Journal of Non-Crystalline Solids 304 (2002) 92100

www.elsevier.com/locate/jnoncrysol

Investigation on kinetics of thermal decomposition in

polysiloxane networks used as precursors of silicon
oxycarbide glasses
M.A. Schiavon, S.U.A. Redondo, S.R.O. Pina, I.V.P. Yoshida *

Instituto de Qu
micaUNICAMP, CP 6154, 13083-970 Campinas, SP, Brazil

Abstract

In this study, polysiloxane networks prepared by hydrosilylation or hydrolysis/condensation reactions were con-
sidered to be potential precursors for SiCO systems. Dierent precursors had dierent pyrolytic properties, which was
essentially due to their molecular architecture. The kinetics parameters, such as the activation energy, E (kJ/mol) in-
volved in the polymer-to-ceramic conversion, were investigated by thermogravimetry using a multiple heating rate
kinetic method. The relationships between the molecular architecture and the precursor composition were compared to
that of a linear poly(dimethylsiloxane) precursor. Solid-state 29 Si nuclear magnetic resonance, infrared spectroscopies,
density measurements, and X-ray diraction measurements were made on the nal samples. These products were
typically amorphous, with a molecular structure formed by a random distribution of dierent silicon sites and variable
amounts of free carbon residue. 2002 Elsevier Science B.V. All rights reserved.

PACS: 81.05.Je; 81.05.Kf; 81.05.Lg; 81.20.Zx

1. Introduction sors of silicon oxycarbide glasses (SiCx Oy ), because

Polymer pyrolysis is a relatively new and
promising technique for processing advanced ce-
ramics [1]. The main advantage of such an ap-
proach is the possibility of building up polymers
from molecular units and controlling their molec-
ular structure, to determine the nanometer and/or
micrometer scale structure and also the phases of
the nal ceramic product [2]. Polysiloxanes have
received particular attention as polymeric precur-
*
Corresponding author. Tel.: +55-19 3788 3130; fax: +55-19
3788 3023.
E-mail address: valeria@iqm.unicamp.br (I.V.P. Yoshida).
this class of polymers provides an easy and inex-
pensive route to the formation of such materials
[3]. It is well established that the polysiloxane-
derived silicon oxycarbide glass is a random three-
dimensional arrangement of tetrahedrally silicon
atoms bonded to carbon and oxygen [4]. This sub-
stitution of oxygen for carbon in the silicon coor-
dination sphere leads to the presence of carbidic
units, in the amorphous network, which strengthen
the structure by increasing its bond density. In
fact, literature data on the characterization of
these materials have indicated diering thermal
and mechanical properties for the carbon-contain-
ing glasses, compared to the fully oxide related
systems [5].

0022-3093/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 2 ) 0 1 0 0 9 - 8
 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100
Several studies on the synthesis of silicon oxy-
carbide glasses, obtained from a polymeric pre-
cursor, have been described [68] resulting in an
improved understanding of the precursor-to-ce-
ramic conversion process. Studies based on the
solgel route, using a large variety of alkoxide
precursors, RSiOR0 3 , were performed to investi-
gate the inuence of the organic R group, on the
incorporation of carbidic units in the structure of
the ceramic glasses and also on their composition
[9].
An alternative class of precursors of SiCx Oy
glasses has employed polymers containing car-
bosilane bridges, SiCx Si. These bridges allow
better control of the carbon content incorporated
in the network precursors, by replacing the SiO
Si bridges, without decreasing crosslinking. In
previous research, the hydrosilylation reaction was
successfully used as a route to produce polysilane
[10,11] and polysiloxane [8,12,13] networks with
carbosilane bridges, which has allowed the control
of the molecular structure of the derived ceramics
and the amount of carbon in the products.
The aim of the present work was to exploit the
thermal decomposition process of dierent poly-
siloxane networks, during the polymer-to-ceramic
conversion, to understand the inuence of the
molecular architecture of the precursors on their
pyrolytic properties and on the structure of the
nal products. Three polysiloxane networks,
with dierent molecular architecture, prepared by
hydrosilylation reaction and one organic-bridge
polysilsesquioxane prepared by hydrolysis/con-
densation of alkoxysilane, were studied. Heat
treatment in inert atmosphere up to 1000 C of
these precursors resulted in silicon oxycarbide
glasses with dierent compositions. The structural
characterization of the nal glasses was performed
by means of dierent techniques such as 29 Si magic
angle spinning nuclear magnetic resonance (29 Si
MAS NMR) and infrared (IR) spectroscopies, X-
ray diraction (XRD), and density measurements.
The activation energy, involved in the conversion
process for each system, was determined using a
dynamic thermogravimetric analysis method de-
veloped by Ozawa [14]. The results were correlated
to the molecular architecture of each polymeric
precursor.
93
2. Experimental procedures
2.1. Starting materials
Commercially available functional siloxane cy-
clic oligomers, the 1,3,5,7-tetramethyl-1,3,5,7-tet-
ravinylcyclotetrasiloxane, CH3 CH2 @CHSiO4 ,
D4 Vi and the 1,3,5,7-tetramethyl-1,3,5,7-tetra-
cyclotetrasiloxane, CH3 HSiO4 , D4 H, and a
linear siloxane polymer with vinyl functionalities,
fCH3 2 SiOn CH2 @CHCH3 SiOm g, (PDMS-
Vi) Mn 13,500 g/mol, were supplied by Dow
Corning; platinum divinylcomplex (Pt-catalyst),
23% in vinyl terminated poly(dimethylsiloxane),
poly(methylsiloxane), CH3 HSiOn (PMHS),
Mn 2300 g/mol, and a poly(dimethylsiloxane)
silanol terminated, HOCH3 2 SiOn H, (PDMS),
Mn 26,000 g/mol, were purchased from
H ulls. Aminopropyltriethoxysilane, H2 NCH2 3
SiOC2 H5 3 , (APS) was purchased from Aldrich,
and the oligomeric epoxy resin derived from po-
lybisphenol A-co-epichlorhydrin (PBFE), Mn
600 g/mol, was supplied from Dow Chemical. All
these materials were used as received.
2.2. Sample preparations
In this study, homogenous neat mixtures of
siloxane cyclics or polymeric materials containing
CH@CH2 and SiH groups were submitted to
platinum-catalyzed hydrosilylation reaction, in the
presence of 1 wt% Pt-catalyst. The preceramic
network, coded PN1, was built by the reaction
between the cyclic oligomer D4 Vi and the linear
polysiloxane chain, PMHS; the second one, coded
PN2, by the same reaction between two cyclic
oligomers D4 Vi and D4 H; and the third one was
a poly(dimethylsiloxane)-based network, coded
PN3, which was built by a mixture of PDMSVi,
PMHS and D4 Vi. The organic-bridged poly-
silsesquioxane precursor, coded PN4, was pre-
pared by amine-epoxy addition reaction between
APS and PBFE, followed by hydrolysis/conden-
sation reactions. The compositions, in wt%, for
each mixture are described in Table 1. All the
samples were prepared by homogenization of the
components under magnetic stirring and then cast
in Teon molds. No solvent was used. These
94 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100

Table 1 diractometer (Shimadzu, model XD3A), using

Compositions of the preceramic networks Cu Ka radiation (k 0:15418 nm). Density mea-
Pre- Mixture Compositions (wt%) surements were performed on a helium picnometer
cursor D4 Vi D4 H PMHS PDMSVi APS PBFE (Micromeritics, model 1305). Ceramic yields were
PN1 50 50 determined from TGA curves, at 980 C. The
PN2 59 41 random error associated to these measurements
PN3 2.5 7.5 90 was
0.1%. The random errors of TMAX , was given
PN4 41.5 58.5
by the oven sensibility of the thermogravimetric
analyzer, and it was
0.2 C.
mixtures were aged up to 72 h producing exible
monolithic pieces for PN1, PN2 and PN3, and a
hard resinous material for PN4. The correspond- 3. Results
ing silicon oxycarbide glasses were obtained by
pyrolysis under owing argon (100 ml/min) in The TGA curves obtained for the preceramic
a tubular alumina furnace (Edgcon 5P) with a polymeric networks and for silanol terminated
heating/cooling rate of 10 C/min and a holding PDMS uid, in owing argon, are shown in Fig. 1.
time of 2 h at the nal temperature. Each sample displayed a distinct thermogravi-
metric prole as well as a ceramic yield, except for
2.3. Sample characterization techniques PN1 and PN2 which, in addition to the similar
proles, produced the same ceramic yield,
The thermogravimetric analyses, TGA, of the 86:1
0:1%. The ceramic yields for PN3 and PN4
precursors were performed on a thermogravimet- were 75:2
0:1 and 25:5
0:1%, respectively. The
ric analyzer (2950, TA Instrument) operating at linear PDMS uid, had no residue at 600 C.
various heating rates (2, 5, 10 and 20 C/min) from The thermal stability, evaluated as a function of
30 up to 980 C in a controlled dry argon ow of the initial weight loss temperature, showed the
100 ml/min. The activation energy (E) of the following order: PN4 < PDMS < PN3 < PN2 <
thermal degradation processes for all samples were PN1. PN4 was the least stable polymer, due to the
determined by the dynamic method, with ther- larger organic content in the macromolecular
mogravimetric curves obtained at various heating chain. PN1 displayed the highest thermal stability,
rates, according to the Ozawa method [14]. Eq. (1) due to the largest crosslinking degree expected for
shows the relationship between the logarithm of this network, as can be seen schematically below.
the heating rate and the reciprocal of the absolute
temperature for a given weight loss:
d log b E
0:457 ; 1
d1=T R
where b, T , and R are heating rate, absolute tem-
perature, and gas constant, respectively. The
weight loss used is the weight fraction of decom-
position (1 a), where a W0 Wt =W0 Wf ,
and W0 is the initial weight, Wt is the weight at
temperature T, and Wf is the nal weight of the
sample. 29 Si MAS NMR spectra were recorded on
a spectrometer (Bruker, model AC300P), operat-
ing at 59.62 MHz for 29 Si nucleus with a rotation
frequency between 3 and 5 kHz. The 29 Si one-pulse
experiments required a recycle delay of 60 s with a Fig. 1. TGA curves of the preceramic networks and PDMS (Ar
30 pulse angle. XRD spectra were recorded on a ow at 20 C/min).
 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100
In polysiloxane chains or polysiloxane networks,
with long linear segments between nodes, i.e. larger
critical molecular weights, Mc, the initial weight
loss has been attributed to the evolution of volatile
siloxane arising from inter or intrachain reactions
[15], while the mineralization process occurs be-
tween 600 and 900 C producing SiOC glasses [16].
0:2, 574:3
0:2, 463:6
0:2 and
0:2 C for PN1, PN2, PN3, and PN4, re-
0:2 C for the PDMS uid.
In the DTGA curves for PN1, PN2 and PN4
(Fig. 2) at least two overlapped steps in the degra-
0:2 to 438:2
0:2 and to 463:6
0:2 C,
dation process, could be observed, while the linear
PDMS showed a single one (Fig. 2). On the other
0:2 and to 716:8
0:2 C, for the
side, the DTA curves for the PN3 sample displayed
two distinct steps, as can be seen in Fig. 3. For a
given heating rate, a material may be characterized
Fig. 2. DTGA curves of PN1, PN2, PN4 and PDMS samples at
20 C/min.
95
Fig. 3. DTGA curves of PN3 sample at dierent heating rates.
by the temperature, TMAX , at which the mass ux
from solid to vapor is a maximum. For the studied
samples, at 20 C/min, the TMAX for the rst process
were 582:1
457:3
spectively, and 482:2
Moreover, TMAX increased with the heating rate for
all samples, as illustrated for the PN3 precursor in
Fig. 3. For this sample, the TMAX changed from
407:4
for the rst degradation process, and from 669:8
0:2 to 695:0
second one, for the heating rates of 2, 10, and 20 C/
min, respectively. These changes in TMAX were re-
lated to the heat ow in the analyzed material,
which is very slow [17]. For this reason, TMAX in-
creased with the heating rate applied.
The activation energies of the global degrada-
tion process for all precursors and PDMS uid,
and also for each degradation process for the PN3
sample, were determined by using the dynamic
method derived by Ozawa [14]. To illustrate these
calculations, the rst decomposition process of
PN3, was chosen, as can be seen in Fig. 4. In Fig.
4(a) the weight fractions of this decomposition
process at various heating rates were plotted in
function of the reciprocal absolute temperature,
and the functions of the log b versus 1=T were
tted to the data (Fig. 4(b)). The correlation co-
ecients of the ts are R0:95 0:999, R0:90 0:997,
R0:85 0:996, R0:80 0:994, R0:75 0:994, R0:70
0:993, R0:65 0:993, R0:60 0:993, R0:55 0:991,
96 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100

Fig. 4. (a) The weight fraction of the rst decomposition process of PN3, plotted against the reciprocal absolute temperature and (b)
linear ts of the logarithms of heating rate versus the reciprocal absolute temperature, for several weight fractions of conversion
(1 a), from 0.95 to 0.15, in the rst decomposition process of PN3.

R0:50 0:992, R0:45 0:993, R0:40 0:992, R0:35
0:994, R0:30 0:995, R0:25 0:995, R0:20 0:999,
R0:15 0:998.
The activation energies obtained are shown in
Table 2. For PN2 and PN3 (rst process) the ac-
tivation energies increased with the decrease in
For PDMS, PN4 and for the second degradation
process of PN3, the changes in Es were similar
until (1 a)s were 0.40, 0.20 and 0.40, respec-
tively. The activation energy in PN1 changed in
a more complex way, regardless of the magni-
tudes of (1 a), with the largest mean E454

(1 a). These results are in accordance with data
obtained from distinct polymers, described in lit-
erature [17,18], and this dependence has been at-
tributed to the decomposition of the polymer. This
decomposition means that the greater activity or
the lesser inert segment of the chain, or the net-
66 kJ/mol
work, decomposes rst in the degradation process,
i.e., this segment has a smaller activation energy.
31 kJ=mol. Based on this E which is close to the
SiO bond energy (465 kJ/mol) [15,19], we suggest
that the degradation process in this precursor was
governed by the thermodynamic aspect, with a
smaller contribution of the kinetics of the reaction.
For the PN2 precursor, a mean of 242
was obtained, which indicates a considerable ki-
netic contributions to the process.

Table 2
Activation energies of the thermal degradation process of the preceramic polysiloxane networks
(1 a) Activation energy (kJ/mol)
PN1 PN2 PN3 PN4 PDMS
First process Second process
0.90 395
8 139
1 135
1 221
2 80
1 143
1
0.80 500
9 169
1 141
1 228
2 83
1 163
1
0.70 472
6 209
1 146
1 251
2 88
1 189
1
0.60 449
4 263
1 156
1 275
1 101
2 209
1
0.50 424
3 263
1 164
1 281
1 117
2 226
1
0.40 423
3 291
2 174
1 282
1 139
2 225
1
0.30 464
4 310
4 182
1 275
1 180
2 213
2
0.20 479
3 330
7 196
1 253
1 256
6 198
2
0.10 464
4 336
9 245
3 195
1 212
7 178
3

Mean 454
31 242
66 157
32 259
29 139
60 192
27
 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100 97

The calculated activation energy for the linear

PDMS degradation process, described in litera-
ture, is 180 kJ/mol [15], which is close to the
192
27 kJ/mol in this work. For this kind of
polymer, the degradation process is governed
mainly by kinetic considerations [15] than by the
scission of bonds. In addition, literature data [20]
suggest a mechanism based on the interchain, in-
trachain and back-bitting reactions, the main
decomposition products of which are volatile cy-
clic and linear oligomers. The PN3 sample was
basically a poly(dimethylsiloxane) with a smaller
crosslinking degree, or larger Mcs, in which al-
kydic bridges join the linear PDMS chains. The
rst stage of the thermal degradation process had Fig. 5. X-ray diractograms of ceramic products derived from
a mean activation energy of 157
32 kJ/mol, that PNs samples pyrolyzed at 1000 C.
we suggest is a process also governed by kinetic
considerations, producing volatile oligomers con- halo, has also a contribution from the amorphous
comitant with the increase in the crosslinking SiO2 diraction. NMR results discussed below
density, when compared to the initial sample. conrmed this hypothesis.
29
Consequently, the second degradation stage, in Si MAS NMR spectra obtained from these
which also the mineralization process took place, samples are reported in Fig. 6. PN1 and PN2
had a mean activation energy of 259
29 kJ/mol, displayed similar spectra with 29 Si resonance peaks
an energy close to that found for PN2. In these in the 0 to 110 ppm chemical shift range, asso-
networks, with considerable crosslinking densities, ciated with a random distribution of silicon oxy-
the rearrangements into cyclic oligomers became carbide sites, SiCx O4 x , with 0 6 x 6 4, i.e.: SiO4 at
more dicult due to the decrease in the mobility of  106 ppm, SiO3 C at  72 ppm, SiC2 O2 at
SiOSi segments. Thus, the thermal degradation  32 ppm, SiC4 at  16 ppm, and SiOC3 at  5
process has some contributions from the bond ppm [4]. The spectrum of PN3 was dominated by
energy factors, which explains the increase in Es. the SiO4 and SiO3 C sites with smaller resonance
The lowest activation energy (139
60 kJ/mol) peaks assigned to the richer carbon sites: SiC2 O2 ,
was obtained for the organic-bridge poly- SiC3 O and SiC4 [9]. However, in the ceramic
silsesquioxane, PN4, richer in organic content. This products derived from PN1 and PN2 the abun-
energy was less than the CC and CH bond ener- dance of SiC4 sites was larger than those usually
gies, which are 348 and 412 kJ/mol, respectively [15]. observed in the ceramic products obtained from the
The ceramic products derived from PNs, at pyrolysis of alcoxysilane gels, which consist pri-
1000 C under argon atmosphere, were amorphous marily of SiO4 , SiO3 C and SiC2 O2 , with a smaller
oxycarbide glasses, with XRD characterized by a amount of, or without, SiC3 O and SiC4 sites [9]. In
broad halo centered in the 2228 (2h) range, as addition, the distribution of silicon sites found for
reported in Fig. 5. However, PN4 sample dirac- both derived ceramics is similar to the one observed
tion had a broader and more intense halo centered in BlackglasTM [22]. On the other hand, the PN4
at 23 (2h), and another less intense one at 44 derived ceramic displayed only a peak centered at
(2h). Based on the periodicity of these halos we  108 ppm attributed to SiO4 sites. Therefore, this
suggest a contribution from a lamellar structure, product can be described as an amorphous silica
such as graphitic carbon, which shows the main dispersed in a graphitic rich phase. Densities of
diractions centered at 26.5, 44.6 and 54.7 (2h), the glass products were 2:19
0:01, 2:12
0:01,
associated to 0 0 2, 1 0 1, and 0 0 4, diraction 2:09
0:01 and 1:72
0:01 g/cm3 for PN1, PN2,
planes, respectively [21]. The rst more intense PN3 and PN4, respectively.
98 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100
Fig. 6. 29 Si MAS NMR spectra of the nal silicon oxycarbide
glasses derived from the preceramic precursors.
4. Discussion
Preceramic polymeric networks, precursors of
silicon oxycarbide glasses, were prepared from hy-
drosilylation or hydrolysis/condensation of silox-
ane units. These reactions allowed the construction
of polysiloxane networks with dierent molecular
architectures. The determination of kinetic pa-
rameters such as the activation energies, from
thermogravimetric data, has received considerable
attention [23] to generate more information for the
understanding of the thermal degradation mecha-
nisms of polymeric precursors. The Ozawa method
has been pointed out as a way of analyzing com-
plicated degradation processes [24], since it is pos-
sible to conrm, if the adopted method is adequate
for the studied system, through the linear t from
the heating rate as a function of the reciprocal
temperature for several degradation rates.
The one-step degradation observed in TGA
curve of linear PDMS sample, is due to the ther-
mal depolymerization, which starts around 200 C
in an inert atmosphere, and involves mainly the
siloxane backbone, with a participation of the Si
OH end groups [15,20]. The mechanism of this
depolymerization is based on the interchain and
intrachain reactions, the main products of which
are cyclic and linear oligomers, such as D3 and D4
[20]. In addition, the SiOH end groups can pro-
mote back-bitting, through a nucleophylic attack
to a Si atom of the main chain, as schematically
represented below. The calculated activation en-
ergy for these processes is 180 kJ/mol [15]. This
energy is less than half the SiO bond energy (465
kJ/mol) [15,19], that we suggest is a process prac-
tically governed by kinetic considerations [15],
having thus a contribution from the molecular
structure.
Crosslinked polymers with greater fraction of
crosslinks usually are more thermally resistant,
because this molecular architecture makes the
 M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100
elimination of end groups, small molecules, or
even the promotion of depolymerization, which
are often responsible for low temperature weight
loss, more dicult [20]. The direct consequence
of the crosslinking density in the preceramic
precursors is the increase of their ceramic yields.
In polysiloxane this parameter determines the
way in which the degradation will occur [8,15,20].
For polysiloxane networks with smaller cross-
linking densities, such as PN3 sample, thermal de-
gradation was similar to that of PDMS uid, with
intra and interchain reactions. What was more
interesting to us was the second weight loss which
had a mean activation energy similar to that of a
more crosslinked network, such as PN2.
PN1 showed major thermal stability and the
largest activation energy for the degradation pro-
cess during its conversion to silicon oxycarbide
glass. These results could be rationalized consid-
ering the molecular architecture of this polymeric
precursor. In this network, there was an excess of
SiH group, in the lateral chain of the PMHS
homopolymer, in relation to CH@CH2 groups of
D4 Vi [8]. Consequently, after the hydrosilylation
reaction, there was a post-cure crosslinking in-
volving remanescent SiH bonds, in the presence
of moisture in the atmosphere, also catalyzed by
Pt-catalyst, which increased the crosslinking den-
sity in this material. Indeed, the full characteriza-
tion of the polymer-to-ceramic conversion process,
followed by 29 Si, 13 C NMR and IR spectroscopies,
pointed out that up to 615 C there were SiH
groups in this system, and just above this tem-
perature the mineralization process took place [8].
Thus, the possible inter/intrachain reactions were
suppressed by the maximization of the crosslinking
density in this polymeric network. These data
could explain the larger activation energy for this
system, mainly when it was compared to PN2, in
which no post-cure reactions took place due to
its well-structured molecular architecture [13].
Indeed, at 400 C no residual SiH or Si
CH@CH2 groups were detected by IR spectrum of
the PN2 precursor [12].
For PN4 precursor the smallest activation en-
ergy was obtained, as expected, since this prece-
ramic network had a bridge of epoxy resin between
siloxane units. Based on this result we suggest that
99
the degradation process in this polymer is also
governed by kinetic considerations, probably with
participation of more active groups, COH and
NH, present in the organic bridge. Consequently,
the eect of SiOSi network was minimized in
this system.
5. Conclusion
The thermal stability and the activation energy
for the degradation process were determined for a
series of preceramic polymeric networks based on
polysiloxane. The relationships between these re-
sults and the molecular architecture of the ceramic
precursors allowed a better comprehension of the
degradation process of these materials. The acti-
vation energies were related to the crosslinking
density, and consequently to the molecular archi-
tecture and composition of the precursors. The
crosslinking density of the polymeric network also
showed an inuence on the ceramic yield as well as
on the nal composition of the glasses.
Acknowledgements
We gratefully acknowledge nancial support
from FAPESP (processes 95/03636-3, 98/07025-7,
99/05491-3 and 00/06882-5) and CNPq.
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