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A New Double Calcium Treatment Method for
Clean Steel Refining
Zhiyin Deng, and Miaoyong Zhu
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2. Experimental
2.1. Experimental Procedure
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
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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-
Figure 2. Variation of total oxygen content in smelting process.
ment with most values <2 mm. Large size inclusions were
not found, so the large inclusions have been removed after
RH refining.
Figure 3b–c and globular CaO—MgO—Al2O3 system CaO—MgO—Al2O3 ternary system is considered
inclusions shown in Figure 3d. It can be seen that the main in Figure 6, and the distribution of inclusions at different
size of inclusions is about 5 mm. stages is marked in these ternary phase diagrams. The
Figure 4 shows the morphologies of inclusions after liquid region (melting point of inclusions below 15508C)
first calcium treatment. As shown in Figure 4, the surrounded by blue solid line is calculated by software
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.
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FactSage 6.1. Before calcium treatment as shown method under the same experimental conditions. The
in Figure 6a, the CaO—MgO—Al2O3 system inclusions types and grades of inclusions were classified according
are the main inclusions. Most of them contain a small to the China national standard GB/T 10561-2005/ISO
amount of CaO with high melting point, while part of them 4967:1998(E). As can be seen from Table 3, the inclusion
are already in the composition region of liquid. Except for grade of D type thin series which is obtained from common
CaO—MgO—Al2O3 system inclusions, there are also some calcium treatment is almost 1.5, while this grade decreased
Al2O3 and MgO—Al2O3 system inclusions as shown to 1.0 obtained from double calcium treatment. Therefore,
in Figure 4. This result was also obtained by Ohta the inclusion grade is more conducive to be reduced by the
et al.[11] and Yang et al.[13] Therefore, the main goal of double calcium treatment.
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 3.4. T.[Ca]/T.[O] Ratio for Clean Steel
inclusions are in the liquid region as shown in Figure 6b
with the increase of CaO content and the decrease of MgO According to the very low content of MgO shown in
content, and the inclusion shape would change into glob- Figure 6b,c, the whole oxide inclusions are considered
ular as shown in Figure 4. After second calcium treatment, approximately as CaO—Al2O3 system inclusions after
the composition distribution is more concentrated than calcium treatment. As shown in Table 4, in order to obtain
that after first calcium treatment, and with the further a good castability, 12CaO 7Al2O3 inclusions are the target
decrease of MgO content, the inclusion are very close to inclusions because of the lowest melting point among the
CaO—Al2O3 system and almost all in liquid region as CaO—Al2O3 system inclusions. In fact, it is impossible to
shown in Figure 6c. It can be seen from Figure 6 that make all the inclusions change into 12CaO 7Al2O3.
the inclusions would change into CaO—MgO—Al2O3 Therefore, at the steelmaking temperature (considered
and then gradually into CaO—Al2O3 system in the calcium above 16058C), the target inclusions are commonly
treatment process.
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Process Sample Type A Type B Type C Type D
T H T H T H T H
Inclusion CaO 6Al2O3 CaO 2Al2O3 CaO Al2O3 12CaO 7Al2O3 3CaO Al2O3
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.
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real compositions of inclusions shown in Figure 6b,c have According to the evolution mechanism of Al2O3
already proved that the calcium treatment was controlled inclusions into calcium aluminate developed by Ye et al.[17]
suitable. Therefore, in order to obtain a good result of and Ito et al.,[12,18] when the edges of CaO—MgO—Al2O3
calcium treatment, the T.[Ca]/T.[O] ratio should be con- inclusions have totally changed into CaO—Al2O3 system,
trolled larger than 0.909. In present work, the T.[Ca]/T.[O] calcium aluminate could change into another state with
ratio is controlled suitable with value in the range between lower melting point as shown in Equation 4.
0.909 and 1.250.
The content ratio between total calcium and dissolved ½Ca þ xCaO yAl2 O3
Al content (T.[Ca]/[Al]s ratio) is commonly applied to con-
1 2
trol calcium content in calcium treatment process,[6–10] so ¼ ðx þ 1ÞCaO y Al2 O3 þ ½Al (4)
if the content of dissolved Al is 0.025 mass% and T.[Ca]/ 3 3
[Al]s ratio is considered as a low value of 0.10, then calcium
content should be 25 ppm. This content is much larger As seen from Equation 2 to 4, the essence of the calcium
than that of present work, so T.[Ca]/T.[O] ratio is more treatment process is Ca element substitution for Mg and Al
suitable to control calcium treatment. 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
3.5. Evolution of Inclusions in Double Calcium with the composition change of inclusions shown
Treatment Process in Figure 6. Based on the above analysis, Figure 9 gives
the unreacted core model of evolution of MgO—Al2O3
According to Ref.,[14] Al2O3 inclusions would transfer system inclusions into CaO—MgO—Al2O3 system and
into MgO—Al2O3 system inclusions as shown in CaO—Al2O3 system inclusions.
Equation 1 when there is a trace of dissolved Mg. As seen According to Figure 9, when the first calcium treatment
from Figure 6a, the main inclusions are CaO—MgO—Al2O3 was carried out, Ca element diffused from the outer part to
system inclusions containing a small amount of CaO, so the inner part of inclusions gradually, and the CaO content
the MgO—Al2O3 system inclusions are considered as the presented larger in edge and lower in center of the
whole inclusions before calcium treatment. inclusions. Due to the constraints of the diffusion kinetics,
the CaO content in center would be lower in large
1 2 inclusions. It causes the CaO content of entire inclusions
½Mg þ xAl2 O3 ¼ MgO x Al2 O3 þ ½Al (1)
3 3 is lower than that of small inclusions, showing the com-
position distribution of inclusions relatively scattered as
Many scholars[13,15,16] found that the distribution of Ca and shown in Figure 7b. Although the CaO content is low, the
Mg elements presents complementary in inclusions after edges of inclusions have changed into CaO—MgO—Al2O3
calcium treatment, and they proposed the mechanism of or CaO—Al2O3 system with melting point lower than liquid
calcium treatment for MgO—Al2O3 inclusions is Ca steel temperature. Therefore, the inclusions present glob-
element substitution for Mg element in MgO—Al2O3 ular shape and grow up easily by collision.
inclusions, and finally the inclusions transfer into After the first calcium treatment, the short and soft
CaO—MgO—Al2O3 system or CaO—Al2O3 system blowing is conducive for uniform distribution of dissolved
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.
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Ca in liquid steel and improves kinetics condition and Acknowledgments
inclusion growth by collision. At the early stage of RH
The authors are grateful for the support provided by
treatment (about the first 5 min), as shown in Figure 1
National Natural Science Foundation of China (grant no.
the calcium content decreased little relatively with a high
51134009) and the Specialized Research Fund for the
gradient of dissolved Ca content still. Therefore, with the
Doctoral Program of Higher Education of China (grant
good kinetics condition created by RH vacuum circulation,
no. 20110042110010). The authors also wish to thank
the early stage of RH treatment is still beneficial for CaO
Mr. Baojun Zhong and Mr. Yonggang Dai in Xingtai
diffusion into the inner part of inclusions. In addition,
Steel of China, for their help in this work.
the large inclusions which grew up by collision would be
removed by RH vacuum circulation, and the size of the
Received: September 16, 2012;
inclusions would be reduced further.
Published online: December 27, 2012
With the RH treatment, the calcium content in liquid steel
decreased gradually, when the calcium content decreased to
Keywords: calcium treatment; clean steel; inclusions;
a certain value, the gradient of dissolved Ca content became
modification; castability
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 References
Ca content in center would change little.
After RH treatment, since the size of inclusions was very [1] S. K. Choudhary, A. Ghosh, ISIJ Int. 2008, 48(11),
small, when the second calcium treatment was carried out, 1552.
the Ca element diffused from the edge to the center of [2] S. Abdelaziz, G. Megahed, I. El-Mahallawi, H.
inclusion quickly. Based on suitable T.[Ca]/T.[O] ratio, the Ahmed, Ironmaking Steelmaking 2009, 36(6), 432.
composition of inclusions would be close to 12CaO 7Al2O3 [3] J. H. Liu, H. J. Wu, Y. P. Bao, H. S. Qin, S. S. Zang,
and more concentrated because of the CaO content in X. J. Zhang, J. Univ. Sci. Technol. Beijing 2010, 32(3),
center after RH treatment. It accords with the result 312.
obtained by Ito et al.[12] [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
4. Conclusions Steelmaking 2000, 27(6), 442.
[6] G. M. Faulring, J. W. Farrell, D. C. Hilty, Ironmaking
A new double calcium treatment method was proposed for Steelmaking 1980, 7(2), 14.
clean steel refining. According to industrial experiment, [7] C. J. Zhang, K. K. Cai, W. X. Yuan, Iron Steel 2006,
the evolution of inclusion was analyzed and the controlling 41(8), 31.
standard of T.[Ca]/T.[O] ratio for calcium treatment was [8] K. Z. Wang, W. Sun, Res. Iron Steel 2005, 3, 38.
discussed with the following conclusions. [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.
(1) Good castability with low calcium content about [10] H. C. Gao, M. L. Liu, L. M. Zhang, H. Yan, H. J.
12 ppm was obtained by the double calcium treatment Wang, Iron Steel 2005, 40(11), 21.
and the inclusion grade of D type thin series decreases [11] H. Ohta, S. Kimura, T. Mimura, H. Matsumoto, R&D
from 1.5 to 1.0 in final product. Kobe Steel Eng. Rep. 2011, 61(1), 98.
(2) CaO—MgO—Al2O3 system inclusion containing small [12] Y. Ito, S. Nara, Y. Kato, M. Suda, Tetsu-to-Hagané
amount of CaO are mainly presented at the end of 2007, 93(5), 355.
LF refining. After the 1st calcium treatment, most [13] S. H. Yang, Q. Q. Wang, L. F. Zhang, J. S. Li, K.
inclusions are in the liquid region with low melting Peaslee, Metall. Mater. Trans. B 2012, 43B(8), 731.
point and the MgO content decreases obviously. After [14] M. Jiang, Xi. H. Wang, B. Chen, W. J. Wang, ISIJ Int.
the 2nd calcium treatment, the distribution of 2008, 48(7), 885.
inclusion composition is more concentrated compared [15] E. B. Pretorius, H. G. Oltmann, T. Cash, Iron Steel
with the 1st calcium treatment, and the MgO content Technol. 2010, 7(7), 31.
decreases further with the inclusion composition close [16] N. Verma, M. Lind, P. C. Pistorius, R. J. Fruehan,
to CaO—Al2O3 system and almost all in liquid region. M. Potter, Iron Steel Technol. 2010, 7(7), 189.
In the calcium treatment process, the inclusions would [17] G. Z. Ye, P. Jonsson, T. Lund, ISIJ Int. 1996, 36(s),
change into CaO—MgO—Al2O3 and then gradually 105.
into CaO—Al2O3 system. [18] Y. Ito, M. Suda, Y. Kato, H. Nakato, K. Sorimachi,
(3) In order to get a good calcium treatment result, T.[Ca]/ ISIJ Int. 1996, 36(s), 148.
T.[O] ratio should be controlled above 0.91, and the [19] Y. Higuchl, M. Numata, S. Fukagawa, K. Shinme, ISIJ
ratio between 0.91 and 1.25 is suitable in present work. Int. 1996, 36(s), 151.
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