Determination of Parabolic Rate Constants from a Local Analysis of Mass-Gain Curves

A method is proposed to allow a more accurate evaluation of thermogravimetric data to identify diffusion or partial diffusion control of scaling kinetics. This method is based on the fitting of mass-gain data to a parabola over a short time interval. The translation of the time interval over the entire test time period provides an actual instantaneous parabolic rate constant independently of any transient stage or simultaneous reaction steps. The usefulness and limitations of this procedure are illustrated from oxidation tests performed on several metallic materials (pure nickel, single-crystal superalloys, and NbTi-Al alloy)

Effect of Cycle Frequency on High Temperature Oxidation Behavior of Alumina-forming Coatings Used for Industrial Gas Turbine Blades

Oxidation kinetics of platinum modified aluminide and overlay coatings on nickel base superalloys were investigated. Isothermal oxidation tests were carried out at 1050°C in synthetic air. Cyclic oxidation tests were performed with 2 cycle frequencies : - Short term cycles : 1h dwells at 1050°C in synthetic air ×1800 cycles - Long term cycles : 300h dwells at 1050°C in laboratory air × 6 cycles (experiment planned to totalize at least 10 000 hours at high temperature) The mass gain curves point out a large effect of the cycle frequency at 1050°C for overlay NiCoCrAlYTa coating whereas the effect is less significant for Pt-modified nickel aluminide coating. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy was used to evaluate the effect of cycle frequency on microstructural evolution. A simple statistical spalling model [1,2], assuming that the parabolic rate constant kp and the spalling probability p are constant, is tentatively applied and discussed in view of the microstructural evolution complexity

Correlations between Growth Kinetics and Microstructure for Scales Formed by High-Temperature Oxidation of Pure Nickel. II. Growth Kinetics

The oxidation kinetics of high-purity nickel were studied between 500 and 1200°C, in pure oxygen at atmospheric pressure, for aûerage oxide-scale thicknesses of 1, 5, 10, and 30 μm. In the oûerall temperature range studied, a decrease in the parabolic rate constant kp with increasing scale thickness was observed. Depending on temperature and oxide-scale thickness, growth kinetics can be interpreted as a mixture of parabolic- and cubic-growth kinetics. Possible correlations between growth kinetics and microstructures of the oxide scales were inûestigated. From this set of experimental data, oxidation-kinetics models were tested. In particular, the effect of grain-boundary diffusion on NiO-growth kinetics was discussed. The correlations between growth kinetics and oxide microstructures appear to be more complex than usually reported

Le nickel, matériau modèle pour les études d’oxydation à haute température : premiers pas vers une modélisation prédictive du phénomène

Les corrélations entre les cinétiques de croissance et les évolutions morphologiques et microstructurales des couches de NiO formées lors de l’oxydation du nickel de haute pureté ont été établies à partir d’essais d’oxydation isothermes et anisothermes. La complexité des mécanismes de transport qui entrent en jeu lors de la croissance de telles couches est démontrée et un modèle de croissance est proposé prenant en compte la diffusion des espèces cationiques en volume et par courts-circuits), le transport de l’oxygène et les réactions interfaciales

In situ ESEM investigations of the oxide growth on hot work tools steel: effect of the water vapour

5th International Conference on the Microscopy of Oxidation, UNIV LIMERICK, LIMERICK, IRELAND, AUG 26-29, 2002International audienceTempered martensitic steel modified AISI H11 is used in forging processes where tool failure can result from the combination of thermo-mechanical and chemical damage. A better knowledge of the oxidation mechanisms in this material could be useful for a better appreciation of its service behaviour and lifetime. the low chromium content of this Fe-Cr type steel allows the development of mainly Fe2-xCrxO3 oxides with corundum structure and leads to enhanced oxidation in the presence of water vapour. In situ FEG-ESEM images show the scale microstructural modifications during high temperature exposure, as well as the lateral growth of oxide particles. Together with GIXRD, SEM/EDS and SIMS analysis. FEG-ESEM also allows assessment of the H2O effect on oxidation behaviour during high temperature exposures (600 and 700degreesC). Water vapour induces either pores or crystallites size increase, favours faceted oxides particles with enhanced density at the highest partial pressure. At this microscopic scale. anisotropic growth of crystallites is observed, and size expansion rates are found to be linear and characteristic of each individual particle. Temperature acts principally on oxide film microstructure. Whatever the environment, homogeneous scale growth is observed at 600degreesC whereas the steel surface is heterogeneously covered by oxides at 700degreesC

Oxidized low density lipoproteins elicit DNA fragmentation of cultured lymphoblastoid cells

AbstractLymphoblastoid cell lines continuously pulsed with mildly oxidized low density lipoproteins, exhibited a significant increase of DNA fragmentation induced by oxidized LDL internalized by cells. DNA fragmentation was associated with an increasing number of morphologically characteristic apoptotic cells simultaneously with the increase of cytotoxicity indexes, and the activation of the poly(ADP-ribose) polymerase, a nuclear enzyme stimulated by DNA strand breaks. The potential involvement of these biochemical and morphological changes in antherogenesis is discussed

Depletion and voids formation in the substrate during high temperature oxidation of Ni-Cr alloys

A numerical model to treat the kinetics of vacancy annihilation at the metal/oxide interface but also in the bulk metal has been implemented. This was done using EKINOX, which is a mesoscopic scale 1D-code that simulates oxide growth kinetics with explicit calculation of vacancy fluxes. Calculations were performed for high temperature Ni-Cr alloys oxidation forming a single chromia scale. The kinetic parameters used to describe the diffusion in the alloy were directly derived from an atomistic model. Our results showed that the Cr depletion profile can be strongly affected by the cold work state of the alloy. In fact, the oversaturation of vacancies is directly linked to the efficiency of the sinks which is proportional to the density of dislocations. The resulting vacancy profile highlights a supersaturation of vacancy within the metal. Based on the classical nucleation theory, the possibility and the rate of void formation are discussed