Diamond Coating Reduces Nuclear Fuel Rod Corrosion at Accidental Temperatures: The Role of Surface Electrochemistry and Semiconductivity

If we want to decrease the probability of accidents in nuclear reactors, we must control the surface corrosion of the fuel rods. In this work we used a diamond coating containing <60% diamond and >40% sp2 “soft” carbon phase to protect Zr alloy fuel rods (ZIRLO ®) against corrosion in steam at temperatures from 850 °C to 1000 °C. A diamond coating was grown in a pulse microwave plasma chemical vapor deposition apparatus and made a strong barrier against hydrogen uptake into ZIRLO® (ZIRLO) under all tested conditions. The coating also reduced ZIRLO corrosion in hot steam at 850 °C (for 60 min) and at 900 °C (for 30 min). However, the protective ability of the diamond coating decreased after 20 min in 1000 °C hot steam. The main goal of this work was to explain how diamond and sp2 “soft” carbon affect the ZIRLO fuel rod surface electrochemistry and semi conductivity and how these parameters influence the hot steam ZIRLO corrosion process. To achieve this goal, theoretical and experimental methods (scanning electron microscopy, Raman spectroscopy, electrochemical impedance spectroscopy, carrier gas hot extraction, oxidation kinetics, ab initio calculations) were applied. Deep understanding of ZIRLO surface processes and states enable us to reduce accidental temperature corrosion in nuclear reactors.

Synthesis, characterization and electrochemistry of triethyl ammonium sulphate ionic liquid

Protic ionic liquids (PILs) being intrinsic proton conducting ionic species are considered as potential green electrolytes for study of electrocatalytic reactions and for fabrication of IL-based fuel cells (FCs) and batteries. We have prepared a sulfate anion based protic ionic liquid (PIL), triethylammonium sulfate (TEAS) through a reaction involving transfer of proton from H2SO4 to triethylamine (TEA). 1H NMR and FT-IR spectroscopic techniques were employed for confirmation of the synthesis of TEAS and water content of the PIL was quantified using coulometric Karl–Fischer (KF) titration. 1H NMR and FT-IR analysis confirm the synthesis of the PILs and KF-titration analysis shows that TEAS contains 1.43 w/w % water. Electrical conductivity of TEAS was determined at different temperatures showing that the PIL has excellent ionic conductivity that enhances with rise in temperature of the medium. The temperature dependence of the conductivity of the PIL follows the Arrhenius equation as the logσ versus 1/T plot is linear. The electrochemical windows (EWs) of the electrolyte were found using cyclic voltammetry at Pt and Au working electrodes and found to decrease with increase in temperature of the medium. The data revealed that the surfaces of the electrodes are covered with oxide layers due to oxidation of trace water (1.43 w/w %) present in the PIL. The oxide layers growth increase and their onset potential moves to less positive values as the temperature of the PILs is increased. The data was compared with the literature and would be helpful in understanding of the surface electrochemistry in this neoteric medium for being used as potential electrolyte in industry for various electrochemical applications.

Staged Local Dissolution of Stainless Steel in Chloride Solutions

The paper defines galvanostatic polarization parameters (current density and test duration), to simulate self-dissolution conditions; the results are confirmed by potentiostatic tests. It is shown that under the conditions of self-dissolution simulation, increasing the solution concentration reduces the nucleation rate, while prolonging the pitting development time. Spectral analysis of chronopotentiograms reveals low-frequency potential fluctuations that characterize the nucleation and passivation of pits at the onset of pitting corrosion. The paper describes the basic regularities, observed in the alteration of surface electrochemistry by impedance spectroscopy; such alteration corresponds to the transition from the passive area to the pitting area. The researchers propose optimal electric equivalent circuits to reflect the surface conditions in early nucleation of pits. The paper also proposes an additional pitting resistance criterion, that is, cumulative electric-charge density.