Pourbaix diagrams for chromium in concentrated aqueous lithium bromide solutions at 25 °C

Pourbaix diagrams (electrode potential-pH diagrams) for Cr-Br⁻-H₂O system at 25 °C were developed in 400, 700, 850, and 992 g/L (4.61, 8.06, 9.79, and 11.42 M) LiBr solutions, common concentrations in different parts of absorption devices. The diagrams were compared with the simple Cr-H₂O system at 25 °C. Equilibria for the Cr-Br⁻-H₂O system at 25 °C were determined for bromide ion activities of 15.61, 194.77, 650.06, and 2042.65, which corresponded to the 400, 700, 850, and 992 g/L LiBr solutions, respectively. Activities of all the dissolved species containing chromium were plotted for 10⁻⁶, 10⁻⁴, 10⁻², and 10⁰. Comparison of the simple Cr-H₂O system at 25 °C with the diagrams for Cr-Br⁻-H₂O system at 25 °C showed that the dominant aqueous Cr(III) species in acid solutions was Cr⁺³ for Br⁻ activities of 15.61, 194.77, and 650.06, whereas it was CrBr⁺² for Br^- activity of 2042.65. Aqueous CrBr⁺² formed at a Br⁻ activity higher than 943.05. The chromium solubility range in the acid area of the diagrams extended slightly to higher pH values with increasing Br⁻ activity and decreasing water activity, as a result of destabilization of Cr₂O₃.     

New insight in the behaviour of Co-H2O system at 25-150 °C, based on revised Pourbaix diagrams

Revised Pourbaix diagrams (potential/pH diagrams) for the Co-H₂O system are presented at 25-150 °C using a new set of standard thermodynamic data in accordance with the recommended CODATA key values.     

Mass-balance and Eh-pH diagrams of Fe green rust in aqueous sulphated solution

The properties of a Fe^II-Fe^III mass-balance diagram are presented. Each compound is represented by a point P(x, R), where x=n_Fe^III/[n_Fe^II+n_Fe^III] is the ferric molar fraction and R=n_OH^-/[n_Fe^II+n_Fe^III] the number of mole of hydroxyl species necessary to precipitate one mole of iron in a given compound. If a chemical reaction leads to a given point P(x, R) in the diagram, the nature and relative abundance of the various iron species can be predicted by using simple rules that resemble those commonly used when studying binary and ternary phase diagrams. Reactions of oxidation of Fe^II species or coprecipitation reactions of Fe^II and Fe^III species are represented by different routes in the diagram. The evolution of the measured pH and redox potential E_h values during a controlled Fe^II oxidation experiment using sodium persulphate is explained by comparing the mass-balance and the E_h-pH Pourbaix diagrams. These values are also measured at the intersecting points of various routes and identical equilibrium conditions are often obtained. By displaying the involved chemical reactions, the Fe^II-Fe^III mass-balance diagram allows to understand the reaction path consequently followed in the E_h-pH Pourbaix diagram.     

Corrosion of niobium in sulphuric and hydrochloric acid solutions at 75 and 95 °C

New Pourbaix diagrams were calculated at 25, 75 and 95 °C for the Nb-H₂O system. The species and were considered. Potentiodynamic polarization and mass loss experiments (14 days) were conducted in concentrated H₂SO₄ (20, 40 and 80 wt%) and HCl (20 and 38 wt%) solutions at 75 and 95 °C. Nb forms a metastable pentoxide (Nb₂O₅) in H₂SO₄ and HCl solutions which dissolves as . Corrosion rates decrease between the 40% and the 80% H₂SO₄ solutions. SEM micrographs show generalized pitting in the 20% and 40% H₂SO₄ solutions. Mass loss corrosion rates did not exceed 306 μm/yr. Corrosion rates estimated by Tafel extrapolation were within two orders of magnitude of those measured by mass loss and it is shown that this finding is consistent with the thickening of the oxide.     

Corrosion behaviour of sensitized and unsensitized Alloy 900 (UNS 1.4462) in concentrated aqueous lithium bromide solutions at different temperatures

Duplex stainless steels can undergo microstructural changes if they are heated improperly. When that happens, duplex stainless steels are sensitized and intermetallic phases appear. The high Chromium and Molybdenum content promotes the formation of secondary phases as a consequence of the heat treatment. These secondary phases, which are rich in alloying elements, such as Cr and Mo, deplete these elements from the neighbouring phases, leading to a reduction in corrosion resistance. In order to study the influence of the secondary phases on the corrosion parameters, samples of duplex stainless steel, Alloy 900 (UNS 1.4462), have been heated in argon atmosphere at 825 °C for 1 h. The corrosion behaviour of sensitized and unsensitized Alloy 900 has been analyzed in a concentrated aqueous lithium bromide (LiBr) solution of 992 g/L by means of cyclic potentiodynamic curves. Secondary phase presence reduces the pitting potential value of Alloy 900. Besides, the pitting potential decreases with temperature. On the other hand, the corrosion potential and open circuit potential values increase with temperature and sensitization.     

Carburization of W- and Re-rich Ni-based alloys in impure helium at 1000 °C

The surface and microstructure stability of experimental W- and Re-rich Ni-based alloys in an impure-helium environment containing only CO and CO₂ as impurities (ppm level) have been investigated at 1000 °C. All the alloys carburized during 50 h of exposure, and, depending on the alloy composition, different carbides of the type M₆C, M₇C₃ and M₂₃C₆ formed on the alloy surface, in grain interiors and at grain boundaries. Microprobe analysis and Calphad-based calculations indicated that the chromium carbides (particularly Cr₂₃C₆) were enriched by rhenium. Extended exposure (225 h) led to the disappearance of surface transient carbides and the growth of surface oxide Cr₂O₃ occurred.     

Galvanic corrosion of titanium coupled to welded titanium in LiBr solutions at different temperatures

The galvanic corrosion generated between the titanium-welded titanium pair has been studied in heavy brine LiBr solutions at 25, 50 and 100 °C under open circuit conditions using a zero-resistance ammeter (ZRA). The results showed that welded titanium was the anode of the pair, so that its corrosion resistance decreases due to the galvanic effect. However, the extremely low galvanic current densities registered by the pair reveal the poor severity of the coupling under the studied conditions. Furthermore, it was observed that the electrodes were in the passive state, increasing the probability of localized corrosion with temperature.     

Oxidation of Cr2AlC at 1300 °C in air

High purity, dense Cr₂AlC compounds were synthesized via a powder metallurgical route, and their oxidation behavior was investigated at 1300 °C in air for up to 336 h. A thin external oxide layer formed, which consisted primarily of not Cr₂O₃ but Al₂O₃. Since Al was consumed to produce the Al₂O₃, Al-depletion and Cr-enrichment occurred underneath the Al₂O₃ layer. This led to the formation of a Cr₇C₃ layer containing voids. These grew during oxidation, eventually destroying the Cr₇C₃ layer formed on the unoxidized Cr₂AlC matrix.     

Oxidation kinetics of an Fe-31.8Mn-6.09Al-1.60Si-0.40C alloy at temperatures from 600 to 900 °C

An Fe-31.8Mn-6.09Al-1.60Si-0.40C alloy was subjected to thermogravimetric tests, in atmospheres of pure oxygen and synthetic air. The alloy showed good oxidation resistance, especially at 600 and 700 °C in air and at 600 °C in oxygen. Owing to autocorrelation identified in the results, kinetic data were analyzed by the statistical method of Cochrane and Orcutt. Parabolic kinetic behaviour was observed for the Fe-Mn-Al-Si-C alloy oxidation process in air at 600, 700 and 800 °C and in pure oxygen at 900 °C.     

Oxidation of single crystal PWA 1483 at 950 °C in flowing air

The oxidation behaviour of single crystal PWA 1483 at 950 °C was investigated by means of XRD, SEM and EDS. The parabolic oxidation behaviour, as defined by mass gain and the respective oxide layer thicknesses, is characterized by a parabolic rate constant of about 4 × 10⁻⁶ mg²/(cm⁴ × s) and the formation of a multi-layered oxide scale. An outer scale contains a Ti-bearing thin film composed of TiO₂ and NiTiO₃ but mostly Cr in Cr₂O₃ and (Ni/Co)Cr₂O₄ besides NiTaO₄. This outer scale is connected to a discontinuous layer of Al₂O₃ and an area of γ′-depletion within the base material.     

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.     

Glass–ceramic coatings on titanium alloys for high temperature oxidation protection: Oxidation kinetics and microstructure

A glass–ceramic coating is applied on Ti–6Al–4V alloy for oxidation protection at 800 °C. Its dynamic oxidation and microstructure evolution are investigated. The titanium alloy substrate is effectively protected by the glass–ceramic coating, of which the oxidation develops at constant rate. The linear relationship of oxidation is deduced dm/dt = Dρ(C₁ − C₂)/(bC′), and the diffusion coefficient of oxygen at 800 °C in glass is obtained. Oxygen diffusion through glass coating is the controlling step. After the initial firing, silicide interlayer forms between the glass coating and titanium alloy substrate, where the ratio of Ti/Si decreases after oxidation due to Si diffusion and Ti consumption.     

Effect of Dy on oxide scale adhesion of NiAl coatings at 1200 °C

The cyclic oxidation behaviour of β-NiAlDy coatings produced by electron beam physical vapour deposition (EB-PVD) was investigated. For the Dy-free NiAl coating, numerous voids developed at the Al₂O₃ scale/NiAl interface and sulfur was found to segregate at the void surfaces, leading to early spallation of the scale. The addition of Dy prevented sulfur segregation and void formation at the scale/NiAl interface. As a result, the scale grown on the NiAlDy coating remained adherent and no spallation occurred even after 400 h cyclic oxidation. The 0.05 at.% Dy doped coating revealed lower oxidation rate than the more Dy doped coatings.     

Effect of water vapor on the phase transformation of alumina grown on NiAl at 950 °C

This particular study includes the analysis of the effect of H₂O on promoting the phase transformation in thermally grown aluminum oxides formed on NiAl at 950 °C. Oxidation of NiAl is carried out at 950 °C in O₂ and O₂ + 15 vol.% H₂O. It is observed that transient alumina initially formed on NiAl transforms to stable α-alumina in the presence of water vapor which promotes the subject transformation and eventually results in a compact scale, offering superior oxidation resistance. Present study includes the analysis of θ to α-alumina transformation under the effect of temperature and environment.     

The effect of hydrogen sulphide on ammonium bisulphite when used as an oxygen scavenger in aqueous solutions

The effectiveness of ammonium bisulphite (ABS) as oxygen scavenger and the behaviour of H₂S in brine/ABS solutions are examined. Deionised water, 1 wt.% NaCl and 3.5 wt.% NaCl with different ABS concentrations are bubbled with H₂S gas, while the dissolved oxygen, sulphide, E_H and pH are measured. With the exception of natural seawater, ABS concentration much greater than 100 ppmw (parts per million by weight) is needed to completely scavenge dissolved oxygen in all the solutions considered. The reaction between ABS and H₂S leads to increase in sulphide. The implications of the results for environment assisted cracking of oil and gas production tubings are discussed.     

Short-term oxidation resistance and degradation of Cr2AlC coating on M38G superalloy at 900–1100 °C

High temperature oxidation behavior of the Cr₂AlC coating was investigated at 900–1100 °C. During the oxidation, a continuous Al₂O₃ scale formed, resulting in the improvement of the oxidation resistance of the substrate. Meanwhile, the oxidation induced depletion of Al within the Cr₂AlC coating resulted in the transformation of Cr₂AlC to Cr–C phases. Compared with bulk Cr₂AlC, the Cr₂AlC coating possessed similar oxidation behavior, but with higher oxidation rate. This is because a great number of columnar grain boundaries existed in the as-deposited coating, through which oxygen and nitrogen could diffuse inwardly, resulting in the internal oxidation and nitridation.     

The influence of microstructure on the oxidation of duplex stainless steels in simulated propane combustion products at 1000 °C

A low nickel Type S32101 duplex stainless steel has been oxidised in simulated industrial reheating conditions. The surfaces have been studied using optical microscopy, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Observations show that local breakaway regions (LBRs) form on the austenitic regions whereas thinner oxides are observed on the ferritic regions of the substrate. The reason proposed for these differences is the formation of a continuous oxide layer on the ferrite region and a discontinuous layer on the austenitic region during the early stages of oxidation. The chemical composition of these LBRs have been shown to be oxide islands of iron and manganese and oxide craters of chromium rich oxides. The more protective regions consist of chromium and manganese rich oxides. A silica layer formed below the oxide which may be attributable to a slight enrichment of silicon in the ferritic regions or due to faster rates of diffusion in ferrite.     

Microstructure and oxidation behaviour of an AlSiY/NiCrAlYSi composite coating at 1150 °C

A composite coating consisting of an outer AlSiY layer and an inner NiCrAlYSi layer has been prepared by a two-step arc ion plating method. The isothermal and cyclic oxidation behaviour of the composite coating at 1150 °C, including the growth of oxide scale and the microstructure transformation of the coatings, have been investigated comparing with the reference coating, NiCrAlYSi. The results show enhanced oxidation performance of the composite coating, which is concerned with its abundant possession of β-NiAl phase reservoirs, providing it the long term healing capacity of re-growing the α-Al₂O₃ scale.     

Cyclic oxidation of Ti3AlC2 at 1000–1300 °C in air

The cyclic-oxidation behavior of Ti₃AlC₂ was investigated at 1000–1300 °C in air for up 40 cycles. It was revealed that Ti₃AlC₂ had excellent resistance to thermal cycling. The cyclic oxidation of Ti₃AlC₂ basically obeyed a parabolic law. In all cases, the scales were dense, resistant to spalling and highly stratified. The inner continuous α-Al₂O₃ layer was well adhesive, while the outermost layer changed from rutile TiO₂ at temperatures below 1100 °C to Al₂TiO₅ at 1200 and 1300 °C, respectively. At 1300 °C, a mechanical-keying structure of inner Al₂O₃ to the Ti₃AlC₂ substrate formed, which improved the resistance to scale-spallation.     

Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150 °C

The effect of γ-radiation on the kinetics of carbon steel corrosion has been investigated by characterizing the oxide films formed on steel coupons at 150 °C and at two pH values. Results show that continuous irradiation enhances surface oxide formation with the type of oxide formed dependant on the solution pH. For experiments at 150 °C and a [OH⁻] equivalent to that for pH_{25 °C} = 10.6, the surface oxide on carbon steel after γ-irradiation was non-porous and uniform, and no localized corrosion was observed. This oxide, however, appears to be susceptible to brittle fracture during cooling. Raman spectroscopy of the surface film indicates that it is a mixture of the phases of Fe₃O₄ and γ-Fe₂O₃. In contrast, at 150 °C with [OH⁻] equivalent to neutral pH_{25 °C}, metal dissolution is significant and the surface oxide film is very porous. Raman spectra show that this oxide film is also composed of a mixture of Fe₃O₄ and γ-Fe₂O_3. The results from this work combined with previously reported electrochemical studies of the same system as a function of pH and temperature can be used to deconvolute the effects of radiation, pH and temperature on the nature of the corrosion process.