| 1. |
- Cassagne, Thierry B., et al.
(author)
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Long term corrosion testing and monitoring of oxygen and corrosion potential in an umbilical design
- 2012
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In: NACE - International Corrosion Conference Series. - 9781622760787 ; , s. 1096-1108
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Conference paper (peer-reviewed)abstract
- Subsea umbilicals are used for control and operation of subsea oil and gas production facilities. Typically an umbilical consists of steel tubes, electrical cables, fiber optic cables, weight or strength elements and fillers. Super duplex stainless steel tube material has been used for almost 20 years within the umbilical industry. However, a recent failure on two orbital welds of 25Cr super duplex of an umbilical installed in the South China Sea was reported. From these results some umbilical end users recommended the use of thermoplastic coating to avoid crevice corrosion on 25Cr super duplex stainless steel above 20°C. However, this limit is based on results obtained for super duplex stainless steel in aerated natural seawater and very little is known on the micro-environment formed by the confined seawater between metallic tubes and polymer matrix of an umbilical. This work reports corrosion potential and oxygen content measurements in the confined zone between the metallic tubes and the polymer matrix of an umbilical. These measurements were performed using micro-electrodes on a 2 meter long real umbilical at 30°C in heated natural seawater. From the measurements, it is shown that the oxygen content in the confined zone is rapidly consumed probably due to the passive current on the stainless steel tubes and then remains below 2 ppm over one year exposure period. From the open-circuit potential measurements performed in the confined zone, it is clear that the open circuit potential remained below -150 mV/AgCl. This translates an absence of electrochemical effect of the biofilm in the confined zone. Visual and metallographic examinations of the tubes after exposure confirmed the results obtained by the microelectrodes and clearly indicate that no corrosion initiation occurred on superduplex stainless steel (base metal and welds) under these experimental conditions. The results are discussed in view of the validity of corrosion tests performed under aerated conditions and the need of further developments of new testing procedures to represent the confined situation in the umbilical design.
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| 2. |
- Eidhagen, Josefin, et al.
(author)
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Synchrotron XPS and Electrochemical Study of Aging Effect on Passive Film of Ni Alloys
- 2023
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In: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 170:2, s. 021506-
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Journal article (peer-reviewed)abstract
- To investigate aging effect on the passive film of Ni23Cr15Mo and Ni22Cr9Mo3Nb, synchrotron-based X-ray photoelectron spectroscopy (XPS) was used to analyze the structure and composition of the air-formed passive film on the alloys. The corrosion resistance of the two Ni alloys in 1 M NaCl solution was evaluated with electrochemical cyclic polarization measurement. The synchrotron XPS measurement provided detailed information about chemical states of alloying elements in the passive film, showing that the passive film consists of an inner oxide layer and an outer hydroxide layer. The XPS data allowed precise determination of the chemical composition and the thickness of the outer hydroxide layer, the inner oxide layer, and the underlying subsurface alloy layer. The Cr-oxide in the inner layer grows thicker with aging time, leading to Cr-depletion in the subsurface region. Mo and Nb in the alloy form mixed oxides and hydroxides, and aging in air leads to transformation of the lower valence oxides into higher valence oxides. The freshly formed oxide film exhibits similar barrier properties as the aged oxide film. The stability of the passive film formed on Ni22Cr9Mo3Nb seems to be better than that on Ni23Cr15Mo.
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| 3. |
- Larsson, Alfred, et al.
(author)
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Dynamics of early-stage oxide formation on a Ni-Cr-Mo alloy
- 2024
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In: NPJ MATERIALS DEGRADATION. - : Springer Nature. - 2397-2106. ; 8:1
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Journal article (peer-reviewed)abstract
- Corrosion results in large costs and environmental impact but can be controlled by thin oxide films that passivate the metal surfaces and hinder further oxidation or dissolution in an aqueous environment. The structure, chemistry, and thickness of these oxide films play a significant role in determining their anti-corrosion properties and the early-stage oxidation dynamics affect the properties of the developed oxide. Here, we use in situ X-ray Photoelectron Spectroscopy (XPS) to study the early-stage oxidation of a Ni-Cr-Mo alloy at room temperature and up to 400 degrees C. Cr and Mo begin to oxidize immediately after exposure to O2, and Cr3+, Mo4+, and Mo6+ oxides are formed. In contrast, Ni does not contribute significantly to the oxide film. A self-limiting oxide thickness, which did not depend on temperature below 400 degrees C, is observed. This is attributed to the consumption of available Cr and Mo near the surface, which results in an enrichment of metallic Ni under the oxide. The self-limited oxide thickness is 6-8 angstrom, which corresponds to 3-4 atomic layers of cations in the oxide. At 400 degrees C, sublimation of Mo6+ oxide is observed, resulting in the formation of an almost pure layer of Cr2O3 on the alloy surface. Lastly, a mechanism is presented that explains the formation of the bi-layer oxide structure observed for Ni-Cr-Mo alloys, which involves the enhanced migration of hexavalent Mo ions in the electric field, which drives mass transport during oxidation according to both the Cabrera Mott model and the Point Defect Model.
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| 4. |
- Larsson, Alfred, et al.
(author)
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In situ quantitative analysis of electrochemical oxide film development on metal surfaces using ambient pressure X-ray photoelectron spectroscopy : Industrial alloys
- 2023
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In: Applied Surface Science. - : Elsevier BV. - 0169-4332 .- 1873-5584. ; 611
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Journal article (peer-reviewed)abstract
- Ambient Pressure X-ray Photoelectron Spectroscopy combined with an electrochemical setup is used to study, in situ, the electrochemical oxide growth on an in-dustrial Ni-Cr-Mo alloy. The native oxide film was characterized in vacuum and in water vapor at 17 mbar, and was found to be 11.4 & ANGS; thick and rich in Cr3+. In 0.1 M NaCl electrolyte, anodic growth of the oxide film at potentials up to 700 mV vs Ag/AgCl nearly doubled the thickness of the oxide film. Moreover, a transformation of the oxide composition occurred, as the oxide became enriched in Mo6+ with a chemical fingerprint more like that of pure MoO3. Both thermodynamics and kinetics of the oxidation of the alloying elements dictate the oxide film growth and composition. Furthermore, we develop the quantitative analysis of oxide composition and thickness to take into account the attenuation through the liquid water and the water vapor atmosphere. Finally, we discuss the differences between ex situ, UHV, in situ, and operando measurements. Our approach is robust, fast, simple, and suitable for systematically probing metal surfaces after aqueous exposure and electro-chemical polarization, which promises wide applications for studies of solid-liquid interfaces in corrosion, batteries, fuel cells, and electrocatalysis.
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| 5. |
- Larsson, Alfred, et al.
(author)
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The Oxygen Evolution Reaction Drives Passivity Breakdown for Ni–Cr–Mo Alloys
- 2023
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In: Advanced Materials. - : Wiley. - 0935-9648 .- 1521-4095. ; 35:39
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Journal article (peer-reviewed)abstract
- Corrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal–liquid interface governing passivity are notoriously challenging to study. In this work, a combination of synchrotron-based techniques and electrochemical methods is used to investigate the passive film breakdown of a Ni–Cr–Mo alloy, which is used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo4+ sites in the oxide film to Mo6+ that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr-containing alloys where Cr6+ is postulated to be dissolved at high anodic potentials, which is not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. The OER plays an important role in the mechanism of passivity breakdown of Ni–Cr–Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys.
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| 6. |
- Larsson, Alfred, et al.
(author)
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Thickness and composition of native oxides and near-surface regions of Ni superalloys
- 2022
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In: Journal of Alloys and Compounds. - : Elsevier BV. - 0925-8388 .- 1873-4669. ; 895
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Journal article (peer-reviewed)abstract
- The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12-13 A, a hydroxide layer of 2-3 A, and a thickness of the sub-surface alloy layer of 20-35 A. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr3+, Mo-(4,Mo-5,Mo-6)+, and Nb5+, while no Ni oxide was detected. The hydroxide layer mainly contained Ni2+ and Cr3+ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.
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