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.     

A simple model for the oxidation of carbon-containing composites

The isothermal oxidation mechanism of the carbon-containing composites has been investigated based on the experimental data reported in the literature. The results showed that the oxidation kinetics was affected not only by temperature and time but also by carbon content and the sample shape. For the oxidation kinetics, a series of quantitative kinetic models have been developed based on the controlling step. In this model, the effects of carbon content, sample size and temperature on the reaction fraction have been especially discussed. Incorporation of the experimental data into the new model indicates that a good agreement has been reached.     

Adsorption of sodium dodecyl sulfate and sodium dodecyl phosphate at the surface of aluminium oxide studied with AFM

Within the framework of water-based aluminium pigments the difference in inhibition offered by the adsorption of sodium dodecyl sulfate (SDS) and sodium dodecyl phosphate (SDP) was studied by atomic force microscopy (AFM). While SDS did not show strong adsorption on aluminium oxide, SDP adsorbed strongly forming bilayers which patches did not change noteworthy over several hours of SDP exposure, indicating irreversible binding to the surface. Quantization of the surface coverage of the adsorbed SDP revealed that only 63% coverage was achieved, which shows surprisingly that a complete coverage is not necessary to inhibit oxidation of aluminium pigment particles.     

Electrochemical corrosion of X65 pipe steel in oil/water emulsion

The electrochemical corrosion behavior of X65 pipeline steel in the simulated oil/water emulsion was investigated under controlled hydrodynamic and electrochemical conditions by rotating disk electrode technique. Results demonstrated that mass-transfer of oxygen plays a significant role in the cathodic process of steel in both oil-free and oil-containing solutions. Electrode rotation accelerates the oxygen diffusion and thus the cathodic reduction. The higher limiting diffusive current density measured in oil-containing solution is due to the elevated solubility of oxygen in oil/water emulsion. The anodic current density decreases with the increase of electrode rotating speed, which is attributed to the accelerated oxygen diffusion and reduction, enhancing the steel oxidation. Addition of oil decreases the anodic dissolution of steel due to the formation of a layer of oily phase on steel surface, increasing the reaction activation energy. The steel electrode becomes more active at the elevated temperature, indicating that the enhanced formation of oxide scale is not sufficiently enough to offset the effect resulting from the enhanced anodic dissolution reaction kinetics. The corrosion reaction mechanism is changed upon oil addition, and the interfacial reaction is activation-controlled, rather than mass-transfer controlled. When sand particles are added in oil/water emulsion, there is a significant increase of corrosion of the steel. The presence of sands in the flowing slurry would impact and damage the oxide film and oily film formed on the steel surface, exposing the bare steel to the corrosive solution.     

Continuous and cyclic oxidation of T91 ferritic steel under steam

The oxidation behaviour of T91 ferritic steel in steam has been studied under isothermal and non-isothermal conditions within a temperature range between 575 and 700 °C. Isothermal treatments resulted in parabolic oxidation kinetics. Three clearly defined oxide layers constituted the oxide scales. The innermost layer was a (Fe,Cr)₃O₄. The intermediate layer was porous magnetite (Fe₃O₄) followed by a compact thinner layer of hematite (Fe₂O₃). Under non-isothermal conditions the oxide scales were irregular and evidently cracked. An increase of the oxidation temperature produces an acceleration of the oxidation process, causing an increase of the oxide scale thickness that depends on the temperature increase and the exposure time.     

Corrosion stability of ferritic stainless steels for solid oxide electrolyser cell interconnects

Long-term oxidation behaviour of eight ferritic steels with 20-29 wt.% chromium (F 20 T, TUS 220 M, AL 453, Crofer 22 APU, Crofer 22 H, Sanergy HT, E-Brite and AL 29-4C) has been studied. The samples were cut into square coupons, ground and annealed for 140-1000 h at 1173 K in flowing, wet hydrogen, air and pure oxygen. The reaction kinetics was followed by mass increase of individual samples over time. Parabolic rate law was observed for most measurements. The respective rate constants have been evaluated and compared. The chemical composition of the oxide scale was investigated by XRD and SEM/EDXS. The major constituent is chromium oxide. Other oxides, such as (Mn, Cr)₃O₄, MnTiO₃, SiO₂ or Al₂O₃, are also present in different amounts depending on the chemical composition of the steel. The oxidation rate increases with increasing oxygen partial pressure and decreasing chromium concentration. Chromium diffusion coefficients in Cr₂O₃ and parabolic rate constants are compared. The reaction mechanism for the chromia formation is suggested. The results are discussed with respect to the applications of the steels in a working solid oxide electrolyser cell stack. Furthermore, suggestions for the development of a superior alloy composition are given.     

Iron oxidation kinetics study by using infrared spectral emissivity measurements below 570 °C

The oxidation kinetics of iron below 570 °C is investigated through the dependence of the spectral emissivity on the surface oxidation state. Using the theory of radiative effects of thin films, the oxide scale thickness is obtained as a function of time. A parabolic growth has been observed in all the cases, and applying Wagner’s theory, the oxidation parabolic rate constants have been calculated at four temperatures. The temperature dependence of these results has additionally been used to obtain the activation energy of the oxidation process in iron. The parabolic rate constants and activation energy values are in good agreement with the theoretical predictions, and this suggests that the lattice diffusion mechanisms for the high temperature magnetite growth also occur until 400 °C. The experimental results are also useful to test the applicability of emissivity measurements for in situ oxidation kinetics studies in the spectral range where the scales are optically thin.     

Selective de-alloying of NiTi by oxochloridation

The systematic modification of a nickel–titanium-alloy by annealing in a complex gas atmosphere was investigated. A mixture of HCl and H₂O in inert argon was chosen. The reaction kinetics was investigated at 600 °C, 700 °C and 800 °C. The reaction kinetics displayed a significant dependence on the temperature. It was monitored by means of a thermogravimetric balance that showed a quasi-parabolic scale growth at 600 °C, a paralinear or so called Tedmon kinetic at 700 °C with a distinct weight maximum after about 35 h, and finally a linear evaporation kinetic at 800 °C. This behaviour is attributed to the concurrent reactions of oxidation, chloridation and evaporation of corrosion products. The kinetics of these reactions is different for the two alloying elements and with respect to the equiatomic composition they are coupled to each other. Cross sections prove that a stochiometric titanium depletion is achieved leading to the formation of a Ni₃Ti layer (d = 50 μm) which is in turn covered by a pure titanium oxide layer (d = 40 μm). The applicability of this technique for tailored surfaces with a high degree of biocompatibility is discussed.     

Formation and characterisation of a chromate conversion coating on AA6060 aluminium

AA6060-T6, an AlMg0.5Si0.4 model alloy and α-Al(Fe,Mn)Si phase electrodes have been subjected to chromate treatment in a commercial chromate-fluoride based solution. The coated surfaces were subsequently examined by use of field emission SEM, TEM, AES and electrochemical measurements in 0.1 M NaCl solution in order to study the effect of substrate microstructure on coating formation and properties. Non-uniform growth of the chromate conversion coating (CCC) on AA6060-T6 resulted in a porous morphology, with cracks extending down to the base metal. Poor coverage was particularly observed at the grain boundaries. The thickness of the CCC after completed treatment was about 150-200 nm, while significantly thinner films were formed on the α-Al(Fe,Mn)Si particles. AlMg0.5Si0.4 in the artificially aged (T6) condition exhibited a coating morphology similar to AA6060-T6, while CCC formation on homogenised AlMg0.5Si0.4 was characterised by growth of localised oxide particles and filaments, resulting in poor coverage. These observations indicated that precipitation of Mg₂Si particles due to heat treatment promoted nucleation of the CCC. Chromate treatment caused a significant reduction of cathodic activity on AA6060 during subsequent polarisation in chloride solution. This was attributed to rapid formation of a thin chromium oxide film on the α-Al(Fe,Mn)Si particles during the chromate treatment, resulting in significant cathodic passivation of the phase. Inhibition of the oxygen reduction reaction at cathodic intermetallic particles is suggested as an important factor contributing to the high performance of chromate pre-treatments on aluminium.     

Oxidation kinetics and mechanisms of Ni-base alloys in pressurised water reactor primary conditions: Influence of subsurface defects

Oxidation of Alloy 690 in PWR primary water conditions has been investigated, considering particularly the role played by subsurface structural defects. To simulate a defective surface state, Xe implantation has been set up on samples. Corrosion experiments were thereafter performed in a corrosion loop simulating the PWR medium with durations between 24 h and 1000 h. Microstructural observations and NRA measurements underlined the role played by defects on the crystallinity of the continuous oxide spinel layer, on the nucleation of Cr₂O₃ nodules and on the oxidation rate. The higher defects concentration seemed to modify the oxygen diffusion in the oxide scale.     

Electrochemical noise from oxygen reduction on stainless steel surfaces

Oxygen reduction occurring at the passive layer is probably the most important cathodic reaction involved in corrosion processes on stainless steel. Furthermore, the influence of the surface state on the oxygen reduction reaction is a key point for the understanding of the mechanism of localized corrosion on stainless steel. In this study, electrochemical noise measurements under cathodic polarization were carried out to obtain new information about this influence. It has been confirmed that the surface state of stainless steel plays a very important role in the kinetic of this cathodic reaction. Oxygen reduction kinetics was significantly reduced on passivated surfaces and improved on pre-reduced and ground surfaces. In addition, electrochemical current noise measurements allowed to differentiate between the electrochemical activity produced by the oxygen reduction reaction and that due to the reduction of the passive layer, in direct dependence on the characteristics of the different surface states investigated.     

Influence of cerium addition on the resistance to oxidation of AM50 alloy prepared by rapid solidification

The influence of various cerium (Ce) additions and starting temperature on the resistance to oxidation of AM50 alloy prepared by rapid solidification (RS, RS-AM50 alloy) has been investigated. The Ce addition has two opposite effects on the oxide scale. To the RS-alloy, the beneficial effect outweighs the detrimental one. However, when the alloy was prepared by slow solidification at the normal cooling rate (SS, SS-AM50 alloy), the detrimental effect was dominant. The improvement of oxide scale is closely related to the adherence of metal/oxide and tightness of oxide scale of the alloy. In addition, the reaction rate at the surface increased with starting temperature, which finally results in the formation of a protective oxide scale.     

Corrosion behavior of 9-12% Cr ferritic-martensitic steels in supercritical water

As important structural materials for advanced power plants, the corrosion of 9-12% Cr ferritic-martensitic steels exposed to both high-temperature water and supercritical water (SCW) was studied using a variety of characterization techniques. Exposure temperature and time showed significant effects on the surface morphologies, oxide scale thickness, and oxide constituents. The steels approximately followed near-parabolic oxidation kinetics in the SCW conditions. The inner spinel layer was found to be porous with a size of tens of nanometers independent upon the exposure temperature and time. High temperature accelerated the formation of a large amount of pores in the outer magnetite layer.     

Chromia layer growth on a Ni-based superalloy: Sub-parabolic kinetics and the role of titanium

Oxidation of the Ni-based superalloy RR1000 has been undertaken in air over the temperature range 600–900 °C for times up to 5000 h. The surface oxide consisted of a protective Ti-doped chromia layer but with rutile forming on its outer surface. Sub-surface oxidation of Al and Ti also occurred. The thickening kinetics of the chromia layer were sub-parabolic with initial rates around two orders of magnitude higher than expected for Ti-free chromia. This enhancement and the sub-parabolic kinetics are accounted for by Ti-doping of the chromia layer. Over time the enhancement reduced because of Ti-depletion in the alloy.     

Effect of oxide film on oxygen reduction current for the platinum-cobalt alloy electrodes in PEFC

Effect of surface oxide on Pt-Co alloy electrodes on the oxygen reduction reaction (ORR) was investigated in 0.5 M sulfuric acid solution by electrochemistry, ellipsometry, laser Raman scattering spectroscopy, and XPS. The oxide as thick as 1-2 nm increases the overpotential of ORR and falls down efficiency of PEFC. The thickness of the oxide films is precisely determined by ellipsometry. The oxide film 1.9 nm thick was formed on Pt-50 mol% Co electrode by constant potential oxidation at 1.20 V and the film 1.5 nm thick remains on the electrode at 0.6 V at which ORR already starts. The remaining oxide decreases the current density of ORR and increases the overpotential. On pure Pt electrode, the similar influence of the oxide film was observed.     

Kinetics inversion in isothermal oxidation of uncoated WC-based carbides between 450 and 800 °C

Oxidation of uncoated WC-based carbides (hard metals) has been investigated between 450 and 800 °C. An anomalous change in the oxidation behaviour has been found in the temperature range between 528 and 630 °C. Instead of the normal increase of the oxidation rates when the temperature increases, a kinetics inversion is produced: an anomalous decrease of the oxidation rates has been observed in this temperature range. Furthermore, this anomalous behaviour produces an important change in the activation energy. At temperatures below the anomaly (below 528 °C), an activation energy of 119 ± 8 kJ/mol has been found, whereas above the anomaly (above 630 °C), an activation energy of 208 ± 8 kJ/mol has been found. This anomalous temperature dependence of the oxidation behaviour can be related to a higher amount of complex oxide CoWO₄ formed on the oxide scale, and to the effect that this oxide produces in the oxidation kinetics of the other oxides.     

Adsorption and inhibitive properties of some new Mannich bases of Isatin derivatives on corrosion of mild steel in acidic media

Adsorption of four derivatives of piperidinylmethylindoline-2-one on mild steel surface in 1 M HCl solution and its corrosion inhibition properties has been studied by a series of techniques, such as polarization, electrochemical impedance spectroscopy (EIS), weight loss and quantum chemical calculation methods. The values of activation energy (E_a) for mild steel corrosion and various thermodynamic parameters were calculated and discussed. Potentiodynamic polarization measurements showed that all inhibitors are mixed type. The degree of surface coverage was determined by using weight loss measurements and it was found that adsorption process of studied inhibitors on mild steel surface obeys Langmuir adsorption isotherm.     

Comparison between the oxidation of iron in oxygen and in steam at 650–750 °C

Oxidation of iron was investigated in oxygen and in steam at 650–750 °C by TGA, OM, SEM, and XRD. In oxygen, parabolic kinetics and multilayer oxide scales composed of typical three iron oxides were observed. Noticeably, the scale adhesion was very poor. In steam, linear-parabolic shape kinetics and multilayer oxide scales with fewer pores were found. As indicated by Pt marking, inward-growing process in steam was considered to result in the improvement of scale contact. Based on the experimental results, scaling mechanism of iron in steam was discussed.     

Electropolishing effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

The corrosion rate of electropolished 304 stainless steel surfaces (UNS S30400) is found to be lower by more than a factor of three relative to that determined previously for machined surfaces in mildly alkaline, hydrogenated water at 260 °C. This favorable result is attributed to significant changes in nanocrystallinity of the corrosion oxide layer caused by the removal of surface microstrain, which had been imparted during the machining process. In the absence of microstrain, a low-porosity, protective, corrosion layer forms that is composed of extremely small and uniformly-sized spinel oxide crystals. Application of scanning electron microscopy (FEG-SEM), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) in conjunction with ion milling and target factor analyses, found the corrosion layer to consist of micrometer-size crystals of a ferrite-based spinel oxide (non-protective) over-laying nanometer-size crystals of a chromite-based spinel oxide (protective). Composition of both phases is unchanged from that previously observed on corroded, machined surfaces and is representative of solvus phases in the immiscible Fe(Fe_1−nCr_n)₂O₄ spinel binary. The smaller size (10 vs. 26 nm) and greater surface density (∼10,000 vs. 835 μm⁻²) of the chromite-based crystals relative to those formed on machined (i.e., cold-worked) surfaces, however, is consistent with the absence of preferred high energy nucleation sites on strain-free surfaces. Therefore, electropolishing, which removes surface microstrain induced by cold-working, represents a preferred reference surface condition.     

The effect of oxidation on the corrosion resistance and mechanical properties of a Zr-based metallic glass

The oxidation kinetics of the Zr₆₄Cu₁₆Ni₁₀Al₁₀ bulk metallic glass (BMG) roughly follows a two-stage rate law at both 433 and 593 K in air. An oxide film of 940 nm can be formed by oxidation at 593 K, which is ZrO₂-enriched but Cu-depleted on the outer surface. The oxide film leads to a superior passivity in 0.5 M NaCl and great corrosion resistance improvements in other solutions. The oxidation effect on mechanical properties were characterized by nanoindentation, wedge indentation and compression tests. The Zr-based BMG still keeps the amorphous nature and its good mechanical properties are retained after oxidation.