CeF3-EuF3-NaCl-KCl体系冻盐熔体的漫反射光谱

V. Zinchenko, O. Ieriomin, I. Stoyanova, G. Volchak, A. Babenko
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引用次数: 0

摘要

用漫反射(DR)光谱法确定了相互作用的性质,并对CeF3-EuF3-NaCl-KCl体系中反应产物的可能组成进行了推断。对CeF3和EuF3的混合物按1:1和1:1的比例进行高温(800和1100℃)热处理,观察到DR在紫外和近红外光谱范围内的光谱曲线性质发生了显著变化。在第一个光谱中,在整个光谱范围内都发现了强烈的吸收,并且在较高的EuF3含量时更明显。另一方面,在光谱的近红外范围内,在DR的光谱曲线上观察到明显的变形和吸收带强度的急剧下降。烧结样品在紫外范围内的DR光谱表明,Ce (III, IV)和Eu (II, III)出现了不同的价态,Ce4+和Eu2+离子比Ce3+和Eu3+离子占优势。在近红外光谱中,由于4f - 4f电子跃迁,Eu3+离子的吸收强度下降,直接证实了固态体系中发生的氧化还原过程。当在NaCl-KCl熔体中处理系统样品时,即使没有预烧结,这些过程也变得更加明显。因此,在盐熔体中处理后的CeF3-EuF3机械混合物样品中,DR光谱上近红外范围的吸收要么完全消失(比例为1:1),要么是F(R)在10-3 μ u左右的轻微残留。DR在紫外范围内的光谱也发生了巨大的变化,表明Eu (II)的含量高于Eu (III)。盐熔液中预烧结样品的处理对DR光谱的性质也产生了类似的影响,即DR光谱曲线在紫外和近红外范围内的性质都发生了变化。这表明在盐熔体的参与下,CeF3-EuF3-NaCl-KCl体系样品的氧化还原过程不断加深。CeF3-EuF3的比例从1:1增加到1:1有助于上述过程。
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DIFFUSE REFLECTION SPECTRA OF FROZEN SALT MELTS OF THE CeF3-EuF3-NaCl-KCl SYSTEMS
The nature of the interaction was determined by the method of diffuse reflection (DR) spectroscopy and conclusions were made about the possible composition of the reaction products in the CeF3-EuF3-NaCl-KCl system. As a result of high-temperature (800 and 1100 °C) heat treatment of a mixture of CeF3 with EuF3 in the ratios 1: 1 and 1: 2, a significant change in the nature of the spectral curves of DR in UV and near IR-spectral ranges is observed. In the first of them, intense absorption was found in the entire spectral range, and more pronounced at higher EuF3 content. On the other hand, significant deformation and a sharp decrease in the intensity of the absorption band are observed on the spectral curves of the DR in the near IR range of the spectrum. The DR spectra of sintered samples in the UV range indicate the emergence of various valent states of Ce (III, IV) and Eu (II, III) with a predominance of Ce4+ and Eu2+ ions compared to Ce3+ and Eu3+. The decrease in the absorption intensity of Eu3+ ions due to 4f‑4f electronic transitions in the near-IR spectra is a direct confirmation of the oxidation-reduction processes occurring in the solid state system. These processes become even more pronounced when processing samples of systems in NaCl-KCl melt, even without pre-sintering. Thus, in the sample, which is a mechanical mixture of CeF3-EuF3 after treatment in the salt melt, the absorption in the near IR range on the DR spectra either disappears altogether (ratio 1: 1), or is a slight residue of F(R) at about 10–3 a. u.). The spectra of DR in the UV range also change dramatically, indicating a predominant content of Eu (II) compared to Eu (III). A similar effect on the nature of the DR spectrum is exerted by the processing of pre-sintered samples in the salt melt, namely, there is a change in the nature of the DR spectral curves both in the UV and in the near IR ranges of the spectrum. This indicates the deepening of the oxidation-reduction processes in the samples of the CeF3-EuF3-NaCl-KCl system with the participation of the salt melt. The increase in the ratio of CeF3-EuF3 from 1: 1 to 1: 2 contributes to above mentioned processes.
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