WO2021103560A1 - 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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WO2021103560A1
WO2021103560A1 PCT/CN2020/101425 CN2020101425W WO2021103560A1 WO 2021103560 A1 WO2021103560 A1 WO 2021103560A1 CN 2020101425 W CN2020101425 W CN 2020101425W WO 2021103560 A1 WO2021103560 A1 WO 2021103560A1
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powder
ablation
ultra
high temperature
hfc
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PCT/CN2020/101425
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French (fr)
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孙威
彭峥
熊翔
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中南大学
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Priority to US17/264,305 priority Critical patent/US12012364B2/en
Publication of WO2021103560A1 publication Critical patent/WO2021103560A1/zh

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Definitions

  • the invention belongs to the technical field of carbide ceramics, and specifically relates to a nitrogen-containing carbide ultra-high temperature ceramic block and its application.
  • Ultra-high temperature ceramics have the advantages of ultra-high melting point, high temperature, high strength, and good chemical stability, and are mainly used in extreme environments with ultra-high temperatures. Common carbides, nitrides and borides of the fourth and fifth subgroups are typical representatives of ultra-high temperature ceramics.
  • hypersonic aircraft is the primary target application field of ultra-high temperature ceramics. When an aircraft flies in the air at more than 5 times the speed of sound, the ultra-high temperature heat flow generated on the surface due to air resistance poses a severe challenge to the aircraft's thermal protection system. The heating rate and surface temperature of the nose cone cap, wing leading edge and other parts of the aircraft are the highest.
  • high melting point performance is the primary selection criterion for aerodynamic control materials that meet the requirements of the nose cone cap and wing leading edge, and the material is resistant to oxidation at high temperatures.
  • the ablation resistance is a necessary condition to ensure the optimization of the aerodynamic performance of hypersonic aircraft.
  • the majority of SiC-based can be formed because of low oxygen diffusion rates in the SiO 2 based protective oxide layer, which has excellent oxidation resistance.
  • the upper limit of the oxidation resistance temperature of silicon-based materials is about 1700°C. Once exceeded, the silicon-based materials will be actively oxidized to form a gaseous SiO instead of SiO 2 protective film, resulting in a sharp increase in the ablation rate of the material surface. Based on the inherent defect that the upper limit of oxidation resistance temperature of silicon-based materials cannot exceed 1700°C, there is an urgent need to develop materials with better temperature tolerance to meet the development needs of a new generation of hypersonic aircraft.
  • hafnium-based and zirconium-based ultra-high-temperature ceramics can generate high-temperature ablation-resistant solid oxide films in high-temperature oxidation environments in order to meet service requirements and break through the use temperature limits of silicon-based materials.
  • hafnium-based materials have superior high-temperature stability and ablation resistance. Therefore, in order to develop a new generation of higher melting point long-term ablation-resistant ultra-high temperature ceramics, the components of hafnium-based ultra-high temperature ceramics are further optimized. Making better use of the ultra-high temperature characteristics of hafnium-based ceramics and increasing their use temperature tolerance have become key issues in current research.
  • the highest melting point material reported in public experiments is Ta 4 HfC 5 , with a melting point of about 4200K.
  • the reason for its ultra-high melting point is that the micro-doping of alloying elements can adjust the position of the Fermi energy level so that it is exactly at the energy level. Valley place.
  • the electronic state with lower energy than energy valley represents the bonding orbital, and the higher energy represents the antibonding orbital.
  • the Fermi energy level is higher than the energy valley, it means that there are some antibonding at the Fermi energy level. The track is occupied.
  • the hot pressing method is used to prepare HfC x N y ; but in terms of the preparation method, due to the strong covalent bond and low diffusivity, other researchers have found that the preparation of the HfC x N y by hot pressing method It is found that it is difficult to obtain dense samples with the increase of nitrogen content, and there is a problem of uneven distribution of C/N content.
  • the sample prepared by the invention has a density of 99.8% and is a uniform single-phase carbonitride solid solution.
  • the present invention provides for the first time HfC x N y ceramics with a density greater than or equal to 99.8% and a uniform C/N content distribution by using ball milling + spark plasma sintering.
  • the new ultra-high melting point ceramic designed and prepared by the present invention overcomes the defects of the existing ultra-high temperature ablation resistant ceramics that the ablation resistance temperature is too low or the high temperature ablation loss is too fast; making it suitable for ultra-high temperature resistance of 3000 °C and above Ablative protection. Through verification, it is found that the ceramic still maintains a state of close to zero ablation rate and a continuous and stable anti-oxidation protective structure after a long time (300s) ablation.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic, which is prepared through the following steps.
  • step one
  • HfC: HfN (1-7):1, preferably 1-3:1; prepare HfC powder and HfN powder, mix the prepared HfC powder, HfN powder with carbon powder and carbon nitride powder Uniform; the mixed powder is obtained; the addition amount of carbon powder does not exceed 8.0wt% of the mass of the mixed powder; the addition amount of carbon nitride powder does not exceed 5.0wt% of the mass of the mixed powder.
  • the mixed powder obtained in step 1 is subjected to spark plasma sintering to obtain long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramics;
  • the conditions for spark plasma sintering are: the temperature in the sintering furnace is 1500-2400°C, and the holding time is 5-60 minutes , The heating rate is 5-150°C/min, the cooling rate is 5-150°C/min, the pressure is 20-60Mpa, and the vacuum degree is less than 5Pa.
  • the preferred sintering conditions are as follows: the temperature in the sintering furnace is 1900-2100°C, the holding time is 10-20 minutes, the heating rate is 100-120°C/min, the cooling rate is 100-120°C/min, the pressure is 30-50Mpa, and the vacuum degree is less than 5Pa.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic.
  • the HfC powder and the HfN powder are nano-level powders or micro-level powders.
  • the particle diameters of the HfC powder and HfN powder are both less than or equal to 10 microns.
  • the particle diameters of the HfC powder and HfN powder are both less than or equal to 3 microns.
  • the particle size of carbon powder is less than or equal to 10 microns, and the particle size of carbon nitride is less than or equal to 10 microns.
  • the particle size of the carbon powder is less than or equal to 3 microns, and the particle size of the carbon nitride is less than or equal to 3 microns.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic.
  • the purity of the HfC powder and the HfN powder are both greater than or equal to 99.9%.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic.
  • HfC powder, HfN powder, carbon powder and carbon nitride powder are mixed uniformly; the mixed powder is obtained; the addition amount of carbon powder is greater than 0 and does not exceed 8.0wt% of the mass of the mixed powder; the addition amount of carbon nitride powder is greater than 0 And it does not exceed 5.0wt% of the mass of the mixed powder.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic, which realizes the uniform mixing of raw material powders through wet ball milling.
  • the rotating speed of the ball mill is controlled to be 200-400r/min, the milling time is 12-24h, and the ball-to-battery ratio is 3-10:1.
  • the invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic.
  • the ball milling medium used is organic; preferably ethanol.
  • wet ball milling dry at 50-150°C for 8-12 hours in a vacuum atmosphere, then pass through a 325-mesh sieve, and take the undersized material as a spare material for plasma sintering. When used in industry, the spare material is sealed and stored under the condition of isolating air.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic, and the resulting product has a density greater than or equal to 98% and a uniform C/N content distribution; preferably, the resulting product has a density greater than or equal to 99.5% and C /N content is evenly distributed.
  • the purity of the carbon powder and carbon nitride powder in the present invention is 99% by mass percentage.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic, which has a mass ablation rate of 8 ⁇ 10 -3 ⁇ 9 ⁇ 10 -1 mg/after ablation for 300s in an oxyacetylene flame environment at 3000°C s, the linear ablation rate is 1 ⁇ 10 -5 mm/s ⁇ 3 ⁇ 10 -3 mm/s.
  • the present invention is a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic.
  • the product is prepared by mixing HfC and HfN powder according to the mass ratio of HfC and HfN powder of 3:1; in an oxyacetylene flame environment at 3000°C
  • the mass ablation rate and the line ablation rate after 300s of lower ablation were 8 ⁇ 10 -3 mg/s and 1 ⁇ 10 -5 mm/s, respectively. This effect greatly exceeded expectations at the time.
  • the application of a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic includes using it for ultra-high temperature and ablation protection at 3000 DEG C and above.
  • the prepared ceramic has good anti-ablation effect.
  • the obtained sample still maintains almost zero ablation rate after ablation at 3000°C for 300s, and there is no obvious ablation pit in the central ablation zone.
  • Figure 1 shows the X-ray diffraction pattern of the HfCxNy ceramic surface in Example 1.2.3.
  • Figure 2 shows the macroscopic morphology of the surface of the HfC0.76N0.24 solid solution in Example 2.
  • Figure 3 shows the microscopic morphology of the surface of the HfC0.76N0.24 solid solution in Example 2. It can be seen that the sample is dense, without obvious holes, and the phase composition is uniform.
  • Figure 4 shows the macroscopic ablation morphology of the HfC0.76N0.24 sample in Example 2 after ablation of the oxyacetylene flame at 3000°C for 300s. No obvious ablation pits were seen after long-term ablation at ultra-high temperature, which proved to be very excellent Anti-ablation performance.
  • Figure 5 shows the surface microstructure of the HfC0.76N0.24 sample in the central area after ablation in Example 2.
  • Figure 6 shows the microstructure of the central area of the HfC0.76N0.24 sample in Example 2 after ablation.
  • Figure 7 shows the surface microstructure of HfC in Comparative Example 1. It can be seen that the sample has obvious holes.
  • Figure 8 is a macroscopic ablation morphology of HfC ceramics in Comparative Example 1 after being ablated at 3000°C with an oxyacetylene flame for 60 seconds. There are obvious ablation pits in the ablation center area.
  • the addition of carbon powder is 5% of the total mass of the powder
  • the addition of carbon nitride is 5% of the total mass of the powder.
  • Ball milled on a planetary ball mill for 15 hours the powder size is 1um, the purity is greater than 99.9%, the ball milling medium is ethanol solution, the speed is 200r/min, the ball-to-battery ratio is 8:1, then it is placed in a drying oven at 80°C for 10 hours, and the mixed powder is obtained after sieving.
  • the vacuum degree in the furnace is less than 5Pa.
  • the temperature is raised to 2100°C at a heating rate of 100°C/min, the temperature is kept for 15 minutes, the pressure is 45Mpa, and then the temperature is lowered at a rate of 100°C/min. Cool to room temperature.
  • the sintered ceramic block was characterized by electron probes and showed that the atomic ratio of C and N was 0.60:0.40, and a homogeneous HfC 0.60 N 0.40 solid solution (density of 99.8%) was obtained.
  • the ablation test was carried out with reference to the ablation experiment equipment described in the national standard GJB323A-96.
  • the mass ablation rate was 9 ⁇ 10 -1 mg/s and the linear ablation rate was 3 ⁇ after ablation for 300 s in an oxyacetylene flame environment at 3000°C. 10 -3 mm/s.
  • the HfC and HfN powders are in a mass ratio of 3:1, the amount of carbon powder added is 4% of the total mass of the powder, and the amount of carbon nitride added is 6% of the total mass of the powder.
  • Ball milled on a planetary ball mill for 20 hours the powder particle size is 1um, the purity is greater than 99.9%, the ball milling medium is ethanol solution, the speed is 200r/min, the ball-to-battery ratio is 8:1, and then it is placed in a drying oven at 50°C for 10 hours and dried to obtain a mixed powder after sieving.
  • the vacuum in the furnace is less than 5Pa.
  • the temperature is raised to 2000°C at a heating rate of 100°C/min, and the temperature is kept for 10 minutes.
  • the pressure is 40Mpa, and then the temperature is reduced at a rate of 100°C/min.
  • a high-purity single-phase face-centered cubic structure ceramic is obtained.
  • the sintered ceramic block was characterized by electron probes and showed that the atomic ratio of C and N was 0.76:0.24, forming a HfC 0.76 N 0.24 solid solution (with a density of 99.6%).
  • the ablation test was carried out with reference to the ablation experimental equipment described in the national standard GJB323A-96.
  • the mass ablation rate and the line ablation rate after ablation for 300s in an oxyacetylene flame environment at 3000°C were only 8 ⁇ 10 -3 mg/s, 1 ⁇ 10 -5 mm/s.
  • the HfC and HfN powders are in a mass ratio of 7:1, the addition of carbon powder is 5% of the total mass of the powder, and the addition of carbon nitride is 5% of the total mass of the powder.
  • the vacuum degree in the furnace is less than 5Pa.
  • the temperature is raised to 2000°C at a heating rate of 100°C/min, the temperature is kept for 10 minutes, the pressure is 45Mpa, and then the temperature is reduced at a rate of 100°C/min.
  • a high-purity single-phase face-centered cubic structure ceramic structure is obtained.
  • the sintered ceramic block was characterized by electron probes and showed that the atomic ratio of C and N was 0.88:0.12, forming a HfC 0.88 N 0.12 solid solution (with a density of 98%).
  • the ablation test was carried out with reference to the ablation experimental equipment described in the national standard GJB323A-96.
  • the mass ablation rate was 6 ⁇ 10 -1 mg/s and the linear ablation rate was 2 ⁇ after ablation for 300 s in an oxyacetylene flame environment at 3000°C. 10 -3 mm/s.
  • the HfC and HfN powders are in a mass ratio of 4:1, the addition amount of carbon powder is 6% of the total mass of the powder, and the addition amount of carbon nitride is 5% of the total mass of the powder.
  • Ball milled on a planetary ball mill for 17 hours the powder particle size is 1um, the purity is greater than 99.9%, the ball milling medium is ethanol solution, the speed is 200r/min, the ball-to-battery ratio is 8:1, and then it is placed in a drying oven at 70°C for 10 hours and dried to obtain a mixed powder after sieving.
  • the HfC and HfN powders according to the mass ratio of 5:2, the addition of carbon powder is 4% of the total mass of the powder, the addition of carbon nitride is 5% of the total mass of the powder, ball milled on a planetary ball mill for 16 hours, the powder size is 1um, the purity is greater than 99.9%, the ball milling medium is ethanol solution, the speed is 200r/min, the ball-to-battery ratio is 8:1, and then it is placed in a drying oven at 70°C for 10 hours and dried to obtain a mixed powder after sieving.
  • the vacuum in the furnace is less than 5Pa.
  • the temperature is raised to 2100°C at a heating rate of 100°C/min, and the temperature is kept for 10 minutes.
  • the pressure is 45Mpa, and then the temperature is reduced at a rate of 100°C/min. Cool to room temperature to obtain high-purity ceramics (with a density of 99.5%).
  • the ablation test was carried out with reference to the ablation experimental equipment described in the national standard GJB323A-96.
  • the mass ablation rate was 9 ⁇ 10 -2 mg/s and the linear ablation rate was 9 ⁇ after ablation for 300 s in an oxyacetylene flame environment at 3000°C. 10 -4 mm/s.
  • the HfC powder was ball milled on a planetary ball mill for 20 hours, the powder size was 1um, the purity was greater than 99.9%, the ball milling medium was ethanol solution, the speed was 200r/min, the ball-to-battery ratio was 8:1, and then placed in a 60°C drying oven Dry for 10 hours, and get mixed powder after sieving.
  • HfC ceramics (with a density of 90%) are obtained.
  • the HfC ceramics without nitrogen doped have obvious ablation pits after ablation for 60s under 3000°C oxyacetylene flame environment. After 60s ablation under 3000°C oxyacetylene flame environment, the mass ablation rate is 9mg/s, and the linear ablation rate is 9mg/s. 5 ⁇ 10 -2 mm/s.
  • the anti-ablation performance is not as good as the new nitrogen-doped carbide ultra-high temperature ceramics in the examples.
  • the HfC and HfN powders are milled on a planetary ball mill for 18 hours at a mass ratio of 10:1.
  • the particle size of the powder is 1um, and the purity is greater than 99.9%.
  • the milling medium is ethanol solution, the rotating speed is 200r/min, and the ball-to-battery ratio is 7:1. Then, it was placed in a drying box at 60°C for 10 hours to dry, and the mixed powder was obtained after sieving.
  • the vacuum in the furnace is less than 5Pa.
  • the temperature is raised to 2100°C at a heating rate of 100°C/min, and the temperature is kept for 10 minutes.
  • the pressure is 40Mpa, and then the temperature is reduced at a rate of 100°C/min. Cool to room temperature.
  • the mass ablation rate of the ceramic sample was 8.7 mg/s after ablation for 60 s in an oxyacetylene flame environment at 3000°C, and the linear ablation rate was 4 ⁇ 10 -2 mm/s.
  • the HfN powder was ball milled on a planetary ball mill for 18 hours, the powder size was 1um, the purity was greater than 99.9%, the ball milling medium was ethanol solution, the rotation speed was 200r/min, the ball-to-battery ratio was 7:1, and then placed in a drying oven at 60°C. Dry for 10 hours, and get mixed powder after sieving.
  • the vacuum in the furnace is less than 5Pa.
  • the temperature is raised to 2100°C at a heating rate of 100°C/min, and the temperature is kept for 10 minutes.
  • the pressure is 40Mpa, and then the temperature is reduced at a rate of 100°C/min. Cool to room temperature.
  • the mass ablation rate of the HfN ceramic sample was 9.5 mg/s and the linear ablation rate was 6 ⁇ 10 -2 mm/s after being ablated in an oxyacetylene flame environment at 3000°C for 60 seconds.

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Abstract

一种含氮碳化物超高温陶瓷块体及应用，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HfC xN y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SiO 2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SiO 2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Ta 4HfC 5，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HfC xN y体系具有极高的熔化焓，预测HfC xN y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HfC xN y；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。
技术问题
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HfC xN y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。
 技术解决方案
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。
 有益效果
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。
 本发明的最佳实施方式
在此处键入本发明的最佳实施方式描述段落。
 本发明的实施方式
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HfC 0.60N 0.40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HfC 0.76N 0.24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HfC 0.88N 0.12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。
工业实用性
在此处键入工业实用性描述段落。
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Claims (10)

  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=（1-7）: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。
  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，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%。
  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、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，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3微米、氮化碳的粒径小于等于3微米。
  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：步骤一中所述HfC粉末和HfN粉末的纯度均大于等于99.9%。
  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：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。
  6. 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；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。
  7. 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：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。
  8. 根据权利要求1-7任意一项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：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。
  9. 根据权利要求7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：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。
  10. 一种如权利要求1-7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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