CN111072388B - 一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷及其应用 - Google Patents

一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷及其应用 Download PDF

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CN111072388B
CN111072388B CN202010091997.1A CN202010091997A CN111072388B CN 111072388 B CN111072388 B CN 111072388B CN 202010091997 A CN202010091997 A CN 202010091997A CN 111072388 B CN111072388 B CN 111072388B
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CN111072388A (zh
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孙威
彭峥
熊翔
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Central South University
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Abstract

本发明属于碳化物陶瓷技术领域，具体涉及一种含氮碳化物超高温陶瓷块体及应用。本发明首次提供了采用球磨+放电等离子烧结来制备致密度大于等于98％且C/N含量分布均匀的HfCxNy陶瓷。本发明所设计和制备的新型超高熔点陶瓷克服了现有超高温抗烧蚀陶瓷存在耐烧蚀温度过低或高温烧蚀损耗过快的缺陷；使得其适用于3000℃及以上超高温抗烧蚀防护。通过验证发现经超长时间(300s)烧蚀后陶瓷仍保持接近零烧蚀率的状态和连续稳定的抗氧化防护结构。

Description

一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷及其应用
技术领域
本发明属于碳化物陶瓷技术领域，具体涉及一种含氮碳化物超高温陶瓷块体及应用。
背景技术
超高温陶瓷具有超高熔点，高温高强度以及良好的化学稳定性等优点，主要用于超高温的极端环境。常见的第四副族和第五副族的碳化物，氮化物及硼化物为超高温陶瓷的典型代表。目前高超音速飞行器是超高温陶瓷的首要目标应用领域。当飞行器在空气中以5倍以上声速飞行时，其表面由于空气阻力而产生的超高温热流对飞行器的热防护***提出了严峻的挑战。飞行器的鼻锥帽、翼前缘等部位的加热速率和表面温度最高，因此，高熔点性能是满足鼻锥帽和翼前缘要求的气动控制材料的首要选择标准，而材料在高温下抗氧化、抗烧蚀性则是保证高超音速飞行器空气动力学性能的最优化的必要条件。
目前在高温氧化环境下的结构材料或涂层大多数以SiC为主，因其在氧化中能形成氧扩散率极低的SiO2基保护层，因而具有优异的抗氧化性。但是硅基材料的抗氧化温度上限约为1700℃，一旦超过，硅基材料将发生主动氧化生成气态SiO而非SiO2保护膜，导致材料表面烧蚀速率急剧增加。基于硅基材料抗氧化温度上限难以超过1700℃的本征缺陷，迫切需要研发具有更好耐温容限的材料来满足新一代高超音速飞行器的发展需求。因此发展铪基和锆基超高温陶瓷，使其在高温氧化环境下生成耐高温烧蚀的固态氧化膜，以期满足服役要求，突破硅基材料的使用温度限制。铪基材料相比于锆基材料具有更优越的高温稳定性和耐烧蚀性，因此为了发展新一代更高熔点的长时耐烧蚀超高温陶瓷，进一步优化铪基超高温陶瓷组分，更好的发挥铪基陶瓷的超高温特性，增加其使用温度容限成为当前研究的关键问题。
目前公开实验报导的最高熔点物质为Ta4HfC5，熔点约为4200K，研究发现它具有超高熔点的原因是因为合金元素的微量掺杂能调节费米能级的位置，使其恰好位于能谷处。一般而言，比能谷能量更低的电子态代表成键轨道，能量更高的代表反键轨道，当费米能级比能谷的能量高，这说明在费米能级处一些反键轨道被占据了。由于反键轨道的占据会削弱化学键的强度，所以如果空出反键轨道，则能够增强化学键，提高材料的硬度和熔点。然而美国Brown大学Axel van de Walle等人基于密度泛函理论的第一性原理计算对固体进行量子力学模拟，发现HfCxNy体系具有极高的熔化焓，预测HfCxNy为超高熔点物质。有研究者展开过相关研究：如采用热压法来制备HfCxNy；但从制备方法而言，因为强共价键和低扩散率的原因，其它研究者通过热压法制备发现制备该材料时，发现随着氮含量的增加很难得到致密的样品，并且存在C/N含量分布不均的问题。本发明制备的样品致密度达到99.8％，且为均一单相碳氮化物固溶体。
发明内容
本发明针对现有技术的不足，首次提供了采用球磨+放电等离子烧结来制备致密度大于等于99.8％且C/N含量分布均匀的HfCxNy陶瓷。
本发明所设计和制备的新型超高熔点陶瓷克服了现有超高温抗烧蚀陶瓷存在耐烧蚀温度过低或高温烧蚀损耗过快的缺陷；使得其适用于3000℃及以上超高温抗烧蚀防护。通过验证发现经超长时间(300s)烧蚀后陶瓷仍保持接近零烧蚀率的状态和连续稳定的抗氧化防护结构。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其通过下述步骤制备：
步骤一
按质量比，HfC：HfN＝(1-7):1，优选1-3:1；配取HfC粉末、HfN粉末，将配取的HfC粉末、HfN粉末与碳粉、氮化碳粉末混合均匀；得到混合粉末；碳粉的加入量不超过混合粉体质量的8.0wt％；氮化碳粉的加入量不超过混合粉体质量的5.0wt％；
步骤二
对步骤一所得混合粉末进行放电等离子烧结，得到长时耐烧蚀超高熔点含氮碳化物超高温陶瓷；放电等离子烧结的条件为：烧结炉内温度为1500-2400℃，保温5-60分钟，升温速率为5-150℃/min，降温速率为5-150℃/min，压力为20-60Mpa，真空度小于5Pa。优选烧结条件为：烧结炉内温度为1900-2100℃，保温10-20分钟，升温速率为100-120℃/min，降温速率为100-120℃/min，压力为30-50Mpa，真空度小于5Pa。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，步骤一中所述HfC粉末和HfN粉末的为纳米级粉末或微米级粉末。作为优选方案，所述HfC粉末和HfN粉末的粒径均小于等于10微米。作为进一步的优选方案，所述所述HfC粉末和HfN粉末的粒径均小于等于3微米。碳粉的粒径小于等于10微米、氮化碳的粒径小于等于10微米。作为进一步的优选方案，碳粉的粒径小于等于3微米、氮化碳的粒径小于等于3微米。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，步骤一中所述HfC粉末和HfN粉末的纯度均大于等于99.9％。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，步骤一中，按质量比，HfC：HfN＝(1-3):1配取HfC粉末、HfN粉末，将配取的HfC粉末、HfN粉末与碳粉、氮化碳粉末混合均匀；得到混合粉末；碳粉的加入量大于0且不超过混合粉体质量的8.0wt％；氮化碳粉的加入量大于0且不超过混合粉体质量的5.0wt％。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，通过湿法球磨的方式实现各原料粉末的混合均匀。所述湿法球磨时：控制球磨转速为200-400r/min，球磨时间为12-24h，球料比为3-10：1。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，湿法球磨时，采用的球磨介质为有机物；优选为乙醇。湿法球磨后，在真空气氛下于50-150℃干燥8-12h后过325目筛，取筛下物作为等离子烧结的备用料。在工业上应用时，备用料在隔绝空气的条件下密封保存。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，所得产品的致密度大于等于98％且C/N含量分布均匀；优选为所得产品的致密度大于等于99.5％且C/N含量分布均匀。
作为优选，本发明中碳粉和氮化碳粉质量百分比纯度99％。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为8×10-3～9×10-1mg/s，线烧蚀率为1×10-5mm/s～3×10-3mm/s。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，按照HfC和HfN粉末的质量比为3:1配取HfC和HfN粉末所制备的产品；在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率和线烧蚀率分别为8×10-3mg/s、1×10-5mm/s。这种效果大大超出了当时的预计。
本发明一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷的应用，包括将其用于3000℃及以上超高温抗烧蚀防护。
发明的优点和积极效果
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)制备陶瓷熔化焓超高，键强超高，熔点极高。
(2)制备陶瓷抗烧蚀效果佳。通过适量和适当比例的HfC和HfN的选取结合放电等离烧结，所得样品在3000℃烧蚀300s后仍保持几乎零烧蚀率的状态，中心烧蚀区无明显烧蚀坑；
(3)制备样品力学性能好。将适量的HfC和HfN复合后改善了碳化物断裂韧性低的本征缺陷，大大提升了陶瓷的弯曲强度和断裂韧性。
附图说明
图1为实例1.2.3中HfCxNy陶瓷表面X射线衍射图谱。
图2为实例2中HfC0.76N0.24固溶体表面宏观形貌。
图3为实例2中HfC0.76N0.24固溶体表面微观形貌。可见样品致密，无明显孔洞，且相成分均一。
图4为实例2中HfC0.76N0.24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见明显烧蚀坑，证明具有非常优异的抗烧蚀性能。
图5为实例2中HfC0.76N0.24试样于烧蚀后中心区表面微观结构。
图6为实例2中HfC0.76N0.24试样于烧蚀后中心区截面微观结构。
图7为对比例1中HfC表面微观形貌。可见样品有明显孔洞。
图8为对比例1中HfC陶瓷于3000℃氧乙炔焰烧蚀60s后的宏观烧蚀形貌图，烧蚀中心区有明显的烧蚀坑现象。
具体实施方式
实施例一
将HfC和HfN粉末按照质量比3:2，碳粉加入量为粉体总质量的5％，氮化碳加入量为粉体总质量的5％，在行星式球磨机上球磨15h，粉末粒度为1um，纯度大于99.9％，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80℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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2100℃，保温15分钟，压力45Mpa，随后以100℃/min的降温速率冷却到室温。烧结后的陶瓷块体经过电子探针表征显示C和N的原子比为0.60:0.40，得到均质HfC0.60N0.40固溶体(致密度为99.8％)。参照国标GJB323A-96所述的烧蚀实验装备进行烧蚀测试，在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为9×10-1mg/s，线烧蚀率为3×10- 3mm/s。
实施例二
将HfC和HfN粉末按照质量比3:1，碳粉加入量为粉体总质量的4％，氮化碳加入量为粉体总质量的6％，在行星式球磨机上球磨20h，粉末粒度为1um，纯度大于99.9％，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。
将混合粉料放置在石墨模具中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10分钟，压力40Mpa，随后以100℃/min的降温速率冷却到室温，得到高纯度单一相面心立方结构的陶瓷。烧结后的陶瓷块体经过电子探针表征显示C和N的原子比为0.76:0.24，形成HfC0.76N0.24固溶体(致密度为99.6％)。参照国标GJB323A-96所述的烧蚀实验装备进行烧蚀测试，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8×10-3mg/s、1×10-5mm/s。
实施例三
将HfC和HfN粉末按照质量比7:1，碳粉加入量为粉体总质量的5％，氮化碳加入量为粉体总质量的5％，在行星式球磨机上球磨20h，粉末粒度为1um，纯度大于99.9％，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70℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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10分钟，压力45Mpa，随后以100℃/min的降温速率冷却到室温，得到高纯度单一相面心立方结构的陶瓷结构。烧结后的陶瓷块体经过电子探针表征显示C和N的原子比为0.88:0.12，形成HfC0.88N0.12固溶体(致密度为98％)。参照国标GJB323A-96所述的烧蚀实验装备进行烧蚀测试，在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为6×10-1mg/s，线烧蚀率为2×10-3mm/s。
实施例四
将HfC和HfN粉末按照质量比4:1，碳粉加入量为粉体总质量的6％，氮化碳加入量为粉体总质量的5％，在行星式球磨机上球磨17h，粉末粒度为1um，纯度大于99.9％，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70℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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2100℃，保温10分钟，压力45Mpa，随后以100℃/min的降温速率冷却到室温，得到高纯度单一相面心立方结构的陶瓷结构。参照国标GJB323A-96所述的烧蚀实验装备进行烧蚀测试，在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为7×10-1mg/s，线烧蚀率为4×10-3mm/s。
实施例五
将HfC和HfN粉末按照质量比5:2，碳粉加入量为粉体总质量的4％，氮化碳加入量为粉体总质量的5％，在行星式球磨机上球磨16h，粉末粒度为1um，纯度大于99.9％，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70℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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2100℃，保温10分钟，压力45Mpa，随后以100℃/min的降温速率冷却到室温，得到高纯度陶瓷(致密度为99.5％)。参照国标GJB323A-96所述的烧蚀实验装备进行烧蚀测试，在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为9×10-2mg/s，线烧蚀率为9×10-4mm/s。
对比例一
将HfC粉末在行星式球磨机上球磨20h，粉末粒度为1um，纯度大于99.9％，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60℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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10分钟，压力40Mpa，随后以100℃/min的降温速率冷却到室温，得到HfC陶瓷(致密度为90％)。未掺氮的HfC陶瓷在3000℃氧乙炔焰环境下烧蚀60s后有明显烧蚀坑，在3000℃氧乙炔焰环境下烧蚀60s后质量烧蚀率为9mg/s，线烧蚀率为5×10-2mm/s。抗烧蚀性能没有实施例中的新型掺氮碳化物超高温陶瓷优异。
对比例二
将HfC和HfN粉末按照质量比10:1，在行星式球磨机上球磨18h，粉末粒度为1um，纯度大于99.9％，球磨介质为乙醇溶液，转速为200r/min，球料比为7:1，随后放置在60℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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2100℃，保温10分钟，压力40Mpa，随后以100℃/min的降温速率冷却到室温。该陶瓷样品在3000℃氧乙炔焰环境下烧蚀60s后质量烧蚀率为8.7mg/s，线烧蚀率为4×10-2mm/s。
对比例三
将HfN粉末在行星式球磨机上球磨18h，粉末粒度为1um，纯度大于99.9％，球磨介质为乙醇溶液，转速为200r/min，球料比为7:1，随后放置在60℃的干燥箱中烘干10小时，过筛后得到混合粉料。
将混合粉料放置在石墨模具中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2100℃，保温10分钟，压力40Mpa，随后以100℃/min的降温速率冷却到室温。该HfN陶瓷样品在3000℃氧乙炔焰环境下烧蚀60s后质量烧蚀率为9.5mg/s，线烧蚀率为6×10-2mm/s。

Claims (6)

1.一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其特征在于；通过下述步骤制备：
步骤一
按质量比，HfC：HfN=（1-3）:1配取HfC粉末、HfN粉末，将配取的HfC粉末、HfN粉末与碳粉、氮化碳粉末混合均匀；得到混合粉末；碳粉的加入量大于0且不超过混合粉体质量的8.0wt%；氮化碳粉的加入量大于0且不超过混合粉体质量的5.0wt%；
步骤二
对步骤一所得混合粉末进行放电等离子烧结，得到长时耐烧蚀超高熔点含氮碳化物超高温陶瓷；放电等离子烧结的条件为：烧结炉内温度为1900-2100℃，保温10-20分钟，升温速率为100-120℃/min，降温速率为100-120℃/min，压力为30-50MPa，真空度小于5Pa；所得产品的致密度大于等于98%且C/N含量分布均匀；所得产品在3000℃氧乙炔焰环境下烧蚀300s后质量烧蚀率为8×10-3~9×10-1mg/s，线烧蚀率为1×10-5mm/s ~3×10-3mm/s。
2.根据权利要求1所述的一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其特征在于：步骤一中所述HfC粉末和HfN粉末的为纳米级粉末或微米级粉末。
3.根据权利要求1所述的一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其特征在于：步骤一中所述HfC粉末和HfN粉末的纯度均大于等于99.9%。
4.根据权利要求1所述的一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其特征在于：通过湿法球磨的方式实现各原料粉末的混合均匀；所述湿法球磨时，控制球磨转速为200-400r/min，球磨时间为12-24h，球料比为3-10：1。
5.根据权利要求1所述的一种长时耐烧蚀超高熔点含氮碳化物超高温陶瓷，其特征在于：湿法球磨时，采用的球磨介质为有机物；湿法球磨后，在真空气氛下于50-150℃干燥8-12h后过325目筛，取筛下物作为等离子烧结的备用料。
6.一种如权利要求1-5任意一项所述长时耐烧蚀超高熔点含氮碳化物超高温陶瓷的应用，其特征在于：包括将其用于3000℃及以上超高温抗烧蚀防护。
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