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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9

Aqueous Synthesis of Technetium-Doped Titanium Dioxide by Direct Oxidation of Titanium Powder, a Precursor for Ceramic Nuclear Waste Forms

Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering-resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry - direct oxidation of titanium powder in the presence of ammonium fluoride - is achieved. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(IV) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H 2 EDTA)TcIV](μ-O) 2 . Technetium-doped TiO 2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LR Tc ) from the TiO 2 particles is low (3 × 10 -6 g m -2 d -1 ), which illustrates the potential utility of TiO 2 as waste form. However, the small size of the as-prepared TiO 2 nanoparticles results in an estimated retention of Tc of 10 4 years, which is only a fraction of the half-life of Tc (2.1 × 10 5 years).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compositional control of radionuclide retention in hollandite-based ceramic waste forms for Cs-immobilization

Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition-metal fission products. In this study, three Ga-doped titanate hollandite-type phases, Ba 1.33 Ga 2.67 Ti 5.33 O 16 , Ba 0.667 Cs 0.667 Ga 2 Ti 6 O 16 , and Cs 1.33 Ga 1.33 Ti 6.67 O 16 , were synthesized using a solid-state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X-ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs 1.33 Ga 1.33 Ti 6.67 O 16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high-temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.

nuclear (including radiation effects), materials a↗

Toward All-Solid-State Lithium Batteries: Three-Dimensional Visualization of Lithium Migration in β-Li 3 PS 4 Ceramic Electrolyte

All-solid lithium batteries are an attractive next-generation technology that use ion-conducting solids such as ..beta..-Li3PS4 (LPS) to enable use of a lithium metal anode, which increases theoretical capacity and widens the stable voltage window over traditional lithium-ion systems. These ion-conductive solids also provide increased safety by replacing flammable liquid electrolytes. Although solid-state electrolytes are significantly more stable and dendrite-resistant than traditional liquid electrolytes, lithium anodes in all-solid systems may nevertheless grow dendrites under high stress or repeated cycling, leading to short circuits and premature battery breakdown. For this reason, we study the formation and propagation of Li metal features within solid electrolytes using synchrotron-based X-ray tomography with in-situ current-voltage cycling supported by our custom sample platform. Our results demonstrate the ability of this technique to delineate different layers of the Li/LPS/Li structure with spatial resolution approaching 1 um. At this resolution, we are able to detect expansion of voids, especially in early stages of cycling. This expansion of voids is observed throughout the volume of the symmetric cells and visually resembles propagation of cracks resulting from interactions between the Li metal and pre-existing voids in the LPS electrolyte.

25 ENERGY STORAGE↗

A thermodynamics-based damage model for the non-linear mechanical behavior of SiC/SiC ceramic matrix composites in irradiation and thermal environments

A damage model is developed and validated with experimental data for the non-linear mechanical behavior of SiC/SiC composite materials in nuclear applications. Cyclic thermal and mechanical loading associated with neutron irradiation effects of these composites leads to wide-spread and progressive micro-cracking that leads to loss of thermal conductivity and further enhancement of thermo-mechanical damage. A physics-based model of wide-spread micro-cracking is developed within the thermodynamic framework of continuum damage mechanics. Evolution equations for damage parameters that describe the growth of continuum damage are developed, where the material variables are obtained from experiments. The model novelty is in coupling mechanical, thermal, and irradiation damage through a consistent thermodynamic framework, including loss of thermal conductivity due to the evolution of mechanically induced micro-cracks. A number of thermo-mechanical experiments were conducted to confirm model assumptions. The model is shown to be validated with out-of-pile experiments, and then implemented using commercial finite element code COMSOL to the fuel cladding problem with normal and high radiation dose cases.

Materials Science↗

Diffraction Methods for Qualitative and Quantitative Texture Analysis of Ferroelectric Ceramics

Crystallographic textures are pervasive in ferroelectrics and underpin the functional properties of devices utilizing these materials because many macroscopic properties (e.g., piezoelectricity) require a non-random distribution of dipoles. Inducing a preferred grain texture has become a viable route to improve these functional properties. X-ray and neutron diffraction have become valuable tools to probe crystallographic textures. This paper presents an overview of qualitative and quantitative methods for assessing crystallographic textures in electroceramics (domain and grain textures) and discusses their strengths and weaknesses.

36 MATERIALS SCIENCE↗

High-temperature ceramic-to-ceramic seals

Noble-metal braze applied to appropriately prepared zirconia parts produces a gas-tight, durable seal that can withstand temperature of 825 C for over 2000 hours without deterioration.

Smart, W.↗