Search NASA⌕ Search

SEARCH · Search NASA

Results for “Structural characteristics”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7

Nano-Ceramic Cathodes via Co-sputtering of Gd–Ce Alloy and Lanthanum Strontium Cobaltite for Low-Temperature Thin-Film Solid Oxide Fuel Cells

We report the electrochemical performance and structural characteristics of porous nanostructured ceramic cathodes for thin-film solid oxide fuel cells (TF-SOFCs) based on yttria-stabilized zirconia (YSZ) electrolytes. The nanostructured cathode is obtained through magnetron co-sputtering of gadolinium–cerium (Gd–Ce) alloy and lanthanum strontium cobaltite perovskite targets. The resultant nanostructure and composition of the ceramic cathode are controlled by adjusting the co-sputtering conditions. The peak power densities in our fabricated TF-SOFCs are the highest reported values for YSZ-based electrolyte SOFCs, showing 0.14, 0.48, 1.21, 2.56, and 3.01 W/cm2 at 450, 500, 550, 600, and 650 °C, respectively, operating under air and pure hydrogen fuel. The results show that the porosity and composition of the cathode greatly affect the resulting peak power densities. This work illustrates the capability of sputtering to produce stable, scalable, nano-ceramic cathodes with superb peak power densities when integrated in TF-SOFCs.

25 ENERGY STORAGE↗

Delta/Lambda Chirality: From Enantiomers to Diastereomers in Heterometallic Complexes with Chelating Ligands

The Δ/Λ chirality observed in octahedral molecules with chelating ligands represents the major group of “chiral-at-metal” complexes. Upon shifting from mononuclear to polynuclear systems with multiple (≥2) chiral centers, not only enantiomers but also diastereomers should be considered. We present the first, to the best of our knowledge, diastereomeric pairs Δ,Δ,Δ/Λ,Λ,Λ (1) and Δ,Δ,Λ/ Λ,Λ,Δ (2) of the pentanuclear assembly [Mn II (ptac) 3 −Na- Co III (acac) 3 −Na-Mn II (ptac) 3 ] (ptac = 1,1,1-trifluoro-5,5-dimethyl- 2,4-hexanedionate; acac = acetylacetonate). Diastereomers 1 and 2 were isolated in pure form and found to exhibit distinctly different structural characteristics. Importantly, for compounds that are applied as single-source precursors for the quaternary oxide cathode material P2−Na 0.67 Mn 0.67 Co 0.33 O 2 , the diastereomers revealed different thermal behaviors in terms of volatility and thermal stability. Unambiguous assignment of the Mn and Co positions in both diastereomers has been confirmed by the synchrotron X-ray resonant diffraction technique. Oxidation states of metal ions have been verified by the synchrotron X-ray fluorescence spectroscopy. The diastereomerization between 1 and 2 is not taking place in the solid state (crystal-to-crystal), as well as in the gas phase. The transformation between two diastereomers was observed in the solutions of noncoordinating solvents and was related to the polarities of the solvents and diastereomeric molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of wafer-scale SWCNT forests with remarkably invariant structural properties in a bulk-diffusion-controlled kinetic regime

Robust synthesis of vertically aligned carbon nanotubes (VACNT) at large scale is required to accelerate deployment of numerous cutting-edge devices to emerging commercial applications. To address this need, this work demonstrates that the structural characteristics of single-walled CNTs (SWCNTs) produced in a growth regime dominated by bulk diffusion of the gaseous carbon precursor are remarkably invariant over a broad range of process conditions (precursor concentration increased up to 30-fold, catalyst substrate area from 1 cm 2 to 180 cm 2 , growth pressure from 20 to 790 mbar, and gas flowrates up to 8-fold). A simple growth kinetics model is derived that accounts for both reactant bulk diffusion and competing byproduct formation in the presence of excess hydrogen, which quantitatively reproduces the experimental data in the entire isothermal parameter space. The model enables critical predictions for process scale-up optimization including a potential 6-fold increase in CNT production rate, a ~90% carbon conversion efficiency in select conditions, and elimination of reaction rate decay observed at high pressures by using a hydrogen-free growth environment. This model-guided opportunity to substantially improve synthesis throughput and efficiency, in conjunction with the remarkably invariant CNT properties, is appealing for reliable VACNT device fabrication at both small and industrial scales.

36 MATERIALS SCIENCE↗

Freestanding Photoresist Film: A Versatile Template for Three-Dimensional Micro- and Nanofabrication

Ultrathin freestanding films with well-defined micro/nanostructures and robust mechanical properties are applied in many engineering applications including microelectronics, optics, filtration and separation, biomedical engineering, and nanotechnology. Although considerable efforts have been made toward the fabrication of freestanding thin films, it is still a significant challenge to develop a simple and reliable process for producing freestanding films with ultrathin thickness, well-regulated micro/nanopatterns, robust mechanical properties, macroscopic coverage area, and multi-layered composite structures. In this work, a significant advancement is reported in this regard. This study shows a new sacrificial-layer-free (SLF) lifting-off process, integrated with conventional micro- and nanolithography, enabling the release of micro- and nanopatterned photoresist (PR) films from the supporting substrate with unprecedented pattern coverage and structure characteristics. The freestanding PR film is resilient, can withstand significant bending and deformation, and is sufficiently flexible to be transferred onto substrates with 3D topography as a conformal soft stencil for further technological processing and applications. Moreover, the SLF lifting-off process provides a simple approach to prepare single-layered and multi-layered freestanding composite films. The results suggest that the novel SLF lifting-off process can significantly extend the capability of 3D micro-/nanofabrication.

36 MATERIALS SCIENCE↗

Deep Eutectic Solvent Extraction of High-Purity Lignin from a Corn Stover Hydrolysate

Here, a lactic acid/chlorine chloride-based deep eutectic solvent (DES) was used for the extraction of high-purity lignin (up to 94.7%) in high yield (up to 75%) from the hydrolysis/fermentation residue corn stover hydrolysate (CSH), which was generated from a pilot-plant-scale biorefinery. A range of extraction conditions were investigated, which involved varying reaction temperature, time, and DES composition. The relationship between lignin yield, purity, and structural characteristics with DES treatment conditions was determined. The extraction of high-purity lignin from hydrolysis/fermentation residues presents a promising approach for enhancing the economic feasibility of a lignocellulose biorefinery. It was also determined that DES extraction can produce lignin with a controlled range of molecular weight and functional group content.

09 BIOMASS FUELS↗

Biocatalytic system for comparatively assessing the functional association of monolignol cytochrome P450 monooxygenases with their redox partners

Lignin is a complex heterogenous polymer derived from oxidative radical polymerization of three monolignols, i.e., p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. These lignin monomeric precursors structurally differ in their methoxy groups of the benzene rings. In phenylpropanoid-monolignol biosynthetic pathway, the endoplasmic reticulum (ER)-resident cytochrome P450 monooxygenases, cinnamate 4-hydroxylase, coumaroyl ester 3´-hydroxylase and ferulate 5-hydroxylase, establish the key structural characteristics of monolignols. The catalysis of cytochrome P450 monooxygenase requires reducing power, which is supplied by the ER electron transfer chains, composed of cytochrome P450 oxidoreductase (CPR), cytochrome b5 reductase (CBR) and/or cytochrome b5 protein (CB5), from cofactor NADPH or NADH. While NADPH-dependent CPR serves as the typical electron donor for most P450 enzymes, in some cases, the CBR-CB5 or CPR-CB5 electron transfer system also transfers electrons to the terminal P450 enzymes. There are tremendous studies focusing on the discovery and characterization of cytochrome P450 monooxygenases. However, very limited attention has been paid to the versatility and the roles of electron transfer components in the P450 catalytic system. Due to the membrane-residence property of both P450 enzymes and electron transfer components, it is challenging to establish an effective experimental system to evaluate the functional association of P450s with their redox partners. This chapter describes a yeast cell biocatalytic system and the related experimental procedures for comparatively assessing the functional relationship of monolignol biosynthetic P450 enzymes and different redox partners in their catalysis.

59 BASIC BIOLOGICAL SCIENCES↗

Symmetry-breaking in double gyroid block copolymer films by non-affine distortion

Soft-matter bicontinuous networks find a double gyroid structure from block copolymer (BCP) self-assembly. A gyroid structure composed of dissimilar blocks has proven its potential as a soft crystal capable of tuning structural periodicity and symmetry, of which the lattice dimension is variable with molecular weight of the polymer. Using an asymmetric polystyrene- b -poly(methyl methacrylate) (PS- b -PMMA), in this study we show that the self-assembled gyroid films formed via a solvent vapor annealing (SVA) process undergo unique structural distortion due to directional deformation immediately upon deswelling. During the SVA process with PS- b -PMMA films, transient cylinders developed from the as-cast morphology transform into a cubic gyroid structure in a swollen state. Rapid and spontaneous deswelling processes -the manners in which the films contract along the z-direction while retaining an enlarged lateral dimension of the cubic form -lead to triclinic gyroid structures with z-directional contraction ratios ( C z ) of 2.5 and 2.0, respectively. Our X-ray analysis reveals that the deswelling process of the swollen gyroid films produces a notable symmetry-breaking in non-affine gyroid structure that elicits several forbidden reflections such as {110} and {200} reflections. For further characterization of the symmetry-breaking, we delineate the structural features of noncubic gyroid films by computing electron-density difference maps assisted with X-ray measurements. Level-set approach is accordingly developed to quantitate the structural characteristics of the maps in terms of inversion symmetry-breaking, suggesting its possible application to optical Weyl photonic crystals.

36 MATERIALS SCIENCE↗

Temperature controlled transformations of giant unilamellar vesicles of amphiphilic triblock copolymers synthesized via microfluidic mixing

We report on a simple approach for synthesis of temperature-responsive giant unilamellar vesicles (GUVs) from poly(N-vinylcaprolactam) 15 -block-poly(dimethylsiloxane) 65 -block-poly(N-vinylcaprolactam) 15 (PVCL 15 -PDMS65-PVCL 15 ) triblock copolymer and non-temperature responsive small and giant vesicles from novel poly(N-vinylpyrrolidone)-block-poly(dimethylsiloxane)-block-poly(N-vinylpyrrolidone) (PVPON 15 -PDMS 65 -PVPON 15 and PVPON 6- PDMS 30- PVPON 6 ) triblock copolymers using microfluidic mixing at 25 °C. We show that temperature-responsive PVCL 15 -PDMS 65- PVCL 15 GUVs with the average diameter of 1.4 ± 0.2 µm while being stable at room temperature for at least 14 days, transformed irreversibly into small vesicles of 168 ± 40 nm after incubation of their aqueous solution at 42 °C for 24 h. We hypothesized that this transformation is induced by local compressive stresses of the vesicle membrane due to the collapse of PVCL blocks above the copolymer lower critical solution temperature (LCST) leading to the decrease of the vesicle membrane thickness. Consequently, we found that the temperature-induced size transformation of the PVCL-based GUVs at 42°C can be suppressed by substituting PVCL with its hydrophilic homologue PVPON, or by suppressing the PVCL's LCST behavior through hydrogen-bonding with tannic acid molecules. In the former case, novel PVPON n -PDMS m -PVPON n triblock copolymers (n = 15, m = 65 and n = 6, m = 30) assemble into vesicles stable from 25 °C to 55 °C as confirmed by optical and electron microscopy, dynamic light scattering (DLS) and small-angle neutron scattering (SANS). In the latter, hydrogen bonding interactions of PVCL with the polyphenol tannic acid (TA) at room temperature resulted in stable PVCL-based GUVs at 42°C as confirmed by optical, electron, and atomic force microscopies. We also found that physical crosslinking of the PVCL corona through hydrogen bonding with TA in PVCL 15- PDMS 65- PVCL 15 GUVs will delay their low pH-induced degradation at 37°C by 48 h compared to non-modified GUVs. Our findings open opportunities for the development of temperature-regulated stable micro-vehicles that would change their structural characteristics in the physiologically relevant temperature range from 25 to 42°C and can be utilized for cell mimicking studies. The developed GUVs also have potential in theranostic drug delivery as substitutes for polymer microcapsules and lipid microbubbles as well as for stimuli-triggered sensing, protection, and rapid response in an aqueous environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Emerging commercial applications of vertically aligned, single-walled carbon nanotube (SWCNT) “forests” require synthesis that minimizes nanotube diameter while maximizing number density across substrate areas exceeding centimeter scale. To address this need, we synthesized SWCNT forests on full silicon wafers with notable reproducibility and uniformity, and co-optimized growth for small diameters and high densities across large areas to access new territory in this 3D parameter space. We mapped the spatial uniformity of key structural features using Raman microscopy, synchrotron X-ray scattering, and Rutherford backscattering spectrometry. Low C 2 H 2 flux over sub-nm Fe/Mo catalysts produced small-diameter SWCNTs (2.1 nm) at high number densities (2.26 × 10 12 cm -2 ) on wafers up to 6 in. Although removing Mo resulted in larger SWCNT diameters and lower densities (<0.7 × 10 12 cm -2 ), mass conversion rates from C 2 H 2 to SWCNT product were high and remarkably invariant for catalyst compositions and densities (i.e., 47.7% or 1.30 × 10 6 % g-catalyst -1 on 4-in. wafers). These carbon conversion efficiencies far exceed typical benchtop reactors and are on par with the best reported literature values. Our detailed elucidation of correlations among structural characteristics within this resource-efficient process is expected to guide future scale-up efforts of SWCNT forest growth beyond wafer scale.

36 MATERIALS SCIENCE↗

Carbon fiber synthesis from pitch: Insights from ReaxFF based molecular dynamics simulations

Despite the potential to lowering fabrication costs of pitch-based carbon fiber (CF) compared to polyacrylonitrile-based CF, large scale utilization is currently limited by the complexity in manufacturing. This is mainly due to the lack of consistency between the pitch structure/chemistry and CF properties under different processing conditions. Here, we employed full atomistic simulations based on reactive force fields to investigate the conversion of pitch precursors to CFs. Additionally, it was found that at the carbonization stage, the consumption rates of precursors, gas formations, and solid yields (carbonized CFs) are all dependent on the composition and arrangement of molecular moieties in the precursor. Specifically, precursors with sp 3 carbons in the cata-condensed core area have limited decomposition pathways (i.e., limited reaction sites), which leads to the formation of carbonized CFs with similar compositions. Furthermore, carbonized CFs possess distinct structural characteristics, and finally lead to the formation of CFs with different moduli. By analyzing CF crystallinity and elemental composition, general rationales are proposed for the selection of optimal precursors and processing conditions, and thus shed lights on parameter screening during industrial CF synthesis. For instance, inclusion of sp 3 carbons in cata- condensed rings can be preferred over the presence of sp 3 carbons on side chains.

01 COAL, LIGNITE, AND PEAT↗

Polymeric ionic liquids containing copper(I) and copper(II) ions as gas chromatographic stationary phases for olefin separations

Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reticulated porous lanthanum strontium manganite structures for solar thermochemical hydrogen production

Porous ceramic foams are utilized in various fields and applications due to their advantageous properties such as high porosity, high specific surface area, and controlled permeability. Non-stoichiometric oxide foams are of particular interest for the solar thermochemical production of hydrogen in directly irradiated solar receivers due to their enhanced heat transfer capabilities and structural integrity. Here we report the fabrication of lanthanum strontium manganite replica foams and their solar thermochemical water splitting performance. Highly porous (>80%) foams were produced with controlled structure and tested in a high temperature water splitting furnace to demonstrate stability and overall performance. The temperature profile of the burnout and sintering of the foam structure were altered based on simultaneous differential scanning calorimetry and thermal gravimetry analysis. Two-step sintering was used both to retain micron-sized pores (D50 = 0.4 μm) on the foam's struts and to limit grain growth to a grain size of ~1 μm. The structural characteristics were confirmed by porosimetry and scanning electron microscopy. The foams were repeatedly cycled, producing approximately 200 μmol/g of H 2 per cycle. Water splitting performance was tested for 50 cycles and approximately 35 h at 1400 °C. No statistical difference in the effective hydrogen production per cycle was observed, which is promising for long-term redox cycle stability.

08 HYDROGEN↗

Effects of the advanced organosolv pretreatment strategies on structural properties of woody biomass

Plants have evolved their lignocellulosic cell walls through complex structural and chemical mechanisms to protect itself against microbial attacks, which makes native lignocellulosic biomass recalcitrant to enzymatic deconstruction. Pretreatment is a crucial step in the biological conversion of biomass as it can render structural changes in the plant cell wall to reduce the biomass recalcitrance, thus enhancing its sugar release performance. There have been many efforts to develop effective pretreatment technologies to overcome the biomass recalcitrance with a primary focus on the efficient conversion of biomass carbohydrates to liquid fuels, while lignin is significantly underutilized despite its bulk amount and high-value opportunities. In this study, the effects of two recent organosolv pretreatment strategies, co-solvent enhanced lignocellulosic fractionation (CELF) and γ-Valerolactone (GVL) pretreatments, on physicochemical properties of poplar were investigated and compared with the effects of conventional ethanol organosolv pretreatment. Diverse physicochemical properties of biomass including chemical compositions, molecular weights of cellulose and lignin, aromatics and inter-unit linkages of lignin, lignin hydroxyl group contents, cellulose crystallinity, and accessible surface area of cellulose were analyzed before and after pretreatments. The results revealed how each organic solvent pretreatment system affected biomass structural characteristics and recalcitrance.

Meng, Xianzhi↗

Beneficial effect of surfactant in adsorption/desorption of lignocellulose-degrading enzymes on/from lignin with different structure

Nonionic surfactant Tween 80 is effective in alleviating the adsorption of lignocellulose-degrading enzymes onto lignin. However, the impacts of lignin structural characteristics on this mitigation effect of Tween 80 were still not clear. Herein, effects of Tween 80 on cellulase and xylanase adsorption on different enzymatic residual lignins (ERLs) and poplar samples were investigated. Besides, effects of Tween 80 on desorption of the two enzyme preparations from different ERLs and poplar samples were also evaluated. By adding Tween 80, the inhibition of ERLs to cellulase hydrolysis was offset and the positive role of Tween 80 in Avicel hydrolysis with presence of ERLs was more effective. Binding strength of cellulase with ERLs was alleviated from 236.0 – 410.9 to 43.9 – 116.6 mL/g after adding 0.5 mg/mL Tween 80. When ERLs was more hydrophobic and had more condensed phenolic OH, the alleviation effect of Tween 80 on cellulase adsorption on ERLs was intensified but its positive effect on enhancing cellulase desorption was weakened. Tween 80 was effective in increasing xylanase activity and preventing xylanase deactivation. Further, with the increase of lignin content and phenolic OH in pretreated poplar, the effect of Tween 80 in alleviating xylanase adsorption on poplar samples was intensified but the effect in enhancing xylanase desorption from poplar samples was weakened. The results provided distinct findings to understand the interaction between Tween 80 and cellulase/xylanase in enzymatic saccharification of lignocelluloses.

59 BASIC BIOLOGICAL SCIENCES↗

Growth mechanisms of large, faceted crystals grown from solutions

Here, the paper describes optical techniques and methods used to study growth mechanisms and phenomena occurring on multiple faces of real bulk crystals grown from aqueous and organic solutions. Using examples of ionic KDP and molecular trans-stilbene crystals, it shows how in-situ and ex-situ surface observations can be applied to identify growth structures characteristic for the dislocation, two-dimensional (2D), and 3D cluster deposition mechanisms. Results are analyzed and applied to understanding of defects origins and methods for their elimination in practical growth of large, high optical quality crystals.

2D growth mechanism↗

Explaining drivers of housing prices with nonlinear hedonic regressions

Housing markets play a critical role in shaping the spatial and demographic evolution of urban areas. Simulating housing price dynamics can enhance projections of future urban development outcomes. However, traditional hedonic regressions for housing prices, which neglect nonlinear interactions among explanatory variables, often exhibit limited predictive performance. While machine learning (ML) methods can provide a more flexible representation of the relationships between predictors, they are often regarded as “black boxes” due to their complexity and lack of transparency. Interpretable ML techniques provide a promising route by combining the flexibility of ML methods with approaches to analyze the relationships between inputs and outputs. In this study, we employ interpretable ML to analyze the patterns driving the housing market in Baltimore, Maryland, USA. We train an Artificial Neural Network (ANN) to predict Baltimore housing prices based on structural characteristics (e.g., home size, number of stories) and locational attributes (e.g., distance to the city center). We then conduct sensitivity and Partial Dependence Plot (PDP) analyses to interpret the fitted ANN model. We find that the ML model achieves higher predictive accuracy and explains 16 % more of housing price variance than a traditional linear regression model. The interpretable ML model also reveals more nuanced and realistic nonlinear relationships between housing sales price and predictors as well as interactive effects underlying Baltimore home price dynamics. For instance, while the linear model indicates a steady housing price increase over time, our interpretable ML model detects a post-2008 decline, with smaller properties experiencing the sharpest drop.

97 MATHEMATICS AND COMPUTING↗

The {10$\overline{1}$2} non-cozone twin-twin interactions in Mg: A stability and mobility study using 3-D atomistic simulations

Due to easy activation of tensile twinning in Mg, multiple {10$\overline{1}$2} twin variants can interact with each other and form twin-twin boundaries over the course of plastic deformation. Previous studies using 2-D settings provide only a partial understanding of these interactions, especially the non-cozone ones. Here, atomistic simulations are used to study the 3-D structural characteristic and evolution of the non-cozone {10$\overline{1}$2} twin-twin junctions. The study reveals the existence of new twin-twin boundaries (TTBs) such as TTB BP and TTB K2 , formed after the interaction between the basal prismatic and conjugate twin interfaces with the coherent twin boundary. Here, for both non-cozone twin-twin interactions, the {10$\overline{1}$2} TTB and its associated twin-twin junctions are found to play a major role in the {10$\overline{1}$2} twin's stability and mobility. Specifically, they promote the growth of the 3-D twin in both the normal and forward directions during the interaction and hinder the detwinning process upon unloading.

36 MATERIALS SCIENCE↗