Anna Yu. Likhacheva, Alexandr V. Romanenko, Sergey V. Rashchenko, Sofija Miloš, Paolo Lotti, Ronald Miletich, Anton Shatskiy
{"title":"压缩至 20 GPa 时合成菱镁矿 K2Ca(CO3)2 弹性行为的晶体学机制","authors":"Anna Yu. Likhacheva, Alexandr V. Romanenko, Sergey V. Rashchenko, Sofija Miloš, Paolo Lotti, Ronald Miletich, Anton Shatskiy","doi":"10.1007/s00269-024-01291-8","DOIUrl":null,"url":null,"abstract":"<div><p>Bütschliite, K<sub>2</sub>Ca(CO<sub>3</sub>)<sub>2</sub>, occurring as inclusions in mantle minerals, is regarded as one of the key phases to understand phase relationships of dense potassium carbonates and thus to evaluate their potential role within the Earth’s deep carbon cycle. Accordingly, the high-pressure behavior of synthetic bütschliite has been investigated by in-situ single-crystal X-ray diffraction under isothermal compression up to 20 GPa at <i>T</i> = 298 K. The compression mechanism before and after the trigonal-to-monoclinic (<i>R</i>-3<i>m</i> to <i>C</i>2/<i>m</i>) phase transition at ∼6 GPa, found previously, is characterized in terms of the evolution of the cation polyhedra and carbonate groups. On this basis, the modulation of the axial compression is interpreted, and the contribution of the cation polyhedra into the bulk compression is estimated. The refined compressibility of the monoclinic phase (<i>K</i><sub>0</sub> = 44(2) GPa) fits to the trend of the carbonate bulk modulus <i>versus</i> average non-carbon cation radius. The analysis of the obtained and literature structural data suggests the distortion of a large cation polyhedron to be an effective tool to strengthen the carbonate structure at high pressure. On the other hand, the observed symmetrization of the cation polyhedra in trigonal bütschliite is apparently a crucial factor of its stabilization at high pressure upon the temperature rise observed previously. The structural crystallography provided in this study supports the enhanced stability of trigonal bütschliite at high <i>P</i>,<i> T</i> conditions and its significance of being considered as a constituent of the inclusions in deep minerals.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":"51 3","pages":""},"PeriodicalIF":1.2000,"publicationDate":"2024-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-024-01291-8.pdf","citationCount":"0","resultStr":"{\"title\":\"Crystallographic mechanism of the elastic behaviour of synthetic bütschliite K2Ca(CO3)2 on compression to 20 GPa\",\"authors\":\"Anna Yu. Likhacheva, Alexandr V. Romanenko, Sergey V. Rashchenko, Sofija Miloš, Paolo Lotti, Ronald Miletich, Anton Shatskiy\",\"doi\":\"10.1007/s00269-024-01291-8\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Bütschliite, K<sub>2</sub>Ca(CO<sub>3</sub>)<sub>2</sub>, occurring as inclusions in mantle minerals, is regarded as one of the key phases to understand phase relationships of dense potassium carbonates and thus to evaluate their potential role within the Earth’s deep carbon cycle. Accordingly, the high-pressure behavior of synthetic bütschliite has been investigated by in-situ single-crystal X-ray diffraction under isothermal compression up to 20 GPa at <i>T</i> = 298 K. The compression mechanism before and after the trigonal-to-monoclinic (<i>R</i>-3<i>m</i> to <i>C</i>2/<i>m</i>) phase transition at ∼6 GPa, found previously, is characterized in terms of the evolution of the cation polyhedra and carbonate groups. On this basis, the modulation of the axial compression is interpreted, and the contribution of the cation polyhedra into the bulk compression is estimated. The refined compressibility of the monoclinic phase (<i>K</i><sub>0</sub> = 44(2) GPa) fits to the trend of the carbonate bulk modulus <i>versus</i> average non-carbon cation radius. The analysis of the obtained and literature structural data suggests the distortion of a large cation polyhedron to be an effective tool to strengthen the carbonate structure at high pressure. On the other hand, the observed symmetrization of the cation polyhedra in trigonal bütschliite is apparently a crucial factor of its stabilization at high pressure upon the temperature rise observed previously. The structural crystallography provided in this study supports the enhanced stability of trigonal bütschliite at high <i>P</i>,<i> T</i> conditions and its significance of being considered as a constituent of the inclusions in deep minerals.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":\"51 3\",\"pages\":\"\"},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2024-07-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-024-01291-8.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/s00269-024-01291-8\",\"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/s00269-024-01291-8","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}
Crystallographic mechanism of the elastic behaviour of synthetic bütschliite K2Ca(CO3)2 on compression to 20 GPa
Bütschliite, K2Ca(CO3)2, occurring as inclusions in mantle minerals, is regarded as one of the key phases to understand phase relationships of dense potassium carbonates and thus to evaluate their potential role within the Earth’s deep carbon cycle. Accordingly, the high-pressure behavior of synthetic bütschliite has been investigated by in-situ single-crystal X-ray diffraction under isothermal compression up to 20 GPa at T = 298 K. The compression mechanism before and after the trigonal-to-monoclinic (R-3m to C2/m) phase transition at ∼6 GPa, found previously, is characterized in terms of the evolution of the cation polyhedra and carbonate groups. On this basis, the modulation of the axial compression is interpreted, and the contribution of the cation polyhedra into the bulk compression is estimated. The refined compressibility of the monoclinic phase (K0 = 44(2) GPa) fits to the trend of the carbonate bulk modulus versus average non-carbon cation radius. The analysis of the obtained and literature structural data suggests the distortion of a large cation polyhedron to be an effective tool to strengthen the carbonate structure at high pressure. On the other hand, the observed symmetrization of the cation polyhedra in trigonal bütschliite is apparently a crucial factor of its stabilization at high pressure upon the temperature rise observed previously. The structural crystallography provided in this study supports the enhanced stability of trigonal bütschliite at high P, T conditions and its significance of being considered as a constituent of the inclusions in deep minerals.
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)