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At least 541 records · Page 30

Photodissociation of Peroxynitric Acid in the Near-IR

Temperature-dependent near-IR photodissociation spectra were obtained for several vibrational overtone transitions of peroxynitric acid (HNO4) with a tunable OPO photolysis/OH laser-induced-fluorescence system. Band-integrated photodissociation cross-sections (definity integral of sigma(sub diss)), determined relative to that for the 3nu(sub 1), OH stretching overtone, were measured for three dissociative bands. Assuming unit quantum efficiency for photodissociation of 3nu(sub 1), we find 2nu(sub 1) + nu(sub 3)(8242/cm) = (1.21 x 10(exp -20) (independent of temperature), 2nu(sub 1) (6900/cm) = 4.09 x 10(exp 18) * e(sup (-826,5/T)) (295 K greater than T greater than 224 K), and nu(sub 1) + 2nu(sub 3) (6252/cm) = 1.87 x 10(exp -19) * e(sup (- 1410.7/T)) (278 K greater than T greater than 240 K) sq cm/molecule cm. The photodissociation cross-sections are independent of pressure over the range 2 to 40 Torr. Temperature-dependent quantum yields (phi) for these transitions were obtained using integrated absorption cross-sections (definity integral of sigma(sub abs)) of HNO4 overtone vibrations measured with a FTIR spectrometer. In the atmosphere, photodissociation in the infrared is dominated by excitation of the first overtone of the OH stretching vibration (2nu((sub 1)). Inclusion of all dissociative HNO4 overtone and combination transitions yields a daytime IR photolysis rate of approximately 1 x 10(esp -1)/s. This process significantly shortens the estimated lifetime of HNO4 in the upper troposphere and lower stratosphere.

Roehl, Coleen M.↗

Inferring Cirrus Size Distributions Through Satellite Remote Sensing and Microphysical Databases

Since cirrus clouds have a substantial influence on the global energy balance that depends on their microphysical properties, climate models should strive to realistically characterize the cirrus ice particle size distribution (PSD), at least in a climatological sense. To date, the airborne in situ measurements of the cirrus PSD have contained large uncertainties due to errors in measuring small ice crystals (D<60 m). This paper presents a method to remotely estimate the concentration of the small ice crystals relative to the larger ones using the 11- and 12- m channels aboard several satellites. By understanding the underlying physics producing the emissivity difference between these channels, this emissivity difference can be used to infer the relative concentration of small ice crystals. This is facilitated by enlisting temperature-dependent characterizations of the PSD (i.e., PSD schemes) based on in situ measurements. An average cirrus emissivity relationship between 12 and 11 m is developed here using the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite instrument and is used to retrieve the PSD based on six different PSD schemes. The PSDs from the measurement-based PSD schemes are compared with corresponding retrieved PSDs to evaluate differences in small ice crystal concentrations. The retrieved PSDs generally had lower concentrations of small ice particles, with total number concentration independent of temperature. In addition, the temperature dependence of the PSD effective diameter De and fall speed Vf for these retrieved PSD schemes exhibited less variability relative to the unmodified PSD schemes. The reduced variability in the retrieved De and Vf was attributed to the lower concentrations of small ice crystals in the retrieved PSD.

Mitchell, David↗

Theory of the water vapor continuum and validations

A far-wing line shape theory based on the binary collision and quasistatic approximations that is applicable for both the low- and high-frequency wings of the vibration-rotational bands has been developed. This theory has been applied in order to calculate the frequency and temperature dependence of the continuous absorption coefficient for frequencies up to 10,000 cm(exp -1) for pure H2O and for H2O-N2 mixtures. The calculations were made assuming an interaction potential consisting of an isotropic Lennard-Jones part with two parameters that are consistent with values obtained from other data, and the leading long-range anisotropic part, together with the measured line strengths and transition frequencies. The results, obtained without the introduction of adjustable parameters, compare well with the existing laboratory data, both in magnitude and in temperature dependence. This leads us to the conclusion that the water continuum can be explained in terms of far-wing absorption. Current work in progress to extend the theory and to validate the theoretically calculated continuum will be discussed briefly.

Tipping, Richard H.↗

(abstract) Experimental and Modeling Studies of the Exchange Current at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

The microscopic mechanism of the alkali ion-electron recombination reaction at the three phase boundary zone formed by a porous metal electrode in the alkali vapor on the surface of an alkali beta'-alumina solid electrolyte (BASE) ceramic has been studied by comparison of the expected rates for the three simplest reaction mechanisms with known temperature dependent rate data; and the physical parameters of typical porous metal electrode/BASE/alkali metal vapor reaction zones. The three simplest reactions are tunneling of electrons from the alkali coated electrode to a surface bound alkali metal ion; emission of an electron from the electrode with subsequent capture by a surface bound alkali metal ion; and thermal emission of an alkali cation from the BASE and its capture on the porous metal electrode surface where it may recombine with an electron. Only the first reaction adequately accounts for both the high observed rate and its temperature dependence. New results include crude modeling of simple, one step, three phase, solid/solid/gas electrochemical reaction.

conversion↗

Estimation of the engineering elastic constants of a directionally solidified superalloy for finite element structural analysis

The temperature-dependent engineering elastic constants of a directionally solidified nickel-base superalloy were estimated from the single-crystal elastic constants of nickel and MAR-MOO2 superalloy by using Wells' method. In this method, the directionally solidified (columnar-grained) nickel-base superalloy was modeled as a transversely isotropic material, and the five independent elastic constants of the transversely isotropic material were determined from the three independent elastic constants of a cubic single crystal. Solidification for both the single crystals and the directionally solidified superalloy was assumed to be along the (001) direction. Temperature-dependent Young's moduli in longitudinal and transverse directions, shear moduli, and Poisson's ratios were tabulated for the directionally solidified nickel-base superalloy. These engineering elastic constants could be used as input for performing finite element structural analysis of directionally solidified turbine engine components.

Abdul-Aziz, Ali↗

Dynamic compensation in the central Pacific Ocean

The intermediate-wavelength geoid (lambda similar to 2000 km) and sea-floor topography fields in the central Pacific Ocean were studied in terms of static and dynamic compensation models. Topographic features on the sea-floor with lambda less than 1000 km were found to be compensated both regionally, by the elastic strength of the lithosphere, and locally, by displacing mantle material to reach isostatic adjustment. The larger-scale sea-floor topography and the corresponding geoid anomalies with lambda similar to 2000 km cannot be explained by either local or regional compensation. The topography and the resulting geoid anomaly at this wavelength were modeled by considering the dynamic effects arising from viscous stresses in a layer of fluid with a highly temperature-dependent viscosity for the cases of: (1) surface cooling, and (2) basal heating. In this model, the mechanical properties of the elastic part of the lithosphere were taken into account by considering an activation energy of about 520 kJ/mol in the Arrhenius law for the viscosity. Numerical predictions of the topography, total geoid anomaly, and admittance were obtained, and the results show that the thermal perturbation in the layer, which accounts for the mass deficit, must be located close to the surface to compensate the gravitational effect of the surface deformation. For the case of basal heating, the temperature dependence of viscosity results in a separation of the upper, quasi-rigid lid from the lower mobile fluid, hence inhibiting the development of a compensating thermal perturbation at shallow depths. The results clearly rule out small-scale, upper-mantle convection as the source of these anomalies. Instead, the geophysical observables can be well explained by a shallow, transient thermal perturbation.

Hinojosa, Juan Homero↗

A new thermal sensor for X-ray microcalorimetry

A concept for a detector is introduced which exploits the significant temperature dependence of the dielectric constant in ferroelectric materials. The concept permits the use of a microcalorimeter without the resistive sensors which are associated with heat dissipation and increased Johnson noise in the electronic conversion circuit. General calorimeter features are listed, and the concepts related to dielectric calorimeters are discussed in terms of operational and detection advantages. The use of the device is delineated both theoretically and experimentally with the results of an operational dielectric material. The mixed-crystal quantum ferroelectric is employed and detects 6 MeV alpha particles while operating at 1.2 K in the first detection conducted. The temperature dependence of the dielectric constant in the materials allows for the elimination of resistive sensors in microcalorimeters, thereby improving the ultimate sensitivity of the instrument.

Silver, Eric↗

Boson localization and universality in YBa2Cu(3-x)M(x)O(7-delta)

We consider a two component mixture of charged fermions on neutralizing background with all sign combinations and arbitrarily small mass ratios. In the two impurity limit for the heavier component we show that the pair forms a bound state for all charge combinations. In the lowest order approximation we derive a closed form expression Veff(r) for the binding potential which has short-range repulsion followed by attraction. In the classical limit, when the mass of embedded particles is large m2 much greater than m, we can calculate from Veff(r) also the cohesive energy E and the bond length R of a metallic crystal such as lithium. The lowest order result is R = 3.1 A, E = -0.9 eV, not entirely different from the experimental result for lithium metal. The same interaction for two holes on a parabolic band with m2 greater than m gives the quantum mechanical bound state which one may interpret as a boson or local pair in the case of high-Te and heavy fermion superconductors. We also show that for compounds of the type YBa2Cu(3 - x)M(x)O(7 - delta) one can understand most of the experimental results for the superconducting and normal states with a single temperature dependent boson breaking function f(T) for each impurity content x governing the decay of bosons into pairing fermions. In the normal state f(T) turns out to be a linear, universal function, independent of the impurity content I and the oxygen content delta. We predict with universality a depression in Tc(x) with slight down bending in agreement with experiment. As a natural consequence of the model the bosons become localized slightly above Tc due to the Wigner crystallization, enhanced with lattice local field minima. The holes remain delocalized with a linearly increasing concentration in the normal state, thus explaining the rising Hall density. The boson localization temperature T(sub BL) shows up as a minimum in the Hall density R(sub ab)(exp -1). We also give explanation for very recently observed scaling of temperature dependent Hall effect in La(2 - x)Sr(x)CuO4.

Kallio, A.↗

Oceanic lithosphere and asthenosphere: The thermal and mechanical structure

A coupled thermal and mechanical solid state model of the oceanic lithosphere and asthenosphere is presented. The model includes vertical conduction of heat with a temperature dependent thermal conductivity, horizontal and vertical advection of heat, viscous dissipation or shear heating, and linear or nonlinear deformation mechanisms with temperature and pressure dependent constitutive relations between shear stress and strain rate. A constant horizontal velocity u sub 0 and temperature t sub 0 at the surface and zero horizontal velocity and constant temperature t sub infinity at great depth are required. In addition to numerical values of the thermal and mechanical properties of the medium, only the values of u sub 0, t sub 0 and t sub infinity are specified. The model determines the depth and age dependent temperature horizontal and vertical velocity, and viscosity structures of the lithosphere and asthenosphere. In particular, ocean floor topography, oceanic heat flow, and lithosphere thickness are deduced as functions of the age of the ocean floor.

Schubert, G.↗

An analytical/numerical correlation study of the multiple concentric cylinder model for the thermoplastic response of metal matrix composites

The utility of a recently developed analytical micromechanics model for the response of metal matrix composites under thermal loading is illustrated by comparison with the results generated using the finite-element approach. The model is based on the concentric cylinder assemblage consisting of an arbitrary number of elastic or elastoplastic sublayers with isotropic or orthotropic, temperature-dependent properties. The elastoplastic boundary-value problem of an arbitrarily layered concentric cylinder is solved using the local/global stiffness matrix formulation (originally developed for elastic layered media) and Mendelson's iterative technique of successive elastic solutions. These features of the model facilitate efficient investigation of the effects of various microstructural details, such as functionally graded architectures of interfacial layers, on the evolution of residual stresses during cool down. The available closed-form expressions for the field variables can readily be incorporated into an optimization algorithm in order to efficiently identify optimal configurations of graded interfaces for given applications. Comparison of residual stress distributions after cool down generated using finite-element analysis and the present micromechanics model for four composite systems with substantially different temperature-dependent elastic, plastic, and thermal properties illustrates the efficacy of the developed analytical scheme.

Pindera, Marek-Jerzy↗

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗

The Present and Future of Secondary Organic Aerosol Direct Forcing on Climate

Secondary organic aerosols (SOA), a subset of organic aerosols that are chemically produced in the atmosphere, are included in climate modeling calculations using very simple parameterizations. Estimates on their shortwave forcing on climate span almost two orders of magnitude, being potentially comparable to sulfate direct forcing. In the longwave, a neglected part of the spectrum when it comes to SOA, the direct SOA forcing could exceed that of sulfate and black carbon, although in absolute values it is much weaker than the shortwave forcing. Critical for these estimates is the vertical distribution of the climate active agents, pointing to SOA temperature-dependent volatility. Over the last few years, research also revealed the highly oxidized character of organic aerosol and its chemical aging in the atmosphere that partially leads to the formation of brown carbon, an absorbing form of organic aerosol. This review summarizes critical advances in the understanding of SOA behavior and properties relevant to direct climate forcing and puts them in perspective with regard to primary organic aerosol and brown carbon. These findings also demonstrate an emerging dynamic picture of organic aerosol that has not yet been integrated in climate modeling. The challenges for the coming years in order to reduce uncertainties in the direct organic aerosol climate impact are discussed. High priority for future model development should be given to the dynamic link between “white” and “brown” organic aerosol and between primary and secondary organic aerosol. The SOA temperature-dependent volatility parameterizations and wavelength-dependent refractive index should be also included.

Kostas Tsigaridis↗

Temperature and intensity dependence of the performance of an electron-irradiated (AlGa)As/GaAs solar cell

The performance of a Hughes, liquid-phase epitaxial 2 centimeter-by-2 centimeter, (AlGa)As/GaAs solar cell was measured before and after irradiations with 1 MeV electrons to fluences of 1 x 10 to the 16th power electrons/sq cm. The temperature dependence of performance was measured over the temperature range 135 to 415 K at each fluence level. In addition, temperature dependences were measured at five intensity levels from 137 to 2.57 mW/sq cm before irradiation and after a fluence of 1 x 10 to the 16th power electrons/sq cm. For the intermediate fluences, performance was measured as a function of intensity at 298 K only.

Swartz, C. K.↗

Improved liquid-level sensor for cryogenics

Liquid-level indicator, consisting of a diode heated by a resistor, allows simultaneous use of two or three of the liquids nitrogen, hydrogen, and helium. Operation depends on strong temperature-dependence of the forward resistance of a germanium diode and the difference between liquid and vapor in heat-transfer properties.

Hyman, L. G.↗

Hydrogen evolution in nickel-water heat pipes.

A study was made of the evolution of hydrogen gas in nickel-water heat pipes for the purpose of investigating methods of accelerated life testing. The data were analyzed in terms of a phenomenological corrosion model of heat pipe degradation which incorporates corrosion and oxidation theory and contains parameters which can be determined by experiment. The gas was evolved with a linear time dependence and an exponential temperature dependence with an activation energy of 1.03 x 10 to the minus 19th joules. A flow-rate dependence of the gas evolution was found in the form of a threshold. The results were used to predict usable lifetimes of heat pipes operated at normal operating conditions from results taken under accelerated operating conditions.

Anderson, W. T.↗

Measurement of the spatial dependence of temperature and gas and soot concentrations within large open hydrocarbon fuel fires

A series of large-scale JP-4 fuel pool fire tests was conducted to refine existing mathematical models of large fires. Seven tests were conducted to make chemical concentration and temperature measurements in 7.5 and 15 meter-diameter pool fires. Measurements were made at heights of 0.7, 1.4, 2.9, 5.7, 11.4, and 21.3 meters above the fires. Temperatures were measured at up to 50 locations each second during the fires. Chemistry samples were taken at up to 23 locations within the fires and analyzed for combustion chemistry and soot concentration. Temperature and combustion chemistry profiles obtained during two 7.5 meter-diameter and two 15 meter-diameter fires are included.

Johnson, H. T.↗