Fundamental studies of passivity and passivity breakdown

This report summarizes the findings of our fundamental research program on passivity and passivity breakdown. During the past three and one half years in this program (including the three year incrementally-funded grant prior to the present grant), we developed and experimentally tested various physical models for the growth and breakdown of passive films on metal surfaces. These models belong to a general class termed point defects models'' (PDMs), in which the growth and breakdown of passive films are described in terms of the movement of anion and cation vacancies

Oxidation of Zircaloy Fuel Cladding in Water-Cooled Nuclear Reactors

Our work involved the continued development of the theory of passivity and passivity breakdown, in the form of the Point Defect Model, with emphasis on zirconium and zirconium alloys in reactor coolant environments, the measurement of critically-important parameters, and the development of a code that can be used by reactor operators to actively manage the accumulation of corrosion damage to the fuel cladding and other components in the heat transport circuits in both BWRs and PWRs. In addition, the modified boiling crevice model has been further developed to describe the accumulation of solutes in porous deposits (CRUD) on fuel under boiling (BWRs) and nucleate boiling (PWRs) conditions, in order to accurately describe the environment that is contact with the Zircaloy cladding. In the current report, we have derived expressions for the total steady-state current density and the partial anodic and cathodic current densities to establish a deterministic basis for describing Zircaloy oxidation. The models are “deterministic” because the relevant natural laws are satisfied explicitly, most importantly the conversation of mass and charge and the equivalence of mass and charge (Faraday’s law). Cathodic reactions (oxygen reduction and hydrogen evolution) are also included in the models, because there is evidence that they control the rate of the overall passive film formation process. Under open circuit conditions, the cathodic reactions, which must occur at the same rate as the zirconium oxidation reaction, are instrumental in determining the corrosion potential and hence the thickness of the barrier and outer layers of the passive film. Controlled hydrodynamic methods have been used to measure important parameters in the modified Point Defect Model (PDM), which is now being used to describe the growth and breakdown of the passive film on zirconium and on Zircaloy fuel sheathing in BWRs and PWRs coolant environments. The modified PDMs recognize the existence of a thick oxide outer layer over a thin barrier layer. From thermodynamic analysis, it is postulated that a hydride barrier layer forms under PWR coolant conditions whereas an oxide barrier layer forms under BWR primary coolant conditions. Thus, the introduction of hydrogen into the solution lowers the corrosion potential of zirconium to the extent that the formation of ZrH2 is predicted to be spontaneous rather than the ZrO2. Mott-Schottky analysis shows that the passive film formed on zirconium is n-type, which is consistent with the PDM, corresponding to a preponderance of oxygen/hydrogen vacancies and/or zirconium interstitials in the barrier layer. The model parameter values were extracted from electrochemical impedance spectroscopic data for zirconium in high temperature, de-aerated and hydrogenated environments by optimization. The results indicate that the corrosion resistance of zirconium is dominated by the porosity and thickness of the outer layer for both cases. The impedance model based on the PDM provides a good account of the growth of the bi-layer passive films described above, and the extracted model parameter values might be used, for example, for predicting the accumulation of general corrosion damage to Zircaloy fuel sheath in BWR and PWR operating environments. Transients in current density and film thickness for passive film formation on zirconium in dearated and hydrogenated coolant conditions have confirmed that the rate law afforded by the Point Defect Model (PDM) adequately describes the growth and thinning of the passive film. The experimental results demonstrate that the kinetics of oxygen or hydrogen vacancy generation at the metal/film interface control the rate of film growth, when the potential is displaced in the positive direction, whereas the kinetics of dissolution of the barrier layer at the barrier layer/solution interface control the rate of passive film thinning when the potential is stepped in the negative direction. In addition, the effects of second phase particles (SPPs) on the electrochemistry of passive zirconium in the hydrogenated, high temperature aqueous solutions were examined by using different heat-treated Zircaloy-4 samples; i.e., as-received, -quenched, and -annealed. The average size of the second phase particles in the Zircaloy-4 samples was in the sequence of -quenched < -annealed < as-received, with the reverse sequence being observed in the areal density. Electrochemical studies show that the size and density of the second phase particles are the determining factors of the electrochemical properties of the passive films. The second phase particles may cause short circuits in the electrical path across the passive film, which would explain the effect of the size and the density of the SPPs, and hence heat treatment, on the corrosion properties of passive Zircaloy-4

Montecarlo based quantitative Kramers-Kronig test for PEMFC impedance spectrum validation

Electrochemical Impedance Spectroscopy (EIS) is a very powerful tool to study the behaviour of electrochemical systems. At present, it is widely used in the fuel cell field in order to study challenging cutting edge issues as membrane drying or gas diffusion layer flooding amongst others. The proper analysis of impedance data requires the fulfilment of four fundamental conditions: causality, linearity, stability and finiteness. The non compliance with any of these conditions may lead to biased, or even misguided, conclusions. Therefore it is critical to verify the compliance of these conditions before accepting any analysis performed on an experimental spectrum. This is even more important in a fuel cell experimental spectrum analysis, since fuel cells are markedly non stationary systems. The aim of this work is to establish an impedance spectrum quantitative validation technique to validate the whole experimental spectrum and to identify the individual points within a spectrum that do not comply any of the four conditions, in order to remove these inconsistent points from the analysis. The designed validation method consists in a Kramers Kronig (KK) validation test, by equivalent electrical circuit fitting, coupled with a Montecarlo error propagation method. In a first step, the experimental spectrum is fitted to a particular electrical equivalent circuit, which satisfies the KK relations. Then, in a second step, a statistical Montecarlo method is used in order to propagate the model fitting parameter uncertainty through the model. Using this approach, a consistency region is built for a given confidence level: the experimental points inside this region are considered consistent for the given confidence level, whereas the outside points are rejected. The method was used on PEMFC experimental impedance spectra; and it successfully managed to identify inconsistent points, associated to no stationarities.The authors are very grateful to the Generalitat Valenciana for its economic support in form of Vali+d grant (Ref: ACIF-2013-268).Giner Sanz, JJ.; Ortega Navarro, EM.; Pérez-Herranz, V. (2015). Montecarlo based quantitative Kramers-Kronig test for PEMFC impedance spectrum validation. International Journal of Hydrogen Energy. 40(34):11279-11293. https://doi.org/10.1016/j.ijhydene.2015.03.135S1127911293403

Characterization of thermal oxide films formed on a duplex stainless steel by means of confocal-Raman microscopy and electrochemical techniques

In this work oxide films have been developed on the surface of a duplex stainless steel (UNS 1.4462) using high temperature confocal microscopy to follow their growth. The characteristics of these oxide films have been analyzed by means of weight-gain measurements, Raman microscopy and electrochemical techniques, namely potentiodynamic polarization curves and electrochemical impedance spectroscopy. The results show an increase in the amount of oxides (particularly γ-Fe2O3 and Fe3O4) with temperature. Regarding the electrochemical properties of these films, the corrosion resistance of the film tends to be lower with the heat treatment temperature, probably due to a more porous and heterogeneous scale. Mott–Schottky plots show the n-type semiconductive behavior of the films with donor densities that decrease with the enhancement of the temperature.We wish to express our gratitude to MICINN (CTQ2009-07518) (UPVO8-3E-012), to Universitat Politecnica de Valencia (CEI-01-11), to the Generalitat Valenciana for its help in the CLSM acquisition (MY08/ISIRM/S/100), and to Dr. Asuncion Jaime for her translation assistance.Sánchez Tovar, R.; Leiva García, R.; García Antón, J. (2015). Characterization of thermal oxide films formed on a duplex stainless steel by means of confocal-Raman microscopy and electrochemical techniques. Thin Solid Films. 576:1-10. https://doi.org/10.1016/j.tsf.2014.12.024S11057

Total harmonic distortion based method for linearity assessment in electrochemical systems in the context of EIS

Electrochemical Impedance Spectroscopy (EIS) is a widely used electrochemical measurement technique that has been used in a great spectrum of fields since it allows deconvolving the individual physic- chemical processes that take place in a given system. Ohm s generalized law, and thus the impedance concept, are only valid if 4 conditions are fulfilled: causality, finiteness, stationarity and linearity. In the case that any of these conditions is not achieved, the obtained impedance spectra will present distortions that may lead to biased or even erroneous results and conclusions. For this reason it is crucial to verify if the 4 conditions are fulfilled, before accepting the results extracted from impedance spectra. In this work, a linearity assessment quantitative method based in the total harmonic distortion (THD) parameter is presented and verified experimentally. The experimental validation of the implemented method showed that the implemented method is able to assess quantitatively the linearity of the system. In addition, it is also able to determine the threshold frequency above which the system will not present significant nonlinear effects even for large perturbation amplitudes. It was observed that the THD method is more sensitive to nonlinear effects than the spectra themselves.The authors are very grateful to the Generalitat Valenciana for its economic support in form of Vali+d grant (Ref: ACIF-2013-268).Giner Sanz, JJ.; Ortega Navarro, EM.; Pérez-Herranz, V. (2015). Total harmonic distortion based method for linearity assessment in electrochemical systems in the context of EIS. Electrochimica Acta. 186:598-612. https://doi.org/10.1016/j.electacta.2015.10.152S59861218

Effect of alloying elements on the electronic properties of thin passive films formed on carbon steel, ferritic and austenitic stainless steels in a highly concentrated LiBr solution

The influence of alloying elements on the electrochemical and semiconducting properties of thin passive films formed on several steels (carbon steel, ferritic and austenitic stainless steels) has been studied in a highly concentrated lithium bromide (LiBr) solution at 25 °C, by means of potentiodynamic tests and Mott-Schottky analysis. The addition of Cr to carbon steel promoted the formation of a p-type semiconducting region in the passive film. A high Ni content modified the electronic behaviour of highly alloyed austenitic stainless steels. Mo did not modify the electronic structure of the passive films, but reduced the concentration of defects

Effect of temperature on passive film formation of UNS N08031 Cr-Ni alloy in phosphoric acid contaminated with different aggressive anions

tThe influence of temperature and the effect of aggressive anions on the electrochemical behaviour of UNSN08031 stainless steel in a contaminated phosphoric acid solution were evaluated. Stabilisation of thepassive film was studied by potentiodynamic polarisation curves, potentiostatic tests, electrochemicalimpedance spectroscopy (EIS) measurements, Mott Schottky analysis and X-ray photoelectron spec-troscopy (XPS). The stability of the passive film was found to decrease as temperature increases. The filmformed on the stainless steel surface was a n-type semiconductor and the XPS spectrum revealed thepresence of fluoride ions.Authors express their gratitude to the Ministry of Education of Spain (MHE2011-00202) for its financial support during the stay at University of Manchester, to MAEC of Spain (PCI Mediterraneo C/8196/07, C/018046/08, D/023608/09 and D/030177/10) and to the Generalitat Valenciana (GV/2011/093) for the financial support. The authors would also like to acknowledge the support of the School of Materials at the University of Manchester for providing analytical and technical support for the study.Escrivá Cerdán, C.; Blasco Tamarit, ME.; García García, DM.; García Antón, J.; Akid, R.; Walton, J. (2013). Effect of temperature on passive film formation of UNS N08031 Cr-Ni alloy in phosphoric acid contaminated with different aggressive anions. Electrochimica Acta. 111:552-561. https://doi.org/10.1016/j.electacta.2013.08.040S55256111

Optimization of the Perturbation Amplitude for Impedance Measurements in a Commercial PEM Fuel Cell Using Total Harmonic Distortion

One of the most important measurement parameters in electrochemical impedance spectroscopy (EIS) is the perturbation amplitude. The optimum perturbation amplitude value corresponds with a balance between the signal-to-noise ratio improvement and the reduction of the harmonic generation due to nonlinear effects. Therefore, the optimum perturbation amplitude is the maximum amplitude that ensures a linear response of the system. Two strategies were considered in this work, i.e., a constant amplitude strategy and a frequency dependent amplitude strategy. On the one hand, for the constant amplitude strategy, the optimum perturbation amplitude for EIS measurements of an individual cell of a commercial PEM fuel cell stack was determined. In order to fulfill this aim, the impedance spectra (at different DC currents) of the individual cell of the commercial PEM fuel cell stack were measured using different perturbation amplitudes. The total harmonic distortion of the recorded voltage signal was determined in each case, applying a FFT based method. The optimum amplitude for each DC current corresponds to the amplitude that minimizes the critical total harmonic distortion value. On the other hand, for the frequency dependent amplitude strategy, the optimum amplitude at each frequency for EIS measurements of an individual cell of a commercial PEM fuel cell stack was determined.Giner Sanz, JJ.; Ortega Navarro, EM.; Pérez Herranz, V. (2016). Optimization of the Perturbation Amplitude for Impedance Measurements in a Commercial PEM Fuel Cell Using Total Harmonic Distortion. Fuel Cells. 16(4):469-479. doi:10.1002/fuce.201500141S46947916