Cerium and boron chemistry in doped borosilicate glasses examined by EELS.

Spatially resolved measurements of boron coordination and cerium valency in a doped borosilicate glass with crystalline nano-precipitates are described. The fine structure of the boron K-edge and the white-line ratio of the cerium M-edge doublet were evaluated from EELS line scans. Due to high beam sensitivity it was found that reliable boron-coordination measurements in some of the glasses studied required extrapolation of results acquired after different periods of irradiation back to a zero-irradiation. However, borosilicates that contained heavy alkali atoms were found to suffer very little structural change. The Ce valency of a 4% (molar) doped alkali-borosilicate glass was found to be mixed +III/+IV in the glass matrix and purely +IV (indicative of CeO2) in the precipitates. A significant dependency of the valence results on the data processing method was found and explained.

Vitrified metal finishing wastes II. Thermal and structural characterisation.

Waste filter cakes from two metal finishing operations were heat treated and vitrified. Substantial weight loss during heating was due to emission of water, volatile sulphur-rich and chlorine-rich compounds, and the combustion of carbonaceous components. Estimations of CO(x), SO(x) and HCl emissions were based on chemical analyses. Upon cooling from molten, one sample remained amorphous but all others partially crystallised. Crystalline nature was dependent upon waste composition and the level of P(2)O(5) addition. Thermal stabilities of the waste forms were good, but less so than MW, a borosilicate glass developed for its high temperature stability. Mossbauer and FTIR analyses showed that iron environments in the different vitrified waste forms were very similar. Iron was present predominantly as Fe(3+), although the exact redox ratio varied slightly between waste forms. Iron in both redox states occupied distorted octahedral coordination polyhedra with similar levels of site distortion. Phosphate networks in the vitreous materials were highly de-polymerised, consisting largely of (PO(4))(3-) monomer and (P(2)O(7))(2-) dimer units. This explained the high chemical durability of these waste forms and their structural insensitivity to compositional change, underlining their suitability as hosts for the immobilisation of toxic and nuclear wastes.

Vitrified metal finishing wastes I. Composition, density and chemical durability.

Durable phosphate glasses were formed by vitrifying waste filter cakes from two metal finishing operations. Some melts formed crystalline components during cooling. Compositional analysis of dried, heat treated and vitrified samples was made using energy-dispersive X-ray spectroscopy, X-ray fluorescence spectroscopy, inductively-coupled plasma spectroscopy and Leco induction furnace combustion analysis. Hydrolytic dissolution, measured by an adapted product consistency test, was reduced by up to 3 orders of magnitude upon heat treatment or vitrification, surpassing the performance of borosilicate glass in some cases. This was attributed to the high levels of iron and zinc in the wastes, which greatly improve the durability of phosphate glasses. One of the wastes arose from a metal phosphating process and was particularly suitable for vitrification due to its high P2O5 content and favourable melting behaviour. The other waste, which arose from a number of processes, was less suitable as it had a low P2O5 content and during heating it emitted harmful corrosive gases and underwent violent reactions. Substantial volume reductions were obtained by heat treatment and vitrification of both wastes. Compositions and performances of some vitrified wastes were comparable with those of glasses which are under consideration for the immobilisation of toxic and nuclear wastes.