Semiconductor properties and protective role of passive films of iron base alloys

Semiconductor properties of passive films formed on the Fe-18Cr alloy in a borate buffer solution (pH = 8.4) and 0.1 M H₂SO₄ solution were examined using a photoelectrochemical spectroscopy and an electrochemical impedance spectroscopy. Photo current reveals two photo action spectra that derived from outer hydroxide and inner oxide layers. A typical n-type semiconductor behaviour is observed by both photo current and impedance for the passive films formed in the borate buffer solution. On the other hand, a negative photo current generated, the absolute value of which decreased as applied potential increased in the sulfuric acid solution. This indicates that the passive film behaves as a p-type semiconductor. However, Mott-Schottky plot revealed the typical n-type semiconductor property. It is concluded that the passive film on the Fe-18Cr alloy formed in the borate buffer solution is composed of both n-type outer hydroxide and inner oxide layers. On the other hand, the passive film of the Fe-18Cr alloy in the sulphuric acid consists of p-type oxide and n-type hydroxide layers. The behaviour of passive film growth and corrosion was discussed in terms of the electronic structure in the passive film.     

Effects of hydrogen on the anodic behavior of Alloy 690 at 60 °C

Polarization and electrochemical impedance spectroscopy (EIS) measurements, Mott-Schottky (M-S) analysis and X-ray photoelectron spectroscopy (XPS) were used to investigate the effects of hydrogen on the anodic behavior of a one-dimensionally (1D) 25% cold worked (CW) Alloy 690 thermal treated (TT) in a boric acid and sodium sulphate solution at 60 °C. The pre-hydrogen-charged specimen exhibited a higher anodic current than that of the uncharged specimen below the transpassive potential. The charged hydrogen can be trapped in the metal. Electrochemical impedance spectroscopy (EIS) showed that the resistance capacitance loop of the hydrogen-charged specimen was significantly smaller than that of the uncharged specimen. Mott-Schottky analyses indicated that the passive film formed on Alloy 690 at −0.2 V_SCE was an n-type semiconductor, with a p-n hetero-junction at 0.2 V_SCE. Charged hydrogen increased the carrier density and the thickness of the passive film both at −0.2 V_SCE and 0.2 V_SCE. The Ni/Cr ratio in the surface film decreased after hydrogen charging, indicating that charged hydrogen could enhance the oxide film growth by increasing the OH⁻ (O²⁻) concentrations through its reaction with vacancies.     

Transgranular SCC mechanism of thermally treated alloy 600 in alkaline water containing lead

This work aims to understand a SCC failure mode of thermally treated steam generator tubing materials in high temperature water containing lead. The effect of lead contents on the anodic polarization curves of alloy 600 (UNS NO6600) and alloy 690 (UNS NO6900) has been studied in a solution of pH 10 at 200 °C and 315 °C. Lead increased the active peaks of alloy 600 and alloy 690 in mild alkaline water at high temperatures. A reduction of PbO to a metallic lead in alloy 690 is easier than that of alloy 600. When lead was added into the solution, a relative ratio of Cr from among the main metallic elements (Cr, Fe, and Ni) of alloy 600 and alloy 690 decreased in the outer corrosion film. Alloy 690 TT showed a transgranular stress corrosion cracking (TGSCC) in a 10 M NaOH solution with 5000 ppm of lead. Intergranular stress corrosion racking (IGSCC) was observed in the 100 ppm lead condition, and some TGSCC was detected on the fracture surface of the alloy 600 MA cracked in the 10,000 ppm lead solution. IGSCC seemed to be retarded by a crack blunting around the grain boundaries, and the TG cracking mode of the thermally treated alloy 600 and 690 seemed to be related to a crack blunting at the grain boundary carbide and a film dissolution by lead in an alkaline solution.     

Effect of the reinforced boron carbide particulate content of AA6061 alloy on formation of the passive film in seawater

The effect of boron carbide (B₄C) reinforcement on the corrosion of AA6061 alloy was studied by investigating passive films formed in seawater. The higher passive current and its potential-dependence for these composites indicated formation of porous passive film. Electrochemical impedance spectroscopy (EIS) graph suggests that the alloy surface is partly or totally active. The formed passive film is n-type semiconductor junction in nature. The difference between corrosion potential (E_corr) and potential at zero charge (PZC) suggests that the chloride ions responsible for film breakdown exist within the passive film. A suitable mechanism is proposed for the passive film breakdown.     

Electrochemical and XPS studies and the potential scan rate dependent pitting corrosion behavior of Zircaloy-2 in 5% NaCl solution

Electrochemical studies of Zircaloy-2 in 5% NaCl solution were carried out using polarization and electrochemical impedance spectroscopy (EIS). Scan rate dependent pitting behavior of Zircaloy-2 was observed when polarization experiments were carried out at different scan rates (5 mV/min, 50 mV/min and 500 mV/min). Polarization resistance, double layer capacitance, and the thickness of passive film were calculated from the EIS study. The slope of the Bode plot in the capacitive region showed non-ideal behaviour, suggesting formation of pits. A distribution of chloride concentration was seen at the surface of the electrode when the test solution was sampled from different parts of the sample surface and analyzed for chloride. Inclusion of chloride ions in the passive film was observed from the XPS study and the chloride concentration increases with the higher anodic polarization. The outermost layer of the passive film was rich in hydroxide and oxy-hydroxide. A bi-layer passive film structure on the alloy surface is proposed.     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.     

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.     

Electrochemical behaviour of the Mg alloy AZ91D in borate solutions

Corrosion and passivation behaviour of Mg-based alloy AZ91D was investigated in aqueous sodium borate solutions (pH 9.2) in relation to some test parameters, using electrochemical techniques. Increasing borate concentration (0.01–0.10 M) or temperature up to 298 K leads to increase the corrosion rate of the alloy. However, at temperatures higher than 298 K borate anions have stronger propensity to passivate the alloy, thereby decreases its corrosion rate. For a fixed borate concentration increasing Cl⁻ addition is correlated with a more negative corrosion potential and a higher corrosion rate, as well as increase the vulnerability of the anodic passive film for breakdown. The influence of oxidizing potentials over the range −1.5 V to 2.75 V (SCE) on the performance of the alloy in the most aggressive borate solution (0.10 M) reveals that higher potentials, induces better passivation due to formation of a rather thick and more protective n-type semiconducting film. A modified Randles circuit including Warburg impedance to account for the diffusion of reactants or products through the surface film was adopted to analyse the EIS data, that gave impedance parameters in good agreement with the results of open circuit potential and dc polarization measurements.     

Hydrogen effects on the passive film formation and pitting susceptibility of nitrogen containing type 316L stainless steels

The effects of hydrogen on the passivity and pitting susceptibility of type 316L stainless steels have been investigated with alloys containing different nitrogen contents (0.015, 0.198 and 0.556 wt.% N). The study revealed that electrochemically pre-charged hydrogen significantly reduced the pitting resistance of alloys conatining 0.015 and 0.198 wt.% nitrogen contents. In alloy with highest nitrogen content (0.556 wt.% N), an increase in the passive film current density with hydrogen was observed without affecting breakdown potential. Auger electron spectroscopy (AES) analysis of the passive film indicated the presence of nitrogen in the passive film. On other hand, for hydrogen charged samples, nitrogen was found to be significantly less in the passive film. In Electrochemical impedance spectroscopy (EIS) measurement, the decrease in semi-circle radius of Nyquist plot, and the polarization resistance, R_P associated with the resistance of the passive film was observed with hydrogen, indicating that hydrogen decreased the stability of the passive film. The present investigation indicated that precharged hydrogen deteriorated the passive film stability and pitting corrosion resistance in these alloys, and the increase in nitrogen content of the alloy offsets the deleterious effect of precharged hydrogen.     

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 and corrosion inhibition of Cu-20%Fe alloy in sodium chloride solution

The electrochemical behavior of copper (Cu), iron (Fe) and Cu-20%Fe alloy was investigated in 1.0 M sodium chloride solution of pH 2. The effect of thiourea (TU) addition on the corrosion rate of the Cu-20%Fe electrode was also studied. Open-circuit potential measurements (OCP), polarization and electrochemical impedance spectroscopy (EIS) were used. The results showed that the corrosion rates of the three electrodes follow the sequence: Cu < Cu-20%Fe < Fe. Potentiostatic polarization of the Cu-20%Fe electrode in the range −0.70 V to −0.45 V (SCE), showed that iron dissolves selectively from the Cu-20%Fe electrode surface and the rate of the selective dissolution reaction depends on the applied potential. At anodic potential of −0.45 V, thiourea molecules adsorb at the alloy surface according to the Langmuir adsorption isotherm. Increasing thiourea concentration (up to 5 mM), decreases the selective dissolution reaction and the inhibition efficiency η reach 91%. At [TU] > 5 mM, the dissolution rate of the Cu-20%Fe electrode increases due to formation of soluble thiourea complexes. At cathodic (−0.6 V), the inhibition efficiency of thiourea decreases markedly owing to a decrease of the rate of the selective dissolution reaction and/or desorption of thiourea molecules. The results indicated that thiourea acts mainly as inhibitor of the selective dissolution reaction of the Cu-20%Fe electrode in chloride solution.     

Corrosion assessment of nitric acid grade austenitic stainless steels

The corrosion resistance of three indigenous nitric acid grade (NAG) type 304L stainless steel (SS), designated as 304L1, 304L2 and 304L3 and two commercial NAG SS designated as Uranus-16 similar to 304L composition and Uranus-65 similar to type 310L SS were carried out in nitric acid media. Electrochemical measurements and surface film analysis were performed to evaluate the corrosion resistance and passive film property in 6 N and 11.5 N HNO₃ media. The results in 6 N HNO₃ show that the indigenous NAG 304L SS and Uranus-65 alloy exhibited similar and higher corrosion resistance with lower passive current density compared to Uranus-16 alloy. In higher concentration of 11.5 N HNO₃, transpassive potential of all the NAG SS shows a similar range, except for Uranus-16 alloy. Optical micrographs of all the NAG SS revealed changes in microstructure after polarization in 6 N and 11.5 N HNO₃ with corrosion attacks at the grain boundaries. Frequency response of the AC impedance of all the NAG SS showed a single semicircle arc. Higher polarization resistance (R_P) and lower capacitance value (CPE-T) revealing higher film stability for indigenous NAG type 304L SS and Uranus-65 alloy. Uranus-16 alloy exhibited the lowest R_P value in both the nitric acid concentration. Auger electron spectroscopy (AES) study in 6 N and 11.5 N HNO₃ revealed that the passive films were mainly composed of Cr₂O₃ and Fe₂O₃ for all the alloys. The corrosion resistance of different NAG SS to HNO₃ corrosion and its relation to compositional variations of the NAG alloys are discussed in this paper.     

Electrochemical oxidation of binary copper-nickel alloys in cryolite melts

Anodic oxidation of copper, nickel and two copper-nickel alloys was studied in cryolite melts at 1000 °C. In an oxide-free melt, anodic dissolution of each material was observed, and the dissolution potential increases with the content of copper. SEM characterization of a Cu55-Ni45 alloy showed that nickel is selectively dissolved according to a de-alloying process. In an alumina-containing melt, a partial passivation occurs at the copper-containing electrodes, at potentials below the oxygen evolution potential. A passive film forms on the copper electrode, while on the nickel electrode no dense oxide layer develops. Copper-nickel alloys were found to form a mixed oxide layer. At higher potentials, the formation of oxygen bubbles on the electrodes results in a degradation of the passive films and a strong corrosion.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Tryptamine as a corrosion inhibitor of mild steel in hydrochloric acid solution

The inhibitor effect of tryptamine on the corrosion of mild steel in 0.5 M hydrochloric acid at 30 °C was investigated using linear polarization, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The inhibition efficiency increases with an increase in concentration of tryptamine. At 500 ppm tryptamine the inhibition efficiency calculated by these techniques is around 97%. Cathodic and anodic polarization curves of mild steel in the presence of different concentrations of tryptamine at 30 °C reveal that it is a mixed type inhibitor. Tryptamine follows Langmuir adsorption with adsorption free energy of −35.07 kJ mol⁻¹.     

Corrosion of metals and alloys in molten glasses. Part 2: nickel and cobalt high chromium superalloys behaviour and protection

Electrochemical methods have been used for the characterisation of high chromium alloys corrosion in molten glasses (cobalt and nickel base alloys in a borosilicate glass at 1050 °C, with rotating working electrodes). All the tested alloys are active but passivable materials. The active state is characterised by a rapid dissolution of the constitutive elements of the alloy in the glass melt. The passive state can be obtained by an air oxidation of the alloys (called preoxidation) or with a temporary anodic polarisation of the alloy. The obtained passive state is due to the presence of a thin protective chromia scale.     

Electrochemical pitting corrosion behaviour of α-brass in LiBr containing solutions

The potentiodynamic anodic polarization curve of α-brass (70% Cu-30% Zn) in 1 M LiBr solution showed an initial active region of the alloy dissolution followed by two well defined anodic current peaks then a narrow passivation region before the pitting potential (E_pit) is reached. The initial active anodic region exhibited Tafel slope with 90 mV dec⁻¹ attributed to the formation of CuBr₂⁻ complexes. The anodic current peaks were attributed to the formation of CuBr and Cu²⁺ ions, respectively. The change of pH values of LiBr solution did not affect the anodic polarization curves of α-brass. Increasing the solution temperature from 30 to 90 °C changed the corrosion type from pitting to general one. The addition of 10⁻² M benzotriazole (BTAH) to 1 M LiBr solution is completely inhibited the pitting corrosion at 30 °C while it did not inhibit the pitting at 90 °C. The inhibition effect was attributed to the adsorption of BTAH molecules on the alloy surface, which obeys Langmuir isotherm. The presence or absence of pitting corrosion was confirmed by using SEM.     

Effect of heat treatment on anodic activation of aluminium by trace element indium

The presence of trace elements in Group IIIA-VA is known to activate aluminium anodically in chloride environment. The purpose of this paper is to investigate the surface segregation of trace element In by heat treatment and resulting surface activation. Model binary AlIn alloys, containing 20 and 1000 ppm by weight of In, were characterized after heat treatment at various temperatures by use of glow discharge optical emission spectroscopy, electron microscopy and electrochemical polarization. Heat treatment for 1 h at 300 °C gave significant segregation of discrete In particles (thermal segregation), which activated the surface. Indium in solid solution with aluminium, obtained by 1 h heat treatment at 600 °C, also activated by surface segregation of In on alloy containing 1000 ppm In, resulting from the selective dissolution of the aluminium component during anodic oxidation (anodic segregation). The effect of anodic segregation was reduced by decreasing indium concentration in solid solution; it had negligible effect at the 20 ppm level. The segregated particles were thought to form a liquid phase alloy with aluminium during anodic polarization, which in turn, together with the chloride in the solution destabilized the oxide.     

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.     

Effects of bovine serum albumin on the corrosion behaviour of AISI 316L, Co–28Cr–6Mo, and Ti–6Al–4V alloys in phosphate buffered saline solutions

The corrosion behaviour of AISI 316L, wrought Co–28Cr–6Mo and Ti–6Al–4V was studied in aerated solutions of phosphate buffered saline (PBS) at various concentrations of bovine serum albumin (BSA) at 37 °C. Open circuit potential, potentiodynamic polarization, linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS) experiments along with X-ray photoelectron spectroscopy (XPS) on Co–28Cr–6Mo oxide layer were conducted to study the interaction of BSA and passive layers and to measure the corrosion rates. Ti–6Al–4V alloy had the lowest corrosion rate and the highest breakdown potential. It was shown that BSA has enhanced the alloy passive film stability at higher concentrations.