Ceramics International 43 (2017) 7177–7183

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Ceramics International
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Mechanical behavior and thermal shock resistance of MgO-C refractories: MARK

Influence of graphite content
⁎ ⁎
Tianbin Zhua,b, , Yawei Lia, , Shaobai Sanga, Zhipeng Xieb
a
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
b
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

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

Keywords: The mechanical and thermo-mechanical properties of MgO-C refractories are of major importance in the
Mechanical behavior industrial applications, and highly depend on the optimization of their microstructural design. In the present
Thermal shock resistance work, the influence of flaky graphite content on mechanical behavior and thermal shock resistance of such
Graphite refractories was investigated with the aid of the wedge splitting test, fractal and microscopic fractographic
MgO-C refractories
analysis. The results showed that the increase of graphite content in the specimens led to an enhanced non-
linear fracture behavior, a reduced nominal notch tensile strength (σNT), and a higher specific fracture energy
(Gf), characteristic length (lch) and thermal shock resistance parameter (Rst). The fractal analysis of the crack
propagation path of the specimens after the wedge splitting test indicated that increasing graphite content in the
refractories can enhance their irregularity of the crack propagation path during fracture. Also, it was suggested
from microscopic fractographic analysis that the improvement of thermal shock resistance of MgO-C
refractories was positively correlated with the increase of interface crack propagation.

1. Introduction expanded graphite, viewed as a three dimensional network composed

MgO-C refractories have been extensively used as the working
lining of steelmaking vessels such as electric furnaces, converters and
ladles for more than three decades [1–3]. Usually, such refractories
withstand a broad range of temperatures (from room temperature to
1600–1700 °C) under operation, and undergo severe thermal shock
cycles. In fact, the achievement of excellent mechanical and thermo-
mechanical properties of the refractories depends not only on the
original design but also on the microstructural and chemical changes
produced by the thermal conditions of the system.
Much effort has been performed to improve the performance of
such refractories, including the treatment of magnesia particles, the
selection of nanocarbons, and the graphitization of pyrolytic carbon
from the binders as well as the incorporation of various additives. For
instance, Kakihara et al. [4] developed MgO-C refractories with high
spalling resistance by making the thin layers composed of organic
compound around the magnesia particles to absorb the thermal
expansion of magnesia. Recently, different kinds of nanocarbons such
as carbon black (CB) [5–8], carbon nanotubes (CNTs) [9] and
graphene oxide nanosheets (GONs) [10] were used to replace flaky
graphite partly to develop nano-structured matrix for such refractories
with outstanding mechanical and thermomechanical properties. Also,
of numerous GONs, was incorporated into MgO-C refractories to
improve their comprehensive properties [11–13]. As for the graphiti-
zation of pyrolytic carbon from the binders during the heat-treating
process or in service, some work was also reported in the past years
[14,15]. For example, Wei et al. [16] used Fe nanosheets to catalyze the
phenolic resin in such refractories and found that their thermal shock
resistance and cold modulus of rupture were obviously enhanced
compared with the specimens without the catalyst. In our previous
studies, the addition of Ni-containing catalyst led to the in-situ
formation of various nanocarbon structures (such as CNTs and
nanocarbon onions) in such refractories and thus improved their
mechanical strength and thermal shock resistance [17,18].
Furthermore, the in-situ formation of ceramic phases from the
incorporation of different additives, as another important approach
for the improvement of mechanical and thermo-mechanical of the
refractories, has been reported by some investigators [19–22].
Generally, most investigators focus mainly on the measurement of
cold modulus of rupture and cold crushing strength of MgO-C
refractories by three-point bending test and compression test, respec-
tively, whereas their mechanical fracture behavior was not well noticed
even if it was of great importance to develop such refractories with high
performance. In addition, concerning the thermal shock resistance of

⁎
Corresponding authors at: The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China.
E-mail addresses: zhutianbin@aliyun.com (T. Zhu), liyawei@wust.edu.cn (Y. Li).

http://dx.doi.org/10.1016/j.ceramint.2017.03.004
Received 19 January 2017; Received in revised form 1 March 2017; Accepted 1 March 2017
Available online 02 March 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
T. Zhu et al.
the refractories, it is often evaluated only by measuring the residual
strength and calculating the residual strength ratio after various
thermal shock cycles [23]. Actually, this method is time-consuming
and the large data error is also easily obtained; meanwhile, it can only
characterize qualitatively the thermal shock resistance of such refrac-
tories. Therefore, Harmuth et al. [24,25] firstly introduced the char-
acteristic length (lch, proportional to the R‴′ parameter and inversely
proportional to a brittleness number) to evaluate the resistance of the
refractories against to crack initiation and propagation owing to
thermal shocks; the lch value can be achieved by calculating the results
from the wedge splitting test according to Tschegg [26,27]. Moreover,
the mechanical fracture behavior of the refractories can be determined
by this test. In the past years, this approach was extensively used to
characterize the mechanical behavior of refractory products (such as
magnesia bricks, magnesia-spinel bricks, Al2O3-MgO castables, etc.)
and to further evaluate their thermal shock resistance [28–32]. So, in
the present work, the mechanical behavior and thermal shock resis-
tance of MgO-C refractories containing various graphite content were
characterized by the wedge splitting test, fractal and microscopic
fractographic analysis with the aim to provide a promising approach
for preparing such refractories with high performances.
2. Experimental
2.1. Preparation of MgO-C specimens
Fused magnesia (3–1 mm, 1–0.5 mm, 0.5–0 mm and < 45 µm, 98 wt
% MgO, Dashiqiao, China), metallic Al ( < 45 µm, 98 wt% Al, Xinxiang,
China), Si powder ( < 45 µm, 98 wt% Si, Anyang, China), and flaky graphite
(FG, < 74 µm, 97.5 wt% fixed carbon, Qingdao, China) were used as raw
materials. Thermosetting phenolic resins, one in liquid form (36 wt% of
carbon yield, Wuhan, China) and one in powder form (55 wt% carbon yield,
Wuhan, China) were used as binder. Different MgO-C compositions were
formulated by changing flaky graphite contents. The investigated MgO-C
compositions are listed in Table 1. All the compositions were mixed for
15 min in an Eirich mixer with a rotating speed of 900 r/min. After mixing,
the specimens (230 mm×114 mm×75 mm) were compacted under a
pressure of 630 t and then cured at 200 °C for 24 h. Then, MgO-C
specimens with various shapes and sizes were cut and processed according
to the requirements of different performance tests. For example, bar shaped
specimens (25 mm×25 mm×140 mm) were for the three-point bending
and modulus of elasticity tests, and columnar specimens (Φ10
mm×50 mm) were used to determine coefficient of thermal expansion.
Also, the specimens for the wedge splitting test (75 mm×100 mm×
100 mm) were achieved, whose specific geometry can be seen in other
work [32]. Finally, all the as-prepared specimens were treated at a heating
rate of 5 °C/min to 1400 °C for 3 h in a sagger filled with coke grit.
2.2. Testing and characterization methods
The crystallographic phases of the coked specimens were detected
Table 1
The compositions of MgO-C refractories containing different graphite content.
Raw materials Specimens (wt%)
S-G1 S-G5 S-G10
Fused magnesia aggregate 70 70 70
Magnesia powder 26 22 17
Flaky graphite 1 5 10
Si powder 1 1 1 1
Metallic Al 2 2 2 2
Resin powder +1 +1 +1
Liquid phenolic resin +4 +4 +4
Ceramics International 43 (2017) 7177–7183
by X-ray diffractometry (XRD) (X′ Pert Pro, Philips, Eindhoven, The
Netherlands); using Ni filtered, Cu Kα radiation at a scanning rate of
6 °/min and a temperature of 16 °C. The microstructural observation of
fracture surfaces was performed with the aid of field emission scanning
electron microscopy (FESEM, Nova 400 NanoSEM, FEI Company,
USA) coupled with energy dispersive X-ray spectroscopy (EDS, INCA
IE 350 PentaFET X-3, Oxford, UK).
Cold modulus of rupture (CMOR) was measured by the three-point
bending test at room temperature with a span of 100 mm and a loading
rate of 0.5 mm/min using an electronic digital control system (EDC
120, DOLI Company, Germany). Modulus of elasticity (E) was deter-
mined by Resonance Frequency and Damping Analyzer (RFDA, IMCE
in Belgium) at room temperature. Also, the thermal shock behavior of
MgO-C specimens after treating at 1400 °C was characterized by oil
quenching method for 5 thermal shock cycles. The detailed illustration
of the thermal shock test was referred to our previous work [10].
Moreover, the coefficient of thermal expansion (α, room temperature to
1400 °C) of the specimens after treating at 1400 °C was measured via a
thermal dilatometer (Unitherm™ model 1161 dilatometer system,
Anter Corp., Pittsburgh, PA); the measurement was made in an
atmosphere of N2 (99.9% N2) to prevent oxidation of the specimens
after treating at 1400 °C. All the above properties measured for each
composition were average values from three test pieces.
Furthermore, the wedge splitting test according to Tschegg was
used for the determination of the specific fracture energy of MgO-C
specimens due to the stable crack propagation in the specimen with
sufficiently large dimension [33]. The specific description of wedge
splitting test can be seen in our recent published work [23] and other
studies [34–36]. Based on this test, the specific fracture energy (Gf),
nominal notch tensile strength (σNT), and characteristic length (lch)
can be calculated by the following formulas:
1 δult
Gf =
A
∫0 FHdδ
(1)
FH , max ⎛ 6y ⎞
σNT = ⎜1 + ⎟
b⋅h ⎝ h⎠ (2)
Gf ⋅E
lch = 2
σNT (3)
where δμlt is the ultimate displacement and A is the area of the
projection of the fracture surface. Note that he Gf was not calculated
until total failure but until 15% of the maximum force in the post-peak
region, as usually done for this test. b and h are the width and height of
the fracture surface area, respectively, and y is the vertical distance of
the center of gravity of the fracture surface from the horizontal force. E
is the modulus of elasticity. The data for each composition were
averaged with three test pieces. It was worth mentioning that the lch
was widely used for characterizing the ability to sustain thermal shocks.
In the meanwhile, the thermal shock resistance parameters (Rst) can be
also achieved by calculating the following formula [37,38]:
Gf
Rst =
2⋅α 2⋅E (4)
3. Results and discussion
S-G14 3.1. Phase compositions and microstructure
70
13 To clearly understand the influence of different graphite contents on
14 the phase compositions, XRD patterns of MgO-C specimens after treating
at 1400 °C were detected and are shown in Fig. 1. Apparently, the verified
phases were periclase, graphite, spinel, AlN and SiC for all the composi-
+1
+4
tions; the remarkable difference lied in the increase of the intensity of
graphite peak with the increase of graphite content added in the speci-
mens. However, Al carbides such as Al4C3 and Al2OC phases could not be
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Fig. 1. XRD patterns of MgO-C specimens.
detected in the MgO-C specimens because of their less content [2,19].
Fig. 2 presents SEM micrographs of MgO-C specimens after
treating at 1400 °C. As for specimen S-G1, besides the octahedral
MgAl2O4 particles, many plate-like AlN particles formed at the site
where metal Al particles originally occupied (Fig. 2a), which was
verified by XRD and EDS. Higher magnification image showed the
mean diameter and thickness of these plate-like AlN were 3–5 µm and
50–500 nm, respectively (Fig. 2b). Similar microstructure was ob-
served in specimen S-G5 (Fig. 2c and d). In specimen S-G10, a great
deal of MgAl2O4 particles grew in the matrix and on the surfaces of
magnesia particles (Fig. 2e); meanwhile, some whisker-like products
with a mean diameter of ~100 nm and a mean length of ~10 µm
formed, which were confirmed as AlN by means of EDS analysis
(Fig. 2f). With regard to specimen S-G14, some Al carbides whiskers
(verified by EDS analysis) also grew in the matrix apart from MgAl2O4
particles and plate-like AlN (Fig. 2g and h).
3.2. Mechanical behavior
The difference in the microstructure may lead to a change of
fracture mechanical behavior of MgO-C specimens. Therefore, their
mechanical behavior after treating at 1400 °C was analyzed by the
Fig. 2. SEM micrographs of MgO-C specimens: (a)–(b) specimen S-G1, (c)–(d) specimen S-G5, (e)–(f) specimen S-G10, (g)–(h) specimen S-G14.
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Ceramics International 43 (2017) 7177–7183
Fig. 3. Force-displacement curves of MgO-C specimens after wedge splitting test.
wedge splitting test, and the representative load-displacement curves
are displayed in Fig. 3. As expected, the mechanical behavior of
specimen S-G1, which was more brittle, was apparently different from
the other ones since it exhibited a much higher maximum force, a lower
strain at the peak, and a more pronounced peak owing to a smaller
post-peak region. With the increase of graphite content in MgO-C
specimens, their non-linear fracture mechanical behavior became more
and more obvious.
On the basis of the load-displacement curves achieved from the
wedge splitting test, the σNT, Gf and Gf/σNT of all the specimens were
calculated, and the results are presented in Fig. 4. As shown in Fig. 4a,
it can be found that the σNT of the specimens decreased from 7.76MPa
to 3.75 MPa with the increase of graphite content. The change of σNT
was similar to that of the corresponding fracture load. However, the Gf
change of MgO-C specimens had an opposite tendency with increasing
graphite content as compared to the σNT (Fig. 4b). For instance, the Gf
value of specimen S-G1 was 269 J/m2, while that of specimen S-G14
was 405 J/m2.
In order to indirectly characterize the brittleness of a material,
Harmuth [39,40] proposed that the Gf/σ NT can be considered as
another indicator of brittleness. Usually, the higher the G f/σ NT
value, the lower the brittleness of a material. Fig. 4c shows the Gf /
σ NT as a function of graphite content. It was apparent that the Gf /
T. Zhu et al. Ceramics International 43 (2017) 7177–7183

Fig. 4. Fracture mechanical properties of MgO-C specimens: (a) nominal notch tensile strength (σNT), (b) specific fracture energy (Gf), and (c) the Gf/σNT ratio.

σ NT became gradually higher with the increase of graphite content,

indicating that increasing graphite content was helpful for the
improvement of toughness of MgO-C refractories. The thermal
shock resistance parameters of such refractories will be illustrated
in the following section.

3.3. Characteristic length (lch), thermal shock resistance parameter

(Rst) and the comparison from the thermal shock tests

To characterize quantitatively thermal shock resistance of MgO-C

specimens, their lch and Rst were calculated and the results are shown
in Figs. 5 and 6, respectively. As indicated in Fig. 5, the lch values of the
specimens increased monotonically with the increase of graphite
addition. For example, the lch value of specimen S-G1 was 110 mm,
whereas 256 mm was for specimen S-G14. In the case of the Rst values
of the specimens (Fig. 6), as expected, their change tendency was the
same with that of lch values. In general, the higher the lch or Rst value, Fig. 6. The thermal shock parameter (Rst) of MgO-C specimens.
the better the thermal shock resistance of a material. So, increasing the
graphite content can contribute to improved thermal shock resistance
of MgO-C specimens.
Furthermore, to compare the methods from the quantitatively
evaluation of the thermal shock resistance mentioned above with
conventional qualitatively characterization method, the CMOR values
of MgO-C specimens coked at 1400 °C before and after 5 thermal shock
cycles in oil bath were measured and their residual strength ratios of
CMOR were also calculated, and the results are shown in Fig. 7. It can
be seen that both the CMOR values of MgO-C specimens after 5
thermal shock times and their residual strength ratios of CMOR
increased gradually with graphite addition, which was consistent with
the lch and Rst results. It was suggested that the wedge splitting test
was a good approach to evaluate the thermal shock resistance of MgO-
C refractories.

Fig. 7. The CMOR of MgO-C specimens before and after thermal shock test and their
residual strength ratio of CMOR.

3.4. Fractal analysis of the crack propagation path of MgO-C

specimens after the wedge splitting test

The fractal dimension, as an important parameter used in fractal

Fig. 5. The characteristic length (lch) of MgO-C specimens.
theory, have been used extensively to solve the nonlinear problems
such as crack paths and fracture surfaces in ceramic materials [41,42].
Generally, the higher the fractal dimension, the more tortuous the
crack propagation path. Also, there was a relationship between the
fractal dimension of cracks and the fracture toughness [43,44]. It was
indicated that the higher the fractal dimension of the crack paths, the

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Fig. 8. An example to illustrate the calculation procedure of the fractal dimension of the crack from MgO-C specimen after wedge splitting test: (a) photograph, (b) crack feature
extraction, (c) image binarization and (d) linear fitting.

higher the fracture toughness. In fact, the crack paths in the interior
portion of MgO-C refractories during the wedge splitting test had a
significant influence on their fracture mechanical properties. So, the
fractal dimension was calculated in this work to investigate the
influence of various graphite content on the irregularity of the crack
propagation path during fracture.
The methods for calculating the fractal dimension mainly included
the yardstick, the box counting, the variation, the structure function
and the power spectrum method [45]. The box counting method was
used widely to calculate the fractal dimension of the image without a
strict iterative relationship, whose main idea was referred to Ref. [46].
The fractal dimension (D) was obtained according to the following
formula:

log10S (k )
D=−
log10k (5)
Fig. 9. Fractal dimension (D) of the crack formed in MgO-C specimens after wedge
splitting test. where k and S(k) are a series of the size of the box and the
corresponding amounts of the boxes for covering the crack propagation
path, respectively.

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Therefore, the fractal dimension of the crack propagation path was

calculated by means of the image processing technology and box
counting method in this work. The detailed steps were as follows: (1)
The photograph with the whole crack propagation path was taken with
a digital camera and further processed by the image enhancement
methods including contrast enhancement, histogram specification,
filtering, sharpening, etc (Fig. 8a); (2) The crack propagation region
was extracted and transformed into a gray-scale image with 256 gray
levels (Fig. 8b); (3) As-obtained gray-scale image was further trans-
formed into a binary image including pixel values of 0 and 1, black and
white (Fig. 8c); (4) A series of k and S(k) were obtained by using
MATLAB software based on the calculation principle of the box
counting method; finally, the fractal dimension was estimated as the
absolute value of the slope of a linear fitting for the data on a log10S(k)–
log10k plot (Fig. 8d).
Fig. 9 shows the D values of the crack propagation path of MgO-C
specimens coked at 1400 °C after the wedge splitting test. The speci-
men S-G1 had the minimal D value, which was 1.07. With increasing
the graphite addition, the D value also became higher. When the
graphite content of the specimens was 14 wt%, the D value was 1.23. It
was suggested that the increase of graphite content in MgO-C
refractories can enhance their irregularity of the crack propagation
path during fracture. By comparing D and Gf values, it was no difficulty
to find that the change tendency of fractal dimension of each specimen
was in consistent with that of specific fracture energy, implying that the
more tortuous the crack propagation path, the higher the Gf value.
Also, the increase of Gf value decreased the brittleness of the speci-
mens, and further improved their thermal shock resistance.

3.5. Microscopic fractographic investigations for MgO–C specimens Fig. 10. Examples to evaluate the crack path for MgO-C specimens: (a) specimen S-G1,
after the wedge splitting test (b) specimen S-G5, (c) specimen S-G10 and (d) specimen S-G14.

To further indicate the relationship between the thermal shock Table 2

Microscopic fractographic investigations for MgO-C specimens after wedge splitting test.
resistance and the microstructure of MgO-C refractories containing
different graphite content, the various crack propagation types (in- Cracks S-G1 S-G5 S-G10 S-G14
cluding the crack propagation within the grains [C, GG], between the
grain and the matrix [C, GM], and within the matrix [C, MM]) were lC, GG(%) 6.6 6.1 4.2 2.8
lC, (%) 35.2 47.2 58.2 72.9
recorded by SEM; their corresponding own lengths in the whole crack GM
lC, MM (%) 58.2 46.7 37.6 24.3
propagation path were designated as LC, GG, LC, MG and LC, MM, lC, GM/lC, GG 5.33 7.74 13.9 26.0
respectively. Finally, their corresponding own proportions in the whole
crack propagation path were calculated by the following formulas (6)–
(8) and named as lC, GG, lC, MG and lC, MM, respectively.
GM . So, designing an appropriate interfacial strength between
LC , GG
lC , GG = magnesia aggregates and the matrix of MgO-C refractories would
LC , GG + LC , MG + LC , MM (6) be a promising approach to improve their thermal shock behavior.
LC , MG
lC , MG =
LC , GG + LC , MG + LC , MM (7) 4. Conclusions
LC , MM
lC , MM = The influence of flaky graphite content on mechanical behavior of
LC , GG + LC , MG + LC , MM (8)
MgO-C refractories investigated by the wedge splitting test in this
Fig. 10 shows the examples for evaluating the crack propagation work; the relationship between thermal shock resistance and the
path of MgO-C specimens after treating at 1400 °C. It can be seen microstructure was also evaluated by fractal and microscopic fracto-
that the crack propagation paths of the specimens with more graphic analysis. The increase of graphite content in such refractories
graphite content became more tortuous. This can be explained by enhanced their non-linear fracture behavior, reduced their nominal
a combination of various graphite content and in-situ formed notch tensile strength (σNT), and improved specific fracture energy
ceramic phases (e.g., the distribution, amounts and morphology (Gf), characteristic length (lch) and thermal shock resistance parameter
of AlN phases or Al carbides formed at 1400 °C). The calculation (Rst). Furthermore, the fractal dimension (D) of the crack propagation
results of lC, GG , lC, MG and l C, MM of all the specimens are illustrated path of MgO-C specimens after the wedge splitting test increased
in Table 2. The specimen S-G1 with the worst thermal shock gradually from 1.07 to 1.23 when the added graphite content increased
resistance possessed the highest l C, GG and lC , MM as well as the from 1 wt% to 14 wt%, which indicated that the increase of graphite
lowest lC, MG. The lC, MG increased gradually with the increase of content in MgO-C refractories can enhance their irregularity of the
graphite content of the specimens. Also, the ratio of lC, GM to lC, GG crack propagation path during fracture. The microscopic fractographic
became higher with the improved thermal shock resistance. It was results suggested that the improvement of thermal shock resistance of
suggested that the improvement of the thermal shock resistance of MgO-C refractories was positively correlated with the increase of
MgO-C specimens was positively correlated with the increase of lC, interface crack propagation.

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Acknowledgements
The authors would like to express their thanks for the financial
support from the National Natural Science Foundation of China
(51574186 and 51372176), and the China Postdoctoral Science
Foundation (2016M600087).
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