Defect and Diffusion Forum Vols. 289-292

Abstract: Jump frequencies of Cd tracer atoms were measured in three lanthanide gallides having the L12 structure: DyGa3, ErGa3 and LuGa3. 111In/Cd impurity probe atoms were observed to occupy the non-cubic Ga-sites through the nuclear quadrupole interaction using the method of perturbed angular correlation of gamma rays (PAC). Measurements at elevated temperatures exhibited nuclear relaxation (damping) of quadrupolar perturbation functions attributed to diffusional jumps of the probes among orientationally inequivalent Ga-sites. Accurate values of jump frequencies were determined from fits of the measured perturbation functions using a model of stochastically fluctuating electric-field gradients, as in previous work [e.g., Matthew O. Zacate, Aurélie Favrot and Gary S. Collins: Physical Review Letters Vol. 92 (2004) p. 225901]. Arrhenius plots of jump frequencies for the three systems exhibited jump-frequency activation enthalpies in the range 0.86-1.05 eV and prefactors of about 2 THz. The activation enthalpy for ErGa3, 0.86(2) eV is compared with those for ErAl3, 1.40(4) eV, and ErIn3, 1.34(5) eV.

Abstract: We present results of the molecular dynamics study of Al selfdiffusion, Al and Fe diffusion in Al-Fe dilute alloys. We found that addition of Fe does not change the vacancy formation energy but considerably slows down Al diffusion. We also found that Al and Fe migration energies, i.e. energies of vacancy exchange with Al and Fe atoms, differ very strongly. Both activation energies for Al and Fe diffusion are in satisfactory agreement with available experimental data.

Abstract: Ultraviolet radiation is one of the major factors that affect weathering of polymers. Indeed, diffusion of oxygen containing groups [-C-O, C=O and C(=O)O-] into the molecular chains of polymers is particularly enhanced by UV irradiation in air, thus entailing structural and chemical changes such as polymeric chain breaking, cross-linking and oxidation. The goal of this study is to predict the photo-chemical ageing of polymers upon UV radiation through a non destructive method: fluorescence spectroscopy. In the case of high density polyethylene (HDPE) the addition of fluorophore is required to make it fluorescent. The spectral features of fluorescence are very sensitive to the interactions between the excited molecules and the matrix. In this way, Fourier-Transform InfraRed spectrophotometry (FTIR) and Differential Scanning calorimetry (DSC) have been employed to correlate the fluorescence spectra with the degradation phenomena.

Abstract: The insertion and diffusion energies of oxygen in presence of vacancies in nickel are studied by using the first-principle projector augmented waves (PAW). When the oxygen atom is located in a substitution site, the formation of a vacancy-oxygen pair is observed. Furthermore, we show that the formation of divacancies allows the oxygen atom to migrate more easily in the metal. A model for the migration process of the three-defect system is proposed. Finally, thermal expansion effects are included in our study; it is shown that temperature effects emphasize the diffusion.

Abstract: Jump frequencies of Cd tracer atoms were measured in three phases having the orthorhombic Al11R3 structure, with R= La, Ce, or Pr. The structure has four inequivalent Al-sites and two inequivalent R-sites. 111In/Cd tracer atoms were observed to occupy several sites via the nuclear quadrupole interaction using perturbed angular correlation of gamma rays (PAC). Time-domain PAC spectra became damped as the temperature increased, which is attributed to nuclear relaxation caused by diffusional jumps of Cd tracer atoms leading to changes in orientations and/or magnitudes of electric field gradients (EFG’s). Maximum relaxations were observed near 770 K. A method is proposed for estimating the mean jump frequency at that temperature, giving a mean jump frequency w averaged over all sites of about 100 MHz. At still higher temperatures, damping decreased due to motional averaging, and the quadrupole perturbations evolved into unique signals having lower frequencies and corresponding in each phase to the averages of EFG tensors of all sites visited by the Cd tracer atoms. For Al11La3, the jump frequency at 1073 K was estimated to be 1.9 GHz. Such jump frequencies imply unusually high diffusivities in these phases.

Abstract: Diffusion controlled processes play a crucial role in the degradation of technical materials. At low temperatures the most significant of them is the diffusion along grain boundaries. In thin film geometry one of the best methods for determining the grain boundary (GB) diffusion coefficient of an impurity element is the Hwang-Balluffi method, in which a surface sensitive technique is used to follow the surface accumulation kinetics. Results of grain boundary diffusion measurements, carried out in our laboratory by this method in three different materials systems (Ag/Pd, Ag/Cu and Au/Ni) are reviewed. In case of Ag diffusion along Pd GBs the surface accumulation was followed by AES method. The data points can be well fitted by an Arrhenius function with an activation energy Q=0.99eV

Abstract: Oxygen self-diffusion and oxygen surface exchange investigations in the yttria-stabilized zirconia (3 and 8 mol% of Y2O3) and in the gadolinia-doped ceria (10 and 20 mol% of Gd2O3) ceramics in the temperature range from 250 to 450°C were performed by means of the 18O isotopic labeling and the SIMS profiling methods. The activation energies of these processes were determined. The results were discussed in comparison with the literature data extrapolated from higher temperatures.

Abstract: Detailed investigations of nonstoichiometry as well as chemical and self-diffusion in nickel oxide have shown that doubly ionised cation vacancies and electron holes are the predominant defects in this material. The present work is an attempt to demonstrate that aliovalent impurities (Cr, Al, Na and Li) may considerably influence the concentration of these defects and, consequently, the oxidation rate of nickel at high temperatures. It has been shown that small amounts of tri-valent impurities (Cr, Al) bring about an increase of the oxidation rate, while mono-valent ones (Li, Na) decrease the rate of oxidation. These phenomena may satisfactorily be explained in terms of a doping effect. All experiments have been carried out as a function of temperature (1373-1673 K) and oxygen pressure (1-105 Pa) and consequently, it was possible to determine the influence of impurities not only on the oxidation rate but also on the activation energy of reaction and its pressure dependence. The results of these investigations could again be elucidated in terms of doping effect.