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Depth Profiling of the Passive Layer on Stainless Steel using Photoelectron Spectroscopy
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström. (Structural chemistry)
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The physical properties of the protective passive films formed on the surface of stainless steels under electrochemical polarization in different electrolytes were studied. The structure of these films was analyzed as a function of depth using photoelectron spectroscopy (PES).

Depth profiling (using PES) of the surface layer was achieved by either changing the angle of incidence to achieve different analysis depths (ARXPS), by argon ion etching, or by varying the energy of the incoming x-rays by the use of synchrotron radiation. The use of hard x-rays with high resolution (HAXPES) provided novel quantified information about the nickel content underneath the passive films.

A complex environment was found in these surface layers composed of an outermost monolayer of iron on top of a layer of chromium hydroxides covering an underlayer of chromium oxides. Molybdenum was enriched in the interface between the metal and oxide. Nickel is enriched underneath the passive film and therefore nickeloxides are only present in the surface layer in low concentrations.

A comparison was performed on austenitic and duplex stainless prepared by hot isostatically pressed (HIP) or cast and forged processes. HIP stainless steel was produced using the burgeoning technique of pressing gas atomized powders together. The structure of these steels is far more homogenous with a lower porosity than that of the conventionally prepared equivalents. It was shown that hot HIP austenitic steel had better pitting corrosion resistance than its conventional counterpart.

Finally, the duplex steel was cycled in a Li-ion battery to explore its potential application as a current collector. It was shown that the passive film formed in the organic solvents is similar in composition and thickness to the films formed in aqueous solutions. However, it is doubtful if steel could be used as current collector in batteries due to its high reactivity with lithium.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. , 69 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 955
Keyword [en]
depth profile, stainless steel, passive film, XPS, HAXPES, corrosion, powder metallurgical
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-179399ISBN: 978-91-554-8430-9 (print)OAI: oai:DiVA.org:uu-179399DiVA: diva2:544494
Public defence
2012-09-28, Å2005, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2012-09-05 Created: 2012-08-14 Last updated: 2013-01-22
List of papers
1. XPS analysis of manganese in stainless steel passive films on 1.4432 and the lean duplex 1.4162
Open this publication in new window or tab >>XPS analysis of manganese in stainless steel passive films on 1.4432 and the lean duplex 1.4162
2010 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 52, no 7, 2505-2510 p.Article in journal (Refereed) Published
Abstract [en]

Passive films were compared on two stainless steels: the recent lean duplex EN 1.4162 and EN 1.4432 (316L). For alloys with significant amount of manganese and nickel, the Mn 2p(3/2) peak will overlap with the Ni-LMM. To resolve this overlap, Ni 2p(3/2) to Ni-LMM intensity ratios were recorded on 1.4432, compensated for overlayer thickness, and then used to fix the Ni-LMM intensities in the Mn 2p spectra on the duplex material. Manganese was found in oxidation states II and V/VI: its film content was not dependent on the bulk composition. (C) 2010 Elsevier Ltd. All rights reserved.

Keyword
Stainless steel, XPS, Passive films
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-136161 (URN)10.1016/j.corsci.2010.03.014 (DOI)000279130600032 ()
Available from: 2010-12-10 Created: 2010-12-10 Last updated: 2017-12-11Bibliographically approved
2. Full depth profile of passive films on 316L stainless steel based on high resolution HAXPES in combination with ARXPS
Open this publication in new window or tab >>Full depth profile of passive films on 316L stainless steel based on high resolution HAXPES in combination with ARXPS
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2012 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 258, no 15, 5790-5797 p.Article in journal (Refereed) Published
Abstract [en]

Depth profiles of the passive films on stainless steel were based on analysis with the non-destructive hard X-ray photoelectron spectroscopy (HAXPES) technique in combination with the angular resolved X-ray photoelectron spectroscopy (ARXPS). The analysis depth with ARXPS is within the passive film thickness, while the HAXPES technique uses higher excitation energies (between 2 and 12 keV) also non-destructively probing the chemical content underneath the film. Depth profiles were done within and underneath the passive film of 316L polarized in acidic solution. The passive film thickness was estimated to 2.6 nm for a sample that was polarized at 0.6 V and the main component in the passive film is, as expected, chromium. From the high resolution HAXPES spectra we suggest chromium in three different oxidation states present. Also for iron three oxides were detected. Gradients of chromium and iron concentrations and oxidation states within the film and an enrichment of nickel within a 0.5 nm layer directly underneath the passive film are some of the results discussed. 

Keyword
Stainless steel, XPS, HAXPES, Passive film
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-173615 (URN)10.1016/j.apsusc.2012.02.099 (DOI)000302135700044 ()
Funder
StandUp
Available from: 2012-05-09 Created: 2012-05-02 Last updated: 2017-12-07Bibliographically approved
3. Cation profiling of passive films on stainless steel bydeconvolution of angle-resolved X-ray photoelectronspectroscopy data
Open this publication in new window or tab >>Cation profiling of passive films on stainless steel bydeconvolution of angle-resolved X-ray photoelectronspectroscopy data
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

A novel way of deconvoluting angle-resolved x-ray photoelectron spectroscopy (ARXPS) data to determine cation depth profiles in oxide films on stainless steels for a ternarysystem is presented. The passive films investigated were formed on AISI 316L EN 1.4432 stainless steel at the open circuit potential (OCP) in deionized water and at potentialsfrom −1.5 to +1.5V vs. Ag/AgCl in two acidic electrolytes: 0.5m H2SO4 and acetic acidcontaining 0.02m Na2B4O7 · 10H2O and 1m H2O. The passive films were about 1–2nmthick and contained concentration gradients of iron, chromium and molybdenum. Ironwas found to be present on the surface, chromium was mainly enriched in the middle, andmolybdenum was only present and strongly enriched in the inner region of the passivefilm. The ability to determine cation profiles in nanometer-thin oxide films provides newpossibilities for tailoring the properties of passive films on stainless steels.

Keyword
passive film, molybdenum, stainless steel, gradients, ARXPS
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-179397 (URN)
Available from: 2012-08-14 Created: 2012-08-14 Last updated: 2012-09-05
4. Corrosion Resistances and Passivation of Powder Metallurgical and Conventionally Cast 316L and 2205 Stainless Steels
Open this publication in new window or tab >>Corrosion Resistances and Passivation of Powder Metallurgical and Conventionally Cast 316L and 2205 Stainless Steels
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2013 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 67, 268-280 p.Article in journal (Refereed) Published
Abstract [en]

The corrosion resistances and passivation of austenitic 316L and duplex 2205 powder metallurgical (P/M) steels, produced by employing gas atomizing and hot isostatic pressing (HIP), have been compared with those of their conventional cast and forged counterparts. The P/M 316L steel is shown to have a significantly higher pitting corrosion resistance than the conventional 316L steel in 0.5 M HCl. Since the chemical composition and the total amount of inclusions were analogous for the two steels, the effect is ascribed to the finer grained microstructure for the P/M 316L steel yielding a better passive layer. This is supported by photoelectron spectroscopy data demonstrating differences between the thickness and composition of the passive layers for the two 316 L steels. Differences in the passivation process were also found for the different steels as three mixed potentials were observed in the polarization curves for the P/M and conventional 316L steels whereas only one mixed potential at about +0.7 V vs. Ag/AgCl was observed for the two duplex steels in 0.5 M HCl. The results indicate that discussions of the shapes of polarization curves and mixed potentials should be based on the anodic and cathodic partial currents, including the reduction of oxygen. HIP:ed P/M steels are clearly well-suited for applications requiring high pitting corrosion resistances.

Keyword
steels, passivation, polarization curve, pitting, corrosion resistance, corrosion potential, hydrochloric acid
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-179398 (URN)10.1016/j.corsci.2012.10.021 (DOI)000313917700029 ()
Available from: 2012-08-14 Created: 2012-08-14 Last updated: 2017-12-07
5. XPS study of duplex stainless steel as a possible current collector in a Li-ion battery
Open this publication in new window or tab >>XPS study of duplex stainless steel as a possible current collector in a Li-ion battery
2012 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 79, 82-94 p.Article in journal (Refereed) Published
Abstract [en]

The surface chemistry and corrosion property of a duplex LDX 2101 steel that had been cycled in a Li-ion battery with a 1 M LiPF6 in EC/DMC 1:1 electrolyte was studied. The results are compared to those of steel stored for the same length of time. Cyclic voltammetry was used to sweep the steel between 0 V and 5 V and the different reduction products were identified with SEM, XRD and XPS. A conversion reaction occurred during the cathodic sweep between 2.0 and 1.5 V where chromium and iron oxides were reduced forming Li2O and metal. At 0.5 V vs. Li+/Li a Solid Electrolyte Interface (SEI) was irreversibly formed predominantly during the first cycle. During the oxidation sweep the typical stainless steel passive layer of chromium and iron oxides/hydroxides formed at 2.5 V vs. Li/Li+. Li2O also decomposed at this potential. Simultaneously metal fluorides are formed. The XPS revealed a thicker SEI containing organic and inorganic species on the cycled electrode than on the stored. The stored sample showed chemical formation of CrF3 on the surface. Depth profiling of the cycled electrode by Ar+ etching showed a thick layer of CrF3 and a thin layer of FeF3. We conclude that the level of corrosion of this duplex steel is acceptable in the 3–4.5 V vs. Li+/Li region. However, in a Li-ion battery it is too reactive at low potentials to be considered as a replacement for copper as an anode current collector. We also observe that the PF6 anion from the electrolyte salt plays an important role in the formation of metal fluorides which is a fact generally neglected in the discussion of conversion reactions of metal-oxide anodes for Li-ion batteries. For stainless steel to be considered as current collectors for Li-ion batteries optimisation of alloy compositions need to be made to reduce corrosion occurring during cycling in organic solvents.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Passive layer; XPS; Li-ion battery; Duplex stainless steel; Voltammetry
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-179310 (URN)10.1016/j.electacta.2012.06.057 (DOI)000307920300011 ()
Funder
StandUp
Available from: 2012-08-13 Created: 2012-08-13 Last updated: 2017-12-07Bibliographically approved

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