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At least 127 records · Page 7

Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was measured in ppmv (parts per million by volume). At higher temperatures, greater amounts of these products are produced, as expected. In all cases, methanol was the predominant concentration detected, followed by methyl formate. At temperatures lower than 320 C for the P-type monolithic catalyst, methanol, acetic acid, and acetone were detected, whereas, for the E-type monolithic catalyst, only methanol was detected at 160 C. Both P and E types of the monolithic catalyst were specified with the same substrates (ceramic), washcoat (Al2O3), and promoter (Pt). However, the manufacturing and treatment procedures were quite different. It was therefore concluded that the performance of the E-type monolithic catalyst is superior to that of the P-type for oxidation of methyl acetate. At higher reaction temperatures, e.g., above 420 C, all reactants and byproducts were completely oxidized using these two types of monolithic catalyst to produce carbon dioxide and water vapor. A complex heterogenous catalytic reaction mechanism was proposed to explain the formation of the byproducts (methanol, acetic acid, and methyl formate) as the methyl acetate traveled through the preheater packed with glass beads. The by-product, 1-propanol, may be formed only through a homogeneous reaction, since it is difficult to develop a reasonable sequence of heterogeneous reaction steps to explain its formation. The homogeneous thermal decomposition of methyl acetate to form free radicals was proposed to explain the formation of 1-propanol, and also methanol, in the preheater. A dual-site catalytic reaction mechanism was proposed for the oxidation of methyl acetate over Pt/Al2O3 monolithic catalyst. The dual-site mechanism describes the chemisorption of oxygen molecules as well as a physical adsorption of methyl acetate on the active sites. On the active sites, methyl acetate is oxidized rapidly to form carbon dioxide and water vapor. A rate equation derived from this mechanism gives the Langmuir-Hinshelwood rate formula which has been observed from the experimental data obtained in this project for high methyl acetate concentration (greater than 1000 ppmv) over a monolithic catalyst. If the oxygen concentration is very high and methyl acetate concentration is very low, the reaction rate equation is then reduced to a first-order with respect to methyl acetate concentration. The first-order model has also been observed from the experimental data obtained in this project for low methyl acetate concentration (less than 1000 ppmv).

Li, Ku-Yen↗

Investigation into the role of NaCl deposited on oxide and metal substrates in the initiation of hot corrosion

Morphological aspects of the conversion to Na2SO4 of NaCl deposits over the temperature range 500-700 C, in air with added SO2 and H2O. Progress of the reaction was observed by withdrawing samples at various times and examining them under the scanning electron microscope using EDAX to assess the extent of chloride to sulfate conversion. These initial results show that the conversion to Na2SO4 proceeds directly on the sodium chloride surface as well as on the surrounding substrate due to evaporation of NaCl from the solid particle. The mechanism of this reaction could involve reaction in the vapor to produce Na2SO4 which then deposits, alternatively Na2SO4 could form directly on the substrate surface due to direct reaction there between the vapors NaCl, SO2 and O2.

Birks, N.↗

Hydrogen reduction mechanisms of ilmenite between 823 and 1353 K

In situ gravimetric measurements and microscopic examinations were used to determine the mechanisms of oxygen removal from synthetic ilmenite disks between 823 and 1353 K. Under a hydrogen atmosphere, iron was observed to form a layer of low porosity on the surface of samples early in the reduction. This created diffusion limitations for hydrogen to the reaction front and for the escape of water vapor. A shrinking core reduction model, modified to include the growth of this iron film, was capable of predicting the conversion-time relationships of ilmenite samples. An activation energy of 43.2 +/- 2.6 kcal/gmole was determined to be representative of reaction control over the temperature range 823-1023 K.

Briggs, R. A.↗

Nonenzymatic formation of 'energy-rich' lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol

The energy rich thioester, N-acetyl-S-lactoylcysteine, is formed under anaerobic conditions from glyceraldehyde and N-acetylcysteine at ambient temperature in aqueous solutions of sodium phosphate (pH 7.0). The conversion occurs at a rate of about 0.4 percent per day in reactions with 10 millimoles (mM) glyceraldehyde, 40 mM thiol, and 500 mM sodium phosphate (pH 7.0). Thioester formation proceeds at an estimated efficiency of 76 percent. The formation of lactoyl thioester most likely occurs by the phosphate catalyzed dehydration of glyceraldehyde to give pyruvaldehyde, which combines with thiol to form a hemithioacetal that rearranges to the thioester. A second energy rich thioester, N-acetyl-S-glyceroylcysteine, is also produced from glyceraldehyde when these reactions are carried out in the presence of oxygen and to a limited extent in the absence of oxygen. In the presence of oxygen, the formation of glyceroyl thioester continues until the thiol disappears completely by oxidation. The significance of these reactions to the energetics of the origin of life is discussed.

Weber, A. L.↗

Application of First Principles Model to Spacecraft Operations

Previous models use a single phase reaction; cycled cell predicts cannot be met with a single phase; interphase conversion provides means for film aging; aging cells predictions display typical behaviors: pressure changes in NiH² cells; voltage fading upon cycling; second plateau on discharge of cycled cells; negative limited behavior for Ni-Cds.

batteries electrodes First Principles Model Ni-Cd ↗

Conversion of para and ortho hydrogen in the Jovian planets

A mechanism is proposed which partially equilibrates the para and ortho rotational levels of molecular hydrogen in the atmospheres of Jupiter, Saturn, and Uranus. Catalytic reactions between the free-radical surface sites of aerosol particles and hydrogen modecules yield significant equilibration near 1 bar pressure, if the efficiency of conversion per collision is between 10 to the -8th and 10 to the -10th and the effective eddy mixing coefficient is 10,000 sq cm/sec. At lower pressures the ortho-para ratio retains the value at the top of the cloud layer, except for a very small effect from conversion in the thermosphere. The influence of conversion on the specific heat and adiabatic lapse rate is also investigated. The effect is found to be generally small, though is can rise to 10% inside the aerosol layer.

Massie, S. T.↗

Development of a Reactor Model for Chemical Conversion of Lunar Regolith

Lunar regolith will be used for a variety of purposes such as oxygen and propellant production and manufacture of various materials. The design and development of chemical conversion reactors for processing lunar regolith will require an understanding of the coupling among the chemical, mass and energy transport processes occurring at the length and time scales of the overall reactor with those occurring at the corresponding scales of the regolith particles. To this end, a coupled transport model is developed using, as an example, the reduction of ilmenite-containing regolith by a continuous flow of hydrogen in a flow-through reactor. The ilmenite conversion occurs on the surface and within the regolith particles. As the ilmenite reduction proceeds, the hydrogen in the reactor is consumed, and this, in turn, affects the conversion rate of the ilmenite in the particles. Several important quantities are identified as a result of the analysis. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the time for hydrogen to diffuse into the pores of the regolith particles and the chemical reaction time. The paper investigates the relationships between these quantities and their impact on the regolith conversion. Application of the model to various chemical reactor types, such as fluidized-bed, packed-bed, and rotary-bed configurations, are discussed.

Hedge, uday↗

Development of a Reactor Model for Chemical Conversion of Lunar Regolith

Lunar regolith will be used for a variety of purposes such as oxygen and propellant production and manufacture of various materials. The design and development of chemical conversion reactors for processing lunar regolith will require an understanding of the coupling among the chemical, mass and energy transport processes occurring at the length and time scales of the overall reactor with those occurring at the corresponding scales of the regolith particles. To this end, a coupled transport model is developed using, as an example, the reduction of ilmenite-containing regolith by a continuous flow of hydrogen in a flow-through reactor. The ilmenite conversion occurs on the surface and within the regolith particles. As the ilmenite reduction proceeds, the hydrogen in the reactor is consumed, and this, in turn, affects the conversion rate of the ilmenite in the particles. Several important quantities are identified as a result of the analysis. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the time for hydrogen to diffuse into the pores of the regolith particles and the chemical reaction time. The paper investigates the relationships between these quantities and their impact on the regolith conversion. Application of the model to various chemical reactor types, such as fluidized-bed, packed-bed, and rotary-bed configurations, are discussed.

Hegde, U.↗

A cure-rate model for the Shuttle filament-wound case

An epoxy and carbon fiber composite has been used to produce a light-weight rocket case for the Space Shuttle. A kinetic model is developed which can predict the extent of epoxy conversion during the winding and curing of the case. The model accounts for both chemical and physical kinetics. In the model, chemical kinetics occur exclusively up to the time the transition temperature equals the reaction temperature. At this point the resin begins to solidify and the rate of this process limits the rate of epoxy conversion. A comparison of predicted and actual epoxy conversion is presented for isothermal and temperature programmed cure schedules.

Cagliostro, D. E.↗

A modified sulfate process to lunar oxygen

A modified sulfate process which produces oxygen from iron oxide-bearing minerals in lunar soil is under development. Reaction rates of ilmenite in varying strength sulfuric acid have been determined. Quantitative conversion of ilmenite to ferrous sulfate was observed over a range of temperatures and concentrations. Data has also been developed on the calcination of by-product sulfates. System engineering for overall operability and simplicity has begun, suggesting that a process separating the digestion and sulfate dissolution steps may offer an optimum process.

Sullivan, Thomas A.↗

The 'Supercritical Pile' GRB Model: Afterglows and GRB, XRR, XRF Unification

We present the general notions and observational consequences of the "Supercritical Pile" GRB model; the fundamental feature of this model is a detailed process for the conversion of the energy stored in relativistic protons in the GRB Relativistic Blast Waves (RBW) into relativistic electrons and then into radiation. The conversion is effected through the $p \, \gamma \rightarrow p \, e circumflex + e circumflex -$ reaction, whose kinematic threshold is imprinted on the GRB spectra to provide a peak of their emitted luminosity at energy \Ep $\sim 1$ MeV in the lab frame. We extend this model to include, in addition to the (quasi--)thermal relativistic post-shock protons an accelerated component of power law form. This component guarantees the production of $e circumflex +e circumflex- - $pairs even after the RBW has slowed down to the point that its (quasi-) thermal protons cannot fulfill the threshold of the above reaction. We suggest that this last condition marks the transition from the prompt to the afterglow GRB phase. We also discuss conditions under which this transition is accompanied by a significant drop in the flux and could thus account for several puzzling, recent observations. Finally, we indicate that the same mechanism applied to the late stages of the GRB evolution leads to a decrease in \Ep $\propto \Gamma circumflex 2(t)\propto t circumflex {-3/4}$, a feature amenable to future observational tests.

Kazanas, D.↗

Investigation of Supercritical Water Phenomena for Space and Extraterrestrial Application

The cost of carrying or resupplying life support resources for long duration manned space exploration missions such as a mission to Mars is prohibitive and requires the development of suitable recycling technologies. Supercritical Water Oxidation (SCWO) has been identified as an attractive candidate for these extended missions because (i) pre-drying of wet waste streams is not required, (ii) product streams are relatively benign, microbially inert, and easily reclaimed, (iii) waste conversion is complete and relatively fast, and (iv) with proper design and operation, reactions can be self-sustaining. Initial work in this area at NASA was carried out at the Ames Research Center in the 1990 s with a focus on understanding the linkages between feed stock preparation (i.e., particle size and distribution) of cellulosic based waste streams and destruction rates under a range of operating temperatures and pressures. More recently, work in SCWO research for space and extra-terrestrial application has been performed at NASA s Glenn Research Center where various investigations, with a particular focus in the gravitational effects on the thermo-physical processes occurring in the bulk medium, have been pursued. In 2010 a collaborative NASA/CNES (the French Space Agency) experiment on the critical transition of pure water was conducted in the long duration microgravity environment on the International Space Station (ISS). A follow-on experiment, to study the precipitation of salt in sub-critical, trans-critical and supercritical water is scheduled to be conducted on the ISS in 2013. This paper provides a brief history of NASA s earlier work in SCWO, discusses the potential for application of SCWO technology in extended space and extraterrestrial missions, describes related research conducted on the ISS, and provides a list of future research activities to advance this technology in both terrestrial and extra-terrestrial applications.

Hicks, Michael C.↗

Photoproduction of I2, Br2, and Cl2 on n-semiconducting powder

The photosynthetic production of Br2 and Cl2 and the photocatalytic production of I2 from aqueous solutions of the respective halide ions in the presence of platinized semiconducting n-TiO2 powder are reported. Reactions were produced in 2-3 M oxygen-saturated aqueous solutions of KI, KBr or NaCl containing Pt-TiO2 powder which were irradiated by a high-pressure mercury lamp at a power of 400 mW/sq cm. Halogens are found to be produced in greater quantities when platinized TiO2 powders are used rather than pure TiO2, and rates of halogen production are observed to increase from Cl2 to Br2 to I2. The presence of the synthetic reactions producing Br2 and Cl2 with a net influx of energy indicates that an effective separation of the photoproduced electron-hole pair occurs in the semiconductor. Quantum efficiencies of the reaction, which increase with decreasing solution pH, are found to be as high as 30%, implying a solar-to-chemical energy conversion efficiency between 0.03% and 3% for the case of chlorine production. It is concluded that the photoproduction of halogens may be of practical value if product halogens are efficiently removed from the reaction cell.

Reichman, B.↗

Investigation of the hydrogenation of SiCl4

A laboratory scale pressure reactor was constructed to study the 3 SiCl + 2H2 + Si yields 4 SiHCl3 reaction at pressures up to 500 psig. Reaction kinetic measurements were carried out as a function of reactor pressure, reaction temperature and H2/SiCl4 feed ratio. Based on the reaction kinetic data, the hydroclorination of SiCl4 and m.g. silicon metal is found to be an efficient process to produce SiHCl3 in good conversions and in high yields. Copper is an effective catalyst. Results of the corrosion study show that conventional nickel chromium alloys are suitable material of construction for the hydrochlorination reactor. The hydrochlorination reaction is relatively insensitive to external process parameters such as silicon particle size distribution and the impurities in the m.g. silicon metal.

Mui, J. Y. P.↗

Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

Hwang, S. M.↗

Atom movements occurring at solid metal-semiconductor interfaces

Solid metal-semiconductor interfaces often undergo chemical reaction at rather low temperatures, in some cases not much above room temperature. After some general discussion of these reactions, more detailed consideration is given to simple noncompound-forming systems, and, in particular, to the Si-Al, Ge-Al, and Si-Au systems. Diffusive transport of Si or Ge in these solid metallizations is very rapid, though the converse process, diffusion of metal in solid Si or Ge, is usually so slow as to be negligible. The interface reaction itself is less well understood but is becoming controllable in intrinsically favorable cases like Ge-Al and in other cases by more sophisticated means.

Mccaldin, J. O.↗

Evaluation of the SSRCT engine with a hydrazine as a fuel, phase 1

The performance parameters for the space shuttle reaction control thruster (SSRCT) when the fuel is changed from monomethylhydrazine to hydrazine were predicted. Potential problems are higher chamber wall temperature during steady state operation and explosive events during pulse mode operation. Solutions to the problems are suggested. To conduct the analysis, a more realistic film cooling model was devised which considers that hydrazine based fuels are reactive when used as a film coolant on the walls of the combustion chamber. Hydrazine based fuels can decompose exothermally as a monopropellant and also enter into bipropellant reactions with any excess oxidizer in the combustion chamber. It is concluded that the conversion of the thruster from MMH to hydrazine fuel is feasible but that a number of changes would be required to achieve the same safety margins as the monomethylhydrazine-fueled thruster.

Minton, S. J.↗

Photoproduction of halogens using platinized TiO2

Unlike electrolysis of halide salt solutions, technique using powdered titanium dioxide catalyst requires no external power other than ultraviolet radiation source. Semiconductor powders photocatalyze and photosynthesize many useful reactions; applications are production of halogen molecules, oxidation of hazardous materials in wastewater, and conversion of carbon monoxide to carbon dioxide.

Reichman, B.↗