Raman Spectroscopic Study on the Structure of Oxide Melts containing Fluoride

含氟氧化物熔体结构的拉曼光谱研究

• 批准号: 60550467
• 负责人: IGUCHI Yasutaka
• 金额: $ 1.15万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60550467/
• 关键词: Raman spectrum; Raman spectra; Oxide Melt; Slag; Fluoride; Glass; Structure Analysis; 融体の構造

In order to elucidate the structure of oxide melts containing fluorine, the quantitative informations are necessary concerning the structure of silicates and aluminates. In this study, at first, a Raman spectral study has been carried out on the structure of the glassy binary silicates containing alkali or alkaline earth oxides and ternary silicates with <Al_2O_3> or <TiO_2> , where an argon-ion laser beam of 4880 A has been used as an exciting light. The obtained Raman spectra were deconvoluted with the Gaussian function and the fraction of each silicate anion was evaluated relating to the number of non-bridging oxygens per each silicon atom. And the effects of anions on the Si-O bondings and behavior of <Al^(3+)> and <Ti^(4+)> were discussed. On the basis of the results described above, Raman measurements of the glassy CaO- <SiO_2> - <CaF_2> and CaO- <Al_2O_3> - <CaF_2> samples melted in the closed crucible and deconvolution of the spectra have been made and the following conclusions were obtained.(1) <CaF_2> in the CaO- <SiO_2> binary basic slags behaves as a diluent and diluent and does not have any effect on the structure of silicates, in which the basicity is larger than unity. On the other hand, a part of <CaF_2> added breaks the silicate networks at the acid slags. (2) The fraction of <CaF_2> which acts as a modifier increases with decrease in the basicity and three dimensional network is broken to chains of silicates. (3) The existence of the silicon-fluorine bonding in the CaO- <SiO_2> - <CaF_2> system with the basicity below 1 was confirmed, and the Raman band caused by the Si-F bonding was asigned. (4) Addition of <CaF_2> to the CaO- <Al_2O_3> binary slags has no effects on the structure of aluminates. <CaF_2> behaves only as a diluent to the CaO- <Al_2O_3> system.

为了阐明含氟氧化物熔体的结构，需要有关硅酸盐和铝酸盐结构的定量信息。本研究首先利用4880a氩离子激光束作为激发光，对含碱或碱土氧化物的玻态二元硅酸盐和<Al_2O_3>或<TiO_2>的三元硅酸盐的结构进行了拉曼光谱研究。用高斯函数对得到的拉曼光谱进行反卷积，并根据每个硅原子中非桥氧的数目来计算每种硅酸阴离子的分数。讨论了阴离子对<Al^(3+)>和<Ti^(4+)>的Si-O键和行为的影响。在此基础上，对闭合坩埚中熔化的CaO- <SiO_2> - <CaF_2>和CaO- <Al_2O_3> - <CaF_2>玻璃样进行了拉曼测量，并对光谱进行了反卷积，得到了以下结论：(1) <CaF_2>在CaO- <SiO_2>二元碱性渣中表现为稀释剂和稀释剂，对碱度大于单位的硅酸盐的结构没有任何影响。另一方面，部分<CaF_2>的加入破坏了酸渣处的硅酸盐网络。(2) <CaF_2>作为改性剂的比例随着碱度的降低而增加，三维网络断裂为硅酸盐链。(3)在碱度低于1的CaO- <SiO_2> - <CaF_2>体系中证实了硅氟键的存在，并确定了Si-F键形成的拉曼带。(4)在CaO- Al_2O_3 - >二元渣中添加<CaF_2>对铝酸盐的结构没有影响。<CaF_2>仅作为CaO- <Al_2O_3>体系的稀释剂。

项目成果

井口泰孝: 日本金属学会誌. 52. (1988)

Yasutaka Iguchi：日本金属研究所杂志 52。（1988）

Yasutaka Iguchi, Youichi Funaoka, Yuichiro Nishina and Shiro Ban-ya: "Raman Spectroscopic Study on the Structure of Oxide Melts containing Fluoride" Journal of the Japan Institute of Metals. 52. (1988)

Yasutaka Iguchi、Youichi Funaoka、Yuichiro Nishina 和 Shiro Ban-ya：“含氟化物的氧化物熔体结构的拉曼光谱研究”日本金属学会杂志。