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Title: Ablation resistance of wedge-shaped C/C-ZrB2 -ZrC-SiC

composites exposed to an oxyacetylene torch
Author: Lei Zhuang Qian-Gang Fu Tian-Yu Liu

CS 6872

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Please cite this article as: Lei Zhuang, Qian-Gang Fu, Tian-Yu Liu, Ablation resistance
of wedge-shaped C/C-ZrB2-ZrC-SiC composites exposed to an oxyacetylene torch,
Corrosion Science http://dx.doi.org/10.1016/j.corsci.2016.08.010
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<AT>Ablation resistance of wedge-shaped

C/C-ZrB2-ZrC-SiC composites exposed to an oxyacetylene torch

<AU>Lei Zhuang, Qian-Gang Fu* ##Email##fuqiangang@nwpu.edu.cn##/Email##,

Tian-Yu Liu
<AFF>State Key Laboratory of Solidification Processing, Science and Technology on
Thermostructural Composite Materials Laboratory, Northwestern Polytechnical
University, Xian, Shaanxi 710072, PR China

<PA>Corresponding author: Tel.: +86 29 88494197; Fax: +86 29 88495764.

<ABS-HEAD>Highlights The tip of specimen suffered the most severe shear
scouring and gas pressure High shear scouring and gas pressure resulted in
fragmented ceramic oxides The addition of UHTCs into C/C contributed to a higher
surface ablation temperature
<ABS-P>The ablation resistance of wedge-shaped C/C-ZrB2-ZrC-SiC composites was
studied under an oxyacetylene torch. As exposed to low heat flux of 2.38 MW/m2, a
porous and homogeneous ZrC-ZrO2 skeleton generated. With the increasing of heat
flux, ceramic oxides at the tip became loose and fragmented instead of sintering
together. Besides that, owing to the wedge-shape of the specimen, high gas pressure
mainly concentrated at this region. The high gas pressure and strong shear scouring of
flame resulted in the limited accumulation of ceramic oxides. This led to an inferior
ablation of wedge-shaped C/C-ZrB2-ZrC-SiC composites in high heat flux of 4.18

<KWD>Keyword: A. Ceramic matrix composites B. SEM B. XRD C. High

temperature corrosion

<H1>1. Introduction
Carbon/carbon (C/C) composites have many attractive properties such as low
coefficient of thermal expansion, high strength-to-weight ratio and good retention of
strength at high temperature and thus regarded as one of the most potential candidate
materials as thermal-structural components in turbine engines, aerospace and reentry
vehicles [1-4]. Unfortunately, rapid oxidation at ultrahigh temperature and pressure and
inferior ablation resistance severely limit their applications in advanced aerospace
systems [5-7].
The addition of ultra-high temperature ceramics (UHTCs) is an effective way to
improve the oxidation and ablation resistance of C/C composites [8-10]. Among
various UHTCs, Zr-based ceramics (ZrB2-ZrC) have attract much attention because of
their higher melting points, lower density and broader availability [11,12]. In addition,
considering C/C-UHTCs composites applied in oxidizing environment, a promising
insight into promoting their performance is to utilize self-healing phases [13].
Self-healing materials are able to seal and heal the damages such as microcracks and
micropores. Therefore, they will be ideal for applications in anti-oxidation and
anti-ablation fields. Up to now, self-healing at relatively low (5001000 C) and high
temperatures (12001600 C) has been achieved by forming B2O3 and SiO2

respectively [14,15]. So C/C composites modified by ZrB2-ZrC-SiC

(C/C-ZrB2-ZrC-SiC) are considered as a promising anti-ablation material.
To date, there are a large number of literatures reporting the preparation and
ablation properties of C/C-UHTCs [16-18]. Li et al. [19] tested the ablation resistance
of C/C-HfC composites. Results showed that C/C composites containing 6.5 wt.% HfC
exhibited a good ablation property. Feng et al. [20] prepared C/C-SiC-ZrC composites
and investigated the effect of SiC/ZrC ratio on the mechanical and ablation properties.
Results revealed that SiC/ZrC ratio of 1:1.5 was the best for ablation resistance of
C/C-SiC-ZrC composites. Paul et al. [21] prepared a range of C/C-UHTCs composites
by a slurry impregnation and carbon CVI method. Analysis displayed that carbon fiber
preforms with UHTCs powders significantly improved the high temperature oxidation
and ablation resistance of the composites. However, most of the ablation results come
from the tests of C/C-UHTCs at 90 (C/C-UHTCs plate). There are few researchers
studying on the ablation properties of wedge-shaped C/C-UHTCs. As a
thermal-structural component of reentry vehicle, it is important to evaluate the ablation
resistance of wedge-shaped C/C-UHTCs composites.
In the present work, C/C-ZrB2-ZrC-SiC composites were processed into
wedge-shape, and then exposed to an oxyacetylene torch to test their ablation
properties. Additionally, COMSOL software was used to further analyze the ablation
behavior and mechanism of the wedge-shaped composites.
<H1>2. Experimental procedure
<H2>2.1 Preparation of C/C composites

T300 PAN-based carbon felts with a density of about 0.45 g/cm3 were densified
using a thermal gradient chemical vapor infiltration (TCVI) technique at 9501150 C
for 120 h. Methane gas was used as the carbon precursor. After the TCVI process, the
densified C/C composites were graphitized at 22002500 C for 2 h at an argon
atmosphere. Finally, C/C composites with density of 1.78 g/cm3 were fabricated. The
porosity of C/C composites is 14% which was measured by Archimedes method with
distilled water as the immersion liquid.
<H2>2.2 Preparation of C/C-ZrB2-ZrC-SiC composites
Thermal gradient chemical vapor infiltration (TCVI) and precursor infiltration and
Pyrolysis (PIP) techniques were employed to fabricate C/C-ZrB2-ZrC-SiC composites.
Firstly, T300 PAN-based carbon felts with a density of about 0.45 g/cm3 were densified
by TCVI to obtain porous C/C composites with a density of 1.11.2 g/cm3. Secondly,
using xylene as solvent, zirconium carbide-containing polymer and polycarbosilane
were mixed with mass ratio of 2:1 by ultrasonic method for 2 h, which were used as
ZrC-SiC precursor. In addition, using xylene as solvent, zirconium boride-containing
polymer was dissolved and used as ZrB2 precursor. The mass ratio of xylene and
polymer was 3:1, and the productivity of precursor was about 28% [22]. After
immersed for 30 min in the precursor under vacuum condition, the composites were
took out and dried in a drying oven at 100 C for 24 h at least. Then, the dried
composites underwent a pyrolysis process at 17731873 K for 24 h in a flowing Ar
atmosphere. The above infiltration-pyrolysis process was repeated until the mass
increase percentage of composites was no more than 1%. The final density and porosity

of C/C-ZrB2-ZrC-SiC composites were 2.1 g/cm3 and 10% respectively. The mass ratio
of ZrC, SiC and ZrB2 in C/C-ZrB2-ZrC-SiC composites was about 4:2:1.
<H2>2.3 Ablation tests
To study the ablation behavior of the wedge-shaped specimens, oxyacetylene torch
tests were carried out. Oxyacetylene torch consisted of inner cone, acetylene feather
and outer envelope. And the highest temperature region of the oxyacetylene torch was
inner cone which was about 5 mm in diameter. Therefore the width of specimens was
designed to 5 mm. The other detailed dimensions were shown in Fig. 1. The ablation
specimens were cut from the as-prepared C/C and C/C-ZrB2-ZrC-SiC composites.
The specimens were divided into two groups based on two different heat fluxes.
The ablation parameters were shown in Table 1. The distance between the gun tip and
the specimen was 10 mm. During ablation, the specimen was fixed in a water cooled
copper holder. An infrared radiation thermometer (Raytek MR1SCSF) was applied to
measure the surface temperature of the specimen tip. The accuracy of the infrared
thermometer was in the 0.75% range. The final results are the average of three
specimens. The linear and mass ablation rates of the specimens were calculated
according to the following formulas:

Rl =

d 0 d1

Rm =

m 0 m1

where Rl is the linear ablation rate; d0 and d1 are the heights of the specimen before and
after ablation, respectively; Rm is the mass ablation rate; m0 and m1 are the masses of

specimens before and after ablation, respectively; S is the ablation surface area (two
rectangular faces of the wedge-shaped specimen in the present work); t is the ablation
<H2>2.4 Characterization
The phase analysis of the C/C-ZrB2-ZrC-SiC specimens before and after ablation
was conducted by X-ray diffraction with Cu K radiation (XRD, X Pert Pro MPD).
The microstructures and element composition of the C/C and the
C/C-ZrB2-ZrC-SiC specimens before and after ablation were analyzed by a scanning
electron microscopy (SEM, TESCANVEGA3) equipped with energy dispersive
spectroscopy (EDS, Oxford INCA).
Thermal conductivity of the composites was measured by a laser flash on a
TC-3000 thermal properties analyzer.
<H1>3. Results and discussion
<H2>3.1 Ablation properties of the composites
Fig. 2 displays the ablation properties of the wedge-shaped composites exposed to
low and high heat fluxes based on experimental results of three specimens. After
ablation in low heat flux for 60 s, the linear ablation rates of wedge-shaped C/C and
C/C-ZrB2-ZrC-SiC specimens (marked as C/C-L and C/C-Z-L respectively) are 23.3
1.2 and 15.7 0.9 m/s, respectively. Compared to the literature testing C/C and
C/C-UHTCs plate [22], the linear ablation rate of wedge-shaped C/C composites is in
the same order of magnitude while that of wedge-shaped C/C-ZrB2-ZrC-SiC
composites increases several times. The ablation resistance of C/C-ZrB2-ZrC-SiC

composites is still superior to C/C composites, but is not so ``well'' anymore. As ablated
in high heat flux, wedge-shaped C/C-ZrB2-ZrC-SiC (marked as C/C-Z-H) specimens
have linear and mass ablation rates of 36.5 1.7 m/s and 22.8 1.0 g/scm2,
respectively. Both quotas of C/C-ZrB2-ZrC-SiC composites are higher over those of
C/C composites (linear ablation rate of 34.3 2.0 m/s and mass ablation rate of 15.0
0.9 g/scm2 respectively). Therefore the wedge-shaped geometry should have a
significant effect on the ablation properties of C/C-UHTCs composites. In addition,
according to Fig. 2b, the tip of C/C-ZrB2-ZrC-SiC composites exhibits higher surface
temperature in both heat fluxes. The reasons will be discussed in the Ablation
<H2>3.2 Phase characterization
Fig. 3 shows the XRD pattern of C/C-ZrB2-ZrC-SiC composites before and after
ablation. According to XRD analysis, as-obtained C/C-ZrB2-ZrC-SiC specimens
consist of ZrB2, ZrC, SiC, and C, which means that all of UHTCs have been
successfully added into porous C/C composites without impurity. After ablation (the
lines in red and blue colors), there are some generated ablation products, which are
detected as ZrO2 and SiO2. No trace of B2O3 is found, so it is inferred that a heavy
evaporation of B2O3 takes place under ultra-high ablation temperature (over 1800 C)
due to the relatively low melting temperature (445 C) of B2O3. It should be noticed that
no C is detected by XRD although some carbon fibers are exposed at the tip after
ablation in high heat flux, as shown in Fig. 4. This should be due to the following two
reasons. Firstly, the detected area of XRD is the whole surface of the specimen.

Therefore, a large amount of ceramic oxides formed on the other region might affect the
detection of a small quantity of exposed carbon fibers at the tip. Secondly, ceramic
oxides partially covering the surface of carbon fibers might result in the difficulty of
detection of underlying carbon materials.
<H2>3.3 Microstructures and morphologies of the composites before and after ablation
Fig. 4 exhibits the macroscopic images of C/C and C/C-ZrB2-ZrC-SiC specimens after
ablation in low and high heat fluxes. The gold color on the surface of
C/C-ZrB2-ZrC-SiC specimens is the result of spraying Au in order to enhance the SEM
image quality. As displayed in Fig.4 a and c, the tips of wedge-shaped C/C specimens
exposed to both heat fluxes are rugged (marked as C/C-L and C/C-H respectively) and
the sides are full of holes. This suggests that the whole specimens have suffered severe
oxidation and ablation. While for wedge-shaped C/C-ZrB2-ZrC-SiC specimens ablated
in low heat flux (marked as C/C-Z-L), the tip is much smoother without obvious holes.
Therefore, the addition of UHTCs should play an active role in ablation resistance of
composites under low heat flux. When C/C-ZrB2-ZrC-SiC specimens are ablated high
heat flux (marked as C/C-Z-H), the macroscopic appearance is totally different. Carbon
fibers are exposed at the tip and the outer ceramics seem to be peeled off from the
specimen surface. This should be the result of powerful shearing scouring of
oxyacetylene torch in high heat flux and is accordance with the high linear and mass
ablation rate of wedge-shaped C/C-ZrB2-ZrC-SiC composites.
Fig. 5 shows the morphologies of C/C and C/C-ZrB2-ZrC-SiC composites before
ablation. It is seen that some closed holes are in the inner of C/C composites, which is

attributed to the blocking of pyrolytic carbon (PyC) during deposition process. As

exhibited in Fig. 5b, C/C-ZrB2-ZrC-SiC composites are more compacted than C/C
composites. This suggests a good infiltration of precursor.
In order to study the microstructures of original ceramics, part of unused polymer
precursor was dried and then heat-treated in high temperature. The morphologies of the
obtained ZrC-SiC ceramics are displayed in Fig. 6. It is seen that there are microcracks
in the ceramics, which should be owing to the shrink of ceramics when the ceramics
cool down from heat-treatment temperature to room temperature. The generated
microcracks might act as the tunnels for solvent to escape during heat-treatment so that
the ceramics are relatively dense as shown in Fig. 6b.
Oxyacetylene torch ablation is an aggressive process involving ultra-high
temperature and severe oxidizing environment. According to the geometry, the
specimen is divided into three parts: tip region, transition region, and tail region.
Fig. 7 displays the microstructures and corresponding EDS pattern of
wedge-shaped C/C and C/C-ZrB2-ZrC-SiC specimens in the tip region after low heat
flux of 2.38 MW/m2 exposure. For C/C composites, it is clear that a big hole have
generated and carbon fibers have been oxidized into needle-shape exhibited in Fig. 7a,
which should result from the high sensitivity of carbon materials under oxygen-rich and
ultra-high temperature environment. After adding ZrB2-ZrC-SiC ceramics into C/C
composites, as shown in Fig. 7b, the ablated ceramics have sintered together with
uniform and porous structure. According to EDS analysis (insert in Fig. 7b), the
ceramic oxides comprise Zr, O, C and a small quantity of Si (only 1.1%) elements, but

no trace of B element is detected. So, the large evaporation and sublimation of B2O3 and
SiO2 should be responsible for the porous structure of ZrC-ZrO2 skeleton. This skeleton
layer formed on the surface might not limit inward diffusion of oxygen to the matrix,
but plays as a barrier to resist the erosion of gas flow. So C/C-ZrB2-ZrC-SiC
composites have a superior ablation resistance in low heat flux compared to C/C
Fig. 8 exhibits the morphologies and EDS analyses of wedge-shaped C/C and
C/C-ZrB2-ZrC-SiC specimens in the transition region after ablation in low heat flux for
60 s. For C/C specimens (Fig.8a), pores between carbon fibers and PyC are smaller
compared to those in the tip region. That is, a relatively milder oxidizing environment
in the transition region is confirmed. In addition, some generated microcracks are found
on the specimen surface. This is because the initial cooling rate is up to approximately
1000 C/s when the specimen is removed from the ablation torch [23], and the high
temperature difference between the surface and the inner matrix leads to the microcrack
generation and propagation. As indicated in Fig. 8b, for C/C-ZrB2-ZrC-SiC
composites, a glassy layer with island-shaped ceramics covers the whole ablation
surface, which is different from the morphology of C/C-UHTCs plate exposed to
oxyacetylene torch [9,19,20]. Combined with EDS analysis (Fig. 8c and d), this glassy
layer involves SiO2, ZrO2, and some unreacted carbides, while the island-shaped
ceramics consist of ZrO2 and ZrC. Therefore, during ablation, a great deal of SiO2
should be consumed by the oxyacetylene torch. The heat flux of oxyacetylene torch
heats the specimen and thus leads to a great evaporation of SiO2. The large

consumption of SiO2 resulted in the emergence of island-shaped ZrO2-ZrC skeleton

whose melting point was in excess of 2000 C.
The morphology of the tail region of C/C composites (Fig. 9a) confirms that both
carbon fiber and PyC survive after exposure for 60 s, which means that the ablation
environment in this region is the mildest. The interface of fiber/PyC is the main
oxidation area and will be oxidized in priority due to its low surface energy. As a result,
circular gaps shown in the insert of Fig. 9a appear. These circular gaps are similar with
the microstructure of C/C composites oxidized in 900 C static environment [25],
illustrating that consumption of carbon materials is the main reason for failure in this
region. For the tail region of C/C-ZrB2-ZrC-SiC composites (Fig. 9b), it is clear that the
SiO2 glassy layer is smoother compared to the front regions and the island-shaped
zirconium compounds skeletons have disappeared. But there are some generated
microcracks (see the insert in Fig. 9b). Such small size of microcracks suggests an
effective sealing of SiO2 thanks to its good fluidity at high temperature. Therefore, the
molten SiO2 with low oxygen diffusion coefficient is beneficial to oxidation resistance
of composites.
As ablated in high heat flux of 4.18 MW/m2, composites undergo higher
temperature, faster corrosion and sharper torch scouring. Fig. 10a shows the
morphology of C/C composites in the tip region after ablation in high heat flux for 60 s.
All of carbon fibers have disappeared and the residual PyC has been oxidized into
annular shape. These results indicate an extremely severe ablation environment in the
tip region under high heat flux. Fig. 10b exhibits the microstructure of

C/C-ZrB2-ZrC-SiC composites in the tip region after high heat flux exposure for 60 s.
Similar with the morphology of ablated C/C composites, the consumption of carbon
fibers result in the formation of a large number of microvoids which serve as diffusion
channels for oxygen to attack inner matrix during ablation. Additionally, the ceramic
oxides are all fragmented instead of sintering together, which is different from the
ablation microstructure of C/C-UHTCs plate [22].
To further analyze the ablation behavior of wedge-shaped composites, COMSOL
software is employed. In the present work, the speed of nozzle gas is 10 m/s [26]. The
nozzle distance is 10 mm based on the experimental condition and the size of wedge is
set according to the experimental specimen. The boundary type for the surface of the
specimen is ``wall'', indicating that the gas is prohibited to penetrate the specimen. The
results in Fig. 11a show that when the ablation torch reaches the wedge-shaped
specimen, the flame will be divided into two parts. Under such condition, the highest
speed flame is not tightly along with but keeps away from the surface of specimen for a
certain distance. This means that the transition and the tail region might not contact the
highest speed flame directly owing to the geometry of specimen, That is, the ablation
environment in these two regions is much milder than that in the tip region. Fig. 11b
displays the simulated pressure field during ablation, from which it is confirmed that
the tip region of specimen resists the highest gas pressure. So, the torch scouring in the
tip region is the most aggressive and therefore leads to the fragmented structure of
ceramic oxides. Combined with the linear and mass ablation rates shown in Fig. 2, it is
inferred that the function of adding PIP-UHTCs might be negative in the high heat flux

owing to the following three reasons. Firstly, unlike hot pressed UHTCs, the structure
of PIP-UHTCs in C/C composites is relatively loose because of the ordinary pressure of
heat-treatment, which is bad for the ablation resistance of C/C-UHTCs composites.
Secondly, without SiO2, the powerful shearing force of oxyacetylene torch in high heat
flux can largely wash ZrO2-ZrC skeleton away, and the left microcracks and
micropores will accelerate the oxidation process by providing an easier route for
oxygen infiltration into the underlying matrix. Thirdly, the content of PyC in
C/C-ZrB2-ZrC-SiC composites (0.70.8 g/cm3) is lower than that in C/C composites
(1.21.4 g/cm3). The coefficient of thermal expansion (CTE) of PyC is similar with
carbon fibers, so it is more in favor of releasing thermal stress at ultra-high temperature.
In addition, PyC is a material which processes good scouring resistance thanks to its
high toughness but has poor anti-oxidation property owing to its high sensibility to
oxygen at ultra-high temperature. Therefore, under such high gas pressure and strong
shearing force condition, the ablation resistance of loose ceramic oxides might not be
better than PyC.
Fig. 12 shows the morphologies of wedge-shaped C/C and C/C-ZrB2-ZrC-SiC
composites in the transition region after exposure in high heat flux for 60 s. For C/C
composites, it is obvious that a wide microcrack has formed on the surface because of
the huge temperature difference between surface and matrix (Fig. 12a). For
C/C-ZrB2-ZrC-SiC composites (Fig. 12c), combined with EDS pattern (insert of Fig.
12c), it is confirmed that the distribution of SiO2 on the surface is discontinuous. So it is
inferred that SiO2 in the transition region is still not stable during ablation tests. Fig.

12d exhibits that the underlying ceramics are granular and discontinuous, which results
from the escape of SiO2 and contributes to the appearance of a large number of
microholes. In general, the transition region surface of C/C-ZrB2-ZrC-SiC composites
is more complete compared to that in the tip region. This morphology indicates a milder
shearing scouring environment and is in accordance with the simulation results.
Fig. 13 shows the microstructure of wedge-shaped composites in the tail region
after ablation in high heat flux for 60 s. For C/C composites (Fig. 13a and b), circular
gaps appear after ablation and the tips of fibers become sharp. Differently, the surface
of C/C-ZrB2-ZrC-SiC composites (Fig. 13c and d) have been basically covered by a
dense and continuous glass-state layer. The lowest surface temperature and the weakest
scouring force should be responsible for this morphology. Moreover, there are also
some craters and broken bubbles on the surface. However, different from the
morphology in Fig. 9b, the underneath carbon fibers are exposed with obvious
oxidation damage. So it is concluded that the increased heat flux and the stronger
shearing scouring hinder the formation of dense and continuous SiO2 layer.
<H2>3.4 Ablation mechanism
<H3>3.4.1 Effect of wedge-shape on ablation behavior of the composites
The ablation resistance of composites is closely related to the surface temperature
of the specimen and the formed protecting layer on the ablated surface. In the present
work, because of the wedge-shape of C/C-ZrB2-ZrC-SiC composites, the inner cone
mostly focuses on the tip region of specimen, which results in a concentration of gas
pressure at this region according to COMSOL simulation result (Fig. 11b). Under such

oxygen-rich (43.02 mol% O2 [27]), high temperature and high gas pressure
environment, severe oxidation and consumption of ceramics and carbon materials are
inevitable, and the left microcracks and micropores at the tip can further accelerate the
corrosion of underlying matrix by providing more oxygen diffusion channels.
Additionally, different from the traditional ablation of C/C-UHTCs plate, ceramic
oxides on the surface of wedge-shaped specimen are more difficult to accumulate
owing to the geometry which increases the shearing force of oxyacetylene torch. The
limited accumulation of ablation products contributes to the inferior ablation resistance
of wedge-shaped C/C-ZrB2-ZrC-SiC composites exposed to high heat flux [8].
Besides, because the tip of wedge-shaped specimen is very thin, the powerful scouring
force of flame can break the carbon fibers and peel the ceramics from the specimen
surface during ablation, as shown in Fig. 4d, and therefore leads to high mass and linear
ablation rates of C/C-ZrB2-ZrC-SiC composites.
<H3>3.4.2 Effect of surface temperature on ablation behavior of the composites
Temperature is a key factor for chemical reactions. The possible reactions occurring
during ablation are listed as followings:
ZrB2(s) + 5/2O2(g) ZrO2(s) + B2O3(l) (3)
ZrC(s) + 2O2(g) ZrO2(s) + CO2(g) (4)
SiC(s) + 2O2(g) SiO2(s) + CO2(g) (5)
C(s) + O2(g) CO2(g) (6)
Standard Gibbs free energy change versus temperature curves of the predicted reactions
is displayed in Fig. 14. Through the calculations, it is anticipated that Eqs. (3-6) can all

take place during ablation because of the negative standard Gibbs energy change. This
result is in accordance with the phase composition of ablated specimen detected by
XRD analysis.
The surface ablation temperature is strongly affected by the following two aspects.
One is the heat flux of oxyacetylene torch decided by flux ratio of O2 and C2H2 and their
contents. In the present tests, the heat fluxes are all fixed values according to GJB
323A-96 [28]. The other one is the thermal conduction of composites, which needs to
be further discussed. Fig. 14 displays the thermal conduction testing results of C/C and
C/C-ZrB2-ZrC-SiC composites. Two trends can be obtained. Firstly, with the
increasing of temperature (over 500 C), the thermal conduction values of C/C are
basically constant whereas those of C/C-ZrB2-ZrC-SiC rise gradually. Secondly, C/C
composites have higher thermal conduction values in all range of temperature. In other
word, the thermal conduction performance of C/C composites is better. So, adding
UHTCs into C/C composites decreases the thermal conduction to some extent.
Experimentally, the transition of phases will affect the thermal conduction of
C/C-UHTCs composites. For instance, when SiC and ZrC react with oxygen to form
SiO2 and ZrO2, their coefficients of thermal conductivity change from 64.4 W/(cmK)
and 20.5 W/(cmK) to 0.3 W/(cmK) and 2.9 W/(cmK), respectively. Thus the
formation of ceramic oxides can further decrease the thermal conduction property of
C/C-ZrB2-ZrC-SiC composites. Moreover, oxidation reactions between ceramics and
oxygen are exothermic processes. The exothermal reactions and lower thermal
conduction result in a higher surface temperature of C/C-ZrB2-ZrC-SiC composites in
both two heat fluxes. Therefore, due to the higher tip temperature of C/C-ZrB2-ZrC-SiC
composites, SiO2 is more difficult to survive during ablation because of the reduction of
viscosity and the increasing of evaporation. Without SiO2 acting as healing and bonding
agent, ZrO2 skeleton with poor adhesive strength should be easily scoured away by the
combustion gas.
<H1>4. Conclusions

The ablation behavior of C/C-ZrB2-ZrC-SiC and C/C composites was studied under
an oxyacetylene torch. When wedge-shaped C/C-ZrB2-ZrC-SiC composites were
ablated in low heat flux of 2.38 MW/m2, evaporation of SiO2 resulted in the formation
of ZrC-ZrO2 skeleton layer with porous and loose structure. This skeleton layer could
act as a barrier to resist the oxyacetylene torch scouring. Therefore C/C-ZrB2-ZrC-SiC
composites had better ablation resistance than C/C composites in low heat flux. When
wedge-shaped C/C-ZrB2-ZrC-SiC composites were exposed to high heat flux of 4.18
MW/m2, severer oxidation of ceramics and carbon matrix took place owing to the
increased heat flux. In addition, due to the geometry of wedge-shaped specimen, the tip
was the main region to withstand the inner cone of oxyacetylene torch. The high gas
pressure at the tip accelerated the diffusion of oxygen into underlying matrix. Besides,
during ablation, the wedge-shape of specimen contributed to a limited accumulation of
ablation products on the specimen surface because the generated ceramic oxides could
be easily peeled off and then washed away by the powerful shearing scouring of flame.
So, wedge-shaped C/C-ZrB2-ZrC-SiC composites exhibited inferior ablation resistance
in high heat flux.
This work has been supported by National Natural Science Foundation of China
under Grant nos. 51521061 and 51572223.
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<Figure>Fig. 1 Schematic illustration of oxyacetylene torch ablation test.

<Figure>Fig. 2 Ablation properties of wedge-shaped C/C and C/C-ZrB2-ZrC-SiC
(C/C-Z) composites exposed to low (-L) heat flux of 2.38 MW/m2 and high (-H) heat
flux of 4.18 MW/m2 for 60 s based on experimental results of three specimens: (a)
Linear ablation rate at the tip and mass ablation rate of the whole specimen; (b) surface
temperatures of the tip recorded every 5 s.


<Figure>Fig. 3 XRD pattern of wedge-shaped C/C-ZrB2-ZrC-SiC specimens before

and after ablation in low heat flux of 2.38 MW/m2 and high heat flux of 4.18 MW/m2
for 60 s.
<Figure>Fig. 4 Macroscopic images of wedge-shaped C/C and C/C-ZrB2-ZrC-SiC
(C/C-Z) specimens after ablation in (a and b): low (-L) heat flux of 2.38 MW/m2; (c and
d): high (-H) heat flux of 4.18 MW/m2.
<Figure>Fig. 5 Morphologies of high-density C/C (a) and C/C-ZrB2-ZrC-SiC
composites (b) before ablation.
<Figure>Fig. 6 Morphologies of PIP-processed ZrC-SiC ceramics before ablation: (a)
low-magnification and (b) high-magnification.
<Figure>Fig. 7 Morphologies and corresponding EDS analysis of wedge-shaped C/C
(a) and C/C-ZrB2-ZrC-SiC (b) composites in the tip region after ablation in low heat
flux of 2.38 MW/m2 for 60 s.
<Figure>Fig. 8 Morphologies and corresponding EDS analyses of wedge-shaped C/C
and C/C-ZrB2-ZrC-SiC composites in the transition region after ablation in low heat
flux of 2.38 MW/m2 for 60 s: (a) C/C specimen; (b) C/C-ZrB2-ZrC-SiC specimen; (c
and d) corresponding EDS patterns.
<Figure>Fig. 9 Morphologies of wedge-shaped C/C (a) and C/C-ZrB2-ZrC-SiC (b)
composites in the tail region after ablation in low heat flux of 2.38 MW/m2 for 60 s.
<Figure>Fig. 10 Morphologies of wedge-shaped C/C (a) and C/C-ZrB2-ZrC-SiC (b)
composites in the tip region after ablation in high heat flux of 4.18 MW/m2 for 60 s.


<Figure>Fig. 11 Numerical simulation of ablation process of wedge-shaped specimen

using COMSOL software: (a) velocity filed and (b) gas pressure field.
<Figure>Fig. 12 Morphologies of wedge-shaped C/C (a and b) and C/C-ZrB2-ZrC-SiC
(c and d) composites in the transition region after ablation in high heat flux of 4.18
MW/m2 for 60 s.
<Figure>Fig. 13 Morphologies of wedge-shaped C/C (a and b) and C/C-ZrB2-ZrC-SiC
(c and d) composites in the tail region after ablation in high heat flux of 4.18 MW/m2 for
60 s.
<Figure>Fig. 14 Plot of standard Gibbs free energy change against temperature from
1800 C to 2400 C using FactSage software for reactant and product.
<Figure>Fig. 15 Thermal conductivity of C/C and C/C-ZrB2-ZrC-SiC composites
tested from room temperature to 1900 C.
<Table>Table 1 Parameters of ablation tests according to GJB323A-96 [28].

Pressure (MPa) Gas flux (L/s)

Heat flux







time (s)

Low heat flux







High heat flux