CN108191434B - 一种高热导率、高致密性氮化硅材料的高压快速制备方法 - Google Patents

一种高热导率、高致密性氮化硅材料的高压快速制备方法 Download PDF

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CN108191434B
CN108191434B CN201810172165.5A CN201810172165A CN108191434B CN 108191434 B CN108191434 B CN 108191434B CN 201810172165 A CN201810172165 A CN 201810172165A CN 108191434 B CN108191434 B CN 108191434B
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silicon nitride
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贾洪声
鄂元龙
李海波
贺雪莲
李加琦
牛瑞
赵兴
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Harbin Haiyida Superhard Materials Co ltd
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Abstract

本发明涉及一种高热导率、高致密性氮化硅材料的高压快速制备方法，该方法采用高温高压烧结技术，具体步骤是：在高压高温条件下(HPHT，4.5～5.5GPa,1400～1500℃)，采用平均粒径为0.5μm及以上的金刚石、石墨烯、TiN、AlN、MgO、Y2O3粉末等作为烧结助剂，不同质量配比的氮化硅(β‑Si3N4)粉末作为骨架材料制备高热导率、高致密性氮化硅块体材料。本发明所述的制备高性能结构材料的方法是通过β‑Si3N4与助剂的混合粉末烧结技术，形成β‑Si3N4、金刚石、陶瓷硬质相等烧结相，其烧结体具有较高的热导率和致密性(低气孔率)。该方法操作性强，工艺简单，不需要超高温度，可以大大缩短结构材料的合成时间，是一种适用于航空航天、军工、电子等领域的新型陶瓷材料。

Description

一种高热导率、高致密性氮化硅材料的高压快速制备方法
技术领域
本发明属于块体结构陶瓷材料及器件制造领域，具体的说是一种具有高致密性(低气孔率)、高热导率优质氮化硅块体陶瓷材料的制备方法。
背景技术
随着我国航天、军工、电子等领域的快速发展，未来对大功率电力电子器件的需求也将越来越大。为了适应更加复杂、苛刻的应用条件，大功率电力电子器件朝着高温、高频、低功耗以及智能化、模块化、系统化方向发展，这对整个电子器件的抗热震性能提出了更严格的要求，制备高热导率陶瓷基板材料已成为研发大功率模块电子产品的关键所在。
通常认为理想的基板材料应该满足以下几个要素，即高硬度、高致密性、高抗热震性。在已知的基板材料中，有Al2O3、AlN、BeO、SiC、BN、Si等，但是它们也存在自身的不足及限制，其中，Al2O3的热导率较低且高纯氧化铝难以烧结造价昂贵；由于AlN的机械性能不能充分满足大功率散热基板材料的要求，导致基板可靠性低。同时AlN的烧结温度很高(1900℃左右)且在水中容易水解形成偏铝酸；BeO线膨胀系数与Si相差很大，高温时热导率急剧下降且制造时有毒；BN虽然具有较好的综合性能，但作为基板材料价格太昂贵，目前只处于研究和推广之中；SiC具有高强度和高热导率，但其电阻和绝缘耐压值都较低，介电常数偏大，不宜作为基板材料。硅作为散热基板材料加工困难，成本高；单一金属材料具有导电及热膨胀系数失配等问题，上述因素限制它们的应用。由此，寻找综合性能优异，可实现获得高效率、高硬度，高致密性、高热抗震性的新型陶瓷材料是基板材料制造行业的一个重要发展方向。氮化硅具有上述的优势，其产业已作为国家战略性新兴产业之一，获得国家大力发展支持。目前，氮化硅陶瓷的烧结方法主要有反应烧结法(RS)、热压烧结法(HPS)、常压烧结法(PLS)和气压烧结法(GPS)、放电等离子烧结(SPS)等。其面临的问题具体如下：反应烧结法需要二次烧结，在1200-1500℃下反应烧结，并将反应烧结的初坯置于气压烧结炉内，在1-9MPaN2压力和1900℃的条件下保温3小时，制备氮化硅陶瓷。烧结样品致密度小，力学性能差，其热导率在1000℃时热导率为19.43W/(m·K)，在1200℃的热导率为17.59W/(m·K)。热压烧结法具有成本高、烧结工艺复杂等特点，需要在N2的氛围下烧结，易引入塞隆相，不利于制备高热导率材料；常压烧结法，在 1700-1800℃温度范围内进行常压烧结后，再在1800-2000℃温度范围内进行气压烧结。该方法制造成本偏高，需要超高温条件，精度得不到控制，热导率不高，为19.4和19.8W/(m ·K)；气压烧结法需要通气体和施加压力，需要在1800℃，4h的条件下完成，粘结剂种类太多，多引入了过多的金属杂质和氧元素；放电等离子烧结的设备昂贵，每次烧结需要的成本极高。综上，可以总结为工艺复杂，多采用a-Si3N4高温相变或者掺杂β-Si3N4晶种进行烧结，烧结后再进行高温氮化处理等；需要超高温度，1650-2000℃；升温需要较长时间，而烧结时间通常需要几个小时才能制得块体材料；同时致密性不高(95-98％)，很难达到99％以上，热导率通常在17.59–35W/(m·K)左右，个别方法烧结材料的成本较高。基于此，发明一种操作性强，工艺简单，不需要超高温度，大大缩短Si3N4结构材料的合成时间，并具有高热导率和致密性(低气孔率)、较低成本的方法迫在眉睫，具有重要的现实意义。
发明内容
本发明的目的在于提供一种可操作性强，具有高致密性、高热导率优质氮化硅块体陶瓷材料的制备方法。
本发明的目的是这样实现的，该方法包括以下步骤：
①、选取骨架材料β-Si3N4和助剂材料：金刚石、石墨烯、TiN、AlN、MgO、Y2O3粉末作为烧结初始材料；
②、将①中骨架材料β-Si3N4和烧结助剂经过混料、压块、组件、真空热处理、叶腊石合成块烘烤、组装、高压高温合成这些程序完成氮化硅块体材料的制备。
所述的烧结助剂粉末根据实际应用需要是金刚石、石墨烯、TiN、MgO、Y2O3粉末的其中一种或组合，平均粒径为0.5-20μm。将上述均匀的混合粉末压块成型后，β-Si3N4粉末所占的质量比例为80-95份，烧结助剂粉末所占的质量比例为5-20份。
混料、压块、组件、真空热处理、叶腊石合成块烘烤、组装、高压高温合成过程是将①中按比例选择的混合粉末经过混料机1h至均匀混合，四柱压机压块成型，放入石墨腔进行真空300-600℃热处理0.5-1h后，将块体材料放入叶腊石合成块中组装(叶腊石组装前需280℃烘烤6小时至自然冷却)，在六面顶压机上进行高压高温一次合成，条件为4.5～5.5GPa，1400～1500℃，加热时间为5-30min，最后停温泄压取出块体材料。
本发明的有益效果如下：
1、本发明采用的方法能够通过高压高温的作用，使得烧结样品在高压的作用下，颗粒迅速破碎、重排到最后致密；在施加高压的同时，能够通过功率的控制在极短的时间内，直接给定温度，使得材料可以在较短的时间内完成烧结，另外石墨腔直接加热的方法可以适度的吸收外界多余的氧气，形成高温高压的密闭环境，排出空气，有利于提高其热导率。因此可以获得一种高热导率(30W/(m·K)以上)、高致密性(99％以上)的Si3N4材料，合成重复性好，可操作性强。
2、本发明所述的制备方法，相对于其它方法，不采用N2等气体环境，一次完成烧结，采用的烧结助剂均有利于提高烧结致密性，且在材料中整体比例较小，有利于制备高含量的氮化硅陶瓷，其合成产品工艺程序简单，合成将在国产的六面顶液压机上完成，设备已广泛工业化，技术成熟，操作简单，同时可以大大缩短合成时间，10min以上即可实现快速烧结，合成温度较现有的方法低，1500℃以下即可完成。
附图说明
图1是本发明中的叶腊石合成块截面图；
图2是合成样品的流程图；
图1中标号：混合粉末1、石墨加热管2、陶瓷片3、石墨片4、铜片5、钢帽6、叶腊石合成块7。
具体实施方式
本申请通过调节β-Si3N4、金刚石、石墨烯、TiN、AlN、MgO、Y2O3粉末的质量配比，优化材料组织结构，同时能够提高材料的热导率和致密性，制备的Si3N4陶瓷结构材料可以根据基本应用要求，经过激光切割、打磨等制作成不同形状及尺寸的块体材料。
下面结合实施例对本申请进行详细说明。
实施例1
如附图1所示：选取粒径2-4μm的金刚石粉末，0.5-1μmβ-Si3N4粉末作为原辅材料，质量份数分别为：5份和95份。将粉末混合1h至均匀，将1.6g混合粉末1经过四柱压机压块成型后，放入石墨腔中，500℃真空热处理1h，然后放入加热石墨管2中，最后将组装部件3-6按顺序放入叶腊石合成块7中，叶腊石合成块尺寸为32.5mm×32.5mm×32.5 mm，合成腔体直径为18mm，石墨管的内径为16mm。在六面顶压机(CS-IV，6×14000KN) 上进行高压高温合成，条件为4.5GPa，1400℃，烧结保温时间10min后慢降温到室温，卸压后得到约Φ14mm×3.5mm的Si3N4材料，其热导率为30.781W/(m·K)，气孔率为0.13 (99.87％)，具有高致密性。全部实施工艺流程见图2所示。
实施例2
如附图1所示：选取粒径0.5-1μm的MgO和Y2O3粉末，0.5-1μmβ-Si3N4粉末作为原辅材料，质量份数分别为：2份，5份和93份。将粉末混合1h至均匀，将1.6g混合粉末1经过四柱压机压块成型后，放入石墨腔中，500℃真空热处理0.5h，然后放入加热石墨管2中，最后将组装部件3-6按顺序放入叶腊石合成块7中，叶腊石合成块尺寸为32.5 mm×32.5mm×32.5mm，合成腔体直径为18mm，石墨管的内径为16mm。在六面顶压机 (CS-IV，6×14000KN)上进行高压高温合成，条件为5.5GPa，1500℃，烧结保温时间20min 后慢降温到室温，卸压后得到约Φ14mm×3.5mm的Si3N4材料，其热导率为38.172 W/(m·K)，气孔率为0.59(99.41％)，具有高致密性。全部实施工艺流程见图2所示。
实施例3
如附图1所示：选取粒径1μm的AlN粉末，0.5-1μmβ-Si3N4粉末作为原辅材料，质量份数分别为：5份和95份。将粉末混合1h至均匀，将1.6g混合粉末1经过四柱压机压块成型后，放入石墨腔中，500℃真空热处理0.5h，然后放入加热石墨管2中，最后将组装部件3-6按顺序放入叶腊石合成块7中，叶腊石合成块尺寸为32.5mm×32.5mm×32.5 mm，合成腔体直径为18mm，石墨管的内径为16mm。在六面顶压机(CS-IV，6×14000KN) 上进行高压高温合成，条件为5GPa，1480℃，烧结保温时间20min后慢降温到室温，卸压后得到约Φ14mm×3.5mm的Si3N4材料，其热导率为34.356W/(m·K)，气孔率为0.34 (99.66％)，具有高致密性。全部实施工艺流程见图2所示。
实施例4
如附图1所示：选取粒径1μm的TiN粉末，0.5-1μmβ-Si3N4粉末作为原辅材料，质量份数分别为：20份和80份。将粉末混合1h至均匀，将1.6g混合粉末1经过四柱压机压块成型后，放入石墨腔中，500℃真空热处理0.5h，然后放入加热石墨管2中，最后将组装部件3-6按顺序放入叶腊石合成块7中，叶腊石合成块尺寸为32.5mm×32.5mm×32.5 mm，合成腔体直径为18mm，石墨管的内径为16mm。在六面顶压机(CS-IV，6×14000KN) 上进行高压高温合成，条件为4.5GPa，1450℃，烧结保温时间10min后慢降温到室温，卸压后得到约Φ14mm×3.5mm的Si3N4材料，其热导率为29.734W/(m·K)，气孔率为0.16 (99.84％)，具有高致密性。全部实施工艺流程见图2所示。

Claims (2)

1.一种高热导率、高致密性氮化硅材料的高压快速制备方法，其特征在于：该方法包括以下步骤：
①、选取骨架材料β-Si3N4和烧结助剂材料作为烧结初始材料；
②、将①中骨架材料β-Si3N4和烧结助剂材料经过混料、压块、组件、真空热处理、叶腊石合成块烘烤、组装、高压高温合成这些程序完成氮化硅块体材料的制备；
所述烧结助剂材料为金刚石，所述的烧结助剂材料平均粒径为0.5-20μm；
所述混料、压块、组件、真空热处理、叶腊石合成块组装、高压高温合成过程是将①中按比例选择的混合粉末经过混料机1h至均匀混合，四柱压机压块成型，放入石墨腔进行真空300-600℃热处理0.5-1h后，将块体材料放入叶腊石合成块中组装，组装前叶腊石需280℃烘烤6小时至自然冷却，最后在六面顶压机上进行高压高温一次合成，条件为4.5～5.5GPa，1400～1500℃，加热时间为5-30min，最后停温泄压取出块体材料。
2.根据权利要求1所述的一种高热导率、高致密性氮化硅材料的高压快速制备方法，其特征在于：所述的β-Si3N4粉末要求通过酸碱处理处理掉杂质，平均粒径≥0.5μm的一种粒度或者多种粒度的组合；将上述均匀的混合粉末压块成型后，β-Si3N4粉末所占的质量比例为80-95份，烧结助剂粉末所占的质量比例为5-20份。
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