Vaclav Tyrpekl

On the Role of the Electrical Field in Spark Plasma Sintering of UO2+x

The electric field has a large effect on the stoichiometry and grain growth of UO2+x during Spark Plasma Sintering. UO2+x is gradually reduced to UO2.00 as a function of sintering temperature and time. A gradient in the oxidation state within the pellets is observed in intermediate conditions. The shape of the gradient depends unequivocally on the direction of the electrical field. The positive surface of the pellet shows a higher oxidation state compared to the negative one. An area with larger grain size is found close to the positive electrode, but not in contact with it. We interpret these findings with the redistribution of defects under an electric field, which affect the stoichiometry of UO2+x and thus the cation diffusivity. The results bear implications for understanding the electric field assisted sintering of UO2 and non-stoichiometric oxides in general.

Homogeneous hydrolysis of thorium by thermal decomposition of urea

Abstract Thorium was precipitated homogeneously from a thorium nitrate solution by the thermal decomposition products of urea. The kinetics of the hydrolysis were studied at 90 and 100°C by pH measurement during the initial 5 h and the precipitation efficiencies of thorium and radium were measured over a 24 h period. Precipitation of the radium daughters was closely followed with the aim of co-precipitation of radium with thorium. The CO2 formed during urea decomposition dissolved in the solution, forming CO32− during the experiment upon reaching a sufficiently high pH level (>7). This allowed radium to co-precipitate partially, thus reducing the activity of the filtrate. After filtration or centrifugation, the precipitate is composed of nanocrystalline thorium dioxide (crystallite size ~10 nm), with weakly bound H2O and CO2.