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Acta Metall Sin  2017, Vol. 53 Issue (1): 10-18    DOI: 10.11900/0412.1961.2016.00120
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Mechanism on Modification of MnO-SiO2-Type Oxide by Interfacial Solid-State Reaction During Heat Treatment
Chengsong LIU(),Fei YE
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
Cite this article: 

Chengsong LIU,Fei YE. Mechanism on Modification of MnO-SiO2-Type Oxide by Interfacial Solid-State Reaction During Heat Treatment. Acta Metall Sin, 2017, 53(1): 10-18.

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Abstract  

In order to control physicochemical characteristics of inclusions in steel through appropriate heat treatment process, solid-state interface reaction between solid alloy deoxidized by Mn and Si and MnO-SiO2-FeO oxide during heat treatment was studied. Using confocal scanning laser microscope (CSLM) and high temperature induction furnace, the reaction between the Fe-Mn-Si alloy and MnO-SiO2-FeO oxide during heat treatment at 1473 K and its influence on the compositions and phases in the alloy and oxide were investigated by diffusion couple method. A suitable method for pre-melting oxide and producing diffusion couple of Fe-Mn-Si alloy and MnO-SiO2-FeO oxide was proposed to obtain good contact between them. After that, the diffusion couple sample with Ti foil for reducing oxygen partial pressure and bulk alloy containing the same compositions was sealed in a quartz tube for carrying out subsequent heat treatment experiment. In addition, equilibrium compositions and phases of the oxide and alloy during solidification and the solid-state reaction mechanism between them were analyzed and discussed. Quantitative analysis of each element in alloy and oxide was calibrated by standard sample before analysis. Results showed that solid-state interface reaction and element diffusion between the Fe-Mn-Si alloy and MnO-SiO2-FeO oxide were observed which indicated that the alloy and oxide in the diffusion couple was not equilibrated at 1473 K, even though the liquid phases of them were equilibrated at 1873 K. The activity of FeO in MnO-SiO2-FeO oxide decreased with the decrease of temperature and excess oxygen diffused from oxide to alloy. Mn and Si contents in the alloy were consumed by the chemical reaction and some MnO-SiO2 particles in the alloy near the interface generated. As the heat treatment time increased from 10 h to 50 h, the widths of particle precipitation zone (PPZ) and manganese depleted zone (MDZ) increased from 79 and 120 μm to 138 and 120 μm, respectively. During the heat treatment, the width of MDZ was always greater than that of PPZ. Moreover, due to the separation of the FeO, pure Fe particles formed in the oxide. The MnO and FeO contents in the oxide increased and decreased respectively with the increase of the heat treatment time.

Key words:  oxide      diffusion couple      interfacial solid-state reaction      heat treatment     
Received:  06 April 2016     
Fund: Supported by National Natural Science Foundation of China (No.51604201)

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2016.00120     OR     https://www.ams.org.cn/EN/Y2017/V53/I1/10

Fig.1  Experimental set-up for pre-melting oxide in confocal scanning laser microscope (CSLM)
Fig.2  Schematic of the diffusion couple specimen sealed in a quartz tube
Fig.3  Temperature curve of the heat treatment for the diffusion couple specimen
Table 1  Chemical composition analyses of positions in Fig.4a

(mass fraction / %)

Position MnO SiO2 FeO MnS
1 65.1 31.8 3.1 0
2 64.9 31.6 3.5 0
3 64.8 31.8 3.4 0
4 48.7 47.1 4.2 0
5 48.1 47.5 4.4 0
6 77.1 22.7 0 0.2
7 91.5 8.4 0 0.1
  
Fig.4  EPMA images of the interface between the alloy and oxide after the oxide pre-melting experiment (a), and after heat treatment at 1473 K for 10 h (b) and 50 h (c)
Position MnO SiO2 FeO MnS
1 65.6 32.5 1.9 0
2 64.2 33.6 2.2 0
3 65.0 32.9 2.1 0
4 49.8 48.7 1.5 0
5 50.4 47.9 1.7 0
6 64.3 35.7 0 0
7 82.8 17.2 0 0
Table 2  Chemical composition analyses of positions in Fig.4b (mass fraction / %)
Position MnO SiO2 FeO MnS
1 66.2 32.6 1.2 0
2 67.1 31.8 1.1 0
3 68.9 30.5 0.6 0
4 54.1 45.2 0.7 0
5 52.0 47.6 0.4 0
6 54.8 45.2 0 4.7
7 63.6 36.4 0 2.7
Table 3  Chemical composition analyses of positions in Fig.4c (mass fraction / %)
Fig.5  Changes of Mn (a) and Si (b) contents in the diffusion couple alloy after the oxide pre-melting experiment (specimen H-0), and after heat treatment at 1473 K for 10 h (specimen H-10) and 50 h (specimen H-50)
Fig.6  Width of particle precipitation zone (PPZ) and manganese depleted zone (MDZ) of the diffusion couple after the oxide pre-melting experiment, and after heat treatment at 1473 K for 10 and 50 h
Fig.7  Composition (a) and size distribution (b) of particles in the diffusion couple alloy near the interface after the oxide pre-melting experiment, and after heat treatment at 1473 K for 10 and 50 h
Fig.8  Changes in composition and phase in Fe-Mn-Si alloy (a) and MnO-SiO2-FeO oxide (b) during solidification
Fig.9  Changes of activities of oxygen and FeO (aO and aFeO) with temperature in equilibrium calculation
Fig.10  Schematic for the mechanism of solid-state interface reaction between the alloy and inclusion
[1] Hou Y H, Zheng W, Wu Z H, et al.Study of Mn absorption by complex oxide inclusions in Al-Ti-Mg killed steels[J]. Acta Mater., 2016, 118: 8
[2] Ono H, Nakajima K, Ibuta T, et al.Equilibrium relationship between the oxide compounds in MgO-Al2O3-Ti2O3 and molten iron at 1873 K[J]. ISIJ Int., 2010, 50: 1955
[3] Zhang B W, Deng K, Lei Z S, et al.A mathematical model on coalescence and removal of inclusion particles in continuous casting tundish[J]. Acta Metall. Sin., 2004, 40: 623
[3] (张邦文, 邓康, 雷作胜等. 连铸中间包中夹杂物聚合与去除的数学模型[J]. 金属学报, 2004, 40: 623)
[4] Lei H, He J C.Fluid flow and inclusion's collision-growth in the slab continuous casting mold[J]. Acta Metall. Sin., 2007, 43: 1195
[4] (雷洪, 赫冀成. 板坯连铸机内钢液流动和夹杂物碰撞长大行为[J]. 金属学报, 2007, 43: 1195)
[5] Hasegawa M, Takeshita K.Strengthening of steel by the method of spraying oxide particles into molten steel stream[J]. Metall. Trans., 1978, 9B: 383
[6] Zhang J, Wang F M, Li C R.Thermodynamic analysis of the compositional control of inclusions in cutting-wire steel[J]. Int. J. Miner. Metall. Mater., 2014, 21: 647
[7] Yang S F, Wang Q Q, Zhang L F, et al.Formation and modification of MgOAl2O3-based inclusions in alloy steels[J]. Metall. Mater. Trans., 2012, 43B: 731
[8] Zhou B W, Li G Q, Wan X L, et al.In-situ observation of grain refinement in the simulated heat-affected zone of high-strength low-alloy steel by Zr-Ti combined deoxidation[J]. Met. Mater. Int., 2016, 22: 267
[9] Ono H, Ibuta T.Equilibrium relationships between oxide compounds in MgO-Ti2O3-Al2O3 with iron at 1873 K and variations in stable oxides with temperature[J]. ISIJ Int., 2011, 51: 2012
[10] Wang X H, Li X G, Li Q, et al.Control of string shaped non-metallic inclusions of CaO-Al2O3 system in X80 pipeline steel plates[J]. Acta Metall. Sin., 2013, 49: 553
[10] (王新华, 李秀钢, 李强等. X80管线钢板中条串状CaO-Al2O3系非金属夹杂物的控制[J]. 金属学报, 2013, 49: 553)
[11] Park J H, Kim D S.Effect of CaO-Al2O3-MgO slags on the formation of MgO-Al2O3 inclusions in ferritic stainless steel[J]. Metall. Mater. Trans., 2005, 36B: 495
[12] Lee C, Nambu S, Inoue J, et al.Ferrite formation behaviors from B1 compounds in steels[J]. ISIJ Int., 2011, 51: 2036
[13] Takahashi I, Sakae T, Yoshida T.Changes of nonmetallic inclusion by heating[J]. Tetsu Hagané, 1967, 53: 350
[13] (高橋市朗, 栄豊幸, 吉田毅. 非金属介在物の加熱による変化[J]. 鉄と鋼, 1967, 53: 350)
[14] Takahashi I, Sakae T, Yoshida T.Changes of the nonmetallic inclusion by forging and rolling[J]. Tetsu Hagané, 1967, 53: 352
[14] (高橋市朗, 栄豊幸, 吉田毅. 非金属介在物の鍛造および压延加工による変化[J]. 鉄と鋼, 1967, 53: 352)
[15] Takano K, Nakao R, Fukumoto S, et al.Grain size control by oxide dispersion in austenitic stainless steel[J]. Tetsu Hagané, 2003, 89: 61
[15] 6(高野光司, 中尾隆二, 福元成雄等. オーステナイト系ステンレス鋼の酸化物の分散を利用した結晶粒径調整[J]. 鉄と鋼, 2003, 89: 616)
[16] Kim H S, Lee H G, Oh K S.MnS precipitation in association with manganese silicate inclusions in Si/Mn deoxidized steel[J]. Metall. Mater. Trans., 2001, 32A: 1519
[17] Wakoh M, Sawai T, Mizoguchi S.Effect of S content on the MnS precipitation in steel with oxide nuclei[J]. ISIJ Int., 1996, 36: 1014
[18] Wakoh M, Sawai T, Mizoguchi S.Effect of oxide particles on MnS precipitation in low S steels[J]. Tetsu Hagané, 1992, 78: 1697
[18] (若生昌光, 澤井隆, 溝口庄三. 低硫鋼でのMnS析出に及ぼす鋼中酸化物の影響[J]. 鉄と鋼, 1992, 78: 1697)
[19] Shibata H, Tanaka T, Kimura K, et al.Composition change in oxide inclusions of stainless steel by heat treatment[J]. Ironmaking Steelmaking, 2010, 37: 522
[20] Shibata H, Kimura K, Tanaka T, et al.Mechanism of change in chemical composition of oxide inclusions in Fe-Cr alloys deoxidized with Mn and Si by heat treatment at 1473 K[J]. ISIJ Int., 2011, 51: 1944
[21] Choi W, Matsuura H, Tsukihashi F.Changing behavior of non-metallic inclusions in solid iron deoxidized by Al-Ti addition during heating at 1473 K[J]. ISIJ Int., 2011, 51: 1951
[22] Ohba Y, Yamashita Y, Ohno K, et al.Formation mechanism of oxide particles in subscale layer around surface cracks of steel[J]. Tetsu Hagané, 2009, 95: 531
[22] (大塲康英, 山下祐樹, 大野光一郎等. 鋼材表面疵近傍におけるサブスケール層内の粒状酸化物の生成機構[J]. 鉄と鋼, 2009, 95: 531)
[23] Kim K H, Kim S J, Shibata H, et al.Reaction between MnO-SiO2-FeO oxide and Fe-Mn-Si solid alloy during heat treatment[J]. ISIJ Int., 2014, 54: 2144
[24] Kim K H, Shibata H, Kitamura S.Influence of sulfur on the reaction between MnO-SiO2-FeO oxide and Fe-Mn-Si solid alloy by heat treatment[J]. ISIJ Int., 2014, 54: 2678
[25] Sasaki R, Ueda S, Kim S J, et al.Reaction behavior between B4C, 304 grade of stainless steel and Zircaloy at 1473 K[J]. J. Nucl. Mater., 2016, 477: 205
[26] Hino M, Ito K.Thermodynamic Data for Steelmaking [M]. Sendai: Tohoku University Press, 2010: 167
[27] Ban-Ya S.Mathematical expression of slag-metal reactions in steelmaking process by quadratic formalism based on the regular solution model[J]. ISIJ Int., 1993, 33: 2
[28] The Japan Institute of Metals. Physical Chemistry of Metals [M]. Tokyo: Maruzen Press, 1996: 198
[29] Turkdogan E T.Physical Chemistry of High Temperature Technology [M]. New York: Academic Press, 1980: 81
[30] Zhang J, Cheng G G, Wang L J, et al.Computational Thermodynamics of Metallurgical Melts and Solutions [M]. Beijing: Metallurgical Industry Press, 2007: 254
[30] (张鉴, 成国光, 王力军等. 冶金熔体和溶液的计算热力学 [M]. 北京: 冶金工业出版社, 2007: 254)
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