热处理对锂铝硅玻璃微观结构及机械性能的影响

摘要/Abstract

摘要： 锂铝硅玻璃在深加工过程中会经历曲面成形和离子交换等热处理步骤,其压应力分布、结构强度均受到影响。本试验通过单杆静压测试、抗跌落性能测试及拉曼光谱等测试与表征,探究了420~640 ℃的热处理对锂铝硅玻璃性能的影响。结果表明,在低于玻璃应变点温度60 ℃至玻璃应变点温度范围内,热处理可以使锂铝硅玻璃机械性能增强,表现为密度提升、单位交换应力值增大、压应力深度减小以及单杆静压强度有所提高;拉曼光谱分析表明,上述温度范围内热处理使玻璃内部呈六元环的硅氧四面体、铝氧四面体的键长变短,对应拉曼振动峰强度下降,网络结构更加致密;而当热处理温度超过应变点,硅氧四面体之间的桥氧开始断裂,形成大量松散的“岛状”结构硅氧四面体,在高温情况下发生移动,机械性能下降。

关键词: 热处理, 锂铝硅玻璃, 离子交换, 拉曼光谱, 玻璃结构

Abstract: Chemical strengthened lithium aluminum silicon (LAS) glass undergoes heat treatment steps such as curved surface forming and ion exchange during further processing, which affects its compressive stress distribution and structural strength. In this experiment, the influence of heat treatment process at 420~640 ℃ on the properties of LAS glass was investigated and characterized by single rod static pressure test, drop resistance test and Raman spectroscopy. The results show that the mechanical properties of LAS glass can be enhanced by heat treatment at the temperature range from the strain point 60 ℃ blow to the strain point, which is characterized by the increase of density, the increase of unit exchange stress, the decrease of compressive stress depth and the increase of static compressive strength of single rod. Raman spectrum analysis shows that the structure of the glass network is changed during the heat treatment process in this temperature range. The length of the silicon oxygen and aluminum oxygen tetrahedral bonds of the six-membered rings in the glass becomes shorter, and the structure of the linked network becomes denser. However, when the heat treatment temperature exceeds the strain point, the bridging oxygen between the silico-oxygen tetrahedrons begins to break, forming a relatively loose structure, and the mechanical properties decline.

Key words: heat treatment, lithium aluminum silicon, ion exchange, Raman spectroscopy, glass structure

中图分类号:

TQ171

胡伟, 尹勇明, 孟鸿. 热处理对锂铝硅玻璃微观结构及机械性能的影响[J]. 硅酸盐通报, 2023, 42(7): 2613-2620.

HU Wei, YIN Yongming, MENG Hong. Effect of Heat Treatment on Microstructure and Mechanical Properties of Lithium Aluminum Silicon Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(7): 2613-2620.

参考文献

[1] 张心明, 田爽, 付为杰, 等. 光学玻璃离心熔铸过程中成型热历史对反射镜的影响[J]. 光学精密工程, 2018, 26(10): 2475-2483.
ZHANG X M, TIAN S, FU W J, et al. Effects of thermal history on reflector formation in an optical glass centrifugal casting process[J]. Optics and Precision Engineering, 2018, 26(10): 2475-2483 (in Chinese).
[2] 汤李缨, 程金树, 袁坚. 热历史对CaO(MgO)-Al₂O₃-SiO₂系统晶化性能和硬度的影响[J]. 武汉工业大学学报, 1998, 20(1): 34-36.
TANG L Y, CHENG J S, YUAN J. Effect of thermal history on the crystallization behaviour and hardness of a glass-ceramic in the CaO(MgO)-Al₂O₃-SiO₂ system[J]. Journal of Wuhan University of Technology, 1998, 20(1): 34-36 (in Chinese).
[3] 王自明. 热历史对有机玻璃残余应力分布的影响[J]. 航空材料, 1987, 7(6): 5-9.
WANG Z M. Effect of thermal history on residual stress distribution of plexiglass[J]. Journal of Aeronautical Materials, 1987, 7(6): 5-9 (in Chinese).
[4] 赵凤阳, 曹欣, 王萍萍, 等. 无碱硼铝硅酸盐玻璃组分对其应变点、退火点、软化点温度影响的正交实验研究[J]. 材料导报, 2022, 36(增刊2): 94-97.
ZHAO F Y, CAO X, WANG P P, et al. Orthogonal experimental study on the influence of alkali-free boroaluminosilicate glass composition on its strain point, annealing point and softening point temperature[J]. Materials Reports, 2022, 36(supplement 2): 94-97 (in Chinese).
[5] 刘景涛. 热历史对非晶合金的玻璃形成能力和性能的影响[D]. 泰安: 山东农业大学, 2015.
LIU J T. Effect of thermal history on glass-forming ability and properties of amorphous alloys[D]. Taian: Shandong Agricultural University, 2015 (in Chinese).
[6] MACRELLI G, VARSHNEYA A K, MAURO J C. Ultra-thin glass as a substrate for flexible photonics[J]. Optical Materials, 2020, 106: 109994.
[7] 王明忠, 梁新辉, 宋占财, 等. 锂铝硅酸盐玻璃的化学强化工艺参数研究[J]. 玻璃搪瓷与眼镜, 2021, 49(2): 18-22.
WANG M Z, LIANG X H, SONG Z C, et al. Study on chemical strengthening process parameters of lithium aluminosilicate glass[J]. Glass Enamel & Ophthalmic Optics, 2021, 49(2): 18-22 (in Chinese).
[8] GUO X J, PIVOVAROV A L, SMEDSKJAER M M, et al. Non-conservation of the total alkali concentration in ion-exchanged glass[J]. Journal of Non-Crystalline Solids, 2014, 387: 71-75.
[9] 胡伟, 覃文城, 谈宝权, 等. 二强处理的盖板玻璃抗跌落性内在影响因素研究[J]. 玻璃搪瓷与眼镜, 2021, 49(2): 1-7+33.
HU W, QIN W C, TAN B Q, et al. Study on the internal influencing factors of falling resistance of cover glass treated with two strong chemicals[J]. Glass Enamel & Ophthalmic Optics, 2021, 49(2): 1-7+33 (in Chinese).
[10] 刘亚茹, 李俊杰, 丁佐鑫, 等. 触控屏用盖板玻璃的硬度分析[J]. 玻璃搪瓷与眼镜, 2021, 49(12): 7-13.
LIU Y R, LI J J, DING Z X, et al. Analysis of hardness of cover glass for touch screen[J]. Glass Enamel & Ophthalmic Optics, 2021, 49(12): 7-13 (in Chinese).
[11] WANG Z, SUO T, MANES A. Effect of chemical strengthening residual stress on the flexural performance and fracture behavior of aluminosilicate glass[J]. Engineering Fracture Mechanics, 2021, 258: 108104.
[12] 倪明堂, 卢亚, 于海深, 等. 3D超薄曲面玻璃热弯工艺优化及分析[J]. 机电工程技术, 2021, 50(3): 97-100+177.
NI M T, LU Y, YU H S, et al. Performance analysis of hot bending process for ultra-thin glass of mobile phone[J]. Mechanical & Electrical Engineering Technology, 2021, 50(3): 97-100+177 (in Chinese).
[13] KUANG R, YANG P, LIU R, et al. Analysis of the variation in surface roughness of a glass sheet after hot bending[J]. Glass Technology European Journal of Glass Science and Technology Part A, 2015, 56(6): 214-220.
[14] 田昊东, 王大明, 徐驰, 等. 化学强化提升薄型锂铝硅玻璃抗冲击性能研究[J]. 玻璃搪瓷与眼镜, 2023, 51(2): 1-6.
TIAN H D, WANG D M, XU C, et al. Study on mechanics performance optimization of chemical strengthening thin lithium aluminum silicate glass[J]. Glass Enamel & Ophthalmic Optics, 2023, 51(2): 1-6 (in Chinese).
[15] 胡传杰, 张喆颖, 刘超, 等. 热处理与二次化学强化对玻璃应力层深度的影响[J]. 硅酸盐通报, 2019, 38(3): 783-787.
HU C J, ZHANG Z Y, LIU C, et al. Effect of heat-treatment and second chemical strengthening on the depth of layer of glass[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(3): 783-787 (in Chinese).
[16] 穆洪杨. 二次离子交换增强超薄高铝硅玻璃的性能研究[D]. 上海: 东华大学, 2018.
MU H Y. Study on properties of ultra-thin high alumina silica glass strengthened by secondary ion exchange[D]. Shanghai: Donghua University, 2018 (in Chinese).
[17] 展贵鑫, 宫汝华, 何根, 等. 不同化学强化条件对玻璃盖板性能影响性研究[J]. 硅酸盐通报, 2017, 36(增刊1): 1-6.
ZHAN G X, GONG R H, HE G, et al. Effects of different chemical reinforcement on the performance of glass cover plate[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(supplement 1): 1-6 (in Chinese).
[18] MAKISHIMA A, MACKENZIE J D. Calculation of bulk modulus, shear modulus and Poisson's ratio of glass[J]. Journal of Non-Crystalline Solids, 1975, 17(2): 147-157.
[19] AALDENBERG E M, LEZZI P J, SEAMAN J H, et al. Ion-exchanged lithium aluminosilicate glass: strength and dynamic fatigue[J]. Journal of the American Ceramic Society, 2016, 99(8): 2645-2654.
[20] 蒋国昌, 尤静林, 吴永全, 等. 硅酸盐熔体微结构单元的探讨[J]. 地质地球化学, 2003, 31(4): 80-86.
JIANG G C, YOU J L, WU Y Q, et al. A discussion on the micro-structural units of silicate melt[J]. Geology-geochemistry, 2003, 31(4): 80-86 (in Chinese).
[21] 曾麟, 黄守佳, 林鸿剑, 等. 混合碱效应对Li₂O-Al₂O₃-SiO₂系玻璃结构和热膨胀性能的影响[J]. 硅酸盐通报, 2021, 40(11): 3813-3821.
ZENG L, HUANG S J, LIN H J, et al. Influence of mixed alkali effect on structure and thermal expansion properties of Li₂O-Al₂O₃-SiO₂ glass[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(11): 3813-3821 (in Chinese).
[22] 杨伟钰. 金属玻璃中程序的分子动力学研究[D]. 哈尔滨: 哈尔滨师范大学, 2022.
YANG W Y. Molecular dynamics study of program in metallic glass[D]. Harbin: Harbin Normal University, 2022 (in Chinese).
[23] YOU J L, JIANG G C, HOU H Y, et al. Quantum chemistry study on superstructure and Raman spectra of binary sodium silicates[J]. Journal of Raman Spectroscopy, 2005, 36(3): 237-249.
[24] AKAOGI M, ROSS N, MCMILLAN P, et al. The Mg₂SiO₄ polymorphs (olivine, modified spinel and spinel); thermodynamic properties from oxide melt solution calorimetry, phase relations, and models of lattice vibrations[J]. American Mineralogist, 1984, 69: 499-512.
[25] XU K D, JIANG G C, HUANG S P, et al. A study on the bonding structure of CaO-SiO₂ slag by means of molecular dynamics simulation[J]. Science in China Series E: Technological Sciences, 1999, 42(1): 77-82.
[26] 尤静林, 吴志东, 王敏, 等. 硅酸盐玻璃和熔体结构的拉曼光谱定量解析[J]. 光谱学与光谱分析, 2018, 38(增刊1): 247-248.
YOU J L, WU Z D, WANG M, et al. Quantitative studies on glasses and melts of silicates[J]. Spectroscopy and Spectral Analysis, 2018, 38(supplement 1): 247-248 (in Chinese).
[27] 梁晓峰, 余涛, 任慧. 拉曼光谱技术在玻璃材料研究中的应用[J]. 玻璃, 2013, 40(9): 12-15.
LIANG X F, YU T, REN H. Application of Raman spectroscopy to investigation of glass materials[J]. Glass, 2013, 40(9): 12-15 (in Chinese).
[28] 杨胜赟. 化学强化制备高强度玻璃纤维的分子动力学模拟及实验研究[D]. 济南: 济南大学, 2022.
YANG S Y. Molecular dynamics simulation and experimental study on preparation of high strength glass fiber by chemical strengthening[D]. Jinan: University of Jinan, 2022 (in Chinese).
[29] 李保卫, 欧阳顺利, 张雪峰, 等. 温度对CaO-MgO-Al₂O₃-SiO₂系纳米晶玻璃陶瓷结构影响的拉曼光谱研究[J]. 光谱学与光谱分析, 2014, 34(7): 1869-1872.
LI B W, OUYANG S L, ZHANG X F, et al. Effect of temperature on the structure of CaO-MgO-Al₂O₃-SiO₂ nanocrystalline glass-ceramics studied by Raman spectroscopy[J]. Spectroscopy and Spectral Analysis, 2014, 34(7): 1869-1872 (in Chinese).
[30] 吴永全. 硅酸盐熔体微观结构及其与宏观性质关系的理论研究[D]. 上海: 上海大学, 2004.
WU Y Q. Theoretical study on microstructure of silicate melt and its relationship with macroscopic properties[D]. Shanghai: Shanghai University, 2004 (in Chinese).