MgF2助剂对MgAl1.9Ga0.1O4透明陶瓷的制备与光学性能的影响

doi:10.15541/jim20230587

无机材料学报 ›› 2024, Vol. 39 ›› Issue (5): 531-538.DOI: 10.15541/jim20230587

MgF₂助剂对MgAl_1.9Ga_0.1O₄透明陶瓷的制备与光学性能的影响

吕朝阳¹^,²(), 徐勇¹^,², 杨久延¹^,², 涂广升¹^,², 涂兵田¹^,², 王皓¹^,²()

1.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
2.武汉理工大学襄阳示范区湖北隆中实验室,襄阳 441000

收稿日期:2023-12-21 修回日期:2024-01-20 出版日期:2024-05-20 网络出版日期:2024-02-22
通讯作者: 王皓, 教授. E-mail: shswangh@whut.edu.cn
作者简介:吕朝阳(1999-), 男, 硕士研究生. E-mail: lvzhaoyang2021@163.com
基金资助:
国家重点研发计划(2023YFB3812000);国家自然科学基金(52272072);湖北隆中实验室自主创新研究项目(2022ZZ-13)

Effect of MgF₂ Additive on Preparation and Optical Properties of MgAl_1.9Ga_0.1O₄ Transparent Ceramics

LÜ Zhaoyang¹^,²(), XU Yong¹^,², YANG Jiuyan¹^,², TU Guangsheng¹^,², TU Bingtian¹^,², WANG Hao¹^,²()

1. State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. Hubei Longzhong Laboratory, Wuhan University of Technology Xiangyang Demonstration Zone, Xiangyang 441000, China

Received:2023-12-21 Revised:2024-01-20 Published:2024-05-20 Online:2024-02-22
Contact: WANG Hao, professor. E-mail: shswangh@whut.edu.cn
About author:LÜ Zhaoyang (1999-), male, Master candidate. E-mail: lvzhaoyang2021@163.com
Supported by:
National Key Research and Development Program of China(2023YFB3812000);National Natural Science Foundation of China(52272072);Hubei Longzhong Laboratory Independent Innovation Research Project(2022ZZ-13)

摘要/Abstract

摘要：

MgAl_1.9Ga_0.1O₄透明陶瓷具有优异的光学性能, 其制备依赖于高质量坯体的凝胶注模成型和长时间的无压预烧。本研究选择MgF₂为烧结助剂, 并通过瞬时液相调节无压预烧的致密化过程。采用干压成型、无压预烧和热等静压烧结制备了不同尺寸的MgAl_1.9Ga_0.1O₄透明陶瓷样品, 并系统分析了MgF₂对材料显微结构、光学和机械性能的影响。研究表明：MgF₂在~1230 ℃熔化形成的液相促使陶瓷的致密度与晶粒尺寸增大, 后续烧结过程中残留的MgF₂氧化为MgO并固溶进入MgAl_1.9Ga_0.1O₄晶格。添加质量分数0.2% MgF₂的2.04 mm厚透明陶瓷样品在紫外和可见光区域具有76.5%~83.4%的直线透过率和较高的光学质量。此外, 该陶瓷的特征抗弯强度为167.1 MPa, 与细晶MgAl₂O₄透明陶瓷相近, 但是前者的Weibull模数(8.81±0.29)更高。本研究为制备光学性能良好的大尺寸MgAl_1.9Ga_0.1O₄透明陶瓷提供了新的选择。

关键词: 透明陶瓷, MgAl_1.9Ga_0.1O₄, MgF₂, 瞬时液相烧结, 光学性能

Abstract:

Currently, the preparation of MgAl_1.9Ga_0.1O₄ transparent ceramics which possess excellent optical properties, is still relying on combining aqueous gel-casting and prolonged pressureless pre-sintering. In this work, MgF₂ was used as a sintering additive, and densification process of pressureless pre-sintering was adjusted by a transient liquid phase. MgAl_1.9Ga_0.1O₄ transparent ceramics with different sizes were prepared by dry pressing, pressureless pre-sintering, and hot isostatic pressing treatment. The effects of MgF₂ additive on microstructure, optical, and mechanical properties of the samples were systematically analyzed. The results indicated that MgF₂ melted at ~1230 ℃, contributing to increase of density and grain size of the pre-sintered body, while the residual MgF₂ was oxidized to MgO and dissolved into the MgAl_1.9Ga_0.1O₄ lattice in the subsequent sintering process. The 2.04 mm thick transparent ceramic sample with 0.20% (in mass fraction) MgF₂ has an in-line transmittance of 76.5%-83.4% in the UV and visible regions. Moreover, the sample has high optical quality with low scattering on incident light. In addition, the characteristic flexural strength of this ceramics is 167.1 MPa, which is close to that of the fine-grained MgAl₂O₄ transparent ceramics, but the Weibull modulus (8.81±0.29) is higher. This study provided a new option for the preparation of large MgAl_1.9Ga_0.1O₄ transparent ceramic materials with good optical properties.

Key words: transparent ceramic, MgAl_1.9Ga_0.1O₄, MgF₂, transient liquid phase sintering, optical property

中图分类号:

TQ174

吕朝阳, 徐勇, 杨久延, 涂广升, 涂兵田, 王皓. MgF₂助剂对MgAl_1.9Ga_0.1O₄透明陶瓷的制备与光学性能的影响[J]. 无机材料学报, 2024, 39(5): 531-538.

LÜ Zhaoyang, XU Yong, YANG Jiuyan, TU Guangsheng, TU Bingtian, WANG Hao. Effect of MgF₂ Additive on Preparation and Optical Properties of MgAl_1.9Ga_0.1O₄ Transparent Ceramics[J]. Journal of Inorganic Materials, 2024, 39(5): 531-538.

图/表 11

图1 含0.1%、0.2%、0.5% MgF2的MAGS-0.1陶瓷与无助剂MAGS-0.1陶瓷的烧结轨迹曲线

Fig. 1 Sintering trajectories of MAGS-0.1 ceramics with 0.1%, 0.2% and 0.5% MgF2 and the unaided MAGS-0.1 ceramics Colorful figure is available on website

图2 含0、0.2% MgF2的MAGS-0.1陶瓷坯体收缩率和收缩速率随温度的变化曲线

Fig. 2 Variations of the shrinkage and shrinkage rate of MAGS-0.1 ceramic green bodies containing 0 and 0.2% MgF2 as a function of temperature (a) Shrinkage curves; (b) Shrinkage rate curves

图3 含10% MgF2 MAGS-0.1粉体的TG-DSC曲线与不同温度保温后含10% MgF2 MAGS-0.1粉体的XRD图谱

Fig. 3 TG-DSC curves of MAGS-0.1 powder containing 10% MgF2 and XRD patterns of MAGS-0.1 powder containing 10% MgF2 after heating and holding at different temperatures (a) TG-DSC curves of MAGS-0.1 powder containing 10% MgF2 heated at 10 ℃/min; (b) XRD patterns of MAGS-0.1 powder containing 10% MgF2 after heating and holding at 1150, 1250, 1350 and 1450 ℃ for 5 min followed by quenching; (c) Enlarged XRD patterns of the (220) crystal face in (b)

图4 含MgF2的MAGS-0.1陶瓷预烧机理

Fig. 4 Presintering mechanism of MAGS-0.1 ceramics with MgF2

图5 粉体、预烧体与透明陶瓷样品的物相组成

Fig. 5 Phase compositions of powder, pre-sintered and transparent ceramic samples

图6 无压预烧后经化学刻蚀的不同助剂含量的MAGS-0.1陶瓷的表面SEM照片及粒度分布图

Fig. 6 Surface SEM images and grain size distributions of MAGS-0.1 ceramics with different additive contents after pressureless presintering and chemical etching (a, d) Sample with 0.2% MgF2; (b, e) Sample with 0.5% MgF2; (c, f) Sample without additive

图7 HIP烧结后经化学刻蚀的MAGS-0.1陶瓷的表面SEM照片与粒度分布图

Fig. 7 Surface SEM images and grain size distributions of MAGS-0.1 ceramics after HIP sintering and chemical etching (a, c) Sample with 0.2% MgF2; (b, d) Sample without additive

图8 无助剂与含0.2% MgF2的MAGS-0.1透明陶瓷的表观照片

Fig. 8 Appearance images of MAGS-0.1 transparent ceramics without additive and with 0.2% MgF2 (a) Sample with 0.2% MgF2; (b) Sample without additive

图9 无助剂与含0.2% MgF2的MAGS-0.1透明陶瓷的光学偏振透射显微镜照片

Fig. 9 Optical polarized transmission micrographs of transparent ceramics without additive and with 0.2% MgF2 (a) Sample with 0.2% MgF2; (b) Sample without additive

图10 不同助剂含量与不同尺寸样品的光学性能

Fig. 10 Optical properties of samples with different additive contents and sizes Inset: Appearance image of a sample containing 0.2% MgF2 with ϕ108.8 mm×9.36 mm

图11 MAGS-0.1透明陶瓷抗弯强度的Weibull统计图

Fig. 11 Weibull plots of fracture strength for MAGS-0.1 transparent ceramics (a) Sample without additive[6]; (b) Sample with 0.2% MgF2

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MgF₂助剂对MgAl_1.9Ga_0.1O₄透明陶瓷的制备与光学性能的影响

Effect of MgF₂ Additive on Preparation and Optical Properties of MgAl_1.9Ga_0.1O₄ Transparent Ceramics

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