Search NASA⌕ Search

SEARCH · Search NASA

Results for “solvent effect”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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

At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Charge transfer states impact the triplet pair dynamics of singlet fission polymers

Polymers are desirable optoelectronic materials, stemming from their solution processability, tunable electronic properties, and large absorption coefficients. An exciting development is the recent discovery that singlet fission (SF), the conversion of a singlet exciton to a pair of triplet states, can occur along the backbone of an individual conjugated polymer chain. Here, compared to other intramolecular SF compounds, the nature of the triplet pair state in SF polymers remains poorly understood, hampering the development of new materials with optimized excited state dynamics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Manipulating meso-scale solvent structure from Pd nanoparticle deposits in deep eutectic solvents

Deep Eutectic Solvents (DESs) are complex solutions that present unique challenges compared to traditional electrolytes. Unlike most electrolytes and ionic liquids, DESs have delicate hydrogen bond networks that are responsible for their highly sensitive compositional dependence on the melting point. Prior work has demonstrated unique nanoscale structure both experimentally and theoretically that brings both challenges and opportunities to their adoption in traditional electrochemical processes. In this study, we use in-situ sample-rotated ultra-small angle X-ray scattering to resolve the near-interface solvent structure after electrodepositing Pd nanoparticles onto a glassy carbon electrode in choline chloride:urea and choline chloride:ethylene glycol DESs. Our results indicate that solvent structure can be observed on the meso-scale in the choline chloride:urea and choline chloride:ethylene glycol systems. Importantly, this extended solvent structure peaks at -0.5 V (vs. Ag/AgCl) and decreases slightly with higher overpotentials during Pd electrodeposition. Experimentally, the nature of this structure is more pronounced in the ethylene glycol system, as evidenced by both the X-ray scattering as well as the electrochemical impedance spectroscopy (EIS). Here, molecular dynamics simulations and dipolar orientation analysis reveal that chloride delocalization near the Pd interface and long-range interactions between the choline and each hydrogen bond donor are very different and qualitatively consistent with the experimental data. These results show how the long-range solvent-deposit interactions can be tuned by changing the hydrogen bond donor in the DES and the applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solvation of furfural at metal–water interfaces: Implications for aqueous phase hydrogenation reactions

Metal–water interfaces are central to understanding aqueous-phase heterogeneous catalytic processes. However, the explicit modeling of the interface is still challenging as it necessitates extensive sampling of the interfaces’ degrees of freedom. Herein, we use ab initio molecular dynamics (AIMD) simulations to study the adsorption of furfural, a platform biomass chemical on several catalytically relevant metal–water interfaces (Pt, Rh, Pd, Cu, and Au) at low coverages. We find that furfural adsorption is destabilized on all the metal–water interfaces compared to the metal–gas interfaces considered in this work. This destabilization is a result of the energetic penalty associated with the displacement of water molecules near the surface upon adsorption of furfural, further evidenced by a linear correlation between solvation energy and the change in surface water coverage. To predict solvation energies without the need for computationally expensive AIMD simulations, we demonstrate OH binding energy as a good descriptor to estimate the solvation energies of furfural. Using microkinetic modeling, we further explain the origin of the activity for furfural hydrogenation on intrinsically strong-binding metals under aqueous conditions, i.e., the endothermic solvation energies for furfural adsorption prevent surface poisoning. In conclusion, our work sheds light on the development of active aqueous-phase catalytic systems via rationally tuning the solvation energies of reaction intermediates.

aqueous-phase hydrogenation↗
DOE OSTI2025

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗
DOE OSTI2023

Review—Effects of Solution and Alloy Composition on Critical Crevice Temperature

Critical temperature for localized corrosion can be a good design parameter because localized corrosion is not likely to occur below that temperature. The critical temperature depends on alloy composition, microstructure, and environment chemistry (including its redox potential). This paper reviews the literature on critical temperature for localized corrosion, expressed either as Critical Pitting Temperature (CPT) or Critical Crevice Temperature (CCT). A history of various testing methods is presented. Different approaches for modeling the temperature of transition to active pit growth are reviewed, including probabilistic aspects of critical temperature. A semi-empirical, electrolyte-based, model is described that can be useful in predicting CCT in service environments that differ from standard laboratory test environments. The model predictions are compared to experimental data for various alloys. The effect of solvent on CCT/CPT is described briefly and future avenues of research are recommended.

02 PETROLEUM↗
DOE OSTI2017

Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity

The effects of solvents, salts, electrolyte additives and surface coatings on LiNi 0.4 Mn 0.4 Co 0.2 O 2 (NMC442) or LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) have been probed using positive electrode Li-ion symmetric cells coupled with dV/dQ analysis. A robust symmetric cell design is presented which prevents hardware corrosion for over at least 800 hours of testing to 4.5 V vs. Li/Li + at 40°C. Positive electrode symmetric cells using uncoated positive electrode materials and 1M LiPF 6 EC:EMC 3:7 or 1M LiPF 6 EMC electrolyte rapidly developed high impedance and showed poor capacity retention. However, if 1% pyridine boron trifluoride (PBF) was added to these electrolytes, cell performance was dramatically improved. Replacing LiPF 6 by LiBF 4 in the electrolytes above, with or without PBF, yielded positive electrode symmetric cells with good capacity retention. Two types of surface coatings were explored on NMC622 positive electrodes. Cells using surface-coated positive electrodes demonstrated better capacity retention for all electrolytes compared to cells without surface coatings. Finally, this work can be used as a guide by those attempting to find electrolyte/electrode pairs suitable for use in NMC/graphite cells that can operate with long lifetime to 4.5 V.

25 ENERGY STORAGE↗
DOE OSTI2019

Thermodynamic Cycles Relevant to Hydrogenation of CO 2 to Formic Acid in Water and Acetonitrile

The formation of formic 1 acid via the reduction (hydrogenation or electrochemical methods) of carbon dioxide (CO 2 ) has been receiving great attention, not only in the context of the production of renewable fuels or synthons, but also since it is a convenient carrier of hydrogen gas in the form of a liquid at ambient conditions. In this study, in order to help elucidate the effect of solvent on the thermodynamic parameters for the hydrogenation of CO 2 in water and acetonitrile, the acidity constant for formic acid in acetonitrile was determined experimentally, for the first time, to be 20.7 ± 0.2 at 25 °C, and, additionally, the standard Gibbs energy changes for the transfers of formic acid and formate anion from water to acetonitrile were established.

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

A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-Column Heat Transfer (Final Report)

This report summarizes the work conducted on project DE-FE0031604 where University of Kentucky Center for Applied Energy (UK CAER) has validated its intensified CO 2 capture process through substantial enhancements to the kinetics of the absorption process and energy reductions by absorber temperature profile modification, dewatering and heat integration technologies for achieving significant capital and operating cost reductions. To address DOE’s objective of improving post-combustion CO 2 capture technology and reducing associated cost, UK CAER employed an intensified process which combined three key aspects targeted at overcoming inherent limitations or barriers in the conventional CO 2 capture and desorption process. The process designed to be independent of the type of solvent used, included (1) the use of 3-D printed two-channel structured packing material to control the temperature profile and increase the CO 2 absorption rate in the absorber, (2) a zeolite membrane dewatering unit for dewatering of the carbon-rich solvent to decouple solvent concentration needs for CO 2 absorption and desorption, and (3) a rich-split feed with two-phase flow heat transfer prior to the stripper that provided a secondary point of vapor generation to provide energy savings in steam extraction and solvent regeneration. The project was executed over two budget periods. This involved testing of individual process components which included the advanced heat transfer packing and the dewatering membrane on UK CAER’s 30 liter per minute (L/min) CO 2 (3” Column) capture bench unit with simulated flue gas in the first budget period. Subsequent scaled-up testing of these components together with the split-feed configuration were also tested in UK CAER’s 0.1 MWth CO 2 capture unit with coal-derived flue gas in the second-budget period. Long term studies were done during this period to assess process and solvent performance over extended duration. Project partners Lawrence Livermore National Laboratory (LLNL) and Media & Process Technology (MPT) led the development efforts for the advanced packing material and dewatering membrane respectively. Data from the long term testing was used as input for an environmental, health and safety (EH&S) assessment for the process and scaled technology performed by ALL4 LLC. Trimeric Corporation also completed a techno-economic analysis (TEA) for the UK CAER technology which was compared to the DOE reference Case B12B. Tests on the 3” column capture unit showed that the advanced heat transfer packing could be used to lower the bulge temperature in the absorber, and this was also proven in the scaled testing in the 0.1 MWth CO 2 capture unit. The bulge temperature could be lowered by >10 °C, changing the temperature profile in the absorber, and showed potential to enhance absorption with the ability to tailor the profile to provide conditions suitable for a solvent’s properties and kinetics. Conditions for short term evaluation of a 19” zeolite dewatering membrane on the 3” column capture unit yielded desirable fluxes and sustained rejection rates of >80%. However, for the scaled testing of six membrane modules consisting of 21 parts of 31-inch-long membrane tubes in each bundle (surface area 0.3 m 2 ), over a more extended duration, similar rejection rates could not be achieved. With the split-feed of the rich stream to the stripper, improved heat recovery minimized waste heat exiting the top of the stripper. The stripper exhaust temperatures could be reduced by >10 °C; reducing the amount of water vaporization contributed to lowering the regeneration energy by ~ 15%. The energy benefit could be sustained from the long term monitoring of the solvent performance. The solvent properties were not significantly impacted over the long-term operations. The benefits of the UK CAER process demonstrated experimentally were mostly validated from the TEA comparing a commercial scale application of the technology to DOE reference Case B12B. The cost of CO 2 capture for the UK CAER technology was estimated to be ~$34.97/tonne of CO 2 captured; a reduction of 23% compared to Case B12B. The increase in cost of electricity was also shown to be 16% lower than that of Case B12B. The total parasitic demand was also shown to be 11% lower. The key drivers for the benefits are a result of the process intensification approaches employed in the UK CAER technology for enhanced solvent performance, effective heat recovery and improved energy performance. The EH&S assessment did not find any major environmental concerns or barriers to the full scale implementation of the technology.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2019

Stabilizing Li-rich NMC Materials by Using Precursor Salts with Acetate and Nitrate Anions for Li-ion Batteries

Lithium-rich layered oxide cathode materials of Li 1.2 Mn 0.5100 Ni 0.2175 Co 0.0725 O 2 have been synthesized using metal salts with acetate and nitrate anions as precursors in glycerol solvent. The effects of the precursor metal salts on particle size, morphology, cationic ordering, and ultimately, the electrode performance of the cathode powders have been studied. It was demonstrated that the use of cornstarch as a gelling agent with nitrate-based metal salts results in a reduction of particle size, leading to higher surface area and initial discharge capacity. However, the cornstarch gelling effect was minimized when acetate salts were used. As observed in the Fourier-transform infrared spectroscopy analysis, cornstarch can react with acetates to form acetyl groups during the synthesis, effectively preventing the cornstarch gel from capping the particles, thus leading to larger particles. A tradeoff was found when nitrate and acetate salts were mixed in the synthesis. It was shown that the new cathode powder has the best cationic ordering and capacity retention, promising a much stable Li-rich cathode material for lithium-ion batteries.

25 ENERGY STORAGE↗
NASA NTRS1988

Characterization of cobalt(II) chloride-modified condensation polyimide films

The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

Rancourt, J. D.↗
NASA NTRS1990

Freeze drying for morphological control of inter-penetrating polymer networks

The intrinsic brittleness of BMI resins can be reduced through the creation of an interpenetrating network (IPN) of BMI with a reactive-encapped thermoplastic, such as the presently considered polyimidesulfone, PISO2. The PISO2 and BMI were dissolved in a common solvent, which was then removed from the constituents by freeze drying; in an alternative method, an IPN was formed through dissolution of the constituent in a common solvent with either high or low melting point, followed by evaporative removal of the solvent. The effectiveness of the freeze-drying approach for morphological control is evaluated.

Hansen, Marion G.↗
NASA NTRS1995

A new method for the preparation of polymeric porous layer open tubular columns for GC application

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

NASA Discipline Exobiology↗
NASA NTRS2014

Processing and Characterization of Carbon Nanotube Composites

Recent advances in the synthesis of large-scale quantities of carbon nanotubes (CNT) have provided the opportunity to study the mechanical properties of polymer matrix composites using these novel materials as reinforcement. Nanocomp Technologies, Inc. currently supplies large sheets with dimensions up to 122 cm x 244 cm containing both single-wall and few-wall CNTs. The tubes are approximately 1 mm in length with diameters ranging from 8 to 12 nm. In the present study being conducted at NASA Langley Research Center (LaRC), single and multiple layers of CNT sheets were infused or coated with various polymer solutions that included commercial toughened-epoxies and bismaleimides, as well as a LaRC developed polyimide. The resulting CNT composites were tested in tension using a modified version of ASTM D882-12 to determine their strength and modulus values. The effects of solvent treatment and mechanical elongation/alignment of the CNT sheets on the tensile performance of the composite were determined. Thin composites (around 50 wt% CNT) fabricated from acetone condensed and elongated CNT sheets with either a BMI or polyimide resin solution exhibited specific tensile moduli approaching that of toughened epoxy/ IM7 carbon fiber unidirectional composites.

Can, Roberto J.↗
DOE OSTI2016

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. It was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.

CMPO↗