Preparation of MgO coatings on magnesium alloys for corrosion protection

MgO coating is formed on magnesium alloy by anodic electrodeposition in 6 M KOH solution, whereas Mg(OH)₂ coating is produced by anodization in 10 M KOH solution, which could be successively converted to MgO by calcination in air at 450 °C. The evolution of morphology, structure and composition of anodic film obtained on Mg alloy is investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD). Potentiodynamic polarization measurements show that the as-grown MgO protective coatings are very effective in improving the corrosion resistance of magnesium alloy compared to bare metallic magnesium.     

Electrochemical reactivity, surface composition and corrosion mechanisms of the complex metallic alloy Al3Mg2

A corrosion mechanism is proposed for Al₃Mg₂, based on electrochemical tests, XPS, and depth profiling using XPS and ToF-SIMS. After short (∼2 min) solution exposure, the surface consists of a surface film above dealloying. The dealloying is attributed to selective Mg dissolution and the surface rearrangement of Al into islands, although the metallic Al could alternatively be formed by two reduction reactions. The surface film thickness was ∼10 nm. After exposure to ultra-pure water, the composition was AlMg_1.3O_0.2(OH)_5.1 corresponding to Al(OH)₃·1.1 Mg(OH)₂·0.2MgO. After exposure to 0.01 M Na₂SO₄, the composition was AlMg_0.2O_0.4(OH)_2.5 corresponding to Al(OH)₃·0.1Al₂O₃·0.2MgO. Longer exposure produced a thicker surface film, more pronounced metallic Al islands and more MgH₂. Three possibilities are identified for MgH₂ formation. Al(OH)₃ formation is attributed to a precipitation reaction. Bulk nanoporous Al₃Mg₂ formation is predicted to be possible by Mg dealloying of Mg₁₇Al₁₂.     

A first quantitative XPS study of the surface films formed, by exposure to water, on Mg and on the Mg-Al intermetallics: Al3Mg2 and Mg17Al12

An XPS investigation was carried out of the surface films, formed by exposure to ultrapure water, on mechanically ground Mg and the two Mg-Al intermetallic compounds: Al₃Mg₂ and Mg₁₇Al₁₂. The mechanically ground Mg surface had a film of MgO at the Mg metal surface covered by a Mg(OH)₂ layer, formed by the reaction of the MgO with water vapour in the air. Upon immersion in ultrapure water, this film converted to a duplex film with an inner MgO layer next to the Mg metal and an external porous hydroxide layer. For both intermetallics, the XPS data is consistent with (i) preferential dissolution of Mg and (ii) a 10 nm thick film on the surface after immersion in ultrapure water; the film composition on Al₃Mg₂ was AlMg_1.4O_0.2(OH)_5.4 whilst on Mg₁₇Al₁₂ the composition was AlMg_2.5(OH)₈.     

Anodic oxidation and dielectric behaviour of aluminium-niobium alloys

The anodizing behaviour of sputtering-deposited Al-Nb alloys, containing 21, 31 and 44 at.% niobium, has been examined in 0.1 M ammonium pentaborate electrolyte with interest in the composition and the dielectric properties of the anodic oxides. RBS and TEM revealed amorphous oxides, containing units of Nb₂O₅ and Al₂O₃ in proportion to the alloy composition. Xenon marker experiments indicated their growth through migration of the Nb⁵⁺, Al³⁺ and O²⁻ species, with cation transport numbers, in the range 0.31-0.35, and formation ratios, in the range 1.35-1.64 nm V⁻¹, intermediate between those of anodic alumina and anodic niobia. Al³⁺ ions migrate slightly faster than Nb⁵⁺ ions, promoting a thin alumina layer at the film surface, although this layer is penetrated by fingers of the underlying niobium-containing oxide of relatively reduced ionic resistivity. The incorporation of units of Nb₂O₅ into anodic alumina increases the dielectric constant from about 9 to the range 11-22 for the investigated alloys.     

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.     

Electrochemical behavior of anodized Mg alloy AZ91D in chloride containing aqueous solution

Electrochemical behavior in aerated 3.5 wt.% NaCl solution of Mg alloy AZ91D anodized or not has been investigated by using electrochemical impedance spectroscopy, potentiodynamic polarization and E_corr-t curve. Their microstructures before and after corrosion have been examined under scanning electron microscope. Testing results from E_corr-t and polarization curves indicate that the corrosion behavior of Mg alloy makes significant, characteristic changes due to anodization. Impedance spectra obtained show a regular evolution with exposure time revealing the development of corrosion damage. SEM micrographs confirm that there are pores, defects and microcracks in anodic film which determine the existence of film-vulnerable regions. Electrochemical data are combined with micrographs to explain protection mechanism of anodic film and corrosion mechanism of Mg alloy.     

The protective surface film formed on molten ZK60 magnesium alloy in 1,1,1,2-tetrafluoroethane/air atmospheres

The composition, microstructure and growth kinetics of the surface film formed on molten ZK60 magnesium alloy in 1,1,1,2-tetrafluoroethane/air mixture were investigated by using SEM, EDS, XRD, XPS and TG. The results show that the film formed in 0.01% 1,1,1,2-tetrafluoroethane/air was non-protective, and its phase composition changed with melt temperature. At 760 °C, the film was mainly composed of MgO and some MgF₂ and ZrO₂, whereas at 660 °C it consisted mainly of MgO and Mg₃N₂. The film formed in air containing 0.1% 1,1,1,2-tetrafluoroethane or higher was comprised of MgF₂ and C with small amounts of MgO, and it was protective.     

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.     

Corrosion behaviour of die-cast AZ91D magnesium alloy in aqueous sulphate solutions

The corrosion behaviour of die-cast AZ91D magnesium alloys in sulphate solutions was investigated by SEM, FTIR and polarization measurements. For immersion times less than 48 h, no pitting corrosion occurred and only generalized corrosion was apparent. According to the polarization curves, the corrosion rate order of the die-cast AZ91D Mg alloy in three aqueous solutions was: NaCl > MgSO₄ > Na₂SO₄. The main corrosion products were Mg(OH)₂ and MgAl₂(SO₄)₄·22H₂O in the sulphate solutions and the product film was compact. Precipitation of MgAl₂(SO₄)₄·22H₂O required a threshold immersion time.     

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 of Al-Sn-Bi alloys in alcohols at high temperatures. Part II: Effect of anodizing on corrosion

Nine kinds of Al alloys were anodized to form porous anodic oxide films, and then anodized specimens were immersed in 2-(2-(2-methoxyethoxy)ethoxy)ethanol (MEEE) and 2-(2-(2-butoxyethoxy)ethoxy)ethanol (BEEE) at 415 K. Al-1.0%Sn-1.0%Bi alloy was corroded severely in both BEEE and MEEE, whereas other eight alloys showed no corrosion. The corrosion proceeded under the anodic oxide films through cracks formed in the film. Cathodic polarization in Cu electroplating solution after corrosion suggested that the crack formation during immersion in hot MEEE is due to thermal expansion of the substrate and Sn and Bi containing particles included in the anodic oxide film.     

Oxidation and corrosion of silicon nitride ceramics with different sintering additives at 1200 and 1500 °C in air, water vapour, SO2 and HCl environments - A comparative study

The effect of different sintering additives on the high temperature oxidation and corrosion behaviour of silicon nitride based ceramics was investigated. Comparative tests were conducted at 1200 and 1500 °C in air, in water vapour, and with the highly corrosive gases HCl and SO₂. Si₃N₄ was prepared with MgO, Al₂O₃, Y₂O₃ and Al₂O₃ + Y₂O₃ sintering additives. Hot pressed discs were tested for a total time of up to 128 h. The electrically conductive ceramic composites Si₃N₄ + TiN and Si₃N₄ + MoSi₂ were also tested under the same conditions. The effects that the different corrosion environments have on the different ceramics are presented. SEM studies of the oxidised ceramics show the direct transformation of Si₃N₄ grains into SiO₂ through a reaction interface layer.     

Discontinuities in the porous anodic film formed on AA2099-T8 aluminium alloy

The anodizing behaviour of constituent particles (Al–Fe–Mn–Cu) and dispersoids (Al–Cu–Mn–Li and β′(Al₃Zr)) in AA2099-T8 has been investigated. Low-copper-containing Al–Fe–Mn–Cu particles anodized more slowly than the alloy matrix, forming a highly porous anodic oxide film. Medium- and high-copper-containing Al–Fe–Mn–Cu particles were rapidly dissolved, resulting in defects in the anodic film. The anodizing of Al–Cu–Mn–Li dispersoids is slightly slower than the alloy matrix, forming a less regular anodic oxide film. β′(Al₃Zr) dispersoids anodized at a similar rate to the alloy matrix. Further, the potential impact of the discontinuities in the resultant anodic films on the performance of the filmed alloy is discussed.     

The role of TiN inclusions in stress corrosion crack initiation for Alloy 690TT in high-temperature and high-pressure water

Microchemistry and microstructure of TiN in Alloy 690TT were analyzed using SEM and TEM. Constant loading test was conducted on Alloy 690TT in 325 °C water to study effect of TiN on SCC initiation. It was found that TiN-inclusion stringers existed along the longitudinal axis. Numerous micron-size TiN with Al₂O₃ and/or MgO nuclei and submicron-size TiN existed in this alloy. After holding a constant load equal to 180% of the yield strength for 40 days, cracks about 1-3 μm initiated at micron-size TiN and TiN-inclusion stringers in the near surface. The mechanisms of Alloy 690TT crack initiation at these TiN are discussed.     

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.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Nucleation and growth of selective oxide particles on ferritic steel

In the continuous annealing process, steel sheets are annealed at 800 °C in an atmosphere of nitrogen and hydrogen (5 vol.%) containing low partial water pressure (20-50 Pa). Under these conditions, the most oxidizable alloying elements in the steel segregate towards the surface where they form oxide particles. The nucleation and growth of those oxides were examined. Oxide nucleation mainly occurs between 650 and 750 °C. During their growth, the oxides take the form of a spherical cap and are composed of MnO, Mn₂SiO₄ (or MnSiO₃), MnAl₂O₄, SiO₂, Al₂O₃ and B₂O₃. Particle nucleation and growth are favored on grain boundaries.     

Sulphidation/oxidation behaviour of TiAlCr and Al2Au coated Ti45Al8Nb alloy at 750 °C

In this paper, we present the sulphidation/oxidation behaviour of a Ti45Al8Nb (at%) alloy coated with different protective surface films. Two intermetallic coatings are considered; TiAlCr and Al₂Au deposited by physical vapour deposition. The coated alloy was subjected to a H₂/H₂S/H₂O yielding pS₂ - 10⁻¹ Pa and pO₂ - 10⁻¹⁸ Pa potentials at 750 °C for up to 1000 h. The corrosion kinetics were determined by means of discontinuous gravimetry and the as-received and exposed samples were characterised using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction analysis (XRD). The materials showed the development of a multilayered structure. In the case of the TiAlCr coated Ti45Al8Nb - base alloy, Al₂O₃, TiO₂ and Cr₂S₃ developed. For the Al₂Au coated Ti45Al8Nb samples an Al₂O₃ scale containing TiO₂ nodules was observed at the surface.     

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.     

Changes in mass and stress during anodic oxidation and cathodic reduction of the Cu/Cu2O multilayer film

The anodic oxidation and cathodic reduction processes of the Cu/Cu₂O multilayer film and pure Cu film in pH 8.4 borate buffer solution were analyzed by electrochemical quartz crystal microbalance (EQCM) for gravimetry and bending beam method (BBM) for stress measurement. The mass loss of the multilayer film during anodic oxidation at 0.8 V (SHE) in the passive region was less than that of the pure Cu film. The comparison between current transients and mass changes during anodic oxidation has succeeded in separating the anodic current density into two partial current densities of oxide film growth, i_O^2-, and of Cu²⁺ dissolution through the passive film, i_Cu²⁺. As a result, in the case of the pure Cu film, the anodic current density was mainly due to i_Cu²⁺, while in the case of the multilayer film, i_Cu²⁺ was almost equal to i_O^2-. The compressive stress for the multilayer film was generated during anodic oxidation, while the tensile stress for the pure Cu film was generated.The mass loss of the multilayer film during cathodic reduction at a constant current density (i_c = −20 μA cm⁻²) was significantly less than that estimated from coulometry, suggesting that H₂O produced by cathodic reduction remained in the multilayer film. The compressive stress was generated during cathodic reduction of the multilayer film, which was ascribed to H₂O remained in the multilayer film.