Surface & Coatings Technology 260 (2014) 429432

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Improving oxidation resistance and fracture strength of MgOC

refractory material through precursor coating
Geun-Ho Cho a, Eun-Hee Kim a, Yeon-Gil Jung a,, Yun-Ki Byeun b
a
b

School of Advanced Materials Science and Engineering, Changwon National University, Changwon, Gyeongman 641-773, Republic of Korea
Technical Research Laboratories Pohang Research Lab., Steelmaking Research Group, POSCO, Pohang, Gyeongbuk 790-300, Republic of Korea

a r t i c l e

i n f o

Available online 21 November 2014

Keywords:
Precursor
Graphite
Coating
MgOC refractory
Oxidation resistance
Fracture strength

a b s t r a c t
An Al precursor was coated onto the surface of graphite in a MgOC refractory material to improve the oxidation
resistance and the fracture strength by controlling the amount of antioxidant and the coating thickness. To
enhance the coating efciency, the surface of the graphite used as the carbon source was treated with an
acid. In oxidation tests, the Al-coated graphite showed a smaller weight loss than the pristine graphite.
The MgOC refractory material with the Al-coated graphite showed a similar fracture strength to that
with commercial graphite, despite the use of a smaller amount of antioxidant. The highest fracture strength of
the MgOC refractory material was about 17 MPa; it was obtained with the Al-coated graphite. The increase in
fracture strength was a result of the homogeneos coating of Al precursor in the modied MgO-C refractory
material. Based on the properties observed, we discuss the relationship between fracture strength and process
parameters.
2014 Published by Elsevier B.V.

1. Introduction
MgOC refractory material is widely used in basic furnaces, electric
arc furnaces, and steel ladles because of its corrosion resistance by low
wettability with the molten metal, excellent thermal shock resistance
by its low thermal expansion, and high thermal conductivity [1,2].
These desirable properties are achieved by the use of graphite as the
carbon source in the MgOC. However, the graphite in the MgOC is
highly vulnerable to oxidation, which causes a deterioration in the mechanical properties. The damage through erosion or corrosion is serious,
and structural spalling is easily generated in real applications because of
slag penetration and pore generation by the oxidation of graphite [3,4].
To impede the oxidation phenomena, antioxidants that have high reactivity with oxygen are usually added to batches of the MgOC [5,6]. The
added antioxidants include metals/alloys such as Al, Al/Mg alloys,
carbides such as B4C and SiC, and borides such as CaB6 and ZrB2[5],
which show a stronger oxidation entropy than graphite. Theoretically, it
means that graphite does not react with oxygen until the oxidation of
the antioxidant has progressed considerably. In practice, graphite reacts
with oxygen even though the oxidation of the antioxidant has not
progressed considerably. Pore generation at inner sites of the MgOC is
an unavoidable phenomenon because the antioxidant cannot effectively

Corresponding author. Tel.: +82 55 213 3712; fax: +82 55 262 6486.
E-mail address: jungyg@changwon.ac.kr (Y.-G. Jung).

http://dx.doi.org/10.1016/j.surfcoat.2014.11.035
0257-8972/ 2014 Published by Elsevier B.V.

obstruct the oxidation of graphite in real environments. Further disadvantages include volume expansion, limited content, and high cost.
In previous works, we studied methods for improving the oxidation
resistance of graphite by coating the graphite surface with a metal precursor, in particular an Al precursor [7,8]. The Al-coated graphite
showed a higher oxidation resistance due to the barrier effect of the Al
layer formed on the surface of graphite. In the coating process, the coating reagent should be homogeneously coated on the surface of the
graphite to obtain a sufcient coating effect [911]. Four key points
should be considered in the preparation of graphite with a high coating
efciency: (1) the process of coating the graphite with the metal precursor is performed in an aqueous solution to increase the dispersibility of
the metal precursor on the surface of the graphite [1214]; (2) the
graphite surface is puried and modied with an acid to create hydrophilic groups; (3) to improve coating efciency, a metal precursor that
has high water solubility is used; and (4) a metal with high reactivity
with oxygen is selected.
The aim of this study was to prepare a MgOC refractory material
not only with graphite coated with Al precursor, but also with a smaller
amount of antioxidant than that used in the conventional process.
Therefore, in the present study, Al precursor was coated onto the modied graphite with an acid reagent to enhance the coating efciency. To
investigate the effect of the precursor coating on the oxidation resistance of the MgOC, the content of antioxidant in the MgOC was controlled. The oxidation behavior of the MgOC is discussed based on the
results of oxidation tests and the measured fracture strength during the
development of the new process.

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Table 1
Formulations used to prepare the MgOC refractory materials in this work.
Run number

MgO (g)

Graphite (g)

Antioxidants (g)

Phenolic resin (g)

Preheating (Al-coated powder)

Al precursor

Run-1
Run-2
Run-3
Run-4

84

10

3.0
3.0
1.5
0

500 C/1 h

Without coating
With coating
With coating
With coating

2. Experimental procedure

by cool isostatic pressing at 200 MPa for measuring fracture strength,

and at a pressure of 110 MPa with a cylindrical shape of 50 mm diameter
and 50 mm length for oxidation tests. After pressing, the MgOC refractory samples were heat-treated at 300 C for 3 h.

2.1. Materials and preparation methods

Aluminum nitrate (Al(NO3)3) (Sigma-Aldrich Korea, Yongin, Korea)
was used as a metal precursor [15]. Platy graphite (POSCO, Pohang,
Korea), usually used in commercial MgOC refractory materials, was
suspended in a mixture of sulfuric and nitric acids (3:1 by vol.%) that
served as a modication reagent for the surface of the graphite. The mixture was sonicated for 3 h and stirred for 24 h. The acid-treated graphite
was ltered and washed with distilled water until pH 7, and then dried
at 80 C for 48 h. Al(NO3)3 was rst dissolved in a 3 M aqueous solution.
The graphite particles modied by the acid were mixed with the
Al(NO3)3 solution, and then stirred for 1 h at room temperature. The
graphite coated with Al precursor was ltered, and then dried at 80 C
for 1 h. The prepared powder was held at 500 C for 1 h under H2 atmosphere to increase the adhesion of the Al precursor onto the graphite
surface. Commercially fused magnesia (MgO, particle size 1 mm),
platy graphite or modied graphite, antioxidant (AlSi mixture,
POSCO, Pohang, Korea), and phenolic resin were used to prepare the
MgOC refractory material. The formulations used to prepare the
MgOC are shown in Table 1. The modied or pristine graphite, MgO,
antioxidant, and phenolic resin were mixed by a dry ball-milling process for 24 h at room temperature, and then formed under a 60 MPa
pressure with a cuboid shape of 10 mm 10 mm 50 mm, followed

2.2. Characterization
The combustion tests for the graphite particles, with and without
modication, were conducted at 1000 C for 1, 2, and 3 h. The prepared
refractory samples were also subjected to combustion tests at 1000 C
for 3 h to investigate the oxidation resistance of the MgOC refractory
material, depending on the formulation. The Al coating on the graphite
surface was analyzed with X-ray photoelectron spectroscopy (XPS, VG
Scientic ESCALAB 250, East Sussex, United Kingdom). The fracture
strength of the samples before and after heat treatment was measured
using a universal testing machine (Instron 5566, Instron, Norwood,
MA, USA) in a four-point bending mode at a rate of 0.5 mm min1.
Tests were carried out at room temperature. At least ve runs were performed to determine the standard deviation of the strength.
3. Results and discussion
The Al precursor has to be coated onto the surface of the graphite to
achieve sufcient coating efciency and impart oxidation resistance to
the MgOC. The XPS results are shown in Fig. 1, for the elements of

Fig. 1. XPS results for (a) pristine graphite and (b) Al-coated graphite.

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431

Fig. 2. Photographs of graphite particles with and without precursor coating: (a) pristine graphite and (b) Al-coated graphite. Each number indicates graphite particles after combustion
tests conducted for 1, 2, and 3 h.

carbon (C), oxygen (O), and aluminum (Al). The Al peak was detected in
the Al-coated graphite from the short wavelength, as shown in
Fig. 1(b-3), while only C and O peaks were detected in pristine graphite
(Fig. 1(a-1) and (a-2)). The O was detected by the carboxylic group,
which was reformed, along with C, on the surface of the graphite with
the acid, indicating that graphite was modied by the acid. It was also
veried that the Al precursor was coated and then the Al layer was generated on the surface of the graphite. The generated coating layer
restricts the access of oxygen to the graphite, and hence adequately
controls the oxidation of the graphite.
The pristine graphite was drastically affected by oxidation after combustion tests, showing a weight loss of 82.2% after heat treatment for
3 h. The oxidation rate was calculated from the weight loss of graphite;
it was found to increase with time. The oxidation rate decreased with
the precursor coating due to the Al layer formed on the graphite surface.
In addition, the weight loss also increased signicantly, from 8.9% to
76.1%, with an increase in test time from 1 to 3 h, showing the same
oxidation trend as that for pristine graphite. When graphite was modied with the Al precursor, its color changed to white after heat treatment, because of the formation of the alumina phase, converted from
the Al precursor on the graphite surface, as presented in Fig. 2(b). This
means that the graphite was well coated with the Al precursor. It was
therefore evident that the Al coating enhanced the oxidation resistance
of graphite even though the weight loss caused by the oxidation of
graphite should be taken into consideration.
The fracture strength values of MgOC samples prepared using
pristine and Al-coated graphite, as a function of composition, are
shown in Fig. 3. The fracture strength of the MgOC with Al-coated
graphite in the Run-2 composition was slightly increased, independent

of heat treatment, even though the increase was within the error range.
The highest fracture strength values of about 17 and 7 MPa were obtained in Run-2 before and after heat treatment, respectively. The asprepared samples showed values similar to each other, meaning that
the antioxidants added to the MgOC did not affect the green strength.
However, the effect of the antioxidant on the strength after heat treatment was undesirable. The sample prepared with the conventional
composition, Run-1, showed a similar fracture strength to that prepared

Fig. 3. Fracture strength values of MgOC samples depending on formulations. Each number
refers to the values before and after heat treatment at 1000 C for 3 h.

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Fig. 4. Photographs of MgOC samples with different formulations after combustion tests at 1000 C: (a) Run-1, (b) Run-2, (c) Run-3, and (d) Run-4.

with less antioxidant, Run-3. When the antioxidant was not added to
the batch, the fracture strength value was signicantly lower than that
of the as-prepared sample, indicating that the Al-coated graphite had
a limited effect on improving the strength value, in terms of the antioxidant content. Oxidation by heat treatment leads to a deterioration in
the thermal and mechanical properties of the MgOC, which shortens
the lifetime. The sectional images measured after combustion tests at
1000 C for 1 h, carried out for an application, are shown in Fig. 4. The
size of MgOC samples prepared using standard amount of the antioxidant, added in the conventional process, remained unchanged after
combustion tests at 1600 C, independent of the precursor coating.
However, when the content of antioxidant was reduced to 50%, in
Run-3, size reduction caused by the oxidation of graphite was detected,
and this was even further advanced in the case of no antioxidant, in
Run-4.
4. Conclusions
MgOC samples were prepared with the Al-coated graphite, and the
effect of the antioxidant content on the oxidation behavior of the MgO
C with the pristine and Al-coated graphite particles was investigated.
The coating of the Al precursor onto the surface of the graphite was conrmed by XPS results. The Al-coated graphite showed a relatively higher
oxidation resistance than the MgOC with pristine graphite and less
antioxidant. The fracture strength of the MgOC was successfully
increased by using the Al-coated graphite, even when the antioxidant
content was reduced to 50% of the standard composition. The highest
fracture strength values of about 17 and 7 MPa (before and after heat
treatment, respectively) were obtained in the MgOC with the Alcoated graphite in the standard antioxidant content. The thermal stability of the MgOC was conrmed in combustion tests. The Al precursor
coating had limited effects on the fracture strength and oxidation in
samples containing up to 50% of the standard antioxidant content.

Acknowledgment
This research was nancially supported by Changwon National
University in 20132014.
References
[1] S. Zhang, W.E. Lee, Inuence of additives on corrosion resistance and corroded
microstructures of MgOC refractories, J. Eur. Ceram. Soc. 21 (2001) 2393.
[2] B. Hashemi, Z.A. Nemati, M.A. Faghihi-Sani, Effects of resin and graphite content on
density and oxidation behavior of MgOC refractory bricks, Ceram. Int. 32 (3) (2006)
313.
[3] L. Xiaowei, R. Jean-Charles, Y. Suyuan, Effect of temperature on graphite oxidation
behavior, Nucl. Eng. Des. (2004) 273.
[4] A.P. Luz, D.O. Vivaldini, F. Lopez, P.O. Brant, V.C. Pandolfelli, Recycling MgOC refractories and dolomite nes as slag foaming conditioners: experimental and thermodynamic evaluations, Ceram. Int. 39 (2013) 8079.
[5] S. Zhang, N.J. Marriott, W.E. Lee, Thermochemistry and microstructures of MgOC
refractories containing various antioxidants, J. Eur. Ceram. Soc. 21 (2001) 1037.
[6] S.K. Sadrnezhaad, S. Mahshid, B.H. Ashemi, Z.A. Nemati, Oxidation mechanism of C
in MgOC refractory bricks, J. Am. Ceram. Soc. 89 (2006) 1308.
[7] E.H. Kim, G.H. Cho, Y.S. Yoo, S.M. Seo, Y.G. Jung, Development of a new process in high
functioning ceramic core without shape deformation, Ceram. Int. 39 (2013) 9014.
[8] G.H. Cho, E.H. Kim, J. Li, J.H. Lee, Y.G. Jung, Y.K. Byeun, C.Y. Jo, Improvement of oxidation resistance in graphite for MgOC refractory through surface modication,
Trans. Nonferrous Met. Soc. China 24 (2014) s119.
[9] M. Barsoum, Fundamentals of Ceramics, McGraw-Hill, Seoul, 1997.
[10] E.H. Kim, J.H. Lee, Y.G. Jung, C.S. Lee, U. Paik, A new in situ process in precision casting for mold fabrication, J. Eur. Ceram. Soc. 31 (2011) 1581.
[11] D.A. Buttry, F.C. Anson, New strategies for electrocatalysis at polymer-coated electrodes. Reduction of dioxygen by cobalt porphyrins immobilized in naon coatings
on graphite electrodes, J. Am. Chem. Soc. 106 (1) (1984) 59.
[12] E.H. Kim, D. Lee, U. Paik, Y.G. Jung, Size effect in Ni-coated TiC particles for metal matrix composites, J. Nanosci. Nanotechnol. 11 (2011) 1746.
[13] E.H. Kim, J.H. Lee, Y.G. Jung, C.G. Lee, M.K. Lee, J.J. Park, Preparation of Ni-coated TiC
particles using potential hydrogen (pH) for dispersion into a molten metal, Prog.
Org. Coat. 70 (2011) 310.
[14] P.C. Pandey, S.U. Upadhyay, N.K. Shukla, S. Sharma, Studies on the electrochemical performance of glucose biosensor based on ferrocene encapsulated ORMOSIL and glucose
oxidase modied graphite paste electrode, Biosens. Bioelectron. 18 (2003) 1257.
[15] C.H. Hou, C. Liang, S. Yiacoumi, S. Dai, C. Tsouris, Electrosorption capacitance of
nanostructured carbon-based materials, J. Colloid Interface Sci. 302 (2006) 54.