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Journal of Non-Crystalline Solids 304 (2002) 92100

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 QumicaUNICAMP, CP 6154, 13083-970 Campinas, SP, Brazil


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

this class of polymers provides an easy and inex-
Polymer pyrolysis is a relatively new and pensive route to the formation of such materials
promising technique for processing advanced ce- [3]. It is well established that the polysiloxane-
ramics [1]. The main advantage of such an ap- derived silicon oxycarbide glass is a random three-
proach is the possibility of building up polymers dimensional arrangement of tetrahedrally silicon
from molecular units and controlling their molec- atoms bonded to carbon and oxygen [4]. This sub-
ular structure, to determine the nanometer and/or stitution of oxygen for carbon in the silicon coor-
micrometer scale structure and also the phases of dination sphere leads to the presence of carbidic
the nal ceramic product [2]. Polysiloxanes have units, in the amorphous network, which strengthen
received particular attention as polymeric precur- the structure by increasing its bond density. In
fact, literature data on the characterization of
these materials have indicated diering thermal
Corresponding author. Tel.: +55-19 3788 3130; fax: +55-19
and mechanical properties for the carbon-contain-
3788 3023. ing glasses, compared to the fully oxide related
E-mail address: (I.V.P. Yoshida). 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 93

Several studies on the synthesis of silicon oxy- 2. Experimental procedures

carbide glasses, obtained from a polymeric pre-
cursor, have been described [68] resulting in an 2.1. Starting materials
improved understanding of the precursor-to-ce-
ramic conversion process. Studies based on the Commercially available functional siloxane cy-
solgel route, using a large variety of alkoxide clic oligomers, the 1,3,5,7-tetramethyl-1,3,5,7-tet-
precursors, RSiOR0 3 , were performed to investi- ravinylcyclotetrasiloxane, CH3 CH2 @CHSiO4 ,
gate the inuence of the organic R group, on the D4 Vi and the 1,3,5,7-tetramethyl-1,3,5,7-tetra-
incorporation of carbidic units in the structure of cyclotetrasiloxane, CH3 HSiO4 , D4 H, and a
the ceramic glasses and also on their composition linear siloxane polymer with vinyl functionalities,
[9]. fCH3 2 SiOn CH2 @CHCH3 SiOm g, (PDMS-
An alternative class of precursors of SiCx Oy Vi) Mn 13,500 g/mol, were supplied by Dow
glasses has employed polymers containing car- Corning; platinum divinylcomplex (Pt-catalyst),
bosilane bridges, SiCx Si. These bridges allow 23% in vinyl terminated poly(dimethylsiloxane),
better control of the carbon content incorporated poly(methylsiloxane), CH3 HSiOn (PMHS),
in the network precursors, by replacing the SiO Mn 2300 g/mol, and a poly(dimethylsiloxane)
Si bridges, without decreasing crosslinking. In silanol terminated, HOCH3 2 SiOn H, (PDMS),
previous research, the hydrosilylation reaction was Mn 26,000 g/mol, were purchased from
successfully used as a route to produce polysilane H ulls. Aminopropyltriethoxysilane, H2 NCH2 3
[10,11] and polysiloxane [8,12,13] networks with SiOC2 H5 3 , (APS) was purchased from Aldrich,
carbosilane bridges, which has allowed the control and the oligomeric epoxy resin derived from po-
of the molecular structure of the derived ceramics lybisphenol A-co-epichlorhydrin (PBFE), Mn
and the amount of carbon in the products. 600 g/mol, was supplied from Dow Chemical. All
The aim of the present work was to exploit the these materials were used as received.
thermal decomposition process of dierent poly-
siloxane networks, during the polymer-to-ceramic 2.2. Sample preparations
conversion, to understand the inuence of the
molecular architecture of the precursors on their In this study, homogenous neat mixtures of
pyrolytic properties and on the structure of the siloxane cyclics or polymeric materials containing
nal products. Three polysiloxane networks, CH@CH2 and SiH groups were submitted to
with dierent molecular architecture, prepared by platinum-catalyzed hydrosilylation reaction, in the
hydrosilylation reaction and one organic-bridge presence of 1 wt% Pt-catalyst. The preceramic
polysilsesquioxane prepared by hydrolysis/con- network, coded PN1, was built by the reaction
densation of alkoxysilane, were studied. Heat between the cyclic oligomer D4 Vi and the linear
treatment in inert atmosphere up to 1000 C of polysiloxane chain, PMHS; the second one, coded
these precursors resulted in silicon oxycarbide PN2, by the same reaction between two cyclic
glasses with dierent compositions. The structural oligomers D4 Vi and D4 H; and the third one was
characterization of the nal glasses was performed a poly(dimethylsiloxane)-based network, coded
by means of dierent techniques such as 29 Si magic PN3, which was built by a mixture of PDMSVi,
angle spinning nuclear magnetic resonance (29 Si PMHS and D4 Vi. The organic-bridged poly-
MAS NMR) and infrared (IR) spectroscopies, X- silsesquioxane precursor, coded PN4, was pre-
ray diraction (XRD), and density measurements. pared by amine-epoxy addition reaction between
The activation energy, involved in the conversion APS and PBFE, followed by hydrolysis/conden-
process for each system, was determined using a sation reactions. The compositions, in wt%, for
dynamic thermogravimetric analysis method de- each mixture are described in Table 1. All the
veloped by Ozawa [14]. The results were correlated samples were prepared by homogenization of the
to the molecular architecture of each polymeric components under magnetic stirring and then cast
precursor. 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 95

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].

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
0:2, 574:3
0:2, 463:6
0:2 and
0:2 C for PN1, PN2, PN3, and PN4, re-
spectively, and 482:2
0:2 C for the PDMS uid.
Moreover, TMAX increased with the heating rate for
all samples, as illustrated for the PN3 precursor in
In the DTGA curves for PN1, PN2 and PN4 Fig. 3. For this sample, the TMAX changed from
(Fig. 2) at least two overlapped steps in the degra- 407:4
0:2 to 438:2
0:2 and to 463:6
0:2 C,
dation process, could be observed, while the linear for the rst degradation process, and from 669:8

PDMS showed a single one (Fig. 2). On the other 0:2 to 695:0
0:2 and to 716:8
0:2 C, for the
side, the DTA curves for the PN3 sample displayed second one, for the heating rates of 2, 10, and 20 C/
two distinct steps, as can be seen in Fig. 3. For a min, respectively. These changes in TMAX were re-
given heating rate, a material may be characterized 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,
Fig. 2. DTGA curves of PN1, PN2, PN4 and PDMS samples at R0:85 0:996, R0:80 0:994, R0:75 0:994, R0:70
20 C/min. 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 For PDMS, PN4 and for the second degradation
0:994, R0:30 0:995, R0:25 0:995, R0:20 0:999, process of PN3, the changes in Es were similar
R0:15 0:998. until (1 a)s were 0.40, 0.20 and 0.40, respec-
The activation energies obtained are shown in tively. The activation energy in PN1 changed in
Table 2. For PN2 and PN3 (rst process) the ac- a more complex way, regardless of the magni-
tivation energies increased with the decrease in tudes of (1 a), with the largest mean E454

(1 a). These results are in accordance with data 31 kJ=mol. Based on this E which is close to the
obtained from distinct polymers, described in lit- SiO bond energy (465 kJ/mol) [15,19], we suggest
erature [17,18], and this dependence has been at- that the degradation process in this precursor was
tributed to the decomposition of the polymer. This governed by the thermodynamic aspect, with a
decomposition means that the greater activity or smaller contribution of the kinetics of the reaction.
the lesser inert segment of the chain, or the net- For the PN2 precursor, a mean of 242
66 kJ/mol
work, decomposes rst in the degradation process, was obtained, which indicates a considerable ki-
i.e., this segment has a smaller activation energy. 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)
First process Second process
0.90 395
8 139
1 135
1 221
2 80
1 143
0.80 500
9 169
1 141
1 228
2 83
1 163
0.70 472
6 209
1 146
1 251
2 88
1 189
0.60 449
4 263
1 156
1 275
1 101
2 209
0.50 424
3 263
1 164
1 281
1 117
2 226
0.40 423
3 291
2 174
1 282
1 139
2 225
0.30 464
4 310
4 182
1 275
1 180
2 213
0.20 479
3 330
7 196
1 253
1 256
6 198
0.10 464
4 336
9 245
3 195
1 212
7 178

Mean 454
31 242
66 157
32 259
29 139
60 192
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
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.
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
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

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
Fig. 6. 29 Si MAS NMR spectra of the nal silicon oxycarbide
glasses derived from the preceramic precursors. 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-
4. Discussion tically governed by kinetic considerations [15],
having thus a contribution from the molecular
Preceramic polymeric networks, precursors of structure.
silicon oxycarbide glasses, were prepared from hy- Crosslinked polymers with greater fraction of
drosilylation or hydrolysis/condensation of silox- crosslinks usually are more thermally resistant,
ane units. These reactions allowed the construction because this molecular architecture makes the
M.A. Schiavon et al. / Journal of Non-Crystalline Solids 304 (2002) 92100 99

elimination of end groups, small molecules, or the degradation process in this polymer is also
even the promotion of depolymerization, which governed by kinetic considerations, probably with
are often responsible for low temperature weight participation of more active groups, COH and
loss, more dicult [20]. The direct consequence NH, present in the organic bridge. Consequently,
of the crosslinking density in the preceramic the eect of SiOSi network was minimized in
precursors is the increase of their ceramic yields. this system.
In polysiloxane this parameter determines the
way in which the degradation will occur [8,15,20].
For polysiloxane networks with smaller cross- 5. Conclusion
linking densities, such as PN3 sample, thermal de-
gradation was similar to that of PDMS uid, with The thermal stability and the activation energy
intra and interchain reactions. What was more for the degradation process were determined for a
interesting to us was the second weight loss which series of preceramic polymeric networks based on
had a mean activation energy similar to that of a polysiloxane. The relationships between these re-
more crosslinked network, such as PN2. sults and the molecular architecture of the ceramic
PN1 showed major thermal stability and the precursors allowed a better comprehension of the
largest activation energy for the degradation pro- degradation process of these materials. The acti-
cess during its conversion to silicon oxycarbide vation energies were related to the crosslinking
glass. These results could be rationalized consid- density, and consequently to the molecular archi-
ering the molecular architecture of this polymeric tecture and composition of the precursors. The
precursor. In this network, there was an excess of crosslinking density of the polymeric network also
SiH group, in the lateral chain of the PMHS showed an inuence on the ceramic yield as well as
homopolymer, in relation to CH@CH2 groups of on the nal composition of the glasses.
D4 Vi [8]. Consequently, after the hydrosilylation
reaction, there was a post-cure crosslinking in-
volving remanescent SiH bonds, in the presence Acknowledgements
of moisture in the atmosphere, also catalyzed by
Pt-catalyst, which increased the crosslinking den- We gratefully acknowledge nancial support
sity in this material. Indeed, the full characteriza- from FAPESP (processes 95/03636-3, 98/07025-7,
tion of the polymer-to-ceramic conversion process, 99/05491-3 and 00/06882-5) and CNPq.
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-
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