超低膨胀微晶玻璃热处理工艺优化研究

摘要/Abstract

摘要： 采用熔融法制备了Li₂O-Al₂O₃-SiO₂系透明玻璃,以TiO₂、ZrO₂和P₂O₅为复合晶核剂对该玻璃进行热处理,获得了超低膨胀微晶玻璃。采用正交试验研究了热处理工艺参数对微晶玻璃热膨胀系数的影响,并通过计算分析获得了最优的热处理工艺参数,即核化温度为600 ℃,核化时间为3 h,晶化温度为820 ℃,晶化时间为5 h。在此热处理工艺制度下获得的微晶玻璃主晶相为β-石英固溶体,热膨胀系数为1.6×10^-8 ℃^-1。采用差热分析、X射线衍射分析、扫描电子显微镜分析、透射电子显微镜分析等手段研究了微晶玻璃的析晶情况和微观结构,并进一步分析了热处理工艺与微晶玻璃热膨胀性能和微观结构之间的对应关系。结果表明,微晶玻璃的热膨胀系数由晶相种类和含量决定,微晶玻璃内部晶相的尺寸和含量与热处理工艺密切相关。

关键词: Li₂O-Al₂O₃-SiO₂系微晶玻璃, 低膨胀, β-石英固溶体, 复合晶核剂, 热处理, 透明

Abstract: Li₂O-Al₂O₃-SiO₂ system transparent glass was prepared by melting method, and ultra-low expansion glass-ceramics were obtained by heat treatment with TiO₂, ZrO₂ and P₂O₅ as composite nucleating agents. The effects of heat treatment parameters on thermal expansioncoefficient of glass-ceramics were studied by orthogonal experiments. The optimal heat treatment parameters were obtained through calculation and analysis, that is, the nucleation temperature is 600 ℃, the nucleation time is 3 h, the crystallization temperature is 820 ℃, and the crystallization time is 5 h. The main crystalline phase of glass-ceramics obtained under this heat treatment process is β-quartz solid solution, and the thermal expansioncoefficient is 1.6×10^-8 ℃^-1. The crystallization and microstructure of glass-ceramics were studied by means of differential thermal analysis, X-ray diffraction analysis, scanning electron microscopy analysis and transmission electron microscopy analysis. The relationship between heat treatment process, thermal expansion properties and microstructure of glass-ceramics was analyzed. The results show that the thermal expansion coefficient of glass-ceramics is determined by the type and content of crystalline phase, and the size and content of crystalline phase which formed inside glass-ceramics are closely related to heat treatment process.

Key words: Li₂O-Al₂O₃-SiO₂ system glass-ceramics, low expansion, β-quartz solid solution, composite nucleating agent, heat treatment, transparency

中图分类号:

TQ171

赵春霞, 范仕刚, 刘杰, 何粲, 李跃. 超低膨胀微晶玻璃热处理工艺优化研究[J]. 硅酸盐通报, 2022, 41(11): 3870-3876.

ZHAO Chunxia, FAN Shigang, LIU Jie, HE Can, LI Yue. Heat Treatment Process Optimization of Ultra-Low Expansion Glass-Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(11): 3870-3876.

参考文献

[1] 武丽华,王雅婷,冯建业,等.晶化温度对锂铝硅微晶玻璃热膨胀系数和热稳定性的影响[J].玻璃,2015,42(12):23-26.
WU L H, WANG Y T, FENG J Y, et al. Effect of crystallization temperature on linear thermal expansion coefficient and thermo-stability of las-glass ceramics[J]. Glass, 2015, 42(12): 23-26 (in Chinese).
[2] KLEEBUSCH E, PATZIG C, KRAUSE M, et al. The titanium coordination state and its temporal evolution in Li₂O-Al₂O₃-SiO₂ (LAS) glasses with ZrO₂ and TiO₂ as nucleation agents-A XANES investigation[J]. Ceramics International, 2020, 46(3): 3498-3501.
[3] 赵春霞,范仕刚,张丽红,等.高品质超低膨胀透明微晶玻璃实现批量化生产[J].硅酸盐通报,2021,40(9):3185-3187.
ZHAO C X, FAN S G, ZHANG L H, et al. High quality ultra-low expansion transparent glass-ceramics achieve mass production[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(9): 3185-3187 (in Chinese).
[4] 陈福,续芯如,贾立丹.晶化温度对零膨胀锂铝硅微晶玻璃性能的影响[J].建筑玻璃与工业玻璃,2016(10):17-20.
CHEN F, XU X R, JIA L D. Effect of crystallization temperature on properties of zero-expansion Li-Al-Si glass-ceramics[J]. Architectural Glass and Industrial Glass, 2016(10): 17-20 (in Chinese).
[5] 石成利.透明微晶玻璃的研究与应用现状及其发展趋势[J].陶瓷,2012(8):44-46.
SHI C L. Research and application status and development trend of transparent glass-ceramics[J]. Ceramics, 2012(8): 44-46 (in Chinese).
[6] 肖汉宁,赵运才,刘付胜聪.功能微晶玻璃的研究现状及发展趋势[J].材料导报,2002,16(8):39-41.
XIAO H N, ZHAO Y C, LIU F S C. Current status and future trends of functional glass-ceramics[J]. Materials Review, 2002, 16(8): 39-41 (in Chinese).
[7] 齐亚范,方敬忠,谢才清.高能粒子辐照对零膨胀微晶玻璃光学性质和面形光学稳定性的影响[J].光电工程,1996,23(1):40-46.
QI Y F, FANG J Z, XIE C Q. Radiation effects of high energy particles on optical properties and surface optical stability of zero thermal expansion coefficient glass ceramic[J]. Opto-Electronic Engineering, 1996, 23(1): 40-46 (in Chinese).
[8] 黄伟胜.超低膨胀锂铝硅透明微晶玻璃的研究与应用现状[J].中国陶瓷工业,2011,18(5):20-23.
HUANG W S. Research and application of lithium aluminosilicate transparent glass-ceramic with zero thermal expansion[J]. China Ceramic Industry, 2011, 18(5): 20-23 (in Chinese).
[9] 陈建华,孙方明.锂铝硅微晶玻璃[J].材料导报,1995,9(5):42-45+13.
CHEN J H, SUN F M. Lithium aluminosilicate glass-ceramics[J]. Materials Review, 1995, 9(5): 42-45+13 (in Chinese).
[10] 沃尔夫拉姆·霍兰,乔治·H.比尔.微晶玻璃技术[M].第2版.北京:化学工业出版社,2019.
WOLFRAM H, GEORGE H. B. Glass-ceramic technology[M]. 2nd ed. Beijing: Chemical Industry Press, 2019 (in Chinese).
[11] 范仕刚,余明清,赵春霞,等.超低膨胀微晶玻璃应用及发展现状[J].人工晶体学报,2012,41(s1):210-214.
FAN S G, YU M Q, ZHAO C X, et al. Application and development of ultra low expansion glass-ceramics[J]. Journal of Synthetic Crystals, 2012, 41(s1): 210-214 (in Chinese).
[12] 楼贤春,程金树,郑伟宏,等.锂铝硅系统微晶玻璃热处理制度优化研究[J].玻璃,2005,32(3):7-10+26.
LOU X C, CHENG J S, ZHENG W H, et al. Investigation on schedule of heat treatment for lithium-aluminum-silicate glass ceramics[J]. Glass, 2005, 32(3): 7-10+26 (in Chinese).
[13] 赵莹,陆雷,张乐军,等.锂铝硅系统微晶玻璃的析晶及热处理工艺研究[J].中国陶瓷,2007,43(4):10-14.
ZHAO Y, LU L, ZHANG L J, et al. Research on crystallization and heat treatment process of Li₂O-Al₂O₃-SiO₂ glass-ceramics[J]. China Ceramics, 2007, 43(4): 10-14 (in Chinese).
[14] SHELBY J E, NICHOLS M C. Effect of thermal history on the properties of a willemite glass-ceramic[J]. Journal of the American Ceramic Society, 1983, 66: 200-204.
[15] SHELBY J E. Effect of crystal content on the properties of willemite glass-ceramics[J]. Journal of Non-Crystalline Solids, 1981, 43(2): 255-265.
[16] 成岳.工程试验设计方法:现代陶瓷教科丛书[M].第2版.武汉:武汉理工大学出版社,2010.
CHENG Y. Design method of engineering experiment: modern ceramics textbook series [M]. 2nd ed. Wuhan: Wuhan University of Technology Press, 2010 (in Chinese).
[17] CHEN M T, 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): 4988-4995.
[18] 隋普辉,陆雷,张翠玲.正交试验法研究锂锌铝硅微晶玻璃的热处理工艺[J].兵器材料科学与工程,2009,32(3):48-51.
SUI P H, LU L, ZHANG C L. Research on heat treatment process of Li₂O-ZnO-Al₂O₃-SiO₂ glass-ceramics by orthogonal testing method[J]. Ordnance Material Science and Engineering, 2009, 32(3): 48-51 (in Chinese).
[19] LUISA B,CRISTINA L,TIZIANO M, et al. Nucleation and crystallization of a lithium aluminosilicate glass[J]. Journal of the American Ceramic Society, 1997, 80(12): 3077-3083.
[20] 何峰.微晶玻璃制备与应用[M].北京:化学工业出版社,2017.
HE F. Preparation and application of glass-ceramics[M]. Beijing: Chemical Industry Press, 2017 (in Chinese).