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The focus of this presentation is on multiscale modeling in order to link processing, microstructure, and properties of materials. Overview of problems we study includes: Growth mechanisms in chemical and physical vapor epitaxy; thin films of zeolites for separation and sensing; thin Pd films for hydrogen separation and pattern formation by self-regulation routes.
The results of three experimental studies related to the inorganic/organic battery separator operating mechanism are described: saponification of the plasticizer, resistivity of the simulated separators, and zincate diffusion through the separators. The inorganic/organic separator appears to be a particular example of a general class of ionic conducting films composed of inorganic fillers and/or substrates bonded together by an organic polymer containing an incompatible plasticizer that may be leached by the electrolyte. The I/O separator functions as a microporous film of varying tortuosity with essentially no specific chemical inhibition to zincate diffusion.
The Development of a new, robust, portable life support system (PLSS) is currently a high NASA priority in order to support longer and safer extravehicular activity (EVA) missions that will be necessary as space travel extends to near-Earth asteroids and eventually Mars. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. The Metal Oxide (MetOx) canister has a finite CO2 adsorption capacity and therefore in order to extend mission times, the unit would have to be larger and heavier, which is undesirable; therefore new CO2 control technologies must be developed. While recent work has centered on the use of alternating sorbent beds that can be regenerated during the EVA, this strategy increases the system complexity and power consumption. A simpler approach is to use a membrane that vents CO2 to space but retains oxygen(O2). A membrane has many advantages over current technology: it is a continuous system with no theoretical capacity limit, it requires no consumables, and it requires no hardware for switching beds between absorption and regeneration. Conventional gas separation membranes do not have adequate selectivity for use in the PLSS, but the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous film filled with a liquid that selectively reacts with CO2 over oxygen (O2). In a recently completed Phase II Small Business Innovative Research project, Reaction Systems developed a new reactive liquid that has effectively zero vapor pressure, making it an ideal candidate for use in an SLM. Results obtained with the SLM in a flat sheet configuration with representative pressures of CO2, O2, and water (H2O) have shown that the CO2 permeation rate and CO2/O2 selectivity requirements have been met. In addition, the SLM vents moisture to space very effectively. The SLM has also been prepared and tested in a hollow fiber form, which will be necessary to meet size requirements in the PLSS. In initial tests, the required CO2 permeance values have been obtained, while the current CO2/O2 selectivity values are somewhat lower than needed. However, the performance of the SLM is a strong function of the method used to impregnate the sorbent in the hollow fiber walls and rapid progress is being made in that area.
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The focus of cluster chemistry studies at the University of Minnesota is on the adsorption of small hydrocarbon molecules on metal and graphite surfaces, and on the substitution defects in diamond and silicon. Of particular interest is the study of very large systems such as the C60 molecule and the C150H30 molecule. Many of the properties of such clusters converge extremely slowly toward bulk values. Ultrathin films and microporous media are discussed as well as the Brownian dynamics of polymers.
Primarily interest was in the determination of the population of micrometeoroids and space debris and interpretation of the hole size in a thin film or in a micropore foam returned from space with theoretical calculations describing the event. In order to augment the significance of the theoretical calculations of the impact event, an experiment designed to analyze the charge production due to hypervelocity impacts on thin films also produced data which described the penetration properties of micron and sub-micron sized projectiles. The thin film penetration sites in the 500 A and 1000 A aluminum films were counted and a size distribution function was derived. In the case of the very smallest dust grains, there were no independent measurements of velocities like that which existed for the larger dust grains (d(sub p) is less than or equal to 1 micron). The primary task then became to assess the relationship between the penetration hole and the particle diameter of the projectile which made the hole. The most promising means to assess the measure of the diameters of impacting grains came in the form of comparing cratering mechanics to penetration mechanics. Future experimentation will produce measurements of the cratering as opposed to the penetrating event. Particles encountered by surfaces while being flown in space will degrade that surface in a systematic manner even when the impact is with small hypervelocity particles, d(sub p) is less than or equal to 10 microns. Though not to a degree which would precipitate a catastrophic failure of a system, the degradation of the materials comprising the interconnected system will occur. It is the degradation of the optical system and the subsequent embrittlement of other materials that can lead to degradation if not to failure. It is to this end that research was conducted to compare the primary consequences for experiments which will be flown to those which have been returned.
The diffusion rates of several ions through some membranes developed as battery separators were measured. The ions investigated were Li(+), Rb(+), Cl(-), and So4. The members were crosslinked polyvinyl alcohol, crosslinked polyacrylic acid, a copolymer of the two, crosslinked calcium polyacrylate, cellulose, and several microporous polyphenylene oxide based films. No true specificity for diffusion of any of these ions was found for any of the membranes. But the calcium polyacrylate membrane was found to exhibit ion exchange with the diffusing ions giving rise to the leaching of the calcium ion and low reproducibility. These findings contrast earlier work where the calcium polyacrylate membrane did show specificity to the diffusion of the copper ion. In general, Fick's law appeared to be obeyed. Except for the microporous membranes, the coefficients for ion diffusion through the membranes were comparable with their values in water. For the microporous membranes, the values found for the coefficients were much less, due to the tortuosity of the micropores.
The impact of a hypervelocity projectile (greater than 3 km/s) is a process that subjects both the impactor and the impacted material to a large transient pressure distribution. The resultant stresses cause a large degree of fragmentation, melting, vaporization, and ionization (for normal densities). The pressure regime magnitude, however, is directly related to the density relationship between the projectile and target materials. As a consequence, a high-density impactor on a low-density target will experience the lowest level of damage. Historically, there have been three different approaches toward achieving the lowest possible target density. The first employs a projectile impinging on a foil or film of moderate density, but whose thickness is much less than the particle diameter. This results in the particle experiencing a pressure transient with both a short duration and a greatly reduced destructive effect. A succession of these films, spaced to allow nondestructive energy dissipation between impacts, will reduce the impactor's kinetic energy without allowing its internal energy to rise to the point where destruction of the projectile mass will occur. An added advantage to this method is that it yields the possibility of regions within the captured particle where a minimum of thermal modification has taken place. Polymer foams have been employed as the primary method of capturing particles with minimum degradation. The manufacture of extremely low bulk density materials is usually achieved by the introduction of voids into the material base. It must be noted, however, that a foam structure only has a true bulk density of the mixture at sizes much larger than the cell size, since for impact processes this is of paramount importance. The scale at which the bulk density must still be close to that of the mixture is approximately equal to the impactor. When this density criterion is met, shock pressures during impact are minimized, which in turn maximizes the probability of survival for the impacting particle. The primary objectives of the experiment are to (1) Examine the morphology of primary and secondary hypervelocity impact craters. Primary attention will be paid to craters caused by ejecta during hypervelocity impacts of different substrates. (2) Determine the size distribution of ejecta by means of witness plates and collect fragments of ejecta from craters by means of momentum-sensitive mcropore foam. (3) Assess the directionality of the flux by means of penetration-hole alignment of thin films placed above the cells. (4) Capture intact the particles that perforated the thin film and entered the cell. Capture media consisted of both previously flight-tested micropore foams and aerogel. The foams had different latent heats of fusion and, accordingly, will capture particles over a range of momenta. Aerogel was incorporated into the cells to determine the minimum diameter than can be captured intact.
A filtering apparatus comprises a microporous membrane and an actuator. The membrane is positioned to traverse across the hollow interior of a conduit used for the transport of molecules in bulk. In one example, the pores of the membrane comprise a plurality of open-ended carbon nanotubes. The actuator comprises a transducing material such as a polyvinyledene fluoride film that is operatively positioned in contact with the membrane and is capable of propagating acoustic vibration onto the membrane at a particular frequency so as to hasten the movement of the molecules through the membrane. Similarly, a method of filtering water comprises the steps of: (a) sifting molecules of water through the membrane, the pores of the membrane comprising a plurality of carbon nanotubes; and (b) propagating acoustic vibration onto the microporous membrane at a libration frequency of ice so as to hasten movement of the water molecules within the carbon nanotubes.
The NASA Glenn Research Center (GRC) has been testing high efficiency free-piston Stirling convertors for potential use in radioisotope power systems since 1999. Stirling convertors are being operated for many years to demonstrate a radioisotope power system capable of providing reliable power for potential multi-year missions. Techniques used to monitor the convertors for change in performance include measurements of temperature, pressure, energy addition, and energy rejection. Micro-porous bulk insulation is used in the Stirling convertor test set up to minimize the loss of thermal energy from the electric heat source to the environment. The insulation is characterized before extended operation, enabling correlation of the net thermal energy addition to the convertor. Aging microporous bulk insulation changes insulation efficiency, introducing errors in the correlation for net thermal energy addition. A thin-mm heat flux sensor was designed and fabricated to directly measure the net thermal energy addition to the Stirling convertor. The fabrication techniques include slip casting and using Physical Vapor Deposition (PVD). One micron thick noble metal thermocouples measure temperature on the surface of an Alumina ceramic disc and heat flux is calculated. Fabrication, integration, and test results of a thin film heat flux sensor are presented.
The fifth year of the Center for Advanced Materials was marked primarily by the significant scientific accomplishments of the research programs. The Electronics Materials program continued its work on the growth and characterization of gallium arsenide crystals, and the development of theories to understand the nature and distribution of defects in the crystals. The High Tc Superconductivity Program continued to make significant contributions to the field in theoretical and experimental work on both bulk materials and thin films and devices. The Ceramic Processing group developed a new technique for cladding YBCO superconductors for high current applications in work with the Electric Power Research Institute. The Polymers and Composites program published a number of important studies involving atomistic simulations of polymer surfaces with excellent correlations to experimental results. The new Enzymatic Synthesis of Materials project produced its first fluorinated polymers and successfully began engineering enzymes designed for materials synthesis. The structural Materials Program continued work on novel alloys, development of processing methods for advanced ceramics, and characterization of mechanical properties of these materials, including the newly documented characterization of cyclic fatigue crack propagation behavior in toughened ceramics. Finally, the Surface Science and Catalysis program made significant contributions to the understanding of microporous catalysts and the nature of surface structures and interface compounds.