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Tamalonis, Anthony

Publications and source records attributed to Tamalonis, Anthony.

10 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Plutonium oxide melt structure and covalency

Advances in nuclear power reactors include the use of mixed oxide fuel, containing uranium and plutonium oxides. The high-temperature behaviour and structure of PuO 2-x above 1,800 K remain largely unexplored, and these conditions must be considered for reactor design and planning for the mitigation of severe accidents. Here, in this study, we measure the atomic structure of PuO 2-x through the melting transition up to 3,000 +/- 50 K using X-ray scattering of aerodynamically levitated and laser-beam-heated samples, with O/Pu ranging from 1.57 to 1.76. Liquid structural models consistent with the X-ray data are developed using machine-learned interatomic potentials and density functional theory. Molten PuO 1.76 contains some degree of covalent Pu-O bonding, signalled by the degeneracy of Pu 5f and O 2p orbitals. The liquid is isomorphous with molten CeO 1.75 , demonstrating the latter as a non-radioactive, non-toxic, structural surrogate when differences in the oxidation potentials of Pu and Ce are accounted for. These characterizations provide essential constraints for modelling pertinent to reactor safety design. The molten structure of plutonium oxide-a component of mixed oxide nuclear fuels-is measured, showing some degree of covalent bonding. Its atomic structure is similar to that of cerium oxide, which could be a non-radioactive structural surrogate.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

The structure of molten calcium ferrite under various redox conditions

Laser-heated melts based on the 43CaO–57Fe 2 O 3-x eutectic, close to the calcium ferrite (CF) composition, were measured with high-energy X-ray diffraction using aerodynamic levitation over a range of redox states controlled by CO/CO 2 gas atmospheres. The iron–oxygen coordination number was found to rise from 4.4 ± 0.3 at 15% Fe 3+ to 5.3 ± 0.3 at 87% Fe 3+ . Empirical potential structure refinement modelling was used to obtain the ferric and ferrous partial pair distribution functions. It was found that the Fe 2+ iron–oxygen coordination number is consistently approximately 10% higher in CF than in pure iron oxide, while Fe 3+ is essentially identical in all but the most oxygen-rich environments (where it is higher in CF compared with FeO x ). The model also shows calcium octahedra to be the dominant species across all redox environments, although the population of CaO 7 increases with the availability of oxygen at the expense of CaO 4 and CaO 5 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

EXPLORING THE STRUCTURE OF GLASS-FORMING LIQUIDS USING HIGH ENERGY X-RAY DIFFRACTION, CONTAINERLESS METHODOLOGY AND STATE-OF-THE-ART MOLECULAR DYNAMICS SIMULATION

High energy X-ray diffraction can be combined with containerless techniques to provide information on the atomic arrangements in glass-forming liquids in stable and metastable regimes. The high incident energies provide bulk diffraction data to high values of scattering vector which enables significantly more robust analysis of the local and medium-range order that influences important physical properties such as viscosity and crystal nucleation. These combined techniques have been applied to a range of oxide liquids. In this contribution we illustrate addition of further dimensions to phase space by controlling the partial pressure of oxygen that permits the study liquids containing iron. The advantages of rapid data acquisition are also demonstrated in a study of tellurite glass-forming systems where a transition from ergodic to non-ergodic regimes in the deeply supercooled liquid is shown. Finally we demonstrate how descriptions of the liquid structure can be developed by combining HEXRD with molecular dynamics simulations.

containerless techniques↗
DOE OSTI2019

Temperature gradients for thermophysical and thermochemical property measurements to 3000 °C for an aerodynamically levitated spheroid

This study examines thermal gradients in ceramic oxide spheroids being aerodynamically levitated in a conical nozzle levitator (CNL) system equipped with a CO 2 laser (10.6 μm wavelength). The CNL system is a versatile piece of equipment that can easily be coupled with advanced thermophysical and thermochemical measuring devices, such as diffraction/scattering (X-ray and neutron), nuclear magnetic resonance, and calorimetry, for the analysis of bulk spheroidal solids and liquids. The thermal gradients of a series of single crystal, polycrystalline solids, and liquid spheroids have been measured spatially in the CNL system, by means of a disappearing filament pyrometer (800-3000 °C) and by X-ray diffraction with reference to an internal standard (Pt: 800-1600 °C). The thermal gradient in a levitated sample being heated by a laser from the top can be minimized by: (i) maximizing the sphericity, (ii) maximizing the density, and (iii) minimizing microstructural features. A spheroid with these properties can be manufactured via machining a perfect sphere from a highly dense, chemically and phase pure pellet. These properties promote rotation of the sample about multiple axes in the air stream, enabling homogeneous heating. This homogeneous heating is the dominant factor in reducing thermal gradients in solid state samples. It was found that the thermal gradient in an similar to 3 mm diameter solid sample could be reduced from 1000 °C to 30 °C, by having a perfectly spherical shape that could rotate on multiple axes in a high velocity gas stream (similar to 1500-2000 cm 3 /min). As a result, these findings will allow accurate thermophysical and thermochemical property measurements of solids in situ at high temperatures, using the CNL system.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Amorphous tantala and its relationship with the molten state

The structure factors of molten Ta 2 O 5 and Nb 2 O 5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, Ta 0.8 Nb 1.2 O 5 . Nonetheless, peak Nb-O bond lengths are about 1% shorter than those for Ta-O, at temperatures, T*=T/T melt , scaled to the melting points. Mean coordination numbers are n MO ≃5.6(1),n OM ≃2.23(4) in the liquid state, and n TaO ≃6.6(2),n OTa ≃2.63(8) in the solid. The liquids are built from five- and six-fold M-O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-Ta 2 O 5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous Ta 2 O 5 , coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. In conclusion, nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction

Borate melts containing <20 mol% Na 2 O have been studied using high-energy synchrotron X-ray diffraction. Temperature dependencies of the mean B–O bond lengths are shown to vary strongly with soda content, by comparison to previous measurements on liquid B 2 O 3 and Na 2 B 4 O 7 . Whereas in liquid B 2 O 3 linear thermal expansion of the BØ 3 units is observed, with coefficient α BO = 3.7(2) × 10 -6 K -1 , this expansion is apparently slightly suppressed in melts containing <20 mol% Na 2 O, and is dramatically reversed at the diborate composition. These effects are interpreted in terms of changes in the mean B–O coordination number, where the reaction BØ 4 - + BØ 3 ⇌ BØ 3 + BØ 2 O- shifts to the right with increasing temperature. The empirical bond-valence relationship is used to convert measured bond lengths, r BO , to coordination numbers, n BO , including a correction for the expected thermal expansion. This method is more accurate and precise than direct determination of n BO from peak areas in the radial distribution functions. Gradients of Δn BO /ΔT = -3.4(3) × 10 -4 K -1 close to the diborate composition, and Δn BO /ΔT = -0.3(1) × 10 -4 K -1 for a 13(3) mol% Na 2 O melt are observed, in reasonable agreement with Raman spectroscopic observations and thermodynamic modeling, with some quantitative differences. These observations go toward explaining isothermal viscosity maxima and changes in fragility across the sodium borate system.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Structure and Liquid Fragility in Sodium Carbonate

In this paper, the relationship between local structure and dynamics is explored for molten sodium carbonate. A flexible fluctuating-charge model, which allows for changes in the shape and charge distribution of the carbonate molecular anion, is developed. The system shows the evolution of highly temperature-dependent complex low-dimensional structures which control the dynamics (and hence the liquid fragility). By varying the molecular anion charge distribution, the key interactions responsible for the formation of these structures can be identified and rationalized. Finally, an increase in the mean charge separation within the carbonate ions increases the connectivity of the emerging structures and leads to an increase in the system fragility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The structure of liquid alkali nitrates and nitrites

State of the art high energy X-ray diffraction experiments and simulation models (employing a description of charge transfer) are applied to pure molten alkali nitrates and nitrites and uncover significant emerging structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Low-Dimensional Network Formation in Molten Sodium Carbonate

Molten carbonates are highly inviscid liquids characterized by low melting points and high solubility of rare earth elements and volatile molecules. An understanding of the structure and related properties of these intriguing liquids has been limited to date. We report the results of a study of molten sodium carbonate (Na2CO3) which combines high energy X-ray diffraction, containerless techniques and computer simulation to provide insight into the liquid structure. Total structure factors (F-x(Q)) are collected on the laser-heated carbonate spheres suspended in flowing gases of varying composition in an aerodynamic levitation furnace. The respective partial structure factor contributions to Fx(Q) are obtained by performing molecular dynamics simulations treating the carbonate anions as flexible entities. The carbonate liquid structure is found to be heavily temperature-dependent. At low temperatures a low-dimensional carbonate chain network forms, at T = 1100 K for example similar to 55% of the C atoms form part of a chain. The mean chain lengths decrease as temperature is increased and as the chains become shorter the rotation of the carbonate anions becomes more rapid enhancing the diffusion of Na+ ions.

Wilding, Martin C.↗