Cr35Ni45钢高温长期服役过程的氧化与渗碳机理

High temperature oxidation and carburizing mechanisms of Cr35Ni45 heat-resistant steel under service conditions

采用扫描电镜、电子探针和X射线衍射等手段对不同服役时间(原始态、1.5a和6a)Cr35Ni45乙烯裂解炉管内壁的氧化与渗碳机理进行了系统分析.结果表明:高温长时服役后炉管内壁出现了氧化层、碳化物贫化区和碳化物富集区三个区域,其氧化行为包括Cr2O3外氧化和SiO2内氧化,且服役过程中外氧化膜发生反复破坏和重建;炉管服役过程的渗碳行为主要由内表面结焦引起,外氧化膜的反复破坏可以加重渗碳,但外氧化膜在破坏后能自动修复,所以服役态两个炉管的渗碳程度较轻;外氧化膜的反复破坏和重建使亚表层贫铬,导致形成碳化物的临界碳浓度增加,在内壁亚表层形成贫碳化物区,多余的碳原子在其内侧析出,形成碳化物富集区.

The oxidation and carburizing mechanisms of Cr35Ni45 type pyrolysis furnace tubes serviced for different time（ as-cast,1. 5 a and 6 a） were systematically investigated by scanning electron microscopy（ SEM）,electron probe and X-ray diffraction（ XRD）.Compared with original uniform microstructure distribution,there are three zones including an oxidation layer,a carbide depletion zone and a carbide-rich zone at the subsurface region of the Cr35Ni45 tube inner wall after long time service. The oxidation behavior of the Cr35Ni45 tubes at high temperature consists of the external oxidation of chromium and the internal oxidation of silicon,and the outer oxidation layer is greatly affected by repeated destruction and reformation in decoking. The carburizing behavior of the Cr35Ni45 tubes mainly results from coking on the inner wall surface,and repeated destruction of the outer oxidation layer can aggravate this carburization. But due to auto-remediation of the outer oxidation layer,carburization of both the serviced tubes is at a lesser degree. Also,repeated destruction and reformation of the outer oxidation layer cause the depletion of Cr,the increase in critical concentration of C in the subsurface of the inner wall and carbide participation at the below region,leading to the formation of a carbide depletion zone and a carbide-rich zone.