Enhanced oxidation resistance of low-carbon MgO-C refractories with ternary carbides: a review

Abstract

The demand for low-carbon MgO–C refractories is ever growing to meet the development of advanced steelmaking technologies and efficient energy conservation. Meanwhile, to improve the oxidation resistance and inhibit the weakness of low-carbon MgO–C refractories, antioxidants are necessary. The application of ternary carbides that focused on improving the oxidation performance of MgO–C refractories has been explored, and the ternary carbides including Al4O4C, Al8B4C7, Al4SiC4, Ti2AlC, Ti3AlC2, and Ti3SiC2 have been proved effective. The crystal structure, physical properties, oxidation behavior, and synthesis of these ternary carbides were summarized, and their oxidation mechanism in assisting anti-oxidation of MgO–C refractories was discussed. In addition, the potential aspects related to the usage and development of ternary carbides in low-carbon MgO–C refractories were proposed.

Full text

REVIEW
Enhanced oxidation resistance of low-carbon MgO–C refractories
with ternary carbides: a review
Chao Yu
1
•Bo Dong
1
•Yu-feng Chen
1
•Bei-yue Ma
2
•Jun Ding
1
•Cheng-ji Deng
1
•Hong-xi Zhu
1
•
Jing-hui Di
1
Received: 20 February 2022 / Revised: 20 March 2022 / Accepted: 18 April 2022 / Published online: 17 June 2022
ÓChina Iron and Steel Research Institute Group 2022
Abstract
The demand for low-carbon MgO–C refractories is ever growing to meet the development of advanced steelmaking
technologies and efficient energy conservation. Meanwhile, to improve the oxidation resistance and inhibit the weakness of
low-carbon MgO–C refractories, antioxidants are necessary. The application of ternary carbides that focused on improving
the oxidation performance of MgO–C refractories has been explored, and the ternary carbides including Al
4
O
4
C, Al
8
B
4
C
7
,
Al
4
SiC
4
,Ti
2
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
have been proved effective. The crystal structure, physical properties, oxidation
behavior, and synthesis of these ternary carbides were summarized, and their oxidation mechanism in assisting anti-
oxidation of MgO–C refractories was discussed. In addition, the potential aspects related to the usage and development of
ternary carbides in low-carbon MgO–C refractories were proposed.
Keywords Low-carbon MgO–C refractory Ternary carbide MAX phase Oxidation mechanism Oxidation resistance
1 Introduction
MgO–C refractory materials have been extensively used in
metallurgical vessels and components like lining bricks for
converters, furnace walls for electric arc furnaces, slag
refractory bricks for ladles, and slide plate for sliding gate
[1–3]. The carbon source improves the resistance to ther-
mal shock and slag corrosion of MgO–C refractories [4,5].
However, the molten steel can easily pick up C from tra-
ditional high-carbon MgO–C refractories (up to 20 wt.%)
and thus increases the C content of steel [6]. Consequently,
the demand of high-quality steel products, energy-saving,
carbon neutralization, and carbon peak provides growing
motive to reduce the carbon content in MgO–C refractories
[7–9]. Therefore, improving the oxidation resistance of
low-carbon MgO–C refractories is becoming more crucial.
Extensive and in-depth studies on the promotion of
oxidation resistance of low-carbon MgO–C refractories
have been performed, such as the nanocrystallization of
carbon source [10], the modification of binders or graphite
[11,12], the addition or in situ formation of ceramic
bonded phases [13–15], and the addition of antioxidants
[16]. The most common approach is the application of
antioxidant in the form of metal powders (Al, Si, etc.)
[8,17], alloys (Al–Mg, Si–Al, Si–Fe, etc.) [18,19], car-
bides (SiC, B
4
C, Al
3
C
4
,Cr
7
C
3
, etc.) [11,19,20], and
borides (ZrB
2
, CaB
2
, MgB
2
, etc.) [21,22]. However, the
by-product of these antioxidants like Al
4
C
3
, AlN, etc., may
lead to the disintegration of MgO–C refractories due to the
poor hydration resistance [23,24], while other low-melting
by-products may damage the elevated-temperature perfor-
mance [17,20]. To improve the service performance of
MgO–C refractories, research attention has been focused
on the application of compound additive, but the key
problem of these approaches is poor dispersion and dis-
tribution between the different materials [25].
In order to find a solution, some efforts have been made
to develop alternative antioxidants presenting
&Cheng-ji Deng
cjdeng@wust.edu.cn
&Jing-hui Di
jinghui.di@magmax.cn
1
The State Key Laboratory of Refractories and Metallurgy,
Wuhan University of Science and Technology,
Wuhan 430081, Hubei, China
2
School of Metallurgy, Northeastern University,
Shenyang 110819, Liaoning, China
123
J. Iron Steel Res. Int. (2022) 29:1052–1062
https://doi.org/10.1007/s42243-022-00804-5(0123456789().,-volV)(0123456789().,-volV)

suitable properties but with less drawbacks. Ternary car-
bides possess outstanding properties such as low density,
low thermal expansion coefficient, high strength, excellent
stability under hydration condition, good thermal conduc-
tivity, and high resistance to thermal shock, and the
application of this type of materials focusing on improving
the oxidation performance of MgO–C refractories has been
explored [26–29]. To better understand the advantage and
difference of ternary carbides with traditional antioxidants,
the crystal structure, physical properties, oxidation resis-
tance, and synthesis process of ternary carbides are intro-
duced, and the oxidation behavior and mechanism of
ternary carbides in MgO–C refractories are thoroughly
summarized.
2 Properties of ternary carbides
2.1 Crystal structure
The ternary carbides including Al
4
O
4
C, Al
8
B
4
C
7
,Al
4
SiC
4
,
Ti
2
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
have been proved effective
in assisting anti-oxidation of the MgO–C refractories.
According to the difference of chemical composition, these
ternary carbides can be divided into two types. (1) The
general chemical formula of Al
4
O
4
C, Al
8
B
4
C
7
, and Al
4-
SiC
4
can be written as Al–C–X, where X represents non-
metallic elements oxygen, boron or silicon [30]; (2) Ti
2-
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
are known as MAX phases, of
which the general formula is M
n?1
AX
n
(n= 1–3) where M
represents an early transition metal, A stands for an ele-
ment from groups IIIA or IVA, and X is C or N [31].
Table 1shows the structure parameters and atom types of
the ternary carbide [32–37]. The Al
4
O
4
C has an
orthorhombic crystal structure with the Cmc2
1
space group,
and the crystal system of Al
8
B
4
C
7
,Al
4
SiC
4
,Ti
2
AlC, Ti
3-
AlC
2
, and Ti
3
SiC
2
is consistent with each other
(hexagonal).
In the crystal structure of Al–C–X phase, the interatomic
bonds are mainly covalent. In the case of Al
4
SiC
4
, the
intergrown structure of Al
4
SiC
4
can be viewed as Al
4
C
3
and 4H–SiC units arranged along the alternative c-axis.
Therefore, its structural, electronic, and mechanical prop-
erties are mainly attributed to the strength of the coupling
between each binary carbide [38]. Figure 1shows the
schematic diagram of Al
4
SiC
4
cell structures [39]. The
combination of ionic–covalent interactions is between
layers which are relatively weaker than covalent Si–C
bonds, and that is the reason for the innate character of its
relatively weak compressibility [38–40].
The MAX phases of Ti
2
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
have
both metallic and covalent bonding [41,42]. By compar-
ison, the A-group atoms like Al and Si are the most reac-
tive species because of the relatively weak bonding.
Figure 2shows the charge density contours on the (1120)
plane for Ti
3
AlC
2
and Ti
3
SiC
2
[43]. The charge densities
around C atoms are larger than those around Al/Si atoms,
which demonstrating that the stronger covalent bonding
between Ti and C. Moreover, the crystal structure of Ti
2-
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
can be deemed as alternative
stacking of two layers of edge-sharing Ti
6
C octahedra and
a planar close-packed Al/Si layer [43,44]. Both Ti
3
AlC
2
and Ti
3
SiC
2
belong to 312 phases with the same crystal
(Fig. 3)[44], which are based on layers of hexagonally
close-packed Ti and Al/Si layers with C occupying octa-
hedral centers between the Ti layers.
2.2 Physical properties
The exceptional performances of ternary carbides are
related to their crystal structure. The Al–C–X phase has
excellent properties of low density and high melting point
owing to their strong covalent bonds. For instance, the
density of Al
4
O
4
C is 2.68 g cm
-3
[32], and it will not melt
until up to 1890 °C[45]. The MAX phase (Ti
2
AlC, Ti
3-
AlC
2
, and Ti
3
SiC
2
) is also called metal ceramics because it
has both metallic and covalent bonds; thus, it is a kind of
material with the advantages of high fracture toughness and
high bending resistance of metal as well as high hardness
and high-temperature resistance of ceramics. Table 2
shows the physical properties of these ternary carbides
[33,36,38,40,46–57]. It can be conducted that the ternary
Table 1 Crystal parameter of ternary carbides [32–37]
Ternary carbide Crystal system Hermann Mauguin a/nm b/nm c/nm Reference
Al
4
O
4
C Orthorhombic Cmc2
1
(No.36) 0.5193 0.5193 0.9171 [32]
Al
8
B
4
C
7
Hexagonal P6
3
/mcm (No.193) 0.5906 0.5906 1.5901 [33]
Al
4
SiC
4
Hexagonal P6
3
/mc (No.186) 0.3277 0.3277 2.1676 [34]
Ti
2
AlC Hexagonal P6
3
/mmc (No.194) 0.3040 0.3040 1.3600 [35]
Ti
3
AlC
2
Hexagonal P6
3
/mmc (No.194) 0.3075 0.3075 1.8580 [36]
Ti
3
SiC
2
Hexagonal P6
3
/mmc (No.194) 0.3070 0.3070 1.7690 [37]
Enhanced oxidation resistance of low-carbon MgO–C refractories with ternary carbides: a review 1053
123

carbides have superior mechanical and thermal properties,
such as high flexural strength, fracture toughness, hardness,
Young’s modulus, thermal conductivity, and low thermal
expansion coefficient. By contrast, the MAX phases have
even more excellent fracture toughness due to their
metallic bonds, while Al–C–X phase has lower thermal
expansion coefficient and higher hardness because of the
covalent bonding. It is noteworthy that Ti
3
SiC
2
has the
maximum melting point (*3000 °C) of all these ternary
carbides. In Ti
3
SiC
2
, the adjacent covalent bond chains of
Ti–C–Ti–C–Ti–Si form a chain couple with a length equal
to the c-direction dimension, and the chains are bonded
together by inhomogeneous metallic bonds; this specific
bonding nature contributes to its high melting point [58].
Compared with Al
4
C
3
and AlN, these ternary carbides
have excellent hydration resistance. Specifically, the Al
4
C
3
was hydrated rapidly under the water vapor environment,
while only a trace of hydration was found for Al
4
O
4
C and
Al
4
SiC
4
in the same condition [23,24]. The MAX phase is
recommended for usage in nuclear reactors as accident
tolerant fuel coatings, owing to its potential application in
high-temperature water vapor environment [59,60]. Fig-
ure 4shows the mass gain of the Ti
2
AlC and Ti
3
AlC
2
after
corrosion tests in static supercritical water (Pressure
P= 25 MPa, oxygen content B20 910
-9
) at 500 °C
[60]. The results show that the Ti
2
AlC and Ti
3
AlC
2
have
good corrosion resistance in the water vapor atmosphere
with high temperatures, and the corrosion mass gain and
corrosion time obeyed the linear rate law.
2.3 Oxidation of ternary carbide powders
The fundamental principle of antioxidants in carbon-con-
taining refractories is to inhibit the oxidation of carbon by
means of its priority reaction with oxygen. The oxidation
products can also fill the internal porosity, which improve
the density of refractories and slow down the oxidation. Li
et al. [11] reported that the graphite flakes with a particle
size of B74 lm begin to be oxidized at about 500 °C, and
the carbon black smaller than 15 lm shows obvious
oxidative mass loss above 600 °C[26]. The oxidation
resistance of ternary carbide powders is displayed in
Table 3[37,61–65]. Compared with common antioxidants
such as aluminum powder (D
50
=18lm, T
S
= 490 °C,
where D
50
means the median diameter, and T
S
represents
the starting oxidation temperature) [66], silicon powder
(B44 lm, T
S
= 500 °C) [67], and boron carbide powder
(D
50
= 22.5 lm, T
S
= 540 °C) [68], the Al–C–X phase
powders have better high-temperature stability in air due to
its strong covalent bonds, and they will not be oxidized
until 700–820 °C, while the oxidation of the MAX phase
powders begins at about 400–450 °C, which indicates that
they are comparably more susceptible to oxidation.
Fig. 1 Schematic diagram of Al
4
SiC
4
(a), 4H–SiC (b), and Al
4
C
3
(c) cell structures [39]
Fig. 2 Valence charge density of Ti
3
SiC
2
(a) and Ti
3
AlC
2
(b)[43]
Fig. 3 Crystal structures of Ti
3
SiC
2
and Ti
3
AlC
2
.aConventional cell;
bsupercell used to model defect configurations [44]
1054 C. Yu et al.
123

Although the powder with smaller particle size is easily
oxidized due to the high specific surface area, it can be
determined that the affinity of the Al–C–X phase powders
for oxygen is less than that of graphite or carbon black,
while the MAX phase powders have stronger oxygen
affinity than the carbon source. In fact, these ternary car-
bides function in different reactions and mechanisms for
MgO–C refractories, and the main oxidation reaction in
MgO–C refractories is the Al–C–X phase with CO(g) or
the MAX phase with O
2
(g).
It is believed that Al
2
O
3
firstly generated on the surface
of the Al–C–X phase powders, which is caused by the
lower strength of Al–C bonds. With the continuous pro-
ceeding of oxidation reaction, the intermediate products of
Al
8
B
4
C
7
or Al
4
SiC
4
will further react to produce novel
compounds, such as Al
18
B
4
O
33
or mullite. For MAX
phases, the Ti–C bonds have higher strength than that of
the Ti–Al bonds in Ti
2
AlC and Ti
3
AlC
2
, and the oxygen
adsorption energy of Al atomic layer is much higher than
that of Ti atomic layer [69]. Consequently, TiO
2
is the
radically oxidative product during the preliminary stage of
oxidation in Ti
2
AlC and Ti
3
AlC
2
. Besides that, Zhao et al.
[70] investigated the defect properties of Ti
3
SiC
2
by using
the first-principles calculations. The result indicates that
the most abundant native defects in Ti
3
SiC
2
are Si and C
vacancies (V), and the Si atom is the most weakly bonded,
which gives rise to the lowest formation energy of V
Si
. The
vacancy was usually substituted by O atoms under O-rich
environments [42], which means that Si atoms in Ti
3
SiC
2
are easily substituted by O atoms.
For the oxidation behavior of ternary carbides, the
experimental results show that the mass gain of ternary
carbide powders has a similar parabolic relation with the
increasing temperature in air, which suggests that the
oxidation process of ternary carbides is mainly controlled
by diffusion. And a kinetic model, which is called real
physical picture model (RPP model), is often used to
analyze and calculate the oxidation activation energy of
ternary carbides [62,63]. Figure 5shows the isothermal
oxidation data of Al
4
SiC
4
powder and the calculated curves
from RPP model in the temperature range of 800–1400 °C
for 2 h in air [62]. It is found that the RPP model has good
fit and low calculation error with original data. The growth
rate of Al
4
SiC
4
powder increases gradually to its maximum
with increasing oxidation time at 1400 °C. It should be
Table 2 Physical properties of ternary carbides [33,36,38,40,46–57]
Ternary carbide Al
8
B
4
C
7
Al
4
SiC
4
Ti
2
AlC Ti
3
AlC
2
Ti
3
SiC
2
Density/(g cm
-3
) 2.69 [46] 3.03 [48] 4.11 [50] 4.25 [53] 4.52 [56]
Flexural strength/
MPa
500 [47] 297.1 ±22 [49] 432 ±12 [50] 630 ±20 [53]; 500
[54]
260 ±20 [56];
410 ±25 [57]
Fracture
toughness/(MPa
m
1/2
)
3.9 [46]; 2.3 [47] 3.98 ±0.05 [49] 6.5 ±0.2 [50] 7.35 [54] 11.2 ±0.5 [57]
Hardness/GPa 12.1 [46]; 15.2
[47]
10.6 ±1.8 [49] 5.8 ±0.5 [50] 5.7 ±0.5 [53]; 5.26
[54]; 6.55 [55]
4[56,57]
Young’s modulus/
GPa
136.6 [46] 302.4 [40] 277.6 ±0.7 [51] 221.5 ±4[55] 343 [51]; 320
[56]; 283 [57]
Thermal expansion
coefficient/°C
-1
6.67 910
-6
[46]
(RT–1200 °C)
7.16 910
-6
[38] (RT–1200 °C);
6.2 910
-6
[49] (200–1450 °C)
(9.2 ±0.1) 910
-6
[52] (RT–1200 °C)
(9.0 ±0.1) 910
-6
[52] (RT–1200 °C)
10
-5
[56] (RT–
1000 °C)
Thermal
conductivity/(W
m
-1
K
-1
)
29.2 [46]80[38]27[50] 22.9 [55]43[56]
Melting point/°C[1830 [33][2080 [48] 1625 [36] 1360 [36] 3000 [56]
0 102030405060708090100110
0
2
4
6
8
10
12
14
t/h
W/A/(μg mm-2)
Ti
2
AlC
R
2
=0.9940
Ti
3
AlC
2
R
2
=0.9972
Δ
Fig. 4 Mass gain per unit area versus time for oxidation of Ti
3
AlC
2
and Ti
2
AlC in static supercritical water [60]. DW—Mass change of
samples after corrosion tests; A—total surface area of sample; t—
corrosion time; R
2
—coefficient of determination
Enhanced oxidation resistance of low-carbon MgO–C refractories with ternary carbides: a review 1055
123

noted that the oxidation behavior of ternary carbides
exhibits different characteristics. For example, the mass
gain during the oxidation of Al
8
B
4
C
7
increases rapidly and
reaches its maximum at around 1200 °C, and then obvious
mass loss happened due to the volatilization of B
2
O
3
(g),
but no mass losses occurred during the oxidation of Al
4-
SiC
4
,Ti
2
AlC, or Ti
3
AlC
2
powders.
3 Enhanced oxidation resistance of MgO–C
refractories
The function mechanism of different kinds of ternary car-
bides in MgO–C refractories exhibits differences. The
oxidation behavior and mechanism of Al
4
O
4
C in MgO–C
refractories have been analyzed [26]. As shown in Fig. 6,
the T
S
value of the mixture of Al
4
O
4
C?graphite is higher
than that of single graphite, revealing that the oxidation of
C is delayed with Al
4
O
4
C addition. Under the oxidizing
conditions with carbon phases, Al
4
O
4
C initially reacts with
CO to form Al
2
O
3
and C according to Eq. (1). Once alu-
mina is formed, it further reacts with MgO to form
MgAl
2
O
4
via Eq. (2). The MgAl
2
O
4
protective layers of
MgO–C refractories can inhibit the further oxidation of the
C and therefore enhance the oxidation resistance. Aside
from the effect of restricting the oxidation of MgO–C
refractories, as Al
4
O
4
C itself is a carbide, carbon phase is
left behind when alumina generates via Eq. (1); thus, the
cavity structure does not form in the refractories. As a
result, the thickness of decarbonization layers of the
specimens containing Al
4
O
4
C is almost the same as that of
the Al-containing ones.
Al4O4CsðÞþ 2CO gðÞ¼2Al2O3sðÞþ 3C sðÞ ð1Þ
Al2O3sðÞþ MgO sðÞ¼ MgAl2O4sðÞ ð2Þ
Different from Al
4
O
4
C, a denser protective layer con-
sisting of 3MgOB
2
O
3
and MgAl
2
O
4
is generated on the
surface of MgO–C refractories with Al
8
B
4
C
7
addition
[27,71]. Similar to the Al
4
O
4
C, Al
8
B
4
C
7
is considered to
Table 3 Oxidation resistance of ternary carbide powders [37,61–65]
Ternary carbide Particle size/lmT
S
/°CT
C
/°C Final product after oxidation at T
C
Activation energy/(kJ mol
-1
) Reference
Al
4
O
4
C*10 *820 *1250 Al
2
O
3
(s) – [37]
Al
8
B
4
C
7
5–20 *700 *1100 Al
18
B
4
O
33
(s), B
2
O
3
(s) 25.8 [61]
Al
4
SiC
4
6.5–13.3 *800 *1400 Mullite(s), Al
2
O
3
(s), SiO
2
(s) 176.9 (800–1100 °C),
267.1 (1300–1400 °C)
[62]
Ti
3
AlC
2
*5.96 *450 *900 Al
2
O
3
(s), TiO
2
(s) (rutile) 156.45 (450–600 °C),
247.75 (700–900 °C)
[63]
Ti
2
AlC *10 *400 *1040 Al
2
O
3
(s), TiO
2
(s) (rutile) – [64]
Ti
3
SiC
2
–*400 *1150 SiO
2
(s), TiO
2
(s) (rutile) – [65]
T
C
—Complete oxidation temperature
Fig. 5 Isothermal oxidation data (black line) of Al
4
SiC
4
powder and
calculated curves from RPP model (red dash line) in temperature
range of 800–1400 °C for 2 h in air [62]. Dm—Mass change; m
0
—
original mass of sample; DE
d
—apparent activation energy
400 600 800 1000 1200 1400
0
20
40
60
80
100
120
Temperature/°C
TG/%
(c) Al
4
O
4
C+Graphite oxidation
(b) Al
4
O
4
C oxidation
(a) Graphite oxidation
Fig. 6 Thermogravimetric (TG) curves of specimens heated to
1500 °C in flowing air [26]
1056 C. Yu et al.
123

react with CO to produce Al
2
O
3
,B
2
O
3
, and carbon at the
beginning (Eq. (3)). Al
2
O
3
and B
2
O
3
further react with
MgO to form MgAl
2
O
4
and 3MgOB
2
O
3
, engendering a
liquid phase when it coexists with MgO at about 1300 °C.
The coexistence of MgAl
2
O
4
and liquid phase makes the
protective layer denser, thus restricting their oxidation.
Figure 7shows the thicknesses of the decarbonization layer
of MgO–C refractories treated at various temperatures. The
results show that the oxidation resistance of specimen with
Al
8
B
4
C
7
powder was better than that of the specimens with
Al or Al ?B
4
C composite antioxidants. Furthermore, the
high-temperature performance of refractories is better
promoted when the antioxidant layer contains both
3MgOB
2
O
3
and MgAl
2
O
4
composites [20].
Al8B4C7sðÞþ 18CO gðÞ¼4Al2O3sðÞþ 2B2O3lðÞþ
25C sðÞ
ð3Þ
For Al
4
SiC
4
antioxidant, Zhang and Yamaguchi [28]
concluded that Al
4
SiC
4
will initially react with CO to form
Al
2
O
3
, SiC, and C at temperatures above 1000 °C, as
shown in Eq. (4). The formed Al
2
O
3
and SiC further react
with CO to form mullite (Al
6
Si
2
O
13
) and carbon via
Eq. (5). In such a manner, the Al
2
O
3
–SiO
2
protective
layers were generated on the surfaces of MgO–C speci-
mens. Compared with silicon powder, there will be less
low melting phase in MgO–C refractories with the addition
of Al
4
SiC
4
[17]. However, Yao et al. [72] found that no
mullite phase was detected in MgO–C matrix with Al
4
SiC
4
addition by X-ray diffractometer. The MgAl
2
O
4
and SiC
(only in the open pores) are generated after the oxidation
test at 1500 °C, while the SiC will be formed in both open
and closed pores at 1600 °C. For a better understanding of
the oxidation, the cross section and element distribution of
Al
4
SiC
4
crystals were introduced, as shown in Fig. 8. The
outer layers of the Al
4
SiC
4
particle mainly consist of Mg,
Al, and O elements, while the internal layers are mainly
composed of Si, C, and a trace of Al element. These results
indicate that the migration of Al from interior to exterior is
much rapider than that of Si in Al
4
SiC
4
crystals at high
temperature. Such migration behavior leads to the gener-
ation of alumina and silica on the surface of Al
4
SiC
4
;
meanwhile, some magnesium aluminate spinel phase
formed by Al
2
O
3
and MgO are also detected on the Al
4-
SiC
4
surface due to abundant MgO. This is the reason why
no mullite is detected with an X-ray diffractometer while
massive MgAl
2
O
4
is found.
Al4SiC4sðÞþ 6CO gðÞ¼2Al2O3sðÞþ SiC sðÞþ 9C sðÞ
ð4Þ
3Al2O3sðÞþ 2SiC sðÞþ 4CO gðÞ¼
Al6Si2O13 sðÞþ 6C sðÞ ð5Þ
Compared with Al–C–X phases, the layered structures
of MAX phases are similar to that of graphite [73–75].
Chen et al. [76] concluded that Ti
3
AlC
2
can act as an
alternative carbon source in low-carbon MgO–C refracto-
ries. However, Ti
3
AlC
2
is inappropriate for MgO–C
refractories as a single antioxidant due to the high volume
expansion at high temperature, which had a negative effect
on the density of refractories. The combination of Ti
3
AlC
2
and silicon could restrict both oxidation of refractories and
excessive expansion of MAX phase. Because silicon has a
higher affinity to O
2
than that of Ti
3
AlC
2
and reacted first
as the antioxidant, Ti
3
AlC
2
remained in the refractories,
and enhanced properties are achieved. Cai [29] studied the
influence of Ti
2
AlC, Ti
3
AlC
2
, and Ti
3
SiC
2
on the oxidation
resistance of low-carbon MgO–C refractories. Different
from other oxidation resistance experiments, the specimens
were first subjected to heat treatment at 1100 °C for 3 h in
a sagger filled with coke grit. It is concluded that the
oxidation process of MgO–MAX–C refractories is con-
trolled by the diffusion process, and the M and X atoms
diffuse outward at high temperatures, whereas oxygen
atoms diffuse inward. When oxygen diffuses into the
refractory, M and X atoms will immediately react with it.
Table 4shows the area of decarbonization layer, oxidation
layer, and intact layer in MgO–C refractory samples with
different MAX phases, and the results show that the oxi-
dation resistance of MgO–C refractories is enhanced by
MAX phases only at 1500 °C. This is because Ti, Al, Si,
and other elements in MAX phase were decomposed and
have not reached the reaction temperatures with other
substances at 1100 °C.
Figure 9shows the cross section of oxidation specimens
with Ti
3
AlC
2
addition [29]. The specimen has obvious
Fig. 7 Thickness of decarbonization layer of MgO–C samples heated
at different temperatures for 3 h in air [27]
Enhanced oxidation resistance of low-carbon MgO–C refractories with ternary carbides: a review 1057
123

oxidation at 1100 °C, and the area of the intact layer is only
24.3%. At 1300 °C, the decarbonization layer of specimen
expands continuously. The oxidation boundary of MgO–C
is obvious at 1500 °C, and the combination of TiO
2
–Al
2
O
3
protective layers could well protect the interior of the
refractories from oxidation. The surface images of
Fig. 8 Energy-dispersive spectrometry mapping of cross section oxide scale of Al
4
SiC
4
crystal at 1600 °C[72]
Fig. 9 Cross section of specimens with Ti
3
AlC
2
addition after oxidation at 1100–1500 °C[29]
Table 4 Oxidation analysis of MgO–C refractories at 1100–1500 °C[29]
Oxidization temperature/°C Additive Decarbonization layer/% Oxidation layer/% Intact layer/% Total area/%
1100 Ti
2
AlC 53.9 24.6 21.5 100
Ti
3
AlC
2
47.7 28.0 24.3 100
Ti
3
SiC
2
48.4 33.0 18.6 100
No additive 31.4 24.9 43.7 100
1300 Ti
2
AlC 54.8 21.2 24.0 100
Ti
3
AlC
2
56.4 14.7 28.9 100
Ti
3
SiC
2
60.3 15.5 24.2 100
No additive 56.0 – 44.0 100
1500 Ti
2
AlC 53.6 – 46.4 100
Ti
3
AlC
2
47.1 – 52.9 100
Ti
3
SiC
2
36.3 – 63.7 100
No additive 56.3 12.1 31.6 100
1058 C. Yu et al.
123

oxidation specimens containing different particle sizes of
Ti
3
AlC
2
were further studied, as shown in Fig. 10 [29]. The
specimen with Ti
3
AlC
2
(D
50
= 20.7 lm) produces large
cracks during oxidation at 1100 °C, which increases the
channels for oxygen diffusion (Fig. 10a). The cracks in
oxidation specimen can be effectively decreased by
reducing the particle size of Ti
3
AlC
2
powder at the same
temperature (Fig. 10b). As the temperature rises to
1300 °C, the protective layer formed by Ti
3
AlC
2
in MgO–
C refractories becomes denser and plays a role in healing
cracks (Fig. 10c).
Based on above-mentioned investigations, two distin-
guished mechanism of Al–C–X and MAX ternary carbides
on the low carbon MgO–C refractories can be found: for
the Al–C–X phase, the antioxidant property is enhanced by
the dense oxidation layer formed on the surfaces of the
refractories at elevated temperatures, and when Al–C–X
phase reacts with CO, the generated C fill the vacancies
due to the oxidation; the MAX preferentially reacts with O
2
than C. The formed oxides can also fill the internal pores,
which improves the density of refractories and slows down
the oxidation. However, excessive expansion will increase
the porosity with increasing the MAX amount, leading to
the decreased antioxidant property. Therefore, the optimum
amount of MAX phase and appropriate combination with
other antioxidants are effective ways for the improvement
in anti-oxidation of MgO–C refractories.
4 Synthesis of ternary carbides
Except as an antioxidant, ternary carbides are also used in
the preparation of porous ceramics and carbon composite
refractories [77–82]. The key to restrict the application of
ternary carbides is their synthesis cost. Therefore, it has
great significance to understand the synthesis process of
ternary carbides for its large-scale industrial production in
the future. Frequently, ternary carbides are synthesized by
hot-press sintering or spark plasma sintering, and finally,
the dense ceramics are prepared [83,84]. However, for the
purpose of the addition to refractories, it is necessary to
crush the ternary carbide ceramic into powders. The con-
venient process is to directly synthesize ternary carbide
powders or prepare them into ceramic materials with low
strength, so that they can be easily treated as powders in the
later stage. Table 5shows some synthesis methods of
ternary carbide powders [26,47,53,63,85–99]. The
synthesis methods of ternary carbide powders mainly
include carbothermal reduction, solid-state reaction, mol-
ten salt synthesis, self-propagating high-temperature syn-
thesis (SHS), microwave sintering, and mechanically
induced self-propagating reaction. It is noteworthy that
most synthesis processes require high-purity chemicals as
raw materials, leading to a higher cost.
It is an important way for the cost reduction of the
ternary carbides by utilization of natural raw minerals and
decreasing of both the synthesis temperature and synthesis
time. For instance, ternary carbides can be synthesized at
low temperatures (\1250 °C) by utilizing molten salt
synthesis. At high temperatures, all reactants are in the
molten salt when they were completely melted, which
enlarges the total contact surface and reduces the distance
between reactants. Liu et al. [91] synthesized Al
8
B
4
C
7
at
1250 °C by using NaCl–NaF salts, and the results revealed
that it has irregular morphologies and average size of about
200 nm. The sintering temperature could also be decreased
by selecting sintering aids. Yamamoto et al. [89] obtained
the Al
4
SiC
4
at 1200 °C by adding triethanolamine. The
additive modifies the surface of Al and Si, forming a thin
layer of Al–C and Si–C; as a result, the direct reaction of
Al and Si with C is induced. Compared with other synthesis
processes, high-purity ternary carbides can be produced by
using self-propagating high-temperature synthesis in a very
short time (a few minutes). It is mainly attributed to the
utilization of highly exothermic chemical reactions, when
the released heat further promotes the reaction. For
Fig. 10 Surface image of specimens containing Ti
3
AlC
2
with different particle sizes after oxidation at 1100–1300 °C. aMC-3AC,
D
50
= 20.7 lm; b,cA, D
50
=12lm[29]
Enhanced oxidation resistance of low-carbon MgO–C refractories with ternary carbides: a review 1059
123

example, by using SHS methods, Al
4
SiC
4
powders are
synthesized at 1200 W power in 2 min [95].
Although these methods can reduce the sintering tem-
perature or the holding time, the yield of ternary carbides is
still low due to the process limitations. What is more,
security issues may exist when the raw material contains
some metal powders with high activity, such as Al pow-
ders. Therefore, using low-cost raw materials and selecting
carbothermal reduction method have great advantages in
the synthesis of low-cost and high-purity ternary carbides.
For example, bauxite has been successfully used for the
synthesis of Al
4
SiC
4
[87]. Besides that, TiO
2
, SiO
2
, and C
can be used for the synthesis of Ti
3
SiC
2
[88].
5 Conclusions and prospect
This paper summarized the applications of ternary carbide
usage as antioxidants in low-carbon MgO–C refractories.
The exceptional performances and oxidation behavior of
ternary carbides are closely related to their crystal
structure. The Al–C–X phase have excellent properties of
low density and high melting point owing to their strong
covalent bonds, while the MAX phase has both metallic
and covalent bonds with the advantages of high fracture
toughness, high bending resistance as well as high hard-
ness. Two distinguished oxidation mechanism of Al–C–X
and MAX ternary carbides in assisting anti-oxidation of the
MgO–C refractories are discussed. Besides that, the
refractories achieve self-healing depending on the carbon
produced by decomposition of ternary carbides. Currently,
the major problem in the industrialization of ternary car-
bides lies in the cost, which calls for a new synthesis
method of ternary carbides with low cost, security, and
high efficiency in mass production. To be better prepared
for their industrialization, some suggestions for the future
directions are listed below:
It is an important way for the cost reduction of the
ternary carbides by utilization of natural raw minerals
and decreasing of both the synthesis temperature and
synthesis time. Thus, relative research on their synthesis
methods can be very helpful for their industrialization.
Table 5 Synthesis process of ternary carbide powders [26,47,53,63,85–99]
Synthesis method Ternary
carbide
Raw material Sintering system Reference
Carbothermal reduction Al
4
O
4
Ca-Al
2
O
3
, carbon black 1700 °C, 2 h, Ar [26]
Al
8
B
4
C
7
Al, B
2
O
3
, activated carbon 1800 °C, 2 h, Ar [85]
Al
4
SiC
4
Al
2
O
3
, SiO
2
, graphite 1900 °C, 8 h, Ar [86]
Calcined bauxite, silica, carbon
black
1800 °C, 3 h, Ar [87]
Ti
3
SiC
2
TiO
2
, SiO
2
, graphite 1527 °C, 1.5 h, Ar [88]
Solid state reaction Al
4
O
4
Ca-Al
2
O
3
, Al, carbon black 1700 °C, 2 h, Ar [26]
Al
8
B
4
C
7
Al, B
4
C, graphite 1600 °C, 1 h, Ar [47]
Al
4
SiC
4
Al, Si, graphite 1800 °C, 3 h, Ar [63]
Al, Si, carbon black,
triethanolamine
1200 °C, 6 h, Ar [89]
Ti
3
AlC
2
Ti, Al, TiC 1300 °C, 0.5 h, Ar [53]
Ti
3
SiC
2
Ti, Si, TiC 1250 °C, 2 h, vacuum [90]
Molten salt synthesis Al
8
B
4
C
7
Al, B
4
C, carbon black 1250 °C, 6 h, Ar (NaCl–NaF) [91]
Ti
2
AlC Ti, Al, graphite 1100 °C, 1.5 h, Ar (NaCl–
KCl)
[92]
Ti
3
AlC
2
Ti, Al, cetylene black 1000 °C, 2 h, Ar [93]
Ti
3
SiC
2
Ti, Si, Al, C 1250 °C, 1 h, air (KBr) [94]
SHS Al
4
SiC
4
Al, Si, carbon black 1200 W, 2 min, Ar
(1361 °C)
[95]
Ti
3
AlC
2
Ti, Al, graphite 1673 °C, vacuum [96]
Ti
3
SiC
2
Ti, Si, graphite 1000 W, Ar [97]
Microwave sintering Ti
3
AlC
2
TiH
2
, Al, graphite 1300 °C, 0.5 h, Ar [98]
Mechanically induced self-propagating
reaction
Ti
3
SiC
2
Ti, TiC, SiC, Al 1380 °C, 1 h, vacuum [99]
1060 C. Yu et al.
123

The size and the morphology of the ternary carbides are
of great importance on the service performance of MgO–
C refractories. Their control methods by particle size,
sintering parameters, and sintering additives in relation
to their service performance need to be investigated.
The future research can be focused on the more cost-
efficient synthesis method of ternary carbides, the in-situ
ternary carbides in low-carbon MgO–C, the appropriate
combination of ternary carbides with other antioxidants,
and the replacement of carbon phases with ternary car-
bides, etc.
Acknowledgements The authors acknowledge the financial support
from the National Natural Science Foundation of China (U20A20239)
and Natural Science Foundation of Hubei Province (2020CFB692).
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