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At least 523 records · Page 29

A dynamic parameterization of sulfuric acid–dimethylamine nucleation and its application in three-dimensional modeling

Sulfuric acid (SA) is a governing gaseous precursor for atmospheric new particle formation (NPF), a major source of global ultrafine particles, in environments studied around the world. In polluted urban atmospheres with high condensation sinks (CSs), the formation of stable SA–amine clusters, such as SA–dimethylamine (DMA) clusters, usually initializes intense NPF events. Coagulation scavenging and cluster evaporation are dominant sink processes of SA–amine clusters in urban atmospheres, yet these loss processes are not quantitatively included in the present parameterizations of SA–amine nucleation. We herein report a parameterization of SA–DMA nucleation, based on cluster dynamic simulations and quantum chemistry calculations, with certain simplifications to greatly reduce the computational costs. Compared with previous SA–DMA nucleation parameterizations, this new parameterization was able to reproduce the dependences of particle formation rates on temperature and CSs. We then incorporated it in a three-dimensional (3-D) chemical transport model to simulate the evolution of the particle number size distributions. Simulation results showed good consistency with the observations in the occurrence of NPF events and particle number size distributions in wintertime Beijing and represented a significant improvement compared to that using a parameterization without coagulation scavenging. Quantitative analysis shows that SA–DMA nucleation contributes significantly to nucleation rates and aerosol population during the 3-D simulations in Beijing (>99 % and >60 %, respectively). These results broaden the understanding of NPF in urban atmospheres and stress the necessity of including the effects of coagulation scavenging and cluster stability in simulating SA–DMA nucleation in 3-D simulations. Representing these processes is thus likely to improve model performance in particle source apportionment and quantification of aerosol effects on air quality, human health, and climate.

Li, Yuyang↗

Polyimidazopyrrolone model compounds.

The model reactions between phthalic anhydride and o-phenylenediamine were studied under conditions analogous to the polymerization and post-cyclization of dianhydrides with bis(o-diamines) to form polyimidazopyrrolones (Pyrrones). The route from the initial amide-acid-amine to the tetracyclic Pyrrone model when the reactions are conducted in aprotic solvents is highly competitive between isolatable benzimidazole-acid and imide-amine intermediates. Solid-state thermal conversion of the amide-acid-amine affords a unique dimeric species containing amide, imide, and benzimidazole functions. It was confirmed that melt techniques lead to disproportionation products. The application of these findings to related polymer synthesis is discussed.

Young, P. R.↗

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

Three polyfunctional amines were synthesized. Polyimide films containing varying amounts of the amine crosslinking agents were prepared. Their thermomechanical properties were compared with those of control film samples prepared from difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperature is discussed.

Delvigs, P.↗

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

The potential of high temperature resistant polymers such as polyimides (PI) and polyphenylquinoxalines (PPQ) as matrix resins in fiber-reinforced composites has not been fully realized to date. One of the problems associated with these resins is that they exhibit creep, or thermoplastic yielding under load at temperatures approaching 316 C (600 F). The purpose of this investigation was to further reduce thermoplastic behavior of polyimide resins by substituting a controlled amount of the diamine monomer with crosslinking agents having a higher amine functionality. The knowledge gained from a study of the thermomechanical properties of the crosslinked resins would then be used in the fabrication of fiber-reinforced polyimide composites. This report describes the synthesis and characterization of three new polyfunctional amines. Polyimide films containing varying amounts of the cross-linking agents were prepared, and their properties compared with those of control samples prepared with difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperatures is discussed.

Delvigs, P.↗

Monomers for thermosetting and toughening epoxy resins

Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

Pratt, J. R.↗

Imide modified epoxy matrix resins

Results of a program designed to develop tough imide modified epoxy (IME) resins cured by bisimide amine (BIA) hardeners are presented. State of the art epoxy resin, MY720, was used. Three aromatic bisimide amines and one aromatic aliphatic BIA were evaluated. BIA's derived from 6F anhydride (3,3 prime 4,4 prime-(hexafluoro isopropyl idene) bis (phthalic anhydride) and diamines, 3,3 prime-diam nodiphenyl sulfone (3,3 prime-DDS), 4,4 prime-diamino diphenyl sulfone (4,4 prime-DDS), 1.12-dodecane diamine (1,12-DDA) were used. BIA's were abbreviated 6F-3,3 prime-DDS, 6F-4,4 prime-DDS, 6F-3,3 prime-DDS-4,4 prime DDS, and 6F-3,3 prime-DDS-1,12-DDA corresponding to 6F anhydride and diamines mentioned. Epoxy resin and BIA's (MY720/6F-3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA and a 50:50 mixture of a BIA and parent diamine, MY720/6F-3,3 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA/3,3 prime-DDS were studied to determine effect of structure and composition. Effect of the addition of two commercial epoxies, glyamine 200 and glyamine 100 on the properties of several formulations was evaluated. Bisimide amine cured epoxies were designated IME's (imide modified epoxy). Physical, thermal and mechanical properties of these resins were determined. Moisture absorption in boiling water exhibited by several of the IME's was considerably lower than the state of the art epoxies (from 3.2% for the control and state of the art to 2.0 wt% moisture absorption). Char yields are increased from 20% for control and state of the art epoxies to 40% for IME resins. Relative toughness characteristics of IME resins were measured by 10 deg off axis tensile tests of Celion 6000/IME composites. Results show that IME's containing 6F-3,3 prime-DDS or 6F-3,3 prime-DDS-1,12-DDA improved the "toughness" characteristics of composites by about 35% (tensile strength), about 35% (intralaminar shear strength), and about 78% (shear strain to failure) relative to the control composite.

Scola, D. A.↗

Synthesis of N-Substituted Silaneamines: Monomeric Precursors of Silicon Carbide-Nitride Fibers

Silanetriamines are prepared by the condensation of methyl or phenyl trichlorosilane with a primary amine. The amines used were methyl, n-propyl, n-butyl and allyl. The silaneamines were prepared by adding the chlorosilane to a solution of the amine in either petroleum ether or toluene. The compounds were purified by distillation and characterized by infrared and nuclear magnetic resonance spectroscopy.

Crouse, D. J.↗

Toughening of BIS maleimide resins: Synthesis and characterization of maleimide terminated poly(arylene ether) oligomers and polymers

Amine functional poly(arylene ether) sulfones were previously reported. Herein, the chemistry was extended to amorphous poly(arylene ether) ketones because of their higher fracture toughness values, relative to the polysulfones. It was demonstrated that the amino functional oligomers undergo a self-crosslinking reaction at temperatures above about 220 C. This produces an insoluble, but ductile network that has excellent resistance. A ketamine structure hypothesis was proposed and verified using solid state magic angle NMR. In most cases, the water generated upon ketamine formation is too low to produce porosity and solid networks are obtained. The stability of the ketamine networks towards hydrolysis is excellent. The chemistry was further demonstrated to be able to crosslink preformed nonfunctional poly(arylene ether) ketones if a difunctional amine was utilized. This concept has the possibility of greatly improving the creep resistance of thermoplastics. Also, a new technique was developed for converting the amine functional oligomers cleanly into maleimide structures. This method involves reacting maleic anhydride with monomeric aminophenols in the presence of solvent mixtures.

Mcgrath, J. E.↗

Diamines Containing Pendent Phenylethynyl Groups

Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as and N,N-dimethylacetamide under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204 C under wet conditions without sacrificing melt flow behavior and processability as compared to similar materials. These materials are useful as adhesives, coatings, films, moldings, and composite matrices.

Connell, John W.↗

Fluorescence Studies of Protein Crystallization Interactions

We are investigating protein-protein interactions in under- and over-saturated crystallization solution conditions using fluorescence methods. The use of fluorescence requires fluorescent derivatives where the probe does not markedly affect the crystal packing. A number of chicken egg white lysozyme (CEWL) derivatives have been prepared, with the probes covalently attached to one of two different sites on the protein molecule; the side chain carboxyl of ASP 101, within the active site cleft, and the N-terminal amine. The ASP 101 derivatives crystallize while the N-terminal amine derivatives do not. However, the N-terminal amine is part of the contact region between adjacent 43 helix chains, and blocking this site does would not interfere with formation of these structures in solution. Preliminary FRET data have been obtained at pH 4.6, 0.1M NaAc buffer, at 5 and 7% NaCl, 4 C, using the N-terminal bound pyrene acetic acid (PAA, Ex 340 nm, Em 376 nm) and ASP 101 bound Lucifer Yellow (LY, Ex 425 nm, Em 525 nm) probe combination. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10 (exp 5) M respectively), and all experiments were carried out at approximately Csat or lower total protein concentration. The data at both salt concentrations show a consistent trend of decreasing fluorescence yield of the donor species (PAA) with increasing total protein concentration. This decrease is apparently more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations (reflected in the lower solubility). The estimated average distance between protein molecules at 5 x 10 (exp 6) M is approximately 70 nm, well beyond the range where any FRET can be expected. The calculated RO, where 50% of the donor energy is transferred to the acceptor, for the PAA-CEWL * LY-CEWL system is 3.28 nm, based upon a PAA-CEWL quantum efficiency of 0.41.

Pusey, Marc L.↗

Strained Hydrocarbons as Potential Hypergolic Fuels

A storable combination of high-energy hypergolic fuel and oxidizer is advantageous to the future of reusable launch vehicles (RLVs). The combination will allow an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Strained systems have been studied as potential high-density fuels. Adding hypergolic functional groups, such as amino groups, to these hydrocarbons will potentially allow auto ignition of strained systems with hydrogen peroxide. Several straight chain amines and their strained counterparts containing an equivalent number of carbon atoms have been purchased and synthesized. These amines provide initial studies to determine the effects of fuel vapor pressure, strain energy, fuel miscibility, and amine substitution upon fuel ignition time and hypergolicity with hydrogen peroxide as an oxidizer.

Source record↗

Recent Selected Ion Flow Tube (SIFT) Studies Concerning the Formation of Amino Acids in the Gas Phase

Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.

Jackson, Douglas M.↗

Elastomer Reinforced with Carbon Nanotubes

Elastomers are reinforced with functionalized, single-walled carbon nanotubes (SWNTs) giving them high-breaking strain levels and low densities. Cross-linked elastomers are prepared using amine-terminated, poly(dimethylsiloxane) (PDMS), with an average molecular weight of 5,000 daltons, and a functionalized SWNT. Cross-link densities, estimated on the basis of swelling data in toluene (a dispersing solvent) indicated that the polymer underwent cross-linking at the ends of the chains. This thermally initiated cross-linking was found to occur only in the presence of the aryl alcohol functionalized SWNTs. The cross-link could have been via a hydrogen-bonding mechanism between the amine and the free hydroxyl group, or via attack of the amine on the ester linage to form an amide. Tensile properties examined at room temperature indicate a three-fold increase in the tensile modulus of the elastomer, with rupture and failure of the elastomer occurring at a strain of 6.5.

Hudson, Jared L.↗

Water-Free Proton-Conducting Membranes for Fuel Cells

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Narayanan, Sekharipuram↗

Improvements in Fabrication of Sand/Binder Cores for Casting

Three improvements have been devised for the cold-box process, which is a special molding process used to make sand/binder cores for casting hollow metal parts. These improvements are: The use of fiber-reinforced composite binder materials (in contradistinction to the non-fiber-reinforced binders used heretofore), The substitution of a directed-vortex core-blowing subprocess for a prior core-blowing process that involved a movable gassing plate, and The use of filters made from filtration-grade fabrics to prevent clogging of vents. For reasons that exceed the scope of this article, most foundries have adopted the cold-box process for making cores for casting metals. However, this process is not widely known outside the metal-casting industry; therefore, a description of pertinent aspects of the cold-box process is prerequisite to a meaningful description of the aforementioned improvements. In the cold-box process as practiced heretofore, sand is first mixed with a phenolic resin (considered to be part 1 of a three-part binder) and an isocyanate resin (part 2 of the binder). Then by use of compressed air, the mixture is blown into a core box, which is a mold for forming the core. Next, an amine gas (part 3 of the binder) that acts as a catalyst for polymerization of parts 1 and 2 is blown through the core box. Alternatively, a liquid amine that vaporizes during polymerization can be incorporated into the sand/resin mixture. Once polymerization is complete, the amine gas is purged from the core box by use of compressed air. The finished core is then removed from the core box.

Bakhitiyarov, Sayavur I.↗

Efficacy of FTIR Analysis in Determining CO2 Loading on Diglycolamine

In support of advanced air revitalization technologies to enable human spaceflight beyond low earth orbit, performance studies have been conducted using a liquid amine, Diglycolamine (DGA) between teams at NASA?s Johnson Spaceflight Center (JSC) and Ames Research Center (ARC). Liquid amines have been used in regenerable earth-based systems to remove CO2 from industrial systems as well as for closed-environment air revitalization because they can be regenerated at lower temperatures than solid sorbent systems. As an additional advantage to solid sorbent based systems, liquid sorbents can be cycled between an adsorbing contactor and degassing chamber, thereby reducing system complexity by operation in a continuous loop. In an effort to inform a regeneration system design for micro-gravity applications, ARC has performed a number of tests to characterize the degas mechanics of DGA. In order to accurately measure the amount of CO2 captured or released by the amine, methods such as gravimetric weighing and chemical decomposition are reasonable, however the initial design for a scaled down degas system required analysis on small sample sizes. In order to accomplish CO2 loading measurements with a sample size of approximately 500µL, Fourier-transform infrared spectroscopy (FTIR) was used. Calibration against acid decomposition showed relatively good correlation and test data showed reasonable adherence to expected trends, however more extensive testing should be conducted to fully validate the usage of FTIR to determine CO2 loading on DGA.

Diglycolamine↗

Analytical Methods and Testbeds for Characterizing Adsorbents and Catalysts for Atmosphere Revitalization of Crewed Spacecraft

Spacecraft environmental control and life support systems (ECLSS) include a number of air revitalization (AR) technologies to provide breathable air and a comfortable living environment to the crew. Crew health and comfort is ensured by controlling human produced CO2 (1 kg person-1 day-1) and water vapor (~2 kg person-1 day-1), and by removing trace contaminants (TCs) from cabin air. These life support functions on-board the International Space Station (ISS) are carried out by the Carbon Dioxide Removal Assembly (CDRA), the Water Processor Assembly (WPA), and the trace contaminant control system (TCCS). During the development of the TCCS, new analytical and theoretical methods were developed in the 1970s for characterizing adsorption and desorption characteristics of activated carbons for the purpose of designing suitable AR technologies required for controlling airborne trace contaminants within spacecraft cabins during long exploration missions. The TCCS removes harmful volatile organic compounds and other trace contaminants from the circulating air. It consists of a granular activated carbon (GAC) bed for the removal of high molecular weight contaminants and ammonia followed by a heated catalytic bed for low molecular weight hydrocarbons. The high temperature catalytic oxidizer (HTCO) of the TCCS, which operates at 400°C and requires 120W average power, removes low molecular weight compounds such as carbon monoxide (CO), formaldehyde (CH2O), and methane (CH4), that pass through the GAC bed. The Air Revitalization Laboratory at the Kennedy Space Center (KSC) was established to develop new analytical methods for evaluating emerging ECLSS technologies for use in future AR architectures. General properties of adsorbents and catalysts are required for trace contaminant control system design calculations and vendor-supplied data are seldom available at relevant process conditions of interest to spacecraft cabin applications. To address this shortcoming, appropriate testbeds were developed to measure the desired properties of AR technologies being considered for use in ECLS architectures. Generally, the testbeds developed at KSC challenge the test media (activated carbon, impregnated activated carbon, catalysts, zeolites, solid amines, or pleated filters) with simulated spacecraft gas streams containing representative mixtures of trace contaminants (volatile organic compounds, ammonia, CO, CO2, or siloxanes) at the flow rates, temperatures, and relative humidity that will be encountered within manned spacecraft. Work performed at KSC funded by NASA’s Advanced Exploration (AES) Program has included: Identifying candidate sorbents to replace commercially obsolete impregnated carbons for NH3 control within the TCCS, characterizing their adsorptive capacities using simulated spacecraft gas streams, and ranking their appropriateness in various AR applications; evaluating novel low temperature catalysts for controlling CO and formaldehyde by traditional and photocatalytic methods for trace contaminant control; development of analytical methods to assess regenerable solid amine performance for CO2 control via pressure swing adsorption. The Air Revitalization lab was also funded to study trace contaminant control by other NASA programs. These include: screening of candidate sorbents for the design of new Charcoal HEPA Integrated Particle Scrubber (CHIPS) filters for removing siloxanes from cabin air; characterizing the performance of an impregnated activated carbon at low humidity for use in ORION ECLS; screening of sorbents for protecting the Sabatier 2.0 catalyst from DMSO2, siloxanes, NH3, and solid amine byproducts.

Monje, Oscar↗

Move That Goo!

On May 5, 1961, Alan B. Shepard became the first American in space (K. Mars); since then, NASA has made leaps and bounds in space exploration and continues to develop new technologies. Through their X-Hab program, NASA has teamed up with the National Space Grant Foundation to fund our student-centered project with one main goal: Move That Goo! Liquid amine absorption is a method by which CO2 is removed from an environment and is intended to be the primary method for CO2 removal for NASA’s sustained human presence on extraterrestrial bodies such as the Moon and Mars. Liquid amines can be highly viscous when absorbing CO2, thus the team needed to produce a design that could move a high viscosity fluid while staying under the power requirement of 1 kW and allowing a few square meters in a closed system. Prompted by NASA and with the support of our faculty mentors, we have been tasked with the research, development, production, and testing of a system able to move a high viscosity liquid amine which requires adequate air exposure to absorb carbon dioxide from a habitat atmosphere in low gravity. The system is split into two main groups, fluids, and materials, with two separate teams of students assigned to their half of the design. The fluids team is responsible for everything in the design that directly touches the fluid. The materials team is responsible for the test stand to which the fluids team’s design is attached to as well as additive manufacturing material selection. In the first semester, the team focused on brainstorming ideas, design selection, budget creation, and CAD modeling. Multiple concepts were generated but the team decided on a design to get the high viscosity fluid to move around a rectangular channel using a screw conveyor mechanism. The liquid must be moved by the turning screw from the thermal chamber going around a rectangular trough back to the thermal chamber. The screw and the trough geometry will be important to allow for the high viscosity fluid to flow, utilizing surface tension to maintain contact to the trough as seen in Figure 1 below.

Olivia Angst↗