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At least 253 records · Page 14

Fundamental Studies of Droplet Combustion at Reduced Gravity

Reduced gravity is used to carry out scientific investigations of droplet combustion. In earlier work a preliminary conceptual design had been developed for droplet burning experiments for Spacelab. Refinements of the earlier work with special consideration given to possible experiments for Mid-Deck Modules of the Space Shuttle is discussed. A re-evaluation of suitable experiments on droplet combustion is done to ascertain whether influences of reduced buoyancy on time-dependent processes of heat and mass transfer in the gas or in the liquid on extinction processes or on disruptive burning phenomena are best suited for further investigation. Components of the experimental apparatus, which include a droplet dispensing system, a droplet positioning system, a droplet ignition system and provision for recording, primarily photographically, the combustion of the individual droplet in a chamber having a controlled gas atmosphere, are studied to determine optimal approaches to the experimental design. Methods for data reduction and interpretation are being made more specific, particularly in the context of an objective to calculate overall gas-phase chemical-kinetic parameters for the combustion from observations of extinction conditions in different atmospheres.

Williams, F. A.↗

Analyzing Nonisothermal Crystallization of Thermoplastics

Method developed for analysis of nonisothermal cold crystallization in thermoplastics. Does not require prior knowledge of isothermal kinetic parameters. Based upon observation: During nonisothermal crystallization at constant rate, relative crystallinity develops with time dependence sigmoidal at low degrees of conversion. Application for method is study of cold crystallization in advanced thermoplastics.

Cebe, Peggy↗

Experimental observation of electrochemical rate limitations affecting sodium ion-electron recombination at electrodes of the alkali metal thermoelectric converter at T about 1200 K

This paper considers a model of the internal impedances of thin porous Mo and W alkali metal thermoelectric converter (AMTEC), in which the kinetic parameters associated with the reaction of the beta-double-prime alumina solid electrolite (BASE)/porous metal/gas three-phase boundary can be evaluated. Impedance data in the frequency range 0.01-100,000 Hz were collected over a range of AMTEC cell operating voltages for small-area thin porous Mo and W electrodes, yielding apparent charge transfer resistances at a series of cell potentials/currents. The ohmic resistance in the AMTEC cell could be broken down and characterized with three parameters: the BASE ionic resistance, the electrode film sheet resistance, and the contact/lead resistance, all of which could be calculated or measured independently and used to calculate power curves in good agreement with observed power curves. It is shown that these calculations can be used to predict the properties of electrodes with optimized parameters or to detect enhanced transport modes.

Williams, R. M.↗

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

The electrochemical behavior of NbSe3 in the battery electrolyte 1.5M LiAsF6/2Me-THF is reported. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe3 as well as the rate governing processes in the reduction of NbSe3. An equivalent circuit has been formulated to represent the NbSe3-solution interface. The kinetic parameters for the reduction of NbSe3 were evaluated from the ac and dc measurements. The structural change in NbSe3 on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe3 was identified to be a loss of crystallographic order.

Ratnakumar, B. V.↗

Computer Simulation Of Cyclic Oxidation

Computer model developed to simulate cyclic oxidation of metals. With relatively few input parameters, kinetics of cyclic oxidation simulated for wide variety of temperatures, durations of cycles, and total numbers of cycles. Program written in BASICA and run on any IBM-compatible microcomputer. Used in variety of ways to aid experimental research. In minutes, effects of duration of cycle and/or number of cycles on oxidation kinetics of material surveyed.

Probst, H. B.↗

Electrochemistry of metal chloride cathodes in sodium batteries

Fundamental electrochemical studies on three candidate materials, i.e., FeCl2, NiCl2, and CuCl2, were carried out using various techniques, such as cyclic voltammetry, linear polarization, potentiodynamic polarization, and ac impedance. These studies were aimed at identifying various rate processes in the reduction, elucidating the reaction mechanisms, and determining the kinetic parameters for the reduction. The limitations in the performance of these cathode materials in high power density applications were also examined. Finally, recommendations were made from these studies for the selection of a candidate system among these materials for future NASA applications.

Ratnakumar, B. V.↗

High speed turbulent reacting flows: DNS and LES

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Givi, Peyman↗

High energy efficiency and high power density proton exchange membrane fuel cells: Electrode kinetics and mass transport

The development of proton exchange membrane (PEM) fuel cell power plants with high energy efficiencies and high power densities is gaining momentum because of the vital need of such high levels of performance for extraterrestrial (space, underwater) and terrestrial (power source for electric vehicles) applications. Since 1987, considerable progress has been made in achieving energy efficiencies of about 60 percent at a current density of 200 mA/sq cm and high power densities (greater than 1 W/sq cm) in PEM fuel cells with high (4 mg/sq cm) or low (0.4 mg/sq cm) platinum loadings in electrodes. The following areas are discussed: (1) methods to obtain these high levels of performance with low Pt loading electrodes - by proton conductor impregnation into electrodes, localization of Pt near front surface; (2) a novel microelectrode technique which yields electrode kinetic parameters for oxygen reduction and mass transport parameters; (3) demonstration of lack of water transport from anode to cathode; (4) modeling analysis of PEM fuel cell for comparison with experimental results and predicting further improvements in performance; and (5) recommendations of needed research and development for achieving the above goals.

Supramaniam Srinivasan↗

A mathematical model of a sealed nickel-cadmium battery

A mathematical model for the charge and discharge of a sealed nickel-cadmium (Ni-Cd) battery is presented. The model is used to study the effect of transport properties of the electrolyte and kinetic parameters of the electrode reactions on the cell performance during the charge and discharge period. The model can also be used to demonstrate the changes of cell performance during cycling. Some comparisons between model predictions and experimental results indicate that the model predictions appear to fit the experimental data well. Sensitivity analyses illustrate that the sealed nickel-cadmium battery operates under activation control. It is also shown theoretically that oxygen generated on the positive electrode during charge is reduced electrochemically on the negative electrode.

Fan, Deyuan↗

Surface reaction and pore diffusion in flow-tube reactors

The interaction of gas diffusion with surface reaction in porous solids is discussed and applied specifically to heterogeneous rate measurements in flow-tube reactors. External diffusion to the outer surface of a reactive solid, internal diffusion within the pores, surface reaction, and laminar flow are considered. A procedure is developed to correct observed surface rate constants for the interaction of these processes. Measured surface areas and bulk densities are used to construct a semiempirical model for porous diffusion in vapor-formed HNO3-H2O ices which are used to simulate polar stratospheric cloud surfaces. The model is tested experimentally by varying the thickness of these ices from about 15 to 120 microns. The results are consistent with the model predictions and show that the HNO3-H2O ices used are highly porous, and the internal surface must be considered in calculating kinetic parameters from observed loss rates. The best fit of the data yields a tortuosity factor of 3.3 +/-1.1 for the ice substrates.

Keyser, Leon F.↗

The crystallization and crystalline properties of LARC-TPI

LARC-TPI, a thermoplastic polyimide, has been studied in order to develop an understanding of its crystalline phase transition. Our experiments suggest that samples synthesized in different laboratories apparently had different degrees of imidization and their thermal behaviors differed accordingly. When the most crystalline of these polyimides was studied in some detail, we found that it melted irreversibly in that once a sample was completely melted it would not recrystallize. A polymer that did not recrystallize displayed a glass transition, which increased in temperature upon subsequent cooling and reheating. Solubility experiments indicated that heating above the crystalline melting temperature led to network formation in the polymer, a conclusion that is consistent with other behavior just mentioned. Differential calorimetric studies revealed that annealing at slow heating rates or under isothermal conditions resulted in dual melting transitions. These studies, supported by X-ray diffraction results, strongly indicate that the annealing process involves a solid-liquid-solid transformation. From an existing phenomenological model for the kinetics of phase transitions, kinetic parameters for these crystallizations have been evaluated. The Avrami exponents n increased with the annealing temperature in the protocol used in this study. Their values were about 2 or lower, thus indicating that crystallization may have followed a mechanism that included heterogeneous nucleation of a low dimensional order in which all the embryonic crystallites formed at the beginning of the process. A positive temperature coefficient for these crystallizations indicated that diffusion may have had a rate controlling influence and affected the values of n.

Theil, Michael H.↗

Prediction of Chemical Vapor Deposition Rates on Monofilaments and Its Implications for Fiber Properties

Deposition rates are predicted in a cylindrical upflow reactor designed for chemical vapor deposition (CVD) on monofilaments. Deposition of silicon from silane in a hydrogen carrier gas is chosen as a relevant example. The effects of gas and surface chemistry are studied in a two-dimensional axisymmetric flow field for this chemically well-studied system. Model predictions are compared to experimental CVD rate measurements. The differences in some physical and chemical phenomena between such small diameter (about 150 microns) fiber substrates and other typical CVD substrates are highlighted. The influence of the Soret mass transport mechanism is determined to be extraordinarily significant. The difficulties associated with the accurate measurement and control of the fiber temperature are discussed. Model prediction sensitivities are investigated with respect to fiber temperatures, fiber radii, Soret transport, and chemical kinetic parameters. The implications of the predicted instantaneous rates are discussed relative to the desired fiber properties for both the batch and the continuous processes.

Gokoglu, S. A.↗

Electrochemical impedance spectroscopy of lithium-titanium disulfide rechargeable cells

The two-terminal alternating current impedance of Li/TiS2 rechargeable cells was studied as a function of frequency, state-of-charge, and extended cycling. Analysis based on a plausible equivalent circuit model for the Li/TiS2 cell leads to evaluation of kinetic parameters for the various physicochemical processes occurring at the electrode/electrolyte interfaces. To investigate the causes of cell degradation during extended cycling, the parameters evaluated for cells cycled 5 times were compared with the parameters of cells cycled over 600 times. The findings are that the combined ohmic resistance of the electrolyte and electrodes suffers a tenfold increase after extended cycling, while the charge-transfer resistance and diffusional impedance at the TiS2/electrolyte interface are not significantIy affected. The results reflect the morphological change and increase in area of the anode due to cycling. The study also shows that overdischarge of a cathode-limited cell causes a decrease in the diffusion coefficient of the lithium ion in the cathode.

Narayanan, S. R.↗

Kinetics of phase transformation in glass forming systems

The objectives of this research were to (1) develop computer models for realistic simulations of nucleation and crystal growth in glasses, which would also have the flexibility to accomodate the different variables related to sample characteristics and experimental conditions, and (2) design and perform nucleation and crystallization experiments using calorimetric measurements, such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA) to verify these models. The variables related to sample characteristics mentioned in (1) above include size of the glass particles, nucleating agents, and the relative concentration of the surface and internal nuclei. A change in any of these variables changes the mode of the transformation (crystallization) kinetics. A variation in experimental conditions includes isothermal and nonisothermal DSC/DTA measurements. This research would lead to develop improved, more realistic methods for analysis of the DSC/DTA peak profiles to determine the kinetic parameters for nucleation and crystal growth as well as to assess the relative merits and demerits of the thermoanalytical models presently used to study the phase transformation in glasses.

Ray, Chandra S.↗

In-plant testing of membranes to treat electroplating wastewater

This is the final report submitted for the work performed under the NASA Cooperative Agreement NCC3-301 for the project entitled 'In-Plant Testing of Membranes To Treat Electroplating Waste water'. The main objective of the research project was to determine if the crosslinked polyacrylic acid salt films developed by NASA scientists could be used for heavy metal removal from the wastewater generated by the metals-finishing or electroplating industry. A variety of tasks identified in the original proposal were completed. These included: (1) analysis of our industrial partner Aetna Plating's zinc electroplating process and its wastewater treatment needs for zinc removal; (2) design and construction of a laboratory-scale unit to continuously supply and remove the ion exchange films from the zinc wastewater; (3) performance of a series of runs on such a unit to determine its operating characteristics; and (4) design of a prototype unit for use at the industrial site. In addition, there were a number of tasks that had not been identified in the original proposal but were later judged to be necessary for the successful completion of the project. These were: (1) batch equilibrium and kinetic experiments with analysis of the experimental results to accurately determine the equilibrium and kinetic parameters for the ion exchange films; (2 ) simulation studies for proper design of the prototype unit; and (3) preliminary runs to exchange the films from H form to Calcium form.

Shah, D. B.↗

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.↗

Proton exchange membrane fuel cells for space and electric vehicle applications: From basic research to technology development

The proton exchange membrane fuel cell (PEMFC) is one of the most promising electrochemical power sources for space and electric vehicle applications. The wide spectrum of R&D activities on PEMFC's, carried out in our Center from 1988 to date, is as follows (1) Electrode Kinetic and Electrocatalysis of Oxygen Reduction; (2) Optimization of Structures of Electrodes and of Membrane and Electrode Assemblies; (3) Selection and Evaluation of Advanced Proton Conducting Membranes and of Operating Conditions to Attain High Energy Efficiency; (4) Modeling Analysis of Fuel Cell Performance and of Thermal and Water Management; and (5) Engineering Design and Development of Multicell Stacks. The accomplishments on these tasks may be summarized as follows: (1) A microelectrode technique was developed to determine the electrode kinetic parameters for the fuel cell reactions and mass transport parameters for the H2 and O2 reactants in the proton conducting membrane. (2) High energy efficiencies and high power densities were demonstrated in PEMFCs with low platinum loading electrodes (0.4 mg/cm(exp 2) or less), advanced membranes and optimized structures of membrane and electrode assemblies, as well as operating conditions. (3) The modeling analyses revealed methods to minimize mass transport limitations, particularly with air as the cathodic reactant; and for efficient thermal and water management. (4) Work is in progress to develop multi-kilowatt stacks with the electrodes containing low platinum loadings.

Srinivasan, Supramaniam↗

Stratospheric Chlorine partitioning: Constraints from Shuttle-borne Measurements of [HCl], [ClNO3] and [ClO]

Measured stratospheric mixing ratios of HCl, ClNO3, and ClO from ATMOS and MAS are poorly reproduced by models using recommended kinetic parameters. This discrepancy is not resolved by new rates for the reactions Cl+CH4 and OH+HCl derived from weighted fits to laboratory measurements. A deficit in modeled [HCl] and corresponding overprediction of [ClNO3] and [ClO], which increases with altitude, suggests that production of HCl between 20 and 50 km is much faster than predicted from recommended rates.

Michelsen, H. A.↗