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Journal Articles

X-ray absorption fine structure spectra of rust layers on Fe-based binary alloys exposed to Cl-rich environment

Konishi, Hiroyuki; Yamashita, Masato*; Uchida, Hitoshi*; Mizuki, Junichiro

Proceedings of 16th International Corrosion Congress (CD-ROM), 6 Pages, 2005/09

XANES measurements of rust layers formed on Fe, Fe-Cr alloys and Fe-Ni alloys exposed to a Cl-rich atmosphere have been performed using synchrotron radiation in order to clarify the relation between the structural properties of the rust layer on weathering steel and anticorrosive alloying elements and/or chloride ions. The XANES spectra around Cl K-edge revealed that the rust layer on the Fe-based binary alloys contains unidentified chloride in addition to akagan$'e$iteite. The Fe K-edge XANES results indicated that the rust layers are composed mainly of well-known iron oxides, goethite, akagan$'e$ite, lepidocrocite and magnetite. In particular, the mole ratio of akagan$'e$ite in the rust layers on the Fe-Ni alloys is relatively higher than that of the Fe-Cr alloys. The Cr K-edge XANES spectra of the rust layers on the Fe-Cr alloys depends on the Cr alloy content. Therefore, the local structure of Cr in the rust layer is variable with the Cr density. In contrast, the Ni K-edge XANES results show that the local structure of Ni in the rust layer are unique in a certain Ni content range.

Journal Articles

Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

Konishi, Hiroyuki; Yamashita, Masato*; Uchida, Hitoshi*; Mizuki, Junichiro

Materials Transactions, 46(2), p.329 - 336, 2005/02

 Times Cited Count:28 Percentile:80.32(Materials Science, Multidisciplinary)

Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of a mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akagan$'e$ite, lepidocrocite and magnetite. Among these iron oxides, akagan$'e$ite in particular is the major component in the rust. Additionally, the amount of akagan$'e$ite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akagan$'e$ite is generally considered to facilitate the corrosion of steel, but our results indicate that akagan$'e$ite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akagan$'e$ite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel.

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