The kinetics of the isotope exchange between gaseous oxygen enriched with the 18O
isotope and two LaMnO3+δ oxide samples – a nanopowder and a bulk nanocrystal – has been
studied. The 18O isotope concentration has been measured by the acceleration nuclear microanalysis
method. The coefficients of the volume and the nanograin boundary self-diffusion of oxygen have
been evaluated at 500 °C. They are equal to 3.5·10
−20 and 1.5·10
−13 cm2/s, respectively.
It is shown that investigations of the isotope exchange kinetics in nanocrystalline oxides allows one not only to solve problems connected with determination of process parameters and characteristic scenarios, but also to substantially extend experimental opportunities in analysis of diffusion properties of oxides. A specific behavior of the oxygen isotope exchange was studied in nanocrystalline LaMnO3 and ZrO2:Y2O3 oxides. The former oxide is characterized by very small values of oxygen volume diffusion coefficients, while the latter one is, on the contrary, an ionic conductor. The study was carried out using powdered nanomaterials prepared from original ceramic materials by grinding in planetary mills or by laser evaporation. The study revealed future trends in the use of nanomaterials for analysis of the diffusion kinetics in oxides. It is demonstrated that in this case the sensitivity of traditional isotope methods increases considerably and fundamentally new opportunities are provided for analysis of processes on the "gas phase solid state" interface as well as for the study of volume diffusion in polycrystals.
Considering a strong dependence of the isotope exchange rate on the particle size, it is also topical to conduct studies dealing, along with determination of kinetic parameters of the process, with the use of the obtained data for certification of dimensional characteristics of oxide nanopowders.
The tracer diffusion coefficient D* and the mobility of protons in proton-conducting
oxides of the АIIВIV
1-xRIII
xO3-δ family have been calculated using the Monte Carlo method as
functions of temperature and concentration x of the acceptor impurity RIII. The effect of protondopant
interactions (proton trapping) and the effect of protonic sites blocking caused by protonproton
and proton - oxygen vacancy interactions, are analyzed. It is shown that the proton
diffusivity depends significantly on the dopant content and is considerably reduced already at small
x. The D* value weakly depends on the concentration of oxygen vacancies at fixed, not too large
values of x. The conductivity dependence on the doping concentration σ(x) can have a maximum
due to the proton-defect and proton-proton interactions. The Haven ratio deviates slightly from
unity at the expected intensity of interparticle correlations. The calculated values of both the
diffusivity activation energy increase (with x), and the location of the σ(x) maxima agree with the
experimental data for a number of proton-conducting oxides.
sotope exchange of oxygen 18О2 with oxides NdMnO3+δ was investigated. The oxide was obtained from oxides Nd2O3 and Mn2O3 using a ceramic technology with annealing in air at 1400°C for 90 hours followed by cooling in a furnace. A planetary mill AGO-2 with a centrifugal factor of g = 60 was used for mechanical treatment of oxides. The study of isotope exchange was carried out by nuclear microanalysis. The concentration of the isotopes 18O and 16O in oxides was determined using a Van de Graaff accelerator and 18O(p, α)15N and 16O(d, p)17O* reactions at the energies of incident beams 762 and 900 keV. Isothermal annealing of powders was carried out in oxygen, enriched to 80% by the isotope 18O. It was established that the concentration of the isotope 18O in mechanically activated powders was several times higher than in the initial micropowder under the same conditions of annealing. The effect increased with increasing of mechanical activation time (30 - 300 s). The isotope exchange parameters connected with the processes at the boundaries of the particles of mechano-activated powder and within their volume were analyzed.
The results of preliminary experimental researches of possibility of metallurgical processing of ores of Actually Kachkanarsky deposit are presented in the work.
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