碳酸锰掺杂氧化镁基陶瓷的烧结行为和介电性能

doi:10.15541/jim20240214

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 97-103.DOI: 10.15541/jim20240214 CSTR: 32189.14.10.15541/jim20240214

所属专题：【信息功能】介电、铁电、压电材料（202506）

碳酸锰掺杂氧化镁基陶瓷的烧结行为和介电性能

王智祥¹^,²^,³(), 陈莹²^,³^,⁴(), 逄清阳²^,³, 李鑫², 王根水¹^,²^,³^,⁴()

1.国科大杭州高等研究院化学与材料科学学院, 杭州 310024
2.中国科学院上海硅酸盐研究所, 无机功能材料与器件重点实验室, 上海 200050
3.中国科学院大学材料科学与光电工程中心, 北京 100049
4.中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海 200050

收稿日期:2024-04-25 修回日期:2024-05-21 出版日期:2025-01-20 网络出版日期:2024-05-31
通讯作者: 王根水, 研究员. E-mail: genshuiwang@mail.sic.ac.cn;
陈莹, 副研究员. E-mail: chenying@mail.sic.ac.cn
作者简介:王智祥(1999-), 男, 硕士研究生. E-mail: wangzhixiang21@mails.ucas.ac.cn

Sintering Behaviour and Dielectric Properties of MnCO₃-doped MgO-based Ceramics

WANG Zhixiang¹^,²^,³(), CHEN Ying²^,³^,⁴(), PANG Qingyang²^,³, LI Xin², WANG Genshui¹^,²^,³^,⁴()

1. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China
2. Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
4. The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2024-04-25 Revised:2024-05-21 Published:2025-01-20 Online:2024-05-31
Contact: WANG Genshui, professor. E-mail: genshuiwang@mail.sic.ac.cn;
CHEN Ying, associated professor. E-mail: chenying@mail.sic.ac.cn
About author:WANG Zhixiang (1999-), male, Master candidate. E-mail: wangzhixiang21@mails.ucas.ac.cn
Supported by:
Student Training Program for Innovation and Entrepreneurship of Hangzhou Institute for Advanced Study, UCAS(CXCY20230305);Chinese Academy of Sciences Key Project(ZDRW-CN-2021-3-1-18)

摘要/Abstract

摘要：

追求具有高介电强度的陶瓷介质材料, 探究影响介电强度的内在因素, 对选择合适的高功率微波传输器件介质窗材料、保证功率传输的可靠性具有重大的科学研究和工程应用价值。氧化镁(MgO)陶瓷具有高理论介电强度和低介电损耗的介电性能, 在高功率微波传输器件应用方面潜力巨大, 但其烧结温度过高, 阻碍了设计与应用。本工作通过传统固相反应法制备了MgO-1%ZrO₂-1%CaCO₃-x%MnCO₃(MZCM_x, x = 0、0.25、0.50、1.00、1.50, 摩尔比)系列陶瓷, 并对其相结构、形貌特征和介电性能等进行表征分析。研究发现: 引入ZrO₂和CaCO₃形成了第二相, 显著抑制了MgO晶粒的过分长大; 添加MnCO₃促进了陶瓷烧结初期的晶界扩散过程, 降低了陶瓷的晶粒生长激活能, 从而有效降低了陶瓷烧结温度。最终在1350 ℃下烧结制备的MZCM_1.00陶瓷获得了高介电强度和品质因数(E_b = 92.3 kV/mm, Q × f = 216642 GHz), 同时具有低介电损耗(<0.03%)、低电容温度系数(20.3×10^-6 ℃^-1, 85 ℃)和相对接近于零的谐振频率温度系数(-12.54×10^-6 ℃^-1)。本研究为高功率微波传输器件选择介质窗材料以及提升综合性能提供了一种简单有效且可满足实际生产应用的解决方案。

关键词: 氧化镁陶瓷, 介电强度, 烧结温度, 生长激活能

Abstract:

Ceramic dielectric materials with high dielectric strength and mechanisms of their internal factors affecting dielectric strength are significantly valuable for industrial application, especially for selection of suitable dielectric materials for high-power microwave transmission devices and reliable power transmission. Pure magnesium oxide (MgO), a kind of ceramic dielectric material, possesses great application potential in high-power microwave transmission devices due to its high theoretical dielectric strength, low dielectric constant, and low dielectric loss properties, but its application is limited by high sintering temperature during preparation. This work presented the preparation of a new type of multiphase ceramics based on MgO, which was MgO-1%ZrO₂-1%CaCO₃-x%MnCO₃ (MZCM_x, x = 0, 0.25, 0.50, 1.00, 1.50, in molar), and their phase structures, morphological features, and dielectric properties were investigated. It was found that inclusion of ZrO₂ and CaCO₃effectively inhibited excessive growth of MgO grains by formation of second phase, while addition of MnCO₃ promoted the grain boundary diffusion process during the sintering process and reduced activation energy for the grain growth, resulting in a lower ceramic sintering temperature. Excellent performance, including high dielectric strength (E_b = 92.3 kV/mm) and quality factor (Q × f = 216642 GHz), simultaneously accompanying low dielectric loss (< 0.03%), low temperature coefficient of dielectric constant (20.3×10^-6 ℃^-1, 85 ℃) and resonance frequency (-12.54×10^-6 ℃^-1), was achieved in MZCM_1.00 ceramics under a relatively low sintering temperature of 1350 ℃. This work offers an effective solution for selecting dielectric materials for high-power microwave transmission devices.

Key words: MgO ceramic, dielectric strength, sintering temperature, growth activation energy

中图分类号:

TQ174

王智祥, 陈莹, 逄清阳, 李鑫, 王根水. 碳酸锰掺杂氧化镁基陶瓷的烧结行为和介电性能[J]. 无机材料学报, 2025, 40(1): 97-103.

WANG Zhixiang, CHEN Ying, PANG Qingyang, LI Xin, WANG Genshui. Sintering Behaviour and Dielectric Properties of MnCO₃-doped MgO-based Ceramics[J]. Journal of Inorganic Materials, 2025, 40(1): 97-103.

图/表 7

Fig. 1 Densities of the pure MgO and MZCMx (x = 0, 0.25, 0.50, 1.00, 1.50) ceramics at different sintering temperatures (1300-1560 ℃, 2 h)

Fig. 2 Kinetic curves of grain growth in MZCM1.00 ceramics (a) Grain growth index n at different sintering temperatures; (b-e) Activation energy of grain growth with different sintering time

Fig. 3 XRD patterns of pure MgO and MZCMx (x = 0, 0.25, 0.50, 1.00, 1.50) ceramics

Fig. 4 FESEM images of thermal etched surface morphologies of ceramics with insets showing grain size distribution of ceramics (a) Pure MgO; (b-f) MZCMx (x = 0, 0.25, 0.50, 1.00, 1.50) ceramics

Fig. 5 XPS spectra of O1s of ceramics (a) MZCM1.00; (b) MZCM1.50. Colorful figures are available on website

Fig. 6 Dieletric properties of pure MgO and MZCMx (x = 0, 0.25, 0.50, 1.00, 1.50) ceramics (a) Linear fitting for dielectric strength of Weibull distribution; (b) Temperature dependence of the dielectric constant and loss in 1 MHz. Colorful figures are available on website

Table 1 Microwave dielectric properties of pure MgO and MZCMx ceramics

Sample	τ_c/(×10^-6, ℃^-1, -25 ℃)	τ_c/(×10^-6, ℃^-1, 85 ℃)	(Q × f)/GHz	τ_f/(×10^-6,℃^-1)
Pure MgO	79.6	85.1	138240	-35.62
MZCM₀	63.9	74.4	124623	-32.36
MZCM_0.25	28.6	34.4	130330	-20.64
MZCM_0.50	20.1	46.1	156196	-18.36
MZCM_1.00	4.91	20.3	216642	-12.54
MZCM_1.50	16.06	78.4	123216	-14.60

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碳酸锰掺杂氧化镁基陶瓷的烧结行为和介电性能

Sintering Behaviour and Dielectric Properties of MnCO₃-doped MgO-based Ceramics

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碳酸锰掺杂氧化镁基陶瓷的烧结行为和介电性能

Sintering Behaviour and Dielectric Properties of MnCO3-doped MgO-based Ceramics

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Sintering Behaviour and Dielectric Properties of MnCO₃-doped MgO-based Ceramics