C. Melai, T. Boffa Ballaran, L. Uenver-Thiele, A. Kurnosov, A. I. Chumakov, D. Bessas, D. J. Frost
{"title":"磁铁矿-镁铁素体固溶体的可压缩性","authors":"C. Melai, T. Boffa Ballaran, L. Uenver-Thiele, A. Kurnosov, A. I. Chumakov, D. Bessas, D. J. Frost","doi":"10.1007/s00269-022-01217-2","DOIUrl":null,"url":null,"abstract":"<div><p>To calculate the thermodynamic properties of recently discovered high-pressure mixed valence iron oxides in the system Fe–Mg–O, information on the equation of state of precursor inverse spinel phases along the magnetite–magnesioferrite join is needed. The existing equation of state data, particularly for magnesioferrite, are in poor agreement and no data exist for intermediate compositions. In this study, the compressibility of nearly pure magnesioferrite as well as of an intermediate <span>\\({{\\mathrm{Mg}}_{0.5}}^{\\vphantom{2+}}\\mathrm{Fe}_{0.5}^{2+}{\\mathrm{Fe}}_{2}^{3+}{\\mathrm{O}}_{4}^{\\vphantom{2+}}\\)</span> sample have been investigated for the first time up to approximately 19 and 13 GPa, respectively, using single-crystal X-ray diffraction in a diamond anvil cell. Samples were produced in high-pressure synthesis experiments to promote a high level of cation ordering, with the obtained inversion parameters larger than 0.83. The room pressure unit cell volumes, <i>V</i><sub>0</sub>, and bulk moduli, <i>K</i><sub><i>T</i>0</sub>, could be adequately constrained using a second-order Birch–Murnaghan equation of state, which yields <i>V</i><sub>0</sub> = 588.97 (8) Å<sup>3</sup> and <i>K</i><sub><i>T</i>0</sub> = 178.4 (5) GPa for magnesioferrite and <i>V</i><sub>0</sub> = 590.21 (5) Å<sup>3</sup> and <i>K</i><sub><i>T</i>0</sub> = 188.0 (6) GPa for the intermediate composition. As magnetite has <i>K</i><sub><i>T</i>0</sub> = 180 (1) GPa (Gatta et al. in Phys Chem Min 34:627–635, 2007. https://doi.org/10.1007/s00269-007-0177-3), this means the variation in <i>K</i><sub><i>T</i>0</sub> across the magnetite–magnesioferrite solid solution is significantly non-linear, in contrast to several other Fe–Mg spinels. The larger incompressibility of the intermediate composition compared to the two end-members may be a peculiarity of the magnetite–magnesioferrite solid solution caused by an interruption of Fe<sup>2+</sup>–Fe<sup>3+</sup> electron hopping by Mg cations substituting in the octahedral site.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":"50 1","pages":""},"PeriodicalIF":1.2000,"publicationDate":"2022-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-022-01217-2.pdf","citationCount":"0","resultStr":"{\"title\":\"Compressibilities along the magnetite–magnesioferrite solid solution\",\"authors\":\"C. Melai, T. Boffa Ballaran, L. Uenver-Thiele, A. Kurnosov, A. I. Chumakov, D. Bessas, D. J. Frost\",\"doi\":\"10.1007/s00269-022-01217-2\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>To calculate the thermodynamic properties of recently discovered high-pressure mixed valence iron oxides in the system Fe–Mg–O, information on the equation of state of precursor inverse spinel phases along the magnetite–magnesioferrite join is needed. The existing equation of state data, particularly for magnesioferrite, are in poor agreement and no data exist for intermediate compositions. In this study, the compressibility of nearly pure magnesioferrite as well as of an intermediate <span>\\\\({{\\\\mathrm{Mg}}_{0.5}}^{\\\\vphantom{2+}}\\\\mathrm{Fe}_{0.5}^{2+}{\\\\mathrm{Fe}}_{2}^{3+}{\\\\mathrm{O}}_{4}^{\\\\vphantom{2+}}\\\\)</span> sample have been investigated for the first time up to approximately 19 and 13 GPa, respectively, using single-crystal X-ray diffraction in a diamond anvil cell. Samples were produced in high-pressure synthesis experiments to promote a high level of cation ordering, with the obtained inversion parameters larger than 0.83. The room pressure unit cell volumes, <i>V</i><sub>0</sub>, and bulk moduli, <i>K</i><sub><i>T</i>0</sub>, could be adequately constrained using a second-order Birch–Murnaghan equation of state, which yields <i>V</i><sub>0</sub> = 588.97 (8) Å<sup>3</sup> and <i>K</i><sub><i>T</i>0</sub> = 178.4 (5) GPa for magnesioferrite and <i>V</i><sub>0</sub> = 590.21 (5) Å<sup>3</sup> and <i>K</i><sub><i>T</i>0</sub> = 188.0 (6) GPa for the intermediate composition. As magnetite has <i>K</i><sub><i>T</i>0</sub> = 180 (1) GPa (Gatta et al. in Phys Chem Min 34:627–635, 2007. https://doi.org/10.1007/s00269-007-0177-3), this means the variation in <i>K</i><sub><i>T</i>0</sub> across the magnetite–magnesioferrite solid solution is significantly non-linear, in contrast to several other Fe–Mg spinels. The larger incompressibility of the intermediate composition compared to the two end-members may be a peculiarity of the magnetite–magnesioferrite solid solution caused by an interruption of Fe<sup>2+</sup>–Fe<sup>3+</sup> electron hopping by Mg cations substituting in the octahedral site.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":\"50 1\",\"pages\":\"\"},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2022-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-022-01217-2.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/s00269-022-01217-2\",\"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/s00269-022-01217-2","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}
Compressibilities along the magnetite–magnesioferrite solid solution
To calculate the thermodynamic properties of recently discovered high-pressure mixed valence iron oxides in the system Fe–Mg–O, information on the equation of state of precursor inverse spinel phases along the magnetite–magnesioferrite join is needed. The existing equation of state data, particularly for magnesioferrite, are in poor agreement and no data exist for intermediate compositions. In this study, the compressibility of nearly pure magnesioferrite as well as of an intermediate \({{\mathrm{Mg}}_{0.5}}^{\vphantom{2+}}\mathrm{Fe}_{0.5}^{2+}{\mathrm{Fe}}_{2}^{3+}{\mathrm{O}}_{4}^{\vphantom{2+}}\) sample have been investigated for the first time up to approximately 19 and 13 GPa, respectively, using single-crystal X-ray diffraction in a diamond anvil cell. Samples were produced in high-pressure synthesis experiments to promote a high level of cation ordering, with the obtained inversion parameters larger than 0.83. The room pressure unit cell volumes, V0, and bulk moduli, KT0, could be adequately constrained using a second-order Birch–Murnaghan equation of state, which yields V0 = 588.97 (8) Å3 and KT0 = 178.4 (5) GPa for magnesioferrite and V0 = 590.21 (5) Å3 and KT0 = 188.0 (6) GPa for the intermediate composition. As magnetite has KT0 = 180 (1) GPa (Gatta et al. in Phys Chem Min 34:627–635, 2007. https://doi.org/10.1007/s00269-007-0177-3), this means the variation in KT0 across the magnetite–magnesioferrite solid solution is significantly non-linear, in contrast to several other Fe–Mg spinels. The larger incompressibility of the intermediate composition compared to the two end-members may be a peculiarity of the magnetite–magnesioferrite solid solution caused by an interruption of Fe2+–Fe3+ electron hopping by Mg cations substituting in the octahedral site.
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)