天然萤石中的镧系元素和钇取代

IF 1.2 4区 地球科学 Q4 MATERIALS SCIENCE, MULTIDISCIPLINARY Physics and Chemistry of Minerals Pub Date : 2023-04-27 DOI:10.1007/s00269-023-01239-4
Nicola J. Horsburgh, Adrian A. Finch, Henrik Friis
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引用次数: 1

摘要

萤石是地壳中最常见的矿物之一,具有广泛的经济意义。它表现出强烈的紫外光激发发光,不同的原因是萤石结构的缺陷和镧系元素的取代。我们在这里介绍了一套天然萤石样品的详细化学特征,选择代表自然界中观察到的成分范围。我们对250-800 nm波长范围内温度(20-673 K)的样品进行x射线激发发光光谱分析,以深入了解晶格中的物理缺陷及其与天然萤石中镧系取代基的相互作用。紫外线中的大多数宽频带归因于萤石晶格中的电子缺陷,而尖锐的发射归因于三价镧系元素中的离子内能量级联。萤石中的镧系元素是通过取代Ca2+和间隙的F−、O2−(取代F−)以及提供局部电荷平衡的各种电子缺陷结构来容纳的。球粒正态镧系元素剖面显示,随着稀土元素(REE)总浓度的增加,萤石中重镧系元素(和Y)的比例增大;而细胞参数则随着置换的进行先减小后增大。发光强度随稀土浓度的变化也先达到最大值,然后逐渐减小。所有三个数据集都与一个模型相一致,即镧系元素最初作为孤立的中心,但超过临界阈值(~ 1000ppm),聚集成富镧系元素域。聚类导致更短的REE-O键距离(有利于较小的重离子),更大的单元电池,但更有效的镧系元素之间的能量转移,从而促进非辐射能量损失和镧系元素发射强度的下降。
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Lanthanide and yttrium substitution in natural fluorite

Fluorite is one of the most common minerals in the crust and is of widespread economic importance. It shows strong UV-excited luminescence, variously attributed to defects within the fluorite structure and lanthanide substitutions. We present here a detailed chemical characterisation of a suite of natural fluorite samples, chosen to represent the range of compositions observed in nature. We perform X-ray excited luminescence spectroscopy on the samples as a function of temperature (20–673 K) in the wavelength range 250–800 nm to provide insights into physical defects in the lattice and their interactions with lanthanide substituents in natural fluorite. Most broad bands in the UV are attributed to electronic defects in the fluorite lattice, whereas sharp emissions are attributed to intra-ion energy cascades in trivalent lanthanides. Lanthanides are accommodated in fluorite by substitution for Ca2+ coupled with interstitial F, O2− (substituting for F) and a variety of electronic defect structures which provide local charge balance. The chondrite-normalised lanthanide profiles show that fluorite accommodates a greater proportion of heavy lanthanides (and Y) as the total Rare Earth Element (REE) concentration increases; whereas cell parameters decrease and then increase as substitution continues. Luminescence intensity also goes through a maximum and then decreases as a function of REE concentration. All three datasets are consistent with a model whereby lanthanides initially act as isolated centres, but, beyond a critical threshold (~ 1000 ppm), cluster into lanthanide-rich domains. Clustering results in shorter REE-O bond distances (favouring smaller heavier ions), a larger unit cell but more efficient energy transfer between lanthanides, thereby promoting non-radiative energy loss and a drop in the intensity of lanthanide emission.

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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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