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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. In conclusion, these insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts

Surface segregation, restructuring, and sintering phenomena in size-selected copper–nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile of the elemental composition of the particles was determined under operando CO 2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. In conclusion, this leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Effect of Hydrophilicity and Interfacial Water Structure on Particle Attachment

Oriented attachment (OA) of nanoparticles is an important and common crystallization pathway. Efforts to isolate and quantify the interparticle forces that underlie OA have only recently been initiated and the role played by the interfacial solvent structure in the confined region between nanocrystal surfaces in enabling and controlling OA remains an open question. In this work, classical molecular dynamics (MD) simulations were performed to compute the free energy landscape of nanoparticles approaching mineral substrates in both vacuum and pure water. Periclase (MgO), muscovite (KAl 3 Si 3 O 10 (OH) 2 ), and pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ) nanoparticles exposing the (100), (001), and (001) surfaces, respectively, were brought to contact with substrates exposing the same surfaces. These mineral surfaces were selected to investigate a range of hydrophilicities (periclase > muscovite > pyrophyllite). The MD simulations revealed that the interfacial water structure created free energy minima for nanoparticle approach that corresponded to integer numbers of intervening water layers. The depth of the free energy minima and the free energy barriers between minima correlated positively with the hydrophilicity of the mineral surface. While the range of solvent-mediated interactions was predicted to be short (a few intervening water layers at most for MgO), the free energy barriers were calculated to be large (fraction of an eV per nm 2 ) and the effect of misalignment diminished rapidly with the number of intervening water layers. The results help explain the formation of mesocrystals and the observed ability of nanoparticles to rotate before attachment while in a long-lived solvent-separated state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Ion-Gated Gas Separation through Porous Graphene

Porous graphene holds great promise as a one-atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size down to 3–5 Å proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid-coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise nonselective large pores on the order of 1 nm in size to be selective for gases whose diameters range from 3 to 4 Å. We show from molecular dynamics simulations that CO 2 , N 2 , and CH 4 all can permeate through a 6 Å nanopore in graphene without any selectivity. But when a monolayer of [emim][BF 4 ] ionic liquid (IL) is deposited on the porous graphene, CO 2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO 2 , while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO 2 /CH 4 separation, yielding a CO 2 /CH 4 selectivity of about 42 and CO 2 permeance of ~10 5 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size, pore size, and IL thickness. The present work points toward a promising direction of using the atom-thin ionic liquid/porous graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Understanding the Activity and Enantioselectivity of Acetyl-Protected Aminoethyl Quinoline Ligands in Palladium-Catalyzed β-C(sp 3 )–H Bond Arylation Reactions

Chiral acetyl-protected aminoalkyl quinoline (APAQ) ligands were recently discovered to afford highly active and enantiose-lective palladium catalysts for the arylation of methylene C(sp 3 )-H bonds, and herein, we investigate the origins of these heightened properties. Unprecedented amide-bridged APAQ-Pd dimers were predicted by DFT calculations and were con-firmed by single crystal X-ray diffraction studies. Comparison of structural features between APAQ-Pd complexes and an acetyl-protected aminoethyl pyridine APAPy-Pd complex strongly suggests that the high activity of the former originates from the presence of the quinoline ring which slows the formation of the off-cycle palladium dimer. Furthermore, steric topographic maps for a representative subset of monomeric, monoligated palladium complexes allowed us to draw a unique parallel between the 3-dimensional structures of these catalysts and their reported asymmetric induction in β-C(sp 3 )-H bond arylation reactions. Lastly, cooperative non-covalent interactions present between the APAQ ligand and the substrate were identified as a crucial factor for imparting selectivity between chemically equivalent methylenic C(sp 3 )-H bonds prior to con-certed metalation deprotonation activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Molecular-channel driven actuator with considerations for multiple configurations and color switching

The ability to achieve simultaneous intrinsic deformation with fast response in commercially available materials that can safely contact skin continues to be an unresolved challenge for artificial actuating materials. Rather than using a microporous structure, here we show an ambient-driven actuator that takes advantage of inherent nanoscale molecular channels within a commercial perfluorosulfonic acid ionomer (PFSA) film, fabricated by simple solution processing to realize a rapid response, self-adaptive, and exceptionally stable actuation. Selective patterning of PFSA films on an inert soft substrate (polyethylene terephthalate film) facilitates the formation of a range of different geometries, including a 2D (two-dimensional) roll or 3D (three-dimensional) helical structure in response to vapor stimuli. Chemical modification of the surface allowed the development of a kirigami-inspired single-layer actuator for personal humidity and heat management through macroscale geometric design features, to afford a bilayer stimuli-responsive actuator with multicolor switching capability.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Space- and time-resolved small angle X-ray scattering to probe assembly of silver nanocrystal superlattices

Abstract The structure of nanocrystal superlattices has been extensively studied and well documented, however, their assembly process is poorly understood. In this work, we demonstrate an in situ space- and time-resolved small angle X-ray scattering measurement that we use to probe the assembly of silver nanocrystal superlattices driven by electric fields. The electric field creates a nanocrystal flux to the surface, providing a systematic means to vary the nanocrystal concentration near the electrode and thereby to initiate nucleation and growth of superlattices in several minutes. Using this approach, we measure the space- and time-resolved concentration and polydispersity gradients during deposition and show how they affect the superlattice constant and degree of order. We find that the field induces a size-selection effect that can reduce the polydispersity near the substrate by 21% leading to better quality crystals and resulting in field strength-dependent superlattice lattice constants.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe 2 O 3 /NiO heterojunction

NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe 2 O 3 /NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni 3+ within 10 ps following selective photoexcitation of the underlying Fe 2 O 3 substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe 2 O 3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this model system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Catalytic reactions within the cavity of coordination cages

Natural enzymes catalyze reactions in their substrate-binding cavities, exhibiting high specificity and efficiency. In an effort to mimic the structure and functionality of enzymes, discrete coordination cages were designed and synthesized. These self-assembled systems have a variety of confined cavities, which have been applied to accelerate conventional reactions, perform substrate-specific reactions, and manipulate regio- and enantio-selectivity. Many coordination cages or cage–catalyst composites have achieved unprecedented results, outperforming their counterparts in different catalytic reactions. This tutorial review summarizes recent developments of coordination cages across three key approaches to coordination cage catalysis: (1) cavity promoted reactions, (2) embedding of active sites in the structure of the cage, and (3) encapsulation of catalysts within the cage. Special emphasis of the review involves (1) introduction of the structure and property of the coordination cage, (2) discussion of the catalytic pathway mediated by the cage, (3) elucidation of the structure–property relationship between the cage and the designated reaction. This work will summarize the recent progress in supramolecular catalysis and attract more researchers to pursue cavity-promoted reactions using discrete coordination cages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nanosecond laser scribing of CIGS thin film solar cell based on ITO bottom contact

Cu(In,Ga)Se2 (CIGS) thin films, a promising photovoltaic architecture, have mainly relied on Molybdenum for the bottom contact. However, the opaque nature of Molybdenum (Mo) poses limitations in module level fabrication by laser scribing as a preferred method for interconnect. We examined the P1, P2, and P3 laser scribing processes on CIGS photovoltaic architecture on the indium tin oxide (ITO) bottom contact with a cost-effective nanosecond pulsed laser of 532 nm wavelength. Laser illuminated from the substrate side, enabled by the transparent bottom contact, facilitated selective laser energy deposition onto relevant interfaces towards high-quality scribing. Parametric tuning procedures are described in conjunction with experimental and numerical investigation of relevant mechanisms, and preliminary mini-module fabrication results are also presented.

Kuk, Seungkuk↗
DOE OSTI2016

Selective Area Growth of GaAs on Si Patterned Using Nanoimprint Lithography

Heteroepitaxial selective area growth (SAG) of GaAs on patterned Si substrates is a potential low-cost approach to integrate III-V and Si materials for tandem or multijunction solar cells. The use of nanoscale openings in a dielectric material can minimize nucleation-related defects and allow thinner buffer layers to be used to accommodate lattice mismatch between Si and an epitaxial III-V layer. For photovoltaic applications, the cost of patterning and growth, as well as the impact on the performance of the Si bottom cell must be considered. We present preliminary results on the use of soft nanoimprint lithography (SNIL) to create patterned nucleation templates for the heteroepitaxial SAG of GaAs on Si. We demonstrate that SNIL patterning of passivating layers on the Si substrate improves measured minority carrier properties relative to unprotected Si. Cost modeling of the SNIL process shows that adding a patterning step only adds a minor contribution to the overall cost of a tandem III-V/Si solar cell, and can enable significant savings if it enables thinner buffer layers.

14 SOLAR ENERGY↗
DOE OSTI2018

Brown Rot-Type Fungal Decomposition of Sorghum Bagasse: Variable Success and Mechanistic Implications

Sweet sorghum is a promising crop for a warming, drying African climate, and basic information is lacking on conversion pathways for its lignocellulosic residues (bagasse). Brown rot wood-decomposer fungi use carbohydrate-selective pathways that, when assessed on sorghum, a grass substrate, can yield information relevant to both plant biomass conversion and fungal biology. In testing sorghum decomposition by brown rot fungi ( Gloeophyllum trabeum , Serpula lacrymans ), we found that G. trabeum readily degraded sorghum, removing xylan prior to removing glucan. Serpula lacrymans , conversely, caused little decomposition. Ergosterol (fungal biomarker) and protein levels were similar for both fungi, but S. lacrymans produced nearly 4x lower polysaccharide-degrading enzyme specific activity on sorghum than G. trabeum , perhaps a symptom of starvation. Linking this information to genome comparisons including other brown rot fungi known to have a similar issue regarding decomposing grasses (Postia placenta, Fomitopsis pinicola) suggested that a lack of CE 1 feruloyl esterases as well as low xylanase activity in S. lacrymans (3x lower than in G. trabeum ) may hinder S. lacrymans , P. placenta, and F. pinicola when degrading grass substrates. These results indicate variability in brown rot mechanisms, which may stem from a differing ability to degrade certain lignin-carbohydrate complexes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Ablating nanoscale pores in crystalline quartz using laser-induced micro-plasmas in tri-layer structures

We demonstrate a novel approach for achieving rapid, consistent, and controllable micro-pore fabrication in single-crystalline quartz. These micro-pores are essential for applications in biology, i.e., studying ion channels in general and mechano-sensitive channels (MSC) in particular. The fabrication process consists of direct material ablation using pulsed UV light from a 193 nm excimer laser. These pulses ablate single-crystalline quartz chips by burning a laser-induced plasma in a tri-layer structure. Controllable plasma confinement and thus pore size is achieved by sandwiching a thin layer of a selected organic solution between the quartz chip and different substrates. This solution causes the confined micro-plasma to generate special ablation conditions, to create uniformly sized and shaped nanopores.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Identification of novel small molecule inhibitors of twin arginine translocation (Tat) pathway and their effect on the control of Campylobacter jejuni in chickens

Introduction Control ofCampylobacterfrom farm to fork is challenging due to the frequent emergence of antimicrobial-resistant isolates. Furthermore, poultry production systems are known reservoirs ofCampylobacter. The twin-arginine translocation (Tat) pathway is a crucial bacterial secretion system that allowsCampylobacterto colonize the host intestinal tract by using formate as the main source of energy. However, Tat pathway is also a major contributing factor for resistance to copper sulfate (CuSO 4 ). Methods Since mammals and chickens do not have proteins or receptors that are homologous to bacterial Tat proteins, identification of small molecule (SM) inhibitors targeting the Tat system would allow the development of safe and effective control methods to mitigateCampylobacterin infected or colonized hosts in both pre-harvest and post-harvest. In this study, we screened 11 commercial libraries (n = 50,917 SM) for increased susceptibility to CuSO 4 (1 mM) inC. jejuni81–176, a human isolate which is widely studied. Results Furthermore, we evaluated 177 SM hits (2.5 μg/mL and above) that increased the susceptibility to CuSO 4 for the inhibition of formate dehydrogenase (Fdh) activity, a Tat-dependent substrate. Eight Tat-dependent inhibitors (T1–T8) were selected for further studies. These selected eight Tat inhibitors cleared all testedCampylobacterstrains (n = 12) at >10 ng/mL in the presence of 0.5 mM CuSO 4 in vitro. These selected SMs were non-toxic to colon epithelial (Caco-2) cells when treated with 50 μg/mL for 24 h and completely cleared intracellularC. jejunicells when treated with 0.63 μg/mL of SM for 24 h in the presence of 0.5 mM of CuSO 4 . Furthermore, 3 and 5-week-old chicks treated with SM candidates for 5 days had significantly decreased cecal colonization (up to 1.2 log;p < 0.01) with minimal disruption of microbiota.In silicoanalyses predicted that T7 has better drug-like properties than T2 inhibitor and might target a key amino acid residue (glutamine 165), which is located in the hydrophobic core of TatC protein. Discussion Thus, we have identified novel SM inhibitors of the Tat pathway, which represent a potential strategy to controlC. jejunispread on farms.

Microbiology↗
NASA NTRS1983

Solid-state laser sources for remote sensing

Recent progress in slab-geometry and conventional rod Nd:YAG solid-state lasers for applications in remote sensing is presented. Developments in slab geometry lasers, which were aimed at improving pulse energy and tuning range, have been based on the use of a Nd:glass substrate with a zig-zag optical path, with selective Raman shifting in gases and harmonic generation in LiNbO3 and KDP to extend the tuning range into the UV and visible regions. The theoretically predicted advantages of the elimination of birefringence and thermal and stress-induced focusing in the slab-geometry laser have been confirmed in measurements on a test-bed Nd:glass system, and a CW lamp pumped Nd:YAG oscillator, which have also demonstrated an order of magnitude improvement in laser performance. A single axial mode Nd:YAG oscillator has also been designed which, operating in a 3-msec quasi-CW mode, has a chirp rate of 30 kHz/microsec and a free-running stability of + or - 20 MHz. With chirp compensation, this stability is adequate for wind velocity measurements by coherent lidar.

Byer, R. L.↗
NASA NTRS1985

Rocket thrust chamber thermal barrier coatings

A research program was conducted to generate data and develop analytical techniques to predict the performance and reliability of ceramic thermal barrier coatings in high heat flux environments. A finite element model was used to analyze the thermomechanical behavior of coating systems in rocket thrust chambers. Candidate coating systems (using a copper substrate, NiCrAlY bond coat and ZrO2.8Y2O3 ceramic overcoat) were selected for detailed study based on photomicrographic evaluations of experimental test specimens. The effects of plasma spray application parameters on the material properties of these coatings were measured and the effects on coating performance evaluated using the finite element model. Coating design curves which define acceptable operating envelopes for seleted coating systems were constructed based on temperature and strain limitations. Spray gun power levels was found to have the most significant effect on coating structure. Three coating systems were selected for study using different power levels. Thermal conductivity, strain tolerance, density, and residual stress were measured for these coatings. Analyses indicated that extremely thin coatings ( 0.02 mm) are required to accommodate the high heat flux of a rocket thrust chamber and ensure structural integrity.

Batakis, A. P.↗
NASA NTRS1988

Material growth and characterization for solid state devices

During the period of this research grant, the process of liquid phase electroepitaxy (LPEE) was used to grow ternary and quaternary alloy III-V semiconductor thin films. Selective area growth of InGaAs was performed on InP substrates using a patterned sputtered quartz or spin-on glass layer. The etch back and growth characteristics with respect to substrate orientation were investigated. The etch back behavior is somewhat different from wet chemical etching with respect to the sidewall profiles which are observed. LPEE was also employed to grow epitaxial layers of InGaAsP alloys on InP substrates. The behavior of Mn as an acceptor dopant was investigated with low temperature Hall coefficient and photoluminescence measurements. A metal-organic vapor phase epitaxy system was partially complete within the grant period. This atmospheric pressure system will be used to deposit III-V compound and alloy semiconductor layers in future research efforts.

Collis, Ward J.↗
NASA NTRS2002

Mechanical Signal Transduction in Countermeasures to Muscle Atrophy

We have shown that modifications in muscle use result in changes in the expression and activity of calpains and nitric oxide synthase (NOS). Although muscle unloading for 10 days produced no change in the concentrations of calpain 1 or 2 and no change in calpain activation, muscle reloading produced a 90% increase in calpain 2 concentration. We developed an in vitro model to test our hypothesis that nitric oxide can inhibit cytoskeletal breakdown in skeletal muscle cells by inhibiting calpain cleavage of talin. Talin was selected because it is a well-characterized calpain substrate and it is codistributed with calpain in muscle cells. We found that intermittant loading during hindlimb suspension that is sufficient to prevent muscle mass loss that occurs during muscle unloading is also sufficient to prevent the decrease in NOS expression that normally occurs during hindlimb unloading. These findings indicate that therapeutics directed toward regulating the calpain/calpastatin system may be beneficial in preventing muscle mass loss in muscle injury, unloading and disease.

Tidball, James G.↗