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At least 127 records · Page 7

Undercoolability and the exposure of metastable structures

The thermodynamic conditions for exposing metastable states are established by deenergizing a material, as in melt quenching, condensation, etc. When these conditions are met, metastable states may appear because they are kinetically preferred. The understanding of these kinetic preferences is reviewed. Formation of metastable structures by melt quenching requires high resistance to crystal nucleation to deep undercooling through the labile regime between the liquidus and configurational freezing temperature, Tg. Further, the growth of the most stable phase must be thermally activated (and therefore quench-suppressible) if the metastable state is to persist at T less than Tg. In metal systems, selective alloying is often crucial to the provision of the nucleation and/or growth resistance requisite to forming various metastable structures. These alloying effects are surveyed and interpreted.

Turnbull, David↗

Synthesis, curing and physical behavior of maleimide terminated poly(arylene ethers)

This paper describes the synthesis of maleimide terminated poly(ether ketones) using the solution imidization process described by Summers et al. (1987). Amorphous poly(arylene ether ketones), as well as poly(arylene ether sulfones, of controlled end group functionalities and molecular weights were synthesized by nucleophilic step polymerization of bisphehol-A phenolates with activated halides, such as 4,4'-difluorobenzophenone, and 'monofunctional' end cappers such as m-aminophenol. The thermal properties of the system included glass transition temperature (Tg) values of 160-170 C, with modulus above Tg proportional to cross-link density, which in turn was reciprocally related to oligomer molecular weight. The measurements of the fracture toughness values showed the materials to be very ductile, with the toughness increasing with oligomer molecular weight.

Lyle, G. D.↗

The glass transition, crystallization and melting in Au-Pb-Sb alloys

The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

Lee, M. C.↗

Satellite measurements of large-scale air pollution - Measurements of forest fire smoke

The transport, optical properties, total mass, and removal of smoke produced by forest fires in western Canada during late July and early August 1982 are studied using NOAA 7 AVHRR data. Color composite imagery is produced to track the movement of the smoke over Canada and the U.S. as the smoke traveled thousands of km from the source region. Smoke optical thickness, particle size, and single scattering albedo are computed using radiances measured by AVHRR bands 1 and 2. Results show that smoke optical thickness ranged from less that 0.1 to greater than 3.7 and the geometric mean mass radii ranged from 300 to 900 nm. The smoke single scattering albedo ranged from 0.9 to nearly 1.0. The total smoke mass over the eastern U.S. ranged from 0.1 to 0.5 Tg, which is close to the 0.5 Tg estimated from the forest fuel content. The smoke lifetime is estimated to be between 15 and 20 days.

Ferrare, Richard A.↗

A methane flux transect along the trans-Alaska pipeline haul road

This paper reports and analyzes methane flux measurements made during the summer of 1987 at 10 km intervals along a north-south direction from Prudhoe Bay to the Arctic Circle in Alaska. Mean CH4 flux from the arctic tundra was 52 mg/sq m/d while that from high-latitude taiga was 11 mg/sq m/d. Fluxes in mg/sq m/d for various plant communities were: wet tundra, 90; low brush-muskeg bog, 45; moist tundra, 31; freshwater ponds, 21; spruce forest, 4.6; and alpine tundra, 0.6. Annual CH4 emission from global tundra and taiga environments is estimated at 38 Tg and 15 Tg, respectively. This is about 46 percent of the wetland emission term of 10 percent of the global atmospheric input.

Whalen, S. C.↗

A two-dimensional study of ethane and propane oxidation in the troposphere

The chemistry of ethane and propane is studied using a global two-dimensional 'zonally averaged' height- and latitude-dependent tropospheric model. The purpose of the study is to derive theoretical estimates of the seasonal and latitudinal distributions of a variety of intermediate organic compounds formed by the photochemical oxidation of C2H6 and C3H8. It is shown that C2H6 and C3H8 emitted at rates of 16 Tg C2H6/a and 23 Tg C3H8/a do not affect the overall photochemistry of the troposphere significantly. Major global effects on O3 and OH concentrations are suggested to be coming from the formation of peroxyacetyl nitrate by the interactions of NOx with other hydrocarbons with strong and spatially correlated anthropogenic or natural sources at the earth's surface. It is pointed out that attention should be given to organic nitrates produced by the oxidation of NMHC other than C2H6 and C3H8.

Kanakidou, M.↗

A model for inferring canopy and underlying soil temperatures from multi-directional measurements

A model is presented of thermal emission from a canopy/soil surface, where the soil and the leaves are at different temperatures, Tg and Tc, respectively. The temperature Tm corresponding to a radiometer reading is given by B sub lambda(Tm) = chi-B sub lambda(Tg) + (1-chi)B sub lambda(Tc), where B sub lambda denotes the Planck blackbody function at wavelength lambda, chi specifies the fraction of the field of view occupied by the soil at a given view direction, and an emissivity of 1.0 is assumed for the plants and the soil. It is observed that at large view zenith angles, only the plants are effectively seen, and therefore Tc can be determined from the observations a large zenith angles, to the extent that such observations are practical. Water stress can produce an increase of chi and thus tends to produce an exaggerated increase in the observed temperature compared to the actual increase in canopy temperature. These effects are analyzed for a simulated soybean canopy.

Otterman, J.↗

The atmospheric CH4 increase since the Last Glacial Maximum. II - Interactions with oxidants

Results of two studies of the effect of changing CH4 fluxes on global tropospheric oxidant levels, O3, OH, and H2O2, performed with a multibox photochemical model, are presented. A sensitivity study is conducted by scaling back CH4, CO, and NO emissions relative to the present-day budget. When the CH4 ice core record is compared to calculated CH4 abundances, corresponding CH4 fluxes for the preindustrial Holocene (PIH) and Last Glacial Maximum (LGM) are fairly well-constrained: 175-225 Tg CH/4/yr for PIH and 100-130 Tg CH4/yr for LGM. Specific scenarios for CH4/CO/NO are selected to represent sources for the PIH and LGM. The CH4 budget is taken from an evaluation of wetlands and other natural sources.

Thompson, Anne M.↗

Role of the Hudson Bay lowland as a source of atmospheric methane

Based on point measurements of methane flux from wetlands in the boreal and subarctic regions, northern wetlands are a major source of atmospheric methane. However, measurements have not been carried out in large continuous peatlands such as the Hudson Bay Lowland (HBL) (320,000 sq km) and the Western Siberian lowland (540,000 sq km), which together account for over 30% of the wetlands north of 40 deg N. To determine the role the Hudson Bay Lowland as a source of atmospheric methane, fluxes were measured by enclosures throughout the 1990 snow-free period in all the major wetland types and also by an aircraft in July. Two detailed survey areas were investigated: one (approximately 900 sq km) was in the high subarctic region of the northern lowland and the second area (approximately 4,800 sq km) straddled the Low Subarctic and High Boreal regions of the southern lowland. The fluxes were integrated over the study period to produce annual methane emissions for each wetland type. The fluxes were then weighted by the area of 16 different habitats for the southern area and 5 habitats for the northern area, as determined from Landsat thematic mapper to yield an annual habitat-weighted emission. On a per unit area basis, 1.31 +/- 0.11 and 2.79 +/- 0.39 g CH4 m(exp -2)/yr were emitted from the southern and northern survey areas, respectively. The extrapolated enclosure estimates for a 3-week period in July were compared to within 10% of the flux derived by airborne eddy correlation measurements made during the same period. The aircraft mean flux of 10 +/- 9 mg CH4 m(exp -2)/d was not statistically different from the extrapolated mean flux of 20 +/- 16 mg CH4 m(exp -2)/d. The annual habitat-weighted emission for the entire HBL using six wetland classes is estimated as 0.538 +/- 0.187 Tg CH4/yr (range of extreme cases is 0.057 to 2.112 Tg CH4/yr). This value is much lower than expected, based on previous emission estimates from northern wetlands.

Roulet, Nigel T.↗

Synthesis of low color, atomic oxygen resistant polyimides

The purpose of this project was to develop low color, atomic oxygen resistant polyimides for potential applications on spacecraft in low earth orbit. The material is needed in order to protect satellites and spacecraft from the gases and radiation found at those altitudes. Phosphorous containing polyimides have been shown to be especially resistant to corrosion and weight loss under oxygen plasma. Unfortunately the color of these phosphorous containing polyimides is still too high for them to be good heat insulators. While they are not as effective as teflon, the current material of choice. polyimides are much less dense than teflon and would be especially valuable if they could be made with low color. The approach taken was to synthesize a monomer which would contain the elements needed for giving the final polyimide its desired properties. In particular the monomer should incorporate phosphine or phosphine oxides and have bulky side groups to block any color forming charge transfer structures. The target molecule, 3,5-di-(trifluoromethylphenyl)-bis(3-aminophenyl) phosphine oxide, (containing both a phosphine oxide group and a bulky ditrifluoromethylphenyl group) was synthesized via three reactions in overall yield of 21 percent. In addition, a model compound, bis(3-phenylamine) phenyl phosphine oxide, was synthesized two different ways in order to establish the conditions for the nitration of phosphine oxides and their reduction to the amine. Finally, a trisubstituted phosphine oxide was synthesized. In all, seven phosphorus containing organic compounds were synthesized, purified and characterized. The model compound was reacted with oxydiphthalic anhydride to form a polyamic acid with inherent viscosity of 0.34. This material was cast into a film and heated, forming a normally colored fairly strong polyimide with a Tg of 240 C. The target compound was reacted with 6-fluorodiphthalic anhydride to give a polyamic acid with inherent viscosity of 0.19 and cast to give a heavily cracked colored film with a Tg of 230 C.

MacInnes, Dave↗

Regular Topologies for Gigabit Wide-Area Networks: Congestion Avoidance Testbed Experiments

This document is Volume 3 of the final technical report on the work performed by SRI International (SRI) on SRI Project 8600. The document includes source listings for all software developed by SRI under this effort. Since some of our work involved the use of ST-II and the Sun Microsystems, Inc. (Sun) High-Speed Serial Interface (HSI/S) driver, we have included some of the source developed by LBL and BBN as well. In most cases, our decision to include source developed by other contractors depended on whether it was necessary to modify the original code. If we have modified the software in any way, it is included in this document. In the case of the Traffic Generator (TG), however, we have included all the ST-II software, even though BBN performed the integration, because the ST-II software is part of the standard TG release. It is important to note that all the code developed by other contractors is in the public domain, so that all software developed under this effort can be re-created from the source included here.

Denny, Barbara A.↗

Development of Polyimides-Based NLO Materials for Electrooptical Applications

Development of thermally stable optical materials for nonlinear optics have recently focused on the covalent incorporation of NLO chromophores into high performance polymers, especially thermally stable and processable polyamides. One key aspect for the incorporation of robust NLO chromophores into high Tg polymers is to sustain poling induced order. Other advantages include high loading level of chromophores, and elimination of possible phase separation as well as chromophore sublimation at processing or working temperature. We have prepared several polyimide based polymers which are covalently linked with thermally stable chromophores that we have developed, since polyamides generally exhibit high Tg and good film transparency. Here, we report the development and subsequent incorporation of indoline based chromophores into polyamides, leading to thermally stable NLO polymers.

Rutherford, Jacqueline↗

Comparison of Oxygen Gauche Effects in Poly(Oxyethylene) and Poly(ethylene terephtylene) Based on Quantum Chemistry Calculations

The so-called oxygen gauche effect in poly(oxyethylene) (POE) and its model molecules such as 1,2-dimethoxyethane (DME) and diglyme (CH3OC2H4OC2H4OCH3) is manifested in the preference for gauche C-C bond conformations over trans. This has also been observed for poly(ethylene terephthalate) (PET). Our previous quantum chemistry calculations demonstrated that the large C-C gauche population in DME is due, in part, to a low-lying tg +/- g+ conformer that exhibits a substantial 1,5 CH ... O attraction. New calculations will be described that demonstrate the accuracy of the original quantum chemistry calculations. In addition, an extension of this work to model molecules for PET will be presented. It is seen that the C-C gauche preference is much stronger in 1,2 diacetoxyethane than in DME. In addition, there exist low-lying tg +/- g+/- and g+/-g+/-g+/- conformers that exhibit 1,5 CH ... O attractions involving the carbonyl oxygens. It is expected that the -O-C-C-O- torsional properties will be quite different in these two polymers. The quantum chemistry results are used to parameterize rotational isomeric states models (RIS) and force fields for molecular dynamics simulations of these polymers.

Jaffe, Richard↗

Thermal Expansion and Diffusion Coefficients of Carbon Nanotube-Polymer Composites

Classical molecular dynamics (MD) simulations employing Brenner potential for intra-nanotube interactions and van der Waals forces for polymer-nanotube interface have been used to investigate thermal expansion and diffusion characteristics of carbon nanotube-polyethylene composites. Addition of carbon nanotubes to polymer matrix is found to significantly increase the glass transition temperature Tg, and thermal expansion and diffusion coefficients in the composite above Tg. The increase has been attributed to the temperature dependent increase of the excluded volume for the polymer chains, and the findings could have implications in the composite processing, coating and painting applications.

Wei, Chengyu↗

Infrared Spectroscopy as a Chemical Fingerprinting Tool

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. The technique is rapid, reproducible and usually non-invasive. With the appropriate accessories, the technique can be used to examine samples in either a solid, liquid or gas phase. Solid samples of varying sizes and shapes may be used, and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be examined. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Both aqueous and non-aqueous free-flowing solutions can be analyzed using appropriate IR techniques, as can viscous liquids such as heavy oils and greases. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

Huff, Tim↗

High Temperature Transfer Molding Resins Based on 2,3,3',4'-Biphenyltetracarboxylic Dianhydride

As part of an ongoing effort to develop materials for resin transfer molding (RTM) processes to fabricate high performance/high temperature composite structures, phenylethynyl containing imides have been under investigation. New phenylethynyl containing imide compositions were prepared using 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) and evaluated for cured glass transition temperature (Tg), melt flow behavior, and for processability into flat composite panels via RTM. The a-BPDA imparts a unique combination of properties that are desirable for high temperature transfer molding resins. In comparison to its symmetrical counterpart (i.e. 3,3',4,4'-biphenyltetracarboxylic dianhydride), a-BPDA affords oligomers with lower melt viscosities and when cured, higher Tgs. Several candidates exhibited the appropriate combination of properties such as a low and stable melt viscosity required for RTM processes, high cured Tg, and moderate toughness. The chemistry, physical, and composite properties of select resins will be discussed.

Smith, J. G., Jr.↗

Infrared Spectroscopy as a Chemical Fingerprinting Tool

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. Any sample material that will interact with infrared light produces a spectrum and, although normally associated with organic materials, inorganic compounds may also be infrared active. The technique is rapid, reproducible and usually non-invasive to the sample. That it is non-invasive allows for additional characterization of the original material using other analytical techniques including thermal analysis and RAMAN spectroscopic techniques. With the appropriate accessories, the technique can be used to examine samples in liquid, solid or gas phase. Both aqueous and non-aqueous free-flowing solutions can be analyzed, as can viscous liquids such as heavy oils and greases. Solid samples of varying sizes and shapes may also be examined and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be analyzed. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

Huff, Timothy L.↗

Do Integrins Mediate the Skeletal Response to Altered Loading?

In vivo experiments were performed to examine the role of B1 integrin in skeletal adaptation to reduced and increased loading. Transgenic mice were generated with a dominant negative form of the B1 integrin cytoplasmic domain with expression driven by the osteocalcin promoter (pOCb1DN). This fragment consists of the transmembrane and intracellular domains and interferes with endogenous integrin signalling in vitro. This promoter targets expression of the transgene to mature bone cells. Expression of the transgene was confirmed by immunoprecipitation and western blotting. Reduced loading was generated by hindlimb suspension and increased loading the resumption of normal loading following hindlimb suspension. Two groups of female 35-day old mice were examined: poCb1DN transgenic mice (TG) and wild-type littermate controls (WT). Animals were hindlimb suspended for 1 week (HU, n = l0/gp) or 4 weeks (HU, n = 4 - 7/gp) or suspended for 4 weeks followed by reloading by normal ambulation for 4 weeks (RL, n = l0/gp). Age-matched controls (CT) were pairfed based on the HU food intake. The protocols were approved by the NASA Ames Research Center IACUC. Upon completion of the experimental protocol, body mass was recorded and tissues of interest removed and analyzed following standard procedures. Femoral whole bone structural behavior was measured in torsion to failure to obtain whole bone strength (failure torque) and torsional rigidity. Ash content (ash) and fraction (% ash) were determined for the tibia. Total ash is indicative of bone size whereas %ash is a material property. Tibial curvature was measured from microradiographs. For each experiment, the effects of genotype (TG, WT) and treatment (CT, HU/RL) were assessed by two-factor ANOVA followed by the Tukey-Kramer posthoc to identify significant differences at an alpha level of 0.05. Our goal was to understand differences resulting from altered integrin function in the adaptation to altered loading.

vanderMeulen, Marjolein C. H.↗