硅酸盐学报

真空烧结非计量La_1-_xErZr₂O_7-3_x_/2透明陶瓷

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江小娥 ¹ , 张魁宝 ¹^,² , 郭海燕 ¹ , 曾建军 ¹

硅酸盐学报 | 研究论文 2024,52(3): 853-861

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硅酸盐学报 |研究论文 2024 , 52 (3) : 853 -861

真空烧结非计量La_1-_xErZr₂O_7-3_x_/2透明陶瓷

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江小娥¹, 张魁宝¹^,², 郭海燕¹, 曾建军¹

作者信息

^1．西南科技大学环境友好能源材料国家重点实验室，四川绵阳 621010

^2．西南科技大学核废物与环境安全国防重点学科实验室，四川绵阳 621010

通讯作者:

张魁宝（1981—），男，研究员。

作者简介:

江小娥（1998—），女，硕士研究生。

Preparation of Non-stoichiometric La_1-_xErZr₂O_7-3_x_/2 Transparent Ceramics via Vacuum Sintering

Xiaoe JIANG¹, Kuibao ZHANG¹^,², Haiyan GUO¹, Jianjun ZENG¹

Affiliations

^1.State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

^2.Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

Corresponding Author:

ZHANG Kuibao (1981-), male, Professor. E-mail: xiaobao320@163.com

JIANG Xiaoe (1998-), female, Master candidate. E-mail: jxiaoe@126.com

出版时间: 2024-03-20 doi: 10.14062/j.issn.0454-5648.20230554

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摘要

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制备光学性能优异的陶瓷材料是无机材料研究和发展的重要方向。近年来，结构与功能一体化的透明陶瓷已然是材料研究的热点。非计量La_1-_xErZr₂O_7-3_x_/2透明陶瓷采用燃烧法和真空烧结技术成功制备，通过X射线衍射仪、Raman光谱仪、扫描电子显微镜等测试技术，研究了La含量对相组成、微观结构和光学性能的影响。结果表明，随着La含量的降低，样品中烧绿石相和缺陷萤石相的共存状态逐渐转变为缺陷萤石相。x=0.1的样品在红外区域2.5~7.0 μm表现出稳定的透过率，其透过率约为74.8%（厚度1 mm），最大红外截止值在8.5~9.0 μm。x=0.2的样品在可见光到中红外区域表现出出色的透过率，并且在980 nm波长激发下，该陶瓷在684 nm处呈现出强烈的红光发射，在561 nm处呈现出微弱的绿光发射，在446 nm处呈现出微弱的蓝光发射。此外，La_1-_xErZr₂O_7-3_x_/2透明陶瓷的透过率光谱中出现大量吸收峰，La的适量降低有助于提高光学质量。与化学计量LaErZr₂O₇透明陶瓷相比，非化学计量陶瓷表现出更高的透过率，在光学基质材料上有很好的潜在应用。

关键词

透明陶瓷 / 非计量 / 光学性能

Abstract

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Introduction

Conventional transparent materials mainly include glass and polymers, and the materials both are widely used. However, they have shortcomings such as low mechanical strength, strong infrared spectral absorption, and unstable chemical properties, which restrict their applications. The degradation of the service environment for materials and the increasing strength requirements have generated an urgent demand for the development of transparent materials with the superior performance. The preparation of ceramic materials with superior optical properties becomes an important aspect in the development of inorganic materials, and the structure and function of the integration of transparent ceramics is a hot spot in materials research. The existing transparent ceramics with various functions can be prepared through the continuous optimization of the ceramic preparation process and the exploration of different ceramic systems. However, enhancing their optical properties is a challenge. A₂B₂O₇ pyrochlore ceramics have excellent properties that can break through the limitations of conventional material design and broaden the application prospects. The preparation of non-stoichiometric ceramics has attracted recent attention, but research in this aspect is still in its nascent stage. In this paper, La_1-_xErZr₂O_7-3_x_/2 transparent ceramics were synthesized via combustion sintering with subsequent combustion. The impact of La content on the phase composition, morphology, and transmittance of ceramics was investigated, and the optical properties of the ceramics under non-stoichiometric conditions were analyzed.

Materials and method

La(NO₃)₃·6H₂O, Er(NO₃)₃·5H₂O, Zr(NO₃)₃·5H₂O and glycine were used. The ceramic powder was prepared by a combustion method, and the powder was subsequently shaped into blocks through ball milling, freeze drying and cold isostatic pressing. After the samples were pre-sintered, they were sintered in vacuum (<10^-3 Pa) at 1 825 ℃ for 6h, and then subjected to subsequent treatment to obtain transparent ceramics.

The phase compositions of powders and ceramics were analyzed by a model X'Pert Pro X-ray diffractometer (XRD) at Cu K_α rays λ of 0.154 426 nm with a scanning step size of 0.03°. The structure and chemical composition of the sample were determined by a model InVia Raman spectrometer. The hot corrosion surface and cross-sectional morphology of ceramics were examined by a model Ultra-55 scanning electron microscope (SEM). The 200 particle sizes of their thermally eroded surfaces were labeled and statistically analyzed by a software named Nano Measurer. The ceramic transmittance was tested in the wavelength range from 200 nm to 2 500 nm by a model Solidspec-3700 solid ultraviolet absorption spectrophotometer. The fluorescence spectra of La_1-_xErZr₂O₇-3_x_/2 transparent ceramics were characterized by a model F-4500 fluorescence spectrophotometer. The linear transmittance of La_1-_xErZr₂O_7-3_x_/2 transparent ceramics in the near-mid infrared band was measured by a model Spectrum Fourier transform infrared spectrometer (FT-IR). The up-conversion emission spectra of ceramics were determined by a model FLS980 steady-state transient fluorescence spectrometer.

Results and discussion

For the prepared non-stoichiometric La_1-_xErZr₂O_7-3_x_/2 transparent ceramics, changes in the crystal structure occur at different La contents in the A-site. For instance, the coexistence of the dual phase in the ceramic gradually transitions to single-phase when La content in the A-site decreases. The lattice distortions in the internal structure of ceramics appear as the nonstoichiometry in the A-site increases.

La_1-_xErZr₂O_7-3_x_/2 transparent ceramics exhibit a good and stable transmittance in the infrared range of 2.5-7.0 μm. In the wavelength range of 200-1 400 nm, La_0.8ErZr₂O_6.7 transparent ceramic has the maximum transparency with a transmittance of approximately 68.8% (1.0 mm in thickness). The main reason for the high transmittance of the ceramic is due to the presence of a few pores and impurities in the grain boundaries, resulting in a lower light scattering. The appropriate reduction of La content effectively eliminates the pores in the grain boundaries of the ceramic and alters the transmittance of the material. Under laser excitation at 980 nm, La_0.8ErZr₂O_6.7 transparent ceramic exhibits three emission peaks, including two main emission peaks centered at 446 nm and 561 nm, which originate from the ²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions of Er³⁺, respectively. Besides, theintense red emission located at 684 nm originates from the ⁴F_9/2→⁴I_15/2 leap. The fluorescence emission intensity gradually weakens as La content decreases. The possible reason is that the decrease in La content leads to the lattice distortion and vacancies in the crystal structure, resulting in a decrease in the cell parameters and the distance between Er ions.

Conclusions

Non-stoichiometric La_1-_xErZr₂O_7-3_x_/2 transparent ceramics with the micron-sized particles were synthesized via combustion sintering and subsequent combustion. The results showed that the La content could have an impact on the ultimate phase composition, morphology and transmittance of the ceramics. The transmittance of ceramics in the visible light range firstly increased and then decreased as the La content decreased, and the moderate decrease of La content could favor the improvement of the optical quality. The ceramic with x of 0.2 had a superior transmittance in the visible to mid-infrared region. As the La content decreased, there existed a gradual transition from a coexistence of pyrochlore phase/defective fluorite phase to predominantly defective fluorite phase in the ceramic, and the average grain size was 96.6 μm at x of 0.5. The ceramic with the thickness of 1.0 mm and x of 0.1 in the infrared range of 2.5-7.0 μm exhibited a stable transmittance level (i.e., 74.8%).

Key words

transparent ceramics / non-stoichiometry / optical performance

引用本文

江小娥, 张魁宝, 郭海燕, 曾建军. 真空烧结非计量La_1-_xErZr₂O_7-3_x_/2透明陶瓷. 硅酸盐学报, 2024 , 52 (3) : 853 -861 . DOI: 10.14062/j.issn.0454-5648.20230554

Xiaoe JIANG, Kuibao ZHANG, Haiyan GUO, Jianjun ZENG. Preparation of Non-stoichiometric La_1-_xErZr₂O_7-3_x_/2 Transparent Ceramics via Vacuum Sintering[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (3) : 853 -861 . DOI: 10.14062/j.issn.0454-5648.20230554

基金

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国家自然科学基金(52272028)
环境友好能源材料国家重点实验室自主课题（西南科技大学）(21fksy14; 22fksy13)

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2024年第52卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230554

接收时间：2023-07-29
首发时间：2026-10-22
出版时间：2024-03-20

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收稿日期：2023-07-29
修回日期：2023-08-17

基金

国家自然科学基金(52272028)

环境友好能源材料国家重点实验室自主课题（西南科技大学）(21fksy14; 22fksy13)

作者信息

^1．西南科技大学环境友好能源材料国家重点实验室，四川绵阳 621010

^2．西南科技大学核废物与环境安全国防重点学科实验室，四川绵阳 621010

通讯作者:

张魁宝（1981—），男，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230554

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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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