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Shielding, the bulk chemical potential, and cohesion in alloys

It is shown that the bulk chemical potential in alloys is intimately related to the spatial dependence of the shielding cloud that results when the electronic charge rearranges itself as one atom type is replaced by another at a given site. Such a relationship fixes the relative energy scale between the alloy and its pure constituents, important in determining the stability of alloys. A correct treatment of shielding is thus essential to quantitative calculations of alloy stability. A model calculation of the bulk chemical potential and cohesion of alloys in the tight-binding approximation is presented as a numerical example. In the course of this investigation a general invariant of an integral over the shielding cloud is derived.

Stern, E. A.

Affordable, Robust Ceramic Joining Technology (ARCJoinT) Given 1999 R and D 100 Award

Advanced ceramics and fiber-reinforced ceramic matrix composites with high strength and toughness, good thermal conductivity, thermal shock resistance, and oxidation resistance are needed for high-temperature structural applications in advanced high-efficiency and high-performance engines, space propulsion components, and land-based systems. The engineering designs of these systems require the manufacturing of large parts with complex shapes, which are either quite expensive or impossible to fabricate. In many instances, it is more economical to build complex shapes by joining together simple geometrical shapes. Thus, joining has been recognized as an enabling technology for the successful utilization of advanced ceramics and fiber-reinforced composite components in high-temperature applications. However, such joints must retain their structural integrity at high temperatures and must have mechanical strength and environmental stability comparable to those of the bulk materials. In addition, the joining technique should be robust, practical, and reliable. ARCJoinT, which is based on the reaction-forming approach, is unique in terms of producing joints with tailorable microstructures. The formation of joints by this approach is attractive since the thermomechanical properties of the joint interlayer can be tailored to be very close to those of the base materials. In addition, high-temperature fixturing is not needed to hold the parts at the infiltration temperature. The joining process begins with the application of a carbonaceous mixture in the joint area, holding the items to be joined in a fixture, and curing at 110 to 120 C for 10 to 20 min. This step fastens the pieces together. Then, silicon or a silicon alloy in tape, paste, or slurry form is applied around the joint region and heated to 1250 to 1425 C (depending on the type of infiltrant) for 10 to 15 min. The molten silicon or silicon-refractory metal alloy reacts with carbon to form silicon carbide with controllable amounts of silicon and other phases as determined by the alloy composition. Joint thickness can be readily controlled through adjustments of the properties of the carbonaceous paste and the applied fixturing force. The photograph shows various shapes of silicon-carbide-based ceramics and fiberreinforced composites that have been joined using ARCJoinT. Thermomechanical and thermochemical characterization of joints is underway for a wide variety of silicon-carbidebased advanced ceramics and fiber-reinforced composites under the hostile environments that will be encountered in engine applications. ARCJoinT, which was developed by researchers at the NASA Glenn Research Center at Lewis Field, received R&D Magazine's prestigious R&D 100 Award in 1999.

Singh, Mrityunjay

Impurity Extraction by Droplets

The goals are to model and to measure the phase equilibrium properties of a finely divided fluid containing a large number of chemically similar species. The objective is to develop an accurate, usable model for such phenomena as pollutant extraction of rain clouds, industrial separation in spray towers, and separation in emulsions. The project was designed as a hierarchy of complementary theoretical and experimental steps. A theory was developed to describe the segregation of complex impurities at the interface of a solvent. This phenomenon is important in phase behavior when a large fraction of molecules in a material are near an interface, the situation in a finely divided material. The theory will be modified to account for the effect of surface curvature on the surface tension. The study of mixtures differs from pure fluids not only because of the surface effects but also because composition differences between the droplet and the surrounding vapor can stabilize a droplet with respect to a bulk phase.

Morrison, G.

A cloudiness transition in a marine boundary layer

In situ aircraft data and lidar data are used to analyze a transition in the boundary layer thermodynamic structure from a clear boundary layer through small cumulus and broken stratocumulus to a deck of solid stratocumulus. The data was collected in conjunction with a Landsat overpass on July 7, 1987 off the coast of southern California. A steady progression in mixing line stability is seen associated with the change in cloudiness. The (empirically based) stability threshold for the breakup of this stratocumulus is that the slope of the mixing line is 0.66 + or - 0.04 of the slope of the wet virtual adiabat. A simple linear parameterization is proposed for cloud fraction in terms of mixing line stability. Surface flux measurements are consistent with bulk aerodynamic estimates.

Boers, Reinout

Perovskite oxides: Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.

Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.

Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite [1]. Morris et al. [1] propose that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks [2,3]. Magnetite stability in terrestrial magmas is well understood, as are the stability of FeO and Fe2O3 in terrestrial magmas [4,5]. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas we have undertaken an experimental study with two emphases. First we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition. Second, we determine the FeO and Fe2O3 contents of the same shergottite bulk composition at 1 bar and variable fO2 at 1250 C, and at variable pressure. These two goals will help define not only magnetite stability, but pyroxene-melt equilibria that are also dependent upon fO2.

Righter, K.

Exploring the Frequency Stability Limits of Whispering Gallery Mode Resonators for Metrological Applications

Whispering gallery mode resonators are attracting increasing interest as promising frequency reference cavities. Unlike commonly used Fabry-Perot cavities, however, they are filled with a bulk medium whose properties have a significant impact on the stability of its resonance frequencies. In this context that has to be reduced to a minimum. On the other hand, a small monolithic resonator provides opportunity for better stability against vibration and acceleration. this feature is essential when the cavity operates in a non-laboratory environment. In this paper, we report a case study for a crystalline resonator, and discuss the a pathway towards the inhibition of vibration-and acceleration-induced frequency fluctuations.

meterology

Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability

Recent interest in propellants with non-toxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because peroxide is sensitive to contaminants, material interactions, stability and storage issues, monitoring decomposition rates is important. Stennis Space Center (SSC) uses thermocouples to monitor bulk fluid temperature (heat evolution) to determine reaction rates. Unfortunately, large temperature rises are required to offset the heat lost into the surrounding fluid. Also, tank penetration to accomodate a thermocouple can entail modification of a tank or line and act as a source of contamination. The paper evaluates a method for monitoring oxygen evolution as a means to determine peroxide stability. Oxygen generation is not only directly related to peroxide decomposition, but occurs immediately. Measuring peroxide temperature to monitor peroxide stability has significant limitations. The bulk decomposition of 1% / week in a large volume tank can produce in excess of 30 cc / min. This oxygen flow rate corresponds to an equivalent temperature rise of approximately 14 millidegrees C, which is difficult to measure reliably. Thus, if heat transfer were included, there would be no temperature rise. Temperature changes from the surrounding environment and heat lost to the peroxide will also mask potential problems. The use of oxygen flow measurements provides an ultra sensitive technique for monitoring reaction events and will provide an earlier indication of an abnormal decomposition when compared to measuring temperature rise.

Ross, H. Richard

A time dependent theory of crazing behavior in polymers

The development of crazing is not only a function of stress, but also a function of time. Under a simple state of tension, a craze opening displacement is closely associated with the viscoelastic behavior of the original bulk polymer medium in which individual crazes initiate and develop. Within each craze region, molecular orientation takes place when conditions permit, and a new phase of rearranged molecules governs its local behavior. Based upon a time-dependent viscoelastic two-dimensional model, using a computer program the craze opening displacement field has been calculated, time-dependent craze length was also computed by taking into consideration the molecular orientation mechanism and large deformations in the craze region. Examples are given for simple viscoelastic media with simplified stress distributions. It is interesting to find out that the occurrence of crazing may be interpreted in terms of the stability or instability of the constitutive behavior of the bulk polymer.

Chern, S. S.

Coated oxidizers for combustion stability in solid-propellant rockets

Experiments are conducted in a laboratory-scale (6.25-cm diameter) end-burning rocket motor with state-of-the-art, ammonium perchlorate hydroxy-terminated polybutadiene (HTPB), nonmetallized propellants. The concept of tailoring the stability characteristics with a small amount (less than 1 percent by weight) of COATING on the oxidizer is explored. The thermal degradation characteristics of the coat chemical are deduced through theoretical arguments on thermal diffusivity of the composite material (propellant). Several candidate coats are selected and propellants are cast. These propellants (with coated oxidizers) are fired in a laboratory-scale end-burning rocket motor, and real-time pressure histories are recorded. The control propellant (with no coating) is also tested for comparison. The uniformity of the coating, confirmed by SEM pictures and BET adsorption measurements, is thought to be an advance in technology. The frequency of bulk mode instability (BMI), the pressure fluctuation amplitudes, and stability boundaries are correlated with parameters related to the characteristic length (L-asterisk) of the rocket motor. The coated oxidizer propellants, in general, display greater combustion stability than the control (state-of-the-art). The correlations of the various parameters are thought to be new to a field filled with much uncertainty.

Helmy, A. M.

Unusual Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite. Morris et al. proposed that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks. Magnetite stability in terrestrial magmas is well understood, as are the stabilities of FeO and Fe2O3 in terrestrial magmas. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas, we have undertaken an experimental study with two emphases. First, we determine the FeO and Fe2O3 contents of super- and sub-liquidus glasses from a shergottite bulk composition at 1 bar to 4 GPa, and variable fO2. Second, we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition.

Danielson, L.

Effects of high temperature and e-beam irradiation on the stability of refractory thin films

Refractory thin films of Al2O3, ZrO2, MgO, ThO2, and BN have been investigated in situ in an UHV transmission electron microscope. The electron transparent refractory films were prepared by electron-beam evaporation, anodization, RF sputtering, and thinning of bulk crystal materials. The study concentrates on monitoring the thermal and mechanical stability of the films, phase and structural changes, and electron irradiation effects as a function of film-preparation conditions. With increasing temperatures, five different crystallographic phases were observed for both anodized and electron-beam-evaporated alumina films. Zirconia films exhibited two phase transitions upon heating to 1200 C and electron-irradiation-induced crystallization of ZrO2 even at room temperature. MgO, ThO2, and BN films did not undergo any noticeable phase transformation but ruptured due to sintering below 1200 C.

Lee, E. H.

TRMM/LIS Lightning: Going Beyond Climatological Composites

The high sensitivity, accuracy and pointing stability of the TRMM/LIS allows analysis of not only tropical bulk lightning production, but of storm cell-based statistics. Issues associated with per-storm flash rate identification are presented, including minimum detectable flash rate, 'unbiasing' the low end of observed storm flash rate spectra, and cell identification. Global lightning bulk composites are disaggregated into contributions from storm frequency of occurrence and per-storm flash rate, with the former dominating the global spatial distribution. Local examination of these fields reveals offsets between peaks in flashing storm occurrence and peaks in storm flash rate, often related to geographic effects and diurnal storm evolution. The correlation of storm-level statistics with theoretical measures of meso/large scale coupling (e.g., the gross moist stability of the tropical atmosphere as calculated by Neelin et al) is shown.

Boccippio, Dennis J.

Deposit formation in hydrocarbon fuels

The hydrocarbon fuels RP-1, commercial-grade propane, JP-7 and chemically pure propane were subjected to tests in a high pressure fuel coking apparatus in order to evaluate their thermal decomposition limits and carbon deposition rates in heated copper tubes. A fuel thermal stability parametric evaluation was conducted at 136-340 atmospheres, bulk fuel velocities of 6-30 m/sec, and tube wall temperatures of 422-811 K, and the effect of inside wall material on deposit formation was evaluated in tests using nickel-plated tubes. Results show RP-1 deposit formation at wall temperatures between 600 and 800 K, with peak deposit formation near 700 K. Substitution of deoxygenated JP-7 for RP-1 showed no improvement, and the carbon deposition rates for propane fuels were found to be higher than those of either of the kerosene fuels. Nickel plating of the tube walls significantly reduced RP-1 carbon deposition rates.

Roback, R.

Streaming tearing mode

The magnetohydrodynamic stability of streaming tearing mode is investigated numerically. A bulk plasma flow parallel to the antiparallel magnetic field lines and localized in the neutral sheet excites a streaming tearing mode more strongly than the usual tearing mode, particularly for the wavelength of the order of the neutral sheet width (or smaller), which is stable for the usual tearing mode. Interestingly, examination of the eigenfunctions of the velocity perturbation and the magnetic field perturbation indicates that the streaming tearing mode carries more energy in terms of the kinetic energy rather than the magnetic energy. This suggests that the streaming tearing mode instability can be a more feasible mechanism of plasma acceleration than the usual tearing mode instability.

Shigeta, M.

Chemical spray pyrolysis of Tl-Ba-Ca-Cu-O high-T(sub c) superconductors for high-field bitter magnets

The deposition of Tl-Ba-Ca-Cu-O thick films by spray pyrolyzing a Ba-Ca-Cu-O precursor film and diffusing thallium into the film to form the superconducting phase is examined. This approach was taken to reduce exposure to thallium and its health and safety hazards. The Tl-Ba-Ca-Cu-O system was selected because it has very attractive features which make it appealing to device and manufacturing engineering. Tl-Ba-Ca-Cu-O will accommodate a number of superconducting phases. This attribute makes it very forgiving to stoichiometric fluctuations in the bulk and film. It has excellent thermal and chemical stability, and appears to be relatively insensitive to chemical impurities. Oxygen is tightly bound into the systems, consequently there is no orthorhombic (conductor) to tetragonal (insulator) transition which would affect a component's lifetime. More significantly, the thallium based superconductors appear to have harder magnetic properties than the other high-Tc oxide ceramics. Estimates using magnetoresistance measurements indicate that at 77 K Tl2Ba2CaCu2O10 will have an upper critical field, H(sub c2) fo 26 Tesla for applied fields parallel to the c-axis and approximately 1000 Tesla for fields oriented in the a-b plane. Results to date have shown that superconducting films can be reproducibly deposited on 100 oriented MgO substrates. One film had a zero resistance temperature of 111.5 K. Furthermore, x ray diffraction analysis of the films showed preferential c-axis orientation parallel to the plane of the substrate. These results have now made it possible to consider the manufacture of a superconducting tape wire which can be configured into a topology useful for high-field magnet designs. The research which leads to the preparation of these films and plans for further development are reviewed.

Derochemont, L. Pierre

Simulation studies of plasma waves in the electron foreshock - The generation of downshifted oscillations

The generation of waves with frequencies downshifted from the plasma frequency, as observed in the electron foreshock, is analyzed by particle simulation. Wave excitation differs fundamentally from the familiar excitation of the plasma eigenmodes by a gentle bump-on-tail electron distribution. Beam modes are destabilized by resonant interaction with bulk electrons, provided the beam velocity spread is very small. These modes are stabilized, starting with the higher frequencies, as the beam is broadened and slowed down by the interaction with the wave spectrum. Initially a very cold beam is also capable of exciting frequencies considerably above the plasma frequency, but such oscillations are quickly stabilized. Low-frequency modes persist for a long time, until the bump in the electron distribution is completely 'ironed' out. This diffusion process also is quite different from the familiar case of well-separated beam and bulk electrons. A quantitative analysis of these processes is carried out.

Dum, C. T.