Li2O·Al2O3·4SiO2-Ta2O5系微晶玻璃分相与析晶机理研究

doi:10.3724/SP.J.1077.2011.01319

无机材料学报 ›› 2011, Vol. 26 ›› Issue (12): 1319-1326.DOI: 10.3724/SP.J.1077.2011.01319 CSTR: 32189.14.SP.J.1077.2011.01319

Li₂O·Al₂O₃·4SiO₂-Ta₂O₅系微晶玻璃分相与析晶机理研究

李要辉¹, 梁开明², 成惠峰¹, 吴云龙¹

(1. 中国建筑材料科学研究总院, 北京100024; 2. 清华大学材料科学与工程系, 北京100084)

收稿日期:2010-12-31 修回日期:2011-02-28 出版日期:2011-12-20 网络出版日期:2011-11-11

Phase Separation and Crystallization of Li₂O·Al₂O₃·4SiO₂-Ta₂O₅ Glass-ceramics

LI Yao-Hui¹, LIANG Kai-Ming², CHENG Hui-Feng¹, WU Yun-Long¹

(1. China Building Material Academy, Beijing 100024, China; 2. Department of Materials and Engineering, Tsinghua University, Beijing 100084, china)

Received:2010-12-31 Revised:2011-02-28 Published:2011-12-20 Online:2011-11-11

摘要/Abstract

摘要： 采用Ta₂O₅为晶核剂制备Li₂O·Al₂O₃·4SiO₂-Ta₂O₅微晶玻璃, 并研究其分相、析晶机理, 构建晶化模型. 结果表明Ta₂O₅能有效促进玻璃的体积析晶, 获得了晶粒尺寸为50nm的精细组织. 非等温动力学计算显示随Ta₂O₅含量增加, 析晶活化能降低, 析晶指数增加, 析晶动力学参数K(T_p)作为析晶判据更为合理. 研究发现, LAST玻璃冷却时因亚稳分解导致互锁分相, 形核前期又借助成核生长机制发生微滴分相, 晶体生长则在继承亚稳分相形貌基础上发生“他形”析晶. 最终构建了LAST微晶玻璃的晶化模型.

关键词: 锂铝硅微晶玻璃, Ta₂O₅, 分相, 析晶机制

Abstract: Li₂O·Al₂O₃·4SiO₂-Ta₂O₅ glass-ceramics were prepared with Ta₂O₅ as nucleating agent, and the phase separation and crystallization mechanism were investigated. The results show that addition of Ta₂O₅ promotes internal crystallization effectively, which result in fine-grained microstructure with dimension of 50nm. The non-isothermal crystallization kinetics indicates that the crystallization activation energy decrease and crystallization index increase apparently with increasing amount of Ta₂O₅, the parameter of K(T_p) is recommended as a better crystallization criterion. It is considered that spinodal decomposition occur primarily and result in an interlocking phase separation on cooling of glass, metastable droplet phase separate by nucleation and growth mechanism upon reheating process, then, “anhedral” crystallization takes place and inherits the morphology of the original phase separation. Consequently, the crystallization model of LAST glass-ceramics is put forward successfully.

Key words: lithium aluminosilicate glass-ceramics, Ta2O5, phase separation, crystallization mechanism

中图分类号:

TQ171

李要辉, 梁开明, 成惠峰, 吴云龙. Li₂O·Al₂O₃·4SiO₂-Ta₂O₅系微晶玻璃分相与析晶机理研究[J]. 无机材料学报, 2011, 26(12): 1319-1326.

LI Yao-Hui, LIANG Kai-Ming, CHENG Hui-Feng, WU Yun-Long. Phase Separation and Crystallization of Li₂O·Al₂O₃·4SiO₂-Ta₂O₅ Glass-ceramics[J]. Journal of Inorganic Materials, 2011, 26(12): 1319-1326.

参考文献

[1] Muller G. Low Thermal Expansion Glass Ceramics. Berlin: Spinger Verlag Press, 2005.

[2] Beall G H, Pinckney L R. Nanophase glass-ceramics. J. Am. Ceram. Soc., 1999, 82(1): 5-16.

[3] Riello P, Canton P, Comelato N, et al. Nucleation and crystallization behavior of glass-ceramic materials in the Li2O-Al2O3-SiO2 system of interest for their transparency properties. J. Non-Cryst. Solids, 2001, 288(1/2/3): 127-139.

[4] 胡安民, 梁开明, 周峰, 等(HU An-Min, et al). 形核剂对Li2O-Al2O3-SiO2系微晶玻璃晶化过程的影响. 无机材料学报(Journal of Inorganic Materials), 2005, 20(2): 279-284.

[5] 李要辉, 曹建尉, 卢金山, 等(LI Yao-Hui, et al). 锂铝硅微晶玻璃结构与性能热稳定性研究. 无机材料学报(Journal of Inorganic Materials), 2009, 24(5): 1031-1035.

[6] Apel E, van't Hoen C, Rheinberger V, et al. Influence of ZrO2 on the crystallization and properties of lithium disilicate glass-ceramics derived from a multi-component system. J. Eur. Ceram. Soc., 2007, 27(2/3): 1571-1577.

[7] Arvind A, Sarkar A, Shrikhande V K, et al. The effect of TiO2 addition on the crystallization and phase formation in lithium aluminum silicate (LAS) glasses nucleated by P2O5. J. Phys. Chem. Solids, 2008, 69(11): 2622-2627.

[8] Doherty P E, Lee D W, Davis R S. Direct observation of the crystallization of Li2O-A12O3-SiO2 glasses containing TiO2. J. Am. Ceram. Soc., 1967, 52(2): 77-81.

[9] Hu A M, Liang K M, Wang G, et al. Effect of nucleating agents on the crystallization of Li2O-Al2O3-SiO2 system glass. J. Therm. Anal. Calorim., 2004, 78(3): 991-997.

[10] Safonov V V, Tsygankov V N. Glass formation in the Li2O-Ta2O5-TeO2 system. Russ. J. Inorg. Chem., 2007, 52(12): 1991-1993.

[11] Hsu J Y, Speyer R F. Comparison of the effects of titania and tantalum oxide nucleating-agents on the crystallization of Li2O-Al2O3-6SiO2 glasses. J. Am. Ceram. Soc., 1989, 72(12): 2334-2341.

[12] Donald I W, Metcalfe B L, Gerrard L A, et al. The influence of Ta2O5 additions on the thermal properties and crystallization kinetics of a lithium zinc silicate glass. J. Non-Cryst. Solids, 2008, 354(2-9): 301-310.

[13] Li Y H, Liang K M, Xu B. Crystallization mechanism and microstructure evolution of Li2O-Al2O3-SiO2 glass-ceramics with Ta2O5 as nucleating agent. J. Therm. Anal. Calorim., 2010, 101(3): 941-948.

[14] Tanaka H, Koga N. Thermal analysis and kinetics of solid-state reactions - its application to education in chemistry. J. Therm. Anal. Calorim., 1999, 56(2): 855-861.

[15] Soliman A A. Derivation of the Kissinger equation for non-isothermal glass transition peaks. J. Therm. Anal. Calorim., 2007, 89(2): 389-392.

[16] Ozawa T. Kinetic analysis of derivative curves in thermal analysis. J. Therm. Anal. Calorim., 1970, 2(3): 301-324.

[17] Augis J A, Bennett J E. Calculation of Avrami parameters for heterogeneous solid-state reactions using a modification of Kissinger method. J. Therm. Anal., 1978, 13(2): 283-292.

[18] Moricova E, Jona E, Plsko A, et al. Thermal stalbility of Li2O-SiO2-TiO2 gels evaluated by the induction period of crystallization. J. Therm. Anal. Calorim., 2010, 100(3): 817-820.

[19] Pinckney L R, Beall G H. Microstructural evolution in some silicate glass-ceramics: a review. J. Am. Ceram. Soc., 2008, 91(3): 773-779.

[20] Beall G H. Anhedral crystallisation in phase separated glasses. Glass Technol., 2004, 45(2): 54-58.

Li₂O·Al₂O₃·4SiO₂-Ta₂O₅系微晶玻璃分相与析晶机理研究

Phase Separation and Crystallization of Li₂O·Al₂O₃·4SiO₂-Ta₂O₅ Glass-ceramics

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李家科, 韩效奇, 刘欣, 王艳香, 郭平春, 杨志胜. 低温分相法制备高比表面积微/介孔SiOC陶瓷[J]. 无机材料学报, 2018, 33(12): 1360-1364.
[2]	孙科, 李垚, 杨艳, 兰中文, 余忠, 郭荣迪. 添加Ta₂O₅对NiCuZn铁氧体显微结构及磁性能的影响[J]. 无机材料学报, 2014, 29(6): 633-638.
[3]	董伟, 卢金山, 冯志军, 李要辉. 玻璃冷却速率对锂铝硅微晶玻璃晶化行为和结构的影响[J]. 无机材料学报, 2012, 27(4): 400-404.
[4]	李要辉,曹建尉,卢金山,梁开明. 锂铝硅微晶玻璃结构与性能热稳定性研究[J]. 无机材料学报, 2009, 24(5): 1031-1035.
[5]	李乐中,兰中文,余忠,孙科,罗明,姬海宁. 添加Ta₂O₅对MnZn功率铁氧体性能的影响[J]. 无机材料学报, 2009, 24(2): 379-382.
[6]	朱冬梅,罗发,周万城,RAY C S,DAY D E. 不同重力条件对 PbO-B₂O₃玻璃分相的影响[J]. 无机材料学报, 2006, 21(4): 855-860.
[7]	曹国喜,胡和方,干福熹. 含AlF₃和ZrF₄氟化物玻璃的分相与析晶[J]. 无机材料学报, 2005, 20(1): 53-58.
[8]	张文丽,金建国,张晓丽. Na₂O-B₂O₃-SiO₂-SnO₂系统的分相与析晶[J]. 无机材料学报, 2005, 20(1): 205-209.
[9]	罗仲宽,姜中宏,刘剑洪,蔡弘华,洪伟良,徐宏. 二元玻璃系统的混合热力学与分相边界的预测[J]. 无机材料学报, 2004, 19(3): 529-535.
[10]	许仕龙,朱满康,黄安平,王波,严辉. 衬底负偏压对溅射Ta₂O₅薄膜晶化温度及介电性能的影响[J]. 无机材料学报, 2004, 19(3): 701-704.
[11]	连芳,徐利华,王福明,李文超. 一种新型湿化学方法合成Ba(Mg_1/3Ta_2/3)O₃纳米粉末的研究[J]. 无机材料学报, 2002, 17(2): 247-252.
[12]	迟玉山,沈菊云,陈学贤. MgO-Al₂O₃-SiO₂微晶玻璃的IR、DTA和XRD研究[J]. 无机材料学报, 2002, 17(1): 45-50.
[13]	孙洪巍,陈显求,高力明,封鉴秋,王淑玲. 组成对R₂O-CaO-ZnO-Al₂O₃-SiO₂系统分相的影响[J]. 无机材料学报, 2001, 16(3): 398-404.
[14]	刘平,王鸿,陈显求. CaO-Al₂O₃-SiO₂系玻璃分相的计算机模拟[J]. 无机材料学报, 1999, 14(4): 553-557.
[15]	刘平,陈显求. K₂O-MgO-Al₂O₃-SiO₂系玻璃的分相与析晶[J]. 无机材料学报, 1999, 14(2): 275-279.