Award Date


Degree Type


Degree Name

Doctor of Philosophy (PhD)

First Committee Member

Kenneth Czerwinski

Second Committee Member

Frederic Poineau

Third Committee Member

Alfred Sattelberger

Fourth Committee Member

Jacimaria Batista

Number of Pages



The isotope Technetium-99 (99Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO4]-, Tc represents long-term concern to the biosphere. Various options have been considered to manage 99Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric acid and extraction of U and Tc in organic media, previously developed methods can be used to separate Tc from U, convert the separate Tc stream to the metal and reuse the uranium component of the fuel. A variety of metallic waste forms, ranging from pure Tc metal to ternary Tc alloys combined with stainless steel (SS) and Zr are proposed. The goal of this work was to examine three major questions: What is the optimal method to separate Tc from U? After separation, what is the most efficient method to convert the Tc stream to Tc metal? Finally, what is the corrosion behavior of Tc metal, Tc-SS alloys and Tc-Zr-SS alloys in 0.01M NaCl? The goal is to predict the long term behavior of Tc metallic waste in a hypothetical storage environment.

In this work, three methods have been used to separate Tc from U: anionic exchange resin, liquid-liquid extraction and precipitation. Of the three methods studied, anionic exchange resins is the most selective. After separation of Tc from U, three different methods were studied to convert the Tc stream to the metal: thermal treatment under hydrogen atmosphere, electrochemical and chemical reduction of pertechnetate in aqueous media. The thermal treatment of the Tc stream under hydrogen atmosphere is the preferred method to produce Tc metal. After Tc metal is isolated, it will be incorporated into a metal host phase. Three different waste forms were produced for corrosion studies in this work: Pure Tc metal, SS(Tc 2 wt%)Zr and SS(Tc 1.34 wt%) alloys. Corrosion rate measurements indicate that both SS(Tc 2 wt%)Zr and SS(Tc 1.34 wt%) alloys corrode more slowly than metallic Tc in the solutions tested.


Alloys; Corrosion; Radioactive wastes; Separation (Technology); Technetium – Corrosion; Technetium – Separation; Uranium – Separation; Waste form


Analytical Chemistry | Chemistry | Oil, Gas, and Energy | Radiochemistry