Electrochemical and XPS studies of sputter-deposited ternary Mn-Ta-Cr alloys in chloride-free and chloride-containing sulphuric acid solutions

Amorphous manganese-rich (67-80 at.%) Mn-Ta-Cr alloy films were prepared by DC magnetron sputtering method. The corrosion behavior and stability of the Mn-Ta-Cr alloy films were examined in chloride-free and -containing 1 M H₂SO₄. AC and DC electrochemical techniques in combination with XPS analysis were used. Mn-Ta-Cr alloys exhibited very high corrosion resistance and stability up to transpassive dissolution region of chromium. The high corrosion resistance of Mn-Ta-Cr sputtered films is based on the formation of double oxyhydroxide passive film composed mainly of chromium and tantalum. The partial substitution of tantalum with chromium improves the corrosion resistance of the sputter-deposited alloys via accelerating the preferential dissolution of manganese and stabilizing alloy/passive film interface. A change in the passive film structure was observed when the alloys were anodically polarized at potentials higher than 0.6 V (SCE).     

Electrochemical,SEM and XPS investigations on phosphoric acid treated surgical grade type 316L SS for biomedical applications

A simple surface pre-treatment method was attempted to establish a stable passive layer on the surface of surgical grade stainless steel (SS) of type 316L for biomedical applications. Surgical grade type 316L SS specimens were subjected to H₃PO₄ treatment for 1 h by completely immersing them in the acid solutions to develop a passive barrier film. The effect of various concentrations of phosphoric acid on the localized corrosion resistance behavior of type 316L SS was investigated through electrochemical techniques using cyclic polarization studies and electrochemical impedance spectroscopy (EIS). X-ray photoelectron spectroscopy (XPS) was used to evaluate the nature and composition of the passive films. The surface morphology and relative elemental composition of the untreated and acid treated surfaces subjected to anodic polarization was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) techniques, respectively. Compared with untreated (pristine) 316L SS, the 40% acid treated surface formed a stable passive layer that had superior corrosion resistance.     

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.     

Electrochemical behavior of centrifuged cast and heat treated Ti-Cu alloys for medical applications

The aim of this study was to evaluate the general electrochemical corrosion resistance of Ti-5, 7.1 and 15 wt.% Cu alloys with a view to medical applications. A centrifuged casting set-up and a solution heat treatment at 900 °C for 2 h were used to prepare the samples. Electrochemical impedance spectroscopy (EIS) and potentiodynamic anodic polarization techniques were used to analyze the corrosion resistance in a 0.15 M NaCl solution at 25 °C. An equivalent circuit analyses was also conducted. It was found that the corrosion rate increased with increasing Cu content. The results have shown that the addition of Cu has not stabilized the β phase. Martensite and Ti₂Cu intermetallic particles provided by casting and heat treatment processes, respectively, have important roles on the resulting impedance parameters and passive current densities of the Ti-Cu alloys.     

Effects of cold work and sensitization treatment on the corrosion resistance of high nitrogen stainless steel in chloride solutions

The effects of cold work and sensitization treatment on the microstructure and corrosion resistance of a nickel-free high nitrogen stainless steel (HNSS) in 0.5 M H₂SO₄ + 0.5 M NaCl, 3.5% NaCl and 0.5 M NaOH + 0.5 M NaCl solutions have been investigated by microscopic observations, electrochemical tests and surface chemical analysis. Cold work introduced a high defect density into the matrix, resulting in a less protective passive film as well as reduced corrosion resistance for heavily cold worked HNSS in a 3.5% NaCl solution. No obvious degradation in corrosion resistance took place in a 0.5 M H₂SO₄ + 0.5 M NaCl solution, possibly due to the stability of the passive film in this solution. Sensitized HNSSs showed reduced corrosion resistance with increasing cold work level in both 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions due to a reduction in the anti-corrosion elements in the matrix during the cold work-accelerated precipitation process. The cold work and sensitization treatment had no influence on the corrosion resistance of the HNSS in the 0.5 M NaOH + 0.5 M NaCl solution even though the property of the passive film changed. The effects of cold work and sensitization treatment on the characteristics of passive films formed in the three solutions are discussed.     

Effects of pH value and temperature on the corrosion behavior of a Ta2N nanoceramic coating in simulated polymer electrolyte membrane fuel cell environment

To improve the corrosion resistance and electrical conductivity of Ti-6Al-4V bipolar plates used in polymer electrolyte membrane fuel cells (PEMFCs), a novel electro-conductive Ta₂N nanoceramic coating was developed by reactive sputter-deposition using a double cathode glow discharge plasma technique. The microstructure of the coating consisted of fine equiaxed Ta₂N grains with an average grain size of ∼13 nm, which exhibited a strong (101) preferred orientation. To explore the influence of both pH values and temperatures on the corrosion resistance of the coating, the electrochemical behaviors and electronic properties of passive films grown on the Ta₂N coating were systematically investigated using different electrochemical techniques in simulated PEMFC operating environment. It was shown that either increasing the acidity or the temperatures of the solution, the corrosion potential (E_corr) decreased and the corrosion current density (i_corr) increased. At a given temperature or pH value, the Ta₂N coating had a higher E_corr and lower i_corr as compared with uncoated Ti-6Al-4V. The results of EIS measurements showed that with increasing temperature or acidity of the solution, the resistance of the passive film (R_p) formed on the Ta₂N coating decreased slightly, being of the order of magnitude of 10⁷ Ω cm², which was an order of magnitude higher than that of uncoated Ti-6Al-4V. The interfacial contact resistance (ICR) values were found to increase with increasing pH value or decreasing solution temperature, and the ICR values of the Ta₂N coating were markedly lower than that of uncoated Ti-6Al-4V, due to the thinner thickness of passive films. Furthermore, the Ta₂N-coated Ti-6Al-4V is more hydrophobic than bare Ti-6A1-4V, which was favorable for both the simplification of water management and improving corrosion resistance in PEMFC operating environment.     

Effects of nanocrystallization on the corrosion behavior of 309 stainless steel

Nanocrystallized (NC) 309 stainless steel (309SS) coating has been fabricated on glass substrate by DC magnetron sputtering. The coating, with an average grain size less than 50 nm, had ferritic (bcc) structure rather than the austenitic (fcc) structure of the bulk steel. The electrochemical corrosion behavior of the NC coating and the bulk steel in solutions of 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ was investigated by using potentiodynamic polarization, potentiostatic polarization and AC impedance techniques. The results showed that the corrosion behavior of the NC 309SS coating and 309SS bulk steel depended on the composition of the solutions. In the Na₂SO₄ solution there was only a little difference between the corrosion resistance of the passive films on the NC coating and the bulk steel. However, in the solution with chloride ions, the localized corrosion resistance of 309SS was greatly enhanced by nanocrystallization due to the formation of a compact and stable passive film on the NC coating. The electronic structure of the passive film formed on the NC coating and on the bulk steel was analyzed by means of capacitance measurements, and a corrosion mechanism is proposed.     

Influence of grain size on the corrosion behavior of a Ni-based superalloy nanocrystalline coating in NaCl acidic solution

The effects of grain size on the electrochemical corrosion behavior of a Ni-based superalloy nanocrystalline (NC) coating fabricated by a magnetron sputtering technique, has been investigated in 0.5 M NaCl + 0.05 M H₂SO₄ solution. Coatings with grain sizes 10 nm, 50 nm and 100 nm were fabricated on glass and the superalloy substrates. The results indicate that a passive film with porous property, n-type semiconductive property and incorporation of chloride ions formed on the NC coating with 100 nm grain size, which increased the susceptibility to pitting corrosion. The NC coatings with 10 nm and 50 nm grain size formed compact, non-porous and p-type passive films without chloride ions, which improved resistance to pitting corrosion. The smaller grain size of the material decrease the amount of chloride ions adsorbed on the surface and promoted the formation of compact passive film, which significantly increased the material's resistance to pitting corrosion in acidic solution.     

The use of local electrochemical probes and surface analysis methods to study the electrochemical behaviour and pitting corrosion of stainless steels

In this paper, the electrochemical microcell technique is combined with ex situ (SIMS and XPS) and in situ (SVET) techniques to study the electrochemical behaviour and pitting corrosion of inclusion-contaning stainless steels. Dissolution of metallurgical heterogeneities, depassivation and pitting mechanisms are first discussed in 1 M NaClO₄, pH 3, and 1 M NaCl, pH 3, by considering the chemical composition and morphology of inclusions. The influence of the chemical composition of passive films on the electrochemical reactions and the microgalvanic coupling processes occurring at the corrosion potential is also investigated on the same specimen microstructure.     

Electrochemical behavior of aluminum bronze in sulfate-chloride media

The electrochemical behavior, especially the corrosion and passivation, of a Cu–Al bronze was investigated. Conventional electrochemical techniques including open-circuit potential, anodic polarization, cyclic voltammetry and electrochemical impedance spectroscopy were used. It was found that the addition of chloride ion up to 0.15 M in 0.5 M Na₂SO₄ solution decreases the corrosion rate due to the formation of CuCl, whereas at higher concentration of the chloride ion, the corrosion rate increases due to the formation of the soluble CuCl₂⁻. The activation energy was found to be 10 kJ mol⁻¹. This value indicates that the corrosion process is under diffusion control. The impedance measurements showed that the passive film can be represented by a duplex layer, a relatively thick porous outer film on top of a thin compact layer. An equivalent circuit was used to explain and analyze the impedance data. The model includes another R-C combination and Warburg impedance in addition to the simple Randles cell to account for the spontaneously formed passive film and the diffusion phenomena.     

The tribological performance of BCN films under ionic liquids lubrication

Boron carbon nitride films were deposited onto silicon substrates by medium frequency magnetron sputtering from graphite and boron targets with Ar and N₂ as feedstock. The three elements of B, C and N were bonded to each other and an atomic-level hybridized B–C–N had been formed in the films. The tribological performances of the boron carbon nitride film with 1-butyl, 3-methylimidazolium tetrafluoroborate ionic liquid as lubricant and the electrochemical corrosive behaviors of the BCN film were investigated. The boron carbon nitride film demonstrated excellent tribological properties and corrosion resistance as compared with diamond like carbon film. An extensive discussion of the effect of film intrinsically structure on both lubrication and corrosion under ionic liquid condition is given. In addition, the interrelation between the tribological properties and corrosion resistance is illustrated.     

The synergetic effect of benzylamine on the corrosion inhibition of copper by benzotriazole

Passivating films, formed by the anodization of copper in alkaline benzotriazole (BTA) solutions, have been investigated. Addition of benzylamine to the anodizing solutions was found to lead to much faster passivation and greater corrosion resistance in aqueous chloride. These passivating films appear to consist mainly of a [Cu(II)BTA₂]_n polymeric network.     

Corrosion protection of carbon steel by thin films of poly(3-alkyl thiophenes) in 0.5 M H2SO4

Poly(3-octyl thiophene) (P3OT) and poly(3-hexylthiophene) (P3HT) dissolved in toluene were deposited onto 1018 carbon steel and corroded in 0.5 M H₂SO₄. P3OT and P3HT films were chemically deposited by drop casting onto 1018-type carbon steel with two surface finishing, i.e. abraded with 600-emery paper and with alumina (Al₂O₃) particles of 1.0 μm in diameter (mirror finish). Their corrosion resistance was estimated by using potentiodynamic polarization curves, linear polarization resistance (LPR), and electrochemical impedance spectroscopy, EIS, techniques. In all cases, polymeric films protected the substrate against corrosion, but the protection was improved if the surface was polished with Al₂O₃ particles of 1.0 μm in diameter. The polymer which gave the best protection was P3HT because the amount of defects was much lower than that for the P3OT films. The polymers did not act only as a barrier layer against aggressive environment, but they improved the passive film properties by decreasing the critical current necessary to passivate the substrate, increasing the pitting potential and broadening the passive interval.     

Influence of the micro-addition of Mo on glass forming ability and corrosion resistance of Cu-based bulk metallic glasses

(Cu₄₇Zr₁₁Ti₃₄Ni₈)_100−xMo_x bulk metallic glasses (BMGs) with x = 0, 1 and 2 at.% and a bulk metallic glass matrix composite with x = 5 at.% were successfully prepared by water-cooled copper mold casting. The effect of the addition of a small amount of Mo on the glass forming ability (GFA), thermal properties of the base alloy (i.e. x = 0) were investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and differential thermal analyzer (DTA). It is found that the addition of appropriate amount of Mo can enhance the GFA of the Cu-based BMG, as indicated by the increase in the reduced glass transition temperature T_rg (=T_g/T_l) and the parameter γ (=T_x/(T_g + T_l)) with the increase of Mo. On the other hand, the corrosion resistance of the Cu-based BMGs with different Mo contents was examined by electrochemical polarization and weight loss measurement in 1 mol/L H₂SO₄ and 1 mol/L NaOH solutions, respectively. It is found that the corrosion resistance of Cu-based BMGs increased with increasing Mo content with the lowest corrosion rate of (0.9 ± 0.2) × 10⁻³ mm/year in 1 mol/L H₂SO₄ solution and (0.3 ± 0.1) × 10⁻³ mm/year in 1 mol/L NaOH solution, respectively, for the BMG containing 2 at.% Mo. X-ray photoelectron spectroscopy (XPS) results revealed that the improvement of corrosion resistance of Cu-based BMG containing appropriate amount of Mo originated from the enrichment of ZrO₂ and TiO₂, but depletion in Cu- or Ni-oxides in the passive films formed during electrochemical polarization. Finally, the galvanostatic-step measurement was performed to investigate the kinetics of the formation of passive films on the BMG surfaces. It is demonstrated that the addition of an appropriate amount of Mo can effectively improve the stability and uniformity of the passive film. The role of Mo addition on the glass forming ability and corrosion behavior is discussed.     

Effects of a small addition of Mn on the corrosion behaviour of Zn in a mixed solution

The effects of a small addition of Mn (0.4 wt%) on the corrosion behaviour of pure Zn (99.995 wt%) in a mixed solution (0.1 M NaCl + 0.1 M Na₂SO₄ + 0.01 M NaHCO₃, pH 8.4) were investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and X-ray photoelectron spectroscopy (XPS). The electrochemical impedances of both Zn and Zn–0.4Mn have been successfully fitted with a suitable EIS equivalent circuit model. Fitted impedance results revealed that 0.4 wt% Mn improved both the pore resistance and charge transfer resistance of Zn in the mixed solution. As a result, both anodic and cathodic reaction rates were reduced. X-ray photoelectron spectroscopy (XPS) analysis showed that the corrosion films formed in the mixed solution consisted of zinc oxide (ZnO), zinc hydroxide (Zn(OH)₂) and zinc hydrozincite (Zn₅(CO₃)₂(OH)₆). The role of small addition of Mn is that it promotes the precipitation of hydrozincite in the pores of corrosion film. An “alleviation of local acidification” mechanism is proposed to explain the investigated results.     

Hydrogen effects on pitting corrosion and semiconducting properties of nitrogen-containing type 316L stainless steel

The effects of hydrogen pre-charging on pitting corrosion resistance and semiconducting nature of passive film formed on two different nitrogen-containing type 316L stainless steel (0.076 and 0.086 wt% N) have been studied. Auger electron spectroscopy (AES) analysis of the alloys after passivation indicated weak nitrogen peak, but the presence of nitrogen and NH₃/NH₄⁺ was confirmed by the X-ray photoelectron spectroscopy (XPS) analysis. The results of pitting corrosion in 0.5 M NaCl (pH ≈ 5.7) solution revealed that hydrogen increased the passive current density and significantly reduced the pitting resistance. In 0.3 M H₃BO₃ + 0.075 M Na₂B₄O₇·10H₂O (pH ≈ 8.45) solution, increase in passive current density without affecting the breakdown or transpassive potential was observed for both the alloys. Electrochemical impedance spectroscopy (EIS) measurement after hydrogen pre-charging showed decrease in semi-circle radius of Nyquist plot, and the polarization resistance, R_P associated with the resistance of the passive film. The decrease was significant with increasing hydrogen-charging current density (−50 to −100 mA/cm²). The results of the capacitance measurement and Mott–Schottky plots revealed that passive films exhibit n-type and p-type semiconductivity films for both the uncharged and hydrogen charged specimens of the investigated alloys. Doping densities obtained from Mott–Schottky plots increased with hydrogen pre-charging. The overall results indicated that hydrogen pre-charging deteriorated the passive film stability and lowered pitting corrosion resistance. The effects of hydrogen pre-charging on pitting corrosion, passive film and semiconducting properties are discussed in light of the above results.     

Electrochemical studies on electroless ternary and quaternary Ni-P based alloys

The autocatalytic (electroless) deposition of Ni-P based alloys is a well-known commercial process that has found numerous applications because of their excellent anticorrosive, wear, magnetic, solderable properties, etc. It is a barrier coating, protecting the substrate by sealing it off from the corrosive environments, rather than by sacrificial action. The corrosion resistance varies with the phosphorus content of the deposit: relatively high for a high-phosphorus electroless nickel deposit but low for a low-phosphorus electroless nickel deposit. In the present investigation ternary Ni-W-P alloy films were prepared using alkaline citrate-based bath. Quaternary Ni-W-Cu-P films were deposited by the addition of 3 mM copper ions in ternary Ni-W-P bath. X-ray diffraction (XRD) studies indicated that all the deposits were nanocrystalline, i.e. 1.2, 2.1 and 6.0 nm, respectively, for binary, ternary and quaternary alloys. Corrosion resistance of the films was evaluated in 3.5% sodium chloride solution in non-deaerated and deaerated conditions by potentiodynamic polarization and electrochemical impedance (EIS) methods. Lower corrosion current density values were obtained for the coatings tested in deaerated condition. EIS studies showed that higher charge transfer resistance values were obtained for binary Ni-P coatings compared to ternary or quaternary coatings. For all the coatings a gradual increase in the anodic current density had been observed beyond 740 mV. In deaerated condition all the reported coatings exhibited a narrow passive region and all the values of E_p, E_tp and i_pass were very close showing no major changes in the electrochemical behavior. In the non-deaerated conditions no passivation behavior had been observed for all these coatings.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

Influence of nanocrystallization on passive behavior of Ni-based superalloy in acidic solutions

The electrochemical corrosion behaviors of Ni-based superalloy nanocrystalline coating (NC) fabricated by a magnetron sputtering technique have been investigated in comparison with cast alloy in 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ solution, respectively. Compared with cast alloy, the NC coating had a little higher passive current density in Na₂SO₄ acidic solution, while it had superior resistance to pitting corrosion in NaCl acidic solution. The semiconductive type of passive film of the NC coating was p-type in both acidic solutions, while, that of cast alloy changed from p-type in Na₂SO₄ acidic solution to n-type in NaCl acidic solution. XPS results indicated that Cr₂O₃ was the main component for the passive films of the NC coating as well as those of the cast alloy. No chloride ion was found in the passive film of NC coating while it was in the passive film of cast alloy. The chloride ions adsorbing on the surface of cast alloy incorporated into the passive film, which induced the formation of n-type oxide film. The nanocrystallization of Ni-base superalloy obviously weakened the adsorption of chloride ions on surface, which decreased the susceptibility of pitting corrosion in acidic solution.     

Evaluation of corrosion resistance of polypyrrole/functionalized multi-walled carbon nanotubes composite coatings on 60Cu–40Zn brass alloy

Polypyrrole/multi-walled carbon nanotubes (PPy/MWCNT) and its carboxylic functionalized (PPy/MWCNT-COO⁻) composite films were successfully electropolymerized by cyclic voltammetry as protective coating against corrosion on 60Cu–40Zn brass alloy surface. It yielded to strongly adherent and smooth nanocomposite films. Kinetics of the corrosion protection was investigated in 3.5 wt% NaCl solutions by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The results showed that the presence of MWCNT in PPy coat considerably reduces the corrosion rate of 60Cu–40Zn brass alloy. The enhanced inhibition is most likely due to interaction between MWCNT and PPy. This in turn, improves the alloy passivation improvement and alters the permselectivity of the coating from anionic selectivity to the cationic selectivity. Moreover, PPy/MWCNT-COO⁻ functionalized nanocomposite provided higher corrosion resistance coating than PPy/MWCNT alone.