Applied Surface Science 258 (2012) 49774982

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Applied Surface Science

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

A supercial coating to improve oxidation and decarburization resistance

of bearing steel at high temperature
Xiaojing Wang a,b , Lianqi Wei a , Xun Zhou a,b , Xiaomeng Zhang a , Shufeng Ye a, , Yunfa Chen a
a
b

State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, P. O. BOX 353, Beijing 100190, China
Graduate University of Chinese Academy of Sciences, No. 19(A) Yuquan Road, Beijing 100049, China

a r t i c l e

i n f o

Article history:
Received 2 November 2011
Received in revised form
18 December 2011
Accepted 24 January 2012
Available online 2 February 2012
Keywords:
Bearing steel
High temperature oxidation
Decarburization
Coatings

a b s t r a c t
The coating material consisted of aqueous slurry of dolomite, bauxite and silicon carbide mixture. Such
a coating material when applied supercially on the steel surface not only enhances oxidation resistance but also helps in inhibiting the decarburization even up to 1250 C. Metalloscope, XRD and TG-DTA
thermal analysis revealed that the formation of a newly densied coating comprised of spinels and the
reducing atmosphere formed by the oxidation of SiC improved the resistance of oxidation and decarburization.
2012 Elsevier B.V. All rights reserved.

1. Introduction
In recent years high carbon chromium bearing steel has been
widely used because it has the advantages of comprehensive performance, convenient operation and low production cost [1,2].
However, Annealing and reheating treatments on bearing steels are
generally carried out in furnaces having an oxidizing atmosphere.
Scales are formed on the steel materials during their heating, resulting in a lowered product yield, accompanied with various problems,
such as lowering in the commercial value of the products due to
surface imperfection and lowering in the strength of the steel products due to decarburization [3,4]. Decarburization is a loss of carbon
atoms from the surface of the work pieces, thereby producing a surface with lower carbon content than at some other distance beneath
the surface. It implies changes of mechanical properties as, e.g., the
changes of hardness and of fatigue resistance [5]. Particularly in the
case of steel materials, such as bearing billets, which contain about
1.5% carbon, the inuence on the steel quality by the lowering in
strength due to the surface decarburization is very signicant [6].
Decarburization and oxidation occur simultaneously. The reaction
rates are high, and there is competition between the two phenomena: oxidation rapidly consumes the decarburized metal [3].

Corresponding author. Tel.: +86 10 62588029; fax: +86 10 82544919.

E-mail address: sfye@home.ipe.ac.cn (S. Ye).
0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.01.135

Therefore, it has a lot of difculties to prevent steel from oxidation

and decarburization simultaneously.
The aim of this work is to fabricate a high temperature corrosion
resistant coating. The microstructure and sintering behaviors of the
coatings were investigated. The corrosion resistant mechanism also
is discussed.
2. Experimental
2.1. Preparation of the coating
The chemical composition (in weight percent) of the bearing
steel used in the present study is C 1.00%, Cr 1.50%, Mn 0.30%, Si
0.25%, S 0.01%, P 0.01%, and Fe balance. Specimens with dimensions
of 10 mm 10 mm 10 mm were prepared by rolling and intermediate annealing (at 500 C) operations. Subsequently, the specimens
were mechanically polished by abrading on SiC papers in succession up to 800 grit followed by cleaning and rinsing in supersonic
treatment and dried for coating protective layers.
The coating materials, consisted of dolomite, bauxite and silicon carbide, were mixed in various proportions. The compositions
of the dolomite and bauxite are listed in Tables 1 and 2. The mixture was diluted with water to secure the proper viscosity, which
enabled deposition by painting or spraying. The addition of the
binding agent (citric acid) was necessary for good adhesion to the
surface of the steel after drying.

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X. Wang et al. / Applied Surface Science 258 (2012) 49774982

Table 1
Compositions of the dolomite.

Table 3
Compositions and the corrosion resistance of the coatings.

Component

MgO

CaO

SiO2

Fe2 O3

Al2 O3

Parts by weight

Content [wt.%]

39.82

58.72

0.64

0.46

0.36

Dolomite
Silicon carbide
Bauxite
Citric acid
distilled water
Anti-oxidation effect,
%
Anti-decarburization
effect, %

Table 2
Compositions of the bauxite.
Component

Al2 O3

SiO2

TiO2

Fe2 O3

CaO

K2 O

Content [wt.%]

63.96

29.15

3.36

2.41

0.76

0.36

2.2. Experimental method

Two types of bearing steel specimens, bare and coated, were
weighted, heated for 0120 min at temperatures of 9501250 C,
and then weighed again without scale.
m = m1 m2

(1)

m1 m2
100%
Steel loss  =
m1

(2)

Anti-oxidation effect oxi =

mbare mcoated
100%
mbare

(3)

where m1 and m2 are the weights of the specimens before and after
oxidation without scale, g. mbare and mcoated are the weight loss
of the bare specimen and the coated one.
Every specimen was cut into two parts by cutter bar and one of
them was polished by abrading on SiC papers. The specimens were
etched by 4 vol% admixture of nitric acid and absolute ethyl alcohol.
Finally, they were dehydrated by absolute ethyl alcohol and used
for metallographic observation to determine the decarburization
layer.
Anti-decarburization effect dec =

dbare dcoated
100%
dbare

(4)

where dbare and dcoated are the decarburized depths of the bare and
the coated specimens, m.
2.3. Characterization
Oxidation-kinetics studies of bare and coated specimens were
carried out by a thermobalance (RZ, Luoyang Precondar, China)
which was equipped with a continuous weighing capacity of 500 g,
sensitivity of 1 mg and data recorded every 60 s. The heating rate
employed was 10 C/min up to a nal temperature of 1250 C.
Energy change with the temperature rising was detected by a
TG-DTA thermal analysis system (TG-DTA, Beijing Scientic Instrument Factory, China). Microstructures of the decarburization were
observed by an optical microscope (polarization microscope, DM
LP/P, Leica, Germany). Data of X-ray diffractometer (XRD, XPert
Pro, Philips, Netherlands) were collected to analyze the change of
phases in the coating.

64
20
0
7
25
64.00

64
0
20
7
25
56.00

64
20
40
7
37
48.00

64
40
20
7
37
68.00

100.00

14.03

3.36

100.00

100.00

is because the ne SiC powder was oxidized and changed gradually to protective cristobalite-SiO2 layer which acted as an excellent
barrier to oxygen diffusion from atmosphere. The protective SiO2
was not formed from the SiO2 which was added initially but was
newly formed through the oxidation process of the SiC. Graphite
(C) was also formed due to the oxidation of SiC, keeping a reducing atmosphere even at quite high temperatures [7]. The presence
of considerable graphite in this way indicated that the diffusion of
C and O is impeded and the decarburization was effectively prevented.
Compared B (without bauxite in the coating), the specimen A
remarkably increased the decarburization resistance and also had
a better anti-oxidation effect. This is based on the decomposition of
bauxite and its reaction with Fe and dolomite. The products SiO2 ,
FeOAl2 O3 , -Al2 O3 and spinel were nonpermeable to oxygen [8,9].
However, by comparing specimens A and D, it has been found
that overmuch bauxite would make the oxidation resistance drop
down because the anti-oxidation effect of the silicon oxide produced by the decomposition of bauxite actually deteriorated at
temperatures in excess of 1200 C. This is due to the formation of
fayalite (2FeOSiO2 ), which had a low melting point. Fayalite formed
a eutectic with wustite above 1177 C that promoted the rapid grow
of the oxide by liquid oxide attack [7,10]. The decarburization resistance did not decrease due to the increase of oxide scale which
consumed the decarburized layer produced below 1177 C [3]. This
can be explained by the competition between oxidation and decarburization. As shown in Fig. 1, the practical oxidation equals to the
theoretical oxidation. The depth difference between the theoretical decarburization and the theoretical oxidation determines the
practical decarburization.
3.2. The effects of heating temperature
Coating A in Table 3 was applied in the test and the effects of
heating temperature are shown in Table 4.
From both the curves in Fig. 2, which shows the difference in the
weight of the cleaned specimens before and after heating, it can be

3. Results and discussion

3.1. The effects of coating components
The coating materials were mixed according to Table 3 and the
effects of anti-oxidation and anti-decarburization at 1250 C for
60 min were evaluated.
Dolomite was chosen as the main raw material because magnesium oxide has high melting point and can be regarded as the
framework of the coating. As shown in Table 3, the oxidation and
decarburization prevention were obviously improved when SiC is
admixed into the coating by comparing the specimens A and C. This

64
20
20
7
29
68.00

Fig. 1. The competition between oxidation and decarburization.

X. Wang et al. / Applied Surface Science 258 (2012) 49774982

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Table 4
The oxidation and decarburization resistance of coating A heated for 0120 min at temperatures of 9501250 C.
Temperature, time

oxi , %

dec ,%

Temperature, time

oxi , %

dec ,%

950 C, 60 min
1050 C, 60 min
1150 C, 60 min
1250 C, 60 min

44.20
60.43
61.93
64.44

6.45
6.85
7.05
100.00

1250 C, 0 min
1250 C, 30 min
1250 C, 90 min
1250 C, 120 min

67.19
67.17
60.43
63.60

65.14
100.00
100.00
100.00

observed that the steel loss increased with increasing temperature,

for both types (bare and coated) of specimens. The steel loss of the
coated specimen was smaller than that of the bare one during the
heating process. The amount of SiO2 in bauxite was much higher
than that in mullite; the excess SiO2 together with the impurities in
bauxite formed an amorphous SiO2 and cristobalite to accompany
the formation of mullite at temperature about 1000 C [11].
Bauxite is composed of diaspore (Al2 O3 H2 O) and kaolinite
(Al2 O3 2SiO2 2H2 O). The reactions (5) and (6) occurred because
alumina and metakaolinite (Al2 O3 2SiO2 ) were formed when diaspore and kaolinite were heated up to 500 C [1214]. Heating at
980 C leaded to a direct formation of -alumina and amorphous
SiO2 or spinel (SiAl2 O4 ) according to reactions (7) and (8). Mullite
phase rst appeared at a temperature around 1100 C according
to reactions (9) and (10), its amount increased with the increase
of temperature. The amorphous SiO2 changed to cristobalite above
1200 C according to reaction (11).
Al2 O3 H2 O (diaspore) Al2 O3 (-alumina) + H2 O
Al2 O3 2SiO2 2H2 O (kaolinite)
Al2 O3 2SiO2 (metakaolinite) + 2H2 O

(5)
(6)

Al2 O3 2SiO2 (metakaolinite)

Al2 O3 (-alumina) + 2SiO2 (amorphous)

(7)

Al2 O3 2SiO2 (metakaolinite)

SiAl2 O4 (spinel) + SiO2 (amorphous)

(8)

SiAl2 O4 (spinel) + SiO2 (amorphous)

1/3(3Al2 O3 2SiO2 ) (mullite) + 4/3SiO2 (amorphous)

(9)

Al2 O3 (-alumina) + 2SiO2 (amorphous)

1/3(2Al2 O3 2SiO2 ) (mullite) + 4/3SiO2 (amorphous)

(10)

Fig. 2. Steel loss of GCr15 bearing steel specimens during heating for 60 min after
scaling.

3Al2 O3 2SiO2 (mullite) + 4SiO2 (amorphous)

3Al2 O3 2SiO2 (mullite) + 4SiO2 (cristobalite)

(11)

The amorphous SiO2 , cristobalite and mullite had certain effect

in impeding the diffusion of oxygen. However, the coating was not
compact enough that oxidation still existed [15]. At higher temperatures, the protection was much effective (Table 4), because
on one hand, graphite (C) was formed due to the oxidation of SiC,
keeping a reducing condition within the coating even at quite high
temperatures [7]. On the other hand, new sintered phases were
nonpermeable to oxygen at high temperature. Fig. 3 shows the new
phases formed at 1150 C, including several spinels (MgCr2 O4 , (Mg,
Fe) (Cr, Al)2 O4 , MgAl2 O4 and Fe (Cr, Al)2 O4 ) [8,9].
From Fig. 4 it is evident that the decarburization of the bare
specimen increased below 1150 C. With increasing temperature
above 1150 C, the growth rate of the decarburized layer decreased
because the diffusions of C and O were retarded by the thick oxide
scale of the bare specimen in a certain degree when heated at high
temperature [16]. Below 1150 C, the anti-decarburization effect of
the coating was less than 7.05%, because the decarburized depth of
the bare specimen dbare was not large after the scale was cleaned.
The bare specimen generated more serious oxidation on the surface
(Fig. 2), consuming certain depth of decarburized layer. Although
for the coated specimen, the coating protected it from decarburization in a certain degree due to the formation of mullite and glassy
phase, the anti-decarburization effect dec was still small according
to Eq. (4). At higher temperature, above 1150 C, the protection of
decarburization was much effective, because the main reactions in
the coating, which gave the protective properties, started at around
1050 C, as evident from the DTA curve. The scale and decarburized layer, formed at the previous stage, reacted with the coating
materials to produce the newly densied lm, which hindered the
secondary decarburization. Therefore the coated specimen heated
at 1250 C had no decarburization after scaling.

Fig. 3. XRD patterns of bare specimen (a) and coated specimen (b) after heating at
1150 C.

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X. Wang et al. / Applied Surface Science 258 (2012) 49774982

Fig. 4. Decarburization growth of bare and coated specimens during heating for
60 min.

Fig. 6. Isothermal oxidation kinetics of bare and coated specimens at 1250 C in air.

Fig. 5 shows the bare specimen experienced endothermic process at 780 C because of austenization. And at about 950 C, an
evident exothermal process happened because of the oxidation. By
contrast, the coated specimen experienced an endothermic process below 100 C because of the dehydration of coating. At 175 C

a stronger endothermic reaction started, assumed to be the melting

process of citric acid. The exothermic reactions are observed from
450 C to 540 C due to the decarburization of the excessive citric
acid and the combustion of the residual carbon [17,18]. However,
metakaolinite were formed at around 500 C, therefore, there was
an endothermic peak separating the exothermal peak of citric acid
[1214]. The reactions (12) and (13) are the two steps of thermal
decomposition of dolomite. The reaction (12), happened at around
790 C, was not been clearly expressed in Fig. 5 because similar with
the bare specimen, the coated specimen experienced austenization process at 780 C and its peak covered the peak of reaction
(12). The endothermal peak can be seen at around 935 C due to
reaction (13) and the peak of the decomposition of metakaolinite
was overlapped with the reaction (13). The exothermal peak can
be seen at around 1100 C and 1200 C because the formation of
mullite phases according to reactions (9) and (10) and cristobalite
according to reaction (11).
CaMg(CO3 )2 CaCO3 + MgO + CO2

(12)

CaCO3 CaO + CO2

(13)

The reaction of coating materials with scale and decarburized

layer started above 1000 C.

Fig. 5. DTA curve of specimens with and without coating: (a) complete and (b)
partial enlarged.

Fig. 7. Steel loss of GCr15 bearing steel specimens at 1250 C in air.

X. Wang et al. / Applied Surface Science 258 (2012) 49774982

Fig. 8. Decarburization growth of bare and coated specimens at 1250 C in air.

3.3. The effects of holding time

Coating A in Table 3 was applied in the test and the effects of
holding time are shown in Table 4.

4981

The isothermal oxidation kinetic curves of bare and coated specimens at 1250 C in air for 6 h were plotted as a graph of weight gain
versus time and are illustrated in Fig. 6. It can be seen the coating
reduce oxidation rate of GCr15 bearing steel.
Fig. 7 shows the bare specimens severely suffered oxidation, and
quite a lot of steel was lost in the form of oxide scale. There was a
marked reduction in loss of steel volume in the whole heating process when the specimens were coated. The effect of the coating was
based on the formation of spinels, which exhibit low permeability
to oxygen at temperature up to 1250 C.
It can be observed in Fig. 8 that the decarburization of the
bare specimen increased with the extension of holding time. On
the contrary, the decarburization of the coated specimen inversely
decreased with the increase of holding time. When the temperature
just increased to 1250 C, the coated specimen had decarburization
layer formed below 1250 C, because the reactions of the coating
materials, which produced new densied coating, did not start at
low temperature. Despite the glassy phase, cristobalite and mullite,
formed by the decomposition of bauxite at low temperature, had
certain effect in impeding the diffusion of oxygen, decarburization
still existed when holding time was less than 30 min.
When the holding time was prolonged at 1250 C, the coating
materials, decarburization layer and the scale quickly took part
in the formation of effective lm and the decarburization, previously generated, disappeared quickly as a result. Then the lm was
so compact that it blocked the secondary diffusion of carbon and
oxygen at high temperature. Fig. 9 shows that the decarburization
depth of the bare specimen reached 839.51 m after heating for 2 h
at 1250 C. In contrast, the coated specimen had no decarburization
completely. The coating could diminish the decarburization on the
steel surface for up to 100% (Table 4).
4. Conclusions
1. A novel coating was successfully fabricated by using dolomite,
bauxite, silicon carbide and binding agent to prevent oxidation
and decarburization during reheating process of bearing steels.
2. The performed tests conrmed that SiO2 in bauxite formed a
glassy phase and cristobalite to accompany the formation of
mullite at 1000 C. The products had certain effect in preventing
oxidation and decarburization, but the coating was not compact
enough that oxidation and decarburization still existed.
3. At higher temperature, the protection was much effective,
because on one hand, graphite was formed due to the oxidation
of SiC, keeping a reducing atmosphere. On the other hand, the
scale and decarburized layer, formed at previous stage, reacted
with the coating materials to produce the newly densied lm
above 1150 C. The lm was mainly composed of spinels and it
could hinder the secondary oxidation and decarburization.
Acknowledgments
The authors gratefully acknowledge the nancial supports from
Key Topics in Innovation Engineering Funded by the Chinese
Academy of Sciences (No. KGCX2-YW-224), Key Projects in the
National Science & Technology Pillar Program in the Eleventh Fiveyear Plan Period (No. 2006BAC02A14), and the National Natural
Science Foundation of China (No. 50774073).
References

Fig. 9. Microstructure of steel GCr15, after heating for 2 h at 1250 C in a mufe

furnace: (a) bare and (b) coated.

[1] D.W. Hetzner, Laser glazed bearings, ASTM Spec. Tech. Publ. 1327 (1998)
471495.
[2] S. Ganguly, I. Chakrabarti, M.D. Maheshwari, T. Mukherjee, Ultra clean steel for
anti-friction bearing applications, in: J.M. Beswick (Ed.), Bearing Steel Technology, 2002, 100 Barr harbor drive, West Conshohochen, pp. 4770.

4982

X. Wang et al. / Applied Surface Science 258 (2012) 49774982

[3] J. Baud, A. Ferrier, J. Manenc, J. Bnard, The oxidation and decarburizing of FeC
alloys in air and the inuence of relative humidity, Oxid. Met. 9 (1975) 6997.
[4] Y. Prawoto, N. Sato, I. Otani, M. Ikeda, Carbon restoration for decarburized layer
in spring steel, J. Mater. Eng. Perform. 13 (2004) 627636.
[5] M. Hajduga, J. Kucera, Decarburization of FeCrC steels during hightemperature oxidation, Oxid. Met. 29 (1988) 419433.
[6] M. Kitayama, H. Odashima, Method for preventing decarburization of steel
materials, USA Patent no. 4,227,945 (1980).
[7] H. Odashima, M. Kitayama, Oxidation-inhibition mechanism and performance
of a new protective coating for slab reheating of 3-percent Si-steel, ISIJ Int. 30
(1990) 255264.
[8] M. Torkar, B. Glogovac, F. Kaucic, D. Finzgar, S. Triglav, Diminution of scaling
by the application of a protective coating, J. Mater. Process. Technol. 58 (1996)
217222.
[9] L. Wei, P. Liu, S. Ye, Y. Xie, Y. Chen, Preparation and properties of anti-oxidation
inoganic nano-coating for low carbon steel at an elevated temperature, J.
Wuhan Univ. Technol. 21 (2006) 4852.
[10] L. Surez, P. Rodrguez-Calvillo, Y. Houbaert, R. Cols, Oxidation of ultra low
carbon and silicon bearing steels, Corros. Sci. 52 (2010) 20442049.

[11] O. Castelein, B. Soulestin, J.P. Bonnet, P. Blanchart, The inuence of heating rate
on the thermal behaviour and mullite formation from a kaolin raw material,
Ceram. Int. 27 (2001) 517522.
[12] C.Y. Chen, G.S. Lan, W.H. Tuan, Microstructural evolution of mullite during the
sintering of kaolin powder compacts, Ceram. Int. 26 (2000) 715720.
[13] C.J. McConville, W.E. Lee, J.H. Sharp, Microstrctural evolution inred kaolinite,
Br. Ceram. Trans. 97 (1998) 162168.
[14] W.E. Lee, G.P. Souza, C.J. McConville, T. Tarvornpanich, Y. Iqbal, Mullite formation in clays and clay-derived vitreous ceramics, J. Eur. Ceram. Soc. 28 (2008)
465471.
[15] C.Y. Chen, G.S. Lan, W.H. Tuan, Preparation of mullite by the reaction sintering
of kaolinite and alumina, J. Eur. Ceram. Soc. 20 (2000) 25192525.
[16] N.P. Zhetvin, L.N. Podvoiskii, L.I. Krylova, Investigation of the kinetics of surface
decarburization in ball bearing steel when heat treated, Met. Sci. Heat Treat. 2
(1960) 105108.
[17] M.M. Barbooti, D.A. Al-Sammerrai, Thermal decomposition of citric acid, Thermochim. Acta 98 (1986) 119126.
[18] J. Mastowska, Thermal decomposition and thermofractochromatographic
studies of metal citrates, J. Therm. Anal. 29 (1984) 895904.