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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Surface Potentials of (001), (012), (113) Hematite (α-Fe2O3) Crystal Faces in Aqueous Solution

Hematite (α-Fe2O3) is an important candidate electrode for energy system technologies such as photoelectrochemical water splitting. Conversion efficiency issues with this material are presently being addressed through nanostructuring, doping, and surface modification. However, key electrochemical properties of hematite/electrolyte interfaces remain poorly understood at a fundamental level, in particular those of crystallographically well-defined hematite faces likely present as interfacial components at the grain scale. We report a combined measurement and theory study that isolates and evaluates the equilibrium surface potentials of three nearly defect-free single crystal faces of hematite, titrated from pH 3 to 11.25. We link measured surface potentials with atomic-scale surface topology, namely the ratio and distributions of surface protonation/deprotonation site types expected from the bulk structure. The data reveal face-specific points of zero potential (PZP) relatable to points of zero net charge (PZC) that lie within a small pH window (8.35-8.85). Over the entire pH range the surface potentials show strong non-Nernstian charging at pH extremes separated by a wide central plateau in agreement with surface complexation modeling predictions, but with important face-specific distinctions. We introduce a new surface complexation model based on fitting the entire data set that depends primarily only on the proton affinities of two site types and the two associated electrical double layer capacitances. The data and model show that magnitudes of surface potential biases at the pH extremes are on the order of 100 mV, similar to the activation energy for electron hopping mobility. An energy band diagram for hematite crystallites with specific face expression and pH effects is proposed that could provide a baseline for understanding water splitting performance enhancement effects from nanostructuring, and guide morphology targets and pH for systematic improvements in efficiency.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2019

Sodium Pumping via Condensation within a Non-Wetting Porous Structure

The transfer of liquid sodium from a low-pressure condenser to a high-pressure evaporator is required to complete the thermodynamic cycle of a sodium thermal electrochemical converter (Na-TEC). A unique capillary pump is explored in this work, whereby low-pressure sodium vapor is condensed within a non-wetting (i.e. contact angle > pi/2) stainless steel porous structure. Due to the curvature of the non-wetting liquid-vapor interface, the liquid adjacent to the interface is at a higher pressure than the vapor. This is in contrast to traditional wicks, where the liquid adjacent to the interface has a lower pressure. Conjugate heat transfer techniques are used to model the coupled momentum and thermal transport processes within this non-wetting porous structure. Due to the low mass flowrates in the Na-TEC (< 0.1 mg/s), higher order friction terms are neglected and the classical Darcy’s law is used for the non-isothermal, compressible vapor flow. At lower temperatures, the sodium vapor density becomes sufficiently small and there is a transition from classic Poiseuille flow (Kn < 0.1) to Knudsen flow (Kn > 10). Furthermore, transport due to binary diffusion is also considered for situations where there is a substantial presence of non-condensable argon in the sodium vapor plenum. Initial modeling results showing expected mass flowrates, temperature profiles, and liquid-vapor interface locations are presented for various physical conditions. The main design features of an experimental set-up used to demonstrate this capillary pumping is also described in detail, including the method used to measure the low sodium mass flowrates. Initial experimental results demonstrating sodium pumping for a range of temperatures (800K – 1100K) will be presented and compared against the model predictions. Finally, several of the challenges with this experiment will be discussed, and specific strategies used to address these are presented.

14 SOLAR ENERGY↗
DOE OSTI2021

Data Mining of Polymer Phase Transitions upon Temperature Changes by Small and Wide-Angle X-ray Scattering Combined with Raman Spectroscopy

The complex physical transformations of polymers upon external thermodynamic changes are related to the molecular length of the polymer and its associated multifaceted energetic balance. The understanding of subtle transitions or multistep phase transformation requires real-time phenomenological studies using a multi-technique approach that covers several length-scales and chemical states. A combination of X-ray scattering techniques with Raman spectroscopy and Differential Scanning Calorimetry was conducted to correlate the structural changes from the conformational chain to the polymer crystal and mesoscale organization. Current research applications and the experimental combination of Raman spectroscopy with simultaneous SAXS/WAXS measurements coupled to a DSC is discussed. In particular, we show that in order to obtain the maximum benefit from simultaneously obtained high-quality data sets from different techniques, one should look beyond traditional analysis techniques and instead apply multivariate analysis. Data mining strategies can be applied to develop methods to control polymer processing in an industrial context. Crystallization studies of a PVDF blend with a fluoroelastomer, known to feature complex phase transitions, were used to validate the combined approach and further analyzed by MVA.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Direct dynamics simulation of dioxetane formation and decomposition via the singlet ·O–O–CH2–CH2 · biradical: Non-RRKM dynamics

Electronic structure calculations and direct chemical dynamics simulations are used to study the formation and decomposition of dioxetane on its ground state singlet potential energy surface. The stationary points for 1O2 + C2H4, the singlet {center_dot}O-O-CH2-CH2{center_dot} biradical, the transition state (TS) connecting this biradical with dioxetane, and the two transition states and gauche {center_dot}O-CH2-CH2-O{center_dot} biradical connecting dioxetane with the formaldehyde product molecules are investigated at different levels of electronic structure theory including UB3LYP, UMP2, MRMP2, and CASSCF and a range of basis sets. The UB3LYP/6-31G* method was found to give representative energies for the reactive system and was used as a model for the simulations. UB3LYP/6-31G* direct dynamics trajectories were initiated at the TS connecting the {center_dot}O-O-CH2-CH2{center_dot} biradical and dioxetane by sampling the TS's vibrational energy levels, and rotational and reaction coordinate energies, with Boltzmann distributions at 300, 1000, and 1500 K. This corresponds to the transition state theory model for trajectories that pass the TS. The trajectories were directed randomly towards both the biradical and dioxetane. A small fraction of the trajectories directed towards the biradical recrossed the TS and formed dioxetane. The remainder formed 1O2 + C2H4 and of these {approx} 40% went directly from the TS to 1O2 + C2H4 without getting trapped and forming an intermediate in the {center_dot}O-O- CH2-CH2{center_dot} biradical potential energy minimum, a non-statistical result. The dioxetane molecules which are formed dissociate to two formaldehyde molecules with a rate constant two orders of magnitude smaller than that predicted by Rice-Ramsperger-Kassel-Marcus theory. The reaction dynamics from dioxetane to the formaldehyde molecules do not follow the intrinsic reaction coordinate or involve trapping in the gauche {center_dot}O-CH2-CH2-O{center_dot} biradical potential energy minimum. Important non-statistical dynamics are exhibited for this reactive system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Cross-nucleation between clathrate hydrate polymorphs: Assessing the role of stability, growth rate, and structure matching

Cross-nucleation is a phenomenon where a new crystal nucleates and grows upon the surface of a different polymorph. Previous studies indicate that faster growth rate of the new crystal is a necessary but not sufficient condition for cross-nucleation. The thermodynamic stability of the different polymorphs can also affect cross-nucleation by modulating the rates of crystal growth. The interplay between thermodynamic stability of the polymorphs involved, the growth rate of the crystals, and the need for creation of an interfacial transition layer that seamlessly connects the two structures has not yet been fully elucidated. Predicting cross-nucleation is particularly challenging for clathrate hydrates, for which there are sometimes several polymorphs with similar stability and for which growth rates are not known. In this work, we use molecular dynamics simulations to investigate which factor (stability, growth rate, or formation of interfacial transition layer) controls cross-nucleation between the four known Frank-Kasper clathrate hydrate polymorphs: sI, sII, TS, and HS-I. We investigate the growth and cross-nucleation of these four hydrates filled with a set of guest molecules that produce different order of stabilities for the four crystal structures. We determine that the growth rate of sII clathrate is the fastest, followed by TS, HS-I, and sI. We find that cross-nucleation into or from sII clathrates is preceded by the formation of an interfacial transition layer at the seed crystal/liquid interface because sII does not share a crystal plane with sI, HS-I, or TS. Cross-nucleation between the latter three can occur seamlessly and is determined only by their growth rates. Our results indicate that nucleation of an interfacial transition layer between non-matching polymorphs can control cross-nucleation or lack thereof under conditions of small driving force. Under conditions of sufficient supercooling clathrate hydrate polymorphs cross-nucleate into the fastest growing phase even if that new phase is less stable and does not share a common crystal plane with the initial polymorph.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Machine-Learned Manifold-Based Models for Large Eddy Simulation of Turbulent Combustion

Reduced-order manifold combustion models are commonly used to lower the cost of reacting Large Eddy Simulations (LES) and may be derived either from physical principles as in flamelet models or from data-driven methods like Principal Component Analysis (PCA). In either case, neural networks are increasingly used as part of these models to provide a nonlinear mapping between a small set of pre-defined variables that parameterize the manifold and outputs of interest, such as reaction rates. In this work, we propose a new manifold-based modeling approach that combines the definition of the manifold-parameterizing variables (linear combinations of species), the nonlinear mapping to the outputs, and closure of filtered quantities for LES into the structure of a single neural network. This allows the process used to train the neural network to simultaneously optimize both the functional form of the model and the identities of the inputs to the model. The new approach can flexibly incorporate thermochemical data from any combustion system; if trained on data from 1D flames it can be interpreted as an optimized flamelet model, but it can also be used to learn models from data from more complex configurations. This work presents a priori evaluations of the new approach in both contexts. Evaluation using data from 1D premixed flames demonstrates the physical interpretability of the manifold variables generated by the new approach. Evaluation using data from direct numerical simulations of turbulent flames shows improved predictions relative to either flamelet or PCA-based models in a more complex configuration.

47 OTHER INSTRUMENTATION↗
DOE OSTI2011

Dynamic Bertrand Oligopoly

We study continuous time Bertrand oligopolies in which a small number of firms producing similar goods compete with one another by setting prices. We first analyze a static version of this game in order to better understand the strategies played in the dynamic setting. Within the static game, we characterize the Nash equilibrium when there are N players with heterogeneous costs. In the dynamic game with uncertain market demand, firms of different sizes have different lifetime capacities which deplete over time according to the market demand for their good. We setup the nonzero-sum stochastic differential game and its associated system of HJB partial differential equations in the case of linear demand functions. We characterize certain qualitative features of the game using an asymptotic approximation in the limit of small competition. The equilibrium of the game is further studied using numerical solutions. We find that consumers benefit the most when a market is structured with many firms of the same relative size producing highly substitutable goods. However, a large degree of substitutability does not always lead to large drops in price, for example when two firms have a large difference in their size.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS2008

Micro-Vibration Measurements on Thermally Loaded Multi-Layer Insulation Samples in Vacuum

Some scientific missions require to an extreme extent the absence of any on-board microvibration. Recent projects dedicated to measuring the Earth's gravity field and modeling the geoid with extremely high accuracy are examples. Their missions demand for extremely low micro-vibration environment on orbit for: (1) Not disturbing the measurement of earth gravity effects with the installed gradiometer or (2) Even not damaging the very high sensitive instruments. Based on evidence from ongoing missions multi-layer insulation (MLI) type thermal control blankets have been identified as a structural element of spacecrafts which might deform under temperature variations being caused by varying solar irradiation in orbit. Any such deformation exerts tiny forces which may cause small reactions resulting in micro-vibrations, in particular by exciting the spacecraft eigenmodes. The principle of the test set-up for the micro-vibration test was as follows. A real side wall panel of the spacecraft (size about 0.25 m2) was low-frequency suspended in a thermal vacuum chamber. On the one side of this panel, the MLI samples were fixed by using the standard methods. In front of the MLI, an IR-rig was installed which provided actively controlled IR-radiation power of about 6 kW/m2 in order to heat the MLI surface. The cooling was passive using the shroud temperature at a chamber pressure <1E-5mbar. The resulting micro-vibrations due to MLI motion in the heating and the cooling phase were measured via seismic accelerometers which were rigidly mounted to the panel. Video recording was used to correlate micro-vibration events to any visual MLI motion. Different MLI sample types were subjected to various thermal cycles in a temperature range between -60 C to +80 C. In this paper, the experience on these micro-vibration measurements will be presented and the conclusions for future applications will be discussed

Deutsch, Georg↗
DOE OSTI2025

Design of light- and chemically responsive protein assemblies through host-guest interactions

Host-guest (HG) interactions have been widely used to build responsive materials and molecular machines owing to their inherently dynamic nature, interaction specificity, and responsiveness to diverse stimuli. Here, in this work, we have set out to exploit these advantages of HG chemistry in the design of dynamic protein assemblies, using a C 4 symmetric protein, C98 RhuA, as a building block. We show that a C98 RhuA variant individually modified with β-cyclodextrin (βCD) (host) or azobenzene (guest) functionalities can specifically pair with each other to form highly ordered 1D and 2D assemblies. Association and dissociation of βCD RhuA- azo RhuA assemblies can be controlled by UV and visible light as well as by small-molecule modulators of βCD-azobenzene interactions. Kinetics analyses reveal that βCD RhuA- azo RhuA nanotubes assemble without a nucleation barrier, a highly unusual occurrence for helical supramolecular systems. Taken together, our findings provide a compelling example for achieving complex structural and dynamic outcomes in protein assembly through simple chemical design.

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

Cosmology and stellar equilibrium using Newtonian hydrodynamics with general relativistic pressure

We revisit the analysis made by Hwang and Noh [JCAP 1310 (2013)] aiming the construction of a Newtonian set of equations incorporating pressure effects typical of the General Relativity theory. We explicitly derive the Hwang-Noh equations, comparing them with similar computations found in the literature. Then, we investigate i ) the cosmological expansion, ii ) linear cosmological perturbations theory and iii ) stellar equilibrium by using the new set of equations and comparing the results with those coming from the usual Newtonian theory, from the Neo-Newtonian theory and from the General Relativity theory. We show that the predictions for the background evolution of the Universe are deeply changed with respect to the General Relativity theory: the acceleration of the Universe is achieved with positive pressure. On the other hand, the behaviour of small cosmological perturbations reproduces the one found in the relativistic context, even if only at small scales. We argue that this last result may open new possibilities for numerical simulations for structure formation in the Universe. Finally, the properties of neutron stars are qualitatively reproduced by Hwang-Noh equations, but the upper mass limit is at least one order of magnitude higher than the one obtained in General Relativity.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

3D Printed Silicones with Shape Memory

Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and T g on compressive behavior and compression set in siloxane matrix printed structures. The lower T g microsphere structures exhibit substantial compression set when heated near and above T g , with full structural recovery upon reheating without constraint. By contrast, the higher T g microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuning the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Harmonic analysis of discrete tracers of large-scale structure

It is commonplace in cosmology to analyze fields projected onto the celestial sphere, and in particular density fields that are defined by a set of points e.g. galaxies. When performing an harmonic-space analysis of such data (e.g. an angular power spectrum) using a pixelized map one has to deal with aliasing of small-scale power and pixel window functions. We compare and contrast the approaches to this problem taken in the cosmic microwave background and large-scale structure communities, and advocate for a direct approach that avoids pixelization. We describe a method for performing a pseudo-spectrum analysis of a galaxy data set and show that it can be implemented efficiently using well-known algorithms for special functions that are suited to acceleration by graphics processing units (GPUs). The method returns the same spectra as the more traditional map-based approach if in the latter the number of pixels is taken to be sufficiently large and the mask is well sampled. The method is readily generalizable to cross-spectra and higher-order functions. It also provides a convenient route for distributing the information in a galaxy catalog directly in harmonic space, as a complement to releasing the configuration-space positions and weights, and a route to spectral apodization. Finally, we make public a code enabling the application of our method to existing and upcoming datasets.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Customizable wave tailoring nonlinear materials enabled by bilevel inverse design

Abstract Passive wave transformation via nonlinearity is ubiquitous in settings from acoustics to optics and electromagnetics. It is well known that different nonlinearities yield different effects on propagating signals, which raises the question of “what precise nonlinearity is the best for a given wave tailoring application?” In this work, considering a one-dimensional spring-mass chain connected by polynomial springs (a variant of the Fermi-Pasta-Ulam-Tsingou system), we introduce a bilevel inverse design method which couples the shape optimization of structures for tailored constitutive responses with reduced-order nonlinear dynamical inverse design. We apply it to two qualitatively distinct problems—minimization of peak transmitted kinetic energy from impact, and pulse shape transformation—demonstrating our method’s breadth of applicability. For the impact problem, we obtain two fundamental insights. First, small differences in nonlinearity can drastically change the dynamic response of the system, from severely under- to outperforming a comparative linear system. Second, the oft-used strategy of impact mitigation via “energy locking” bistability can be significantly outperformed by our optimal nonlinearity. We validate this case with impact experiments and find excellent agreement. This study establishes a framework for broader passive nonlinear mechanical wave tailoring material design, with applications to computing, signal processing, shock mitigation, and autonomous materials.

Science & Technology - Other Topics↗
DOE OSTI2014

Temperature-dependent radiation sensitivity and order of 70S ribosome crystals

All evidence to date indicates that at T = 100 K all protein crystals exhibit comparable sensitivity to X-ray damage when quantified using global metrics such as change in scaling B factor or integrated intensity versus dose. This is consistent with observations in cryo-electron microscopy, and results because nearly all diffusive motions of protein and solvent, including motions induced by radiation damage, are frozen out. But how do the sensitivities of different proteins compare at room temperature, where radiation-induced radicals are free to diffuse and protein and lattice structures are free to relax in response to local damage? It might be expected that a large complex with extensive conformational degrees of freedom would be more radiation sensitive than a small, compact globular protein. As a test case, the radiation sensitivity of 70S ribosome crystals has been examined. At T = 100 and 300 K, the half doses are 64 MGy (at 3 Å resolution) and 150 kGy (at 5 Å resolution), respectively. The maximum tolerable dose in a crystallography experiment depends upon the initial or desired resolution. When differences in initial data-set resolution are accounted for, the former half dose is roughly consistent with that for model proteins, and the 100/300 K half-dose ratio is roughly a factor of ten larger. 70S ribosome crystals exhibit substantially increased resolution at 100 K relative to 300 K owing to cooling-induced ordering and not to reduced radiation sensitivity and slower radiation damage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Thermoelectric characterization of suspended single silicon%3CU%2B2010%3Egermanium alloy nanowires.

The use of nanowires for thermoelectric energy generation has gained momentum in recent years as an approach to improve the figure of merit (ZT) due in part to larger phonon scattering at the boundary resulting in reduced thermal conductivity while electrical conductivity is not significantly affected. Silicon-germanium (SiGe) alloy nanowires are promising candidates to further reduce thermal conductivity by phonon scattering because bulk SiGe alloys already have thermal conductivity comparable to reported Si nanowires. In this work, we show that thermal and electrical conductivity can be measured for the same single nanowire eliminating the uncertainties in ZT estimation due to measuring the thermal conduction on one set of wires and the electrical conduction on another set. In order to do so, we use nanomanipulation to place vapor-liquid-solid boron-doped SiGe alloy nanowires on predefined surface structures. Furthermore, we developed a contact-annealing technique to achieve negligible electrical contact resistance for the placed nanowires that allows us, for the first time, to measure electrical and thermal properties on the same device. We observe that thermal conductivity for SiGe nanowires is dominated by alloy scattering for nanowires down to 100 nm in diameter between the temperature range 40-300 K. The estimated electronic contribution of the thermal conductivity as given by the Wiedemann-Franz relationship is about 1 order of magnitude smaller than the measured thermal conductivity which indicates that phonons carry a large portion of the heat even at such small dimensions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Fast Real-Time Time-Dependent Density Functional Theory Calculations with the Parallel Transport Gauge

Real-time time-dependent density functional theory (RT-TDDFT) is known to be hindered by the very small time step (attosecond or smaller) needed in the numerical simulation, because of the fast oscillation of electron wave functions, which significantly limits its range of applicability for the study of ultrafast dynamics. In this paper, we demonstrate that such oscillation can be considerably reduced by optimizing the gauge choice using the parallel transport formalism. RT-TDDFT calculations can thus be significantly accelerated using a combination of the parallel transport gauge and implicit integrators, and the resulting scheme can be used to accelerate any electronic structure software that uses a Schrödinger representation. Here, using absorption spectrum, ultrashort laser pulse, and Ehrenfest dynamics calculations for example, we show that the new method can utilize a time step that is on the order of 10–100 attoseconds using a planewave basis set. Thanks to the significant increase of the size of the time step, we also demonstrate that the new method is more than 10 times faster, in terms of the wall clock time, when compared to the standard explicit fourth-order Runge–Kutta time integrator for silicon systems ranging from 32 to 1024 atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Advancing Understanding of the Role of Belowground Processes in Terrestrial Carbon Sinks trhrough Ground-Penetrating Radar. Final Report

Coarse roots play a significant role in belowground carbon cycling and will likely play an increasingly crucial role in belowground carbon sequestration as atmospheric CO 2 levels continue to rise, yet they are one of the most difficult ecosystem parameters to quantify. Despite promising results with ground-penetrating radar (GPR) as a nondestructive method of quantifying biomass of coarse roots, this application of GPR is in its infancy and neither the complete potential nor limitations of the technology have been fully evaluated. The primary goals and questions of this study fell into four groups: (1) GPR methods: Can GPR detect change in root biomass over time, differentiate live roots from dead roots, differentiate between coarse roots, fine roots bundled together, and a fine root mat, remain effective with varied soil moisture, and detect shadowed roots (roots hidden below larger roots); (2) CO 2 enrichment study at Kennedy Space Center in Brevard County, Florida: Are there post-fire legacy effects of CO 2 fertilization on plant carbon pools following the end of CO 2 application ? (3) Disney Wilderness Study: What is the overall coarse root biomass and potential for belowground carbon storage in a restored longleaf pine flatwoods system? Can GPR effectively quantify coarse roots in soils that are wetter than the previous sites and that have a high percentage of saw palmetto rhizomes present? (4) Can GPR accurately represent root architecture in a three-dimensional model? When the user is familiar with the equipment and software in a setting that minimizes unsuitable conditions, GPR is a relatively precise, non-destructive, useful tool for estimating coarse root biomass. However, there are a number of cautions and guidelines that should be followed to minimize inaccuracies or situations that are untenable for GPR use. GPR appears to be precise as it routinely predicts highly similar values for a given area across multiple scanning events; however, it appears to lack sufficient accuracy at small scales. Knowledge of soil conditions and their effects on GPR wave propagation and reception are paramount for the collection of useful data. Strong familiarity with the software and equipment is both important and necessary for GPR use in estimating coarse root biomass. GPR must be utilized at low soil moisture levels in order to accurately represent existing coarse root structures. Our results from Disney Wilderness Preserve highlight the need for a strong understanding of the limitations of GPR, specifically knowledge of root structures (saw palmetto rhizomes) or environmental factors (low moisture content) that may hinder its application within a given system. The 3D modeling of course roots with GPR appears quite promising, as it has become more accurate and precise as the software has advanced and become more robust, but there is still a need for more precision before it will likely be able to model anything more than simple root systems comprised mostly of large diameter roots. Our results from Kennedy Space Center suggest that there are legacy effects from CO 2 fertilization in the form of more root mass providing a greater capacity for aboveground plant regrowth following fire, even 7 years after treatment ended.

54 ENVIRONMENTAL SCIENCES↗