| 1. |
- Aastrup, T., et al.
(författare)
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Experimental in situ studies of copper exposed to humidified air
- 2000
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Ingår i: Corrosion Science. - 0010-938X .- 1879-0496. ; 42:6, s. 957-967
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Tidskriftsartikel (refereegranskat)abstract
- Three complementary experimental techniques for in situ surface analysis have been combined for the first time in order to explore the chemistry and physics of a copper surface exposed to humidified air. Infrared reflection absorption spectroscopy, quartz crystal microbalance and atomic force microscopy provide a congruent picture of the processes occurring at the surface. At a given relative humidity, cuprous oxide forms according to an approximately logarithmic rate law. In addition, an aqueous adlayer of constant mass physisorbs on the surface. Increased relative humidity stimulates the physisorption of water and enhances the nucleation rate of oxide grains, thereby increasing the formation rate of cuprous oxide.
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| 2. |
- Aastrup, T., et al.
(författare)
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In situ studies of the initial atmospheric corrosion of copper influence of humidity, sulfur dioxide, ozone, and nitrogen dioxide
- 2000
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 147:7, s. 2543-2551
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Tidskriftsartikel (refereegranskat)abstract
- Infrared reflection absorption spectroscopy and quartz crystal microbalance, integrated into a one-surface analytical system, and complemented with tapping mode atomic force microscopy, has been used to explore the metal/atmosphere interfacial region under atmospheric pressure conditions. This unique combination of ill situ techniques, all possessing submonolayer sensitivity, has revealed information on the different accelerating roles of ozone (O-3) and nitrogen dioxide (NO2) on the SO2-induced atmospheric corrosion of copper. The formation of reaction products could be followed quantitatively with respect to chemical identity and kinetics. Exposure in SO2-containing humidified air resulted in CuSO3. xH(2)O-like species, formed atop a cuprous oxide, designated Cu2O, all over the copper surface. O-3 introduction resulted in an accelerated mass gain with an increased formation rate of both Cu2O and of CuSO4. xH(2)O all over the surface. NO2 introduction resulted in less mass gain than observed under SO2 and O-3, with no formation of new Cu2O, an initial oxidation of CuSO3. xH(2)O to CuSO4. xH(2)O, and with sulfite oxidation gradually replaced by copper nitrate formation, possibly as CuNO3(OH)(3) The formation rates of the dominating end products, CuSO4. xH(2)O in SO2/O-3 and Cu2NO3(OH)(3) in SO2/NO2 seemed to be limited by the supply of the gaseous constituents.
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| 3. |
- Adhikari, Arindam, et al.
(författare)
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Electrochemical behavior and anticorrosion properties of modified polyaniline dispersed in polyvinylacetate coating on carbon steel
- 2008
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 53:12, s. 4239-4247
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Tidskriftsartikel (refereegranskat)abstract
- Conducting polyaniline (Pani) was prepared in the presence of methane sulfonic acid (MeSA) as dopant by chemical oxidative polymerization. The Pani-MeSA polymer was characterized by FT-IR, UV-vis, X-ray diffraction (XRD) and impedance spectroscopy. The polyrner was dispersed in polyvinylacetate and coated oil carbon steel samples by a dipping method. The electrochemical behavior and anticorrosion properties of the coating, oil carbon steel in 3% NaCl were investigated using Open-circuit Potential (OCP) versus time of exposure, and electrochemical techniques including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and cyclic voltammetry (CV). During initial exposure, the OCP dropped about 0.35 V and the interfacial resistance increased several times, indicating I certain reduction of the polymer and oxidation of the steel surface. Later the OCP shifted to the noble direction and remained at a stable value during the exposure up to 60 days. The EIS monitoring also revealed the initial change and later stabilization of the coating. The stable high OCP and low coating impedance Suggest that the conducting polymer maintains its oxidative state and provides corrosion protection for carbon steel through out the investigated period. The polarization curves and CV show that the conducting polymer coating induces a passive-like behavior and greatly reduces the corrosion of carbon steel.
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| 4. |
- Alipour, Yousef
(författare)
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High temperature corrosion in a biomass-fired power boiler : Reducing furnace wall corrosion in a waste wood-fired power plant with advanced steam data
- 2013
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The use of waste (or recycled) wood as a fuel in heat and power stations is becoming more widespread in Sweden (and Europe), because it is CO2 neutral with a lower cost than forest fuel. However, it is a heterogeneous fuel with a high amount of chlorine, alkali and heavy metals which causes more corrosion than fossil fuels or forest fuel.A part of the boiler which is subjected to a high corrosion risk is the furnace wall (or waterwall) which is formed of tubes welded together. Waterwalls are made of ferritic low-alloyed steels, due to their low price, low stress corrosion cracking risk, high heat transfer properties and low thermal expansion. However, ferritic low alloy steels corrode quickly when burning waste wood in a low NOx environment (i.e. an environment with low oxygen levels to limit the formation of NOx). Apart from pure oxidation two important forms of corrosion mechanisms are thought to occur in waste environments: chlorine corrosion and alkali corrosion.Although there is a great interest from plant owners to reduce the costs associated with furnace wall corrosion very little has been reported on wall corrosion in biomass boilers. Also corrosion mechanisms on furnace walls are usually investigated in laboratories, where interpretation of the results is easier. In power plants the interpretation is more complicated. Difficulties in the study of corrosion mechanisms are caused by several factors such as deposit composition, flue gas flow, boiler design, combustion characteristics and flue gas composition. Therefore, the corrosion varies from plant to plant and the laboratory experiments should be complemented with field tests. The present project may thus contribute to fill the power plant corrosion research gap.In this work, different kinds of samples (wall deposits, test panel tubes and corrosion probes) from Vattenfall’s Heat and Power plant in Nyköping were analysed. Coated and uncoated samples with different alloys and different times of exposure were studied by scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDX), X-ray diffraction (XRD) and light optical microscopy (LOM). The corrosive environment was also simulated by Thermo-Calc software.The results showed that a nickel alloy coating can dramatically reduce the corrosion rate. The corrosion rate of the low alloy steel tubes, steel 16Mo3, was linear and the oxide scale non-protective, but the corrosion rate of the nickel-based alloy was probably parabolic and the oxide much more protective. The nickel alloy and stainless steels showed good corrosion protection behavior in the boiler. This indicates that stainless steels could be a good (and less expensive) alternative to nickel-based alloys for protecting furnace walls.The nickel alloy coated tubes (and probe samples) were attacked by a potassium-lead combination leading to the formation of non-protective potassium lead chromate. The low alloy steel tubes corroded by chloride attack. Stainless steels were attacked by a combination of chlorides and potassium-lead.The Thermo-Calc modelling showed chlorine gas exists at extremely low levels (less than 0.1 ppm) at the tube surface; instead the hydrated form is thermodynamically favoured, i.e. gaseous hydrogen chloride. Consequently chlorine can attack low alloy steels by gaseous hydrogen chloride rather than chlorine gas as previously proposed. This is a smaller molecule than chlorine which could easily diffuse through a defect oxide of the type formed on the steel.
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| 5. |
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| 6. |
- Bahar, Babak, et al.
(författare)
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Corrosion-induced copper release from rain gutters
- 2008
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Ingår i: Metall (Berlin. 1947). - 0026-0746. ; 62:3, s. 129-135
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Tidskriftsartikel (refereegranskat)abstract
- While runoff rates from copper roofs have been extensively studied during the last years, corresponding studies from copper rain gutters have been missing. A laboratory investigation has been undertaken to examine the influence of important runoff water parameters on the copper runoff from rain gutters. At a given rainfall quantity, the release rate of copper increases with decreasing runoff water intensity and decreasing degree of gutter inclination, and with increasing runoff acidity and increasing Cu2+-ion concentration in the runoff water. A comparison of the predicted long-term copper release from the gutter-system compared to the roof on a real building suggests that less than 5% of the total copper runoff originates from the gutter. However, single rain events may result in higher release rates, especially during the initial rain portion.
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| 7. |
- Bahar, B., et al.
(författare)
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The interaction between concrete pavement and corrosion-induced copper runoff from buildings
- 2008
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Ingår i: Environmental Monitoring & Assessment. - : Springer Science and Business Media LLC. - 0167-6369 .- 1573-2959. ; 140:1-3, s. 175-189
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Tidskriftsartikel (refereegranskat)abstract
- Changes in chemical speciation of copper and the capacity of concrete pavement to retain copper in runoff water from external buildings have been investigated at urban field conditions, and in parallel laboratory experiments simulating outdoor scenarios. The research study showed the concrete surface to form a copper rich surface layer (approximate to 50 mu m thick) upon exposure, and a high capacity to significantly reduce the bioavailable fraction of released copper (20-95%). The retention capacity of copper varied between 5 and 20% during single runoff events in the laboratory, and between 10 and 40% of the total copper release during single natural runoff events. The capacity to retain and reduce the bioavailable fraction of non-retained copper increased with increasing wetness of the concrete surfaces, increasing pH of the runoff water and decreasing flow rates. Bioassay testing with bacterial and yeast bioreporters showed the bioavailable fraction of non-retained copper to be significantly lower than the total copper concentration in the runoff water, between 22 and 40% for bacteria and between 8 and 31% for yeast. The application of generated data to simulate a fictive outdoor scenario, suggests a significant reduction of bioavailable and total copper to background values during environmental entry as a result of dilution, and the interaction with solid surfaces, organic matter and complexing agents already in the drainage system.
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| 8. |
- Belonoshko, Anatoly B., et al.
(författare)
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First-principles study of hydrogen diffusion in α-Al 2O3 and liquid alumina
- 2004
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Ingår i: Physical Review B Condensed Matter. - 0163-1829 .- 1095-3795. ; 69:2, s. 243021-243026
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the energetics and mobility of neutral hydrogen in alumina Al2O3 using ab initio density-functional calculations. The mobility of hydrogen was studied in corundum (α-Al2O 3) as well as in liquid alumina. Using both static as well as molecular-dynamics calculations, and applying classical transition state theory, we derive the temperature-dependent diffusivity of hydrogen in α-Al 2O3 as D(T)=(21.7 × 10-8 m 2/s)exp(-1.24 eV/kT). The corresponding diffusivity of hydrogen in liquid/amorphous alumina, derived directly from ab initio molecular dynamics calculations, is D(T)=(8.71 × 10-7 m2/s)exp(-0.91 eV/kT). The computed diffusivity compares very well to experimental data. We conclude that diffusion of neutral hydrogen through the bulk of alumina is a good approximation of the mechanism for hydrogen mobility in corrosion scales. The representation of grain-boundary structures by amorphous alumina is, probably, realistic at higher temperatures.
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| 9. |
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| 10. |
- Bertling, Sofia, et al.
(författare)
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Environmental effects of zinc runoff from roofing materials : a new multidisciplinary approach
- 2002
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Ingår i: Outdoor Atmospheric Corrosion. - 0803128967 ; , s. 200-215
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Konferensbidrag (refereegranskat)abstract
- The objective of this work is to study changes in concentration and bioavailability of zinc-containing runoff water, released from roofing materials, upon passage through soil. The experimental approach is based on simulating the interaction between zinc in artificial runoff water and soil in a column system. The total zinc concentration of runoff was substantially reduced when passing through the soil and suggests marked zinc retention, During a constant flow and supply of zinc into the soil, equivalent to three and a half years of precipitation in Stockholm, a zinc retention capacity of approximately 99% was recorded, Not only the total concentration, but also the bio-available portion of the total zinc concentration was reduced after passage through soil, Most of the retained zinc was located in top 3 cm of the soil core and suggests the total capacity for zinc retention of the investigated soil to be about 140 years per kilogram soil in an isolated system in real systems, changes of temperature, pH, microbial activity, weathering of minerals and deposition of new organic material must be considered. The results form part of the effect assessment, preceding future risk assessment of the environmental effects of dispersed zinc.
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| 11. |
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| 12. |
- Bertling, Sofia, et al.
(författare)
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Long-term corrosion-induced copper runoff from natural and artificial patina and its environmental impact
- 2006
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Ingår i: Environmental Toxicology and Chemistry. - 0730-7268 .- 1552-8618. ; 25:3, s. 891-898
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Tidskriftsartikel (refereegranskat)abstract
- The overall objective of this paper is to present an extensive set of data for corrosion-induced copper dispersion and its environmental interaction with solid surfaces in the near vicinity of buildings. Copper dispersion is discussed in terms of total copper flows, copper speciation and bioavailability at the immediate release situation, and its changes during transport from source to recipient. Presented results are based on extensive field exposures (eight years) at an urban site, laboratory investigations of the runoff process, published field data, generated predictive site-specific runoff rate models, and reactivity investigations toward various natural and manmade surfaces, such as those in soil, limestone, and concrete. Emphasis is placed on the interaction of copper-containing runoff water with different soil systems through long-term laboratory column investigations. The fate of copper is discussed in terms of copper retention, copper chemical speciation, breakthrough capacities, and future mobilization based on changes in copper concentrations in the percolate water, computer modeling using the Windermere Humic Aqueous Model, and sequential extractions. The results illustrate that, for scenarios where copper comes in extensive contact with solid surfaces, such as soil and limestone, a large fraction of released copper is retained already in the immediate vicinity of the building. In all, both the total copper concentration in runoff water and its bioavailable part undergo a significant and rapid reduction.
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| 13. |
- Bertling, Sofia, et al.
(författare)
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Model studies of corrosion induced copper runoff fate in soil
- 2006
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Ingår i: Environmental Toxicology and Chemistry. - 0730-7268 .- 1552-8618. ; 25:3, s. 683-691
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Tidskriftsartikel (refereegranskat)abstract
- Laboratory experiments have been performed with 3-cm soil columns simulating the fate of corrosion-induced copper runoff in contact with soil. The investigation simulates approximately 30 years (assuming an infiltration surplus of 25 cm/year) of continuous percolation of copper containing runoff water of a concentration realistic at the immediate release situation (4.8 mg/L) into four soils representative of urban conditions. Two of the three investigated topsoils reached their breakthrough of copper within the simulated time, while the third topsoil did not show a breakthrough. The subsoil reached a breakthrough after approximately 10 years of simulated exposure. To simulate more realistic outdoor scenarios, the laboratory-obtained breakthrough curves were modeled with Hydrus-1D (R) using a Langmuir-Freundlich model to describe copper sorption, the parameters of which were estimated from soil properties (pH, organic carbon content). The model predicts longer breakthrough times with increasing pH and organic content of the soil and with decreasing concentrations of copper and dissolved organic carbon in the runoff water. The time span for copper in runoff water (at concentrations of 0.01-10 mg/L) to reach a soil depth of 50 cm varied between 170 and more than 8,000 years for the predicted field scenarios.
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| 14. |
- Bertling, Sofia, et al.
(författare)
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Occurrence and fate of corrosion-induced zinc in runoff water from external structures
- 2006
-
Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 367:2-3, s. 908-923
-
Tidskriftsartikel (refereegranskat)abstract
- This paper comprises data from an extensive cross-disciplinary research project aiming to elucidate the environmental fate of corrosion-induced zinc release from external structures. It includes an exposure assessment that provide long-term runoff rates, concentrations and chemical speciation of zinc, from 14 zinc-based materials exposed during 5 years in Stockholm, Sweden, and an effect assessment including bioavailability and ecotoxicity measurements, both at the immediate release situation and after soil interaction.Runoff rates of total zinc ranged from 0.07 to 2.5g Znm(-2) yr(-1) with zinc primarily released as the free ion for all materials investigated. The average effect concentration, causing a 50% growth reduction after 72h to the green algae Raphidocelis subcapitata, was at the immediate release situation 69 mu g ZnL-1. Upon interaction of runoff water with soil, which simulated 18 to 34years of exposure, the total zinc concentration was significantly reduced, from milligram per litre to microgram per litre levels. Simultaneously, the most bioavailable fraction of zinc in runoff, the hydrated zinc(II)-ion, decreased from more than 95% to about 30%. The major fraction, 98-99%, of the introduced total zinc concentration in the runoff water was retained within the soil. As long as the soil retention capacity was not reached, this resulted in zinc concentrations in the percolate water transported through the soil layer, close to background values and below growth inhibition concentrations for the green algae investigated. Zinc retained in soil was to a large extent (85-99.9%) extractable with EDTA, and available for plant uptake after 5 to 7months of ageing.
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| 15. |
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| 16. |
- Bettini, Eleonora, et al.
(författare)
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Influence of Grain Boundaries on Dissolution Behavior of a Biomedical CoCrMo Alloy : In-Situ Electrochemical-Optical, AFM and SEM/TEM Studies
- 2012
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 159:9, s. C422-C427
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Tidskriftsartikel (refereegranskat)abstract
- In this study, preferential sites for metal dissolution during anodic polarization were investigated for a biomedical CoCrMo alloy. As-cast and heat treated materials were compared through a combination of complementary techniques. Scanning Kelvin probe force microscopy mapping suggested the matrix areas adjacent to the carbides to be preferential sites for metal dissolution. By means of in situ electrochemical-optical microscopy it was observed that localized dissolution initiated from the matrix areas adjacent to carbides and grain boundaries in both materials at high anodic potential. By using scanning electron microscopy and transmission electron microscopy/energy dispersive spectroscopy analysis, submicron-sized carbides were found along the grain boundaries, and significant Cr depletion was detected across the grain boundaries for both materials, providing an explanation for the initiation of metal dissolution. A slightly higher metal dissolution was observed for the as-cast sample at high anodic potential, probably due to a more heterogeneous microstructure.
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| 17. |
- Bettini, Eleonora, et al.
(författare)
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Influence of metal carbides on dissolution behavior of biomedical CoCrMo alloy : SEM, TEM and AFM studies
- 2011
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 56:25, s. 9413-9419
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Tidskriftsartikel (refereegranskat)abstract
- The influence of precipitate carbides on dissolution tendency and behavior of a biomedical CoCrMo alloy was investigated at microscopic scale. SEM/EDS, TEM/EDS and XRD were performed to characterize crystallographic structure and composition of different precipitate carbides. Scanning Kelvin probe force microscope (SKPFM) was used to evaluate relative nobility of the carbides. In addition to polarization curves, in situ electrochemical AFM (EC-AFM) measurements were performed to investigate the effect of the carbides on local dissolution processes. SEM/EDS, TEM/EDS and XRD characterizations showed non-uniform structure and composition of Cr and Mo carbides. SKPFM analysis suggested the carbide boundaries as preferential sites for corrosion/dissolution process. Cyclic polarization curves of the alloy in phosphate-buffered saline (PBS) solution showed a large current density increase above a certain potential, but only a small hysteresis loop during reverse scan. No noticeable pitting corrosion was observed by SEM after the experiments. In situ AFM images of the sample in PBS showed a stable surface at potentials in the passive region and around the potential corresponding to the current increase and slight etching-like dissolution around the carbides at higher potentials. Carbide boundaries are preferential sites for metal dissolution and carbides with non-uniform composition might exhibit different dissolution rates.
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| 18. |
- Bettini, Eleonora, et al.
(författare)
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Nature of current increase for a CoCrMo alloy : "transpassive" dissolution vs. water oxidation
- 2013
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Ingår i: International Journal of Electrochemical Science. - 1452-3981. ; 8:10, s. 11791-11804
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Tidskriftsartikel (refereegranskat)abstract
- The “transpassive” behavior of a CoCrMo alloy has been investigated to clarify the nature of the current increase at high anodic potential (0.5-0.7 VAg/AgCl). The total amount of released metal ions was determined after the potentiostatic measurements. According to the calculation through Faradays’ law, the metal dissolution only contributes to part of the total current recorded. Electrochemical AFM mapping did not show pronounced topography changes at 0.65 VAg/AgCl, while light optical microscopy observation revealed fast evolution of oxygen bubbles. Evidently water oxidation is another important process largely contributing to the current increase at the high potential.
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| 19. |
- Bettini, Eleonora, et al.
(författare)
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Study of corrosion behavior of a 22% Cr duplex stainless steel : influence of nano-sized chromium nitrides and exposure temperature
- 2013
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 113, s. 280-289
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Tidskriftsartikel (refereegranskat)abstract
- Chromium nitrides may precipitate in duplex stainless steels during processing and their influence on the corrosion behavior is of great importance for the steel performance. In this study, the influence of nano-sized quenched-in chromium nitrides on the corrosion behavior of a heat treated 2205 duplex stainless steel was investigated at room temperature and 50 °C (just above critical pitting temperature). The microstructure was characterized by SEM/EDS and AFM analyses, and quenched-in nitrides precipitated in the ferrite phase were identified by TEM analysis. Volta potential mapping at room temperature suggests lower relative nobility of the ferrite matrix. Electrochemical polarization and in-situ AFM measurements in 1 M NaCl solution at room temperature show a passive behavior of the steel despite the presence of the quenched-in nitrides in the ferrite phase, and preferential dissolution of ferrite phase occurred only at transpassive conditions. At 50 °C, selective dissolution of the austenite phase was observed, while the ferrite phase with the quenched-in nitrides remained to be stable. It can be concluded that the finely dispersed quenched-in nitrides do not cause localized corrosion, whereas the exposure temperature has a strong influence on the corrosion behavior of the duplex stainless steel.
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| 20. |
- Bettini, Eleonora, et al.
(författare)
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Study of Corrosion Behavior of a 2507 Super Duplex Stainless Steel : Influence of Quenched-in and Isothermal Nitrides
- 2014
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Ingår i: International Journal of Electrochemical Science. - 1452-3981. ; 9:1, s. 61-80
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Tidskriftsartikel (refereegranskat)abstract
- Precipitation of different types of chromium nitrides may occur during processing of super duplex stainless steels, affecting the properties of the material. In this study the influence of quenched-in (size range ca. 50-100 nm) and isothermal (size range ca. 80-250 nm) types of nitrides on the corrosion behavior of a 2507 super duplex stainless steel has been investigated at room temperature and at 90 degrees C (above the critical pitting temperature) in 1 M NaCl solution. The microstructure has been characterized by scanning electron microscopy and magnetic force microscopy. The isothermal nitrides exhibit a higher Volta potential compared to the matrix, but such difference could not be observed for the quenched-in nitrides. In-situ electrochemical AFM measurements at room temperature show stable surfaces for a wide range of applied potentials despite the presence of either type of nitrides. In the transpassive region isothermal nitrides appear to be slightly more deleterious than quenched-in nitrides. At 90 degrees C isothermal nitrides largely reduce the corrosion resistance of the austenite phase, while the quenched-in nitrides reduce the corrosion resistance of the material to a much lesser extent. The size difference between isothermal and quenched-in chromium nitrides may be crucial, in particular above the critical pitting temperature.
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| 21. |
- Bjorkbacka, Asa, et al.
(författare)
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Role of the Oxide Layer in Radiation-Induced Corrosion of Copper in Anoxic Water
- 2016
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:21, s. 11450-11455
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Tidskriftsartikel (refereegranskat)abstract
- The influence of a pregrown copper oxide layer on radiation-induced corrosion of polished copper in pure anoxic water has been explored. The resulting amount of copper oxide formed during corrosion was measured with cathodic reduction, and the concentration of dissolved copper in solution was measured with inductively coupled plasma atomic emission spectroscopy. The identity of corrosion products and their topography was determined with Raman spectroscopy and scanning electron microscopy, respectively. Nonirradiated reference samples were analyzed for comparison. The results show that radiation-induced corrosion of copper in anoxic water is significantly more effective on preoxidized copper compared to polished copper. The total amount of oxidized copper exceeds the amount expected solely from radiation chemistry of water by more than 3 orders of magnitude. To explain this discrepancy a mechanism is suggested where the hydroxyl radical (HO center dot) is the main radiolytic oxidative species driving the corrosion process. If the thermodynamic driving force would be large enough (such as for the hydroxyl radical or its precursor, H2O+), the oxide layer could conduct electrons from the metal to the hydroxyl radicals formed at oxide surfaces. The formation of an oxide layer will then result in an increased reactive surface area partly accounting for the observed discrepancy.
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| 22. |
- Björkbacka, Åsa, et al.
(författare)
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Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides
- 2015
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Ingår i: Dalton Transactions. - 1477-9226 .- 1477-9234. ; 44:36, s. 16045-16051
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Tidskriftsartikel (refereegranskat)abstract
- One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO[radical dot]). Both H2O2 and HO[radical dot] are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO[radical dot] are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.
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| 23. |
- Björkbacka, Åsa, 1983-
(författare)
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Radiation induced corrosion of copper
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The process of radiation induced corrosion of copper is not well understood. The most obvious situation where the knowledge of this process is crucial is in a deep repository for high level spent nuclear fuel where the fuel will be sealed inside copper canisters. The radiation will penetrate the canisters and be absorbed by the surrounding environment. In this study gamma irradiations of polished and pre-oxidized copper cubes in anoxic pure water, air of 60-100 % RH and in humid argon were performed. The copper surfaces were examined using IRAS, XPS, cathodic reduction, SEM, AFM, and Raman spectroscopy. The concentration of copper in the reaction solutions was measured using ICP-OES. Also the formation of oxidative species caused by radiation absorption of water was studied by numerical simulations using MAKSIMA software. The corrosion of copper during gamma irradiation vastly exceeds what is expected. The production of oxidative species caused by radiation absorption of water is hundreds of times too low to explain the amount of oxidized copper. A possible explanation for this mismatch is an enhanced radiation chemical yield of HO· on the copper surface. Another one is an increased surface area due to oxidation of copper. One speculation is that HO· interacting with the copper oxide can cause oxidation of the metal. If the thermodynamic driving force is large enough then electrons can be conducted from the metal through the oxide to the oxidant. A dramatic increase in surface area together with an increased interfacial yield of HO· might explain the radiation enhanced corrosion process.
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| 24. |
- Björkbacka, Åsa, et al.
(författare)
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Radiation induced corrosion of copper for spent nuclear fuel storage
- 2013
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Ingår i: Radiation Physics and Chemistry. - : Elsevier BV. - 0969-806X .- 1879-0895. ; 92, s. 80-86
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Tidskriftsartikel (refereegranskat)abstract
- The long term safety of repositories for radioactive waste is one of the main concerns for countries utilizing nuclear power. The integrity of engineered and natural barriers in such repositories must be carefully evaluated in order to minimize the release of radionuclides to the biosphere. One of the most developed concepts of long term storage of spent nuclear fuel is the Swedish KBS-3 method. According to this method, the spent fuel will be sealed inside copper canisters surrounded by bentonite clay and placed 500 m down in stable bedrock. Despite the importance of the process of radiation induced corrosion of copper, relatively few studies have been reported. In this work the effect of the total gamma dose on radiation induced corrosion of copper in anoxic pure water has been studied experimentally. Copper samples submerged in water were exposed to a series of total doses using three different dose rates. Unirradiated samples were used as reference samples throughout. The copper surfaces were examined qualitatively using IRAS and XPS and quantitatively using cathodic reduction. The concentration of copper in solution after irradiation was measured using ICP-AES. The influence of aqueous radiation chemistry on the corrosion process was evaluated based on numerical simulations. The experiments show that the dissolution as well as the oxide layer thickness increase upon radiation. Interestingly, the evaluation using numerical simulations indicates that aqueous radiation chemistry is not the only process driving the corrosion of copper in these systems.
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| 25. |
- Björkbacka, Åsa, et al.
(författare)
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Radiation Induced Corrosion of Copper in Anoxic Aqueous Solution
- 2012
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Ingår i: Electrochemical and solid-state letters. - : ELECTROCHEMICAL SOC INC. - 1099-0062 .- 1944-8775. ; 15:5, s. C5-C7
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Tidskriftsartikel (refereegranskat)abstract
- The effect of gamma radiation on corrosion of copper under anoxic conditions in pure water has been studied experimentally. Copper samples submerged in water were exposed to dose rates of 0.37 or 0.77 kGy/h. Reference samples were used throughout. The copper surfaces have been examined using the techniques of SEM-EDS, IRAS, CR spectroscopy and AFM. Dissolution of copper was measured using ICP-OES. The results show that irradiated samples are more corroded than corresponding reference samples. This is also reflected by the increased concentration of copper in water after irradiation. Surface examination also reveals local corrosion features.
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