]OURNA L OY

ELSEVIER Journal of Non-CrystallineSolids 186 (1995) 96-103

Preparation and properties of monolithic silica xerogels

from TEOS-based alcogels aged in silane solutions
S. H~ereid, M. Dahle, S. Lima, M.-A. Einarsrud *
Department of lnorganic Chemistry, Norwegian Institute of Technology, University of Trondheim, 7034 Trondheim, Norway

Abstract

In previous work, tetramethoxysilane-based alcogels were strengthened and stiffened by providing new monomers to the
alcogel subsequent to gelation. It is shown that also by aging tetraethoxysilane (TEOS)-based alcogels in solutions of
TEOS/ethanol (EtOH) the strength and stiffness can favourably be increased and hence reduce the shrinkage during drying
at ambient pressure. Low-density silica xerogels ( p --- 0.24 g/cm 3) are obtained by changing aging parameters such as time
and temperature. The water content in the pore liquid is important for the aging process and is increased by changing the
pore liquid prior to providing the monomers for aging. The shear modulus has been increased by 23 times and the modulus
of rupture by five times, reducing the corresponding shrinkage during drying to --- 0.5%.

I. Introduction such as strength, stiffness and permeability might,

For a large-scale commercial application of aero-
gels, ways to circumvent the high costs and risk of
supercritical drying must be found. In recent years
processes for producing monolithic aerogels using
ambient pressure drying have been described [1,2].
The achievement of this goal depends on factors
such as the pressure gradient developed during dry-
ing and the strength and permeability of the wet gel.
Because of the higher permeability of base-catalyzed
gels compared with acid-catalyzed gels, they are
favourable as precursors for ambient pressure dried
aerogels [3]. However, the strength and stiffness of
these base-catalyzed gels are generally lower than
for acid-catalyzed gels [4,5]. Properties of the gel
* Corresponding author. Tel: +47-7 359 4002. Telefax: +47-7
359 3992. E-maih einrud@kjemi.unit.no.
however, be influenced by aging of the wet gel
[6-11].
Our previous work has been concentrated on in-
creasing the strength and stiffness of the wet gel by
aging the gel in a silane solution [12]. New monomers
are added to the already formed network and hydrol-
ysis, condensation and specific precipitation of these
monomers favorably increase the strength and stiff-
ness of the alcogel. For tetramethoxysilane
(TMOS)-based gels, the shear modulus, G, was in-
creased by 15 times and the corresponding shrinkage
was reduced by about 30% giving xerogels with a
considerably lower density compared with unaged
samples [12,13].
The present work examined the effect of aging
tetrathoxysilane (TEOS)-based alcogels in solutions
of TEOS/ethanol. The increase in strength and stiff-
ness of the wet gels has been reported as a function
of aging time and temperature in the TEOS/ethanol

0022-3093/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0022-3093(95)00039-9
 S. Hcereid et al. /Journal of Non-Crystalline Solids 186 (1995) 96-103
solution. Properties of the corresponding ambient
pressure dried xerogels are compared with CO 2 su-
percritical dried aerogels.
The mechanism for the aging process will be
discussed. To show the importance of the specific
precipitation of the TEOS monomers from the aging
solution, properties of these gels have been com-
pared with thermally aged alcogels with the same
silica content prepared from a sol with a decreased
amount of solvent.
2. Experimental procedure
Alcogels were made from TEOS, H20, ethanol,
HC1, and NH4OH in the total molar ratio
1 : 3.5 : 3.9 : 7.8 × 10 - 4 : 5 . 7 X 10 - 3 by a similar
procedure as described by Brinker et al. [14]. The
TEOS was hydrolyzed in a solution with molar ratios
T E O S / H 2 0 / e t h a n o l / H C 1 equal to 1 : 1 : 3.9 : 7.8 ×
10 - 4 under reflux for 1.5 h at 60°C. This solution
was mixed with the remaining water and NHaOH ,
cast into Teflon tubes with an inner diameter of 8.6
mm and kept at 40°C for 1 h for gelation. To study
the effect of aging time and temperature in
TEOS/EtOH, the gel rods were soaked first in a
washing solution (20 vol.% H20/ethanol) for 24 h
at 60°C and secondly in an aging solution (70 vol.%
TEOS/ethanol) for various lengths of time (6-96 h)
and at various temperatures (40-70°C). The samples
were then washed in ethanol four times within 24 h
at 50°C before the mechanical properties were mea-
sured and further in acetone four times within 24 h at
room temperature. As a reference sample for 0 h
aging time, gels were only washed in 20 vol.%
H 2 0 / E t O H . The gels were soaked in the washing
solution for 24 h at 60°C and the mechanical proper-
ties were measured prior to further washing in ethanol
and acetone. Samples were also immersed directly
into ethanol after gelation for 1 h at 40°C or after a
thermal aging in the mother liquor in well sealed
tubes for 24 h at 60°C. Generally the volume ratio
gel : solution was 1 : 3.1.
The wet gels were dried (1) from ethanol or
acetone at ambient pressure in the temperature range
20-180°C within 96 h, or (2) above the critical point
of CO 2 after replacing the acetone with liquid CO 2.
All dried gels were heat treated in air at 300°C
97
before measurements of surface area, density, linear
shrinkage and skeleton density, and before gravimet-
ric measurements.
The load deflection data for the measurement of
the wet gel shear modulus, G, and the modulus of
ruptures (MOR) were determined by using a three-
point beam bending apparatus (ASTM C674-81).
The solution in the bath with the bending fixture was
the same as the pore liquid, which was ethanol in all
cases except for gels only washed in 20 vol.%
H 2 0 / E t O H at 60°C. The ratio between the span of
the bending fixture and the wet gel radius was = 10
and the deflection versus load was measured at a
down drive rate of 2.2 mm/min. The MOR was
obtained from the load at which the rods broke and
the G modulus was obtained from the slope of the
load-deflection curve. Nine rods were broken to
obtain an average value for the MOR. Load-relaxa-
tion experiments were done as described by Scherer
[15] to measure the permeability, D, the G modulus
and the Young's modulus, E. The relaxation time
was obtained by measuring the load necessary to
keep the deflection of the gel rod constant. The
deflection of the gel rod was chosen to give an
acceptable load ( = 30 g) and the data analysis was
performed using a non-linear fitting routine de-
scribed by Scherer [16].
The surface area of the supercritically dried aero-
gels was measured by N 2 adsorption (Micromeritics,
ASAP 2000) and calculated from five-point
Brunauer, Emmett and Teller (BET) theory and the
skeletal density was measured by helium pycnometry
(Micromeritics, Accupync 1330). The samples were
heat treated at 250°C under vacuum for 24 h prior to
surface area measurements. The xerogel and aerogel
bulk densities were calculated from the weight and
volume of the samples. The wet densities are the
bulk densities of dried gels if there were no shrink-
age during drying; it is calculated from the volume
of the wet gel and gravimetric measurements of the
heat-treated gel. The linear shrinkage during drying
is calculated from the diameter of the wet gel rod
after aging and after heat treatment.
3. Results
Aging the wet gel in solutions of TEOS/EtOH
causes silica to precipitate from the aging solution
98 S. Haereid et al. /Journal of Non-Crystalline Solids 186 (1995) 96-103

onto the silica network [13]. The effect of aging time 25 i i i I i , i I F i f i i , } , , ,

and temperature in the TEOS solution can be seen in 40°C

50°C
Figs. 1 and 2, where the physical properties of 20
- - - - O - - 60°C
samples aged for different times and temperatures Z 60"C (rel.)
are compared. Aging time is the time the gel rods 15 - - - - O - - 70°C
4 70"C (rel.)
were immersed in the T E O S / E t O H solution after
washing in H 2 0 / E t O H . Fig. 1 shows the wet den- 1o
sity, the xerogel density for gels dried from acetone,
and surface area versus aging time and temperature.
5
Wet densities represent the amount of silica precipi-

0.30 40ocl /o
0.35 + 501c I /~
"~ 0.30
0.25
0.25
.~ 0.20 e¢
© 0.20
.g
0.15
~0.15
0.10 ]
0.05 ! , ' ' I , , , I , , , i , , , I,, ,"
0 20 40 60 80 100
0.50 Aging time (hours)
0.45 Fig. 2. Effect of aging time at different temperatures in the
TEOS/EtOH solution on G modulus from both standard three-
~ 0.40 point beam bending and load-relaxation (rel.) experiments and
MOR. The errors (determinedfrom standard deviation)are +5%
-~ 0.35
= in the G values and _+20% in the MOR values. Lines are drawn
0.30 as guide to the eye.

0.25

i ,,litl~l~,,lll~L,Ir-
tated from the aging solution, and is therefore a
measure of the effect of the aging process. As can be
seen from Fig. 1, the wet density increases while the
xerogel density and the surface area decrease with
increasing aging time and aging temperature. The
surface areas were measured on supercritically dried
aerogels; however no difference in surface areas was
observed between aerogels and xerogels from the
same sol and with the same aging treatment of the
650 : , , , I [ ,_1 , I ivJ
wet gel. Fig. 2 shows the increase in G modulus and
0 20 40 60 80 100
Aging time (hours) MOR with increasing aging time and aging tempera-
ture. Generally, MOR data show considerable scatter
Fig. 1. Effect of aging time at different temperatures in the since the strength is controlled by random surface
TEOS/EtOH solutionon wet density, xerogel density when dried
from acetone, and on surface area measured on supereritically flaws. The constant MOR values between 48 and 72
dried aerogels. The error is _+0.01g/cm 3 in the density and + 10 h for the samples aged at 40 and 50°C are expected
m2/g in surface area. Lines are drawn as guides to the eye. to be an experimental error and that a similar in-
 S. Ha•reid et al. / J o u r n a l of Non-Crystalline Solids 186 (1995) 96-I03 99

Table 1 xerogels dried from acetone and ethanol and super-

Relaxation time % G modulus, Young's E modulus, E, and critically dried aerogels versus wet density. The den-
permeability, D, given from load-relaxation experiments
sity of the xerogels decreases with increasing wet gel
Aging time in Pwet 7" G E D density until it reaches a minimum of -- 0.25 g / c m 3
TEOS/EtOH ( g / c m 3) (s) (MPa) (MPa) (nm 2)
at 70°C (h)
in the wet density range 0.21-0.26 g / c m 3 where it
increases again. The linear shrinkage during drying
24 0.171 101 5.41 13.7 11.9
48 0.259 65.9 9.22 23.9 9.94 at ambient pressure reaches a minimum level of
96 0.281 34.6 23.5 61.9 6.93 --- 0.5% when the wet density is 0.26 g / c m 3. Gener-
ally monolithic rods were obtained. The density of
the supercritically dried aerogels increases with in-
crease in the MOR values as observed for the 60 and creasing wet density as expected since the linear
70°C samples is more probable. shrinkage during the supercritical drying is low (Fig.
Table 1 shows the effect of aging time in the 3). There is also a small decrease in the linear
TEOS solution at 70°C on relaxation time, r, G shrinkage during the supercritical drying as the wet
modulus, Young's modulus, E, and the permeability, density increases. Fig. 4 shows the surface area and
D, measured from the load-relaxation-time experi- the hydraulic radius, r h, versus wet density. The
ments. hydraulic radius was calculated from
Fig. 3 shows the density and linear shrinkage of 2Vp 2(1-p .... /Ps)

rh = SA P .... SA ' (1)

0.6 , ,,, i I , r , l , , , , [ ~ , T

1100 i , , , l l l , l l l , l l TII
0.5 ~ • Acetone
O Ethanol
~ © CO 2 1000
0.4
E 900 f
'~ 0.3 o oeO- • 00
o o,Oo ~D
800
0.2 @

7OO
,°,,p,,,ll,,i,f,,,,
, , , , I , , , , i , , J ,
40 O • Acetone - .... r .... j .... II

¢~ ~ O ~ O © Ethanol
~a 30 o co 2
o~-~ tO0
• •
•~ 20
80

.= l0 • o

l
o • 60
'-' o °S°ooocoO OO •
4O

0.! 0.15 0.2 0.25 0.3

Wet density (g/cm 3) 20
0.10 0.15 0.20 0.25 0.30
Fig. 3. Change in density and linear shrinkage versus wet density
Wet density (g/cm 3)
of xerogels dried from acetone and ethanol and supercritical dried
aerogels. The error is + 0.01 g / c m 3 in the density and _+0.5% in Fig. 4. Surface area and hydraulic radius of the xerogels versus
linear shrinkage. wet density.
100 S. Hcereid et al. /Journal of Non-Crystalline Solids 186 (1995) 96-103
- - y = 2558.7 * x^(3.3802) R= 0.98362
100
i(a)
l0
40.C
50"C
60"C
70"C
[]
1 0
0.1 0.2 0.3 0.4 0.5
Wet density (g/cm3)
Fig. 5. (a) Bulk modulus versus wet density on a log-log scale and (b) bulk modulus versus the (xerogel density)/(wet density) ratio for
samples aged in T E O S / E t O H solutions for different times and at different temperatures.
where SA is the surface area and Vp is the specific
pore volume of the xerogel given by the xerogel bulk
density, p ..... and the skeletal density, Ps [17]. The
skeletal density was measured to be 2.15 + 0.05
g / c m 3 for both aged and untreated gels. The surface
area decreases while the hydraulic radius increases
with increasing wet density.
The bulk modulus of the silica network, Kp, can
be described by a power law of the form [18,19]
= Ko( P/Po) m
The bulk modulus is related to the G modulus by
2(1 +
Kp = G 3(1 - 2 % ) '
where % is the Poisson's ratio of the silica network.
The Poisson's ratio is assumed to be 0.2 [20]. Fig.
5(a) shows the bulk modulus of the wet gel versus
the wet density for samples aged for different times
and temperatures. The power law exponent of 3.4 is
from a fit of all the data. Fig. 5(b) shows the bulk
modulus of the wet gel versus the (xerogel density)/
(wet density) ratio, showing that a high bulk modu-
lus gives xerogel densities closest to the wet density.
4. D i s c u s s i o n
Earlier work has shown that ambient pressure
dried aerogels can be obtained by increasing the
mechanical strength and stiffness of the wet gel prior
35
i6 ..... ' ......... ' ......... ' ..........
30 A 40°C
<> 50°C
25 [] 60"C
o 70°C
2o -•
M= 15
10
5
1.0 2.0 3.0 4.0 5.0
Pxero/Pwet
to drying [1,12,13]. The data from this study give the
relation between the mechanical properties of the
wet gel, the density and structure of the dried gel,
and the aging parameters used during aging in the
T E O S / E t O H solution. Increasing the aging tempera-
ture causes the wet density to increase (Fig. 1) which
is caused by a higher hydrolysis and condensation
rate of TEOS at higher temperatures [21,22]. A
higher wet density is also obtained with longer aging
times caused by an increase in the amount of TEOS
(2) reacted and precipitated (Fig. 1). As the strength and
stiffness of the wet gel are improved (Fig. 2), the
linear shrinkage during drying is reduced and a low
(3) xerogel density is obtained (Fig. 1). It is of special
interest that a xerogel density of 0.24 g / c m 3 and a
linear shrinkage of -~ 0.5% during drying can be
obtained by increasing the wet density. The fact that
the xerogel density reaches a minimum before it
increases again (Fig. 3) shows that the xerogel den-
sity is a result of both gained weight and reduced
shrinkage during drying. As the wet density is in-
creased, a decrease in surface area as silica precipi-
tates is observed (Fig. 4(a)). It is expected that the
necks between the primary particles where the silica
solubility is lowest are filled up first and second the
smallest pores [13].
In Fig. 5(a) the log-log plot demonstrates a
power-law wet density dependence of the bulk mod-
ulus, Kp. Lemay et al. [23] measured the compres-
sive modulus as a function of density by preparing
silica aerogels from sols with various solvent con-
 S. Hcereid et aL /Journal of Non-Crystalline Solids 186 (1995) 96-103
centrations. The exponent was 2.9 for a base-cata-
lyzed aerogel, 3.8 for a pre-hydrolyzed aerogel and
2.4 for an acid-catalyzed aerogel. Woignier et al.
[18] found a power-law behavior with an exponent of
3.7 of the Young's modulus for supercritical dried
aerogels prepared under acidic, neutral, and basic
conditions and with various solvent concentrations.
This work demonstrates that gels with silica precipi-
tated after gelation show a similar power-law be-
haviour as gels prepared with various solvent con-
centrations in the sol and that the exponent of 3.4 is
in the same range as reported in the literature
[18,19,23]. As can also be seen from Figs. 5(a) and
(b), the increase in K modulus is mainly dependent
on the increase in wet density and shows no signifi-
cant dependence on the aging temperature. H~ereid et
al. [24] have reported the increase in G modulus with
thermal aging in water, which is dominated by the
dissolution and reprecipitation of silica, and found a
strong dependence on aging temperature. By aging in
a solution of monomers, the solubility of silica from
the original gel network is low and as a result aging
in TEOS is dominated by the precipitation of silica
from the TEOS solution and not by dissolution and
reprecipitation of silica from the original gel net-
work.
Precipitation of silica during aging in the TEOS
solution gives a higher G modulus; however, it also
gives a decrease in permeability with increasing wet
density (see Table 1). It is, however, interesting that,
even if the increase in the wet density is largest
between 24 and 48 h aging time, there is only a
small decrease in permeability, indicating that the
necks between primary particles and the smallest
pores are filled up (Table 1). During further aging
(48-96 h) there is only a small difference in the wet
density, but the decrease in permeability is larger,
hence the general network thickness probably in-
creases.
The drying stresses, orx, at the surface of a plate
of gel (with thickness 2L) can be approximated by
[25]
crx = L r k f I E / 3 D , (4)
where I2e is the evaporation rate and 7k is the
viscosity of the pore liquid. In our experiment, the
only quantity that varies is the permeability giving
Cx a/3-'. (5)
101
However, the precipitation of silica during aging
gives an increase in strength (Fig. 1) and the increase
in strength is expected to be more prominent than the
decrease in permeability [12].
A simple model of structural changes in the net-
work due the precipitation of silica from the aging
solution is developed by calculating the increase in
cylinder radius, a, of the network and change in
permeability from the cubic cell model [26]. The
cylinder radius, a, of the network can be calculated
by comparing the surface area, SA, with the cubic
cell model giving [26]
= 1 ( 1.666- 3X)
a PsSa -0.--~-3--X . (6)
If the porosity is > 30%, an approximation to give X
in terms of p for the cubic cell is [27]
0.925
[3/(O/Os) 'j2] - 1 (7)
The permeability can be estimated from [17]
P rw
D= 1--- (8)
Ps 41% '
where r w is the size of the 'window' in the side of
the cell and Kw is the Kozeny constant
Kw = 1.824 + 4.254 ( p / p ~ )
for 0.06 < ( p / p ) ~ < 0.14, (9)
and r w is related to the cylinder radius, a, by [17]
Thus, using the calculated values of a and X, the
permeability is obtained from Eq. (8)-(10).
The increase in calculated cylinder radius with
increasing wet density and the decrease in calculated
permeability are shown in Fig. 6. The calculation
assumes that there is a single pore size, and all the
cylinders grow at the same rate. In reality, there is a
pore size distribution causing the smallest pores to
fill first. However, the calculation is useful to give
an idea of the scale of the structure and indicates that
the effective thickness of the polymer strands is = 1
nm. The calculated permeability (Fig. 6) is lower
102 S. Htereid et al. / J o u r n a l of Non-Crystalline Solids 186 (1995) 96-103

Table 2
Wet density, P,~.~t, xerogel density (dried from acetone), Px~o, linear shrinkage, G modulus, MOR, surface area and hydraulic radius, rh, for
samples with different treatment histories; the TEOS : EtOH ratio in the sol was 1 : 3.9 for sample (1) and 1 : 1.5 sample (2), while the water
and catalyst content in the sol were the same for both samples
Treatment history Pwct Px~,o Linear G MOR SA rh
( g / c m ~) ( g / c m -~) shrinkage (MPa) (MPa) (m2/g) (,~)
(%)
(1) Washed in H 2 0 / E t O H 24 h 60°C, 0.204 0.32 13.9 10.7 0.23 734 72
aged in T E O S / E t O H 48 h 60°C
(2) Thermal aging 48 h 60°C, 0.197 0.39 20.7 6.82 0.31 923 45
washed in H 2 0 / E t O H 24 h 60°C

than the measured permeability, probably since it is draulic radius is 72 A for xerogel (1) prepared b~¢
calculated from a single pore size. However both the aging in T E O S / E t O H solution while it is only 45 A
calculated and measured permeabilities decrease by for xerogel (2). One feasible explanation is that the
~- 50% within the same wet density range. cylinder thickness is higher for the sample aged in
A critical question concerns whether the same the TEOS solution giving a stiffer gel; the calculated
high mechanical strength and stiffness achieved by cylinder radius is 1.2 nm for sample (1), TEOS aged
precipitation of silica from the aging solution can be gel, compared with 0.94 nm for sample (2) prepared
obtained for samples with a higher silica concentra- from a sol with higher silica concentration (Eq. (6)).
tion in the sol. Gels with similar wet density, but
obtained (1) by aging an alcogel with a lower wet
density in a TEOS solution and (2) by decreasing the
5. Conclusions
ethanol content in the sol are compared in Table 2.
The gels were given the same thermal history: (1) by
aging in the TEOS solution or (2) by thermal aging (a) A gel network with a considerably higher
in the mould. Since the G modulus is higher for the mechanical strength and stiffness is obtained as silica
sample aged in TEOS, the shrinkage is reduced and precipitates from the aging solution onto the gel
hence a lower xerogel density is obtained. The hy- network causing the linear shrinkage during drying
to decrease and a lower xerogel density is obtained.
A corresponding decrease in surface area and in-
crease in hydraulic radius has been observed.
1.4 E' '' I' ''' I ' ' ' ' I ' ~' ' 3.5 (b) Shrinkage during drying can be almost com-
0 pletely eliminated. Xerogels with a density of 0.24
1.3 3.0
0 0 g / c m 3 are reported.
oo ooo oo 2.5 (c) The bulk modulus is dependent only on the
1.2 0 0o
• o--~ 2.0 amount of silica precipitated from the aging solution,
• •
1.1 not on the aging temperature.
0 0
1.5 (d) A gel prepared by precipitating silica from the
~ 1.0 aging solution shows a higher G modulus, less
1.0
shrinkage during drying, and a lower xerogel density
0.9 0.50 compared with a thermally aged gel prepared by
0.8 0.0 using a higher silica concentration in the sol.
0.10 0.15 0.20 0.25 0.30
Wet density (g/cm3) This work has been supported by the Research
Fig. 6. Calculated cylinder radius, a, and calculated permeability, Council of Norway. The authors thank Dr G.W.
D, as a function of wet density. Scherer for helpful discussions and calculations.
 S. Haereid et aL /Journal of Non-Crystalline Solids 186 (1995) 96-103
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