Crystal structure of calcite-type Ca1–xMnxCO3 solid solution by X-ray diffraction and Raman spectroscopy

IF 1.2 4区 地球科学 Q4 MATERIALS SCIENCE, MULTIDISCIPLINARY Physics and Chemistry of Minerals Pub Date : 2024-03-15 DOI:10.1007/s00269-024-01269-6
Shanrong Zhang, Wen Liang, Mengzeng Wu, Qifa Zhong, Dawei Fan
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Abstract

To investigate the quantitative relationship between the crystal structure and composition of Mn-bearing calcite, the solid solutions of Ca1–xMnxCO3 (x = 0.1, 0.3, 0.5, 0.7, 0.9) with continuous MnCO3 mol% content were synthesized at 1 GPa and 700 °C using high-purity CaCO3 and MnCO3 powders as starting materials. The run products were analysized by electron probe, powder X-ray diffraction and Raman spectroscopy. The CaO wt% and MnO wt% of the resulting products are consistent with the expected compositions. The powder X-ray diffraction results show that the products are single phase without any impurities. All diffraction peaks of samples with varying MnCO3 mol% contents can be indexed by the calcite-type structure carbonates ACO3 (R-3c space group; A is a divalent cation), confirming the previous results that there is the completely continuous solid solution between CaCO3 and MnCO3 end members. The unit-cell parameters and volumes of the solid solutions decrease as the MnCO3 mol% content increases, presenting a linear relationship of Ca–Mn ideal miscibility, which is perfectly consistent with the rigid body model of A-site substitution in ACO3. Besides, as MnCO3 mol% content increases, the bond distance of A–O decreases linearly, while the bond distance of C–O changes like a parabola. Therefore, the addition of Mn makes the bond distance of A–O shorten, resulting in the decrease of unit-cell parameters and volumes for Ca1–xMnxCO3. Furthermore, two exterior vibrations (T and L) of the crystal lattice and two internal vibrations (ν4 and ν1) within the CO32− unit are assigned in the Raman spectra of these solid solutions. The characteristic vibration modes T, L, and ν4 as a whole increase with the increasing of MnCO3 mol% content, whereas the characteristic vibration mode ν1 as a whole decreases with the increase of MnCO3 mol% content. These variations in Raman vibration modes are related to the radius of substituted ions.

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通过 X 射线衍射和拉曼光谱分析钙钛矿型 Ca1-xMnxCO3 固溶体的晶体结构
为了研究含锰方解石晶体结构与成分之间的定量关系,我们以高纯度 CaCO3 和 MnCO3 粉末为起始材料,在 1 GPa 和 700 ℃ 下合成了含 MnCO3 mol% 的 Ca1-xMnxCO3(x = 0.1、0.3、0.5、0.7、0.9)固溶体。运行产物通过电子探针、粉末 X 射线衍射和拉曼光谱进行了分析。所得产品的 CaO wt% 和 MnO wt% 与预期成分一致。粉末 X 射线衍射结果表明,产品为单相,不含任何杂质。MnCO3 mol% 含量不同的样品的所有衍射峰都可以用方解石型结构碳酸盐 ACO3(R-3c 空间群;A 为二价阳离子)来表示,这证实了之前的结果,即 CaCO3 和 MnCO3 端部成员之间存在完全连续的固溶体。固溶体的单胞参数和体积随着 MnCO3 mol% 含量的增加而减小,呈现出 Ca-Mn 理想混溶性的线性关系,这与 ACO3 中 A 位取代的刚体模型完全一致。此外,随着 MnCO3 mol% 含量的增加,A-O 的键距呈线性减小,而 C-O 的键距呈抛物线变化。因此,锰的加入使 A-O 的键距缩短,导致 Ca1-xMnxCO3 的单胞参数和体积减小。此外,这些固溶体的拉曼光谱还显示出晶格的两个外部振动(T 和 L)以及 CO32- 单元的两个内部振动(ν4 和 ν1)。特征振动模式 T、L 和 ν4 整体上随着 MnCO3 摩尔百分含量的增加而增加,而特征振动模式 ν1 整体上随着 MnCO3 摩尔百分含量的增加而减少。拉曼振动模式的这些变化与取代离子的半径有关。
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来源期刊
Physics and Chemistry of Minerals
Physics and Chemistry of Minerals 地学-材料科学:综合
CiteScore
2.90
自引率
14.30%
发文量
43
审稿时长
3 months
期刊介绍: Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are: -Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.) -General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.) -Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.) -Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.) -Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems -Electron microscopy in support of physical and chemical studies -Computational methods in the study of the structure and properties of minerals -Mineral surfaces (experimental methods, structure and properties)
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