Passivation oxide film on Nd-Fe-B permanent magnets in borate buffer solution by ellipsometry

The passivation of Nd-Fe-B permanent magnet was investigated in neutral borate solution at pH 8.4. The thickness of the passive oxide film on the magnets was measured by ellipsometry and the composition was estimated by glow discharge optical emission spectroscopy (GD-OES).The passivation of the magnets takes place in the potential range between −0.2 and 1.0 V vs. Ag/AgCl/Sat. KCl. In the potential range, current density decays to the lower than 10⁻⁶ A cm⁻² after potentiostatic oxidation for 1800 s. The passive oxide film growth is assumed to be optically simulated from a model with a homogeneous film with complex refractive index, N = 2.1 − j0.086. The thickness estimated from the refractive index linearly increases with potential from 3.6 nm at −0.2 V to 7.8 nm at 1.0 V. The passive film growth follows the ionic migration model under high electric field, i.e., the Cabrera-Mott growth model. The ionic conductivity estimated from the model is about κ = 1.7 × 10⁻¹⁶ Ω⁻¹ cm⁻¹. The passive oxide film is preferentially composed of iron oxide/hydroxide. Boron and neodymium are, respectively, concentrated at the surface of the oxide film and at the inner layer in the oxide film.     

Ellipsometry of passive oxide films on nickel in acidic sulfate solution

Nickel passive film has been studied in acidic sulfate solutions at pH 2.3 and 3.3 by ellipsometry. During anodic passivation followed by cathodic reduction, the roughness increases with dissolution of nickel, being indicated by gradual decrease of reflectance. However, the ellipsometric parameters, Ψ (arctan of relative amplitude ratio) and Δ (relative retardation of phase), are relatively insensitive to the roughness increase. From the change of Ψ and Δ, δΨ and δΔ, during the anodic passivation and reduction, thickness of the passive oxide film was estimated with assumption of refractive index of n_f = 2.3 of the film. The thickness estimated is a range between 1.4 and 1.7 nm in the passive potential region from 0.8 to 1.4 V vs. RHE, having a tendency of thickening with increase of potential. Cathodic reduction at constant potential induces a change of the oxide film to an oxide film with lower refractive index of n_f = 1.7, accompanied by thickening of the film about 30% more in the initial stage of reduction for 30 s. The gradual decrease of thickness takes place for the oxide with the lower refractive index in the latter stage. The potential change from the passive region to cathodic hydrogen evolution region may initially cause hydration of the passive oxide of NiO, i.e., NiO + H₂O = Ni(OH)₂, and during the latter stage of reduction, the hydrated nickel oxide gradually dissolves.     

The aging of the anodic oxide of titanium during potentiostatic condition by ellipsometry

The aging effect of the anodic oxide film on titanium under constant potential oxidation was investigated by 3-parameter (3-P) ellipsometry in 0.1 mol dm⁻³ sulfuric acid solution. The oxide film was initially formed by a potential sweep oxidation, where the film with a low refractive index grew at relatively high rate. From the low value of the refractive index, the oxide film is assumed to be a hydrated structure. After the sweep oxidation to 4.26 V vs. reversible hydrogen electrode, the constant potential oxidation was performed at a potential of 4.26 V to examine the aging effect of the hydrated oxide film by 3-P ellipsometry. It was found that the refractive index of the oxide film increased from 2.39 to 2.59 during the aging of the constant potential oxidation, and the thickness decreased. The increase of the refractive index and the decrease of thickness may be explained by conversion from the hydrated oxide to a dehydrated oxide during the aging.     

Growth kinetics and mechanism of the initial oxidation of Al-based Al-Mg alloys

The relationship between the growth kinetics and the local chemical states of Al, Mg and O ions in ultrathin (<3 nm) oxide films grown on Al-based Al-Mg substrates at T = 300-610 K was established by ellipsometry and XPS. At T ? 385 K, an Al-oxide film of near-limiting thickness (∼1 nm) is formed, which exhibits interfacial and bulk-like states for the Al cations. At T > 385 K, continued growth is realized by the preferential oxidation of interfacially segregated Mg, resulting in the sequential appearance of interfacial and bulk-like states for the Mg cations.     

Characterisation of fresh surface oxidation films formed on pure molten magnesium in different atmospheres

This paper examines the early stages of surface oxidation of liquid magnesium under argon, air, and air mixed with protective fluorine-bearing gases. Surface film characteristics such as morphology, thickness and composition are determined. In all cases except argon the film was locally uniform with no evidence of specific nuclei.In air, the film thickness was 15-150 nm. Under fluorine-bearing gas mixtures the surface film was a mixed fluoride and oxide and more even: 70-100 nm thick under SF₆ and 30-50 nm under 1,1,1,2-tetrafluoroethane. The latter had a substantially lower O:F ratio. Complete conversion of available fluorine into the film was indicated.     

Multicycle chronoammetry of RRDE in the investigation of the anodic oxide formation

The method of multicycle chronoammetry of RRDE makes it possible to obtain separately the partial currents of metal electrode ionization, anodic oxide formation and chemical oxide dissolution. The method is tested for Ag∣Ag₂O∣OH⁻(H₂O) system. In the range of low anodic potentials (0.48 ÷ 0.51 V) the process of active silver dissolution prevails; the phase formation current rapidly drops. At higher potentials (0.52 ÷ 0.53 V) the phase formation current prevails and noticeably exceeds the rate of the chemical oxide dissolution. The thickness of Ag₂O film rapidly increases; and the net phase formation current is close to 100%.     

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 °C

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i_c = −50 μA cm⁻² in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i_c = −50 μA cm⁻² or −2.5 mA cm⁻². The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively.The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu₂O layer is reduced to metallic Cu.     

Photo-luminescence from passive oxide films on nickel and chromium by photo-excitation of UV light

Photo-luminescence emission was measured from the thin passive oxide film on nickel and chromium under the in-situ condition in 0.1 kmol m⁻³ (M) sulfuric acid solution at pH 0.9 and neutral buffer solution of borate-boric acid mixture at pH 8.4 in order to obtain the insight of the electronic properties in the passive oxide film as thin as a few nm. The photo-luminescence induced by UV laser beam at 325 nm wavelength from nickel oxidized in both pH 0.9 sulfuric acid and pH 8.4 borate buffer solutions exhibited a broad spectrum feature with a peak at 400-420 nm. The energy of the peak wavelength from 400 to 420 nm is 2.95-3.10 eV which may correspond to the band-gap energy of the semiconduncting NiO. The photo-luminescence spectra from chromium oxidized in the sulfuric acid and neutral borate solutions had a peak at 400 nm and about 440 nm, respectively. These photo-emission from nickel and chromium oxidized is assumed to correspond to luminescence accompanied by recombination between excess electrons produced by UV light illumination in the conduction band and positive holes in the valence band. The broad tailing of the luminescence at longer wavelength side may represent high density of localized states originated in an amorphous nature of the passive oxides.     

Corrosion and corrosion inhibition of Cu-20%Fe alloy in sodium chloride solution

The electrochemical behavior of copper (Cu), iron (Fe) and Cu-20%Fe alloy was investigated in 1.0 M sodium chloride solution of pH 2. The effect of thiourea (TU) addition on the corrosion rate of the Cu-20%Fe electrode was also studied. Open-circuit potential measurements (OCP), polarization and electrochemical impedance spectroscopy (EIS) were used. The results showed that the corrosion rates of the three electrodes follow the sequence: Cu < Cu-20%Fe < Fe. Potentiostatic polarization of the Cu-20%Fe electrode in the range −0.70 V to −0.45 V (SCE), showed that iron dissolves selectively from the Cu-20%Fe electrode surface and the rate of the selective dissolution reaction depends on the applied potential. At anodic potential of −0.45 V, thiourea molecules adsorb at the alloy surface according to the Langmuir adsorption isotherm. Increasing thiourea concentration (up to 5 mM), decreases the selective dissolution reaction and the inhibition efficiency η reach 91%. At [TU] > 5 mM, the dissolution rate of the Cu-20%Fe electrode increases due to formation of soluble thiourea complexes. At cathodic (−0.6 V), the inhibition efficiency of thiourea decreases markedly owing to a decrease of the rate of the selective dissolution reaction and/or desorption of thiourea molecules. The results indicated that thiourea acts mainly as inhibitor of the selective dissolution reaction of the Cu-20%Fe electrode in chloride solution.     

The influence of the conditions of the ZrO2 passive film formation on its properties in 1 M NaOH

In this paper, results of the potentiodynamic-potentiostatic formation of a homogeneous, passive films of ZrO₂ onto a Zr electrode in 1 M NaOH solution at different potentials (2.0, 4.0, 6.0 and 8.0 V vs. SCE) are presented. The properties of such films were investigated by EIS measurements at different potentials. After fitting the EIS spectra by an appropriate equivalent circuit, the capacitance (C_pf) and resistance (R_pf) of these films were determined. All films were found to become insulators at the potentials equal and/or more positive than 2.0 V, with their thicknesses increasing linearly with the potential from about 7 nm at 2.0 V to about 20 nm at 8.0 V. In the potential range 0.8 V < E < 2.0 V a transition from a semiconducting to insulating behaviour has been recorded for all films (except for the one formed at 2.0 V). The donor densities (N_sc) for all films, as well as their flat band potentials (E_fb) and their thicknesses of the space charge layer (d_sc), were determined from the corresponding Mott-Schottky plots (MS) recorded in the potential range (0.0 V < E < 0.8 V), where all films behaved as n-type semiconductors.     

Influence of pre-treatment on the surface composition of Al-Zn alloys

The influences of pre-treatments on the composition of Al-Zn alloys, containing 0.6-1.9 at.%Zn, are investigated using scanning and transmission electron microscopies, glow discharge optical emission spectroscopy and ion beam analysis. Alkaline etching, anodic alkaline etching and electropolishing result in zinc enrichments, just beneath the oxide/hydroxide films on the alloy surfaces. The enriched alloy, about 4-5 nm thick, contains zinc in solid-solution with aluminium, up to about 18 at.%. The highest and lowest enrichments are produced by alkaline etching and electropolishing respectively. For a given pre-treatment, the enrichment increases with increase in zinc content of the bulk alloy.     

The effect of atmospheric corona treatment on AA1050 aluminium

The effect of atmospheric corona discharge on AA1050 aluminium surface was investigated using electrochemical polarization, SEM-EDX, FIB-SEM, and XPS. The corona treatment was performed with varying time (1, 5, and 15 min) in atmospheric air. A 200 nm oxide layer was generated on AA1050 after the 15 min air corona treatment. A significant reduction in anodic and cathodic reactivities was observed starting from 1 min exposure, which further decreased with prolonged exposure (15 min) and after delayed testing (after 30 days). The reduction in surface reactivity is due to the formation of thicker and denser oxide film.     

Photocurrent spectroscopy applied to the characterization of passive films on sputter-deposited Ti-Zr alloys

A photoelectrochemical investigation on thin (?13 nm) mixed oxides grown on sputter-deposited Ti-Zr alloys of different composition by air exposure and by anodizing (formation voltage, U_F = 4 V/SCE) was carried out. The experimental results showed that the optical band gap, , increases with increasing Zr content in both air formed and anodic films. Such behaviour is in agreement with the theoretical expectation based on the correlation between the band gap values of oxides and the difference of electronegativity of their constituents. The flat band potential of the mixed oxides was found to be almost independent on the Ti/Zr ratio into the film and more anodic with respect to those estimated for oxide grown on pure Zr. The semiconducting or insulating character of the investigated films was strongly influenced by the forming conditions and the alloy composition.     

Electrochemical and XPS studies and the potential scan rate dependent pitting corrosion behavior of Zircaloy-2 in 5% NaCl solution

Electrochemical studies of Zircaloy-2 in 5% NaCl solution were carried out using polarization and electrochemical impedance spectroscopy (EIS). Scan rate dependent pitting behavior of Zircaloy-2 was observed when polarization experiments were carried out at different scan rates (5 mV/min, 50 mV/min and 500 mV/min). Polarization resistance, double layer capacitance, and the thickness of passive film were calculated from the EIS study. The slope of the Bode plot in the capacitive region showed non-ideal behaviour, suggesting formation of pits. A distribution of chloride concentration was seen at the surface of the electrode when the test solution was sampled from different parts of the sample surface and analyzed for chloride. Inclusion of chloride ions in the passive film was observed from the XPS study and the chloride concentration increases with the higher anodic polarization. The outermost layer of the passive film was rich in hydroxide and oxy-hydroxide. A bi-layer passive film structure on the alloy surface is proposed.     

Effects of pretreatment on the aluminium etch pit formation

The effect of chemical pretreatments on the electrochemical etching behavior of aluminium was investigated with the topographic studies of surface and the analysis of initial potential transients. Two-step pretreatments with H₃PO₄ and H₂SiF₆ result in a high density of pre-etch pits on aluminium surface by the incorporation of phosphate ion inside the oxide film and the removal of surface layer by aggressive fluorosilicic acid solution. It generates a high density of etch pits during electrochemical etching and results in the capacitance increase of etched Al electrode by expanding the surface area, up to 61.3 μF/cm² with the pretreatment solution of 0.5 M H₃PO₄ at 65 °C and 10 mM H₂SiF₆ at 45 °C.     

Electrochemical oxidation of binary copper-nickel alloys in cryolite melts

Anodic oxidation of copper, nickel and two copper-nickel alloys was studied in cryolite melts at 1000 °C. In an oxide-free melt, anodic dissolution of each material was observed, and the dissolution potential increases with the content of copper. SEM characterization of a Cu55-Ni45 alloy showed that nickel is selectively dissolved according to a de-alloying process. In an alumina-containing melt, a partial passivation occurs at the copper-containing electrodes, at potentials below the oxygen evolution potential. A passive film forms on the copper electrode, while on the nickel electrode no dense oxide layer develops. Copper-nickel alloys were found to form a mixed oxide layer. At higher potentials, the formation of oxygen bubbles on the electrodes results in a degradation of the passive films and a strong corrosion.     

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.     

Field crystallization of anodic niobia

Influences of electrolyte, pre-thermal treatment and substrate composition have been examined to elucidate the mechanism of field crystallization of anodic niobia formed on magnetron-sputtered niobium. The field crystallization occurs during anodizing at 100 V in 0.1 mol dm⁻³ ammonium pentaborate electrolyte at 333 K, with the crystalline oxide growing more rapidly than the amorphous oxide, resulting in petal-like defects. The nucleation of crystalline oxide is accelerated by pre-thermal treatment of the niobium at 523 K in air, while vacuum treatment hinders nucleation. Notably field-crystallization is also absent in 0.1 mol dm⁻³ phosphoric acid electrolyte or when anodizing Nb-10at.%N and Nb-29at.%W alloys in the ammonium pentaborate electrolyte. The behaviour is explained by the role of the air-formed oxide in providing nucleation sites for field crystallization at about 25% of the thickness of the subsequently formed anodic film, the location being due to the growth mechanism of the anodic oxide and the nature of crystal nuclei. Incorporation of tungsten, nitrogen and phosphorus species to this depth suppresses the field crystallization. However, boron species occupy a relatively shallow layer and are unable to affect the nucleation sites.     

Polypyrrole electrodeposited on copper from an aqueous phosphate solution: Corrosion protection properties

Highly adherent and homogenous polypyrrole films were electrodeposited at copper from a dihydrogen phosphate solution. The polypyrrole films were electrosynthesized in the overoxidized state by cycling the copper electrode from -0.4 to 1.8 V (SCE) in a pyrrole-containing phosphate solution. The growth of the polypyrrole films was facilitated by the initial oxidation of the copper electrode in the phosphate solution to generate a mixed copper-phosphate, copper oxide or hydroxide layer. This layer was sufficiently protective to inhibit further dissolution of the copper electrode and sufficiently conductive to enable the electropolymerization of pyrrole at the interface, and the generation of an adherent polypyrrole film.Potentiodynamic polarization measurements, Tafel analyses and open-circuit potential data revealed that the polypyrrole coating effectively protects the copper substrate from corrosion in a chloride solution. However, the corrosion protection properties were reduced with longer immersion times.     

Oxide film formation on zinc in borate solutions under open circuit

The open circuit potentials of Zn electrode were followed as a function of time in different concentration of Na₂B₄O₇ solution until steady-state, E_st., values were attained. The potential shifts immediately towards positive values, indicating film thickening and repair. The rate of oxide film thickening was determined from the linear relationship between the open circuit potential, E, of the Zn electrode and the logarithm of immersion time t as E = a₁ + b₁ log t. The liner plots consist of two segments indicating the duplex nature of the formed oxide film on the Zn surface. The final steady- state potential, E_st., varied with the logarithm of molar concentration of Na₂B₄O₇ solution according to: E_st. = a₂ − b₂ log C_Na2B4O7. The effect of rising pH and temperature was also studied. It was found that the rising of pH and temperature of the solution affect on the rate of oxide film thickening and the final steady- state potential.