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NASA NTRS1992

Comparison of dermal and inhalation routes of entry for organic chemicals

The quantitative comparison of the chemical concentration inside the body as the result of a dermal exposure versus an inhalation exposure is useful for assessing human health risks and deciding on an appropriate protective posture. In order to describe the relationship between dermal and inhalation routes of exposure, a variety of organic chemicals were evaluated. The types of chemicals chosen for the study were halogenated hydrocarbons, aromatic compounds, non-polar hydrocarbons and inhalation anesthetics. Both dermal and inhalation exposures were conducted in rats and the chemicals were in the form of vapors. Prior to the dermal exposure, rat fur was closely clipped and during the exposure rats were provided fresh breathing air through latex masks. Blood samples were taken during 4-hour exposures and analyzed for the chemical of interest. A physiologically based pharmacokinetic model was used to predict permeability constants (cm/hr) consistent with the observed blood concentrations of the chemical. The ratio of dermal exposure to inhalation exposure required to achieve the same internal dose of chemical was calculated for each test chemical. The calculated ratio in humans ranged from 18 for styrene to 1180 for isoflurane. This methodology can be used to estimate the dermal exposure required to reach the internal dose achieved by a specific inhalation exposure. Such extrapolation is important since allowable exposure standards are often set for inhalation exposures, but occupational exposures may be dermal.

Jepson, Gary W.↗

NASA NTRS1991

High temperature adhesives

The aerospace and electronics industries have an ever increasing need for higher performance materials. In recent years, linear aromatic polyimides have been proven to be a superior class of materials for various applications in these industries. The use of this class of polymers as adhesives is continuing to increase. Several NASA Langley developed polyimides show considerable promise as adhesives because of their high glass transition temperatures, thermal stability, resistance to solvents/water, and their potential for cost effective manufacture.

St.clair, Terry L.↗

NASA NTRS1991

Polyimides containing pendent siloxane groups

The incorporation of siloxane units into the backbone of aromatic polyimides has been shown to impart certain advantages over the unmodified polyimides. These include enhanced solubility, lower moisture adsorption, lower dielectric constant, improved toughness and surface modification. Also, when exposed to an atomic oxygen environment these materials form an in-situ silicate (SiO2) surface coating which protects the underlying material from further erosion. These unique advantages make polyimide-siloxanes useful in a variety of electronic and aerospace applications. As part of an effort on high performance polymeric materials for potential aerospace applications, polyimides containing pendent siloxane groups are under study. These materials were prepared by reacting a functionalized siloxane compound with polyimides containing benzhydrol groups. Thin films of the polymers exhibited glass transition temperatures ranging from 167 to 235 C. Tensile strengths and moduli measured at 23 C ranged from 11 to 14 ksi and 250 to 450 ksi, respectively. The dielectric constant was lowered substantially from that of the unmodified polyimide.

Connell, John W.↗

NASA NTRS1992

LDEF impact craters formed by carbon-rich impactors: A preliminary report

Two impact craters found in Al from the Long Duration Exposure Facility (LDEF) experiment tray have residues concentrated in the bottoms, along the walls, and on top of overturned rims. Analyses indicate a 'chondritic' compositional signature (Si, S, Ca, Fe, Mg, and Ni) for the bulk residue. In one crater (number 74), round to irregular silicate grains are overlain by carbon. In addition, carbon also partially covers the crater walls, the top of the raised overturned rim, and extends outward from the crater. The second crater (number 31) also contains carbon with similar distribution in and about the crater, although the silicate residue appears to be glassy. Silver, I, K, and F (possibly some of the Ca, S, and Cl) appear to be contaminants as well as analyzed aromatic carbonaceous species associated with the raised rim and the area surrounding the crater. The origin of the impactors is assumed to be extraterrestrial. The existence of impactor residue in two craters implies impact velocities less than or equal to 6 km, based on experimental hypervelocity studies.

Bunch, T. E.↗

NASA NTRS1992

Lab-scale Lidar Sensing of Diesel Engines Exhausts

Combustion technology and its environmental concerns are being considered with increasing attention, not only for global-scale effects, but also for toxicological implications, particularly in the lift conditions of traffic-congested areas and industrial sites. Majority combustion by-products (CO, NO(sub x)) and unburned hydrocarbons (HC), are already subject to increasingly severe regulations; however other, non-regulated minority species, mainly soot and heavy aromatic molecules, involve higher health risks, as they are suspected to be agents of serious pathologies and even mutagenic effects. This is but one of the reasons why much research work is being carried out worldwide on the physical properties of these substances. Correspondingly, the need arises to detect their presence in urban environments, with as high a sensitivity as is required by their low concentrations, proper time- and space-resolutions, and 'real-time' capabilities. Lidar techniques are excellent candidates to this purpose, although severe constraints limit their applicability, eye-safety problems and aerosol Mie scattering uncertainties above all. At CNR's Istituto Motori in Napels, a Lidar-like diagnostic system is being developed, aimed primarily at monitoring the dynamic behavior of internal combustion engines, particularly diesel exhausts, and at exploring the feasibility of a so-called 'Downtown Lidar'.

Borghese, A.↗

NASA NTRS1992

Remote Detection of Biological Particles and Chemical Plumes Using UV Fluorescence Lidar

A lidar system based on ultraviolet (UV) laser induced fluorescence (LIF) was developed for the remote detection of atmospherically dispersed biological particles and chemical vapors. This UV fluorescence lidar has many potential applications for monitoring environmental pollution, industrial waste emission, agricultural insect control, illicit chemical processing, and military defense operations. The general goal of this work is to investigate the research issues associated with the long range detection and identification of chemicals, e.g. aromatic solvents and chemical precursors, and biological materials, e.g. bacillus thuringiensis (BT) and bacillus globiggi (BG). In the detection of biological particulates, we are particularly interested in extending the detection range of an existing solar-blind 248-nm lidar system. We are investigating the use of longer excitation laser wavelengths (i.e. lambda greater than 280-nm to have more favorable atmospheric light transmission characteristics) for improving detection range to better than 10 km. In the detection of chemical plumes, our main research objectives are to determine how accurately and sensitively a chemical plume can be located at range, and how well spectrally the chemical species can be measured to allow their identification.

J J Tiee↗

NASA NTRS1992

Measurements of fugitive hydrocarbon emissions with a tunable infrared DIAL

A tunable infrared differential absorption lidar (DIAL) system has been designed and developed at the National Physics Lab (NPL) which is capable of making measurements throughout the spectral region 3.0 to 4.2 micro-m. It is ideally suited to measuring a range of organic and inorganic species including methane, propane, and butane. The system also has an ultraviolet channel that is capable of making simultaneous measurements of aromatic hydrocarbons such as Toluene and benzene. This paper describes the source and detection system, together with some measurements of fugitive hydrocarbon emissions performed at various petrochemical plants.

Milton, M. J. T.↗

NASA NTRS1992

Surface characterization and adhesion of oxygen plasma-modified LARC-TPI

LARC-TPI, an aromatic thermoplastic polyimide, was exposed to an oxygen plasma as a surface pretreatment for adhesive bonding. Chemical and physical changes which occurred in the polyimide surface as a result of the plasma treatment were investigated using X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IR-RAS), contact-angle analysis, ellipsometry, and high resolution SEM. A 180-deg peel test with an acrylate-based pressure sensitive adhesive as a flexible adherent was utilized to study the interactions of the plasma-treated polyimide surface with other polymeric materials. The surface characterization and adhesion testing results showed that the oxygen plasma treatment, while creating a more hydrophilic, polar surface, also caused chain scission, resulting in the formation of a weak boundary layer which inhibited adhesion.

Chin, J. W.↗

NASA NTRS1992

IRAS LRS spectroscopy of galaxies

The study presents IRAS LRS data for 350 galaxies with pointlike IRAS sources having either S(12) or S(25) not less than 1.5 Jy. Techniques are presented which form the mean of an ensemble of LRS spectra, ll of which are only of low signal-to-noise ratio, by quantitative evaluation of the significance of the individual spectra for each object rather than mere acceptance of the 'average spectrum' present in the complete LRS data base. Average LRS spectra for groups of galaxies with distinct optical nuclear properties are formed. Average LRS spectra for several categories of objects are presented and interpreted. H II region galaxies show the polycyclic aromatic hydrocarbon spectrum of bands in emissions; type 2 Seyferts present a broad emission feature parking near 16 microns; LINERs and galaxies without optical emission lines have LRS spectra that decline with wavelength, whereas type 1 Seyferts and WR galaxies have red spectra suggestive of nonthermal emission processes.

Cohen, M.↗

NASA NTRS1992

Quenched carbonaceous composite - Fluorescence spectrum compared to the extended red emission observed in reflection nebulae

The photoluminescence (fluorescence) of a film of the laboratory-synthesized quenched carbonaceous composite (filmy QCC) is shown to have a single broad emission feature with a peak wavelength that varies from 670 to 725 nm, and coincides with that of the extended red emission observed in reflection nebulae. The rapid decay of the filmy QCC red fluorescence in air and of the stable blue fluorescence of the filmy QCC dissolved in liquid Freon suggests that the red fluorescence originates from the interaction of active chemical species and aromatic components in the filmy QCC. A material similar in nature to that of the filmy QCC may be a major component of interstellar dust.

Sakata, Akira↗

NASA NTRS1992

Is a pyrene-like molecular ion the cause of the 4,430-A diffuse interstellar absorption band?

The diffuse interstellar band (DIB) absorption features of astronomical spectra are suggested by recent results to be separable from the grains that cause visual extinction. Attention is presently given to laboratory measurements of the optical spectrum of the pyrene cation C16H10(+), which is one of the polycyclic aromatic hydrocarbon (PAH) molecular candidates proposed as carriers for DIBs. This ion exhibits an intense but strangely broad continuum similar to that of the naphthalene cation, so that this may be a common feature of all PAH cations and the basis of an explanation for PAHs' converting of an interstellar radiation fraction as large as that from the UV and visible range down to the IR.

Salama, F.↗

NASA NTRS1992

Chemistry and properties of poly(arylene ether benzoxazole)s

Several new poly(arylene ether benzoxazole)s (PAEBs) were prepared by the nucleophilic displacement reaction of activated aromatic difluorides with two novel bis(hydroxyphenyl benzoxazole), using potassium carbonate. The 6F-containing PAEBs exhibited better solubility and higher Tgs than did the 6,6'-bis-(2-(4-hydroxyphenyl)benzoxazole)-derived polymers. Several of the 6,6'bis(2-(4-hydroxyphenyl)benzoxazole)-derived polymers exhibited crystallinity by DSC and wide-angle X-ray diffraction. Unorientated thin film properties of the 6F-containing PAEBs were comparable to those of other 6F-containing PAEBS that were previously reported. The chemistry and the physical and mechanical properties of the above polymers are discussed.

Smith, J. G., Jr.↗

NASA NTRS1993

Polyimides Containing Amide And Perfluoroisopropyl Links

New polyimides synthesized from reactions of aromatic hexafluoroisopropyl dianhydrides with asymmetric amide diamines. Soluble to extent of at least 10 percent by weight at temperature of about 25 degrees C in common amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Polyimides form tough, flexible films, coatings, and moldings. Glass-transition temperatures ranged from 300 to 365 degrees C, and crystalline melting temperatures observed between 543 and 603 degrees C. Display excellent physical, chemical, and electrical properties. Useful as adhesives, laminating resins, fibers, coatings for electrical and decorative purposes, films, wire enamels, and molding compounds.

Dezem, James F.↗

NASA NTRS1993

Molecular-Weight-Controlled, End-Capped Polybenzimidazoles

Novel molecular-weight-controlled end-capped poly(arylene ether benzimidazole)s (PAEBI's) prepared by nucleophilic displacement reaction of di(hydroxyl)benzimidazole monomers with activated aromatic dihalides. Polymers prepared at various molecular weights by upsetting stoichiometry of monomers and end-capped with monohydroxybenzimidazole. Exhibit favorable physical and mechanical properties, improved solubility in polar aprotic solvents and better compression moldability. Potential applications as adhesives, coatings, films, fibers, membranes, moldings, and composite matrix resins.

Connell, John W.↗

NASA NTRS1992

Modification of primordial ices by cosmic rays as simulated by cyclotron irradiation

Frozen CH4 and CH4/Ar mixtures closed into metal cuvettes and open to the vacuum were irradiated at 15 and 77 K with 10 - 20 MeV p and He-3(2+) ions in order to simulate the effect of cosmic rays on solid organic matter in space. Ices exposed to vacuum represent surfaces of icy systems whereas closed systems stand for bulk ices. The products were analyzed by MS, SEM, RBS, ERDA, H-1-NMR, HPLC, GC-MS, NEXAFS, and FT-IR. Volatile products consisted of a mixture of low molecular species, e.g., C2H2, C2H4, C2H6, and long linear aliphatic and olefinic compounds. The formation of polycyclic aromatic hydrocarbons (PAH's) and related species in solid CH4 is due to a multi-center reaction within one collision cascade and is governed by energy density effects with critical linear energy transfer values L(sub T) between 2 and 10 keV/micron. Open ices exhibit preferential hydrogen release resulting in an increased carbonization as compared to more hydrogen rich molecules protected inside large icy bodies.

Kaiser, R. I.↗

NASA NTRS1993

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photo absorption, photo dissociation, and fluorescence cross sections of interstellar molecules and radicals were measured in the vacuum ultraviolet region. These quantitative optical data are useful for understanding of the formation and destruction processes of molecules under the intense interstellar W radiation field. Infrared (IR) emissions from W excitation of aromatic molecules were also observed in this research program. The research results are useful for studying the sources of the 'unidentified' interstellar infrared (UIR) emission bands.

Lee, Long C.↗

NASA NTRS1993

Measurements of soot formation and hydroxyl concentration in near critical equivalence ratio premixed ethylene flame

The testing and development of existing global and detailed chemical kinetic models for soot formation requires measurements of soot and radical concentrations in flames. A clearer understanding of soot particle inception relies upon the evaluation and refinement of these models in comparison with such measurements. We present measurements of soot formation and hydroxyl (OH) concentration in sequences of flat premixed atmospheric-pressure C2H4/O2/N2 flames and 80-torr C2H4/O2 flames for a unique range of equivalence ratios bracketting the critical equivalence ratio (phi(sub c)) and extending to more heavily sooting conditions. Soot volume fraction and number density profiles are measured using a laser scattering-extinction apparatus capable of resolving a 0.1 percent absorption. Hydroxyl number density profiles are measured using laser-induced fluorescence (LIF) with broadband detection. Temperature profiles are obtained from Rayleigh scattering measurements. The relative volume fraction and number density profiles of the richer sooting flames exhibit the expected trends in soot formation. In near-phi(sub c) visibility sooting flames, particle scattering and extinction are not detected, but an LIF signal due to polycyclic aromatic hydrocarbons (PAH's) can be detected upon excitation with an argon-ion laser. A linear correlation between the argon-ion LIF and the soot volume fraction implies a common mechanistic source for the growth of PAH's and soot particles. The peak OH number density in both the atmospheric and 80-torr flames declines with increasing equivalence ratio, but the profile shape remains unchanged in the transition to sooting, implying that the primary reaction pathways for OH remain unchanged over this transition. Chemical kinetic modeling is demonstrated by comparing predictions using two current reaction mechanisms with the atmospheric flame data. The measured and predicted OH number density profiles show good agreement. The predicted benzene number density profiles correlate with the measured trends in soot formation, although anomalies in the benzene profiles for the richer and cooler sooting flames suggest a need for the inclusion of benzene oxidation reactions.

Inbody, Michael Andrew↗

NASA NTRS1993

Polyimides with improved compression moldability

The semicrystalline polyimide prepared by reaction of 3,3',4,4' benzophenonetetracarboxylic (BTDA) and 1,3-bis(4-aminophenoxy 4' benzoyl) benzene (1,3-BABB) is modified so that it can be more readily processed to form adhesive bonds, moldings, and composites. The stoichiometric ratio of the two monomers, BTDA and 1,3-BABB is controlled so that the intermediate polyamide acid is of a calculated molecular weight. A polyimide acid with excess anhydride groups is then reacted with the stoichiometrically required amount of monofunctional aromatic or aliphatic amine required for complete endcapping. The stoichiometrically offset, encapped polyimide is processed at lower temperatures and pressures than the unmodified high molecular weight polyimide with the same repeat unit, and exhibits an improved melt stability.

Hergenrother, Paul M.↗