目的 提高高超声速飞行器用铌合金构件的高温抗氧化性能,拓展其在复杂服役环境中的应用范围。方法 采用微弧氧化粒子（HfC+HfO2）沉积烧结技术,在渗硅铌合金表面制备HfC-HfO2改性硅化物基复合涂层。通过1 200 ℃下的静态空气氧化试验,研究复合涂层的高温氧化行为。采用扫描电子显微镜、X射线衍射仪和高分辨透射电镜研究复合涂层的组织结构、相成分,以及复合涂层在不同氧化时间下的微观结构演变规律。结果 渗硅铌合金表面HfC-HfO2粒子沉积层的厚度约为45 μm。复合涂层在整个等温氧化过程中表现出最佳的抗氧化性,其质量增益仅为6.41 mg/cm2,抛物线速率常数为0.367 mg2/(cm4·h),而单一NbSi2涂层则呈加速氧化的趋势,其质量增益达到13.6 mg/cm2。结论 将HfC作为耗氧相引入复合涂层,最终在高温下形成了HfSiO4骨架结构,从而提高了氧化皮的稳定性,且富Hf氧化物锚定了SiO2氧化皮,形成了致密的氧扩散阻挡层,显著减缓了铌氧化物的生长和裂纹的萌生,这是复合涂层具有优异高温抗氧化性能的主要原因。
Abstract
Niobium alloy is one of the most promising candidate materials as the critical components of hypersonic vehicles due to its excellent high-temperature performance. However, poor high-temperature oxidation resistance is the major problem that needs to be solved for industrial applications at present because of the catastrophic oxidation of niobium alloy at high temperatures. Silicide coating is considered an effective method to broaden the engineering application of niobium alloys due to the formed dense oxygen shielding layer at high temperatures. However, the thermal growth stress will continue to accumulate when the silicide coating is exposed to air at high temperatures, greatly restricting the long-term service. It is proven that a novel coating with altered chemical compositions, functionalities can be prepared by the micro arc oxidation technique with the functional particle incorporated into the electrolyte. The work aims to propose a micro arc oxidation particle deposition sintering technology by introducing HfC-HfO2nanoparticles, forming a multilayer ceramic protective coating on the siliconized niobium alloy. |||, Nb521alloy sheet with a nominal composition of Nb-5W-2Mo-1Zr was cut into10mm×10mm×1mm by wire cutting, polished with SiC sandpaper. Then, the NbSi2bottom layer was obtained by HAPC treatment on Nb521alloys. The polished samples were buried in a mixture powder of Si, NaF, Al2O3,with a weighted ratio of16∶5∶9. HAPC treatment was in a vacuum atmosphere furnace with the argon shield, heated from room temperature to1,300℃ at a heating rate of5℃/min, held for8h. HfC-HfO2outer layer was deposited on the NbSi2layer by micro arc oxidation particle deposition sintering technology, which was carried out on a double electrodes system with the AC power facility. The NbSi2coated sample acted as the anode, while the cathode was the stainless steel sheet. The used electrolyte consisted of Na2SiO3,6,NaOH, HfC particles, HfO2particleswith a size of500nm, completely dispersing in the distilled water. The electrical parameters were set to a frequency of600Hz, a duty cycle of10%, a voltage of600V, an optimized applied time of11min. All the samples were subject to isothermal oxidation tests by a muffle furnaceat1,200℃ in air to evaluate the high-temperature oxidation resistance. A scanning electron microscopeequipped with an energy dispersive spectrometer, a transmission electron microscopewere used to characterize the microstructures of the coatings. An X-ray diffractometerwas used to analyze the phase composition. |||, The thickness of the HfC-HfO2particle deposition layer on the siliconized niobium alloy surface was approximately45μm. The composite coating demonstrated optimal oxidation resistance throughout the isothermal oxidation process, with a mass gain of only6.41mg/cm, , a parabolic rate constant of0.367mg, /. In contrast, a single NbSi2coating exhibited accelerated oxidation, with a mass gain of13.6mg/cm, . The incorporation of HfC as an oxygen-consuming phase in the composite coating ultimately formed the HfSiO4skeletal structure at high temperatures, enhancing the stability of the oxide scale. Additionally, Hf-rich oxides anchored the SiO2oxide scale, forming a dense oxygen diffusion barrier layer, which significantly suppressed the growth of niobium oxides, crack initiation
关键词
渗硅铌合金 /
微弧氧化 /
复合涂层 /
高温抗氧化
Key words
siliconized niobium alloy /
micro arc oxidation /
composite coating /
high-temperature oxidation resistance
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基金
国家自然科学基金（523B2010, U21B2053）
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