以YbH2-MgO体系为烧结助剂制备高热导率高强度氮化硅陶瓷

doi:10.15541/jim20200705

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 959-966.DOI: 10.15541/jim20200705

所属专题：【结构材料】超高温结构陶瓷

以YbH₂-MgO体系为烧结助剂制备高热导率高强度氮化硅陶瓷

王为得¹^,²(), 陈寰贝³, 李世帅¹^,², 姚冬旭¹(), 左开慧¹, 曾宇平¹

1.中国科学院上海硅酸盐研究所, 上海 200050
2.中国科学院大学, 北京 100049
3.南京电子器件研究所, 南京 210016

收稿日期:2020-12-08 修回日期:2021-01-31 出版日期:2021-09-20 网络出版日期:2021-03-01
通讯作者: 姚冬旭, 副研究员. E-mail: yaodongxu@mail.sic.ac.cn
作者简介:王为得, 博士研究生. E-mail: wangweide@student.sic.ac.cn
基金资助:
国家重点研发计划(2017YFB0310400)

Preparation of Silicon Nitride with High Thermal Conductivity and High Flexural Strength Using YbH₂-MgO as Sintering Additive

WANG Weide¹^,²(), CHEN Huanbei³, LI Shishuai¹^,², YAO Dongxu¹(), ZUO Kaihui¹, ZENG Yuping¹

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Nanjing Electronic Devices Institute, Nanjing 210016, China

Received:2020-12-08 Revised:2021-01-31 Published:2021-09-20 Online:2021-03-01
Contact: YAO Dongxu, associate professor. E-mail: yaodongxu@mail.sic.ac.cn
About author:WANG Weide, PhD candidate. E-mail: wangweide@student.sic.ac.cn
Supported by:
National Key Research and Development Project(2017YFB0310400)

摘要/Abstract

摘要：

以YbH₂-MgO体系为烧结助剂, 采用两步法烧结制备了高热导率高强度氮化硅陶瓷, 研究了YbH₂-MgO对氮化硅致密化行为、相组成、微观形貌、热导率和抗弯强度的影响。在预烧结阶段, YbH₂在还原SiO₂的同时原位生成了Yb₂O₃, 进而形成“缺氧-富氮”液相。该液相不仅有利于晶粒的生长, 更有利于阻碍晶格氧的生成, 相较于Yb₂O₃-MgO助剂体系, β-Si₃N₄晶粒尺寸更大, 晶格缺陷更少, 低热导晶间相更少, 在1900 ℃保温24 h后, 热导率最优可达131.15 W·m^-1·K^-1, 较Yb₂O₃-MgO体系提升13.7%。用YbH₂代替Yb₂O₃, 在低温条件下烧结制备得到的氮化硅抗弯强度有所改善, 在1800 ℃保温4 h的抗弯强度可达(1008±35) MPa; 但在高温烧结时强度略有下降, 这与微观结构的变化密切相关。研究表明, YbH₂-MgO体系是制备高热导率高强度氮化硅陶瓷的有效烧结助剂。

关键词: 氮化硅, YbH₂, 热导率, 抗弯强度

Abstract:

Silicon nitride with high thermal conductivity was obtained by two-step sintering method using YbH₂-MgO as sintering additive. The effect of YbH₂-MgO on shrinkage behavior, phase composition, microstructure, thermal conductivity, and flexural strength was investigated. The nitrogen-riched and oxygen-lacked oxynitride liquid phase was generated owing to the elimination of SiO₂ by YbH₂. Both the removal of lattice oxygen and the growth of β-Si₃N₄ were stimulated by the liquid phase. Therefore, compared to Yb₂O₃-MgO doped sample, silicon nitride with enlarged grains, purified lattice and reduced intergranular phase was obtained. Ultimately, its thermal conductivity increased by 13.7% from 115.32 to 131.15 W·m^-1·K^-1 after sintering at 1900 ℃ for 24 h by substituting Yb₂O₃ with YbH₂. Although the replacement of Yb₂O₃ by YbH₂ leads to enhanced flexural strength at low temperature, it tends to reduce the flexural strength at high temperature. The optimal flexural strength of (1008±35) MPa was achieved after sintering at 1800 ℃ for 4 h. This variation related mainly to the exaggerated bimodal microstructure. This work signifies that YbH₂-MgO is effective for obtaining Si₃N₄ ceramics with both high flexural strength and high thermal conductivity.

Key words: silicon nitride, YbH₂, thermal conductivity, flexural strength

中图分类号:

TQ174

王为得, 陈寰贝, 李世帅, 姚冬旭, 左开慧, 曾宇平. 以YbH₂-MgO体系为烧结助剂制备高热导率高强度氮化硅陶瓷[J]. 无机材料学报, 2021, 36(9): 959-966.

WANG Weide, CHEN Huanbei, LI Shishuai, YAO Dongxu, ZUO Kaihui, ZENG Yuping. Preparation of Silicon Nitride with High Thermal Conductivity and High Flexural Strength Using YbH₂-MgO as Sintering Additive[J]. Journal of Inorganic Materials, 2021, 36(9): 959-966.

图/表 9

图1 (a)YbHM球磨后的元素分布图, (b)α-Si3N4原料、YbHM球磨及预烧结后XRD图谱, (c)YbHM预烧结后的元素分布图

Fig. 1 (a) Elemental distributions of YbHM after ball milling, (b) XRD patterns of α-Si3N4 raw powder, YbHM after ball milling, and YbHM after pre-sintering, (c) elemental distributions of YbHM after pre-sintering

图2 摩尔比为n(YbH2) : n(SiO2)=1 : 1的混合物热处理前后的XRD图谱

Fig. 2 XRD patterns of powder mixture of YbH2 and SiO2 with moler ratio of 1 : 1 before and after pre-sintering

图3 (a)样品原位热收缩行为, (b)不同烧结条件下样品的相对密度, (c)不同烧结条件下样品的失重率

Fig. 3 (a) In-situ observation of shrinkage behaviors of the Si3N4 ceramics, (b) relative density after gas-pressure sintering, and (c) weight loss after gas-pressure sintering

图4 1900 ℃ 保温4及24 h后样品的XRD图谱

Fig. 4 XRD patterns of Si3N4 samples after being sintered at 1900 ℃ for 4 and 24 h

图5 1900 ℃保温12 h后YbHM样品的元素分布

Fig. 5 Elemental distributions of sample YbHM after being sintered at 1900 ℃ for 12 h

图6 样品抛光面的SEM照片

图7 样品晶间相组成分析

Fig. 7 EDS analysis of the intergranular phases in YbOM and YbHM specimens

图8 不同烧结条件得到样品的(a)热导率和(b)抗弯强度

Fig. 8 (a) Thermal conductivities and (b) flexural strengths of Si3N4 samples after gas pressure sintering

表1 添加不同种类稀土氢化物作为烧结助剂制备得到氮化硅陶瓷的热导率

Table 1 Thermal conductivities of Si3N4 doped with different rare-earth hydride

Additive	Ionic radius /nm	Annealing time at 1900 ℃/h	Thermal conductivity /(W·m^-1·K^-1)
GdH₂ ^[25]	0.094	4 h	98.07
		12 h	119.07
		24 h	134.90
YH₂ ^[23]	0.089	4 h	101.80
		12 h	123.00
		24 h	131.60
YbH₂	0.086	4 h	100.20
		12 h	118.90
		24 h	131.15

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以YbH₂-MgO体系为烧结助剂制备高热导率高强度氮化硅陶瓷

Preparation of Silicon Nitride with High Thermal Conductivity and High Flexural Strength Using YbH₂-MgO as Sintering Additive

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