Hf-Si-La-O-N体系中HfN的形成及相关系

doi:10.15541/jim20200382

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 443-448.DOI: 10.15541/jim20200382 CSTR: 32189.14.10.15541/jim20200382

• 研究论文 • 上一篇

Hf-Si-La-O-N体系中HfN的形成及相关系

刘洋(), 陆有军(), 李彦瑞, 林立群, 袁振侠, 黄振坤

北方民族大学材料科学与工程学院, 银川 750021

收稿日期:2020-07-07 修回日期:2020-08-20 出版日期:2021-04-20 网络出版日期:2020-09-20
通讯作者: 陆有军, 教授. E-mail: youjunlu518@hotmail.com
作者简介:刘洋(1995-), 男, 硕士研究生. E-mail: Yang.Liu_CN@hotmail.com
基金资助:
国家自然科学基金(51662002);国家自然科学基金(51762002);宁夏重点研发计划项目(2018YBZD0625);宁夏重点研发计划项目(2019BFH02021)

HfN Formation and Phase Relationships in the Hf-Si-La-O-N System

LIU Yang(), LU Youjun(), LI Yanrui, LIN Liqun, YUAN Zhenxia, HUANG Zhenkun

School of Materials Science and Engineering, North Minzu University, Yinchuan 750021, China

Received:2020-07-07 Revised:2020-08-20 Published:2021-04-20 Online:2020-09-20
Contact: LU Youjun, professor. E-mail: youjunlu518@hotmail.com
About author:LIU Yang(1995-), male, Master candidate. E-mail: Yang.Liu_CN@hotmail.com
Supported by:
Natural Science Foundation of China(51662002);Natural Science Foundation of China(51762002);Key Research and development plan of Ningxia(2018YBZD0625);Key Research and development plan of Ningxia(2019BFH02021)

摘要/Abstract

摘要：

本研究探讨了一步法制备HfN复合硅酸镧盐陶瓷材料的可行性和配方设计问题, 并对HfO₂-Si₃N₄-La₂O₃三元系统反应合成HfN进行了实验验证。因为在HfO₂-Si₃N₄-La₂O₃三元系统的反应过程中涉及到硅酸镧盐Si₃N₄-SiO₂- La₂O₃系统, 所以将其延伸为HfO₂-Si₃N₄-La₂O₃-SiO₂-HfN (Hf-Si-La-O-N)五元系统, 研究了HfO₂-Si₃N₄二元系统的反应途径以及Hf-Si-La-O-N体系的相关系, 阐明了HfN与系统内镧盐相的共存关系, 并绘制了HfO₂-SiO₂-La₂O₃三元系统和Hf-Si-La-O-N五元系统1500 ℃的实验相图, 提出的HfO₂-Si₃N₄-La₂O₃截面图为HfN复合硅酸镧盐陶瓷材料的配方设计提供了思路。实验发现: HfO₂-Si₃N₄二元系统高温下合成HfN的反应中存在中间产物Hf₇O₈N₄; 引入La₂O₃促进了系统生成HfN, 并降低了陶瓷烧失率; Hf-Si-La-O-N五元系统内存在HfN与La_4.67Si₃O₁₃、La₅Si₃NO₁₂、LaSiNO₂、La₄Si₂N₂O₇和La₂Hf₂O₇五种镧盐的共存相。

关键词: 氮化铪, 氧化铪-氮化硅-氧化镧, 相关系, 复合物相

Abstract:

In this study, the synthesis is feasibility and formulation design of HfN composite lanthanum silicate ceramics were explored. The feasibility of HfN synthesis by ternary reaction of HfO₂-Si₃N₄-La₂O₃ system was verified by experiments, and the relationship between reaction pathway of HfO₂-Si₃N₄ binary system and Hf-Si-La-O-N was studied. Considering that the lanthanum silicate salt in the reaction of HfO₂-SiO₂-La₂O₃ ternary system was contained in the Si₃N₄-SiO₂-La₂O₃ system, lanthanum silicate was extended to the HfO₂-Si₃N₄-La₂O₃-SiO₂-HfN (Hf-Si-La-O-N) system, which clarified the coexistence of HfN and the lanthanum salt phases in the system. Experimental phase diagrams of HfO₂-SiO₂-La₂O₃ ternary system and Hf-Si-La-O-N system at 1500 ℃ were proposed. The results show that intermediate product Hf₇O₈N₄ formed in the synthesis of HfN at high temperature in HfO₂-Si₃N₄ binary system. Introduction of La₂O₃ promoted the system to generate HfN which was beneficial to reduce the burning loss rate of ceramics. There existed HfN and La_4.67Si₃O₁₃, La₅Si₃NO₁₂, LaSiNO₂, La₄Si₂N₂O₇, La₂Hf₂O₇ five lanthanum salt phases in the Hf-Si-La-O-N system.

Key words: hafnium nitride, hafnium oxide-silicon nitride-lanthanum oxide, phase relationship, composite phase

中图分类号:

TQ174

刘洋, 陆有军, 李彦瑞, 林立群, 袁振侠, 黄振坤. Hf-Si-La-O-N体系中HfN的形成及相关系[J]. 无机材料学报, 2021, 36(4): 443-448.

LIU Yang, LU Youjun, LI Yanrui, LIN Liqun, YUAN Zhenxia, HUANG Zhenkun. HfN Formation and Phase Relationships in the Hf-Si-La-O-N System[J]. Journal of Inorganic Materials, 2021, 36(4): 443-448.

图/表 12

参考文献 24

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Sample	n(Si₃N₄) : n(HfO₂)	T/℃	Phase composition by XRD	Mass loss/%
1Si1.5Hf	1 : 1.5	1400	HfO₂, Hf₇O₈N₄, Si₃N₄	8.1
		1600	HfO₂, Hf₇O₈N₄, Si₃N₄, HfN	18.3
		1800	HfO₂, HfN	26.4

Sample	n(Si₃N₄) : n(HfO₂)	T/℃	Phase composition by XRD	Mass loss/%
1Si1.5Hf	1 : 1.5	1400	HfO₂, Hf₇O₈N₄, Si₃N₄	8.1
		1600	HfO₂, Hf₇O₈N₄, Si₃N₄, HfN	18.3
		1800	HfO₂, HfN	26.4

Sample	n(HfO₂) : n(SiO₂) : n(La₂O₃)	Phase composition by XRD (1500 ℃)	Mass loss/%
a	6 : 5 : 14	La₂O₃, La₂Hf₂O₇, La₂SiO₅	1.30
b	12 : 45 : 43	La₂Hf₂O₇, La_4.67Si₃O₁₃, La₂SiO₅	1.60
c	12 : 3 : 5	HfO₂, La₂Hf₂O₇, La_4.67Si₃O₁₃	0.80
d	9 : 26 : 15	HfO₂, La₂Si₂O₇, La_4.67Si₃O₁₃	1.10
e	5 : 4 : 1	HfO₂, La₂Si₂O₇, HfSiO₄	1.90
f	15 : 73 : 12	SiO₂, La₂Si₂O₇, HfSiO₄	2.30
a′	2 : 1 : 2	La₂SiO₅, La₂Hf₂O₇	1.13
b′	2 : 3 : 3	La_4.67Si₃O₁₃, La₂Hf₂O₇	0.96
c′	5 : 3 : 2	La_4.67Si₃O₁₃, HfO₂	0.87
d′	1 : 2 : 1	La₂Si₂O₇, HfO₂	0.23
e′	1 : 3 : 1	La₂Si₂O₇, HfSiO₄	1.20

Sample	n(HfO₂) : n(SiO₂) : n(La₂O₃)	Phase composition by XRD (1500 ℃)	Mass loss/%
a	6 : 5 : 14	La₂O₃, La₂Hf₂O₇, La₂SiO₅	1.30
b	12 : 45 : 43	La₂Hf₂O₇, La_4.67Si₃O₁₃, La₂SiO₅	1.60
c	12 : 3 : 5	HfO₂, La₂Hf₂O₇, La_4.67Si₃O₁₃	0.80
d	9 : 26 : 15	HfO₂, La₂Si₂O₇, La_4.67Si₃O₁₃	1.10
e	5 : 4 : 1	HfO₂, La₂Si₂O₇, HfSiO₄	1.90
f	15 : 73 : 12	SiO₂, La₂Si₂O₇, HfSiO₄	2.30
a′	2 : 1 : 2	La₂SiO₅, La₂Hf₂O₇	1.13
b′	2 : 3 : 3	La_4.67Si₃O₁₃, La₂Hf₂O₇	0.96
c′	5 : 3 : 2	La_4.67Si₃O₁₃, HfO₂	0.87
d′	1 : 2 : 1	La₂Si₂O₇, HfO₂	0.23
e′	1 : 3 : 1	La₂Si₂O₇, HfSiO₄	1.20

Sample	n(HfO₂) : n(Si₃N₄) : n(La₂O₃)	Expected product	Phase composition by XRD (1500 ℃)	Mass loss/%
1	1 : 1/3 : 1	HfN, La₂SiO₅	HfN(w), La₂Hf₂O₇(s), La₅Si₃NO₁₂(vs)	3.20
2	2 : 2/3 : 1	HfN, La₂Si₂O₇	HfN(vs), La₂Hf₂O₇(s), La_4.67Si₃O₁₃(w), Si₃N₄(vw)	2.40
3	3 : 1 : 7/3	HfN, La_4.67Si₃O₁₃	HfN(vs), La₂Hf₂O₇(s), La_4.67Si₃O₁₃(s)	4.70
4	9/4 : 1 : 5/2	HfN, La₅Si₃NO₁₂	HfN(s), La₅Si₃NO₁₂(vs), La₂Hf₂O₇(w)	4.20
5	1/4 : 1/3 : 1/2	HfN, LaSiNO₂	HfN(w), LaSiNO₂(vs)	3.70
6	1/2 : 2/3 : 2	HfN, La₄Si₂N₂O₇	HfN(w), La₅Si₃NO₁₂ (vw), La₄Si₂N₂O₇(s)	4.40

Hf-Si-La-O-N体系中HfN的形成及相关系

HfN Formation and Phase Relationships in the Hf-Si-La-O-N System

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