Impact of boron complexation by Tris buffer on the initial dissolution rate of borosilicate glasses.

Tris(hydroxymethyl)aminomethane is a commonly used buffer for leaching studies on glasses. In this work, we demonstrate that it plays a role on the alteration kinetics of borosilicate glasses. Comparative dissolution experiments on a soda-lime silicate glass and a sodium borosilicate glass, in several solutions with or without Tris at neutral pH, are carried out in order to assess the specific effects of the ionic strength and of the Tris molecules on the initial dissolution kinetics. Tris has no effect on the dissolution of the soda-lime silicate glass, while it significantly enhances the dissolution of the borosilicate glass, by increasing the B, Na, and Si release rates. This specific effect on the borosilicate glass is attributed to the Tris-boron complexation and discussed. The bidentate complexation of boron by Tris(hydroxymethyl)aminomethane (Tris) with a 1:1 stoichiometry is directly demonstrated by infrared and NMR spectroscopies. Complexation constants are determined for the Tris-borate complex and its protonated form Tris-boric, from the (11)B and (1)H NMR spectra. This complexation should be taken into account when using the Tris/HCl buffer in alteration experiments of borosilicate glasses.

Paramagnetic defects induced by electron irradiation in barium hollandite ceramics for caesium storage.

We have studied by electron paramagnetic resonance the mechanism of defect production by electron irradiation in barium hollandite, a material used for immobilization of radioactive caesium. The irradiation conditions were the closest possible to those occurring in Cs storage waste forms. Three paramagnetic defects were observed, independently of the irradiation conditions. A hole centre (H centre) is attributed to a superoxide ion O(2)(-) originating from hole trapping by interstitial oxygen produced by electron irradiation. An electron centre (E(1) centre) is attributed to a Ti(3+) ion adjacent to the resulting oxygen vacancy. Another electron centre (E(2) centre) is attributed to a Ti(3+) ion in a cation site adjacent to an extra Ba(2+) ion in a neighbouring tunnel, originating from barium displacement by elastic collisions. Comparison of the effects of external irradiations by electrons with the ß-decay of Cs in storage waste forms is discussed. It is concluded that the latter would be dominated by E(1) and H centres rather than E(2) centres.