热压烧结法制备大尺寸La2O3-TiO2-SiO2非晶材料的研究

doi:10.15541/jim20160619

无机材料学报 ›› 2017, Vol. 32 ›› Issue (8): 851-856.DOI: 10.15541/jim20160619

热压烧结法制备大尺寸La₂O₃-TiO₂-SiO₂非晶材料的研究

李仁意^{1, 2}, 李晓禹², 李建强², 赵建玲¹, 马晓光², 贺刚³, 李江涛³

(1. 河北工业大学材料科学与工程学院, 天津300130; 2. 中国科学院过程工程研究所, 湿法冶金清洁生产技术国家工程实验室, 中国科学院绿色过程与工程重点实验室, 北京100190; 3. 中国科学院理化技术研究所, 北京100190)

收稿日期:2016-11-08 修回日期:2016-12-23 出版日期:2017-08-10 网络出版日期:2017-07-19
作者简介:李仁意(1992–), 男, 硕士研究生. E-mail: ryli@ipe.ac.cn
基金资助:
国家自然科学基金(51674232, 51471158, 51432004);北京市自然科学基金(2152032, 2131006)

Large-sized La₂O₃-TiO₂-SiO₂ Amorphous Oxide Fabricated by Hot Press Sintering

LI Ren-Yi^{1, 2}, LI Xiao-Yu², LI Jian-Qiang², ZHAO Jian-Ling¹, MA Xiao-Guang², HE Gang³, LI Jiang-Tao³

(1. School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China; 2. National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; 3. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China)

Received:2016-11-08 Revised:2016-12-23 Published:2017-08-10 Online:2017-07-19
About author:LI Ren-Yi. E-mail: ryli@ipe.ac.cn
Supported by:
National Natural Science Foundation of China (51674232, 51471158, 51432004);Beijing Natural Science Foundation (2152032, 2131006)

摘要/Abstract

摘要：

La₂O₃-TiO₂非晶氧化物是一种具有优异光学性能的材料, 有着广泛的应用前景, 但其非晶形成能力较差, 通过无容器凝固制备的材料尺寸通常在10 mm以下。为了获得大尺寸La₂O₃-TiO₂非晶氧化物材料, 本研究在La₂O₃-TiO₂氧化物体系中加入少量SiO₂。先通过气动悬浮技术制备非晶粉末, 然后用真空热压烧结的方式制备出了高致密度的大块La₂O₃-TiO₂-SiO₂材料, 并用XRD、SEM等技术手段进行表征。结果表明: SiO₂可以提高La₂O₃-TiO₂体系的非晶形成能力, 通过气动悬浮技术获得的原料粉末呈完全非晶态, 通过热压烧结方式获得的块体材料高度致密, 仅存在少量的气孔。烧结样品有微弱的晶化, 晶化是其无法完全致密的一个重要原因。通过研究烧结曲线, 分析了La₂O₃-TiO₂-SiO₂非晶粉末的烧结机制。烧结的La₂O₃-TiO₂-SiO₂材料在可见光区域的折射率大于2.2, 具有优异的光学性能。

关键词: 非晶氧化物, 气动悬浮, 热压烧结, 大尺寸, 致密

Abstract:

La₂O₃-TiO₂ amorphous oxide has prospective applications because of its remarkable optical properties. However, due to its poor glass-forming abilities, it is difficult to prepare this material in a traditional way. The containerless solidification method can overcome this shortcoming, but the formed material size is generally restricted to be less than 10 mm. In order to obtain large-sized La₂O₃-TiO₂ amorphous oxide, a small amount of SiO₂ was added to the La₂O₃-TiO₂ oxide system to form the amorphous oxide powders by aerodynamic levitation furnace. Subsequently, the high-density La₂O₃-TiO₂-SiO₂ materials were fabricated by vacuum hot press sintering. Compositions and microstructure properties were systematically studied by XRD and SEM. The results showed that SiO₂ could improve the glass-forming ability of La₂O₃-TiO₂. The raw powders made by aerodynamic levitation furnace were completely non-crystal, while the sintered samples had weak crystallization, which affected fully densification of sintered samples. There was a small amount of porosity in the high-density product made by vacuum hot press sintering. In addition, sintering densification mechanism of the La₂O₃-TiO₂-SiO₂ amorphous powders was analyzed. Finally, the optical property of hot pressed La₂O₃-TiO₂-SiO₂ material was investigated. It is found that La₂O₃-TiO₂-SiO₂ material still kepts high refractive index of above 2.2 in the visible light region. Small amount addition of SiO₂ species improves the glass-forming abilities, yet decreases the refractive index slightly.

Key words: amorphous oxide, aerodynamic levitation, hot-press sintering, large-size, densification

中图分类号:

TQ171

李仁意, 李晓禹, 李建强, 赵建玲, 马晓光, 贺刚, 李江涛. 热压烧结法制备大尺寸La₂O₃-TiO₂-SiO₂非晶材料的研究[J]. 无机材料学报, 2017, 32(8): 851-856.

LI Ren-Yi, LI Xiao-Yu, LI Jian-Qiang, ZHAO Jian-Ling, MA Xiao-Guang, HE Gang, LI Jiang-Tao. Large-sized La₂O₃-TiO₂-SiO₂ Amorphous Oxide Fabricated by Hot Press Sintering[J]. Journal of Inorganic Materials, 2017, 32(8): 851-856.

图/表 9

图1 La2O3-TiO2-SiO2玻璃球的DSC曲线

Fig. 1 DSC curve of La2O3-TiO2-SiO2 glass ball

图2 非晶粉末的SEM照片

Fig. 2 SEM image of amorphous powders

图3 不同温度烧结样品的XRD图谱

Fig. 3 XRD patterns of samples sintered at different temperatures

图4 不同温度烧结样品的断面SEM照片

Fig. 4 Fracture SEM images of samples sintered at different temperatures(a, b) 860℃; (c, d) 870℃

图5 LTS非晶粉末在不同烧结压力下的收缩曲线

Fig. 5 Shrinkage curves of LTS amorphous powders sintered at different pressuresThe inset shows the dependence of shrinkage time on applied pressure

图6 烧结温度Ts、相对密度θ及ln[1/(1-θ)]与烧结时间t的关系

Fig. 6 Relationships between sintering temperature Ts , relative density θ and ln[1/(1-θ)] and the sintering time t

图7 烧结初期的ln[1/(1-θ)]~t曲线

Fig. 7 ln[1/(1-θ)]~t curve of initial sintering stage

图8 烧结中期的ln[1/(1-θ)]~t曲线

Fig. 8 ln[1/(1-θ)]~t curve of intermediate sintering stage

图9 30.8LaO3/2-69.2TiO2玻璃球和60 MPa、860℃下烧结样品的折射率

Fig. 9 Refractive index curves of 30.8LaO3/2-69.2TiO2 glass ball and sample sintered at 60 MPa and 860℃

参考文献 21

[1]	WEBER J K R, FELTEN J J, CHO B, et al. Glass fibres of pure and erbium- or neodymium-doped yttria-alumina compositions.Nature, 1998, 393(6687): 769-771.
[2]	NASIKAS N K, SEN S, PAPATHEODOROU G N.Structural nature of polyamorphism in Y2O3-Al2O3 glasses.Chemistry of Materials, 2011, 23(11): 2860-2868.
[3]	WEBER J K R, ABADIE J G, KEY T S, et al. Synthesis and optical properties of rare-earth-aluminum oxide glasses.Journal of the American Ceramic Society, 2002, 33(85): 1309-1311.
[4]	MASUNO A, INOUE H, YU J, et al. Refractive index dispersion, optical transmittance,Raman scattering of BaTi2O5 glass. Journal of Applied Physics, 2010, 108(6): 063520-1-5.
[5]	ARAI Y, ITOH K, KOHARA S, et al. Refractive index calculation using the structural properties of La4Ti9O24 glass. Journal of Applied Physics, 2008, 103(9): 094905-1-6.
[6]	XIANG H, GUAN L, PENG Z, et al.Preparation of high refractive index La2O3-TiO2 glass by aerodynamic levitation technique and effects of Bi2O3 substitution on its thermal and optical properties.Ceramics International, 2014, 40(3): 4985-4988.
[7]	MASUNO A, INOUE H, YOSHIMOTO K, et al.Thermal and optical properties of La2O3-Nb2O5 high refractive index glasses.Optical Materials Express, 2014, 4(4): 710-718.
[8]	MA X, PENG Z, LI J.Effect of Ta2O5 substituting on thermal and optical properties of high refractive index La2O3-Nb2O5 glass system prepared by aerodynamic levitation method.Journal of the American Ceramic Society, 2015, 98(3): 770-773.
[9]	LI J, LI J, LI B, et al.An upconversion niobium pentoxide bulk glass codoped with Er3+/Yb3+ fabricated by aerodynamic levitation method.Journal of the American Ceramic Society, 2015, 98(6): 1865-1869.
[10]	YOSHIMOTO K, MASUNO A, INOUE H, et al.Transparent and high refractive index La2O3-WO3 glass prepared using containerless processing. Journal of the American Ceramic Society, 2012, 95(11): 3501-3504.
[11]	MASASHI K, YU J, ATSUNOBU M, et al.Glass formation in LaO3/2-TiO2 binary system by containerless processing.Journal of the American Ceramic Society, 2012, 95(1): 79-81.
[12]	MASUNO A, INOUE H. High refractive index of 0.30La2O3- 0.70Nb2O5 glass prepared by containerless processing. Applied Physics Express, 2010, 3(10): 102601-1-3.
[13]	YODA S, CHO W S, IMAI R.Aerodynamic levitator for large- sized glassy material production.Review of Scientific Instruments, 2015, 86(9): 2127.
[14]	ROSENFLANZ A, FREY M, ENDRES B, et al.Bulk glasses and ultrahard nanoceramics based on alumina and rare-earth oxides.Nature, 2004, 430(7001): 761-764.
[15]	WANG L, MEI L, HE G, et al.Preparation of Ce: YAG glass- ceramics with low SiO2.Journal of the American Ceramic Society, 2011, 94(94): 3800-3803.
[16]	MEI L, HE G, WANG L L, et al.Fabrication of transparent LaAlO3/t-ZrO2 nanoceramics through controlled amorphous crystallization.Journal of the European Ceramic Society, 2011, 31(9): 1603-1609.
[17]	MEI L, LIU G H, HE G, et al.Controlled amorphous crystallization: an easy way to make transparent nanoceramics.Optical Materials, 2012, 34(6): 981-985.
[18]	王丽丽. 非晶烧结-控制晶化法制备纳米功能陶瓷及性能研究. 北京: 北京科技大学博士学位论文, 2012.
[19]	LIU SHI-QUAN, XU SHU-HUI, YUAN YI-SONG, et al.The sinter of glass powder.Glass & Enamel, 1995, 23(5): 34-38.
[20]	SHI JIAN-LIN, LIN ZU-XIANG, YANG ZHI-ZHOU.Hot pressed Na-Beta-AluminaⅡ. Densification mechanism of hot pressed Na-Beta-Al2O3.Journal of the Chinese Ceramic Society, 1987, 15(3): 241-247.
[21]	梅林. 非晶烧结-晶化法制备纳米结构稀土铝酸盐透明陶瓷. 北京: 中国科学院研究生院博士学位论文, 2011.

热压烧结法制备大尺寸La₂O₃-TiO₂-SiO₂非晶材料的研究

Large-sized La₂O₃-TiO₂-SiO₂ Amorphous Oxide Fabricated by Hot Press Sintering

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