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Alternative techniques for the regeneration of carbon contaminated with various spacecraft contaminants were evaluated. Four different modes of regeneration were evaluated: (1) thermal desorption via vacuum, (2) thermal desorption via nitrogen purge, (3) in-situ catalytic oxidation of adsorbed contaminants, and (4) in-situ non-catalytic oxidation of adsorbed contaminants.
The device concerns the circulation of cabin air through canisters which absorb and adsorb carbon dioxide, together with excess moisture, and return the scrubbed air to the cabin for recirculation. A coating on an inert substrate in granular form absorbs and adsorbs the impurities at standard temperatures and pressures, but desorbs such impurities at low pressures (vacuum) and standard temperatures. This fact is exploited by making the device in a stack of cells consisting of layers or cells which are isolated from one another flow-wise and are connected to separate manifolds and valving systems into two separate subsets. A first subset may be connected for the flow breathable air therethrough until the polyethyleneimine of its cells is saturated with CO2 and H2O. During the same period the second subset of cells is manifolded to a vacuum source.
The adsorption of oxygen on W(100) single-crystal surfaces is studied by Auger electron spectroscopy (AES), flash desorption, low-energy electron diffraction (LEED), and retarding-field work-function measurements. The AES results reveal stepwise changes in the sticking coefficients in the coverage range 0 to 1 and activated adsorption at higher coverages. Upon room-temperature adsorption, a series of complex LEED patterns is observed. In layers adsorbed at 1050 K and cooled to room temperature, the p(2 x 1) structure is the first ordered structure observed. This structure shows a reversible order-disorder transition between 700 and 1000 K and is characterized by a work function which is lower than that of the clean surface. Heating room-temperature adsorbates changes their structure irreversibly. At temperatures below 750 K, some new structures are observed.
A quantitative model for atmosphere-regolith exchange of CO2 on Mars is presented. The model, based on new laboratory measurements of CO2 adsorption on ground rock at 158, 175, 196, and 231 K for CO2 pressures from 1.0 to 80 mbar, is consistent with Viking observations, while models involving a massive residual CO2 cap and no long-term atmosphere-regolith CO2 exchange are not consistent. The model indicates: (1) the atmosphere-plus-cap system is buffered on a long-term basis by exchangeable CO2 adsorbed in the regolith; (2) if the atmosphere-plus-cap system suddenly disappeared, the system would eventually be almost completely restored by reequilibration with the regolith; (3) exchange with the adsorbed phase in the regolith has greatly restricted O-18 enrichment of the atmosphere; (4) the layered terrain primarily represents current periodic pressure increases; and (5) pressures of 100-300 nbar might have existed during the early history of the planet.
Auger spectra and work function measurements are used to study the surface reactions between tungsten surface and adsorbed layers of barium, and barium and oxygen. The barium on an impregnated tungsten cathod seems to be an intermediate state, probably a coadsorbed barium-oxygen layer on tungsten. A slightly revised version of the previously suggested (1976) impregnated tungsten cathode model is proposed. This revised model assumes that the cathode surface during life has an adsorbed surface layer of a monolayer or less of both barium and oxygen on the surface. At end of life, steep drop in electron emission and resultant cathode failure occur. Recent NASA life test results on TWT type tubes are reported and explained by the proposed model.
The development and evaluation of proprietary coatings of pure silicon carbide, silicon nitride, and aluminum nitride on less pure hot pressed substrates of the respective ceramic materials, is described. Silicon sessile drop experiments were performed on coated test specimens under controlled oxygen partial pressure. Prior to testing, X-ray diffraction and SEM characterization was performed. The reaction interfaces were characterized after testing with optical and scanning electron microscopy and Auger electron spectroscopy. Increasing the oxygen partial pressure was found to increase the molten silicon contact angle, apparently because adsorbed oxygen lowers the solid-vapor interfacial free energy. It was also found that adsorbed oxygen increased the degree of attack of molten silicon upon the chemical vapor deposited coatings. Cost projections show that reasonably priced, coated, molten silicon resistant refractory material shapes are obtainable.
Polyuridylic acid is adsorbed completely from aqueous solution by hydroxyapatite under conditions that permit template-directed synthesis of oligoadenylates in free solution. The yield of oligoadenylates is enhanced to almost the same extent by poly(U) in the presence or the absence of hydroxyapatite. Under very similar conditions small quantities of hydroxyapatite adsorb higher-molecular-weight oligoadenylates selectively from a mixture of oligomers. On the basis of these results a mechanism for prebiotic oligonucleotide formation is proposed in which selective adsorption on hydroxyapatite or some other immobilized anion-exchanging material plays a major role. Monomers are released from the surface for reactivation, while oligomers are retained in a protected environment by adsorption to the apatite surface.
The replacement of water (H2O) by deuterium oxide (D2O) and the exchange between atmospheric water and adsorbed or absorbed D2O were investigated for the polymeric materials Kapton and Mylar using thermal gravimetric analysis and infrared spectroscopy. Replacement of H2O by D2O is easily accomplished. However, exposure of D2O samples to the ambient atmosphere or gases containing H2O results in rapid proton and deuteron exchange between H2O vapor and adsorbed D2O. Replacement of H2O by D2O would not be a practical solution to alleviate spectral interferences that would result from water outgassing in spacecraft orbital environments. Maintaining the materials of interest in a dehydrated state is a more reasonable approach.
Thermal faceting was observed for the high index planes of LaB6. The (100), (110), and (111) planes were found to be the most thermodynamically stable faces in vacuum in a study of electrode materials for thermionic emitters. The properties of adsorbed carbon, cesium, and cesium-oxygen layers were investigated on LaB6 single crystal surfaces as well as on Zr/0/W(100) and W(100). Cesium was found to increase electron reflection near the collision threshold on LaB6(100) and W(100) and to decrease the reflection on Zr/0/W(100). This difference may be explained by the unusually high threshold reflection coefficient of Zr/0/W without adsorbed cesium.
The Langevin equation was used to explore an adsorbate desorption mechanism. Calculations were performed using iterative extended Hueckel on a silica model site with various small adsorbates, e.g., H, CH, OH, NO, CO. It was found that barriers to free traversal from one site to another are substantial (about 3-10 eV). A bootstrap desorption mechanism for some molecules in the process of forming at a site also became apparent from the calculations. The desorption mechanisms appear to be somewhat balanced by a counterforce - the attraction of sites for the newly desorbed molecule. The order of attraction to a silica grain site for the diatomic molecules considered was OH greater than CH greater than CO greater than NO, when these entities were sufficiently distant. The nature of the silica grain and that of the 'cold' desorption mechanism, when considered together, suggest that the abundance of very small grains might be less common than anticipated.
The isothermal transmission through activated carbon adsorber beds at 25 C of acetaldehyde-propane and acetylene-ethane mixtures in a helium carrier gas was measured. The inlet concentration of each component was in the range between 10 ppm and 500 ppm. The constant inlet volumetric flow rate was controlled at 200 cc (STP)/min in the acetaldehyde-propane experiments and at 50 cc (STP)/min in the acetaldehyde-ethane experiments. Comparison of experimental results with the corresponding single-component experiments under similar conditions reveals interference phenomena between the components of the mixtures as evidenced by changes in both the adsorption capacity and the dispersion number. Propane was found to displace acetaldehyde from the adsorbed state. The outlet concentration profiles of propane in the binary mixtures tend to become more diffuse than the corresponding concentration profiles of the one-component experiments. Similar features were observed with mixtures of acetylene and ethane; however, the displacement of acetylene by ethane is less pronounced.
More sophisticated cooling systems for the employed detectors will be needed to satisfy the demand for higher resolution and sensitivity of various detectors used in space missions. The design of the cooling system must take into consideration the unique environment of space vehicles. It is pointed out that a deep space vehicle usually has an ample supply of waste heat from a radioisotope thermoelectric generator (RTG) and has a heat sink near zero Kelvin. Passive radiative coolers have been used for cooling temperatures above 90 K. Cooling below 90 K is currently handled by phase changes of solid or liquid cryogens or mechanical refrigeration. However, the weight of the cryogen may be a problem in a long duration space mission. Refrigerators of small cooling capacity are required in many spacecraft applications. For some future NASA missions, a multistage Joule-Thomson refrigerator using adsorption compressors appears particularly attractive. A study is discussed of four different refrigeration stages which use charcoal as the adsorbent. The adsorbed gases are nitrogen, helium, hydrogen, and neon.
The surface composition of liquid gallium-tin alloys is studied in an Auger electron spectrometer as a function of bulk composition and temperature. The sessile drop samples are cleaned by argon ion bombardment sputtering of the liquid. This technique produces surfaces that are entirely free of impurities within the sensitivity of the spectrometer and remain so for many days. Tin is found to be strongly adsorbed at the liquid-vacuum interface. Surface concentrations based on Auger measurements are found to be in reasonably good agreement with values calculated from surface tension measurements interpreted in terms of a monolayer depth distribution model for the adsorbed tin.
Clays and other minerals have been investigated in context with prebiotic processes, mainly in polymerization of amino acids. It was found that peptides adsorbed on the clay, prior to polymerization, influence the reaction. The ratio between the amount of the peptides adsorbed and that of the clay is important for the yield as well as for the degrees of polymerization obtained. Adsorption prior to reaction produces a certain order in the aggregates of the clay particles which might induce better reaction results. Excess of added peptides disturbs this order and causes lesser degrees of polymerization. In addition to adsorption, clays are also able to occlude between their layers substances out of the environment, up to very high concentrations.
The adhesion and friction behavior of boron nitride films on 440 C bearing stainless steel substrates was examined. The thin films containing the boron nitride were synthesized using an ion beam extracted from a borazine plasma. Sliding friction experiments were conducted with BN in sliding contact with itself and various transition metals. It is indicated that the surfaces of atomically cleaned BN coating film contain a small amount of oxides and carbides, in addition to boron nitride. The coefficients of friction for the BN in contact with metals are related to the relative chemical activity of the metals. The more active the metal, the higher is the coefficient of friction. The adsorption of oxygen on clean metal and BN increases the shear strength of the metal - BN contact and increases the friction. The friction for BN-BN contact is a function of the shear strength of the elastic contacts. Clean BN surfaces exhibit relatively strong interfacial adhesion and high friction. The presence of adsorbates such as adventitious carbon contaminants on the BN surfaces reduces the shear strength of the contact area. In contrast, chemically adsorbed oxygen enhances the shear strength of the BN-BN contact and increases the friction.
Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.
Spectral data for smectite clays, particularly for montmorillonite, which contain various adsorbed ions and are measured in the UV, VIS, and NIR ranges are analyzed and compared with Martian soil and dust spectra. It is shown that the structural octahedral iron in smectite clays affects their light absorbance in the UV at 240-260 nm, which results from an O(2-) to Fe(3+) charge transfer, similar to one observed in the Martian spectrum. Adsorbed iron affects, via crystal field absorptions, the reflectance of montmorillonite in the VIS and NIR ranges, resulting in stronger absorption and higher opacity in the range 0.40-0.65 micron. Both in spectral contrast and presence of (or lack of) spectral features, the Fe-montmorillonite spectra in the VIS and NIR are in reasonable agreement with the Martian spectrum. It is found that the spectral characteristics of iron-saturated smectite clays cannot be used to preclude the presence of clays in Martian soils and dust.
The interaction of 5-prime-AMP with montmorillonite saturated with various ratios of two metals found ubiquitously on the surface of earth, that is, iron and calcium, is investigated. Adsorption and desorption of the nucleotide were studied in the pH range of 2-12 at three levels of addition: 0.080, 0.268 and 0.803 mmole 5-prime-AMP per gram of clay. Two desorption stages were employed - H2O wash and NaOH extraction (pH = 12.0). 5-prime-AMP was preferentially adsorbed on the Fe-containing clays relative to the Ca clay. The nucleotide was fully recovered by the two desorption stages, mostly by the NaOH extraction. The evidence at hand indicates that 5-prime-AMP reaction with clay is affected by electrostatic interactions involving both attraction and repulsion forces. Some specific adsorption, possibly the result of covalent bonding and complex formation with the adsorbed ion, cannot be ruled out for iron but does not appear to operate for calcium. Changes in pH cause varying degrees of attaction and repulsion of 5-prime-AMP and may have been operating on the primitive earth, leading to sequences of adsorption and release of this biomolecule.