Influence of microstructure and alloying elements on corrosion behavior of Ti-13Nb-13Zr alloy

This work reports the effect of heat treatment on the corrosion behavior of Ti-13Nb-13Zr alloy in Ringer’s solution. The microstructural evolution of various phases after beta solution treatment (βST) and alpha + beta solution treatment (α+β ST), is studied using optical microscope, electron probe microanalysis and XRD techniques. Corrosion behavior of the solution treated samples is studied in Ringer’s solution using open circuit potential-time measurements and cyclic polarization. Corrosion studies reveal that, the heat-treated samples with depletion of Nb to very high levels in alpha phase exhibit inferior corrosion behavior. Amongst all the heat-treated samples investigated, the water quenched α+β ST specimen exhibit superior corrosion resistance due to the even distribution of the alloying elements in the three phases, namely α,α″ and β.     

Identifying the role of nanoscale heterogeneities in pitting behaviour of Al-based metallic glass

To clarify the correlation of nanoscale heterogeneity with corrosion in Al-based metallic glasses, three model alloys with a single nanoscale α-Al, Al₃Ni or Al₁₁Ce₃ phase embedded in amorphous Al-Ni-Ce alloy matrix were obtained directly by melt quenching. The results indicated that the high pitting corrosion resistance of AM alloys was not deteriorated by nanocrystalline α-Al precipitation; whereas the pitting potential was slightly decreased and considerably reduced relative to their amorphous state due to the precipitation of nanocrystalline Al₃Ni or Al₁₁Ce₃ respectively. Such a pitting sensitivity of different types of heterogeneities attributes to the nano-scale pit initiation events.     

Chemical composition and electronic structure of passive films formed on Alloy 600 in acidic solution

The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer conferring improved protection.     

Understanding corrosion via corrosion product characterization: I. Case study of the role of Mg alloying in Zn-Mg coating on steel

In the present work the corrosion inhibitive role of Mg in Zn-Mg coatings is considered for different stages of corrosion. Corrosion product characterization was carried out using XRD, IRRAS, MEB-FEG-EDS on technical Zn-Mg coatings after various exposure times in a standardized cyclic corrosion test. The results are compared with artificial corrosion products obtained by chemical and electrochemical synthesis. The importance of the ageing and the role of the atmospheric CO₂ on the nature and morphology of the corrosion products are discussed. The corrosion resistance of Zn-Mg alloy is correlated with the stabilization of simonkolleite against its transformation into smithsonite, hydrozincite, and zincite during ageing cycles in presence of CO₂. The stabilization appears to be due to the preferential formation of magnesium carbonates. Thermodynamic modeling and titrometric analysis demonstrate that Mg²⁺ enhances simonkolleite during dry-wet cycling by (1) removing carbonate from the environment and thereby limiting of the transformation of simonkolleite into zincite, smithsonite, and hydrozincite and by (2) buffering the pH of the electrolyte around 10.2 due to the precipitation of Mg(OH)₂ preventing the dissolution of zinc based corrosion products into soluble hydroxide complexes.     

Oxide networks, graph theory, and the passivity of Ni–Cr–Mo ternary alloys

The passivity of Ni–Cr–Mo ternary alloys is considered in terms of a continuous network of –Cr–O–Cr– bridges in the oxide film (which also contains Ni²⁺ and Mo⁴⁺ ions), or in terms of a continuous network of –Ni–O–Ni– bridges in the oxide film (which also contains Cr³⁺ and Mo⁴⁺ ions). The structure of the oxide is represented by a mathematical graph, and graph theory is used to calculate the connectivity of the oxide. This approach shows that a continuous network of –Cr–O–Cr– bridges occurs when the cation fraction of Cr³⁺ ions in the oxide is 0.35 or greater. A continuous network of –Ni–O–Ni– bridges occurs when the cation fraction of Ni²⁺ ions in the oxide is 0.55 or greater. Experimental results support the –Cr–O–Cr– model.     

Effect of nickel alloying on crevice corrosion resistance of stainless steels

The crevice corrosion behaviour of stainless steels containing 25 mass% Cr, 3 mass% Mo and various amounts of Ni was investigated in natural seawater. The results showed that ferritic steels containing nickel were more resistant to corrosion than both ferritic steels without nickel and austenitic steels. The superiority of the Ni bearing ferritic steel over the other steels was in close agreement with the depassivation pH of those steels in acidic chloride solutions. The results showed that the addition of Ni to ferritic steel was effective in decreasing the depassivation pH and the dissolution rate in acidic chloride solutions at crevices.     

Enrichment of alloying elements in anodized magnesium alloys

The possibility of enrichment of alloying elements in magnesium alloys as a consequence of growth of an anodic film has been investigated for sputtering-deposited Mg-0.4 at.% W and Mg-1.0 at.% W alloys. The alloys were anodized at 10 mA cm⁻² to various voltages, up to 150 V, in 3 M ammonium hydroxide/0.05 M ammonium phosphate electrolyte at 293 K. The alloys revealed enrichments of tungsten to at least 1.7×10¹⁵ and 2.9×10¹⁵ W atoms cm⁻² for the Mg-0.4 at.% W and Mg-1.0 at.% W alloys respectively. The enrichment behaviour appears to be similar to that in dilute aluminium alloys, which occurs for alloying elements with oxides having Gibbs free energies per equivalent for formation exceeding that for formation of alumina.     

The effect of oxidation on the corrosion resistance and mechanical properties of a Zr-based metallic glass

The oxidation kinetics of the Zr₆₄Cu₁₆Ni₁₀Al₁₀ bulk metallic glass (BMG) roughly follows a two-stage rate law at both 433 and 593 K in air. An oxide film of 940 nm can be formed by oxidation at 593 K, which is ZrO₂-enriched but Cu-depleted on the outer surface. The oxide film leads to a superior passivity in 0.5 M NaCl and great corrosion resistance improvements in other solutions. The oxidation effect on mechanical properties were characterized by nanoindentation, wedge indentation and compression tests. The Zr-based BMG still keeps the amorphous nature and its good mechanical properties are retained after oxidation.     

Electrochemical and surface studies on the passivity of a dental Pd-based casting alloy in alkaline sulphide solution

The corrosion and tarnish behavior of a dental casting Pd-25Ag-18Cu-12Au alloy in 0.1% Na₂S solution at 37 °C was investigated using potentiodynamic polarization and spectrocolorimetric techniques. The surface film was characterized by X-ray photoelectron spectroscopy (XPS).This alloy exhibited markedly higher resistance to corrosion and tarnish than did the Ag-20Pd-18Cu-12Au alloy in current clinical use. XPS spectra indicated the presence of a thin sulphide film composed of PdS. It was found that the PdS film is very protective and is responsible for the passivity of the Pd-25Ag-18Cu-12Au alloy in 0.1% Na₂S solution.     

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy in 3.5% NaCl solution

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy with varying Ag content were investigated in 3.5% NaCl solution. The value of Ag content i.e X varied from 0.1 wt% to 2 wt%. An increase in the Ag content up to 2 wt% resulted in a progressive increase in the corrosion current density and shifted the corrosion potential (E_corr) towards more active values. These changes were also reflected in the corrosion rate of the solder alloy. However the linear polarization resistance values decreased with increase in the weight content of silver. Increasing the Ag content from 0.1 to 2 wt% did not show a significant improvement in the passivation behaviour of the solder alloy as reflected in the passivation current density (i_p) and critical current density (i_cc) values. XPS and SIMS depth profile results revealed that the oxides of Zn and Sn were present in high concentrations on the outer surface of the solder alloy along with very low concentration of Al₂O₃.     

Localized corrosion (pitting): A model of passivity breakdown including the role of the oxide layer nanostructure

A model of passivity breakdown including the role of the inter-granular boundaries of the barrier oxide layer on the redistribution of the potential at the metal/oxide/electrolyte interfaces in the passive state is presented. Different mechanisms of breakdown at the oxide grain boundaries are considered, depending on which interface governs the potential drop: (i) local thinning and dissolution of the oxide layer, (ii) metal voiding or (iii) particle growth at the metal/oxide interface followed by rupture of the barrier layer. The role of chloride ions is discussed in each case. The key experimental observations made at the nanometre scale and validating the model are discussed.     

Passivity of polycrystalline NiMnGa alloys for magnetic shape memory applications

The corrosion and passivation behaviour of bulk polycrystalline martensite Ni₅₀Mn₃₀Ga₂₀ and austenite Ni₄₈Mn₃₀Ga₂₂ alloys was compared in electrolytes with different pH values. Linear anodic and cyclic potentiodynamic polarisation methods and anodic current transient measurements have been conducted for the alloys and their constituents to analyze free corrosion, anodic dissolution and passive layer formation processes. Electrochemically treated alloy surfaces were characterized with scanning electron microscopy (SEM) and angle-resolved x-ray photoelectron spectroscopy (XPS). The electrochemical response of both alloys is in principal similar and is dominated by the Ni oxidation. In acidic solutions (pH 0.5 and 5) a slightly higher reactivity is detectable for the martensitic alloy which is mainly attributed to enhanced dissolution processes at the multiple twin boundaries. In weakly acidic to strongly alkaline solutions (pH 5-11) both alloys exhibit a low corrosion rate and a stable anodic passivity. While air-formed films comprise NiOOH, Ga₂O₃ and MnO₂, passive films formed in near neutral media (pH 5-8.4) are composed of Ni(OH)₂, NiOOH and Ga₂O₃ in the outer region and of NiO, MnO₂ and MnO in the metal-near region.     

Improvement of corrosion resistance of AZ91D magnesium alloy by holmium addition

The corrosion behaviour of two Mg–9Al–Ho alloys (Mg–9Al–0.24Ho and Mg–9Al–0.44Ho) was evaluated by general corrosion measurements and electrochemical methods in 3.5% NaCl solution saturated with Mg(OH)₂. The experimental results were compared with that of Mg–9Al alloy without Ho addition. Various corrosion rate tests showed that the addition of Ho obviously enhanced corrosion resistance of Mg–9Al alloy. The microstructure of the three magnesium alloys and the morphology of their corrosion product film were examined by Electron Probe Microanalysis (EPMA) and Energy Dispersion Spectroscopy (EDS). The alloys with Ho addition showed a microstructure characterized by α phase solid solution, which was surrounded by some β phase and grain-like Ho-containing phase. The improvement of corrosion resistance of the Mg–9Al–Ho alloys could be explained by the fact that the deposited Ho-containing phases were less cathodic. Moreover, the corrosion product films on the Ho-containing alloy surface demonstrated their ability to restrain further corrosion.     

Corrosion, passivation and breakdown of passivity of neodymium

The anodic polarisation behaviour of neodymium was investigated in various solutions (pH 1-12). While in sulphuric acid solution high dissolution rates were observed, spontaneous passivity occurred in phosphoric acid solutions, oxalic acid solutions and sodium hydroxide solutions. However, the stability of these protecting layers strongly depends on the kind and concentration of anions present, especially in acidic environments. A mechanism of the passive layer breakdown is proposed. During pitting corrosion erosive degradation of the electrode was observed. In all solutions, abnormal hydrogen evolution was observed when neodymium was in the active state during anodic polarisation.     

Electrochemical behaviour of Ni-base alloys exposed under oil/gas field environments

The electrochemical behaviour of Ni-base alloys (Inconel 625, Inconel 718, G3 and Incoloy 825) is carried out at 80 °C in CO₂/H₂S corrosion environments using cyclic potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. The passivity mechanisms are analysed and discussed. In addition, some significant characterisation parameters such as E_corr, I_pass, E_pit, E_pp, ΔE and I_pass in cyclic polarisation curves are analysed and compared to reveal the corrosion resistance of various Ni-base alloys. The equivalent circuit model and ZsimpWin software are utilised to discuss the Nyquist plots of various Ni-base alloys. The diffusion mechanism in EIS measurement is discussed. The result shows that the corrosion resistance of the Ni-base alloys to CO₂ corrosion or CO₂/H₂S corrosion follows the sequence: Inconel 625 > G3 > Inconel 718 > Incoloy 825. H₂S works as a cathodic depolariser with accelerating initiation of the corrosion process.     

Comparative evaluation of corrosion behaviour of type K thin film thermocouple and its bulk counterpart

This paper investigates the corrosion behaviour of type K thermoelements and their thin films, and compares the performance of chromel–alumel thin film thermocouple with its wire counterpart before and after exposure to 5% NaCl medium. Potentiodynamic polarisation tests reveal that chromel and alumel films are more “noble” than their respective wires. Alumel corrodes faster when coupled with chromel in films than as wires. Secondary electron micrographs and electrochemical impedance spectroscopy measurements suggest that chromel shows localised corrosion while alumel undergoes uniform corrosion. Corrosion adversely affects the thermocouple output and introduces an uncertainty in the measurement.     

Temperature effect in the corrosion resistance of Ni-Fe-Cr alloy in chloride medium

The corrosion susceptibility of alloy 33 in 0.5 mol/L sodium sulphate solutions containing or not 0.1 mol/L sodium chloride was tested at three different temperatures: 22 °C, 40 °C and 60 °C. Electrochemical studies were performed using corrosion potential measurements (E_corr) as well as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Corrosion potential measurements showed that alloy 33 was passivated by a previously air formed film which was not destroyed during immersion in both solutions. No corrosion was observed during these tests although the temperature affected the film. Potentiodynamic polarization experiments showed that at high anodic potentials the previous film was broken up, and localized corrosion occurred in both solutions and at the three temperatures tested. Electrochemical impedance spectroscopy tests confirmed the presence of a stable passive film on the alloy surface at open circuit potential. Mott-Schottky analysis indicated that the passive film is an n-type semiconductor due to the presence of point defects of donor species, such as oxygen vacancies and interstitial metallic cations. As the potential increases the Cr(III) present in the barrier layer oxidizes producing Cr(VI) soluble species. The dissolution creates metallic cation vacancies that are acceptor species and the film changes from n-type to p-type semiconductor. The passive film rupture and the following localized attack are related to the drastic oxidative dissolution of the film at high anodic potentials, independent of its p-nature, chloride presence or increased temperature.     

Effect of the aluminium content of AlxCrFe1.5MnNi0.5 high-entropy alloys on the corrosion behaviour in aqueous environments

High-entropy alloys (HEAs) are a newly developed family of multi-component alloys. The potentiodynamic polarization and electrochemical impedance spectroscopy of the Al_xCrFe_1.5MnNi_0.5 alloys, obtained in H₂SO₄ and NaCl solutions, clearly revealed that the corrosion resistance increases as the concentration of aluminium decreases. The Al_xCrFe_1.5MnNi_0.5 alloys exhibited a wide passive region, which extended >1000 mV in acidic environments. The Nyquist plots of the Al-containing alloys had two capacitive loops, which represented the electrical double layer and the adsorptive layer. SEM micrographs revealed that the general and pitting corrosion susceptibility of the HEAs increased as the amount of aluminium in the alloy increased.     

Polypyrrole coatings as a treatment for zinc-coated steel surfaces against corrosion

A single-step electropolymerization of pyrrole on zinc-coated steel electrodes in aqueous medium was investigated under several techniques (potentiodynamic, galvanostatic and potentiostatic modes) by using carboxylate salts, such as the citrate, the succinate, the oxalate, the malate and the tartrate. Adherent and homogeneous PPy coatings were obtained only with tartrate counter-ions.The corrosion behaviour of zinc-coated steel electrodes electrochemical modified by PPy films were estimated by open circuit potential and DC polarization in NaCl, HCl and H₂SO₄ aggressive solutions. The obtained results show that the PPy coatings increase the corrosion potential and reduce the corrosion current. The salt spray test results show that the PPy coating prepared under ultrasonic waves is more resistant than those obtained in normal conditions.