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Magnetic Resonance as a Structural Probe of a Uranium (Vi) Sol-Gel Process

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Abstract

Nuclear Magnetic Resonance (NMR) investigations on the Oak Ridge National Laboratory process for sol-gel synthesis of microspherical nuclear fuel (UO2), has been extremely useful in sorting out the chemical mechanism in the sol-gel steps. 13C, 15N, and 1H NMR studies on the HMTA gelation agent (hexamethylenetetramine, C6H12N4) 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. 17O NMR of uranyl (UO2 ++) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO2)3 (μ3-O)(μ2-OH)3]+, induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results will be presented to illustrate that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH+ 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 (NH4)2 [(UO2)8 O4 (OH)10]- 8H2)O. This compound is the precursor to sintered UO2 ceramic fuel.

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Authors and Affiliations

  1. Westinghouse Savannah River Company, Aiken, SC, USA

    Charles M. King, Major C. Thompson & Bruce R. Buchanan

  2. Department of Chemistry, University of Georgia, Athens, GA, USA

    R. Bruce King

  3. Department of Chemistry, University of South Carolina, Columbia, SC, USA

    A. Ronald Garber

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  1. Charles M. King
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  2. R. Bruce King
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  3. A. Ronald Garber
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  4. Major C. Thompson
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  5. Bruce R. Buchanan
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King, C.M., Bruce King, R., Ronald Garber, A. et al. Magnetic Resonance as a Structural Probe of a Uranium (Vi) Sol-Gel Process. MRS Online Proceedings Library 180, 1075 (1990). https://doi.org/10.1557/PROC-180-1075

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