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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Determination and verification of a 2D pencil-beam kernel for a radiosurgery system with cones

The quality and correctness of dosimetric data of small fields in stereotactic radiosurgery (SRS) depends significantly on the election of the detector employed in the measurements. This work provides an independent method of verification of these data through the determination of a polyenergetic 2-dimensional pencil-beam kernel for a BrainLAB SRS system with cones, employing the deconvolution/convolution of a reference experimental off-axis ratio (OAR) profile (cone diameter c{sub 0} = 35 mm). The kernel in real space k{sub c{sub 0}}(r,z{sub 0}) is convolved with the ideal fluence Φ for the cones 7.5 to 35 mm in diameter to obtain the OAR profiles, and the total scatter factors, S{sub t}, which are compared with experimental values of the same quantities. The experimental OARs and S{sub t} factors are measured in water with a PTW 60003 diamond detector. Additionally, the reference OAR is corrected for beam divergence and spectral fluence fluctuations defining a function of boundary correction factors (BF). The BF and Φ functions are transformed to the conjugate space with the zeroth-order Hankel transform, appropriated to the radial symmetry of the cones. Therefore, the kernel in real space k{sub c{sub 0}}(r,z{sub 0}) is the inverse Hankel transform of the ratio of the Hankel transforms of BF and Φ. Finally, an uncertainty analysis according to the Guide to the Expression of Uncertainty in Measurement is carried out for 3 different values of k{sub c{sub 0}}(r,z{sub 0}). Calculated and measured OARs agree within the dose/distance-to-agreement criteria of 2%/0.12 mm; while, S{sub t} factors agree within 2%. This procedure supplies an independent method to validate the dosimetric data necessary to feed treatment planning systems for SRS with cones.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2025

Combining geometric-optical and spectral invariants theories for modeling canopy fluorescence anisotropy

The spectral invariants theory ( p -theory) has received much attention in the field of quantitative remote sensing over the past few decades and has been adopted for modeling of canopy solar-induced chlorophyll fluorescence (SIF). However, the spectral invariant properties (SIP) in simple analytical formulae have not been applied for modeling canopy fluorescence anisotropy primarily because they are parameterized in terms of leaf total scattering, which precludes the differentiation between forward and backward leaf SIF emissions. In this study, we have developed the canopy-SIP SIF model by combining geometric-optical (GO) theory to account for asymmetric leaf SIF forward and backward emissions at the first-order scattering and by modeling multiple scattering based on the p-theory, thus avoiding the dependence on radiative transfer models. The applicability of the model simulations especially over 3D heterogeneous canopies was improved by incorporating canopy structure through multi-angular clumping index, and by modeling single scattering from the four components of the scene in view according to the GO approach. The results show good consistency with both the state-of-the-art SIF models and multi-angular field SIF observations over grass and chickpea canopies. Further, the coefficient of determination (R²) between the simulated SIF and field measurements was 0.75 (red) and 0.74 (far-red) for chickpea, and 0.65 (both red and far-red) for grass. The average relative error was approximately 3% for 1D homogeneous scenes when comparing the canopy-SIP SIF model simulations to the SCOPE model simulations, and around 4% for the 3D heterogeneous scene when comparing to the LESS model simulations. The results indicate that the proposed approach for separating asymmetric leaf SIF emissions is a robust way to keep a balance between satisfactory simulation accuracy and efficiency. Model simulations suggest that neglecting the leaf SIF asymmetry can lead to an underestimation of canopy red SIF by 6.3% to 42.6% for various leaf biochemical and canopy structural parameters. This study presents a simple but efficient analytical approach for canopy fluorescence modeling, with potential for large-scale canopy fluorescence simulations.

3D heterogeneous structure↗
DOE OSTI2024

An atomistic structural description of the ferrielectric polar phase involving non-coplanar cation displacements

Materials with antipolar-polar transformation are attractive for their large functional responses. However, the antipolar state remains controversial in many materials. For example, recent studies on archetypical antiferroelectric (AFE) materials indicate an incomplete compensation of antiparallel dipoles, which prompted their alternative definition as ferrielectric. Here, we investigated the origin of the ferrielectric (FIE) state in a classical AFE material using X-ray and neutron total scattering. We show that the FIE state arises from 3-dimensional modulation of the cation-centric electric dipoles, which can be viewed as periodic arrangement of 180° twin boundaries with non-Ising characteristics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Crystal Structure and Atomic Vacancy Optimized Thermoelectric Properties in Gadolinium Selenides

Thermoelectric materials enable the energy conversion of waste heat into electricity, helpful to relieve global energy crisis. Here, we report a systematic investigation on high-temperature thermoelectric gadolinium selenides, cubic Gd 3-x Se 4 (x = 0.16, 0.21 and 0.25) and orthorhombic Gd 2 Se 3-y (y = 0.02, 0.06 and 0.08). High energy synchrotron x-ray diffraction and total scattering have been used to investigate the crystallographic and local structures. Atomic-scale clusters of Gd vacancy in the cubic phase are observed by employing the reverse Monte Carlo simulation. For cubic Gd 3-x Se 4 , adjusting Gd vacancy triggers the effect of multiple conduction bands, confirmed by the increase in effective masses and theoretical calculations. A reasonable peak zT value of 0.27 is achieved at 850 K for Gd 3-x Se 4 (x = 0.16). On the other hand, tuning Se vacancy enables the optimization of electron concentration for the orthorhombic Gd 2 Se 3-y . More significantly, its low deformation potential (Ξ = 12eV) gives rise to enhanced electron mobility and higher peak zT value of 0.54 at 850 K for Gd 2 Se 3-y (y = 0.02). Intriguingly, a higher zT of 1.2 at 1200 K is reasonably predicted by quality factor analysis. Finally, this work extends the scope of high-temperature thermoelectric materials and facilitates the exploration of novel high-temperature thermoelectric materials

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lattice Disorder and Oxygen Migration Pathways in Pyrochlore and Defect-Fluorite Oxides

Atomic-scale disorder plays an important role in the chemical and physical properties of oxide materials. The structural flexibility of pyrochlore-type oxides allows for crystal-chemical engineering of these properties. Compositional modification can push pyrochlore oxides toward a disordered defect-fluorite structure with anion Frenkel pair defects that facilitate oxygen migration. The local structure of the long-range average cubic defect-fluorite was recently claimed to consist of randomly arranged orthorhombic weberite-type domains. Here, we show, using low-temperature neutron total-scattering experiments, that this is not the case for Zr-rich defect-fluorites. By analyzing data from the pyrochlore/defect-fluorite Y 2 Sn 2–x Zr x O 7 series using a combination of neutron pair distribution function and big-box modelling, we have differentiated and quantified the relationship between anion sub-lattice disorder and Frenkel defects. These details directly influence the energy landscape for oxygen migration and are crucial for simulations and design of new materials with improved properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species

Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe 9.4(2) S 10 ][Fe(en) 3 ] 0.6(1) ·en 0.9 ( 3 ). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57 Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe 8 S 10 ][Fe(en) 3 ] 1 ·en 0.5 and tetragonal FeS. The new compound has flat Fe 9.4 S 10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 , the interlayer space is occupied by [Fe(en) 3 ] 2+ complexes and neutral ethylenediamine molecules in a ~2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (~6%) of iron vacancies at the Fe-S layer in [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Here, our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure–property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks

Robust and versatile metal–organic frameworks (MOFs) have emerged as sophisticated scaffolds to meet the critical needs of the nuclear community, but their performance depends on their underexplored structural integrities in high- radiation fields. The contributions of selected metal nodes in the radiation stability of MOFs within the isostructural M-UiO-66 series (where M = Zr, Ce, Hf, Th, and Pu; Zr-UiO-66 experiments were executed in a previous work) have been determined. Ce-, Hf-, and Th-UiO-66 MOF samples were irradiated via gamma and He-ion methodologies to obtain doses up to 3 MGy and 85 MGy, respectively, the latter strikingly higher than that obtained in most other studies. Appreciable self-irradiation constituted the total absorbed doses, up to 31 MGy of the gamma-irradiated Pu-UiO-66 samples. Structural degradation was ascertained by powder X-ray diffraction, X-ray total scattering, vibrational spectroscopy, and, where possible, N 2 physisorption isotherms. Diffuse reflectance infrared Fourier transform spectroscopy provided atomic-level mechanistic insights to reveal that the node-linker connection was most susceptible to radiation damage. Density functional theory calculations were performed on cluster models to evaluate the binding energy of the linkers to each metal node. Here, while the isostructures disclosed the same breakdown signatures, distinct radiation sensitivity as a function of metal selection was evident and followed the trend Hf-UiO-66 ~ Zr-UiO-66 > Th-UiO-66 > Pu-UiO-66 > Ce-UiO-66. We anticipate that these endeavors will contribute to the rational design of radiation-resistant materials for targeted applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structure and Stability of the Iodide Elpasolite, Cs 2 AgBiI 6

Iodide elpasolites (or double perovskites, A 2 B'B"I 6 , B' = M + , B" = M 3+ ) are predicted to be promising alternatives to lead-based perovskite semiconductors for photovoltaic and optoelectronic applications, but no iodide elpasolite has ever been definitively prepared or structurally characterized. Iodide elpasolites are widely predicted to be unstable due to favorable decomposition to the competing A 3 B 2 I 9 (B = M 3+ ) phase. Here, we report the results of synchrotron XRD and X-ray total scattering measurements on putative Cs 2 AgBiI 6 nanocrystals made via anion exchange from parent Cs 2 AgBiBr 6 nanocrystals. Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed exhibit a tetragonal ($I$$\overline{4}$$m$) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. In conclusion, a series of experiments probing structural relaxation and the effects of surface ligation or grain size all point to the critical role of surface free energy in stabilizing the iodide elpasolite phase in these nanocrystals.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A reversible phase transition for sodium insertion in anatase TiO 2

Anatase TiO 2 is a potential negative electrode for sodium-ion batteries. The sodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanning transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na 0.43 Ti 0.57 ) 3a 0.22 Na 0.39 Ti 0.39 ) 3b O 2 , where refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO 2 , suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Lastly, a comparison between the intercalation of lithium and sodium into anatase TiO 2 performed by DFT calculations confirmed that, for the sodiated phase, the rhombohedral structure is more stable than the tetragonal phase observed during the lithiation of nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Direct Evidence of Significant Cation Intermixing in Upconverting Core@Shell Nanocrystals: Toward a New Crystallochemical Model

Core@shell design represents an important class of architectures because of its capability to dramatically increase the absolute upconversion quantum yield (UCQY) of upconverting nanocrystals (UCNCs) but also to tune energy migration pathways. A relatively new trend towards the use of very thick optically inert shells affording significantly higher absolute UCQYs raises the question of the crystallographic and chemical characteristics of such nanocrystals (NCs). In this article, local chemical analyses performed by scanning transmission electron microscopy (STEM) combined with energy dispersive x-ray spectroscopy (EDXS) and x-ray total scattering experiments together with pair distribution function (PDF) analyses were used to probe the local chemical and structural characteristics of hexagonal β-NaGd0.78Yb0.2Er0.02F4@NaYF4 core@shell UCNCs. The investigations lead to a new crystallochemical model to describe core@shell UCNCs that considerably digresses from the commonly accepted epitaxial growth concept with sharp interfaces. The results obtained on ultra-small (4.8 ± 0.5 nm) optically active cores (β-NaGd0.78Yb0.2Er0.02F4) surrounded by an optically inert shell (NaYF4) of tunable thickness (roughly 0, 1, 2, and 3.5 nm) clearly indicate the massive dissolution of the starting seeds and the inter-diffusion of the shell element (such as Y) into the Gd/Yb/Er-containing core giving rise to the formation of a non-homogeneous solid solution characterized by concentration gradients and the lack of sharp interfaces. Independently of the inert shell thickness, core/interface/shell architectures were observed for all synthesized UCNCs. The presented results constitute a significant step towards the comprehensive understanding of the “structure - property” relationship of upconverting core@shell architectures, which is of prime interest not only in the development of more efficient structures but also to provide new physical insights at the nanoscale to better explain upconversion (UC) properties alterations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Zero Thermal Expansion and Abrupt Amorphization on Compression in Anion Excess ReO 3 -Type Cubic YbZrF 7

In this paper, heat treatment of cubic YbZrF 7 , after quenching from 1000 °C, leads to a material displaying precisely zero thermal expansion at ~300 K and negative thermal expansion at lower temperatures. The zero thermal expansion is associated with a minimum in the lattice constant at ~300 K. X-ray total scattering measurements are consistent with a previously proposed model in which the incorporation of interstitial fluoride into the ReO 3 -related structure leads to both edge and corner sharing coordination polyhedra. The temperature dependence of the experimental pair correlation functions suggests that the expansions of edge and corner sharing links partly compensate for one another, supporting the hypothesis that the deliberate incorporation of excess fluoride into ReO 3 structure materials can be used as a design strategy for controlling thermal expansion. Cubic YbZrF 7 has a bulk modulus, K 0 , of 55.4(7) GPa and displays pronounced pressure-induced softening [K 0 ' = -27.7(6)] prior to an abrupt amorphization on compression above 0.95 GPa. Finally, the resulting glass shows a single sharp scattering maximum at Q ~ 1.6 Å –1 .

36 MATERIALS SCIENCE↗
DOE OSTI2019

Controlling the Negative Thermal Expansion and Response to Pressure in ReO 3 -type Fluorides by the Deliberate Introduction of Excess Fluoride: Mg 1– x Zr 1+ x F 6+2 x , x = 0.15, 0.30, 0.40, and 0.50

Cubic ReO 3 -type fluorides often display negative or very low thermal expansion. However, they also typically undergo phase transitions upon cooling and/or modest compression, which are undesirable from the perspective of potential applications. Density measurements and total scattering data for Mg 1– x Zr 1+ x F 6+2 x , x = 0.15, 0.30, 0.40, and 0.50, indicate that the introduction of excess fluoride into cubic MgZrF 6 is accompanied by the population of interstitial fluoride sites and the conversion of corner to edge shared coordination polyhedra. Unlike MgZrF 6 , no phase transitions are seen upon cooling these materials to 10 K, and the first high pressure phase transition in these compositions occurs at pressures much higher than that previously reported for MgZrF 6 (0.37 GPa). The introduction of excess fluoride also provides for control of thermal expansion. Overall, for all of the compositions studied, negative thermal expansion is seen at the lowest temperature examined, and positive thermal expansion is observed at the highest temperature. The temperature at which zero thermal expansion occurs varies from ~150 K for x = 0.50 to ~500 K for x = 0.00. High pressure diffraction also indicates that increasing the amount of excess fluoride elastically stiffens the cubic ReO 3 related structure and reduces the extent of pressure induced softening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides

Partial anion substitution in transition metal oxides provides rich opportunities to control and tune physical and chemical properties, for example, combining the merits of oxides and nitrides. In addition, the possibility of resulting anion sublattice order provides a means to target polar and chiral structures based on a wide array of accessible structural archetypes by design. Here, in this work, we investigate the local structures of a family of perovskite tantalum oxynitrides—ATaO 2 N (A = Ba, Sr, and Ca)—using a combination of experimental and theoretical approaches including neutron total scattering, density functional theory (DFT), and ab initio molecular dynamics (AIMD) simulations. We present the first experimental study of chemical short-range order (CSRO) in CaTaO 2 N, confirming local cis N ordering of the anion sub-lattice. Our systematic exploration of a local structure across the A cation size series (from the larger Ba to the smaller Ca) reveals a perovskite motif increasingly distorted with respect to long-range average structures. DFT and AIMD simulations support the observed trends. Overall, structures with cis ordering of the nitrogen anions in each TaO 4 N 2 octahedron are favored over those with trans ordering. With diminishing A cation size, local cis ordering and Ta off-centering play decreasing roles in overall lattice stability, overshadowed by the stabilizing effects of octahedral tilting. The influence of these factors on local dipole formation and frustrated dipole ordering are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

In Situ Visualization of Local Distortions in the High- T c Molecule-Intercalated Li x (C 5 H 5 N) y Fe 2– z Se 2 Superconductor

A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron–selenide host by organic molecular donors, aiming at the formation of the expanded-lattice Li x (C 5 H 5 N) y Fe 2– z Se 2 hybrid superconductor. The intercalates are found to crystallize in the tetragonal ThCr 2 Si 2 -type structure at the average level, however, with an enhanced interlayer iron–selenide spacing ( d = 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution function (PDF) analysis at variable times suggests distorted FeSe 4 tetrahedral local environments that appear swollen with respect to those in the parent β-FeSe. Simultaneously acquired in situ synchrotron X-ray powder diffraction data disclose that secondary phases (α-Fe and Li 2 Se) grow significantly when a higher lithium concentration is used in the solvothermal reaction or when the solution is aged. These observations are in line with the strongly reducing character of the intercalation medium’s solvated electrons that mediate the defect chemistry of the expanded-lattice superconductor. In the latter, intralayer correlated local distortions indicate electron-donating aspects that reflect in somewhat enlarged Fe–Se bonds. Additionally, they also reveal a degree of relief of chemical pressure associated with a large distance between Fe and Se sheets (“taller” anion height) and a stretched Fe–Fe square planar topology. The elongation of the latter, derived from the in situ PDF study, speaks for a plausible increase in the Fe-site vacancy concentration. The evolution of the local structural parameters suggests an optimum reaction window where kinetically stabilized phases resemble the distortions of the edge-sharing Fe–Se tetrahedra, required for a high- T c in expanded-lattice iron-chalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗