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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Isotopic fractionation in proteins as a measure of hydrogen bond length

If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor Φ is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate Φ as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric O–H⋯O bonds [R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the O–H stretch vibration, O–H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total Φ as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization Φ(R), used previously to determine bond lengths.

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

Influence of Charge Scaling on the Solvation Properties of Ionic Liquid Solutions

Scaled-charge force fields (FFs) are widely employed in the simulation of neat ionic liquids (ILs), where the charges on the ions are empirically scaled to approximately account for electronic polarization and/or charge transfer. Such charge scaling has been found to yield significant improvement in liquid-state thermodynamic and dynamic properties (when compared to experiment). However, the mean field approximation inherent in charge scaling becomes suspect when applied to IL mixtures or solutions. In this work, we simulate solutions of IL with various nonpolar and polar gas solutes and compare results of charge-scaled and polarizable FFs to experiment. Our results demonstrate that scaling of the Coulomb interaction inherent in scaled-charge FFs leads to an underestimation of the solute–solvent electrostatic interaction and thus also the enthalpy and free energy of solvation; this effect is particularly pronounced for polar solutes. In some cases, we find that this artificial reduction in the solute–solvent interaction can also alter the apparent phase behavior of the resulting solution. Altogether, the totality of our results suggests that explicit polarization (rather than charge scaling) is likely necessary to provide high transferability to both neat IL and IL mixtures and solutions.

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

Natural deep eutectic solvents for lignocellulosic biomass pretreatment: Recent developments, challenges and novel opportunities

Conversion of lignocellulosic biomass to fuels and chemicals has attracted immense research and development around the world. Lowering recalcitrance of biomass in a cost-effective manner is a challenge to commercialize biomass-based technologies. Deep eutectic solvents (DESs) are new ‘green' solvents that have a high potential for biomass processing because of their low cost, low toxicity, biodegradability, easy recycling and reuse. This article discusses the properties of DESs and recent advances in their application for lignocellulosic biomass processing. The effectiveness of DESs in hydrolyzing lignin-carbohydrate complexes, removing lignin/hemicellulose from biomass as well as their effect on biomass deconstruction, crystallinity and enzymatic digestibility have been discussed. Moreover, this review presents recent findings on the compatibility of natural DESs with enzymes and microorganisms.

09 BIOMASS FUELS↗
DOE OSTI2016

Water-induced nanochannel networks in self-assembled block ionomers

Block ionomers cast from solution exhibit solvent-templated morphologies that can be altered by solvent-vapor annealing. When cast from a mixed solvent, a midblock-sulfonated pentablock ionomer self-assembles into spherical ionic microdomains that are loosely connected. Upon exposure to liquid water, nanoscale channels irreversibly develop between the microdomains due to swelling and form a continuous mesoscale network. In this work, we use electron tomography and real-time X-ray scattering to follow this transformation and show that the resultant morphology provides a highly effective diffusive pathway.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Coal desulfurization process

A method for chlorinolysis of coal is an organic solvent at a moderate temperautre and atmospheric pressure has been proven to be effective in removing sulfur, particularly the organic sulfur, from coal. Chlorine gas is bubbled through a slurry of moist coal in chlorinated solvent. The chlorinated coal is separated, hydrolyzed and the dechlorinated. Preliminary results of treating a high sulfutr (4.77%S) bituminous coal show that up to 70% organic sulfur, 90% hyritic sulfur and 76% total sulfur can be removed. The treated coal is dechlorinated by heating at 500 C. The presence of moisture helps to remove organic sulfur.

Hsu, G. C.↗
DOE OSTI2015

Modeling solvation effects in real-space and real-time within density functional approaches

The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Solvent and solute ingress into hydrogels resolved by a combination of imaging techniques

Using simultaneous neutron, fluorescence, and optical brightfield transmission imaging, the diffusion of solvent, fluorescent dyes, and macromolecules into a crosslinked polyacrylamide hydrogel was investigated. This novel combination of different imaging techniques enables us to distinguish the movements of the solvent and fluorescent molecules. Additionally, the swelling or deswelling of the hydrogels can be monitored. From the sequence of images, dye and solvent concentrations were extracted spatially and temporally resolved. Diffusion equations and different boundary conditions, represented by different models, were used to quantitatively analyze the temporal evolution of these concentration profiles and to determine the diffusion coefficients of solvent and solutes. Solute size and network properties were varied and their effect was investigated. Increasing the crosslinking ratio or partially drying the hydrogel was found to hinder solute diffusion due to the reduced pore size. By contrast, solvent diffusion seemed to be slightly faster if the hydrogel was only partially swollen and hence solvent uptake enhanced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Green Solvents for Precision Cleaning

Aerospace machinery used in liquid oxygen (LOX) fuel systems must be precision cleaned to achieve a very low level of non-volatile residue (< 1 mg0.1 m2), especially flammable residue. Traditionally chlorofluorocarbons (CFCs) have been used in the precision cleaning of LOX systems, specifically CFC 113 (C2Cl3F3). CFCs have been known to cause the depletion of ozone and in 1987, were banned by the Montreal Protocol due to health, safety and environmental concerns. This has now led to the development of new processes in the precision cleaning of aerospace components. An ideal solvent-replacement is non-flammable, environmentally benign, non-corrosive, inexpensive, effective and evaporates completely, leaving no residue. Highlighted is a green precision cleaning process, which is contaminant removal using supercritical carbon dioxide as the environmentally benign solvent. In this process, the contaminant is dissolved in carbon dioxide, and the parts are recovered at the end of the cleaning process completely dry and ready for use. Typical contaminants of aerospace components include hydrocarbon greases, hydraulic fluids, silicone fluids and greases, fluorocarbon fluids and greases and fingerprint oil. Metallic aerospace components range from small nuts and bolts to much larger parts, such as butterfly valves 18 in diameter. A fluorinated grease, Krytox, is investigated as a model contaminant in these preliminary studies, and aluminum coupons are employed as a model aerospace component. Preliminary studies are presented in which the experimental parameters are optimized for removal of Krytox from aluminum coupons in a stirred-batch process. The experimental conditions investigated are temperature, pressure, exposure time and impeller speed. Temperatures of 308 - 423 K, pressures in the range of 8.3 - 41.4 MPa, exposure times between 5 - 60 min and impeller speeds of 0 - 1000 rpm were investigated. Preliminary results showed up to 86 cleaning efficiency with the moderate processing conditions of 323 K, 13.8 MPa, 30 min and 750 rpm.

solvents↗
DOE OSTI2026

Deep Eutectic Solvents for Pretreatment of Lignocellulose Biomass: Physical Properties, Solubility Mechanisms, and Their Interactions

As the most accessible and abundant renewable resource on earth, lignocellulosic biomass mainly consists of cellulose, hemicelluloses, and lignin with a small amount of protein, pectin, minerals, and extractives (e.g., tannins, lipids, and resins). Lignocellulosic biomass has gained extensive attention in industry and research owing to its renewability, availability, and low cost. However, achieving efficient fractionation of lignocellulose components and all-component utilization in a green and cost-effective manner remains a challenge dueto biomass recalcitrance. Deep eutectic solvents (DESs) have received considerable attention because they are biocompatible, inexpensive, biodegradable, have low toxicity, and are easy to prepare and recycle; these characteristics strongly depend on individual components involved in DESs preparation. This review systematically summarizes recent progress in the fractionation of carbohydrates (cellulose and hemicelluloses) and lignin from biomass using DESs, with particular emphasis on the effects of DES types and pretreatment parameters on fractionation efficiency. The subsequent conversion and upgrading of the DES-fractionated products (i.e., carbohydrates and lignin) are comprehensively analyzed. Finally, the challenges and future prospects of lignocellulose biomass fractionation using DESs are proposed in view of the existing limitations. This review provides an in-depth understanding of lignocellulose biomass fractionation during DESs processing, offering insights to improve current pretreatment methods and/or to explore new pretreatment methods aimed at mitigating the global energy crisis.

Mqoni, Ntebogeng [North-West University (Mafikeng ↗
DOE OSTI2015

Structure and Dynamics of NaCl Ion Pairing in Solutions of Water and Methanol

Ion pairing can have profound effects upon the ionic strength of electrolyte solutions but is poorly understood in solutions containing more than one solvent. In this paper, a combined density functional theory and molecular dynamics approach is used to examine the effect of both methanol concentration and interionic distance upon the structure and dynamics within successive solvation shells of Na + and Cl – in water/methanol binary solutions. The structure and dynamics of the first and second solvation shells were studied along a reaction coordinate associated with ion pair formation using potential of mean force simulations. The lifetimes of the solvent–solvent hydrogen bonds become perturbed when the second solvation shells of the ions begin to interact. In contrast, the structural properties within the first and second solvation shells of the ions were found to be largely independent of both methanol concentration and interionic distance until a contact ion pair is formed. Thus, as the ions are brought together, the effect of the opposing ion manifests itself in the solvation dynamics before any structural changes are observed. Lastly, as anticipated based upon the decreased dielectric constant of the binary solution, ion pair formation becomes energetically more favorable as the concentration of methanol increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

Effect of Bearing Cleaning on Long Term Bearing Life

For many years chlorofluorocarbon (CFC ) based solvents, such as Freon and 1,1,1, Trichloroethane (TCA), were used as bearing cleaning solvents for space mechanisms. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change to new ODC-free cleaners for the precision bearing cleaning. With this change the question arises what effect if any do these new cleaners have on long term bearing life. The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0* 10(exp -6) torr) at a temperature of 90C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition the bearings were visually examined and analyzed using an optical microscope.

Jett, Timothy Raymond↗
DOE OSTI2023

Solvent Phase Optimizations Improve Correlations with Experimental Stability Constants for Aqueous Lanthanide Complexes

Stability constants provide insight into ion complexation in water. While computational studies have been shown to model the energy of the complexation successfully using a thermodynamic cycle approach, it does not extend to calculating the stability constants for 1:1 lanthanide to ligand complexes in solution. Using B3LYP and 6-31+G* Pople basis with small core effective core potential (ECP) on the lanthanum ion, and a solvent model based on the full solute electron density (SMD) solvation model we computed and compared with previously published stability constants of the ligands: acetate, acetohydroximate, acetylacetonate, methanoate, tropolonate, hydroxide, catecholate, malonate, oxalate, phthalate, and sulfate. The best R 2 values for the thermodynamic cycle can only be determined by separating the mono and divalent ions to achieve an R 2 value of 0.86 and 0.74 for mono and divalent ions, respectively. We show that by optimizing the lanthanide-ligand structures in implicit solvent, we achieve an improved correlation between experimental and computed stability constants of R 2 value of 0.89 for the combined mono and divalent ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Stochastic interactions of two Brownian hard spheres in the presence of depletants

A quantitative analysis is presented for the stochastic interactions of a pair of Brownian hard spheres in non-adsorbing polymer solutions. The hard spheres are hypothetically trapped by optical tweezers and allowed for random motion near the trapped positions. The investigation focuses on the long-time correlated Brownian motion. The mobility tensor altered by the polymer depletion effect is computed by the boundary integral method, and the corresponding random displacement is determined by the fluctuation-dissipation theorem. From our computations it follows that the presence of depletion layers around the hard spheres has a significant effect on the hydrodynamic interactions and particle dynamics as compared to pure solvent and uniform polymer solution cases. The probability distribution functions of random walks of the two interacting hard spheres that are trapped clearly shift due to the polymer depletion effect. The results show that the reduction of the viscosity in the depletion layers around the spheres and the entropic force due to the overlapping of depletion zones have a significant influence on the correlated Brownian interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Effect of Bearing Cleaning on Long Term Bearing Life

For many years chlorofluorocarbon (CFC) based solvents, such as CFC-113 and 1,1,1, trichloroethane (TCA), were used as bearing cleaning solvents for space mechanism bearings. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change requiring the use of ODC-free cleaners for precision bearing cleaning. With this change the question arises; what effect if any do these new cleaners have on long term bearing life? The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0 x 10(exp -6) torr) at a temperature of 90 C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing, the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition, the bearings were visually examined and analyzed using an optical microscope.

Jett, Tim↗
NASA NTRS2013

Dimmable Electronic Ballast for a Gas Discharge Lamp

Titanium dioxide (TiO2) is the most efficient photocatalyst for organic oxidative degradation. TiO2 is effective not only in aqueous solution, but also in nonaqueous solvents and in the gas phase. It is photostable, biologically and chemically inert, and non-toxic. Low-energy UV light (approximately 375 nm, UV-A) can be used to photoactivate TiO2. TiO2 photocatalysis has been used to mineralize most types of organic compounds. Also, TiO2 photocatalysis has been effectively used in sterilization. This effectiveness has been demonstrated by its aggressive destruction of microorganisms, and aggressive oxidation effects of toxins. It also has been used for the oxidation of carbon monoxide to carbon dioxide, and ammonia to nitrogen. Despite having many attractive features, advanced photocatalytic oxidation processes have not been effectively used for air cleaning. One of the limitations of the traditional photocatalytic systems is the ballast that powers (lights) the bulbs. Almost all commercial off-the-shelf (COTS) ballasts are not dimmable and do not contain safety features. COTS ballasts light the UV lamp as bright as the bulb can be lit, and this results in shorter bulb lifetime and maximal power consumption. COTS magnetic ballasts are bulky, heavy, and inefficient. Several iterations of dimmable electronic ballasts have been developed. Some manifestations have safety features such as broken-bulb or over-temperature warnings, replace-bulb alert, logbulb operational hours, etc. Several electronic ballast boards capable of independently lighting and controlling (dimming) four fluorescent (UV light) bulbs were designed, fabricated, and tested. Because of the variation in the market bulb parameters, the ballast boards were designed with a very broad range output. The ballast boards can measure and control the current (power) for each channel.

Raducanu, Marius↗
DOE OSTI2018

Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush

The effects of added salt on a planar dipolar polymer brush immersed in a polar solvent are studied using a field theoretic approach. The field theory developed in this work provides a unified framework for capturing effects of the inhomogeneous dielectric function, translational entropy of ions, crowding due to finite sized ions, ionic size asymmetry, and ion solvation. In this paper, we use the theory to study the effects of ion sizes, their concentration, and ion-solvation on the polymer segment density profiles of a dipolar brush immersed in a solution containing symmetric salt ions. The interplay of crowding effects, translational entropy, and ion solvation is shown to exhibit either an increase or decrease in the brush height. Translational entropy and crowding effects due to finite sizes of the ions tend to cause expansion of the brush as well as uniform distribution of the ions. By contrast, ion-solvation effects, which tend to be stronger for smaller ions, are shown to cause shrinkage of the brush and inhomogeneous distribution of the ions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries

Functional electrolyte is the key to stabilizing the highly reductive lithium (Li) metal anode (LMA) and high voltage cathode for long life, high energy-density rechargeable Li metal batteries (LMBs). However, fundamental knowledge of the interaction principles between reactive electrodes and electrolytes is still limited. Recently localized high-concentration electrolytes (LHCEs) are emerging as promising electrolyte design strategies for LMBs. They can also serve as an ideal platform for understanding the reactivity characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. Here, we study the effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate and ether) in high voltage LMBs. Varied electrode stabilities exhibited in different LHCEs indicate the intricate synergies between the salt and the solvent on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.

Solvation sheath, salt-solvent complex, electrode/↗