Structure of alkali magnesium, zinc, and calcium metasilicate glasses

Henrick Bradtmuller; Esther Giron Lange; Anita Zeidler; Marcos de Oliveira Jr; Rafaella Bartz Pena; Hellmut Eckert; Hesameddin Mohammadi; Gabriel J. Cuello; Philip S. Salmon

doi:10.1063/5.0300986

Structure of alkali magnesium, zinc, and calcium metasilicate glasses

Henrick Bradtmuller, Esther Giron Lange, Anita Zeidler, Marcos de Oliveira Jr, Rafaella Bartz Pena, Hellmut Eckert, Hesameddin Mohammadi, Gabriel J. Cuello, Philip S. Salmon

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Abstract

The structure of the metasilicate composition glasses (A2O)x(XO)0.50−x(SiO2)0.50, with A = Na or K, X = Mg, Zn, or Ca, and x = 0.25 or 0.33, was investigated by combining neutron and high-energy x-ray diffraction with Raman scattering and 29Si and 25Mg magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The latter employed the rotor-assisted population transfer approach for signal enhancement. The diffraction results show a substantial population of four-coordinated X2+ cations in the majority of the magnesium- and zinc-bearing glasses. Based on the average degree of polymerization of the silicate networks obtained from the solid-state 29Si NMR results, and supported by the findings from Raman spectroscopy, no compelling evidence could be found for a network-forming role for the four-coordinated Mg2+ and Zn2+ species. The relationship between the Mg–O coordination numbers measured by diffraction and the mean isotropic chemical shifts found from 25Mg MAS NMR spectroscopy is considered for a variety of silicate glasses. A clear correlation between these parameters could not be found.

Original language	English
Article number	204502
Number of pages	19
Journal	The Journal of Chemical Physics
Volume	163
Issue number	20
DOIs	https://doi.org/10.1063/5.0300986
Publication status	Published - 28 Nov 2025

Data Availability Statement

Several of the data sets created during this research are openly available from the University of Bath Research Data Archive at https://doi.org/10.15125/BATH-01593.85 The D4c diffraction data sets are available from Ref. 86.

Acknowledgements

We thank Gavin Vaughan (ESRF) for help with the ESRF experiments and Alain Bertoni (Grenoble) for help with the D4c experiments.

The solid-state NMR and Raman experiments were carried out on equipment of the Center for Research, Technology, and Education in Vitreous Materials (CeRTEV), funded by FAPESP, process number 2013/07793-6. The authors gratefully acknowledge Professor Edgar D. Zanotto and Professor Paulo S. Pizani for granting access to the LaMaV and GEOR laboratory facilities at the Federal University of São Carlos. R.B.P. and H.B. acknowledge FAPESP postdoctoral fellowships, Process Nos. 2023/17069-5 and 2019/26399-3, respectively. Funding by CNPq to M.d.O., H.E., and H.B. via personal fellowships, Process Nos. 312802/2023-4, 310870/2020-8, and 309285/2025-9, respectively, is also gratefully acknowledged. H.B. made the alkali magnesium silicate samples. H.M. and P.S.S. made the alkali zinc and calcium silicate samples. P.S.S. and A.Z. designed the diffraction project. P.S.S., H.E., E.G.L., and G.J.C. performed the diffraction experiments, and E.G.L. and P.S.S. analyzed the data. The solid-state NMR experiments were planned, conducted, analyzed, and interpreted by H.B., M.d.O., and H.E. The thermal analysis and Raman spectroscopic measurements were conducted and analyzed by R.B.P. All the authors contributed to the writing and editing of the manuscript.

The solid-state NMR and Raman experiments were carried out on equipment of the Center for Research, Technology, and Education in Vitreous Materials (CeRTEV), funded by FAPESP, process number 2013/07793-6. The authors gratefully acknowledge Professor Edgar D. Zanotto and Professor Paulo S. Pizani for granting access to the LaMaV and GEOR laboratory facilities at the Federal University of São Carlos. R.B.P.

Funding

E.G.L. was supported by funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Grant Agreement No. 847439, and from Corning Inc. (Grant Agreement No. CM00003814). H.M. was supported by Corning Inc. (Grant Agreement No. CM00002159/SA/01). We acknowledge use of the EPSRC-funded Physical Sciences Datascience Service hosted by the University of Southampton and STFC under Grant No. EP/S020357/1. P.S.S. and H.E. appreciate support via the FAPESP/Bath University SPRINT program, Process No. 2022/14232-0. H.B. acknowledge FAPESP postdoctoral fellowships, Process Nos. 2023/17069-5 and 2019/26399-3, respectively. Funding by CNPq to M.d.O., H.E., and H.B. via personal fellowships, Process Nos. 312802/2023-4, 310870/2020-8, and 309285/2025-9, respectively, is also gratefully acknowledged.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/S020357/1

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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Cite this

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title = "Structure of alkali magnesium, zinc, and calcium metasilicate glasses",

abstract = "The structure of the metasilicate composition glasses (A2O)x(XO)0.50−x(SiO2)0.50, with A = Na or K, X = Mg, Zn, or Ca, and x = 0.25 or 0.33, was investigated by combining neutron and high-energy x-ray diffraction with Raman scattering and 29Si and 25Mg magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The latter employed the rotor-assisted population transfer approach for signal enhancement. The diffraction results show a substantial population of four-coordinated X2+ cations in the majority of the magnesium- and zinc-bearing glasses. Based on the average degree of polymerization of the silicate networks obtained from the solid-state 29Si NMR results, and supported by the findings from Raman spectroscopy, no compelling evidence could be found for a network-forming role for the four-coordinated Mg2+ and Zn2+ species. The relationship between the Mg–O coordination numbers measured by diffraction and the mean isotropic chemical shifts found from 25Mg MAS NMR spectroscopy is considered for a variety of silicate glasses. A clear correlation between these parameters could not be found.",

author = "Henrick Bradtmuller and \{Giron Lange\}, Esther and Anita Zeidler and \{de Oliveira Jr\}, Marcos and \{Bartz Pena\}, Rafaella and Hellmut Eckert and Hesameddin Mohammadi and Cuello, \{Gabriel J.\} and Salmon, \{Philip S.\}",

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AU - Giron Lange, Esther

AU - Zeidler, Anita

AU - de Oliveira Jr, Marcos

AU - Bartz Pena, Rafaella

AU - Eckert, Hellmut

AU - Mohammadi, Hesameddin

AU - Cuello, Gabriel J.

AU - Salmon, Philip S.

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AB - The structure of the metasilicate composition glasses (A2O)x(XO)0.50−x(SiO2)0.50, with A = Na or K, X = Mg, Zn, or Ca, and x = 0.25 or 0.33, was investigated by combining neutron and high-energy x-ray diffraction with Raman scattering and 29Si and 25Mg magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The latter employed the rotor-assisted population transfer approach for signal enhancement. The diffraction results show a substantial population of four-coordinated X2+ cations in the majority of the magnesium- and zinc-bearing glasses. Based on the average degree of polymerization of the silicate networks obtained from the solid-state 29Si NMR results, and supported by the findings from Raman spectroscopy, no compelling evidence could be found for a network-forming role for the four-coordinated Mg2+ and Zn2+ species. The relationship between the Mg–O coordination numbers measured by diffraction and the mean isotropic chemical shifts found from 25Mg MAS NMR spectroscopy is considered for a variety of silicate glasses. A clear correlation between these parameters could not be found.

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Structure of alkali magnesium, zinc, and calcium metasilicate glasses

Abstract

Data Availability Statement

Acknowledgements

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ASJC Scopus subject areas

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Data sets for "Structure of alkali magnesium, zinc, and calcium metasilicate glasses"

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Structure of alkali magnesium, zinc, and calcium metasilicate glasses

Abstract

Data Availability Statement

Acknowledgements

Funding

ASJC Scopus subject areas

Access to Document

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Fingerprint

Datasets

Data sets for "Structure of alkali magnesium, zinc, and calcium metasilicate glasses"

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