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Cation profiling of passive films on stainless steel formed in sulphuric and acetic acid by deconvolution of angle-resolved X-ray photoelectron spectra
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.ORCID iD: 0000-0003-2817-8209
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
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2013 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 284, 700-714 p.Article in journal (Refereed) Published
Abstract [en]

An approach for determining depth gradients of metal-ion concentrations in passive films on stainlesssteel using angle-resolved X-ray photoelectron spectroscopy (ARXPS) is described. The iterative method,which is based on analyses of the oxidised metal peaks, provides increased precision and hence allowsfaster ARXPS measurements to be carried out. The method was used to determine the concentrationdepth profiles for molybdenum, iron and chromium in passive films on 316L/EN 1.4432 stainless steelsamples oxidised in 0.5 M H2SO4 and acetic acid diluted with 0.02 M Na2B4O7 · 10H2O and 1 M H2O,respectively. The molybdenum concentration in the film is pin-pointed to the oxide/metal interface andthe films also contained an iron-ion-enriched surface layer and a chromium-ion-dominated middle layer.Although films of similar composition and thickness (i.e., about 2 nm) were formed in the two electrolytes,the corrosion currents were found to be three orders of magnitude larger in the acetic acid solution.The differences in the layer composition, found for the two electrolytes as well as different oxidationconditions, can be explained based on the oxidation potentials of the metals and the dissolution rates ofthe different metal ions.

Place, publisher, year, edition, pages
2013. Vol. 284, 700-714 p.
Keyword [en]
XPS, Stainless steel, Passive films, Deconvolution, Cation distribution, Ion solubility
National Category
Materials Chemistry
Research subject
Materials Science
Identifiers
URN: urn:nbn:se:uu:diva-208400DOI: 10.1016/j.apsusc.2013.07.158ISI: 000324248600099OAI: oai:DiVA.org:uu-208400DiVA: diva2:652226
Available from: 2013-09-30 Created: 2013-09-30 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Corrosion and Surface Studies of Stainless Steel and Chromium Carbide Thin-Films
Open this publication in new window or tab >>Corrosion and Surface Studies of Stainless Steel and Chromium Carbide Thin-Films
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Although the passive films that form on stainless steels have been extensively studied, the concentration depth profiles are not fully understood. Their thinness makes passive films hard to study, but angle-resolved X-ray photoelectron spectroscopy (ARXPS) is a non-destructive technique that can be used to obtain depth information. An iterative approach to deconvolute ARXPS measurements into depth profiles is discussed, and the chemistry of passive films on a molybdenum-containing 316L stainless steel is investigated. Bipolar electrochemistry, in which the sample is placed along an electric field created by two driving electrodes in an electrolyte, is investigated as a screening tool. It is shown that the method is useful to create corrosion gradients on 304 stainless steel, both under pitting and non-pitting conditions. Chromium carbide thin films were deposited by magnetron sputtering with a variety of deposition parameters on stainless steel, and subsequently analyzed. It is shown that these films present a promising material system for protective coatings to improve the corrosion resistance of stainless steels while also maintaining other useful properties, such as low interfacial contact resistance. Particular attention is given to the electrochemical evaluation of the films, whose high carbon concentrations necessitates different interpretations of the electrochemical results compared to for stainless steels.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. 66 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1082
Keyword
corrosion, electrochemistry, thin film, stainless steel, passive film, chromium carbide, carbon oxidation, surface, depth profile, XPS, SEM, EQCM, sputtering
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-208410 (URN)978-91-554-8766-9 (ISBN)
Public defence
2013-11-08, Ångström 2001, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
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Available from: 2013-10-18 Created: 2013-09-30 Last updated: 2017-01-20

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Högström, JonasEdström, KristinaBjörefors, FredrikNyholm, Leif

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