高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1242-1248.doi: 10.7503/cjcu20180795

• 物理化学 • 上一篇    下一篇

CaF2-Al2O3-MgO电渣微结构的原位拉曼光谱及27Al魔角旋转核磁共振研究

曹培明1, 尤静林1(), 周灿栋2, LU Liming3, 王建1, 王敏1, 丁雅妮1, 徐琰东1   

  1. 1. 省部共建高品质特殊钢冶金与制备国家重点实验室, 上海市钢铁冶金新技术开发应用重点实验室, 上海大学材料科学与工程学院, 上海 200444
    2. 宝钢股份中央研究院, 上海 200940
    3. CSIRO Mineral Resources, Technology Court, Pullenvale, Queensland 4069
  • 收稿日期:2018-11-26 出版日期:2019-06-10 发布日期:2019-03-27
  • 作者简介:

    联系人简介: 尤静林, 男, 博士, 教授, 博士生导师, 主要从事分子光谱和无机结构研究. E-mail: jlyou@staff.shu.edu.cn

  • 基金资助:
    国家自然科学基金(批准号: 21773152)、 上海市科学技术委员会项目(批准号: 12520709200)、 国家“111”引智项目(批准号: D17002)、 省部共建高品质特殊钢冶金与制备国家重点实验室开放课题(批准号: SKLASS2015-01, SKLASS2017-02)和科技部中央引导基金(批准号: YDZX20173100001316)资助.

In-situ Studies of Microstructure of CaF2-Al2O3-MgO Electroslag by Raman Spectroscopy and 27Al MAS NMR

CAO Peiming1, YOU Jinglin1(), ZHOU Candong2, LU Liming3, WANG Jian1, WANG Min1, DING Yani1, XU Yandong1   

  1. 1. State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of AdvancedFerrometallurgy, School of Materials Science and Engineering, Shanghai University,Shanghai 200444, China
    2. Central Research Institute of Baosteel, Shanghai 200940, China
    3. CSIRO Mineral Resources, Technology Court, Pullenvale, Queensland 4069, Australia
  • Received:2018-11-26 Online:2019-06-10 Published:2019-03-27
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21773152), the Shanghai Committee of Science and Technology Fund, China(No.12520709200), the National “111” Project(the Programme of Introducing Talents of Discipline to Universities) of China(No.D17002), the Open Project of State Key Laboratory of Advanced Special Steel, Shanghai University, China(Nos.SKLASS2015-01, SKLASS2017-02) and the Special Fund Project of Shanghai Municipality for Science and Technology Development, China(No.YDZX20173100001316).

摘要:

运用原位拉曼光谱和 27Al魔角旋转核磁共振研究了CaF2-Al2O3-MgO电渣重熔渣晶体、 玻璃和熔体的微结构及铝配位数的变化. 利用X射线粉末衍射分析获得该晶体样品中存在的物相, 分别基于密度泛函理论及量子化学从头算分析了S-6530晶体和熔体中相关物相的拉曼振动波数及散射活性, 并对其主要振动模式进行了归属. 结果表明, S-6530晶体中铝主要以六配位形式存在, 并有少量的四、 五配位. 在升温过程中, 其中MgAl2O4物相的Al-O多面体由[AlO6]转变成[AlO4]与[AlO5]共存. Al在熔体和玻璃结构中主要以[AlO4]四面体的形式存在, 其占比高达71.1%, 相较于其晶态, [AlO5]的占比也增加至28.6%. 基于构建的熔体团簇模型的量子化学从头算表明, [AlO4]构型倾向于以Q3, Q4连接方式为主的层状和架状结构, 而[AlO5]构型则倾向于单体形式.

关键词: CaF2-Al2O3-MgO电渣重熔渣, 原位拉曼光谱, 27Al魔角旋转核磁共振, 密度泛函理论, 铝配位数

Abstract:

The microstructure and Al coordination of crystalline, glassy and molten states of CaF2-Al2O3-MgO electroslag remelting slag were investigated by in-situ Raman spectroscopy and 27Al magic angle spinning nuclear magnetic resonance(MAS NMR). X-Ray diffraction was used to analyze phase of the crystal sample. Raman vibrational wavenumber and scattering activity of S-6530 crystal and melt were calculated based on density functional theory(DFT) and ab initio quantum chemical studies, respectively, and the major vibrational modes were assigned. The results showed that six-fold coordinated aluminum mainly exists in the S-6530 crystal, supplemented by a small amount of four or five-fold coordinated aluminum. During the heating process, the Al—O polyhedron of MgAl2O4 phase is transformed from [AlO6] to [AlO4] or [AlO5]. Al is present predominantly in [AlO4] tetrahedron in both S-6530 glass and melt, the proportion of [AlO4] is as high as 71.1%, compared with its crystalline state, the proportion of [AlO5] also increases to 28.6%. Based on quantum chemistry ab-initio calculation of the constructed molten cluster models, the [AlO4] configuration tends to be layered and frame structure dominated by Q3 and Q4 connections, and [AlO5] configuration remains isolated.

Key words: CaF2-Al2O3-MgO electroslag remelting slag, In-situ Raman spectroscopy, 27Al MAS NMR, Density fuctional theory(DFT), Al coordination

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