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DOE OSTI2020

An interface-aware sub-scale dynamics multi-material cell model for solids with void closure and opening at all speeds

Here, we present a multi-material cell model (closure model) for demanding arbitrary Lagrangian-Eulerian (ALE) simulations of fluids and solids. It is based on the interface-aware sub-scale dynamics (IASSD) approach which utilizes the exact material interface geometry within the computational cell to calculate internal material interactions. Our formulation of the closure model also aims to improve the accuracy in low-speed impact events. Voids are used to represent ambient vacuum and internal free boundaries of the distinct materials. Void regions can close and open at contact surfaces, allowing a transition from contact physics to free motion in vacuum. The coupling of void closure and opening with a new formulation of the IASSD model for solids is tested on several one- and two-dimensional numerical examples, ranging from gas expansion in vacuum to planar and round object impacts at various speeds.

42 ENGINEERING↗

DOE OSTI2022

High repetition rate mapping of the interaction between a laser plasma and magnetized background plasma via laser induced fluorescence

In this work, the laminar coupling of energy between a laser-produced plasma and a background magnetized plasma was investigated via planar laser induced fluorescence diagnostic and magnetic flux probes. Experiments performed on the Large Plasma Device at the University of California, Los Angeles, mapped out the two-dimensional spatiotemporal evolution of the laser-plasma (debris) ion velocity distribution function (VDF) to assess debris-background coupling in a sub-Alfvénic regime. The acquisition of these data necessitates high repetition rate (1 Hz) as each dataset is the accumulation of thousands of laser shots, which would not be feasible in single-shot experiments. Fully kinetic, three-dimensional particle-in-cell simulations are compared to the measured VDFs to provide a framework in which we can understand the coupling of a sub-Alfvénic plasma flow through a preformed, magnetized plasma. The simulations display the same departure from the expected gyromotion of the debris plasma as observed in the experimental data, and in conjunction with the measured magnetic field traces, have led to the direct observation of the collisionless coupling via laminar fields.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Improved charge extraction in inverted perovskite solar cells with dual-site-binding ligands

Inverted (pin) perovskite solar cells (PSCs) afford improved operating stability in comparison to their nip counterparts but have lagged in power conversion efficiency (PCE). The energetic losses responsible for this PCE deficit in pin PSCs occur primarily at the interfaces between the perovskite and the charge-transport layers. Additive and surface treatments that use passivating ligands usually bind to a single active binding site: This dense packing of electrically resistive passivants perpendicular to the surface may limit the fill factor in pin PSCs. We identified ligands that bind two neighboring lead(II) ion (Pb 2+ ) defect sites in a planar ligand orientation on the perovskite. We fabricated pin PSCs and report a certified quasi–steady state PCE of 26.15 and 24.74% for 0.05– and 1.04–square centimeter illuminated areas, respectively. The devices retain 95% of their initial PCE after 1200 hours of continuous 1 sun maximum power point operation at 65°C.

Science & Technology - Other Topics↗

NASA NTRS1990

A Hardened CARS System Utilized for Temperature Measurements in a Supersonic Combustor

A coherent anti-Stokes Raman scattering (CARS) system has been hardened for use in a NASA Langley supersonic combustion test cell. The system can obtain temperature cross sections of the flow at three locations. The system is environmentally protected and remotely operated. Measurements were made in a scram-jet combustor model consisting of a rear- ward-facing step, followed by an expansion duct. The duct is nominally 4 feet in length. The free stream conditions were Mach 2, with static pressure which ranged from 0.8 to 1.9 atm, and a static temperature of approximately 800K. Three vertical slots were machined into each side of the duct to allow optical access. The CARS system utilized a planar BOXCARS beam arrangement. This arrangement allowed the laser beams to pass through the vertical slots in the tunnel. Translation stages were utilized to move the focussing volume within the tunnel. These stages allowed complete cross sections to be obtained at each slot location. A fiber optic carried the signal to a remotely located monochrometer and reticon detector.Data for two different flow conditions were taken at each of the three slot locations. These two conditions provided a comparison between reacting and non-reacting mixing of injected hydrogen fuel with the combustion heated supersonic stream.

Antcliff, Richard R.↗

NASA NTRS2003

Computer Simulation of a Digital Global Velocimeter

The objective is to continue the development of a Monte-Carlo simulation of a Doppler Global Velocimetry (DGV) optical system starting with the Mie scattering from the particles in the fluid to the collection optics, through the beamsplitter, Iodine absorption cell and finally to the CCD sensor. The simulation program will read in a configuration file that completely describes the attributes of a DGV system (optical, physical layout, location of detectors, laser properties, CCD sensor noise characteristics...). The simulation program will output a set of images that simulate the data collected from a DGV system. NASA GRC has the DGV software developed at NASA Langley and this simulation program will prove invaluable for determining the accuracy of the DGV technique and provide insight into optimizing the data reduction techniques. The DGV simulation software will also prove valuable in a DDF funded projected entitled Planar Particle Imaging Doppler Velocimetry (PPIDV), which was recently awarded in March 2002.

Cheung, H. Mike↗

NASA NTRS2013

Unit-Sphere Multiaxial Stochastic-Strength Model Applied to Anisotropic and Composite Materials

Models that predict the failure probability of brittle materials under multiaxial loading have been developed by authors such as Batdorf, Evans, and Matsuo. These "unit-sphere" models assume that the strength-controlling flaws are randomly oriented, noninteracting planar microcracks of specified geometry but of variable size. This methodology has been extended to predict the multiaxial strength response of transversely isotropic brittle materials, including polymer matrix composites (PMCs), by considering (1) flaw-orientation anisotropy, whereby a preexisting microcrack has a higher likelihood of being oriented in one direction over another direction, and (2) critical strength, or K (sub Ic) orientation anisotropy, whereby the level of critical strength or fracture toughness for mode I crack propagation, K (sub Ic), changes with regard to the orientation of the microstructure. In this report, results from finite element analysis of a fiber-reinforced-matrix unit cell were used with the unit-sphere model to predict the biaxial strength response of a unidirectional PMC previously reported from the World-Wide Failure Exercise. Results for nuclear-grade graphite materials under biaxial loading are also shown for comparison. This effort was successful in predicting the multiaxial strength response for the chosen problems. Findings regarding stress-state interactions and failure modes also are provided.

Nemeth, Noel, N.↗

DOE OSTI2025

The structures of mcgovernite and carlfrancisite reconsidered: static disorder or ordered defects and twinning?

Here, the minerals mcgovernite and carlfrancisite possess an extraordinary rhombohedral unit cell [mcgovernite: a = b = 8.206 Å and c = 204.118 Å, with the complex formula unit M 2+ 19 Zn 3 (OH) 21 (AsO 3 )(AsO 4 ) 3 (SiO 4 ) 3 (M = Mn, Mg, Zn); carlfrancisite similar]. Hawthorne [(2018), Mineral. Mag. 82, 1101–1118] reported a single-crystal study using a centrosymmetric model ($R\bar{3}c$) containing disorder on three cationic sites and an AsIII lone-pair site for both mcgovernite and carlfrancisite. A solution of the structure of mcgovernite from high-resolution synchrotron powder diffraction data suggests a reinterpretation of the crystal structures of mcgovernite and carlfrancisite as noncentrosymmetric R3c with ordered planar defects which allows for merohedral twinning.

carlfrancisite↗

DOE OSTI2022

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2003

The Highly Robust Electrical Interconnects and Ultrasensitive Biosensors Based on Embedded Carbon Nanotube Arrays

We report on our recent breakthroughs in two different applications using well-aligned carbon nanotube (CNT) arrays on Si chips, including (1) a novel processing solution for highly robust electrical interconnects in integrated circuit manufacturing, and (2) the development of ultrasensitive electrochemical DNA sensors. Both of them rely on the invention of a bottom-up fabrication scheme which includes six steps, including: (a) lithographic patterning, (b) depositing bottom conducting contacts, (c) depositing metal catalysts, (d) CNT growth by plasma enhanced chemical vapor deposition (PECVD), (e) dielectric gap-filling, and (f) chemical mechanical polishing (CMP). Such processes produce a stable planarized surface with only the open end of CNTs exposed, whch can be further processed or modified for different applications. By depositing patterned top contacts, the CNT can serve as vertical interconnects between the two conducting layers. This method is fundamentally different fiom current damascene processes and avoids problems associated with etching and filling of high aspect ratio holes at nanoscales. In addition, multiwalled CNTs (MWCNTs) are highly robust and can carry a current density of 10(exp 9) A/square centimeters without degradation. It has great potential to help extending the current Si technology. The embedded MWCNT array without the top contact layer can be also used as a nanoelectrode array in electrochemical biosensors. The cell time-constant and sensitivity can be dramatically improved. By functionalizing the tube ends with specific oligonucleotide probes, specific DNA targets can be detected with electrochemical methods down to subattomoles.

Li, Jun↗

DOE OSTI2023

Excitation of surface waves in 3D ion beam neutralization

Neutralization of beams with 2D and 3D geometries by the electrons emitted from an external source is studied using particle-in-cell simulations. Our work reveals that the high-energy electrons excite Trivelpiece–Gould (TG) surface waves in the beams with 3D axisymmetric geometries. These high-energy electrons are generated because of a large amplitude electrostatic solitary wave (ESW) that forms near the electron source and has an electric potential amplitude more than three times the electron thermal energy. Here, we also find that surface wave excitation only happens when the beam radius is large enough at the ion source to attract enough electrons that could form the large amplitude ESW. A comparison of the 3D TG surface wave dispersion relation with an expression for 2D surface waves reveals that they become excited in 3D axisymmetric but not in 2D planar beam because of a higher phase speed requirement in the latter case.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2003

Plasma Interactions with High Voltage Solar Arrays for a Direct Drive Hall Effect Thruster System

The Environmental Effects Group of NASA s Marshall Space Flight Center (MSFC) is conducting research into the effects of plasma interaction with high voltage solar arrays. These high voltage solar arrays are being developed for a direct drive Hall Effect Thruster propulsion system. A direct drive system configuration will reduce power system mass by eliminating a conventional power-processing unit. The Environmental Effects Group has configured two large vacuum chambers to test different high-voltage array concepts in a plasma environment. Three types of solar arrays have so far been tested, an International Space Station (ISS) planar array, a Tecstar planar array, and a Tecstar solar concentrator array. The plasma environment was generated using a hollow cathode plasma source, which yielded densities between 10(exp 6) - 10(exp 7) per cubic centimeter and electron temperatures of 0.5-1 eV. Each array was positioned in this plasma and biased in the -500 to + 500 volt range. The current collection was monitored continuously. In addition, the characteristics of arcing, snap over, and other features, were recorded. Analysis of the array performance indicates a time dependence associated with the current collection as well as a tendency for "conditioning" over a large number of runs. Mitigation strategies, to reduce parasitic current collection, as well as arcing, include changing cover-glass geometry and layout as well as shielding the solar cell edges. High voltage performance data for each of the solar array types tested will be presented. In addition, data will be provided to indicate the effectiveness of the mitigation techniques.

Schneider, T.↗

DOE OSTI2020

Dispersion of cryogenic hydrogen through high-aspect ratio nozzles

Liquid hydrogen is increasingly being used as a delivery and storage medium for stations that provide compressed gaseous hydrogen for fuel cell electric vehicles. In efforts to provide scientific justification for separation distances for liquid hydrogen infrastructure in fire codes, the dispersion characteristics of cryogenic hydrogen jets (50–64 K) from high aspect ratio nozzles have been measured at 3 and 5 bar abs stagnation pressures. These nozzles are more characteristic of unintended leaks, which would be expected to be cracks, rather than conventional round nozzles. Spontaneous Raman scattering was used to measure the concentration and temperature field along the major and minor axes. Within the field of interrogation, the axis-switching phenomena was not observed, but rather a self-similar Gaussian-profile flow regime similar to room temperature or cryogenic hydrogen releases through round nozzles. The concentration decay rate and half-widths for the planar cryogenic jets were found to be nominally equivalent to that of round nozzle cryogenic hydrogen jets indicating a similar flammable envelope. The results from these experiments will be used to validate models for cryogenic hydrogen dispersion that will be used for simulations of alternative scenarios and quantitative risk assessment.

08 HYDROGEN↗

DOE OSTI2022

2,3-Diphenylthieno[3,4-b]pyrazines as Hole-Transporting Materials for Stable, High-Performance Perovskite Solar Cells

High-performance and durable perovskite solar cells (PSCs) have advanced rapidly, enabled in part by the development of superior interfacial hole-transporting layers (HTLs). Here, in this study, a new series of 2,3-diphenylthieno[3,4-b]pyrazine (DPTP)-based small molecules containing bis- and tetrakis-triphenyl amino donors (1–3) was synthesized from simple, low-cost, and readily available starting materials. The matched energy levels, ideal surface topographies, high hole mobilities of 8.57 × 10 –4 cm 2 V –1 S –1 , and stable chemical structures of DPTP-4D (3) make it an effective hole-transporting material, delivering a PCE of 20.18% with high environmental, thermal, and light-soaking stability when compared to the reference HTL materials, doped Spiro-OMeTAD and PTAA in PSC n-i-p planar devices. Overall, these DPTP-based molecules are promising HTM candidates for the fabrication of stable PSCs.

14 SOLAR ENERGY↗

NASA NTRS2009

Lattice-Matched Semiconductor Layers on Single Crystalline Sapphire Substrate

SiGe is an important semiconductor alloy for high-speed field effect transistors (FETs), high-temperature thermoelectric devices, photovoltaic solar cells, and photon detectors. The growth of SiGe layer is difficult because SiGe alloys have different lattice constants from those of the common Si wafers, which leads to a high density of defects, including dislocations, micro-twins, cracks, and delaminations. This innovation utilizes newly developed rhombohedral epitaxy of cubic semiconductors on trigonal substrates in order to solve the lattice mismatch problem of SiGe by using trigonal single crystals like sapphire (Al2O3) as substrate to give a unique growth-orientation to the SiGe layer, which is automatically controlled at the interface upon sapphire (0001). This technology is different from previous silicon on insulator (SOI) or SGOI (SiGe on insulator) technologies that use amorphous SiO2 as the growth plane. A cubic semiconductor crystal is a special case of a rhombohedron with the inter-planar angle, alpha = 90 deg. With a mathematical transformation, all rhombohedrons can be described by trigonal crystal lattice structures. Therefore, all cubic lattice constants and crystal planes (hkl) s can be transformed into those of trigonal crystal parameters. These unique alignments enable a new opportunity of perfect lattice matching conditions, which can eliminate misfit dislocations. Previously, these atomic alignments were thought to be impossible or very difficult. With the invention of a new x-ray diffraction measurement method here, growth of cubic semiconductors on trigonal crystals became possible. This epitaxy and lattice-matching condition can be applied not only to SiGe (111)/sapphire (0001) substrate relations, but also to other crystal structures and other materials, including similar crystal structures which have pointgroup rotational symmetries by 120 because the cubic (111) direction has 120 rotational symmetry. The use of slightly miscut (less than plus or minus 10 deg.) sapphire (0001) substrate can be used to improve epitaxial relationships better by providing attractive atomic steps in the epitaxial process.

Choi, Sang↗

DOE OSTI2020

Competitive Pi-Stacking and H-Bond Piling Increase Solubility of Heterocyclic Redoxmers

Redoxmers are organic molecules that carry electric charge in flow batteries. In many instances, they consist of heteroaromatic moieties modified with appended groups to prevent stacking of the planar cores and increase solubility in liquid electrolytes. This higher solubility is desired as it potentially allows achieving greater energy density in the battery. However, the present synthetic strategies often yield bulky molecules with low molarity even when they are neat and still lower molarity in liquid solutions. Fortunately, there are exceptions to this rule. Here, we examine one well-studied redoxmer, 2,1,3-benzothiadiazole, which has solubility similar to 5.7 M in acetonitrile at 25 degrees C. We demonstrate computationally and prove experimentally that the competition between two packing motifs, face-to-face it-stacking and random N-H bond piling, introduces frustration that confounds nucleation in crowded solutions. Our findings and examples from related systems suggest a complementary strategy for the molecular design of redoxmers for high energy density redox flow cells.

25 ENERGY STORAGE↗

DOE OSTI2023

Inferring assembly-curving trends of bacterial micro-compartment shell hexamers from crystal structure arrangements

Bacterial microcompartments (BMC) are complex macromolecular assemblies that participate in varied chemical processes in about one fourth of bacterial species. BMC-encapsulated enzymatic activities are segregated from other cell contents by means of semipermeable shells, justifying why BMC are viewed as prototype nano-reactors for biotechnological applications. Herein, we undertook a comparative study of bending propensities of BMC hexamers (BMC-H), the most abundant shell constituents. Published data show that some BMC-H, like β -carboxysomal CcmK, tend to assemble flat whereas other BMC-H often build curved objects. Inspection of available crystal structures presenting BMC-H in tiled arrangements permitted us to identify two major assembly modes with a striking connection with experimental trends. All-atom molecular dynamics (MD) supported that BMC-H bending is triggered robustly only from the arrangement adopted in crystals by BMC-H that experimentally form curved objects, leading to very similar arrangements to those found in structures of recomposed BMC shells. Simulations on triplets of planar-behaving hexamers, which were previously reconfigured to comply with such organization, confirmed that bending propensity is mostly defined by the precise lateral positioning of hexamers, rather than by BMC-H identity. Finally, an interfacial lysine was pinpointed as the most decisive residue in controlling PduA spontaneous curvature. Globally, results presented herein should contribute to improve our understanding of the variable mechanisms of biogenesis characterized for BMC, and of possible strategies to regulate BMC size and shape.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1993

Time-domain analysis of planar microstrip devices using a generalized Yee-algorithm based on unstructured grids

The generalized Yee-algorithm is presented for the temporal full-wave analysis of planar microstrip devices. This algorithm has the significant advantage over the traditional Yee-algorithm in that it is based on unstructured and irregular grids. The robustness of the generalized Yee-algorithm is that structures that contain curved conductors or complex three-dimensional geometries can be more accurately, and much more conveniently modeled using standard automatic grid generation techniques. This generalized Yee-algorithm is based on the the time-marching solution of the discrete form of Maxwell's equations in their integral form. To this end, the electric and magnetic fields are discretized over a dual, irregular, and unstructured grid. The primary grid is assumed to be composed of general fitted polyhedra distributed throughout the volume. The secondary grid (or dual grid) is built up of the closed polyhedra whose edges connect the centroid's of adjacent primary cells, penetrating shared faces. Faraday's law and Ampere's law are used to update the fields normal to the primary and secondary grid faces, respectively. Subsequently, a correction scheme is introduced to project the normal fields onto the grid edges. It is shown that this scheme is stable, maintains second-order accuracy, and preserves the divergenceless nature of the flux densities. Finally, for computational efficiency the algorithm is structured as a series of sparse matrix-vector multiplications. Based on this scheme, the generalized Yee-algorithm has been implemented on vector and parallel high performance computers in a highly efficient manner.

Gedney, Stephen D.↗

DOE OSTI2026

Dual-precipitates enhance fatigue resistance in an additively manufactured high-entropy alloy

To accomplish the intense desire of high-strength materials for enhanced energy-efficiency, recent research applies a combined strategy of additive-manufacturing and precipitation-strengthening in high entropy alloys. In a context, Al 0.2 Co 1.5 CrFeNi 1.5 Ti 0.3 nanoprecipitation-strengthened system was developed, demonstrating very convincing strength and toughness. Moreover, additive-manufacturing facilitated additional strength by well-decorated cell-boundaries with blocky L2 1 precipitates and homogeneously distributed L1 2 precipitates. However, fatigue research of this alloy remained unexplored despite being the main precursor for structural applications. In this study low-cycle fatigue behavior of this alloy in both as-built and precipitation-strengthened (aged) conditions has been explored, combined with in-situ neutron diffraction investigation. Findings revealed a substantial cyclic-stress profile and a notable fatigue-life below ±0.50% strain-amplitude, exceeding 10 5 cycles at ±0.30% strain-amplitude. These demonstrate the potential to carry higher payloads with marked engineering-reliability. Residual-stress estimation revealed strain-compatibility between the matrix and L1 2 precipitate, indicating a crack-initiation immune interface. A comparative examination of dislocation character revealed shifting towards pure edge-character in aged alloy indicates precipitates promoted planar-slip during deformation.

36 MATERIALS SCIENCE↗