Al₂O₃ Content Dependency on Microstructure, Crystallization Behavior and Mechanical Properties of Li₂O-Al₂O₃-SiO₂ Glass-ceramics

Abstract

In current research, Li₂O-Al₂O₃-SiO₂ glass-ceramics were prepared by conventional melt-quenching and subsequent heat treatment method. The effect of Al₂O₃ content on microstructures, thermal properties, crystallization behaviours and mechanical properties were investigated. FTIR, Raman spectroscopy and nuclear magnetic resonance spectroscopy microstructure analysis showed that the silico-oxygen network was damaged, while the increase of [AlO₄] content repaired the glass network, and finally made the glass network have better connectivity, with the decrease of SiO₂. The thermal analysis confirmed the increasing glass transition and crystallization temperatures from growing Al₂O₃ content. In addition, different crystal phases can be precipitated in the glass matrix, such as LiAlSi₄O₁₀, Li₂Si₂O₅ in glass with low Al₂O₃ content, the combination of Li_xAl_xSi_1−xO₂, LiAlSi₃O₈, Li₂SiO₃ in glass with intermediate Al₂O₃ content, and the combination of LiAlSi₂O₆, SiO₂ in glass with high Al₂O₃ content. The hardness of as-prepared glass gradually increases with the increase of the Al₂O₃ content. The Vickers hardness of the glass-ceramics is highly dependent on the Al₂O₃ content in the glass and the heat treatment temperatures, reaching a maximum of 10.11 GPa. Scanning electron microscope images show that the crystals change from spherical to massive and finally to sheet. The change of glass structure, crystal phase and morphology is the main reason for the different mechanical properties.

Keywords

microstructure / glass-ceramics / crystallization / hardness

References

[1] Höland W, Beall G H. Glass-Ceramic Technology, 20122nd EditionHoboken, John Wiley & Sons, Inc. M]

[2] Serbena FC, Soares VO, Peitl O, et al.. Internal Residual Stresses in Sintered and Commercial Low Expansion Li₂O-Al₂O₃-SiO₂ Glass-Ceramics[J]. Journal of the American Ceramic Society, 2011, 94(4): 1 206-1 214

[3] Kumar A, Chakrabarti A, Shekhawat MS, et al.. Transparent Ultra-Low Expansion Lithium Aluminosilicate Glass-Ceramics: Crystallization Kinetics, Structural and Optical Properties[J]. Thermochimica Acta, 2019, 676: 155-163

[4] Zanotto ED. A Bright Future for Glass-Ceramics[J]. American Ceramic Society Bulletin, 2010, 89(8): 19-27

[5] Venkateswaran C, Sreemoolanadhan H, Vaish R. Lithium Aluminosilicate (LAS) Glass-Ceramics: A Review of Recent Progress[J]. International Materials Reviews, 2021, 67(6): 620-657

[6] Tian S, Zhou M, Shen HY, et al.. Low Thermal Expansion Coefficient LAS Glass-Ceramics with Petalite as the Main Crystal Phase[J]. Journal of Non-Crystalline Solids, 2025, 649: 123 338

[7] Zheng WH, Gao ZP, Huang M, et al.. Chemical Strengthening of Lithium Aluminosilicate Glass-Ceramic with Different Crystallinity [J]. Journal of Non-Crystalline Solids, 2022, 598: 121 940

[8] Zheng WH, Li CQ, Yuan J, et al.. The Crystallization and Fracture Toughness of Transparent Glass-Ceramics with Various Al₂O₃ Additions for Mobile Devices[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2022, 37: 378-384

[9] Fu L, Engqvist H, Xia W. Glass-Ceramics in Dentistry: A Review[J]. Materials, 2020, 13(5): 1 049

[10] Soares VO, Serbena FC, Mathias I, et al.. New, Tough and Strong Lithium Metasilicate Dental Glass-Ceramic[J]. Ceramics International, 2021, 47(22 793-2 801

[11] Soares RS, Monteiro RCC, Lima MMRA, et al.. Crystallization of Lithium Disilicate-Based Multicomponent Glasses-Effect of Silica/Lithia Ratio[J]. Ceramics International, 2015, 41(1): 317-324

[12] Kolay S, Bhargava P. Role of Mgo in Lowering Glass Transition Temperature and Increasing Hardness of Lithium Silicate Glass and Glass-Ceramics[J]. Ceramics International, 2022, 48(9): 12 699-12 711

[13] Chen MT, He F, Shi J, et al.. Low Li₂O Content Study in Li₂O-Al₂O₃-SiO₂ Glass-Ceramics[J]. Journal of the European Ceramic Society, 2019, 39(15): 4 988-4 995

[14] Shi HN, Hou XH. Effect of MgO on The Crystallization Behavior and Properties of Glass-Ceramics[J]. Transactions of the Indian Ceramic Society, 2018, 77(2): 118-122

[15] Nnakwo KC, Amadi FE, Mbah CN, et al.. Influence of Heat Treatment Regimes on Crystalline Phase Formation and Physical Properties of Li₂O-SiO₂-Al₂O₃ Glass System[J]. Materials Research Express, 2019, 6: 1-11

[16] Zhang XY, Wang J, Han JJ. Crystallization Kinetics, Structural and Mechanical Properties of Transparent Lithium Aluminosilicate Glass-Ceramics[J]. Journal of Non-Crystalline Solids, 2023, 603: 122 113

[17] Bai Y, Peng L, Zhu QS, et al.. Non-isothermal Crystallization Kinetics of Stoichiometric Lithium Disilicate-Based Glasses with Al₂O₃ Additives[J]. Journal of Non-Crystalline Solids, 2016, 446: 116-122

[18] Ke XF, Shan ZT, Li ZH, et al.. Toward Hard and Highly Crack Resistant Magnesium Aluminosilicate Glasses and Transparent Glass-ceramics[J]. Journal of the American Ceramic Society, 2020, 103: 3 600-3 610

[19] Thieme K, Riissel C. Nucleation Inhibitors-The Effect of Small Concentrations of Al₂O₃, La₂O₃, Or TiO₂ on Nucleation and Crystallization of Lithium Disilicate[J]. Journal of the European Ceramic Society, 2014, 34(15): 3 969-3 979

[20] Keyvani N, Marghussian VK, Rezaie HR, et al.. Effect of Al₂O₃ Content on Crystallization Behavior, Microstructure, and Mechanical Properties of SiO₂-Al₂O₃-CaO-MgO Glass-Ceramics[J]. International Journal of Applied Ceramic Technology, 2011, 8(1): 203-213

[21] Cui HN, Yang HC, Wang H, et al.. Crystallization and Microwave Dielectric Properties of Novel CaO-Al₂O₃-B₂O₃ Glass-Ceramics with Different Al₂O₃ Content[J]. Journal of the European Ceramic Society, 2023, 43(16): 7 478-7 484

[22] Zhao YL, Zhong YH, Chang H, et al.. Luminescent Properties of Tm³⁺-Dy³⁺ Co-Doped P₂O₅-SrO-BaO-B₂O₃-ZnO Glasses for White LED Applications[J]. Journal of Non-Crystalline Solids, 2021, 573: 121 121

[23] Aliyah LH, Katrina AT, Hasmaliza M, et al.. Preliminary Study on the Development of New Composition Lithium Aluminosilicate Glass Ceramic[J]. Materials Today: Proceedings, 2019, 17: 946-952

[24] Kapoor S, Goel A, Pascual MJ, et al.. Thermo-Mechanical Behaviour of Alkali Free Bioactive Glass-Ceramics Co-doped with Strontium and Zinc[J]. Journal of Non-Crystalline Solids, 2013, 375: 74-82

[25] Hao XJ, Luo ZW, Hu XL, et al.. Effect of Replacement of B₂O₃ by ZnO on Preparation and Properties of Transparent Cordierite-Based Glass-Ceramics[J]. Journal of Non-Crystalline Solids, 2016, 432: 265-270

[26] Li YH, Liang KM, Cao JW, et al.. Spectroscopy and Structural State of V⁴⁺ Ions in Lithium Aluminosilicate Glass and Glass-Ceramics[J]. Journal of Non-Crystalline Solids, 2010, 356(9–10): 502-508

[27] Arnault L, Gerland M, Rivière A. Microstructural Study of Two LAS-Type Glass-Ceramics and Their Parent Glass[J]. Journal of Materials Science, 2000, 35(9): 2 331-2 345

[28] Edén M. Chapter Four-²⁷Al NMR Studies of Aluminosilicate Glasses [J]. Annual Reports on Nmr Spectroscopy, 2015, 86: 237-331

[29] Furukawa T, Fox KE, White WB. Raman Spectroscopic Investigation of the Structure of Silicate Glasses. III. Raman Intensities and Structural Units in Sodium Silicate Glasses[J]. The Journal of Chemical Physics, 1981, 75: 3 226-3 237

[30] Ross S, Welsch AM, Behrens H. Lithium Conductivity in Glasses of the Li₂O-Al₂O₃-SiO₂ System[J]. Physical Chemistry Chemical Physics, 2015, 17(1): 465-474

[31] Park SY, Lee SK. 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[J]. Geochimica et Cosmochimica Acta, 2014, 147: 26-42

[32] Jakobsen HJ, Skibsted J, Bildsøe H, et al.. Magic-Angle Spinning NMR Spectra of Satellite Transitions for Quadrupolar Nuclei in Solids [J]. Journal of Magnetic Resonance, 1989, 85(1): 173-180(1969)

[33] Karlsson S, Mathew R, Ali S, et al.. Mechanical, Thermal, and Structural Investigations of Chemically Strengthened Na₂O-CaO-Al₂O₃-SiO₂ Glasses[J]. Frontiers in Materials, 2022, 9: 953 759

[34] Gaddam A, Fernandes HR, Tulyaganov DU, et al.. The Roles of P2O5 and SiO₂/Li₂O Ratio on the Network Structure and Crystallization Kinetics of Non-Stoichiometric Lithium Disilicate Based Glasses[J]. Journal of Non-Crystalline Solids, 2018, 481: 512-521

[35] Risbu S H, Kirkpatri RJ, Tagliala AP, et al.. Solid-State NMR Evidence of 4-, 5-, and 6-Fold Aluminum Sites in Roller-Quenched SiO₂-Al₂O₃ Glasses[J]. Jounal of the American Ceramic Society, 1987, 70(1): C-10-C-2

[36] Schmücker M, MacKenzie KJD, Schneider H, et al.. NMR Studies on Rapidly Solidified SiO₂ Al₂O₃ and SiO₂ Al₂O₃ Na₂O- Glasses[J]. Journal of Non-Crystalline Solids, 1997, 217(1): 99-105

[37] Stebbins JF, Kroeker S, Lee SK, et al.. Quantification of Five- and Six-Coordinated Aluminum Ions in Aluminosilicate and Fluoride-Containing Glasses by High-Field, High-Resolution ²⁷Al NMR[J]. Journal of Non-Crystalline Solids, 2000, 275(1–2): 1-6

[38] Xie J, Tang HR, Wang J, et al.. Network Connectivity and Properties of Non-Alkali Aluminoborosilicate Glasses[J]. Journal of Non-Crystalline Solids, 2018, 481: 403-408

[39] Fuss T, Moguš-Milanković A, Ray CS, et al.. Ex situ XRD, TEM, IR, Raman and NMR Spectroscopy of Crystallization of Lithium Disilicate Glass at High Pressure[J]. Journal of Non-Crystalline Solids, 2006, 352(38–39): 4 101-4 111

[40] Horst B. Werkstoffpüfung, 1984, Leipzig, VEB Deutscher Verlag für Grundstoffindustrie[M]

[41] Gaddam A, Fernandes HR, Tulyaganov DU, et al.. The Roles of P₂O₅ and SiO₂/Li₂O Ratio on The Network Structure and Crystallization Kinetics of Nonstoichiometric Lithium Disilicate Based Glasses[J]. Journal of Non-Crystalline Solids, 2018, 481: 512-521

[42] Zhao T, Li AJ, Qin Y, et al.. Influence of SiO₂ Contents on the Microstructure and Mechanical Properties of Lithium Disilicate Glass-Ceramics by Reaction Sintering[J]. Journal of Non-Crystalline Solids, 2019, 512: 148-154

[43] Huang SF, Zhang B, Huang ZH, et al.. Crystalline Phase Formation, Microstructure and Mechanical Properties of a Lithium Disilicate Glass-Ceramic[J]. Journal of Materials Science, 2013, 48(1): 251-257

[44] Soares P CJr, Zanotto E D, Fokin V M, et al.. TEM and XRD Study of Early Crystallization of Lithium Disilicate Glasses[J]. Journal of Non-Crystalline Solids, 2003, 331(1–3): 217-227

[45] Shi J, He F, Xie JL, et al.. Effects of Na₂O/BaO Ratio on the Structure and the Physical Properties of Low-Temperature Glass-Ceramic Vitrified Bonds[J]. Ceramics International, 2018, 44(9): 10 871-10 877

[46] Li ZH, He F, Zhang WT, et al.. Structure and Properties of Glass-Ceramics from Blast Furnace Slag with Different Al₂O₃/SiO₂ Ratio[J]. Ceramics-Silikáty, 2021, 65(2): 187-197

[47] Liu JL, Wang QK, Zhang Z, et al.. Investigation on Crystallization Behavior, Structure, and Properties of Li₂O-Al₂O₃-SiO₂ Glasses and Glass-Ceramics with Co-doping ZrO₂/P₂O₅[J]. Journal of Non-Crystalline Solids, 2022, 576: 121 226-121 235

[48] Aliyah L H, Izzat B M, Hasmaliza M, et al.. Effect of Mechanical Properties on Sintered Lithium Aluminosilicate Glass Ceramic and Its Thermal Shock Resistance Properties[C]. AIP Conf. Proc., 2020020 0472 267

[49] Dechandt ICJ, Soares P, Pascual MJ, et al.. Sinterability and Mechanical Properties of Glass-Ceramics in the System SiO₂-Al₂O₃-MgO/ZnO [J]. Journal of the European Ceramic Society, 2020, 40(15): 6 002-6 013

[50] Chen LN, Sun TF, Hao ZB, et al.. Ultrahigh Hardness Li₂O-MgO-Al₂O₃-SiO₂ Glass-Ceramics Containing Multiphase Nanocrystals[J]. Journal of the American Ceramic Society, 2022, 105: 7 614-7 624

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