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At least 235 records · Page 13

Solidification of II-VI Compounds in a Rotating Magnetic Field

This project is aimed at using a rotating magnetic field (RMF) to control fluid flow and transport during directional solidification of elemental and compound melts. Microgravity experiments have demonstrated that small amounts of residual acceleration of less than a micro-g can initiate and prolong fluid flow, particularly when there is a static component of the field perpendicular to the liquid solid interface. Thus a true diffusion boundary layer is not formed, and it becomes difficult to verify theories of solidification or to achieve diffusion controlled solidification. The RMF superimposes a stirring effect on an electrically conducting liquid, and with appropriate field strengths and frequencies, controlled transport of material through a liquid column can be obtained. As diffusion conditions are precluded and complete mixing conditions prevail, the technique is appropriate for traveling solvent zone or float zone growth methods in which the overall composition of the liquid can be maintained throughout the growth experiment. Crystals grown by RMF techniques in microgravity in previous, unrelated missions have shown exceptional properties. The objective of the project is two-fold, namely (1) using numerical modeling to simulate the behavior of a solvent zone with applied thermal boundary conditions and demonstrate the effects of decreasing gravity levels, or an increasing applied RMF, or both, and (2) to grow elements and II-VI compounds from traveling solvent zones both with and without applied RMFs, and to determine objectively how well the modeling predicts solidification parameters. Numerical modeling has demonstrated that, in the growth of CdTe from a tellurium solution, a rotating magnetic field can advantageously modify the shape of the liquid solid interface such that the interface is convex as seen from the liquid. Under such circumstances, the defect structure is reduced as any defects which are formed tend to grow out and not propagate. The flow of liquid, however, is complex due to the competing flow induced by the rotating magnetic field and the buoyancy driven convection. When the acceleration forces are reduced to one thousandth of gravity, the flow pattern is much simplified and well controlled material transport through the solvent zone can be readily achieved. Triple axis diffractometry and x-ray synchrotron topography have demonstrated that there is no significant improvement in crystal quality for HgCdTe grown on earth from a tellurium solution when a rotating magnetic field is applied. However, modeling shows that the flow in microgravity with a rotating magnetic field would produce a superior product.

Gillies, D. C.↗

Effects of Aqueous Solutions on the Slow Crack Growth of Soda-Lime-Silicate Glass

The slow crack growth (SCG) parameters of soda-lime-silicate were measured in distilled and saltwater of various concentrations in order to determine if the presence of salt and the contaminate formation of a weak sodium film affects stress corrosion susceptibility. Past research indicates that solvents affect the rate of crack growth; however, the effects of salt have not been studied. The results indicate a small but statistically significant effect on the SCG parameters A and n at high concentrations; however, for typical engineering purposes, the effect can be ignored.

salt↗

Screening green solvents for multilayer plastic film recycling processes

Multilayer (ML) plastic films are essential packaging materials that help protect products from diverse external factors; however, only 5% of all ML films are recycled in the United States. Solvent-based technologies are a promising alternative for recycling ML films because they enable recovery of constituent polymer resins. For example, the Solvent Targeted Recovery and Precipitation (STRAPTM) process sequentially dissolves and separates polymer components using a series of targeted solvent washes. A crucial design aspect of this process is the impact of selected solvents on human health and on the environment. Here, this work introduces a computational framework that integrates molecular modeling, process modeling, techno-economic analysis (TEA), and life-cycle analysis (LCA) to quickly screen green solvents for solvent-based ML recycling processes. Initial screening for solvents based on selectivity is performed by estimating temperature-dependent solubilities using molecular-scale models. Subsequent screening uses basic estimates of energy use and octanol-water partition coefficients (logP) as key measures of health, safety, and environmental hazards. Detailed process modeling, TEA, and LCA are used on a reduced set of promising solvents identified in early screening steps to more accurately determine how solvent selection and associated operating conditions impact overall economics and environmental impacts. The framework is used for the identification of green solvents (from a database of 1,000 solvents) that separate an industrial ML film composed of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET). Our analysis shows the effectiveness of the framework and reveals fundamental trade-offs between solvent greenness, solubility, and economics. Our work emphasizes the importance of taking a holistic systems view during solvent design and aims to inform the development of new processes for ML film recycling and the identification of new ML films that are easier to recycle.

economics↗

A Universal Model of Cation Effects in Electrocatalysis

Electrolyte cations are conventionally viewed as inert spectators in electrocatalysis. However, a wealth of observations show that catalytic rates are often highly sensitive to cation identity. Despite their prevalence, these cation effects have resisted a unified mechanistic explanation, with different physical phenomena implicated across reaction chemistries, catalyst compositions, and choice of solvent. In this perspective, we describe a general framework for understanding cation effects in electrocatalysis based on electrostatics. We argue that cations influence reaction rates by modifying the strength of the electric field present at the catalyst surface, which alters the energetics of adsorbed intermediates and transition states according to their dipole moments and polarizabilities. The magnitude of this field depends on how cations arrange at the electrode surface, controlled by their size, shape, solvation, and packing efficiency. Cations that can arrange more densely result in a steeper potential drop at the electrode surface and consequently a stronger electric field. Our model further identifies two criteria for observing cation effects: (1) the operating potential must be negative of the electrode’s potential of zero total charge, ensuring that cations accumulate at the interface, and (2) the energetics of the kinetically relevant elementary step must be field sensitive. This framework reconciles previously inconsistent trends, including why cation effects appear only for some catalysts, why reaction selectivity is sensitive to cation identity, and why activity can increase with cation size on certain metals but decrease on others. Supported by kinetic measurements, spectroscopy, and atomistic simulations, the model provides both conceptual value for building intuition about catalysis at charged interfaces and predictive value for anticipating trends for new reactions, catalysts, and electrolytes. We conclude by highlighting the importance of electric fields across electrochemical, thermochemical, and biological catalysis and propose that considering the electrostatic environment around active sites offers new opportunities for improving activity and selectivity.

cation effects↗

Chiral Electrokinetic Phenomena in Single Nanopores

Abstract The arrangement of solvent molecules and ions at solid–liquid interfaces determines electrochemical properties that are important in separations platforms, sensing technologies, and energy‐storage systems. Here we show that single glass and polymer pores in contact with propylene carbonate (PC) solutions of LiClO 4 exhibit an effective surface potential that is modulated by the enantiomeric excess of the solvent. In particular, electrochemical and electrokinetic measurements of ionic transport through glass pipettes and polymer pores reveal that the effective surface potential is significantly lower in solutions prepared using enantiomerically pure PC than in solutions prepared using racemic PC. Both pore systems became positively charged in all racemic solutions examined in the range of LiClO 4 concentrations between 1 mM and 100 mM, whereas solutions in ( R )‐(+)‐PC induced a positive surface potential only at concentrations above ~5 mM. The effective surface potential is quantified through asymmetry in current–voltage curves and zeta‐potential measurements. Vibrational sum‐frequency‐generation experiments on LiClO 4 solutions in racemic and enantiomerically pure PC indicate that the surface lipid‐bilayer‐like region in the former is more strongly organized than in the latter, dictating the favorable positions for lithium and perchlorate ions in each case. The more ordered molecular packing in the racemic liquid leads to accumulation of lithium ions on the outside of the bilayer, creating a higher effective positive charge. Our results highlight the extreme sensitivity of the interfacial potential on molecular organization of the solvent, and the relatively unexplored role that chirality can play in electrokinetic phenomena.

Alanis, Kristen↗

Harnessing Redox-Active Molecules in Alkylammonium Halide-Based Eutectic Solvents for Redox Flow Batteries

Redox flow batteries (RFBs) are promising for large-scale energy storage, however, advancements in performance and cost-effectiveness are critical factors for adoption. Here we report on alkylammonium halide based eutectic solvents (ESs) and found that a ESs comprising of diethylammonium chloride or bromide, in ethylene glycol demonstrated exceptional stability and a wide electrochemical stability window, making it a promising candidate for RFB applications. The electrochemical stability and redox behavior of the alkylammonium halide-based ESs are significantly influenced by hydrogen-bonding interactions, modulated by the alkyl chain length of the cation and the nature of the anion. A redox-active eutectic electrolyte containing 0.45 M methyl viologen dichloride (MV 2+ ) paired with acetylferrocene exhibited reversible redox behavior with a maximum open-circuit voltage of ∼1.34 V. The first redox couple, representing the viologen dication to radical cation transition, exhibited remarkable stability with consistent performance, achieving an energy efficiency near 70% at charge-discharge current densities of 10 mA cm −2 over 160 cycles with about 3% loss of the initial capacity. This study highlights the potential of alkylammonium halide DES systems for implementing eutectic-based RFB technologies in the future.

25 ENERGY STORAGE↗

Membrane-based solvent extraction for the recovery of rare earths from phosphate mining process streams

This study reports on the capture of rare earth elements (REEs) from phosphate industry process streams, including phosphoric acid (PA) sludge and phosphogypsum (PG), using a membrane solvent extraction (MSX) process. While MSX has been proven effective for a relatively concentrated feed, its effectiveness for dilute REEs solutions remains unexplored. Investigated PA-sludge and PG particles contain total REEs concentrations of ∼1100 and ∼320 ppm, respectively. Acid leaching, implemented to dissolve the REEs, significantly dilutes the REEs concentration to ∼210 ppm for PA-sludge leachate and ∼60 ppm for PG leachate. These low concentrations, compounded by the higher levels of non-REE ions and radioactive species, uranium (U) and thorium (Th), poses challenges to the MSX process. Here, we demonstrated that N,N,N′,N′-tetraoctyl-diglycolamide (TODGA) selectively binds REEs from a >3 M nitric-acid leachate while effectively rejecting U and Th. Concentrations of light REEs in strip solution were doubled compared to the feed, while heavy REEs were preferentially extracted. Furthermore, >99% purity gypsum, free of U and Th, was precipitated during the acid leaching process, aiding separation by removing significant amounts of non-REEs species (e.g., calcium) prior to the MSX process. Molecular simulations support the experimental data, suggesting preferential separation of heavy over light REEs. Based on these results, a cost-effective integrated process including pretreatment, acid leaching, MSX, and wastewater treatment is proposed for the co-recovery of REEs, phosphoric acid, gypsum, and U. This study shows MSX as a technically and economically feasible process for the recovery of REEs from low-concentration process streams, offering advantages over conventional solvent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy-efficient carbon capture from industrial point sources via commercially available green solvent and hollow fiber membrane contactors

Solvent-based absorption systems have emerged in the carbon capture space due to their high absorption capacities, reusability, and favorable energy requirements. Using diethyl sebacate as a solvent for pre- and post-combustion carbon capture has advantages over other solvents, including high hydrophobicity, low viscosity, low vapor pressure, high CO 2 solubility, high CO 2 selectivity, and being commercially available in large quantities. Despite these advantageous properties, the use of diethyl sebacate as a solvent for post-combustion carbon capture has not been studied in detail. To examine the capability of diethyl sebacate, a scalable, energy-efficient, hollow fiber membrane (microporous polypropylene and polyvinylidene fluoride) contactor (HFMC)-based process with low-cost and high surface area is investigated. A purity of 95.3 % CO 2 with 46 % recovery in one absorption stage was achieved, with a permeate flux over one magnitude greater than using a deep eutectic solvent in the same system. Technoeconomic analysis determined a ∼ 0.8 GJ per ton of CO 2 at a processing cost of ∼$93 per ton of CO 2 . Results from this work underscore the potential for utilizing green solvents in HFMC-based separation processes for effective carbon capture and provide a pathway towards practical deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing the performance of solvent-borne poly(ethyl methacrylate) coatings for high-power laser applications via low-temperature drying

Organic polymers are a versatile class of materials employed in a broad range of optical coating applications. However, their use as coatings in high-power laser applications, particularly in the UV spectral region, has been limited in scope due to their relatively low laser-induced damage thresholds (LIDTs), which decrease further with exposure to multiple pulses. This study explores the effect of post-deposition drying temperature and residual solvent on the LIDT of solvent-borne polymer coatings. In this work, poly(ethyl methacrylate) (PEMA) coatings were deposited by first spin coating solutions of PEMA (dissolved in 2,2,2-trichloroethanol (TCE)) onto fused silica substrates, then baking at temperatures of either 130°C (soft-bake) or 180°C (hard-bake). Analysis of the two coatings revealed that the soft-bake coating retained a significant amount of TCE within the polymer matrix, which functioned to plasticize the coating and reduce internal stress. The laser-induced damage resistance of the two coatings was evaluated using 351-nm, 1-ns laser pulses. The testing protocols included single-pulse (1-on-1), 1-pulse ramp (R-on-1), and a 1000-pulse ramp (1000R-on-1) test. The results showed that the plasticized, soft-bake coating exhibits a significantly increased LIDT, especially for multipulse irradiation conditions.

36 MATERIALS SCIENCE↗

Equally high efficiencies of organic solar cells processed from different solvents reveal key factors for morphology control

The power conversion efficiency of organic solar cells (OSCs) is exceeding 20%, an advance in which morphology optimization has played a significant role. It is generally accepted that the processing solvent (or solvent mixture) can help optimize morphology, impacting the OSC efficiency. Here we develop OSCs that show strong tolerance to a range of processing solvents, with all devices delivering high power conversion efficiencies around 19%. By investigating the solution states, the film formation dynamics and the characteristics of the processed films both experimentally and computationally, we identify the key factors that control morphology, that is, the interactions between the side chains of the acceptor materials and the solvent as well as the interactions between the donor and acceptor materials. Our work provides new understanding on the long-standing question of morphology control and effective guides to design OSC materials towards practical applications, where green solvents are required for large-scale processing.

14 SOLAR ENERGY↗

Transient Covalent Polymers through Carbodiimide‐Driven Assembly

Biochemical systems make use of out-of-equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of hours to weeks. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, temperature, pyridine concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine-tuned kinetic control in nonequilibrium polymerization systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pathways for Nucleation and Growth in Confined Spaces and at Interfaces

Mineral crystallization is central to myriad natural processes from the formation of snowflakes to stalagmites, but the molecular-scale mechanisms are often far more complex than models reflect. Feedbacks between the hydro-, bio-, and geo-spheres drive complex crystallization processes that challenge our ability to observe and quantify them, motivating an expansion of crystallization theories. Here, in this article, we discuss how the driving forces and timescales of nucleation are influenced by factors ranging from simple geometric confinement to distinct interfacial solution structures involving solvent organization, electrical double layers, and surface charging effects. Taken together, these ubiquitous natural phenomena can preserve metastable intermediates, drive precipitation of undersaturated phases, and modulate crystallization in time and space.

biosphere↗

Replacing Chlorinated-Solvent-Based Cleaners And Adhesives

Brief report describes tests conducted to assess feasibility of using selected chemicals as replacements for selected cleaners, primers, and adhesives containing chlorinated solvents. Cleaners, primers, and adhesives in question used in bonding insulating material in steel cases of solid-fuel rocket motors. Necessary to phase out use of chlorinated solvents because of concerns over toxicity and adverse effects on ozone layer in upper atmosphere.

Heaton, Harley↗

Colloids in Microgravity

Colloidal particles are important in a broad range of applications in technology and materials processing. Due to high sensitivity to thermal fluctuations, a suspension of colloidal particles is considered as an assembly of super-atoms in condensed matter physics. This feature provides an excellent experimental model in statistical mechanics for fundamental studies of microstructural evolution and phase transformation at the individual particle level. However, using colloids to probe three-dimensional phase transitions on Earth remains a challenge as they can be influenced by the gravity force causing the particles to sediment and the solvent to flow. To suppress the undesirable gravity effects, experiments on concentrated colloids were carried out in the International Space Station (ISS) Light Microscopy Module. We will present results of these experiments.

Colloids↗

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.↗

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↗

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 ↗

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↗