固相-熔盐法非平衡骤热骤冷工艺制备高纯BiFeO3及性能

doi:10.15541/jim20130603

无机材料学报 ›› 2014, Vol. 29 ›› Issue (11): 1151-1155.DOI: 10.15541/jim20130603

固相-熔盐法非平衡骤热骤冷工艺制备高纯BiFeO₃及性能

吴星, 栗海峰, 周金玲, 霍敏锋, 程呈, 沈绪根, 严春杰

(纳米矿物材料及应用教育部工程研究中心(中国地质大学), 中国地质大学(武汉) 材料与化学学院, 武汉430074)

收稿日期:2013-11-19 修回日期:2014-05-05 出版日期:2014-11-20 网络出版日期:2014-10-24
作者简介:吴星(1990–), 男, 硕士研究生. E-mail:1214927579@qq.com
基金资助:
纳米矿物材料及应用教育部工程研究中心基金(CUGNGM20135);全国大学生创新训练项目(201210491018)

Fabrication and Properties of Highly Pure BiFeO₃ Using A Method of Solid State Reaction-molten Salt Synthesis with Non-equilibrium Process

WU Xing, LI Hai-Feng, ZHOU Jin-Ling, HUO Min-Feng, CHENG Cheng, SHEN Xu-Gen, YAN Chun-Jie

(Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences, Wuhan 430074, China; Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074, China)

Received:2013-11-19 Revised:2014-05-05 Published:2014-11-20 Online:2014-10-24
About author:WU Xing. E-mail:1214927579@qq.com

摘要/Abstract

摘要：

采用固相-熔盐法非平衡骤热骤冷工艺(SSR-MSS-SHCN)制得粒径分布均匀、高纯度的BiFeO₃粉体。通过XRD、FT-IR、TG-DSC、VSM及SEM等对样品物相结构、性能及形貌进行表征。结果表明, 骤热骤冷的非平衡工艺更有利于提高BiFeO₃纯度。单一的固相法或熔盐法采用骤热骤冷非平衡工艺合成的产物均含有Bi₂₅FeO₃₉和/或Bi₂Fe₄O₉杂相。固相-熔盐法骤热骤冷非平衡工艺制得了几近单相的高纯度BiFeO₃粉体。高纯度BiFeO₃粉体磁性能室温呈反铁磁性, 而低温呈弱铁磁性和/或超顺磁性, 而非自旋玻璃态。

关键词: 铁酸铋, 非平衡骤热骤冷工艺, 固相-熔盐法

Abstract:

High pure Bismuth ferrite (BiFeO₃) powders were prepared by a solid state reaction-molten salt synthesis method (SSR-MSS method) using shock heating and chilling non-equilibrium process (SHCN process). The structure, morphology and electromagnetic properties were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectroscope (FTIR), Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) and Vibrating Sample Magnetometer (VSM). The results indicated that SHCN process was better to get higher purity of BiFeO₃ powders than conventional equilibrium process (C process), but still has a certain number of impurity phases like Bi₂₅FeO₃₉ and/or Bi₂Fe₄O₉ as found in the products prepared by either SSR-SHCN process or MSS-SHCN process. In contrast, single-phase BiFeO₃ powders could be obtained by SSR-MSS-SHCN process. The micro-nanoscale BiFeO₃ powders presented antiferromagnetism, superparamagnetism, and/or weak ferromagnetism behavior at room temperature, but not spin-glass state at low temperature (5 K).

Key words: BiFeO3, solid state reaction-molten salt synthesis method, shock heating &amp, chilling non-equilibrium process

中图分类号:

TB34

吴星, 栗海峰, 周金玲, 霍敏锋, 程呈, 沈绪根, 严春杰. 固相-熔盐法非平衡骤热骤冷工艺制备高纯BiFeO₃及性能[J]. 无机材料学报, 2014, 29(11): 1151-1155.

WU Xing, LI Hai-Feng, ZHOU Jin-Ling, HUO Min-Feng, CHENG Cheng, SHEN Xu-Gen, YAN Chun-Jie. Fabrication and Properties of Highly Pure BiFeO₃ Using A Method of Solid State Reaction-molten Salt Synthesis with Non-equilibrium Process[J]. Journal of Inorganic Materials, 2014, 29(11): 1151-1155.

图/表 9

图1 固相法骤热骤冷工艺不同保温时间煅烧产物的XRD图谱

Fig. 1 XRD patterns of samples prepared by of SSR-SHCN method after being calcinated at 700℃ for different soaking time (1)15 min; (b) 30 min; (c) 60 min; (d) 90 min; (e) 120 min

图2 熔盐法骤热骤冷工艺不同保温时间煅烧产物的XRD图谱

Fig. 2 XRD patterns of samples prepared by MSS-SHCN method after being calcinated at 700℃ for different soaking time (a) 15 min; (b) 30 min; (c) 60 min; (d) 120 min; (e) 240 min

图3 固相-熔盐法骤热骤冷工艺不同保温时间煅烧产物XRD图谱

Fig. 3 XRD patterns of SSR-MSS-SHCN method calcinated samples for different soaking time (a) 15 min; (b) 30 min; (c) 60 min; (d) 90 min; (e) 120 min

图4 固相-熔盐法平衡(a)与非平衡(b)工艺煅烧产物XRD图谱

Fig. 4 XRD patterns of the samples prepared by (a) SSR- MSS-C method; (b) SSR-MSS-SHCN method

图5 固相-熔盐法骤热骤冷工艺合成BiFeO3粉体FTIR图谱

Fig. 5 FT-IR spectrum of as-synthetized BiFeO3 by using SSR-MSS-SHCN method

图6 固相-熔盐法骤热骤冷工艺合成BiFeO3 TG-DSC曲线

Fig. 6 TG-DSC curves of as-synthetized BiFeO3 by using SSR-MSS-SHCN method

图7 固相-熔盐法骤热骤冷工艺合成BiFeO3介电频谱

Fig. 7 Dielectric spectra of as-prepared BiFeO3 by using SSR-MSS-SHCN method

图8 固相-熔盐法骤热骤冷工艺合成BiFeO3磁滞回线

Fig. 8 M-H hysteresis loops of as-synthetized BiFeO3 by using SSR-MSS-SHCN at 5 K and 300 K (a), and insets are the partially enlarged curves at 300 K (b) and 5 K (c), respectively

图9 SSR-SHCN (a)及SSR-MSS-SHCN (b)煅烧产物SEM照片

Fig. 9 SEM images of BiFeO3 powder prepared by SSR- SHCN method (a) and SSR-MSS-SHCN method (b)

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固相-熔盐法非平衡骤热骤冷工艺制备高纯BiFeO₃及性能

Fabrication and Properties of Highly Pure BiFeO₃ Using A Method of Solid State Reaction-molten Salt Synthesis with Non-equilibrium Process

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