Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy
Crystal-chemical properties of synthetic Almandine-Pyrope (Alm-Pyr) solid solutions were investigated by X-ray single-crystal diffraction and Raman spectroscopy. Garnet solid solution with different compositions were synthesized from powder at 4.0 GPa and annealed at 1200 °C for 48 h by a m...
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MDPI AG
2019-10-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/9/10/541 |
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| author | Yunqian Kuang Jingui Xu Bo Li Zhilin Ye Shijie Huang Wei Chen Dongzhou Zhang Wenge Zhou Maining Ma |
| author_facet | Yunqian Kuang Jingui Xu Bo Li Zhilin Ye Shijie Huang Wei Chen Dongzhou Zhang Wenge Zhou Maining Ma |
| author_sort | Yunqian Kuang |
| collection | DOAJ |
| description | Crystal-chemical properties of synthetic Almandine-Pyrope (Alm-Pyr) solid solutions were investigated by X-ray single-crystal diffraction and Raman spectroscopy. Garnet solid solution with different compositions were synthesized from powder at 4.0 GPa and annealed at 1200 °C for 48 h by a multi-anvil pressure apparatus. Garnet crystals with different sizes (about 60−1000 μm) were obtained from synthesis. The results of X-ray single-crystal diffraction show that the unit cell constants decrease with increasing Pyr contents in the synthetic Alm-Pyr crystals due to the smaller ionic radius of Mg<sup>2+</sup> in eightfold coordination than that of Fe<sup>2+</sup>. The data exhibit obviously positive deviations from ideal mixing volumes across the Alm-Pyr join which may be caused by the distortion of the SiO<sub>4</sub> tetrahedron. Moreover, the significant decrease in the average M-O bond length and volume of the [MgO<sub>8</sub>]/[FeO<sub>8</sub>] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell constant and volume. On the other hand, selected bond distances (average <M-O>, <Al-O>, and <D-O> distances) have a linear correlation with the unit-cell parameter, but the <Si-O> distance has nonlinear correlation. With increasing the unit-cell parameter, the average <M-O> distance increases significantly, followed by the average <D-O> and <Al-O> distances. While the <Si-O> distance changes negligibly further confirming the conclusion that the significant decrease of the average M-O bond length of the [MgO<sub>8</sub>]/[FeO<sub>8</sub>] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell volume. In the Raman spectra collected for the Alm-Pyr solid solutions, Raman vibration mode assignments indicate that the Raman vibrational spectra change along the Alm-Pyr binary solution. The mode frequencies of Si-O stretching, Si-O bending, and the rotation of the SiO<sub>4</sub>-tetrahedron (R(SiO<sub>4</sub>)) decrease linearly, while the translational modes of the SiO<sub>4</sub>-tetrahedron (T(SiO<sub>4</sub>)) increase with increasing Alm contents. |
| first_indexed | 2024-12-10T07:22:06Z |
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| language | English |
| last_indexed | 2024-12-10T07:22:06Z |
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| spelling | doaj.art-f6843653981946d19b1ea4ace10a52832022-12-22T01:57:47ZengMDPI AGCrystals2073-43522019-10-0191054110.3390/cryst9100541cryst9100541Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman SpectroscopyYunqian Kuang0Jingui Xu1Bo Li2Zhilin Ye3Shijie Huang4Wei Chen5Dongzhou Zhang6Wenge Zhou7Maining Ma8Key Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaHawaii Institute of Geophysics and Planetology, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, Honolulu, HI 96822, USAKey Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaKey Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaKey Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaKey Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaHawaii Institute of Geophysics and Planetology, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, Honolulu, HI 96822, USAKey Laboratory for High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, ChinaKey Laboratory of Computational Geodynamics, College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, ChinaCrystal-chemical properties of synthetic Almandine-Pyrope (Alm-Pyr) solid solutions were investigated by X-ray single-crystal diffraction and Raman spectroscopy. Garnet solid solution with different compositions were synthesized from powder at 4.0 GPa and annealed at 1200 °C for 48 h by a multi-anvil pressure apparatus. Garnet crystals with different sizes (about 60−1000 μm) were obtained from synthesis. The results of X-ray single-crystal diffraction show that the unit cell constants decrease with increasing Pyr contents in the synthetic Alm-Pyr crystals due to the smaller ionic radius of Mg<sup>2+</sup> in eightfold coordination than that of Fe<sup>2+</sup>. The data exhibit obviously positive deviations from ideal mixing volumes across the Alm-Pyr join which may be caused by the distortion of the SiO<sub>4</sub> tetrahedron. Moreover, the significant decrease in the average M-O bond length and volume of the [MgO<sub>8</sub>]/[FeO<sub>8</sub>] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell constant and volume. On the other hand, selected bond distances (average <M-O>, <Al-O>, and <D-O> distances) have a linear correlation with the unit-cell parameter, but the <Si-O> distance has nonlinear correlation. With increasing the unit-cell parameter, the average <M-O> distance increases significantly, followed by the average <D-O> and <Al-O> distances. While the <Si-O> distance changes negligibly further confirming the conclusion that the significant decrease of the average M-O bond length of the [MgO<sub>8</sub>]/[FeO<sub>8</sub>] dodecahedron with increasing Pyr contents are the most important factors to the decrease in the Alm-Pyr crystal unit cell volume. In the Raman spectra collected for the Alm-Pyr solid solutions, Raman vibration mode assignments indicate that the Raman vibrational spectra change along the Alm-Pyr binary solution. The mode frequencies of Si-O stretching, Si-O bending, and the rotation of the SiO<sub>4</sub>-tetrahedron (R(SiO<sub>4</sub>)) decrease linearly, while the translational modes of the SiO<sub>4</sub>-tetrahedron (T(SiO<sub>4</sub>)) increase with increasing Alm contents.https://www.mdpi.com/2073-4352/9/10/541synthetic almandine-pyrope solid solutioncrystal-chemical propertyx-ray single-crystal diffractionraman spectroscopy |
| spellingShingle | Yunqian Kuang Jingui Xu Bo Li Zhilin Ye Shijie Huang Wei Chen Dongzhou Zhang Wenge Zhou Maining Ma Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy Crystals synthetic almandine-pyrope solid solution crystal-chemical property x-ray single-crystal diffraction raman spectroscopy |
| title | Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy |
| title_full | Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy |
| title_fullStr | Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy |
| title_full_unstemmed | Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy |
| title_short | Crystal-Chemical Properties of Synthetic Almandine-Pyrope Solid Solution by X-Ray Single-Crystal Diffraction and Raman Spectroscopy |
| title_sort | crystal chemical properties of synthetic almandine pyrope solid solution by x ray single crystal diffraction and raman spectroscopy |
| topic | synthetic almandine-pyrope solid solution crystal-chemical property x-ray single-crystal diffraction raman spectroscopy |
| url | https://www.mdpi.com/2073-4352/9/10/541 |
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