Magnetic resonance as a structural probe of a uranium (VI) sol-gel process

NMR investigations on the ORNL process for sol-gel synthesis of microspherical nuclear fuel (UO{sub 2}), has been useful in sorting out the chemical mechanism in the sol-gel steps. {sup 13}C, {sup 15}N, and {sup 1}H NMR studies on the HMTA gelation agent (Hexamethylene tetramine, C{sub 6}H{sub l2}N{sub 4}) has revealed near quantitative stability of this adamantane-like compound in the sol-Gel process, contrary to its historical role as an ammonia source for gelation from the worldwide technical literature. {sub 17}0 NMR of uranyl (UO{sub 2}{sup ++}) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO{sub 2}){sub 3}({mu}{sub 3}-O)({mu}{sub 2}-OH){sub 3}]{sup +}, induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results show that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH{sup +} is occluded as an ``intercalation`` cation. Subsequent sol-gel processing of microspheres by ammonia washing results in in-situ ion exchange and formation of a layered hydrous ammonium uranate with a proposed structural formula of (NH{sub 4}){sub 2}[(UO{sub 2}){sub 8}O{sub 4}(OH){sub 10}] {center_dot} 8H{sub 2}0. This compound is the precursor to sintered U0{sub 2} ceramic fuel.