大尺寸La2O3-TiO2-ZrO2非晶塑性烧结行为

doi:10.15541/jim20180289

无机材料学报 ›› 2019, Vol. 34 ›› Issue (4): 433-438.DOI: 10.15541/jim20180289 CSTR: 32189.14.10.15541/jim20180289

大尺寸La₂O₃-TiO₂-ZrO₂非晶塑性烧结行为

王椎^1,²,韩建军¹,李建强²(),李晓禹²,李江涛³,贺刚³,谢俊¹

^1. 武汉理工大学硅酸盐建筑材料国家重点实验室, 武汉 430070
^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:2018-06-29 修回日期:2018-10-31 出版日期:2019-04-20 网络出版日期:2019-04-15
作者简介:王椎(1994-), 男, 硕士研究生. E-mail:wangzhui@ipe.ac.cn
基金资助:
国家自然科学基金(51674232);国家自然科学基金(51471158);国家自然科学基金(51432004)

Plastic Sintering Behavior of Large-sized La₂O₃-TiO₂-ZrO₂ Amorphous Bulk

Zhui WANG^1,²,Jian-Jun HAN¹,Jian-Qiang LI²(),Xiao-Yu LI²,Jiang-Tao LI³,Gang HE³,Jun XIE¹

^1. State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
^2. CAS Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, 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:2018-06-29 Revised:2018-10-31 Published:2019-04-20 Online:2019-04-15
Supported by:
National Natural Science Foundation of China(51674232);National Natural Science Foundation of China(51471158);National Natural Science Foundation of China(51432004)

摘要/Abstract

摘要：

La₂O₃-TiO₂-ZrO₂玻璃具有很高的折射率, 在镜头材料和上转换发光基质材料等领域表现出良好的应用前景, 但其玻璃形成能力低, 通常只能采用快速冷却的方法制备, 因此难以获得大尺寸材料。为了获得大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 本研究采用La₂O₃-TiO₂-ZrO₂非晶粉末为原料, 利用非晶在玻璃转变温度以上的塑性行为, 在温度动力学窗口ΔT内进行热压烧结制备了大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 在保持非晶的前提下实现了La₂O₃-TiO₂-ZrO₂粉末的完全致密化。采用SEM、XRD等方法研究了样品的显微结构和相组成。研究发现, 当烧结温度高于910 ℃时, 烧结过程中会析出La₄Ti₉O₂₄晶相; 当烧结温度低于900 ℃时, 样品保持良好的非晶性, 并随着烧结温度的增加, 样品的致密度有所升高。烧结压力也会影响烧结过程, 样品的致密度随着烧结压力升高而增加。大尺寸La₂O₃-TiO₂-ZrO₂非晶材料具有很高的折射率, 在587.6 nm处折射率可达到2.33。在La₂O₃-TiO₂-ZrO₂非晶粉末烧结过程中, 塑性流动是其主要的传质机理。

关键词: 无容器凝固, 非晶, 热压烧结, 致密化, 塑性流动

Abstract:

La₂O₃-TiO₂-ZrO₂glass has great potential applications in lens and upconversion host materials for its ultrahigh refractive index. However, due to its low glass forming ability, it can only be prepared by some extremely rapid melt cooling method, which is hard to produce large-sized materials. On the basis of amorphous plastic behavior above the glass transition temperature T_g, large-sized La₂O₃-TiO₂-ZrO₂ bulk glasses were obtained by hot pressed sintering within the thermodynamic window ΔT. 30.8% LaO_3/2-59.2% TiO₂-10% ZrO₂ amorphous spheres were firstly prepared by aerodynamic levitation furnace. Whereafter, these spheres were smashed and ground into powders. Then these glass powders were hot pressed into a bulk glass with dimension of ?20 mm×1 mm. The effects of sintering temperature and pressure on the process of hot pressed sintering were investigated. Microstructures and phase compositions of samples were studied by SEM and XRD. The results show that the samples sintered above 910 ℃ contain a few La₄Ti₉O₂₄ crystal phases, while the samples sintered below 900 ℃ are totally amorphous. When the sintering temperature is below 900 ℃, the increase of sintering temperature in a certain range can reduce the number of pores apparently to improve the density of samples. And with the increase of pressure from 20 MPa to 60 MPa, the density of bulk glass prepared by hot pressing at 900 ℃ increases from 4.8797 g/cm ³ to 5.1178 g/cm ³. The large-sized La₂O₃-TiO₂-ZrO₂ glass displays excellent optical performance with refractive index of 2.33 at the wavelength of 587.6 nm and the abbe number of 13.2. By analyzing the shrinkage curve of the samples, it is confirmed that the plastic flow is the main mass transfer way during densification process.

Key words: containerless method, amorphous, hot-pressed sintering, densification, plastic flow

中图分类号:

TQ174

王椎, 韩建军, 李建强, 李晓禹, 李江涛, 贺刚, 谢俊. 大尺寸La₂O₃-TiO₂-ZrO₂非晶塑性烧结行为[J]. 无机材料学报, 2019, 34(4): 433-438.

Zhui WANG, Jian-Jun HAN, Jian-Qiang LI, Xiao-Yu LI, Jiang-Tao LI, Gang HE, Jun XIE. Plastic Sintering Behavior of Large-sized La₂O₃-TiO₂-ZrO₂ Amorphous Bulk[J]. Journal of Inorganic Materials, 2019, 34(4): 433-438.

图/表 8

图1 无容器凝固技术得到的La2O3-TiO2-ZrO2粉末的XRD图谱

Fig. 1 XRD pattern of the La2O3-TiO2-ZrO2 powders prepared by containerless method

图2 La2O3-TiO2和La2O3-TiO2-ZrO2粉末的DTA曲线

Fig. 2 DTA results of La2O3-TiO2 and La2O3-TiO2-ZrO2 glass powders

图3 不同烧结温度下得到的LTZO样品的XRD图谱

Fig. 3 XRD patterns of the LTZO samples sintered at different temperatures

图4 不同烧结温度下得到的LTZO样品的断面SEM照片

Fig. 4 Fracture SEM images of LTZO bulk glasses prepared by hot press sintering at different temperatures (a) 890 ℃; (b) 900 ℃; (c) 910 ℃

图5 非晶粉末在不同烧结压力下的收缩曲线

Fig. 5 Shrinkage behaviors of LTZO glass powders sintered at different pressures The inset shows the densities of LTZO samples sintered at different pressures

图6 不同烧结压力下得到的LTZO样品的断面SEM照片

Fig. 6 Fracture SEM images of LTZO bulk glasses prepared by hot press and sintering at different pressures (a) 20 MPa; (b) 40 MPa; (c) 60 MPa

图7 热压烧结得到的LTO和LTZO样品的折射率

Fig. 7 Refractive index curves of LTO and LTZO samples obtained by hot-pressed sintering

图8 LTZO非晶粉末致密化过程中的ln[1/(1-θ)]~t关系图

Fig. 8 ln[1/(1-θ)]~t curve of LTZO samples in densification process

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大尺寸La₂O₃-TiO₂-ZrO₂非晶塑性烧结行为

Plastic Sintering Behavior of Large-sized La₂O₃-TiO₂-ZrO₂ Amorphous Bulk

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