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Zhang Ju was born in 1991． He got his bachelor’s degree on materials science and engineering from
Wanfang College of Science ＆ Technology，Henan Polytechnic University in 2013． Now he is studying for
his master’s degree in Zhengzhou University，majoring in materials science．
Abstract
Damage reasons of purging plugs for refining ladle
and research progress on thermal shock resistance of co-
rundum － spinel purging plugs were summarized． Ｒe-
search achievements and application results of nonoxides
bonded corundum purging plugs for refining ladle were
briefly reviewed． The further research and developing
trend of purging plugs was proposed．
Key words： purging plugs； corundum － spinel； nonox-
ides； thermal shock resistance； refining ladle
China’s crude steel production reached 779 mil-
lion tons in 2013， accounting for 49． 27% of the
world’s total，but there were still gaps in the perform-
ances of high quality steel and special steel in compari-
son with those of the developed countries． The seconda-
ry refining technology has become the most important
modern refining technique，and bottom argon blowing
process has been widely applied in secondary refining
technology． Moreover，purging plugs are the key func-
tional refractories in refining process of steel．
With the increase of refining ladles in size，smel-
ting temperature and smelting time，the service condi-
tions of the refractories for ladles become more severe，
which require the refractories with higher performance．
Nowadays，bottom blowing purging plugs for ladles are
the barrier in prolonging the service life of ladle due to
their special position and severe service conditions． To
make their service life match with that of ladle lining or
bottom refractories and to keep the higher blowing-
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through rate are the common dreams of steel plants，
producers and researchers．
The intermittent process of purging plugs for ladle
is as follows： catching steel → blowing → refining → tap-
ping → pouring slag → oxygen cleaning． The purging
plugs endure the above process repeatedly until the end
of their lives． Among the factors affecting the service
life of purging plugs， thermal spalling and oxygen
cleaning are the key reasons for damage of purging
plugs［1］． Air blowing time and stirring intensity also
have significant influence on damage of purging
plugs［2］． During the refining process，thermal spalling
and penetration of steel in the slits lead to the disfunc-
tion of plugs［3 － 4］． There are transverse cracks under
the surface of slot corundum － spinel purging plugs con-
tacting with the molten steel，resulting in the thermal
spalling，and reducing the service life of purging plugs．
Penetration and erosion of liquid steel are the major
causes of purging plugs damage［5 － 6］． The microstruc-
ture analysis of used purging plugs debris showed
that［7］： there are significant slag penetration and ero-
sion through the slit or the crack of purging plugs ap-
pears during LF refining process，while there is liquid
steel penetration through the slit and the crack of pur-
ging plugs appears during LF + VD refining process． In
the cyclic operation，cracks caused by the enlargement
of slit and thermal stress can worsen the penetration of
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liquid steel or slag erosion and thermal spalling． If the
slits of purging plugs are clogged，oxygen cleaning is
necessary in the process［8］．
In order to improve the performance and service
life of slot purging plugs，some measures should be
considered： （ 1 ） taking corrosion resistance into ac-
count，materials with good thermal shock resistance
should be selected； （ 2） in view of penetration resist-
ance，materials should not be easily wetted by molten
steel at operating temperatures． The order of the wet-
ting angle between oxide refractories and molten steel
is： ZrO2 ＞ Al2 O3 ＞ MgO［9］．
2． 1 Corundum － spinel Purging Plugs
Currently， purging plugs for ladle are mainly
chrome corundum or corundum － spinel based refracto-
ries，which are usually cast and fired at high tempera-
tures． However，Cr6 + forms when firing the chrome co-
rundum purging plugs at high temperatures causing pol-
lution，and adding chrome oxide has negative effect on
the thermal shock resistance of corundum － spinel pur-
ging plugs［10］，thus the purging plugs are gradually re-
placed by corundum － spinel purging plugs． The serv-
ice life of corundum － spinel material is limited due to
its poor thermal shock resistance resulting in thermal
spalling and structure spalling in the application． Kha-
lil［11］ researched the thermal mechanical behavior of
cement bonded castables，and found that there were
three high melting point mineral phases in calcium alu-
minate cement bonded corundum － spinel castables af-
ter firing at high temperatures： hexaluminate calcium
（ melting point 1 890 ℃ ） ，spinel （ melting point 2 100
℃ ） and corundum （ melting point 2 050 ℃ ） ； tabular
hexaluminate calcium in matrix had a good combination
with corundum or spinel making the material possess
excellent thermal shock resistance and high hot
strength， thus they were known as the best matrix
system．
Li Daibing，et al． ［12 － 13］ investigated that the cold
modulus of rupture and strength retention ratio of corun-
dum － spinel castables after thermal shock （ 1 300 ℃
air cooling and 1 000 － 1 600 ℃ thermal shock cycle）
increased firstly then decreased with the heat treatment
temperature rising． The thermal shock resistance of the
castables fired at 1 600 ℃ was the best； moreover，
CA6 clearly developed to tabular，there was obvious in-
terwoven structure releasing the thermal stress，while
40 2014 /2 China’s Ｒefractories www． China-refractories． cn
appropriate alumina solid solution in spinel resulted in
the increase of bonding strength． Destruction of 1 000
－ 1 600 ℃ thermal shock cycle was more severe than
that of 1 300 ℃ air cooling．
The result of Ko ’s［14］ showed that residual
strength of corundum － spinel castable after thermal
shock decreased significantly with the increase of fines
content （ ≤0． 074 mm） of castables from 31 mass% to
35 mass% and to 41 mass% ．
With the increase of spinel fine powders，hot mod-
ulus of rupture of corundum － spinel castables increased
gradually，and thermal shock resistance decreased sig-
nificantly first and then improved［15］． Moreover，ther-
mal shock resistance of corundum － spinel castables im-
proved with the increase of spinel grains and decrease
of fines［16 － 17］． Solid solution of alumina in spinel oc-
curred，the lattice constants of spinel became large；
some micro-cracks formed around spinel and corundum
particles，thus thermal shock resistance improved［17］．
Introducing an appropriate amount of monoclinic
zirconia or zirconia corundum to corundum － spinel ma-
terials， microcracks can be formed in the matrix
through phase transformation of zirconia，which was
beneficial to the absorption of thermal stress and ther-
mal shock resistance． Moreover，the number and size
of cracks in castables could be controlled by selecting
the particle size and content of zirconia corundum，
thereby improving the thermal shock resistance［18 － 20］．
A previous work by Jia Quanli，et al． ［21］ showed
that changing cement amount of corundum － spinel
castable to adjust CaO content in the matrix，more CA6
formed in the matrix resulting in significant improve-
ment of thermal shock resistance （ Fig． 1） ． The reason
was that tabular CA6 formed at high temperatures，and
developed gradually with temperature rising，filling in
the framework and enhancing the strength of corundum
－ spinel castables．
Fig． 1 Effect of cement content on thermal shock resistance
of corundum － spinel castables
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2． 2 Non-oxide Bonded Corundum Purging Plugs
Non-oxides （ Si3 N4 ，β -SiAlON，etc． ） have high
hot strength，good thermal shock resistance and good
wetting resistance to molten metal and slag． Corundum
－ silicon nitride purging plugs were prepared by intro-
ducing silicon into corundum － silicon nitride materi-
als［22］． It was found that this kind of purging plugs had
a good wetting resistance to iron slag and it was superi-
or to corundum － spinel，chrome corundum and corun-
dum － mullite purging plugs in the properties of corro-
sion resistance to iron slag and the rate of blowing-
through． Lu Xiangyang，et al． ［23］ prepared SiAlON
bonded corundum purging plugs by using tabular alumi-
na as aggregate，Al2 O3 powder and Si powder as ma-
trix，adding a small amount of Ln2 O3 as sintering aid，
vibration casting，firing in nitride atmosphere； the pur-
ging plugs possessed high strength，good thermal shock
resistance，excellent slag resistance， etc． When Si
powder ranged from 9． 5 mass% to 11． 5 mass% ，the
performance was better．
In the previous works［24 － 25］，SiAlON bonded co-
rundum castables were prepared by in-situ nitriding re-
action． The results showed that with the increase of
SiAlON amount，water demand for molding increased，
cold strength and bulk density decreased，but apparent
porosity increased slightly． The castables first shrank
and then expanded slightly resulting in significant im-
provement of thermal shock resistance （ see Fig． 2） ． On
this basis，nitride bonded corundum purging plugs were
used in the refining ladle，showing good gas permeabili-
ty and blowing reliability，low wear rate and ease-of-
oxygen cleaning，and the service life improved by 15%
in comparison with that of corundum － spinel purging
plugs．
Fig． 2 Effect of SiAlON content on thermal shock resistance
of SiAlON bonded corundum castables
In order to improve the blowing-through rate and
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service life of purging plugs，the infiltration depth of
steel in slits should be reduced to retard the erosion of
oxygen cleaning and the thermal shock resistance of
purging plugs should be improved．
In view of improving the durability of corundum －
spinel purging plugs，measures were： （ 1 ） optimizing
the ingredients of corundum － spinel purging plugs by
adjusting the particle size and the amounts of spinel and
cement，adding an appropriate amount of ZrO2 or zirco-
nia corundum，and optimizing the firing temperature；
（ 2） controlling the grain morphology of CA6 ，microc-
racks，size and distribution of pores，and adding an ap-
propriate amount of high viscosity glass phase in the
matrix to improve the thermal shock resistance of the
materials．
Non-oxide （ silicon nitride or SiAlON） bonded co-
rundum purging plugs have good gas permeability and
blowing reliability，low wear rate and ease-of-oxygen
cleaning due to their excellent thermal shock resistance
and wetting resistance to molten steel，and the service
life improves significantly in comparison with that of co-
rundum － spinel purging plugs．
Acknowledgement
The authors would like to thank National Science Founda-
tion of China （ No． 51032007 and No． U1204505） for support-
ing this work．
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Ｒeceived in Sept． ，2013
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