Ceramics International 42 (2016) 14126–14134

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Influence of Ti3AlC2 on microstructure and thermal mechanical

properties of Al2O3-Ti3AlC2-C refractories
Junfeng Chen n, Nan Li n, Wen Yan, Yaowu Wei, Bingqiang Han
The Key State Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, PR China

art ic l e i nf o a b s t r a c t

Article history: Al2O3-Ti3AlC2-C refractories with different carbon content were prepared by using Ti3AlC2 as substitute
Received 18 April 2016 for partially graphite. The influences of Ti3AlC2 on microstructure and thermal mechanical properties of
Received in revised form Al2O3-Ti3AlC2-C refractories were investigated. The drastic deterioration in thermal mechanical proper-
5 June 2016
ties of Al2O3-Ti3AlC2-C refractories was effectively prevented by reducing carbon content from 10 to
Accepted 5 June 2016
Available online 6 June 2016
4 wt%. Particular attention was paid to the microstructure evolution of Ti3AlC2, the formations of Al2TiO5,
SiAlON and Al-Si-C-O whiskers were developed to explain the limited fall in strength after thermal shock
Keywords: test in our works. The formation mechanism of the new bonded phases in the specimen with Ti3AlC2 was
Ti3AlC2 explained in this paper.
Low carbon-refractories
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Microstructures
Thermal shock

1. Introduction research results and theories.

Carbon containing refractories was widely used by introducing
natural graphite into refractories in the 1970s [1,2]. Since then, the
processing, microstructures and properties of carbon containing
refractories have been improved successively, and assisted the
development of metallurgical industry [3–7]. Carbon containing
refractories are truly composite materials, with the oxides con-
ferring oxidation resistance while the graphite provides increased
thermal conductivity which relates to thermal shock resistance
and the non-wetting behavior relating to corrosion resistance. So
carbon-oxides composite refractories have an important attribu-
tion to the development of continuous casting process and the
dramatic reduction of refractory consumption per ton of steel [8–
11].
During the past two decades, there has been a significant ex-
pansion in terms of research and development in optimizing the
microstructures and properties of carbon-oxides composite. The
effect of additives/antioxidants and various kinds of carbon on the
oxidation behavior, corrosion resistance, microstructures and
thermo-chemistry were conducted in different oxides-carbon
systems by different groups such as Yamaguchi [5,7,12,13], Lee and
Zhang [8,14,15], Aneziris [16,17], Yawei Li [18,19] and many others
[20–25]. A further development in the properties of material has
been achieved for extreme environments based on the above
n
Corresponding authors.
E-mail addresses: chenjunfengref@163.com (J. Chen), linan@wust.edu.cn (N. Li).
It was confirmed that high carbon content in brick result in
several disadvantages with the progress of clean steelmaking. The
principal issue is that molten steel can pickup carbon from carbon-
containing refractories that increases the carbon content of steel,
and is harmful to the production of high-quality steel. Bannenberg
[26] as well as Li and his colleagues [27,28] have reported that
Al2O3-C and MgO-C refractories caused carbon pickup by molten
steel. Moreover, the outlet temperature of the refining vessels in
the metallurgy is high because of the high thermal conductivity
along with high carbon content. To ensure metallurgical operation
and to prevent reduction in molten metal temperature, engineers
from steel plants usually increase the lining thickness of steel-
making vessels which leads to vessels capacity being adversely
affected. So in order to meet the demand for high-quality steel,
refractories with ultralow carbon content have to be developed.
But when the carbon content is lower than
8 wt%, thermal
spalling phenomenon frequently occurs during the actual use
processing of carbon composite refractories[3,9,10]. Because sim-
ply reducing the carbon content in refractories will result in the
decrease in the thermal diffusivity and increase in the thermal
expansion coefficient, both of which affect the thermal shock re-
sistance of composites. So it is necessary to reduce the carbon
content of carbon containing refractories while optimizing its
performance properties.
In the recent years, many researchers paid main attention on
obtaining low carbon containing refractories by adding nano-car-
bon materials (nano carbon black, carbon nanotubes, graphite
oxide nanosheets). Although the results showed that the

http://dx.doi.org/10.1016/j.ceramint.2016.06.028
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 J. Chen et al. / Ceramics International 42 (2016) 14126–14134
improvement in mechanical properties has been obtained owing
to the contribution of nano-size materials, it should be recognized
that the cost-effectivity and dispersion of nano-size materials are
still huge challenges for its application in refractory industry.
Hence, in view points of technology promotion, a deeper under-
standing of properties such as thermo-chemical stability, wear
mechanisms and corrosion performances is needed.
In our previous research [29], it has been shown that the car-
bon content can be partially reduced in Al2O3-C refractories by
adding Ti3AlC2 powder in matrix. The result indicated that the
corrosion resistance of Al2O3-Ti3AlC2-Si-C refractory with 4 wt%
graphite increases by 43.0% under laboratory conditions when
compared with regular Al2O3-Si-C refractory with 10 wt% graphite.
The application of Ti3AlC2 in the field of low carbon containing
refractories research, based on the unique oxidation behavior,
properties and layered structure [30–33] is a meaningful attempt
with an interesting result. However, before Ti3AlC2 can be con-
sidered for using in low carbon containing refractories field, more
efforts and works need to be done so that it can be better un-
derstood and quantified. A systematic research effort into the
evolution of microstructure, thermal shock properties and me-
chanical properties of this kind of materials are required to de-
termine their feasibility in refractory industry.
In the present work, the effect of Ti3AlC2 on microstructure and
thermal shock properties of low carbon refractory will be in-
vestigated. It is a basic and a major measurement factor to predict
the feasibility of using the Ti3AlC2 to enhance the performance of
low carbon refractories.
2. Experimental
2.1. Raw materials and refractories fabrication
Al2O3-Ti3AlC2-C refractories were prepared using tabular alu-
mina (3–1 mm, 1–0.5 mm, 0.5–0 mm, Qingdao Almatis Co. Ltd.
Qingdao, China), alumina powder (o45 mm, Qingdao Almatis Co.
Ltd. Qingdao, China), α-Al2O3( o45 mm, Qingdao Almatis Co. Ltd.
Qingdao, China), silicon powder (purity:98%, d0.5 ¼ 27 mm, Lingyun
silicon Co. Ltd. Xuzhou, China), flake graphite (o74 mm, 97.5 wt%
fixed carbon, Qingdao, China) and Ti3AlC2 ( o74 mm, purity: 98%,
XRD patterns as shown in Fig. 1, Hutong Wangyi Technology Co.
Ltd. Beijing, China) as raw materials and thermosetting phenolic
resin (36 wt% of carbon yield, Wuhan, China) as binder. The
Fig. 1. XRD patterns of the Ti3AlC2 powder.
14127
compositions of Al2O3-Ti3AlC2-C refractories specimens are shown
in Table 1 [29]. Based on the Ti3AlC2 contents, the specimens are
designated as RTAC-0, RTAC-2, RTAC-4 and RTAC-6, respectively.
After kneading, bar specimens of 140 mm  25 mm  25 mm were
prepared by cold pressing under a pressure of 150 MPa and cured
at 220 °C for 24 h. Finally, the as-prepared specimens were placed
in a mullite sagger which were filled with petroleum coke. The
whole sagger was placed into an electrical furnace and heated
from room temperature to 1100 °C and 1400 °C using a heating
rate of 3 °C/min and a holding time of 3 h, respectively.
Simultaneously, Ti3AlC2 powder (designated as specimen
Ti3AlC2) was packed into cylindrical mold (Φ10 mm  10 mm)
with about 150 MPa pressure. The green compacts were also coked
at different temperatures with Al2O3-Ti3AlC2-C refractories.
2.2. Testing and characterization methods
The thermal shock resistance of the specimens (after heat-
treatment at 1400 °C for 3 h in coke bed) was tested according to
the following method. The specimens were placed in the re-
sistance furnace at 1100 °C in air, and heated under this tem-
perature for 20 min. Then, the specimens were taken out and
quickly quenched into a water bath. This cycle was repeated for
3 times. The cold modulus of rupture (CMOR) was measured with
dimensions of 140 mm  25 mm  25 mm by three-point bending
strength tests with a span of 100 mm. The residual strength ratio
of CMOR was calculated by dividing CMOR obtained after the
thermal shock by that after coking at 1400 °C.
The crystallographic phases of specimens were determined via
X-ray diffractometry (XRD) (X’Pert Pro, Philips, Eindhoven, The
Netherlands; using Ni filtered, Cu Kα radiation) at a temperature of
20 °C. The microstructure observations were observed in back-
scattered electron (BEI) and secondary electron imaging (SEI)
modes by a field scanning electron microscope (SEM, Nova 400
Nano-SEM, FEI Company, USA) equipped with energy dispersive
X-ray spectroscope (EDS, INCA IE 350 PentaFET X-3, Oxford, UK).
The further characterization of whiskers were investigated using
transmission electron microscopy (HR-TEM, Model JEM-2010,
JEOL, Japan), also equipped with energy dispersive X-ray spectro-
scope (EDS, INCA IE 350 PentaFET X-3, Oxford, UK).
3. Results and discussion
3.1. Phase compositions and microstructure evolution of Ti3AlC2
The XRD patterns of Ti3AlC2 powder specimens after coked at
different temperatures are depicted in Fig. 2. It is shown that the
major crystalline phases of specimen coked at 1100 °C are titanium
carbide, corundum, unreacted Ti3AlC2 and aluminum nitride from
Ti3AlC2 raw material. Besides the major crystalline phases similar
to those at 1100 °C, titanium oxide and aluminum titanate are
detected in specimen after coked at 1400 °C.
Based on the above analysis, it is stated that the oxidation of
Ti3AlC2 occurs via reaction (1) in this experimental condition at
1100 °C. When the temperature is about 1400 °C, reactions (2) and
(3) occur.
Ti3AlC2 þCO-Ti3AlxC2 þ(1  x)/2Al2O3 þC (1)
Ti3AlC2 þCO-Ti3  xC2 þ1/2Al2O3 þxTiO2 (2)
xAl2O3 þ yTiO2-xAl2O3  yTiO2 (3)
Simultaneously, the microstructures of the Ti3AlC2 powder
after coked at 1100 °C and 1400 °C were also observed by SEM and
14128 J. Chen et al. / Ceramics International 42 (2016) 14126–14134

Table 1
The compositions of Al2O3-Ti3AlC2-C refractory specimens (wt%).

RTAC-0 (wt%) RTAC-2 (wt%) RTAC-4 (wt%) RTAC-6 (wt%)

Tabular alumina (3–1 mm) 25 25 25 25

Tabular alumina (1–0.5 mm) 20 20 20 20
Tabular alumina (0.5–0 mm) 20 20 20 20
Tabular alumina ( o45 mm) 12 12 12 12
α-Al2O3 ( o45 mm) 8 8 8 8
Silicon powder (d0.5 ¼ 27 mm) 5 5 5 5
Flake graphite ( o74 mm) 10 8 6 4
Ti3AlC2 ( o 74 mm) 0 2 4 6

Fig. 2. XRD patterns of Ti3AlC2 powder specimen after fired at 1100 °C and 1400 °C.
TEM, both equipped with EDS.
As shown in Fig. 3, a Ti-Al-C-O coating forms on the surface of
Ti3AlC2 grain after coked at 1100 °C. Based on the analysis result of
XRD patterns (Fig. 2), the major crystalline phases are titanium
carbide, corundum, aluminum nitride and unreacted Ti3AlC2. So
the coating is a mixture of titanium carbide and corundum.
Al2TiO5 (Point 1 shown in Fig. 4a) and Ti-Al-C-O whiskers
(shown in Fig. 4b) are observed after Ti3AlC2 coked at 1400 °C for
3 h. Ti-Al-C-O whiskers with an average diameter of about 105 nm
(average of 50 whiskers, standard deviation: 23) are formed on the
surface of Ti3AlC2 (marked by red arrows in Fig. 4b). To better
prove the presence of Ti-Al-C-O whiskers in the specimen Ti3AlC2,
TEM micrograph of specimen Ti3AlC2 is shown in Fig. 5. The EDS
result of TEM confirms that whisker composition is Al, C, O and Ti
elements.
It has been reported that Al2OC whiskers were observed by
treating bulk Ti3AlC2 at 1250–1300 °C in a furnace with carbon
heater, and the formation and growth of whiskers were believed
to obey a vapor-liquid-solid (VLS) process in Ref. [34]. In the pre-
sent work, the a similar formation process could be described for
the Ti-Al-C-O whiskers growth in this system.
It is worth noting that Ti atoms and C atoms are bonded
through typical strong covalent bonding in the molecular structure
of Ti3AlC2. Based on the above mentioned, the formation process
can be described as follows: Al is only weakly bound in the Al
atomic plane or to Ti via weak binding. Therefore, the migration of
Al3 þ is easier from the Al atomic plane in the layered Ti3AlC2
structure than the migration of Ti4 þ [30]. As a result, Al 3 þ first
migrates from the layered Ti3AlC2 structure, then Al vapor ag-
glomerates and forms Al droplets on the surface of Ti3AlC2, which
serve as a preferred site for deposition of feed from the vapor
causing the liquid to become supersaturated. Secondly, CO and Ti-
carrying gases dissolve into the Al droplets and react with Al to
form amorphous Ti-Al-C-O. At last, liquid Al droplets become su-
persaturated and then Ti-Al-C-O precipitates and forms whisker.
3.2. Microstructure evolution of Al2O3-Ti3AlC2-C refractories
In order to understand the influences of Ti3AlC2 on micro-
structure and phase evolution of Al2O3-Ti3AlC2-C refractories; the
microstructures of Al2O3-Ti3AlC2-C refractories after coked at dif-
ferent temperature were first observed by SEM and TEM.
Fig. 6 shows typical BEI microstructures of the Al2O3-C and
Al2O3-Ti3AlC2-C refractories matrix after cured for 24 h at 220 °C.
In the specimen RTAC-0 with 10 wt% graphite, a continuous gra-
phite matrix is found (as shown in Fig. 7a). In M. Ewais’ viewpoint
[10], the continuous and compressible graphite matrix was at-
tributed to the ability of absorbing the expansion from oxide

Fig. 3. Specimen Ti3AlC2 after fired at 1100 °C in coke bed. (a) BEI of Ti-Al-C-O coating formed in the Ti3AlC2 surface; (b) SEI of Ti-Al-C-O coating formed in the Ti3AlC2
surface.
 J. Chen et al. / Ceramics International 42 (2016) 14126–14134
Fig. 4. Specimen Ti3AlC2 after fired at 1400 °C in coke bed. (a) BEI of Al2TiO5 formed; (b) SEI of Ti-Al-C-O whiskers formed.
Fig. 5. TEM micrographs of specimen Ti3AlC2 coked at 1400 °C, confirmed Ti-Al-C-
O whiskers by HR-TEM equipped with EDS.
grains and excellent thermal shock resistance. The continuous
graphite matrix disappeared when graphite content was lower
than 10 wt%, leading to the rapid deterioration of thermal shock
resistance.
It is noted that continuous graphite matrix has been super-
seded in specimen RTAC-6. The matrix is mainly composed of fine
Al2O3, silicon, Ti3AlC2 and graphite. They could be easily dis-
tinguished by EDS.
Fig. 7 presents microstructures of specimen RTAC-6 after coked
at 1100 °C (Fig. 7a) and 1400 °C (Fig. 7b). And the microstructure
evolution of Si and Ti3AlC2 in the specimen RTAC-6 matrix are
revealed at higher magnification (Figs. 8 and 9). With regard to the
specimens RTAC-6, coked at 1100 °C, a shell (identified as Si-C-O
by EDS analysis) has also been occasionally observed on the un-
reacted Si (Figs. 7a and 8a). In Zhang et al. [15] previous studies;
when Si was used as antioxidant, the result indicated that Si could
be directly oxidized to SiO2 (via the reaction (4)) and indirectly
14129
oxidized via reactions (5) and (6). With the diffusion of CO/N2 in
the real specimen, the SiC could be oxidized to SiO2. So it is con-
sidered that the Si-C-O shell is a mixture of SiC and SiO2 because of
the conversion reaction (6). A reaction layer is formed in the
Ti3AlC2 surface, and the product phases are consistent with the
observations of previous studies on specimen Ti3AlC2.
Si(s) þ2CO(g)-SiO2(s) þ2C(s) (4)
Si(s) þC (s)-SiC(s) (5)
SiC(s) þ2CO(g)-SiO2(s) þ3C(s) (6)
With increase in temperature from 1100 °C to 1400 °C, the
obvious changes lied in the further reaction of Si and Ti3AlC2.
Higher magnification (Fig. 8b) reveals that much more Si-C-O
precipitated on all the Si surfaces. And new product phases (alu-
minum titanate and mullite, Fig. 9b) of Ti3AlC2 are observed in the
matrix. It clearly shows that further decomposition occurs in the
intra of Ti3AlC2 grains with temperature increasing and the further
reaction.
Central voids or pores are only occasionally observed in the
original Ti3AlC2 grains (Figs. 7 and 10). It can be seen that the
Ti3AlC2 particle grains start to decompose. and O and Si diffuse
into the Ti3AlC2 particles, and Al, Ti, Si, C and O can be detected at
the site of the original Ti3AlC2 surface. To investigate the micro-
structure of Ti3AlC2 grain with a shell-core structure, EDS line-
scans were made along the black line (shown in Fig. 10b). The
results reveal that Si concentration decreases and Al concentration
increases near the Ti3AlC2 grain surface. It indicates that Al mi-
grates from the Al atomic plane in the layered Ti3AlC2 structure
while Si element infiltrate into the Ti3AlC2.
The decomposition of Ti3AlC2 could be explained as follows:
First, Al migrated from the Al atomic plane in the layered Ti3AlC2
structure. Then, Si element in the surrounding atmosphere could
infiltrate into the Ti3AlC2 grains through the Al vacancy which led
to the deterioration of Ti3AlC2 grains.
14130 J. Chen et al. / Ceramics International 42 (2016) 14126–14134

Fig. 6. BEI of specimens after curing for 24 h at 220 °C; (a) specimen RTAC-0; (b) specimen RTAC-6.

Fig. 7. BEI of specimen RTAC-6 after coked at different temperature; (a) 1100 °C; (b) 1400 °C.

Fig. 8. Higher magnification BEI of Si phase in specimen RTAC-6 after coked at different temperature; (a) 1100 °C; (b) 1400 °C.

In traditional Al2O3-C refractories where Si is used as an ad- SiC whiskers which appears in the matrix, another type of whisker
ditive, SiC whiskers are formed after coked at 1400 °C and are used is detected in the specimens containing Ti3AlC2. By means of TEM
as ceramic bonding and toughening phase [19]. Compared with equipped with EDS analysis, the whiskers consist of Al, Si, C and O.
specimen RTAL-0 (10 wt% graphite, without Ti3AlC2); besides the Simultaneously, it can be seen that the Al-Si-C-O whiskers possess
 J. Chen et al. / Ceramics International 42 (2016) 14126–14134 14131

Fig. 9. Higher magnification BEI of Ti3AlC2 phase in specimen RTAC-6 after coked at different temperature; (a) 1100 °C; (b) 1400 °C.

Fig. 10. (a) A shell-core structure formed in the site of original Ti3AlC2 grain; (b) higher magnification SEI of surface area in (a). EDS line-scanning profile along the black line
in (b) shown in the image below.

smaller length/diameter (L/D) than that of SiC whiskers (as shown
in Fig. 12).
The relevant reaction and formation process of Al-Si-C-O
whiskers is believed to be similar to that of Ti-Al-C-O whiskers in
specimen Ti3AlC2 (detailed description above). Whisker compo-
nents strongly depend on the different growing space and the
content of gas absorbed in micro regions [39]. The different sur-
rounding atmospheres lead to the diversity of elements in final
whiskers. In real Al2O3-Ti3AlC2-C refractories, the Si-carrying gases
have higher partial pressure than that of Ti-carrying gases. Ulti-
mately, the Si-carrying gases instead of Ti-carrying gases get dis-
solved into the Al droplets and reacts with Al to form amorphous
14132 J. Chen et al. / Ceramics International 42 (2016) 14126–14134

Fig. 11. Specimen RTAL-6 after fired at 1400 °C for 3 h in coke bed. (a) SiAlON formed in the Al-Si-C-O coating; (b) Al-Si-C-O whiskers formed in specimen.

surface tension effects.

3.3. Influence on the mechanical and thermo-mechanical properties

The cold modulus of rupture (CMOR) of the specimens coked at

Fig. 12. TEM micrographs of specimen RTAC-6 coked at 1400 °C, shown Al-Si-C-O
whiskers and SiC whiskers formed in specimen matrix.
Al-Si-C-O whiskers. It is believed that this fabric structure also
contributed to the increased toughness and bond strength.
In the meanwhile, a certain amount of SiAlON (short column,
shown in Fig. 11a, confirmed by EDS) are formed in specimens
containing Ti3AlC2. The formation temperature of SiAlON phase is
higher than coked temperature in our experimental condition
(1400 °C). But some researchers reported that β-SiAlON with pla-
nar shape are formed while using a catalyst (Ni) in Al2O3-C re-
fractories at 1400 °C [35]. The liquid phase formed from molten
alloy Si and catalyst metals are considered to enhance the for-
mation of nitrides at lower temperature.
With regard to the specimen containing Ti3AlC2, Al elements
which migrated from Ti3AlC2 structure have high reactivity, com-
pared to the inert chemistry of Al elements in Al2O3 powder. It is a
preferred source of Al element to form SiAlON phase at low tem-
perature. So the SiAlON phase is also observed, although without
catalytic effects. It is worth noting that short column shape of
SiAlON is preferred as compared to the one dimensional structures
like whiskers and rods. The latter ones are believed to result from
elevated temperatures are shown in Table 2. CMOR of all speci-
mens increases with elevating temperature (except for specimen
RTAC-6 at 1400 °C) due to enhancement of the sintering process
which therefore enhances the bonding [35]. In contrast, the spe-
cimens containing Ti3AlC2 show much higher strengths than that
of specimen RTAC-0 at 220 °C and 1100 °C. The increase of CMOR
while increasing the Ti3AlC2 and reducing graphite is due to the
inherently poor bonding of graphite with oxides in refractories.
Further, a dense coating with a mixture of TiC and Al2O3 formed on
the Ti3AlC2 grain surface contributes to the bond strength of ma-
trix. And the Ti3AlC2 reaction with limited volume expansion at
1100 °C is also conducive to the densification of the specimen
containing Ti3AlC2. It is believed that this microstructure con-
tributes to the higher CMOR results of Al2O3-Ti3AlC2-C refractories
at 1100 °C.
The influence of graphite content on the mechanical properties
is significant in many aspects. On the one hand, the increase in
CMOR with reducing graphite content by using Ti3AlC2 as a sub-
stitute, is due to the inherently poor bonding with oxides in re-
fractories. On the other hand, it has also been demonstrated that
the co-efficient of thermal expansion of carbon-containing re-
fractories decreases with increasing graphite content. The com-
pressible graphite matrix has the ability to absorb the expansion of
oxides grains. As a result, any cracks formed fail to propagate [10].
When the sintering temperature is about 1400 °C, CMOR of
specimen RTAC-2 has the largest value of 14 MPa, compared with
specimen RTAC-0 or other batches specimens with higher Ti3AlC2
content. At 1400 °C, mainly two competitive phenomena develop
to affect CMOR of refractories, namely (i) expansion due to further
oxidations of Ti3AlC2 at higher temperature, and (ii) enhancement
of the bonding due to the formation of SiAlON (short column) and
Al-Si-C-O whiskers. The further oxidation of Ti3AlC2 at 1400 °C (via
to the reaction (2)) leads to larger volume expansion than that of

Table 2
The cold modulus of rupture of specimen after heat-treatment and thermal shock test.

Specimen 220 °C (MPa) 1100 °C  3 h (MPa) 1400 °C  3 h (MPa) Thermal shock test (MPa) (3 cycles, water, 1100–20 °C) The residual CMOR ratio (%)

RTAC-0 5.65(7 0.1) 8.19( 7 1.5) 13.03(7 2.6) 7.00( 71.3) 53.7
RTAC-2 6.54(7 1.3) 8.32( 7 1.1) 14.05(7 1.2) 7.10( 70.5) 50.5
RTAC-4 6.25(7 1.2) 11.15( 7 1.4) 12.33(7 2.1) 6.30( 70.1) 51.1
RTAC-6 6.26(7 0.3) 15.21( 7 1.3) 10.10( 7 0.2) 4.90( 70.5) 48.5
 J. Chen et al. / Ceramics International 42 (2016) 14126–14134
specimens at 1100 °C, which causes mismatch between grain and
matrix and cracks form/propagate. Expansion effects due to fur-
ther oxidation of Ti3AlC2 and change in graphite compete with
enhancement due to formation of SiAlON phase and Al-Si-C-O
whisker, which can even overpass it at 1400 °C. So after coked at
1400 °C, the diversity of CMOR in different specimens may be
considered as a combination of all the above factors.
Further, the decrease of graphite content in the Al2O3-Ti3AlC2-C
refractories unquestionably affected the ability of absorbing and
relieving the stress at elevated temperature. It is worth noting that
the formation of ceramic bond (SiAlON and Al-Si-C-O whiskers)
has positive effects on CMOR. Therefore, the CMOR of specimen
RTAC-2 has the maximum value of 14 MPa due to the above
competitive factors.
As for the thermo-mechanical behavior of the coked speci-
mens, expressed by the residual CMOR ratio after 3 thermal shock
cycles (with water quenching), all compositions with Ti3AlC2 ex-
hibited higher strength losses compared to the regular Al2O3-C
(53.7%, with 10 wt% graphite), as shown in Table 2. But it is to be
noted that the residual CMOR ratio only slightly decreased by
50.5% with 2 wt% Ti3AlC2 and 8 wt% graphite; 51.1% with 4 wt%
Ti3AlC2 and 6 wt% graphite; 48.5% with 6 wt% Ti3AlC2 and 4 wt%
graphite.
A comparison was made with the results reported in Ref. [10],
the decreasing extent becomes much more significant especially
when the graphite content was lower than 5 wt%. The results in
Table 2 demonstrates that the rapid deterioration of strength after
thermal shock test does not occur, although after significantly
decrease in the graphite content (from 10 wt% to 4 wt% graphite).
The limited fall in strength after thermal shock test in our research
is explained by the reduction in the amount of graphite in speci-
mens associated with the in situ formation of Al2TiO5. As it is
known from the literatures [17,36–38], Al2TiO5 exhibits, conse-
quently, an excellent thermal shock resistance.
4. Conclusions
Al2O3-Ti3AlC2-C refractories with low carbon content were
fabricated by using Ti3AlC2 as substitute for partial graphite. The
main results are summarized as follows:
(1) Microstructure development of Ti3AlC2 after coked at 1100 °C
and 1400 °C has been investigated. The deterioration of
Ti3AlC2 when coked at 1100 °C occurred mainly via the reac-
tion Ti3AlC2 þCO-Ti3AlxC2 þ(1  x)/2Al2O3 þ C. A further oxi-
dation occurred at 1400 °C via the reaction Ti3AlC2 þCO-
Ti3  xC2 þ1/2Al2O3 þxTiO2.
(2) The microstructures, mechanical properties and thermal shock
resistance of Al2O3-Ti3AlC2-C refractories fired at different
temperatures were investigated. After coked at 1100 °C, com-
pared to the regular Al2O3-C refractory, the CMOR of specimen
containing 6 wt% Ti3AlC2 markedly increased from 8.19 MPa to
a maximum value of 15.21 MPa. A dense coating of a mixture
of TiC and Al2O3 were formed on the Ti3AlC2 grains boundary
which contributed to the bond strength of the matrix. In ad-
dition, the Ti3AlC2 reaction with limited volume expansion at
1100 °C was also contributed to the densification of the spe-
cimen containing Ti3AlC2. It was believed that this micro-
structure contributes to the higher CMOR results of
Al2O3-Ti3AlC2-C refractories at 1100 °C. Up to 1400 °C, the
addition of Ti3AlC2 played essential roles in the formation of
the Al-Si-C-O whiskers and SiAlON phase. It was believed that
this extra binding phase contributes to the limited deteriora-
tion in thermal mechanical properties of Al2O3-Ti3AlC2-C re-
fractories when carbon content was reduced from 10 to 4 wt%.
14133
(3) It was also found that the CMOR of specimen started to decline
when the Ti3AlC2 content reached up to 6 wt%, owning to the
further oxidation of Ti3AlC2 fired at 1400 °C. To offset these
factors, Ti3AlC2 with finer size may be an alternative.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (51572203) and 973 Program Earlier Research
Project (2014CB660802). The authors would like to thank Mrs. Yu
Zhang and Mr. Changsong Ye who provides carefully helps during
our experiments test. The authors are grateful to Mr. Paul of Indian
institute of technology (IIT) for his helpful discussion and correc-
tion in the manuscript.
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