元素配比对BiFeO3反应烧结相变影响的高温X射线衍射研究

doi:10.15541/jim20190024

摘要/Abstract

摘要：

多铁性材料BiFeO₃样品中Bi₂₅FeO₃₉、Bi₂Fe₄O₉等杂相的存在增加了漏电流, 影响了对其磁电耦合机制与调控的深入研究, 然而纯相BiFeO₃陶瓷的制备一直是材料合成中的难点, 其中一个主要原因是对其相变规律的认识还不充分。本研究采用高温原位X射线衍射技术(HT-XRD)及Rietveld精修定量的方法, 并结合高温拉曼光谱技术(HT-Raman), 系统地研究了不同配比(1 : 1, 1.03 : 1, 1.05 : 1)Bi₂O₃/Fe₂O₃在相同升温速率和保温时间下的反应烧结相变过程, 以及降温时反应产物的热力学稳定性, 同时利用背散射电子衍射(EBSD)技术定性研究了降温冷却后烧结产物的物相分布。结果表明: Bi₂O₃必须经历结构相变(斜方-立方)才能与Fe₂O₃反应生成BiFeO₃, 当Bi过量时, BiFeO₃、Bi₂Fe₄O₉、Bi₂₅FeO₃₉三元产物在降温过程中处于热力学不稳定状态, 能有效抑制杂相的生成, 促进BiFeO₃相生成, 且Bi₂O₃/Fe₂O₃在配比为1.03 : 1时相的纯度最高。结合本课题组前期研究结果, 发现Bi过量以及快速升降温是提高BiFeO₃陶瓷相纯度的有效手段。本研究结果可为制备纯相BiFeO₃基陶瓷提供实验依据。

关键词: 铁酸铋, 元素配比, 反应烧结, 结构相变, 高温X射线衍射

Abstract:

The existence of impuritiy phases such as Bi₂₅FeO₃₉ and Bi₂Fe₄O₉ has led to high leakage current in BiFeO₃ multiferric materials, which consequently restricts further understanding of its coupling between magnetic and polarization orders. Prior to the attempts to synthesize pure-phase BiFeO₃ceramics, the phase transition involved in the reaction sintering should be clarified. In the present, the phase transformations during the reaction sintering process of BiFeO₃ ceramics with different molar ratio of Bi₂O₃/Fe₂O₃in air were studied via High Temperature X-ray Diffraction technique (HT-XRD), Rietveld refinement quantification, and High Temperature Raman Spectroscopy (HT-Raman). The thermal stabilities of BiFeO₃, Bi₂₅FeO₃₉ and Bi₂Fe₄O₉ceramics were also studied by such methods. The qualitative phase distributions after heating were analyzed by Electron Backscattered Diffraction (EBSD). Results show that the phase transition from monoclinic to cubic for Bi₂O₃ was well done, which usually taken place at 700 ℃. The Fe₂O₃ did not react with Bi₂O₃ to form BiFeO₃ until that transition finished. In addition, BiFeO₃, Bi₂₅FeO₃₉ and Bi₂Fe₄O₉phases are not in thermodynamic stable state during the cooling process for Bi excess samples. Bi₂O₃ excess can effectively inhibit the formation of impurities and promote the sintering of BiFeO₃ phase. The phase content of BiFeO₃ mainly depends on the molar ratio of Bi₂O₃/Fe₂O₃, and 1.03 : 1 is optimum. Combining with our previous research results, it is found that the effective parameters for the synthesis of BiFeO₃ strongly depend on the excessive Bi and rapid heating and cooling rate. This work may provide useful experimental guidance for the preparation of pure-phase BiFeO₃ ceramics.

Key words: BiFeO₃, molar ratio of Bi₂O₃/Fe₂O₃, reaction sintering, phase transition, High Temperature X-ray Diffraction

中图分类号:

TQ174

程国峰, 阮音捷, 孙玥, 尹晗迪, 解其云. 元素配比对BiFeO₃反应烧结相变影响的高温X射线衍射研究[J]. 无机材料学报, 2019, 34(10): 1035-1040.

CHENG Guo-Feng, RUAN Yin-Jie, SUN Yue, YIN Han-Di, XIE Qi-Yun. Stoichiometric Ratio on Phase Transformation in Reaction Sintering of BiFeO₃Ceramics Study: a High Temperature X-ray Diffraction Study[J]. Journal of Inorganic Materials, 2019, 34(10): 1035-1040.

图/表 8

图1 (a)0%、(b)3%和(c)5%样品的部分HT-XRD图谱

Fig. 1 HT-XRD patterns of (a) 0%, (b) 3% and (c) 5% samples at selected temperatures

图2 代表性的(900 ℃时3%样品)Rietveld精修图谱

Fig. 2 Observed (black solid lines), calculated (red solid lines) and difference (blue solid lines) XRD patterns of 3% sample at 900 ℃

表1 0%样品在升温过程中的Rietveld定量结果

Table 1 Rietveld quantitative results of 0% sample in the heating process

	600 ℃	700 ℃	750 ℃	800 ℃	850 ℃	900 ℃	930 ℃
BiFeO₃			6.2(5)	23.5(6)	37.9(7)	44.3(8)	53.7(8)
Bi₂Fe₄O₉					18.2(10)	28.6(8)	27.5(9)
Bi₂₅FeO₃₉					29.0(6)	21.9(5)	18.8(6)
Bi₂O₃(C)	9.8(9)	44.4(12)	57.9(10)	48.3(8)
Fe₂O₃	41.6(15)	37.1(14)	35.9(10)	28.2(9)	14.9(9)	5.3(10)
Bi₂O₃(M)	48.6(13)	18.6(8)

表2 3%样品在升温过程中的Rietveld定量结果

Table 2 Rietveld quantitative results of 3% sample in the heating process

	600 ℃	700 ℃	750 ℃	800 ℃	850 ℃	900 ℃
BiFeO₃		10.3(3)	27.9(5)	36.9(13)	73.0(3)	78.6(13)
Bi₂Fe₄O₉				23.1(9)	11.9(13)	7.2(14)
Bi₂₅FeO₃₉				25.0(2)	15.0(2)	14.1(7)
Bi₂O₃(C)	19.7(1)	50.6(7)	44.0(7)
Fe₂O₃	47.9(5)	39.1(7)	28.1(8)	15.2(11)
Bi₂O₃(M)	32.4(5)

表3 5%样品在升温过程中的Rietveld定量结果

Table 3 Rietveld quantitative results of 5% sample in the heating process

	600 ℃	700 ℃	750 ℃	800 ℃	850 ℃	900 ℃
BiFeO₃		6.9(5)	22.7(4)	29.5(5)	54.4(6)	70.6(9)
Bi₂Fe₄O₉				26.2(5)	22.9(7)	18.1(5)
Bi₂₅FeO₃₉				31.1(4)	22.8(4)	18.1(5)
Bi₂O₃(C)	24.0(4)	54.4(8)	47.7(6)
Fe₂O₃	44.0(9)	38.7(9)	29.6(7)	13.2(7)
Bi₂O₃(M)	32.0(5)

图3 降温过程(a)0%、(b)3%和(c)5%样品的物相含量

Fig. 3 Phase contents of (a) 0%, (b) 3% and (c) 5% samples in the cooling process

图4 降温冷却后(a)0%、(b)3%和(c)5%样品的EBSD相分布图

Fig. 4 Phase distribution of (a) 0%, (b) 3% and (c) 5% samples analyzed by EBSD after cooling process

图5 (a)0%、(b)3%和(c)5%样品的部分HT-Raman谱图

Fig. 5 HT-Raman spectra of sample (a) 0%, (b) 3% and (c) 5% at selected temperatures

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元素配比对BiFeO₃反应烧结相变影响的高温X射线衍射研究

Stoichiometric Ratio on Phase Transformation in Reaction Sintering of BiFeO₃Ceramics Study: a High Temperature X-ray Diffraction Study

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