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At least 145 records · Page 8

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Fielder, W. L.

Enhancement of molecular weight build up in polyimides using ether solvents

Two linear polyimides were prepared in various ether and amide solvents. The inherent viscosity was then monitored as a function of time. The polymers made in the ether solvents consistently gave higher inherent viscosities, and thus molecular weights, than the same polymers made in the amide solvents. This molecular weight buildup is attributed to the unique solvation mechanism of the ether solvents which enhances the basicity of the amines via hydrogen bonding.

Egli, Annemarie H.

Life of Pennzane and 815Z-Lubricated Instrument Bearings Cleaned with Non-CFC Solvents

Life tests were conducted on instrument scanner ball bearings cleaned with 3 types of non-ozone depleting solvents and compared with those cleaned with a conventional CFC-113 (Freon) solvent. The test bearings were lubricated with the standard space oil (Bray 815Z, Fomblin Z25) and a more recent synthetic space oil (Pennzane 2001). Lives with replacement solvents equaled or exceeded those obtained with CFC-113 baseline, indicating that alternate cleaning solvents were acceptable. Pennzane lubricated bearings enjoyed a significant life advantage (>5X) over those lubricated with Bray 815Z oil in these oscillatory gimbal bearing tests. Many of the Pennzane bearings are still exhibiting acceptable torque traces after more than 25,000 hr of test.

Loewenthal, Stuart H.

Reactivities of Precision Cleaning Solvents with Hypergolic Propellants

The reactivities of several selected halogenated precision cleaning solvents with hypergolic propellants has been determined by analysis of the rates of formation of halide ion decomposition products. The solvents were Asahiklin AK 225, Asahiklin AK 225 AES, HFE 7100, HFE 7100 DE, Vertrel XF, Vertrel MCA, Vertrel MCA Plus, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and trans-1,2-dichloroethylene (DCE). The propellants were hydrazine (HZ), monomethylhydrazine (MMH), and mixed oxides of nitrogen (MON-3). The Vertrel solvents showed significant reactivity with HZ. All of the solvents except DCE exhibited significant reactivity with MMH, particularly HFE 7100 DE and CFC-113. HFE 7100 DE, Vertrel MCA, and Vertrel MCA Plus also showed significant reactivity with MON-3 oxidizer.

Davis, Dennis D.

ODC-Free Solvent Implementation for Phenolics Cleaning

During phenolic liner manufacture, resin-impregnated (pre-preg) bias tape of silica, glass, or carbon cloth is tape-wrapped, cured, machined, and then wiped with 1,1,1 tri-chloroethane (TCA) to remove contaminants that may have been introduced during machining and handling. Following the TCA wipe, the machined surface is given a resin wet-coat and over-wrapped with more prepreg and cured. A TCA replacement solvent for these wiping operations must effectively remove both surface contaminants, and sub-surface oils and greases while not compromising the integrity of this interface. Selection of a TCA replacement solvent for phenolic over-wrap interface cleaning began with sub-scale compatibility tests with cured phenolics. Additional compatibility tests included assessment of solvent retention in machined phenolic surfaces. Results from these tests showed that, while the candidate solvent did not degrade the cured phenolics, it was retained in higher concentrations than TCA in phenolic surfaces. This effect was most pronounced with glass and silica cloth phenolics with steep ply angles relative to the wiped surfaces.

Wurth, Laura

Mixed solvent electrolytes for ambient temperature secondary lithium cells

The present invention comprises an improved electrolyte for secondary lithium-based cells as well as batteries fabricated using this electrolyte. The electrolyte is a lithium containing salt dissolved in a non-aqueous solvent, which is made from a mixture of ethylene carbonate, ethylene propylene diene terpolymer, 2-methylfuran, and 2-methyltetrahydrofuran. This improved, mixed solvent electrolyte is more conductive than prior electrolytes and much less corrosive to lithium anodes. Batteries constructed with this improved electrolyte utilize lithium or lithium alloy anodes and cathodes made of metal chalcogenides or oxides, such as TiS.sub.2, NbSe.sub.3, V.sub.6 O.sub.13, V.sub.2 O.sub.5, MoS.sub.2, MoS.sub.3, CoO.sub.2, or CrO.sub.2, dissolved in a supporting polymer matrix, like EPDM. The preferred non-aqueous solvent mixture comprises approximately 5 to 30 volume percent ethylene carbonate, approximately 0.01 to 0.1 weight percent ethylene propylene diene terpolymer, and approximately 0.2 to 2 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The most preferred solvent comprises approximately 10 to 20 volume percent ethylene carbonate, about 0.05 weight percent ethylene propylene diene terpolymer, and about 1.0 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The concentration of lithium arsenic hexafluoride can range from about 1.0 to 1.8 M; a concentration 1.5 M is most preferred. Secondary batteries made with the improved electrolyte of this invention have lower internal impedance, longer cycle life, higher energy density, low self-discharge, and longer shelf life.

Shen, David H.

Selection of Environmentally Friendly Solvents for the Extravehicular Mobility Unit Secondary Oxygen Pack Cold Trap Testing

Freon-113(TradeMark) has been used as a chemistry lab sampling solvent at NASA/JSC for EMU (extravehicular Mobility Unit) SOP (Secondary Oxygen Pack) oxygen testing Cold Traps utilized at the USA (United Space Alliance) Houston facility. Similar testing has occurred at the HSWL (Hamilton Sundstrand Windsor Locks) facility. A NASA Executive Order bans the procurement of all ODS (ozone depleting substances), including Freon-113 by the end of 2009. In order to comply with NASA direction, HSWL began evaluating viable solvents to replace Freon-113 . The study and testing effort to find Freon-113 replacements used for Cold Trap sampling is the subject of this paper. Test results have shown HFE-7100 (a 3M fluorinated ether) to be an adequate replacement for Freon-113 as a solvent to remove and measure the non-volatile residue collected in a Cold Trap during oxygen testing. Furthermore, S-316 (a Horiba Instruments Inc. high molecular weight, non-ODS chlorofluorocarbon) was found to be an adequate replacement for Freon-113 as a solvent to reconstitute non-volatile residue removed from a Cold Trap during oxygen testing for subsequent HC (hydrocarbon) analysis via FTIR (Fourier Transform Infrared Spectroscopy).

Steele, John

Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents

A number of experimental lithium-ion cells, consisting of MCMB (meso-carbon microbeads) carbon anodes and LiNi(0.8)Co(0.2)O2 cathodes, have been fabricated with increased safety and expanded capability. These cells serve to verify and demonstrate the reversibility, low-temperature performance, and electrochemical aspects of each electrode as determined from a number of electrochemical characterization techniques. A number of Li-ion electrolytes possessing fluorinated ester co-solvents, namely trifluoroethyl butyrate (TFEB) and trifluoroethyl propionate (TFEP), were demonstrated to deliver good performance over a wide temperature range in experimental lithium-ion cells. The general approach taken in the development of these electrolyte formulations is to optimize the type and composition of the co-solvents in ternary and quaternary solutions, focusing upon adequate stability [i.e., EC (ethylene carbonate) content needed for anode passivation, and EMC (ethyl methyl carbonate) content needed for lowering the viscosity and widening the temperature range, while still providing good stability], enhancing the inherent safety characteristics (incorporation of fluorinated esters), and widening the temperature range of operation (the use of both fluorinated and non-fluorinated esters). Further - more, the use of electrolyte additives, such as VC (vinylene carbonate) [solid electrolyte interface (SEI) promoter] and DMAc (thermal stabilizing additive), provide enhanced high-temperature life characteristics. Multi-component electrolyte formulations enhance performance over a temperature range of -60 to +60 C. With the need for more safety with the use of these batteries, flammability was a consideration. One of the solvents investigated, TFEB, had the best performance with improved low-temperature capability and high-temperature resilience. This work optimized the use of TFEB as a co-solvent by developing the multi-component electrolytes, which also contain non-halogenated esters, film forming additives, thermal stabilizing additives, and flame retardant additives. Further optimization of these electrolyte formulations is anticipated to yield improved performance. It is also anticipated that much improved performance will be demonstrated once these electrolyte solutions are incorporated into hermetically sealed, large capacity prototype cells, especially if effort is devoted to ensure that all electrolyte components are highly pure.

Prakash, G. K. Surya

SiC growth by Solvent-Laser Heated Floating Zone

In an effort to grow single crystal SiC fibers for seed crystals the following two growth methods have been coupled in this work: traveling solvent and laser heated floating zone to create the solvent-laser heated floating zone (Solvent-LHFZ) crystal growth method. This paper discusses the results of these initial experiments, which includes: source material, laser heating, and analysis of the first ever Solvent-LHFZ SiC crystals (synchrotron white beam x-ray topography confirmed).

Woodworth, Andrew A.

Is Water a Universal Solvent for Life?

There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation of cellular boundary structures or protein folding. Strengths of electrostatic and hydrophobic interactions are similar and can be balanced over a wide range of temperatures, which considerably increases the repertoire of interactions that can be used to modulate biological functions. Some properties of water, e.g. its chemical activity against polymerization reactions, are considered as unfavorable to life. In actuality, this might be a favorable trait because life requires a balance between constructive and destructive processes. For example, molecules synthesized in response to specific conditions must be degraded once these conditions change. Otherwise regulation of biological processes would be virtually impossible. Water might not be the only liquid with favorable properties for supporting life. It has been proposed that formamide, which might be present elsewhere in the universe in sufficient quantities to warrant interest, could be a potential alternative to water for the origin of life. However, this will remain highly hypothetical until it is demonstrated in further studies on its physical, chemical and biological properties it is capable of mediating self-organization of matter and providing proper balance between different types of non-covalent interactions.

Pohorill, Andrew

The Search for Nonflammable Solvent Alternatives for Cleaning Aerospace Oxygen Systems

To obtain a high degree of cleanliness without risk of corrosion or hazardous reactivity, hydrochlorofluorocarbon (HCFC)-225 is used for cleaning and cleanliness verification of oxygen system components used on NASA fs bipropellant launch vehicles, associated test stands and support equipment. HCFC-225 is a Class II Ozone Depleting Substance (ODS ]II) that was introduced to replace chlorofluorocarbon (CFC)-113, a Class I ODS solvent that is now banned. To meet environmental regulations to eliminate the use of ozone depleting substances, a replacement solvent is required for HCFC ]225 that is effective at removing oils, greases, and particulate from large oxygen system components, is compatible with materials used in the construction of these systems, and is nonflammable and non ]reactive in enriched oxygen environments. A solvent replacement is also required for aviator fs breathing oxygen systems and other related equipment currently cleaned and verified with HCFC ]225 and stockpiled CFC -113. Requirements and challenges in the search for nonflammable replacement solvents are discussed.

Mitchell, Mark A.

The Search for Nonflammable Solvent Alternatives for Cleaning Aerospace Oxygen Systems

Oxygen systems are susceptible to fires caused by particle and nonvolatile residue (NVR) contaminants, therefore cleaning and verification is essential for system safety. . Cleaning solvents used on oxygen system components must be either nonflammable in pure oxygen or complete removal must be assured for system safety. . CFC -113 was the solvent of choice before 1996 because it was effective, least toxic, compatible with most materials of construction, and non ]reactive with oxygen. When CFC -113 was phased out in 1996, HCFC -225 was selected as an interim replacement for cleaning propulsion oxygen systems at NASA. HCFC-225 production phase-out date is 01/01/2015. HCFC ]225 (AK ]225G) is used extensively at Marshall Space Flight Center and Stennis Space Center for cleaning and NVR verification on large propulsion oxygen systems, and propulsion test stands and ground support equipment. . Many components are too large for ultrasonic agitation - necessary for effective aqueous cleaning and NVR sampling. . Test stand equipment must be cleaned prior to installation of test hardware. Many items must be cleaned by wipe or flush in situ where complete removal of a flammable solvent cannot be assured. The search for a replacement solvent for these applications is ongoing.

Mitchell, Mark

United States Air Force Wipe Solvent Testing

The Wright-Patterson Air Force Base (WPAFB), as part of the Air Force Material Command, requested that NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) conduct testing and analyses in support of the United States Air Force Wipe Solvent Development Project. The purpose of the wipe solvent project is to develop an alternative to be used by Air Force flight line and maintenance personnel for the wipe cleaning of oxygen equipment. This report provides material compatibility, liquid oxygen (LOX) mechanical impact, autogenous ignition temperature (AIT), and gauge cleaning test data for some of the currently available solvents that may be used to replace CFC-113 and methyl chloroform. It provides data from previous WSTF test programs sponsored by the Naval Sea Systems Command, the Kennedy Space Center, and other NASA programs for the purpose of assisting WP AFB in identifying the best alternative solvents for validation testing.

Hornung, Steven D.

Development of a rate-based ENRTL-RK process model for a water-lean solvent

Advanced water-lean solvents (WLS) for post-combustion CO2 capture offer several advantages over the aqueous amine solvents . WLS have lower parasitic energy penalty, lower corrosion, lower temperature and high-pressure CO2 regeneration leading to lower cost of CO2 capture. RTI International, with funding from the US Department of Energy, has been developing its novel water-lean solvent, that has shown specific reboiler duty of 2.3 GJ/t-CO2 at the 60-kWe pilot testing unit (Tiller Plant, SINTEF, Norway) and 2.6 GJ/t-CO2 at the engineering scale testing system (12 MWe) at the Technology Centre Mongstad (TCM) in Norway. All heat duties, including the one from TCM testing, were consistent with Aspen Plus modeling of the specific configuration of each test plant. This work focuses on the development of a detailed process model using in-house laboratory measurements and process data at pilot scale. The eNTRL-RK model used in this work is based on an unsymmetric activity coefficient model with the reference states chosen to be pure liquids for solvents and ideal dilute solution at unit solute molality (resulting in activity coefficient of unity at infinite dilution) for electrolytes. It uses the Redlich-Kwong equation of state for vapor phase properties and Henry’s law for solubility of supercritical gases. The model was validated using process data from the pilot-scale campaign at the Tiller plant, and the engineering scale test campaign at TCM. Data on CO2 capture rate, absorber, and regenerator temperature profiles and specific reboiler duties from two different test campaigns at Tiller and TCM, were used to further refine and validate the model and the model compares favorably to experimental data. The validation results against TCM campaign will be presented in this work.

CO2 capture

Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling

Nitrogen oxides, present in flue gas, can cause negative impacts on amine carbon capture solvents by the formation of heat-stable salts and suspected carcinogens. Thus, to maximize the performance of water-lean solvents, a better understanding of this process in these systems is necessary. Here, a computational study for the fixation of the CO 2 capture solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) to nitramine/nitrosamine was conducted. The first step involves the dissociation of the NH bond of EEMPA, in which the homolytic mechanism is energetically more favorable than the heterolytic mechanism. The second step involves radical recombination to form N–N bonds. While NO 2 directly reacts with EEMPA, NO has almost no effect. However, in the presence of O 2 , fixation of EEMPA by NO is enhanced via the formation of N 2 O 4 species. Finally, low reaction energies indicate that the formation of nitramine/nitrosamine may be a reversible process, suggesting that EEMPA could be recovered under thermal stripping conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

1,4-cineole: a bio-derived solvent for highly stable graphene nanoplatelet suspensions and well-dispersed UHMWPE nanocomposite fibers

The exceptional properties of carbon nanoparticles, such as graphene, promise to expand the performance and functionality of many materials. The reinforcement of polymers is of keen interest due to their low density and flexible manufacturing methods. However, dispersing graphene in them has proven to be an enduring challenge due to the particles’ propensity to form performance degrading agglomerations. Furthermore, effective solvents for nanoparticle dispersion are commonly harmful, non-renewable, petrochemicals. In this work, a bio-derived solvent, 1,4-cineole, is demonstrated as a renewable alternative to these solvents that can be used to form highly stable graphene nanoplatelet (GnP) suspensions and used to gel spin well-dispersed UHMWPE/GnP nanocomposite fibers. The GnP concentration in the fibers was varied across three orders of magnitude, 0.01 wt% to 1 wt%, to examine its effect on fiber microstructure and properties. At low concentrations the particles act as point defects without affecting the fiber microstructure, and poor particle/matrix interfacial adhesion results in significantly reduced mechanical properties. At 1 wt% GnPs, a network effect takes hold thereby reinforcing the fibers, but the particles also impede the growth and orientation of crucial load-carrying crystalline structures in the fiber. Furthermore, unveiling the microstructural effects of GnPs on highly oriented and crystalline polymers in this study provides crucial insights for future work developing high-performance polymer nanocomposite fibers.

36 MATERIALS SCIENCE

Green co-solvent-assisted one-pot synthesis of high-performance flexible lignin polyurethane foam

Although lignin is a promising candidate as a source of polyol for producing eco-friendly polyurethane foam (PUF), its direct application has limitations, primarily stemming from the brittleness of the resulting products and poor processibility at high lignin loadings. To address these technical challenges, we introduced an effective co-solvent for the lignin-based polyurethane foams (LPUFs) with up to 80wt% of lignin substitution for petroleum polyols. As a green co-solvent that involves carbon dioxide fixation during its production, propylene carbonate (PC), was blended with lignin and improved the distribution of lignin by decreasing the viscosity, providing a room-temperature reaction. The LPUFs demonstrated a comparable thermal insulation performance (R-values greater than 5 in -1 ) with commercially available PUF with a uniform size of closed-cell structure induced by the reduced viscosity of lignin-based polyol. LPUFs also showed enhanced fire retardancy and moisture resistance compared to the control PUFs, benefiting from lignin’s intrinsic fire-resistant and hydrophobic properties. To mitigate the brittleness issue at high lignin loadings, flexible polyethylene glycols (PEGs) with a high molecular weight (i.e., PEG-1000) were dissolved in PC at room temperature to further improve the mechanical strength of LPUFs. The compressive strength of LPUFs with 80 wt% lignin substitution content was remarkably improved to 226 kPa by the employment of co-solvent and PEG-1000 compared to the control PUF (<140 kPa). Moreover, the flexibility of the LPUFs was successfully controlled by simply adjusting the PEG-400/PEG-1000 ratio. In conclusion, the results of this study provide valuable insights for accelerating and broadening the utilization of lignin in sustainable materials and manufacturing areas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Probing the potential of type V Deep eutectic solvents as sustainable electrolytes

The increasing interest within the scientific community in environmentally friendly solvents has led to a focus on Deep Eutectic Solvents (DES), which have natural components. DES are viewed as alternatives to traditional organic solvents and have the potential to be used as electrolytes. For the first time, transport properties of four Type V Deep Eutectic Salt Solutions (DESS) were accessed to investigate the potential of this technology, selecting precursors ranked as excellent in Eco-Scale metrics. The DESS were composed of terpene and trioctylphosphine oxide (TOPO), and varying concentrations of lithium bis(trifluoromethane)sulfonimide (LiTFSI), and their properties were assessed through self-diffusion, viscosity, density, and conductivity measurements. While Type V DESS are capable of dissolving significant amounts of LiTFSI (up to 30 % molar), their ionic conductivity is low, with values ranging from 3.6·10 –3 to 9.3·10 –2 mS·cm –1 at 25 °C, thus limiting their suitability as electrolytes, for instance, for lithium-ions batteries applications. Similar diffusion coefficients for Li + and TFSI – ions suggest the formation of long-lived ion pairs moving as a neutral species. As a result, future research aims to introduce additives to disrupt contact ion pairs and enhance transport properties, leveraging the sustainable appeal of DES and their use in advanced energy storage technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH