Behaviour of copper during alkaline corrosion of Al–Cu alloys

Enrichment of copper beneath amorphous anodic films on relatively dilute, solid-solution Al–Cu alloys is necessary before copper can be oxidized and incorporated into the oxide layer. A similar enrichment arises during electropolishing, which also develops an amorphous oxide. In these cases, external polarization is applied, usually generating a relatively high oxidation rate. In contrast, enrichment behaviour at the corrosion potential has received less attention. The present study examines the corrosion of Al–Cu alloys, containing up to 6.7 at.% Cu, in 0.1 M sodium hydroxide solution at 293 K. Copper is again found to enrich in the alloy, similarly to behaviour with anodic polarization. However, following enrichment, discrete copper-rich particles appear to be generated in the corrosion product. These are suggested to be nanoparticles of copper, since the corrosion potentials of the alloys are low relative to that required for oxidation of copper. The corrosion rate increases with increase of both time and copper content of the alloy, probably associated with a greater cathodic activity due to an increasing number of nanoparticles. The corrosion proceeds with loss of aluminium species to the sodium hydroxide solution, but with retention of copper in the layer of hydrated alumina corrosion product.     

Barrier and porous anodic oxides on InSb

Anodizing of InSb at 5 mA cm⁻² in sodium tungstate electrolyte is shown to produce barrier-type amorphous oxide at relatively low voltages, to about 40 V, and porous-type amorphous oxide at increased voltages. The barrier-type amorphous oxide, consisting of units of In₂O₃ and Sb₂O₃, distributed relatively uniformly throughout the film, develops at a formation ratio of 2.2 ± 0.2 nm V⁻¹. The outer 15–20% of the film also contains tungsten species. The relatively high efficiency of barrier film growth reduces significantly with transition to porous oxide, which is associated additionally with generation of oxygen at the film surface. The final oxide, at 65 V, comprises pores, of typical diameter 80 nm, orientated approximately normal to the substrate and extending from a barrier region to the film surface.     

Electrochemical behaviour assessment of novel Mg-rich Mg–Al–RE alloys (RE = Ce, Er)

The electrochemical behaviour of new Mg–Al–RE (RE = Ce, Er) alloys AE91 was investigated in 0.01 M NaCl electrolyte (pH = 12) and compared with that of the most commonly used Mg alloy in the automotive field, the AZ91D. Scanning electron microscopy and quantitative electron probe microanalysis were used to characterize the samples prior to the electrochemical tests. AE91 alloys showed very similar microstructures characterized by a three-phase appearance: a Mg-based solid solution containing only Al and two intermetallic phases γ(Mg₁₇Al₁₂) and (Al_1 − xMg_x)₃Ce or (Al_1 − xMg_x)₂Er. Free corrosion potential measurements, potentiodynamic polarization curves and electrochemical impedance spectroscopy revealed improved passivity behaviour compared to AZ91D alloy. The apparent presence of trace amounts of rare earth oxides in the passive film is presumed to be the reason for the enhanced corrosion resistance of AE91 alloys in the aggressive environment considered.     

Crystallization of anodic titania on titanium and its alloys

Crystallization of amorphous anodic films grown at constant current density on sputtering-deposited titanium, and Ti-Si and Ti-Al alloys, in ammonium pentaborate electrolyte, has been examined directly by transmission electron microscopy. In the case of titanium, anatase develops at relatively low voltage in the inner film region, formed by inward migration of oxygen species. In contrast, the outer film region, formed at the film/electrolyte interface, is composed of amorphous oxide only. Oxide crystals are particularly found near the plane, separating the two regions, which is located at a depth of 35-38% of the film thickness. Oxide zones, of size ∼ 1 nm, with a relatively ordered structure, developed at the metal/film interface, are considered to lead to transformation of the inner region structure. The incorporation into the film of either aluminium or silicon species suppresses the formation of crystalline oxide to much increased voltages. However, eventually nanocrystals form at ∼40% of the film thickness, probably originating from pre-cursor nuclei in the air-formed on the as-deposited alloy.     

Using EIS to analyse samples of Al–Mg alloy AA5083 treated by thermal activation in cerium salt baths

This paper describes a study undertaken of the morphological and anticorrosive characteristics of surface layers formed on the Al–Mg alloy AA5083 from solutions of Ce(III), by means of various heat treatments while immersed in baths of cerium salts. SEM/EDS studies have demonstrated the existence of a heterogeneous layer formed by a film of aluminium oxide/hydroxide on the matrix and a series of dispersed islands of cerium deposited on the cathodic intermetallics. With the object of evaluating the degree of protection provided by the layers formed and of characterising the particular contribution of the electrochemical response of the system in NaCl, the results obtained by means of EIS are presented and discussed.     

稀土La对铁基耐蚀合金抗氧化性能的影响

通过X射线衍射(XRD)、扫描电镜(SEM)及能谱分析(EDS)等手段对不同La含量的铁基耐蚀合金850 ℃下的抗氧化性能进行了研究。结果表明,在850 ℃条件下,随着稀土La含量的增加,在一定程度上降低了合金的抗氧化性能,但氧化膜与基体的粘附性却得到了大大提高。La含量增加后,促进了氧的内扩散,使内氧化层呈树枝状深入合金基体,对氧化膜起到钉固作用。氧化膜主要由3个区域组成:外层是Fe₂O₃与CuO混合层,并含有少量CuFe₂O₄;中间层是以NiFe₂O₄为主的保护层,并含有少量的Fe₂O₃、NiO;内层则是以Fe₂O₃为主并含有少量NiO氧化物的内氧化区。     

Effects of the solution temperature and the pH on the electrochemical properties of the surface oxide films formed on Alloy 600

The surface oxide films on Alloy 600 have been investigated as a function of the solution temperature and the pH by using a cyclic voltammetry, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and a depth profiling by Auger electron spectroscopy (AES). H₃BO₃, Na₂SO₄ and NaOH aqueous solutions with temperatures in the range of 30–300 °C were used as the test solutions. As the solution temperature of the 0.5 M H₃BO₃ increased, the thickness of the passive film increased but the resistance of the passive film was diminished, which is coincident with a solution temperature dependency of the passive current in the potentiodynamic curve. The inner oxide film on Alloy 600 was distinguishable from the Cr-rich outer oxide film above 100 °C. From the Mott–Schottky relation, the oxide formed in 0.5 M H₃BO₃ at 300 °C showed a p-type semiconductor property, accompanied by a Cr-rich oxide film throughout the whole oxide film unlike the n-type oxide films up to 250 °C. The oxide resistance of the passive film decreased in the order of 0.5 M H₃BO₃, 0.1 M NaOH and 0.5 M Na₂SO₄, which is consistent with the pH dependency of the passive current. Ni-rich oxide films of a p-type were formed in the 0.5 M Na₂SO₄ or 0.1 M NaOH.     

Incorporation of transition metal ions and oxygen generation during anodizing of aluminium alloys

Enrichment of nickel at the alloy/film interface and incorporation of nickel species into the anodic film have been examined for a sputtering-deposited Al-1.2at.%Ni alloy in order to assist understanding of oxygen generation in barrier anodic alumina films. Anodizing of the alloy proceeds in two stages similarly to other dilute aluminium alloys, for example Al-Cr and Al-Cu alloys, where the Gibbs free energies per equivalent for formation of alloying element oxide exceeds the value for alumina. In the first stage, a nickel-free alumina film is formed, with nickel enriching in an alloy layer, 2 nm thick, immediately beneath the anodic oxide film. In the second stage, nickel atoms are oxidized together with aluminium, with oxygen generation forming gas bubbles within the anodic oxide film. This stage commences after accumulation of about 5.4 × 10¹⁵ nickel atoms cm⁻² in the enriched alloy layer. Oxygen generation also occurs when a thin layer of the alloy, containing about 2.0 × 10¹⁹ nickel atoms m⁻², on electropolished aluminium, is completely anodized, contrasting with thin Al-Cr and Al-Cu alloy layers on electropolished aluminium, for which oxygen generation is essentially absent. A mechanism of oxygen generation, based on electron impurity levels of amorphous alumina and local oxide compositions, is discussed in order to explain the observations.     

Corrosion processes of Mg–Y–Nd–Zr alloys in Na2SO4 electrolyte

The corrosion behavior of Mg–Y–Nd–Zr (WE43 commercial alloy) was investigated in Na₂SO₄ electrolyte using potentiodynamic polarization curves, X-Ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) depth profiles, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS) analyzes. SEM and EDS data show that Nd-rich precipitates are mainly located at the grains boundaries. Zr/Y-rich zones are distributed inside the most of the grains. XPS study indicates a depletion of Mg on surface that could be attributed to Mg dissolution and an enrichment of the addition element oxides. XPS and ToF-SIMS analyzes demonstrate that the corrosion films are made up of a magnesium hydroxide (Mg(OH)₂) outer layer and an inner layer containing magnesium oxide (MgO), yttrium oxide (Y₂O₃) and hydroxide (Y(OH)₃), mixed with a small amount of MgH₂, zirconium oxide (ZrO₂) and neodymium oxide (Nd₂O₃). The Y₂O₃ and Y(OH)₃ signals increase slightly in the inner layer towards the corrosion film/alloy interface. Unlike these compounds, ZrO₂ and Nd₂O₃ compound signals are constant inside the inner layer. It is concluded that: (i) neodymium, zirconium and yttrium play a key role in the slightly improved corrosion resistance of the alloy and (ii) the cathodic reaction is slower on WE43 than on pure Mg and AZ91.     

Anodic behaviour of a model second phase: Al-20at.%Mg-20at.%Cu

The anodic behaviour of sputtering-deposited Al-20at.%Mg-20at.%Cu alloy is investigated during anodizing and potentiodynamic polarization treatments using transmission electron microscopy, X-ray photoelectron spectroscopy and medium energy ion scattering. The composition of the alloy is close to that of the S-phase in 2024 aluminium alloy. The anodizing behaviour in both 0.1 M ammonium pentaborate and 0.1 M sodium hydroxide electrolytes follows the behaviour of more dilute, solid-solution, aluminium alloys, with enrichment of copper developing in the alloy during the growth of an alumina-based initial oxide containing incorporated magnesium species. Oxygen gas is generated following sufficient enrichment of copper for its oxidation to proceed and hence, for copper species to enter the oxide film. The generation of oxygen gas causes extensive damage to the film, which limits the voltage to relatively low values. Potentiodynamic polarization in 0.1 M sodium hydroxide electrolyte revealed mainly passive behaviour following an initial period of corrosion during which the passive film is developed. In this initial period, copper enriches in the alloy, beneath an oxide film containing aluminium and magnesium species. The magnesium species migrate faster through the film than the aluminium species and form a surface layer of MgO/Mg(OH)₂, which protects against losses of aluminium species to solution and permits the establishment of the passive film. The steady open-circuit potential of the passivated alloy in the hydroxide solution is about −550 mV (SCE), compared with about −1940 mV (SCE) for aluminium.     

Sodium enrichment of an Al-Mg alloy surface after alkaline etching

This paper reports a case of sodium enrichment of the surface of an Al-Mg alloy that contains sodium impurities in its bulk and has been subjected to etching treatment in an alkaline solution. This phenomenon has only occurred in the case of the aforementioned Al-Mg alloy and has not been observed in other tested Al-Cu, Al-Mg-Si or pure Al type alloys, despite the fact that these also contain sodium as an impurity. The origin of the sodium ions incorporated in the aluminium oxide film that covers the surface of the Al-Mg alloy is discussed, and an explanation is suggested for this difference in behaviour compared with the other alloys.     

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.     

High resistivity magnesium-rich layers and current instability in anodizing a Mg/Ta alloy

Strikingly different morphologies of amorphous anodic films on a Mg/40 at.%Ta alloy are shown to result from single-stage and sequential anodizing procedures. The alloy, prepared by magnetron sputtering, was anodized galvanostatically in ammonium pentaborate (pH 8.3) and sodium silicate (pH 12.6) electrolytes at 293 K and studied by transmission electron microscopy, Rutherford backscattering spectroscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy. For one-step anodizing in the pentaborate electrolyte, a single-layered film, of approximate composition Ta₂O₅ · MgO, forms at a ratio of ∼1.8 nm V⁻¹. In the silicate electrolyte, an outer, magnesium-rich layer, containing silicon species, also forms, with a ratio of 0.8 nm V⁻¹. The outer layer can develop due to relatively fast migration of magnesium ions in the inner layer and the stabilization of the pH at the film surface, probably linked to generation of a silica gel that also limits loss of magnesium species to the electrolyte. Further thickening of the anodic film, in ammonium pentaborate electrolyte, produces fingers of low resistivity, inner oxide that penetrate the pre-existing, high resistivity outer layer, with a bi-modal distribution of finger sizes. When fingers reach the film surface, magnesium ions are ejected to the electrolyte. The absence of fingers in films grown in sodium silicate electrolyte is possibly due to prevention, by the silica gel, of their initiation.     

The performance of Al–Ti–C grain refiners in twin-roll casting of aluminium foilstock

The master alloys based on the Al–Ti–B system have been used extensively for refining the grain structure of aluminum alloys. The quality-related problems linked with the TiB₂ particles, however, have generated an interest in the Al–Ti–C grain refiners as an acceptable replacement for Al–Ti–B master alloys. TiC particles are smaller than the TiB₂ particles and are less prone to agglomeration. Al–3Ti–0.15C grain refiners have been in use for some time in several alloy systems. Much of the work reported on this alloy, however, has been from DC casting while performance data in strip casting is not available. In the present work, a commercial Al–3Ti–0.15C grain refiner was employed in the twin-roll casting of AA8111 foilstock. Its grain refining efficiency was compared with that of the Al–5Ti–0.2B master alloy, the standard grain refiner in aluminium industry for the manufacture of aluminium foil products.     

镁合金环保型阳极氧化工艺研究

通过环保型阳极氧化工艺在MB2镁合金表面获得了表面质量良好的银灰色氧化膜层,用金相显微硬度计、扫描电镜和X射线衍射等表面分析手段,研究了氧化膜层的显微硬度、截面形貌和相结构,并采用动电位扫描的电化学方法考察了氧化膜的耐腐蚀性能.结果表明：氧化膜层的主要成分为MgO、MgAl2O4、Al2O3;膜层具有多孔结构,孔径较为均匀,分为内外两层,外层为疏松层,内层为与基体结合牢固的致密层;阳极氧化电流密度和电解液中铝盐浓度是影响阳极氧化膜层性能的主要因素;所得膜层的显微硬度值高达558.4 HV,同时其耐蚀性能也远优于传统含铬DOW17工艺所成的防护膜,且所用电解液无铬无磷更为环保经济.     

Optimisation of precipitation for controlling recrystallisation of wrought Fe3Al based alloys

A Fe–26Al–5Cr (at.%) single-phase (:A2/B2/D0₃) alloy and two-phase (+TiC) alloys with different amounts of TiC particles have been hot rolled at 800 °C and the kinetics of static recrystallisation have been studied. In the alloys with a high amount of TiC, needle-like TiC of more than 1 μm in length formed during cooling after homogenisation in the single-phase region and coarsened during hot rolling. The large particles cause particle stimulated nucleation (PSN) and hence accelerate recrystallisation. In order to accomplish both strengthening by precipitates and inhibition of recrystallisation that deteriorates room-temperature ductility, a thermo-mechanical treatment consisting of hot deformation with a low amount of precipitates and a subsequent heat treatment for further precipitation is proposed. This process is difficult to carry out in the (Fe–26Al–5Cr)–TiC system due to the high precipitation temperature of TiC. The precipitation temperature is significantly decreased by replacing TiC by VC or MoC.     

Interactive effect of cerium and aluminum on the ignition point and the oxidation resistance of magnesium alloy

This paper focused on the interactive effect of cerium (Ce) addition and aluminum (Al) content in magnesium alloy on ignition point and oxidation resistance. Ce content played an important role in improving the oxidation resistance of Mg alloy. Ignition point ascended with increasing Ce content. 0.25 wt% Ce content in Mg alloys could greatly improve tightness of the oxide film of Mg alloys. However, when Ce content in the alloy exceeded its solid solubility, ignition point descended. Furthermore, Al content in the alloy also influenced the ignition point. The higher the Al content was, the lower the ignition point.     

Spark anodizing behaviour of titanium and its alloys in alkaline aluminate electrolyte

Spark anodizing of titanium, Ti-6Al-4V and Ti-15V-3Al-3Cr-3Sn in alkaline aluminate electrolyte produces highly crystalline anodic films consisting mainly of Al₂TiO₅ with α- and γ-Al₂O₃ as minor oxide phases, irrespective of substrate composition. However, the apparent efficiency for film formation decreases in the following order: Ti-6Al-4V, titanium and Ti-15V-3Al-3Cr-3Sn. A large amount of aluminium species are incorporated from the electrolyte, probably by plasma-chemical reaction, and become distributed throughout the film thickness. This distribution indicates that the electrolyte penetrates near to the film/substrate interface through the discharge channels. Thus, the outwardly migrating aluminium ions under a high electric field can be present even in the inner part of the anodic films. Voids are developed at the film/substrate interface, particularly on the vanadium-containing alloys, reducing the adhesion of the anodic film to the substrate.     

Anodic film growth in the Al-Ta alloy system

The ionic transport numbers, relative migration rates of cation species and formation ratios are reported for barrier anodic films formed on metastable, solid solution Al-Ta alloys, with compositions extending from the aluminium-rich to the tantalum-rich ends of the system. The data were obtained by marker experiments, using ion implanted xenon, transmission electron microscopy, Rutherford backscattering spectroscopy and medium energy ion scattering. The films are amorphous and form by migration of metal and oxygen species. The ionic transport numbers and the formation ratios depend approximately linearly upon the composition of the alloy, between the values for anodic alumina and anodic tantala. The migration rate of Al³⁺ ions exceeds that of Ta⁵⁺ ions, but reduces in relative magnitude as the tantalum content of film increases. The faster migration of Al³⁺ ions is consistent with the higher energy of the Ta⁵⁺-O bond compared with that of the Al³⁺-O bond. Due to the difference in mobilities of the cation species, the films comprise an outer layer of alumina and an inner layer containing units of both alumina and tantala. The two-layered films can develop fingers of inner layer oxide that penetrate the outer alumina layer due to the higher ionic resistivity of the alumina. Such channelling of current can lead to mixing of inner layer oxide and alumina and thereby hinder formation of an alumina layer, particularly in films on the more tantalum-rich alloys.     

Atmospheric corrosion of field-exposed magnesium alloy AZ91D

The magnesium alloy AZ91D was exposed in three different types of atmospheric environment, viz. urban, rural and marine exposure sites. Corrosion rates, corrosion products formed, and the influence of the microstructure on the corrosion behaviour of the alloy were investigated. The corrosion rate of AZ91D exposed in the marine environment was 4.2 μm/year, and in the rural and urban environments 2.2 and 1.8 μm/year, respectively. The main corrosion product found was magnesium carbonate hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O), which was formed at all three exposure sites. The corrosion attack started in the -phase in larger grains at the boundary between the -phase and the eutectic -/β-phase. Microgalvanic elements were formed with the eutectic -/β-Mg phase as cathodic site and the -Mg grains as anodes. The Al–Mn particles played a minor roll in the initiation process, even though these particles are the most noble in the microstructure and thus the driving force for a corrosion attack around these particles could be expected to be high. A close resemblance was observed between the corrosion mechanisms operating under the field-exposure conditions described here and the mechanisms operating under the previously reported laboratory conditions.