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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

The factors that affect the preferred positions of cations in ionic solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La(+3) and Ca(+2) in a KBr host lattice were examined as a function of the polyvalent cation concentration. The cation-anion pairing process was found to be random for Ca(+2), whereas the formation of La(+3)-SO4(-2) ion pairs with a C2 sub v bonding geometry is highly preferential to any type of La(+3)-CrO4(-2) ion pair formation. The relative populations of ion pair site configurations are discussed in terms of an energy-entropy competition model which can be applied to the partition of trace elements during magmatic processes.

Grzybowski, J. M.↗
NASA NTRS1981

A molecular model for ice nucleation and growth, attachment 1

The quantum mechanical technique is used to study ionic, configurational, and impurity defects in the ice surface. In addition to static calculations of the energetics of the water monomer-ice surface interactions, molecular dynamics studies were initiated. The calculations of the monomer-ice surface interaction, molecular dynamics studies were initiated. The calculations of monomer-ice surface interactions indicate that many adsorption sites exist on the ice surfaces and that the barriers between bonding sites are relatively low. Bonding on the prism face of ice is preferentially above lattice sites.

Plummer, P. L. M.↗
DOE OSTI2023

Atomic Level Interactions and Suprastructural Configuration of Plant Cell Wall Polymers in Dialkylimidazolium Ionic Liquids

Ionic liquids (ILs) have been widely investigated for the pretreatment and deconstruction of lignocellulosic feedstocks. However, the modes of interaction between IL-anions and cations, and plant cell wall polymers, namely, cellulose, hemicellulose, and lignin, as well as the resulting ultrastructural changes are still unclear. In this study, we investigated the atomic level and suprastructural interactions of microcrystalline cellulose, birch wood xylan, and organosolv lignin with 1,3-dialkylimidazolium ILs having varying sizes of carboxylate anions. Analysis by 13 C NMR spectroscopy indicated that cellulose and lignin exhibited stronger hydrogen bonding with acetate ions than with formate ions, as evidenced by greater chemical shift changes. Small-angle X-ray scattering analysis showed that while both cellulose and xylan adopted a single-stranded conformation in acetate-ILs, twice as many acetate ions were bound to one anhydroglucose unit than to an anhydroxylose unit. Further, we also determined that a minimum of seven representative carbohydrate units must interact with an anion for that IL to effectively dissolve cellulose or xylan. Lignin is associated as groups of four polymer molecules in formate-ILs and dispersed as single molecules in acetate-ILs, which indicates that it is highly soluble in the latter. In summary, our study demonstrated that 1,3-dialkylimidazolium acetates displayed stronger binding interactions with cellulose and lignin, as compared to formates, and thus have superior potential to fractionate these polymers from lignocellulosic feedstocks.

13C NMR↗
DOE OSTI2016

Influence of aqueous ionic strength upon liquid:liquid interfacial structure and microsolvation

Ionic strength of an aqueous solution is often used to alter the efficacy of industrial processes that rely upon liquid:liquid phase boundaries (e.g. solvent extraction), however there is little understanding of how this condition may alter the properties of the phase boundary itself. The current work examines the interfacial structure and processes within the biphasic system (NaNO3)aq:n-hexane from 0 to 10 M NaNO3 at 298 K and 1 atm pressure. The extent of ion-pairing was quantified, alongside the primary solvation environments of both water and ions. Ion concentration was found to be depressed in the interfacial region relative to the bulk, and as such there is less likelihood of the formation of contact ion-pairs or ion-clusters at the interface. This in turn, leads to the interesting observation of more hydrogen bonds per water at the interface than in the bulk. At 10 M NaNO3 enough ions are present at the interface to severely perturb the mesoscopic interfacial properties of width and tension (the latter doubling in size relative to the neat water interface with n-hexane). Chemical theories, like the Kelvin equation and its analogs for liquid:vapor interfaces, would intuit that such a large change in interfacial tension should influence the microsolvation processes of the immiscible solvents (microsolvation being the rare event where water can penetrate n-hexane and n-hexane may penetrate and be fully solvated by water). However, there is no statistical difference between the concentrations of water and n-hexane in their respective co-solvents as a function of interfacial tension in these non-ideal solutions. Based upon these data, the ability of electrolyte concentration to alter transport across the interface does not appear to be related to the perturbation imparted by the electrolyte upon the interfacial properties themselves.

Chemistry↗
DOE OSTI2022

Synthesis, Crystal and Electronic Structure of the New Ternary Compound Ca3InAs3

Crystals of a new ternary compound in the Ca-In-As family, Ca3InAs3, have been successfully synthesized via flux growth techniques. This is only the third known compound between the respective elements. As elucidated by single-crystal X-ray diffraction measurements, Ca3InAs3 crystallizes in the orthorhombic space group Pnma (No. 62, Pearson symbol oP28) with unit cell parameters a = 12.296(2) Å, b = 4.2553(7) Å, and c = 13.735(2) Å. The smallest building motifs of the structure are InAs4 tetrahedra, which are connected to one another by shared As corners, forming infinite [InAs2As2/2] chains. The latter propagate along the crystallographic b-axis. The As-In-As bond angles within the InAs4 tetrahedra deviate from the ideal 109.5° value and range from 98.12(2)° to 116.53(2)°, attesting to a small distortion from the regular tetrahedral geometry. Electronic structure calculations indicate the opening of a bandgap, consistent with the expected (Ca2+)3(In3+)(As3–)3 formula breakdown based on conventional oxidation numbers. The calculations also show that the Ca–As interactions are an intermediate between covalent and ionic, while providing evidence of strong covalent features of the In–As interactions. Weak s-p hybridization of In states was observed, supporting the experimentally found deviation of the InAs4 moiety from the ideal tetrahedral symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2009

NASA Tech Briefs, June 2009

Topics covered include: Device for Measuring Low Flow Speed in a Duct, Measuring Thermal Conductivity of a Small Insulation Sample, Alignment Jig for the Precise Measurement of THz Radiation, Autoignition Chamber for Remote Testing of Pyrotechnic Devices, Microwave Power Combiners for Signals of Arbitrary Amplitude, Synthetic Foveal Imaging Technology, Airborne Antenna System for Minimum-Cycle-Slip GPS Reception, Improved Starting Materials for Back-Illuminated Imagers, Multi-Modulator for Bandwidth-Efficient Communication, Some Improvements in Utilization of Flash Memory Devices, GPS/MEMS IMU/Microprocessor Board for Navigation, T/R Multi-Chip MMIC Modules for 150 GHz, Pneumatic Haptic Interfaces, Device Acquires and Retains Rock or Ice Samples, Cryogenic Feedthrough Test Rig, Improved Assembly for Gas Shielding During Welding or Brazing, Two-Step Plasma Process for Cleaning Indium Bonding Bumps, Tool for Crimping Flexible Circuit Leads, Yb14MnSb11 as a High-Efficiency Thermoelectric Material, Polyimide-Foam/Aerogel Composites for Thermal Insulation, Converting CSV Files to RKSML Files, Service Management Database for DSN Equipment, Chemochromic Hydrogen Leak Detectors, Compatibility of Segments of Thermoelectric Generators, Complementary Barrier Infrared Detector, JPL Greenland Moulin Exploration Probe, Ultra-Lightweight Self-Deployable Nanocomposite Structure for Habitat Applications, and Room-Temperature Ionic Liquids for Electrochemical Capacitors.

Source record↗
DOE OSTI2019

Electronic Tuning of Mixed Quinoida-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains

The synthesis of conjugated polymers with ionic substituents directly bound to their main chain repeat units is a strategy for generating strongly electron-accepting conjugated polyelectrolytes, as demonstrated through the synthesis of a series of ionic azaquinodimethane (iAQM) compounds. The introduction of cationic substituents onto the quinoidal para-azaquinodimethane (AQM) core gives rise to a strongly electron-accepting building block, which can be employed in the synthesis of ionic small molecules and conjugated polyelectrolytes (CPEs). Electrochemical measurements alongside theoretical calculations indicate notably low-lying LUMO values for the iAQMs. The optical band gaps measured for these compounds are highly tunable based on structure, ranging from 2.30 eV in small molecules down to 1.22 eV in polymers. The iAQM small molecules and CPEs showcase the band gap reduction effects of combining the donor-acceptor strategy with the bond-length alternation reduction strategy. Finally, as a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.

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

Electronic Tuning of Mixed Quinoidal-Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main-Chains

The synthesis of conjugated polymers with ionic substituents directly bound to their main chain repeat units is a strategy for generating strongly electron-accepting conjugated polyelectrolytes, as demonstrated through the synthesis of a series of ionic azaquinodimethane (iAQM) compounds. The introduction of cationic substituents onto the quinoidal para -azaquinodimethane (AQM) core gives rise to a strongly electron-accepting building block, which can be employed in the synthesis of ionic small molecules and conjugated polyelectrolytes (CPEs). Electrochemical measurements alongside theoretical calculations indicate notably low-lying LUMO values for the iAQMs. The optical band gaps measured for these compounds are highly tunable based on structure, ranging from 2.30 eV in small molecules down to 1.22 eV in polymers. Here, the iAQM small molecules and CPEs showcase the band gap reduction effects of combining the donor-acceptor strategy with the bond-length alternation reduction strategy. As a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.

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

A comprehensive first-principles study of solute elements in dilute Ni alloys: Diffusion coefficients and their implications to tailor creep rate

Diffusion regulates a vast number of materials properties and phenomena such as creep, the focus of the present work. However, a deep understanding of the effect of how each alloying element in a Ni-base superalloy affects properties such as diffusion and creep is far from complete. Here, in this study, we report temperature-dependent dilute solute diffusion coefficients and their implications to tailor the creep rate for 26 transition metal solute elements, X's, in fcc Ni using first-principles calculations. Calculations are performed using the five-frequency model for dilute solute diffusion and the nudged elastic band method within the local density approximation. Thermodynamic properties at finite temperatures for all configurations are calculated using the quasi-harmonic Debye model. In general, the fastest diffusing solute elements in Ni are found at the left side of the periodic table and the slowest diffusing solute elements are found in group VIIB. In particular, the present work indicates that the diffusivity of the dilute solute elements is correlated to the compressibility of each solute element on the respective Ni 31 X supercell, and not as strongly to the ionic radius of the solute elements, as previously suggested. Finally, results from the diffusivity study are combined with the previous results of elastic constants and stacking fault energies, and hence, a relative creep rate ratio for these 26 solute elements is modeled. It is shown that in most cases, slower diffusing solute elements provide the most creep resistance. This is true even at higher temperatures, due mainly to the solute's strong bonding with Ni atoms in the host lattice.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Enhanced lithium ion transport in garnet-type solid state electrolytes

Al-substituted Li 7 La 3 Zr 2 O 12 samples processed under argon show enhanced Li-ion transport and interfacial properties in symmetrical cells with lithium electrodes, compared to those prepared in air. In particular, the samples prepared under argon have higher ionic conductivities and lower interfacial impedances in symmetrical lithium cells, and show better DC cycling characteristics. The electronic conductivities are also somewhat higher. Pellets subjected to thermal treatment under the two types of atmospheres have different colors but exhibit similar microstructures. X-ray diffraction experiments suggest that there are slight structural differences between the two types of samples, but few dissimilarities were observed in elemental composition, distribution of ions, oxidation states, or bond lengths using laser-induced breakdown spectroscopy (LIBS), x-ray photoelectron spectroscopy (XPS), and extended x-ray absorption fine structure spectroscopy (EXAFS) to analyze the materials. Additionally, there was no evidence that La or Zr were reduced during the processing under Ar. Possible explanations for the improved electrochemical properties of the sample prepared under Ar compared to the one prepared in air include differences in grain boundary chemistries and conductivities and/or a small concentration of oxygen vacancies in the former.

25 ENERGY STORAGE↗
DOE OSTI2018

Dielectric Behavior as a Screen in Rational Searches for Electronic Materials: Metal Pnictide Sulfosalts

Dielectric screening plays an important role in reducing the strength of carrier scattering and trapping by point defects for many semiconductors such as the halide perovskite solar materials. However, it was rarely considered as a screen to find new electronic semiconductors. We performed a material search study using the dielectric properties as a screen to identify potential electronic materials in the class of metal-pnictide ternary sulfosalts, containing Bi or Sb. These salts are basically ionic due to the electronegativity difference between the S and both the metal and pnictogen elements. However, we do find significant cross-gap hybridization between the S p-derived valence bands and pnictogen p-derived conduction bands in many of the materials. This leads to enhanced Born effective charges and, in several cases, highly enhanced dielectric constants. We find a chemical rule for high dielectric constants in terms of the bond connectivity of the pnictogen-chalcogen part of the crystal structure. We additionally find a series of compounds with low effective mass, high dielectric constant, and other properties that suggest good performance as electronic materials and also several potential thermoelectric compounds. Experimental optical data and solar conversion efficiency are reported for Sn-Sb-S samples, and results in accord with predicted good performance are found. The results illustrate the utility of dielectric properties as a screen for identifying complex semiconductors.

14 SOLAR ENERGY↗
DOE OSTI2016

Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties

This study describes the application of a ferricyanide-based assay as a simple and inexpensive assay for rapid analysis of aqueous lignin samples. The assay measures the formation of Prussian blue from the redox reaction between a mixture of potassium ferricyanide and ferric chloride, and phenolic hydroxyl groups of lignin or lignin-derived phenolic moieties. This study revealed that soluble lignin moieties exhibited stronger ferricyanide reactivity than insoluble aggregates. The soluble lignin moieties exhibited higher ferricyanide reactivity because of increased access of the phenolic hydroxyl groups to the ferricyanide reagents. Ferricyanide reactivity of soluble lignin moieties correlated inversely with the molecular weight distributions of the molecules, probably due to the involvement of phenolic hydroxyl groups in bond formation. The insoluble lignin aggregates exhibited low ferricyanide reactivity due to sequestration of the phenolic hydroxyl groups within the solid matrix. The study also highlighted the sequestration of polydispersed water-soluble lignin moieties by insoluble aggregates. The sequestered moieties were released by treatment with 0.01 M NaOH at 37 °C for 180 min. The redox assay was effective on different types of lignin extracts such as Klason lignin from switchgrass, ionic-liquid derived lignin from Eucalyptus and alkali lignin extracts. The assay generated a distinct profile for each lignin sample that was highly reproducible. The assay was also used to monitor consumption of syringic acid by Sphingobium sp. SYK-6. The simplicity and reproducibility of this assay makes it an excellent and versatile tool for qualitative and semi-quantitative characterization and comparative profiling of aqueous lignin samples.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Macrocyclic β‐Sheets Stabilized by Hydrogen Bond Surrogates

Abstract Mimics of protein secondary and tertiary structure offer rationally‐designed inhibitors of biomolecular interactions. β‐Sheet mimics have a storied history in bioorganic chemistry and are typically designed with synthetic or natural turn segments. We hypothesized that replacement of terminal inter‐β‐strand hydrogen bonds with hydrogen bond surrogates (HBS) may lead to conformationally‐defined macrocyclic β‐sheets without the requirement for natural or synthetic β‐turns, thereby providing a minimal mimic of a protein β‐sheet. To access turn‐less antiparallel β‐sheet mimics, we developed a facile solid phase synthesis protocol. We surveyed a dataset of protein β‐sheets for naturally observed interstrand side chain interactions. This bioinformatics survey highlighted an over‐abundance of aromatic–aromatic, cation‐π and ionic interactions in β‐sheets. In correspondence with natural β‐sheets, we find that minimal HBS mimics show robust β‐sheet formation when specific amino acid residue pairings are incorporated. In isolated β‐sheets, aromatic interactions endow superior conformational stability over ionic or cation‐π interactions. Circular dichroism and NMR spectroscopies, along with high‐resolution X‐ray crystallography, support our design principles.

Chemistry↗
NASA NTRS2015

Evaluation of Two Ionic Liquid-Based Epoxies from the MISSE-8 (Materials International Space Station Experiment-8) Sample Carrier

Two sets of epoxy mixtures, both containing the same ionic liquid (IL) based resin but utilizing two different curing agents, were evaluated after spending more than two years of continual space exposure outside of the International Space Station on the MISSE-8 sample rack. During this period the samples, positioned on nadir side, also experienced some 12,500 thermal cycles between approximately -40C and +40 C. Initial examination showed some color change, a miniscule weight variance, and no cracks or de-bonding from the sample substrate. Microscopic examination of the surface reveled some slight deformities and pitting. These observations, and others, are discussed in view of the ground-based control samples. Finally, the impetus of this study in terms of space applications is presented.

Rabenberg, Ellen↗
DOE OSTI2023

Surpassing the Performance of Phenolate-derived Ionic Liquids in CO 2 Chemisorption by Harnessing the Robust Nature of Pyrazolonates

Superbase-derived ionic liquids (SILs) are promising sorbents to tackle the carbon challenge featured by tunable interaction strength with CO 2 via structural engineering, particularly the oxygenate-derived counterparts (e. g., phenolate). However, for the widely deployed phenolate-derived SILs, unsolved stability issues severely limited their applications leading to unfavorable and diminished CO 2 chemisorption performance caused by ylide formation-involved side reactions and the phenolate-quinone transformation via auto-oxidation. Here, in this work, robust pyrazolonate-derived SILs possessing anti-oxidation nature were developed by introducing aza-fused rings in the oxygenate-derived anions, which delivered promising and tunable CO 2 uptake capacity surpassing the phenolate-based SIL via a carbonate formation pathway (O-C bond formation), as illustrated by detailed spectroscopy studies. Further theoretical calculations and experimental comparisons demonstrated the more favorable reaction enthalpy and improved anti-oxidation properties of the pyrazolonate-derived SILs compared with phenolate anions. The achievements being made in this work provides a promising approach to achieve efficient carbon capture by combining the benefits of strong interaction strength of oxygenate species with CO 2 and the stability improvement enabled by aza-fused rings introduction.

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

Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites

Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first principles calculations are performed on (MA/Cs/FA)Pb(I/Br) 3 and MASnI 3 . Across the materials studied, electron small polaron formation is manifested by Jahn-Teller like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed, are established for optimization in specific optoelectronic applications.

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

Spectroscopic Characterization of Aqua [ fac -Tc(CO) 3 ] + Complexes at High Ionic Strength

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I–VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac -Tc(CO) 3 (OH 2 ) 3– n (OH) n ] 1– n (where n = 0–3) were examined by a range of spectroscopic techniques including 99 Tc/ 13 C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc–C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac -Tc(CO) 3 (OH 2 ) 3 ] > [ fac -Tc(CO) 3 (OH 2 ) 2 (OH)] > [ fac -Tc(CO) 3 (OH 2 )(OH) 2 ] – . These results correlate with established trends of the 99 Tc upfield chemical shift and carbonyl 13 C downfield chemical shift. The lone exception is [ fac -Tc(CO) 3 (OH)] 4 which exhibits a comparatively low electron density at the metal center attributed to the μ 3 -bridging nature of the –OH ligands causing less σ-donation and no π-donation. As a result, this work also reports the first observations of these compounds by XPS and [ fac -Tc(CO) 3 Cl 3 ] 2– by XAS. The unique and distinguishable spectral features of the aqua [ fac -Tc(CO) 3 ] + complexes lay the foundation for their identification in the complex aqueous matrixes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Concentration Dependent Interfacial Chemistry of the NaOH(aq):Gibbsite Interface

Caustic conditions are often employed for dissolution of a wide variety of minerals, where ion sorption, surface diffusion, and interfacial organization impact surface reactivity. In the case of gibbsite, gamma-Al(OH)3, the chemistry at the NaOH(aq) interface is deeply intertwined with industrial processing of aluminum, including metal production and the disposition of Al-containing wastes. To date, little is known about the structure, speciation, and dynamic behavior of gibbsite interfaces (and that of many other minerals) with NaOH(aq)—particularly as a function of ionic strength. Yet concentration-dependent interfacial organization and dynamics are a critical starting point to develop a fundamental understanding of the factors that influence dissolution. This work reports equilibrium molecular dynamics simulations of the gamma-Al(OH)3:NaOH(aq) interface, revealing the sorption behavior and speciation of ions from 0.5–10 M [NaOH]. As inner-sphere complexes, Na+ primarily coordinates to the side of the gibbsite hexagonal cavities, while OH accepts hydrogen-bonding from the surface-OH groups. The mobility of inner-sphere Na+ and OH ions is significantly reduced due to a strong surface affinity in comparison to previous reports of NaCl, CaCl2, or BaCl2 electrolytes. At high [NaOH], contact ion pairing that is observed in the bulk solution is partially disrupted upon sorption to the gibbsite surface by the individual ion–surface interactions. The molecular-scale changes to surface speciation and competition between ion–surface vs. ion–ion interactions influence surface characterization of gibbsite and potential dissolution processes, providing a valuable baseline for starting conditions needed within future reactive molecular simulations.

alkaline solutions, IDREAM, gibbsite, molecular dy↗