Proceedings of ASME Turbo Expo 2003

Power for Land, Sea, and Air

June 16–19, 2003, Atlanta, Georgia, USA
Proceedings of IGTI:
ASME Turbo EXPO 2003
June 2003, Atlanta, USA

GT2003-38561
GT2003-38561

POLYMER-DERIVED SI-AL-C-N-O CERAMICS FOR HIGH TEMPERATURE

APPLICATIONS

Lavanya Bharadwaj 1, Abhijeet Dhamne1, Linan An1,2∗, Barry Fookes 3, Jay Kapat 2 and Louis Chow2
1
Advanced Materials Processing and Analysis Center (AMPAC)
2
Mechanical, Materials and Aerospace Engineering Department
3
Chemistry Department
University of Central Florida, Orlando, FL 32816

ABSTRACT elements can be incorporated into the network for the

Polymer-derived ceramics are a new class of materials modification of properties [3].
synthesized by thermal decomposition of polymeric precursors.
The resultant materials are amorphous alloys of silicon, carbon,
and nitrogen, which can be converted to crystalline materials by
annealing at higher temperatures. This novel chemical-to- Synthesize
Start
ceramic route offers a unique opportunity to tailor the structures Precursors
chemicals
and compositions, therefore the properties, of the resultant
materials by designing the chemistry of the precursors. In this Shaping
paper we report the studies on synthesis and oxidation behavior Cross-linking
of polymer-derived SiAlCN materials. The precursor was
synthesized by mixing a polysilazane and aluminum Infusible
Pyrolysis Ceramic
isopropoxide. The mixture was then pyrolyzed at 1000oC in polymer
components
Ar/N2 to convert to SiAlCNO ceramics. The oxidation studies components
revealed that the SiAlCNO possesses a lower oxidation rate
than SiCN. It is believed that the better oxidation resistance
exhibited by SiAlCN is due to the oxide layer containing Al, Figure 1. Processing of polymer-derived ceramics.
which makes oxygen diffusion more difficult than in pure SiO2.
The materials are promising for many high temperature The novel chemical-to-ceramic route illustrated in Fig. 1 has
applications, e.g. environmental barrier coatings, high at least the following two advantages over conventional
temperature fibers, matrixes for composites, and even monolithic processing:
components. • It is leading to a flexible and cost-efficient approach to
manufacture ceramic components and devices from these
INTRODUCTION interesting materials. For example, complex shapes can be
Recently, a novel class of Si-based ceramics has been made in the organic form, just prior to pyrolysis, which
synthesized by thermal decomposition of polymeric precursors. yield ceramic components and devices upon consolidation.
The basic processing steps are shown in Fig. 1 [1]: (i) The fabrication of high temperature fibers [4, 5], protective
synthesize and modify polymer precursors, (ii) shape and cross- coatings [6], ceramic matrix composites [7, 8], and ceramic
link the precursor to form infusible polymer components with Micro-Electro-Mechanical Systems (MEMS) [9-11], has
desired structures, and (iii) convert the polymer component to a been demonstrated.
ceramic one by pyrolysis at about 1000oC. The so-called • It offers an unusual opportunity to manipulate the structure
polymer-derived ceramics (PDCs) thus obtained are based on and composition, and thereby the properties, of ceramics
amorphous alloys of silicon, carbon and nitrogen [2]. Other by designing the chemistry of the polymer precursors.

∗
Corresponding author. Tel.:+1 407 823 1009; fax: +1 407 823 0208.
E-mail address: lan@mail.ucf.edu

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 While synthesized at relatively low temperatures, this new
class of materials has shown excellent thermo -mechanical
properties at very high temperatures . For example, it has been
demonstrated that polymer-derived silicoboron carbonitride
(SiBCNO) is stable up to 1800oC [3]. The creep resistance of
SiCN and SiBCN is comparable or even higher than that of
polycrystalline SiC and Si3N4 [12-14]. Due to the absence of
grain boundary phases (results from sintering aids in
conventional polycrystalline Si-based ceramics), it can be
expected that the high strength of PDCs can be retained at high
temperatures. These excellent high temperature properties make
the PDCs very attractive for high temperature applications.
400oC under isostatic pressure of 50 MPa in Ar. The use of
isostatic pressure during cross-linking is essential to prevent
the sample from the formation of crack and pores that destroyed
the integration of the materials. The transparency of the cross-
linked sample indicated the absence of defects such as pores
and microcracks. The cross-linked polymer samples were then
converted to SiAlCNO and SiCN ceramics by pyrolysis at
1000oC in Ar/N2. The ceramic thus obtained is fully dense and
defect free. Figure 3 shows the microstructure of SiAlCNO
observed with SEM and no defect was were detected.
CH(CH3)2

Besides mechanical properties, high temperature O

applications also require materials that possess high
oxidation/corrosion resistance. As other Si-based ceramics, the Al
oxidation of PDCs results in the formation of silicon dioxide O
layers on the surface of the materials [15, 16]. This oxide layer O CH(CH3)2
acts as a barrier layer and protects the inner materials from CH(CH3)2
further oxidation. However, the protection of the SiO2 layer will
be destroyed by impurities such as moisture and sodium under
combustion conditions. For example, the silicon dioxide reacts (1) (2)
with H2O to form volatile species according to following
reaction:

Figure 2. Chemical Structures of Ceraset (1) and aluminum

SiO2 + 2H 2 O = Si( OH ) 4 (1)
isopropoxide (2)

That dramatically lowers the use temperatures and life of

components [17].

In this paper we report studies on the synthesis and

oxidation behavior of polymer-derived SiAlCNO ceramics,
together with those of SiCN for comparison. The aluminum was
added into the SiCN network by simply modifying the
polysilazane precursor. Our results demonstrated that while the
SiCN exhibited typical parabolic oxidation behavior with a rate
constant of 3.1x10 -18 m2/sec, the SiAlCNO ceramics with only ~ 1
atm% Al addition not only showed a much lower oxidation rate
but also exhibited exponential behavior.
20 µm
EXPERIMENTS
The precursor for the SiAlCNO was synthesized by mixing
95 wt% of commercially available polysilazane (Ceraset SN, Figure 3. SEM micrograph showing the microstructure of fully
Kion) with 5 wt% of aluminum isopropoxide (Al[OCH(CH3)2]3) dense SiAlCN.
(Alfa Aesar, USA). The chemical structures of these two
chemistries are shown in Fig. 2. It was observed that the solid The materials evolution during the heat-treatment is studied
aluminum isopropoxide can be fully dissolved into liquid with FTIR.
Ceraset to form a liquid mixture with light yellow color.
The oxidation experiments are performed on the ceramic
For oxidation studies, fully dense SiAlCNO and SiCN
discs obtained above. The surface of the discs is ground and
ceramics were prepared with novel press-assisted processing
polished to 0.5 µm finish. The polished samples are then heat-
[9]. The liquid precursors were first solidified by heat-treatment
treated at 1100oC in air for different annealing times of 20, 50, 100
at 150 oC in air. The solid polymers were then cross-linked at

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 and 200 hrs. After oxidation, the cross-sections of the samples
are polished to 0.5 µm finish, and then etched using buffered
oxide etchants (buffered oxide etch - BOE, HF solution). This
etching process helps to reveal the oxidation layers. The
thickness and microstructure of the oxide layer are then
observed using SEM.
RESULTS AND DISCUSSION
The FTIR spectra of as -obtained Ceraset are similar to
those reported [18]. The existence of vinyl groups (CH=CH2) is
indicated by the absorption peak at 1592 cm-1 (C=C). The
absorption peak at 3384 cm-1 indicates the existence of aminosily
groups (Si-NH-Si). The results are consistent with the chemical
structure of Ceraset reported by Kion company (Fig. 2).
Al-N
Si-O Al-O
Figure 4. FTIR spectra of the mixture of 95 wt% Ceraset + 5 wt%
aluminum isopropoxide at different temperatures.
Figure 4 shows the FTIR spectra of the mixture of 95 wt% of
Ceraset and 5 wt% of aluminum isopropoxide obtained from as
mixed samples that were heat-treated at different temperatures.
The spectrum of the as-mixed mixture is similar to that of pure
Ceraset, consisting of vinyl groups (1592 cm-1) and aminosily
groups (3384 cm-1). However, a small absorption peak appears
at 442 cm-1, indicating the formation of the Al-N bond. The
spectrum of the mixture heat-treated at 150 oC shows the
existence of the Si-O bond (1038 cm-1) and the Al-O bond (903
cm-1 and 769 cm-1). Compared to the spectrum of the as-mixed
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sample, the intensity of the Al-N peak (428 cm-1) is increased,
indicating the increase in Al-N bond content in the material.
When the mixture is heated to higher temperatures, the intensity
of the Al-O peaks (903 cm-1 and 769 cm-1) is decreased while the
Si-O peak becomes wide and overlaps with the stretching of Al-
O. Meanwhile, the intensity of the Al-N peak (428 cm-1) is
continuously increased. This can be interpreted as the
combination effect of the mixing of Si-O and Al-O and the
reaction between Si-N and Al-O:
Si − N + Al − O = Si − O + Al − N (2)
The reaction is favored thermodynamically, since the sum of the
bond energies of Si-O (442 kJ/mole) + Al-N (511 kJ/mole) is much
higher than that of Si-N (316 kJ/mole) + Al-O (287 kJ/mole).
Based on the chemistry and weight loss of Ceraset and
aluminum isopropoxide during heat-treatment, the final Al
content in SiAlCNO ceramics is estimated ~ 1 at%.
Oxidation, 1100 oC, Air
2.5
SiCN
2
Thickness (mm^2)
SiAlCNO
1.5
0.5
0
0 50 100 150 200 250
Time (hr)
Figure 5. Plot of the thickness of the oxide scale as a function of
annealing time for SiCN and SiAlCNO.
Figure 5 is the plot of the thickness of the oxide scale as a
function of annealing times for both SiCN and SiAlCNO at
1100oC in air. It can be seen that the oxide scale of SiCN follows
parabolic behavior with apparent parabolic rate constant of
3.32x10-18 m2/s, which is in the same range as that of silicon [19]
at the same temperature. The parabolic behavior indicates that
the oxidation of SiCN is controlled by a diffusion process, which
agrees with previous studies on similar materials [20].
Compared to SiCN, SiAlCNO exhibits different oxidation
behavior: (i) the oxidation rate of SiAlCNO is much lower than
that of SiCN and (ii) the growth of the oxide scale of SiAlCNO
follows asymmetric behavior. For the short term (< 100 hrs), the
oxide scales follow parabolic behavior, while for the long term
3 Copyright © 2003 by ASME
 (>100 hrs) the oxide layer seems to reach saturation. The
saturation behavior exhibited by SiAlCNO ceramics is highly
unusual. Similar behavior has been observed in porous samples
[20, 21], where the weight gain due to oxidation exhibited
exponential behavior and saturated to a certain value because
the sealing of open porosity. However, current observations
cannot be satisfactorily explained by the mechanisms of pore
sealing for the following reasons. First, SiCN ceramics prepared
by a similar processing procedure shows parabolic behavior and
there is no reason to assume that these two materials have
different porosity structures. Secondly, in the present study the
thickness of the oxide scale rather than weight is measured and
fully dense oxide scales were observed at all annealing times
(Fig. 6). A possible explanation may be inferred from the effect
of Al in the oxide scale. Al either forms the Al2O3 phase or is
incorporated into the Si-glass network which can be expected to
slow down the diffusion of oxygen. Further work is needed to
clarify the mechanism.
Figure 6. SEM micrograph showing the oxide scale of SiAlCNO
ceramic obtained at 1100oC for 200 hrs .
While the oxidation mechanism of SiAlCNO is not clear, the
high oxidation resistance exhibited by this new kind of material
suggests that it could be useful for many high-temperature
engineering applications such as fibers, matrixes for composites,
and environmental barrier coatings (EBC). It has been reported
[22, 23] that a small amount of Al in the oxide scale can
dramatically reduce the sodium-accelerated oxidation.
SUMMARY
In this paper we synthesized a polymer precursor for
SiAlCNO ceramics by mixing Ceraset and aluminum
isopropoxide. FTIR studies indicated that the Al is forming a
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network structure with Si, C, N and O by bonding to O and N.
The SiAlCNO ceramics thus obtained show better oxidation
resistance than SiCN. This result suggests that the high
oxidation and corrosion resistance of Si-based ceramics can be
further enhanced by adding Al into the network through
polymer-derived ceramic processing.
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