Defect and Diffusion Forum Vols. 289-292

Abstract: Based on the X-ray method an experimental research has been carried out aimed to estimate the pulsed magnetic field influence on the heterodiffusion of Al in -Fe within the temperature interval of 700-820 °С and at the amplitude intensity of the magnetic field pulse equal to 0–557.2 kА/m and its frequency ranging from 0 to 8 Hz. It is established that the pulsed magnetic field changes noticeably the value of the measured coefficient of Al diffusion in -Fe. Possible mechanisms of the pulsed magnetic field influence on the diffusion process are considered on taking into account the interaction of moving domain walls, dislocations and impurity atoms.

Abstract: Atom redistribution during crystallization of a B and P co-doped amorphous Si layer produced by Si and P chemical vapor co-deposition and B implantation has been investigated. The crystallization of the entire layer is quasi-instantaneous for annealing temperature greater than 650 °C. The crystallization rate is well reproduced by the Avrami-Johnson-Mehl-Kolmogorov model of transformation. The Avrami n is found equal to 4, which is corresponding to 3D bulk crystallization. Crystallization promotes a non-Fickian redistribution of B atoms, allowing for an abrupt interface between B-doped and B-undoped regions. After crystallization, B diffuses in the polycrystalline Si layer for concentrations lower than 1.5  1020 at cm3 via the type B kinetic regime. Crystallization has no significant (or detectable) influence on the P profile. For temperatures higher than 750 °C, P diffuses in the poly-Si layer towards the region of highest B concentration via the type B kinetic regime, leading to P uphill diffusion. This phenomenon can be simulated considering chemical interactions between B and P atoms in both grains and grain boundaries.

Abstract: Oxygen diffusion coefficients were determined in a commercial ZnO-based varistor by means of the gas-solid exchange method using the isotope 18O as the oxygen tracer. The diffusion annealings were performed at 892, 942, 992 and 1092oC, in an Ar + 18O2 atmosphere under an oxygen partial pressure of 0.2 atm. After the diffusion annealings, the 18O diffusion profiles were established by secondary ion mass spectrometry (SIMS). The results show an increase of the oxygen diffusion in the varistor, both in bulk and in grain boundaries, when compared to the oxygen diffusion in undoped ZnO. The increase of the oxygen bulk diffusion in the varistor agrees with an interstitial mechanism for the oxygen diffusion. The results also show that the grain boundary is a fast path for the oxygen diffusion in the varistor. However, the oxygen diffusion in the grain boundaries of the varistor seems to depend on several chemical and microstructural parameters and does not allow a simple explanation.

Abstract: We investigate the effect of cation size in the dc activation energy needed for oxygen ion conductivity, Edc, in highly disordered pyrochlore-type ionic conductors A2B2O7. Twenty compositions of general formula Ln2Zr2-yTiyO7 (Ln = Y, Dy and Gd) and Gd2-yLayZr2O7, were prepared by mechanical milling and their electrical properties measured by using impedance spectroscopy at different temperatures. We also evaluate, by using Ngai’s Coupling Model, the effect of cation radii RA and RB, on the microscopic potential-energy barrier, Ea, that oxygen ions encounter when jumping into neighboring vacant sites. We find that for a fixed B-site cation radius RB, both activation energies decrease with increasing A-site cation size, RA, as a consequence of the increment in the unit cell volume. In contrast, and for a given RA size, the dc activation energy Edc of the Ln2Zr2-yTiyO7 series increases when the average RB size increases. The latter behavior is explained in terms of the enhanced interactions among mobile oxygen ions as the structural disorder increases when RB approaches RA.

Abstract: A visible four-layers structure with anomalous nano-sturucture was formed from a homogeneous -phase Bi3Pb7 intermetallic compound under a strong gravitational field (1.02x106 G, 130°C, 100 hours). In the 4th layer (lowest-gravity region), pure Bi particles precipitate. In the 2nd 3rd layers, composition graded structures, where Pb content increased along the gravity direction, were formed. It was found that the very broad XRD peak appeared in the 2nd layer, which indicated that an amorphous structure was contained.

Abstract: Surprisingly low rate of “order-order” kinetics in stoichiometric NiAl intermetallic known of very high vacancy concentration suggested a specific triple-defect mechanism of ordering/disordering in this system [1]. This mechanism implies a correlation between the concentrations of antisite defects and vacancies; the latters being trapped in triple defects and thus, inactive as atomic migration agents. The process was modelled by means of Monte Carlo (MC) simulations recognised as a powerful tool for such tasks [2], but requiring now the implementation of thermal vacancy thermodynamics. Temperature dependence of vacancy concentration in an AB B2 binary system was determined within an Ising-type model solved first in Bragg-Williams approximation [3] and then by means of MC simulation of a Grandcanonical Ensemble. Without any a priori assumptions concerning the formation of particular types of point defects the model yielded temperature domains where the concentrations of antisite defects and vacancies were proportional. The effect associated with the formation of triple defects appeared for specific values of atomic pair-interaction energies. Moreover, non-stoichiometric A-B systems with the same atomic pair-interaction energies showed the existence of constitutional vacancies at low temperatures. Monte Carlo simulations of “order-order” (disordering) kinetics in B2 AB systems modelled with triple-defect-promoting atomic pair-interaction energies were run with temperature-dependent concentra-tion (i.e. number) of vacancies given by the above model. The simulated relaxations showed two stages: (i) rapid formation of triple defects engaging almost all vacancies present in the system, (ii) very slow process of further generation of antisite defects until the equilibrium concentration was reached. The result reproduced very well the experimental observations [1].

Abstract: X-ray standing wave technique has been used to measure the kinetics of CoSi intermetallic phase growth in a-Si/Co/a-Si sandwich structure. The a-Si/Co/a-Si arrangement were placed into a waveguide structure formed by two Ta films. X-ray fluorescence and extended X-ray absorption fine structure analysis has been used in a combination with X-ray standing wave technique for depth profiling with sub-nanometer resolution of specimens annealed at 493K for different annealing time. The position and the thickness of the growing CoSi intermetallic phase have been monitored.

Abstract: Diffusion of both titanium and nickel was measured in the near stoichiometric Ni-49.4at.%Ti alloy with the B2 ordered structure. The radiotracer technique and the 44Ti and 63Ni isotopes were applied in the temperature interval from 900 to 1300 K. The penetration profiles were determined by precision parallel grinding or by ion beam sputtering at larger and smaller penetration depths, respectively. Titanium and nickel diffusivities were found to follow linear Arrhenius dependencies with the pre-exponential factors of 2.710-7 and 4.710-9 m2/s and the activation enthalpies of 205 and 143 kJ/mol, respectively. A vacancy mediated diffusion mechanism is suggested to provide diffusion of both nickel and titanium in the compound NiTi.

Abstract: This paper reviews briefly the relationship between the growth mechanism and matter transport using as an example the best currently applied metallic materials being alumina formers. The attention is paid to the experimental approach as well as to the interpretation procedure of experimental results. The scale structure, microstructure, morphology and phase composition are indicated as factors strongly affecting its growth mechanism. The attempt is made to elucidate the possible relationships between the obtained experimental results and actual scale growth mechanisms operating during oxidation exposures.

Abstract: Surface modifications with well defined amounts of fluorine have proven to improve significantly the oxidation resistance of titanium aluminides and to offer the potential to decrease the sensibility of TiAl-based alloys against environmental embrittlement. By means of combined EPMA and SEM analyses the formation of an oxide layer on fluorine treated specimens was characterised. The thicknesses of the external oxide layer as well as the oxygen and nitrogen-rich subsurface layer were measured. Their growth kinetics was found to follow a cubic and a parabolic law, respectively. By subtracting the mass variation due to the ingress of oxygen and nitrogen into 2-Ti3Al, underneath the alumina layer, this allowed calculating the true value of the kinetic constant for the growth of a pure alumina layer on titanium aluminides.