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At least 109 records · Page 6

Design of A CVD Reactor for the Deposition of Diamond in A Microgravity Environment

There is a growing body of theoretical and experimental evidence suggesting that the uniformity, rate, adhesion, quality, and other key properties of Chemical Vapor Deposition (CVD) diamond coatings are influenced by the gas mixing kinetics in the thermal plasma environment of the reaction chamber. The implementation of, for example, Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) process in microgravity has, thus, been suggested. Such a diamond deposition system, which overcomes the limitations of present systems and which is distiguishable from them by the use of high pressure MPECVD and recirculation of the would be effluent hydrogen and carbon, is described. Given the key fact that there is nothing in the effluent of the MPECVD process that is truly a byproduct or 'waste', the system can, at least in principle, lend itself to being closed loop yet dynamic. The exhaust contains hydrogen and carbon species which can be recirculated to the plasma reactor, that is, since there are no unusable reaction byproducts, the effluent can be fed back to the reaction chamber with no detriment, thus allowing deployment in a microgravity environment.

M L Languell↗

VRA Modeling, phase 1

The destruction of organic contaminants in waste water for closed systems, such as that of Space Station, is crucial due to the need for recycling the waste water. A co-current upflow bubble column using oxygen as the gas phase oxidant and packed with catalyst particles consisting of a noble metal on an alumina substrate is being developed for this process. The objective of this study is to develop a plug-flow model that will predict the performance of this three phase reactor system in destroying a multicomponent mixture of organic contaminants in water. Mass balances on a series of contaminants and oxygen in both the liquid and gas phases are used to develop this model. These mass balances incorporate the gas-to-liquid and liquid-to-particle mass transfer coefficients, the catalyst effectiveness factor, and intrinsic reaction rate. To validate this model, a bench scale reactor has been tested at Michigan Technological University at elevated pressures (50-83 psig,) and a temperature range of 200 to 290 F. Feeds consisting of five dilute solutions of ethanol (approx. 10 ppm), chlorobenzene (approx. 20 ppb), formaldehyde (approx. 100 ppb), dimethyl sulfoxide (DMSO approx. 300 ppb), and urea (approx. 20 ppm) in water were tested individually with an oxygen mass flow rate of 0.009 lb/h. The results from these individual tests were used to develop the kinetic parameter inputs necessary for the computer model. The computer simulated results are compared to the experimental data obtained for all 5 components run in a mixture on the differential test column for a range of reactor contact times.

Kindt, Louis M.↗

Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

Moser, Thomas P.↗

Hybrid Reduced Order Model for N2-N2 Interactions for Application to Dissociation and Energy Transfer Processes

Recent work in the aerothermodynamics community has focused on the development of reduced-order models for thermo-chemical non-equilibrium which avoid the restrictive assumptions of multi-temperature models and the prohibitive cost associated with State-to-State (StS) models. In the present work, this is accomplished by lumping energy states together and assuming groups of states are roughly in equilibrium. As a result, the non-equilibrium behavior of a gas can be captured at a reduced computational cost from a full StS simulation. In this work, we present a hybrid grouping model for studying energy transfer and dissociation in a mixture of nitrogen molecules due to N2-N2 reactions. This is accomplished by making use of a grouping strategy informed by data from the N2-N StS kinetic data. However, due to the massive computational cost associated with constructing StS data for the N2-N2 system, the kinetic data for the hybrid grouping model are calculated using the quasi-classical trajectory (QCT) method by sampling states for trajectory within the groups. This general framework is called the Maximum-Entropy Quasi-Classical Trajectory (ME-QCT) method. The primary challenge associated with this method is that rates for reverse grouped reactions cannot be obtained through detailed balance at a group level, due to the variation of group internal temperatures. To construct the full model for N2-N2 grouped kinetics using the ME-QCT method, detailed balance is invoked at the microscopic level, allowing for the calculation of the full kinetic data from QCT. Results will be presented using the full ME-QCT model for the N2-N2 system in an isothermal and isochoric reactor simulation. In addition, simple CFD test cases for a one-dimensional standing shock and for a quasi-one-dimensional nozzle will be used for demonstration of the ME-QCT method. This method allows for the calculation of non-equilibrium behavior for the N2-N2 system without the prohibitive cost of a full StS simulation. Moreover, it enables the construction of a unified model for the dissociating and recombining non-equilibrium flows.

nonequilibrium modeling↗

Sulfur poisoning of hydrocarbon oxidation by palladium

Using a differential bed recycle reactor the oxidation of ethane and diethyl ketone by a Pd catalyst was studied at the 0-30 ppm level in air. In both cases first order kinetics were observed. The ethane oxidation rate was characterized n the Arrhenius form by a pre-exponential of 1.0 x 10 to the 8th power cm/sec and an E sub a of 27 kcal/mole. The diethyl ketone oxidation rate was characterized by a pre-exponential of 5.7 x -1000 cm/sec and E sub a of 14 kcal/mole. Poisoning of ethan oxidation was also investigated by hydrogen sulfide and to a smaller extent by the refrigerants Freon 22 and Gentron 142-B. Poisoning by Gentron 142-B was much more severe than by hydrogen sulfide. Kinetic experiments indicated that only the pre-exponential was changing.

Baumgartner, A. J.↗

Potentials of fissioning plasmas

Successful experiments with the nuclear pumping of lasers have demonstrated that in a gaseous medium the kinetic energy of fission fragments can be converted directly into nonequilibrium optical radiation. This confirms the concept that the fissioning medium in a gas-phase nuclear reactor shows an internal structure such as a plasma in near thermal equilibrium varying up to a state of extreme nonequilibrium. During 20 years of research under NASA support major elements of the fissioning plasma reactor were demonstrated in theory and experiment, culminating in a proof-of-principle reactor test conducted at the Los Alamos Scientific Laboratory. It is concluded that the construction of a gaseous fuel reactor power plant is within the reach of present technology.

Thom, K.↗

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

Gokoglu, S. A.↗

Kinetics of the HO2 + BrO Reaction Over the Temperature Range 233-348 K

The reaction BrO + HO2 products is the rate-limiting step in a key catalytic ozone destruction cycle in the lower stratosphere. In this study a discharge flow reactor coupled with molecular beam mass spectrometry has been used to study the BrO + HO2 reaction over the temperature range 233-348 K.

flow velocity↗

Experimental Studies of the Formation/Deposition of Sodium Sulfate in/from Combustion Gases

Processes related to the hot corrosion of gas turbine components were examined in two separate investigations. Monochromatic laser light was used to probe condensation onset and condensate film growth (via interference of reflected light) on electrically heated ribbons immersed in seeded, flat flame combustion product gases. Boron trichloride is used as the seed gas in these preliminary experiments conducted to obtain precise measurements of the dew point/deposition rates. Because of the importance of gaseous Na(g) as a precursor to NaSO4 formation, the kinetics and mechanisms of the heterogeneous reaction H(g) + NaCl(s) yields Na(g) + HCl(g) was studied using atomic absorption spectroscopy combined with microwave discharge-vacuum flow reactor techniques at moderate temperatures. Preliminary results indicate the H-atom attack of solid NaCl vaporization is negligible; hence the corresponding gas phase (homogeneous) reaction no role in the observed Na(g) production.

Rosner, D. E.↗

Performance assessment of low pressure nuclear thermal propulsion

An increase in Isp for nuclear thermal propulsion systems is desirable for reducing the propellant requirements and cost of future applications, such as the Mars Transfer Vehicle. Several previous design studies have suggested that the Isp could be increased substantially with hydrogen dissociation/recombination. Hydrogen molecules (H2), at high temperatures and low pressures, will dissociate to monatomic hydrogen (H). The reverse process (i.e., formation of H2 from H) is exothermic. The exothermic energy in a nozzle increases the kinetic energy and therefore, increases the Isp. The low pressure nuclear thermal propulsion system (LPNTP) system is expected to maximize the hydrogen dissociation/recombination and Isp by operating at high chamber temperatures and low chamber pressures. The process involves hydrogen flow through a high temperature, low pressure fission reactor, and out a nozzle. The high temperature (approximately 3000 K) of the hydrogen in the reactor is limited by the temperature limits of the reactor material. The minimum chamber pressure is about 1 atm because lower pressures decrease the engines thrust to weight ratio below acceptable limits. This study assumes that hydrogen leaves the reactor and enters the nozzle at the 3000 K equilibrium dissociation level. Hydrogen dissociation in the reactor does not affect LPNTP performance like dissociation in traditional chemical propulsion systems, because energy from the reactor resupplies energy lost due to hydrogen dissociation. Recombination takes place in the nozzle due primarily to a drop in temperature as the Mach number increases. However, as the Mach number increases beyond the nozzle throat, the static pressure and density of the flow decreases and minimizes the recombination. The ideal LPNTP Isp at 3000 K and 10 psia is 1160 seconds due to the added energy from fast recombination rates. The actual Isp depends on the finite kinetic reaction rates which affect the amount of monatomic hydrogen recombination before the flow exits the nozzle. A LPNTP system has other technical issues (e.g. flow instability and two-phase flow) besides hydrogen dissociation/recombination which affect the systems practicality. In this study, only the effects of hydrogen dissociation/recombination are examined.

Gerrish, Harrold P., Jr.↗

Low cost silicon solar array project: Feasibility of low-cost, high-volume production of silane and pyrolysis of silane to semiconductor-grade silicon

Silicon epitaxy analysis of silane produced in the Process Development Unit operating in a completely integrated mode consuming only hydrogen and metallurgical silicon resulted in film resistivities of up to 120 ohms cm N type. Preliminary kinetic studies of dichlorosilane disproportionation in the liquid phase have shown that 11.59% SiH4 is formed at equilibrium after 12 minutes contact time at 56 C. The fluid-bed reactor was operated continuously for 48 hours with a mixture of one percent silane in helium as the fluidizing gas. A high silane pyrolysis efficiency was obtained without the generation of excessive fines. Gas flow conditions near the base of the reactor were unfavorable for maintaining a bubbling bed with good heat transfer characteristics. Consequently, a porous agglomerate formed in the lower portion of the reactor. Dense coherent plating was obtained on the silicon seed particles which had remained fluidizied throughout the experiment.

Breneman, W. C.↗

Spectra from nuclear-excited plasmas

The paper discusses the spectra taken from He-3(n,p)H-3 nuclear-induced plasmas under high thermal neutron flux, lasing conditions. Also, initial spectra are presented for U-235F6 generated plasmas. From an evaluation of these spectra, important atomic and molecular processes that occur in the plasma can be inferred. The spectra presented are the first to be generated by He-3 and U-235F6 nuclear reactions under high neutron flux, lasing conditions. The U-235(n,ff)FF reaction, which liberates 165 MeV of fission-fragment kinetic energy, creates plasmas that are of great interest, since at sufficiently high densities of U-235F6 the gas becomes self-critical; thus, there is no need for an external driving reactor (source of neutrons). The spectra from mixtures of He-3 and Ar, Xe, Kr, Ne, Cl2, F2 and N2 indicate little difference between high-pressure nuclear-induced plasmas and high-pressure electrically pulsed afterglow plasmas for noble-gas systems

De Young, R. J.↗

Effect of Porosity on Surface Catalytic Efficiency

This paper describes the effect of surface porosity of thermal protection materials on surface catalytic efficiency using test data taken from both arc-jet and side-arm reactor facilities. Relative surface porosity of the samples varied from 6% to 50%. Surface porosity was measured using a flow apparatus and Bernoulli equation. The surface catalytic efficiency of the materials was calculated using aerothermodynamic, and kinetic theories. The catalytic efficiency of the materials are compared at surface temperatures between room temperature and 2500 F. The data are presented in the form of graphs and tables.

Stewart, David A.↗

Model of ASTM Flammability Test in Microgravity: Iron Rods

There is extensive qualitative results from burning metallic materials in a NASA/ASTM flammability test system in normal gravity. However, this data was shown to be inconclusive for applications involving oxygen-enriched atmospheres under microgravity conditions by conducting tests using the 2.2-second Lewis Research Center (LeRC) Drop Tower. Data from neither type of test has been reduced to fundamental kinetic and dynamic systems parameters. This paper reports the initial model analysis for burning iron rods under microgravity conditions using data obtained at the LERC tower and modeling the burning system after ignition. Under the conditions of the test the burning mass regresses up the rod to be detached upon deceleration at the end of the drop. The model describes the burning system as a semi-batch, well-mixed reactor with product accumulation only. This model is consistent with the 2.0-second duration of the test. Transient temperature and pressure measurements are made on the chamber volume. The rod solid-liquid interface melting rate is obtained from film records. The model consists of a set of 17 non-linear, first-order differential equations which are solved using MATLAB. This analysis confirms that a first-order rate, in oxygen concentration, is consistent for the iron-oxygen kinetic reaction. An apparent activation energy of 246.8 kJ/mol is consistent for this model.

Steinberg, Theodore A↗

Investigation of the hydrochlorination of SiCl4

The hyrochlorination of SiC14 and m.g. silicon metal to produce SiHC13, was investigated. Reaction kinetic measurements were carried out to collect additional rate data at 525 C and 550 C. A theoretical study was carried out to provide a kinetic model and a rate equation for the hydrochlorination reaction. Results of this preliminary study show that the rate of formation of SiHC13 follows a pseudo first order kinetics. The rate constants were measured at three temperatures, 550 C, 500 C and 450 C, respectively. The activation energy was determined from the Arrhenius plot to give a value of 13.2 Kcal/mole. The design of a quartz reactor to measure reaction rates and equilibrium conversion of SiHC13 at reaction temperature up to 650 C was completed.

Mui, J. Y. P.↗

Production of large-particle-size monodisperse latexes

The research program achieved two objectives: (1) it has refined and extended the experimental techniques for preparing monodisperse latexes in quantity on the ground up to a particle diameter of 10 microns; and (2) it has demonstrated that a microgravity environment can be used to grow monodisperse latexes to larger sizes, where the limitations in size have yet to be defined. The experimental development of the monodisperse latex reactor (MLR) and the seeded emulsion polymerizations carried out in the laboratory prototype of the flight hardware, as a function of the operational parameters is discussed. The emphasis is directed towards the measurement, interpretation, and modeling of the kinetics of seeded emulsion polymerization and successive seeded emulsion polymerization. The recipe development of seeded emulsion polymerization as a function of particle size is discussed. The equilibrium swelling of latex particles with monomers was investigated both theoretically and experimentally. Extensive studies are reported on both the type and concentration of initiators, surfactants, and inhibitors, which eventually led to the development of the flight recipes. The experimental results of the flight experiments are discussed, as well as the experimental development of inhibition of seeded emulsion polymerization in terms of time of inhibition and the effect of inhibitors on the kinetics of polymerization.

Vanderhoff, J. W.↗

Magnetic-Nozzle Studies for Fusion Propulsion Applications: Gigawatt Plasma Source Operation and Magnetic Nozzle Analysis

This project has been a multiyear effort to assess the feasibility of a key process inherent to virtually all fusion propulsion concepts: the expansion of a fusion-grade plasma through a diverging magnetic field. Current fusion energy research touches on this process only indirectly through studies of plasma divertors designed to remove the fusion products from a reactor. This project was aimed at directly addressing propulsion system issues, without the expense of constructing a fusion reactor. Instead, the program designed, constructed, and operated a facility suitable for simulating fusion reactor grade edge plasmas, and to examine their expansion in an expanding magnetic nozzle. The approach was to create and accelerate a dense (up to l0(exp 20)/m) plasma, stagnate it in a converging magnetic field to convert kinetic energy to thermal energy, and examine the subsequent expansion of the hot (100's eV) plasma in a subsequent magnetic nozzle. Throughout the project, there has been a parallel effort between theoretical and numerical design and modelling of the experiment and the experiment itself. In particular, the MACH2 code was used to design and predict the performance of the magnetoplasmadynamic (MPD) plasma accelerator, and to design and predict the design and expected behavior for the magnetic field coils that could be added later. Progress to date includes the theoretical accelerator design and construction, development of the power and vacuum systems to accommodate the powers and mass flow rates of interest to out research, operation of the accelerator and comparison to theoretical predictions, and computational analysis of future magnetic field coils and the expected performance of an integrated source-nozzle experiment.

Gilland, James H.↗

Mechanisms of ilmenite reduction and their impact on the design of effective reactor systems

One of the first activities at a lunar base could be oxygen recovery from ilmenite (FeTiO3). Oxygen produced from lunar soils could be used to fuel transportation vehicles operating in near-earth space. The first step in developing a suitable reactor system for lunar operation is to determine the mechanisms and rates of oxygen removal from ilmenite. In-situ gravimetric measurements and microscopic examinations were used to determine the hydrogen reduction mechanisms of synthetic ilmenite discs between 823 to 1353 K. A shrinking core reaction model, modified to account for the growth of an iron film on the surface of discs, was capable of predicting experimentally observed conversion-time relationships. The observed reduction mechanism, kinetic rates, and associated activation energy established a base line from which comparisons could be made to improve oxygen yield and removal rates. One proposed technique to improve the rate and extent of oxygen removal was to preoxidize ilmenite. Preoxidation is commonly used during the reduction of ilmenite ores in the iron industry and has been employed for many years to lower operating temperatures and increase reduction rates. This technology could prove beneficial for oxygen production facilities on the Moon as less massive reactor vessels and/or less energy could be associated with a process including preoxidation. X ray diffraction and energy dispersive spectroscopy were utilized to follow the progression of ilmenite oxidation at 1123 and 1140 K and the reduction of pseudobrookite (Fe2TiO5) at 873 and 973 K. Structures formed during the progress of oxidation were related to the system's phase diagrams. Results indicated that after initially producing ilmenite-hematite solutions and rutile (TiO2), pseudobrookite was the end product of oxidation at all temperatures examined (1049 to 1273 K). Initial results from the reduction of pseudobrookite indicate a series of phases are produced including ferropseudobrookite (FeTi2O5), ulvospinel (Fe2TiO4), and ilmenite. Rates of pseudobrookite reduction were typically 50 to 200 times that of ilmenite.

Briggs, R. A.↗