硅酸盐学报

含烧结助剂氮化硅陶瓷粉体的先驱体法制备及其烧结

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李天昊 ¹^,² , 张健宁 ¹^,² , 何流 ¹^,² , 宋育杰 ¹^,²^,³

硅酸盐学报 | 聚合物先驱体陶瓷专题—研究论文 2024,52(9): 2767-2772

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硅酸盐学报 |聚合物先驱体陶瓷专题—研究论文 2024 , 52 (9) : 2767 -2772

含烧结助剂氮化硅陶瓷粉体的先驱体法制备及其烧结

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李天昊¹^,², 张健宁¹^,², 何流¹^,², 宋育杰¹^,²^,³

作者信息

^1．宁波杭州湾新材料研究院，浙江宁波 315336

^2．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

^3．先进能源科学与技术广东省实验室，广东惠州 516029

通讯作者:

宋育杰（1986—），男，博士，研究员。

作者简介:

李天昊（1992—），男，博士，助理研究员。

Preparation and Sintering of Silicon Nitride Ceramic Powders with Sintering Additives via Precursor Method

Tianhao LI¹^,², Jianning ZHANG¹^,², Liu HE¹^,², Yujie SONG¹^,²^,³

Affiliations

^1.Qianwan Institute of CNITECH, Ningbo 315336, Zhejiang, China

^2.Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

^3.Advanced Energy Science and Technology Guangdong Laboratory, Huizhou 516029, Guangdong, China

Corresponding Author:

SONG Yujie (1986-), male, Ph.D., Professor. E-mail: songyujie@nimte.ac.cn

LI Tianhao (1992-), male, Ph.D., Assistant Professor. E-mail: litianhao2057@nimte.ac.cn

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20240138

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摘要

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将金属钇和镁接枝三甲基硅基取代聚硅氮烷先驱体中，先驱体在热解过程中就可以原位生成金属氮化物烧结助剂，烧结助剂含量可通过钇、镁的接枝量进行精准调控。热解陶瓷为高纯氮化硅陶瓷，碳元素含量低于0.1%（质量分数），氧元素含量低于1.6%。含烧结助剂的氮化硅陶瓷可直接低温烧结制备高纯多孔氮化硅陶瓷块体，相对密度可达到99.4%，具有良好的硬度和导热性能。原位生成烧结助剂避免了额外添加烧结助剂造成的杂质引入和混合不均匀的问题，在高纯陶瓷烧结领域具有独特的优势。

关键词

氮化硅 / 先驱体 / 烧结助剂 / 原位 / 多孔陶瓷

Abstract

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Introduction

Uniform distribution in molecular level of ceramics could be achieved by polymer-derived method. Comparing to other methods, fewer crystal seeds existed in microstructure of polymer-derived ceramics, which made it more difficult to sinter. Up to now, few reports focused on the direct sintering of the polymer-derived ceramics. For silicon nitride sintering, the introduction of metal oxide additives caused defects in the lattice of silicon nitride because of oxygen atoms, which could affect the properties of the material. This work focused on the sintering behavior of polymer-derived ceramics and the issue of performance degradation caused by introducing oxygen elements in sintering additives. The metal elements were connected to the precursor molecule and formed the metal nitride sintering additives during pyrolysis process. The method could help to achieve the in-situ non-oxygen addition and uniformly mixing of sintering additives, and the followed low-temperature sintering could achieve the high-purity silicon nitride ceramics.

Methods

4 mL of propylamine was added into a solution of trimethylsilyl chlorosilane monomer (14 g), yttrium chloride (0.14 g) and magnesium chloride (0.085 g) in pyridine (20 mL) at room temperature in N₂ atmosphere. The mixture was warmed up to 120 ℃ and stirred for 2 d. The mixture was then heated to 400 ℃ for 4 h in N₂ atmosphere and further heated to 1 000 ℃ with the rate of 10 ℃/min, finally the mixture were holding at 1 000 ℃ for 4 h and then cooled to room temperature naturally. A white silicon nitride powder SiN-1 was obtained. Silicon nitride powders SiN-2 and SiN-3 were prepared by the same method, in which 0.055 g magnesium chloride was added in SiN-2 and no magnesium chloride was added in sample SiN-3. Silicon nitride ceramics was prepared through spark plasma sintering of silicon nitride powders in 1 450 ℃, 45 MPa for 30 min. Before characterization of the silicon nitride ceramics, surface of it was pre-polished.

Results and discussion

Based on trimethylsilyl-substituted polysilazane precursors, the Y and Mg elements were successfully connected to N with the reaction of M-Cl to N-H and coordination. Through pyrolosis process, three kinds of ceramic powders SiN-1, SiN-2 and SiN-3 were obtained. The main component of these powders was silicon nitride, and content of C was below 0.1%, that of O was below 1.6%. As the content of metal decreased, there is a slight decrease in oxygen contents, being due to the high reactivity of metal nitrides. When treated at 1 000 ℃, a large amount of amorphous silicon nitrides with small amount of magnesium nitrides via the dope of magnesium. Small amount of YSi₃N₅ with Si₃N₄ via the dope of yttrium. When ceramics were heated to 1 500 ℃, amorphous silicon nitride began to crystallize, and sample SiN-3 only contained α-Si₃N₄. As the amount of magnesium increased, the content of β-Si₃N₄ crystal gradually increased. These results demonstrate that magnesium nitrides could promoted the transformation of amorphous Si₃N₄ to β-Si₃N₄ crystalline, while yttrium nitrides activated the lattice of Si₃N₄ crystal.

Silicon nitride ceramics were prepared by spark plasma sintering when three types of silicon nitride ceramic powders acted as main raw materials, but only SiN-1 powders with the highest magnesium content could obtain pure β-Si₃N₄. The frame of the obtained ceramics was mainly composed of stacked rod-shaped β-Si₃N₄ crystals. These results prove that the pores in porous ceramics were mainly through-pores, and few closed-pores. The porous ceramics showed a hardness of 29.1 GPa, an elastic modulus of 229.1 GPa, which attributed to the speical porous structure. At 25 ℃, the ceramics possessed a thermal conductivity of 20.451 (W/m·K), a specific heat capacity of 0.355 J/(g·K), a thermal diffusion coefficient of 18.169 mm²/s, and an overall thermal expansion coefficient less than 4×10^-6/K in the range of room temperature to 1 200 ℃. Due to the presence of pores, a significant decrease in thermal conductivity and thermal diffusion coefficient can be obtained, while the coefficient of thermal expansion remained relatively low.

Conclusions

Metal element Y and Mg were successfully connected to trimethylsilyl-substituted polysilazane precursors and contents could be adjusted as needed. Metal nitride sintering additives were in-situ generated during pyrolysis process and polymer-derived high-purity silicon nitride ceramics with sintering additives were prepared. This method could help to achieve both in-situ non- oxygen addition and molecular level uniform mixing of sintering additives in ceramic powders. Low-temperature sintering could help to achieve the silicon nitride ceramic powders which resulting in the obtained silicon nitride ceramics with good mechanical and thermal properties.

Key words

silicon nitride / precursor / sintering additive / in situ / porous

引用本文

李天昊, 张健宁, 何流, 宋育杰. 含烧结助剂氮化硅陶瓷粉体的先驱体法制备及其烧结. 硅酸盐学报, 2024 , 52 (9) : 2767 -2772 . DOI: 10.14062/j.issn.0454-5648.20240138

Tianhao LI, Jianning ZHANG, Liu HE, Yujie SONG. Preparation and Sintering of Silicon Nitride Ceramic Powders with Sintering Additives via Precursor Method[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2767 -2772 . DOI: 10.14062/j.issn.0454-5648.20240138

基金

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国家重点研发计划(2021YFB3200500)
宁波3315计划(2018 A-03-A)
先进能源科学与技术广东省实验室(HND20TDTH GC00)

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2024年第52卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240138

接收时间：2022-02-22
首发时间：2026-10-22
出版时间：2024-09-20

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收稿日期：2022-02-22
修回日期：2024-03-16

基金

国家重点研发计划(2021YFB3200500)

宁波3315计划(2018 A-03-A)

先进能源科学与技术广东省实验室(HND20TDTH GC00)

作者信息

^1．宁波杭州湾新材料研究院，浙江宁波 315336

^2．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

^3．先进能源科学与技术广东省实验室，广东惠州 516029

通讯作者:

宋育杰（1986—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240138

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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