锶钽氧氮化物功能陶瓷的高效合成、致密化及介电性能研究

doi:10.15541/jim20230026

无机材料学报 ›› 2023, Vol. 38 ›› Issue (8): 885-892.DOI: 10.15541/jim20230026 CSTR: 32189.14.10.15541/jim20230026

所属专题：【信息功能】介电、铁电、压电材料（202409）

锶钽氧氮化物功能陶瓷的高效合成、致密化及介电性能研究

李俊生(), 曾良, 刘荣军, 王衍飞, 万帆, 李端()

国防科技大学空天科学学院, 新型陶瓷纤维及其复合材料重点实验室, 长沙 410073

收稿日期:2023-01-16 修回日期:2023-02-09 出版日期:2023-08-20 网络出版日期:2023-03-17
通讯作者: 李端, 副研究员. E-mail: duan_li_2016@163.com
作者简介:李俊生(1982-), 男, 副研究员. E-mail: charlesljs@163.com
基金资助:
国家自然科学基金(51702361)

Functional Strontium Tantalum Oxynitride Ceramics: Efficient Synthesis, Densification and Dielectric Performance

LI Junsheng(), ZENG Liang, LIU Rongjun, WANG Yanfei, WAN Fan, LI Duan()

Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Received:2023-01-16 Revised:2023-02-09 Published:2023-08-20 Online:2023-03-17
Contact: LI Duan, associate professor. E-mail: duan_li_2016@163.com
About author:LI Junsheng (1982-), male, associate professor. E-mail: charlesljs@163.com
Supported by:
National Natural Science Foundation of China(51702361)

摘要/Abstract

摘要：

AB(O,N)₃型钙钛矿氮氧化物是一类新型功能陶瓷材料, 具有独特的介电/磁/光催化等性能, 在能源存储与转化领域应用前景广阔, 但传统制备工艺耗时长且产物纯度较低。本研究以尿素为氮源、金属氧化物为前驱体, 采用无压放电等离子烧结设备一步合成了钙钛矿氮氧化物SrTa(O,N)₃陶瓷粉体, 并实现了快速致密化。深入研究了升温速率和合成温度对粉体组成与微观形貌的影响, 并对优化后制备的陶瓷块体进行了介电性能表征。结果表明, 较高的升温速率和适中的合成温度有利于氮化反应的充分进行, 在100 ℃/min和1000 ℃下制得的SrTa(O,N)₃粉体纯度最高, 氧氮化物相含量约97%, 粒径分布区间为100~300 nm, Sr、Ta、O、N 四种元素分布均匀。较优的致密化工艺为烧结温度1300 ℃、升温速率300 ℃/min、保温时间1 min, 经烧结制得的SrTa(O,N)₃陶瓷试片致密度可达94%以上, 且纯度很高, 该材料在300 Hz时的介电常数高达8349, 介电损耗为10^-4量级, 优于文献报道值。本研究制备的SrTa(O,N)₃陶瓷的高介电常数与致密度和纯度的调控密不可分, 这是因为气孔和杂质会降低材料介电常数, 高致密度和高纯度是SrTa(O,N)₃氧氮化物陶瓷获得优异介电性能的关键。

关键词: 钙钛矿, 氧氮化物, 尿素, 放电等离子烧结, 介电常数

Abstract:

The perovskite-type oxynitride with AB(O,N)₃ formula is a new type of functional ceramic materials, which have unique dielectric/magnetic/photocatalytic properties and prospective applications in the field of energy storage and conversion. However, the traditional preparation process takes a long time and the product purity is low. In this study, SrTa(O,N)₃ ceramic powder was synthesized and densified by a pressureless spark plasma sintering equipment with urea as nitrogen source and metal oxides as precursors. Effects of heating rate and synthesis temperature on the composition and microstructure of the powder were deeply investigated, and the dielectric properties of the optimized ceramic bulks were characterized. The results show that higher heating rate and moderate synthesis temperature are beneficial to sufficient nitridation, while the SrTa(O,N)₃ powder prepared at 100 ℃/min and 1000 ℃ possesses the highest purity (~97% oxynitride phase content) with a particle size distribution of 100-300 nm. Elements of Sr, Ta, O and N are evenly distributed. The optimized densification process is firstly sintering at 1300 ℃, with heating rate of 300 ℃/min, and dwelled for 1 min. After sintering, the density of SrTa(O,N)₃ ceramic pellet can reach >94% with a high purity. Dielectric constant and loss tangent of the material are 8349 and 10^-4 level at 300 Hz, respectively, which are superior to that reported in the literature. The high dielectric constant prepared in this study is closely related to standard density and purity, because the existence of pores and impurities can reduce the dielectric constant of materials. Therefore, high density and purity are the key factors to obtain excellent dielectric properties of SrTa(O,N)₃ oxynitride ceramics.

Key words: perovskite, oxynitride, urea, spark plasma sintering, dielectric constant

中图分类号:

TQ174

李俊生, 曾良, 刘荣军, 王衍飞, 万帆, 李端. 锶钽氧氮化物功能陶瓷的高效合成、致密化及介电性能研究[J]. 无机材料学报, 2023, 38(8): 885-892.

LI Junsheng, ZENG Liang, LIU Rongjun, WANG Yanfei, WAN Fan, LI Duan. Functional Strontium Tantalum Oxynitride Ceramics: Efficient Synthesis, Densification and Dielectric Performance[J]. Journal of Inorganic Materials, 2023, 38(8): 885-892.

图/表 13

图1 SrTa(O,N)3陶瓷试片的制备流程图

Fig. 1 Preparation flow chart of the SrTa(O,N)3 ceramic bulk

表1 样品合成条件(升温制度)及元素含量

Table 1 Synthesis conditions (heating strategy) and element content

Sample	Synthesis temperature /℃	Heating rate /(℃·min^-1)	Composition/% (in atomic)				O/N
Sample	Synthesis temperature /℃	Heating rate /(℃·min^-1)	Sr	Ta	O	N	O/N
STON-1000-10	1000	10	9.19	11.05	61.51	18.25	3.37
STON-800-100	800	100	14.59	7.74	57.10	20.57	2.78
STON-900-100	900	100	12.60	10.98	50.24	26.18	1.92
STON-1000-100	1000	100	11.74	11.92	47.83	28.51	1.68
STON-1100-100	1100	100	10.63	13.02	44.86	31.49	1.42
STON-1200-100	1200	100	10.11	13.50	44.17	32.22	1.37

图2 不同升温速率所得产物的XRD谱图(a)和Raman谱图(b)

Fig. 2 XRD patterns (a) and Raman spectra (b) of the products obtained at different heating rates

图3 不同升温速率所得产物的光学与SEM照片

Fig. 3 Optical and SEM images of the products obtained at different heating rates (a) 10 ℃/min; (b) 100 ℃/min

图4 不同合成温度所得产物的XRD图谱(a)和Raman图谱(b)

Fig. 4 XRD patterns (a) and Raman spectra (b) of the products obtained at different synthesis temperatures

图5 不同合成温度所得产物的光学与SEM照片

Fig. 5 Optical and SEM images of the products obtained at different synthesis temperatures (a) 800 ℃; (b) 900 ℃; (c) 1000 ℃; (d) 1100 ℃; (e) 1200 ℃

图6 SrTa(O,N)3粉体X射线衍射的Rietveld精修谱图

Fig. 6 Rietveld refinement of XRD pattern for SrTa(O,N)3 Vertical marks indicate the standard Bragg position for SrTaNO2 (upper) and Sr2Ta2O7 (lower)

图7 优化合成制得SrTa(O,N)3粉体的SEM照片和EDS元素分布图

Fig. 7 SEM image and EDS mappings of SrTa(O,N)3 powder prepared under optimized conditions (a) SEM image; (b) Sr; (c) Ta; (d) O; (e) N

表2 不同SPS工艺所得氧氮化物陶瓷的密度及孔隙率(100 MPa)

Table 2 Density and porosity of oxynitride ceramics prepared by different SPS processes (100 MPa)

Sample	Heating rate/ (℃·min^-1)	Sintering temperature/℃	Dwell time/min	Density/ (g·cm^-3)	Relative density/%	Open porosity/%	(Open porosity/ Total porosity)/%
STON-SPS-1	300	1100	1	5.69	70.94	3.12	10.77
STON-SPS-2	300	1200	1	6.30	78.54	7.54	35.28
STON-SPS-3	300	1250	0	6.93	86.40	4.37	21.90
STON-SPS-4	300	1250	1	7.13	88.89	0.43	3.89
STON-SPS-5	300	1250	3	7.24	90.26	0.57	5.88
STON-SPS-6	200	1300	1	7.37	91.88	0.69	8.53
STON-SPS-7	300	1300	1	7.55	94.13	0.55	9.52
STON-SPS-8	300	1400	1	7.67	95.62	0.49	11.53

图8 SPS烧结所得SrTa(O,N)3块体的XRD谱图

Fig. 8 XRD patterns of SrTa(O,N)3 bulk obtained by SPS

图9 SPS烧结所得SrTa(O,N)3块体的SEM和光学照片

Fig. 9 SEM and optical images of SrTa(O,N)3 bulk obtained by SPS process (a) STON-SPS-1; (b) STON-SPS-4; (c) STON-SPS-7

图10 SrTa(O,N)3陶瓷块体的介电特性曲线(300 Hz~1 MHz)

Fig. 10 Dielectric performance curves of SrTa(O,N)3 ceramic bulk (300 Hz-1 MHz)

图11 本工作制备的SrTa(O,N)3陶瓷低频介电常数与文献报道值比较[11-12,14,24]

Fig. 11 Dielectric constants at low frequency ranges of SrTa(O,N)3 ceramic bulk in this work and literatures[11-12,14,24]

参考文献 24

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锶钽氧氮化物功能陶瓷的高效合成、致密化及介电性能研究

Functional Strontium Tantalum Oxynitride Ceramics: Efficient Synthesis, Densification and Dielectric Performance

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