Passivation and corrosion behaviours of cobalt and cobalt-chromium-molybdenum alloy

Passivation and corrosion behaviour of the cobalt and cobalt-base alloy Co30Cr6Mo was studied in a simulated physiological solution containing chloride and bicarbonate ions and with pH of 6.8. The oxido-reduction processes included solid state transformations occurring at the cobalt/electrolyte interface are interpreted using theories of surface electrochemistry. The dissolution of cobalt is significantly suppressed by alloying it with chromium and molybdenum, since the alloy exhibited “chromium like” passivity. The structural and protective properties of passive oxide films formed spontaneously at the open circuit potential or during the anodic polarization were studied using electrochemical impedance spectroscopy in the wide frequency range.     

Corrosion evaluation and surface characterization of the corrosion product layer formed on Cu-6Sn bronze in aqueous Na2SO4 solution

The binary bronze alloy Cu-6Sn corrosion, and formation and properties of corrosion product layer (patinas) during 12 days of exposure to 15 mM Na₂SO₄ aqueous solution were investigated by a range of diverse experimental techniques. For the reasons of comparison, some techniques were applied, in parallel, to copper. Gravimetric measurements revealed lower corrosion rates of bronze than those of copper, probably caused by the presence of tin compounds in the corrosion product layer. Cyclic voltammetry results showed that the oxidation processes on bronze are affected by the formation of tin oxide species. Electrochemical impedance spectroscopy showed that, as opposed to copper which produced only two time constants, bronze corrosion resistance was dominated by the additional high-frequency time constant representing redox processes occurring at the corrosion product surface. SEM, ATR FTIR and PIXE results suggest that Cu-6Sn bronze corrosion in 15 mM Na₂SO₄ solution was impeded by the formation of two-layered structure of corrosion products that formed due to selective dissolution of copper at the layer/solution interface, leaving the outer layer enriched in highly corrosion resistant Sn oxi/hydrohide species.     

Surface characterization and corrosion behavior of a novel gold-imitation copper alloy with high tarnish resistance in salt spray environment

A novel gold-imitation copper alloy (CuZnAlNiSnBRe) was designed and its corrosion behavior in salt spray environment was investigated. The new alloy has better tarnish resistance and corrosion resistance than the current coinage alloy used in China (H7211). A multi-layer film formed on the surface of the new alloy after a period of exposure to salt spray was responsible for the good resistance of the alloy. The corrosion products were a mixture of CuO, Cu₂O, ZnO, Al₂O₃ and Al(OH)₃, with the transition from Cu₂O to CuO occurring during the corrosion process.     

An SFG and ERS investigation of the corrosion of CoW0.013C0.001 alloys and WC-Co cermets in CN-containing aqueous solutions

In order to increase the knowledge of the corrosion mechanism, in situ spectroelectrochemical methodologies were employed in the investigation of the electrochemical interface of WC-Co hardmetals. Together with standard cyclic voltammetries (CV), ElectroReflectance Spectroscopy (ERS) and Sum Frequency Generation (SFG) spectroscopy measurements were performed both on a Co-base alloy, simulating the metallic binder of hardmetal composites, and on a model WC-Co system. A cyanide solution, encountered in the gold extraction industry, was employed as electrolyte. Electrochemical cells and experimental apparatuses were designed to allow in situ experiments. CV measurements showed corrosion attack to run at potentials more anodic than −500 mV vs. Ag/AgCl, both for the alloy and the composite. The high reactivity of the alloy in cyanide environment was witnessed by the time-dependence of the surface vibrational (SFG) and electronic (SFG and ERS) properties under cathodic polarisation. Furthermore, SFG measurements highlighted two different adsorbation sites for cyanide ion, probably α- and ε-Co. The WC-Co system showed a pseudo-passivation peak, typical of the corrosion behaviour of this material, due to precipitation of corrosion products. ERS data at 532 nm showed an ennobling of the potential at which the reflectivity increase was recorded.     

Development of novel brasses to resist dezincification

The effect of alloying Sn, Pb, As, Sb and P on the dezincification of commercial brass 60Cu-39Zn-1Pb has been investigated in 1% CuCl₂ solution by immersion studies and electrochemical measurements. Specimens with a smooth surface finish exhibited more resistance to dezincification. Appreciable inhibitive effect on dezincification was observed for the 55Cu-40Zn-3Pb-2Sn brass composition. The galvanic coupling of lead phase with the matrix accelerated corrosion. To improve the dezincification resistance of the Sn containing brass, As, Sb and P were added at two different levels (0.05% and 0.1%). Brass of composition 48.95Cu-45Zn-5Pb-1Sn-0.05As was more resistant indicating the synergistic effect of Sn and As. The effect of 0.05 and 0.1% of arsenic addition with various concentrations of zinc was also studied. The alloy of composition 57.90Cu-40Zn-2Pb-0.1As showed better corrosion resistance than the alloy containing 1% Sn and 0.05% As (48.95Cu-45Zn-5Pb-1Sn-0.05As). To understand the influence of Sn and As on the dezincification of commercial brass, linear polarization and cyclic voltammetry experiments were conducted for the alloys 60Cu-39Zn-1Pb, 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As. Linear polarization measurements indicated that the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As possessed higher resistance to corrosion than commercial brass. Inspection of cyclic voltammograms revealed that the peak current densities as well as the passive current density were lower for the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As than the alloy 60Cu-39Zn-1Pb. The surface layer on the alloys 60Cu-39Zn-1Pb, 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As after immersion of 72 h in 1% CuCl₂ solution were analyzed by X-ray diffraction and scanning electron microscopy. Higher enrichment of Sn and As at the interface of surface layer and metal was indicated for the alloys 55Cu-40Zn-3Pb-2Sn and 57.90Cu-40Zn-2Pb-0.1As, respectively.     

The effect of different exposure conditions on the biofilm/copper interface

The effects of the different exposure conditions on the electrochemical behavior of copper were evaluated in a growth medium containing Shewanella oneidensis MR-1. Impedance spectra were recorded at the corrosion potential (E_corr) in three different cells for one week of exposure followed by cyclic voltammetry. A second time constant was observed in the impedance spectra of copper that was partially immersed in the test cell, where the electrode was in contact with an air/liquid interface (cell B). These spectra resembled those usually observed for metals covered with a polymer coating. Complete immersion of copper in the electrolyte (no air/liquid interface) or deaeration of cell B resulted in one-time-constant spectra that are typical of those found for passive metals. Excellent corrosion protection was provided by MR-1 regardless of exposure condition. E_corr increased with time for the partially immersed Cu electrode exposed to the aerated solution in cell B, while it decreased for the other two exposure conditions. Cathodic polarization curves recorded after exposure for 7 days showed two reduction peaks for copper tested in cell B, while no reduction peaks were observed for the other cases. Similar results were obtained using cyclic voltammetry.     

Film formation and surface growth on tin electrodes in bicarbonate solutions: an impedance spectroscopy study

The electrochemical behaviour of potentiodynamically formed thin anodic films of polycrystalline tin in aqueous sodium bicarbonate solutions (pH ≈ 8.3) were studied using cyclic voltammetry and electrochemical impedance spectroscopy. Different equivalent circuits corresponding to various potential regions were employed to account for the electrochemical processes taking place under each condition.     

Behaviour of the alloy AA2017 in aqueous solutions of NaCl. Part I: Corrosion mechanisms

This paper reports a study carried out on the morphological characteristics the Al-Cu alloy AA2017-T3; its behaviour against corrosion in aqueous solutions of NaCl 0.59 M has been evaluated by immersion during 0-48 h. The techniques employed for this study are SEM and EDS. The results obtained have been verified by electrochemical assays based on monitoring the corrosion potential of the system in OCP, LP and EIS. The behaviour of the intermetallics present in the matrix of the alloy suggests that the design of an effective system of protection should involve the use of cathodic inhibitors.     

The corrosion behaviour of austenitic and duplex stainless steels in artificial saliva with the addition of fluoride

The evolution of the passive films on 2205 duplex stainless steel (2205 DSS) and AISI 316L stainless steel in artificial saliva, and with the addition of fluoride, was studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic measurements. The extent of the passive range increased for the 2205 DSS compared to the AISI 316L in both solutions. The formation of the passive film was studied by EIS at the open-circuit potential (OCP). The passive layers were studied at the OCP by X-ray photoelectron spectroscopy (XPS). The passive films on both materials predominantly contained Cr-oxides, whereas the Fe species were markedly depleted.     

Localized electrochemical investigations of Pd73Cu13.5 ceramic firing dental alloy in DIN-saliva

Corrosion resistance is a very important property of dental alloys, in addition to, e.g., strength, ductility and casting accuracy. The processing (casting and ceramic firing) of the with ceramic veneerable dental alloy Pd73Cu13.5 leads to a preferential accumulation of the less noble element copper in eutectic micro-structural constitutes at the surface and mainly at the grain boundaries. The occurrence of locally corrosion phenomena of copper, which induce toxic effects in vivo, and which lead furthermore to a roughening of grains and to the formation of pits and crevices was proven by spatially resolved electrochemical measurements using a capillary-based droplet cell.     

Kinetic peculiarities of anodic dissolution of silver and Ag–Au alloys under the conditions of oxide formation

The kinetics of anodic dissolution of silver and Ag–Au alloys (X_Au = 0.1–30 at.% Au) in aqueous alkaline solution under the conditions of the formation of silver oxides has been examined. The techniques of cyclic voltammetry, chronoammetry, and photopotential measurements have been used. It was established that the anodic formation and cathodic reduction of Ag₂O on silver and alloys are controlled by migration in the oxide layer. Ag₂O oxide is an n-type semiconductor with an excess of silver atoms. Oxide layers formed on monocrystalline Ag(1 1 1) and Ag(1 1 0) are more stoichiometric than the layer formed on polycrystalline Ag.     

Photocurrent and capacitance investigations into the nature of the passive films on austenitic stainless steels

Photocurrent and capacitance measurements of semiconductor passive films formed on metals and alloys can be used to study the electronic properties and reveal indirect information about structure and composition. The current work used these techniques to investigate the electronic properties of the passive films formed on three austenitic stainless steels, types 304L, 316L and 254SMO, in borate. Evidence was found for the existence of a large number of localised mid bandgap states, consistent with amorphous oxides. However, the flat-band potentials of the austenitic stainless steel passive films were found to be independent of both composition and measuring frequency. The most credible explanation for the bandgap values determined from photocurrent measurements is that the passive films are formed as dual layers, iron oxide outer layer and chromium oxide inner layer. This model does not need to evoke the potential dependent bandgaps used by previous authors.     

Tribological, electrochemical and tribo-electrochemical characterization of bare and nitrided Ti6Al4V in simulated body fluid solution

Tribological, electrochemical and tribo-electrochemical behaviour of bare and nitrided Ti6Al4V alloy was studied. Scanning Electron Microscopy (SEM), X-ray diffraction and microhardness profile were used to characterize the nitrided Ti6Al4V. The anticorrosive properties of nitrided Ti6Al4V in phosphate buffer saline solution (PBS), simulating the body environment, were evaluated by Electrochemical Impedance Spectroscopy (EIS). Nitriding increased the alloy resistance to corrosion and to dry wear. Resistance to tribocorrosion in PBS at the open circuit potential (OCP) for the nitrided alloy was also significantly increased compared to the bare alloy; nevertheless at an anodic potential this influence became less important.     

Corrosion protection of magnesium alloys by cerium, zirconium and niobium-based conversion coatings

A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na₂SO₄ electrolyte, and accelerated atmospheric corrosion tests (humid, SO₂ polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24 h in the Ce-Zr-Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce-Zr-Nb-treated samples, with or without an additional layer of epoxy-polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO₂, Ce₂O₃, ZrO₂, Nb₂O₅, MgO, and MgF₂ as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na₂SO₄. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys.     

Preparation and electrochemical characterization of amoxicillin-doped cellulose acetate films for AA2024-T3 aluminum alloy coatings

Cellulose acetate films doped with amoxicillin were deposited onto AA2024-T3 aluminum alloy and the corrosion protection in 0.05 M NaCl was evaluated by Electrochemical Impedance Spectroscopy (EIS) and the Scanning Vibrating Electrode Technique (SVET). The doping of the cellulose acetate film with amoxicillin resulted in a significant increase in the high frequency resistance and a decrease in the capacitance of the material. The protective effect could be observed under anodic polarization by way of a marked decrease in the anodic current. These results show the promising potential for the deposition of cellulose acetate films doped with amoxicillin onto AA2024-T3.     

Effect of sulphide on the corrosion behaviour of AISI 316L stainless steel and its constituent elements in simulated Kraft digester conditions

The electrochemical behaviour of AISI 316L steel and its constituent metals in simulated Kraft digester white liquor at 170 °C has been studied by registering slow scan rate voltammograms and impedance spectra at the corrosion potential. Interpretation of the results in terms of two approaches - the Mixed-Conduction Model for passive films and a two-step dissolution reaction - allowed for the estimation of corrosion currents and polarisation resistances as depending on the material and electrolyte medium. Tentative conclusions on the effect of sulphur-containing species in the white liquor on the corrosion mechanism of the studied materials are drawn.     

Influence of hydrolysis time on the structure and corrosion protective performance of (3-mercaptopropyl)triethoxysilane film on copper

Films of (3-mercaptopropyl)triethoxysilane with different hydrolysis time were formed on copper surface. To evaluate the influence of hydrolysis time on structures and corrosion resistance of these films, Fourier-transform infrared spectroscopy, polarization curves, cyclic voltammetry and electrochemical impedance spectroscopy tests were performed on covered and uncovered copper specimens. Results indicate that the optimum hydrolysis time is 48 h. The film obtained in this case shows the best corrosion resistance in 3.5% (w) NaCl solution.     

Kinetic peculiarities of anodic dissolution of copper and its gold alloys accompanied by the formation of insoluble Cu(I) products

The kinetics of anodic dissolution of Cu and Cu-Au alloys (0.1-30 at.% Au) in aqueous chloride-containing universal buffer mixture (pH 1.25-11.90) in the potential range of insoluble Cu(I) products formation has been examined using the technique of multicyclic voltammetry and chronoamperometry of stationary and rotating electrodes. After the formation of anodic film, mass transport controls the dissolution; the phase where the transport is localised depends on the nature of the film, pH of the solution and the alloy composition. The initial stage of CuCl formation on Cu and low-concentration Cu-Au alloys is controlled by 2D-nucleation.     

Inhibition of copper corrosion in sodium chloride solution by the self-assembled monolayer of sodium diethyldithiocarbamate

Sodium diethyldithiocarbamate (DDTC) self-assembled monolayer (SAM) on copper surface has been investigated by SERS and EDS and the results show that DDTC SAM is chemisorbed on copper surface by its S atoms with tilted orientation. Corrosion inhibition ability of DDTC SAM was measured in 3% NaCl solution using electrochemical methods. The impedance results indicate that the maximum inhibition efficiency of DDTC SAM can reach 99%. Quantum chemical calculations show that DDTC has relatively small ΔE between HOMO and LUMO and large negative charge in its two sulfur atoms, which facilitates the formation of a DDTC SAM on copper surface.     

De-alloying of 316 stainless steel in the presence of a mixture of metal-oxidizing bacteria

The corrosion behavior of 316 stainless steel was investigated in the presence of a mixture of metal-oxidizing bacteria isolated from marine environments. Ennoblement of stainless steel in the presence of these bacteria can lead to localized corrosion that confirmed by ESEM images. The corrosion rate of the metals also increased. EDS results showed that these bacteria caused the segregation of Si elements in the metal structure and promoted the depletion of Cr and Fe contents in the corrosion products. Thus, the de-alloying of stainless steel can occur in the presence of metal-oxidizing bacteria.