Tribocorrosion Mechanisms of Martensitic Stainless Steels

In the present study, the influence of the electrochemical potential on the tribocorrosion behavior of X20Cr13 in 0.15 molar NaCl-solution was investigated with the aid of a universal-tribometer under potentiostatic control. The resulting material loss was determined through laser confocal microscopy, while the morphology of the wear tracks and the deformation of the material structure near the surface were observed using light and scanning electron microscopy. The results showed a clear dependence of the material loss and the wear mechanisms from the applied potential. Within the cathodic region, a small amount of the material degradation could be attributed to a strong adhesion and resulting strain hardening as a consequence of an electrochemical weakening and mechanical destruction of the passive layer. The maximum of wear during polarization at the free corrosion potential under friction was explained by galvanic coupling between the wear track and the passive surface near the stability threshold between Fe2+-Ion and Fe2O3 development. Through increasing Polarization onto the free corrosion potential in the absence of friction and into the passive region, a decrease in material loss could be observed which is presumably attributed to the stable passive layer that inhibits electrochemical degradation and favors the formation of a grain refinement zone that slows down mechanical destruction.

On the extrema on the potential dependence of the charge transfer resistance in the hydrogen evolution reaction

The shape of the charge transfer resistance Rct versus overpotentialh curves for the hydrogen evolution reaction (Volmer – Heyrovsky mechanism, Langmuir isotherm for adsorbed hydrogen) was analyzed. It was shown that, depending on the kinetic parameters of reaction steps, three cases are possible: (i) there are no extrema on these curves; (ii) there is one maximum; (iii) there are a minimum and a maximum. Some ways for obtaining kinetic parameters from the curves with extrema are discussed. It was shown that the rate constants and transfer coefficients of all steps can be determined from logRct–h curve alone if there are a minimum and maximum of Rct in cathodic region. In the absence of the extrema, the amount of kinetic information gained from logRct–h plots is considerably reduced.

On the Application of Bipolar Electrochemistry to Characterise the Localised Corrosion Behaviour of Type 420 Ferritic Stainless Steel

Bipolar electrochemistry has been applied to Type 420 ferritic stainless steel in order to determine the full spectrum of anodic-to-cathodic polarisation behaviour. The occurrence of crevice corrosion, pitting corrosion in combination with general corrosion, pitting corrosion only, general corrosion only, followed by a cathodic region has been observed. Instances of pitting corrosion initiated near chromium-rich carbides with Cr23C6, Cr3C2, and Cr7C3 identified as pit nucleation sites. The observed pit growth kinetics were independent of the electrochemical over-potential. Characterisation of the pit size distributions supports the presence of a critical dissolved volume for the transition of metastable to stable pit growth and pit coalescence.

Semiconducting p-Type Copper Iron Oxide Thin Films Deposited by Hybrid Reactive-HiPIMS + ECWR and Reactive-HiPIMS Magnetron Plasma System

A reactive high-power impulse magnetron sputtering (r-HiPIMS) and a reactive high-power impulse magnetron sputtering combined with electron cyclotron wave resonance plasma source (r-HiPIMS + ECWR) were used for the deposition of p-type CuFexOy thin films on glass with SnO2F conductive layer (FTO). The aim of this work was to deposit CuFexOy films with different atomic ratio of Cu and Fe atoms contained in the films by these two reactive sputtering methods and find deposition conditions that lead to growth of films with maximum amount of delafossite phase CuFeO2. Deposited copper iron oxide films were subjected to photoelectrochemical measurement in cathodic region in order to test the possibility of application of these films as photocathodes in solar hydrogen production. The time stability of the deposited films during photoelectrochemical measurement was evaluated. In the system r-HiPIMS + ECWR, an additional plasma source based on special modification of inductively coupled plasma, which works with an electron cyclotron wave resonance ECWR, was used for further enhancement of plasma density ne and electron temperature Te at the substrate during the reactive sputtering deposition process. A radio frequency (RF) planar probe was used for the determination of time evolution of ion flux density iionflux at the position of the substrate during the discharge pulses. Special modification of this probe to fast sweep the probe system made it possible to determine the time evolution of the tail electron temperature Te at energies around floating potential Vfl and the time evolution of ion concentration ni. This plasma diagnostics was done at particular deposition conditions in pure r-HiPIMS plasma and in r-HiPIMS with additional ECWR plasma. Generally, it was found that the obtained ion flux density iionflux and the tail electron temperature Te were systematically higher in case of r-HiPIMS + ECWR plasma than in pure r-HiPIMS during the active part of discharge pulses. Furthermore, in case of hybrid discharge plasma excitation, r-HiPIMS + ECWR plasma has also constant plasma density all the time between active discharge pulses ni ≈ 7 × 1016 m−3 and electron temperature Te ≈ 4 eV, on the contrary in pure r-HiPIMS ni and Te were negligible during the “OFF” time between active discharge pulses. CuFexOy thin films with different atomic ration of Cu/Fe were deposited at different conditions and various crystal structures were achieved after annealing in air, in argon and in vacuum. Photocurrents in cathodic region for different achieved crystal structures were observed by chopped light linear voltammetry and material stability by chronoamperometry under simulated solar light and X-ray diffraction (XRD). Optimization of depositions conditions results in the desired Cu/Fe ratio in deposited films. Optimized r-HiPIMS and r-HiPIMS + ECWR plasma deposition at 500 °C together with post deposition heat treatment at 650 °C in vacuum is essential for the formation of stable and photoactive CuFeO2 phase.

Mediated Electrosynthesis of Cobalt Nanoparticles from Ionic Liquids

The electrochemical behavior of cobalt in the presence of methylviologen (MV2+) dichloride was investigated in choline chloride-urea (1:2 molar ratio) deep eutectic solvent containing 1 mM CoSO4 and 1 mM MV2+. Cyclic voltammetry of cobalt electrolyte after reduction process at stationary potential has shown the shift of oxidation peak to cathodic region with increase of reduction process time. The investigations carried out after electrolysis of the system containing 1 mM CoSO4 and 1 mM MV2+ at the reduction peak of methylviologen dichloride have shown that there was an accumulation of cobalt reduced form in near-electrode region whereas the concentration of methylviologen reduced form has not changed. This may indicate that methylviologen dichloride is a mediator in electrochemical processes with respect to cobalt in the system under consideration.

Investigations of argon and neon abnormal glow discharges in the presence of metastable atom density with fluid model

In this manuscript an investigation of a DC argon and neon abnormal glow discharges with metastable atom density is presented. The values of pressure lie between 133.32 and 330 Pa, and the voltage ranges from 250 to 400 V in the case of argon gas. In the case of neon gas, the pressure has a value of 399.92 Pa (3 Torr) and the voltage ranges from 300 to 500 V. In this framework, an analysis of abnormal glow discharge characteristics is carried out in the case of input data taken from the Boltzmann equation in the multi-term approximation, and in the case of input data obtained from BOLISG+ code. With these differences of input data in the same gas, the output results are different; it appears in the cathodic region. The spatio-temporal distributions of electron and ion densities, the potential and electric field, the mean electron energy and the metastable atom density are shown. A 1D fluid model is used to solve self-consistently the first three moments of the Boltzmann’s equation coupled with the Poisson’s equation. The role of the presence of metastable atom density in the fluid model is clearly because of the domination of ionization processes by both stepwise and penning ionizations. Our results are validated with those obtained by both recent paper and experimental results.

Corrosion depth profiles of nitrided titanium alloy in acidified sulphate solution

Thick (400 µm) glow-discharge nitrided layers, TiN+Ti2N + αTi(N) type, have been produced on the Ti-1Al-1Mn titanium alloy. Using a progressive thinning method, the polarization characteristics at different depths of nitrided layers have been measured. From the plots of obtained potentiodynamic polarization curves the depth profiles of characteristic anodic and cathodic currents (at potentials corresponding to (a) hydride formation, (b) hydrogen evolution, (c) primary passivation, (d) oxygen evolution and (e) secondary passivation) as well as polarization resistance have been determined in 0.5 M Na2SO4 solution acidified to pH = 2. The anomalously high slope of the polarization curves in the cathodic region has been ascribed to the formation of titanium hydride. It has been shown that outer nitrided layers (up to 25 µm) exhibit excellent acid corrosion resistance owing to strong inhibition of the anodic process by TiN phase. Corrosion resistance of deeper situated layers gradually decreases and at depths of 250–370 µm the corrosion process is accelerated by presence of TiO2 precipitations. Nitrided layers, unlike the alloy core, allow oxygen evolution on the oxy-nitrided surface at potential of +1.6 V and at more positive potentials gradual transformation of the surfacial film into TiO2 takes place. Secondary passivation on nitrided titanium is less efficient than that in the absence of Ti-N species.

Comparative Cathodic Behavior of ~9% Cr and Plain Steel Reinforcement in Concrete

The extent of the oxygen reduction reaction in concrete was evaluated for ~9% Cr rebar approaching the ASTM A1035 specification and compared to that of conventional carbon steel rebar, at ages of up to ~1 year. Cathodic strength was measured by the cathodic current density developed at −0.35 V vs. copper/copper sulfate (Cu/CuSO4 [CSE]) and −0.40 VCSE in cyclic cathodic potentiodynamic polarization tests, both in the as-received condition with mill scale and with scale removed by glass bead surface blasting. In both conditions the ~9% Cr alloy was a substantially weaker cathode, by a factor of several fold, than carbon steel. Within each material, the surface-blasted condition yielded also much lower cathodic current density than the as-received condition. For a small anode-large cathode system with a given anode polarization function, and no important oxygen reduction concentration polarization, the corrosion current was projected to be significantly lower if the cathodic region were ~9% Cr instead of plain steel rebar with comparable surface condition. There was strong correlation between the charge storage capability of the interface and the extent of cathodic reaction of oxygen. The result cannot be ascribed solely to differences in effective surface area between the different materials and conditions.