Abstract
MgO–Al2O3–SiO2 (MAS) glass has widespread applications due to the excellent chemical stability and mechanical strength. Accommodation of macroscopic properties requires a systematic investigation of the microstructure of glass caused by compositional adjustment. In this work, effects of progressive replacement of MgO by Al2O3 or SiO2 on glass structure and Vickers hardness were investigated. With the replacement of MgO by Al2O3 or SiO2, the glass network was strengthened, as a result, the glass transition temperature was increased and the crystallization tendency was weakened. The degree of structural changes caused by substitution of SiO2 for MgO is more significant than that of Al2O3 substitute for MgO. The strengthened glass network promotes the increase of Vickers hardness, and the coefficient of thermal expansion can be tailored in a large range. The results show that MAS glass maybe useful in the field of glass substrates for TFT–LCDs.
Similar content being viewed by others
REFERENCES
Tiegel, M., Herrmann, A., Rüssel, C., Körner, J., Klöpfel, D., Hein, J., and Kaluza, M.C., Magnesium aluminosilicate glasses as potential laser host material for ultrahigh power laser systems, J. Mater. Chem. C, 2013, vol. 1, no. 33, pp. 5031–5039.
Chen, C., Zhong, C., Zhang, Y., Li, A., Huang, S., Ze-ng, H., and Zu, Q., Structural and dynamic properties of MgO–Al2O3–SiO2 glasses from molecular dynamics simulations and NMR, Ceram. Int., 2022, vol. 48, no. 15, pp. 22 444–22 450.
Dittmer, M., Müller, M., and Rüssel, C., Self-organized nanocrystallinity in MgO–Al2O3–SiO2 glasses with ZrO2 as nucleating agent, Mater. Chem. Phys., 2010, vol. 124, nos. 2–3, pp. 1083–1088.
Belis, J., Louter, C., Nielsen, J.H., and Schneider, J., Architectural glass, in Springer Handbook of Glass, Musgraves, J.D., Hu, J., and Calvez, L., Eds., Part of Springer Handbooks, Cham: Springer, 2019.
Hao, X., Hu, X., Luo, Z., Liu, T., Li, Z., Wu, T., Lu, A., and Tang, Y., Preparation and properties of transparent cordierite-based glass-ceramics with high crystallinity, Ceram. Int., 2015, vol. 41, no. 10, pp. 14130–14136.
Lee, S.K., Kim, H., Kim, E.J., Mun, K.Y., and Ryu, S., Extent of disorder in magnesium aluminosilicate glasses: Insights from 27Al and 17O NMR, J. Phys. Chem. C, 2016, vol. 120, no. 1, pp. 737–749.
Li, X., Cao, J., Wang, L., and Peng, M., Predictable tendency of Bi NIR emission in Bi-doped magnesium aluminosilicate laser glasses, J. Am. Ceram. Soc., 2018, vol. 101, no. 3, pp. 1159–1168.
Han, L., Li, C., Lin, C., Liu, J., Wu, J., Gui, H., Zhang, Q., Luo, Z., Liu, T., and Lu, A., A novel Nd3+-doped MgO–Al2O3–SiO2-based transparent glass-ceramics: Toward excellent fluorescence properties, J. Am. Ceram. Soc., 2019, vol. 102, no. 7, pp. 4213–4225.
Laguta, A.V., Denker, B.I., Sverchkov, S.E., and Razdobreev, I.M., A magneto-optical study of bismuth-doped MgO–Al2O3–SiO2 glass: On the nature of near-infrared luminescence, Quantum Electron., 2017, vol. 47, no. 2, pp. 123–134.
Podda, O., Tissandier, L., Laplace, A., and Deloule, E., Solubility of uranium oxide in ternary aluminosilicate glass melts, J. Non-Cryst. Solids, 2022, vol. 595, pp. 121 845–121 854.
Seidel, S., Dittmer, M., Wisniewski, W., Höland, W., and Rüssel, C., Effect of the ZrO2 concentration on the crystallization behavior and the mechanical properties of high-strength MgO–Al2O3–SiO2 glass-ceramics, J. Mater. Sci., 2017, vol. 52, no. 4, pp. 1955–1968.
Ke, X., Shan, Z., Li, Z., Tao, Y., Yue, Y., and Tao, H., Toward hard and highly crack resistant magnesium aluminosilicate glasses and transparent glass-ceramics, J. Am. Ceram. Soc., 2020, vol. 103, no. 6, pp. 3600–3609.
Li, H., Yin, Z., Deng, L., Wang, S., Fu, Z., and Ma, Y., Effect of SiO2/Al2O3 ratio on the structure and electrical properties of MgO–Al2O3–SiO2 glass-ceramics doped with TiO2, Mater. Chem. Phys., 2020, vol. 256, pp. 123 653–123 659.
Lu, J., Wang, H., Li, Y., Zhou, Y., and Jiang, W., Effect of metastable phase on the crystallization and mechanical properties of MgO–Al2O3–SiO2 glass-ceramics without nucleating agents, Ceram. Int., 2023, vol. 49, no. 5, pp. 7737–7745.
Machida, S., Maeda, K., Katsumata, K.-i., and Yasumori, A., Microstructural control of MgO–Al2O3–SiO2 glass-ceramics using titanium oxides with varying particle sizes and crystallinities as nucleation agents, J. Ceram. Soc. Jpn., 2023, vol. 131, no. 3, pp. 42–48.
Liu, J., Li, C., Peng, H., Zeng, Q., and Lu, A., Preparation and characterization of alkali-free glass substrates with enhanced properties for TFT-LCDs applications, Ceram. Int., 2021, vol. 47, no. 15, pp. 21 650–21 659.
Liu, J., Zou, Q., Zhang, Z., Zeng, Q., Peng, H., Wang, Q., and Chang, Q., Research on mixed alkaline-earth effect in non-alkali glass substrates for TFT-LCDs, J. Non-Cryst. Solids, 2022, vol. 579, pp. 121 372–121 379.
Neuville, D., Cormier, L., Montouillout, V., Florian, P., Millot, F., Rifflet, J., and Massiot, D., Structure of Mg- and Mg/Ca aluminosilicate glasses: 27Al NMR and Raman spectroscopy investigations, Am. Mineral., 2008, vol. 93, nos. 11–12, pp. 1721–1731.
Guignard, M. and Cormier, L., Environments of Mg and Al in MgO–Al2O3–SiO2 glasses: A study coupling neutron and X-ray diffraction and reverse Monte Carlo modeling, Chem. Geol., 2008, vol. 256, nos. 3–4, pp. 111–118.
Kalampounias, A., Nasikas, N., and Papatheodorou, G., Glass formation and structure in the MgSiO3–Mg2SiO4 pseudobinary system: From degraded networks to ioniclike glasses, J. Chem. Phys., 2009, vol. 131, no. 11, pp. 114 513–114 520.
Shimoda, K., Tobu, Y., Hatakeyama, M., Nemoto, T., and Saito, K., Letter: Structural investigation of Mg local environments in silicate glasses by ultra-high field 25Mg 3QMAS NMR spectroscopy, Am. Mineral., 2007, vol. 92, no. 4, pp. 695–698.
Sen, S., Maekawa, H., and Papatheodorou, G., Short-range structure of invert glasses along the pseudo-binary join MgSiO3–Mg2SiO4: Results from 29Si and 25Mg MAS NMR spectroscopy, J. Phys. Chem. B, 2009, vol. 113, no. 46, pp. 15 243–15 248.
Wilding, M., Benmore, C., Tangeman, J., and Sampath, S., Evidence of different structures in magnesium silicate liquids: Coordination changes in forsterite- to enstatite-composition glasses, Chem. Geol., 2004, vol. 213, nos. 1–3, pp. 281–291.
Kubicki, J. and Lasaga, A., Molecular dynamics simulations of pressure and temperature effects on MgSiO3 and Mg2SiO4 melts and glasses, Phys. Chem. Miner., 1991, vol. 17, no. 8, pp. 661–673.
Fiske, P. and Stebbins, J., The structural role of Mg in silicate liquids: A high-temperature 25Mg, 23Na, and 29Si NMR study, Am. Mineral., 1994, vol. 79, nos. 9 10, pp. 848–861.
Watts, S., Hill, R., O’Donnell, M., and Law, R., Influence of magnesia on the structure and properties of bioactive glasses, J. Non-Cryst. Solids, 2010, vol. 356, nos. 9–10, pp. 517–524.
Kolay, S. and Bhargava, P., Role of MgO in lowering glass transition temperature and increasing hardness of lithium silicate glass and glass-ceramics, Ceram. Int., 2022, vol. 48, no. 9, pp. 12 699–12 711.
Merzbacher, C.I. and White, W.B., The structure of alkaline earth aluminosilicate glasses as determined by vibrational spectroscopy, J. Non-Cryst. Solids, 1991, vol. 130, no. 1, pp. 18–34.
Neuville, D., Cormier, L., and Massiot, D., Al environment in tectosilicate and peraluminous glasses: A 27Al MQ-MAS NMR, Raman, and XANES investigation, Geochim. Cosmochim. Acta, 2004, vol. 68, no. 24, pp. 5071–5079.
Neuville, D., Cormier, L., and Massiot, D., Al coordination and speciation in calcium aluminosilicate glasses: Effects of composition determined by 27Al MQ-MAS NMR and Raman spectroscopy, Chem. Geol., 2006, vol. 229, nos. 1–3, pp. 173–185.
Neuville, D., Cormier, L., Montouillout, V., and Massiot, D., Local Al site distribution in aluminosilicate glasses by 27Al MQMAS NMR, J. Non-Cryst. Solids, 2007, vol. 353, no. 2, pp. 180–184.
Neuville, D., Cormier, L., Ligny, D., Roux, J., Flank, A., and Lagarde, P., Environments around Al, Si, and Ca in aluminate and aluminosilicate melts by X-ray absorption spectroscopy at high temperature, Am. Mineral., 2008, vol. 93, no. 1, pp. 228–234.
Smedskjaer, M., Youngman, R., and Mauro, J., Impact of ZnO on the structure and properties of sodium aluminosilicate glasses: Comparison with alkaline earth oxides, J. Non-Cryst. Solids, 2013, vol. 381, pp. 58–64.
Park, S. and Lee, S., High-resolution solid-state NMR study of the effect of composition on network connectivity and structural disorder in multi-component glasses in the diopside and jadeite join: Implications for structure of andesitic melts, Geochim. Cosmochim. Acta, 2014, vol. 147, no. 1, pp. 26–42.
Seidel, S., Dittmer, M., Höland, W., and Rüssel, C., High-strength, translucent glass-ceramics in the system MgO–ZnO–Al2O3–SiO2–ZrO2, J. Eur. Ceram. Soc., 2017, vol. 37, no. 7, pp. 2685–2694.
Sun, L., Fang, J., Guo, S., Shan, T., Wen, Y., Liu, C., and Zhang, J., Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic, Ceram. Int., 2022, vol. 48, no. 14, pp. 20 053–20 061.
Lao, X. and Xu, X., Effect of MgO/SiO2 ratio and Al2O3 content on crystallization behavior and properties of cordierite-based glass-ceramics, J. Eur. Ceram. Soc., 2021, vol. 41, no. 2, pp. 1593–1602.
Veit, U. and Rüssel, C., Viscosity and liquidus temperature of quaternary glasses close to an eutectic composition in the CaO–MgO–Al2O3–SiO2 system, J. Mater. Sci., 2017, vol. 52, no. 13, pp. 8280–8292.
Sun, K.-H., Fundamental condition of glass formation, J. Am. Ceram. Soc., 1947, vol. 30, no. 9, pp. 277–281.
Sun, Y., Wang, H., and Zhang, Z., Understanding the relationship between structure and thermophysical properties of CaO–SiO2–MgO–Al2O3 molten slags, Metall. Mater. Trans. B, 2018, vol. 49, no. 2, pp. 677–687.
Zhang, Y., Li, H., Liu, S., Wu, N., and Ou Yang, S., Raman spectroscopic study of irregular network in the process of glass conversion to CaO–MgO–Al2O3–SiO2 glass-ceramics, J. Non-Cryst. Solids, 2021, vol. 563, pp. 120 701–120 707.
Matson, D., Sharma, S., and Philpotts, J., The structure of high-silica alkali-silicate glasses. A Raman spectroscopic investigation, J. Non-Cryst. Solids, 1983, vol. 58, nos. 2–3, pp. 323–352.
Yadav, A.K. and Singh, P., A review of the structures of oxide glasses by Raman spectroscopy, RSC Adv., 2015, vol. 5, no. 83, pp. 67 583–67 609.
McKeown, D., Galeener, F., and Brown, G., Raman studies of Al coordination in silica-rich sodium aluminosilicate glasses and some related minerals, J. Non-Cryst. Solids, 1984, vol. 68, nos. 2–3, pp. 361–378.
Losq, C., Neuville, D., Florian, P., Henderson, G., and Massiot, D., The role of Al3+ on rheology and structural changes in sodium silicate and aluminosilicate glasses and melts, Geochim. Cosmochim. Acta, 2014, vol. 126, no. 1, pp. 495–517.
Kim, T. and Park, J., Structure-viscosity relationship of low-silica calcium aluminosilicate melts, ISIJ Int., 2014, vol. 54, no. 9, pp. 2031–2038.
Guo, Y., Liu, C., Wang, J., Ruan, J., Xie, J., Han, J., Deng, Z., and Zhao, X., Effects of alkali oxides and ion-exchange on the structure of zinc–alumino–silicate glasses and glass-ceramics, J. Eur. Ceram. Soc., 2022, vol. 42, no. 2, pp. 576–588.
McMillan, P.F., Poe, B.T., Gillet, P.H., and Reynard, B., A study of SiO2 glass and supercooled liquid to 1950 K via high-temperature Raman spectroscopy, Geochim. Cosmochim. Acta, 1994, vol. 58, no. 17, pp. 3653–3664.
Zheng, K., Liao, J., Wang, X., and Zhang, Z., Raman spectroscopic study of the structural properties of CaO–MgO–SiO2–TiO2 slags, J. Non-Cryst. Solids, 2013, vol. 376, pp. 209–215.
Mysen, B., Physics and chemistry of silicate glasses and melts, Eur. J. Mineral., 2003, vol. 15, no. 5, pp. 781–802.
Lin, S. and Hwang, C., Structures of CeO2–Al2O3–SiO2 glasses, J. Non-Cryst. Solids, 1996, vol. 202, nos. 1–2, pp. 61–67.
Aronne, A., Esposito, S., and Pernice, P., FTIR and DTA study of lanthanum aluminosilicate glasses, Mater. Chem. Phys., 1997, vol. 51, no. 2, pp. 163–168.
Guo, Y., Wang, J., Ruan, J., Han, J., Xie, J., and Liu, C., Microstructure and ion-exchange properties of glass-ceramics containing ZnAl2O4 and β-quartz solid solution nanocrystals, J. Eur. Ceram. Soc., 2021, vol. 41, no. 10, pp. 5331–5340.
Han, L., Song., J., Lin, C., Liu, J., Liu, T., Zhang, Q., Luo, Z., and Lu, A., Crystallization, structure and properties of MgO–Al2O3–SiO2 highly crystalline transparent glass-ceramics nucleated by multiple nucleating agents, J. Eur. Ceram. Soc., 2018, vol. 38, no. 13, pp. 4533–4542.
McMillan, P. and Piriou, B., The structures and vibrational spectra of crystals and glasses in the silica-alumina system, J. Non-Cryst. Solids, 1982, vol. 53, no. 3, pp. 279–298.
Hutton, W. and Thorp, J.S., The vibrational spectra of MgO–Al2O3–SiO2 glasses containing TiO2, J. Mater. Sci., 1985, vol. 20, no. 2, pp. 542–551.
Saikia, B.J. and Parthasarathy, G., Fourier transform infrared spectroscopic characterization of kaolinite from Assam and Meghalaya, Northeastern India, J. Mod. Phys., 2010, vol. 1, no. 4, pp. 206–210.
Merzbacher, C.I., Sherriff, B.L., Hartman, J.S., and White, W.B., A high-resolution 29Si and 27Al NMR study of alkaline earth aluminosilicate glasses, J. Non-Cryst. Solids, 1990, vol. 124, nos. 2–3, pp. 194–206.
Guo, Y., Liu, C., Wang, J., Ruan, J., Li, X., Han, J., and Xie, J., Effect of ZrO2 crystallization on ion exchange properties in aluminosilicate glass, J. Eur. Ceram. Soc., 2020, vol. 40, no. 5, pp. 2179–2184.
Merzbacher, C.I., McGrath, K.J., and Higby, P.L., 29Si NMR and infrared reflectance spectroscopy of low-silica calcium aluminosilicate glasses, J. Non-Cryst. Solids, 1991, vol. 136, no. 3, pp. 249–259.
Diallo, B., Allix, M., Véron, E., Sarou-Kanian, V., Bardez-Giboire, I., Montouillout, V., and Pellerin, N., Deconvolution method of 29Si MAS NMR spectra applied to homogeneous and phase separated lanthanum aluminosilicate glasses, J. Non-Cryst. Solids, 2019, vols. 503–504, pp. 352–365.
Lin, X., Huang, Q., Liu, L., Zhang, Y., Ning, T., Lu, A., and Jiang, Y., Analysis of unconventional boron-aluminum anomaly induced by mixed alkaline earth effect in glass substrate, Mater. Chem. Phys., 2022, vol. 282, pp. 125 973–125 983.
Helfinstine, J.D., Gulati, S.T., and Ono, T., 6.2: Mechanical properties of Jade™ glass substrate for LTPS application, SID Symp. Digest Tech. Papers, 2012, vol. 39, no. 1, pp. 51–53.
Lapp, J.C., Glass substrates for AMLCD applications: Properties and implications, Proc. SPIE, 1997, vol. 3014, pp. 2–9.
Ellison, A. and Cornejo, I.A., Glass substrates for liquid crystal displays, Int. J. Appl. Glass Sci., 2010, vol. 1, no. 1, pp. 87–103.
Funding
This work is supported by the National Natural Science Foundation of China (52202026, 62175192).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Additional information
Publisher’s Note.
Pleiades Publishing remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Yadong Lu, Xie, J., Guo, Y. et al. Compositional Effect on the Structure and Properties of MgO–Al2O3–SiO2 Ternary Glasses. Glass Phys Chem 49, 573–583 (2023). https://doi.org/10.1134/S1087659623600242
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1087659623600242