PNNL

Abstract

Glasses are found in most reduction-oxidation (redox) items that are used everyday; from automobiles to planes. With stability of most glasses, they are being used to store hazardous waste materials. Many elements have different oxidation states and are found in multiple states in glasses. Redox of glasses has significant effect on processing of waste glass melts in melters as well as properties of the waste forms. Nuclear waste glasses generally have complex chemistry (including several redox ions) and form corrosive melts. Basic objective: study the redox of the glasses containing Fe and Ni with square wave voltammetry. A basic simulated frit glass was used for vitrification. The frit composition used was 57.90% SiO2, 17.70% Na2O, 14.70% B2O3, 5.70% Li2O, 2.00% MgO, 1.00% TiO2, 0.50% ZrO2, and 0.50% La2O3. Batch glasses were synthesized and then dopants of Fe2O3 , NiO, and a combination of Fe2O3-NiO were added in 1-wt % amounts. The glass was melted at 1150 C and held for 24 hours. It was poured to the top of a medium sized Pt/Rh crucible and placed in a furnace at 1150 C. The glass powder was allowed to melt for five minutes before the testing apparatus was placed in the melt. The testing apparatus was composed of a Pt/Rh working electrode, Pt/Rh counter electrode, and a Zr/Al reference electrode. The counter electrode is placed in the melt until it is touching the bottom of the crucible creating a closed circuit. Both the reference electrode and working electrode are located half way down the counter electrode. The test showed that melt resistivity was high indicating the amount of conductivity in the melt. Sample melt volume and area of the working electrode were high. Adjusting the crucible size and sizing other electrodes will improve the measurements. Future work: testing NiO glass and Fe2O3-NiO glass to see the interaction between the Fe and the Ni and synthesis of 2 wt %, 3 wt %, and 5-wt % Fe2O3 doped glasses to study effects of Fe concentration.