Journal of Non-Crystalline Solids 134 (1991) 1-13 1

North-Holland
Hydrol ysi s-condensati on processes of the tetra-alkoxysilanes
TPOS, TEOS and TMOS in some alcoholic solvents
T. N. M. Bernards, M.J. van Bommel and A. H. Boonstra
Philips Research Laboratories, PO Box 80000, 5600 JA Eindhoven, Netherlands
Received 31 January 1991
Revised manuscript received 18 April 1991
The effects of methanol, ethanol, 1-propanol and 2-propanol on the kinetics and the mechanisms of the hydrolysis-con-
densation reactions of the silanes TPOS, TEOS and TMOS were studied. Also, the influence of the amount of water on the
hydrolysis-condensation processes of TMOS and TPOS was investigated. Accordingly, hydrolysis time versus condensation
time curves were recorded and 29Si-NMR investigations were performed. The hydrolyzability of the silanes in an acidic
environment was found to decrease in the sequence TMOS > TEOS > TPOS. The effect of the alcohols, in the sequence
methanol > ethanol, 1-propanol > 2-propanol, upon the hydrolysis rate of each of the silanes is explained by differences in
degree of dissociation of HCI in the different alcohols. Also, the exchange of alkoxy groups, observed when an alcoholic
solvent was used with an alkoxy group different from the alkoxy group of the silane, may influence the hydrolysis rate of the
silane. Differences in dimerization are ascribed to differences in base strength of the activated silanol complexes with regard to
those of the protonated alcohols.
1. I nt r oduc t i on
The preparation of silica glass by a sol-gel
process is receiving world-wide interest [1-4]. At
the moment, thin films deposited on substrates by
a sol-gel procedure are produced in large quanti-
ties. Particular attention is being accorded to the
preparation of reflection-reducing films [5-6].
These reflection-reducing films are used for televi-
sion sets and computer monitors [7].
For these purposes, coating solutions are used
which consist of hydrolyzed alkoxysilane com-
pounds in different solvents. Often a combination
of solvents is used to obtain a solution with suita-
ble rheological properties, necessary to obtain films
with the desired characteristics. The use of differ-
ent solvents may have a considerable influence on
the hydrolysis-condensation behaviour of the al-
koxysilane compounds. To obtain a good repro-
ducibility of the properties of the films, a funda-
mental knowledge of the chemistry of the hydroly-
sis-condensation processes is essential.
It has been found that exchange of alkoxy
groups occurs when an alcohohc solvent is used
with an alkoxy group different from the alkoxy
groups of the silane [8-12]. Brinker et al. [10] and
Pouxviel et al. [11] reported such a transesterifica-
tion on a system of TEOS and n-propanol, whereas
Hasegawa and Sakka [12] studied the exchange
reactions between TEOS and isomers of butanol.
In this study the influence of methanol, ethanol,
1-propanol and 2-propanol on the hydrolysis-con-
densation processes of tetra-l-propoxysilane
(TPOS), tetra-ethoxysilane (TEOS) and tetra-
methoxysilane (TMOS) are investigated.
To obtain an understanding of the mechanisms
of these processes many techniques have been
used [13-19]. We found that the recording of the
hydrolysis time versus gelation time of TEOS,
ethanol and water mixtures gives insight into both
the hydrolysis and the condensation reactions in
this two-step sol-gel process of TE(~S [20-23].
Therefore, we used this procedure t~.investigate
the influence of the different alcohols on the hy-
0022-3093/91/$03.50 1991 - Elsevier Science Publishers B.V. All rights reserved
2 T. N. M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and T MOS
dr ol ys i s - condens at i on behavi our of met hoxy- ,
et hoxy- and 1-propoxysi l ane.
Addi t i onal l y, we used 29Si-NMR spect r oscopy
for these investigations. I t has al r eady been f ound
t hat 29Si-NMR studies give chemi cal i nf or mat i on
on the initial stages of the hydr ol ys i s - con-
densat i on processes, pr ovi ded t hat these measur e-
ment s are carri ed out at a low t emper at ur e. At
r oom t emper at ur e these hydr ol ys i s - condens at i on
processes pr oceed subst ant i al l y duri ng measur e-
ment s [24,25].
2. Experimental
2.1. Procedure
The i nfl uence of the a mount of wat er upon t he
hydr ol ys i s - condens at i on processes of TPOS and
TMOS was i nvest i gat ed usi ng the wel l - known
t wo-st ep s ol - gel process. The rel at i on bet ween t he
hydrol ysi s t i me in the aci d st ep and t he gel at i on
t i me in the basi c st ep was st udi ed for the mi xt ur es
of a t et ra-al koxysi l ane, its cor r espondi ng al cohol
and wat er wi t h a final mol ar rat i o of l : 6 : a ,
where a = 1, 2, 3 and 4, respectively. The amount s
of wat er were added in the aci d st ep to excl ude
secondar y react i ons as a consequence of the ad-
di t i on of a basi c wat er fract i on. Therefore, 61- of
t he amount of al cohol was selected in whi ch the
requi red amount of a mmoni a was dissolved. To
pr event i mmi sci bi l i t y duri ng t he process, espe-
cially in t he case of TPOS mi xt ures, in the aci d
st ep a mol ar rat i o of the silane c ompound and its
cor r espondi ng al cohol of 1 : 5 was used. The acidic
cat al yst concent r at i on was adapt ed to obt ai n equal
hydrol ysi s rat es for t he TPOS and TMOS mi x-
tures. Also, t he net a mmoni a concent r at i on was
chosen so t hat si mi l ar gel at i on t i mes were ob-
t ai ned, t aki ng i nt o account the amount of wat er
added in t he aci d st ep [24].
The effect of t he al cohol i c sol vent on the ki net -
ics and the mechani sms of the hydr ol ys i s - con-
densat i on react i ons of t he silica s ol - gel process
was also studied. We i nvest i gat ed mi xt ur es of
met hanol , et hanol , 1- pr opanol or 2- pr opanol wi t h
each of the silanes TPOS, TEOS and TMOS.
To compar e t he effect of t he solvents, a con-
st ant silane concent r at i on in t he mi xt ur es is de-
sirable. For these exper i ment s a mol ar rat i o of
silane and wat er of I : 2.5 was selected. The amount
of wat er was di vi ded i nt o an aci di c (HC1) and a
basi c ( NHa OH) f r act i on in a r at i o of 4 : 1 . The
compos i t i on ar ea of st abl e sol ut i ons of silane,
al cohol and wat er was t he smal l est for mi xt ur es of
TPOS, 2- pr opanol and wat er. For these mi xt ures,
i mmi sci bi l i t y coul d onl y be pr event ed when at
least a mol ar r at i o of TPOS and 2- pr opanol of
1 : 5 was used. To obt ai n a const ant vol ume for
t he di f f er ent al cohol s, we sel ect ed a mol ar r at i o of
si l ane and al cohol of 1 : 9 usi ng met hanol , of 1 : 6.5
for et hanol and of 1 : 5 usi ng 1- pr opanol or 2-pro-
panol . We r enounced an ext ensi on of our investi-
gat i ons wi t h but anol s because the composi t i on
ar ea of st abl e sol ut i ons of silane, but anol and
wat er were f ound t o be ver y smal l and cor r espond
wi t h mi xt ur es of ver y l ow silane concent r at i ons.
To si mpl i fy a compar i s on of the resul t s ob-
t ai ned for the di f f er ent mi xt ures, t he exper i ment al
ci r cumst ances were mat ched as f ar as possi bl e.
The acid st ep and the basi c st ep were per f or med
at 50 o C. The wat er f r act i ons were di l ut ed wi t h an
equal wei ght of the appl i ed al cohol to avoi d i m-
mi sci bi l i t y dur i ng t he addi t i on. The r emai nder of
the al cohol was mi xed wi t h t he sel ect ed silane.
The aci di c wa t e r - a l c ohol mi xt ur e was added in
about 0.5 mi n t o t he wel l -st i rred s i l ane- al cohol
mi xt ure. The hydr ol ysi s exper i ment was per-
f or med for about 200 mi n, in whi ch per i od several
sampl es were dr awn regul arl y. To each of these
al i quot s t he speci fi c a mount of the basi c f r act i on
was added and t he gel at i on t i me of each sampl e
was t hen det ect ed. Because t he gel at i on t i me de-
pends l argel y on t he net NH4 OH concent r at i on, a
const ant concent r at i on was selected for each silane
so t hat f or all hydr ol ysi s t i me versus gel at i on t i me
curves a gel at i on t i me in t he r ange bet ween 5 mi n
and 2 h was measur ed.
The hydr ol ysi s time, tH, of each sampl e was
defi ned as the t i me i nt er val bet ween the addi t i on
of t he aci di c f r act i on and t he mo me n t its basi c
f r act i on was added. The gel at i on time, t r , was
def i ned as t he t i me i nt er val bet ween the mome nt
t he basi c f r act i on was added and t he mome nt no
mor e fl ui di t y of t he sol was obser ved when tilting
t he t est tube. Thi s st at e was al ways pr eceded by a
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS 3
short peri od of great l y increasing viscosity and
t herefore i naccuracy in gelation time was less t han
+_15 s.
2.2. Techniques
The results of the hydr ol ysi s- condensat i on
processes might be i nfl uenced by exchange reac-
tions which may occur when a mi xt ure of silane
and alcohol cont ai ni ng di fferent al koxy groups
was heat ed to 50 o C. To verify this, a sample was
drawn f r om each of such mi xt ures j ust before the
hydrol ysi s st art ed and its composi t i on det er mi ned
using a capillary gas chr omat ogr aphy technique.
Wi t h 29Si-NMR measurement s at - 7 5 C we
followed t he hydr ol ysi s- condensat i on react i ons in
the acid step of the two-step sol - gel processes,
drawi ng samples f r om these mi xt ures at di f f er ent
hydrolysis times. It had al ready been f ound t hat
the drawn samples have to be cool ed very rapi dl y
to about - 1 0 0 C to reduce the react i on rat e
drastically. Also, duri ng the measurement s the low
t emper at ur e has t o be mai nt ai ned. A det ai l ed de-
scri pt i on of the measuri ng procedures has al ready
been given elsewhere [24,25]. Wi t h the 29Si-NMR
technique, di fferences in degree of di meri zat i on in
the acid step, especially at pr ol onged hydrolysis
times, were investigated as a f unct i on of the al-
cohol i c solvent used. Wi t h this t echni que exchange
effects coul d also be det ect ed easily.
3. Re s ul t s
The effect of the amount of wat er in t he hy-
drol ysi ng mi xt ure upon t he rel at i on bet ween t he
hydrol ysi s time in t he acid step and t he gelation
t i me in t he basic step is shown in fig. 1 for TPOS,
1-propanol and wat er mi xt ures and in fig. 2 for
TMOS, met hanol and wat er mixtures, bot h havi ng
a final mol ar rat i o of 1 : 6 : a with a = 1, 2, 3 and
4. The acidic cat al yst concent r at i ons of the TPOS
mi xt ures and of the TMOS mi xt ures were 2 x 10 2
M HC1 and 5 x 10 - 4 M HC1 in water, respec-
tively. For the TPOS mixtures, t he net ammoni a
concent r at i on was 6 x 10 -1 M for a = 1, 6 x 10 -2
Mf o r a = 2 a n d 6 x 1 0 - 3 Mf o r a = 3 a n d 4 . For
t he TMOS mixtures, t he net ammoni a eoncent ra-
t i on was 10 3 M for a = 1 and 2 x 10 - 4 M for
a = 2, 3 and 4. In the figures showing the rel at i on
bet ween the hydrol ysi s time and t he gelation time,
t hrough the measuri ng points, lines are dr awn to
guide the eye. The results of the TPOS- l - p r o -
panol mi xt ures agree closely with those f ound for
TEOS- e t ha nol mi xt ures [24]. The consi derabl e in-
crease in gel at i on t i me at pr ol onged hydrol ysi s
times had been ascribed to a reduct i on of the
amount of silanols caused by condensat i on in the
acid step [20]. The absence of such an increase in
gelation t i me as observed for TMOS- me t ha nol
mi xt ures suggests t hat in these mi xt ures pract i -
cally no r educt i on of silanols by condensat i on
occurs in the acidic envi ronment . To verify this,
29Si-NMR measur ement s were per f or med on sam-
ples dr awn as a f unct i on of the hydrol ysi s time
f r om these hydr ol yzi ng si l ane- al cohol mixtures.
As an example, the results are given for a = 2 in
figs. 3 and 4, because for this amount of wat er the
largest di fferences in gelation behavi our were
measured. As shown, subst ant i al condensat i on ef-
fects were observed for TPOS- l - p r o p a n o l mix-
tures, whereas for TMOS- me t ha nol mi xt ures onl y
small condensat i on effect s were found. In table 1
the 29Si chemi cal shifts of TMOS, TPOS and their
hydr oxy monomer s are given.
The di fferences in condensat i on behavi our can
be ascribed to di fferences in acid cat al yst con-
cent rat i on, to the al cohol i c solvent used and to the
silanols f or med duri ng the hydrolysis. To dis-
tinguish bet ween these possibilities, first t he effect
of the al cohol i c sol vent was investigated for each
of the silanes mai nt ai ni ng a const ant cat al yst con-
cent rat i on. In fig. 5 t he effect of t he alcoholic
solvent upon t he rel at i on bet ween the hydrolysis
t i me in the acid step and t he gelation t i me in the
basic step is given for TPOS, al cohol and wat er
mi xt ures wi t h a TPOS concent r at i on of 1.5 mol / 1
and a final mol ar rat i o of TPOS and H2 0 of
1: 2. 5. As t he acidic catalyst, an HC1 concent ra-
t i on of 10 -3 M was used. For gelation, a net
NH4 OH concent r at i on of 1.5 10 -2 M was cho-
sen. It is shown t hat using the same HC1 con-
cent rat i on, t he mi ni mum gelation time was at-
t ai ned aft er a hydrol ysi s time of 6 mi n with
met hanol as the sol vent and 16 rain with et hanol
and 1-propanol , whereas with 2- pr opanol the
4 TN.M. Bernards et aL / Hydrolysis-condensation processes of TPOS, TEOS and TMOS
t--
o ~
E 1 6 0
t
12080
40
0 " ' ' ' ' " ~ # ' ' ' " ' + =
0 2 0 4 0 6 0 8 0 ~ 0 0
t H ( m i n )
Fig. 1. The gel at i on time, tG, as a f unct i on of t he hydr ol ysi s time, tH, of TPOS, 1- pr opanol and wat er mi xt ur es of a final mol ar rat i o
of 1 : ( 5 + 1 ) : a wi t h a =1 (A), 2 ( ) , 3 (11) and 4 ( +) .
mi ni mum gel at i on t i me was f ound onl y after a
hydrol ysi s t i me o f about 45 mi n. It was stri ki ng
that after prol onged hydrol ysi s the largest i ncrease
i n gel at i on t i me was obs erved usi ng 2- propanol as
the sol vent.
Wi t h TEOS or TMOS as the si l ane c ompound,
1 0 0
E
f 80
60
4O
2O
0 I I k I I
0 2 0 4 0 6 0 8 0 100
- ' t H ( r a i n )
Fi g. 2. T h e g e l a t i o n t i me, t G, as a f u n c t i o n o f t he h y d r o l y s i s t i me, t H, o f T M O S , mc t h a n o ] a n d w a t e r mi x t u r e s o f a f i n a l m o l a r r a t i o
of 1 : ( 5 + 1 ) : a wi t h a =1 (&), 2 ( ) , 3 (11) and 4 ( + ) .
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS
TPOS: 1 - Pr OH: H20
1:5:2
I . . . . I . . . . r . . . . ~ l 120
z
/
/
/
~xx
i i i i { , ~ i
-70 -80 -90 -100
PPM
Fig. 3. 29Si-NMR spectra measured at - 75C of samples, drawn after different hydrolysis times from a hydrolyzing mixture of
TPOS, 1-propanol and water with a molar ratio of 1 : 5 : 2.
si mi l ar results were obt ai ned, as shown i n figs. 6
and 7, respectively. However, to realize hydrol ysi s
t i me- gel at i on t i me curves compar abl e wi t h those
of TPOS, the acidic cat al yst concent r at i on has to
be reduced to 3x10 4 M HC1 us i ngTEOS and
to 7 10 -5 M HC1 wi t h TMOS, whi ch can be
ascri bed to di fferences i n affi ni t y for hydrol ysi s of
the di fferent silanes. For gel at i on, a net ammoni a
TMOS: MeOH: H20
1:5:2
. . . . . . . . . . . . . . . . 60
"30
" 15 / 2'
-70 -80 -90 -100
PPM
Fig. 4. 29Si-NMR spectra measured at -75 C of samples, drawn after different hydrolysis times from a hydrolyzing mixture of
TMOS, methanol and water with a molar ratio of 1 : 5 : 2.
6 T.N.M. Bernards et aL / Hydrolysis-condensation processes of TPOS, TEOS and TMOS
Table 1
29Si-NMR chemical shifts with respect to TMS in ppm meas-
ured at -75C of the monomers Si(OCH3)4_n(OH)n and
Si(OCH2CH2CH3) 4 ,(OH),
n Si(OCH3)4_n(OH), Si(OCH2CH2CH3) 4 ,(OH),
0 -78.1_+0.2 -81.5_+0.2
1 -76.0 -78.5
2 -74.4 -76.1
3 - 73.1 - 74.0
4 -72.1 -72.2
concentration was used of 10 -2 M for the TEOS
mixtures and of 2 x 10 -3 M for the TMOS mix-
tures.
As shown in figs. 5-7, similar influences of the
different alcoholic solvents were found for each of
the silanes. The effect of the alcohols may be
caused by differences in degree of dissociation of
HC1 in the different alcohols. Another possibility
may be the phenomenon of exchanges of alkoxy
groups between silane and alcohol. Therefore, a
check on exchange reactions was made for all the
mixtures of silane and alcohol having different
alkoxy groups. Before the hydrolysis process of
such mixtures was started, by adding the acidic
fraction, a sample was drawn from the mixture.
This sample was investigated using capillary gas
chromatography. For none of the mixtures was an
exchange of alkoxy groups observed. Some of
these mixtures were additionally heated to 50 C
and kept at that temperature for 2 h under exclu-
sion of water vapour. Even after this treatment, no
exchange of alkoxy groups was observed.
The silane-alcohol mixtures were also investi-
gated with respect to exchange reactions in the
presence of different concentrations of the acidic
catalyst under the exclusion of water. It was found
that at 50 C fast exchange reactions already oc-
cur at moderate catalyst concentrations. There-
fore, the samples were investigated with 29Si-NMR
at - 75 o C. It is shown in fig. 8 that for the acidic
catalyst concentration, as used in the hydrolysis
experiments, the exchange reactions are strong for
a TPOS- met hanol mixture (A) but negligible for a
TMOS- l - pr opanol mixture (B). However, when
the catalyst concentration for the TMOS- l - pr o-
panol mixture is increased to 10 -3 M, exchange
reactions are also observed (C). From the occur-
rence of the different peaks as a function of the
.---- 160
C
E
120
8O
0 ' - - - - A ~ ' ' ' ' ' '
0 40 80 120 160 200
- ' tH (min)
F i g . 5 . The gelation time, to, a s a function of the hydrolysis time, tH, of TPOS, alcohol and w a t e r m i x t u r e s o f a final molar ratio of
1 : x : 2.5 with x = 9 for methanol (A), 6.5 for ethanol ( + ), 5 for 1-propanol (o) and 2-propanol (B).
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS 7
E
E
v
T
1 6 0
1 2 o l
80
4O
o _A $ , _ - , _ _ ~ , ,
0 4 0 8 0 1 2 0 1 6 0 2 0 0
- - ' tH (min)
Fig. 6. The gel at i on t i me, t G, as a f unc t i on of t he hydr ol ys i s t i me, t H, of TEOS, al cohol a nd wa t e r mi xt ur e s of a fi nal mo l a r r at i o of
1 : x : 2.5 wi t h x = 9 f or me t ha nol (A), 6.5 f or e t ha nol ( + ), 5 f or 1- pr opa nol ( ) a nd 2 - p r o p a n o l ( I ) .
exchange time, the peaks coul d be l abel l ed si mpl y,
as shown in t abl e 2. We obser ved a chemi cal shift
of about 0.85 p p m for each - OCH 3 ~ - OCH 2
CHz CH 3 exchange.
The di f f erences i n c o n d e n s a t i o n be havi our us i ng
di f f erent al c ohol s , as s h o wn i n figs. 5 - 7 , were
i nves t i gat ed wi t h 29Si - NMR o n mi xt ures of TMOS,
wi t h each o f t he f our s el ect ed al c ohol s us i ng a
"-"._C 1 6 0 - - - -
E ,
t 120 .a
8 O
4 0
0 4 0 8 0 1 2 0 1 6 0 2 0 0
- - ' t . ( m i n )
Fi g. 7. The gel at i on t i me, t G, as a f unc t i on of t he hydr ol ys i s t i me, t H, of TMOS, al cohol a nd wa t e r mi xt ur e s of a fi nal mol a r r at i o of
1 : x : 2.5 wi t h x = 9 f or me t h a n o l (A), 6.5 f or e t ha nol ( + ), 5 f or 1- pr opa nol ( ) a nd 2- pr opa nol (11).
8 T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS
A
-78 -82 -78 -82 -78 -82
PPM PPM PPM
Fig. 8. 29Si-NMR spectra measured at - 7 5 C of samples,
drawn after an exchange time of 2 min from a mixture of
TPOS and methanol, using 10 -3 M HC1 (A) and after an
exchange time of 300 rnin from mixtures of TMOS and 1-pro-
panol using 710 -5 M HC1 (B) and 10 -3 M HC1 (C),
respectively.
Table 2
29Si-NMR chemical shifts with respect to TMS in ppm meas-
ured at - 75 o C of the monomers Si(OCH3) 4-, . (OCH 2CH 2
CH3)m
m
0 - 78. 10. 2
1 - 78. 9
2 -79. 8
3 - 80.7
4 -81. 5
c o n s t a n t c a t a l y s t c o n c e n t r a t i o n of 7 10 - 5 M
HC1. We i n v e s t i g a t e d T MOS mi x t u r e s b e c a u s e at
t he c a t a l y s t c o n c e n t r a t i o n we us e d f or t he h y d r o l -
ysi s, e x c h a n g e r e a c t i o n s i n t he s e mi x t u r e s wer e
a l mo s t ne gl i gi bl e wh e n wa t e r was e x c l u d e d (fi g. 8).
As a n e x a mp l e , i n fi g. 9 29Si - NMR s p e c t r a a r e
gi ven of s a mp l e s d r a wn at di f f e r e nt h y d r o l y s i s
t i me s f r o m a n a c i di c TMOS , 1 - p r o p a n o l a n d wa t e r
mi x t u r e wi t h t he mo l a r r a t i o of 1 : 5 : 2. On c om-
p a r i n g t he s e s p e c t r a wi t h t hos e of TMOS ,
me t h a n o l a n d wa t e r mi x t u r e s of t he s a me mo l a r
r a t i o as s h o wn i n fi g. 4, l a r ge di f f e r e nc e s i n
o l i g o me r i z a t i o n wer e obs e r ve d. Al s o, t he n u mb e r
of p e a k s i n fi g. 9 b e l o n g i n g t o h y d r o x y mo n o me r s
was mu c h l a r g e r t h a n e xpe c t e d. Th e r e s ul t s of fig.
9 s ugges t t h a t i n t he p r e s e n c e of wa t e r , i n a d d i t i o n
T MOS : I - P r OH: H2 0
1:5:2
r l [ ' / I . . . . i ' ' '
i . . . . I . . . . ( 1 0
-70 -80 -90 -100
PPM
I . . . . ,1 320
' ' , i 6 0 ~+
/
Fig. 9. 29Si-NMR spectra measured at - 7 5 C of samples, drawn after different hydrolysis times from a hydrolyzing mixture of
TMOS, 1-propanol and water with a molar ratio of 1 : 5 : 2.
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS 9
t o the hydrolysis, a st rong exchange of al koxy
groups bet ween TMOS and 1- pr opanol also oc-
curred, followed by hydrol ysi s of the newly f or med
silanes. At pr ol onged hydrolysis times, the con-
densat i on rat e is i nfl uenced by all these t ypes of
hydr oxy monomers.
The effect of the acidic cat al yst concent r at i on
upon the exchange behavi our of hydrol ysi ng mix-
tures of TMOS, 1-propanol and wat er with a
mol ar rat i o of 1 : 5 : 2 . 5 was also investigated. In
fig. 10 the i nfl uence of the cat al yst concent r at i on
upon the hydrol ysi s t i me- gel at i on t i me curves is
given. Because of t he low hydrolysis rates at low
acidic cat al yst concent rat i ons, l onger hydrol ysi s
times were requi red to find represent at i ve curves.
Usi ng a TEOS mi xt ure it was al ready f ound t hat
the hydrolysis rat e is inversely pr opor t i onal to the
HC1 concent r at i on [20], except at very low acid
concent rat i ons [22]. Ther ef or e the gelation t i me is
pl ot t ed versus the pr oduct of hydrol ysi s time and
cat al yst concent r at i on (tr~ CHCl). For gelation, a
net concent r at i on of 4 10 - s M NH4 OH was
used. In fig. 11 the 29Si-NMR spect ra of samples
of these hydrol ysi ng TMOS, 1-propanol and wat er
mi xt ures with di fferent acidic cat al yst concent ra-
Table 3
29Si-NMR chemical shifts with respect to TMS in ppm meas-
ured at - 75 C of monomers present after hydrolysis of a
TMOS-1-PrOH or a TPOS- MeOH mixture
S i ( O C H 3 ) 4 - 78.1 + 0.2
Si(OCH 3) s OH - 76.0
Si(OCH 3) 2 (OH) 2 - 74.4
Si(OCH3)(OH) 3 - 73.1
Si(OH)4 - 72.1
Si(OCH2CH2CHg)(OCH3) 3 - 78.9
Si(OCH2CH 2CH3)(OCH 3)2 OH - 76.8
Si(OCH 2CH2 CH3)(OCH3)(OH) 2 - 75.3
Si(OCH 2CH 2CH 3)(OH) 3 - 74.0
Si(OCH2CH 2CH3)2(OCH3) 2 - 79,8
Si(OCH 2CH 2CH 3) 2 (OCH 3 ) O H - 77,7
Si(OCH 2CH 2CH 3 ) 2 (OH) 2 - 76.1
Si(OC H 2CH 2CH 3) 30CH 3 - 80.7
Si(OCH 2CH 2CH 3 ) 3 OH - 78.5
Si(OCH2CH2CH~) 4 - 81.5
tions but with a const ant val ue of t n HCI are
given. Fr om the results it is shown t hat t he de-
crease in t he cat al yst concent r at i on is accompa-
ni ed by a decrease in the condensat i on rat e and at
1 o o
~- [
- [
E
t 8 0
4 0 ' ~ "}" "1" 5
O ' _ _ 1 I _ _ 2
0 20 4 0 6 0 8 0 100
- - . t . x C . c , ' l 0 4 ( m i n - m o l e . 1 - 1 )
Fi g. 10. T h e r e l a t i o n b e t we e n t he g c l a t i o n t i me, t G, a n d t he p r o d u c t o f h y d r o l y s i s t i me a n d c a t a l y s t c o n c c n t r a t i o n , t H x cHcl, o f a
TMOS, 1-propanol and water mixture with a final molar ratio of 1: 5: 2. 5 using an HCI concentration, cl i o, in the acid step of
6. 410 -5 M (1), 3. 210 -5 M (2), 2, 9x10 -5 M(3), 2. 610 -5 M (4) and 2. 1x10 -5 M (5).
10 T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS
TMOS: I - Pr OH: Hz O
1:5:2
I ' ' I ' ' ' ' I ' ' ' ' I
I . . . . I ' ' ~ ' I ' ' ' ' I
C
B
A
I ' ' ' ' I ' ' ~ ' 1 . . . . I
-70 -80 -90 -100
PPM
Fig. i l . ZgSi-NMR spectra measured at - 75 C of samples,
drawn at t H x CHCl = 25 X 10 -4 min mo1-1 from hydrolyzing
mixtures of TMOS, 1-propanol and water in a final molar ratio
of 1: 5: 2 with an HC1 concentration of 6.4X10 -5 M (A),
2.9 10- 5 M (B) and 2.1 x 10- 5 M (C).
even lower cat al yst concent rat i ons fol l owed by a
significant decrease of t he hydrol ysi s rate. These
results are in agreement with those al ready f ound
for TEOS- et hanol mi xt ures [22].
We at t empt ed to i dent i fy the peaks present in
figs. 9 and 11. We succeeded in labelling all t he
monomer s on t he basis of the following two as-
sumptions. First, a chemical shift of about 0.85
ppm for each - OCH 3 - - ~- OCH2CH2CH 3 ex-
change (table 2) and second t hat t he chemical shift
caused by the repl acement of a n - OCH 3 group by
an - OH group or of an - OCH2 CH2 CH 3 group by
an - OH gr oup as shown in t abl e 1 is i ndependent
of the ot her al koxy groups whi ch are at t ached to
t he same silicon at om. The results of the monomer
labelling are given in t abl e 3.
4. Di s c u s s i o n
On compar i ng t he results of the hydr ol ysi s-
condensat i on process of TPOS- l - p r o p a n o l and
TMOS- me t ha nol mi xt ures, as shown in figs. 1- 4,
we f ound t hat under i dent i cal condi t i ons the hy-
drolysis rat e in the acid step of TMOS is much
larger t han t hat of TPOS. However, the dimeriza-
t i on rat e in t he acid step of silanols ori gi nat i ng
f r om TPOS is larger t han t hat of silanols pr epar ed
f r om TMOS. The results of the TPOS- l - p r o p a n o l
mi xt ures are closely correl at ed with t he results of
TEOS- e t h a n o l mi xt ur es descr i bed el sewhere
[20,24].
A larger amount of wat er in the mi xt ure in-
creases bot h t he hydrol ysi s rat e and the con-
densat i on rate. When no excess of wat er was used
in t he mi xt ur e ( a < 2), t he increase in gelation
t i me f ound for TEOS- e t ha nol and TPOS- l - p r o -
panol mi xt ures was not observed for TMOS -
met hanol mixtures. As shown in fig. 4, pract i cal l y
no ol i gomeri zat i on effect s were f ound in the acidic
TMOS mixtures. Ther ef or e, at pr ol onged hydrol y-
sis times a const ant maxi mum silanol concent ra-
t i on is mai nt ai ned, resulting in a const ant low
gel at i on t i me in t he basic step. Because of t he high
silanol concent r at i on, a much l ower NH4 OH con-
cent r at i on is needed for gelation of the TMOS
mi xt ures t han for gel at i on of the TPOS mixtures.
The effect s of t he al cohol i c solvent upon the
hydr ol ys i s - c onde ns a t i on processes of TPOS,
TEOS and TMOS are given in figs. 5- 7 for the
solvents met hanol , et hanol , 1-propanol and 2-pro-
panol . For each silane, the hydrol ysi s rat e in the
acid step is the highest in met hanol , whereas with
2- pr opanol as t he solvent t he lowest react i vi t y was
observed and about equal hydrol ysi s rat es were
f ound for t he solvents et hanol and l - pr opanol .
Thi s di fference can be ascribed to di fferences in
pr ot on act i vi t y of the cat al yst in t he solvents or to
exchange react i ons. However, regardi ng t he equal
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS 11
hydrolysis rates in et hanol and 1-propanol as well
as the di fferences in hydrol ysi s rates f ound for
TEOS and TPOS, the effect of t he pr ot on activity
of the catalyst is domi nant . Wi t h respect to et hanol
and 1-propanol, the activity of the catalyst in
met hanol will be larger, whereas for 2-propanol it
will be smaller.
For the three silanes, the di meri zat i on rates in
the acid step are also dependent on the al cohol
used, but now in the opposi t e sequence: 2-pro-
panol > 1-propanol > et hanol > met hanol , where
the di meri zat i on rat e is very small using met hanol .
However, a significant increase in gelation t i me at
pr ol onged hydrol ysi s times is observed for the
TPOS- me t ha nol mi xt ure in fig. 5. Thi s increase
has to be ascribed to the high degree of exchange
of al koxy groups (fig. 8) in this mixture, resulting
in the f or mat i on of di fferent t ypes of silanes (t abl e
2) in the solvent, bei ng a mi xt ure of met hanol and
1-propanol .
It has al ready been f ound [12] t hat in the
absence even of traces of water, exchange reac-
tions in si l ane- al cohol mi xt ures occur when an
acidic cat al yst is present. The rat e of exchange
depends strongly on t he cat al yst concent r at i on
and is negligible wi t hout the catalyst. We f ound
t hat when the exchange react i ons at low HCI
concent rat i ons were followed with 29Si-NMR,
peaks of di fferi ng chemi cal shifts arose as a func-
tion of time which coul d be simply labelled. As
shown in table 3, a chemical shift of about 0.85
ppm at - 7 5 C was measured for the - OCH 3
- OCH2CH2CH 3 exchange, i ndependent of t he
t ype of group (al koxy or - OH) also at t ached to
t hat silicon atom. As a result of the exchange
react i ons we finally observed a chemical shift of
- 81.5 ppm at - 7 5 C, correspondi ng with the
chemical shift observed for TPOS. Thi s value dif-
fered from the results recorded by Pouxviel and
co-workers [11] for mi xt ures of TEOS and n-pro-
panol. In their 29Si-NMR spectra, measured at
r oom t emperat ure, t hey also f ound a const ant
chemical shift when an et hoxy group was repl aced
by a pr opoxy group. However, t hey r epor t ed for
TPOS a chemical shift of - 85.9 ppm wi t h respect
to TMS whereas we f ound a chemical shift of
- 8 2 . 0 ppm at 25 C for bot h TEOS and TPOS
( t et r a- l - pr opoxysi l ane) . The use of 2- pr opanol in-
stead of 1- pr opanol in t hei r mi xt ure may be the
expl anat i on. The chemi cal shifts they r epor t ed can
be realized si mpl y by exchange react i ons of mix-
tures of TEOS and 2-propanol .
Fr om the labelling pr esent ed in t abl e 3, it can
also be concl uded t hat the change in chemical
shift caused by hydrol ysi s is pract i cal l y i ndepen-
dent of t he nat ur e of the al koxy groups still at-
t ached to the silicon at om, but is largely depend-
ent on the nat ur e of t he repl aced al koxy group
and on the number of - OH groups al ready at-
t ached to t he silicon at om.
Fr om the results given in figs. 10 and 11 it can
be concl uded t hat at low cat al yst concent r at i ons
the di meri zat i on effect decreases consi derabl y. At
even lower HC1 concent rat i ons, t he hydrol ysi s rat e
also becomes very small. Similar results had al-
r eady been r epor t ed for TEOS [22].
The di fferences in di meri zat i on rat e in t he acid
step can be expl ai ned st art i ng f r om the di meri za-
tion mechani sm of silanols in an acidic environ-
ment given by
( RO) 3 - Si - OH + H+ ~ ( RO) 3- Si - OH~- , (1)
followed by
( RO) 3 - S i - OH ~" + HO- S i - ( OR) 3
-o ( RO) 3 - S i - O- S i - ( OR) 3 + H3 O+, (2)
where R is given by H, any alkyl group, or by
Si - ( OR) 3. The di meri zat i on rat e depends on t he
concent r at i on of t he act i vat ed silanol compl ex,
which in t urn depends on the concent r at i on and
the degree of di ssoci at i on of the catalyst in the
solvent.
The results pr esent ed in figs. 10 and 11 can
t herefore be ascri bed to the decrease of the
act i vat ed silanol compl ex concent r at i on as a result
of the decrease of t he cat al yst concent rat i on.
However, t he di fferences in di meri zat i on f ound
for the di fferent solvents, as shown in figs. 5- 7,
cannot be expl ai ned by di fferences in pr ot on ac-
tivity of t he catalyst. For instance, using met hanol ,
for which t he pr ot on activity of the cat al yst is the
st rongest and t her ef or e t he hydrol ysi s rat e the
highest, pract i cal l y no di meri zat i on was found.
In our opi ni on, t he pr ot ons f r om the cat al yst
12 T. N. M. Bernards et al. / Hydrolysis--,condensation processes of TPOS, TEOS and TMOS
can react with silanols and also with wat er or
alcohol to form an act i vat ed compl ex accordi ng to
H+ + H: O ~ H3 0 + (3)
and
R' - OH + H+ ~ R' - OH . (4)
The nat ure of the alkyl group R' will i nfl uence the
equi l i bri um posi t i on of eq. 4 [26]. The sequence of
pr ot onat i on of the compl exes is given by
H3 0 + > CH3OH f > ( RO) 3- Si - OH~-
> CH3CH2OH2 ~ > CH3CHzCHzOH ~
> ( CH3 ) 2 CHOH; .
The concent r at i on of each act i vat ed compl ex de-
pends on the composi t i on of t he mixture. The
base strength of the ( RO) 3- Si - OH~- compl exes
depends on the nat ur e of the - OR groups and is
smaller when mor e non- pol ar al koxy groups are
present and great er with an increasing number of
- OH groups.
Starting f r om these hypot heses, the results can
be expl ai ned unambi guousl y. When wat er is pres-
ent in the mixture, t he H3 O+ compl ex is domi nant
[26], resulting in high hydrolysis rates of the dif-
ferent silanes. In the absence of water, the distri-
but i on of the pr ot ons of the cat al yst over the
compl exes of eqs. (1) and (4), depends on the
alcoholic solvent and the nat ur e of the silanol
compl ex accordi ng to
( RO) 3- Si - OH2 ~ + R' - OH
( RO) 3 - Si - OH + R' - OH~- . (5)
When met hanol is used as the solvent, the con-
cent rat i on of the act i vat ed silanol compl ex is small
and the concent r at i on of the met hanol compl ex
high. The low concent r at i on of the silanol com-
plex results in small di meri zat i on effects. Usi ng
2-propanol as the solvent, the act i vat ed silanol
compl ex concent r at i on is high compar ed with t hat
of the act i vat ed 2- pr opanol compl ex, resulting in
strong di meri zat i on effects. Wi t h et hanol or 1-pro-
panol as the solvent, i nt ermedi at e effects were
observed.
The relative amount of wat er in the mi xt ures
has a strong i nfl uence on the composi t i on of the
activated silanol compl exes and t herefore on their
strengths. A larger amount of wat er results in a
silanol compl ex with a larger number of - OH
groups. Thi s effect increases the base st rengt h of
the act i vat ed compl ex and results in an increase in
the concent r at i on of this compl ex, thus decreasi ng
the i nfl uence of t he al cohol i c compl exes upon the
hydr ol ys i s - condens at i on processes of the silanes.
It is shown t hat by using an alcoholic solvent
with an al koxy gr oup di fferent f r om those of the
silane, the number of t ypes of silanol monomer s
may i ncrease f r om f our to ten monomer s (tables 1
and 3). Also, the number of types of dimers etc.,
may i ncrease drastically. When a mi xt ure of mor e
alcohols is used as t he solvent, an even mor e
compl ex si t uat i on may occur. In practice, to real-
ize coat i ng sol ut i ons with the requi red rheological
propert i es, mi xt ures of several alcohols are used.
As a consequence of exchange reactions, fol l owed
by hydrol ysi s of t he newl y f or med product s, the
composi t i on of such coat i ng sol ut i ons may var y as
a funct i on of time, t emperat ure, etc. Wi t hout a
f undament al knowl edge of the possible reactions,
t he propert i es of such coat i ng solutions will change
in an unpr edi ct abl e way.
5. Conclusions
(1) The hydrol ysi s rat es of t he silanes in an
acidic envi r onment decreases in the sequence:
TMOS > TEOS > TPOS.
(2) For all the silanes used it hol ds t hat an
increase in the acidic cat al yst concent r at i on as
well as an increase of t he relative amount of wat er
in the mi xt ur e results in a hi gher hydrol ysi s rat e in
t he acid step.
(3) The al cohol i c solvents have a remarkabl e
i nfl uence on t he hydrol ysi s rat e of the silanes in
t he acid step in the sequence met hanol > et hanol ,
1-propanol > 2-propanol , caused by di fferences in
the pr ot on act i vi t y of cat al yst in the alcohols.
(4) An opposi t e sequence for the i nfl uence of
the al cohol i c solvents was observed for the dimeri-
zat i on rat e of silanols in the acid step. The dif-
ferences in di meri zat i on rat e are ascribed to dif-
ferences in base st rengt h of t he act i vat ed silanol
compl exes with regard to those of the pr ot onat ed
alcohols.
T.N.M. Bernards et al. / Hydrolysis-condensation processes of TPOS, TEOS and TMOS 13
T h e a u t h o r s l i ke t o t h a n k J . M. E. B a k e n f o r ma n y
v a l u a b l e d i s c u s s i o n s a n d W. P . M. R u t t e n f o r p e r -
f o r mi n g t h e 2 9 S i - NMR s p e c t r o s c o p y e x p e r i me n t s .
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