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At least 91 records · Page 5

Homogeneity of pristine and bromine intercalated graphite fibers

Wide variations in the resistivity of intercalated graphite fibers and to use these materials for electrical applications, their bulk properties must be established. The homogeneity of the diameter, the resistivity, and the mass density of 50 graphite fibers, before and after bromine intercalation was measured. Upon intercalation the diameter was found to expand by about 5%, the resistivity to decrease by a factor of five, and the density to increase by about 6%. Each individual fiber was found to have uniform diameter and resistivity over macroscopic regions for lengths as long as 7 cm. The ratio of pristine to intercalated resistivity increases as the pristine fiber diameter increases at a rate of 0.16 micron, but decreases with the increasing ratio of intercalated diameter to pristine diameter at a rate of 0.08.

Gaier, J. R.↗

Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

Payne, W. A.↗

In search of stratospheric bromine oxide

The Imaging Spectrometric Observatory (ISO) is capable of recording spectra in the wavelength range of 200 to 12000 Angstroms. Data from a recent Spacelab 1 ATLAS mission has imaged the terrestrial airglow at tangent ray heights of 90 and 150 km. These data contain information about trace atmospheric constituents such as bromine oxide (BrO), hydroxyl (OH), and chlorine dioxide (OClO). The abundances of these species are critical to stratospheric models of catalytic ozone destruction. Heretofore, very few observations were made especially for BrO. Software was developed to purge unwanted solar features from the airglow spectra. The next step is a measure of the strength of the emission features for BrO. The final analysis will yield the scale height of this important compound.

Lestrade, John Patrick↗

Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

Gaier, James R.↗

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

Savinell, Robert F.↗

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

Savinell, R. F.↗

Effect of lightning strike on bromine intercalated graphite fiber/epoxy composites

Laminar composites were fabricated from pristine and bromine intercalated pitch based graphite fibers. It was found that laminar composites could be fabricated using either pristine or intercalated graphite fibers using standard fabrication techniques. The intercalated graphite fiber composites had electrical properties which were markedly improved over both the corresponding pitch based and polyacrylonitrile (PAN) based composites. Despite composites resistivities more than an order of magnitude lower for pitch based fiber composites, the lightning strike resistance was poorer than that of the Pan based fiber composites. This leads to the conclusion that the mechanical properties of the pitch fibers are more important than electrical or thermal properties in determining the lightning strike resistance. Based on indicated lightning strike tolerance for high elongation to failure materials, the use of vapor grown, rather than pitch based graphite fibers appears promising.

Gaier, James R.↗

Properties of novel CVD graphite fibers and their bromine intercalation compounds

A hybrid fiber with a PAN core surrounded by a vapor grown carbon fiber (VGCF) sheath was fabricated using a proprietary process. The density, ultimate tensile strength, Young's modulus, and resistivity of pristine and bromine intercalated fibers made by this technique having diameters varying from 5 to 50 microns were compared with the values predicted from the rule of mixtures model. For both the pristine and intercalated fibers, the density, ultimate tensile strength, and Young's modulus of the fibers were lower than predicted, but the resistivity was measured to be consistent with predictions. The lower than theoretical mechanical properties may be evidence of a low density disordered interface between the core and the sheath which would lower the density and degrade the mechanical properties, but would leave the resistivity nearly unaffected. Intercalation had little if any effect on the ultimate tensile strength and Young's modulus, but raised the density by about 11 pct., and lowered the resistivity by an order of magnitude. The diameter dependence of the resistivity showed evidence of a depletion layer of the type found in VGCF.

Gaier, James R.↗

Future chlorine-bromine loading and ozone depletion

The prediction of future ozone requires three elements: (1) a scenario for the net emissions of chemically and radiatively active trace gases from the land and oceans; (2) a global atmospheric model that projects the accumulation of these gases; and (3) a chemical transport model that describes the distribution of ozone for a prescribed atmospheric composition and climate. This chapter, of necessity, presents models for all three elements and focuses on the following: (1) atmospheric abundance of chlorine and bromine in the form of halocarbons; and (2) the associated perturbations to stratospheric ozone.

Prather, Michael J.↗

Properties of hybrid CVD/PAN graphite fibers and their bromine intercalation compounds

A hybrid fiber with a PAN core surrounded by a vapor grown carbon fiber (VGCF) sheath was fabricated using a proprietary process. The density, ultimate tensile strength, Young's modulus, and resistivity of pristine and bromine intercalated fibers made by this technique having diameters varying from 5 to 50 microns were compared with the values predicted from the rule of mixtures model. For both the pristine and intercalated fibers, the density, ultimate tensile strength, and Young's modulus of the fibers were lower than predicted, but the resistivity was measured to be consistent with predictions. The lower than theoretical mechanical properties may be evidence of a low density disordered interface between the core and the sheath which would lower the density and degrade the mechanical properties, but would leave the resistivity nearly unaffected. Intercalation had little if any effect on the ultimate tensile strength and Young's modulus, but raised the density by about 11 pct., and lowered the resistivity by an order of magnitude. The diameter dependence of the resistivity showed evidence of a depletion layer of the type found in VGCF.

Gaier, James R.↗

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBRO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Lee. Timothy J.↗

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBrO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Lee, Timothy J.↗

The Sensitivity of Arctic Ozone Loss to Polar Stratospheric Cloud Volume and Chlorine and Bromine Loading in a Chemistry and Transport Model

The sensitivity of Arctic ozone loss to polar stratospheric cloud volume (V(sub PSC)) and chlorine and bromine loading is explored using chemistry and transport models (CTMs). A simulation using multi-decadal output from a general circulation model (GCM) in the Goddard Space Flight Center (GSFC) CTM complements one recycling a single year s GCM output in the Global Modeling Initiative (GMI) CTM. Winter polar ozone loss in the GSFC CTM depends on equivalent effective stratospheric chlorine (EESC) and polar vortex characteristics (temperatures, descent, isolation, polar stratospheric cloud amount). Polar ozone loss in the GMI CTM depends only on changes in EESC as the dynamics repeat annually. The GSFC CTM simulation reproduces a linear relationship between ozone loss and Vpsc derived from observations for 1992 - 2003 which holds for EESC within approx.85% of its maximum (approx.1990 - 2020). The GMI simulation shows that ozone loss varies linearly with EESC for constant, high V(sub PSC).

Douglass, A. R.↗

Shuttle Environmental Assurance: Brominated Flame Retardants - Concerns, Drivers, Potential Impacts and Mitigation Strategies

Brominated Flame Retardants (BFRs) are widely used in the manufacture of electrical and electronic components and as additives in formulations for foams, plastics and rubbers. The United States (US) and the European Union (EU)have increased regulation and monitoring of of targeted BFRs, such as Polybrominated Diphenyl Ethers (PBDEs) due to the bioaccumulative effects in humans and animals. In response, manufacturers and vendors of BFR-containing materials are changing flame-retardant additives, sometimes without notifying BFR users. In some instances, Deca-bromodiphenylether (Deca-BDE) and other families of flame retardants are being used as replacement flame retardants for penta-BDE and octa-BDE. The reformulation of the BFR-containing material typically results in the removal of the targeted PBDE and replacement with a non-PBDE chemical or non-targeted PBDE. Many users of PBDE -based materials are concerned that vendors will perform reformulation and not inform the end user. Materials performance such as flammability, adhesion , and tensile strength may be altered due to reformulation. The requalification of newly formulated materials may be required, or replacement materials may have to be identified and qualified. The Shuttle Enviornmental Assurance (SEA) team indentified a risk to the Space Shuttle Program associated with the possibility that targeted PBDEs may be replaced without notification. Resultant decreases in flame retardancy, Liquid Oxygen (LOX) compatibility, or material performance could have serious consequences.

Clark-Ingram, Marceia↗

Bromine Dioxide, OBrO: The Rotational Spectrum and Molecular Properties

The spectra are well descrie by Hamiltonian which included centrifugal distortion efects for fine and hyperfine terms. The molecular structure and the harmonic force field have been derived, and they as well as fine and hyperfine structure constants, are compared with data of related molecules and ESR data from OBrO isolated in cryogenic salt matrices.

Bromine Dioxide Rotational Spectrum↗