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.     

Effects of thermal and mechanical treatments on a titanium-based conversion coating for aluminium alloys

The influence of mechanical deformation and heating on the protective performance of a chromium-free conversion treatment for aluminium alloys has been assessed by polarisation and AC impedance measurements. Protection is unlikely to be seriously compromised by typical production operations.     

Influence of pH on the passivation behavior of 254SMO stainless steel in 3.5% NaCl solution

The potentiodynamic polarization measurement of 254SMO stainless steel (UNS 31254) was conducted in 3.5% NaCl solutions with pH ranging from 0.1 to 5. The results indicated that this stainless steel offered excellent pitting corrosion resistance in corrosive environments. Further, it also exhibited various features on the polarization curves in different pH solutions. The electrochemical constant-potential passivation treatment performed at different pH followed by XPS analysis revealed that the primary constituents of the outermost layer of the passive films formed in the weak (pH 5) and strong (pH 0.8) acid solutions are iron oxides and Cr₂O₃ and Cr(OH)₃, respectively. Molybdenum oxides, primarily in the six-valence state, existed in the outermost layer of the passive film. Only very weak signals corresponding to that of nickel oxides were detected in the film formed in the weak acid (pH 5) solution. The ICP-MS analyses indicated selective dissolution of a significant amount of Fe and a few Mo and Ni ions during the passivation treatment in the strong acid (pH 0.8) solution. No Cr dissolution was observed; this indicated that the Cr in the film is relatively stable. XPS depth profiling results showed that a similar bilayer-structured film was formed in both the solutions (pH 0.8 and 5); the outer layer of this film is primarily composed of Cr(OH)₃ and Mo(VI), and the inner layer, Cr₂O₃ and Mo(IV). The results of the examinations of passive film formations and dissolution by XPS and ICP-MS were consistent with the polarization curves.     

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.     

Potential control under thin aqueous layers using a Kelvin Probe

Kelvin Probes can be modified to control as well as monitor potential. The design and operation of two different Kelvin Probe Potentiostats (KPPs) are described in this paper. One approach uses a permanent magnet and double coil to oscillate the needle at a fixed frequency, an AC backing potential, and software analysis and control schemes. This technique can also control the distance between the tip and sample, thereby tracking the topography of the sample. Both KPPs were used to make measurements on Type 304L stainless steel under thin layers of electrolyte. Cathodic polarization curves exhibited a limiting current density associated with oxygen reduction. The limiting current density varied with solution layer thickness over a finite range of thickness. Anodic polarization curves on 304L in a thin layer of chloride solution resulted in pitting corrosion. The breakdown potential did not vary with solution layer thickness. However, the thin layer was observed to increase in volume remarkably during pit growth owing to the absorption of water from the high humidity environment into the layer with ionic strength increased by the pit dissolution. The open circuit potential (OCP) and solution layer thickness were monitored during drying out of a thin electrolyte layer. Pitting corrosion initiated, as indicated by a sharp drop in the OCP, as the solution thinned and increased in concentration.     

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.