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Results for “activation energies”

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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1973

The activation energy for creep of columbium /niobium/.

The activation energy for creep of nominally pure columbium (niobium) was determined in the temperature range from 0.4 to 0.75 T sub M by measuring strain rate changes induced by temperature shifts at constant stress. A peak in the activation energy vs temperature curve was found with a maximum value of 160 kcal/mole. A pretest heat treatment of 3000 F for 30 min resulted in even higher values of activation energy (greater than 600 kcal/mole) in this temperature range. The activation energy for the heat-treated columbium (Nb) could not be determined near 0.5 T sub M because of unusual creep curves involving negligible steady-state creep rates and failure at less than 5% creep strain. It is suggested that the anomalous activation energy values and the unusual creep behavior in this temperature range are caused by dynamic strain aging involving substitutional atom impurities and that this type of strain aging may be in part responsible for the scatter in previously reported values of activation energy for creep of columbium (Nb) near 0.5 T sub M.

Klein, M. J.↗
NASA NTRS1990

Stress versus temperature dependent activation energies in creep

The activation energy for creep at low stresses and elevated temperatures is lattice diffusion, where the rate controlling mechanism for deformation is dislocation climb. At higher stresses and intermediate temperatures, the rate controlling mechanism changes from that of dislocation climb to one of obstacle-controlled dislocation glide. Along with this change, there occurs a change in the activation energy. It is shown that a temperature-dependent Gibbs free energy does a good job of correlating steady-state creep data, while a stress-dependent Gibbs free energy does a less desirable job of correlating the same data. Applications are made to copper and a LiF-22 mol. percent CaF2 hypereutectic salt.

Freed, A. D.↗
NASA NTRS1992

Stress versus temperature dependence of activation energies for creep

The activation energy for creep at low stresses and elevated temperatures is associated with lattice diffusion, where the rate controlling mechanism for deformation is dislocation climb. At higher stresses and intermediate temperatures, the rate controlling mechanism changes from dislocation climb to obstacle-controlled dislocation glide. Along with this change in deformation mechanism occurs a change in the activation energy. When the rate controlling mechanism for deformation is obstacle-controlled dislocation glide, it is shown that a temperature-dependent Gibbs free energy does better than a stress-dependent Gibbs free energy in correlating steady-state creep data for both copper and LiF-22mol percent CaF2 hypereutectic salt.

Freed, A. D.↗
NASA NTRS1998

Assessment of Uncertainty in the Determination of Activation Energy for Polymeric Materials

An assessment of the experimental uncertainty in obtaining the kinetic activation energy from thermogravimetric analysis (TGA) data is presented. A neat phenolic resin, Borden SC1O08, was heated at three heating rates to obtain weight loss vs temperature data. Activation energy was calculated by two methods: the traditional Flynn and Wall method based on the slope of log(q) versus 1/T, and a modification of this method where the ordinate and abscissa are reversed in the linear regression. The modified method produced a more accurate curve fit of the data, was more sensitive to data nonlinearity, and gave a value of activation energy 75 percent greater than the original method. An uncertainty analysis using the modified method yielded a 60 percent uncertainty in the average activation energy. Based on this result, the activation energy for a carbon-phenolic material was doubled and used to calculate the ablation rate In a typical solid rocket environment. Doubling the activation energy increased surface recession by 3 percent. Current TGA data reduction techniques that use the traditional Flynn and Wall approach to calculate activation energy should be changed to the modified method.

Darby, Stephania P.↗
NASA NTRS1982

Surface diffusion activation energy determination using ion beam microtexturing

The activation energy for impurity atom (adatom) surface diffusion can be determined from the temperature dependence of the spacing of sputter cones. These cones are formed on the surface during sputtering while simultaneously adding impurities. The impurities form clusters by means of surface diffusion, and these clusters in turn initiate cone formation. Values are given for the surface diffusion activation energies for various materials on polycrystalline Cu, Al, Pb, Au, and Ni. The values for different impurity species on each of these substrates are approximately independent of impurity species within the experimental uncertainty, suggesting the absence of strong chemical bonding effects on the diffusion.

Rossnagel, S. M.↗
NASA NTRS1975

The elastic modulus correction term in creep activation energies Applied to oxide dispersion strengthened superalloy

The effect of elastic modulus and the temperature dependence of elastic modulus on creep activation energies for an oxide dispersion strengthened nickel-base superalloy are investigated. This superalloy is commercially known as Inconel Alloy MA 753, strengthened both by gamma-prime precipitates and by yttria particles. It is shown that at intermediate temperatures, say below 1500 F, where elastic modulus is weakly dependent on temperature, the modulus correction term to creep activation energy is small. Accordingly, modulus corrections are insignificant for the superalloy considered, which shows high apparent creep activation energies at this temperature. On the contrary, at very high temperatures, the elastic modulus correction term can be significant, thus reducing the creep activation energy to that of vacancy self-diffusion. In order to obtain high-temperature creep resistance, a high-value elastic modulus with a weak dependence on temperature is required.

Malu, M.↗
DOE OSTI2020

DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys

A density functional theory investigation of the process of dissolution of Ni and Cr adatoms from model Ni–Cr(111) alloy surfaces is presented, both in vacuum and with explicit water molecules. The goal is to understand how the electronic structures solved using DFT can provide insights as to changes in valence, energy and coordination of the adatoms in the process of dissolving from the alloy surface. It is found that nearby Cr solute atoms increase the dissolution activation energy of Ni. Cr adatoms have a similar dissolution activation energy as Ni adatoms, except for one particular surface configuration that has a much smaller dissolution activation energy, which might promote selective dissolution of Cr in Ni–Cr alloys. To interpret the first-principles modeling results for the potential energy trajectory along the dissolution reaction coordinate, we provide a thermodynamic breakdown of the various terms that contribute to the dissolution activation and total reaction energy. The role of addition of Cr is explored on the dissolution kinetics of a Ni–Cr alloys of varying composition by constructing a model for the corrosion current density with DFT-based activation energies. Lastly, dissolution resistance index is proposed as a quantifiable descriptor of the dissolution resistance of corrosion resistant alloys.

36 MATERIALS SCIENCE↗
NASA NTRS1988

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

The effects of nine metal cations (Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water: TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or, Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion (Mg(2+), Ca(2+), Y(3+) or the water: TEOS mole ratio had no appreciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Bansal, Narottam P.↗
NASA NTRS1990

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

The effects of nine metal cations Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water:TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion Mg(2+), Ca(2+), Y(3+) or the water:TEOS mole ratio had no appreaciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Bansal, Narottam P.↗
NASA NTRS2015

Thermodynamic Derivation of the Activation Energy for Ice Nucleation

Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the development of parameterizations for cloud formation.

Cirrus clouds↗
NASA NTRS1981

Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

Brown, R. L.↗
DOE OSTI2020

Phase Change-Driven Negative Activation Energies in Pd/Carbon-Based/Organic Getter Hydrogenation Reactions

In this study, the hydrogenation of 1,4-diphenylbutadiyne (DPB) blended with carbon-supported Pd (DPB–Pd/C) in the form of pellets was investigated by isothermal–isobaric experiments at 1333 Pa of H 2 and in the temperature range of 291–315 K. The extracted kinetics were then used in conjunction with a complementary constant rate of H 2 input experimentation to model the performance of a DPB-catalysis/support system as a function of temperature and H 2 partial pressure. First-principles density functional theory (DFT) calculations were also performed to shed light on the molecular level energetics of DPB and its intermediate states. A seemingly puzzling formation of alternate positive activation energy barrier (higher reaction rate with higher temperature) and negative activation energy barrier (higher reaction rate with lower temperature) zones during the hydrogenation process was discovered. However, this observed phenomenon can be logically explained in terms of the associated phase changes and H 2 transport in the material. This work provides a good illustration of a rarely encountered chemical process with a negative activation energy barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Activation Energy for End-of-Life Solder Bond Degradation: Thermal Cycling of Field-Aged PV Modules

The longevity of solar photovoltaic modules depends on the durability and reliability of their components, one of which is the solder bonds in interconnect ribbons. The solder joints experience stresses from thermal cycling and constant elevated temperatures (40 °C-70 °C) in regular field operation leading to thermo-mechanical fatigue and intermetallic compound formation. To study the end-of-life wear-out mechanisms and to obtain activation energy of solder bond degradation, here two field-aged modules from Arizona-a 21-year-old Solarex MSX60 module (with Sn62Pb36Ag2 at the solder joints) and an 18-year-old Siemens M55 module (with Sn60Pb40 at the solder joints)-underwent 800 and 400 modified thermal cycles, respectively. Using three heating blankets, each module had three temperature zones maintained at 85, 95, and 105 °C during the 15-min hot dwell time of the thermal cycle. Cell-level series resistance data obtained from three temperature zones enabled the calculation of activation energy for solder bond degradation for the MSX60 and the M55 modules to be 0.12 eV and 0.35 eV, respectively. From each temperature zone in both modules, busbar-solder samples were obtained, imaged through SEM, and analyzed with energy-dispersive X-ray spectroscopy. In the MSX60 module with traces of Ag in the solder material, phase segregation and growth were primarily observed at high temperatures. For M55 modules without Ag in the solder material, major phase segregation was observed in all temperature zones. The IMC thickness for both modules increased with increasing module temperature. The beneficial effect of Ag in solder material on mitigating solder bond degradation is presented.

14 SOLAR ENERGY↗
DOE OSTI2021

Heavily Tungsten–Doped Sodium Thioantimonate Solid–State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na 2.895 W 0.3 Sb 0.7 S 4 and Na 2.7 W 0.3 Sb 0.7 S 4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At –15 °C the Na 2.895 W 0.3 Sb 0.7 S 4 displays a total ionic conductivity of 5.5 mS/cm. Here, the 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na 2.895 W 0.3 Sb 0.7 S 4 as the primary SSE and a sodium sulfide (Na 2 S) cathode achieves a reversible capacity of 400 mAh g –1 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na 2.895 W 0.3 Sb 0.7 S 4 and Na 2.7 W 0.3 Sb 0.7 S 4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At –15 °C the Na 2.895 W 0.3 Sb 0.7 S 4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Here, calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na 2.895 W 0.3 Sb 0.7 S 4 as the primary SSE and a sodium sulfide (Na 2 S) cathode achieves a reversible capacity of 400 mAh g –1 .

sodium metal battery (SMB)↗