CN111285691A - 一种钨网增韧碳氮化铪基金属陶瓷及其制备方法 - Google Patents

一种钨网增韧碳氮化铪基金属陶瓷及其制备方法 Download PDF

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CN111285691A
CN111285691A CN202010090926.XA CN202010090926A CN111285691A CN 111285691 A CN111285691 A CN 111285691A CN 202010090926 A CN202010090926 A CN 202010090926A CN 111285691 A CN111285691 A CN 111285691A
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孙威
彭峥
熊翔
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Abstract

本发明公开了一种钨网增韧碳氮化铪基金属陶瓷及其制备方法，所述钨网增韧碳氮化铪基金属陶瓷由碳氮化铪基体以及间隔分布于碳氮化铪基体中的钨网组成；其制备方法，包括如下步骤：将HfC粉，HfN粉，碳粉、氮化碳粉混合、球磨、干燥、过筛获得混合粉末；所述混合粉末中，按质量比计，HfC粉：HfN粉＝1‑7:1，将混合粉末、钨网交替层叠铺设于模具中获得待烧结体，将待烧结体进行放电等离子体烧结，即得钨网增韧碳氮化铪基金属陶瓷。本发明所提供的钨网增韧碳氮化铪基金属陶瓷具有优异的抗热震效果以及抗烧蚀性能。

Description

一种钨网增韧碳氮化铪基金属陶瓷及其制备方法
技术领域
本发明属于碳化物陶瓷技术领域，具体涉及一种钨网增韧碳氮化铪基金属陶瓷及其制备方法。
背景技术
超高温陶瓷一般是指熔点大于3000℃的过渡金属碳化物、硼化物、氮化物及其复相陶瓷，如HfC、ZrC、ZrB2等。超高温陶瓷及其复合材料具有高熔点、低密度、高强度、优异的化学稳定性等优点，在航天航空、能源等领域有着广泛的应用，其中过渡金属碳氮化物超高温陶瓷因其优异的物理内涵和优异的材料性能受到研究者的关注。一方面过渡金属元素的价电子浓度和配位数较高，而C、N这类轻元素的原子半径较小，易形成键长较短、键强较强的共价键，从而具有很高的熔点和硬度，另一方面其化学键中同时具有金属键、离子键和共价键，从而易调控形成多种不同的化学计量比和晶体结构。过渡金属原子向主族原子的电荷转移，使本来空间分布比较局域的d电子受到的电子屏蔽更少，增强了d电子的局域性和相互关联。特别是HfCxNy固溶体陶瓷经过第一性原理计算，预测具有超高熔点，在超高温方面具有巨大的应用前景。但是陶瓷材料具有韧性过低的本征缺陷满足不了工程可靠性的需求，严重的影响其应用，改善陶瓷韧性成为高温陶瓷材料领域内亟待解决的重要问题。
发明内容
针对现有技术中超高温抗烧蚀陶瓷存在断裂韧性过低的缺陷，本发明的目的在于提供一种具有优异抗热震性能、优异抗烧蚀性能的钨网增韧碳氮化铪基金属陶瓷及其制备方法，所述钨网增韧碳氮化铪基金属陶瓷(HfCxNy)适用于3000℃超高温抗烧蚀防护，长时间烧蚀后金属陶瓷仍保持完整，未发生脆性断裂，并且具有稳定的抗氧化防护结构。
为了实现上述目的，本发明采用如下技术方案：
本发明一种钨网增韧碳氮化铪基金属陶瓷，所述钨网增韧碳氮化铪基金属陶瓷由碳氮化铪基体以及间隔分布于碳氮化铪基体中的钨网组成。
本发明采用多层钨网以增韧HfCxNy陶瓷，钨作为熔点最高的金属，具有高强度、高熔点、塑性好、抗冲击韧性强等特点；另外发明人发现，碳氮化铪和金属钨之间具有优异的化学相容性和热匹配性，加入多层间隔均匀分布的钨网后能有效提高碳氮化铪高温下的断裂韧性和抗弯强度，形成一种增强增韧型超高熔点碳氮化铪基复合材料。当高温热应力作用时，裂纹扩展至钨网处时，发生偏转所受的拉应力降低，扩展路径延长，材料的断裂能增加。当剪切应力达到钨网与固溶体基体界面的初始脱粘应力，即界面剪切强度时，发生脱粘，一方面克服界面摩擦力做功增加了断裂能；另外一方面，导致裂纹尖端应力松弛，延缓裂纹扩展。并且规律排列的网络状结构能起到桥联裂纹，抑制裂纹扩展的效果。
优选的方案，所述碳氮化铪基体中，按质量比计，C：N＝1-7:1；优选为1-3:1。
当碳氮化铪基体中，碳与氮的质量比在上述范围时，所述钨网增韧碳氮化铪基金属陶瓷具有最优异的抗烧蚀性能。
优选的方案，所述钨网的层数为3-8层，优选为3-6层，进一步优选为4-6层，每一层钨网由一片钨网组成，钨网间隔均匀的分布于碳氮化铪基体中，所述钨网增韧碳氮化铪基金属陶瓷的厚度为3-6mm。
优选的方案，所述钨网的目数为80-300目，优选为100-200目。
在本发明中，钨网的目数为钨网网孔的目数，当控制钨网的目数在上述范围内，即可以使得钨网增韧碳氮化铪基金属陶瓷具有优异的韧性，亦可使钨网增韧碳氮化铪基金属陶瓷具有优异的烧蚀性能，而如果目数过小，则会影响到韧性，目数过大则会影响以烧蚀性能。
本发明一种钨网增韧碳氮化铪基金属陶瓷的制备方法，包括以下步骤：
将HfC粉，HfN粉，碳粉、氮化碳粉混合、球磨、干燥、过筛获得混合粉末；所述混合粉末中，按质量比计，HfC粉：HfN粉＝1-7:1，将混合粉末、钨网交替层叠铺设于模具中获得待烧结体，将待烧结体进行放电等离子体烧结，即得钨网增韧碳氮化铪基金属陶瓷。
优选的方案，所述混合粉末中，按质量比计，HfC粉：HfN粉＝1-3:1；优选为1.5-3:1。
优选的方案，所述HfC粉和HfN粉的纯度均大于99.9％，所述HfC粉和HfN粉的粒度均为微米级或纳米级。
优选的方案，所述碳粉在混合粉末中的质量分数≤8.0wt％，优选为3wt％-wt5％。
优选的方案，所述氮化碳粉在混合粉末中的质量分数≤5.0wt％，优选为4wt％-5wt％。
本发明中，对于球磨的设备不受限制，优选为高能行星式球磨机，球磨的方式优选为采用湿法球磨，球磨介质为乙醇溶液。
优选的方案，所述球磨转速为200-400r/min，球磨时间为12-24h，球料比为3-10：1。
优选的方案，所述干燥的时间为8-12h，干燥的温度为50-150℃，所述干燥在真空环境下进行；干燥后过325目筛，取筛下物即为混合粉末。所得混合粉末隔绝空气密封保存。
优选的方案，将混合粉末、钨网交替均匀层叠铺设于模具中，所述钨网的层数为3-8层，优选3-6层，进一步优选为4-6层，同一层钨网由一片钨网组成。
将混合粉末、钨网交替层叠铺设于模具是指：将混合粉末分为均等的若干份，然后在石墨模具内馅铺设一层混合粉末，接着铺设一层钨网，然后再铺设一层混合粉末，以此方式，反复铺设多层。
在实际操作过程中，钨网先经乙醇超声处理后表面平整且洁净。
优选的方案，所述钨网的目数为80-300目，优选为100-200目。
优选的方案，所述待烧结体的厚度为6-12mm，优选为8-10mm。在本发明中，待烧结体在SPS设备中进行加压烧结，烧结致密后金属陶瓷的厚度为3-6mm。
优选的方案，所述放电等离子烧结在真空的环境下进行，真空度＜5Pa；其烧结程序为：先以50-150℃/min的升温速率升温至1500-2400℃，保温5-30min，保温完成后，再以100-120℃/min的降温速率降温，烧结压力为20-60Mpa。
进一步的优选，所述烧结程序为：先以100-120℃/min的升温速率升温至1900-2100℃，保温10-20min，保温完成后，再以100-120℃/min的降温速率降温，烧结压力为30-40Mpa。
烧结完成后，将烧结体进行脱模处理即得钨网增韧碳氮化铪基金属陶瓷。
原理与优势
本发明首创的采用多层钨网以增韧HfCxNy陶瓷，钨作为熔点最高的金属，具有高强度、高熔点、塑性好、抗冲击韧性强等特点；另外发明人发现，碳氮化铪和金属钨之间具有优异的化学相容性和热匹配性，加入多层间隔均匀分布的钨网后能有效提高碳氮化铪高温下的断裂韧性和抗弯强度，形成一种增强增韧型超高熔点碳氮化铪基复合材料。当高温热应力作用时，裂纹扩展至钨网处时，发生偏转所受的拉应力降低，扩展路径延长，材料的断裂能增加。当剪切应力达到钨网与固溶体基体界面的初始脱粘应力，即界面剪切强度时，发生脱粘，一方面克服界面摩擦力做功增加了断裂能；另外一方面，导致裂纹尖端应力松弛，延缓裂纹扩展。并且规律排列的网络状结构能起到桥联裂纹，抑制裂纹扩展的效果。
与现有技术相比，本发明的优点和积极效果体现在：
(1)制备工艺流程简单易行，制备周期短；
(2)制备样品抗热震效果佳。在3000℃氧乙炔焰环境下烧蚀300s后金属陶瓷仍保存完整，未发生脆性断裂；
(3)制备样品抗烧蚀性能好。在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率和线烧蚀率仅为3.67×10-4mg/s、2.34×10-3mm/s。
附图说明
图1为实施例2中多层网络增韧HfCxNy基金属陶瓷宏观表面图。
图2为实施例2中多层网络增韧HfCxNy基金属陶瓷宏观截面图。
图3为实施例1中试样于3000℃氧乙炔焰烧蚀300s后宏观烧蚀形貌图。在超高温长时烧蚀后未发生脆性断裂，证明具有非常优异的抗热震性能。
图4为对比例1中HfC陶瓷于3000℃氧乙炔焰烧蚀180s后的宏观烧蚀形貌图，发生了明显的脆性断裂。
图5为实施例2中试样表面打磨抛光后的EPMA显微结构图。
图6为实施例2中试样截面微观结构图。
具体实施方式
实施例1
将HfC粉，HfN粉，碳粉、氮化碳粉混合，然后在行星式球磨机上球磨10h，，球磨介质为乙醇溶液，转速为300r/min，球料比为10:1，随后放置在60℃的干燥箱中烘干8小时，过筛后得到混合粉料。其中各原料粉末的纯度均大于99.9％，粉末平均粒度均为1um，在混合粉末中，HfC粉与HfN粉的质量比为3:2；而碳粉在混合粉末中的质量分数为5％，氮化碳在混合粉末中的质量分数为5％。
选取100目钨网，纯度大于99.9％，经过乙醇超声30分钟清洁处理后干燥取出，裁剪成磨具直径大小。随后将混合粉料和钨网均匀交替放置在石墨模具中，分5层排列，待烧结体厚度为10mm，进行放电等离子烧结，炉内真空度小于5Pa，以100℃/min的升温速率升温到2000℃，保温15分钟，压力40Mpa，随后以100℃/min的降温速率冷却到室温。经脱模处理后得到厚度为4.79mm的多层网络增韧碳氮化铪基金属陶瓷。在3000℃氧乙炔焰环境下烧蚀300s后未发生脆性断裂，样品保持完整，质量烧蚀率仅为3.67×10-4mg/s，线烧蚀率为2.34×10-3mm/s。
实施例2
将HfC粉，HfN粉，碳粉、氮化碳粉混合，然后在行星式球磨机上球磨12h，，球磨介质为乙醇溶液，转速为200r/min，球料比为8:1，随后放置在50℃的干燥箱中烘干10小时，过筛后得到混合粉料，其中各原料粉末的纯度均大于99.9％，粉末平均粒度均为1um，在混合粉末中，HfC粉与HfN粉的质量比为2:1；而碳粉在混合粉末中的质量分数为4％，氮化碳在混合粉末中的质量分数为4％。
选取80目钨网，纯度大于99.9％，经过乙醇超声20分钟清洁处理后干燥取出，裁剪成磨具直径大小。随后将混合粉料和钨网均匀交替放置在石墨模具中，一共四层钨网，待烧结体厚度为8mm，进行放电等离子烧结，炉内真空度小于5Pa，以120℃/min的升温速率升温到2100℃，保温15分钟，压力为35Mpa，随后以100℃/min的降温速率冷却到室温。经脱模处理后得到厚度3.84mm的多层钨网增韧碳氮化铪基金属陶瓷。在3000℃氧乙炔焰环境下烧蚀180s后未发生脆性断裂，样品保持完整，质量烧蚀率仅为4.53×10-4mg/s，线烧蚀率为3.97×10-3mm/s。
实施例3
将HfC粉，HfN粉，碳粉、氮化碳粉混合，然后在行星式球磨机上球磨12h，球磨介质为乙醇溶液，转速为200r/min，球料比为9:1，随后放置在70℃的干燥箱中烘干10小时，过筛后得到混合粉料。其中各原料粉末的纯度均大于99.9％，粉末平均粒度均为1um，在混合粉末中，HfC粉与HfN粉的质量比为3:1；而碳粉在混合粉末中的质量分数为3％，氮化碳在混合粉末中的质量分数为4％。
选取120目钨网，纯度大于99.9％，经过乙醇超声处理后干燥。裁剪成磨具直径大小，随后将混合粉料和钨网均匀交替放置在石墨模具中，一共六层钨网，待烧结体厚度为12mm，进行放电等离子烧结，炉内真空度小于5Pa，以120℃/min的升温速率升温到1900℃，保温20分钟，压力为40Mpa，随后以100℃/min的降温速率冷却到室温。经脱模处理后得到多层钨网增韧碳氮化铪基金属陶瓷。在3000℃氧乙炔焰环境下烧蚀300s后未发生脆性断裂，样品保持完整，质量烧蚀率仅为5.38×10-4mg/s，线烧蚀率为4.56×10-3mm/s。
对比例1
未加入钨网增韧，其他条件均与实施例2相同，在3000℃氧乙炔焰环境下烧蚀180s后发生脆性断裂。
对比例2
仅加入一层钨网，其他条件均与实施例2相同，在3000℃氧乙炔焰环境下烧蚀180s后发生脆性断裂。
对比例3
加入目数为30的钨网增韧，其他条件均与实施例2相同，在3000℃氧乙炔焰环境下烧蚀180s后发生脆性断裂。
对比例4
将HfC和HfN粉末按照质量比8:1在行星式球磨机上球磨，其他条件均与实施例2相同，在3000℃氧乙炔焰环境下烧蚀180s后质量烧蚀率和线烧蚀率大大增加，分别为7.83×10-2mg/s，线烧蚀率为6.27×10-1mm/s。

Claims (10)

1.一种钨网增韧碳氮化铪基金属陶瓷，其特征在于：所述钨网增韧碳氮化铪基金属陶瓷由碳氮化铪基体以及间隔分布于碳氮化铪基体中的钨网组成。
2.根据权利要求1所述的一种钨网增韧碳氮化铪基金属陶瓷，其特征在于：所述碳氮化铪基体中，按质量比计，C：N＝1-7:1；优选为1-3:1。
3.根据权利要求1或2所述的一种钨网增韧碳氮化铪基金属陶瓷，其特征在于：所述钨网的层数为3-8层，优选为3-6层，每一层钨网由一片钨网组成，钨网间隔均匀的分布于碳氮化铪基体中，所述钨网增韧碳氮化铪基金属陶瓷的厚度为3-6mm。
4.根据权利要求1或2所述的一种钨网增韧碳氮化铪基金属陶瓷，其特征在于：所述钨网的目数为80-300目，优选为100-200目。
5.制备如权利要求1-4任意一项所述的一种钨网增韧碳氮化铪基金属陶瓷的方法，其特征在于：包括以下步骤，将HfC粉，HfN粉，碳粉、氮化碳粉混合、球磨、干燥、过筛获得混合粉末；所述混合粉末中，按质量比计，HfC粉：HfN粉＝1-7:1，将混合粉末、钨网交替层叠铺设于模具中获得待烧结体，将待烧结体进行放电等离子体烧结，即得钨网增韧碳氮化铪基金属陶瓷。
6.根据权利要求5所述的一种钨网增韧碳氮化铪基金属陶瓷的制备方法，其特征在于：所述混合粉末中，按质量比计，HfC粉：HfN粉＝1-3:1；所述碳粉在混合粉末中的质量分数≤8.0wt％，所述氮化碳粉在混合粉末中的质量分数≤5.0wt％。
7.根据权利要求5所述的一种钨网增韧碳氮化铪基金属陶瓷的制备方法，其特征在于：所述球磨转速为200-400r/min，球磨时间为12-24h，球料比为3-10：1；
所述干燥的时间为8-12h，干燥的温度为50-150℃，所述干燥在真空环境下进行；干燥后过325目筛，取筛下物即为混合粉末。
8.根据权利要求5所述的一种钨网增韧碳氮化铪基金属陶瓷的制备方法，其特征在于：将混合粉末、钨网交替均匀层叠铺设于模具中，所述钨网的层数为3-8层，优选为3-6层，同一层钨网由一片钨网组成；所述钨网的目数为80-300目，优选为100-200目。
9.根据权利要求5所述的一种钨网增韧碳氮化铪基金属陶瓷的制备方法，其特征在于：所述待烧结体的厚度为6-12mm，优选为8-10mm。
10.根据权利要求5所述的一种钨网增韧碳氮化铪基金属陶瓷的制备方法，其特征在于：所述放电等离子烧结在真空的环境下进行，真空度＜5Pa；其烧结程序为：先以50-150℃/min的升温速率升温至1500-2400℃，保温5-30min，保温完成后，再以100-120℃/min的降温速率降温，烧结压力为20-60Mpa。
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