Journal of Materials Processing Technology 153–154 (2004) 401–407

Development of polymer–ceramic composites for

improved fire resistance
L.G. Hanu a,∗ , G.P. Simon a , J. Mansouri b , R.P. Burford b , Y.B. Cheng a
a School of Physics and Materials Engineering/CRC-P, Monash University, Australia
b School of Chemical Engineering and Industrial Chemistry/CRC-P, University of New South Wales, Australia

Abstract

Materials that provide protection of lives and property from fire are highly desirable across many industries. Conventional polymers are
generally completely consumed in a fire situation and require either halogenated additives that give off toxic and corrosive gases with large
volumes of smoke or high filler loadings of non-halogen based additives in order to impart fire resistance. Attention has been shifted to the area
of “ceramifiable” polymers as a means of improving passive fire protection, and silicones have been shown to possess desirable properties
on firing, such as a slow burning rate without a flaming drip and low emissions of non-toxic smoke. However, the ceramic formed by firing
silicones alone is very weak and powdery. Addition of certain inorganic fillers improves the strength, giving a near-net shape ceramic. The
fire protection properties of silicone and silicone-based composites are investigated at temperatures up to 1100 ◦ C. The microstructure of
the resultant ceramics has been studied and the mechanism for the conversion of silicone-based composites to ceramics is proposed.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Composites; Fillers; Fire resistance; Microstructure

1. Introduction preceramic polymers for conversion to ceramics via pyroly-

Employing materials of improved fire resistance may re-
duce the devastating costs of fires in terms of both property
damage and human lives. Silicones have lower heat release
rates, toxic gas emissions and smoke output in comparison
to conventional organic polymers [1–3]. Thermal degrada-
tion of silicones has been thoroughly studied in the past with
several mechanisms proposed, depending on the end-groups
attached to the siloxane backbone [4–6]. In the presence of
oxygen and on exposure to high temperatures, silicones de-
compose in a series of thermal depolymerisation and oxida-
tion reactions forming a silica residue and releasing volatile
compounds [7–10]. This layer of silica initially forms and
deposits on the surface of the silicone polymer and performs
the fire retarding action in silicones. This silica layer slows
down the diffusion of fuel through to the underlying poly-
mer and also serves to protect it from heat generated [11,12].
The ability of silicones to burn to an inorganic residue is one
of the reasons why they have been investigated as potential
∗ Corresponding author.
E-mail addresses: hanu@spme.monash.edu.au (L.G. Hanu),
george.simon@spme.monash.edu.au (G.P. Simon),
j.mansouri@unsw.edu.au (J. Mansouri), r.burford@unsw.edu.au
(R.P. Burford), yibing.cheng@spme.monash.edu.au (Y.B. Cheng).
sis. However, despite offering good thermal protection, the
silica residue formed during pyrolysis is very fragile and
weak.
This paper reports on the thermal degradation of silicone-
based polymer composites that are converted to ceramic
residues of improved strength when fired in air up to
1100 ◦ C. Based on evidence from residue microstructure
analysis, a mechanism is proposed to explain the basis for
the observed improvement in residue strength.
2. Experimental
2.1. Specimen preparation
Commercially available silicone gum of high molecular
weight was mixed with 2 wt.% organic peroxide using a
two-roll mill then heat-cured under pressure at 180 ◦ C for
30 min in a flat sheet mould. This composition is denoted
from hereon as SP-0. Two additional compositions were
prepared containing 20 wt.% alkali alumino-silicate mineral
fillers. These compositions are denoted as SP-1 and SP-2 in
this paper. The two fillers differ in both alkali content and
particle size with the filler used to prepare SP-1 belonging
to the K2 O–Al2 O3 –SiO2 system and having of an average

0924-0136/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2004.04.104
402 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407

particle size of 110 ␮m, whereas the filler used in the prepa-
ration of SP-2 belonged to a K2 O–MgO–Al2 O3 –SiO2 sys-
tem and had an average particle size of 20 ␮m.
2.2. Tube furnace pyrolysis
Five rectangular test pieces of 50 mm×15 mm dimensions
were cut out and placed in an alumina boat sandwiched be-
tween 3 mm thick, rectangular stainless steel sheets to ensure
samples remained flat after firing as required for three-point
bend flexural test. The specimens were fired in tube furnace
in air to 600, 800 and 1100 ◦ C at a heating rate of 10 ◦ C/min
and held at the maximum temperature for 2 h before cooling
to room temperature at the same rate as the heating rate.
Square samples were cut out for dimensional analysis,
with the size accurately measured before and after being
fired in the tube furnace under the same conditions as out-
lined above. However, these square specimens were not
sandwiched between stainless steel sheets in order to ob-
serve sample behaviour during firing in terms of dimensional
change.
to ASTM C1161-94 using the Minimat 2000 (a miniature
extensometer) available from Rheometric scientific instru-
ments. Five specimens were tested for each of the three
compositions. The flexural strength of each specimen was
determined according to Eq. (1):
3PL
S= (1)
2bd2
where S is the flexural strength of the material (MPa), P the
break-load (N), L the outer (support) span (mm) and b, d
the specimen’s width and thickness (mm), respectively.
2.7. Microstructure analysis
Ceramic residue composites were gold (sputter) coated
and analysed using a Hitachi S570 scanning electron micro-
scope. Analysis was performed at magnifications of 1000×
and 10,000×.
3. Results

2.3. Thermal gravimetric analysis 3.1. Thermal gravimetric analysis

Thermal gravimetric analysis was conducted using Se-
taram TG92. Polymer composites of 30–40 mg were placed
in a platinum crucible and pyrolysed in air to a maximum
temperature of 1100 ◦ C at a heating rate of 10 ◦ C/min. The
weight loss was recorded in response to increasing temper-
ature, with final residue yield, onset of degradation temper-
ature and number of degradation steps reported.
2.4. Infrared analysis
A thin layer of cured polymer (SP-0) was analysed in
the mid-infrared by attenuated total reflectance infrared
(ATR–IR).
Ceramic residue from the pyrolysis of SP-0 in air at
1100 ◦ C was analysed by FT-IR in the mid-infrared using
the potassium bromide pellet technique. The KBr to sample
ratio was 300:1 and a 0.15 mg disc was pressed under vac-
uum. By comparing the spectrum for the polymer against
that of the ceramic residue, the disappearance of organic
moieties attached to the siloxane backbone was confirmed
with increasing pyrolysis temperature.
2.5. X-ray diffraction
The weight loss recorded during polymer pyrolysis as a
function of increasing temperature is shown in Fig. 1 as
TG%. The temperature at which 5% weight loss is recorded
indicates the onset of thermal degradation and it is cited
as T5 . Both residue yield and T5 are indicative of ther-
mal stability of the polymer composites and are outlined in
Table 1. The residue yield has improved upon filler addi-
tion, however the filler used to prepare SP-2 decreased the
onset degradation temperature by as much as 60 ◦ C. This
suggests that, despite an increase in char yield due to a
dilution of organic species in the composite, the thermal
stability of SP-2 is lower and this is attributed to particle
size and the chemical differences existing between the two
fillers.
It should be noted that both fillers, when fired on their
own record, a small weight loss of the order of 3–6%, which
explains the lower than expected residue yield for the poly-
mer composites containing 20% filler.
3.2. Infrared analysis
In Fig. 2a, the ATR–IR spectrum of SP-0 polymer shows
the absorbance peaks identified as C–H stretching vibra-

XRD analysis of ceramic residue was conducted using a

Rigaku X-ray diffractometer using Cu K␣ radiation and a Table 1
scan range between 5 and 60◦ . Effect of filler addition on thermal stability of silicone elastomer
Sample Residue T5 (◦ C) T at highest
2.6. Flexural strength test yield (%) degradation rate (◦ C)
SP-0 54 430 528
Ceramic residue samples from the pyrolysis of polymer SP-1 63 430 530
SP-2 60 372 470
composites were tested in 3-point bending mode according
 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407 403

Fig. 1. TG analysis of polymer composites fired in air to 1100 ◦ C.

Fig. 2. IR trace showing the disappearance of C–Si and C–H bonds with increasing temperature in air: (a) SP-0 polymer; (b) SP-0 ceramic residue.

tion at 2962 cm−1 , Si–CH3 asymmetric deformations at
1412 cm−1 , rocking frequencies at 1258 and stretching fre-
quencies at 860 cm−1 [13]. Peaks in the 1000–1100 cm−1
region are assigned to Si–O–Si stretching vibrations and
that at 807 cm−1 is due to Si–O deformations [13]. Thus
by comparison of the two spectra in Fig. 2, it is confirmed
that as the temperature increases, the absorbance intensities
from the organic species attached to the siloxane backbone
decrease such that by 1100 ◦ C, only absorbances from Si–O
functionality is observed.

Fig. 3. XRD trace of SP-0 fired in air at 1100 ◦ C.

404 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407

3.3. X-ray analysis Table 2

Effect of filler addition and pyrolysis temperature on the appearance of
ceramic residue
XRD trace in Fig. 3 indicates that the ceramic residue
formed by the pyrolysis of silicone polymer in air at 1100 ◦ C Sample Dimensional change (length ×
width × height) (mm)
is an amorphous silica.
600 ◦ C 800 ◦ C 1100 ◦ C

3.4. Dimensional analysis PS-0

Before firing 21 × 21 × 1.9 20 × 21 × 2.0 21 × 20 × 2.3
After firing 20 × 20 × 3.0 19 × 21 × 4.0 17 × 19 × 9.7
Table 2 outlines the dimensional changes in terms of
shrinkage or expansion that take place during the conversion PS-1
of polymer to ceramic after firing in air from room temper- Before firing 19 × 21 × 3.2 20 × 21 × 3.2 20 × 21 × 3.2
After firing 20 × 21 × 8.0 21 × 21 × 7.3 17 × 19 × 9.5
ature (RT) to 1100 ◦ C.
PS-2
Before firing 20 × 21 × 3.2 21 × 21 × 3.3 20 × 22 × 3.3
3.5. Flexural strength of ceramic residue After firing 21 × 21 × 5.4 21 × 21 × 5.3 12 × 19 × 8.8
A thick silica layer covered all samples after firing at these temperatures.
The strength of the ceramic residue formed by the py-
This contributed to the increase in height observed.
rolysis in air to the three different temperatures is reported
in Fig. 4. The ceramic residue obtained from the pyroly-
sis of SP-0 was too fragile to be tested, even after fired with that for polymer–ceramic composites. The flexural
at 1100 ◦ C, with the specimens containing large surface strength of ceramic residue for the composites increased,
cracks. Therefore, their strength values have been arbitrar- as expected, with increasing temperature. Both inorganic
ily assigned as 0 and serve as a baseline for comparison fillers were found to improve the strength of the residue,

Fig. 4. Effect of filler chemical composition and pyrolysis temperature on flexural strength of ceramic residues.

Fig. 5. SEM microstructures of sample SP-0 fired in air at (a) 600 ◦ C and (b) 1100 ◦ C.
 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407 405

but the improvement was more dramatic for the SP-2
composite.
3.6. Microstructure analysis
Fig. 5 shows sample SP-0 fired in air at 600 and 1100 ◦ C,
respectively. The polymer matrix has already been converted
to a ceramic by 600 ◦ C, as indicated from TG analysis, with
silica particles closely agglomerated to form a weak, pow-
dery matrix. Upon heating to higher temperature, silica par-
ticles appear to fuse together, forming a less powdery matrix
containing micro-cracks, responsible for the weak residue
formed.
Figs. 6 and 7 show respectively the microstructures of
SP-1 and SP-2 ceramic residues after pyrolysis at 600, 800
and 1100 ◦ C at 1000× and 10,000× magnifications. At
600 ◦ C, the corners of the filler particles appear rounded
when in contact with the powdery ceramic matrix (Figs. 6a
and 7a). This roundness of filler particles is evidence of a
reaction that takes place between the filler and the silica

Fig. 6. SEM of basal plane surface of SP-1 ceramic residue fired in air at (a) 600 ◦ C, (b) 800 ◦ C and (c) 1100 ◦ C.
406 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407

Fig. 7. SEM of basal plane surface of SP-2 ceramic residue after firing in air at (a) 600 ◦ C, (b) 800 ◦ C and (c) 1100 ◦ C.

powder from the decomposing polymer matrix. As the py-
rolysis temperature is increased the roundness of the filler
particles becomes more pronounced (Figs. 6b and 7b). By
1100 ◦ C, a melting effect is observed around the edges of
the filler particles and the liquid phase appears to spread
into the surrounding matrix (Figs. 6c and 7c). The solidifi-
cation of the melted regions upon cooling is responsible for
the observed increase in strength upon addition of fillers.
It should be pointed out, however that the melting tem-
perature of the fillers in both samples is much higher than
1100 ◦ C [14]. However, when the fillers are in close con-
tact with the silica powder, liquid formation is observed to
commence at a lower temperature. This eutectic point can
be theoretically determined from phase equilibria diagrams
and knowledge of filler chemical composition. Theoretically
the lowest eutectic point for the K2 O–SiO2 –Al2 O3 system
 L.G. Hanu et al. / Journal of Materials Processing Technology 153–154 (2004) 401–407
as applicable to specimen SP-1 is 695 ◦ C [15] and for the
filler used in SP-2 is 990 ◦ C [16]. However, the melting ef-
fect observed in SP-2 (Fig. 7) appears to be more extensive
than in SP-1. This is also in line with the results from flex-
ural tests, where the strength of SP-2 is higher than that of
SP-1. It is thus obvious that other factors have influenced
the extent of liquid formation. Factors such as the size of
the filler is a possible explanation in this case as the filler
mixed into SP-2 is approximately five times finer than that
in SP-1, however the filler particle size alone may not be
enough to warrant such a difference in the expected eutectic
point and the observed melting reaction at a temperature as
low as 800 ◦ C. The presence of other alkali impurities in the
filler used in SP-2 will serve to further lower the eutectic
point of the reaction, resulting in the increased melting and
solidification observed in Fig. 7c explaining the difference
in the strength between samples SP-1 and SP-2.
4. Conclusion
Silicone polymers can be converted to ceramics via py-
rolysis. They undergo thermo-oxidative reactions to decom-
pose to ceramic residue that is essentially amorphous silica
with little inherent strength. The strength of this residue is
improved by increasing the pyrolysis temperature, but it can
be more effectively improved with the addition of certain
inorganic fillers. The reaction between the inorganic fillers
and the silica from the decomposed polymer matrix forms a
eutectic liquid phase at the edges of the fillers, which pene-
trate into the matrix region with increasing temperature and
exposure time. The extent of the eutectic formation is fur-
ther influenced by factors such as particle size and chemical
composition of the fillers.
Acknowledgements
This work has been supported by the Cooperative Re-
search Centre for Polymers.
407
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