高熵陶瓷(Zr1/7Hf1/7Ce1/7Y2/7La2/7)O2-δ的制备及烧结行为

doi:10.15541/jim20200374

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 372-378.DOI: 10.15541/jim20200374 CSTR: 32189.14.10.15541/jim20200374

高熵陶瓷(Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ的制备及烧结行为

张丰年(), 郭猛, 苗洋(), 高峰, 成楚飞, 程富豪, 刘宇峰

太原理工大学材料科学与工程学院, 太原 030024

收稿日期:2020-07-06 修回日期:2020-08-28 出版日期:2021-04-20 网络出版日期:2021-04-19
通讯作者: 苗洋, 副教授. E-mail: miaoyang@tyut.edu.cn
作者简介:张丰年(1998-), 男, 硕士研究生. E-mail: zhangfn1998@163.com
基金资助:
国家自然科学基金青年基金(51802213);山西省应用基础研究计划面上青年基金(201901D211118)

Preparation and Sintering Behavior of High Entropy Ceramic (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ

ZHANG Fengnian(), GUO Meng, MIAO Yang(), GAO Feng, CHENG Chufei, CHENG Fuhao, LIU Yufeng

College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Received:2020-07-06 Revised:2020-08-28 Published:2021-04-20 Online:2021-04-19
Contact: MIAO Yang, associate professor. E-mail: miaoyang@tyut.edu.cn
About author:ZHANG Fengnian(1998-), male, Master candidate. E-mail: zhangfn1998@163.com
Supported by:
Natural Science Foundation of China(51802213);Program of Applied Basic Research Program of Shanxi Province(201901D211118)

摘要/Abstract

摘要：

近年来, 不同体系的高熵陶瓷迅猛发展, 但萤石结构高熵氧化物仍处于研发初期。本研究采用机械球磨和常压烧结的方法合成一种新型高熵萤石氧化物, 利用XRD, SEM, TG-DSC和可视化形变分析仪研究了陶瓷的物相转变、表面形貌以及烧结行为。研究结果表明, (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ是一种非等摩尔的“高熵”陶瓷, 其内部各元素分布均匀。湿法球磨和干法球磨制备的粉末结构和粒度均有所不同, 单相转变温度为1600和1300 ℃, 圆盘状坯体在1600 ℃保温1 h, 尺寸收缩率约为8.5%和17.8%, 致密度分别为82.25%和93.23%, 说明球磨工艺是影响高熵陶瓷烧结的重要因素。此外, 常压烧结制备(Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ时, 在1300~1600 ℃应适当减缓升温速率并延长保温时间, 避免生坯收缩开裂, 并提高陶瓷致密度。

关键词: 高熵氧化物, 非等摩尔, 萤石结构, 球磨工艺

Abstract:

High entropy ceramics (HECs) typically refer to a kind of solid solution consisting of five or more principal elements. In recent years, different kinds of HECs have developed rapidly whereas high entropy oxides with fluorite structure are still in their nascent state. In this study, a new type of high entropy fluorite oxide was successfully synthesized using mechanical ball-milling followed by conventional sintering. Phase transformation, surface morphology and sintering behavior of ceramic were characterized. The results demonstrate that (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ is a non-equimolar high entropy ceramic in which all elements distribute homogenously. The powders derived from wet-milling or dry-milling possess different crystal structure and particle size. Raw materials transform into single-phase structure at 1600 ℃ and 1300 ℃, respectively. After dwelling at 1600 ℃ for 1 h, the shrinkage of two discs are 8.5% and 17.8%, approximately, at the same time, the relative densities are 82.25% and 93.23%. These miscellaneous distinctions indicate that ball-milling process is a crucial factor affecting sinterability of HECs. In order to avoid cracks caused by rapid shrinkage and improve density of ceramic, it is vital to decrease heating rate and prolong dwell time in the range of 1300-1600 ℃ as preparing (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ by conventional sintering.

Key words: high entropy oxide, non-equimolar, fluorite structure, ball-milling process

中图分类号:

TB332

张丰年, 郭猛, 苗洋, 高峰, 成楚飞, 程富豪, 刘宇峰. 高熵陶瓷(Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ的制备及烧结行为[J]. 无机材料学报, 2021, 36(4): 372-378.

ZHANG Fengnian, GUO Meng, MIAO Yang, GAO Feng, CHENG Chufei, CHENG Fuhao, LIU Yufeng. Preparation and Sintering Behavior of High Entropy Ceramic (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ[J]. Journal of Inorganic Materials, 2021, 36(4): 372-378.

图/表 10

表1 氧化物的晶体结构、空间群及对应阳离子配位数和半径[42]

Table 1 Crystal structures, space groups (number), cation coordination numbers (CN) and corresponding cationic radii (rc) of selected oxides[42]

Oxides	Crystal structure	Space group (number)	CN	r_c/nm
ZrO₂	Cubic	Fm-3m (225)	8	0.084
HfO₂	Monoclinic	P21/c (14)	8	0.083
CeO₂	Fluorite	Fm-3m (225)	8	0.097
Y₂O₃	Bixbyite	Ia-3 (206)	6	0.090
La₂O₃	Trigonal	P-3m (164)	6	0.1032

表2 制备生料的工艺、球料比、转速、时间及其他参数

Table 2 Process, ball-to-powder-ratio (BPR), speed, time and others for raw material preparation

Sample	Process	BPR	Speed /(r·min^-1)	Time /h	Disperser	Desiccation	Energy
A	Wet milling	6 : 1	250	6	Ethanol	60 ℃ /24 h	Low
B	Dry milling	10 : 1	400	40	-	-	High

图1 (a)生料的煅烧工艺和(b)不同温度煅烧生料A的XRD图谱

Fig. 1 (a) Calcining process of raw materials and (b) XRD patterns of raw material A calcined at different temperatures

图2 1600 ℃烧结ZHCYLO的XRD图谱和Rietveld精修拟合

Fig. 2 XRD pattern together with Rietveld fits of the ZHCYLO sintered at 1600 ℃

图3 经不同温度退火的ZHCYLO的XRD图谱

Fig. 3 XRD patterns of ZHCYLO annealed at different temperatures

图4 在1600 ℃下烧结1 h的ZHCYLO的SEM-EDS图片

Fig.4 SEM-EDS images of ZHCYLO sintered at 1600 ℃ for 1 h

图5 生料粉末A的TG-DSC曲线

Fig. 5 TG-DSC curves of raw material A

图6 (a)生料A和(b)生料B的粒度分布曲线

Fig. 6 Particle size distribution of (a) raw material A and (b) B

图7 (a) 生料A和B的XRD图谱对比, (b)不同温度下煅烧生料B的XRD图谱

Fig. 7 (a) Comparation of XRD patterns from raw material A and B; (b) XRD patterns of raw material B sintered at different temperatures

图8 不同坯体在不同温度下烧结的光学照片以及坯体随时间变化的温度/线性收缩

Fig. 8 Digital camera photographs of different pellets sintered at different temperatures and temper ature/linear shrinkage of different pellets as a function of time (a,c) Pellet A; (b,d) Pellet B

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高熵陶瓷(Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ的制备及烧结行为

Preparation and Sintering Behavior of High Entropy Ceramic (Zr_1/7Hf_1/7Ce_1/7Y_2/7La_2/7)O_2-_δ

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