La2NiMnO6双钙钛矿陶瓷的等离子活化烧结

doi:10.15541/jim20180291

摘要/Abstract

摘要：

针对常压烧结La₂NiMnO₆ (简称LNMO)双钙钛矿陶瓷存在的烧结温度高、致密度低、工艺周期长等问题, 采用等离子活化烧结技术(Plasma Activated Sintering, 简称PAS)制备LNMO陶瓷, 主要研究了烧结工艺(温度、压力) 对其物相结构、显微形貌、致密度和介电性能的影响, 以期得到物相单一、结构致密、性能良好的LNMO双钙钛矿陶瓷。利用X射线衍射仪、阿基米德排水法、扫描电子显微镜、阻抗分析仪等手段, 系统测试表征了LNMO陶瓷的结构与性能。结果表明: 升高烧结温度有利于改善LNMO陶瓷的结晶性并增大晶粒尺寸, 但过高温度会导致杂相生成; 增大烧结压力对物相无明显影响, 但在一定程度上提升了致密度。确定了较适宜的PAS条件为: 烧结温度975~1000 ℃、烧结压力80 MPa, 在此条件下烧结得到的LNMO陶瓷为单一的正交结构, 致密度为92%, 具有较大的介电常数(~10 ⁶)。与常压烧结相比, 等离子活化技术集等离子体活化、压力、电阻加热为一体, 可在更低温度(降低400~500 ℃)和更短时间(缩短2~20 h)内获得较为致密的LNMO陶瓷。

关键词: La₂NiMnO₆陶瓷, 等离子活化烧结, 烧结温度, 烧结压力, 介电性能

Abstract:

La₂NiMnO₆ (LNMO) double-perovskite ceramics are normally prepared by the conventional pressureless sintering technique, which is difficult to produce dense structure and usually needs high sintering temperature as well as long sintering period. In this study, highly-dense La₂NiMnO₆ ceramics with good performance were prepared by a novel Plasma Activated Sintering (PAS) method. The influence of PAS parameters, including sintering temperature and pressure, on crystalline phase, microstructure, relative density and dielectric properties of the LNMO ceramics were systematically studied by the means of XRD, SEM, Archimedes method, and impedance analyzer. The results showed that the crystallinity and grain size of the LNMO ceramics increased with the increase of sintering temperature, but the impurity phases might emerge if the sintering temperature further increased above 1000 ℃. The sintering pressure had little effect on crystalline phase, while the relative density of the LNMO ceramics could be effectively enhanced with the sintering pressure increasing. LNMO ceramics in single orthorhombic structure with relative density of 92% and giant dielectric constant (~10 ⁶) were successfully obtained at the optimum PAS conditions, i.e., sintering temperature of 975-1000 ℃ and sintering pressure of 80 MPa. Compared to the traditional pressureless sintering, LNMO ceramics with dense structure could be obtained by PAS at a relative lower sintering temperature (reduced by 400-500 ℃) with a shorter sintering period (reduced by 2-20 h), which should be attributed to the coupling effect of temperature and stress as well as activation during the sintering process.

Key words: La₂NiMnO₆ ceramics, plasma activated sintering, sintering temperature, sintering pressure, dielectric property

中图分类号:

TM28

甘慧, 王传彬, 沈强, 张联盟. La₂NiMnO₆双钙钛矿陶瓷的等离子活化烧结[J]. 无机材料学报, 2019, 34(5): 541-545.

Hui GAN, Chuan-Bin WANG, Qiang SHEN, Lian-Meng ZHANG. Preparation of La₂NiMnO₆ Double-perovskite Ceramics by Plasma Activated Sintering[J]. Journal of Inorganic Materials, 2019, 34(5): 541-545.

图/表 6

表1 实验原料的性能

Table 1 Properties of raw materials

药品名	分子量	纯度	生产商家
La₂O₃	325.81	99%	国药集团化学试剂有限公司
Mn₂O₃	157.87	99%	成都麦卡希化工有限公司
NiO	74.71	99%	阿拉丁试剂(上海)有限公司

图1 LNMO粉体和不同温度烧结的LNMO陶瓷的XRD图谱

Fig. 1 XRD patterns of LNMO powders and LNMO ceramics sintered at different temperatures

图2 不同温度烧结的LNMO陶瓷的SEM照片

Fig. 2 SEM images of LNMO ceramics sintered at different temperatures

图3 (a)80 MPa和(b)50 MPa压力下烧结的LNMO陶瓷的XRD图谱和显微形貌

Fig. 3 XRD patterns and SEM images of LNMO ceramics sintered at (a) 80 MPa and (b) 50 MPa

图4 (a)80 MPa和(b)50 MPa压力下烧结的LNMO陶瓷的致密度随烧结温度的变化图

Fig. 4 Density of LNMO ceramics sintered at different temperatures and pressures

图5 不同频率下LNMO陶瓷的(a)介电常数与(b)介电损耗随温度的变化曲线

Fig. 5 Temperature dependence of (a) dielectric constant and (b) dielectric loss of LNMO ceramics at different frequencies

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La₂NiMnO₆双钙钛矿陶瓷的等离子活化烧结

Preparation of La₂NiMnO₆ Double-perovskite Ceramics by Plasma Activated Sintering

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