Defect and Diffusion Forum Vols. 237-240

Abstract: In this conference we try to give a survey of the main characteristics of aging of oxides under irradiation in the perspective of the recent developments of the ab-initio modeling capabilities. After a brief recall of the relevant radiation – matter interactions, we present the main aspects of materials aging under irradiation, I) defect creation either elastically or inelastically, ii) microstructure evolution due to defect elimination, iii) radiation enhanced diffusion, iv) phase changes under irradiation.

Abstract: Polycrystalline Ni3Al and TiAl are attractive materials for high temperature structural applications due to their stability in oxidizing and sulphidizing environment upto700 0 C. They possess significantly higher specific stiffness and similar specific strength as that of super alloys. Hence, these materials can replace super alloys for high temperature applications (~900°C). TiAl has lesser density and can be used for reducing component weight up to 50% and suitable for aerospace and automobile (high performance vehicles) sectors. The major difficulty for putting Ni3Al for engineering applications is its extremely low ductility and inter-granular fracture at ambient temperatures. TiAl, apart from the said brittleness it also suffers from high temperature corrosion. However the brittleness of these aluminides can be reduced by micro-alloying and by subjecting them to Thermo Mechanical Treatments, TMT. This paper deals with the recrystallization studies on nickel aluminides, deformed to different extents by rolling. The average grain size dependence with the % elongation is evaluated in the grain size range of 10-35micron. For the nickel aluminide deformed for 50% by rolling, the variation of resistivity and hardness with annealing time is determined. The homogenized TiAl samples were cold worked and annealed at 1000 0 C. Since the aluminide suffers from low ductility at room temperature, an arbitrary parameter, electrical resistivity, was chosen. Corresponding hardness values were also obtained. Finally a qualitative determination of ductility was made by studying the flow behavior of alloy around the hardness indentation. Thus a correlation was developed between resistivity, hardness and ductility values. It was then to some extent possible to investigate the TMT cycles on the microstructure and hence on the ductility of the TiAl without going for the actual tensile tests.

Abstract: Irradiation of metals leads to the formation of point-defects (vacancies and selfinterstitials) that usually agglomerate in the form of dislocation loops. Due to the elastic interaction between SIA (self-interstitial atoms) and dislocations, the loops absorb in most cases more SIA than vacancies. That is why the loops observed by transmission electron microscopy are almost always interstitial in nature. Nevertheless, vacancy loops have been observed in zirconium following electron or neutron irradiation (see for example [1]). Some authors proposed that this unexpected behavior could be accounted for by SIA diffusion anisotropy [2]. Following the approach proposed by Woo [2], the cluster dynamics model presented in [3] that describes point defect agglomeration was extended to the case where SIA diffusion is anisotropic. The model was then applied to the loop microstructure evolution of a zirconium thin foil irradiated with electrons in a high-voltage microscope. The main result is that, due to anisotropic SIA diffusion, the crystallographic orientation of the foil has considerable influence on the nature (vacancy or interstitial) of the loops that form during irradiation.

Abstract: By following the densification kinetics of nanocrystalline g alumina and corresponding microstructural evolution we showed that the diffusive transformation gamma-alpha involves several processes such as nucleation of alpha phase, rearrangement of gamma crystallite at alpha seed and grain surfaces, formation of porous alpha alumina monocrystalline colonies. Results concerning the effects of seeding and doping elements on the transformation-densification behaviour of the same g-alumina raw powder batch are also presented. Doping elements seem to have no influence on nucleation rate but could modify the redistribution rate of the ions during the transformation by short range diffusion of doping elements.

Abstract: We test the main approximations of the classical laws for nucleation, growth and coarsening by comparison with atomistic simulations of the kinetics of precipitation. We investigate the kinetics of phase separation in dilute A-B solid solutions by precipitation of B atoms in the Arich matrix. Classically, the kinetics is represented by the time evolution of the total number of particles and their mean radius. In this work, the kinetics is predicted by three types of models: (a) an Atomic-scale Kinetic Monte Carlo (AKMC) model based on a vacancy diffusion mechanism, (b) a Cluster Dynamics model, and (c) the MultiPreci model, based on the coupling of the classical laws of nucleation, growth and coarsening. Cluster Dynamics and the Multipreci model have been parameterized such that the thermodynamic and kinetic parameters (solubility, diffusion coefficient, interface energy) be identical to that of the AKMC. Under these conditions we find that the classical laws are in good agreement with the atomistic simulations as long as the thermodynamics of the solid solution remains strictly regular. As expected, Cluster Dynamics compares better with the atomistic simulations, especially if a precise description of the energetics of the smallest clusters is applied.

Abstract: A model Ni-Bi system has been used to investigate intergranular penetration (IGP) phenomenon. All experiments have been done on Ni 26°<110> bicrystal at 700°C using bismuth vapour condensation as a source of liquid bismuth. Such a procedure results at room temperature in either partial or total Liquid Metal Induced Embrittlement (LMIE) of a unique grain boundary, depending on the duration of liquid Bi / solid Ni contact at 700°C. Auger Electron Spectrometry (AES) and Rutherford Backscattering Spectrometry (RBS) have been used to measure the Bi concentration profile between the source of liquid bismuth and the penetration front. Two zones have been clearly identified : the first one of almost constant Bi concentration called nanometrethick film which is interpreted in terms of Fowler-Guggenheim multi-layer segregation under local equilibrium conditions and the second one with a progressive decrease of Bi concentration over a distance of the order of 20-200µm. Such a long transition zone, together with parabolic diffusion kinetics indicates diffusion-based mechanism of intergranular penetration as opposed to the direct grain boundary wetting.

Abstract: The consequences of the contact between liquid bismuth and a copper bicrystal are investigated at 500°C. Atoms of bismuth are shown to penetrate and embritlle the copper grain boundary. Grain boundary concentration profiles of bismuth are obtained on fracture surfaces by both Auger electron spectroscopy and He4+ Rutherford backscattering spectroscopy. The maximum bismuth intergranular concentration is calculated from experimental data to be about 1.7 monolayers (near the liquid bismuth / solid copper interface). The overall profiles are significantly different from typical erfc profiles and an interpretation is proposed, based on the coupling effect between grain boundary diffusion and non-linear segregation. These results allow us to conclude on the absence of grain boundary wetting for the Cu / Bi system at 500°C.

Abstract: Annealing in a hydrogen atmosphere of silicate glass plates doped by Ag+ ions leads to the reduction of silver to a metallic state (Ag0) and to the formation of silver nanoclusters. The kinetics of clustering during hydrogen diffusion into the glass and diffusion of Ag0 atoms in the glass matrix have been studied in a temperature ranging from 160 to 200oC by SEM, AFM and optical spectrometry. The absorption spectra have a peak near 410 nm corresponding to the surface plasmon resonance in Ag clusters. The position of the peak moves as the clusters grow. A theoretical analysis of the absorption spectra allowed us to estimate the cluster size as a function of time, as well as the thickness of the layer filled by clusters, which also changes with time. From AFM data we could measure the kinetics of cluster growth on the surface. We have theoretically analyzed the kinetics of cluster growth during reactive hydrogen diffusion, the kinetics of bulk cluster growth, surface cluster growth, and thickening of the layer filled by clusters.