Browsing by Author "Betova I."
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Item Anodic Oxidation of Tungsten under Illumination-Multi-Method Characterization and Modeling at the Molecular Level(2023-11-01) Bojinov M.; Penkova Y.; Betova I.; Karastoyanov V.Tungsten oxide has received considerable attention as photo-anode in photo-assisted water splitting due to its considerable advantages such as significant light absorption in the visible region, good catalytic properties, and stability in acidic and oxidative conditions. The present paper is a first step in a detailed study of the mechanism of porous WO3 growth via anodic oxidation. In-situ electrochemical impedance spectroscopy (EIS) and intensity modulated photocurrent spectroscopy (IMPS) during oxidation of W illuminated with UV and visible light are employed to study the ionic and electronic processes in slightly acidic sulfate-fluoride electrolytes and a range of potentials 4–10 V. The respective responses are discussed in terms of the influence of fluoride addition on ionic and electronic process rates. A kinetic model is proposed and parameterized via regression of experimental data to the EIS and IMPS transfer functions.Item Composition, structure, and properties of corrosion layers on ferritic and austenitic steels in ultrasupercritical water(2006-10-17) Betova I.; Bojinov M.; Kinnunen P.; Lehtovuori V.; Peltonen S.; Penttilä S.; Saario T.In situ electrical and electrochemical measurements during oxidation of ferritic steel P91 and austenitic steel AISI 316L(NG), as well as of their main constituents (Fe, Cr, and Ni) in ultrasupercritical water (500-700°C, 30 MPa) have been reproducibly performed. Features observed in those measurements were substantiated by ex situ results on the thickness, composition, and morphology of the formed oxide layers from weight gain measurements, scanning electron microscopic observations, and in-depth glow-discharge optical emission spectroscopic analyses of corrosion layers. The oxidation process was followed in situ by using the contact electric resistance and contact electric impedance techniques. Impedance spectra of the Ni-Ni and Cr-Cr contacts during oxidation have been reproducibly measured. They could be quantitatively interpreted by using general considerations of the corrosion process and the mixed-conduction model for oxide films. Preliminary estimates of the diffusion coefficients of principal ionic and electronic current carriers have been obtained and their relevance with respect to available data on Ni and Cr oxidation is discussed. © 2006 The Electrochemical Society.Item Corrosion Mechanism and Electrochemical Reactions on Alloy 690 in Simulated Primary Coolant of Water–Water Energy Reactors(2024-04-01) Bojinov M.; Betova I.; Karastoyanov V.During the power operation of the primary loop of a water cooled–water moderated energy reactor (WWER), the water chemistry evolves from a high-boron high-potassium composition to significantly lower concentrations of both constituents at the end of a campaign, and the Li concentration reaches ca. 0.7–0.9 ppm. In the present paper, the effect of primary water chemistry evolution during operation on the corrosion rate and conduction mechanism of oxides on Alloy 690 is studied by in situ impedance spectroscopy at 300 °C/9 MPa during 1-week exposures in an autoclave connected to a re-circulation loop. At the end of exposure, the samples were anodically polarized at potentials −0.8 to −0.1 V vs. SHE to evaluate the stability of the passive oxide. Simultaneously exposed samples of Alloy 690 were subsequently analyzed by XPS to estimate the thickness and in-depth composition of oxides. Impedance data were quantitatively interpreted using the mixed-conduction model (MCM) for oxide films. The effect of water chemistry evolution on the corrosion rate and conduction mechanism in the oxide on Alloy 690 in a primary coolant is discussed based on the obtained parameters.Item Corrosion of Alloy 690 in Simulated Steam Generator Crevices: Effect of Applied Potential, pH and Pb Addition(2022-01-01) Betova I.; Bojinov M.; Ikäläinen T.; Saario T.; Sipilä K.The mechanism of general corrosion of Alloy 690 in simulated steam generator crevices is investigated by voltammetry, electrochemical impedance spectroscopy and slow strain rate tests, combined with ex-situ characterization of the oxides using Xray photoelectron and Glow-discharge optical emission spectroscopies. Quantitative interpretation of impedance spectra with the Mixed-Conduction Model furnishes estimates of kinetic and transport parameters of the corrosion and anodic oxidation processes. The results indicate a beneficial effect of Pb addition on general corrosion regardless of crevice solution composition.Item Corrosion of Stainless Steel in Simulated Nuclear Reactor Primary Coolant—Experiments and Modeling(2024-03-01) Bojinov M.; Betova I.; Karastoyanov V.; Avdeev G.In the present paper, the effect of the evolution of primary water chemistry during power operation on the corrosion rate and conduction mechanism of oxide films on stainless steel is studied by in situ impedance spectroscopy at 300 °C/9 MPa during 1-week exposure periods in an autoclave connected to a recirculation loop. At the end of the exposure period, the samples were anodically polarized in a wide range of potentials to evaluate the stability of the passive oxide. Separate samples of the same steel were simultaneously exposed to the coolant and subsequently analyzed by glow discharge optical emission spectroscopy (GDOES) in order to estimate the thickness and the in-depth composition of the formed oxides. Impedance data were quantitatively interpreted using the mixed-conduction model for oxide films (MCM) to estimate the rates of metal oxidation at the alloy/oxide interface, oxide dissolution and restructuring at the film/coolant interface, and ion transport in the protective corrosion layer.Item Decomposition products of oxygen scavengers and their effect on corrosion of steam generator materials – I. Diethyl-hydroxylamine and carbohydrazide(2024-11-01) Sipilä K.; Ferreirós P.; Ikäläinen T.; Mikkelson A.; Betova I.; Bojinov M.Hydrazine used as oxygen scavenger in the secondary circuit of pressurized water reactors is hazardous to the environment and potentially carcinogenic, thus, suitable replacement chemicals for it are actively sought. In the present paper, decomposition products of two potential replacements – carbohydrazide and diethyl-hydroxylamine – are analyzed, and their effect on secondary water chemistry and corrosion of the main steam generator materials – carbon steel 22 K, stainless steel 0X18H10T and Alloy 690 – is studied by in-situ electrochemical techniques complemented by ex-situ analyses of the formed oxides by spectroscopic and microscopic methods. Quantitative interpretation of the electrochemical impedance data with the Mixed-Conduction Model allowed for the estimation of oxidation and corrosion release rates depending on scavenger formulation, alloy type and temperature. Conclusions on the extent of interaction of decomposition products with construction materials are drawn based on the experimental and calculational results.Item Deposition of Colloidal Magnetite on Stainless Steel in Simulated Steam Generator Conditions—Experiments and Modeling(2022-12-01) Betova I.; Bojinov M.; Karastoyanov V.Sludge formation via colloidal magnetite deposition in steam generators is an important phenomenon that significantly influences the thermohydraulic properties and corrosion of structural materials. This paper aims to verify a model of sludge deposition and consolidation with emphasis on its most significant parameters and their experimental estimation. In-situ electrochemical impedance spectroscopic (EIS) measurements are employed for quantitative evaluation of magnetite deposition kinetics on stainless steel in ammonia-ethanolamine (AMETA) secondary coolant at different temperatures. Parameterization of the model by quantitative comparison of the mixed-conduction model (MCM) with experimental data is discussed. Model predictions are compared with literature data from laboratory experiments and plant operation. Conclusions are drawn about the applicability of the model for quantitative assessment of sludge deposition and consolidation rates.Item Flow-Assisted Corrosion of Carbon Steel in Simulated Nuclear Plant Steam Generator Conditions(2023-07-01) Betova I.; Bojinov M.; Karastoyanov V.Flow-assisted corrosion occurs via increased dissolution and/or mechanical degradation of protective oxide formed on the surface of construction materials in direct contact with coolant liquids. In the present paper, this phenomenon is studied on carbon steel in an ammonia-ethanolamine-hydrazine electrolyte by in situ electrochemical impedance spectroscopy in conditions that closely simulate those that prevail in nuclear plant steam generators. Based on the obtained results, a quantitative kinetic model of the process is proposed and parameterized by nonlinear regression of experimental data to the respective transfer function. On the basis of the experimental and calculational results, it is concluded that flow-assisted corrosion of carbon steel is limited by oxide dissolution and cation ejection processes and the protective layer–coolant interface. Expressions for the film growth and corrosion release processes are proposed and successfully compared to operational data.Item Influence of ionic strength on hydrogen generation during interaction of copper with deoxygenated neutral solution(2021-08-01) Betova I.; Bojinov M.; Lilja C.Interaction of copper with deoxygenated solutions is key to quantify corrosion during long-term exposure in a final high-level nuclear waste repository. To evaluate the effect of ionic strength on such interaction, electrochemical measurements in 0.001−0.1 mol dm−3 NaClO4 were performed at 22, 50 and 70 °C. An extended model including a homogeneous reaction is proposed to account for the extra features in impedance spectra, and the effect of perchlorate concentration (i. e. ionic strength) on its kinetic parameters is discussed. Using the model predictions, the rates of hydrogen production in pure water are estimated and compared to literature data.Item Long-Term Oxidation of Zirconium Alloy in Simulated Nuclear Reactor Primary Coolant—Experiments and Modeling(2023-04-01) Betova I.; Bojinov M.; Karastoyanov V.Oxidation of Zr-1%Nb fuel cladding alloy in simulated primary coolant of a pressurized water nuclear reactor is followed by in-situ electrochemical impedance spectroscopy. In-depth composition and thickness of the oxide are estimated by ex-situ analytical techniques. A kinetic model of the oxidation process featuring interfacial reactions of metal oxidation and water reduction, as well as electron and ion transport through the oxide governed by diffusion-migration, is parameterized by quantitative comparison to impedance data. The effects of compressive stress on diffusion and ionic space charge on migration of ionic point defects are introduced to rationalize the dependence of transport parameters on thickness (or oxidation time). The influence of ex-situ and in-situ hydrogen charging on kinetic and transport parameters is also studied.Item Mechanism of Anodic Dissolution of Tungsten in Sulfate–Fluoride Solutions(2024-09-01) Bojinov M.; Penkova Y.; Betova I.; Karastoyanov V.Thin passive films on tungsten play an important role during the surface levelling of the metal for various applications and during the initial stages of electrochemical synthesis of thick, nanoporous layers that perform well as photo-absorbers and photo-catalysts for light-assisted water splitting. In the present work, the passivation of tungsten featuring metal dissolution and thin oxide film formation is studied by a combination of in situ electrochemical (voltammetry and impedance spectroscopy) and spectro-electrochemical methods coupled with ex situ surface oxide characterization by XPS. Voltametric and impedance data are successfully reproduced by a kinetic model featuring oxide growth and dissolution coupled with the recombination of point defects, as well as a multistep tungsten dissolution reaction at the oxide/electrolyte interface. The model is in good agreement with the spectro-electrochemical data on soluble oxidation products and the surface chemical composition of the passive oxide.Item Oxidation model for construction materials in supercritical water-Estimation of kinetic and transport parameters(2015-11-01) Penttilä S.; Betova I.; Bojinov M.; Kinnunen P.; Toivonen A.An upgraded model was employed to obtain estimates of kinetic parameters of oxidation of stainless steel Sanicro 28 (UNS N08028) and nickel-based alloy 690 (UNS N06690) in supercritical water at 650. °C/25. MPa up to 2000. h. In the present approach, it is assumed that the growth of the outer layer is governed by the transport of cations through the inner layer via an interstitialcy mechanism. The model is able to reproduce quantitatively the depth profiles of constituent elements oxide layer, as well as in the transition layer situated between the inner layer and the bulk alloy.Item Parameterization and Extension of a Model of Oxide Growth by a Multi-Method Approach(2021-03-01) Bojinov M.; Betova I.; Karastoyanov V.; Stancheva M.The technology to form anodic oxides on valve metals will strongly benefit from optimization of process parameters based on deterministic modelling. The relatively large number of adjustable parameters precludes the unambiguous interpretation of steady-state and transient electrochemical data in terms of a unique kinetic model. An approach to overcome this challenge by parameterization of a model of film growth and dissolution using a combination of in situ electrochemical impedance spectroscopy (EIS) in a large frequency range, dynamic high-frequency impedance and photocurrent measurements, with ex situ characterization of the oxides by X-ray photoelectron spectroscopy (XPS) is presented. Additional mechanistic information is derived from density functional theory modelling of adsorption of water and fluoride on TiO2. An extension of the model allowing for a multistep transpassive dissolution reaction at the film/solution interface is also parameterized using voltametric, EIS and XPS data for the anodic oxidation of Mo in concentrated H3PO4.Item Study of Ammonia Adsorption on Magnetite Surfaces with Molecular Dynamics Simulations(2024-07-01) Ivanova N.; Karastoyanov V.; Betova I.; Bojinov M.The present study proposes an atomistic molecular dynamics model system of a magnetite (Fe3O4) {111} surface. The effect of temperature on the adsorption process of ammonia (NH3) at low concentrations in the aqueous phase has been considered. The molecular dynamics simulations were carried out using the Clay force field (Clay FF) with a modification for the iron atoms in the NPT ensemble at a pressure of 90 bar. The considered system was heated in a temperature range from 293 to 473 K, and additional relaxations were performed at temperatures of interest. Within the scope of this study, the basic parameters of the magnetite surface were calculated and the distances between the ammonia molecules and the surface were determined. A general idea of the degree and rate of adsorption at specific temperatures was obtained. The calculation results were compared to the experimental data where possible and to other available simulations of adsorption processes on metal oxides.