The corrosion behavior of sputter-deposited aluminum-tungsten alloys

Thin films on aluminum-tungsten alloys were prepared by co-deposition of pure aluminum and pure tungsten, each sputtered by an independently controlled magnetron source, on glass and sapphire substrates. Completely amorphous films were obtained in the Al₈₀W₂₀-Al₆₇W₃₃ composition range. Passivity and corrosion behavior of amorphous Al-W alloys were investigated in 1 M deaerated hydrochloric acid solution using polarization and impedance spectroscopy measurements and have been correlated with the properties of pure alloy components. Tungsten and sputter-deposited Al-W thin films are inherently passive materials while aluminum undergoes pitting corrosion in hydrochloric acid solution. The passive film formed at the OCP on each alloy possesses excellent electric and dielectric properties comparable to those of the isolating film on tungsten. The absolute impedance increases with increasing tungsten content in the alloy. According to electrochemical polarization measurements, alloying Al with W in solid solution significantly enhances the material's resistance to pitting corrosion by shifting the breakdown potential above 2000 mV (Al₆₇W₃₃) and lowering the corrosion rate at the OCP by more than two orders of magnitude. The most likely mechanism explaining the passivity of amorphous Al-W alloys, the Solute Vacancy Interaction Model (SVIM), involves the formation of complexes between highly oxidized solute atoms (W⁺⁶) and mobile cation vacancies, which restrict the transport of Cl⁻ through the oxide film and inhibit its breakdown in hydrochloric acid solution. The role that film stress relaxation effects and microscopic defects in amorphous Al-W films, of the some composition, and deposited on various substrates play in their corrosion resistance is discussed.     

Austenitizing treatment influence on the electrochemical corrosion behavior of 0.3C-14Cr-3Mo martensitic stainless steel

Effects of austenitizing treatment temperatures on aqueous corrosion properties of martensitic stainless steels were investigated by electrochemical tests (potentiodynamic test, potentiostatic test and electrochemical impedance spectroscopy), and surface analyses (optical microscopy and XRD). The results of potentiodynamic test revealed that the breakdown potential increased with the increased austenitizing temperature, indicating increased relative resistance to initiation of localized corrosion. EIS measurements showed that MSS3 (1030 °C) exhibits larger polarization resistance value than MSS1 (970 °C) and MSS2 (1000 °C) at passive and breakdown states. This was caused by decreasing the amount of Cr-rich M₂₃C₆ carbide which acts as preferential sites for pitting corrosion.     

Validity of dynamic electrochemical impedance spectra of some amine corrosion inhibitors in petroleum/water corrosive mixtures by Kramers-Kronig transformation

In our previous works, the corrosion inhibition properties of propylamine (PA), iso-propylamine (i-PA), butylamine (BA), tert-butylamine (t-BA), hexylamine (HA), ethylenediamine (EDA), diethanolamine (DEA), 3-amino-1-propanol (3-AP), 2-dimethylethanolamine (2-DEA), cyclohexylamine (CHA), N-methylcyclohexylamine (N-MCA) and dicyclohexylamine (DCHA) have been investigated by means of electrochemical impedance spectroscopy (EIS) with a carbon steel rotating disc electrode in some petroleum/water corrosive mixtures containing acetic acid and NaCl at 25 °C. In this work, the Kramers-Kronig transformations (KKTs) were applied to evaluate the validity of the impedance data of these amine compounds in hydrodynamic condition. The results obtained showed that experimental impedance data did not satisfy in K-K relations completely viz. indicated some errors. These errors were related to stray capacitances, external transmission line effects, pits formation and change in interface during data acquisition at high and low frequencies regions. In addition, the selection of a suitable equivalent circuit strongly emphasized to better interpret of EIS data which in turn cause better resulted KKTs spectra. With considering obtained transformations, more effective inhibitor was selected with regard to its charge transfer resistance, the corrosion capacitance and well satisfying in K-K relations.     

Pit to crack transition in stress corrosion cracking of a steam turbine disc steel

Long term exposure tests have been carried out on a 3 NiCrMoV steam turbine disc steel in the form of cylindrical tensile test specimens self-loaded to 90% of σ_0.2 and exposed to three environmental conditions, viz. deaerated pure water, aerated pure water, and aerated water containing 1.5 ppm of chloride ion. Pitting occurred in all environments but the density and depth of pits in the chloride-containing medium was markedly greater. No cracking was observed in deaerated pure water but cracks initiated in aerated water between 13 and 19 months and in less than 7 months in aerated 1.5 ppm Cl⁻ solution. The probability of a crack initiating from a pit of specific depth in aerated solution could be described well by a Weibull function. Profiling of pits and cracks in the disc steel tested in aerated 1.5 ppm Cl⁻ solution showed that there while there were many cracks with a depth greater than that of the corresponding pit the depth of some cracks was smaller than that of the corresponding pit, suggesting that cracks do not necessarily initiate from the bottom of the pits. The growth rate of short cracks emerging from pits appeared greater than that of long cracks in fracture mechanics specimens.     

A model to predict the evolution of pitting corrosion and the pit-to-crack transition incorporating statistically distributed input parameters

A model based on deterministic equations with statistically distributed input parameters has been developed for simulating the evolution of the pit depth distribution at different exposure times and the percentage of pits that transform to stress corrosion cracks. The model has been applied to the specific case of steam turbine disc steel exposed to a range of environments under applied stress. With preliminary fitting at one exposure time, the simulation not only reflects the trends in the experimental measurement but also the model, uniquely, reproduces the statistical variability or “noise” associated with the measurements.     

Behavior of laser welded steel in chloride solution studied using difference imaging

In situ imaging techniques in conjunction with electrochemical measurements were used to study the behavior of steel surfaces in simple chloride solutions. The imaging method detected the presence of significantly thicker uniform layers than the original passive oxide. The layers were found to form in chloride after the steel was anodically polarized following reduction of the passive oxide film. The growth of the layer depended on the degree of prior passive oxide reduction. Formation of the layer was also sensitive to underlying structure and enabled rapid location of regions of higher corrosion rate across laser welds in steels.     

Passivation and pitting corrosion of nanostructured Sn-Ni alloy in NaCl solutions

The passivation and pitting corrosion of tin-nickel alloy (34% Ni-66% Sn) in NaCl solution was studied using potentiodynamic, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques complemented by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of concentration of the chloride ion, the switching potential, scans rate and pH on the electrochemical behavior of Sn-Ni alloy is discussed. The data indicate that the corrosion rate and the pitting corrosion of Sn-Ni alloy increases by the increasing of chloride ion concentration. The observed corrosion resistance of electrodeposited Sn-Ni alloy is due to the formation of a thin passive film from tin and nickel oxides.     

Electrochemical behaviour of heat-treated AlZnMg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al5Zn1.7Mg0.23Cu0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone.     

二次过热器炉管的腐蚀损伤分析与表征

采用金相检验、扫描电镜、三维视频系统及能谱分析等方法，对350MW火力发电机组经13万h运行后二次过热器炉管内表面严重腐蚀损伤进行了检测与表征。结果表明，该炉管内表面的损伤主要是由水中的氯离子及溶解氧作用下引起的点腐蚀所致，为此提出了相应的预防措施。