Publications

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Techniques for mitigating the adsorption of {sup 137}Cs and {sup 60}Co on metal surfaces (e.g. RAM packages) exposed to contaminated water (e.g. spent-fuel pools) have been developed and experimentally verified. The techniques are also effective in removing some of the {sup 60}Co and {sup 137}Cs that may have been adsorbed on the surfaces after removal from the contaminated water. The principle for the {sup 137}Cs mitigation technique is based upon ion-exchange processes. In contrast, {sup 60}Co contamination primarily resides in minute particles of crud that become lodged on cask surfaces. Crud is an insoluble Fe-Ni-Cr oxide that forms colloidal-sized particles as reactor cooling systems corrode. Because of the similarity between Ni{sup 2+} and Co{sup 2+}, crud is able to scavenge and retain traces of cobalt as it forms. A number of organic compounds have a great specificity for combining with nickel and cobalt. Ongoing research is investigating the effectiveness of chemical complexing agent EDTA with regard to its ability to dissolve the host phase (crud) thereby liberating the entrained {sup 60}Co into a solution where it can be rinsed away.

Techniques for mitigating the adsorption of {sup 137}Cs and {sup 60}Co on metal surfaces (e.g. RAM packages) exposed to contaminated water (e.g. spent-fuel pools) have been developed and experimentally verified. The techniques are also effective in removing some of the {sup 60}Co and {sup 137}Cs that may have been adsorbed on the surfaces after removal from the contaminated water. The principle for the {sup 137}Cs mitigation technique is based upon ion-exchange processes. In contrast, {sup 60}Co contamination primarily resides in minute particles of crud that become lodged on cask surfaces. Crud is an insoluble Fe-Ni-Cr oxide that forms colloidal-sized particles as reactor cooling systems corrode. Because of the similarity between Ni{sup 2+} and Co{sup 2+}, crud is able to scavenge and retain traces of cobalt as it forms. A number of organic compounds have a great specificity for combining with nickel and cobalt. Ongoing research is investigating the effectiveness of chemical complexing agent EDTA with regard to its ability to dissolve the host phase (crud) thereby liberating the entrained {sup 60}Co into a solution where it can be rinsed away.

A novel layered manganese(II) phosphate, Mn{sub 3}(PO{sub 4}){sub 4} {center_dot} 2(H{sub 3}NCH{sub 2}CH{sub 2}){sub 3}N {center_dot} 6(H{sub 2}O), has been synthesized solvothermally using tris(2-aminoethyl)amine (TREN) as a template. The structure was solved ab initio using X-ray powder diffraction data and confirmed by molecular modeling. The compound was further characterized by SEM, IR spectroscopy, photoluminescence, and elemental and thermal analysis. The compound crystallizes in the trigonal space group P{sub 3}c1 with a = 8.8706(4) {angstrom}, c = 26.158(2) {angstrom}, and V = 1782.6(2) {angstrom}{sup 3}. The structure consists of layers of corner sharing Mn(II)O{sub 4} and PO{sub 4} tetrahedra forming infinite [Mn{sub 3}(PO{sub 4}){sub 4}]{sup 6-} macroanions with 4.6 net topology, sandwiched by layers of TREN and water molecules. The protonated TREN molecules provide charge balancing for the inorganic sheets; the interlayer stability is accomplished mainly by a network of hydrogen bonds between water molecules and the inorganic macroanions. This hybrid organic/inorganic layered material can be reversibly dehydrated.

Polyoxoniobate chemistry, both in the solid state and in solution is dominated by [Nb{sub 6}O{sub 19}]{sup 8-}, the Lindquist ion. Recently, we have expanded this chemistry through use of hydrothermal synthesis. The current publication illustrates how use of heteroatoms is another means of diversifying polyoxoniobate chemistry. Here we report the synthesis of Na{sub 8}[Nb{sub 8}Ti{sub 2}O{sub 28}] {center_dot} 34H{sub 2}O [{bar 1}] and its structural characterization from single-crystal X-ray data. This salt crystallizes in the P-1 space group (a = 11.829(4) {angstrom}, b = 12.205(4) {angstrom}, c = 12.532(4) {angstrom}, {alpha} = 97.666(5){sup o}, {beta} = 113.840(4){sup o}, {gamma} = 110.809(4){sup o}), and the decameric anionic cluster [Nb{sub 8}Ti{sub 2}O{sub 28}]{sup 8-} has the same cluster geometry as the previously reported [Nb{sub 10}O{sub 28}]{sup 6-} and [V{sub 10}O{sub 28}]{sup 6-}. Molecular modeling studies of [Nb{sub 10}O{sub 28}]{sup 6-} and all possible isomers of [Nb{sub 8}Ti{sub 2}O{sub 28}]{sup 8-} suggest that this cluster geometry is stabilized by incorporating the Ti{sup 4+} into cluster positions in which edge-sharing is maximized. In this manner, the overall repulsion between edge-sharing octahedra within the cluster is minimized, as Ti{sup 4+} is both slightly smaller and of lower charge than Nb{sup 5+}. Synthetic studies also show that while the [Nb{sub 10}O{sub 28}]{sup 6-} cluster is difficult to obtain, the [Nb{sub 8}Ti{sub 2}O{sub 28}]{sup 8-} cluster can be synthesized reproducibly and is stable in neutral to basic solutions, as well.

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Exploratory hydrothermal synthesis in the system Cs2O-SiO2-TiO2 has produced a new polymorph of Cs2TiSi6O15 (SNL-A), whose structure was determined using a combination of experimental and theoretical techniques (29Si and 133Cs NMR, X-ray powder diffraction, and density functional theory). SNL-A crystallizes in the monoclinic space group Cc with unit cell parameters a = 12.998(2) Å, b = 7.5014(3) Å, c = 15.156(3) Å, and β = 105.80(3)°. The SNL-A framework is an unbranched drier single-layer silicate with silicon tetrahedra and titanium octahedra that are linked in 3-, 5-, 6-, 7-, and 8-membered rings in three dimensions. SNL-A is distinctive from a previously reported C2/c polymorph of Cs2TiSi6O15 by orientation of the Si2O52- layers and by different ring geometries. Similarities and differences between the two structures are discussed. Other characterizations of SNL-A include TGA-DTA, Cs/Si/Ti elemental analyses, and SEM/EDS. Furthermore, the chemical and radiation durability of SNL-A was studied in interest of ceramic waste form applications. These studies show that SNL-A is durable in both radioactive and rigorous chemical environments. Finally, calculated cohesive energies of the two Cs2TiSi6O15 polymorphs suggest that the Cc SNL-A phase (synthesized at 200 °C) is energetically more favorable than the C2/c polymorph (synthesized at 1050 °C).

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