Si3N4-ZrO2-La2O3系统反应合成ZrN及相图构建

doi:10.15541/jim20190404

摘要/Abstract

摘要：

本工作研究了Si₃N₄-ZrO₂-La₂O₃三元系统的相关系, 采用X射线衍射仪分析了物相组成。结果表明, 在1500 ℃/1 h/N₂气氛条件下固相反应, 生成了ZrN和La_4.67Si₃O₁₃、La₅Si₃NO₁₂、La₄Si₂N₂O₇、LaSiNO₂、La₂Zr₂O₇等镧盐化合物的共存相。由于生成的氮化锆和硅酸镧等化合物不在Si₃N₄-ZrO₂-La₂O₃三元系统内, 需引入SiO₂测定SiO₂-La₂O₃-ZrO₂三元分系统相图, 进而扩大成Si₃N₄-ZrO₂-La₂O₃-SiO₂-ZrN五元系统, 本工作绘制并提出了此五元系统相图, 且提出了1570 ℃时SiO₂-La₂O₃-ZrO₂三元分系统实验相图。此外, 验证了La₂O₃在Si₃N₄-ZrO₂-La₂O₃三元系统反应中促进Si₃N₄-ZrO₂取代反应生成ZrN的作用。

关键词: 氮化锆, 相关系, 固相反应, 复相陶瓷

Abstract:

Si₃N₄-ZrO₂-La₂O₃ ternary system were prepared via solid-state reaction at 1500 ℃ for 1 h with N₂ protection, yielding coexistence phase of ZrN and lanthanum-based compounds, such as La_4.67Si₃O₁₃, La₅Si₃NO₁₂, La₄Si₂N₂O₇, LaSiNO₂, and La₂Zr₂O₇. Since the generated ZrN and lanthanum-based compounds are not located on the triangle plane of Si₃N₄-ZrO₂-La₂O₃ system, it is necessary to add SiO₂ to extend the ternary into quinary system of Si₃N₄-SiO₂-La₂O₃-ZrO₂-ZrN. After the phase diagram of this quinary system is confirmed and presented, the phase diagram of La₂O₃-SiO₂-ZrO₂ ternary subsystem at 1570 ℃ is further proposed for the first time. In addition, La₂O₃ in the Si₃N₄-ZrO₂-La₂O₃ ternary system can help to simulate the substitution reaction between Si₃N₄ and ZrO₂ to produce ZrN.

Key words: zirconium nitride, phase relationships, solid state reaction, multiphase ceramics

中图分类号:

TQ174

李彦瑞,陆有军,刘洋,袁振侠,黄振坤. Si₃N₄-ZrO₂-La₂O₃系统反应合成ZrN及相图构建[J]. 无机材料学报, 2020, 35(7): 822-826.

LI Yanrui,LU Youjun,LIU Yang,YUAN Zhenxia,HUANG Zhenkun. Reaction Synthesizes of ZrN and Phase Diagram in the Si₃N₄-ZrO₂-La₂O₃ System[J]. Journal of Inorganic Materials, 2020, 35(7): 822-826.

图/表 9

表1 SiO2-La2O3-ZrO2系统样品在1570 ℃烧结后的相组成

Table 1 Phase compositions of the SiO2-La2O3-ZrO2 system after sintered at 1570 ℃

Sample	SiO₂/La₂O₃/ZrO₂	Phase composition (XRD analysis results*)
0.3S′0.5Z0.2L	0.3/0.5/0.2	La₂Zr₂O₇(s) La₂SiO₅(m) La₂O₃(w)
0.43S′0.46Z0.11L	0.43/0.46/0.11	La₂Zr₂O₇(s) La_4.67Si₃O₁₃(s) La₂SiO₅(m)
0.2S′0.3Z0.5L	0.2/0.3/0.5	La₂Zr₂O₇(vs) La_4.67Si₃O₁₃(vs) ZrO₂(w)
0.5S′0.3Z0.2L	0.5/0.3/0.2	La₂Si₂O₇(vs) La_4.67Si₃O₁₃(vs) ZrO₂(w)
0.4S′0.1Z0.5L	0.4/0.1/0.5	ZrSiO₄(vs) La₂Si₂O₇(s) ZrO₂(m)
0.7S′0.1Z0.2L	0.7/0.1/0.2	ZrSiO₄(vs) La₂Si₂O₇(m) SiO₂(w)

图1 (a) 0.3S′0.5Z0.2L和0.43S′0.46Z0.11L, (b) 0.2S′0.3Z0.5L和0.5S′0.3Z0.2L及(c) 0.4S′0.1Z0.5L和0.7S′0.1Z0.2L系统样品在1570 ℃恒温1 h的XRD图谱

Fig. 1 XRD patterns of the samples of 0.3S′0.5Z0.2L and 0.43S′0.46Z0.11L (a), 0.2S′0.3Z0.5L and 0.5S′0.3Z0.2L (b),0.4S′0.1Z0.5L and 0.7S′0.1Z0.2L (c) sintered at 1570 ℃ for 1 h

图2 SiO2-La2O3-ZrO2三元系统在1570 ℃的相图

Fig. 2 Phase diagram of SiO2-La2O3-ZrO2 ternary system at 1570 ℃

表2 Si3N4-ZrO2-La2O3系统1500 ℃烧结样品的相组成

Table 2 Phase compositions of the Si3N4-ZrO2-La2O3 system samples at 1500 ℃

Sample	Si₃N₄/ZrO₂/La₂O₃	Phase composition (XRD analysis results*)
1S3Z3L	1/3/3	La₅Si₃NO₁₂(s) La₂Zr₂O₇(s) ZrN(m)
2S6Z3L	2/6/3	La_4.67Si₃O₁₃ (vs) ZrN(vs)
		ZrO₂(vw)
3S9Z7L	3/9/7	La_4.67Si₃O₁₃(vs) ZrN(m),
4S9Z10L	4/9/10	La₅Si₃NO₁₂₍vs) ZrN(m)
4S3Z6L	4/3/6	LaSiNO₂ (vs) ZrN(w) La₅Si₃NO₁₂(w)
4S3Z12L	4/3/12	La₄Si₂N₂O₇(vs) ZrN(w) La₅Si₃NO₁₂(w)
8S3Z8L (1550 ℃)	8/3/8	LaSiNO₂(vs) ZrN(w) La₂Si₆N₈O₃(w)

表3 反应(4)的热力学计算结果

Table 3 (4)Thermodynamic calculation results of reaction formula

T/℃	ΔG/(kJ·mol^-1)	T/℃	ΔG/(kJ·mol^-1)
1400	-122.513	1600	-139.531
1500	-130.893	1700	-148.436

图3 1S3Z3L和2S6Z3L系统样品在1500 ℃恒温1 h后的XRD图谱

Fig. 3 XRD patterns of the samples 1S3Z3L and 2S6Z3L after sintered at 1500 ℃ for 1 h

图4 Si3N4-ZrO2-La2O3三元系统在1500 ℃的相图

Fig. 4 Phase diagram of Si3N4-ZrO2-La2O3 ternary system at 1500 ℃

图5 (a) 3S9Z7L和4S9Z10L、(b) 4S3Z6L和4S3Z12L系统样品在1500 ℃恒温1 h后, 以及(c) 8S3Z8L系统样品在1550 ℃和2S0Z3L系统样品在1500 ℃恒温1 h后的XRD图谱

Fig. 5 XRD patterns of the samples (a) 3S9Z7L and 4S9Z10L, (b) 4S3Z6L and 4S3Z12L after sintered at 1500 ℃ for 1 h, and (c) 8S3Z8L after sintered at 1550 ℃ for 1 h and the samples 2S0Z3L after sintered at 1500 ℃ for 1 h

图6 Si3N4-ZrO2-La2O3-SiO2-ZrN五元系统在1500 ℃的相图

Fig. 6 Phase diagram of Si3N4-ZrO2-La2O3-SiO2-ZrN quinary system at 1500 ℃

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Si₃N₄-ZrO₂-La₂O₃系统反应合成ZrN及相图构建

Reaction Synthesizes of ZrN and Phase Diagram in the Si₃N₄-ZrO₂-La₂O₃ System

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