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At least 109 records · Page 6

Molecular modeling of polymer composite interactions with analytes in electronic nose sensors for environmental monitoring in International Space Station

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL Electronic Nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings (with no hydrogens). The Dreiding 2.21 force field is used for the polymer and solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4- vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic (ammonia) and organic (methanol, toluene, hydrazine) compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites.

electronic noise environmental monitoring polymer ↗

Methods of Functionalization of Carbon Nanotubes by Photooxidation

A method of photooxidizing carbon nanotubes, such as single-walled and multi-walled carbon nanotubes. The nanotubes are purified and dispersed in a solvent, such as n-methyl pyrrolidinone or dimethylformamide. A singlet oxygen sensitizer like Rose Bengal is added to the solution. Oxygen gas is continuously supplied while irradiating the solution while irradiating the solution with ultraviolet light to produce singlet oxygen to oxidize the single-walled carbon nanotubes. Advantageously, the method significantly increases the level of oxidation compared with prior art methods.

Lebron-Colon, Marisabel↗

Cleaning With Supercritical CO2

Supercritical carbon dioxide effective industrial cleaning agent. Replaces conventional halocarbon solvents for degreasing parts becoming coated with oil during such manufacturing procedures as forming and machining. Presents none of environmental threats and occupational hazards associated with halocarbon solvents. Spontaneously evaporates after use and leaves no waste to be disposed of. Evaporated gas readily collected and recycled.

Herzstock, James J.↗

Searching for Alien Life Having Unearthly Biochemistry

The search for alien life in the solar system should include exploring unearth-like environments for life having an unearthly biochemistry. We expect alien life to conform to the same basic chemical and ecological constraints as terrestrial life, since inorganic chemistry and the laws of ecosystems appear to be universal. Astrobiologists usually assume alien life will use familiar terrestrial biochemistry and therefore hope to find alien life by searching near water or by supplying hydrocarbons. The assumption that alien life is likely to be based on carbon and water is traditional and plausible. It justifies high priority for missions to search for alien life on Mars and Europa, but it unduly restricts the search for alien life. Terrestrial carbon-water biochemistry is not possible on most of the bodies of our solar system, but all alien life is not necessarily based on terrestrial biochemistry. If alien life has a separate origin from Earth life, and if can survive in an environment extremely different from Earth's, then alien life may have unearthly biochemistry. There may be other solvents than water that support alien life and other elements than carbon that form complex life enabling chain molecules. Rather than making the exploration-restricting assumption that all life requires carbon, water, and terrestrial biochemistry, we should make the exploration-friendly assumption that indigenous, environmentally adapted, alien life forms might flourish using unearthly biochemistry in many places in the solar system. Alien life might be found wherever there is free energy and a physical/chemical system capable of using that energy to build living structures. Alien life may be discovered by the detection of some general non-equilibrium chemistry rather than of terrestrial biochemistry. We should explore all the potential abodes of life in the solar system, including those where life based on terrestrial biochemistry can not exist.

Jones, Harry↗

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗

Li-Ion Batteries for Space Applications: High Specific Energy and Wide-Operating Temperature

Compared to the conventional Ni-Co oxides (with or without AI additions), the NMC (1/3:1/3:1/3) cathode provides marginal improvement in specific capacity. However, some of the formulations based on the solid solutions of layered Li2Mn03 and LiM02 (M = Mn0.5Ni0.5} have shown capacities as high as 250 mAh/g, combined with high cell voltages (4.5 V) and with the likelihood of enhanced thermal stability. Multi-component electrolytes with low EC-proportions and selected co-solvents provide significant improvement in the low temperature performance, down to -60 C, combined with the non-flammable attribute from the co-solvents. The NMC cathode shows good compatibility with the carbonate-based low temperature electrolytes. Impressive performances have been realized at low temperatures of <= 30 C. Electrolytes with high salt concentration and high EC content fare well at room temperatures, while the formulations with low EC content and low salt concentration are preferred at low temperatures. DPA studies reveal increased SEI growth on the electrodes, especially anode, upon irradiation. Performance of low temperature electrolytes in prototype cells corroborate the findings from laboratory cells.

storage↗

Effect of Alignment on Transport Properties of Carbon Nanotube/Metallic Junctions

Ballistic and spin coherent transport in single walled carbon nanotubes (SWCNT) are predicted to enable high sensitivity single-nanotube devices for strain and magnetic field sensing. Based upon these phenomena, electron beam lithography procedures have been developed to study the transport properties of purified HiPCO single walled carbon nanotubes for development into sensory materials for nondestructive evaluation. Purified nanotubes are dispersed in solvent suspension and then deposited on the device substrate before metallic contacts are defined and deposited through electron beam lithography. This procedure produces randomly dispersed ropes, typically 2 - 20 nm in diameter, of single walled carbon nanotubes. Transport and scanning probe microscopy studies have shown a good correlation between the junction resistance and tube density, alignment, and contact quality. In order to improve transport properties of the junctions a technique has been developed to align and concentrate nanotubes at specific locations on the substrate surface. Lithographic techniques are used to define local areas where high frequency electric fields are to be concentrated. Application of the fields while the substrate is exposed to nanotube-containing solution results in nanotube arrays aligned with the electric field lines. A second electron beam lithography layer is then used to deposit metallic contacts across the aligned tubes. Experimental measurements are presented showing the increased tube alignment and improvement in the transport properties of the junctions.

Wincheski, Buzz↗

Utilization of non-conventional systems for conversion of biomass to food components: Recovery optimization and characterizations of algal proteins and lipids

Protein isolate obtained from green algae (Scenedesmus obliquus) cultivated under controlled conditions was characterized. Molecular weight determination of fractionated algal proteins using SDS-polyacrylamide gel electrophoresis revealed a wide spectrum of molecular weights ranging from 15,000 to 220,000. Isoelectric points of dissociated proteins were in the range of 3.95 to 6.20. Amino acid composition of protein isolate compared favorably with FAO standards. High content of essential amino acids leucine, valine, phenylalanine and lysine makes algal protein isolate a high quality component of closed environment life support system (CELSS) diets. To optimize the removal of algal lipids and pigments supercritical carbon dioxide extraction (with and without ethanol as a co-solvent) was used. Addition of ethanol to supercritical CO2 resulted in more efficient removal of algal lipids and produced protein isolate with a good yield and protein recovery. The protein isolate extracted by the above mixture had an improved water solubility.

Karel, M.↗

Non-conventional approaches to food processing in CELSS. I - Algal proteins: Characterization and process optimization

Protein isolate obtained from green algae (Scenedesmus obliquus) cultivated under controlled conditions was characterized. Molecular weight determination of fractionated algal proteins using SDS-polyacrylamide gel electrophoresis revealed a wide spectrum of molecular weights ranging from 15,000 to 220,000. Isoelectric points of dissociated proteins were in the range of 3.95 to 6.20. Amino acid composition of protein isolate compared favorably with FAO standards. High content of essential amino acids leucine, valine, phenylalanine and lysine makes algal protein isolate a high quality component of CELSS diets. To optimize the removal of algal lipids and pigments supercritical carbon dioxide extraction (with and without ethanol as a co-solvent) was used. Addition of ethanol to supercritical CO2 resulted in more efficient removal of algal lipids and produced protein isolate with a good yield and protein recovery. The protein isolate extracted by the above mixture had an improved water solubility.

Nakhost, Z.↗

Alternative Solvents and Technologies for Precision Cleaning of Aerospace Components

Precision cleaning solvents for aerospace components and oxygen fuel systems, including currently used Vertrel-MCA, have a negative environmental legacy, high global warming potential, and have polluted cleaning sites. Thus, alternative solvents and technologies are being investigated with the aim of achieving precision contamination levels of less than 1 mg/sq ft. The technologies being evaluated are ultrasonic bath cleaning, plasma cleaning and supercritical carbon dioxide cleaning.

Green solvents↗

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↗

Electrolytes for Low-Temperature Operation of Li-CFx Cells

A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

Smart, Marshall C.↗

Test Of Protective Coatings On Carbon Steel

Report describes results of tests in which carbon-steel panels coated with one-or two-component solvent-based inorganic zinc primers and top-coated with inorganic topcoat or any of various organic topcoats, placed on outdoor racks at beach at Kennedy Space Center for 5 years. From time to time, slurry of Al(2)O(3) in 10-percent HCI solution applied to some of panels to simulate corrosive effect of effluent from solid-fuel rocket booster engines. Panels coated with inorganic topcoat performed much better than organic-topcoated panels.

Macdowell, Louis↗

Fabrication of Polyimide-Matrix/Carbon and Boron-Fiber Tape

The term HYCARB denotes a hybrid composite of polyimide matrices reinforced with carbon and boron fibers. HYCARB and an improved process for fabricating dry HYCARB tapes have been invented in a continuing effort to develop lightweight, strong composite materials for aerospace vehicles. Like other composite tapes in this line of development, HYCARB tapes are intended to be used to build up laminated structures having possibly complex shapes by means of automated tow placement (ATP) - a process in which a computer-controlled multiaxis machine lays down prepreg tape or tows. The special significance of the present process for making dry HYCARB for ATP is that it contributes to the reduction of the overall cost of manufacturing boron-reinforced composite-material structures while making it possible to realize increased compression strengths. The present process for making HYCARB tapes incorporates a "wet to dry" process developed previously at Langley Research Center. In the "wet to dry" process, a flattened bundle of carbon fiber tows, pulled along a continuous production line between pairs of rollers, is impregnated with a solution of a poly(amide acid) in N-methyl-2-pyrrolidinone (NMP), then most of the NMP is removed by evaporation in hot air. In the present case, the polyamide acid is, more specifically, that of LaRC. IAX (or equivalent) thermoplastic polyimide, and the fibers are, more specifically, Manganite IM7 (or equivalent) polyacrylonitrile- based carbon filaments that have a diameter of 5.2 m and are supplied in 12,000-filament tows. The present process stands in contrast to a prior process in which HYCARB tape was made by pressing boron fibers into the face of a wet carbon-fiber/ poly(amide acid) prepreg tape . that is, a prepreg tape from which the NMP solvent had not been removed. In the present process, one or more layer(s) of side-by-side boron fibers are pressed between dry prepreg tapes that have been prepared by the aforementioned gwet to dry h process. The multilayer tape is then heated to imidize the matrix material and remove most of the remaining solvent, and is pressed to consolidate the multiple layers into a dense tape. For tests, specimens of HYCARB tapes and laminated composite panels made from HYCARB tape were prepared as follows: HYCARB tapes were fabricated as described above. Each panel was made by laying down ten layers of tape, containing, variously, one, two, or three boron-fiber plies and the remainder carbon- fiber-only plies (see figure). Each panel was made by laying down ten layers of tape. Each panel was then cured by heating to a temperature of 225 C for 15 minutes, then pressing at 200 psi (A1.4 MPa) while heating to 371 C, holding at 371 C for 1 hour, then continuing to hold pressure during cooling. Control specimens that were otherwise identical except that they did not contain boron fibers also were prepared. In room-temperature flexural tests, the HYCARB specimens performed comparably to the control specimens; in room-temperature, open-hole compression tests, the HYCARB specimens performed slightly better, by amounts that increased with boron content.

Belvin, Harry L.↗

Tough composite materials: Recent developments

The present volume broadly considers topics in composite fracture toughness and impact behavior characterization, composite system constituent properties and their interrelationships, and matrix systems' synthesis and characterization. Attention is given to the characterization of interlaminar crack growth in composites by means of the double cantilever beam specimen, the characterization of delamination resistance in toughened resin composites, the effect of impact damage and open holes on the compressive strength of tough resin/high strain fiber laminates, the effect of matrix and fiber properties on compression failure mechanisms and impact resistance, the relation of toughened neat resin properties to advanced composite mechanical properties, and constituent and composite properties' relationships in thermosetting matrices. Also treated are the effect of cross-link density on the toughening mechanism of elastomer-modified epoxies, the chemistry of fiber/resin interfaces, novel carbon fibers and their properties, the development of a heterogeneous laminating resin, solvent-resistant thermoplastics, NASA Lewis research in advanced composites, and opportunities for the application of composites in commercial aircraft transport structures.

Vosteen, L. F.↗

Poly(1,3,4-oxadiazoles) via aromatic nucleophilic displacement

Poly(1,3,4-oxadiazoles) (POX) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) 1,3,4-oxadiazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) 1,3,4-oxadiazole monomers are synthesized by reacting 4-hydroxybenzoic hydrazide with phenyl 4-hydrobenzoate in the melt and also by reacting aromatic dihydrazides with two moles of phenyl 4-hydroxybenzoate in the melt. This synthetic route has provided high molecular weight POX of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the large variety of activated aromatic dihalides which are available.

Connell, John W.↗

Di(hydroxyphenyl)- 1,2,4-triazole monomers

The di(hydroxyphenyl)- 1,2,4-triazole monomers were first synthesized by reacting bis (4-hydroxyphenyl) hydrazide with aniline hydrochloride at 250 C in the melt and also by reacting 1,3 or 1,4-bis- (4-hydroxyphenyl)- phenylene- dihydrazide with 2 moles of aniline hydrochloride in the melt. Purification of the di(hydroxyphenyl)- 1,2,4-triazole monomers was accomplished by recrystallization. Poly (1,2,4-triazoles) (PT) were prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)- 1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions were carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. This synthetic route has provided high molecular weight PT of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides.

Connell, John W.↗