Crystallization of A3Ln(BO3)2 (A = Na, K; Ln = Lanthanide) from a Boric Acid Containing Hydroxide Melt: Synthesis and Investigation of Lanthanide Borates as Potential Nuclear Waste Forms.

A series of alkali metal rare-earth borates were prepared via high-temperature flux crystal growth, and their structures were characterized by single crystal X-ray diffraction (SXRD). Na3Ln(BO3)2 (Ln = La-Lu) crystallize in the monoclinic space group P21/n, the potassium series K3Ln(BO3)2 (Ln = La-Tb) crystallize in the orthorhombic space group Pnma, while the Ln = Dy, Ho, Tm, Yb analogues crystallize in the orthorhombic space group Pnnm. To demonstrate the generality of this synthetic technique, high-entropy oxide (HEO) compositions K3Nd0.15(1)Eu0.20(1)Gd0.20(1)Dy0.22(1)Ho0.23(1)(BO3)2 and K3Nd0.26(1)Eu0.29(1)Ho0.22(1)Tm0.14(1)Yb0.10(1)(BO3)2 were obtained in single crystal form. Radiation damage investigations determined that these borates have a high radiation damage tolerance. To assess whether trivalent actinide analogues of Na3Ln(BO3)2 and K3Ln(BO3)2 would be stable, density functional theory was used to calculate their enthalpies of formation, which are favorable.

Applications of Thermochemical Modeling in Molten Salt Reactors.

The extensively evaluated and consistent thermodynamic database, the Molten Salt Thermal Properties Database-Thermochemical (MSTDB-TC), was used along with additional thermodynamic values from other sources as examples of ways to examine molten salt reactor (MSR) fuel behavior. Relative stability with respect to halide potential and temperature for likely fuel and fission product components were mapped in Ellingham diagrams for the chloride and fluoride systems. The Ellingham diagrams provide a rich, visual means for identifying halide-forming components in proposed fuel/solvent salt systems. Thermochemical models and values from MSTDB-TC and ancillary sources were used in global equilibrium calculations to provide compositions for a close analysis of the behavior of a possible Molten Chloride Salt Fast Reactor and a Molten Salt Reactor Experiment-type system at high burnup (100 GWd/t). The results illustrated the oxidative nature of burnup in MSRs and provided information about redox behavior and possible control.

Identification and Decomposition of Uranium Oxychloride Phases in Oxygen-Exposed UCl3 Salt Compositions.

Complementary X-ray absorption fine structure (XAFS) spectroscopy and Raman spectroscopy studies were conducted on several UCl3 concentrations in several chloride salt compositions. The samples were 5% UCl3 in LiCl (S1), 5% UCl3 in KCl (S2), 5% UCl3 in LiCl-KCl eutectic (S3), 5% UCl3 in LiCl-KCl eutectic (S4), 50% UCl3 in KCl (S5), and 20% UCl3 in KCl (S6) molar concentrations. Sample S3 had UCl3 sourced from Idaho National Laboratory (INL), and all other samples were UCl3 sourced from TerraPower. The initial compositions were prepared in an inert and oxygen-free atmosphere. XAFS measurements were performed in the atmosphere at a beamline, and Raman spectroscopy was conducted inside a glovebox. Raman spectra were able to confirm initial UCl3. XAFS and later Raman spectra measured, however, did not correctly match the literature and computational spectra for the prepared UCl3 salt. Rather, the data shows some complex uranium oxychloride phases at room temperature that transition into uranium oxides upon heating. Oxygen pollution due to failure of the sealing mechanism can result in oxidation of the UCl3 salts. The oxychlorides present may be both a function of the unknown O2 exposure concentration, depending on the source of the leak and the salt composition. Evidence of this oxychloride claim and its subsequent decomposition is justified in this work.

Magnetic sludge byproducts for adsorptive phosphorus removal: Resource recovery from iron-based anaerobic sewage sludge.

This study evaluated feasibility of resource recovery from iron-based sewage sludge from a novel Fe(III)-dosed anaerobic bioreactor used for wastewater treatment. Sludge samples were calcined at five different temperatures (300, 350, 400, 450, and 500 °C) to investigate the transformation of the sludge into different magnetic phases of iron oxide particles. The material phase analysis revealed the presence of 14 to 39 wt% magnetite and 8 to 19 wt% maghemite for different temperature treatments, which indicate the successful conversion of sludge materials into magnetic particles. This magnetic conversion was further confirmed by magnetization measurements of the sludge byproducts that found a 6.3 to 10.9 emu/g saturation magnetization and a 0.7 to 2.0 emu/g remanent magnetization. Due to surface effects phenomenon of nanocrystals, the magnetization values were observed to increase with calcination temperature along with the crystallinity and crystallite size of the thermally-treated sludge materials. This indicates the crystallinity of the samples played a significant role in determining the magnetization properties of the sludge byproducts. Phosphate adsorption capacity and kinetics of the sludge byproducts were evaluated for the samples calcined at 350 and 500 °C. Both samples showed a high phosphate adsorption capacity, but the sample treated at 350 °C showed relatively higher capacity presumably due to smaller crystallite size and reduced crystallinity of the particles in the sample. This study demonstrated that a simple thermal treatment of the sludge can render dual benefits of recovering magnetic particles and further utilizing them for beneficial applications.

Observation and interpretation of negative remanent magnetization and inverted hysteresis loops in a thin film of La0.7Sr0.3MnO3.

The observation of inverted magnetic hysteresis loops and negative magnetic remanence (NRM) in a 7.6 nm thin film of La0.7Sr0.3MnO3 grown on SrTiO3 substrates is reported. The film was grown employing pulsed laser deposition and characterized by reflection high-energy electron diffraction during growth and using x-ray reflectivity measurements post-growth. Magnetic properties of the film were measured from 5 K to 400 K under both the field-cooled (FC) and zero-field-cooled (ZFC) conditions. The observed results of inverted magnetic hysteresis loops and NRM are interpreted in terms of the co-existence of a magnetically inhomogeneous region consisting of superparamagnetic spin clusters with a blocking temperature T B = 240 K and the ferromagnetic state with an ordering temperature T C = 290 K. Hysteresis loop inversion is observed in the temperature region of T B < T < T C whereas NRM appears in the mixed superparamagnetic and ferromagnetic states for T < T C down to 5 K. These observations of hysteresis loop inversion and NRM are related to the magneto-static interaction between the superparamagnetic and ferromagnetic phases leading to anti-alignment of spin of both magnetic phases with respect to each other.