硅酸盐学报

高熵尖晶石型（Li,Mg,Al,Zn,Ga）₃O₄透明陶瓷的制备与光学性能

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张超杰 ¹^,² , 涂广升 ¹ , 靖正阳 ¹ , 涂兵田 ¹^,² , 王皓 ¹^,²

硅酸盐学报 | 研究论文 2024,52(12): 3806-3814

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3806 -3814

高熵尖晶石型（Li,Mg,Al,Zn,Ga）₃O₄透明陶瓷的制备与光学性能

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张超杰¹^,², 涂广升¹, 靖正阳¹, 涂兵田¹^,², 王皓¹^,²

作者信息

^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．湖北隆中实验室，湖北襄阳 441000

通讯作者:

涂兵田（1984—），男，博士，教授。

作者简介:

张超杰（1998—），男，硕士研究生。

Preparation and Optical Properties of High-Entropy Spinel-type (Li,Mg,Al,Zn,Ga)₃O₄ Transparent Ceramics

Chaojie ZHANG¹^,², Ghuangsheng TU¹, Zhengyang JING¹, Bingtian TU¹^,², Hao WANG¹^,²

Affiliations

^1.State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

^2.Hubei Longzhong Laboratory, Xiangyang 441000, Hubei, China

Corresponding Author:

TU Bingtian (1984-), male, Ph.D., Professor. E-mail: tubt@whut.edu.cn

ZHANG Chaojie (1998-), male, Master candidate. E-mail: 1716966142@qq.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240197

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摘要

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高熵化合物可能展现出的优异物理化学性能，为新型透明陶瓷体系开发和性能调控提供了新的研究思路。本研究设计了一种高熵尖晶石型氧化物（Li,Mg,Al,Zn,Ga）₃O₄（LMAZGO），采用高温固相反应法合成了目标产物。以子晶格模型计算了体系的构型熵为3.38R，并通过长时间低温保温验证了LMAZGO高熵化合物的稳定性。结果表明：经无压烧结工艺并通过热等静压处理后，可得到光学和力学性能优异的LMAZGO高熵透明陶瓷材料，其光学透过范围为0.23~7.35 μm，最高直线透过率达到85.2%；Vickers硬度、杨氏模量和弯曲强度分别为12.7 GPa、265 GPa，（332±30）MPa。高熵LMAZGO透明陶瓷的研究为新型透明陶瓷的开发提供思路。

关键词

高熵尖晶石 / 透明陶瓷 / 烧结工艺 / 光学性能

Abstract

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Introduction

Transparent ceramics are a kind of ceramic materials integrating structural and functional properties. A variety of ceramic materials such as oxides, nitrides, oxynitrides and fluorides are developed. Among them, spinel transparent ceramics are suitable for transparent armor, mid-wave infrared windows and fairings due to their low density, high hardness, high strength, high temperature stability, especially the wide transmittance range and high transmittance from near ultraviolet to mid-infrared. The development of transparent ceramics becomes a hot research spot. The design and performance optimization of new transparent ceramics are mainly realized through composition design because transparent ceramics have some strict requirements for microstructure and phase purity.

In recent years, the novel properties of the high-entropy effect in materials provide an approach for the development of materials. In this paper, a spinel-type (Li,Mg,Zn,Al,Ga)₃O₄ (LMAZGO) compound was designed with MgAl₂O₄, MgGa₂O₄, ZnAl₂O₄, ZnGa₂O₄, LiGa₅O₈ and LiAl₅O₈ as components. The sintering process of LMAZGO high-entropy transparent ceramic materials was investigated, and the microstructure of transparent ceramics was optimized. In addition, the optical transmittance and mechanical properties of LMAZGO high-entropy transparent ceramic materials were also analyzed.

Methods

Commercial powders of Li₂CO₃, MgO, α-Al₂O₃, ZnO, and Ga₂O₃ (purity of 99.99%) were used as raw materials, and the proportion of each raw material was calculated according to the elemental composition of LMAZGO. After mixing evenly, the high-entropy ceramic was synthesized in air by a high-temperature solid-state reaction method, and then ground to the target powder. LMAZGO blanks with a diameter of 20 mm were prepared via axial compression combined with cold isostatic pressing. Subsequently, the transparent ceramic pre-sintered body was prepared via pressureless pre-sintering in a muffle furnace, and the residual pores were further removed by hot isostatic post-treatment. The prepared LMAZGO transparent ceramics were ground and polished on the both sides for further characterization.

The phases of LMAZGO powders and bulk were characterized by a model X'Pert PRO X-ray diffractometer under Cu target at 40 kV and 40 mA. The density of ceramics was measured based on the Archimedes drainage principle. The thermal behavior of the blank was determined by a model DIL402SE thermodilatometer at different temperatures from room temperature to 1 500 ℃ at a heating rate of 10 ℃/min. The microstructure of powders and ceramics was characterized by a model S-3 400 scanning electron microscope, and the average grain size of the grains was determined by a linear intercept method. The linear transmission spectra of the samples were measured by a model Lambda 750S UV-NIR spectrophotometer and a model 6 700 Fourier transform infrared absorption spectrometer. The Vickers hardness was measured by a model 430SVD hardness tester. The flexural strength of high-entropy transparent ceramics was determined based on a three-point flexure test by a model MTS810 universal materials testing machine. The elastic properties of transparent ceramics were determined by a model MK7 elastic modulus meter.

Results and discussion

The spinel LMAZGO compounds were synthesized at 1 100 ℃ for 2 h. Based on the XRD and SEM results, the synthesized powder has a spinel phase, uniform and fine grains and little agglomeration, and the average grain size is 290 nm. The configuration entropy of LMAZGO is 3.18R, calculated by the sublattice model, which has a high crystal structure stability.

The results of thermal expansion show that the shrinkage densification rate of LMAZGO ceramic blank is further accelerated from 1 200 ℃, and the maximum densification rate of LMAZGO ceramic blank occurs at 1 380 ℃ in the middle stage of sintering. According to the thermal expansion analysis of LMAZGO, 1 300, 1 350, 1 400 and 1 450 ℃ were selected as the pressureless pre-firing temperatures, and the pre-firing process of the green body was optimized. The optical transmittance of the transparent ceramic samples obtained by subsequent HIP sintering firstly increases and then decreases with the increase of pre-firing temperature. Based on the results of the sintering curve, the pressureless sintering process of LMAZGO transparent ceramics can be optimized at a sintering temperature of 1 400 ℃ for holding time of 6 h. The average grain size of the prepared LMAZGO transparent ceramic pre-burned body is 1.81 μm, and the density is 98.7%. The superior optical transparency is obtained after hot isostatic sintering (sintering conditions: argon atmosphere, incubation at 1 550 ℃ for 5 h), and there is no abnormal growth of grain size.

The optical transmittance range of the obtained high-entropy spinel LMAZGO transparent ceramics is 0.23-7.35 μm, the maximum linear transmittance is 85.2%, the Vickers hardness (H_V1) is 12.7 GPa, the Young modulus is 265 GPa, and the flexural strength is (332±30) MPa.

Conclusions

A spinel LMAZGO high-entropy compound with a configuration entropy of 3.18R and a high crystal structure stability was synthesized. The preparation process of LMAZGO high-entropy transparent ceramics was systematically optimized via pressureless sintering combined with hot isostatic post-treatment, and the prepared LMAZGO transparent ceramics had an excellent optical transparency, with an optical transmittance range of 0.23-7.35 μm, the maximum linear transmittance of 85.2%, the Vickers hardness (H_V1) of 12.7 GPa, the Young modulus of 265 GPa, and the flexural strength of (332±30) MPa. The results showed that the high-entropy spinel LMAZGO transparent ceramic material exhibited broad spectral transparency and excellent mechanical properties, having a promising application in the field of mid-infrared transparent window. This study provided some ideas for the development of new transparent ceramics.

Key words

high-entropy spinel / transparent ceramics / sintering process / optical property

引用本文

张超杰, 涂广升, 靖正阳, 涂兵田, 王皓. 高熵尖晶石型（Li,Mg,Al,Zn,Ga）₃O₄透明陶瓷的制备与光学性能. 硅酸盐学报, 2024 , 52 (12) : 3806 -3814 . DOI: 10.14062/j.issn.0454-5648.20240197

Chaojie ZHANG, Ghuangsheng TU, Zhengyang JING, Bingtian TU, Hao WANG. Preparation and Optical Properties of High-Entropy Spinel-type (Li,Mg,Al,Zn,Ga)₃O₄ Transparent Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3806 -3814 . DOI: 10.14062/j.issn.0454-5648.20240197

基金

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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)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240197

接收时间：2024-03-08
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-03-08
修回日期：2024-03-31

基金

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)

作者信息

^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．湖北隆中实验室，湖北襄阳 441000

通讯作者:

涂兵田（1984—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240197

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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