Ceramics International 43 (2017) 10661–10667

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Ceramics International
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Microstructure and ablation mechanism of C/C-ZrC-SiC composites in a MARK

plasma flame
⁎
Shaolei Wang, Hong Li , Musu Ren, Yazhuo Zuo, Min Yang, Jiabao Zhang, Jingliang Sun
Research Center of Composite Materials, Shanghai University, Shanghai 200072, China

A R T I C L E I N F O A BS T RAC T

Keywords: Ablation behavior of C/C-ZrC-SiC composites was investigated using a plasma flame. The composites exhibited
C/C-ZrC-SiC composites excellent ablation performance. After ablation for 180 s, three kinds of ablation behavior appeared from the
Microstructure border to the center on the surface, which were closely related to the temperature and denudation force.
Ablation mechanism Additionally, the ablation behavior in the cross-sectional direction of the composites was mainly controlled by
the temperature. During the ablation, ZrC and SiC were oxidized into ZrO2 and SiO2, respectively, resulting in
the formation of a ZrO2-SiO2 binary eutectic system. The ablation mechanism was also discussed, which could
provide strong illustration of the evolution processes of the eutectic system at different temperatures.

1. Introduction the matrix.

Carbon/carbon (C/C) composites are considered as a promising
candidate material for aerospace applications due to their excellent
characteristics [1–3], such as low density, high strength, low thermal
expansion coefficient, high thermal conductivity, outstanding thermal
shock resistance and excellent ablation property at ultrahigh tempera-
tures. However, C/C composites are vulnerable to ablation in oxidizing
environments. This greatly restricts their potential applications [4,5].
Therefore, improving the anti-oxidation ablation ability of C/C com-
posites has become an attractive new subject.
As widely proved, introducing ultrahigh temperature ceramics
(UHTCs), such as SiC, HfC, TaC, ZrC, and ZrB2 [6–10], into C/C
composites is an effective method to improve the anti-oxidation
ablation resistance. Among this UHTC family, ZrC possesses many
merits, including a high melting point (3813 K), low evaporation,
excellent chemical inertness, and resistance to thermal shock and
ablation [11,12]. Meanwhile, SiC is also a fascinating ceramic with low
density, high hardness and a thermal expansion coefficient close to that
of carbon matrix (αSiC: 3.8–5.12×10−6/K; αPyC: 1–2×10−6/K). These
properties enable the matrix to withstand thermal shocks during
fabrication and service. In addition, SiC can be oxidized into SiO2,
with a melting point of 1996 K, under an oxidizing environment, while
ZrC can be oxidized into ZrO2, with a melting point of 2950 K [13,14].
The molten SiO2 bonds with ZrO2 to help seal defects such as cracks
and pores during the ablation at ultrahigh temperature. Thus, there is
an enormous advantage to improve the anti-oxidation ablation perfor-
mance of C/C composites by introducing ZrC-SiC ceramic phases into
Recently, many studies have investigated the anti-ablation proper-
ties of C/C-ZrC-SiC composites. The effects of porous C/C density
[15,16], SiC/ZrC ratio [17–19] ceramic coating [20,21], and ablation
variables [22–24] on the ablation performance of composites were
studied. Most of these studies were focused on the ablation behavior of
C/C-ZrC-SiC composites [25,26]. Actually, ZrC-SiC ceramic phases as
modified constitutions play a significant role in improving the anti-
oxidation ablation performance. However, the specific mechanism of
ZrO2 and SiO2 oxidized from ZrC and SiC during ablation in the
oxidizing environment is unclear.
In the present study, C/C-ZrC-SiC composites were fabricated by
chemical vapor infiltration (CVI) combined with polymer infiltration
and pyrolysis (PIP). The ablation properties were analyzed using a
plasma flame for 180 s. The microstructure and ablation behavior of
the composites were studied in detail. The purpose of this work was to
elucidate the ablation mechanism of C/C-ZrC-SiC composites, based on
a heterogeneous ablation reaction model and the phase diagram of
ZrO2- SiO2 system.
2. Experimental procedures
2.1. Material preparation
The needled carbon fiber integer preforms (0.2 g/cm3) were
deposited through the chemical vapor infiltration process (CVI) by
using propene (C3H6) as the precursor. A homogeneous solution
containing zirconium-containing polymer (PNZ, Institute of

⁎
Corresponding author.
E-mail address: lihong2007@shu.edu.cn (H. Li).

http://dx.doi.org/10.1016/j.ceramint.2017.04.089
Received 17 March 2017; Received in revised form 10 April 2017; Accepted 14 April 2017
Available online 15 April 2017
0272-8842/ © 2017 Published by Elsevier Ltd.
S. Wang et al.
Table 1
Basic parameters of C/C-ZrC-SiC composites.
Samples Initial Density Final density Vol/％
/g cm−3 /g cm−3
PyC ZrC
C/C-ZrC-SiC 1.27 1.98 53 7.28
Chemistry, Chinese Academy of Sciences, Beijing, China) and poly-
carbosilane (PCS, Institute of Chemistry, Chinese Academy of Sciences,
Beijing, China) was used as a ZrC-SiC precursor. The C/C skeleton was
infiltrated by the precursor through vacuum impregnation equipment
and then solidified in a drying oven and heat-treated at 1873 K for 2 h
in an argon atmosphere. The C/C-ZrC-SiC composites were prepared
by the PIP process for cycling 10 times until the mass increase
percentage of the composites was no more than 1%. The basic
parameters of the final C/C-ZrC-SiC composites are presented in
Table 1.
2.2. Ablation testing
The ablation properties of the C/C-ZrC-SiC composites were
determined using a plasma flame with cylindrical samples
(Ø30 mm×10 mm). The ablation direction of the flame was parallel
to the needle punching direction. The flux was 40 L/min for Ar and
10 L/s for H2. The working current and voltage were 652 A and 62 V,
respectively. The sample was exposed to the flame for 180 s, and the
maximum temperature of the ablation center surface of the samples
reached as high as 2615 K, measured by an optical pyrometer. The
linear and mass ablation rates were calculated by the thickness and
mass changes before and after ablation. The final ablation rates of the
composites were the average results for three specimens.
2.3. Characterizations
The bulk density and open porosity of C/C-ZrC-SiC composites
were obtained by the Archimedes method. The phase compositions and
morphology of the composites were investigated by X-ray diffraction
(XRD, Rigaku D/MAX) using Cu Kα radiation and scanning electron
microscopy (SEM, HITACHI SU-1500), along with energy dispersive
spectroscopy (EDS) for elemental analysis.
3. Result and discussion
3.1. Ablation properties of C/C-ZrC-SiC composites
The ablation properties of C/C-ZrC-SiC composites and C/C-
UHTCs composites reported in other studies are listed in Table 2,
which were calculated by the changes in the mass of the sample and
depth at the center due to ablation. It can be seen that the as-produced
composites show low average linear and mass ablation rates, which
indicate that the C/C composites modified by ZrC-SiC ceramic phase
exhibit excellent ablation performance.
Fig. 1 shows the macro-morphologies and XRD analysis of C/C-
ZrC-SiC composites before and after ablation. A clear oxide layer on the
ablated surface can be observed in Fig. 1(a), which includes three
Table 2
Ablation properties of C/C-ZrC-SiC composites and C/C-UHTCs composites reported in other studies.
Materials Ablation time (s) Surface or flame temperature (K)
C/C-ZrC-SiC in this study 180 2615
C/C-ZrC-SiC [27] 60 2573
C/C-SiC [13] 20 3300
C/C-ZrC [28] 20 3300
Ceramics International 43 (2017) 10661–10667
annular areas: a central region (region I), a transition region (region
II), and a border region (region III). According to the XRD analysis in
Fig. 1(b), the as-prepared samples consist of C, SiC and ZrC, while the
analysis results from region I indicate that ZrO2 and ZrSiO4 are
SiC formed. As reported previously [25], ZrC and SiC phases can be
oxidized into SiO2 and ZrO2, and then, SiO2 (whose boiling point is
4.88
2507 K) will readily evaporate as the ablation temperature reaches
2615 K. In addition, rapid cooling after ablation prior to the crystal-
lization of SiO2 means that no detectable SiO2 can be discovered by
XRD. The ZrSiO4 phase crystallizes from the eutectic SiO2-ZrO2 when
the ablated sample cools down.
3.2. Ablation morphology and behavior of C/C-ZrC-SiC composites
3.2.1. The surface micro-morphology of the ablated sample
Fig. 2 shows a quite different micro-morphology for regions I_III of
the ablated surface. As shown in Fig. 2(a), the structure of the surface
on region III remained intact except for a few ditches, which resulted
from the burnt-out carbon (including the carbon fibers and pyrolytic
carbon matrix) at the beginning of ablation. Fig. 2(b) indicates that the
surface is actually covered by a layer with low liquidity, which is a
mixture of a few glass-like phases and solid particles, and both of them
are composed of SiO2 and ZrO2 based on EDS analysis. In region III,
there are few glass-like phases sealing the defects due to the low
temperature. Fortunately, the erosive force of the plasm flame is too
weak to destroy the surface.
As shown in Fig. 2(c), the appearance of the ablated surface in
region II proves that a more continuous oxide layer is formed, with the
oxidized ditches being sealed effectively. Fig. 2(d) demonstrates that
the surface is actually covered by a great deal of glass-like phases and
solid particles, which are mainly the eutectic SiO2-ZrO2 and solid-state
ZrO2 based on the EDS result. The molten eutectic SiO2-ZrO2 can seal
the defects (including the cracks and holes) effectively and then retard
infiltration of the oxidation atmosphere. However, a synergistic effect
can be produced between the molten eutectic SiO2-ZrO2 and solid-state
ZrO2, where the solid-state ZrO2 can help protect the molten eutectic
SiO2-ZrO2 from being blown away; meanwhile, the molten eutectic can
also cover up the defects of isolated ZrO2 particles or clusters to avoid
the exposure of flame denudation directly. In addition, it is worth
noting that the zirconium content in the molten eutectic has increased
relatively, which illustrates that ZrO2 can be dissolved into the molten
eutectic gradually with increasing temperature. In region II, many
more glass-like phases are generated to fill the defects as the ablation
temperature increases, which has a positive effect on withstanding the
strong erosion.
As observed in Fig. 2(e), a coarse oxide layer with more obvious
oxidized ditches is generated, which is closely related to the higher
temperature and stronger erosion in region I. According to Fig. 2(f),
there are many ZrO2 particles or clusters and few molten eutectic SiO2-
ZrO2 based on the EDS result. What's more, it is interesting that solid-
state ZrO2 particles have the largest diameter among regions I_III,
which results from the sintering of ZrO2 in the highest-temperature
environment. The molten eutectic also features the highest content of
zirconium due to the significant evaporation of SiO2. Furthermore, the
concentrated ZrO2 particles on the surface, which pin into the molten
eutectic, are not only resistant to being blown away but also contribute
Linear ablation rate (mm/s) Mass ablation rate (g/s)
1.94×10−4 1.73×10−3
−1.88×10−3 −3.51×10−3
2.00×10−3 7.3×10−3
2.00×10−3 4.00×10−3
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Fig. 1. Macro-morphologies and XRD analysis of C/C-ZrC-SiC composites before and.after ablation: (a) samples; (b) XRD analysis.

to reducing the transfer of heat into the interior [15], which can be
noticed from the strong white light emitted by the samples after
approximately 90 s of ablation (ablation phenomenon). In region I, a
combination of reasons, such as the heat absorption for SiO2 evapora-
tion, thermal radiation of the ZrO2 concentration layer and pinning
effect of ZrO2 particles, protects the matrix from being ablated.
mechanism of the ZrB2–SiC [31], C/C-ZrC-SiC [17,19], C/C-ZrB2-SiC
[32], C/C-ZrB2-ZrC-SiC [33] composites has been widely studied, along
with a similar oxide layer consisted of ZrO2-SiO2 products on the
ablated surface. However, the specific generation, consumption and
evolution mechanism of the ZrO2-SiO2 binary eutectic system during
ablation are rarely reported.

3.2.2. The cross-section micro-morphology of the ablated sample 3.3.1. Chemical reactions
Fig. 3 shows the cross-sectional micro-morphologies and EDS The above analysis of the ablation behavior of C/C-ZrC-SiC compo-
analysis of different regions of the ablated sample. According to sites may contribute to understanding the ablation mechanism of the
Fig. 3(a_c), the matrix of regions I_III are in good condition, without composites. The following reactions would be the most representative:
being further oxidized, which indicates that the generated oxide layer 2C (s) + O2 (g) → 2CO (g) (1)
has successfully protected the C/C-ZrC-SiC composites from ablation.
Compared with the erosive force, the temperature will play the leading C (s) + O2 (g) → CO2 (g) (2)
role in impacting the cross-sectional structure of the oxide layer.
Fig. 3(a) indicates that an oxide layer with a thickness of approximately 2CO (g) + O2 (g) → 2CO2 (g) (3)
200 µm comes into view. As seen in the inset of Fig. 3(a), many small
pores are formed by the escape of gas produced during the ablation CO2 (g) + C (s) → 2CO (g) (4)
process. However, ablation is not serious because the temperature in
this area is the lowest among the three regions. Two distinct layers a 2/3SiC (s) + O2 (g) → 2/3SiO2 (s, l) + 2/3CO (g) (5)
dense area and an oxidized zone can be found in Fig. 3(b). The inset
image of Fig. 3(b) shows that the outside dense zone, with a thickness 1/2SiC (s) + O2 (g) → 1/2SiO2 (s, l) + 1/2CO2 (g) (6)
of approximately 100 µm, is composed of a great deal of glass-like
phases and solid particles, which can provide a sealing mechanism to SiC (s) + O2 (g) → SiO (g) + CO (g) (7)
the defects in the oxide layer.
The cross-sectional morphology of region I is completely different 2/3SiC (s) + O2 (g) → 2/3SiO (g) + 2/3CO2 (g) (8)
from those of regions II_III. It can be concluded in Fig. 3(c) that an
oxide layer with a thickness of approximately 300 µm is coated on the SiO (g) + O2 (g) → 2SiO2 (s, l) (9)
surface. The oxide layer can be divided into three temperature sections:
the low-temperature oxidized zone close to the matrix, the higher- 2/3ZrC (s) + O2 (g) → 2/3ZrO2 (s) + 2/3CO (g) (10)
temperature self-healing zone, and the highest-temperature ablation
zone. It is easy to draw a direct comparison from Fig. 3(d_f), which 1/2 ZrC (s) + O2 (g) → 1/2ZrO2 (s) + 1/2CO2 (g) (11)
clearly reflects the influences of temperature on the ablation situation.
Both the zirconium content in the molten eutectic SiO2-ZrO2 and the ZrC (s) + O2 (g) → ZrO (g) + CO (g) (12)
size of particles decrease gradually from exterior to interior, which is
attributed to the reduction in temperature with increasing depth. 2/3ZrC (s) + O2 (g) → 2/3ZrO (g) + 2/3CO (g) (13)
Obviously, the thick ZrO2 scale spreading on the top edge of the
cross-section is regarded as the ultimate layer against the highest 2ZrO (g) + O2 (g) → 2ZrO2 (s) (14)
temperatures and strongest erosion forces.
2SiO2 (s, l) → 2SiO (g) + O2 (g) (15)
3.3. Ablation mechanism of C/C-ZrC-SiC composites
SiO2 (s, l) → SiO2 (g) (16)
The ablation of C/C-ZrC-SiC composites involves a series of
ZrO2 (s) → ZrO2 (g) (17)
complex processes including mechanical denudation, thermochemical
factors, and thermophysical factors from a high-temperature, high-
2ZrO2 (s) → 2ZrO (g) + O2 (g) (18)
pressure, and high-velocity combustion flame [29,30]. The ablation

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Fig. 2. Micro-morphology and EDS analysis of different regions of the ablated surface: (a, b) region III, (c, d) region II and (e, f) region I.

The Gibbs free energies of the chemical reactions, which reflects the
tendency to occur at different temperatures, are shown in Fig. 4(a–c).
The lower the value is, the greater the tendency of the reaction to occur.
When the plasma flame reaches the surface of C/C-ZrC-SiC composites,
the temperature will increase rapidly. According to Fig. 4(a–c), ZrC and
SiC will react with the oxidative gases preferentially, preventing the
carbon (including Cf and CPyC) from being consumed prematurely. The
thermo-chemical reactions (1), (5) and (10) play the main role while
the temperature is below 2150 K, which can perfectly match the surface
appearance in regions II–III. SiO2 and ZrO2 oxidized from SiC and ZrC
can form the ZrO2-SiO2 binary eutectic system, which can act as an
effective barrier against the ablation at different temperatures. When
the temperature is above 2150 K, Eqs. (1), (7) and (10) are the leading
reactions in region I. A portion of SiC oxidized into SiO is consumed
quickly under the ultrahigh-temperature ablation flame. According to
Eqs. (3) and (9), the formed gaseous phases such as SiO and CO will
react with oxidative gases when spread to the lower-temperature area,
which is advantageous in hindering oxidation.
To further study the vaporization mechanism of the ZrO2-SiO2
binary eutectic system, the vapor pressures of SiO2 and ZrO2 are
calculated at different temperatures, as presented in Fig. 4(d). The
higher the value is, the greater the tendency to evaporate. It can be
noted that the reaction of SiO2 into SiO can be considered as the most
likely pathway to vaporization.
3.3.2. The evolution mechanism of the ZrO2-SiO2 binary eutectic
system
As discussed above, the ZrO2-SiO2 binary eutectic system plays an
important role in the excellent ablation properties of C/C-ZrC-SiC
composites. Therefore, it is necessary to analyze the evolution mechan-
ism of the ZrO2-SiO2 binary eutectic system, which can be well
illustrated by the phase diagram of the SiO2-ZrO2 binary system
(Fig. 5(a)). Assume that SiC–ZrC ceramic matrix has been completely
oxidized into SiO2 and ZrO2 and that the ratios of SiO2/(SiO2+ZrO2)

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Fig. 3. Cross-sectional micro-morphology and EDS analysis of different regions of the ablated sample: low magnification (a) region III, (b) region II and (c) region I; (d), (e) and (f)
larger magnification of areas D, E, and F in (c), respectively.
are marked as S0 in Fig. 5(a). During the initial ablation course, the
molten eutectic SiO2-ZrO2 will be generated by the solid-state SiO2 and
ZrO2 at the eutectic point near 1950 K (marked as 2 in Fig. 5(b)), which
is a point without any variable, and the temperature will not increase
until the solid-state SiO2 is absolutely converted into the liquid phase
(marked as 3 in Fig. 5(b)), revealing a relatively high Si content and low
Zr content. After that, ZrO2 becomes the only solid phase, which can
form the ZrO2-SiO2 binary eutectic system combined with molten
eutectic SiO2-ZrO2. With increasing temperature, solid-state ZrO2 will
be gradually dissolved into the molten eutectic. As a consequence, an
increasing Zr content in the molten eutectic can be noted, which is
intuitive for the composites to accommodate the diverse temperature
range of the ablation environment. As the ablation process persists, the
ablation temperature will continue to rise and exceed the boiling point
of SiO2 (marked as 5 in Fig. 5(b)), which is higher than that of pure
SiO2 for the dissolution of ZrO2. The SiO2 then can evaporate from the
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Ceramics International 43 (2017) 10661–10667
molten eutectic, which is an endothermic process, helping to slow the
rate of the increasing in temperature. However, once the concentration
of ZrO2 in the molten eutectic reaches saturation, the new ZrO2 phase
begins to precipitate from the molten eutectic. When the temperature
reaches 2615 K, the ZrO2-SiO2 binary eutectic system shows a rela-
tively high content of ZrO2 particles and low molten eutectic content
(marked as 6 in Fig. 5(b)). Therefore, a dynamic change in composition
of the eutectic system with increasing temperature contributes to
protecting the composites from being ablated. The whole process
including the heating curve and structural evolution of the ZrO2-SiO2
binary eutectic system can be illustrated by the schematic in Fig. 5(b).
4. Conclusion
C/C-ZrC-SiC composites were fabricated by CVI combined with PIP
by using porous C/C skeletons. The composites exhibited excellent
S. Wang et al. Ceramics International 43 (2017) 10661–10667

Fig. 4. Gibbs free energies of chemical reactions at different temperatures: (a, b, c) sublimation and oxidation of carbon, silicon carbide and zirconium carbide; (d) vapor pressure of
SiO2 and ZrO2.

Fig. 5. Phase diagram of SiO2-ZrO2 binary system [34] (a) and the corresponding schematic illustration (b) showing its structural evolution during ablation.

ablation properties during ablation with a plasma flame for 180 s, SiO2 binary eutectic system indicated that a dynamic change in the
which is closely related to the formation of an oxide layer that consisted composition of the eutectic system with increasing temperature was a
of a ZrO2-SiO2 binary eutectic system on the sample surface. During valuable phenomenon, which made the composites accommodate the
the ablation, ZrC and SiC preferentially reacted with the oxidative different ablation temperatures.
gases, consuming some of the oxidative gases. When T＜2150 K, ZrC
and SiC were oxidized into non-gaseous SiO2 and solid ZrO2, respec-
tively, which can form a binary eutectic system, acting as an effective
Acknowledgements
barrier against ablation. When T＞2150 K, SiC was mainly oxidized
into gaseous SiO; as a consequence, the oxidation product of solid ZrO2
The works were supported by the Shanghai Municipal Education
with a small amount of molten eutectic was spread over the top edge of
Commission (Peak Discipline Construction Program), and the Key
the cross-section, being considered as the ultimate layer against the
Program for International Science and Technology Cooperation
highest temperatures and strongest erosion forces. The investigation by
Projects of Ministry of Science and Technology of China (No.
phase diagram and the analysis of the structural evolution of the ZrO2-
2016YFE0111200).

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