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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 253 records · Page 14

Charging and Heating Dynamics of Nanoparticles in Nonthermal Plasmas

The focus of this award was to understand the interactions of nanometer-sized particles with ionized gases, also called plasmas. Plasmas are widely used in the fabrication of electronic circuits such as microprocessors and memory devices, in plasma display panels, as well as in medical applications. Recently, these ionized gases are finding applications in the synthesis of advanced nanomaterials with novel properties, which are based on nanometer-sized particulate (nanoparticles) building blocks. As these nanoparticles grow in the plasma environment, they interact with the plasmas species such as electrons and ions which critically determines the nanoparticle properties. The University of Minnesota researchers conducting this project performed numerical simulations and developed analytical models that described the interaction of plasma-bound nanoparticles with the plasma ions. The plasma ions bombard the nanoparticle surface with substantial energy, which can result in the rearrangement of the nanoparticles’ atoms, giving them often desirable structures at the atomic scale. Being able to tune the ion energies allows to control the properties of nanoparticles produced in order to tailor their attributes for certain applications. For instance, when used in high efficiency light emitting devices, nanoparticles produced under high fluxes of highly energetic ions may show superior light emission to particles produced under low fluxes of less energetic ions. The analytical models developed by the University of Minnesota researchers enable the research community to easily determine the energy of ions bombarding the nanoparticles. The researchers extensively tested the validity of the analytical models by comparing them to sophisticated computer simulations based on stochastic particle modeling, also called Monte Carlo modeling, which simulated the motion of hundreds of thousands of ions and their interaction with the nanoparticle surfaces. Beyond the scientific intellectual merits, this award had significant broader impacts. Two graduate students received their doctoral degrees and both have joined a U.S. manufacturer of plasma-based semiconductor processing equipment. Four undergraduate students participated in research conducted under this grant and gained valuable hands-on laboratory experience. A middle school science teacher observed research conducted under this grant and developed three new course modules that introduce middle school students to the concepts of nanometer scale, the atomic structure of matter, and the composition of matter of different chemical elements.

42 ENGINEERING↗

The GFDL Global Atmosphere and Land Model AM4.0/LM4.0: 1. Simulation Characteristics With Prescribed SSTs

In this two–part paper, a description is provided of a version of the AM4.0/LM4.0 atmosphere/land model that will serve as a base for a new set of climate and Earth system models (CM4 and ESM4) under development at NOAA's Geophysical Fluid Dynamics Laboratory (GFDL). This version, with roughly 100 km horizontal resolution and 33 levels in the vertical, contains an aerosol model that generates aerosol fields from emissions and a “light” chemistry mechanism designed to support the aerosol model but with prescribed ozone. In Part 1, the quality of the simulation in AMIP (Atmospheric Model Intercomparison Project) mode—with prescribed sea surface temperatures (SSTs) and sea–ice distribution—is described and compared with previous GFDL models and with the CMIP5 archive of AMIP simulations. Here, the model's Cess sensitivity (response in the top–of–atmosphere radiative flux to uniform warming of SSTs) and effective radiative forcing are also presented. In Part 2, the model formulation is described more fully and key sensitivities to aspects of the model formulation are discussed, along with the approach to model tuning.

54 ENVIRONMENTAL SCIENCES↗

A molecular conveyor belt-associated protein controls the rotational direction of the bacterial type 9 secretion system

ABSTRACT Many bacteria utilize the type 9 secretion system (T9SS) for gliding motility, surface colonization, and pathogenesis. This dual-function motor supports both gliding motility and protein secretion, where rotation of the T9SS plays a central role. Fueled by the energy of the stored proton motive force and transmitted through the torque of membrane-anchored stator units, the rotary T9SS propels an adhesin-coated conveyor belt along the bacterial outer membrane like a molecular snowmobile, thereby enabling gliding motion. However, the mechanisms controlling the rotational direction and gliding motility of T9SS remain elusive. Shedding light on this mechanism, we find that in the gliding bacteriumFlavobacterium johnsoniae, deletion of the C-terminus of the conveyor belt-associated protein GldJ controls and, in fact, reverses the rotational direction of T9SS from counterclockwise (CCW) to clockwise (CW). This suggests that the interface between the conveyor belt-associated protein GldJ and the T9SS ring protein GldK plays an important role in controlling the directionality of T9SS, potentially by modulating its interaction with the stator complex GldLM, which drives motor rotation. Combined with MD simulation of the T9SS stator units GldLM, we suggest a “tri-component gearset” model where GldJ controls the rotational direction of its driver, the T9SS, thus providing adaptive sensory feedback to influence the motility of the gliding bacterium. IMPORTANCE The type 9 secretion system (T9SS) is fundamental to bacterial gliding motility, pathogenesis, and surface colonization. Our findings reveal that the C-terminal region of the conveyor belt-associated protein GldJ functions as a molecular switch which is capable of reversing the rotational direction of T9SS. Through the coordinated actions of the T9SS stator units (akin to a driving motor), the GldK ring (the gear that converts rotational energy into linear movement), and GldJ, this machinery forms a smart conveyor belt system reminiscent of flexible or cognitive mechanical conveyors. Such advanced conveyors can alter their direction to adapt to shifting demands. Here, we show that the bacterial T9SS similarly adjusts its rotational bias based on feedback from the conveyor belt-associated protein GldJ. This dual-role feedback mechanism underscores an evolved, controllable biological snowmobile, offering new avenues for studying how bacteria fine-tune motility in dynamic environments.

Microbiology↗

Strong laser polarization control of coherent phonon excitation in van der Waals material Fe 3 GeTe 2

Optical manipulation of coherent phonon frequency in two-dimensional (2D) materials could advance the development of ultrafast phononics in atomic-thin platforms. However, conventional approaches for such control are limited to doping, strain, structural or thermal engineering. Here, we report the experimental observation of strong laser-polarization control of coherent phonon frequency through time-resolved pump-probe spectroscopic study of van der Waals (vdW) materials Fe 3 GeTe 2 . When the polarization of the pumping laser with tilted incidence is swept between in-plane and out-of-plane orientations, the frequencies of excited phonons can be monotonically tuned by as large as 3% (~100 GHz). Our first-principles calculations suggest the strong planar and vertical inter-atomic interaction asymmetry in layered materials accounts for the observed polarization-dependent phonon frequencies, as in-plane/out-of-plane polarization modifies the restoring force of the lattice vibration differently. Our work provides insightful understanding of the coherent phonon dynamics in layered vdW materials and opens up new avenues to optically manipulating coherent phonons.

36 MATERIALS SCIENCE↗

Spontaneous rearrangement of acetylated xylan on hydrophilic cellulose surfaces

The interaction of xylan, an abundant plant polysaccharide, with cellulose microfibrils is essential for secondary cell wall strength. A deeper understanding of these interactions is crucial both to improve our understanding of plant cell wall architecture and to design alternate strategies to overcome cellulose recalcitrance for the production of biofuels and sustainable biomaterials. Naturally occurring acetate or glucuronic acid substitutions on xylan have been shown to influence xylan-cellulose interactions. In this work, we use unrestrained molecular dynamics simulations to determine the interactions with the (110) hydrophilic face of cellulose fibers of four different xylans. In the absence of cellulose, all xylans, independent of the substitution pattern, adopt a highly flexible threefold helical screw conformation. However, when xylan is spatially close to a cellulose surface 1,2 linked acetyl xylans (2AcX) adopt rigid twofold helical screw conformations. The 2AcX conformations are primarily stabilized by interactions between the acetylated oxygen and the glycosidic linkage with C-O6 of cellulose. In contrast, the glycosidic oxygens and acetyl decorations for 1,3 linked acetyl groups (3AcX) are oriented away from the cellulose surface and the 3AcX xylans maintain threefold helical screw conformations on the cellulose surface. Our results show that evenly spaced chemical functionalization (with acetyl groups) and the position of substitution (1,2) on xylan backbone play key roles in tuning the xylan-cellulose interactions to stabilize the twofold helical screw conformations of xylan on the cellulose surface. A comparison with previous experimental findings further suggests that 1,2 substitutions induce twofold helical screw conformations of xylan on the cellulose surface irrespective of the chemical nature of the substituent, while 1,3 substitutions primarily bind lignin in threefold helical screw conformations rather than cellulose in plant cell walls.

1,2 Ac↗

Nonvolatile Ionic Modification of the Dzyaloshinskii-Moriya Interaction

The possibility of tuning the Dzyaloshinskii-Moriya interaction (DMI) by electric (E)-field gating in ultrathin magnetic materials has opened up new perspectives in terms of controlling the stabilization of chiral spin structures. The most recent efforts have used voltage-induced charge redistribution at the interface between a metal and an oxide to modulate the DMI. This approach is attractive for active devices but tends to be volatile, making it energy-demanding, and it is limited by Coulomb screening in the metal. Here we demonstrate nonvolatile E-field manipulation of the DMI by ionic-liquid gating of Pt/Co/Hf ⁢O 2 ultrathin films. The E-field effect on the DMI scales with the E-field exposure time, and we propose that it is linked to the migration of oxygen species from the Hf⁢ O 2 layer into the Co and Pt layers and subsequent anchoring. Here, this effect permanently changes the properties of the material, showing that E fields can be used not only for local gating in devices but also as a highly scalable materials design tool for postgrowth tuning of the DMI.

Domain walls↗

Final Technical Report for DE-SC0008135, Modulating Thermal Transport Phenomena in Nanostructures via Elastic Strain at Extreme Limits of Strength

Nanoscale materials fabricated with nearly pristine crystal structure are often endowed with ultra-strength behavior, where material failure occurs at a significant fraction of its ideal limit. The thermal conductivity exhibited by such materials is also uniquely affected by the high surface-to-volume ratio at the nanoscale. The juxtaposition of the vastly increased dynamic range of elastic strain available in ultra-strength nanomaterials and altered thermal transport shows promise for tunable thermal properties. This project aims to exploit these properties of high-strength nanostructures to elucidate the coupling between large mechanical strains and thermal conductivity (both electron and phonon) leading to better understanding and control of the thermal performance in these materials. Unique fabrication methods to produce nanosized quasi-defect free single crystals and modern nanomechanical testing will be used to identify the size-dependent dynamic range of elastic strain and understand deformation mechanisms near the ideal limit. Identifying and quantifying thermal transport phenomena as a function of mechanical strain in these nanostructures will open the door to using elastic strain engineering in high-strength nanomaterials to tune thermal transport. The results of these investigations will be used to improve the performance, efficiency, and versatility of advanced thermal management and energy conversion devices with tunable response.

36 MATERIALS SCIENCE↗

Assembly of three-dimensional binary superlattices from multi-flavored particles

Binary superlattices constructed from nano- or micron-sized colloidal particles have a wide variety of applications, including the design of advanced materials. Self-assembly of such crystals from their constituent colloids can be achieved in practice by, among other means, the functionalization of colloid surfaces with single-stranded DNA sequences. However, when driven by DNA, this assembly is traditionally premised on the pairwise interaction between a single DNA sequence and its complement, and often relies on particle size asymmetry to entropically control the crystalline arrangement of its constituents. The recently proposed “multi-flavoring” motif for DNA functionalization, wherein multiple distinct strands of DNA are grafted in different ratios to different colloids, can be used to experimentally realize a binary mixture in which all pairwise interactions are independently controllable. Here we use various computational methods, including molecular dynamics and Wang–Landau Monte Carlo simulations, to study a multi-flavored binary system of micron-sized DNA-functionalized particles modeled implicitly by Fermi–Jagla pairwise interactions. We show how self-assembly of such systems can be controlled in a purely enthalpic manner, and by tuning only the interactions between like particles, demonstrate assembly into various morphologies. Although polymorphism is present over a wide range of pairwise interaction strengths, we show that careful selection of interactions can lead to the generation of pure compositionally ordered crystals. Additionally, we show how the crystal composition changes with the like-pair interaction strengths, and how the solution stoichiometry affects the assembled structures.

36 MATERIALS SCIENCE↗

Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag 0.03 Au 0.97

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag 0.03 Au 0.97 alloy and their subsequent evolution under steady-state CH 3 OH oxidation conditions are investigated. Activation using O 3 results in AgO and Au 2 O 3 , strongly enriching the near-surface region in Ag. These oxides reduce in the O 2 /CH 3 OH mixture, yielding CO 2 and producing a highly Ag-enriched surface alloy. At the reaction tem-perature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher tem-peratures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These find-ings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes

Atomic layer deposition (ALD) is a powerful strategy to engineer hybrid organic-inorganic membranes with emergent functionalities. The combination of atomic-level thickness control, a wide materials palette, and unprecedented conformality allows the physiochemical properties (e.g., hydrophilicity) of mesoporous polymer membranes to be precisely tuned. The nucleation of ALD material growth on polymer surfaces relies on Lewis acid-base interactions and remains an overlooked motif with tremendous potential to accelerate ALD nucleation and growth. Strategies to enhance these interactions could enable desirable properties such as antifouling behavior to be imparted on inert polymer surfaces that lack the necessary functional groups for ALD nucleation. Here, in this study, we demonstrate that the reactivity of polyacrylonitrile (PAN) membranes toward ALD metal oxide (MO) precursors with Lewis acid characteristics is enhanced by introducing strong Lewis base functional groups (amidoxime: Am) on the PAN backbone (Am-PAN). The resulting Lewis acid-base interactions accelerate the MO nucleation in Am-PAN and reduce the number of deposition cycles required to achieve hydrophilicity compared with the untreated PAN membrane. Unveiling the reaction mechanism, in situ Fourier transform infrared (FTIR) spectroscopy measurements established enhanced interaction dynamics between the ALD MO precursors and the Am-PAN membrane, unlike the PAN membrane. Spectroscopic ellipsometry and thermogravimetric analysis measurements revealed higher MO loadings in Am-PAN membranes compared to PAN membranes for the same number of ALD cycles. We found that strong Lewis acid-base interactions accelerated the ALD for a range of materials including Al 2 O 3 , TiO 2 , SnO 2 , and ZnO. More broadly, our work demonstrates that tailoring metal-precursor-polymer interactions is a powerful strategy to accelerate and modulate the ALD. We used this design strategy to fabricate Al 2 O 3 -Am-PAN hybrid membranes that showed 2-fold higher antifouling capability compared to pristine PAN membranes prepared with an equivalent number of Al 2 O 3 ALD cycles. Our approach expands the scope of design options for fouling-resistant porous hybrid inorganic-organic membranes and may ultimately reduce the operational costs of water treatment.

36 MATERIALS SCIENCE↗

Addition of P3HT-grafted Silica nanoparticles improves bulk-heterojunction morphology in P3HT-PCBM blends

We present molecular dynamics simulations of a ternary blend of P3HT, PCBM and P3HT-grafted silica nanoparticles (SiNP) for applications in polymer-based solar cells. Using coarse-grained models, we study the effect of SiNP on the spatial arrangement of PCBM in P3HT. Our results suggest that addition of SiNP not only alters the morphology of PCBM clusters but also improves the crystallinity of P3HT. We exploit the property of grafted SiNP to self-assemble into a variety of anisotropic structures and the tendency of PCBM to preferentially adhere to SiNP surface, due to favorable interactions, to achieve morphologies with desirable characteristics for the active layer, including domain size, crystallinity of P3HT, and elimination of isolated islands of PCBM. As the concentration of SiNP increases, the number of isolated PCBM molecules decreases, which in turn improves the crystallinity of P3HT domains. We also observe that by tuning the grafting parameters of SiNP, it is possible to achieve structures ranging from cylindrical to sheets to highly interconnected network of strings. The changes brought about by addition of SiNP shows a promising potential to improve the performance of these materials when used as active layers in organic photovoltaics.

42 ENGINEERING↗

Aerosol Complexity and Implications for Predictability and Short-Term Forecasting

There are clear NWP and climate impacts from including aerosol radiative and cloud interactions. Changes in dynamics and cloud fields affect aerosol lifecycle, plume height, long-range transport, overall forcing of the climate system, etc. Inclusion of aerosols in NWP systems has benefit to surface field biases (e.g., T2m, U10m). Including aerosol affects has impact on analysis increments and can have statistically significant impacts on, e.g., tropical cyclogenesis. Above points are made especially with respect to aerosol radiative interactions, but aerosol-cloud interaction is a bigger signal on the global system. Many of these impacts are realized even in models with relatively simple (bulk) aerosol schemes (approx.10 -20 tracers). Simple schemes though imply simple representation of aerosol absorption and importantly for aerosol-cloud interaction particle-size distribution. Even so, more complex schemes exhibit a lot of diversity between different models, with issues such as size selection both for emitted particles and for modes. Prospects for complex sectional schemes to tune modal (and even bulk) schemes toward better selection of size representation. I think this is a ripe topic for more research -Systematic documentation of benefits of no vs. climatological vs. interactive (direct and then direct+indirect) aerosols. Document aerosol impact on analysis increments, inclusion in NWP data assimilation operator -Further refinement of baseline assumptions in model design (e.g., absorption, particle size distribution). Did not get into model resolution and interplay of other physical processes with aerosols (e.g., moist physics, obviously important), chemistry

Predictability↗

Is Betelgeuse the Outcome of a Past Merger?

We explore the possibility that the star α Orionis (Betelgeuse) is the outcome of a merger that occurred in a low-mass-ratio (q= $\mathcal{M}$ 2 /$\mathcal{M}$ 1 = 0.07–0.25) binary system some time in the past hundreds of thousands of years. To that goal, we present a simple analytical model to approximate the perturbed internal structure of a post-merger object following the coalescence of a secondary in the mass range 1–4 M ⊙ into the envelope of a 15–17 M ⊙ primary. We then compute the long-term evolution of post-merger objects for a grid of initial conditions and make predictions about their surface properties for evolutionary stages that are consistent with the observed location of Betelgeuse in the Hertzsprung–Russell diagram. We find that if a merger occurred after the end of the primary’s main-sequence phase, while it was expanding toward becoming a red supergiant star and typically with radius ∼200–300 R ⊙ , then its envelope is spun up to values that remain in a range consistent with Betelgeuse observations for thousands of years of evolution. We argue that the best scenario that can explain both the fast rotation of Betelgeuse and its observed large space velocity is one where a binary was dynamically ejected by its parent cluster a few million years ago and then subsequently merged. An alternative scenario in which the progenitor of Betelgeuse was spun up by accretion in a binary and released by the supernova explosion of the companion requires a finely tuned set of conditions but cannot be ruled out.

79 ASTRONOMY AND ASTROPHYSICS↗

Spin-Orbit Torque Switching of a Nearly Compensated Ferrimagnet by Topological Surface States

Utilizing spin-orbit torque (SOT) to switch a magnetic moment provides a promising route for low-power-dissipation spintronic devices. Here, the SOT switching of a nearly compensated ferrimagnet Gd x (FeCo) 1-x by the topological insulator [Bi 2 Se 3 and (BiSb) 2 Te 3 ] is investigated at room temperature. The switching current density of (BiSb) 2 Te 3 (1.20 × 10 5 A cm -2 ) is more than one order of magnitude smaller than that in conventional heavy-metal-based structures, which indicates the ultrahigh efficiency of charge-spin conversion (>1) in topological surface states. By tuning the net magnetic moment of Gd x (FeCo) 1-x via changing the composition, the SOT efficiency has a significant enhancement (6.5 times) near the magnetic compensation point, and at the same time the switching speed can be as fast as several picoseconds. Combining the topological surface states and the nearly compensated ferrimagnets provides a promising route for practical energy-efficient and high-speed spintronic devices.

36 MATERIALS SCIENCE↗

Solution Structure and Hydration Forces between Mica and Hydrophilic Versus Hydrophobic Surfaces

Solid-liquid interfaces are central to a range of interesting phenomena including catalysis, heterogeneous nucleation, water desalination, and biomolecular assembly. While three-dimensional Fast Force Mapping (3D FFM) has emerged as a technique for resolving interfacial solution structure at the molecular scale, key challenges for data interpretation persist, most notably regarding the influence of the probe on the measured structure. Using the mica-water system as a case study, we investigate the effect of hydrophilic and hydrophobic probes on interfacial solution structure measured by 3D FFM. Data from hydrophilic silicon-based probes are in good agreement with molecular dynamics simulations, wherein the innermost water molecules adsorb preferentially at the surface ditrigonal cavity sites followed by two subsequent hydration layers. In contrast, the hydrophobic carbon-based probes detect vertical oscillatory features, but do not show lateral patterning that matches the underlying mica lattice. At high ionic strength, up to six of these oscillatory features are observed extending 2 nm into the solution phase with an average spacing of 0.29 ± (0.04) nm. Further, we also determine that the repulsive hydration force between mica and the hydrophilic probe depends on the nature and concentration of ions in solution. Specifically, solutions with stronger ion-water and ion-ion interactions increase the interfacial viscosity, which results in a stronger repulsive hydration force as the probe approaches the surface. Based on these observations, we present a scheme for controlling the outcomes of particle attachment and aggregation by varying the solution conditions to tune the hydration force.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substrate-Directed Dimensional and Phase Control of Peptide Assemblies on Two-Dimensional van der Waals Materials

Understanding and controlling biomolecular self-assembly on van der Waals (vdW) materials has the potential to advance hybrid bioelectronic devices by enabling precise tuning of the interface and modulation of the resulting electronic properties of the biomolecule-vdW heterostructure. However, how surface properties of vdW materials direct biomolecule assembly remains poorly understood. To fill this knowledge gap, we investigated the assembly of a peptide known to assemble into two-dimensional (2D) crystalline films on MoS 2 on three representative vdW surfaces: WS 2 , MoS 2 , and highly oriented pyrolytic graphite (HOPG). Using in situ atomic force microscopy (AFM), we find that assembly is substrate-dependent, resulting in multilayers on WS 2 , monolayers on MoS 2 , and multiple coexisting phases on HOPG. WS 2 exhibits a higher negative charge, strong long-range electrostatic interactions, and extensive hydration layering that may promote multilayer stacking. In contrast, MoS 2 has stronger short-range interactions with the peptides but much weaker long-range interactions and hydration structure, which may favor monolayer formation. Molecular dynamics simulations predict a corresponding switch from monolayer to multilayer aggregates of the adsorbed monomers, reflected in their relative mobilities. On hydrophobic HOPG, the peptides bind most strongly and remain as monomers with high surface mobility. The peptide dimers comprising the basic unit of the crystals are more compact on HOPG, which has a smaller lattice constant than WS 2 or MoS 2 , suggesting strain contributes to stabilizing multiple phases. Our results provide mechanistic insights into how surface charge and hydration structure, and the lattice structure of the substrates governs peptide assembly on vdW materials, offering a framework to rationally control the 2D peptide-vdW heterostructures.

Molecular dynamics simulations↗

Photochemistry of the Martian atmosphere

A critical analysis is carried out for models which may be fine tuned to give agreement with observational constraints for O2, CO, and O3 in the Martian lower atmosphere and which are in accord also with upper atmospheric data for O and CO. The models have a number of features in common: dynamic mixing must be exceedingly rapid at heights above 90 km; if heterogeneous processes are not assumed to play a major role in the removal of atmospheric CO and O2, mixing must be rapid at heights between 30 and 40 km. The value implied for the diffusion coefficient in this region depends on the assumptions made regarding the rates for reaction of OH with HO2 to form H2O and the rate of reaction of HO2 with itself to form H2O2. If these reaction rates are taken to have values similar to those used in current models of the earth's stratosphere, the eddy diffusion coefficient at 40 km above the Martian surface should be about 5 by 10 to the seventh power sq cm/sec.

Kong, T. Y.↗