Breakdown of cadmium passivity in alkaline solution

The electrochemical behaviour of a Cd anode was investigated in 0.05–2 M NaOH solutions by the potentiodynamic technique. The polarization curves exhibit active to passive transition prior to oxygen evolution. The threshold potential of the active dissolution is very close to the reversible potential of the system Cd/Cd(OH)₂. X-Ray diffraction and XPS measurements reveal that the passive layer is composed of both Cd(OH)₂ and CdO. The influence of increasing amounts of Cl^?, Br^? or I^? ions on the anodic behaviour of Cd in NaOH solution has been investigated. The halides stimulate the anodic dissolution in the active region and tend to break-down the passive layer in the passive region, leading to pitting attack. The pitting potential shifts to more negative values with increasing halide ion concentration but to the reverse direction with increasing alkali concentration.     

Electrochemical characterization of Ni47.7Ti37.8Nb14.5 shape memory alloy in artificial saliva

Electrochemical corrosion behaviour of the studied Ni_47.7Ti_37.8Nb_14.5 (NiTiNb) shape memory alloy was investigated for dental applications. An equiatomic NiTi alloy was used in some tests as reference material. Electrochemical techniques such as anodic potentiodynamic polarization, open circuit potential and electrochemical impedance spectroscopy (EIS) were employed. Experiments were carried out using artificial saliva. Very low passive current densities were obtained from the anodic polarization curve, indicating a typical passive behaviour for NiTiNb alloy. Over the surface of the NiTiNb alloy uniform corrosion appears, while in case of the NiTi alloy surface pitting corrosion is developed. The role that Nb plays as an alloying element is by increasing the resistance of NiTi alloy to localized corrosion. The EIS results exhibited high impedance values (order of 10⁶ Ω cm²) obtained from medium to low frequencies which are indicative of the formation of a highly stable passive film on NiTiNb alloy in the artificial saliva.     

Electrochemical behaviour of nickel anode in H2SO4 solutions and the effect of halide ions

The electrochemical behaviour of pure nickel in H₂SO₄ solutions has been potentiodynamically investigated. The effects of the following factors on the anodic dissolution and passivation of the metal are discussed: potential scan rate, successive cyclic voltammetry and progressive additions of Cl^?, Br^? and I^? ions. Increasing the potential scan rate increases the critical current density i_cc, denoting that the active dissolution of nickel in H₂SO₄ is a diffusion controlled process. Cyclic voltammetry shows that the reverse excursion does not restore the anode to its active state. On successive cycling, the height of i_cc decreases; this could be attributed to the decrease in the reduction efficiency of passivating oxide film during the cathodic half cycles. The presence of the halogen ions below a certain concentration specific to each anion inhibits the anodic dissolution both in the active and passive states. The inhibitive action of these additives decreases in the order I^?, Br^?, Cl^?. Beyond the specific concentrations, the halogen ions accelerate the anodic dissolution and shift the active passive transition to more positive values. The aggressiveness of these anions decreases in the sequence Cl^?, Br^?, I^?, Further increase in the halogen ion concentrations can lead to breakdown of the passive film and initiate pitting. The susceptibility of nickel to pitting attack enhances with increasing H₂SO₄ concentration.     

Galvanic reactions during localized corrosion on stainless steel

During localized (crevice and pitting) corrosion, a local cell is established between an anode within a crevice or pit and a cathode on the surrounding passive surface. Data are presented to show that concentrated acidic chloride solutions, simulating corrosion product hydrolysis within a crevice or pit, produce potentials which are active (negative) to the normal surface passive potential. This behaviour explains the previously observed active drift of corrosion potential after initiation of crevice or pitting attack in dilute chloride solutions. The active state in concentrated chloride solutions was quite noble (positive) compared to the active state in more dilute solutions. Thus, there is no need to invoke ohmic resistance effects to account for the active state within a crevice or pit.Experiments were devised in which the local anode within a crevice was physically separated from the nearby passive-surface cathode. When the two were coupled together electrically, the cathode surfaces were polarized nearly to the unpolarized local anode potential, with only a few millivolts anodic polarization at the anode within the crevice. The rate of localized corrosion appears from the data to be limited by the rate of dissolved-oxygen reduction on the cathode surfaces. Thus, localized corrosion in dilute chloride solutions will be increased by (a) raising the temperature, (b) adding an oxidizer such as Fe³⁺ ions, or (c) substituting external anodic polarization for dissolved oxidizers.The overall potential, E_corr acquired by a specimen undergoing pitting or crevice corrosion is demonstrated to be near the protection potential, E_p below which pitting corrosion cannot propagate. Any potential active to E_corr and E_p results in cathodic polarization and suppression of the anode reaction in a crevice or pit. Since both E_corr and E_p vary with the extent of previous localized attack, E_p is not a unique property of the alloy as has been sometimes suggested and is of limited value in classifying alloy resistance to localized corrosion.     

The corrosion and passivation of iron in the presence of halide ions in aqueous solution

The anodic dissolution behaviour of iron in halide solutions has been studied with both stationary and rotating electrodes. With stationary electrodes active dissolution kinetics are observed, whereas with rotation a pronounced active/passive transition occurs. A distinct pitting potential (E_c) was noted in each solution, the value of E_c increasing in the order I>Br>Cl>F. Halide ion concentration and electrode velocity did not have any effect on the value of E_c, indicating that the kinetics of pit initiation are independent of mass-transfer effects.During anodic dissolution at potentials more regative than E_c, an inhibiting effect was noted, the degree of which depended on the atomic radius of the anion. A model is suggested which involves three electrode reactions of iron with the electrolyte: (1) Active dissolution involving the well-known FeOH⁺ (ads) rate-determining step. (2) Above the passivation potential, increased reaction of the metal surface with hydroxyl ions causes passivation due to the enhanced access of OH^? to the surface and accelerated removal of solvated protons caused by rotation and a thinning of the diffusion layer. (3) At the pitting potential, direct reaction of the metal with electro-adsorbed halide ions produces pit initiation and growth by a complex ion formation reaction not possible at lower electrode potentials.     

The corrosion and passivation of iron in the presence of halide ions in aqueous solution

The anodic dissolution behaviour of iron in halide solutions has been studied with both stationary and rotating electrodes. With stationary electrodes active dissolution kinetics are observed, whereas with rotation a pronounced active/passive transition occurs. A distinct pitting potential (E_c) was noted in each solution, the value of E_c increasing in the order I>Br>Cl>F. Halide ion concentration and electrode velocity did not have any effect on the value of E_c, indicating that the kinetics of pit initiation are independent of mass-transfer effects.During anodic dissolution at potentials more negative than E_c, an inhibiting effect was noted, the degree of which depended on the atomic radius of the anion. A model is suggested which involves three electrode reactions of iron with the electrolyte: (1) Active dissolution involving the well-known FeOH⁺ (ads) rate-determining step. (2) Above the passivation potential, increased reaction of the metal surface with hydroxyl ions causes passivation due to the enhanced access of OH^? to the surface and accelerated removal of solvated protons caused by rotation and a thinning of the diffusion layer. (3) At the pitting potential, direct reaction of the metal with electro-adsorbed halide ions produces pit initiation and growth by a complex ion formation reaction not possible at lower electrode potentials.     

Breakdown of passive film on nickel in borate solutions containing halide anions

The effect of Cl⁻, Br⁻ and I⁻ anions as aggressive agents on the anodic behaviour of nickel electrode in deaerated Na₂B₄O₇ solutions have been investigated by galvanostatic polarization technique. Lower concentrations of the halide anions have no effect on the mechanism of nickel passivation. An increase in the halide anions concentration causes oscillation of the potential in the oxygen evolution region. This could be attributed to the destruction of the passivity by halide anions and repassivation of the film by anodic current and/or OH⁻ anions. Higher aggressive anion concentrations cause breakdown of the passive film and initiated pitting corrosion. As the temperature increases, the breakdown potential is shifted towards the more negative direction. On the other hand, as the pH of the solution increases, the breakdown potential is shifted toward more positive direction, indicating increased protection of the passive film. The activation energy, , of the oxide film formation in the presence of Cl⁻ anions was calculated and was found to be 21 kJ/mol.     

Role of ClO4 in breakdown of tin passivity in NaOH solutions

The anodic behaviour of a tin electrode in NaOH solutions containing different concentrations of NaClO₄ was studied by employing potentiodynamic, potential transient under constant current density methods and complemented with scanning electron microscopy (SEM). In perchlorate-free NaOH solutions, the E/i response exhibits active/passive transition. The active region involves two anodic peaks corresponding to the formation of Sn(II) and Sn(IV) species respectively. The permanent passive layer is duplex and consists of SnO and SnO₂. Additions of NaClO₄ to the alkali solution, accelerates the active dissolution of tin and tends to breakdown the duplex passive layer at a certain breakdown potential. SEM examination confirms the occurrence of film breakdown. The breakdown potential decreases with an increase in ClO₄⁻ concentration, but increases with increasing both OH⁻ concentration and scan rate. The potential-time transients display that the incubation time for pit initiation decreases with increasing both ClO₄⁻ concentration and anodic current density.     

Corrosion of stainless steel grades in H2O/KOH 50% at 120 °C: AISI304 austenitic and 2205 duplex

We report on the corrosion of austenitic (AISI304) and duplex (2205) stainless steels in H₂O/KOH 50% at 120 °C. The research is based on a combination of electrochemical, structural and compositional analyses, aimed at assessing the surface modifications resulting from anodic attack and their impact on corrosion resistance. Linear sweep voltammetry and electrochemical impedance spectrometry measurements were carried out in an air‐tight high‐temperature cell. In‐plane and cross‐sectional SEM micrography, X‐ray diffractometry and EDX profiling were used to characterise samples attacked under electrochemically controlled conditions. Electrochemical results have shown that AISI304 exhibits a complex passivating behaviour, while the anodic electrokinetics of the duplex is characterised by mixed kinetic control. AISI304 was found to fail by intergranular corrosion and to be covered: in passive conditions by acicular compounds and in transpassive conditions by a compact layer of corrosion products. Duplex samples, instead, exhibit an uniform form of corrosion morphology and bear a compact layer of corrosion products both in passive and in transpassive conditions.     

Corrosion behaviour of zirconium electrode in sodium azide electrolyte as compared to the alkali halide solutions

The kinetics of open circuit growth of an oxide film on zirconium electrode in NaN₃ solution of various concentrations was investigated using potential and capacitance measurements. The protective oxide film formed in azide solutions was found to thicken with time in two steps, the rate of oxide growth was found to decrease as the azide concentration increased. The corrosion behaviour of the electrode was characterized by ac impedance measurements to obtain detailed information about the effect of azide ion concentration on the electrical properties of the Zr electrode surface. The impedance response for the metal‐metal oxide‐electrolyte system was modeled with a transfer function. The potentiodynamic oxidation of Zr was also studied as a function of the azide ion concentration. The polarization curves showed the peak‐shaped active‐to‐passive transition and the corrosion rate was found to increase with increase of azide ion concentration. The activation energy of corrosion was calculated according to Arrhenius plot and found to be 14.5 kJ mol^?1. The polarization results in azide solutions were compared to those obtained in solutions of different halide ions, namely, F^?, Cl^?, Br^? and I^? ions. The rate of corrosion was found to decrease in the order Br^? > Cl^? > F^?, I^? > azide. Opposite to the behaviour in azide solutions, the halide ions do not show the active‐passive transition.     

Oxydation anodique du zinc en milieu faiblement basique

The anodic behaviour of zinc electrode has been studied in weakly alkaline solution (borate buffer). In this pH range the solubility of Zn(OH)₂ and the corrosion of zinc are both reduced to a minimum when solution contains specific anions, active anodic dissolution of the zinc electrode is observed with intermediate Zn²⁺ formation. On the anode appears a gelatinous Zn(OH)₂ precipitate which is not adherent nor passivating.     

Initiation and Inhibition of Pitting Corrosion in Alkali Solutions under potentiostatic polarization conditions

The variation of the critical pitting potential of a zincalloy was studied in aerated NaOH solutions as a function of the concentration of the aggressive ions, Cl^?, Br^? and I^?. Curves with segmented nature were obtained when E_pitting was plotted versus logarithm of the halogen ion concentrations. Initiation of pitting corrosion was discussed on the basis of formation of complex halo-compounds with the oxides/hydroxides that constitute the passive surface film. Addition of chromate, phosphate and carbonate ions to the halogen-containing solutions causes the shift of the critical pitting potential in the noble direction, accounting for increased resistance to pitting attack. Nitrite-ion additions contribute with the halogen ions in the destruction of the passive film. Sufficient concentrations of the carbonate ions cause complete inhibition of pitting corrosion.     

Complete protection of a passive film on iron from breakdown in a borate buffer containing 0.1 M of Cl by coverage with an ultrathin film of two-dimensional polymer

An ultrathin film of two-dimensional polymer was prepared on a passivated iron electrode by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. This film prevented passive film breakdown examined by potentiodynamic anodic polarization of the coated electrode in the borate buffer solution containing 0.1 M of Cl⁻. Neither current spikes nor the pitting potential was observed in the passive and transpassive regions of polarization curve. The anodic current density was decreased in these regions markedly, implying hindrance to permeation of Cl⁻ and water through the film. Structure of the film was clarified by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement with a drop of water. Electron-probe microanalysis of the passivated surface coated with the film after anodic polarization scanning up to the transpassive region revealed that the polymer film prevents pit initiation by an attack on the passive film with Cl⁻.     

The effect of chromate in the corrosion behavior of duplex stainless steel in LiBr solutions

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and chromate presence in the solutions on the corrosion behavior of DSS was studied. It was found, by cyclic polarization curves analyses, that there was different pitting susceptibility of passive films formed on DSS depending on the chromate/bromide ratio: pitting corrosion susceptibility highly decreased from a chromate/bromide ratio lower than 0.01.The comparative investigations carried out in LiBr and LiBr + 0.032Li₂CrO₄ verify the assumption that the halide ions facilitate inhibitor adsorption. The addition of halides increased inhibition efficiency to a considerable extent. Passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

Direct modification of a passivated iron electrode with alkyltriethoxysilanes for preventing passive film breakdown in a borate buffer containing 0.1 M of chloride ion

A passive film on an iron electrode was modified with alkyltriethoxysilanes directly. In order to examine the protective ability of the modified passive film against breakdown, the pitting potential, E_pit was measured by anodic polarization of the modified electrode in a borate buffer solution (pH 8.49) containing 0.1 M of Cl⁻. The value of E_pit for the modified electrode shifted in the positive direction from that of the unmodified electrode, indicating prevention of passive film breakdown. The modified passive film was not broken down in the passive and transpassive regions of polarization curve in some cases. However, many current spikes appeared in the all curves of the modified electrodes. The modified surface of passivated electrode was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement. There were defects and clusters of associated water within the modified film and hence, Cl⁻ could permeate through the defects, leading to appearance of current spikes and occurrence of breakdown.     

Electrochemical behavior of nickel in HNO<Subscript>3</Subscript> and the effect of chloride ions

The electrochemical behavior of nickel in HNO₃ solutions of varying concentrations was examined using the cyclic voltammetry and potentiodynamic anodic polarization techniques. The anodic branch of the cyclic voltammogram is characterized by one anodic dissolution peak and a passivation region before oxygen evolution. The cathodic branch shows only one cathodic reduction peak corresponding to the reduction of HNO₃. Analysis of the anodic polarization data shows features of both reversible and irreversible reactions pointing to the complexity of the system. CT⁻ ions enhance the active dissolution of nickel in HNO₃ due to the adsorption on the bare metal surface and cause destruction of the passive film and initiation of pitting corrosion.     

Anodic behaviour and pitting corrosion of plain carbon steel in NaOH solutions containing Cl- ions

The anodic behaviour of hot-rolled and hardened carbon steel was investigated potentiodynamically in NaOH solutions with and without NaCl as a pitting corrodent. The pitting corrosion potential of the steel electrodes shifts in the negative direction with increasing concentration of the Cl^- ions, following sigmoidal curves. Increasing the tempering temperature of the hardened steel from 125 to 600 °C enhances the susceptibility to pitting corrosion owing to sequential structure changes. Addition of soluble starch shifts the pitting corrosion potential in the noble direction denoting inhibition of the pitting attack.     

Effect of halide ions on passivation and pitting Corrosion of copper in alkaline solutions

The passivity of copper in NaOH and borate buffer solutions containing chloride, bromide and fluoride ions was studied by using cyclic voltammetry and potentiostatic current transient measurements. At scan rates ≥ 20 mVs^?1, the addition of halide ions does not nearly affect the cyclic voltammograms in the absence of pitting. But they differ considerably in presence of pitting. The pitting potential was found to depend on the solution pH and decreased linearly with increase of logarithm of halide ion concentration. The current transients in the passivity as well as in the pitting potential regions were analyzed. Before the pitting, i-time curves were rather similar to those obtained in the plain solutions. At times > 20 seconds, the current varies linearly with the reciprocal of the square root of time indicating diffusional characteristics of the metal corrosion through the passive layer. In presence of pitting, the pitting current versus time relations fit the Engell-Stolica equation.     

Electrochemical behavior of Ni3Al-based intermetallic alloys in NaOH

The corrosion behavior of Ni₃Al-based intermetallic alloys in a 0.5 M NaOH solution was studied at 25 °C. The open circuit potential, cathodic and anodic potentiodynamic polarization, Tafel plots and linear polarization resistance measurements were used to characterize the corrosion behavior. For the Ni₃Al(B, Zr) alloy, potentiodynamic polarization curves showed a wide passive region that can be found between about ?0.220 V_SCE and 0.520 V_SCE. On the other hand, a narrow passive region, in the range of potentials from about ?0.180 V_SCE to 0.180 V_SCE, was observed for the Ni₃Al(B, Zr, Cr, Mo) alloy. Chromium, as an alloying element in the Ni₃Al(B, Zr, Cr, Mo) alloy, contributes to transpassive dissolution of the passive film at much lower anodic potentials and remarkably reduces the passivation region. The experiments indicated also that damaged passive films on alloys repairs itself and pits do not initiate. The surface of both alloys and passive films possess extremely high corrosion resistance in a studied solution. However, Tafel and linear polarization tests revealed that freshly exposed surfaces of the Ni₃Al(B, Zr) alloy exhibited better corrosion resistances than the Ni₃Al(B, Zr, Cr, Mo) alloy. Both methods, used for the determination of corrosion rates gave very similar results. The calculated corrosion rates are about 2.8 ·10^?3 and 6.0·10^?3 mm year^?1 for the Ni₃Al(B, Zr) alloy and B, respectively.     

Anodic behaviour of tin in maleic acid solution and the effect of some inorganic inhibitors

The anodic behaviour of a tin electrode in maleic acid solutions was investigated by potentiodynamic and chronopotentiometric methods. Measurements were conducted under different experimental conditions. The results demonstrated that the polarization curves exhibit active/passive transition. In active regions, tin dissolves as Sn²⁺ which is subsequently oxidized to Sn⁴⁺ and the dissolution process is controlled partly by diffusion of the solution species. The passivity is due to the presence of thin film of SnO₂ on the anode surface formed by dehydration of precipitated Sn(OH)₄. The active dissolution of tin increases with increasing acid concentration, temperature and scan rate. The potential transients showed that the passivation time decreases with increasing applied current density. The effect of adding increasing concentrations of CrO₄²⁻, MoO₄²⁻ and NO₂⁻ ions on the anodic behaviour of tin in maleic acid was studied. These ions inhibit the active dissolution of tin and promote the attainment of passivity. The extent of these changes depends upon the type and concentration of the inhibitor.