A study of a sorption process.
Sorption process for determining sticking probability of molecules on surface of sorbents, diffusion coefficient of molecules through sorbents and adsorption isotherms
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Sorption process for determining sticking probability of molecules on surface of sorbents, diffusion coefficient of molecules through sorbents and adsorption isotherms
Researchers reexamined radiative transfer models of early Mars that were advanced to show the existance of a greenhouse effect. These models were reexamined with regard to the effect that regolith adsorption may have had. It is argued that while the precipitation of carbonates has probably been an important process during Mars history, the rates at which this process could have taken place under early Mars conditions would have dropped sharply once liquid water was fairly scarce. Furthermore, conditions under which liquid water was available may have involved efficient recycling of carbonate so that steady state conditions rather than irreversible CO2 removal prevailed. In contrast, the growth of regolith surface area demands corresponding and predictable CO2 removal from the atmosphere-cap system and is fully capable of terminating any enhanced temperature regime on early Mars in the absence of any other effects.
Nitrogen is an essential nutrient for all life on Earth and possibly elsewhere. Burial of nitrogen bound to organic matter constitutes the major flux of nitrogen into sediments today, which has led to the inference that nitrogen enrichments in sedimentary rocks may be a biosignature. However, abiotic processes such as lightning or volcanism can fix atmospheric N2 and contribute to sedimentary nitrogen burial in the absence of life. It is therefore uncertain whether observed nitrogen enrichments of up to 430 ppm in Paleoarchean metasedimentary biotite grains are indeed biogenic. This study seeks to address that problem with a numerical model. The NH4(+) concentration of an abiotic ocean is modeled as a function of source fluxes, pH-dependent NH3 volatilization, and equilibrated adsorption of NH4(+) onto clay particles. The results suggest that the observed nitrogen concentrations in Paleoarchean biotite can only be reconciled with purely abiotic processes if the ocean was more acidic (pH <6) and/or if the source fluxes from lightning and volcanism were at least an order of magnitude higher (≥10(exp 12) mol/yr) than previously thought. The bulk of the nitrogen is thus most likely of biological origin. While this does not necessitate a particular metabolism such as biological N2 fixation, the data provide evidence of nitrogen utilization back to 3.8 Gyr. Nitrogen abundances could thus provide useful information in extraterrestrial missions.
A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.
To improve the increasing CO 2 levels on Earth, technology for carbon capture and utilization must be efficient and cost effective. One major contributor of atmospheric CO 2 is post-combustion flue gas, which can contain up to 20% CO 2 . Scrubbing this CO 2 could reduce the environmental impact of this common industrial process. In off-Earth environments, capturing and utilizing CO 2 from space resources is useful for crewed spaceflight life support. Specifically, the Bosch process, which produces water and carbon powder by reacting CO 2 and hydrogen, is a possible in-situ resource utilization (ISRU) architecture for the Moon and Mars. The Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump is an innovative technology designed to capture CO 2 efficiently. The RC-TSA leverages a stacked plate geometry to cycle multiple zeolite-coated beds. The thin layers allow for rapid heat transfer of the zeolite coating, which improves performance over previously tested pump designs. The design is favorable for scalability and manufacturability, which are forward work. Initial testing of the sorption pump using a simulated flue gas environment shows favorable breakthrough capacities and reduced cycle times. Results show promise for on- and off-Earth applications, such as a Martian surface and crewed spaceflight environments.
A study of the decomposition of various compounds adsorbed on charcoal was made, with a view toward providing a critical appraisal of previous data from charcoal adsorption studies. It was found that thermal decomposition occurs at temperature lower than previously suspected during the charcoal stripping process. A discussion is presented dealing with the various types of reactions found. A rough, quantitative scheme for correcting previous analytical results is developed and presented.
Coordinated studies of the kinetics of crack growth and of hydrogen adsorption and diffusion were initiated to develop information that is needed for a clearer determination of the rate controlling process and possible mechanism for hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Inconel 718 alloy and 18Ni(200) maraging steel were selected for these studies. 18Ni(250) maraging steel, 316 stainless steel, and iron single crystal of (111) orientation were also included in the chemistry studies. Crack growth data on 18Ni(250) maraging steel from another program are included for comparison. No sustained-load crack growth was observed for the Inconel 718 alloy in gaseous hydrogen. Gaseous hydrogen assisted crack growth in the 18Ni maraging steels were characterized by K-independent (Stage 2) extension over a wide range of hydrogen pressures (86 to 2000 torr or 12 kN/m2 to 266 kN/m2) and test temperatures (-60 C to +100 C). The higher strength 18Ni(250) maraging steel was more susceptible than the lower strength 200 grade. A transition temperature was observed, above which crack growth rates became diminishingly small.
To study the effects of atmospheric species on the fatigue crack growth behavior of an a+B titanium alloy (Ti 6-2-2-2-2) at room temperature and 177 C, fatigue tests were performed in laboratory air, ultrahigh vacuum, and high purity water vapor, oxygen, nitrogen and helium at various partial pressures. Accelerated fatigue crack growth rates in laboratory air compared to ultrahigh vacuum are linked to the damaging effects of both water vapor and oxygen. Observations of the fatigue crack growth behavior in ultrahigh purity environments, along with surface film analysis using X-ray photoelectron spectroscopy (XPS), suggest that multiple crack-tip processes govern the damaging effects of air. Three possible mechanisms are proposed: 1) at low pressure (less than 10(exp -1) Pa), accelerated da/dN is likely due to monolayer adsorption on crack-tip surfaces presumably resulting in decreased bond strengths at the fatigue crack tip, 2) for pressures greater than 10(exp -1) Pa, accelerated da/dN in oxygen may result from oxidation at the crack tip limiting reversible slip, and 3) in water vapor, absorption of atomic hydrogen at the reactive crack tip resulting in process zone embrittlement.
The State-of-the-Art (SOA) air revitalization architecture onboard the International Space Station (ISS) recovered approximately 50% of the oxygen (O 2 ) from metabolic carbon dioxide (CO 2 ) via the Sabatier process from 2011 to 2017. O 2 recovery is currently constrained by the limited availability of reactant hydrogen (H 2 ) preventing complete conversion of CO 2 to H 2 O. Increasing O 2 recovery within Closed-Loop ECLSS is essential to reducing resupply mass for long-duration manned missions; specifically focusing on water (H 2 O) which supplies H 2 for Sabatier via water electrolysis. Past ground test endeavors at Marshall Space Flight Center (MSFC) have attempted to recover H 2 from Sabatier-produced CH 4 using technologies such as carbon vapor deposition (CVD) and plasma pyrolysis. The byproducts of these technologies can act as a catalyst poison or reactor deadload to the Sabatier reactor. Hydrogen separation techniques must be utilized to maintain the Sabatier catalyst during gas recycling and must be scalable, non-energy intensive, and safe to operate in a habitation setting. Research indicated that metal-organic frameworks (MOFs) could meet these criteria and were tested for their capability to capture the various carbon-based gaseous products of CVD and plasma pyrolysis such as acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), and carbon monoxide (CO) which would purify the hydrogen gas stream passing through the MOF. A sub-scale adsorption column was developed by Marshall Space Flight Center to test three MOF candidates against a synthetic gas mixture comprised of process-relevant carbonous gases and hydrogen to evaluate the separation capability of the MOFs. The results of the hydrogen separation capability, isothermal desorption capability, and demonstrated cyclic reuse of the MOF are presented in this paper.
The Trace Contaminant Control Simulation computer program is a tool for assessing the performance of various process technologies for removing trace chemical contamination from a spacecraft cabin atmosphere. Included in the simulation are chemical and physical adsorption by activated charcoal, chemical adsorption by lithium hydroxide, absorption by humidity condensate, and low- and high-temperature catalytic oxidation. Means are provided for simulating regenerable as well as nonregenerable systems. The program provides an overall mass balance of chemical contaminants in a spacecraft cabin given specified generation rates. Removal rates are based on device flow rates specified by the user and calculated removal efficiencies based on cabin concentration and removal technology experimental data. Versions 1.0 through 8.0 are documented in NASA TM-108409. TM-108409 also contains a source file listing for version 8.0. Changes to version 8.0 are documented in this technical memorandum and a source file listing for the modified version, version 8.1, is provided. Detailed descriptions for the computer program subprograms are extracted from TM-108409 and modified as necessary to reflect version 8.1. Version 8.1 supersedes version 8.0. Information on a separate user's guide is available from the author.
The additive is for a raw sewage treatment process of the type where settling tanks are used for the purpose of permitting the suspended matter in the raw sewage to be settled as well as to permit adsorption of the dissolved contaminants in the water of the sewage. The sludge, which settles down to the bottom of the settling tank is extracted, pyrolyzed and activated to form activated carbon and ash which is mixed with the sewage prior to its introduction into the settling tank. The sludge does not provide all of the activated carbon and ash required for adequate treatment of the raw sewage. It is necessary to add carbon to the process and instead of expensive commercial carbon, coal is used to provide the carbon supplement.
A water vapor and carbon dioxide sorbent material (designated HS-C) was developed for potential application to the space shuttle and tested at full scale. Capacities of two percent for carbon dioxide and four percent for water vapor were achieved using space shuttle cabin adsorption conditions and a space vacuum for desorption. Performance testing shows that water vapor can be controlled by varying the air process flow, while maintaining the ability to remove carbon dioxide. A 2000 hour life test was successfully completed, as were tests for sensitivity to cleaning solvent vapors, vibration resistance, and flammability. A system design for the space shuttle shows a 200 pound weight advantage over competitive systems and an even larger advantage for longer missions.
The study presents a model that incorporates the physics and physical chemistry of ice surfaces relevant to polar stratospheric clouds. Surface concentrations of H2O, HCl, HOCl, ClONO2, and N2O5 on ice and nitric acid trihydrate (NAT) crystals are computed, and surface reaction rates and reaction probabilities (sticking coefficients) are determined. For gas pressures of about 10 exp -7 torr and temperatures in the range of 180-200 K, HCl completely coats ice and water-rich NAT surfaces, while HOCl, ClOHO2, and N2O5 may cover 0.01-1 percent of these surfaces. The energy parameters are used to calculate surface temperatures such as adsorption and desorption constants, surface coverages, reaction rate coefficients, surface diffusion coefficients, and reaction probabilities for various species and chemical interactions on ice and NAT surfaces. Implications for chemical processing on polar stratospheric clouds are discussed.
Low-gravity (microgravity) studies relevant to prebiotic evolution and the history of the biogenic elements (C, H, N, O, P, S) are particularly suited to orbital platforms. Relevant to these topics are phenomena such as gas-particle interactions (e.g., formation of organic aerosols via photolytic reactions) including nucleation, condensation, evaporation, adsorption, and catalytic reactions on surfaces; and, small-particle or grain interactions (e.g., growth of interstellar dust particles and planetesimals) including processes such as aggregation (or coagulation), scavenging, and collisions. Both gas-particle and grain (i.e., dust, crystals, organic aerosols, etc.) interactions studies can benefit from microgravity and are pertinent to studies in the areas of chemical evolution in the solar nebula, the interstellar medium, and planetary atmospheres; growth of planetesimals; and prebiotic evolution. In general, the microgravity environment allows for long duration and controlled simulations of processes occurring in exobiologically significant systems such as Titan's atmosphere, interstellar dust clouds, and the solar nebula in which gas-particle or particle-particle interactions play a significant role.
An extensive set of ground-based measurements of the diurnal variation of medium frequency radio wave adsorption and virtual height is analyzed in terms of current understanding of the D- and lower E-region ion production and loss process. When this is done a gross discrepancy arises, the source of which is not known.
It has been demonstrated that synergistic metal-support effects can occur which markedly enhance specific activity and alter selectivity in certain reactions. Because of the presence of such effects in certain reactions conducted under reducing conditions (that is, under H2 pressure), but not others, the creation of unique sites at the metal-support interface seems to be the best model at the present time to explain this behavior. The postulation of these sites, which are specific for a certain reactant such as CO, provides an effective explanation for the higher methanation rates that have been reported over some catalysts. The creation of these sites in the adlineation zone is facilitated by hydrogen spillover from the metal surface, and this same process can also enhance the reduction of many oxide supports. Although oxygen spillover is much less probable due to its higher heat of adsorption, it is much less well understood and the possibility of rate enhancements in CO oxidation caused by special interface sites cannot be discounted at the present time. Consequently, this seems to be an important area of future research.
An analysis of the transient behavior of heat and fluid flow in porous annuli is reported. The problem analyzed has relevance to the design of adsorption compressors. Consideration is given to filling a porous annulus with a fluid while cooling is applied. The governing equations for the transport process considered have been solved numerically using a finite-difference method. A parametric study has been conducted to reveal the influence of the different parameters. The conditions for maximizing the mass intake are identified.
Engineered structured (ES) sorbents are being developed to meet the technical challenges of future crewed space exploration missions. ES sorbents offer the inherent performance and safety attributes of zeolite and other physical adsorbents but with greater structural integrity and process control to improve durability and efficiency over packed beds. ES sorbent techniques that are explored include thermally linked and pressure-swing adsorption beds for water-save dehumidification and sorbent-coated metal meshes for residual drying, trace contaminant control, and carbon dioxide control. Results from sub-scale performance evaluations of a thermally linked pressure-swing adsorbent bed and an integrated sub-scale ES sorbent system are discussed.