the case at values of a ~< 2, dimerisa-
ysis time of 7 rain of a hydro!ysing mixture of TEOS, ethanol
tion of silanols becomes the dominant reaction,
and water with a molar ratio of 1:4:3 m e a s u r e d at - 7 5 ° C
a n d a f t e r 5 r a i n 0 o C , m e a s u r e d a t 0 o C. resulting in a decrease in the monomeric silanol
concentration and an increase of dimers having
scarcely any - O H groups [20]. For values of a > 2,
dimerisation of silanols results in the formation of
dimeric silanols, where most of the - O E t groups
are already replaced by - O H groups. Dimerisa-
Table 3
tion is followed by a prolonged hydrolysis with
295i c h e m i c a l s h i f t s g i v e n i n p p m w i t h r e s p e c t t o T M S
the liberated water and compensates the relatively
-75°C 0°C slight decrease in numbers of - O H groups of the
(a) Species with no bridging oxygen Si(OEl)4_ n(on)n silanols. This process explains why practically no
n = 0 - 81.5 - 82.1 increase of the gelation time is found under these
n =1 -78.7 -78.8
n = 2 - 76.5 - 76.5
circumstances.
n = 3 - 74.7 - 74.5 As shown in fig. 2, the hydrolysis times corre-
n = 4 - 73.1 -72.7 sponding with the minimum gelation times, are
inversely proportional to the HC1 concentration
(b) Species with one bridging oxygen
--Si - 0 - Si(OEt) 3 _ . ( O H ) . for all the compositions of the mixture. The hy-
n = 0 - 88.4 -- 88.8 drolysis reaction in the acid step proceeds by the
n = 1 - 86.1 - 86.0 following electrophylic reaction mechanism sug-
n = 2 - 84.3 - 84.0 gested by Aelion et al. [30] and described by
n = 3 - 82.8 - 81.7
Keefer et al. [31], that is
 A.H. Boonstra, T.N.M. Bernards / Two-step silica sol-gel process
RO~ / OR
H30 + +
Ro/SI~oR
H RO H + .OR
H'RO / ~OR
HO~ ./OR
+ H O R + H +, (1)
Ro/SI~oR
where R = H or Et, depending on the hydrolysis
step and explains the linear relation between the
hydrolysis rate and the H ÷ concentration. The
slopes of the straight lines are different but when
the hydrolysis time per unit water is considered,
the differences in slope are relatively slight (fig. 3),
suggesting minor differences in reaction rates for
the four hydrolysis steps. These differences are
still smaller taking into account the following ef-
fects. The dimerisation rate of the silanols is higher
at increasing numbers of - O H groups in
Si(OEt)4_,(OH),, resulting in too small values of
the hydrolysis time. A second effect is, in spite of
the efforts to maintain a constant hydrolysis tem-
perature, a short-lived increase of the temperature,
depending on the relative amount of water, ob-
served shortly after the addition of the acidic
fraction.
It is seen in tables 1 and 2 that the volume
shrinkage ( S ) of the samples dried in the auto-
clave strongly depends on the hydrolysis time in
the acid step. At short hydrolysis times the mix-
tures contain a lower concentration of polyhydro-
lysed silanols than those of longer hydrolysis times,
which may result in the formation of gels being
less cross-linked. From the calculated values of
d ( 1 - S) it is shown that some loss of weight
occurs in the first two samples of each series. This
loss can be ascribed to the evaporation of some
remaining TEOS which reacts with water vapour,
resulting in fluffy white silica powder on top of
these test tubes and in the autoclave.
The differences in specific surface area between
the two series are ascribed to differences in rela-
tive amounts of water present during the con-
densation. The particle growth is stimulated by
the presence of - O H groups at their surfaces but
257
obstructed by the presence of - O C 2 H 5 groups.
The relative amounts of these groups is de-
termined by the water/ethanol ratio in the liquid
phase during the condensation [8]. This ratio may
also explain the lower values of specific surface
area at short hydrolysis times in each series.
From these measurements it can be concluded
that in each series the differences in mean particle
size are slight, which seems to be in contradiction
with the light transmission measurements.
A possible explanation of the considerable dif-
ferences in light scattering by the samples may be
the presence of a few large particles in the samples
with short hydrolysis times. Such small numbers
of large particles have a relatively slight influence
on the specific surface area but considerable effect
on the light scattering. These large particles have
to form the moment the basic water fraction is
added because after short hydrolysis times the
amount of TEOS is still relatively large and that
of ethanol relatively small. This composition may
result in immiscibility effects and possibly, at the
phase boundaries, in the formation of these large
particles. The increased differences in light scatter-
ing among the samples of the mixture with the
molar ratio of 1 : 4 : (3 + 0.5), as shown in table 2
support this hypothesis. Another explanation may
be the presence of large pores, which perhaps
influence the light scattering in samples with a low
density [32]. Up to now in view of the results
obtained, no clear choice can be made.
Figure 4 shows 29Si N M R spectra of samples of
a hydrolysing mixture of TEOS, ethanol and water
with a molar ratio of 1 : 4 : 1, quenched after dif-
ferent hydrolysis times and measured at - 7 5 ° C
so as to prevent hydrolysis during measurement.
In the spectra of the early state of the hydrolysis,
only a peak at a chemical shift of - 81.5 ppm with
respect to TMS, due to TEOS and a low-intensity
peak at - 7 8 . 7 ppm corresponding to Si(OEt)3OH
exists. After 26 min, a hydrolysis time halfway
between the minimum and maximum gelation
times, beyond the TEOS and Si(OEt)3OH high-in-
tensity peaks, peaks occur at - 7 6 . 5 and - 8 6 . 1
ppm due to Si(OEt)2(OH)2 and its dimerisation
product HO(EtO)2SiOSi(OEt)2OH. In spite of the
high concentration of Si(OEt)3OH a small peak
occurs at - 8 8 . 4 ppm only after long hydrolysis
258 A.H. Boonstra, T.N.M. Bernards / Two-step silica sol-gel process
times, corresponding to the dimer (EtO)3SiOSi
(OEt) 3.
Figure 5 shows the spectra measured at - 75 o C
of a mixture of TEOS, ethanol and water with a
molar ratio of 1 : 4 : 2 , quenched after different
hydrolysis times. After short hydrolysis times,
peaks of Si(OEt)4_,(OH), for n = 1 to 4 are
already evident. However, after longer hydrolysis
times the intensity of the Si(OH)4 and Si(OEt)
(OH)3 peaks decreases quickly as a result of the
formation of the corresponding dimers (peaks at
- 82.8 and - 84.3 ppm, respectively). The peak at
- 8 6 . 1 ppm corresponds to HO(EtO)2SiOSi
(OEt)2OH. The dimerisation of Si(OEt)3OH takes
place very slowly, as represented by the peak at
- 8 8 . 4 ppm. The peak with a chemical shift of
- 9 4 . 0 ppm has to be ascribed to the formation of
a hydroxy trimer.
After short hydrolysis times, the spectra of the
mixture with a molar ratio of 1 : 4 : 3 (fig. 6), have
nearly the same peaks as the spectra of the mix-
ture with a ratio of 1 : 4 : 2, only with a somewhat
higher intensity of the Si(OEt)(OH)3 and Si(OH)4
peaks. The intensities of the peaks due to the
dimerisation products of di- and tfihydrolysed
monomers at - 82.8 and - 84.3 ppm increase with
increasing hydrolysis times. Also peaks corre-
sponding to hydrolysed trimerisation products oc-
cur. After longer hydrolysis times the intensity of
the peaks decreases due to polymerisation. The
absorption ascribed to this process at a chemical
shift of about - 1 1 5 ppm is overlapped by the
absorption band of glass of the test tube.
For all three compositions it can be concluded
that, after hydrolysis times corresponding to
minimum gelation times, dimerisation becomes
important and the higher the value of n in
Si(OEt)4_,(OH),, the higher the dimerisation rate
of silanols becomes.
5. Summary
The composition of the TEOS, ethanol and
water mixtures has a considerable influence on the
relation between the hydrolysis time in the acid
step and the gelation time in the basic step. The
gelation time is shorter the higher the concentra-
tion of S i - O H groups. At a low degree of hydroly-
sis of Si(OR)4_,(OH), dimerisation causes there-
fore a strong increase in gelation time.
The hydrolysis times of the minima in gelation
time were found to be inversely proportional to
the HC1 concentration. The differences in hydrol-
ysis rate of the four hydrolysis steps of
Si(OR)4_,(OH), are relatively small.
The differences in volume shrinkage of gels
dried in the autoclave are ascribed to the forma-
tion of polyhydrolysed silanols at longer hydroly-
sis times. In the basic step this results in the
formation of strongly cross-linked chains.
29Si N M R measurements at low temperatures
have the advantage of extremely low reaction rates
during the measurements, resulting in dis-
tinguishable spectra with a good signal-to-noise
ratio for each well-defined hydrolysis time. Em-
ploying this method on samples drawn from a
reacting mixture, followed by quenching, it is
shown to be a suitable manner to investigate the
hydrolysis process at each hydrolysis temperature.
Both the presence of large pores in samples
with a low density and the presence of large
particles, caused by immiscibility effects, may be
an explanation for the large differences in light
scattering measured on samples prepared after
different hydrolysis times. This will be the subject
of further investigations.
The authors would like to thank M.J. van Bom-
mel, A.F. Boonstra, C.A.M. Mulder and T.P.M.
Meeuwsen for their valuable contributions to the
discussion and H.M. van den Bogaert and J.J.T.
Smits for helpful advice and work on the 29Si
N M R measurements, R.M. Salemink for his auto-
clave activities and G.V.A. Aben for the light
transmission measurements.
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