Aleksandra A. Bendeliani, Nikolay N. Eremin, Andrey V. Bobrov
{"title":"地幔辉云母中Ti和Cr掺入的机制和条件:原子模拟的结果","authors":"Aleksandra A. Bendeliani, Nikolay N. Eremin, Andrey V. Bobrov","doi":"10.1007/s00269-023-01232-x","DOIUrl":null,"url":null,"abstract":"<div><p>Modeling of eight mechanisms for the incorporation of Ti<sup>4+</sup> and Cr<sup>3+</sup> impurity components into phlogopite was carried out by a semi-empirical method using the GULP (General Utility Lattice Program) software. The calculation of thermodynamic mixing properties in the range of 1–7 GPa and 373–1573 K and the analysis of the structure geometry for the simulated solid solutions provided the following energy-preferred schemes of isomorphic substitution: <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Si<sup>4+</sup>) = <sup>VI</sup>(Ti<sup>4+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) and <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) = <sup>VI</sup>(□) + 2<sup>IV</sup>(Ti<sup>4+</sup>), <sup>VI</sup>(Mg<sup>2+</sup>) + <sup>IV</sup>(Si<sup>4+</sup>) = <sup>VI</sup>(Cr<sup>3+</sup>) + <sup>IV</sup>(Al<sup>3+</sup>), and 3<sup>VI</sup>(Mg<sup>2+</sup>) = <sup>VI</sup>(Al<sup>3+</sup>) + <sup>VI</sup>(Cr<sup>3+</sup>) + <sup>VI</sup>(□). It is shown the scheme 2<sup>VI</sup>(Mg<sup>2+</sup>) = <sup>VI</sup>(Ti<sup>4+</sup>) + <sup>VI</sup>(□) illustrating entrance of Ti with the formation of a vacancy is realized in the case of microconcentrations of Ti only. Accumulation of high-Ti contents associates with the formation of a vacancy in the octahedral site. This provides incorporation of Ti via the schemes <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) = <sup>VI</sup>(□) + 2<sup>IV</sup>(Ti<sup>4+</sup>) and (Mg, Fe<sup>2+</sup>) + 2OH<sup>−</sup> = Ti<sup>4+</sup> + 2O<sup>2−</sup> only. It is shown that incorporation of high-Cr concentrations (> 5.5 wt % Cr<sub>2</sub>O<sub>3</sub>) is accompanied by an increase in the number of vacancies in the octahedral site with an increase in the proportion of the dioctahedral component K(Al, Cr, □)<sub>2</sub>AlSi<sub>3</sub>O<sub>10</sub>(OH)<sub>2</sub>.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2023-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-023-01232-x.pdf","citationCount":"0","resultStr":"{\"title\":\"Mechanisms and conditions of Ti and Cr incorporation in mantle phlogopite: the results of atomistic simulation\",\"authors\":\"Aleksandra A. Bendeliani, Nikolay N. Eremin, Andrey V. Bobrov\",\"doi\":\"10.1007/s00269-023-01232-x\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Modeling of eight mechanisms for the incorporation of Ti<sup>4+</sup> and Cr<sup>3+</sup> impurity components into phlogopite was carried out by a semi-empirical method using the GULP (General Utility Lattice Program) software. The calculation of thermodynamic mixing properties in the range of 1–7 GPa and 373–1573 K and the analysis of the structure geometry for the simulated solid solutions provided the following energy-preferred schemes of isomorphic substitution: <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Si<sup>4+</sup>) = <sup>VI</sup>(Ti<sup>4+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) and <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) = <sup>VI</sup>(□) + 2<sup>IV</sup>(Ti<sup>4+</sup>), <sup>VI</sup>(Mg<sup>2+</sup>) + <sup>IV</sup>(Si<sup>4+</sup>) = <sup>VI</sup>(Cr<sup>3+</sup>) + <sup>IV</sup>(Al<sup>3+</sup>), and 3<sup>VI</sup>(Mg<sup>2+</sup>) = <sup>VI</sup>(Al<sup>3+</sup>) + <sup>VI</sup>(Cr<sup>3+</sup>) + <sup>VI</sup>(□). It is shown the scheme 2<sup>VI</sup>(Mg<sup>2+</sup>) = <sup>VI</sup>(Ti<sup>4+</sup>) + <sup>VI</sup>(□) illustrating entrance of Ti with the formation of a vacancy is realized in the case of microconcentrations of Ti only. Accumulation of high-Ti contents associates with the formation of a vacancy in the octahedral site. This provides incorporation of Ti via the schemes <sup>VI</sup>(Mg<sup>2+</sup>) + 2<sup>IV</sup>(Al<sup>3+</sup>) = <sup>VI</sup>(□) + 2<sup>IV</sup>(Ti<sup>4+</sup>) and (Mg, Fe<sup>2+</sup>) + 2OH<sup>−</sup> = Ti<sup>4+</sup> + 2O<sup>2−</sup> only. It is shown that incorporation of high-Cr concentrations (> 5.5 wt % Cr<sub>2</sub>O<sub>3</sub>) is accompanied by an increase in the number of vacancies in the octahedral site with an increase in the proportion of the dioctahedral component K(Al, Cr, □)<sub>2</sub>AlSi<sub>3</sub>O<sub>10</sub>(OH)<sub>2</sub>.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2023-02-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-023-01232-x.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physics and Chemistry of Minerals\",\"FirstCategoryId\":\"89\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00269-023-01232-x\",\"RegionNum\":4,\"RegionCategory\":\"地球科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-023-01232-x","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Mechanisms and conditions of Ti and Cr incorporation in mantle phlogopite: the results of atomistic simulation
Modeling of eight mechanisms for the incorporation of Ti4+ and Cr3+ impurity components into phlogopite was carried out by a semi-empirical method using the GULP (General Utility Lattice Program) software. The calculation of thermodynamic mixing properties in the range of 1–7 GPa and 373–1573 K and the analysis of the structure geometry for the simulated solid solutions provided the following energy-preferred schemes of isomorphic substitution: VI(Mg2+) + 2IV(Si4+) = VI(Ti4+) + 2IV(Al3+) and VI(Mg2+) + 2IV(Al3+) = VI(□) + 2IV(Ti4+), VI(Mg2+) + IV(Si4+) = VI(Cr3+) + IV(Al3+), and 3VI(Mg2+) = VI(Al3+) + VI(Cr3+) + VI(□). It is shown the scheme 2VI(Mg2+) = VI(Ti4+) + VI(□) illustrating entrance of Ti with the formation of a vacancy is realized in the case of microconcentrations of Ti only. Accumulation of high-Ti contents associates with the formation of a vacancy in the octahedral site. This provides incorporation of Ti via the schemes VI(Mg2+) + 2IV(Al3+) = VI(□) + 2IV(Ti4+) and (Mg, Fe2+) + 2OH− = Ti4+ + 2O2− only. It is shown that incorporation of high-Cr concentrations (> 5.5 wt % Cr2O3) is accompanied by an increase in the number of vacancies in the octahedral site with an increase in the proportion of the dioctahedral component K(Al, Cr, □)2AlSi3O10(OH)2.
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)