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67 records · Page 4

Diffusion NMR methods applied to xenon gas for materials study

We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. c2002 John Wiley & Sons, Ltd.

NASA Discipline Life Sciences Technologies↗

Lunar Dust and Lunar Simulant Activation and Monitoring

Prior to returning to the moon, understanding the effects of lunar dust on both human physiology and mechanical equipment is a pressing concern, as problems related to lunar dust during the Apollo missions have been well documented (J.R. Gaier, The Effects of Lunar Dust on EVA Systems During the Apollo Missions. 2005, NASA-Glenn Research Center. p. 65). While efforts were made to remove the dust before reentering the lunar module, via brushing of the suits or vacuuming, a significant amount of dust was returned to the spacecraft, causing various problems. For instance, astronaut Harrison Schmitt complained of hay fever effects caused by the dust, and the abrasive nature of the material was found to cause problems with various joints and seals of the spacecraft and suits. It is clear that, in order to avoid potential health and performance problems while on the lunar surface, the reactive properties of lunar dust must be quenched. It is likely that soil on the lunar surface is in an activated form, i.e. capable of producing oxygen-based radicals in a humidified air environment, due to constant exposure to meteorite impacts, UV radiation, and elements of the solar wind. An activated silica surface serves as a good example. An oxygen-based radical species arises from the breaking of Si-OSi bonds. This system is comparable to that expected for the lunar dust system due to the large amounts of agglutinic glass and silicate vapor deposits present in lunar soil. Unfortunately, exposure to the Earth s atmosphere has passivated the active species on lunar dust, leading to efforts to reactivate the dust in order to understand the true effects that will be experienced by astronauts and equipment on the moon. Electron spin resonance (ESR) spectroscopy is commonly used for the study of radical species, and has been used previously to study silicon- and oxygen-based radicals, as well as the hydroxyl radicals produced by these species in solution (V. Vallyathan, et al., Am. Rev. Respir. Dis. 138 (1988) 1213-1219). The size and cost of these instruments makes them unattractive for the monitoring of lunar dust activity. A more suitable technique is based on the change in fluorescence of a molecule upon reaction with a hydroxyl radical (or other radical species). Fluorescence instruments are much less costly and bulky than ESR spectrometers, and small fluorescence sensors for space missions have already been developed (F. Gao, et al., J. Biomed. Opt. 10 (2005) 054005). For the current fluorescence studies, the terephthalate molecule has been chosen for monitoring the production of hydroxyl radicals in solution. As shown in Scheme 1, the reaction between the non-fluorescent terephthalate molecule and a hydroxyl radical produces the highly-fluorescent 2-hydroxyterephthalate molecule.

Wallace, W. T.↗

Estimation of Length-Scales in Soils by MRI

Soil can be best described as an unconsolidated granular media that forms porous structure. The present macroscopic theory of water transport in porous media rests upon the continuum hypothesis that the physical properties of porous media can be associated with continuous, twice-differentiable field variables whose spatial domain is a set of centroids of Representative Elementary Volume (REV) elements. MRI is an ideal technique to estimate various length-scales in porous media. A 0.267 T permanent magnet at NASA GRC was used for this study. A 2D or 3D spatially-resolved porosity distribution were obtained from the NMR signal strength from each voxel and the spin-lattice relaxation time. A classical spin-warp imaging with Multiple Spin Echos (MSE) was used to evaluate proton density in each voxel. Initial resolution of 256 x 256 was subsequently reduced by averaging neighboring voxels and the porosity convergence was observed. A number of engineered "space candidate" soils such as Isolite(trademark), Zeoponics(trademark), Turface(trademark), and Profile(trademark) were used. Glass beads in the size range between 50 microns to 2 mm were used as well. Initial results with saturated porous samples have shown a good estimate of the average porosity consistent with the gravimetric porosity measurement results. For Profile(trademark) samples with particle sizes ranging between 0.25 to 1 mm and characteristic interparticle pore size of 100 microns the characteristic Darcy scale was estimated to be about delta(sub REV) = 10 mm. Glass beads porosity show clear convergence toward a definite REV which stays constant throughout homogeneous sample. Additional information is included in the original extended abstract.

N E Daidzic↗

Cross-Effects in Microgravity Flows

Film growth by chemical/physical vapor deposition is a process of considerable interest in microgravity experiments. The absence of natural convection should allow better control of film growth processes but, in highly non-isothermal ampoules, thermal slip (creep) can become a matter of significant concern. The reported research is a theoretical and experimental investigation of the flow of gas/vapor mixtures under non-continuum conditions. The Boltzmann equation has been solved for a monatomic gas under non-condensing conditions and the various phenomenological coefficients have been computed. Computations for realistic potentials as well as for velocity and creep slip have been completed and the creep slip has been found to be dependent on the type of gas confirming the accuracy of previous variational results. The variational technique has been extended and planar flows calculated via the Burnett solutions. Velocity, diffusion and creep slips have been computed for gas mixtures and previously unknown dependencies of the creep slip on the mixture properties have been observed. Also for gas mixtures, an integral representation of the linearized Boltzmann operator has been developed for use in numerical and variational calculations for all intermolecular force laws. Two, two-bulb capillary systems have been designed, built and tested for the measurements of cross-flows; one of glass for isothermal measurements and one of stainless steel for non-isothermal measurements. Extensive data have been collected for Ar-He and N2-He mixtures at a variety of pressures and mole ratios. Viscosity, velocity slip coefficients and tangential momentum accommodation coefficients have been obtained from measurements with a spinning rotor gauge via a new theory that has been formulated for the spinning rotor gauge in the slip regime. The FIDAP fluid dynamics code has been applied to condensing flows in ampoules in the continuum regime and agreement obtained with the earlier work of Duval.

Loyalka, Sudarshan K.↗

Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Theodornus J Dingemans↗

Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Dingemans, Theodorous J.↗

Fabrication of poly(ethylene glycol) hydrogel microstructures using photolithography

The fabrication of hydrogel microstructures based upon poly(ethylene glycol) diacrylates, dimethacrylates, and tetraacrylates patterned photolithographically on silicon or glass substrates is described. A silicon/silicon dioxide surface was treated with 3-(trichlorosilyl)propyl methacrylate to form a self-assembled monolayer (SAM) with pendant acrylate groups. The SAM presence on the surface was verified using ellipsometry and time-of-flight secondary ion mass spectrometry. A solution containing an acrylated or methacrylated poly(ethylene glycol) derivative and a photoinitiator (2,2-dimethoxy-2-phenylacetophenone) was spin-coated onto the treated substrate, exposed to 365 nm ultraviolet light through a photomask, and developed with either toluene, water, or supercritical CO2. As a result of this process, three-dimensional, cross-linked PEG hydrogel microstructures were immobilized on the surface. Diameters of cylindrical array members were varied from 600 to 7 micrometers by the use of different photomasks, while height varied from 3 to 12 micrometers, depending on the molecular weight of the PEG macromer. In the case of 7 micrometers diameter elements, as many as 400 elements were reproducibly generated in a 1 mm2 square pattern. The resultant hydrogel patterns were hydrated for as long as 3 weeks without delamination from the substrate. In addition, micropatterning of different molecular weights of PEG was demonstrated. Arrays of hydrogel disks containing an immobilized protein conjugated to a pH sensitive fluorophore were also prepared. The pH sensitivity of the gel-immobilized dye was similar to that in an aqueous buffer, and no leaching of the dye-labeled protein from the hydrogel microstructure was observed over a 1 week period. Changes in fluorescence were also observed for immobilized fluorophore labeled acetylcholine esterase upon the addition of acetyl acholine.

NASA Discipline Life Sciences Technologies↗

Melt spinning study

Containerless processing of materials provides an excellent opportunity to study nucleation phenomena and produce unique materials, primarily through the formation of metastable phases and deep undercoolings. Deep undercoolings can be readily achieved in falling drops of molten material. Extended solute solubilities and greatly refined microstructures can also be obtained in containerless processing experiments. The Drop Tube Facility at Marshall Space Flight Center has played an important role in enhancing that area of research. Previous experiments performed in the Drop Tube with refractory metals has shown very interesting microstructural changes associated with deep undercoolings. It is apparent also that the microstructure of the deep undercooled species may be changing due to the release of the latent heat of fusion during recalescence. For scientific purposes, it is important to be able to differentiate between the microstructures of the two types of metallic species. A review of the literature shows that although significant advances have been made with respect to the engineering aspects of rapid solidification phenomena, there is still much to be learned in terms of understanding the basic phenomena. The two major ways in which rapid solidification processing provides improved structures and hence improved properties are: (1) production of refined structures such as fine dendrites and eutectics, and (2) production of new alloy compositions, microstructures, and phases through extended solid solubility, new phase reaction sequences, and the formation of metallic-glass microstructures. The objective of this work has been to determine the optimal methodology required to extract this excess energy without affecting the thermo-physical parameters of the under-cooled melt. In normal containerless processing experiments recalescence occurs as the melt returns toward the melting point in order to solidify. A new type of experiment is sought in which the resultant microstructure of the undercooled species is frozen in without going through the melting point regime and subsequent near equilibrium solidification of the remaining liquid. This experimental approach entails the design of an appropriate melt spinning system which is compatible with Drop Tube operations and processing constraints. That work is the goal of this study.

Workman, Gary L.↗

Steps toward 8m honeycomb mirror blanks. III - 1.8m honeycomb sandwich blanks cast from borosilicate glass

The design, fabrication techniques, and equipment used for producing two 1.8-m honeycomb sandwich blanks, eventually leading to production of 8-m blanks, are reported. The procedure employed 85 cast hexagonal tiles at the bottom section, affixed against flotation by SiC bolts. The two plano concave mirrors are 1.83 m thick, weight 500 kg, and are each designed for 19 supports of astatic-lever type. Both blanks are of high quality and with an adequately low bubble content; one is to be figured to high-precision 0.25-arcsecond images, and is to be tested on the Multiple Mirror Telescope. Construction of a spin-casting facility based on the same principle is being planned for test-fabricating spin-cast mirrors on a smaller scale.

Angel, J. R. P.↗

Manufacturing Precise, Lightweight Paraboloidal Mirrors

A process for fabricating a precise, diffraction- limited, ultra-lightweight, composite- material (matrix/fiber) paraboloidal telescope mirror has been devised. Unlike the traditional process of fabrication of heavier glass-based mirrors, this process involves a minimum of manual steps and subjective judgment. Instead, this process involves objectively controllable, repeatable steps; hence, this process is better suited for mass production. Other processes that have been investigated for fabrication of precise composite-material lightweight mirrors have resulted in print-through of fiber patterns onto reflecting surfaces, and have not provided adequate structural support for maintenance of stable, diffraction-limited surface figures. In contrast, this process does not result in print-through of the fiber pattern onto the reflecting surface and does provide a lightweight, rigid structure capable of maintaining a diffraction-limited surface figure in the face of changing temperature, humidity, and air pressure. The process consists mainly of the following steps: 1. A precise glass mandrel is fabricated by conventional optical grinding and polishing. 2. The mandrel is coated with a release agent and covered with layers of a carbon- fiber composite material. 3. The outer surface of the outer layer of the carbon-fiber composite material is coated with a surfactant chosen to provide for the proper flow of an epoxy resin to be applied subsequently. 4. The mandrel as thus covered is mounted on a temperature-controlled spin table. 5. The table is heated to a suitable temperature and spun at a suitable speed as the epoxy resin is poured onto the coated carbon-fiber composite material. 6. The surface figure of the optic is monitored and adjusted by use of traditional Ronchi, Focault, and interferometric optical measurement techniques while the speed of rotation and the temperature are adjusted to obtain the desired figure. The proper selection of surfactant, speed or rotation, viscosity of the epoxy, and temperature make it possible to obtain the desired diffraction-limited, smooth (1/50th wave) parabolic outer surface, suitable for reflective coating. 7. A reflective coat is applied by use of conventional coating techniques. 8. Once the final figure is set, a lightweight structural foam is applied to the rear of the optic to ensure stability of the figure.

Hermann, Frederick Thomas↗

The potential for bulk undercooling as an industrial process

The main focus is on solidification occurring in highly supercooled melts. Solidification rates in such melts are extremely high, an attractive feature from a commercial standpoint. Thus, the reported growth velocities for pure Ni and Co dendrites at a supercooling of 175 K are in excess of 180 km/hr. Rapidly quenched crystalline alloys produced by various atomization processes (e.g., centrifugal atomization or inert gas atomization) or melt spinning are examples of solidification processes, currently being intensively explored commercially, wherein extremely high solidification rates are achieved. Estimated dendrite tip growth rates are about 2 km/hr in a binary Al-4.5 wt % alloy, with a heat transfer coefficient of 6.4x10 sub 5 w/sq cm K or 15 cal/cu cm sK. In the limit, when the solidification rate exceeds a critical value, a glassy microstructure is obtained even in highly alloyed melts, which under normal conditions would solidity to form one or more crystalline phases. Glassy metals, also called metallic glasses, are candidate materials for distribution transformers because of their very low energy losses and are also being used in brazing and soldering applications.

Laxmanan, V.↗

ZBLAN Viscosity Instrumentation

The past year's contribution from Dr. Kaukler's experimental effort consists of these 5 parts: a) Construction and proof-of-concept testing of a novel shearing plate viscometer designed to produce small shear rates and operate at elevated temperatures; b) Preparing nonlinear polymeric materials to serve as standards of nonlinear Theological behavior; c) Measurements and evaluation of above materials for nonlinear rheometric behavior at room temperature using commercial spinning cone and plate viscometers available in the lab; d) Preparing specimens from various forms of pitch for quantitative comparative testing in a Dynamic Mechanical Analyzer, Thermal Mechanical Analyzer; and Archeological Analyzer; e) Arranging to have sets of pitch specimens tested using the various instruments listed above, from different manufacturers, to form a baseline of the viscosity variation with temperature using the different test modes offered by these instruments by compiling the data collected from the various test results. Our focus in this project is the shear thinning behavior of ZBLAN glass over a wide range of temperature. Experimentally, there are no standard techniques to perform such measurements on glasses, particularly at elevated temperatures. Literature reviews to date have shown that shear thinning in certain glasses appears to occur, but no data is available for ZBLAN glass. The best techniques to find shear thinning behavior require the application of very low rates of shear. In addition, because the onset of the thinning behavior occurs at an unknown elevated temperature, the instruments used in this study must provide controlled low rates of shear and do so for temperatures approaching 600 C. In this regard, a novel shearing parallel plate viscometer was designed and a prototype built and tested.

Kaukler, William↗

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗