Transpassive-repassivation process of Ni-base superalloys: The role of hidden subsurface alloy layer

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science Pub Date : 2025-09-18 DOI:10.1016/j.corsci.2025.113321

Xiaoqi Yue , Alfred Larsson , Dihao Chen , Andrea Grespi , Giuseppe Abbondanza , Ulrich Lienert , Zoltan Hegedüs , Arno Jeromin , Thomas F. Keller , Mattia Scardamaglia , Andrey Shavorskiy , Chaofang Dong , Edvin Lundgren , Jinshan Pan

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Abstract

Passivity refers to spontaneous formation of a passive film on the surface of metals. High stability of the passive film on advanced alloys relies on the repassivation ability of the alloys in corrosive environments. Two Ni-base superalloys (Ni-22Cr-9Mo-5Fe-2Nb and Ni-18Cr-3Mo-20Fe-5Nb) are studied to elucidate the mechanism of repassivation through a combination of multimodal in-situ synchrotron X-ray measurements, electrochemical measurements, and first principles calculations. The synchrotron X-ray analyses enabled in-situ probing of the passive film and the hidden subsurface alloy layer. The results reveal chemical and structural evolutions of both the passive film and the underlying subsurface alloy layer under transpassive condition. The first principles calculations demonstrate a crucial role of the subsurface alloy layer in the repassivation of the alloys. Upon passivity breakdown at high electrochemical potentials, the passive film rich in Cr oxide becomes highly defective with vacancies, and metal dissolution leads to generation of vacancies (mainly Ni) in the subsurface alloy layer. This promotes repassivation process by enhanced outward Cr diffusion strengthening the metal bond (more Cr-Ni bonds) in the subsurface alloy layer and, together with the enrichment of high valence Mo- and Nb-oxides in the passive film, lead to repassivation when the high potential is removed, which is different from Fe-rich alloys.

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镍基高温合金的转被动再钝化过程：隐性亚表面合金层的作用

钝化是指在金属表面自发形成钝化膜。先进合金钝化膜的高稳定性依赖于合金在腐蚀环境中的再钝化能力。通过多模态原位同步x射线测量、电化学测量和第一性原理计算，研究了Ni-22Cr-9Mo-5Fe-2Nb和Ni-18Cr-3Mo-20Fe-5Nb两种镍基高温合金的再钝化机理。同步x射线分析实现了钝化膜和隐藏的亚表面合金层的原位探测。结果揭示了钝化膜及其下的亚表面合金层在透渗条件下的化学和结构演变。第一性原理计算表明，亚表面合金层在合金的再钝化过程中起着至关重要的作用。在高电化学电位下钝化击穿后，富含氧化铬的钝化膜出现高度缺陷和空位，金属溶解导致亚表面合金层中产生空位（主要是Ni）。这促进了再钝化过程，增强了亚表面合金层中的金属键（更多的Cr- ni键），加上钝化膜中高价Mo和nb氧化物的富集，导致高电位去除后再钝化，这与富铁合金不同。

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来源期刊

Corrosion Science 工程技术-材料科学：综合

CiteScore

13.60

自引率

18.10%

发文量

763

审稿时长

46 days

期刊介绍： Corrosion occurrence and its practical control encompass a vast array of scientific knowledge. Corrosion Science endeavors to serve as the conduit for the exchange of ideas, developments, and research across all facets of this field, encompassing both metallic and non-metallic corrosion. The scope of this international journal is broad and inclusive. Published papers span from highly theoretical inquiries to essentially practical applications, covering diverse areas such as high-temperature oxidation, passivity, anodic oxidation, biochemical corrosion, stress corrosion cracking, and corrosion control mechanisms and methodologies. This journal publishes original papers and critical reviews across the spectrum of pure and applied corrosion, material degradation, and surface science and engineering. It serves as a crucial link connecting metallurgists, materials scientists, and researchers investigating corrosion and degradation phenomena. Join us in advancing knowledge and understanding in the vital field of corrosion science.