热处理过程中界面固相反应控制锰硅类氧化物变性的机理研究

doi:10.11900/0412.1961.2016.00120

金属学报

2017, Vol. 53

Issue (1): 10-18 DOI: 10.11900/0412.1961.2016.00120

本期目录 | 过刊浏览

热处理过程中界面固相反应控制锰硅类氧化物变性的机理研究

刘成松(

),叶飞

武汉科技大学省部共建耐火材料与冶金国家重点实验室武汉 430081

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

引用本文:

刘成松,叶飞. 热处理过程中界面固相反应控制锰硅类氧化物变性的机理研究[J]. 金属学报, 2017, 53(1): 10-18.
Chengsong LIU, Fei YE. Mechanism on Modification of MnO-SiO₂-Type Oxide by Interfacial Solid-State Reaction During Heat Treatment[J]. Acta Metall Sin, 2017, 53(1): 10-18.

全文: PDF(2660 KB) HTML

摘要:

采用扩散偶的方法,利用高温共聚焦激光显微镜和高温感应炉研究了1473 K热处理过程中Fe-Mn-Si合金与MnO-SiO₂-FeO氧化物的固相反应及其对二者成分及物相的影响规律,并分析了凝固过程中合金与氧化物平衡成分变化情况,揭示了高温界面固相反应控制MnO-SiO₂-FeO氧化物变性的内在机理。结果表明,热处理过程中合金与氧化物发生的界面固相反应造成合金内Mn、Si元素的损耗,靠近界面处合金内会形成大量MnO-SiO₂颗粒,而氧化物中由于FeO成分的分解,产生了单质Fe颗粒,随热处理时间的延长,MnO和FeO含量分别呈上升和下降的趋势。

关键词 ：氧化物, 扩散偶, 界面固相反应, 热处理

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

收稿日期: 2016-04-06

基金资助:资助项目国家自然科学基金项目No.51604201

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https://www.ams.org.cn/CN/10.11900/0412.1961.2016.00120 或 https://www.ams.org.cn/CN/Y2017/V53/I1/10

图1 氧化物预熔实验装置示意图

图2 扩散偶样品密封于石英管示意图

图3 扩散偶样品热处理实验温度曲线

表1 图4a中各位置的化学成分分析

图4 氧化物预熔黏接实验后、1473 K热处理10和50 h后合金与氧化物界面形貌的EPMA像

表2 图4b中各位置的化学成分分析

表3 图4c中各位置的化学成分分析

图5 氧化物预熔黏接实验后、1473 K热处理10和50 h后扩散偶合金中Mn和Si含量变化

图6 氧化物预熔黏接实验后、1473 K热处理10和50 h后扩散偶合金中颗粒析出区域和Mn元素消耗区域宽度变化

图7 氧化物预熔黏接实验后、1473 K热处理10和50 h后扩散偶合金中析出颗粒成分和尺寸分布

图8 凝固时Fe-Mn-Si合金与MnO-SiO2-FeO氧化物成分及物相变化

图9 平衡时合金中氧活度与氧化物中FeO的活度随温度变化情况

图10 合金基体与夹杂物界面固相反应机理示意图

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