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.     

Vorwort

Investigation into the pitting corrosion of passive austenitic CrNi steels in neutral chloride solutions Stainless steels of the 18/8 CrNi-Type suffer pitting corrosion by halogen ions. Potentiokinetic, galvanostatic and potentiostatic tests as well as the ferro-ferricyanide-tests showed that pitting susceptibility increases with Cl^? content, temperature and oxygen content of the electrolyte, with decreasing homogeneity and purity of the material. Cold-working is without significant influence on the pitting potential. Mn up to 11,2% increases pitting potential by 50 mV, Ni up to 25% increases the potential by 200 mV, Cr up to 30 and Mo up to 4,6% increase the potential by max. 900 mV in 3% NaCl of p_H 7,5 at 22° C. The four methods employed gave the same pitting potentials. Before arriving at the potential of stationary pitting all steels showed a region where formation and repassivation of single pits occur. Cathodic protection to suppress pitting causes H₂-absorption. The amount of absorbed H₂ increases as the potential becomes more negative. Hydrogen embrittlement was not observed. The absorbed H₂ impairs pitting resistance. The study of Cl^?-adsorption as a pitting releasing process by help of the potentiostatic method, working with a reference source of triangular alternating voltage gave no indication of a preferential Cl^?-adsorption or an Cl^?-adsorption-potential near the pitting potential.     

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.     

Effect of ascorbic acid on the pitting resistance of 316L stainless steel in synthetic tap water

This study examined the effect of L-ascorbic acid (A.A) concentration on the pitting corrosion properties of 316L stainless steel (316L STS) of heat exchanger in synthetic tap water containing 400 ppm of Cl- ion. The pitting corrosion of 316L STS can be effectively inhibited by the 10^-4 M of A.A concentration. In this condition, the adsorption of A.A reinforced the passive film of steel by blocking the Cl^- ions at the active site. However, the passive film was deteriorated and severe pitting corrosion occurred above the 10^-4 M of A.A concentration. Above the 10^-4 M of A.A concentration, A.A generates soluble chelate rather than absorbs on the steel surface and it causes passive film deterioration and severe pitting corrosion. The critical ratio, which is a critical ratio of surface coverage of aggressive to inhibitive ion necessary to initiate localized corrosion, calculated 2.93 up to the 10^-4 M. It has approximately 2.93:1 ratio of the coverage of local Cl^- ions to A.A. Above the critical ratio, the pitting corrosion will occur with degradation of the passive film. On the other hands, above the 10^-4 M A.A concentration caused a negative effect because the heat energy for adsorption is increased.     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

Use of Electrochemical Noise (EN) Technique to Study the Effect of sulfate and Chloride Ions on Passivation and Pitting Corrosion Behavior of 316 Stainless Steel

In the present paper, studies were conducted on AISI Type 316 stainless steel (SS) in deaerated solutions of sodium sulfate as well as sodium chloride to establish the effect of sulfate and chloride ions on the electrochemical corrosion behavior of the material. The experiments were conducted in deaerated solutions of 0.5 M sodium sulfate as well as 0.5 M sodium chloride using electrochemical noise (EN) technique at open circuit potential (OCP) to collect the correlated current and potential signals. Visual records of the current and potential, analysis of data to arrive at the statistical parameters, spectral density estimation using the maximum entropy method (MEM) showed that sulfate ions were incorporated in the passive film to strengthen the same. However, the adsorption of chloride ions resulted in pitting corrosion thereby adversely affecting noise resistance (R _N). Distinct current and potential signals were observed for metastable pitting, stable pitting and passive film build-up. Distinct changes in the values of the statistical parameters like R _N and the spectral noise resistance at zero frequency (R°_SN) revealed adsorption and incorporation of sulfate and chloride ions on the passive film/solution interface.     

Effect of halide anions and temperature on initiation of pitting in Cr–Mn–N and Cr–Ni steels

Abstract

The pitting corrosion of Cr₁₈Mn₁₂N and Cr₁₈Ni₉ steels in halide solutions (F^?, Cl^?, Br^? and I^?) has been investigated. The study involved cyclic potentiodynamic polarisation tests with subsequent examination of the specimens by both optical and scanning electron microscopy. Values of the critical concentrations of halide ions, [X^?]_cr, beyond which pitting occurs, as well as breakdown potentials for pitting in chloride solution, have been established. In addition, the effect of the temperature over the range of 5–80°C on the critical chloride ion concentration [Cl^?]_cr has been investigated and it has been found that temperature has a negligible effect beyond 40°C.     

Passivity and passivity breakdown of zinc anode in alkaline medium

The electrochemical behaviour of zinc in NaOH solutions has been investigated by using potentiodynamic technique and complemented by X-ray analysis. The E/i curves exhibit active, passive and transpassive regions prior to oxygen evolution. The active region displays two anodic peaks. The passivity is due to the Formation of a compact Zn(OH)₂ film on the anode surface. The transpassive region is assigned to the electroformation of ZnO₂. The reverse sweep shows an activation anodic peak and one catholic peak prior to hydrogen evolution. The influence of increasing additives of NaCl, NaBr and Nal on the anodic behaviour of zinc in NaOH solutions has been studied. The halides stimulate the active dissolution of zinc and tend to break down the passive film, leading to pitting corrosion. The aggressiveness of the halide anions towards the stability of the passive film decreases in the order: I^? > Br^? > Cl^?. The susceptibility of zinc anode to pitting corrosion enhances with increasing the halide ion concentration but decreases with increasing both the alkali concentration and the sweep rate.     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

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 the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

On the Initiation process of pitting corrosion on austenitic stainless steel in chloride solutions

A literature survey has lead to the conclusion that a theory which postulates an increased anodic reactivity on a local site in the passive film is very probable. Experiments have been set up to confirm these suggestions. By means of the electron-microanalyser, it is shown that CI^?ions are preferentially adsorbed at singular points at the metal surface before the stage that pits can be observed. It has also been demonstrated that pH changes occur at local areas during the induction period. These two observations indicate that corrosion already occurs during the induction period. Induction time measurements have shown that the induction time is not very reproducible. The quantity of transferred charge per initiated pit before the breakdown of the film is redly a better re- producible figure. From this, the quantity of Cl^?ions necessary to create an active site is calculated. Experiments with the static potential band method reveal that pits can initiate at any potential higher than the pitting potential. Growing pits can repassivate at any potential. A model for the initiation is given. The pitting corrosion process starts with adsorption of chloride ion at singular points, mainly local stress points. The local anodic current density will be higher and in this way favourable conditions (low pH, high Cl^?concentration) are created for the formation of a local site in the metal surface free of a passivating film The creation of those conditions is an autocatalytic process. The time required to form those favourable electrochemical conditions corresponds with the observed induction period. The migration of activating ions and the occurring pH change at a singular point must exceed a critical rate, otherwise passive film stabilizing effects will dominate. This model for the pitting corrosion supports the acid theory and links this theory with the peptization theory.     

Formation and Breakdown of Surface Films on Copper in Sodium Hydrogen Carbonate and Sodium Chloride Solutions: I. Effects of anion concentrations

Abstract

The formation, breakdown and composition of surface films on copper in air-saturated solutions at 25°c has been studied by potentiokinetic polarisation. In 0·01 M NaHCO₃, the protective oxide layer breaks down at a critical potential togive pitting corrosion. Increasing the concentration of hydrogen carbonate ions decreases the protectiveness of the oxide film towards general corrosion, but makes the filmmore resistant to breakdown. In 0·01 M NaCl, the oxide film formed is initiallyfairly protective and exhibits a breakdown potential on rapid polarisation. As the chloride concentration is increased, the oxide film becomes less protective and the breakdown potential becomes displaced to more negative potentials and is more poorly defined.     

Zur Lochkorrosionsneigung von austenitischen CrNiMo-Stählen in konzentrierten Ammoniumrhodanidlösungen

Pitting corrosion of austenitic CrNiMo-steels in concentrated ammoniumrhodanide solutions Quasipotentiostatic and potentiokinetic polarisation measurements at various 18 Cr-10 Ni steels with molybdenum contents up to 4,3% were performed in 25 and 45% ammoniumrhodanide solutions. It was found that pitting corrosion is caused by incomplete passivation in the potential range of –300 to +250 m V _H. At these potentials the formation of stable passive layers is hindered by the formation and local oxidative dissolution of sulfidic layers. Above +250 m V _H rhodanide ions act in these weak acidic ammoniumrhodanide solutions as agents which destroy passive layers, comparable with chloride ions. The limiting potentials for stable pitting corrosion, obtained from potentiostatic experiments, are shifted from –300 to –150 m V _H with increasing molybdenum content of the steel. The least tendency of pitting corrosion was found for that steel with the highest molybdenum content.     

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.     

Environmental factors affecting the corrosion behaviour of reinforcing steel. V. Role of chloride and sulphate ions in the corrosion of reinforcing steel in saturated Ca(OH)2 solutions

The corrosion behaviour of reinforcing steel in saturated naturally aerated Ca(OH)₂ solutions in absence and presence of different concentrations of NaCl, NH₄Cl, Na₂SO₄ and (NH₄)₂SO₄ is followed by measuring of the open circuit potential complemented with SEM and EDS investigation. These salts cause breakdown of passivity and initiation of pitting corrosion. The rates of oxide film thickening by OH⁻ ions and oxide film destruction by the aggressive ions follow a direct logarithm law and depend on the concentration and type of aggressive salts anions and cations. The values of the activation energies for oxide film thickening are calculated and discussed.     

The influence of different aggressive anions on the electrochemical behaviour of aluminium in sodium nitrate aqueous solutions

The effects of different experimental parameters influencing the determination of critical pitting and protection potentials of aluminium and its alloys have been studied by potentiostatic and potentiodynamic methods. The resistance of aluminium against corrosion in aqueous media can be attributed to a rapidly formed surface oxide film. The addition of the aggressive anions like: chloride, thiocyanide, hydroxyl, sulphide, formate, and acetate (Cl⁻, SCN⁻, OH⁻, S²⁻, HCOO⁻ and CH₃‐ COO⁻) lead to extensive localized attack in all of the cases. The breakdown of the passive film takes into account the migration of aggressive anions through the film. Breakdown occurs when aggressive anions reach the metal‐film interface. E_π is the critical pitting potential, E_p ist the protection potential and the pitting can be formed only in the E_π–E_p polarization range as it was proved in many experiments [1–3]. The most likely action mechanism of aggressive anions is not a complete dissolution of the film, nor penetration of aggressive anions through solid oxide as suggested for nickel and iron [4]. It is more likely to be somewhere in between the two i.e. action of aggressive anions is that of complexing aluminium ions and pulling in water to hydrate the layer in a way similar to that occurring at cathodic hydrogen evolution, where such dramatic increase of hydrogen evolution rate is observed after a certain cathodic potential is reached. Localized corrosion can be prevented by the action of adsorptive inhibitors which prevent the adsorption of the aggressive anions or by the formation of a more resistant oxide film on the metal surface. The corrosion mechanism is not modified by the addition of ammonium rhodanide but only slowed down.     

Corrosion behavior of hafnium in anhydrous isopropanol and acetonitrile solutions containing bromide ions

The corrosion behaviors of hafnium in Et₄NBr isopropanol and acetonitrile(ACN) solutions were investigated using electrochemical measurements, ICP-AES and SEM techniques. Results revealed that the open circuit potential gets more positive due to the increased passivity of the surface oxide film with increasing immersion time until it reaches a steady state value. The potentiodynamic anodic polarization curves did not exhibit an active dissolution region near corrosion potential due to the presence of an oxide film on the electrode surface, which was followed by pitting corrosion. SEM images confirmed the existence of pits on the electrode surface. Cyclic voltammetry and galvanostatic measurements allowed the pitting potential (?_pit) and the repassivation potential (?_p) to be determined. ?_pit increased with increasing potential scanning rate but decreased with increasing temperature, Br^? concentration and ACN concentration. The impedance spectra showed that the resistances of the solution and charge transfer decreased with the increase of ACN concentration.     

Effects of coolant chemistry on corrosion of 3003 aluminum alloy in automotive cooling system

In this work, effects of coolant chemistry, including concentrations of chloride ions and ethylene glycol and addition of various ions, on corrosion of 3003 Al alloy were investigated by electrochemical impedance spectroscopy measurements and scanning electron microscopy characterization. In chloride‐free, ethylene glycol–water solution, a layer of Al‐alcohol film is proposed to form on the electrode surface. With the increase of ethylene glycol concentration, more Al‐alcohol film is formed, resulting in the increase in film resistance and charge‐transfer resistance. In the presence of Cl^? ions, they would be involved in the film formation, decreasing the stability of the film. In 50% ethylene glycol–water solution, the threshold value of Cl^? concentration for pitting initiation is within the range of 100 ppm to 0.01 M. When the ethylene glycol concentration increases to 70%, the threshold Cl^? concentration for pitting is from 0.01 to 0.1 M. In 100% ethylene glycol, there is no pitting of 3003 Al alloy even at 0.1 M of Cl^?. Even a trace amount of impurity cation could affect significantly the corrosion behavior of 3003 Al alloy in ethylene glycol–water solution. Addition of Zn²⁺ is capable of increasing the corrosion resistance of Al alloy electrode, while Cu²⁺ ions containing in the solution would enhance corrosion, especially pitting corrosion, of Al alloy. The effect of Mg²⁺ on Al alloy corrosion is only slight.     

The effect of fluoride on corrosion of reinforcing steel in alkaline solutions

The influence of fluoride content of alkaline solutions on the corrosion of reinforcements has been studied, by means of electrochemical techniques, in saturated solutions of Ca(OH)₂ and same pH NaOH solutions with additions of NaF, thus simulating the liquid phase of concrete. Fluoride can be present as a minor component in low-energy cements. The joint presence of chlorides and fluorides in the corrosion process of steel has also been analysed. It has been established that fluoride anions are able to produce pitting of reinforced steel in alkaline media of high pH. In Ca(OH)₂ saturated solution, the precipitation of CaF₂ lowers F⁻ concentration below the minimum that promotes a pitting corrosion process; if there is not enough Ca(OH)₂ to precipitate all F⁻ ions, the presence of fluoride in these media causes an increase in passive film dissolution and corrosion rates.     

The effect of molybdate anion on the ion-selectivity of hydrous ferric oxide films in chloride solutions

The ion-selective property of hydrous ferric oxide precipitate films has been investigated by measuring membrane potentials which arise across precipitate membranes of hydrous ferric oxide with and without adsorbed MoO₄^2? ions and of ferric molybdate in solutions of NaCl, KCl, MgCl₂, CaCl₂, BaCl₂, AlCl₃, and FeCl₃. The hydrous ferric oxide membrane was only permeable to Cl^? ions in chloride solutions, whereas the membrane with adsorbed MoO₄^2? ions was permeable to cations in NaCl and KCl solutions, and to both Cl^? and cations in the presence of multivalent cations. The ferric molybdate membrane was permeable to Cl^? and cations in NaCl and KCl solutions, and only to Cl^? ions in the presence of multivalent cations. It is suggested that in chloride solutions, the corrosion of iron covered with a precipitate film of hydrous ferric oxide is accelerated by enrichment of Cl^? ions under the film, which may decrease the local pH and introduce a positive diffusion potential in the film. The adsorption of MoO₄^2? ions on the oxide changes the ion-selectivity of the precipitate film from the anion-selective to the cation-selective in solutions of NaCl and KCl. This cation-selectivity of the film may inhibit the corrosion of iron, because of H⁺ ions diffusing out of the film. The inhibitive effect of MoO₄^2? ions would be reduced in the presence of multivalent cations.     

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.