核级用SiCf/SiC复合材料包壳管致密化工艺研究

Study on the densification process of SiCf/SiC composite cladding tube for nuclear grade

  • 摘要: 针对长尺寸核级SiCf/SiC复合包壳材料的致密化技术难题,运用Fluent数值分析方法研究了CVI化学气相沉积反应室内的流场分布,确定了最优载气(H2)的工艺参数;基于现有热解碳PyC界面层沉积、化学气相渗透CVI和化学气相沉积工艺CVD完成了SiCf/SiC复合包壳的制备,研究了不同管径处的沉积物相结构、化学成分和显微组织特征。结果表明,载气流量为1200 mL/min时,MTS/HCl浓度分布均匀,可以提供适宜的沉积氛围。以C3H6前驱体沉积气体,1000℃沉积10 h,可在SiC纤维表面获得约为288 nm的热解碳PyC层,TEM证实为无形定型的非晶态结构;在MTS/H2体系1000℃沉积400~500 h,CVI-SiC增密层厚度约在618 μm~723 μm之间。等分位置处的CVI-SiC密度均≥ 2.75 g/cm3,TEM解读为F43m空间群、FCC结构的β-SiC相; 1250℃沉积50~60 h,CVD-SiC涂层厚度约在630 μm~671 μm之间,XRD表明全部为β-SiC相,涂层厚度均匀,致密化程度高。研究认为,现有致密化工艺稳定,可得到沉积厚度均匀的双层SiC复合包壳材料。

     

    Abstract: Aiming at the densification technical challenges of long-size nuclear-grade SiCf/SiC composite cladding materials, this paper uses the Fluent numerical analysis method to study the flow field distribution in the CVI (chemical vapor infiltration) chemical vapor deposition reaction chamber, and determines the optimal process parameters for the carrier gas (H2). Based on the existing pyrolytic carbon (PyC) interlayer deposition, chemical vapor infiltration (CVI), and chemical vapor deposition (CVD) processes, the preparation of SiCf/SiC composite cladding is completed. The phase structure, chemical composition, and microstructural characteristics of deposits at different pipe diameters are investigated. The results show that when the carrier gas flow rate is 1200 mL/min, the MTS/HCl concentration distribution is uniform, providing a suitable deposition atmosphere. Using C3H6 as the precursor deposition gas at 1000℃ for 10 h, a pyrolytic carbon (PyC) layer of approximately 288 nm is obtained on the SiC fiber surface. TEM analysis indicates that the structure of the PyC layer is an amorphous structure. The thickness of the CVI-SiC densification layer is 618–723 μm in the MTS/H2 system at 1000℃ for 400–500 hours. The density of CVI-SiC at equidistant positions is ≥ 2.75 g/cm3, and TEM analysis shows a β-SiC phase with an FCC structure (space group F43m). The thickness of the CVD-SiC coating is 630–671 μm at 1250℃ for 50–60 h. XRD indicates a pure β-SiC phase with uniform thickness and high densification. In conclusion, the existing densification processes are stable, enabling the production of double-layer SiC composite cladding materials with uniform deposition thickness.

     

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