Novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.
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.
This report represents completion of milestone deliverable M2SF-19SNO10309013 "Online Waste Library (OWL) and Waste Forms Characteristics Annual Report" that reports annual status on fiscal year (FY) 2019 activities for the work package SF-19SN01030901 and is due on August 2, 2019. The online waste library (OWL) has been designed to contain information regarding United States (U.S.) Department of Energy (DOE)-managed (as) high-level waste (DHLW), spent nuclear fuel (SNF), and other wastes that are likely candidates for deep geologic disposal, with links to the current supporting documents for the data (when possible; note that no classified or official-use-only (OUO) data are planned to be included in OWL). There may be up to several hundred different DOE-managed wastes that are likely to require deep geologic disposal. This annual report on FY2019 activities includes evaluations of waste form characteristics and waste form performance models, updates to the OWL development, and descriptions of the management processes for the OWL. Updates to the OWL include an updated user's guide, additions to the OWL database content for wastes and waste forms, results of the beta testing and changes implemented from it. Also added are descriptions of the management/control processes for the OWL development, version control, and archiving. These processes have been implemented as part of the full production release of OWL (i.e., OWL Version 1.0), which has been developed on, and will be hosted and managed on, Sandia National Laboratories (SNL) systems. The version control/update processes will be implemented for updates to the OWL in the future. Additionally, another process covering methods for interfacing with the DOE SNF Database (DOE 2007) at Idaho National Laboratory on the numerous entries for DOE-managed SNF (DSNF) has been pushed forward by defining data exchanges and is planned to be implemented sometime in FY2020. The INL database is also sometimes referred to as the Spent Fuel Database or the SFDB, which is the acronym that will be used in this report. Once fully implemented, this integration effort will serve as a template for interfacing with additional databases throughout the DOE complex.
In an effort to generate single-source precursors for the production of metal-siloxide (MSiOx) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe3)3 (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as [Ti(SST)2(OR)2] (OR = OPri (2), OBut (3), ONep (4)); [Ti(SST)3(OBun)] (5); [Zr(SST)2(OBut)2(py)] (6); [Zr(SST)3(OR)] (OR = OBut (7), ONep, (8)); [Hf(SST)2(OBut)2] (9); and [Hf(SST)2(ONep)2(py)n] (n = 1 (10), n = 2 (10a)) where OPri = OCH(CH3)2, OBut = OC(CH3)3, OBun = O(CH2)3CH3, ONep = OCH2C(CH3)3, py = pyridine. The crystal structures revealed varied SST substitutions for: monomeric Ti species that adopted a tetrahedral (T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal (TBPY-5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as [V(SST)3(py)2] (11), [Nb(SST)3(OEt)2] (12), [Nb(O)(SST)3(py)] (13), 2[H][(Nb(μ-O)2(SST))6(μ6-O)] (14), [Nb8O10(OEt)18(SST)2·1/5Na2O] (15), [Ta(SST)(μ-OEt)(OEt)3]2 (16), and [Ta(SST)3(OEt)2] (17) where OEt = OCH2CH3. The group 5 monomeric complexes were solved in a TBPY-5 arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiOx materials. The complexes were thermally processed (350-1100 °C, 4 h, ambient atmosphere), but instead of the desired MSiOx, transmission electron microscopy analyses revealed that fractions of the group 4 and group 5 precursors had formed unusual metal oxide silica architectures.