Electrochemical Behavior Assessment of As-Cast Mg-Y-RE-Zr Alloy in Phosphate Buffer Solutions (X Na<Subscript>3</Subscript>PO<Subscript>4</Subscript> + Y Na<Subscript>2</Subscript>HPO<Subscript>4</Subscript>) Using Electrochemical Impedance Spectroscopy and Mott–Schottky Techniques

In the present study, electrochemical behavior of as-cast Mg-Y-RE-Zr alloy (RE: rare-earth alloying elements) was investigated using electrochemical tests in phosphate buffer solutions (X Na₃PO₄?+?Y Na₂HPO₄). X-ray diffraction techniques and Scanning electron microscopy equipped with energy dispersive x-ray spectroscopy were used to investigate the microstructure and phases of the experimental alloy. Different electrochemical tests such as potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS) and Mott–Schottky (M–S) analysis were carried out in order to study the electrochemical behavior of the experimental alloy in phosphate buffer solutions. The PDP curves and EIS measurements indicated that the passive behavior of the as-cast Mg-Y-RE-Zr alloy in phosphate buffer solutions was weakened by an increase in the pH, which is related to formation of an imperfect and less protective passive layer on the alloy surface. The presence of the insoluble zirconium particles along with high number of intermetallic phases of RE elements mainly Mg₂₄Y₅ in the magnesium matrix can deteriorate the corrosion performance of the alloy by disrupting the protective passive layer that is formed at pH values over 11. These insoluble zirconium particles embedded in the matrix can detrimentally influence the passivation. The M–S analysis revealed that the formed passive layers on Mg-Y-RE-Zr alloy behaved as an n-type semiconductor. An increase in donor concentration accompanying solutions of higher alkalinity is thought to result in the formation of a less resistive passive layer.     

Study of the correlation between corrosion resistance and semi‐conducting properties of the passive film of AISI 316L stainless steel in physiological solution

In this work the corrosion resistance of AISI 316L biomedical stainless steel was assessed through electrochemical impedance spectroscopy (EIS) measurements in Hanks' solution at 37 °C. Specimens were immersed in the electrolyte during 21 days. Semi‐conducting properties of the passive film naturally formed on the surface of the metallic material during the test were evaluated through the Mott–Schottky approach. The aim was to investigate the correlation between corrosion resistance and semi‐conducting properties in the physiological solution. The corrosion resistance was found to decrease with the immersion time. The density of defects in the passive film increased accordingly as indicated by the Mott–Schottky plots. The passive film presented a semi‐conducting behavior with a duplex character. Above the flat band potential the behavior was typical of an n‐type semiconductor whilst below such value it was typical of a p‐type semiconductor. The results from EIS measurements and Mott–Schottky were in good agreement, suggesting that the corrosion resistance of biomedical stainless steels may be associated with the semi‐conducting properties of the passive films formed during immersion in physiological medium.     

Effect of hydrostatic pressure on the nature of passive film of pure nickel

The effect of hydrostatic pressure on the nature of passive film of nickel in 3.5% NaCl solution was investigated by means of polarization curves, electrochemical impedance spectroscopy (EIS), and Mott–Schottky measurement. The experimental results revealed that hydrostatic pressure had two opposite effects on passive film of nickel. On one hand, hydrostatic pressure improved the corrosion resistance of passive film of nickel such as the decreased acceptor density. On the other hand, the passive film became unstable and showed a higher diffusivity of acceptor density with the increasing of hydrostatic pressure, which deteriorated the corrosion resistance of passive film of nickel. The deterioration effect had greater influence on the passive film than the improvement effect, which led to the decreasing corrosion resistance of passive film with the increasing of hydrostatic pressure.     

The comparison of the corrosion resistance of advanced ferromagnetic stainless steels by Mott–Schottky approach

Ferromagnetic stainless steels (SSs) have been investigated as potential candidates for dental prosthesis applications in replacement of magnetic attachments made of noble and expensive alloys. In order to be used as biomaterials, their corrosion resistance has to be appropriate. The corrosion resistance of passive materials is related to the characteristics of the passive film formed and their properties might be investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and Mott–Schottky approach. The corrosion resistance and the capacitance of the passive films formed on PM2000, DIN 1.4575, and 17‐4 PH advanced SSs during 2 days of immersion in a phosphate buffered saline solution (PBS), at 25 °C and pH 7.0 were studied by electrochemical techniques. A commercial alloy Dyna EFM was also analyzed for comparison reasons. The results showed that films on tested materials behave as both n‐type and p‐type semiconductors and the PM2000 presented the highest corrosion resistance among all of them.     

Electrochemical behavior assessment of tantalum in aqueous KOH solutions

The current work aims at studying passive and electrochemical behavior of tantalum in KOH solutions of varied concentrations ranging from 0.01 to 1 M using various electrochemical methods. Electrochemical impedance spectroscopy (EIS) results show that the passive film formed on tantalum loses its protectiveness upon addition of KOH concentration. Indeed, the passivity undergoes a drastic change moving toward higher KOH concentrations. The semiconductive behavior of the passive films formed on tantalum is also investigated by employing Mott–Schottky analysis in conjunction with point defect model (PDM). Although semiconducting behavior remains the same as n-type, KOH concentration greatly affects the levels of donor densities. Moreover, Mott–Schottky analysis showed that flat band potential is quite sensitive to KOH concentration.     

Effect of passive film on the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62

Ti alloys exhibit high potential because of the compact passive film. However, the effect of passive film on galvanic corrosion is not clear. On the one hand, the great potential difference can accelerate the galvanic corrosion of other metals with low potential. On the other hand, the passive film can hinder the electrochemical reactions, inhibiting the galvanic corrosion. To clarify this question, the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62 was studied using zero‐resistance ammeter, scanning vibrating electrode technique, scanning electron microscopy, and potentiodynamic polarization measurements. The chemical composition and electrical properties of the passive film on Ti60 were detected using X‐ray photoelectron spectroscopy and Mott‐Schottky plots. The results indicate the galvanic corrosion of Ti60‐H62 coupling is ignorable in spite of the great galvanic potential difference between them. It can be attributed to the low electron donor density of passive film, which inhibits the electron charge transfer process at the film/solution interface, causing the slow cathodic reaction rate on Ti60.     

Correlation between the corrosion resistance and the semiconducting properties of the oxide film formed on AZ91D alloy after solution treatment

The corrosion resistance and semiconducting properties of the oxide film formed on the AZ91D alloy were evaluated. The alloy was tested in the as-cast condition and after a solution annealing treatment. Electrochemical impedance spectroscopy measurements and potentiodynamic polarization curves were obtained in a H₃BO₃ (0.05 M) + Na₂B₄O₇⋅10H₂O (0.075 M) solution with pH = 9.2 at room temperature. The semiconducting properties of the oxide film were evaluated using Mott–Schottky plots. The corrosion resistance of the AZ91D was reduced after the solution treatment while the semiconducting properties of the passive films were little affected.     

Composition and processing effects on the electrochemical characteristics of biomedical titanium alloys

The electrochemical behaviour of the Ti–13Nb–13Zr and Ti–6Al–4V ELI alloys with martensitic microstructures was investigated by polarization and electrochemical impedance spectroscopy (EIS) in Ringer’s solution. The impedance spectra were interpreted by a two time-constants equivalent circuit. Both investigated alloys showed high corrosion resistance, but the thin and uniform passive film on the Ti–6Al–4V ELI alloy surface was more protective. The inner barrier and outer porous layer were highly resistant and capacitive. However, thicker and more porous passive film on the Ti–13Nb–13Zr alloy surface may be beneficial for osteointegration. The suitable thermomechanical processing improved the corrosion resistance of Ti–13Nb–13Zr alloy.     

Passive and Semiconducting Properties Assessment of Commercially Pure Tantalum in Hank’s Physiological Solution

In this study, various electrochemical measurements were used to evaluate the passive and semiconducting properties of commercially pure tantalum (Ta) in Hank’s physiological solution at 310 K (37 °C). Potentiodynamic polarization and electrochemical impedance spectroscopy results show that the passivation of pure Ta immersed in Hank’s physiological solution improves over time. Mott–Schottky (M–S) tests indicate that the passive layers of pure Ta in Hank’s physiological solution behave as n-type semiconductors and longer immersion times do not lead to any inversion of semiconducting behavior. Additionally, M–S tests show that as the immersion time increases, the donor density of the passive layer decreases. Finally, scanning electron microscope micrographs and energy-dispersive spectroscopy results reveal that Ta is less likely to experience significant pitting or buildup of undesirable corrosion products after longer immersion times in this physiological solution.     

Effect of temperature on copper corrosion in high-level nuclear waste environment

The effect of temperature on the corrosion behavior of copper in simulated high-level nuclear waste environment was systematically studied. Electrochemical methods, including electrochemical impendence spectra, Mott–Schottky technology, cyclic polarization, and potentiostatic polarization, were employed to characterize the corrosion behavior of copper at different temperatures. Stereoscopic microscopy and scanning electron microscopy were used to examine the surface morphology, and X-ray photoelectron spectroscopy analysis was used to identify the composition of the passive film. The experimental results show that corrosion resistance of the passive film does not blindly decrease with the increase of temperature but increases at 60 °C owing to a compact outer layer; there is a potential for pitting corrosion, which decreases as the temperature increases. The main product of copper in an anaerobic aqueous sulfide solution is Cu₂S but the content of CuS increases at higher temperatures. The whole passivation range shows p-type semiconductor characteristics and the magnitude of the acceptor density is 10²³ cm^?3, which increases with increasing temperature.     

Optimization of Cr/Mo molar ratio in FeCoCrMoCBY alloys for high corrosion resistance

The corrosion behavior of bulk metallic glasses (BMGs) (Fe₄₁Co₇Cr₁₅Mo₁₄C₁₅B₆Y₂)_100–xCr_x (x=0, 4, 8, 12, molar fraction, %) was investigated in 1 mol/L HCl aqueous solution with electrochemical tests. The electrochemical measurements demonstrate that the passive current density of Fe-based amorphous alloy is reduced by about one order of magnitude, and meanwhile, the stability of passive film can be guaranteed by the Cr/Mo molar ratio. The Mott–Schottky (M–S) curves show that the passive film is the densest when the molar ratio of Cr/Mo is between 1.37 and 1.69. X-ray photoelectron spectroscopy (XPS) analysis was performed to clarify chemical states of elements in the passive films. The results show that the corrosion resistance of the alloy is related to the molar ratio of Cr/Mo. The stability of passive film is determined by the synergistic action of Cr and Mo elements. The main component of the passive film is Cr³⁺ oxide. When the potential is greater than 0.5 V (vs SCE), Mo⁶⁺ ions play an important role in keeping the stability of the passive film. The appropriate molar ratio of Cr/Mo can reduce the dissolution rate of the passive film.     

Effect of chloride concentration on passive film properties on copper

The semiconducting properties of passive films formed on copper, in anaerobic alkaline sodium chloride solution, were studied using Mott–Schottky analysis and electrochemical impedance spectroscopy, based on the point defect model. Results showed that the corrosion resistance increased with increasing potential, which was attributed to a well crystallised, refined grain structure, and a thicker passive film at higher potential. P-type semiconducting characteristics were obtained with or without chloride. The density of copper vacancies was approximately 10²⁰?cm^?3, and increased with the increasing chloride concentration, which was attributed to faster film-formation in a higher chloride environment. The diffusion coefficient of the defects, a key dynamic parameter for passive film breakdown, was in the range of 10^?16–10^?15?cm²?s^?1, and increased with increasing chloride concentration, thus leading to a greater probability of pitting.     

The stability of passive film growth on copper in anaerobic sulphide solutions

The corrosion behaviour of oxygen-free copper in anoxic 0.1?M NaCl?+?2?×?10^?4?M Na₂S·9H₂O solution (pH?=?9.0) was investigated under potentiostatic polarisation for different times. Electrochemical methods, including electrochemical impedance spectroscopy, Mott–Schottky analysis, localised electrochemical impedance spectroscopy (LEIS) and scanning electron microscopy observations, were conducted. The results indicated that the corrosion resistance of oxygen-free copper decreased with increasing applied potential, whereas it increased with increasing polarisation time. The passive film growth kinetics obeyed a logarithmic law (lnD?=?alnt?+?b, where D is the layer thickness, b is a constant taken as the initial growth rate, t is the polarisation time and a is the time exponent). Subsequent to the formation of a compact and coherent passive film, the thicker the film was, the more difficult for ion to migrate, which further resulted in a slower film growth rate. The passive film displayed p-type semiconductor behaviour and the acceptor density (cation vacancy) was approximately 10²² to 10²³?cm^?3. The LEIS results showed that the passive film achieved relative stability after 24?h of immersion under natural conditions, which was longer than the duration of potentiostatic polarisation (4?h at ?0.6?V_SCE).     

Comparison of corrosion behaviour and passive film properties of 316L austenitic stainless steel in CO2 and N2 environments

This study investigated the susceptibility to pitting corrosion of 316L in CO₂ and N₂ environments at temperatures from 30 to 80°C in 3?wt-% NaCl at pH 4. Results from cyclic polarisation technique confirm greater pitting susceptibility of 316L in the CO₂ environment. Electronic properties and composition of the passive film were identified by electrochemical impedance spectroscopy, Mott–Schottky, and X-ray photoelectron spectroscopy. Increasing temperature negatively affects the passive film stability, and its influences are amplified in the presence of CO₂ as compared to N₂. In the CO₂ environment, the passive film becomes porous with the increasing temperature leading to higher defects (donor/acceptor densities).     

The effect of surface modification on the corrosion protection ability of the passive films of sensitized UNS S31803 duplex stainless steel

ABSTRACT

The influence of sensitisation heat treatment, surface roughness and repetitive cyclic voltammetry (RCV) procedure (that was used to create passive films on the surface of sensitised samples) on the corrosion behaviour of UNS S31803 duplex stainless steel was evaluated using sodium hydroxide etching, double-loop electrochemical potentiodynamic reactivation (DLEPR), potentiodynamic polarisation, Mott–Schottky analysis, X-ray diffraction and optical microscopy techniques. The results showed that prolonged sensitisation time leads to the formation of defective passive films on the surface. In addition, as the substrate surface roughness decreases, the defect concentration in the resulting passive film decreases. Moreover, thick passive films that were created at a high number of RCV cycles contain fewer defects than the thin ones. Finally, the specimens with smooth surfaces, thick passive films and low degree of sensitisation exhibit high corrosion resistance due to their intact passive layers formed on their surfaces.     

A comparative study on the electrochemical behaviour of amorphous and nanocrystalline cobalt–tungsten electrodeposited coatings

Amorphous and nanocrystalline cobalt–tungsten coatings were electrodeposited from a citrate-ammonia bath on copper substrates. Both coatings showed a nodular surface morphology, but a microcrack network was observed in the amorphous coating. The cyclic voltammograms of both deposits revealed anodic and cathodic low-current plateaus around the open circuit potential, exhibiting a passive behaviour. Mott–Schottky analysis showed that the passive films exhibit n-type semiconductivity behaviour and that formed on the amorphous coating showed higher crystal defects. Electrochemical impedance spectroscopy revealed that the amorphous coating has higher corrosion resistance than the nanocrystalline one at both open circuit and anodic potentials. This was attributed to the higher pore resistance of passive film formed at the open circuit potential and more chemical stability of the amorphous coating which reduces its dissolution at the anodic potential. The plugging of the microcrack network in the amorphous coating by corrosion products eliminated the negative effect of microcracks.     

Aging of passive film on UNS N08031 in a Green-Death solution

Aging of passive film formed on UNS N08031 was investigated as a function of passivation time in Green-Death solution at 40°C. The specimen surface was in a stable passive state in the solution. The passive current density increased with an increase in the passivation potential. Electrochemical impedance spectroscopy and Mott–Schottky (M–S) analyses revealed that a more defective n-type semiconductive passive film formed as the potential increased while the film became stable as the defects in the film decreased at potential lower than 1.0?V_SSE. The increase of the applied potential and the polarisation time are likely reasons for the change in passive film stability.     

变形量对 690 合金在核电一回路水环境中电化学腐蚀行为的影响

目的研究变形量对690合金电化学行为的影响。方法采用动电位极化、电化学阻抗和高温高压浸泡实验,结合扫描电子显微镜(SEM)、X射线光谱仪(EDX)和X射线光电子能谱(XPS),研究不同变形量的690合金传热管在核电模拟液中的腐蚀行为。结果在常温常压下,50%变形量试样的自腐蚀电位比25%变形量试样正140 m V,维钝电流密度显著降低,阻抗模值高出约10倍。高温高压下浸泡后,XPS分析显示,50%变形量试样表面腐蚀产物膜中的Cr2O3含量远高于25%变形量试样,其富Cr内层致密,氧化层更厚。结论 50%变形量的690合金表面形成的钝化膜及腐蚀产物膜对基体的保护作用更强。     

Influence of pH on the electrochemical behaviour of a duplex stainless steel in highly concentrated LiBr solutions

The objective is to study the influence of pH on the corrosion and passive behaviour of duplex stainless steels (DSS) using potentiodynamic measurements, potentiostatic tests and electrochemical impedance spectroscopy (EIS).DSS are spontaneously passive in heavy brine LiBr solutions. Under potentiostatic conditions at applied anodic potentials within the passive domain an equivalent circuit with two time constants is the most suitable model to describe the corrosion mechanism in the interface electrolyte/passive film/metal. pH modifies the electrochemical properties of the passivity of the alloy in a 992 g/L LiBr solution reducing its resistance with the applied potential.     

Mott–Schottky analysis of passive films on Cu containing Fe–20Cr–xCu (x = 0, 4) alloys

Effect of copper on the defect density of Fe–20Cr–xCu (x?=?0, 4) stainless steel alloys was investigated in deaerated pH 8·5 borate buffer solution at room temperature using Mott–Schottky analysis. Mott–Schottky analysis revealed that the addition of copper increased the acceptor density (N_A, V_Cr^?3), i.e. decreased the Cr⁺³ content of the passive film. Also the donor densities, shallow donor (N_D1, V_O⁺²) and deep donor (N_D2, V_Cr⁺⁶), of the passive films formed were increased. XPS analysis confirmed the decrease in Cr content and enrichment of copper in the passive film of Cu containing alloys, which ultimately dictated their lower corrosion resistance, i.e. decreased film protectiveness and stability.