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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 397 records · Page 22

Open-loop response of a burning liquid monopropellant

A direct comparison was obtained between the theoretical and experimental response of a burning liquid monopropellant surface to imposed pressure oscillations. The comparison extended beyond the quasi-steady frequency regime into the range where the combustion process interacts with the thermal wave in the liquid phase. The theory considered both gas and liquid-phase transient effects, involving a numerically integrated, first-order perturbation analysis. The experiment employed hydrazine as the test fuel, burning as a strand. With kinetic parameters fixed by steady burning rate measurements, the model gave good predictions of liquid-phase temperature distributions during steady combustion as well as the amplitude and phase of the oscillatory component of the burning rate in the presence of imposed pressure oscillations. The combustion response tends to peak in two frequency ranges; one corresponding to interaction with liquid-phase transient effects, which could be verified both theoretically and experimentally; the second corresponding to gas-phase transient effects, which could only be examined theoretically. Both ranges provide conditions where the amplifying power is sufficient to drive combustion instability.

Allison, C. B.↗

Diffusion in mixed solvents - On the viscosity question

Linear plots of reaction rate vs reciprocal of solvent viscosity are generally used as the classifying criteria for diffusion controlled reactions in fluid solutions and to determine reaction mechanisms in mixed hydroxylic solvents like glycerol and water. This paper presents data which shows that the above-mentioned criteria are insufficient in many cases where nonideal mixed solvent systems are used to increase solvent viscosity. Data correlations suggest that the excess functions determine the variation in reaction rate constants. Kinetic parameters are presented for sucrose-water and methanol-water solvent systems for a reaction involving Fe(CN)6 and zinc uroporphyrin.

Carapellucci, P. A.↗

Calorimetric studies of 7000 series aluminum alloys. I - Matrix precipitate characterization of 7075. II - Comparison of 7075, 7050, and RX720 alloys

Correlation between differential scanning calorimetry and high temperature transmission electron microscopy for the characterization of preexisting matrix precipitates in the highest-strength and overaged tempers of 7075 aluminum was demonstrated. The solid state reactions undergone by these tempers in the 20-500 C temperature range were elucidated and expressed in terms of thermodynamic and kinetic parameters. The dissolution parameters for each phase are distinguishable and serve as guidelines for a rapid characterization of the matrix microstructure of these alloys.

Deiasi, R.↗

Further calculations based upon a theory of flame spread across solid fuels

A theory of flame spread above solid fuel beds of finite or infinite thickness is considered. Heat transfer ahead of the flame is allowed through both the solid and gas phases. The simplifying assumption of a surface reaction is made. Temperature profiles in both phases, concentration profiles in the gas phase, heat transfer at the surface, and flame spreading rates are determined. It is found that chemical kinetic parameters together with transport properties strongly influence the spreading rate. Heat transfer through the gas phase is the dominant mechanism for energy transfer ahead of the spreading flame over a wide range of Peclet numbers for the gas and solid phases.

Feng, C. C.↗

A contribution to the knowledge of HMX decomposition and application of results

The decomposition of cyclotramethylenetetranitramine (HMX) in the solid and liquid phase was studied by isothermal and nonisothermal heating at atmospheric pressure. Decomposition rates of solid HMX changed with sample size and gaseous environment. Kinetic parameters were obtained from weight loss measurements in the temperature range 229 C - 269 C. These tests also yielded highly porous solid residues. Qualitative aspects of solid and liquid phase decomposition of HMX with additives were also investigated in isothermal and nonisothermal tests.

Kraeutle, K. J.↗

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.↗