www.steel-research.

de

FULL PAPER
A New Double Calcium Treatment Method for
Clean Steel Refining
Zhiyin Deng, and Miaoyong Zhu

A new double calcium treatment method was proposed according to industrial

experiment. In the new process, the evolution of inclusion was analyzed and the
controlling standard of T.[Ca]/T.[O] ratio for calcium treatment was discussed. The results
show that good castability with low calcium content about 12 ppm was obtained by this
method, and the inclusion grade of D type thin series decreases from 1.5 to 1.0 in final
product. CaO—MgO—Al2O3 system inclusions containing small amount of CaO are mainly
presented after LF refining. After the 1st calcium treatment, most inclusions are in the
liquid region with low melting point and the MgO content decreases obviously. After the
2nd calcium treatment, the distribution of inclusion composition is more concentrated
compared with the 1st calcium treatment, and the MgO content decreases further with the
inclusion composition very close to CaO—Al2O3 system and almost all in liquid region. In
order to get a good calcium treatment result, T.[Ca]/T.[O] ratio should be controlled above
0.91, and the ratio between 0.91 and 1.25 is suitable in present work.

1. Introduction refining process, only few inclusions remain Al2O3 phase,

Poor castability is often presented with nozzle clogging in
Al-killed steel producing. In order to improve castbility,
calcium treatment is commonly applied to modified
the products of deoxidation into the inclusions with
low melting point. The content of calcium is the most
important parameter of calcium treatment, and pure
calcium or calcium alloy are usually added into molten
steel at once before casting. If the content is too low, the
modification is not enough with poor castability as well,
while if the content is too high, CaS would be generated
with increasing probability of nozzle clogging,[1,2] and the
erosion of refractories is also enhanced, affecting the
cleanness of steel.
Since a lot of Al2O3 inclusions are formed when Al added
into molten steel for deoxidation, calcium treatment was
mainly considered to modify the Al2O3 inclusions in most
references,[3–10] and the standard of T.[Ca]/[Al]s ratio were
proposed to evaluate the calcium treatment results.[6]
Because of the difference of thermodynamic data, there
were different T.[Ca]/[Al]s ratios reported by different
scholars.[6–10] In fact, according to slag formation in LF
[] Z. Deng, Prof. M. Zhu
School of Materials and Metallurgy, Northeastern University,
Shenyang 110819, China
Email: myzhu@mail.neu.edu.cn
DOI: 10.1002/srin.201200250
and most have changed into another phase.[11] Besides,
with the development of smelting technology, the clean-
ness of steel were promoted largely, and there is no need of
such more calcium to treat inclusions. Therefore, the
standard of T.[Ca]/[Al]s ratio for calcium treatment is
already unsuitable for modern refining process.
Because of the smaller contact angle and less time to
float into slag, the liquid inclusions are easily to remain in
liquid steel and generate a small number of large
CaO—Al2O3 system inclusions, often worsening inclusions
grades. Double calcium treatment was developed by Ito
et al.[12] in the producing process of pipeline steel, and the
first calcium treatment was carried out after LF refining in
order to remove the large inclusions in the following RH
treatment, while the second calcium treatment was carried
out in tundish, thereby improving the efficiency of calcium
treatment. However, slag would billow with slag entrap-
ment and bareness of liquid steel in the second calcium
treatment process, besides there is no more floating time
for the modified inclusions. So this method is not very
effective as well.
In present work, a new double calcium treatment
method was proposed with the second calcium treatment
after RH refining. According to controlling the calcium
content in industrial experiment, the change of elements
before and after double calcium treatment process was
studied. At the same time, the control standard of
T.[Ca]/T.[O] ratio for calcium treatment was discussed
and the evolution of inclusion was analyzed in double
calcium treatment process.

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 84 (2013) No. 6 519
 www.steel-research.de
FULL PAPER

2. Experimental
2.1. Experimental Procedure

The industrial experiment of 13 heats was made in a steel

plant, and the steel grade 35CrMo with chemical compo-
sition listed in Table 1 was produced by the process of
‘‘hot metal pre-desulfurization ! 80 ton BOF steelma-
king ! 80 ton LF refining ! 80 ton RH refining ! Bloom
continuous casting.’’ In the refining, high basicity refining
slag with low FeO content was chosen shown in Table 2.
The first calcium treatment was carried out after LF refin-
ing by 100 m pure calcium wire feed, and after about 5 min
of soft blowing, the steel was treated by RH vacuum
degassing with the treat time about 25 min. After RH refin-
ing, the second calcium treatment was also carried out by
Figure 1. Variation of calcium content in refining process.
50 m pure calcium wire feed, and then casting after about
15 min soft blowing. In the experimental procedure, liquid
steel samples were taken with barrel type samplers to
analyze the inclusions and compositions. starts to escape from the liquid steel as gaseous calcium,
then the calcium in steel decreases rapidly. After about
15 min of RH treatment, the calcium content in liquid steel
becomes almost stable, and the value is about 5 ppm.
2.2. Sample Analysis
Because of the second calcium treatment, the calcium
content increases with low value about 12 ppm after soft
Steel samples were prepared for chemical analysis, and the
blowing.
acid-soluble Al and Ca contents in steel were analyzed by
Figure 2 gives the total oxygen content in the smelting
ICP method. Total oxygen contents of these samples were
process. It can be seen that the average of total oxygen
measured by fusion and the infrared absorption method.
content is about 16 ppm after LF refining and about 12 ppm
Steel samples for inclusions were analyzed by SEM–EDS to
after RH refining, indicating good deoxidation results after
obtain the morphology, size, and chemical compositions.
LF and RH refining. The total oxygen content commonly
reflects the cleanness of steel, so the inclusions in steel are
less after refining.

3. Results and Discussion

3.1. Total Oxygen and Calcium Contents 3.2. Morphologies and Compositions of Inclusions

Figure 1 shows the calcium content of the smelting proc- Figure 3 presents the morphologies of inclusions before
ess. As can been seen from this figure, after first calcium first calcium treatment. There are three types of inclusions,
treatment, the average content of calcium is about 18 ppm. namely Al2O3 inclusions with irregular shape shown
With the treatment of RH degassing, the dissolved calcium in Figure 3a, MgO—Al2O3 system inclusions shown in

C Si Mn P S Cr Mo Al

0.32–0.40 0.17–0.37 0.40–0.70 0.015 0.005 0.80–1.10 0.15–0.25 0.02–0.04

Table 1. Chemical composition of 35CrMo (in mass%).

CaO SiO2 Al2O3 MgO FeO R

45–55 5–15 20–30 5–8 <1 3–5

Table 2. Composition of experimental slag (in mass%).

520 steel research int. 84 (2013) No. 6 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de
Figure 2. Variation of total oxygen content in smelting process.
Figure 3b–c and globular CaO—MgO—Al2O3 system
inclusions shown in Figure 3d. It can be seen that the main
size of inclusions is about 5 mm.
Figure 4 shows the morphologies of inclusions after
first calcium treatment. As shown in Figure 4, the
Figure 3. Morphology of inclusions before calcium treatment (a): Al2O3; (b) and (c): MgO—Al2O3; (d): CaO—MgO—Al2O3.
Figure 4. Morphology of inclusions after 1st calcium treatment (a)–(c): small inclusions; (d) large inclusions.
Figure 5. Morphology of inclusions after 2nd calcium treatment.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
inclusions are mainly CaO—MgO—Al2O3 system and
CaO—MgO—Al2O3—CaS system, whose shapes are glob-
ular or close to globular. The main sizes of inclusion are
obviously smaller than that before calcium treatment with
the value about 2 mm, as shown in Figure 4a–c. There are
also few inclusions observed with the size even larger than
30 mm as shown in Figure 4d. Therefore, the inclusion size
can be reduced by the first calcium treatment generally,
but a small amount of large inclusions would be generated,
and thus become one of the main reasons for worsening
inclusions grades.
The morphologies of inclusions after second calcium
treatment are presented in Figure 5. As shown in Figure 5,
the inclusions are also mainly globular CaO—MgO—Al2O3
system and CaO—MgO—Al2O3—CaS system, and their
sizes are slightly smaller than that after first calcium treat-
ment with most values <2 mm. Large size inclusions were
not found, so the large inclusions have been removed after
RH refining.
CaO—MgO—Al2O3 ternary system is considered
in Figure 6, and the distribution of inclusions at different
stages is marked in these ternary phase diagrams. The
liquid region (melting point of inclusions below 15508C)
surrounded by blue solid line is calculated by software
steel research int. 84 (2013) No. 6 521
 www.steel-research.de
FULL PAPER

Figure 6. Composition distribution of inclusions.

FactSage 6.1. Before calcium treatment as shown
in Figure 6a, the CaO—MgO—Al2O3 system inclusions
are the main inclusions. Most of them contain a small
amount of CaO with high melting point, while part of them
are already in the composition region of liquid. Except for
CaO—MgO—Al2O3 system inclusions, there are also some
Al2O3 and MgO—Al2O3 system inclusions as shown
in Figure 4. This result was also obtained by Ohta
et al.[11] and Yang et al.[13] Therefore, the main goal of
calcium treatment is not modification for Al2O3 inclusions,
but CaO—MgO—Al2O3 system inclusions containing a
small amount of CaO. After first calcium treatment, most
inclusions are in the liquid region as shown in Figure 6b
with the increase of CaO content and the decrease of MgO
content, and the inclusion shape would change into glob-
ular as shown in Figure 4. After second calcium treatment,
the composition distribution is more concentrated than
that after first calcium treatment, and with the further
decrease of MgO content, the inclusion are very close to
CaO—Al2O3 system and almost all in liquid region as
shown in Figure 6c. It can be seen from Figure 6 that
the inclusions would change into CaO—MgO—Al2O3
and then gradually into CaO—Al2O3 system in the calcium
treatment process.
method under the same experimental conditions. The
types and grades of inclusions were classified according
to the China national standard GB/T 10561-2005/ISO
4967:1998(E). As can be seen from Table 3, the inclusion
grade of D type thin series which is obtained from common
calcium treatment is almost 1.5, while this grade decreased
to 1.0 obtained from double calcium treatment. Therefore,
the inclusion grade is more conducive to be reduced by the
double calcium treatment.
3.4. T.[Ca]/T.[O] Ratio for Clean Steel
According to the very low content of MgO shown in
Figure 6b,c, the whole oxide inclusions are considered
approximately as CaO—Al2O3 system inclusions after
calcium treatment. As shown in Table 4, in order to obtain
a good castability, 12CaO  7Al2O3 inclusions are the target
inclusions because of the lowest melting point among the
CaO—Al2O3 system inclusions. In fact, it is impossible to
make all the inclusions change into 12CaO  7Al2O3.
Therefore, at the steelmaking temperature (considered
above 16058C), the target inclusions are commonly

3.3. Castability and Inclusion Grades

The mold level and stopper rod position are given

in Figure 7. It can be seen from the figure that because
of casting speed adjustment, the mold level waved rela-
tively largely at the beginning of casting, and in the fol-
lowed 12 heats, the level waved slightly. Besides, except for
the beginning stage of casting, the stopper position
decreased slightly in the whole casting process without
any nozzle clogging. These all show that the castability
is very good.
Table 3 presents the inclusion grades from common
calcium treatment method and double calcium treatment Figure 7. Curve of mold level and stopper rod position.

522 steel research int. 84 (2013) No. 6 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de

FULL PAPER
Process Sample Type A Type B Type C Type D

T H T H T H T H

Old process 1 2.0 0 0 0 0 0 1.5 0.5

2 1.5 0 0 0 0 0 1.5 0.5
3 1.5 0 0 0 0 0 1.5 0.5
4 1.0 0 0 0 0 0 1.5 0.5
Present work 1 1.0 0 0 0 0 0 1.0 0.5
2 1.0 0 0 0 0 0 1.0 0.5
3 1.5 0 0 0 0 0 1.0 0.5
4 2.0 0 0 0 0 0 1.0 0.5

Table 3. Types and grades of inclusions.

Inclusion CaO  6Al2O3 CaO  2Al2O3 CaO  Al2O3 12CaO  7Al2O3 3CaO  Al2O3

Tm (8C) 1850 1750 1605 1455 1535

T.[Ca]/T.[O] 0.132 0.357 0.625 0.909 1.250

Table 4. Melting point and T.[Ca]/T.[O] ratio for different inclusions.

expanded as CaO  Al2O3, 12CaO  7Al2O3, 3CaO  Al2O3 and the shadow region is the target liquid region of calcium
their intermediate according to melting points shown treatment. The experimental data are marked in Figure 8,
in Table 4. and it can be seen that the experimental T.[Ca]/T.[O] ratios
The total oxygen content reflects the number of oxide are all in liquid region with most values larger than 0.909
inclusions in steel, and all the calcium and oxygen (12CaO  7Al2O3) and lower than 1.250 (3CaO  Al2O3). The
elements in steel are considered to remain in the
CaO—Al2O3 system inclusions, so the T.[Ca]/T.[O] ratio
can be used to evaluate the modification result of
inclusions.[1,3,5] The T.[Ca]/T.[O] ratios of different
CaO—Al2O3 system inclusions are listed in Table 4. As
can be seen from the table, in order to obtain good modi-
fication results and castability, the T.[Ca]/T.[O] ratio
should be in the region between 0.625 and 1.250. In prac-
tice, except for remaining in the CaO—Al2O3(—MgO) sys-
tem inclusions, little calcium would exist as dissolved
calcium in liquid steel, while little calcium element would
be fixed in the CaS inclusions when precipitated. The sulfur
content is lower than 0.005% in present work, and CaS
would not precipitate in the steel refining process.[1] However,
in the casting and solidification process, CaS would also
precipitate on the surface of CaO—Al2O3(—MgO) system
inclusions with the drop of temperature. Therefore, the
T.[Ca]/T.[O] ratio for actual calcium treatment should be
controlled larger than that range.
Figure 8 gives the relationship between total oxygen and Figure 8. Relationship between T[O] and T[Ca] in inclusion of
calcium contents for CaO—Al2O3 system inclusions, and CaO—Al2O3 system.

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 84 (2013) No. 6 523

FULL PAPER
real compositions of inclusions shown in Figure 6b,c have
already proved that the calcium treatment was controlled
suitable. Therefore, in order to obtain a good result of
calcium treatment, the T.[Ca]/T.[O] ratio should be con-
trolled larger than 0.909. In present work, the T.[Ca]/T.[O]
ratio is controlled suitable with value in the range between
0.909 and 1.250.
The content ratio between total calcium and dissolved
Al content (T.[Ca]/[Al]s ratio) is commonly applied to con-
trol calcium content in calcium treatment process,[6–10] so
if the content of dissolved Al is 0.025 mass% and T.[Ca]/
[Al]s ratio is considered as a low value of 0.10, then calcium
content should be 25 ppm. This content is much larger
than that of present work, so T.[Ca]/T.[O] ratio is more
suitable to control calcium treatment.
3.5. Evolution of Inclusions in Double Calcium
Treatment Process
According to Ref.,[14] Al2O3 inclusions would transfer
into MgO—Al2O3 system inclusions as shown in
Equation 1 when there is a trace of dissolved Mg. As seen
from Figure 6a, the main inclusions are CaO—MgO—Al2O3
system inclusions containing a small amount of CaO, so
the MgO—Al2O3 system inclusions are considered as the
whole inclusions before calcium treatment.
 
1 2
½Mg þ xAl2 O3 ¼ MgO x  Al2 O3 þ ½Al (1)
3 3
Many scholars[13,15,16] found that the distribution of Ca and
Mg elements presents complementary in inclusions after
calcium treatment, and they proposed the mechanism of
calcium treatment for MgO—Al2O3 inclusions is Ca
element substitution for Mg element in MgO—Al2O3
inclusions, and finally the inclusions transfer into
CaO—MgO—Al2O3 system or CaO—Al2O3 system
inclusions. Therefore, at the edges of inclusions contacting
with molten steel, there is a reaction with
CaO—MgO—Al2O3 system inclusions formed as shown
in Equation 2.
x½Ca þ yMgO  zAl2 O3
¼ xCaO  ðy  xÞMgO  zAl2 O3 þ x½Mg (2)
With the diffusion of Ca element, in the inner part of
CaO—MgO—Al2O3 system inclusions and at the edges of
inclusions contacting with liquid steel, the reaction occurs
as shown in Equation 3. For those CaO—MgO—Al2O3
system inclusions formed before calcium treatment, the
evolution process could also be expressed as Equation 3.
½Ca þ CaO  xAl2 O3  yMgO
¼ 2CaO  xAl2 O3  ðy  1ÞMgO þ ½Mg (3)
524 steel research int. 84 (2013) No. 6
www.steel-research.de
According to the evolution mechanism of Al2O3
inclusions into calcium aluminate developed by Ye et al.[17]
and Ito et al.,[12,18] when the edges of CaO—MgO—Al2O3
inclusions have totally changed into CaO—Al2O3 system,
calcium aluminate could change into another state with
lower melting point as shown in Equation 4.
½Ca þ xCaO  yAl2 O3
 
1 2
¼ ðx þ 1ÞCaO  y  Al2 O3 þ ½Al (4)
3 3
As seen from Equation 2 to 4, the essence of the calcium
treatment process is Ca element substitution for Mg and Al
element in the inclusions. Therefore, in the process of
calcium treatment, the CaO content of inclusions increases
continuously while the MgO and Al2O3 contents decrease
with the composition change of inclusions shown
in Figure 6. Based on the above analysis, Figure 9 gives
the unreacted core model of evolution of MgO—Al2O3
system inclusions into CaO—MgO—Al2O3 system and
CaO—Al2O3 system inclusions.
According to Figure 9, when the first calcium treatment
was carried out, Ca element diffused from the outer part to
the inner part of inclusions gradually, and the CaO content
presented larger in edge and lower in center of the
inclusions. Due to the constraints of the diffusion kinetics,
the CaO content in center would be lower in large
inclusions. It causes the CaO content of entire inclusions
is lower than that of small inclusions, showing the com-
position distribution of inclusions relatively scattered as
shown in Figure 7b. Although the CaO content is low, the
edges of inclusions have changed into CaO—MgO—Al2O3
or CaO—Al2O3 system with melting point lower than liquid
steel temperature. Therefore, the inclusions present glob-
ular shape and grow up easily by collision.
After the first calcium treatment, the short and soft
blowing is conducive for uniform distribution of dissolved
Figure 9. Unreacted core model of evolution of MgO—Al2O3
system inclusions.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de
Ca in liquid steel and improves kinetics condition and
inclusion growth by collision. At the early stage of RH
treatment (about the first 5 min), as shown in Figure 1
the calcium content decreased little relatively with a high
gradient of dissolved Ca content still. Therefore, with the
good kinetics condition created by RH vacuum circulation,
the early stage of RH treatment is still beneficial for CaO
diffusion into the inner part of inclusions. In addition,
the large inclusions which grew up by collision would be
removed by RH vacuum circulation, and the size of the
inclusions would be reduced further.
With the RH treatment, the calcium content in liquid steel
decreased gradually, when the calcium content decreased to
a certain value, the gradient of dissolved Ca content became
negative, and the calcium element in inclusions started to
diffuse into liquid steel [19]. Since the diffusion of Ca element
started from the edge of inclusions, and the CaO content in
inclusions distributed higher in edge and lower in center, the
Ca content in center would change little.
After RH treatment, since the size of inclusions was very
small, when the second calcium treatment was carried out,
the Ca element diffused from the edge to the center of
inclusion quickly. Based on suitable T.[Ca]/T.[O] ratio, the
composition of inclusions would be close to 12CaO  7Al2O3
and more concentrated because of the CaO content in
center after RH treatment. It accords with the result
obtained by Ito et al.[12]
4. Conclusions
A new double calcium treatment method was proposed for
clean steel refining. According to industrial experiment,
the evolution of inclusion was analyzed and the controlling
standard of T.[Ca]/T.[O] ratio for calcium treatment was
discussed with the following conclusions.
(1) Good castability with low calcium content about
12 ppm was obtained by the double calcium treatment
and the inclusion grade of D type thin series decreases
from 1.5 to 1.0 in final product.
(2) CaO—MgO—Al2O3 system inclusion containing small
amount of CaO are mainly presented at the end of
LF refining. After the 1st calcium treatment, most
inclusions are in the liquid region with low melting
point and the MgO content decreases obviously. After
the 2nd calcium treatment, the distribution of
inclusion composition is more concentrated compared
with the 1st calcium treatment, and the MgO content
decreases further with the inclusion composition close
to CaO—Al2O3 system and almost all in liquid region.
In the calcium treatment process, the inclusions would
change into CaO—MgO—Al2O3 and then gradually
into CaO—Al2O3 system.
(3) In order to get a good calcium treatment result, T.[Ca]/
T.[O] ratio should be controlled above 0.91, and the
ratio between 0.91 and 1.25 is suitable in present work.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Acknowledgments
The authors are grateful for the support provided by
National Natural Science Foundation of China (grant no.
51134009) and the Specialized Research Fund for the
Doctoral Program of Higher Education of China (grant
no. 20110042110010). The authors also wish to thank
Mr. Baojun Zhong and Mr. Yonggang Dai in Xingtai
Steel of China, for their help in this work.
Received: September 16, 2012;
Published online: December 27, 2012
Keywords: calcium treatment; clean steel; inclusions;
modification; castability
References
[1] S. K. Choudhary, A. Ghosh, ISIJ Int. 2008, 48(11),
1552.
[2] S. Abdelaziz, G. Megahed, I. El-Mahallawi, H.
Ahmed, Ironmaking Steelmaking 2009, 36(6), 432.
[3] J. H. Liu, H. J. Wu, Y. P. Bao, H. S. Qin, S. S. Zang,
X. J. Zhang, J. Univ. Sci. Technol. Beijing 2010, 32(3),
312.
[4] J. H. Liu, H. J. Wu, Y. P. Bao, M. Wang, Int. J. Miner.
Metall. Mater. 2011, 18(5), 527.
[5] J. M. A. Geldenhuis, P. C. Pistorius, Ironmaking
Steelmaking 2000, 27(6), 442.
[6] G. M. Faulring, J. W. Farrell, D. C. Hilty, Ironmaking
Steelmaking 1980, 7(2), 14.
[7] C. J. Zhang, K. K. Cai, W. X. Yuan, Iron Steel 2006,
41(8), 31.
[8] K. Z. Wang, W. Sun, Res. Iron Steel 2005, 3, 38.
[9] S. P. He, C. R. Wang, Z. Y. Lai, Q. Wang, B. C. Huang,
J. C. Peng, J. Univ. Sci. Technol. Beijing 2007, 29(s1), 18.
[10] H. C. Gao, M. L. Liu, L. M. Zhang, H. Yan, H. J.
Wang, Iron Steel 2005, 40(11), 21.
[11] H. Ohta, S. Kimura, T. Mimura, H. Matsumoto, R&D
Kobe Steel Eng. Rep. 2011, 61(1), 98.
[12] Y. Ito, S. Nara, Y. Kato, M. Suda, Tetsu-to-Hagané
2007, 93(5), 355.
[13] S. H. Yang, Q. Q. Wang, L. F. Zhang, J. S. Li, K.
Peaslee, Metall. Mater. Trans. B 2012, 43B(8), 731.
[14] M. Jiang, Xi. H. Wang, B. Chen, W. J. Wang, ISIJ Int.
2008, 48(7), 885.
[15] E. B. Pretorius, H. G. Oltmann, T. Cash, Iron Steel
Technol. 2010, 7(7), 31.
[16] N. Verma, M. Lind, P. C. Pistorius, R. J. Fruehan,
M. Potter, Iron Steel Technol. 2010, 7(7), 189.
[17] G. Z. Ye, P. Jonsson, T. Lund, ISIJ Int. 1996, 36(s),
105.
[18] Y. Ito, M. Suda, Y. Kato, H. Nakato, K. Sorimachi,
ISIJ Int. 1996, 36(s), 148.
[19] Y. Higuchl, M. Numata, S. Fukagawa, K. Shinme, ISIJ
Int. 1996, 36(s), 151.
steel research int. 84 (2013) No. 6 525