Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR
The crystal structures of the lithium aluminosilicate minerals of the Li2O–Al2O3–SiO2 (LAS) system (Li1−xAl1−xSi1+xO4 system for 0.0 ≤ x ≤ 1.0), and bikitaite were determined by X-ray diffraction (XRD) in literature, suggesting several possible lattice models for each of the crystallized phases, bec...
| Autores: | , , , , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2022 |
| País: | España |
| Recursos: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/267255 |
| Acesso em linha: | http://hdl.handle.net/10261/267255 |
| Access Level: | acceso abierto |
| Palavra-chave: | Quartz Cristobalite α-spodumene β-spodumene Petalite Bikitaite Ostwald’s rule of states NMR |
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Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMRSánchez-Muñoz, LuisSanz, Jesús M.Florian, PierreDíaz-Gómez, VirginiaFurio, MartaSobrados, IsabelQuartzCristobaliteα-spodumeneβ-spodumenePetaliteBikitaiteOstwald’s rule of statesNMRThe crystal structures of the lithium aluminosilicate minerals of the Li2O–Al2O3–SiO2 (LAS) system (Li1−xAl1−xSi1+xO4 system for 0.0 ≤ x ≤ 1.0), and bikitaite were determined by X-ray diffraction (XRD) in literature, suggesting several possible lattice models for each of the crystallized phases, because of the intrinsic experimental difficulties of this technique. Here, we correlate powder XRD patterns with Rietveld refinement of cell parameters and magic angle sample spinning multinuclear magnetic resonance (NMR) spectra, including 29Si, 27Al, 7Li, and 6Li spectroscopy at 7.05 T, 9.4 T, and 20 T. The aim is to select appropriate lattice models from short-range order schemes in the lithium aluminosilicate phases, from natural minerals and synthetic crystals from the crystallization of amorphous gel precursors by a ceramic route and also by hydrothermal high-pressure experiments. Solid solutions were found in α-quartz and α-cristobalite up to x ≥ 0.75, and in β-eucryptite and β-spodumene for 0.0 ≤ x ≤ 1.0, when the ceramic synthesis is at work. The local structures of these intermediate members of the β-eucryptite and β-spodumene solid-solution series have 29Si NMR spectra consistent with the Loewenstein’s rule, i.e., they have short-range order but are strictly non-periodic structures. However, β-eucryptite LiAlSiO4 end-member has a short-range structure compatible with the long-range order of the P6422 symmetry, when the crystallization is produced at hydrothermal conditions. The local structure of α-spodumene LiAlSi2O6 is consistent with the C2/c model. α-eucryptite LiAlSiO4 shows a short-range structure as that suggested by the R-3 lattice model. Petalite LiAlSi4O10 has a local structure compatible with the P2/a space group. Finally, the 29Si NMR spectra of bikitaite LiAlSi2O6·H2O indicate a short-range structure well-suited with the P1 symmetry. These results are consistent with the Ostwald‘s rule of stages, forming a order-disorder sequence of increasing long-range order from the starting fully disordered solid gels, through crystalline pseudoperiodic structures in non-stoichiometric solid solution crystals that respect the Lowenstein’s rule, up to fully ordered crystals with short-range structures from NMR close to the long-range structures by XRD, as in the stoichiometric compounds found in some natural minerals.This research was funded by the Ministerio de Ciencia e Innovación PID2019-106662RB-C42, and Ministerio de Economía y Competitividad MAT2017-86450-C4-1-R.Peer reviewedMultidisciplinary Digital Publishing InstituteMinisterio de Ciencia e Innovación (España)Ministerio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202220222022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/267255reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106662RB-C42info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-86450-C4-1-RSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2672552026-05-22T06:33:51Z |
| dc.title.none.fl_str_mv |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| title |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| spellingShingle |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR Sánchez-Muñoz, Luis Quartz Cristobalite α-spodumene β-spodumene Petalite Bikitaite Ostwald’s rule of states NMR |
| title_short |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| title_full |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| title_fullStr |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| title_full_unstemmed |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| title_sort |
Order-Disorder in the Structures of Lithium Aluminosilicate Minerals by XRD and Multinuclear NMR |
| dc.creator.none.fl_str_mv |
Sánchez-Muñoz, Luis Sanz, Jesús M. Florian, Pierre Díaz-Gómez, Virginia Furio, Marta Sobrados, Isabel |
| author |
Sánchez-Muñoz, Luis |
| author_facet |
Sánchez-Muñoz, Luis Sanz, Jesús M. Florian, Pierre Díaz-Gómez, Virginia Furio, Marta Sobrados, Isabel |
| author_role |
author |
| author2 |
Sanz, Jesús M. Florian, Pierre Díaz-Gómez, Virginia Furio, Marta Sobrados, Isabel |
| author2_role |
author author author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Ciencia e Innovación (España) Ministerio de Economía y Competitividad (España) Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Quartz Cristobalite α-spodumene β-spodumene Petalite Bikitaite Ostwald’s rule of states NMR |
| topic |
Quartz Cristobalite α-spodumene β-spodumene Petalite Bikitaite Ostwald’s rule of states NMR |
| description |
The crystal structures of the lithium aluminosilicate minerals of the Li2O–Al2O3–SiO2 (LAS) system (Li1−xAl1−xSi1+xO4 system for 0.0 ≤ x ≤ 1.0), and bikitaite were determined by X-ray diffraction (XRD) in literature, suggesting several possible lattice models for each of the crystallized phases, because of the intrinsic experimental difficulties of this technique. Here, we correlate powder XRD patterns with Rietveld refinement of cell parameters and magic angle sample spinning multinuclear magnetic resonance (NMR) spectra, including 29Si, 27Al, 7Li, and 6Li spectroscopy at 7.05 T, 9.4 T, and 20 T. The aim is to select appropriate lattice models from short-range order schemes in the lithium aluminosilicate phases, from natural minerals and synthetic crystals from the crystallization of amorphous gel precursors by a ceramic route and also by hydrothermal high-pressure experiments. Solid solutions were found in α-quartz and α-cristobalite up to x ≥ 0.75, and in β-eucryptite and β-spodumene for 0.0 ≤ x ≤ 1.0, when the ceramic synthesis is at work. The local structures of these intermediate members of the β-eucryptite and β-spodumene solid-solution series have 29Si NMR spectra consistent with the Loewenstein’s rule, i.e., they have short-range order but are strictly non-periodic structures. However, β-eucryptite LiAlSiO4 end-member has a short-range structure compatible with the long-range order of the P6422 symmetry, when the crystallization is produced at hydrothermal conditions. The local structure of α-spodumene LiAlSi2O6 is consistent with the C2/c model. α-eucryptite LiAlSiO4 shows a short-range structure as that suggested by the R-3 lattice model. Petalite LiAlSi4O10 has a local structure compatible with the P2/a space group. Finally, the 29Si NMR spectra of bikitaite LiAlSi2O6·H2O indicate a short-range structure well-suited with the P1 symmetry. These results are consistent with the Ostwald‘s rule of stages, forming a order-disorder sequence of increasing long-range order from the starting fully disordered solid gels, through crystalline pseudoperiodic structures in non-stoichiometric solid solution crystals that respect the Lowenstein’s rule, up to fully ordered crystals with short-range structures from NMR close to the long-range structures by XRD, as in the stoichiometric compounds found in some natural minerals. |
| publishDate |
2022 |
| dc.date.none.fl_str_mv |
2022 2022 2022 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10261/267255 |
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http://hdl.handle.net/10261/267255 |
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Inglés |
| language_invalid_str_mv |
Inglés |
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#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106662RB-C42 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-86450-C4-1-R Sí |
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info:eu-repo/semantics/openAccess |
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openAccess |
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Multidisciplinary Digital Publishing Institute |
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Multidisciplinary Digital Publishing Institute |
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