Carburisation of ferritic Fe–Cr alloys by low carbon activity gases

Model Fe–Cr alloys were exposed to Ar–CO₂–H₂O gas mixtures at 650 and 800 °C. At equilibrium, these atmospheres are oxidising to the alloys, but decarburising (a_C ≈ 10⁻¹⁵ to 10⁻¹³). In addition to developing external oxide scales, however, the alloys also carburised. Carbon supersaturation at the scale/alloy interface relative to the gas reflects local equilibrium: a low oxygen potential corresponds to a high p_CO/p_CO2 ratio, and hence to a high carbon activity. Interfacial carbon activities calculated on the basis of scale–alloy equilibrium are shown to be in good agreement with measured carburisation rates and precipitate volume fractions, providing support for the validity of the thermodynamic model.     

Steam oxidation resistance of new 12%Cr steels: Comparison with some other ferritic steels

The oxidation resistance in pure steam at the 600-650 °C temperature range of a newly developed 12%Cr steel has been investigated for long-term exposures (224 days = 5,376 h). The laboratory and industrial heats were tested in comparison with other ferritic 9-13% chromium steels. Corrosion rates were determined by direct measurements of mass losses obtained after a reducing descaling process. Weight loss and metallographic results confirm the good corrosion resistance in steam of the new steel and allow classing the tested steels in 2 families: one classical with average oxidation behaviour, “T91-type” and another one with low mass losses, varying very slightly with the temperature and the exposure time increasing. To have a better understanding of the observed phenomena, the possible influences of the main alloying elements (Cr, Si, Mn, Mo, W) of steels mentioned by different authors were reviewed and compared to the results obtained for the ten 9-13%Cr studied steels. It appears that the alloying elements cannot be considered separately: as a matter of fact they have not only a specific influence but also a joint influence on the steam corrosion behaviour of the 9-13%Cr ferritic steels.     

Internal oxidation and phase transformations of multi-phase Fe–Ni–Al and Fe–Ni–Al–Cr alloys induced by KCl corrosion

The corrosion of two multiphase Fe–Ni–Al and Fe–Ni–Al–Cr alloys is studied at 650 °C in KCl-contaminated air. The oxidation rate of the alloys in air alone is low. When KCl is introduced, the corrosion is accelerated, producing a thick external scale of iron oxides, an intermediate layer of spinel, and a region of internal oxidation of Al. Potassium chromate is detected on Fe–Ni–Al–Cr surface that accounts for the degradation of protective chromia. An Al-depleted single phase region is observed in the front of the internal oxidation, due to the selective consumption of Al via an “active oxidation” process.     

Metal dusting behaviour of Cr-Ni steels and Ni-base alloys in a simulated syngas mixture

Long-term laboratory exposure tests for various Cr and Ni content steels and Ni-base alloys were conducted at 650 °C in a 60vol.%CO-26%H₂-11.5%CO₂-2.5%H₂O gas mixture simulating syngas environments. Upon isothermal heating, alloys with 15% and 20% Cr had many pits on the surface after a brief exposure, while no pit was found on alloys containing of 60% Ni and more than 23% Cr exposed for up to 5000 h. The thermal cycling accelerated pit initiation drastically, resulting that all test specimens except 30%Cr-60%Ni alloy suffered from metal dusting. From a measurement of pit depths, Ni proved to be an effective alloying element to retard the pit growth: growth rate for 75% Ni alloy has achieved double-digit decrease compared to that for 20% Ni. Microscopic observations has revealed that platelet graphite aligned perpendicular at the boundary of gas/metal of pits. The length of the platelet graphite for high Ni alloys was appreciably longer than that for low Ni steels. This can be interpreted from the difference of super saturation of carbon.     

A new interpretation of the corrosion loss processes for weathering steels in marine atmospheres

Most available data sets for the long-term corrosion loss of various grades of weathering steel exposed to marine atmospheric environments are demonstrated to be consistent with the multi-phase corrosion model previously proposed for steels exposed to marine environments. This means that the early corrosion of weathering steels by oxidation is gradually inhibited by the build-up of corrosion products. These produce anoxic and sub-oxic conditions that may permit microbiological activity to govern the longer-term corrosion loss process. This new interpretation for the long-term corrosion of weathering steels may have implications for the design of such steels.     

Long-term immersion corrosion of steels in seawaters with elevated nutrient concentration

Data from a variety of field exposure programs is used to quantify the effect of concentration of dissolved inorganic nitrogen (DIN) on long-term seawater immersion corrosion loss of structural steels. A linear correlation model that asymptotes the long-term part of the previously proposed bi-modal corrosion loss model is used. It allows for average seawater temperature. Model parameters and their variability are determined and reported. The model permits prediction of long-term corrosion loss in nutrient polluted waters of known average temperature. An example shows that anthropological pollution of seawater potentially is a major hazard for corrosion of steel infrastructure.     

Modelling immersion corrosion of structural steels in natural fresh and brackish waters

The multi-phase mean-value model previously proposed for modelling the marine immersion corrosion of low carbon and low alloy structural steels is examined for application to fresh and brackish waters. Use is made of field data for brackish and fresh waters available in the literature, supplemented with data or estimates for water temperature, pH, hardness and nutrient levels. It is shown that the data exhibits consistency with the model and that it is a function of average water temperature. Corrosion in brackish and fresh waters corrosion depends on water hardness, pH and nutrient levels, with higher pH levels and lower water hardness associated with higher aerobic levels of corrosion but these are not significant for anaerobic corrosion. In the anaerobic phases 3 and 4 of the model, the available data and associated trends are interpreted as showing that elevated levels of nutrients produce higher rates of corrosion. Conversely, these phases showed very low rates of corrosion for fresh waters with very low nutrient levels. Consistent with basic corrosion theory and with laboratory observations, salinity by itself is not a clear distinguishing characteristic. The model provides a new approach to interpreting the available data for corrosion in fresh and brackish waters. It permits plausible explanations for previous apparently inconsistent observations for corrosion in brackish waters. Finally, it reinforces the need for full and detailed reporting of corrosion testing programs, including details of precise timing, location, orientation and environmental conditions including means and variations in water temperatures, DO, salinity, pH, water hardness, carbonates and various nutrients.     

Sol–gel coating to reduce 1.25Cr–0.5Mo steel oxidation at 700 °C: Catalyst type effect

With the use of sol–gel it is possible to apply zirconia coatings to reduce high temperature oxidation of steel. Some limitations of this technique are high hydrolysis rates and the formation of cracks during the drying stage. In this work, the mole ratio of zirconium butoxide to ethylacetate, and the nature of the catalyst were varied. SEM-EDX was used to evaluate the continuity of the zirconia coatings, and thermo-gravimetric analysis for the oxidation rate of coated samples. Thin and continuous coatings were obtained. With a basic catalyst, the coatings were crack-free and presented lower oxidation rate than acid-catalyzed coatings.     

Electrochemical corrosion performance of Cr and Al alloy steels using a J55 carbon steel as base alloy

Cr- and Al-modified alloy steels using J55 carbon steel as base alloy were produced by remelting in a vacuum. Their corrosion resistance was estimated by open circuit potential, electrochemical polarisation measurements and immersion tests in a 3.5 wt.% NaCl solution. The modified alloy steels exhibit higher corrosion resistance with a more positive open circuit potential, lower corrosion current density and higher impedance than J55 steel. The immersion tests showed that the new alloy steels have lower corrosion rates and smaller pitting depth than J55 steel and a low-Cr steel.     

Raman mapping of corrosion products formed onto spring steels during salt spray experiments. A correlation between the scale composition and the corrosion resistance

There is a growing trend in the automotive industry to reduce vehicles weight so as to increase fuel efficiency and therefore reduce CO₂ emissions. For many automotive components such as springs, weight reduction is sought through an increase in the mechanical properties (allowing smaller components size).For ultra high strength springs, a good corrosion resistance becomes essential to avoid surface damage that will be detrimental to the corrosion-fatigue resistance. Corrosion-fatigue failures indeed often initiate on surface defects caused by corrosion in service (corrosion pits). Therefore, while of moderate importance in conventional spring steels, the corrosion resistance of ultra high strength spring steels is of primary importance.Fine changes in steel chemical composition can have an important effect on corrosion resistance. To understand the individual action of each element on the corrosion resistance of spring steels, corrosion products formed on samples exposed to NaCl environments were characterized using Raman spectroscopy, in a purposely designed experimental tool that allows mapping of corrosion products on the steel surface (by nature and mass fraction).Different steel grades were thus characterized after accelerated corrosion tests, and a clear correlation was established between weight loss and the nature of the corrosion products.     

Localized corrosion of magnetite on ferritic–martensitic steels exposed to supercritical water

Magnetite usually forms on ferritic–martensitic (F–M) stainless steels as a protective barrier when the steels are exposed to supercritical water (SCW). However, a novel localized corrosion was observed on magnetite induced by adsorbed Cu₂S. The morphology and chemistry of the localized corrosion were studied by means of scanning electron microscopy, focused-ion beam, energy dispersive X-ray spectroscopy, and Auger electron spectroscopy. The mechanism of the development of the localized corrosion is elucidated in this paper. The presence of Cu₂S or related species should be eliminated for the applications of F–M stainless steels in SCW environment.     

Corrosion of austenitic and ferritic-martensitic steels exposed to supercritical carbon dioxide

Supercritical carbon dioxide (S-CO₂) is a potential coolant for advanced nuclear reactors. The corrosion behavior of austenitic steels (alloys 800H and AL-6XN) and ferritic-martensitic (FM) steels (F91 and HCM12A) exposed to S-CO₂ at 650 °C and 20.7 MPa is presented in this work. Oxidation was identified as the primary corrosion phenomenon. Alloy 800H had oxidation resistance superior to AL-6XN. The FM steels were less corrosion resistant than the austenitic steels, which developed thick oxide scales that tended to exfoliate. Detailed microstructure characterization suggests the effect of alloying elements such as Al, Mo, Cr, and Ni on the oxidation of the steels.     

Anomalous temperature dependence of oxidation kinetics during steam oxidation of ferritic steels in the temperature range 550-650 °C

The oxidation behavior of a number of selected ferritic steels in a simulated steam environment at temperatures between 550 and 650 °C was studied. In the prevailing test gas, some of the studied 9-12% Cr steels tended to exhibit an anomalous temperature dependence of the oxidation behavior. This means, that the oxidation rates do not steadily increase with increasing temperature. At higher temperatures, some of the studied steels tend to form a very thin and protective oxide scale whereas at lower temperature rapidly growing, less-protective oxides are being developed. The anomalous temperature dependence is related to differences in chromium distribution in the inner part of the oxide scale. The effect is observed for steels with intermediate-Cr contents (∼10-12%) whereas steels with either lower or higher Cr contents exhibit an increasing oxidation rate with increasing temperature.     

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.     

Chemistry and melting characteristics of fireside deposits taken from boiler tubes in waste incinerators

Twenty-three tube deposits taken from seven heat-recovery boilers of municipal solid waste incinerators were examined by chemical analyses and X-ray diffraction. These deposits were measured by Differential Scanning Calorimeter (DSC) in N₂ to investigate their melting characteristics. Sixteen deposits were used to evaluate their corrosiveness to carbon steel by high-temperature corrosion test conducted at 400 °C for 20 h in 1500 ppm HCl – 300 ppm SO₂ – 7.5%O₂ – 7.5%CO₂ – 20%H₂O – N₂. Total heat of endothermic reactions of the deposits taking place between 200 and 400 °C can be related to the corrosion rate of carbon steel at 400 °C. Corrosion initiated at temperatures when the deposits started to melt, became severe when fused salt constituents increased, and alleviated when the majority of the deposits became fused. The corrosion can be interpreted as fused salt corrosion caused by chloride and sulfate salts.     

Resistance to oxidation and ablation of SiC coating on graphite prepared by chemical vapor reaction

A thick SiC coating was prepared on graphite by chemical vapor reaction. The coating reveals a typical crystalline structure with limited porosity and combines well with the substrate. Oxidation tests demonstrate that the coating has a weak self-healing ability at 1100 K and good self-healing ability at temperatures from 1623 to 1823 K. An oxyacetylene torch test verifies that the prepared coating can effectively protect graphite from ablation for 50 s. After the ablation test, the silica microspheres and other interesting silica structures such as microwires, microparticles, microflowers, nanowires and nanoparticles are formed at the ablation center and its surroundings.     

Simulation and experimental approach to CVD-FBR aluminide coatings on ferritic steels under steam oxidation

The ferritic steels used to produce structural components for steam turbines are susceptible to strong corrosion and creep damage due to the extreme working conditions pushed to increase the process efficiency and to reduce pollutants release. The response of aluminide coatings on the P-92 ferritic steel, deposited by CVD-FBR, during oxidation in a simulated steam environment was studied. The analyses were performed at 650 °C in order to simulate the working conditions of a steam turbine, and 800 °C in order to produce a critical accelerated oxidation test.The Thermo-Calc software was used to predict the different solid phases that could be generated during the oxidation process, in both, coated and uncoated samples. In order to validate the thermodynamic results, the oxides scales produced during steam tests were characterized by different techniques such as XRD, SEM and EDS. The preliminary results obtained are discussed in the present work.     

The effects of temperature and hydrodynamics on the CO2 corrosion of 13Cr and 13Cr5Ni2Mo stainless steels in the presence of free acetic acid

This paper describes the effects of temperature and hydrodynamics on the CO₂ corrosion of two stainless steels in the presence of free acetic acid. The experimental set-up developed in this work was able to evaluate the corrosion behavior of 13Cr and 13Cr5Ni2Mo stainless steels in static conditions with a flow velocity of 1 m s⁻¹ at temperatures of 125, 150 and 175 °C. Electrochemical tests of impedance and linear polarization resistance have been carried out, as well as mass loss tests and surface analysis.     

The atmospheric corrosion kinetics of low carbon steel in a tropical marine environment

The atmospheric corrosion kinetics of low carbon steel exposed for up to 36 months in marine and industrial sites was studied by weight loss measurements. The results show that the mechanism and kinetics of the atmospheric corrosion process presents transition behaviour in marine environments with high chloride ion content and high relative humidity, whereas no transition appears in industrial environment. The average corrosion velocity in marine site reaches a maximum during the period of transition and then fluctuates in a certain range; however, the instantaneous corrosion velocity follows different exponential functions before and after the period of transition.     

Oxidation of φ′-aluminium oxynitride

The oxidation in air of single crystal φ′-aluminium oxynitride (AlON) grains has been characterized by thermogravimetry and X-ray diffraction in the 1273–1673 K range. Two oxidation stages have been observed, suggesting the formation of a transitional phase. Below 1473 K, oxidation results in the apparition of platelets and noodle-like crystals on the surface of the initially faceted single crystals. Above 1473 K, low density α-alumina polycrystals start forming on the grain surface and grow towards the grain core with increasing temperature or time. Their low density is mainly due to the presence of a network of nano-porosities.