Effects of SiO₂/Al₂O₃ Ratios on Microstructure, Properties and Elastic Modulus of SiO₂-Al₂O₃-CaO-MgO Alkali-Free Glass

Abstract

Alkali-free SiO₂-Al₂O₃-CaO-MgO with different SiO₂/Al₂O₃ mass ratios was prepared by conventional melt quenching method. The glass network structure, thermodynamic properties and elastic modulus changes with SiO₂ and Al₂O₃ ratios were investigated using various techniques. It is found that when SiO₂ is replaced by Al₂O₃, the Q⁴ to Q³ transition of silicon-oxygen network decreases while the aluminum-oxygen network increases, which result in the transformation of Si-O-Si bonds to Si-O-Al bonds and an increase in glass network connectivity even though the intermolecular bond strength decreases. The glass transition temperature (T_g) increases continuously, while the thermal expansion coefficient increases and high-temperature viscosity first decreases and then increases. Meanwhile, the elastic modulus values increase from 93 to 102 GPa. This indicates that the elastic modulus is mainly affected by packing factor and dissociation energy, and elements with higher packing factors and dissociation energies supplant those with lower values, resulting in increased rigidity within the glass.

Keywords

alkali free glass / glass network structure / viscosity / elastic modulus

References

[1] Ling GH, Li Wen. A Brief Discussion on the Development and Application of High-Strength Glass Fibers[J]. Glass Fibers, 2008(05): 7–10

[2] El-Moneim AA, Alenezy MD. Structural and Acoustic Properties of Lead Silicate Glasses Doped with Alkali and Alkaline Earth Oxides[J]. Physics and Chemistry of Glasses-European Journal of Glass Science and Technology Part B, 2013, (54): 232–237

[3] Meng QH, Liu XY. Research on the Composition of Glass-Ceramic Fibers with High Elastic Modulus[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(06): 1 510-1 513

[4] Gu G, Liu X, Zhang L, et al.. Mixed Alkaline Earth Effect on the Structure and Elastic Modulus of CaO–MgO–Al₂O₃–SiO₂ Glasses: A Molecular Dynamics Simulation[J]. Journal of Non-Crystalline Solids, 2023, 600: 122 027

[5] Tiegel M, Hosseinabadi R, Kuhn S, et al.. Young’s Modulus, Vickers Hardness and Indentation Fracture Toughness of Aluminosilicate Glasses[J]. Ceramics International, 2015, 41(6): 7 267-7 275

[6] Januchta K, Bauchy M, Youngman RE, et al.. Modifier Field Strength Effects on Densification Behavior and Mechanical Properties of Alkali Aluminoborate Glasses[J]. Physical Review Materials, 2017, 1(6063 603

[7] Messier DR, Patel PJ. High Modulus Glass Fibers[J]. Journal of Non-Crystalline Solids, 1995, 182(3271-277

[8] Inaba S, Fujino S, Morinaga K. Young’s Modulus and Compositional Parameters of Oxide Glasses[J]. Journal of the American Ceramic Society, 1999, 82(12): 3 501-3 507

[9] Deguire MR, Brown SD. Dependence of Young’s Modulus on Volume and Structure in Alkali Silicate and Alkali Aluminosilicate Glasses[J]. Journal of the American Ceramic Society, 1984, 67(4): 270-273

[10] Markovic S, Dondur V, Dimitrijevic R. FTIR Spectroscopy of Framework Aluminosilicate Structures: Carnegieite and Pure Sodium Nepheline[J]. Journal of Molecular Structure, 2003, 654(1): 223-234

[11] Reddy AA, Goel A, Tulyaganov DU, et al.. Study of Calcium-Magnesium-Aluminum-Silicate (CMAS) Glass and Glass-Ceramic Sealant for Solid Oxide Fuel Cells[J]. Journal of Power Sources, 2013, 231: 203-212

[12] Sun Y, Zhang Z, Liu L, et al.. FTIR, Raman and NMR Investigation of CaO-SiO₂-P₂O₅ and CaO-SiO₂-TiO₂-P₂O₅ Glasses[J]. Journal of Non-Crystalline Solids, 2015, 420: 26-33

[13] Lu P, Xia WB, Jiang H, et al.. Infrared and Raman Spectral Analysis of High Alumina Silicate Glass[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(03): 878-881

[14] Peng L, Zhao GL, Ying H, et al. Infrared Spectrum of Alkali-Free Aluminum Boron Silicon Glass Structure[J]. Journal of the Chinese Ceramic Society, 2007, (07): 856–860, 865

[15] Junfeng K, Junzhu C, Sheng L, et al.. Structure, Dielectric Property and Viscosity of Alkali-Free Boroaluminosilicate Glasses with the Substitution of Al₂O₃ for SiO₂[J]. Journal of Non-Crystalline Solids, 2020, 537: 120 022

[16] Mccloy J, Washton N, Gassman P, et al.. Nepheline Crystallization in Boron-Rich Alumino-Silicate Glasses as Investigated by Multi-Nuclear NMR, Raman, & Mössbauer Spectroscopies[J]. Journal of Non-Crystalline Solids, 2015, 409: 149-165

[17] Cheng Y, Xiao H, Shuguang C, et al.. Structure and Crystallization of B₂O₃-Al₂O₃-SiO₂ Glasses[J]. Physica B: Condensed Matter, 2009, 404(8–11): 1 230-1 234

[18] Xiao ZF, Cheng JS, Yang K, et al.. Effects of Al/Si and B/Na Mole Ratios on Structure and Durability of Na₂O-CaO-Al₂O₃-SiO₂ Glasses[J]. Journal of the Chinese Ceramic Society, 2014, 42(01): 120-126

[19] Chen ZX, Quan J, Zhong YM. The Influence of Al₂O₃ on the Structure and Properties of Low-Melting Borosilicate Glass[J]. Journal of Wuhan University of Technology, 2009, 31(22): 26-29

[20] Kang S, Wang X, Xu W, et al.. Effect of B₂O₃ Content on Structure and Spectroscopic Properties of Neodymium-Doped Calcium Aluminate Glasses[J]. Optical Materials, 2017, 66: 287-292

[21] Kjeldsen J, Smedskjaer MM, Mauro JC, et al.. Mixed Alkaline Earth Effect in Sodium Aluminosilicate Glasses[J]. Journal of Non-Crystalline Solids, 2013, 369: 61-68

[22] Sen S, Youngman RE. High-Resolution Multinuclear NMR Structural Study of Binary Aluminosilicate and Other Related Glasses[J]. The Journal of Physical Chemistry B, 2004, 108(23): 7 557-7 564

[23] Ramkumar J, Sudarsan V, Chandramouleeswaran S, et al. Structural Studies on Boroaluminosilicate Glasses[J] Journal of Non-Crystalline Solids, 2008, (34): 1 591–1 597

[24] Qing LP, Wei B, Xiao ZF, et al. Influence of Al₂O₃/SiO₂ on the Structure and Properties of Aluminoborosilicate Glass[J]. Contemporary Chemical Research, 2023, (23): 54–56

[25] Yue YL, Xu YC, Wu HT, et al. The Influence of the Molar Ratio of Calcium and Magnesium Oxides in Boron Aluminosilicate Glass on the Properties of the Glass[J]. Journal of the Chinese Ceramic Society, 2007, (07): 926–929

[26] Wang CY, Tao Y. Design and Adjustment of Glass Composition (Twenty-Five)[J]. Glass and Enamel, 2006(01): 54–59, 24

[27] Xiao ZF. Research on the Composition, Structure and Properties of High-Strength Sodium Calcium Aluminum Silicon Float Glass, 2014, Wuhan, Wuhan University of Technology[D]

[28] Zhao JG. Preparation and Properties Research of High-strength SiO₂-Al₂O₃-MgO-CaO Glass Fiber, 2021, Jinan, University of Jinan[D]

[29] Le Losq C, Neuville DR, Florian P, et al.. The Role of Al³⁺ on Rheology and Structural Changes in Sodium Silicate and Aluminosilicate Glasses and Melts[J]. Geochimica et Cosmochimica Acta, 2014, 126: 495-517

[30] Ye SQ. Research on the Structure and Properties of High-Strength and High-Modulus Glass, 2018, Wuhan, Wuhan University of Technology[D]

[31] Zhu QG. Preparation and Performance Characterization of High-Strength and High-Modulus CaO-Al₂O-SiO₂Glass, 2018, Hangzhou, China Jiliang University[D]

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Wuhan University of Technology and Springer-Verlag GmbH Germany, Part of Springer Nature