Effect of ambient air pressure on the oxidation kinetics of Fe-6 at.% Si alloy

Surface oxidation of Fe-6 at.% Si alloy was investigated during annealing in ambient air of various pressures with simultaneous isothermal resistivity registrations. Measurements have been done in the temperature range 500-540 °C. Chemical and phase compositions of the samples were analyzed using X-ray photoelectron spectroscopy, conversion electron Mössbauer spectroscopy (CEMS), transmission Mössbauer spectroscopy (TMS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Phase analysis showed that during isothermal resistivity measurement in a low pressure air 100 mbar a protective film of hematite α-Fe₂O₃ was formed on the surface of FeSi substrate. By decreasing pressure to 10⁻² mbar the time dependence of the resistivity exhibits an increase due to the transformation of hematite to magnetite Fe₃O₄. The activation energy for this transformation is 115 ± 5 kJ/mol. By regressive increasing the pressure back from 10⁻² to 100 mbar a non-protective oxide scale of hematite + magnetite was formed. The results were interpreted in the light of the iron-oxygen phase diagram.     

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.     

EQCN study of anodic dissolution and surface oxide film formation at Au in the presence of Cl or Br ions: A model process for corrosion studies

The anodic dissolution of an Au electrode and associated thin-layer oxide film formation in aq. H₂SO₄ in the presence of Cl⁻ or Br⁻ ions at various concentrations provides a model process for metal corrosion. In the present work such processes were investigated using cyclic voltammetry and chronoamperometry, with complementary nanogravimetry measurements using the EQCN. The results clearly indicate that in 0.5 M H₂SO₄ electrolyte, containing 1 mM Br⁻ or Cl⁻, Au dissolves over the potential range 1.0 - 1.45 V(RHE) through a 3e oxidation process involving Au complex-ion formation that can be followed in situ by means of UV spectroscopy. The linear relationship between mass changes and reciprocal square-root of sweep-rate and between anodic currents in cyclic voltammetry at ca. 1.20 V for Br⁻ (1.39 V for Cl⁻) and square-root of sweep-rate/or electrode rotation rate indicated quantitatively that the dissolution process is diffusion-controlled. It was interesting to find that electrode rotation in the presence of Cl⁻ ions has little effect on the anodic formation of surface oxide, while, on the contrary, with Br⁻ ions present, currents for oxide film reduction are not observed at rotation rates > ca. 400 rpm.     

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.     

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%.     

Porous anodic oxides on titanium and on a Ti-W alloy

The growth of a nanoporous anodic oxide on titanium and a Ti-20 at.% W alloy, both deposited by magnetron sputtering, in a glycerol/phosphate electrolyte at 453 K is reported. The oxide formed on titanium is a mixture of amorphous titania and anatase. However, that on the alloy is amorphous only and forms at increased efficiency, about 27%. The amorphous structure is considered to be stabilized by incorporated units of WO₃, which are distributed uniformly throughout the anodic film. The growth of the porous oxides is suggested to be associated with loss of film species at the film/electrolyte interface at the base of pores, with new oxide forming exclusively at the metal/film interface by inward migration of O²⁻ ions.     

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.     

Fabrication, microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films

a-CN_x/TiN multilayer films were deposited onto high-speed steel substrates by pulsed laser ablation of graphite and Ti target alternately in nitrogen gas. The composition, morphology and microstructure of the films were characterized by energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The tribological properties of the films in humid air were investigated using a ball-on-disk tribometer. The multilayer films consist of crystalline TiN, metallic Ti and amorphous CN_x (a-CN_x). With an increase in thickness ratio of CN_x to bilayer, the hardness of multilayer film decreases, friction coefficient decreases from 0.26 to 0.135, and wear rate increases. The film with thickness ratio of CN_x to bilayer of 0.47 exhibits a maximum hardness of 30 GPa and excellent wear rate of 2.5 × 10^− 7 mm³ N^− 1 m^− 1. The formation of tribo-layer was observed at contact area of Si₃N₄ ball. The film undergoes the combined wear mechanism of abrasion wear and adhesion wear.     

Anodic oxidation of InAlAs

The anodic oxidation of InAlAs is investigated by transmission electron microscopy, Rutherford backscattering spectroscopy and medium energy ion scattering in order to elucidate the mechanism of oxide growth. For this purpose, anodizing was carried out at 5 mA cm⁻² in 0.1 M sodium tungstate and 0.1 M ammonium pentaborate electrolytes at 293 K, which results in relatively efficient film growth over an initial voltage increment of about 70 V. In this period, an amorphous oxide develops with a formation ratio of 2.0 ± 0.2 nm V⁻¹. The film consists mainly of an outer layer of In₂O₃ and an inner layer of units of In₂O₃, Al₂O₃ and As₂O₃, the former representing about 14% of the film. There is suggestion of a fine, intermediate layer containing units of In₂O₃ and Al₂O₃ only. The layering correlates with the bond energies of the cation and oxygen species in the oxide and hence their relative migration rates. Further, for films formed in tungstate electrolyte, tungsten species are incorporated into the outer 40% of the film. Bubbles of oxygen gas are present in the film, probably developed within the In₂O₃ layer. At higher voltages, the film undergoes breakdown, with resulting major changes in the film morphology.     

Optimization of anodic layer properties on aluminium in mixed oxalic/sulphuric acid bath using statistical experimental methods

The properties of oxide layer obtained on aluminium in mixed electrolytes of oxalic acid-sulphuric acid are optimized using experimental design. For this purpose, a four variables Doehlert design (bath temperature, anodic current density, sulphuric acid and oxalic acid concentrations), was achieved. In order to maximize the growth rate and the microhardness of the anodic oxide layer and to minimize in the same time their chemical and abrasion resistances, a multicriteria optimization using desirability function was conducted. Dissolution rate of the oxide in phospho-chromic acid solution (ASTM B 680-80) was used to express its chemical resistance.Under the determined optimal anodizing conditions (C_ox = 12.6 g L^− 1, 10 °C, 2.6 A dm^− 2, C_sul = 183.6 g L^− 1), the estimated response values were 0.73 μm min^− 1, 4.38 g m^− 2 min^− 1, 481 Hv and 53.3 g m^− 2 for growth rate, dissolution rate, microhardness and weight loss after abrasion respectively. The higher abrasion and chemical resistances of the optimum anodic layer can be correlated with its morphology revealed by AFM and SEM observations.     

A SERS investigation of the electrodeposition of Au in a phosphate solution

The spectroelectrochemical behaviour of cyanide and phosphate ions adsorbed on a Au electrode during electrodeposition and corrosion in a KAu(CN)₂ phosphate bath was studied by in situ SERS (Surface Enhanced Raman Spectroscopy) and cyclic voltammetry. SERS spectra exhibiting features corresponding to CN⁻ and PO₄⁻ vibrations were recorded under potentiostatic control in an interval from − 1600 to + 1500 mV vs. Ag/AgCl. Surface CN⁻ species are the dominating ones under both cathodic and anodic polarisations. As far as the phosphate vibrations are concerned, bands related to PO₄⁻ are visible in both cathodic and anodic conditions. A fluorescence background was evident in the potential range − 1300 ÷ + 1300 mV. At cathodic potentials phosphate ion adsorption on electrode surface prevails over cyanide for potentials more cathodic than − 1000 mV. At − 700 mV a discontinuity is noticed in the Stark tuning of CN⁻, probably due to a change of Au(CN)₂⁻ adsorption mechanism. At anodic potentials bands due to cyanide oxidation could be observed.     

Microstructure, mechanical and wear properties of laser processed SiC particle reinforced coatings on titanium

Laser processing of Ti-SiC composite coating on titanium was carried out to improve wear resistance using Laser Engineered Net Shaping (LENS™) — a commercial rapid prototyping technology. During the coating process a Nd:YAG laser was used to create small liquid metal pool on the surface of Ti substrate in to which SiC powder was injected to create Ti-SiC metal matrix composite layer. The composite layers were characterized using X-ray diffraction, scanning and transmission electron microscopy equipped with fine probe chemical analysis. Laser parameters were found to have strong influence on the dissolution of SiC, leading to the formation of TiSi₂, Ti₅Si₃ and TiC with a large amount of SiC on the surface. Detailed matrix microstructural analysis showed the formation of non-stoichiometric compounds and TiSi₂ in the matrix due to non-equilibrium rapid solidification during laser processing. The average Young's modulus of the composite coatings was found to be in the range of 602 and 757 GPa. Under dry sliding conditions, a considerable increase in wear resistance was observed, i.e., 5.91 × 10^− 4 mm³/Nm for the SiC reinforced coatings and 1.3 × 10⁻³ mm³/Nm for the Ti substrate at identical test conditions.     

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.     

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.     

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.     

Lanthanum silicate thin films for SOFC electrolytes synthesized by magnetron sputtering and subsequent annealing

Thin films of La and Si with Si/(La + Si) atomic ratios ranging from 0.36 to 0.44 were produced by magnetron sputtering in pure Ar. For all compositions, the apatite-like La_9.33Si₆O₂₆ phase was formed during annealing in air at 900 °C. A preferential orientation was developed during annealing of the films with higher silicon content while formation of oxide impurities was detected for the films with less silicon. Silicon segregation to the thin film/substrate interface was observed after annealing for thin films with higher Si/(La + Si) atomic ratios. The higher ionic conductivity values were obtained with the films with lower silicon content (2.81 × 10^− 3 Scm^− 1 at 800 °C for the film with Si/(La + Si) atomic ratio of 0.36). This film presented the lower activation energy E_a (0.94 eV).     

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.     

Environmental factors affecting the corrosion behavior of reinforcing steel II. Role of some anions in the initiation and inhibition of pitting corrosion of steel in Ca(OH)2 solutions

Potential-time curves are constructed for the steel electrode in naturally aerated Ca(OH)₂ solutions simulating the corrosion behavior in concrete. Cl⁻ and SO₄²⁻ ions cause the destruction of passivity and initiation of pitting corrosion. The rate of oxide film growth by Ca(OH)₂ and oxide film destruction by Cl⁻ and SO₄²⁻ ions follows a direct logarithmic law as evident from the linear relationships between the open-circuit potential and the logarithm of immersion time. Chromate, phosphate, nitrite, tungstate and molybdate ions inhibit the pitting corrosion of steel. The rate of oxide film healing and thickening increases with their concentrations. In presence of constant inhibitor concentration, the efficiency of pitting inhibition increases in the order: (weak) CrO₄²⁻ < HPO₄²⁻ < NO₂⁻ < WO₄²⁻ < MoO₄²⁻ (strong).     

Characteristics of copper oxide films deposited by PBII&D

Copper oxide films were deposited by plasma based ion implantation and deposition using a copper antenna as rf sputtering ion source. A gas mixture of Ar + O₂ was used as working gas. During the process, copper that was sputtered from the rf antenna reacted with oxygen and was deposited on a silicon substrate. The composition and the chemical state of the deposited films were analyzed by XPS. The structure of the films was detected by XRD. It is observed that Cu₂O film has been prepared on the Si substrate. It is found that the microstructure of the deposited film is amorphous for the applied voltage of − 5 kV. The surface layer of the deposited films is CuO. This is because the surface layer absorbs the oxygen from ambient air after the treated sample was removed from the vacuum chamber. An appropriate applied voltage, 2 kV under the present conditions, brings the lowest resistance. It is also seen that the maximum absorbance of the deposited films moves to a lower wavelength with increased applied voltage.     

Formation of poorly crystalline iron monosulfides: Surface redox reactions on high purity iron, spectroelectrochemical studies

In the use of iron for reductive dehalogenation of chlorinated solvents in ground water, due to presence of sulfate-reducing bacteria the formation of hydrogen sulfide is expected. To simulate those processes the interface between 99.99% pure iron and 0.1 M NaHCO₃ deoxygenated solution with 3.1 × 10⁻⁵-7.8 × 10⁻³ M Na₂S · 9H₂O added was studied. The surface processes were characterised by the in situ normal Raman spectroscopy (NRS) and ex situ techniques; X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The open circuit potential (OCP) was monitored during in situ NRS measurements, and potentiodynamic anodic polarization measurements were carried out to reveal electrochemical behaviour of iron electrode.Open circuit potential-time transients indicated that the native oxide is unstable in deaerated bicarbonate solution and undergoes reductive dissolution (i.e. autoreduction) leaving the metallic Fe covered by Fe(OH)₂, adsorbed OH⁻, and patches of ‘magnetite-like’ oxide. Immediately upon injection of the Na₂S-solution the iron interface undergoes complex redox surface processes and a poorly crystalline FeS film forms. Potentiodynamic anodic polarization measurements indicated a mechanical breakdown of the FeS film. The origin and initiation of this breakdown process is not clear but is probably a result of internal stress developed during film growth. Based on surface studies supported by electrochemical measurements, a conceptual model for the complex redox processes occurring at the iron interface is proposed. This model describes the structural development of a poorly crystalline FeS, which breaks down, allowing further dissolution of the Fe and formation of FeOOH at the interface. Simultaneously and despite the existence of thick layer of FeS the entrance of hydrogen was evident as the typical hydrogen cracks in bulk of the iron material. This work shed the light on the complexity of the iron/sulfide solution interface, this knowledge is important to understand the kinetic of reduction of organic groundwater contaminants.