Papers by Author: W.Joe Quadakkers

Abstract: In the present study the oxidation behaviour of a number of candidate alloys for heat exchanging components was investigated in model gas mixtures containing high amounts of CO₂ and/or water vapour in the temperature range 550-700°C up to exposure times of 1000 h. During exposure in Ar/CO₂ and Ar/CO₂/H₂O base gas mixtures at 550-650°C the oxidation rates and scale compositions of martensitic 9-12%Cr steels were similar to those previously observed in steam environments. Thin and protective Cr-rich oxide scales which are commonly found during air oxidation was observed locally on the specimens surfaces after oxidation in Ar-(1-3%)O₂-CO₂. The tendency for protective chromia base scale formation increased when 3% oxygen was added, especially for the 12%Cr steel. When iron base oxide scales were formed on the metal surface, the martensitic steels tended to exhibit carburisation whereby the extent was reduced by increasing the water vapour and oxygen contents. All three studied austenitic alloys exhibited very slow scale growth rates at 550°C, however, at and above 600°C the steels with lower Cr content started to form two-layered iron rich surface oxide scales whereby the outer oxide was prone to spallation upon thermal cycling. The high-Cr austenitic steel 310N and the nickel base alloy 617 formed very thin, Cr-rich oxide scales at all used test temperatures and atmospheres. For those two materials the oxidation behaviour in gases containing water vapour in combination with intentionally added oxygen was affected by formation of volatile chromium oxyhydroxide.

Abstract: For a number of chromia and alumina forming high temperature alloys and coatings, recent studies revealed, that in some cases the specimen/component or coating thickness may substantially affect the growth rates of the surface oxides. For the alumina formers the thickness dependence is mainly governed by depletion of oxygen active elements such as Y, Zr, Hf, Mg which are either intentionally added alloying elements or manufacturing related alloy impurities. In the case of the chromia forming materials, which tend to exhibit a more substantial dependence of oxidation rate on specimen/component thickness, depletion of minor alloying additions is also an important factor to be considered. However, for these alloys relaxation of oxide growth stresses by plastic deformation of the metallic substrates seems to be the dominant parameter which governs the observed behaviour.

Abstract: In this study, the effects of alloying with Cu and external doping with CeO2 on the oxidation of nickel were evaluated. The materials studied were pure Ni, Ni-5wt% Cu, and Ni with the surface doped with CeO2 by pulsed laser deposition (PLD). The oxidation kinetics were measured using thermogravimetric analysis (TGA). The oxidation microstructures were observed by scanning electron microscopy (SEM) compositional analysis was performed with energy dispersive x-ray analysis (EDS) and sputtered neutrals mass spectrometry (SNMS). Phase identification was performed using X-ray diffraction (XRD). The Cu additions had a negligible effect on the oxidation kinetics but Cu was found to be present in the outer portions of the scale in significant concentrations. Doping with CeO2 resulted in a significant decrease in the NiO growth rate. The scales on doped Ni grew primarily inward whereas those on the undoped Ni grew primarily outward. Deposition of the CeO2 dopant onto Ni with a thin, preformed NiO layer produced a similar reduction in the subsequent NiO growth rate. This suggests that the poisoned interface model, proposed by Pieraggi and Rapp, does not describe the effect of the CeO2 dopant. Mechanisms are presented to attempt to describe the above observations.

Abstract: The oxidation behaviour of binary Fe-Cr alloys containing 10 and 20 mass % Cr, respectively, was studied in Ar-20%O2, Ar-7%H2O and in Ar-4%H2-7%H2O at temperatures between 800 and 1050°C. Thermogravimetric analyses in combination with analytical studies using SEM/EDX and Raman Spectroscopy revealed, that in atmospheres in which water vapor is the source of oxygen, Cr exhibits a higher tendency to become internally oxidized than in the Ar-O2 gas. Contrary to previous studies which showed the presence of water vapor to affect transport processes in the surface oxide scale, the present results reveal that the presence of water vapor also affects the transport processes in the alloy. The enhanced internal oxidation, which is likely the result of water vapor increasing the solubility and/or the diffusivity of oxygen in the alloy, explains the frequently observed effect that Fe(Ni)Cr alloys with intermediate Cr contents (e.g. 10-20%, depending on temperature) exhibit protective oxidation in dry gases but breakaway type oxidation in steam. The temperature dependence of the change from protective to non-protective behaviour in Ar-H2O differs quantitatively, but not qualitatively from that in Ar-O2.

Abstract: The oxidation behaviour of a Ferritic 10%Cr steel in Ar-H2O mixtures was investigated at 650°C. The studies aimed at elucidating the effect of water vapour content as well as the gas flow rate on the mechanisms of oxide scale formation. An important observation of the present investigation is, that H2 produced by the reaction of water vapour with the steel, can play a significant role in the oxidation process. It affects the possibility to form an external haematite layer and may alter the oxide scale growth rate. The extend by which the H2 affects the oxidation behaviour depends on the gas flow conditions, the water vapour content and the exposure time. To confirm these observations a number of specimens were oxidized in Ar-H2-H2O mixtures. This atmosphere guarantees a very low equilibrium oxygen partial pressure, in which H2 formed by reaction of the gas with the metal, does not substantially alter the thermodynamic properties of the gas.