Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Alternative candidate precursors to [Hf(BH4)4] for low-temperature chemical vapor deposition of hafnium diboride (HfB2) films were identified using density functional theory simulations of molecules with the composition [Hf(BH4)2L2], where L = -OH, -OMe, -O-t-Bu, -NH2, -N═C═O, -N(Me)2, and -N(CH2)5NH2 (1-piperidin-2-amine referred to as Pip2A). Disassociation energies (ED), potential energy surface (PES) scans, ionization potentials, and electron affinities were all calculated to identify the strength of the Hf-L bond and the potential reactivity of the candidate precursor. Ultimately, the low ED (2.07 eV) of the BH4 ligand removal from the Hf atom in [Hf(BH4)4] was partially attributed to an intermediate state where [Hf(BH4)3(H)] and BH3 is formed. Of the candidate precursors investigated, three exhibited a similar mechanism, but only -Pip2A had a PES scan that indicated binding competitive with [Hf(BH4)4], making it a viable candidate for further study.

Airborne contaminants from fires containing nuclear waste represent significant health hazards and shape the design and operation of nuclear facilities. Much of the data used to formulate DOE-HDBK-3010-94, “Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities,” from the U.S. Department of Energy, were taken over 40 years ago. The objectives of this study were to reproduce experiments from Pacific Northwest Laboratories conducted in June 1973 employing current aerosol measurement methods and instrumentation, develop an enhanced understanding of particulate formation and transport from fires containing nuclear waste, and provide modeling and experimental capabilities for updating current standards and practices in nuclear facilities. A special chamber was designed to conduct small fires containing 25 mL of flammable waste containing lutetium nitrate, ytterbium nitrate, or depleted uranium nitrate. Carbon soot aerosols showed aggregates of primary particles ranging from 20 to 60 nm in diameter. In scanning electron microscopy, ~200-nm spheroidal particles were also observed dispersed among the fractal aggregates. The 200-nm spherical particles were composed of metal phosphates. Airborne release fractions (ARFs) were characterized by leaching filter deposits and quantifying metal concentrations with mass spectrometry. The average mass-based ARF for 238U experiments was 1.0 × 10−3 with a standard deviation of 7.5 × 10−4. For the original experiments, DOE-HDBK-3010-94 states, “Uranium ARFs range from 2 × 10−4 to 3 × 10−3, an uncertainty of approximately an order of magnitude.” Thus, current measurements were consistent with DOE-HDBK-3010-94 values. ARF values for lutetium and ytterbium were approximately one to two orders of magnitude lower than 238U. Metal nitrate solubility may have varied with elemental composition and temperature, thereby affecting ARF values for uranium surrogates (Yb and Lu). In addition to ARF data, solution boiling temperatures and evaporation rates can also be deduced from experimental data.

Abstract not provided.

The coordination behavior of the tridentate alkoxy ligand 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene)) bis(2,4-di-tert-butylphenol) (termed H3-AM-DBP2) with group 4 metal alkoxides ([M(OR)4]) in a 1:1 ratio was previously found to generate [(ONep)Ti(κ 4 (O,O’,O”,N)-AM-DBP2)] and [(OR)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP2)]2 (M = Zr, Hf). Additional studies revealed that increasing the stoichiometric ratio to 1:2 H3-AM-DBP2:[M(OR)4] led to the isolation of [(ONep)Ti(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-ONep)Ti(ONep)3] (1)•tol, [(OBu t)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t)Zr(OBu t)3] (2) and [(OBu t)Hf(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t)Hf(OBu t)3] (3). The asymmetric dinuclear complexes of 1-3 resemble the chelation of a [M(OR)4] moiety to a “(OR)M(κ 4 (O,O’,O”,N)-AM-DBP2)” fragment. The metal complexed by the AM-DBP2 ligand has a pseudo octahedral geometry while the other metal adopts an intermediate trigonal bipyramidal (TBP-5)/square base pyramidal (SBP-5) geometry for 1 but a distorted SBP-5 for both 2 and 3. The structure and properties of 1-3 were analyzed by computational modeling and fully characterized by standard analytical methods. (Figure presented.).

Abstract not provided.

The behavior of commercially available potential obscurants for cobalt-60 (⁶⁰Co) wet-source storage industrial irradiator facilities (IRFs) were further evaluated for corrosive behavior of Nordion C-188 pencil stubs and obscurant properties under radiation exposure (⁶⁰Co). The potential obscurants studied included: titania aqueous dispersions (TAD - water soluble white paint), Chlorazol Black (CBOD - Chlorazol Black organic dye), powdered milk (COW - calcium obscurant in water), diatomaceous earth (DEA - diatomaceous earth additive), and rhodamine 6G (R6G). For corrosion efforts, stubs from an inert C-188 pencil-source rod were soaked in obscurant solutions and visually inspected. For radiation stability, obscurant samples were exposed to ⁶⁰Co radiation sources at 207 rad/s. The results from these studies reveal: the obscurants had no impact on the surrogate samples and may assist in terms of corrosion resistance; materials that did not rely on organic compounds to provide obscurance performed the best, as the organic compounds decomposed too rapidly in the high radiation environment, whereas the materials survived.

Abstract not provided.

Abstract not provided.

Abstract not provided.

A series of titanium alkoxides ([Ti(OR)₄] (OR = OCH(CH₃)₂ (OPri), OC(CH₃)₃ (OBut), and OCH₂C(CH₃)₃ (ONep)) were modified with a set of substituted hydroxyl-benzaldehydes [HO-BzA-Lx: x = 1, 2-hydroxybenzaldehyde (L = H), 2-hydroxy-3-methoxybenzaldehyde (OMe-3), 5-bromo-2-hydroxybenzaldehyde (Br-5), 2-hydroxy-5-nitrobenzaldehyde (NO₂-5); x = 2, 3,5-di-tert-butyl-2-hydroxybenzaldehyde (Bu^t-3,5), 2-hydroxy-3,5-diiodobenzaldehyde (I-3,5)] in pyridine (py). Instead of the expected simple substitution, each of the HO-BzA-Lx modifiers were reduced to their respective diol [(py)(OR)₂Ti(κ²(O,μ-O')(OC₆H_4–x(CH₂O)-2)(L)_x] (OR = OPrⁱ, x = 1, L = H (1a), OMe-3 (2a), Br-5 (3a·py), NO2-5 (4a·4py); x = 2, But-3,5 (5a), I-3,5 (6a), ONep; x = 1, L = H (1b), OMe-3 (2b), Br-5 (3b·py), NO2-5 (4b); x = 2, Bu^t-3,5 (5b), I-3,5 (6b·py)), as identified by single crystal X-ray studies. The ¹H NMR spectral data were complex at room temperature but simplified at high temperatures (70 °C). Diffusion ordered spectroscopy (DOSY) NMR experiments indicated that 2a maintained the dinuclear structure in a solution independent of the temperature, whereas 2b appears to be monomeric over the same temperature range. On the basis of additional NMR studies, the mechanism of the reduction of the HO-BzA-L_x to the dioxide ligand was thought to occur by a Meerwein–Pondorf–Verley (MPV) mechanism. The structures of 1a–6b appear to be the intermediate dioxide products of the MPV reduction, which became “trapped” by the Lewis basic solvate.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.