无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 711-718.DOI: 10.15541/jim20240517

• 研究快报 • 上一篇    下一篇

基于CuO-TiO2-Nb2O5复合氧化物烧结助剂的ZnAl2O4陶瓷低温烧结研究

杨燕1,2(), 张发强1, 马名生1(), 王墉哲1, 欧阳琪1, 刘志甫1()   

  1. 1.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
    2.宜宾红星电子有限公司 技术中心, 宜宾 644600

Low Temperature Sintering of ZnAl2O4 Ceramics with CuO-TiO2-Nb2O5 Composite Oxide Sintering Aid

YANG Yan1,2(), ZHANG Faqiang1, MA Mingsheng1(), WANG Yongzhe1, OUYANG Qi1, LIU Zhifu1()   

  1. 1. CAS Key Lab of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    2. Technical Center, Yibin Red Star Electronics Co., Ltd., Yibin 644600, China
  • Received:2024-12-12 Revised:2025-02-19 Published:2025-06-20 Online:2025-02-25
  • Contact: LIU Zhifu, professor. E-mail: liuzf@mail.sic.ac.cn;
    MA Mingsheng, professor. E-mail: mamingsheng@mail.sic.ac.cn
  • About author:YANG Yan (1994-), female, PhD. E-mail: yan.yang@hongxing799.com
  • Supported by:
    National Natural Science Foundation of China(U24A2052);Shanghai Eastern Talent Plan

摘要:

ZnAl2O4及ZnAl2O4基陶瓷由于具有优良的微波介电、热学和力学性能, 从而备受研究人员关注。本工作系统研究了不同组成比例的5% CuO-TiO2-Nb2O5(CTN)三元复合氧化物烧结助剂对ZnAl2O4微波介电陶瓷烧结行为和性能的影响。当5% CTN烧结助剂中Cu、Ti、Nb元素的摩尔分数分别为0.625~0.875、0~0.250、0.125~0.625时, ZnAl2O4陶瓷的烧结温度可从1400 ℃以上降低至1000 ℃以下。烧结助剂CN(Cu : Nb=1 : 1, 摩尔比)和CTN(Cu : Ti : Nb=4 : 1 : 3, 摩尔比)可分别将ZnAl2O4陶瓷的烧结温度降低至975和1000 ℃, 同时陶瓷具有优良的介电性能(介电常数εr=11.36, 品质因数Q׃=8245 GHz; εr=9.52, Q׃=22249 GHz)和抗弯强度(200和161 MPa), 有望用于制备铜电极低温共烧陶瓷(LTCC)材料。ZnAl2O4+CTN体系的低温烧结是一种活化烧结机制。晶界处存在含Cu、Ti、Nb元素的纳米级非晶态界面膜, 在ZnAl2O4陶瓷烧结过程中为传质过程提供了快速扩散路径。Ti和Cu离子的化合价改变以及氧空位变化, 降低了ZnAl2O4陶瓷的烧结温度。此外, 晶界上发生的系列反应发挥了活化晶界的作用, 进一步促进烧结致密化。本工作为设计具有优良性能、CuO-TiO2-Nb2O5复合氧化物助烧的ZnAl2O4陶瓷LTCC材料提供了一种参考。

关键词: ZnAl2O4, CuO-TiO2-Nb2O5, 低温烧结, 微波介质陶瓷, 低温共烧陶瓷

Abstract:

ZnAl2O4 and ZnAl2O4-based ceramics have attracted much attention from researchers due to their good microwave dielectric, thermal and mechanical properties. In this work, the influence of 5% (in mass) CuO-TiO2-Nb2O5 (CTN) ternary composite oxide additives with different composition ratios on sintering behavior and properties of ZnAl2O4 microwave dielectric ceramics was investigated. When the molar fraction ranges of Cu, Ti and Nb elements in 5% CTN additives are 0.625-0.875, 0-0.250 and 0.125-0.625, respectively, sintering temperature of ZnAl2O4 ceramics can be reduced from above 1400 ℃ to below 1000 ℃. The sintering additives CN (Cu : Nb=1 : 1, molar ratio) and CTN (Cu : Ti : Nb=4 : 1 : 3, molar ratio) can reduce sintering temperature of ZnAl2O4 ceramics to 975 and 1000 ℃, respectively, while maintaining good dielectric properties (dielectric constant εr=11.36, quality factor Q׃=8245 GHz and εr=9.52, Q׃=22249 GHz) and flexural strengths (200 and 161 MPa), which are expected to be applied in preparation of low temperature co-fired ceramic (LTCC) materials with copper electrodes. Low-temperature sintering of the ZnAl2O4+CTN system is characterized as activated sintering. Nanometer-level amorphous interfacial films containing Cu, Ti, and Nb elements are observed at the grain boundaries, which may provide fast diffusion pathways for mass transportation during the sintering process. Valence changes of Ti and Cu ions, along with changes of oxygen vacancies, are confirmed, which provides a potential mechanism for reduced sintering temperature of ZnAl2O4 ceramics. In addition, a series of reactions occurring at the grain boundaries can activate these boundaries and further promote the sintering densification process. These results suggest a promising way to design a novel LTCC material with excellent properties based on the low temperature sintering of ceramics with the sintering aid of CuO-TiO2-Nb2O5 composite oxide.

Key words: ZnAl2O4, CuO-TiO2-Nb2O5, low-temperature sintering, microwave dielectric ceramic, low temperature co-fired ceramic

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