Selection and Characterization of Carbon Black and Surfactants for Development of Small Scale Uranium Oxicarbide Kernels

Abstract

This report supports the effort for development of small scale fabrication of UCO (a mixture of UO{sub 2} and UC{sub 2}) fuel kernels for the generation IV high temperature gas reactor program. In particular, it is focused on optimization of dispersion conditions of carbon black in the broths from which carbon-containing (UO{sub 2} {center_dot} H{sub 2}O + C) gel spheres are prepared by internal gelation. The broth results from mixing a hexamethylenetetramine (HMTA) and urea solution with an acid-deficient uranyl nitrate (ADUN) solution. Carbon black, which is previously added to one or other of the components, must stay dispersed during gelation. The report provides a detailed description of characterization efforts and results, aimed at identification and testing carbon black and surfactant combinations that would produce stable dispersions, with carbon particle sizes below 1 {micro}m, in aqueous HMTA/urea and ADUN solutions. A battery of characterization methods was used to identify the properties affecting the water dispersability of carbon blacks, such as surface area, aggregate morphology, volatile content, and, most importantly, surface chemistry. The report introduces the basic principles for each physical or chemical method of carbon black characterization, lists the results obtained, and underlines cross-correlations between methods. Particular attention is givenmore » to a newly developed method for characterization of surface chemical groups on carbons in terms of their acid-base properties (pK{sub a} spectra) based on potentiometric titration. Fourier-transform infrared (FTIR) spectroscopy was used to confirm the identity of surfactants, both ionic and non-ionic. In addition, background information on carbon black properties and the mechanism by which surfactants disperse carbon black in water is also provided. A list of main physical and chemical properties characterized, samples analyzed, and results obtained, as well as information on the desired trend or range of values generally associated with better dispersability, is provided in the Appendix. Special attention was given to characterization of several surface-modified carbon blacks produced by Cabot Corporation through proprietary diazonium salts chemistry. As demonstrated in the report, these advanced carbons offer many advantages over traditional dispersions. They disperse very easily, do not require intensive mechanical shearing or sonication, and the particle size of the dispersed carbon black aggregates is in the target range of 0.15-0.20 {micro}m. The dispersions in water and HMTA/urea solutions are stable for at least 30 days; in conditions of simulated broth, the dispersions are stable for at least 6 hours. It is proposed that the optimization of the carbon black dispersing process is possible by replacing traditional carbon blacks and surfactants with surface-modified carbon blacks having suitable chemical groups attached on their surface. It is recognized that the method advanced in this report for optimizing the carbon black dispersion process is based on a limited number of tests made in aqueous and simulated broth conditions. The findings were corroborated by a limited number of tests carried out with ADUN solutions by the Nuclear Science and Technology Division at Oak Ridge National Laboratory (ORNL). More work is necessary, however, to confirm the overall recommendation based on the findings discussed in this report: namely, that the use of surface-modified carbon blacks in the uranium-containing broth will not adversely impact the chemistry of the gelation process, and that high quality uranium oxicarbide (UCO) kernels will be produced after calcination.« less