Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater

The corrosion behavior of the 70/30 Cu-Ni alloy in stagnant, aerated pristine and sulfide-containing simulated seawater as a function of exposure time was investigated with polarization curve measurement and electrochemical impedance spectroscopy (EIS). It was demonstrated that the compact protective oxide film formed on the 70/30 Cu-Ni alloy resulted in the decrease of corrosion rate in aerated pristine seawater; while the corrosion rate of 70/30 Cu-Ni alloy in aerated sulfide-containing seawater increased dramatically due to the catalysis of the sulfide ions or sulfide scale for both the cathodic and anodic reactions. The impedance spectra and the corresponding equivalent circuits confirmed that a duplex layer of a surface film was formed on the 70/30 Cu-Ni alloy in aerated pristine seawater after a period of time and that the inner layer was responsible for the good resistance of the alloy; while only a porous and non-protective corrosion product layer formed on the 70/30 Cu-Ni alloy in aerated sulfide-containing seawater, which made small values of charge transfer resistance (R_ct) to last for a abnormally long time by interfering with the growth of the protective oxide film. The composition of the surface film on the alloy in pristine and sulfide-containing seawater for different exposure times were investigated thoroughly by XPS. It was found that the duplex corrosion product layer formed on the alloy in pristine seawater was composed of an inner Cu₂O and an outer CuO layer. The porous and non-protective corrosion product layer formed on the alloy in aerated sulfide-containing seawater was a mixture of CuCl, Cu₂S, NiS, Cu₂O and NiO with trace amounts of CuO and Ni(OH)₂ and that the most significant component was Cu₂S. In addition, SEM was used to analyze the topography of the 70/30 Cu-Ni alloy in both solutions after different exposure times.     

Effects of blending on surface characteristics of copper corrosion products in drinking water distribution systems

Copper scales formed over 6-months during exposure to ground, surface and saline waters were characterized by EDS, XRD and XPS. Scale color and hardness were light red-brown-black/hard for high alkalinity and blue-green/soft for high SO₄ or Cl waters. Cl was present in surface or saline copper scales. The Cu/Cu₂O ratio decreased with time indicating an e transfer copper corrosion mechanism. Cu₂O, CuO, and Cu(OH)₂ dominated the top 0.5-1 A° scale indicating continuous corrosion. Cu₂O oxidation to CuO increased with alkalinity, and depended on time and pH. Total copper release was predicted using a Cu(OH)₂ model.     

The corrosion behavior of amorphous and nanocrystalline Fe73.5Cu1Nb3Si15.5B7 alloy

The potentiodynamic polarization curves in 0.5 M NaCl solution before and after crystallization of Fe_73.5Cu₁Nb₃Si_15.5B₇ alloy have been studied in relation to the microstructure and alloy composition. It was shown that the corrosion resistance of the alloy strongly depending on these two factors. The observed decrease in corrosion resistance of the alloy after the heat treatment up to 480 °C in comparison to the corrosion resistance of the alloy in the as prepared state is attributed to the increased inhomogeneity of the alloy that coincides with the first appearance of Fe₃Si phase. Further heating (up to 600 °C) resulted in an increase in the number of Fe₃Si nanocrystallites and the appearance of a FeCu₄ phase. After annealing at 600 °C the lowest corrosion rate, 0.004 mm a⁻¹, was observed. Annealing of the samples at higher temperatures (>600 °C) induced formation of six crystalline phases which proved detrimental to the corrosion resistance of the Fe_73.5Cu₁Nb₃Si_15.5B₇ alloy. Solid corrosion products were identified on the surface of the samples after anodic polarization.     

Comparison of the corrosion of Cu50Pd50 and Cu50Pd44M6 (M = Y,Mg, or Al) hydrogen separation membrane alloys in simulated syngas containing H2S

The resistance to sulfidation was examined by exposing coupons including a Cu–Pd binary alloy and three ternary alloys with 6 at% Y, Mg, or Al to simulated syngas containing varying amounts of H₂S. The mass change of the samples was determined and the exposed surfaces were characterized by SEM/EDS and XRD. The best corrosion resistance of the ternary alloys was observed in the Cu₅₀Pd₄₄Al₆ alloy. A slight decrease was observed when Mg was added, but both the Al and Mg alloys were roughly on par with the binary composition. The Y addition resulted in a degradation in the corrosion resistance by forming extensive internal Y₂O₃ and Cu_1−xY_xS and external Pd_4−xCu_xS and Pd ₁₃Cu₃S₇.     

Corrosion behaviour of AIP NiCoCrAlYSiB coating in salt spray tests

NiCoCrAlYSiB coatings were deposited by arc ion plating (AIP) and annealed/pre-oxidised under various conditions. The corrosion behaviour of as-deposited and annealed/pre-oxidised coatings was studied by salt spray testing in a neutral mist of 5 wt% NaCl at 35 °C for 200 h. The results showed that the as-deposited NiCoCrAlYSiB coating behaved poorly while the annealed and pre-oxidised ones performed much better in salt spray tests. The dense microstructure in annealed coatings and formation of α-Al₂O₃ scales on the surface during pre-oxidation improved the corrosion resistance in salt spray test. The corrosion process was investigated from the aspects of corrosion products, and its electrochemical mechanism was proposed as well.     

Corrosion protection of magnesium alloys by cerium, zirconium and niobium-based conversion coatings

A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na₂SO₄ electrolyte, and accelerated atmospheric corrosion tests (humid, SO₂ polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24 h in the Ce-Zr-Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce-Zr-Nb-treated samples, with or without an additional layer of epoxy-polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO₂, Ce₂O₃, ZrO₂, Nb₂O₅, MgO, and MgF₂ as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na₂SO₄. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys.     

Corrosion characteristics of copper microparticles and copper nanoparticles in distilled water

The corrosion characteristics of copper microparticles and copper nanoparticles in distilled water were investigated in this paper. The Cu²⁺ transformations of copper microparticles and copper nanoparticles in distilled water were tested by using absorbance measurement, the structures of their corrosion products were determined by using XRD and TEM techniques. The results of absorbance measurement show that the corrosion characteristics of copper nanoparticles in distilled water are quite different from that of copper microparticles. The Cu²⁺ transformations ratio of copper microparticles increases slowly with the increasing of immersion time and levels off eventually, but the Cu²⁺ transformations ratio of copper nanoparticles increases sharply with the increasing of immersion time and gets to peak rapidly, and then decreases as the immersion time increases and levels off finally. The results of XRD present that they have different corrosion products, the corrosion products of copper microparticles in distilled water are Cu and CuO, but the nanoparticles are Cu, CuO, Cu(OH,Cl)₂ · 2H₂O and Cu₂(CO₃)(OH)₂. All these differences owe to the size effect of copper particles.     

Chemistry of corrosion products on Zn-Al-Mg alloy coated steel

Zn-Al-Mg alloy (ZM) coating provides a decisively enhanced corrosion resistance in a salt spray test according to DIN EN ISO 9227 (NSS) compared to conventional hot-dip galvanised zinc (Z) coating because of its ability to form a very stable, well adherent protecting layer of zinc aluminium carbonate hydroxide, Zn₆Al₂(CO₃)(OH)₁₆·4H₂O on the steel substrate. This protecting layer is the main reason for the enhanced corrosion resistance of the ZM coating. Surface corrosion products on ZM coated steel consist mainly of Zn₅(OH)₆(CO₃)₂, ZnCO₃ and Zn(OH)₂ with additions of Zn₅(OH)₈Cl₂ · H₂O and a carbonate-containing magnesium species.     

Research on Cu transformations of Cu and its oxides particles with different sizes in the simulated uterine solution

Cu²⁺ transformations of Cu and its oxides particles with different sizes in the simulated uterine solution were investigated by absorbance measurements. The corrosion intermediate of Cu nanoparticle in the simulated uterine solution was determined by using XRD technique. The results show that the transformation ratio of Cu nanoparticle is remarkably higher than that of Cu microparticle. Moreover, nanoparticles of CuO and Cu₂O can be further transformed into cupric ion with transformation ratio over 90%. The high transformation ratio and the transformation mechanism of nanoparticles are discussed.     

Effect of Mn/Mo incorporated oxide layer on the corrosion behavior of AA 2024 alloy

The oxide layer formed over AA 2024 using 10 wt.% H₂SO₄ (plain oxide, PO) was modified by Mn/Mo oxyanions (permanganate/molybdate modified oxide, PMMO) as an alternative to Cr(VI) ions to enhance the corrosion resistance. The corrosion current density values obtained for PMMO was found to be 2.8% and 1.4% of hydrothermal treated oxide (HTO) and PO respectively after 168 h immersion in 3.5% NaCl solution. The electrochemical studies showed the higher barrier layer resistance for PMMO. The improved corrosion behavior of PMMO was observed based on the damage function calculated. Similar observations were confirmed by continuous salt spray test.     

Corrosion of friction stir welded magnesium alloy AM50

The microstructure of a friction stir welded magnesium alloy AM50 was examined by means of optical light microscopy. The chemical composition, particularly the iron content, and morphology of the oxide film were analyzed and discerned via auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). Corrosion behaviour of the welds and base materials were investigated by virtue of neutral salt spray tests and potentiodynamic polarization measurements in conventional cells and in a mini cell. The results demonstrate that minor increases in iron concentration as might be speculated to occur as a consequence of tool/work piece interaction during the welding process on the corrosion resistance of the weld can be ignored. The corrosion morphology was predominantly influenced by the distribution of the Mg₁₇Al₁₂ phase. Here, it was also found that the corrosion resistance of the friction stir weld varied in response to changes in the joint microstructure.     

The effect of iron on the corrosion characteristics of 90-10 cupro nickel in quiescent 3·4%NaCl solution

The corrosion resistance of 90-10 cupro nickel is very much dependent on small amounts of added Fe. It has been found that in quiescent 3·4%NaCl solution, corrosion rate decreases with increasing Fe and that both solutionized and precipitated Fe are effective. The corrosion product films were essentially similar in all alloys tested being mainly Cu₂O and Cu₂(OH)₃Cl. A complex Fe phase was identified on a 1·5wt.%Fe alloy which had undergone heat treatment to precipitate most of the Fe. A modification of the defect structure of Cu₂O increasing the electronic resistance of the corrosion product film is proposed as responsible for the increased corrosion resistance in cases where Fe is in solid solution. A complex Fe phase, which was found to have a high ionic resistance, was found responsible for the increased corrosion resistance of the precipitated alloy. The results are discussed with reference to current theories of corrosion product doping.     

Differential reflectometry of corrosion products of copper

The new technique of differential reflectometry was applied to study some fundamental corrosion processes for copper. Free corrosion in air for one day yielded differential reflectograms characteristic of mixed oxides of Cu₂O and CuO. With increasing time of exposure to air, the reflectograms evolved into typical CuO patterns. Similarly, free corrosion of copper in distilled water yielded mixed oxides of Cu₂O and CuO. Holding copper potentiostatically near the boundary between these two corrosion products as shown on the Pourbaix diagram always yielded at first a mixed oxide which turned into the stable species after several days of polarization. It was further found that copper held potentiostatically first in the CuO region and then in the Cu₂O region of the Pourbaix diagram does not lose the characteristic patterns of CuO. This suggests that the sudden shift in potential induces growth of Cu₂O under the existing CuO layer without dissolving the CuO.     

Corrosion Resistance of Copper Coatings Deposited by Cold Spraying

In the article, a study of corrosion resistance of copper and copper-based cermet (Cu+Al₂O₃ and Cu+SiC) coatings deposited onto aluminum alloy substrate using the low-pressure cold spraying method is presented. The samples were subjected to two different corrosion tests at room temperature: (1) Kesternich test and (2) a cyclic salt spray test. The selected tests were allowed to simulate service conditions typical for urban, industrial and marine environment. Examination of corroded samples included analysis changes on the coating surface and in the microstructure. The physicochemical tests were carried out using x-ray diffraction to define corrosion products. Moreover, microhardness and electrical conductivity measurements were conducted to estimate mechanical and physical properties of the coatings after corrosion tests. XRD analysis clearly showed that regardless of corrosion conditions, for all samples cuprite (Cu₂O) was the main product. However, in the case of Cu+Al₂O₃ cermet coating, chlorine- and sulfate-containing phases such as Cu₂Cl(OH)₃ (paracetamite) and Cu₃(SO₄)(OH)₄ (antlerite) were also recorded. This observation gives better understanding of the lowest microstructure changes observed for Cu+Al₂O₃ coating after the corrosion tests. This is also a justification for the lowest decrease in electrical conductivity registered after the corrosion tests for this coating.     

The valence state of copper in anodic films formed on Al-1at.% Cu alloy

During anodising of Al-Cu alloys, copper species are incorporated into the anodic alumina film, where they migrate outward faster than Al³⁺ ions. In the present study of an Al-1at.% Cu alloy, the valence state of the incorporated copper species was investigated by X-ray photoelectron spectroscopy, revealing the presence of Cu²⁺ ions within the amorphous alumina film. However, extended X-ray irradiation led to reduction of units of CuO to Cu₂O, probably due mainly to interactions with electrons from the X-ray window of the instrument and photoelectrons from the specimen. The XPS analysis employed films formed on thin sputtering-deposited alloy/electropolished aluminium specimens. Such an approach enables sufficient concentrations of copper species to be developed in the anodic film for their ready detection.     

Clarification of chemical state for alloying elements in iron rust using a binary-phase potential-pH diagram and physical analyses

A binary-phase potential-pH diagram has been investigated to evaluate the chemical stability of various kinds of double oxide rusts (Fe-X) to get a principle for alloy design enhancing the corrosion resistance of steels. It was found that there are the following types of alloying elements enhancing the corrosion resistance of steels in the rust: (1) iron substitution type (Ni), (2) oxide formation type (Al), (3) metallic type (Ru), and (4) oxygen-acid salt type (WO₄). X-ray photoelectron spectroscopy and transmission electron microscopy analyses have been conducted on the rust formed on the low alloy steel in a saline environment. The analytical results were discussed using potential-pH diagrams. The iron substitution type and the oxide formation type elements make spinel double oxides with iron. In the corrosion tests, steels added with Ni or Al had high corrosion resistance. Thus it is possible to obtain high corrosion resistance by the creation of spinel double oxide such as Fe₂NiO₄ and FeAl₂O₄ in an inner layer.On the other hand it was found that the metallic type and the oxygen-acid salt type elements were not contained into the iron rust. In particular the oxygen-acid salt elements were excluded from the iron rust and concentrated into the defects of the rust. It is suggested that insoluble salts like FeWO₄ are formed on the base metal in the defects to act as an anodic inhibitor. Thus, the addition of a small quantity of W gives high corrosion resistance.The penetration of Cl ions can be prevented by the spinel double oxide in an inner layer and the oxygen-acid salt in the defects. In this way, the high corrosion resistance by the addition of these elements can be understood from the potential-pH diagram and the physical analyses.     

Corrosion product formation during NaCl induced atmospheric corrosion of magnesium alloy AZ91D

Magnesium alloy AZ91D was exposed in humid air at 95% relative humidity (RH) with a deposition of 70 μg/cm⁻² NaCl. The corrosion products formed and the surface electrolyte were analysed after different exposure times using ex situ and in situ FTIR spectroscopy, X-ray diffraction and Ion Chromatography. The results show that magnesium carbonates are the main solid corrosion products formed under these conditions. The corrosion products identified were the magnesium carbonates hydromagnesite (Mg₅ (CO₃)₄ (OH)₂4H₂O) and nesquehonite (MgCO₃ 3H₂O). The corrosion attack starts with the formation of magnesite at locations with higher NaCl contents. At 95% RH, a sequence of reactions was observed with the initial formation of magnesite, which transformed into nesquehonite after 2-3 days. Long exposures result in the formation of pits containing brucite (Mg(OH₂)) covered with hydromagnesite crusts. The hydromagnesite crusts restrict the transport of CO₂ and O₂ to the magnesium surface and thereby favour the formation of brucite. Analysis of the surface electrolyte showed that the NaCl applied on the surface at the beginning was essentially preserved during the initial corrosion process. Since the applied salt was not bound in sparingly soluble corrosion products a layer of NaCl electrolyte was present on the surface during the whole exposure. Thus, Na⁺ and Cl⁻ ions can participate in the corrosion process during the whole time and the availability of these species will not restrict the atmospheric corrosion of AZ91D under these conditions. It is suggested that the corrosion behaviour of AZ91D is rather controlled by factors related to the microstructure of the alloy and formation of solid carbonate containing corrosion products blocking active corrosion sites on the surface.     

Effect of artificial aging on intergranular corrosion of extruded AlMgSi alloy with small Cu content

The effect of artificial aging parameters on the corrosion performance of air cooled AlMgSi(Cu) model alloy extrusions was investigated. Accelerated corrosion test revealed that the extrusions were highly susceptible to intergranular corrosion (IGC) in the naturally aged condition. However, IGC susceptibility was reduced, and finally eliminated, by artificial aging. Overaging introduced slight pitting susceptibility. EDS X-ray mapping in FE-TEM revealed Mg₂Si and Q-phase (Al₄Cu₂Mg₈Si₇) grain boundary precipitates and a continuous Cu-enriched grain boundary film. IGC susceptibility was related to the Cu-enriched grain boundary film. Increased IGC resistance was caused by coarsening of the grain boundary film by aging. Pitting susceptibility by over aging evolved due to coarsening of the Q-phase particles in the grain bodies.     

Corrosion behaviour in salt spray and in 3.5% NaCl solution saturated with Mg(OH)2 of as-cast and solution heat-treated binary Mg–RE alloys: RE = Ce,La, Nd,Y, Gd

Corrosion behaviour was characterised in salt spray and in 3.5% NaCl solution saturated with Mg(OH)₂ of as-cast and solution heat-treated binary Mg–RE alloys. The corrosion rate in the immersion test for the solution heat-treated Mg–RE alloys was substantial, and was greater than that of high-purity Mg. These corrosion rates were probably caused by the particles in the microstructure and/or by Fe rich particles precipitated during the solution heat-treatment. The corrosion rate in the immersion tests for each as-cast Mg–RE alloy was greater than that of high-purity Mg, attributed to micro-galvanic acceleration caused by the second phase. Corrosion rates in salt spray had a general correlation with corrosion rates in the immersion tests, but there were differences. The values of apparent valence were always less than 2 consistent with Mg corrosion being only partly under electrochemical control.     

Characterization of the corrosion products of electrodeposited Zn, Zn–Co and Zn–Mn alloys coatings

The morphology, composition, phase composition and corrosion products of coatings of pure Zn (obtained from two types of electrolytic bath: an acidic bath (Zn_acid) and a cyanide-free alkaline bath (Zn_alkaline)) and of Zn–Mn and Zn–Co alloys on steel substrates were studied. To achieve this, diverse techniques were used, including polarization curves, atomic force microscopy (AFM), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS), X-ray diffraction (XRD), and the salt spray test. In the salt spray test, the exposure time required for the coatings to exhibit red corrosion (associated with the oxidation of steel) decreased in the following order: Zn–Mn_(432h) > Zn–Co_(429h) > Zn_{alkaline(298h)} > Zn_acid(216h). The shorter exposure times required for corrosion of the pure Zn coatings are related to the coating composition and the crystallographic structure. Analysis of the corrosion products disclosed that Zn₅(OH)₈Cl₂·H₂O was a corrosion product of all of the coatings tested. However, the formation of oxides of manganese (MnO, Mn_0.98O₂, Mn₅O₈) in the Zn–Mn coating, and the formation of the hydroxide Zn₂Co₃(OH)₁₀·2H₂O in the Zn–Co coating, produced more compact and stable passive layers, with lower dissolution rates.