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Chemey, Alexander T.

Publications and source records attributed to Chemey, Alexander T..

Preparation of Actinide Targets at Oregon State University

In this paper, we describe the preparation of actinide targets at Oregon State University. The preparation of the actinide fluorides is done by an aqueous precipitation procedure with yields of greater than 90%. A dual glove box system is used for the preparation of the fluorides of the high specific activity actinides and the subsequent vapor deposition. We compare and contrast targets made by vapor deposition and molecular plating. We discuss some new data on the structure of actinide targets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast-neutron-induced fission of Pu 240 and Pu 242

Herein we report the measurement of the total kinetic energy (TKE) release in the fast neutron induced fission of 240 Pu and 242 Pu. The results are compared to the predictions of the GEF model, the CGMF model, and the model of Denisov and Sedykh as well as previous exptl. work on these reactions. Our absolute measurements of the TKE release are in good agreement with the previous measurements of Nethaway et al. for the interaction of 14.8 MeV neutrons with 240 Pu [Phys. Rev. C16, 1907 (1977)] and of Winkelmann and Aumann for the interaction of 15 MeV neutrons with 242 Pu [Phys. Rev. C30, 934 (1984)]. The general trends of the measured TKE values agree with phenomenol. models but the variances of the TKE distributions are significantly less than predicted by various models. The mean postneutron emission TKE release decreases nonlinearly with increasing neutron energy and can be represented as TKE(MeV) = 175.8 ± 0.3 - (2.4 ± 0.8) lo g 10 E n - (1.4 ± 0.4) lo g 10 $E^{2}_{n}$ for 240 Pu and TKE(MeV) = 177.1 ± 0.3 - (1.2 ± 0.9) lo g 10 E n - (1.8 ± 0.5)lo g 10 $E_{n}^{2}$ for 242 Pu.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Compression of curium pyrrolidine-dithiocarbamate enhances covalency

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell. This is even more pronounced in gadolinium, curium’s lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms. Therefore, the question arises of whether the frontier metal orbitals in curium(III)–ligand interactions can also be modified by applying pressure, and thus be induced to form metal–ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium–sulfur bonds in [Cm(pydtc) 4 ] – (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc) 4 ] – and of a Cm(III) mellitate that possesses only curium–oxygen bonds. Compared with the changes observed in the [Cm(pydtc) 4 ] – spectra, we observe smaller changes in the f–f transitions in the [Nd(pydtc) 4 ] – absorption spectrum and in the f–f emission spectrum of the Cm(III) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium–sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Furthermore, our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examination of Molten Salt Reactor Relevant Elements Using Hydrothermal Synthesis

The structural chemistry of elements relevant to the FLiBe molten salt reactor, Th, U, Np, and Zr, including Ce andNd (as analogues for Pu and Am, respectively), have been examined using hydrothermal synthesis at 200 °C. These reactions serve to model the reaction of molten salts under hydrolysis conditions. The results show that U and Np formed LiAnF 5 , while Ce formed Li 4 CeF 8 . The source of U also controlled the crystal quality, where UO 2 gave small crystals, while UO 3 ·2H 2 O gave very large crystals. It is likely that Be incorporation was not observed because of the high solubility of [BeF 4 ] 2– in water. Zr formed a third product, Li 6 BeF 4 ZrF 8 , which features isolated [BeF 4 ] 2– and [ZrF 8 ] 4– units bridged by Li + . Additionally, Li 2 BeF 4 was regularly isolated. As a result, when little to no alkali metal was included in the reaction, M 3 F 12 (H 2 O) was isolated for Np, U, and Ce.

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