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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Enhanced Interfacial Bonding of Graft Copolymers

To understand how thermoplastic welding strength can be tuned through chemical modifications and macromolecular topology, we combined coarse-grained molecular dynamics (MD) simulations with experimental validation. Our simulations examined the diffusion dynamics of both linear and graft polymers across representative interfaces, revealing that diffusion-controlled interdigitation follows a power law, with the exponent decreasing from 0.34 to 0.11 as grafting density increases from 7.5 to 196% (with side chains grafted to both sides of a monomer unit). The addition of side chains enhances welding efficiency, as dense bottlebrush polymers with high grafting density reach maximum rupture strength faster than linear polymers. However, their saturated rupture strength is lower. This observation is subsequently corroborated by experimental lap-shear tests comparing linear polyethylene with octene grafted polyethylene elastomers. Our MD simulations show that unlike linear polymers, where backbone entanglements dominate, the grafted side chains introduce mechanisms in addition to entanglement dilution. The rapid interdigitation of side chains creates a dense mesh of entropic van der Waals contacts, which can also enhance the film welding. Furthermore, our MD simulations reveal a brittle rupture behavior in linear and comb-like (mildly grafted) polymers, while bottlebrush (densely grafted) polymers display elastomeric behavior with a pronounced stress plateau prior to fracture. Our simulations deconvolute the influence of polymer topology on deformation behavior. The rate of polymer deformation becomes lower than the applied strain rate prior to rupture, and the onset of this deviation is progressively delayed from linear to bottlebrush polymers. This trend highlights the critical role of molecular architecture in governing the mechanical response. In conclusion, these results provide deeper insight into the underlying welding mechanisms of topological polymers and present a potential approach for mitigating the interface anisotropy that is inherent in advanced manufacturing techniques such as fused filament fabrication.

graft copolymers↗
DOE OSTI2022

Interlaboratory Reproducibility of Contour Method Data in a High Strength Aluminum Alloy

The contour method for residual stress measurement has seen significant development, but an experimental reproducibility study utilizing physical samples has not been published. A double-blind reproducibly study is reported, having scope beginning with EDM cutting and ending with residual stress calculation. A reinforced I-beam sample geometry is identified for its unique residual stress profile when extracted from residual stress bearing quenched aluminum bar (7050-T74). Contour measurements are prescribed on a midplane of symmetry with dimensions 24.0 mm by 50.0 mm. Fourteen identically prepared samples are fabricated from a single long bar with well characterized and uniform residual stress. Five samples throughout the bar are identified for planning measurements to validate sample uniformity and overall suitability of the residual stress field. The planning measurements employ a range of techniques: contour method, neutron diffraction, and hole-drilling. Eight samples are distributed to an international group of participants to execute their standard measurement practice. A double-blind process is followed to provide anonymity. Results are provided by eight participants: six being self-similar and two being quite different, the latter set aside as outliers. An average residual stress field is established from non-outlying results and the spatial distribution of reproducibility standard deviation is determined. The average stress field ranges from -60 to 70 MPa and the reproducibility standard deviation averages 8.1 MPa on the measurement plane. The average reproducibility standard deviation is about 3 × larger for points within 1.0 mm of plane boundaries (17.6 MPa) than for the remaining points (6.1 MPa). Reproducibility standard deviation (among different labs) for contour method residual stress measurement is found to be very similar to repeatability standard deviation (in a single lab) reported in prior work. The reproducibility observed here, for the entire measurement process, is also similar to that found in a prior reproducibility study limited to contour method data analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Validation of Manufacturing Process Designs for Stamped Microchannel Recuperators

Microchannel recuperators can achieve high-efficiency power cycles and chemical reactions by recovering waste heat from hot turbine exhaust and chemical reaction streams. However, the industrial application of microchannel recuperators are restricted by the high cost of patterning and bonding. The objective of this study was thus to investigate new methods for producing microchannel recuperators for emerging markets. Based on greenfield cost estimates, process designs based on stamping, laser welding and vacuum brazing of 316L stainless steel laminae were found to be more economical than conventional photochemical machining and diffusion bonding. Subsequently, validation experiments were conducted to produce stamped microchannel components using cost model parameters. At a mass flow rate of 0.99 g/s, the test article made with laser welding was found to provide higher effectiveness than the test article produced using vacuum brazing. Preliminary investigations showed that residual stresses during laser welding of the laminae led to significant warpage, collapsing channels and making lamina-to-lamina fit up challenging. In contrast, the test article produced by vacuum brazing of stamped laminae showed no clogging and 4.6% and 10.5% channel height standard deviation for the cold and hot channels, respectively. Channel variation in the vacuum brazing sample was determined to be caused by misregistration of laminae during brazing. In future work, efforts are needed to choose cheaper, more ductile brazing foils as well as design a brazing fixture to improve lamina-to-lamina registration.

42 ENGINEERING↗
DOE OSTI2022

Time Delay of Wide Area Damping Control in Urban Power Grid: Model-Based Analysis and Data-Driven Compensation

Due to the rapid development of economies, large urban cities consume an increasing amount of energy and have a higher requirement for power quality. Voltage source converter based high voltage direct current (VSC-HVDC) is a promising device to transmit clean power from remote regions to urban power systems, while also providing wide area damping control (WADC) for frequency stabilization. However, the time-delay naturally existing in the VSC-HVDC system may degrade the performance of WADC and even result in instability. To address this issue, this paper develops a time-delay correction control strategy for VSC-HVDC damping control in urban power grids. First, a small signal model of WADC is built to analyze the negative impacts of time delay. Then, a data-driven approach is proposed to compensate for the inherent time delay in VSC-HVDC damping control. The extensive training data will be generated under various disturbances. After offline training, the long short-term memory network (LSTM) can be implemented online to predict the actual frequency deviation based on real-time measurements. Finally, the proposed method is validated through MATLAB-Simulink in a two-area four-machine system. The results indicate that the data-driven compensation has a strong generalization ability for random delay time constants and can improve the performance of WADC significantly.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2021

Evaluating the Benefits of Bayesian Hierarchical Methods for Analyzing Heterogeneous Environmental Datasets: A Case Study of Marine Organic Carbon Fluxes

Large compilations of heterogeneous environmental observations are increasingly available as public databases, allowing researchers to test hypotheses across datasets. Statistical complexities arise when analyzing compiled data due to unbalanced spatial sampling, variable environmental context, mixed measurement techniques, and other reasons. Hierarchical Bayesian modeling is increasingly used in environmental science to describe these complexities, however few studies explicitly compare the utility of hierarchical Bayesian models to simpler and more commonly applied methods. Here we demonstrate the utility of the hierarchical Bayesian approach with application to a large compiled environmental dataset consisting of 5,741 marine vertical organic carbon flux observations from 407 sampling locations spanning eight biomes across the global ocean. We fit a global scale Bayesian hierarchical model that describes the vertical profile of organic carbon flux with depth. Profile parameters within a particular biome are assumed to share a common deviation from the global mean profile. Individual station-level parameters are then modeled as deviations from the common biome-level profile. The hierarchical approach is shown to have several benefits over simpler and more common data aggregation methods. First, the hierarchical approach avoids statistical complexities introduced due to unbalanced sampling and allows for flexible incorporation of spatial heterogeneitites in model parameters. Second, the hierarchical approach uses the whole dataset simultaneously to fit the model parameters which shares information across datasets and reduces the uncertainty up to 95% in individual profiles. Third, the Bayesian approach incorporates prior scientific information about model parameters; for example, the non-negativity of chemical concentrations or mass-balance, which we apply here. We explicitly quantify each of these properties in turn. We emphasize the generality of the hierarchical Bayesian approach for diverse environmental applications and its increasing feasibility for large datasets due to recent developments in Markov Chain Monte Carlo algorithms and easy-to-use high-level software implementations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Improved irradiation resistance of accident-tolerant high-strength FeCrAl alloys with heterogeneous structures

In this work, post–neutron irradiation examination is performed on advanced accident-tolerant fuel (ATF) cladding iron-chromium-aluminum (FeCrAl) alloys with ~10–13at. % Cr, ~10–12 at. % Al, ~1 at. % Mo, and minor alloying elements including Y irradiated to a damage level of 7 displacements per atom (dpa) at irradiation temperatures of 267–282 °C. A compositional dependency of the Cr and Al content is observed on the ratio of sessile and glissile dislocation loops, where the density of a$\langle$100$\rangle$ type loops is somewhat higher than the a/2$\langle$111$\rangle$ type loops. The α' precipitate number density is inversely correlated to the starting Cr concentration of the alloys of interest. The irradiation to a higher dose of 7 dpa results in a higher density of dislocation loops and α' precipitates for the same alloys at a lower irradiation dose, such as 1.8 dpa. In this work, the effect of α' precipitates on the dislocation loop density is discussed, and the presence of α' appears to inhibit the nucleation of loops. Compared with first-generation FeCrAl alloys, these advanced alloys with heterogeneous structure exhibit a lower Cr concentration in α' precipitation at the same dose level; they act as weaker obstacles deviating from the primary hardening contribution from the mature α'. Hence, the overall irradiation-induced hardening decreases; our alloys show improved radiation resistance because of their stronger sink strengths. The results presented in this paper could provide insights for the design and optimization of ATF cladding materials for future fission and space applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Statistical properties of homogeneous and isotropic turbulence in He II measured via particle tracking velocimetry

Despite being a quantum two-fluid system, superfluid helium-4 (He II) is observed to behave similarly to classical fluids when a flow is generated by mechanical forcing. This similarity has brought up the feasibility of utilizing He II for high Reynolds number classical turbulence research, considering the small kinematic viscosity of He II. However, it has been suggested that the nonclassical dissipation mechanism in He II at small scales may alter its turbulent statistics and intermittency. In this work, we report our study of a nearly homogeneous and isotropic turbulence (HIT) generated by a towed grid in He II. We measure the velocity field using particle tracking velocimetry with solidified deuterium particles as the tracers. By correlating the velocities measured simultaneously on different particle trajectories or at different times along the same particle trajectory, we are able to conduct both Eulerian and Lagrangian flow analyses. Spatial velocity structure functions obtained through the Eulerian analysis show scaling behaviors in the inertial subrange similar to that for classical HIT but with enhanced intermittency. The Lagrangian analysis allows us to examine the flow statistics down to below the dissipation length scale. Interestingly, abnormal deviations from the classical scaling behaviors are observed in this regime. Lastly, we discuss how these deviations may relate to the motion of quantized vortices in the superfluid component in He II.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Demand Response Analysis for Different Residential Personas in a Comfort-Driven Behavioral Context

Low demand response (DR) participation and high program drop-out rates continue to impede DR goals that could save up to $13 billion in annual grid expansion and electricity demand costs. Yet, the literature lacks a thorough understanding of how different residential customer segments enrolled in DR programs respond to utility signals in view of occupant comfort considerations. The objective of this study is to gain a clear understanding of the effects of four different customer personas on residential DR. Given current data limitations, this work developed an array of hypothetical personas with varied priorities, activity levels, and comfort thresholds based on demographic variables that have been found in previous studies to influence energy consumption. A BEopt DR model for a reference residential single-family building located in Colorado was built to isolate the effect of differences in buildings or climate. The results provide useful evidence on how persona-comfort differences lead to significant deviations in DR goals (especially peak demand reduction), ranging from 0.1% to 20%. This work presents a novel framework representing comfort preferences in DR models. The data generated, albeit synthetic, and the results could inform DR program design considerations of how different people respond to different comfort priorities.

BEopt↗
DOE OSTI2020

Performance Portability Evaluation of OpenCL Benchmarks across Intel and NVIDIA Platforms

We evaluate the capabilities of vendor-provided OpenCL implementations for performance portability across multiple computing platforms. The Rodinia benchmark suite is used for this evaluation. We apply the metric defined by Pennycook et al., and we use roofline efficiency from the Roofline performance model as the "performance efficiency" in the metric's definition. We found that the delivered performance portability is similar for several benchmarks, even if the roofline-based performance efficiencies across platforms are very different among the benchmarks. To help distinguish between these instances, we extend the metric by adding the standard deviation of the performance efficiencies for each benchmark. We argue that the standard deviation gives additional insight into performance portability assessment since it adds the performance variability across platforms. Additionally, we discuss the challenges to measure performance portability associated with algorithms and system software. In terms of algorithms, we need to carefully construct the benchmarks and appropriately use the concurrency available on a platform. In terms of system software, we depend on the vendor performance tools to support the desired programming model and runtime to be able to measure the metrics of interest.

GPU↗
DOE OSTI2022

BOSS DR12 full-shape cosmology: Λ CDM constraints from the large-scale galaxy power spectrum and bispectrum monopole

Here, we present a full Λ CDM analysis of the BOSS DR12 dataset, including information from the power spectrum multipoles, the real-space power spectrum, the reconstructed power spectrum and the bispectrum monopole. This is the first analysis to feature a complete treatment of the galaxy bispectrum, including a consistent theoretical model and without large-scale cuts. Unlike previous works, the statistics are measured using window-free estimators: this greatly reduces computational costs by removing the need to window-convolve the theory model. Our pipeline is tested using a suite of high-resolution mocks and shown to be robust and precise, with systematic errors far below the statistical thresholds. Inclusion of the bispectrum yields consistent parameter constraints and shrinks the σ 8 posterior by 13% to reach < 5 % precision; less conservative analysis choices would reduce the error bars further. Our constraints are broadly consistent with Planck: in particular, we find H 0 = 69.6$^{+1.1}_{–1.3}$ km s –1 Mpc –1 , σ 8 = 0.692$^{+0.035}_{–0.041}$ and n s = 0.870$^{+0.067}_{–0.064}$, including a BBN prior on the baryon density. When n s is set by Planck, we find H 0 = 68.31$^{+0.83}_{–0.86}$ km s –1 Mpc –1 and σ 8 = 0.722$^{+0.032}_{–0.036}$. Our S 8 posterior, 0.751 ± 0.039, is consistent with weak lensing studies, but lower than Planck. Constraints on the higher-order bias parameters are significantly strengthened from the inclusion of the bispectrum, and we find no evidence for deviation from the dark matter halo bias relations. These results represent the most complete full-shape analysis of BOSS DR12 to-date, and the corresponding spectra will enable a variety of beyond-Λ CDM analyses, probing phenomena such as the neutrino mass and primordial non-Gaussianity.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Increased power gains from wake steering control using preview wind direction information

Abstract. Yaw controllers typically rely on measurements taken at the wind turbine, resulting in a slow reaction to wind direction changes and subsequent power losses due to misalignments. Delayed yaw action is especially problematic in wake steering operation because it can result in power losses when the yaw misalignment angle deviates from the intended one due to a changing wind direction. This study explores the use of preview wind direction information for wake steering control in a two-turbine setup with a wind speed in the partial load range. For these conditions and a simple yaw controller, results from an engineering model identify an optimum preview time of 90 s. These results are validated by forcing wind direction changes in a large-eddy simulation model. For a set of six simulations with large wind direction changes, the average power gain from wake steering increases from only 0.44 % to 1.32 %. For a second set of six simulations with smaller wind direction changes, the average power gain from wake steering increases from 1.24 % to 1.85 %. Low-frequency fluctuations are shown to have a larger impact on the performance of wake steering and the effectiveness of preview control, in particular, than high-frequency fluctuations. From these results, it is concluded that the benefit of preview wind direction control for wake steering is substantial, making it a topic worth pursuing in future work.

17 WIND ENERGY↗
DOE OSTI2022

A Universal Refrigerant Charge Fault Detection and Diagnostics Method Based on Pump Down Operation

The performance of the heat pump system varies greatly depending on the refrigerant charge amount. Improving the refrigerant charge fault detection and diagnostics (FDD) method of vapor compression systems have the potential for increasing energy efficiency and reducing service cost. Previous studies to predict refrigerant charge amount are mostly empirical methods which require significant amount of experimental data for high accuracy. The primary goal of this research is to develop a universal charge fault detection method which requires only a few experimental data with high prediction accuracy.Currently, pump down operations are typical practices by HVAC technicians when they need to open the refrigerant circuit to make a repairment. In addition, compressors have a built-in low-pressure cut-off protection function, and the compressor performance maps are commonly available from manufacturers. The proposed method innovatively utilizes the typical pump down operation, the compressor low-pressure cut-off protection, and the compressor performance map. It does not require any geometry information of heat exchangers, refrigerant lines, or charge buffers.The new charge prediction method is firstly formulated through theoretical analysis, then verified and calibrated by a quasi-steady-state simulation of the pump down process for a residential heat pump system. The quasi steady-state simulation uses an HVAC system simulation framework driven by DOE/ORNL Heat Pump Design Model (HPDM). Preliminary experiment validations with heat pump refrigerant leakage tests demonstrate the deviation of the proposed charge prediction method compared with measurement is within 8%. This technology makes refrigerant charge amount available at the technician’s fingertips and leads to shorter maintenance time and fewer site visits.

Li, Zhenning↗
DOE OSTI2021

Characteristics and mechanisms of hydrogen-induced quasi-cleavage fracture of lath martensitic steel

Here this study presents an in-depth characterization of the microstructures, crystallographic orientations, and dislocation characteristics beneath hydrogen-induced quasi-cleavage fracture features of an as-quenched, lath martensitic (α') 22MnB5 steel. The fracture surfaces of gaseous hydrogen-embrittled martensitic specimens were analyzed by a combination of multiple analytical tools: scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), and transmission Kikuchi diffraction (TKD). The dominant fracture mode in the hydrogen-affected zones was quasi-cleavage fracture, which involved significant plasticity, evidenced by plastic zones near tear ridges and a high density of dislocations beneath the quasi-cleavage facets. The martensite constituent sizes, variant orientations, and boundaries influenced the quasi-cleavage surface morphologies. Fractography revealed the occurrence of {100} α' -type cleavage across martensitic laths, developing relatively “flat” quasi-cleavage surfaces, in addition to {110} α' -type cracking likely along lath and block boundaries, and fracture along non-cleavage planes. The likelihood of the formation of the relatively “flat” quasi-cleavage surfaces increased with increasing martensitic constituent sizes. Substantial dislocation bands formed on intersecting {112} α' slip planes within a martensite block below the hydrogen-induced cleavage fractures on {100} α' planes. River markings on the quasi-cleavage surfaces were found to originate from the complex, hierarchical lath martensitic microstructure. Steps and ridges on the quasi-cleavage facets generally linked with the various martensitic boundaries, suggesting that they were produced as a result of crack deviations at those boundaries. The fracture paths and martensite quasi-cleavage mechanisms are discussed in the context of the role of hydrogen and Cottrell cleavage model.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ageing of PBF‐Grade Poly(Phenylene Sulfide) Powder and its Effect on Critical Printability Properties

Abstract Poly(phenylene sulfide) (PPS) is a high‐performance polymer suiting the needs of powder bed fusion (PBF) early‐adopter industries. Although there are many benefits to PBF's powder bed‐based, one drawback is thermal ageing of the powder not incorporated into printed parts. Ideally, unfused powder can be reused in future builds; however, it is unlikely that critical printability properties of the thermally aged powder will remain unchanged. Changes in properties lead to either limited reuse through a practice of mixing used and new powder, or elimination of all powder after each build. In this paper, the authors report effects of thermal ageing in simulated printing conditions on properties of PPS critical to PBF processing. PBF‐grade PPS powder is exposed to process‐mimicking conditions. Properties relevant to the three PBF manufacturing process sub‐functions are assessed for the aged powders. Single‐layer prints are made using aged powder to observe polymer‐PBF interactions ad machina. Significant and systematic deviations from the as‐received state of the powder are observed for thermal and coalescence related properties with increasing exposure time and temperature. These changes are interpreted both in terms of physical and chemical changes in PPS and in terms of how these changes may impact the PBF printing process.

Chatham, Camden A.↗
DOE OSTI2026

An approach for fast and accurate simulation of phase change material based thermal energy storage in buildings

Latent heat thermal energy storage (LHTES) has significant potential for mitigating peak electricity demand and enabling load shifting in buildings. Phase Change Material embedded heat exchangers (PCM-HX) can significantly improve energy demand management due to high storage capacity. However, PCM-HX evaluation typically depends on computationally expensive fully transient simulations, posing significant challenges for scalable system- and building-level energy assessments across different climates and system architectures. This paper presents a generalized, accurate, and computationally efficient methodology for simulating building energy systems integrated with LHTES. The PCM-HX transient performance is represented by performance maps generated using a Generalized Resistance-Capacitance Model (GRCM) that enables accurate predictions of arbitrary PCM-HXs at low computational cost. The feasibility of the proposed approach was verified using a case study considering a dual-mode heat pump-thermal energy storage (HP-TES) system simulated in Modelica with Spawn of EnergyPlus™ for a DOE prototype small office building in two locations: Tampa, FL, and International Falls, MN. The PCM-HX performance maps provided accurate predictions of PCM-HX transient behavior, with mean absolute percentage deviations within 2–4% compared to GRCM while also achieving at least 1800× reduction in computational time. Moreover, the HP-TES system achieved energy savings of up to 17.4% in Tampa, FL, and 62.2% in International Falls, MN, demonstrating the broader applicability of the proposed methodology across different climate zones. This work highlights the importance of robust PCM-HX models in enabling accurate and computationally efficient building-level simulations and enabling future research opportunities for investigating optimized HP-TES designs and advanced control strategies for grid-interactive buildings.

Modelica↗
DOE OSTI2022

Double echo symmetry-based REDOR and RESPDOR pulse sequences for proton detected measurements of heteronuclear dipolar coupling constants

1 H{X} symmetry-based rotational echo double resonance pulse sequences (S-REDOR) and symmetry-based rotational echo saturation pulse double resonance (S-RESPDOR) solid-state NMR experiments have found widespread application for 1 H detected measurements of difference NMR spectra, dipolar coupling constants, and internuclear distances under conditions of fast magic angle spinning (MAS). In these experiments the supercycled $\text{R4}^2_1 (\text{SR4}^2_1)$ symmetry-based recoupling pulse sequence is typically applied to the 1 H spins to reintroduce heteronuclear dipolar couplings. However, the timing of $\text{SR4}^2_1$ and other symmetry-based pulse sequences must be precisely synchronized with the rotation of the sample, otherwise, the evolution of 1 H CSA and other interactions will not be properly refocused. For this reason, significant distortions are often observed in experimental dipolar dephasing difference curves obtained with S-REDOR or S-RESPDOR pulse sequences. Here we introduce a family of double echo (DE) S-REDOR/S-RESPDOR pulse sequences that function in an analogous manner to the recently introduced $t_1$-noise eliminated (TONE) family of dipolar heteronuclear multiple quantum coherence (D-HMQC) pulse sequences. Through numerical simulations and experiments the DE S-REDOR/S-RESPDOR sequences are shown to provide dephasing difference curves similar to those obtained with S-REDOR/S-RESPDOR. However, the DE sequences are more robust to the deviations of the MAS frequency from the ideal value that occurs during typical solid-state NMR experiments. In this work, the DE sequences are shown to provide more reliable 1 H detected dipolar dephasing difference curves for nuclei such as 15 N (with isotopic labelling), 183 W and 35 Cl. The double echo sequences are therefore recommended to be used in place of conventional S-REDOR/S-RESPDOR sequences for measurement of weak dipolar coupling constants and long-range distances.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Experimental Investigation of Uranium Volatility during Vapor Condensation

The predictive models that describe the fate and transport of radioactive materials in the atmosphere following a nuclear incident (explosion or reactor accident) assume that uranium-bearing particulates would attain chemical equilibrium during vapor condensation. Here, we show that kinetically driven processes in a system of rapidly decreasing temperature can result in substantial deviations from chemical equilibrium. This can cause uranium to condense out in oxidation states (e.g., UO 3 vs UO 2 ) that have different vapor pressures, significantly affecting uranium transport. To demonstrate this, we synthesized uranium oxide nanoparticles using a flow reactor under controlled conditions of temperature, pressure, and oxygen concentration. The atomized chemical reactants passing through an inductively coupled plasma cool from ~5000 to 1000 K within milliseconds and form nanoparticles inside a flow reactor. The ex situ analysis of particulates by transmission electron microscopy revealed 2–10 nm crystallites of fcc-UO 2 or α-UO 3 depending on the amount of oxygen in the system. α-UO 3 is the least thermodynamically preferred polymorph of UO 3 . The absence of stable uranium oxides with intermediate stoichiometries (e.g., U 3 O 8 ) and sensitivity of the uranium oxidation states to local redox conditions highlight the importance of in situ measurements at high temperatures. Therefore, we developed a laser-based diagnostic to detect uranium oxide particles as they are formed inside the flow reactor. Our in situ measurements allowed us to quantify the changes in the number densities of the uranium oxide nanoparticles (e.g., UO 3 ) as a function of oxygen gas concentration. Our results indicate that uranium can prefer to be in metastable crystal forms (i.e., α-UO 3 ) that have higher vapor pressures than the refractory form (i.e., UO 2 ) depending on the oxygen abundance in the surrounding environment. This demonstrates that the equilibrium processes may not dominate during rapid condensation processes, and thus kinetic models are required to fully describe uranium transport subsequent to nuclear incidents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Polymorphous nature of cubic halide perovskites

Many common crystal structures can be described by a single (or very few) repeated structural motif (“monomorphous structures”) such as octahedron in cubic halide perovskites. Interestingly, recent accumulated evidence suggests that electronic structure calculations based on such macroscopically averaged monomorphous cubic ($\textit{Pm} – 3m$) halide perovskites obtained from x-ray diffraction, show intriguing deviations from experiment. These include systematically too small band gaps, dielectric constants dominated by the electronic, negative mixing enthalpy of alloys, and significant deviations from the measured pair distribution function. We show here that a minimization of the systems $\textit{T}$ = 0 internal energy via density functional theory reveals a distribution of different low-symmetry local motifs, including tilting, rotations, and B-atom displacements (“polymorphous networks”). This is found only if one allows for larger-than-minimal cell size that does not geometrically exclude low symmetry motifs. As the (super) cell size increases, the energy is lowered relative to the monomorphous cell, and stabilizes after ~32 formula units (≥160 atoms) are included. Being a result of nonthermal energy minimization in the internal energy without entropy, this correlated set of displacements must represent the intrinsic geometry preferred by the underlying chemical bonding (lone pair bonding), and as such has a different origin than the normal, dynamic thermal disorder modeled by molecular dynamics. Indeed, the polymorphous network, not the monomorphous ansatz, is the kernel structure from which high temperature thermal agitation develops. The emerging physical picture is that the polymorphous network has an average structure with high symmetry, yet the local structural motifs have low symmetries. In this work we find that, compared with monomorphous counterparts, the polymorphous networks have significantly lower predicted total energies, larger band gaps, and ionic dominated dielectric constants, and agree much more closely with the observed pair distribution functions. An analogous polymorphous situation is found in the paraelectric phase of a few cubic oxide perovskites where local polarization takes the role of local displacements in halide perovskites, and in the paramagnetic phases of a few 3 d oxides where the local spin configuration takes that role.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗