Defect and Diffusion Forum Vols. 258-260

Abstract: The electrocatalysis of the oxygen reduction reaction by Lanthanum Barium Manganate, (La0.5Ba0.5MnO3) (LBM) has been studied by cyclic voltammetry using the rotating ring-disc electrode technique (RRDE) in alkaline medium. From the ring-disc data and other kinetic parameters it has been assumed that the oxygen reduction occurs by dissociative chemisorption at low overpotentials. At higher overpotentials, the formation of hydrogen peroxide (HO2 - in this case) has been observed on this electrocatalyst. The apparent exchange current density value for oxygen reduction on LBM has been found to be 4 x 10-8 Acm-2, while the corresponding Tafel slope is 0.115 V per decade. The possible reaction mechanism for electroreduction of oxygen on this oxide catalyst has been discussed.

Abstract: Borohydrides present interesting options for electrochemical power generation acting either as hydrogen sources or anodic fuels for direct borohydride fuel cells and batteries. Though there have been several papers concerning electrochemical determination of relevant thermodynamic and kinetic parameters to the borohydride system, a number of its basic aspects have not been yet systematically studied. In this paper we report chronopotentiometric studies of the electrooxidation of sodium borohydride at a gold sphere electrode in 2M NaOH solutions, at temperatures ranging from 25 to 55 °C. Gold displayed a rather good BH4 - oxidation activity, and the overall oxidation process was shown to be irreversible involving a number of electrons very close to the theoretically expected value of 8. The results suggested that the rate-determining step is an irreversible, diffusion controlled, one-electron oxidation step, for which the transfer coefficients were calculated.

Abstract: Oxidation resistance of TiAl3, one of the candidates of coating materials for high temperature structural materials such as Ti3Al and TiAl, has been studied. Specimens were prepared by forming TiAl3 in Al/Ti/Al reaction diffusion couples at 923 K and then TiAl3 layer was exposed to air by dissolving Al plate in a 1N NaOH solution. The obtained TiAl3/Ti/TiAl3 couples were annealed in air in the temperature range from 1173 K to 1468 K. The oxidation rate was compared with that determined by using bulk TiAl3. The present data show a bend on the Arrhenius plot of parabolic phase growth rate constant, k2, at 1323 K. Above 1323K, the constant coincides well with the extrapolated values of bulk data while the value in the lower temperature range is larger than that of bulk specimens. During the oxidation experiments, intermetallic compounds Ti3Al, TiAl and TiAl2 were formed between Ti and TiAl3. Interdiffusion coefficients in the Ti3Al, TiAl phases determined from these diffusion couples are more than one order of magnitude larger than the interdiffusion coefficients determined by previous investigators from single-phase diffusion couples but coincide with the coefficients determined from multi-phase diffusion couples. This difference between interdiffusion coefficients has been discussed and explained by the effect of boundary diffusion in the diffusion layers formed in the multi-phase diffusion couples.

Abstract: Solid-state diffusion is a subject of great interest for many intellectual merits and practical applications. It also provides excellent educational studies with cross-fertilization of science and technology. This paper examines the importance of multicomponent-multiphase interdiffusion with specific examples from materials and coatings for components in advanced energy production systems, including gas turbines and nuclear reactors. Results and analysis from laboratory experiments are presented in terms of interdiffusion fluxes, integrated interdiffusion coefficients, effective interdiffusion coefficients, and average multicomponent interdiffusion coefficients. Applications are highlighted for materials and coatings for components in advanced energy production technologies. Additional consideration is given to the refined approach to assess composition-dependent interdiffusion coefficients in multicomponent alloys.

Abstract: A numerical approach for the segregation of atomic oxygen at Ag/MgO interfaces is presented. A general segregation kinetics is considered and the coupled system of differ- ential equations is solved due to a one-dimensional finite difference scheme which accounts for concentration-dependent diffusion coefficients. Based on a model oxide distribution, the influence of the concentration-dependency is numerically investigated and compared with the solution for constant coefficients. In addition, the numerical approach allows for the consider- ation of general boundary conditions, specimen sizes and time-dependent material and process parameters.

Abstract: Due to economic significance, industry demands on mathematical models, which allow for the prediction of realistic carburization and decarburization depth profiles. Analytical solutions of Fick’s law, however, are of limited aptitude, as the concentration dependence of the diffusion coefficient of carbon in steel cannot be considered. Thus, the present paper presents a numerical simulation tool based on the finite element method (FEM). A widespread commercially available program system was used to ensure industrial applicability and to make a contribution to the standardizing of operation control.

Abstract: A coating consisting of La0.85Sr0.15MnO3 (LSM) was deposited onto two Fe 22 wt % Cr alloys Crofer 22APU and Sandvik 1C44Mo20. The evolution of the oxide layers developing underneath the coatings during oxidation was investigated. The effect of the LSM coating on oxidation rate and microstructure of the oxide scale was investigated, and possible effects on the overall oxidation mechanism are discussed. It was found that the growth rate for coated Crofer 22APU was decreased by a factor of 3 in comparison with the uncoated samples, and the thickness of the chromia layer in the scales decreased in favor for a (Mn,Cr)-spinel layer.

Abstract: The applicability of the Boltzmann-Matano method for evaluation of a diffusion coefficient and its concentration dependency by line profile analysis is tested on three different (model) systems. All systems involve interstitial diffusion. It is shown that the occurrence of trapping corrupts the applicability of the Boltzmann-Matano method.

Abstract: The effect of pressure on the kinetics of grain boundary (GB) segregation in the Cu–50 at. ppm Bi alloy has been studied. It was found by means of Auger electron spectroscopy that at a temperature of 1173 K the segregation level decreases from 2 to 1.5 monolayer as the pressure increases from 0.01 to 1.2 GPa. This behavior was explained by considering the physical parameters controlling kinetics and thermodynamics of GB segregation. A simplified model based on dislocation pipe diffusion, proposed previously and discussed in more details in this work, was used to calculate the non-equilibrium GB segregation during cooling under high pressure. The pressure effect on bulk diffusion is responsible for the suppression of GB segregation, while the pressure effect on the phase stability in Cu–Bi alloys provides a negligible contribution on GB segregation in the pressure range studied.