B. Panicaud

Iron oxidation under the influence of phosphate thin films

Iron phosphate thin films have been obtained under controlled conditions by chemical conversion deposition. The films were formed on polycrystalline α-iron by immersion in acetone, as an organic solvent. After deposition, the films were investigated by x-ray photoelectron spectroscopy (XPS) and their influence on the thermal oxidation of α-iron was studied by means of in situ low incidence x-ray diffraction of synchrotron radiation. The study reveals interesting features related to the structure of both the phosphate and thermal oxide films. The XPS data suggest the iron phosphate to be constituted of long chains of phosphate groups PO43−; these groups being interconnected by Fe2+ and Fe3+ cations. X-ray diffraction measurements have shown a significant modification of the oxidation behavior of α-iron at 400 °C and atmospheric pressure, which is derived from the presence of the thin film: α-Fe2O3 formation is clearly enhanced to the detriment of Fe3O4, compared to the oxidation of pure iron in which Fe3O4...

Growth stresses in α-Cr2O3 thermal oxide films determined by in situ high temperature Raman spectroscopy

Growth stresses have been investigated in relation with the microstructure in the case of α-Cr2O3 growing oxide films on NiCr30 alloy. The equibiaxial growth stresses have been measured thanks to a technique coupling Raman spectroscopy and in situ high temperature oxidation of the NiCr30 alloy in the temperature range (700−900 °C). It is established that the compressive growth stress in such oxide films can reach more than 2 GPa, before additional thermal stress arises on cooling. Moreover, the growth stress kinetics—subsequent establishment and relaxation—are highly microstructure sensitive: in particular, as the oxidation temperature rises, the chromia mean grain size also increases, and it consequently retards the occurrence of the creep relaxation phenomena which needs an additional stress level to start.

Phosphating of bulk α-iron and its oxidation resistance at 400 °C

Fe bulk specimen have been treated with phosphoric acid in order to obtain a conversion surface layer and the oxidation resistance has been studied by means of in situ thermogravimetric experiments in artificial air (20% O2; 80% N2). For oxidation time of 48 h at 400 8C it shows an important decrease of the oxidation kinetic in comparison witha-Fe. Moreover, the kinetic can be described by two successive parabolic stages. This behaviour is respectively related to an X-ray photoelectron spectroscopy (XPS) analysis of the surfaces and to previous results obtained on the oxidation of a-iron. # 2002 Elsevier Science B.V. All rights reserved.

Neutron time-of-flight diffraction used to study aged duplex stainless steel at small and large deformation until sample fracture

Owing to its selectivity, diffraction is a powerful tool for analysing the mechanical behaviour of polycrystalline materials at the mesoscale (phase and/or grain scale). In situ neutron diffraction during tensile tests and elastoplastic self-consistent modelling were used to study slip phenomena occurring on crystallographic planes at small and large deformation. The critical resolved shear stresses in both phases of duplex stainless steel were found for samples subjected to different thermal treatments. The evolution of grain loading was also determined by showing the large differences between stress concentration for grains in ferritic and austenitic phases. It was found that, for small loads applied to the sample, linear elastic deformation occurs in both phases. When the load increases, austenite starts to deform plastically, while ferrite remains in the elastic range. Finally, both phases undergo plastic deformation until sample fracture. By using an original calibration of diffraction data, the range of the study was extended to large sample deformation. As a result, mechanical effects that can be attributed to damage processes initiated in ferrite were observed.

Structural characterisation of phosphated α-iron oxidised at 400 °C

α-Iron specimens were treated with phosphoric acid to obtain a conversion surface layer and the oxidation resistance of samples was studied at 400 °C in air. For oxidation time of 48 h, an important decrease in the oxidation kinetics was obtained in comparison with untreated α-Fe. The samples were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses of the surfaces and these results are related to previous data on the oxidation of α-iron.

Local stress determination in chromia-former thanks to micro-Raman spectroscopy: A way to investigate spontaneous delamination processes

Spontaneous delamination process for α-Cr2O3 thermal oxide films growing on NiCr-30 alloys is studied thanks to micro Raman spectroscopy. In particular, stress maps are performed through and around buckles developed on chromia films. Depending on the cooling rate at the end of the oxidation process, different buckle types appear which are investigated. Associated residual stress distribution clearly evidences the stress release field. In addition, geometrical features are determined for the different buckle types, and from comparison with modelling describing buckle formation and propagation, it is possible to get the interface toughness distribution.

Study of stress localisation in polycrystalline grains using self-consistent modelling and neutron diffraction

The time-of-flight neutron diffraction technique and the elastoplastic self-consistent model were used to study the behaviour of single and multi-phase materials. Critical resolved shear stresses and hardening parameters in austenitic and austenitic–ferritic steels were found by analysing the evolution of the lattice strains measured during tensile tests. Special attention was paid to the changes of the grain stresses occurring due to transition from elastic to plastic deformation. Using a new method of data analysis, the variation of the stress localisation tensor as a function of macrostress was measured. The experimental results were successfully compared with model predictions for both phases of the duplex steel and also for the austenitic sample.

Large Deformation and Mechanical Effects of Damage in Aged Duplex Stainless Steel

The lattice strains in large tensile deformations, up to the fracture of the sample were measured using neutron TOF method. For the first time, the range of large deformation was studied measuring lattice strain in the deformation neck and using special correction for macrostress value. It was found that during large plastic deformation the lattice stresses arise almost linearly with the macrostress value. The relaxation of elastic strains in some groups of ferritic grains (corresponding to reflections 211 and 200) can be connected with initiation of damage process in the ferritic phase.

Chronological study of the oxidation of phosphated α-iron

In the present work, the morphological evolution of the iron-oxide layers growing at 400 °C on α-Fe and phosphated α-Fe in artificial air at 1 atm is investigated. The oxidation kinetics of α-Fe and phosphated α-Fe are firstly presented for various oxidation times. Then a detailed chronological study is undertaken of the microstructural states in the different stages of the complex oxidation kinetics. Correlations are established between the morphology of the oxides layers and the successive parabolic oxidation stages. It is shown that the phosphate conversion layers seem to modify the growth mechanisms of the oxides.

Modelling of the Mechanical Behaviour of a Chromia Forming Alloy Under Thermal Loading

When metals or alloys are oxidized at high temperature, an oxide film generally develops. Stress induced by oxide growth may influence the structure and the protective properties of the oxide scales. Classical models (taking into account elasticity and/or viscoplasticity and/or thermal mismatches) are able to predict some stress evolution. Moreover, the origin of that stress for isothermal condition must be sought-after in a growth strain related to the formation of the oxide above the substrate. In the present work, details are given on the modelling of stress under thermal loadings. The study is performed considering different thermomechanical behaviours and upgraded taking into account the origin of the different thermal couplings (weak and strong ones). Therefore, comparison with experimental results performed at ESRF allows extracting thermomechanical parameters with numerical values for different configurations (isothermal or with thermal evolution). This allows also investigating different mechanisms occurring at high temperature in chromia.