CN115073186B - 一种氮化硅陶瓷烧结体及其制备方法 - Google Patents

一种氮化硅陶瓷烧结体及其制备方法 Download PDF

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CN115073186B
CN115073186B CN202210865969.XA CN202210865969A CN115073186B CN 115073186 B CN115073186 B CN 115073186B CN 202210865969 A CN202210865969 A CN 202210865969A CN 115073186 B CN115073186 B CN 115073186B
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silicon nitride
sintered body
ceramic sintered
nitride ceramic
content
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CN115073186A (zh
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王鲁杰
乔竹辉
李彤阳
王梓岳
于源
汤华国
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Yantai Advanced Materials And Green Manufacturing Shandong Laboratory
Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute
Lanzhou Institute of Chemical Physics LICP of CAS
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Yantai Advanced Materials And Green Manufacturing Shandong Laboratory
Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute
Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明属于陶瓷材料技术领域，具体涉及一种氮化硅陶瓷烧结体及其制备方法。本发明提供的氮化硅陶瓷烧结体中氮化硅结晶相的含量≥98wt％；相对密度≥99％；气孔率≤1％；晶界相元素包括Li元素、O元素、N元素和Si元素；氮化硅陶瓷烧结体中C元素、F元素、Al元素、Mg元素、K元素、Ca元素、Na元素和稀土金属元素的总含量＜0.1wt％。本发明提供的氮化硅陶瓷烧结体氮化硅晶粒排布密集，同时具有高纯度和高致密化的特点，且高温力学性能优异。本发明提供的制备方法将氮化硅粉体和氧化锂源混合进行烧结，以氧化锂源作为烧结助剂，能够烧结得到的氮化硅陶瓷同时具有高纯度和高致密化的特点，且高温力学性能优异。

Description

一种氮化硅陶瓷烧结体及其制备方法
技术领域
本发明属于陶瓷材料技术领域，具体涉及一种氮化硅陶瓷烧结体及其制备方法。
背景技术
氮化硅陶瓷具有优异的高温性能、化学稳定性、力学性能，一直受到人们的广泛关注。而且随着航天、工业等领域的发展，氮化硅陶瓷的性能要求不断提高。
氮化硅陶瓷传统成型方法都是将粉体或者含粉体的料浆进行模具成型，通过烧结等后处理得到陶瓷构件，再通过微加工得到满足要求的陶瓷件。由于氮化硅在烧结过程中发生α相向β相的晶体相变，必然存在Si-N化学键的断裂和生成，而Si-N属于高能共价键，键断裂和键生成均需要较高的能量，导致烧结过程中原子扩散系数比较低，烧结困难。因此，氮化硅的烧结时通常需要加入烧结助剂，以提高氮化硅陶瓷的可烧结性。
氮化硅陶瓷烧结体使用的常规烧结助剂包括金属氧化物和稀土氧化物，具体包括有Al2O3、MgO、ZrO2、SiO2、稀土氧化物等，烧结助剂一般占粉体原料的含量为3～15wt％，最终的氮化硅陶瓷烧结体中烧结助剂会以氮化硅晶粒间玻璃相的形式存在于氮化硅陶瓷烧结体中，但是烧结助剂的高含量对氮化硅陶瓷烧结体的纯度、高温力学性能和导热性能均造成了不利的影响。
发明内容
本发明的目的在于提供一种氮化硅陶瓷烧结体及其制备方法，本发明提供的氮化硅陶瓷烧结体同时具有高纯度和高致密化的特点，且高温力学性能优异。
为了实现上述目的，本发明提供如下技术方案：
本发明提供了一种氮化硅陶瓷烧结体，所述氮化硅陶瓷烧结体中氮化硅结晶相的含量≥98wt％；所述氮化硅陶瓷烧结体的相对密度≥99％；所述氮化硅陶瓷烧结体的气孔率≤1％；所述氮化硅陶瓷烧结体的晶界相元素包括Li元素、O元素、N元素和Si元素；所述氮化硅陶瓷烧结体中C元素、F元素、Al元素、Mg元素、K元素、Ca元素、Na元素和稀土金属元素的总含量＜0.1wt％。
优选的，所述氮化硅陶瓷烧结体中Li元素、O元素、N元素和Si元素的总含量为99.7～100wt％。
优选的，所述氮化硅陶瓷烧结体中Li元素的含量为0.15～0.6wt％。
优选的，所述氮化硅陶瓷烧结体中O元素的含量＜2wt％。
优选的，所述氮化硅陶瓷烧结体中氮化硅结晶相的晶粒尺寸为0.3～20μm。
本发明提供了上述技术方案所述的氮化硅陶瓷烧结体的制备方法，包括以下步骤：
将氮化硅粉体和氧化锂源混合得到混合体；所述氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种；
将所述混合体置于模具中在保护气体氛围中进行烧结，得到所述氮化硅陶瓷烧结体。
优选的，所述氧化锂源中的锂元素在所述混合体中的含量为0.15～0.7wt％。
优选的，所述烧结为热压烧结或放电等离子体烧结；所述烧结的温度为1350～1800℃，所述烧结的压力为10～80MPa，所述烧结的保温保压时间为0.5～5h。
优选的，所述氮化硅粉体的粒径为0.01～20μm；所述氮化硅粉体中氧元素的含量≤1.6wt％，所述氮化硅粉体中金属杂质元素的含量≤0.2wt％。
优选的，所述混合为湿式球磨混合，所述湿式球磨混合的球磨介质包括乙醇和/或水，所述氮化硅粉体和所述氧化锂源的总质量与所述球磨介质的质量比为1:1，所述氮化硅粉体和所述氧化锂源的总质量与研磨球的质量比为1:(2～3)；所述湿式球磨混合的转速为150～300rpm，所述湿式球磨混合的时间为2～10h。
本发明提供了一种氮化硅陶瓷烧结体，所述氮化硅陶瓷烧结体中氮化硅结晶相的含量≥98wt％；所述氮化硅陶瓷烧结体的相对密度≥99％；所述氮化硅陶瓷烧结体的气孔率≤1％；所述氮化硅陶瓷烧结体的晶界相元素包括Li元素、O元素、N元素和Si元素；所述氮化硅陶瓷烧结体中C元素、F元素、Al元素、Mg元素、K元素、Ca元素、Na元素和稀土金属元素的总含量＜0.1wt％。本发明提供的氮化硅陶瓷烧结体晶界相元素包括Li元素、O元素、N元素和Si元素，氮化硅晶粒排布密集，同时具有高纯度和高致密化的特点，且高温力学性能优异。
本发明提供了上述技术方案所述的氮化硅陶瓷烧结体的制备方法，包括以下步骤：将氮化硅粉体和氧化锂源混合得到混合体；所述氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种；将所述混合体置于模具中在保护气体氛围中进行烧结，得到所述氮化硅陶瓷烧结体。本发明提供的制备方法以氧化锂源作为烧结助剂，其中，氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种，所述氧化锂源为在保护气体氛围中烧结时形成氧化锂且不产生其他固体杂质的物质，所述氧化锂源在氮化硅粉体烧结过程中利用活泼的锂元素辅助Si-N化学键的断裂与生成，提高烧结过程中氮化硅粉体中的原子扩散系数，促进氮化硅由α相向β相转变，提高氮化硅粉体的可烧结性能，且促进β相氮化硅晶粒长大，不仅能够制备得到氮化硅陶瓷烧结体，且由于氧化锂源的用量少，烧结体中氮化硅晶粒之间的晶界相含量少，从而烧结得到的氮化硅陶瓷同时具有高纯度和高致密化的特点，且高温力学性能优异。
具体实施方式
本发明提供了一种氮化硅陶瓷烧结体，所述氮化硅陶瓷烧结体中氮化硅结晶相的含量≥98wt％；所述氮化硅陶瓷烧结体的相对密度≥99％；所述氮化硅陶瓷烧结体的气孔率≤1％；所述氮化硅陶瓷烧结体的晶界相元素包括Li元素、O元素、N元素和Si元素；所述氮化硅陶瓷烧结体中C元素、F元素、Al元素、Mg元素、K元素、Ca元素、Na元素和稀土金属元素的总含量＜0.1wt％。
在本发明中，所述氮化硅陶瓷烧结体中Li元素的含量优选为0.15～0.6wt％，更优选为0.2～0.55wt％。
在本发明中，所述氮化硅陶瓷烧结体中O元素的含量优选＜2wt％
在本发明中，所述氮化硅陶瓷烧结体中Li元素、O元素、N元素和Si元素的总含量优选为99.7～100wt％。
在本发明中，所述氮化硅陶瓷烧结体中氮化硅结晶相的平均晶粒尺寸优选为0.3～20μm。
本发明提供了一种氮化硅陶瓷烧结体的制备方法，包括以下步骤：
将氮化硅粉体和氧化锂源混合得到混合体；所述氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种；
将所述混合体置于模具中在保护气体氛围中进行烧结，得到所述氮化硅陶瓷烧结体。
在本发明中，若无特殊说明，所有制备原料/组分均为本领域技术人员熟知的市售产品。
本发明将氮化硅粉体和氧化锂源混合得到混合体；所述氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种。
在本发明中，所述氮化硅粉体的粒径优选为0.01～20μm，更优选为0.05～15μm，进一步优选为1～10μm。
在本发明中，所述氮化硅粉体中氧元素的含量优选≤1.6wt％，更优选≤1.5wt％。
在本发明中，所述氮化硅粉体中金属杂质元素的含量优选≤0.2wt％，更优选≤0.15wt％。
在本发明中，所述氧化锂源优选包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、LiOCH(CH3)2和C2H5OLi中的任意一种。
在本发明中，所述所述氧化锂源为在保护气体氛围中烧结时形成氧化锂且不产生其他固体杂质的物质。
在本发明中，所述氧化锂源中的锂元素在所述混合体中的含量为0.15～0.7wt％，优选为0.15～0.6wt％。
在本发明中，所述氧化锂源中的锂元素在所述混合体中的含量为0.15～0.7wt％时能够实现对氮化硅烧结的辅助作用且得到高纯度和高致密度的氮化硅陶瓷烧结体。
在本发明中，所述混合优选为湿式球磨混合。
在本发明中，所述湿式球磨混合的球磨介质优选包括乙醇和/或水，更优选包括乙醇或水。
在本发明中，所述球磨介质优选为无水乙醇。
在本发明中，所述氮化硅粉体和所述氧化锂源的总质量与所述球磨介质的质量比优选为1:1。
在本发明中，所述氮化硅粉体和所述氧化锂源的总质量与研磨球的质量比优选为1:(2～3)，具体优选为1:2。
在本发明中，所述研磨球优选为氮化硅研磨球、氧化铝研磨球、玛瑙研磨球。
在本发明中，所述湿式球磨混合优选在行星式球磨机中进行。
在本发明中，所述湿式球磨混合的转速优选为150～300rpm，更优选为150rpm～200rpm。
在本发明中，所述湿式球磨混合的时间优选为2～10h，具体优选为2h～4h。
得到混合体后，本发明将所述混合体置于模具中在保护气体氛围中进行烧结，得到所述氮化硅陶瓷烧结体。
在本发明中，置于模具中进行烧结之前，本发明优选对所述混合体进行干燥。在本发明中，所述干燥的具体实施方式优选为喷雾干燥或烘干。
在本发明中，所述烘干的温度优选为40～100℃，具体优选为40℃～60℃。
在本发明中，所述烘干的保温时间优选为2～12h，具体优选为4～8h。
本发明对所述喷雾干燥的具体实施过程没有特殊要求。
本发明优选通过干燥对所述混合体进行造粒。在本发明中，所述干燥的具体实施过程优选为喷雾干燥时，所述喷雾干燥后直接得到混合体粉体。
在本发明中，所述干燥的具体实施方式优选为烘干时，本发明优选对所述烘干得到的物料进行筛分，得到混合体粉体。在本发明中，所述筛分的筛孔直径优选为60～200目，具体优选为60目、80目、200目或100目。
在本发明中，所述烧结的温度优选为1350～1800℃，更优选为1400～1750℃。
在本发明中，所述烧结的压力优选为10～80MPa，更优选为15～75MPa。
在本发明中，所述烧结的保温保压时间优选为0.5～5h，更优选为0.6～4.5h。
在本发明中，所述烧结优选为热压烧结或放电等离子烧结。
在本发明中，所述保护气体氛围优选为氮气氛围或惰性气体氛围，更优选为氮气氛围。
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
称取高纯氮化硅粉体(平均粒径为5μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.3wt％引入Li2CO3粉体，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1：2加入氮化硅研磨球，采用行星式球磨以300rpm速度球磨4h。球磨物料于60℃干燥4h后过60目筛子。将过筛后的样品置于石墨模具中在40MPa压力、1600℃烧结1h得到高纯氮化硅陶瓷烧结体。
实施例2
称取高纯氮化硅粉体(平均粒径为10μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.15wt％引入Li2O粉体，置于氮化硅球磨罐中，按照质量比1:1加入去离子水，按照质量比1:3加入玛瑙研磨球，采用行星式球磨以300rpm速度球磨2h。球磨物料直接喷雾造粒得到粉体。将粉体置于石墨模具中在80MPa压力、1700℃热压烧结5h得到高纯氮化硅陶瓷烧结体。
实施例3
称取高纯氮化硅粉体(平均粒径为20μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.4wt％引入CH3COOLi粉体，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1:2加入玛瑙研磨球，采用行星式球磨以200rpm速度球磨4h。球磨物料于100℃干燥2h后过80目筛子。将过筛后的样品置于石墨模具中在10MPa压力、1750℃热压烧结3h得到高纯氮化硅陶瓷烧结体。
实施例4
称取高纯氮化硅粉体(平均粒径为0.5μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.5wt％引入Li2C2O4粉体，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1:1加入氧化铝研磨球，采用行星式球磨以150rpm速度球磨10h。球磨物料直接喷雾造粒得到粉体。将粉体置于石墨模具中在30MPa压力、1500℃热压烧结0.5h得到高纯氮化硅陶瓷烧结体。
实施例5
称取高纯氮化硅粉体(平均粒径为0.1μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.6wt％引入LiOCH(CH3)2粉体，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1:1加入氮化硅研磨球，采用行星式球磨以150rpm速度球磨10h。球磨物料于40℃干燥12h后过40目筛子。将过筛后的样品置于石墨模具中在60MPa压力、1600℃热压烧结0.5h得到高纯氮化硅陶瓷烧结体。
实施例6
称取高纯氮化硅粉体(平均粒径为10μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.5wt％引入Li3PO4粉体，置于氮化硅球磨罐中，按照质量比1:1加入去离子水，按照质量比1:2加入氮化硅研磨球，采用行星式球磨以150rpm速度球磨10h。球磨物料于60℃干燥4h后过200目筛子。将过筛后的样品置于石墨模具中在40MPa压力、1400℃放电等离子烧结1h得到高纯氮化硅陶瓷烧结体。
实施例7
称取高纯氮化硅粉体(平均粒径为10μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.2wt％引入C2H5OLi粉体，置于氮化硅球磨罐中，按照质量比1:1加入去离子水，按照质量比1:2加入氮化硅研磨球，采用行星式球磨以200rpm速度球磨4h。球磨物料于80℃干燥2h后过100目筛子。将过筛后的样品置于石墨模具中在35MPa压力、1500℃放电等离子烧结0.5h得到高纯氮化硅陶瓷烧结体。
实施例8
称取高纯氮化硅粉体(平均粒径为10μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.4wt％引入LiOCH(CH3)2粉体，置于氮化硅球磨罐中，按照质量比1:1加入去离子水，按照质量比1:2加入氧化铝研磨球，采用行星式球磨以300rpm速度球磨4h。球磨物料于50℃干燥4h后过80目筛子。将过筛后的样品置于石墨模具中在40MPa压力、1550℃热压烧结1h得到高纯氮化硅陶瓷烧结体。
实施例9
称取高纯氮化硅粉体(平均粒径为10μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.3wt％引入LiOCH(CH3)2和Li2O混合粉体，置于氮化硅球磨罐中，按照质量比1:1.2加入去离子水，按照质量比1:2加入氧化铝研磨球，采用行星式球磨以200rpm速度球磨4h。球磨物料于60℃干燥4h后过100目筛子。将过筛后的样品置于石墨模具中在20MPa压力、1600℃热压烧结2h得到高纯氮化硅陶瓷烧结体。
实施例10
称取高纯氮化硅粉体(平均粒径为5μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，按照Li元素占氮化硅粉体和氧化锂源原料总重量的0.4wt％引入LiOCH(CH3)2、Li2O、C2H5OLi混合粉体，置于氮化硅球磨罐中，按照质量比1:1加入去离子水，按照质量比1:2加入氧化铝研磨球，采用行星式球磨以300rpm速度球磨4h。球磨物料于60℃干燥6h后过100目筛子。将过筛后的样品置于石墨模具中在50MPa压力、1800℃热压烧结0.5h得到高纯氮化硅陶瓷烧结体。
对比例1
称取高纯氮化硅粉体(平均粒径为5μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1：2加入氮化硅研磨球，采用行星式球磨以300rpm速度球磨4h。球磨物料于60℃干燥4h后过60目筛子。将过筛后的样品置于石墨模具中在40MPa压力、1600℃烧结1h得到陶瓷烧结体。
对比例2
称取高纯氮化硅粉体(平均粒径为5μm，氧元素含量＜1.6wt％、金属杂质含量＜0.2wt％)，添加2wt％Al2O3和3wt％Y2O3作为烧结助剂，置于氮化硅球磨罐中，按照质量比1:1加入无水乙醇，按照质量比1：2加入氮化硅研磨球，采用行星式球磨以300rpm速度球磨4h。球磨物料于60℃干燥4h后过60目筛子。将过筛后的样品置于石墨模具中在40MPa压力、1600℃烧结1h得到高纯氮化硅陶瓷烧结体。
测试例
将实施例1～10，对比例1～2的样品进行加工并采用阿基米德排水法测试致密度，实施例1～10相对密度结果如下：99.8％，99.1％，99.7％，99.5％，99.6％，99.7％，99.2％，99.4％，99.9％，99.7％。采用X射线衍射检测其物相组成结果均为氮化硅相。采用XRF荧光分析样品的金属杂质含量，结果实施例1～10所有样品的金属杂质含量均低于0.1wt％。采用氮氧分析仪分析样品的氧含量，结果实施例1～10所有样品的氧含量均低于1.8wt％。对比例1的相对密度只有70％。对比例2相对密度达到了99％，但其杂质含量较多，氧含量测试结果为3.4wt％，金属杂质Al、Y等测试值约为2.1wt％。
将对比例和实施例进行不同温度强度测试，检测强度下降为室温的50％的温度转变点。实施例1～10样品弯曲强度可持续到1500℃强度保持80％以上，对比例1因为实现致密化，强度很低，对比例2中虽然致密化，但在1200℃时强度已经下降超过50％。部分数据如表1所示。
表1实施例1与对比例1～2的高温强度数据(强度单位MPa)
Figure BDA0003758546590000091
Figure BDA0003758546590000101
实施例2～10的高温强度数据与实施例1的数据相似。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (10)

1.一种氮化硅陶瓷烧结体，其特征在于，所述氮化硅陶瓷烧结体中氮化硅结晶相的含量≥98wt％；所述氮化硅陶瓷烧结体的相对密度≥99％；所述氮化硅陶瓷烧结体的气孔率≤1％；所述氮化硅陶瓷烧结体的晶界相元素包括Li元素、O元素、N元素和Si元素；所述氮化硅陶瓷烧结体中C元素、F元素、Al元素、Mg元素、K元素、Ca元素、Na元素和稀土金属元素的总含量＜0.1wt％。
2.根据权利要求1所述的氮化硅陶瓷烧结体，其特征在于，所述氮化硅陶瓷烧结体中Li元素、O元素、N元素和Si元素的总含量为99.7～100wt％。
3.根据权利要求1所述的氮化硅陶瓷烧结体，其特征在于，所述氮化硅陶瓷烧结体中Li元素的含量为0.15～0.6wt％。
4.根据权利要求1或3所述的氮化硅陶瓷烧结体，其特征在于，所述氮化硅陶瓷烧结体中O元素的含量＜2wt％。
5.根据权利要求1所述的氮化硅陶瓷烧结体，其特征在于，所述氮化硅陶瓷烧结体中氮化硅结晶相的晶粒尺寸为0.3～20μm。
6.权利要求1～5任一项所述的氮化硅陶瓷烧结体的制备方法，其特征在于，具体为以下步骤：
将氮化硅粉体和氧化锂源混合得到混合体；所述氧化锂源包括Li2O、Li2CO3、CH3COOLi、Li2C2O4、C2H5OLi、CH3OLi、LiOCH(CH3)2、CHLiO2、C6H5Li和C4H9Li中的一种或多种；
将所述混合体置于模具中在保护气体氛围中进行烧结，得到所述氮化硅陶瓷烧结体。
7.根据权利要求6所述的制备方法，其特征在于，所述氧化锂源中的锂元素在所述混合体中的含量为0.15～0.7wt％。
8.根据权利要求6所述的制备方法，其特征在于，所述烧结为热压烧结或放电等离子体烧结；所述烧结的温度为1350～1800℃，所述烧结的压力为10～80MPa，所述烧结的保温保压时间为0.5～5h。
9.根据权利要求6所述的制备方法，其特征在于，所述氮化硅粉体的粒径为0.01～20μm；所述氮化硅粉体中氧元素的含量≤1.6wt％，所述氮化硅粉体中金属杂质元素的含量≤0.2wt％。
10.根据权利要求6所述的制备方法，其特征在于，所述混合为湿式球磨混合，所述湿式球磨混合的球磨介质包括乙醇和/或水，所述氮化硅粉体和所述氧化锂源的总质量与所述球磨介质的质量比为1:1，所述氮化硅粉体和所述氧化锂源的总质量与研磨球的质量比为1:(2～3)；所述湿式球磨混合的转速为150～300rpm，所述湿式球磨混合的时间为2～10h。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06135771A (ja) * 1992-09-08 1994-05-17 Toshiba Corp 高熱伝導性窒化けい素焼結体およびその製造方法
EP0940377A1 (en) * 1998-03-05 1999-09-08 Sumitomo Electric Industries, Ltd. Si3N4 Sintered body with high thermal conductivity and method for producing the same
JP2000034172A (ja) * 1998-05-12 2000-02-02 Toshiba Corp 高熱伝導性窒化けい素焼結体およびその製造方法
JP2002201075A (ja) * 2000-10-27 2002-07-16 Toshiba Corp 窒化けい素セラミックス基板およびそれを用いた窒化けい素セラミックス回路基板並びにその製造方法
CN110590377A (zh) * 2019-10-29 2019-12-20 中钢集团洛阳耐火材料研究院有限公司 一种高β相致密氮化硅陶瓷及低温制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5826077A (ja) * 1981-08-10 1983-02-16 株式会社東芝 セラミツクス焼結体及びその製造方法
JP3034100B2 (ja) * 1991-11-21 2000-04-17 京セラ株式会社 窒化珪素質焼結体およびその製造方法
CN103922749B (zh) * 2014-03-21 2015-11-25 西安交通大学 一种低金属离子残留的多孔氮化硅陶瓷的制备方法
CN109942301A (zh) * 2019-04-22 2019-06-28 中钢集团洛阳耐火材料研究院有限公司 一种低成本氮化硅陶瓷的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06135771A (ja) * 1992-09-08 1994-05-17 Toshiba Corp 高熱伝導性窒化けい素焼結体およびその製造方法
EP0940377A1 (en) * 1998-03-05 1999-09-08 Sumitomo Electric Industries, Ltd. Si3N4 Sintered body with high thermal conductivity and method for producing the same
JP2000034172A (ja) * 1998-05-12 2000-02-02 Toshiba Corp 高熱伝導性窒化けい素焼結体およびその製造方法
JP2002201075A (ja) * 2000-10-27 2002-07-16 Toshiba Corp 窒化けい素セラミックス基板およびそれを用いた窒化けい素セラミックス回路基板並びにその製造方法
CN110590377A (zh) * 2019-10-29 2019-12-20 中钢集团洛阳耐火材料研究院有限公司 一种高β相致密氮化硅陶瓷及低温制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
采用Li2O-Al2O3 助烧剂低温埋碳制备Si3N4 陶瓷;李凌锋等;耐火材料;第53卷(第6期);第405-408页 *

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