CN112358303A - 一种HfCxNy超高温陶瓷粉体材料及其制备方法 - Google Patents

一种HfCxNy超高温陶瓷粉体材料及其制备方法 Download PDF

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CN112358303A
CN112358303A CN202011165632.5A CN202011165632A CN112358303A CN 112358303 A CN112358303 A CN 112358303A CN 202011165632 A CN202011165632 A CN 202011165632A CN 112358303 A CN112358303 A CN 112358303A
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徐敬军
张鑫涛
钱余海
李美栓
左君
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Abstract

本发明涉及超高温陶瓷材料领域，具体为一种HfCxNy超高温陶瓷粉体材料及其制备方法，其中0<x+y≤1。采用感应加热无压烧结制备得到该材料，具体操作步骤如下：1)将Hf、C和HfN粉末按比例放入尼龙罐中，介质采用无水乙醇，以湿法球磨的方法得到粉末浆料；2)将粉末浆料旋转蒸发烘干并过筛得到Hf‑C‑HfN混合粉末，置入不锈钢模具中冷压成型；3)将成型的坯体放入石墨坩埚中并连同坩埚一起放入超高温感应加热炉内，在氮气气氛下无压烧结得到HfCxNy超高温陶瓷。该方法制备的HfCxNy超高温材料具有高纯度、制备工艺流程简便、制备周期短等优势。

Description

一种HfCxNy超高温陶瓷粉体材料及其制备方法
技术领域
本发明涉及超高温陶瓷材料领域，具体为一种HfCxNy超高温陶瓷粉体材料及其制备方法。
背景技术
超高温陶瓷是指一类熔点超过3000℃的非氧化物陶瓷材料，主要包括早期过渡族金属的硼化物、碳化物和氮化物，其中碳化物和氮化物具有一系列独特的性能，包括高密度、化学热稳定性、耐腐蚀性和极高的熔点，使其成为理想的超高温热结构及热防护***的候选材料体系。其中，HfC的熔点极高(3890℃)，是已知单一化合物中熔点最高的。根据理论计算得知三元相的Hf-C-N体系拥有创纪录的高熔点。由于HfCxNy的高熔点、良好的电热传导性、小的热膨胀和好的抗冲击性等性能，都能使其成为一种优异的超高温材料，是最具应用前景的超高温热防护材料之一，因此受到了广泛关注。
然而，现有的HfCxNy材料制备方法需要苛刻的条件，包括极高的温度(≥2400℃)和较长的保温时间(≥2h)。在N2的正压条件下进行粉体的自蔓延燃烧反应，这一制备方法有一定的危险性，易***，而且制备周期较长，工艺流程繁琐。因此，HfCxNy材料的制备是目前亟待解决的技术问题。
发明内容
本发明的目的在于提供一种HfCxNy超高温陶瓷粉体材料及其制备方法，该方法可快速升温到烧结温度，具有操作流程简便、烧结周期短等特点，可实现大规模批量化制备的需求。
本发明的技术方案如下：
一种HfCxNy超高温陶瓷粉体材料，超高温陶瓷粉体材料的化学组成为HfCxNy，其中0<x+y≤1。
所述的HfCxNy超高温陶瓷粉体材料，优选的，x+y＝1，x或y＝0.2～0.8。
所述的HfCxNy超高温陶瓷粉体材料，HfCxNy超高温陶瓷粉体材料实现固溶，颗粒大小均匀，为2～3μm。
所述的HfCxNy超高温陶瓷粉体材料的制备方法，该方法的具体操作步骤如下：
1)按照设计比例称量所需的Hf、C和HfN原料粉末，以“多-少-多”的方式依次倒入装有Si3N4研磨球的尼龙罐中，加入无水乙醇作为介质，其中：Si3N4研磨球和原料粉末的质量比为2.8～3.5：1，无水乙醇和原料粉末的质量比为3～6：10；
2)将装有原料粉末和无水乙醇介质的尼龙罐固定在行星球磨机中进行湿法球磨混合，球磨时间为8～12h，球磨转速为240～300rpm；
3)将湿法球磨后得到的粉末浆料在旋转蒸发仪中旋转烘干，并过筛得到混合粉末，其中：旋转蒸发仪的转速为50～80rpm，蒸发水浴温度为50～70℃，蒸发压力≤10kPa，筛子目数为80～120目；
4)将得到的混合粉末装入不锈钢模具内进行冷压成型，施加的压力范围是10～20kN，保压时间是3～10min，不锈钢模具的直径为8～20mm；
5)将冷压成型后的混合粉末置于石墨坩埚中，并放置于超高温感应加热无压烧结炉中，在流动的惰性气氛中进行无压烧结，升温速率为80～100℃/min，烧结温度为2400～2450℃，烧结时间为0.5～1h；
6)待保温结束后，以60～100℃/min的速率降温至800～1000℃，再随炉冷却至室温，得到HfCxNy超高温陶瓷粉体材料。
所述的HfCxNy超高温陶瓷粉体材料的制备方法，步骤1)中，Hf粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％；C粉末的平均颗粒尺寸为1～2μm，粉末纯度≥99.9wt％；HfN粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％。
所述的HfCxNy超高温陶瓷粉体材料的制备方法，步骤5)中，惰性气氛为N2，其流速范围2～10L/min。
本发明的设计思想是：
本发明用感应加热无压烧结制备得到HfCxNy超高温陶瓷材料，过渡金属碳氮化物超高温陶瓷一方面过渡金属元素Hf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。
本发明的优点及有益效果是：
1、本发明所涉及的新型HfCxNy超高温陶瓷粉体材料，利用超高温感应加热设备进行无压烧结，升降温速率快，制备工艺流程简单易行，制备周期短。
2、本发明所涉及的新型HfCxNy超高温陶瓷粉体材料，制备出的样品纯度较好，无杂相。
3、本发明所涉及的新型HfCxNy超高温陶瓷粉体材料，所制备的材料熔点较高，有良好的热稳定性，物理性能优异。
附图说明
图1为实施例1～5所制备的HfCxNy超高温陶瓷粉体材料的X射线衍射谱，图中横坐标2θ为衍射角(°)。
图2为实施例1所制备的HfC0.5N0.5超高温陶瓷材料的表面形貌照片，四幅图片分别代表不同倍数材料的形貌。
图3为实施例1所制备的HfC0.5N0.5超高温陶瓷材料EDS元素面分布分析图(左图为HfC0.5N0.5超高温陶瓷形貌图；右上图、右中图、右下图分别为Hf、C、N元素面分布分析图)。
具体实施方式
在具体实施过程中，本发明采用粉末冶金方法无压烧结制备得到HfCxNy超高温陶瓷粉体材料，该方法的具体操作步骤如下：
1)按照设计比例称量所需的Hf、C和HfN原料粉末，将三种原料粉末以体积“多-少-多”的方式依次倒入装有Si3N4研磨球的尼龙罐中，采用“多-少-多”方式的作用是：使样品充分接触混合均匀。加入无水乙醇作为球磨介质，Si3N4研磨球和原料粉末的质量比为2.8～3.5：1，无水乙醇和原料粉末的质量比为3～6：10；
其中，Hf粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％；C粉末的平均颗粒尺寸为1～2μm，粉末纯度≥99.9wt％；HfN粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％。
2)将装有原料粉末和无水乙醇介质的尼龙罐固定在行星球磨机中进行球磨混合，目的是减小粉料颗粒尺寸，暴露出粉末的新鲜活性表面，利于后续无压烧结，球磨时间为8～12h，球磨转速为240～300rpm；
3)将混合破碎后得到的粉末浆料在旋转蒸发仪上旋转烘干，并过筛得到混合粉末，其中旋转蒸发仪的转速为50～80rpm，蒸发水浴温度为50～70℃，蒸发压力≤10kPa(优选为3～8kPa)，筛子目数为80～120目；
4)将得到的混合粉末装入不锈钢模具内进行冷压成型，施加的压力范围是10～20kN，保压时间是3～10min，不锈钢模具的直径为8～20mm；
5)将冷压成型后的混合粉末置于石墨坩埚中，并放置于超高温感应加热无压烧结炉中，在流动的惰性气氛中(如：N2，流速范围2～10L/min)进行无压烧结，升温速率为80～100℃/min，烧结温度为2400～2450℃，烧结时间为0.5～1h；
6)待保温结束后，以60～100℃/min的速率降温至800～1000℃，再随炉冷却至室温，得到HfCxNy超高温陶瓷粉体材料。
该陶瓷材料包括的物相主要为HfCxNy，其中0<x+y≤1。所制得的样品实现固溶，颗粒大小均匀，为2～3μm，其中含有的Hf、C、N元素分布均匀。进一步的，通过实施例验证本发明制备的陶瓷材料成分均匀。
下面，通过实施例和附图进一步详述本发明。但这些实施例不得用于解释为对本发明保护范围的限制，所有在本发明技术方案基本思路范围内或本质上等同于本发明技术方案的改变均为本发明的保护范围。
实施例1
首先，将粒度为1μm的Hf粉末23.30g、粒度为1μm的C粉末1.57g和粒度为1μm的HfN粉末25.13g(所制得的HfCxNy材料化学计量比为HfC0.5N0.5)放入尼龙球磨罐中球磨12h。在60℃以65rpm的转速在旋转蒸发仪(蒸发压力5kPa)中旋转烘干后过80目筛，得到混合陶瓷粉末。接着，装入直径为20mm的不锈钢模具中以10kN冷压成型5min。然后，将冷压成型后的混合粉末置于石墨坩埚中，并放置于感应加热炉中在流速为2L/min的保护性N2中无压烧结，以80℃/min的升温速率加热至2400℃，保温0.5h。保温结束后，以60℃/min的降温速率降温至1000℃，空冷至室温，得到HfC0.5N0.5超高温陶瓷材料。
本实施例中，HfC0.5N0.5超高温陶瓷材料的技术指标如下：熔点约为3990℃，具有高的热稳定性，在3000℃热处理仍能保持原有结构，维氏硬度为19.59GPa。
实施例2
首先，将粒度为2μm的Hf粉末19.61g、粒度为2μm的C粉末1.32g和粒度为2μm的HfN粉末9.07g(所制得的HfCxNy材料化学计量比为HfC0.7N0.3)放入尼龙球磨罐中球磨10h。在65℃下以70rpm的转速在旋转蒸发仪(蒸发压力3kPa)中旋转烘干后过100目筛，得到混合陶瓷粉末。接着，装入直径为8mm的不锈钢模具中以15kN冷压成型8min。然后，将冷压成型后的混合粉末置于石墨坩埚中，并放置于感应加热炉中在流速为3L/min的保护性N2中无压烧结，以90℃/min的升温速率加热至2420℃，保温0.5h。保温结束后，以80℃/min的降温速率降温至900℃，空冷至室温，得到HfC0.7N0.3超高温陶瓷材料。
本实施例中，HfC0.7N0.3超高温陶瓷材料的技术指标如下：熔点约为3980℃，具有高的热稳定性，在3000℃热处理仍能保持原有结构，维氏硬度为19.63GPa。
实施例3
首先，将粒度为0.5μm的Hf粉末11.20g、粒度为1μm的C粉末0.75g和粒度为0.5μm的HfN粉末8.05g(所制得的HfCxNy材料化学计量比为HfC0.6N0.4)放入尼龙球磨罐中球磨9h。在55℃下以75rpm的转速在旋转蒸发仪(蒸发压力6kPa)中旋转烘干后过100目筛，得到混合陶瓷粉末。接着，装入直径为10mm的不锈钢模具中以18kN冷压成型10min。然后，将冷压成型后的混合粉末置于石墨坩埚中，并放置于感应加热炉中在流速为5L/min的保护性N2中无压烧结，以100℃/min的升温速率加热至2410℃，保温1h。保温结束后，以90℃/min的降温速率降温至1000℃，空冷至室温，得到HfC0.6N0.4超高温陶瓷材料。
本实施例中，HfC0.6N0.4超高温陶瓷材料的技术指标如下：熔点约为4020℃，具有高的热稳定性，在3100℃热处理仍能保持原有结构，维氏硬度为19.66GPa。
实施例4
首先，将粒度为1μm的Hf粉末7.45g、粒度为1μm的C粉末0.50g和粒度为2μm的HfN粉末12.05g(所制得的HfCxNy材料化学计量比为HfC0.4N0.6)放入尼龙球磨罐中球磨8h。在50℃下以80rpm的转速在旋转蒸发仪(蒸发压力7kPa)中旋转烘干后过100目筛，得到混合陶瓷粉末。接着，装入直径为8mm的不锈钢模具中以13kN冷压成型10min。然后，将冷压成型后的混合粉末置于石墨坩埚中，并放置于感应加热炉中在流速为4L/min的保护性N2中无压烧结，以90℃/min的升温速率加热至2430℃，保温1h。保温结束后，以100℃/min的降温速率降温至800℃，空冷至室温，得到HfC0.4N0.6超高温陶瓷材料。
本实施例中，HfC0.4N0.6超高温陶瓷材料的技术指标如下：熔点约为4000℃，具有高的热稳定性，在3100℃热处理仍能保持原有结构，维氏硬度为20.16GPa。
实施例5
首先，将粒度为2μm的Hf粉末8.37g、粒度为2μm的C粉末0.56g和粒度为1μm的HfN粉末21.07g(所制得的HfCxNy材料化学计量比为HfC0.3N0.7)放入尼龙球磨罐中球磨12h。在70℃下以60rpm的转速在旋转蒸发仪(蒸发压力8kPa)中旋转烘干后过80目筛，得到混合陶瓷粉末。接着，装入直径为8mm的不锈钢模具中以20kN冷压成型8min。然后，将冷压成型后的混合粉末置于石墨坩埚中，并放置于感应加热炉中在流速为2L/min的保护性N2中无压烧结，以100℃/min的升温速率加热至2450℃，保温0.5h。保温结束后，以100℃/min的降温速率降温至800℃，空冷至室温，得到HfC0.3N0.7超高温陶瓷材料。
本实施例中，HfC0.3N0.7超高温陶瓷材料的技术指标如下：熔点约为3970℃，具有高的热稳定性，在3100℃热处理仍能保持原有结构，维氏硬度为19.89GPa。
如图1所示，本发明制备的HfCxNy超高温陶瓷粉体材料(实施例1～5)的X射线衍射谱。由图1可以看出，经过烧结后初始原料Hf、C和HfN合成为HfCxNy，HfC和HfN的XRD特征峰融合实现固溶，得到HfCxNy相。
如图2所示，本发明制备的HfC0.5N0.5超高温陶瓷材料(实施例1)的表面形貌照片。由图2可以看出，HfC0.5N0.5超高温陶瓷材料颗粒大小均匀，均匀分布。
如图3所示，本发明制备的HfC0.5N0.5超高温陶瓷材料(实施例1)元素面分布分析图。由图3可以看出，Hf元素、C元素和N元素在显微结构中分布均匀，烧结体中不存在其他杂质相。
实施例结果表明，本发明制备的HfCxNy超高温陶瓷材料不仅颗粒大小均匀，而且制备出的材料较纯，无杂质相。此外，还具有制备工艺流程简便，制备周期短等优势。

Claims (6)

1.一种HfCxNy超高温陶瓷粉体材料，其特征在于，超高温陶瓷粉体材料的化学组成为HfCxNy，其中0<x+y≤1。
2.按照权利要求1所述的HfCxNy超高温陶瓷粉体材料，其特征在于，优选的，x+y＝1，x或y＝0.2～0.8。
3.按照权利要求1所述的HfCxNy超高温陶瓷粉体材料，其特征在于，HfCxNy超高温陶瓷粉体材料实现固溶，颗粒大小均匀，为2～3μm。
4.一种权利要求1至3之一所述的HfCxNy超高温陶瓷粉体材料的制备方法，其特征在于，该方法的具体操作步骤如下：
1)按照设计比例称量所需的Hf、C和HfN原料粉末，以“多-少-多”的方式依次倒入装有Si3N4研磨球的尼龙罐中，加入无水乙醇作为介质，其中：Si3N4研磨球和原料粉末的质量比为2.8～3.5：1，无水乙醇和原料粉末的质量比为3～6：10；
2)将装有原料粉末和无水乙醇介质的尼龙罐固定在行星球磨机中进行湿法球磨混合，球磨时间为8～12h，球磨转速为240～300rpm；
3)将湿法球磨后得到的粉末浆料在旋转蒸发仪中旋转烘干，并过筛得到混合粉末，其中：旋转蒸发仪的转速为50～80rpm，蒸发水浴温度为50～70℃，蒸发压力≤10kPa，筛子目数为80～120目；
4)将得到的混合粉末装入不锈钢模具内进行冷压成型，施加的压力范围是10～20kN，保压时间是3～10min，不锈钢模具的直径为8～20mm；
5)将冷压成型后的混合粉末置于石墨坩埚中，并放置于超高温感应加热无压烧结炉中，在流动的惰性气氛中进行无压烧结，升温速率为80～100℃/min，烧结温度为2400～2450℃，烧结时间为0.5～1h；
6)待保温结束后，以60～100℃/min的速率降温至800～1000℃，再随炉冷却至室温，得到HfCxNy超高温陶瓷粉体材料。
5.按照权利要求4所述的HfCxNy超高温陶瓷粉体材料的制备方法，其特征在于，步骤1)中，Hf粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％；C粉末的平均颗粒尺寸为1～2μm，粉末纯度≥99.9wt％；HfN粉末的平均颗粒尺寸为0.5～2μm，粉末纯度≥99.5wt％。
6.按照权利要求4所述的HfCxNy超高温陶瓷粉体材料的制备方法，其特征在于，步骤5)中，惰性气氛为N2，其流速范围2～10L/min。
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