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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Rate processes in gas phase

Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies for reaction. The effect of cross section function shape and of excited state contributions to reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved.

Hansen, C. F.↗
NASA NTRS1975

The low-temperature electrical properties of carbonaceous meteorites

Electrical conductivities and dielectric constants have been measured over the temperature range 90-300 K on several carbonaceous chondrites and some terrestrial analogues. The conductivities of meteorites of different petrologic subtypes range over many orders of magnitude and the low-temperature activation energies are typically much smaller than those observed in terrestrial materials at higher temperatures. The electrical properties of carbonaceous chondrites vary systematically with chemical-mineralogical characteristics in that: (1) activation energy at low temperature is greater in the more volatile-rich meteorites containing hydrated silicates, and (2) conductivity is greater in the more reduced meteorites of higher petrologic subtype. These new data on the electrical properties of chondrites hold important implications for both the thermal and magnetic histories of small bodies in the early solar system.

Brecher, A.↗
NASA NTRS1951

Resolution of annealing experiments for the study of nonequilibrium states

The two techniques for conducting annealing experiments for the purpose of determining the distribution of atoms of a solid among non equilibrium states are considered. Related definitions for resolving power for annealing with steadily rising temperature and for annealing at a series of fixed temperatures are given. The necessary separation of activation energies for the resolution of two different non equilibrium states is found to be greater in the case of a steadily rising temperature, but of the order of 10 percent of the activation energy for both techniques. The resolving power in the case of a steadily rising temperature is independent of the rate of temperature rise.

SOLIDS↗
NASA NTRS1984

Thermoluminescence and the shock and reheating history of meteorites. II - Annealing studies of the Kernouve meteorite

Samples of the unshocked, equilibrated chondrite, Kernouve (H6), have been annealed for 1-100 hours at 500-1200 C, their thermoluminescence sensitivity measured and Na, K, Mn, Ca, and Sc determined by instrumental neutron activation analysis. The TL sensitivity decreased with temperature until by 1000 C it had fallen by 40 percent. The process responsible has an activation energy of 8 kcal/mole and probably involves diffusion. Samples annealed 1000-1200 C had TL sensitivities 0.01 times the unannealed values, most of the decrease occurring at 1100 C. This process has an activation energy of 100 kcal/mole and is probably related to the melting of the TL phosphor, feldspar, with some decomposition and loss of Cs, Na and K. Meteorites whose petrography indicates heating above 1100 C by natural shock heating events (shock facies d-f), have TL sensitivities similar to samples annealed above 1100 C.

Sears, D. W. G.↗
NASA NTRS1993

Kinetic parameters from thermogravimetric analysis

High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.

Kiefer, Richard L.↗
NASA NTRS1975

Precipitation of silicon from splat-cooled Al-Si alloys

Splat cooled Al-Si solid solutions with 1 to 11 at.% Si were prepared and their precipitation kinetics were studied by transmission electron microscopy. The time required for appearance of particles visible at a magnification of 35,000 times was determined at temperatures between 248 K and 573 K. The resulting Arrhenius plots yielded activation energies ranging from 55 to 40 plus or minus 2kJ/mol over the composition range. Precipitate densities were higher and denuded zones of 100 to 150 nm were narrower than in comparable solid quenched samples. The activation energies are explained in terms of excess point defect concentrations.

Matyja, H.↗
NASA NTRS1992

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

Sheng, Y. J.↗
NASA NTRS2002

Tensile Creep of Polycrystalline Near-Stoichiometric NiAl

Long term tensile creep studies were conducted on binary NiAl in the temperature range 700-1200 K with the objectives of characterizing and understanding the creep mechanisms. Inverse and normal primary creep curves were observed depending on stress and temperature. It was concluded that the creep of NiAl is limited by dislocation mobility. The stress exponent for creep, n, increased from 5.5 at 1200 K to 13.9 at 700 K. The true activation energy for creep, Qc, was constant and equal to about 400 kJ per mole between 20 and 50 MPa but decreased to a constant value of 250 kJ per mole between 50 and 110 MPa. The activation energy was observed to be stress dependent above 110 MPa. The tensile creep results reported in this investigation were compared with compression creep data reported in the literature. A detailed discussion of the probable dislocation creep mechanisms governing compressive and tensile creep of NiAl is presented. It is concluded that the non-conservative motion of jogs on screw dislocations influenced the nature of the primary creep curves, where the climb of these jogs involves either the next nearest neighbor or the six-jump cycle vacancy diffusion mechanism. The probable nature of the atom vacancy exchange that occur within the core of an edge dislocation undergoing climb in NiAl are schematically examined.

Raj, Sai V.↗
NASA NTRS1972

Thermal release characteristics of spallogenic He, Ne, and Ar from the Carbo iron meteorite.

Analysis of the thermal release patterns of He, Ne, and Ar from samples of the Carbo iron meteorite, showing that virtually no fractionation of He 3, He 4, Ne 21, and Ar 38 occurs. Thus conclusions about iron meteorites based on measured noble gas ratios will be unaffected by gas loss, and measurement of these ratios cannot yield information about possible loss. Further, noble gas loss cannot explain the abnormal elemental and isotopic patterns observed in some iron meteorites, notably hexahedrites. The release of He and Ne was continuously observed throughout the stepwise heating sequence, and ratios of diffusion coefficients at two consecutive temperatures have been determined from measurements of the relative degassing rates at these temperatures at the time of temperature increase. Effective activation energies of 100 plus or minus 20 kcal/mol for both He 3 and Ne 21 are calculated from the diffusion coefficient ratios at temperatures above 1050 C. A sharp maximum at 750 C in both the effective activation energy and the gas release is correlated with the alpha, gamma-phase transition.

Nyquist, L. E.↗
NASA NTRS1983

Dynamic Mechanical Properties of N-Phenylnadimide Modified PMR Polyimide Composites

The rheological behavior of newly developd Celion 6000/N-phenylnadimide modified PMR polyimide and PMR-15 composites was investigated. The dynamic mechanical properties were correlated with the structure of N-phenylnadimide modified PMR polyimides. The storage modulus (G'), loss modulus (G''), and loss tangent (tan delta) of four composite systems were measured over a temperature range from -150 to 400 C. Three well defined peaks were seen in the regions of 360, 100, and -120 C, corresponding to the alpha, beta, and gamma relaxations, respectively, of the matrix resins. The activation energies of the alpha, beta, and gamma relaxations were estimated to be 232, 60, and 14 kcal/mole, respectively, for PMR-15. Addition of N-phenylnadimide to the PMR-15 composition lowered the glass transition temperature and the activation energies of PMR-15 polyimide. The dynamic mechanical data appear to be consistent with the formation of a copolymer from N-phenylnadimide and a PMR-15 prepolymer.

Pater, R. H.↗
NASA NTRS1986

Kinetic study of polymerization/curing of filament-wound composite epoxy resin systems with aromatic diamines

The kinetics of polymerization/curing of a filament-wound composite epoxy resin consisting of an 80/20 DGEBA/DGEBD blend and an MDA/m-PDA blend (Tonox 60/40) was studied at various temperatures and at amine epoxy ratios between 1.1 and 4.4 by means of Fourier-transform (FT) IR and bulk viscosity measurements. The activation energy for the polymerization/curing reaction using an amine/epoxy ratio of 1.1 was 11.9 kcal/mole, in agreement with a previous value. The FT-IR conversion-time plots were fitted to a kinetic expression containing two rate constants with activation energies of 13.7 and 10.0 kcal/mole. The bulk viscosity followed the Williams et al. (1955) equation, with a Di Benedetto (1965) expression for the glass transition temperature.

Golub, M. A.↗
NASA NTRS1980

Accelerated life testing effects on CMOS microcircuit characteristics

The 250 C, 200C and 125C accelerated tests are described. The wear-out distributions from the 250 and 200 C tests were used to estimate the activation energy between the two test temperatures. The duration of the 125 C test was not sufficient to bring the test devices into the wear-out region. It was estimated that, for the most complex of the three devices types, the activation energy between 200 C and 125 C should be at least as high as that between 250 C and 200 C. The practicality of the use of high temperature for the accelerated life tests from the point of view of durability of equipment is assessed. Guidlines for the development of accelerated life-test conditions are proposed. The use of the silicon nitride overcoat to improve the high temperature accelerated life-test characteristics of CMOS microcircuits is described.

Source record↗
NASA NTRS1994

Chemical and Thermal Analysis

Thermal decomposition activation energies have been determined using two methods of Thermogravimetric Analysis (TGA), with good correlation being obtained between the two techniques. Initial heating curves indicated a two-component system for Coflon (i.e. polymer plus placticizer) but a single component system for Tefzel. Two widely differing activation energies were for Coflon supported this view, 15 kcl/mol being associated with plasticizer, and 40 kcal/mol with polymer degradation. With Tefzel, values were 40-45 kcal/mol, the former perhaps being associated with a low molecular weight fraction. Appropriate acceleration factors have been determined. Thermomechanical Analysis (TMA) has shown considerable dimensional change during temperature cycles. For unaged pipe sections heating to 100 C and then holding the temperature resulted in a stable thickness increase of 2%, whereas the Coflon thickness decreased continuously, reaching -4% in 2.7 weeks. Previously strained tensile bars of Tefzel expanded on cooling during TMA. SEM performed on H2S-aged Coflon samples showed significant changes in both physical and chemical nature. The first may have resulted from explosive decompression after part of the aging process. Chemically extensive dehydrofluorination was indicated, and sulfur was present as a result of the aging. These observations indicate that chemical attack of PVDF can occur in some circumstances.

Bulluck, J. W.↗
NASA NTRS2017

Factors Limiting Li+ Charge Transfer Kinetics in Li-ion Batteries

Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.

Delp, Samuel A.↗
NASA NTRS2003

Cellular Instabilities and Self-Acceleration of Expanding Spherical Flames

In the present investigation we aim to provide experimental information on and thereby understanding of the generation and propagation of spark-ignited, outwardly propagating cellular flames, with three major focuses. The first is to unambiguously demonstrate the influence of the four most important parameters in inducing hydrodynamic and diffusional-thermal cellularities, namely thermal expansion, flame thickness, non-unity Lewis number, and global activation energy. The second is to investigate the critical state for the onset of cellularity for the stretch-affected, expanding flame. The third is to identify and consequently quantify the phenomena of self-acceleration and possibly auto-turbulization of cellular flames. Due to space limitation the effects of activation energy and the critical state for the onset of cellularity will not be discussed herein. Experiments were conducted using C3H8-air and H2-O2-N2 mixtures for their opposite influences of non-equidiffusivity. The additional system parameters varied were the chamber pressure (p) and the mixture composition including the equivalence ratio (phi). From a sequence of the flame images we can assess the propensity of cell formation, and determine the instantaneous flame radius (R), the flame propagation rate, the global stretch rate experienced by the flame, the critical flame radius at which cells start to grow, and the average cell size.

Law, C. K.↗
NASA NTRS1988

Dependence of rate constants on vibrational temperatures - An Arrhenius description

An interpretation of the variation of rate constants with vibrational temperature is proposed which introduces parameters analogous to those of the classical Arrhenius expression. The constancy of vibrational activation energy is studied for the dissociaton of NO, the ion-molecular reaction of O(+) with N2, and the atom exchange reaction of I with H2. It is found that when a Boltzmann distribution for vibrational states is applicable, the variation of the rate constant with the vibrational temperature can be used to define a vibrational activation energy. The method has application to exchange reactions where a vibrational energy threshold exists.

Ford, D. I.↗
NASA NTRS1989

Gravimetric measurements of materials outgassing applied to graphite-epoxy laminates

The outgassing rates of two graphite-epoxy laminates, American Cyanamide 985B-626 and HST-7B-112, were obtained using a gravimetric method. The rates as a function of time and temperature were derived from the measurements of their mass losses at temperatures varying from 25 to 150 C and for a time span of up to 400 hours in a vacuum. The data from those measurements were reduced to obtain the outgassing activation energies, the mass losses per unit mass or area, and the corresponding outgassing rates. The rates are expressed in closed-form equations and are directly usable for medling computations. The procedures to obtain these parameters are shown and may be used for the evaluation of other materials. The results of the tests show that the activation energies of the two materials are: 4630 cal/mole for the 985B-626 materials and 4791 cal/mole for the HST-7B-112 sample no. 10 Graphite Exoxy. The outgassing rates of these materials are in the 10E-5 g/sq cm/hr range and they decay according to a power of time of 0.60 at 25 C, indicating that the outgassing process is mainly a diffusion at that temperature. The normalized mass losses versus time obtained from these tests were compared to the discrete results obtained from the ASTM-E595 tests. The comparison provides general indications on the effects of temperature and time in relation to the ASTM test values obtained at 125 C for a 24-hour test duration.

Scialdone, John J.↗
NASA NTRS1990

Gravimetric measurements of materials outgassing applied to graphite-epoxy laminates

The outgassing rates of two graphite-epoxy laminates, American Cyanamide 985B-626 and HST-7B-112, were obtained using a gravimetric method. The rates as a function of time and temperature were derived from the measurements of their mass losses at temperatures varying from 25 to 150 C and for a time span of up to 400 hours in a vacuum. The data from those measurements were reduced to obtain the outgassing activation energies, the mass losses per unit mass or area, and the corresponding outgassing rates. The rates are expressed in closed-form equations and are directly usable for modeling computations. The procedures to obtain these parameters are shown and may be used for the evaluation of other materials. The results of the tests show that the activation energies of the two materials are: 4630 cal/mole for the 985B-626 materials and 4791 cal/mole for the HST-7B-112 sample no. 10 Graphite Epoxy. The outgassing rates of these materials are in the 1OE-5 g sq cm/hr range and they decay according to a power of time of 0.60 at 25 C, indicating that the outgassing process is mainly a diffusion at that temperature. The normalized mass losses versus time obtained from these tests were compared to the discrete results obtained from the ASTM-E595 tests. The comparison provides general indications on the effects of temperature and time in relation to the ASTM test values obtained at 125 C for a 24-hour test duration.

Scialdone, John J.↗