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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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Spore recovery form cured silicone potting compounds using amine solvents to degrade the cured polymers was investigated. A complete list of solvents and a description of the effect of each on two different silicone polymers is provided.
Study suggests carbonated water can dissolve or suspend coal and carry it to surface. Mixture of carbon dioxide and water may be coal solvent that will make unmanned mining reality. When used with proposed process monitoring coal solubility with conventional strain gage, solvent is basis for rapid cost effective extraction of coal from underground seams.
The general equations which describe the electrophoretic transport of components in solution are restated using Newman's general concept of mobilities. A concise derivation of the moving boundary equation and the regulating function from the continuity equation is presented. Various other regulating principles across moving and stationary boundaries are also discussed, which permits a review of the features and interrelationships of the electrophoretic models based on electromigration only. The effect of considering an interactive (dissociating) solvent on the mathematical treatment is discussed.
Since the 1990's, when the Class I Ozone Depleting Substance (ODS) chlorofluorocarbon-113 (CFC-113) was banned, NASA's rocket propulsion test facilities at Marshall Space Flight Center (MSFC) and Stennis Space Center (SSC) have relied upon hydrochlorofluorocarbon-225 (HCFC-225) to safely clean and verify the cleanliness of large scale propulsion oxygen systems. Effective January 1, 2015, the production, import, export, and new use of HCFC-225, a Class II ODS, was prohibited by the Clean Air Act. In 2012 through 2014, leveraging resources from both the NASA Rocket Propulsion Test Program and the Defense Logistics Agency - Aviation Hazardous Minimization and Green Products Branch, test labs at MSFC, SSC, and Johnson Space Center's White Sands Test Facility (WSTF) collaborated to seek out, test, and qualify a replacement for HCFC-225 that is both an effective cleaner and safe for use with oxygen systems. Candidate solvents were selected and a test plan was developed following the guidelines of ASTM G127, Standard Guide for the Selection of Cleaning Agents for Oxygen Systems. Solvents were evaluated for materials compatibility, oxygen compatibility, cleaning effectiveness, and suitability for use in cleanliness verification and field cleaning operations. Two solvents were determined to be acceptable for cleaning oxygen systems and one was chosen for implementation at NASA's rocket propulsion test facilities. The test program and results are summarized. This project also demonstrated the benefits of cross-agency collaboration in a time of limited resources.
Selective catalytic hydrogenolysis of polyolefins is a promising route to convert plastic waste into valuable liquid products, such as lubricants, waxes, and surfactants. However, the high viscosity of polymer melts imposes mass transfer limitations on this reaction. Solvents can mitigate these challenges, but their effects on reaction kinetics and product selectivity remain underexplored. Here, we systematically explore the effects of small n-alkanes and cycloalkanes on the hydrogenolysis of polyethylene and polypropylene over a Ru/TiO 2 catalyst. Using kinetic measurements and isotopic labeling, we show that n-octane at high mass fractions alters the mechanism from direct hydrogenation to solvent-mediated hydrogen transfer, reducing the rate of C–C bond cleavage. Longer alkanes further inhibit reactivity due to stronger surface binding. 1,4-Dimethylcyclohexane suppresses methane formation, favoring heavier products, while decalin likely forms surface-bound aromatics that poison the catalyst. Overall, alkane solvents modulate product selectivity and reduce the yield of methane byproduct, allowing for ∼35–40% selectivity to valuable C 20 -C 30 alkane products. This work highlights the complex impact of polymer–alkane mixtures on hydrogenolysis kinetics relevant to the design of commercial-scale plastic waste valorization processes.
The cleanliness of optical surfaces is recognized as an industry-wide concern for the performance of optical devices such as mirrors and telescopes, microscopes and lenses, lasers and interferometers, and prisms and optical filters. However, no standard has been established for optical cleaning and there is no standard definition of a 'clean' optical element. This study evaluates the effectiveness of commonly used optical cleaning techniques based on wafer configuration, contamination levels, and the number and size of removed particles. It is concluded that cleaning method and exposure time play a significant factor in obtaining a high removal percentage. The detergent bath and solvent rinse method displayed an increase in effective removal percentage as the contamination exposure increased. Likewise, CO2 snow cleaning showed a relatively consistent cleaning effectiveness. The results can help ensure mission success to flight projects developed for the NASA Origins Program. Advantages and disadvantages of each of the optical cleaning methods are described.
This study investigates ion-selective Li/Na metal plating behavior in hybrid Li-Na battery systems, revealing the critical role of electrolyte solvents in these processes. Using a hybrid battery design with a LiFePO 4 cathode, Na metal anode, and NaPF 6 -based electrolytes, we observed contrasting effects of carbonate- and ether-based electrolyte solvents. While ether-based electrolytes showed expected Na plating/stripping, carbonate-based electrolytes surprisingly favored a Li-dominant plating/stripping reaction despite the Na-rich environment. X-ray photoelectron spectroscopy revealed that this selectivity is linked to the composition of the solid electrolyte interphase (SEI) layer, with carbonate electrolytes forming Li-based inorganic-rich SEI layers that facilitate Li-ion diffusion while screening Na ions. In conclusion, these findings challenge the conventional understanding of metal plating in multi-ion environments and offer insights for designing future hybrid battery systems.
Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.
The use of surfactants to attract dissolved ions to water surfaces and interfaces is an essential step in both solvent-based and solvent-free separation processes. Here, we have studied the interactions of lanthanide ions in the aqueous subphase with monolayers of dihexadecyl phosphate at air–water interfaces. With heavier lanthanides (atomic number Z ≥ 65) in the subphase, the floating layer can be compressed to an area/molecule of about half the molecular cross section, indicating bilayer formation. X-ray fluorescence and reflectivity data support this conclusion. In the presence of lighter lanthanides (Z < 65), only monolayers are observed. Subphase-concentration-dependent studies using Er 3+ (heavier) and Nd 3+ (lighter) lanthanides show a stepwise progression, with ions attaching to the monolayer only when the solution concentration is >3 × 10 –7 M. Above ~10 –5 M, bilayers form but only in the presence of the heavier lanthanide. Grazing incidence X-ray diffraction shows evidence of lateral ion–ion correlations in the bilayer structure but not in monolayers. Explicit solvent all-atom molecular dynamics simulations confirm the elevated ion–ion correlation in the bilayer system. This bilayer structure isolates heavier lanthanides but not lighter lanthanides from an aqueous solution and is therefore a potential mechanism for the selective separation of heavier lanthanides.
Abstract Despite the generally accepted role of the hydrophobic effect as the driving force for folding, many intrinsically disordered proteins (IDPs), including those with hydrophobic content typical of foldable proteins, behave nearly as self‐avoiding random walks (SARWs) under physiological conditions. Here, we tested how temperature and ionic conditions influence the dimensions of the N‐terminal domain of pertactin (PNt), an IDP with an amino acid composition typical of folded proteins. While PNt contracts somewhat with temperature, it nevertheless remains expanded over 10–58°C, with a Flory exponent, ν , >0.50. Both low and high ionic strength also produce contraction in PNt, but this contraction is mitigated by reducing charge segregation. With 46% glycine and low hydrophobicity, the reduced form of snow flea anti‐freeze protein (red‐sfAFP) is unaffected by temperature and ionic strength and persists as a near‐SARW, ν ~ 0.54, arguing that the thermal contraction of PNt is due to stronger interactions between hydrophobic side chains. Additionally, red‐sfAFP is a proxy for the polypeptide backbone, which has been thought to collapse in water. Increasing the glycine segregation in red‐sfAFP had minimal effect on ν . Water remained a good solvent even with 21 consecutive glycine residues ( ν > 0.5), and red‐sfAFP variants lacked stable backbone hydrogen bonds according to hydrogen exchange. Similarly, changing glycine segregation has little impact on ν in other glycine‐rich proteins. These findings underscore the generality that many disordered states can be expanded and unstructured, and that the hydrophobic effect alone is insufficient to drive significant chain collapse for typical protein sequences.
Accessing the energy density and sustainability of calcium metal batteries requires mastering reversible calcium electrodeposition through electrolyte design. Several electrolytes support reversible, ambient temperature deposition but at utilization and rate too low for practical applications. These challenges stem from solvation structures characterized by either high barriers for cation desolvation or thermodynamic instability, leading to parasitic decomposition of the salt and solvent. The optimal solvation structure for the effective delivery of calcium to the electrode interface is not known. In this work, we show that adding a relatively small amount of a weakly associating calcium salt (calcium carba-closo-dodecaborate) to an otherwise strongly associated solution (calcium borohydride in tetrahydrofuran) produces a surprising population of fully solvent-coordinated Ca2+ cations in the form of solvent-separated ion pairs (SSIPs). We further demonstrate that the formation of these SSIPs beneficially impacts the kinetics and thermodynamics of calcium electrodeposition, revealing the unexpected finding that direct coordination of Ca2+ by the BH4– anion limits the electrodeposition process. These findings reveal how the competition between solvent and anion coordination to Ca2+ affects calcium deposition kinetics and cycling stability, setting the stage for a new calcium electrolyte design based on mixed anion electrolytes.
We report on the effect of the substrate on electrochemical deposition of Cu from deep eutectic solvent ethaline. We investigated the polarization behavior during electrodeposition of Cu on Pt and glassy carbon (GC) from both Cu 2+ and Cu + containing ethaline using cyclic voltammetry (CV). Formation of bulk Cu deposits on both substrates underwent nucleation and growth processes; however, the nucleation was considerably sluggish on GC compared to Pt. While experiments in Cu+ solutions indicated that coalescence of Cu islands on Pt is a slow process and that its surface may not be fully covered by Cu, such determination of Cu coverage could not be made on GC. Cu dissolution is also slower from GC than from Pt. It was observed that CV of Cu deposition on GC is influenced by the surface preparation method. Since ethaline has high chloride concentration, a parallel study in aqueous 3 M NaCl solution was conducted in order to examine the influence of the chloride medium on the electrodeposition process. Lastly, this revealed that electrodeposition in both media occurred in the same manner but with different charge and mass transfer rates caused by the differences in viscosity and chloride concentrations of the two solutions.
Deep eutectic solvents (DESs) are a class of liquids that offer great potential in alleviating some of the challenges present in today's long-term energy storage methods because they have physical properties that are favorable for storable electrolyte solutions. In this work, a series of glycols (ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol) were studied as potential hydrogen bond donors (HBD) with a common choline chloride (ChCl) as the hydrogen bond acceptor (HBA). The solvation dynamics of the prepared systems were studied by measuring the solvent reorganization response using femtosecond transient absorption spectroscopy (fs-TA). Conductivity, viscosity, density, ET(30) polarity, and dynamics of the prepared DESs were analyzed, with a particular interest in determining the effect of HBD chain length on these parameters. Here, classical molecular dynamics simulations were employed to investigate how the local liquid structure, solvent dynamics, and bulk solvent properties vary with changes in glycol chain length.
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.
Microscopic segregation and molecular heterogeneities in complex liquids are the result of the interplay between different intermolecular forces, all of which contribute to the energy landscape of the system. A consequence of the intricate energy landscape is the nontrivial effect on the solvation dynamics. Here, the impact of molecular heterogeneities on the solvation dynamics is studied using infrared spectroscopies and molecular dynamics simulations. In particular, this study focuses on the dynamical effect of nanoscopic heterogeneities present in deep eutectic solvents (DESs) composed of lauric acid (LA) and N-methylacetamide (NMA). To this end, a molecular probe containing a carbon triple bond is used as an infrared reporter. The results show that the vibrational probe is likely to be located in the NMA polar domains. Furthermore, the probe solvation dynamics derived from the 2DIR spectra presents a slowdown of its timescale with increasing LA concentration in the DES. Kubo modeling of the probe solvation dynamics shows a correlation between the amplitude of its long time component and the presence of molecular heterogeneities in the sample. Semiclassical modeling of the vibrational line shape of the triple bond stretch demonstrates that the heterogeneities affect the whole solvation dynamics of the system through the amplitudes of the frequency fluctuations. Molecular dynamics simulations confirm the experimental results and their interpretation by showing a slowdown of the solvation dynamics when the LA heterogeneities are present. Overall, the study presents a molecular framework to explain the effect of confinement created by nanoscopic LA heterogeneities on the solvation dynamics of the system.
The addition of ionic liquids (ILs) to a mixture containing a molecular solvent and other ionic species can induce the heterogeneous redistribution of cations and anions at the gas–liquid interface. This nonuniform redistribution of cations and anions driven by the differences in the solvophilicity of ions can improve the thermophysical and interfacial properties of such mixtures, creating a local chemical environment that is conducive to some reactions. In this work, ILs are added to a mixture of potassium hydroxide (KOH) and ethylene glycol (EG), used as a reactive absorbent and electrolyte in the migration-assisted moisture-gradient (MAMG) process for CO 2 capture. Molecular dynamics (MD) simulations are employed to probe into the effects of complex ion–ion and ion–solvent interactions and to examine the chemical composition at the gas–liquid interface. A total of 12 systems are investigated using molecular simulations to identify trends in the performance of IL additives based on the choice of cation, anion, and IL concentration. The cation effects are studied using IL additives based on 1-ethyl-3-methylimidazolium ([EMIM] + ) and 1-butyl-3-methylimidazolium ([BMIM] + ), while the impact of anions is examined using additives based on dicyanamide [DCA] − , triflate [TfO] − , bistriflimide [NTf 2 ] − , and hexafluorophosphate [PF 6 ] − anions, respectively. The influence of the IL concentration is also evaluated at molar concentrations between 1% and 4%. The simulation results indicate that the use of IL additives can affect the physical CO 2 solubility, surface tension, and the localization of CO 2 around the [OH] − ions at the gas–liquid interface. It is also evident that the choice of cations, anions, and IL concentration determines the extent to which the IL additives impact the local physicochemical properties. Physical dissolution, diffusive transport, and interaction with [OH] − are critical intermediate steps toward reactive CO 2 capture using a liquid absorbent. Hence, the improvement in one or more of these properties, aided by IL additives, is expected to improve the overall CO 2 capture performance. Experiments reaffirmed the impact of IL additives on CO 2 capture performance and the sensitivity to the choice of the cation, anion, and concentration of the IL additive.
Electrolytes are an essential component of all electrochemical storage and conversion devices, such as batteries. In the history of battery development, the complex nature of electrolytes has often been a bottleneck. Fundamental knowledge of electrolyte systems encompasses elucidation of structure-property relationships of the solution species. Recently, nanometric aggregates have been observed in several classes of electrolytes, including super-concentrated, redox-flow, multivalent, polymer, and ionic liquid-based electrolytes. Compared with the well-studied local solvation structures such as contact ion pairs and solvent-separated ions, these aggregates impose unique effects on the ion distribution and transport both within bulk electrolytes and at electrode/electrolyte interfaces. This Perspective highlights the discovery of the aggregates in various battery electrolytes and their impact on electrolyte properties. We also present an outlook for future studies of this emerging field of nanometric aggregates and the need for the development of new experimental and computational tools to study their properties.
Biomass deconstruction is a crucial step in the production of lignocellulosic biofuels and bioproducts. However, identifying and selecting an optimal pretreatment solvent that enhances enzymatic saccharification while being cost-efficient and ensuring sustainability remains a challenge. In this study, we compare the effectiveness of the biocompatible ionic liquid cholinium lysinate ([Ch][Lys]) against the distillable solvent ethanolamine, when used for the pretreatment of mixed bioenergy feedstocks, including poplar, switchgrass, and sorghum. [Ch][Lys] was used at a concentration of 10 % wt. in a one-pot configuration without biomass washing and ethanolamine was used in a concentrated form and removed with a vacuum oven, before performing enzymatic hydrolysis and microbial conversion. Our results show that ethanolamine pretreatment consistently enhances the glucose yield across various biomass types compared to [Ch][Lys], with improvements ranging from 22.0 % to 52.7 %. The highest combined sugar release was observed when the three feedstocks were combined in equal amounts and pretreated with ethanolamine, achieving a glucose yield of 84.6 % and a xylose yield of 76.6 %. Additionally, ethanolamine exhibited exceptional solvent recovery efficiency, with removal efficiencies exceeding 99.8 % at 120 °C across all feedstocks, highlighting its advantage over non-distillable solvents. While both solvents produced biocompatible hydrolysates, the hydrolysates prepared using ethanolamine resulted in higher bioproduct formation. These findings highlight the industrial relevance of selecting recyclable and biocompatible solvents for scalable, sustainable, and cost-effective bioenergy production. This study contributes to the development of economically viable and scalable pretreatment technologies for bioenergy applications using different feedstocks and process configurations.