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Hobbs, D. T.; Shehee, T. C.; Clearfield, A.
Savannah River Site (SRS), Aiken, SC (United States). Funding organisation: USDOE (United States)2013
Savannah River Site (SRS), Aiken, SC (United States). Funding organisation: USDOE (United States)2013
AbstractAbstract
[en] This project seeks to determine if inorganic or hybrid inorganic ion-exchange materials can be exploited to provide effective americium and curium separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of the tested ion-exchange materials for actinide and lanthanide ions. During FY13, experimental work focused in the following areas: (1) investigating methods to oxidize americium in dilute nitric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium and (2) synthesis, characterization and testing of ion-exchange materials. Ion-exchange materials tested included alkali titanates, alkali titanosilicates, carbon nanotubes and group(IV) metal phosphonates. Americium oxidation testing sought to determine the influence that other redox active components may have on the oxidation of Am(III). Experimental findings indicated that Pu(IV) is oxidized to Pu(VI) by peroxydisulfate, but there are no indications that the presence of plutonium affects the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used. Tests also explored the influence of nitrite on the oxidation of Am(III). Given the formation of Am(V) and Am(VI) in the presence of nitrite, it appears that nitrite is not a strong deterrent to the oxidation of Am(III), but may be limiting Am(VI) by quickly reducing Am(VI) to Am(V). Interestingly, additional absorbance peaks were observed in the UV-Vis spectra at 524 and 544 nm in both nitric acid and perchloric acid solutions when the peroxydisulfate was added as a solution. These peaks have not been previously observed and do not correspond to the expected peak locations for oxidized americium in solution. Additional studies are in progress to identify these unknown peaks. Three titanosilicate ion exchangers were synthesized using a microwave-accelerated reaction system (MARS®) and determined to have high affinities for lanthanide ions in dilute nitric acid. The K-TSP ion exchanger exhibited the highest affinity for lanthanides in dilute nitric acid solutions. The Ge-TSP ion exchanger shows promise as a material with high affinity, but additional tests are needed to confirm the preliminary results. On the other hand, carbon nanotubes and nitrogen-doped carbon nanotubes exhibited low, but measureable affinities for lanthanide ions in dilute nitric acid solutions (pH 3 and 6). The MWCNT exhibited much lower affinities than the K-TSP in dilute nitric acid solutions. However, the MWCNT are much more chemically stable in concentrated nitric acid solutions and, therefore, may be candidates for ion exchange in more concentrated nitric acid solutions
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17 Sep 2013; 15 p; OSTIID--1093854; DE-AC09-08SR22470; Available from http://sti.srs.gov/fulltext/SRNL-STI-2013-00524.pdf; PURL: http://www.osti.gov/servlets/purl/1093854/
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ACTINIDES, CARBON, CHEMICAL REACTIONS, CHLORINE COMPOUNDS, ELECTROMAGNETIC RADIATION, ELEMENTS, HALOGEN COMPOUNDS, HYDROGEN COMPOUNDS, INORGANIC ACIDS, INORGANIC COMPOUNDS, MATERIALS, METALS, NANOSTRUCTURES, NANOTUBES, NITROGEN COMPOUNDS, NONMETALS, ORGANIC COMPOUNDS, ORGANIC PHOSPHORUS COMPOUNDS, OXYGEN COMPOUNDS, RADIATIONS, SILICATES, SILICON COMPOUNDS, TITANIUM COMPOUNDS, TRANSITION ELEMENT COMPOUNDS, TRANSPLUTONIUM ELEMENTS, TRANSURANIUM ELEMENTS
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