放线石的氧化过程及热稳定性

IF 1.2 4区 地球科学 Q4 MATERIALS SCIENCE, MULTIDISCIPLINARY Physics and Chemistry of Minerals Pub Date : 2022-11-22 DOI:10.1007/s00269-022-01223-4
Constanze Rösche, Naemi Waeselmann, Nadia Petrova, Thomas Malcherek, Jochen Schlüter, Boriana Mihailova
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引用次数: 3

摘要

在原子水平上理解含铁角闪石(AB2C5T8O22W2, C5 = M(1) 2m (2) 2m(3))的热行为可能在变质岩石学、地球物理学和环境科学等多个领域具有重要意义。本文通过原位高温拉曼光谱、互补热重/质谱分析以及角闪洞分解产物的x射线衍射研究了放线石的热诱导氧化和分解。比较了CFe2+对放线石和透闪石脱氢/脱羟基作用的影响。我们发现,在1150-1250 K的高温下,光动石中存在着移动电荷载流子,即极化子(与FeO6声子耦合的传导电子)和H+阳离子。温度诱导的放线石分解是一个多步骤的过程,包括:(i) e−从CFe2+中脱出,以及H+从含铁的M(1)M(1)M(3)种共有的羟基中脱出,但这些羟基仍留在晶体体中;(ii)在1250 ~ 1350 K之间发生e−的脱氢和抛射,此时放线石可被认为是“氧-放线石”,因为靠近M(1,3)(mgmgmmg)构型的羟基上的H+也离域,大部分留在晶体体中;(3)在1350 K以上,脱羟基作用完全,结构崩塌,形成富Fe3+缺陷的自晶辉石。透闪石的脱氢发生在1400k,立即触发硅酸盐双链分解为单sio4链,随后在1450k时角闪孔八面体条和BCa2+阳离子重排为辉石型八面体片。透闪石分解的结果也是一种富含缺陷的单相斜辉石,其中间成分位于透辉石-斜辉石接合处。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Oxidation processes and thermal stability of actinolite

Understanding the thermal behaviour of iron-containing amphiboles (AB2C5T8O22W2, C5 = M(1)2 M(2)2 M(3)) at atomic-level scale may have important implications in several fields, including metamorphic petrology, geophysics, and environmental sciences. Here, the thermally induced oxidation and decomposition of actinolite are studied by in situ high-temperature Raman spectroscopy and complementary thermogravimetric/mass-spectrometry analyses as well as X-ray diffraction of the products of amphibole decomposition. The effect of CFe2+ on dehydrogenation/dehydroxylation is followed by comparing the results on actinolite with those for tremolite. We show that mobile charge carriers, namely polarons (conduction electrons coupled to FeO6 phonons) and H+ cations, exist in actinolite at elevated temperatures ~ 1150–1250 K. The temperature-induced actinolite breakdown is a multistep process, involving (i) delocalization of e from CFe2+ as well as of H+ from hydroxyl groups shared by Fe-containing M(1)M(1)M(3) species, which, however, remain in the crystal bulk; (ii) dehydrogenation and ejection of e between 1250 and 1350 K, where actinolite can be considered as “oxo-actinolite”, as H+ also from hydroxyl groups next to M(1,3)(MgMgMg) configurations become delocalized and mostly remain in the crystal bulk; (iii) complete dehydroxylation and consequent structure collapse above 1350 K, forming an Fe3+-bearing defect-rich augitic pyroxene. The dehydrogenation of tremolite occurs at 1400 K, triggering immediately a disintegration of the silicate double-chain into single SiO4-chains and followed by a rearrangement of the amphibole octahedral strips and BCa2+ cations into pyroxene-type octahedral sheets at 1450 K. The result of tremolite decomposition is also a single-phase defect-rich clinopyroxene with an intermediate composition on the diopside–clinoenstatite join.

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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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