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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Activation Energies for Oxide- and Interface-Trap Charge Generation Due to Negative-Bias Temperature Stress of Si-Capped SiGe-pMOSFETs

We investigate negative-bias temperature instabilities in SiGe pMOSFETs with SiO 2 /HfO 2 gate dielectrics. The measured activation energies for interface-trap charge buildup during negative-bias temperature stress are lower for SiGe channel pMOSFETs with SiO 2 /HfO 2 gate dielectrics and Si capping layers than for conventional Si channel pMOSFETs with SiO 2 gate dielectrics. Electron energy loss spectroscopy and scanning transmission electron microscopy images demonstrate that Ge atoms can diffuse from the SiGe layer into the Si capping layer, which is adjacent to the SiO 2 /HfO 2 gate dielectric. Density functional calculations show that these Ge atoms reduce the strength of nearby Si-H bonds and that Ge-H bond energies are still lower, thereby reducing the activation energy for interface-trap generation for the SiGe devices. Activation energies for oxide-trap charge buildup during negative-bias temperature stress are similarly small for SiGe pMOSFETs with SiO 2 /HfO 2 gate dielectrics and Si pMOSFETs with SiO 2 gate dielectrics, suggesting that, in both cases, the oxide-trap charge buildup likely is rate-limited by hole tunneling into the near-interfacial SiO 2 .

activation energy↗
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.↗
DOE OSTI2016

Removing the barrier to the calculation of activation energies

Approaches for directly calculating the activation energy for a chemical reaction from a simulation at a single temperature are explored with applications to both classical and quantum systems. The activation energy is obtained from a time correlation function that can be evaluated from the same molecular dynamics trajectories or quantum dynamics used to evaluate the rate constant itself and thus requires essentially no extra computational work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Activation Energies of Harvested Boston Insulated Wire and Okonite Cable Materials

As part of the Cable Aging Task within the Material Aging and Degradation (MAaD) pathway of the DOE Light Water Reactor Sustainability (LWRS) program, ORNL is collaborating with Pacific Northwest National Laboratory (PNNL), the Electric Power Research Institute (EPRI), and the US Nuclear Regulatory Commission (NCR) to study cable aging mechanisms. Understanding cable aging mechanisms in cable nuclear power plants (NPPs) with needed information as they seek plant life extensions to 80 years of operations. This report summarizes activities in the characterization of harvested electrical I&C cables related to activation energy and their role in determining the remaining margin of time cable insulation in NPPs can be used. Activation energy is the amount of energy that is required to break chemical bonds in a polymer through an endothermic reaction. For I&C cables that are utilized in NPPs, activation energy is used with a time and temperature dependent cable property like elongation at break (EAB) and/or an electrical property like voltage withstand to determine whether a cable insulation material meets the performance requirements for the environmental conditions such as temperature, radiation, and humidity for a given plant location. Considering differences in activation energies that were observed in harvested cable jackets when compared to previous measurements, an assessment of the cable insulation activation energy in harvested I&C cables was performed given that the insulation performance ultimately determines that lifetime performance for a cable. This assessment consisted of the mechanical and chemical characterization of harvested Boston Insulated Wire (BIW) and Okonite cable insulations from Zion NPP from a series of thermal accelerated aging exposures between 140°C and 160°C. Cables were obtained as part of the LWRS Zion Harvesting Project in cooperation with Energy Solutions and the NRC. Activation energies of 1.10 eV and 0.61 eV were obtained for BIW and Okonite manufactured ethylene propylene rubber (EPR) insulation with individual chlorosulfonated polyethylene (CSPE) jackets respectively. When compared to previous measurements, the activation energy of BIW agreed well, while there was a sizeable gap for previous Okonite activation energies near 0.91 eV. The lack of agreement could be attributed to differences in raw materials used in a given insulation and/or jacket, differences in the thicknesses of the EPR insulation and CSPE individual jacket or the environmental conditions that the insulation from previous measurements experienced prior to characterization especially if cables were not stored at manufacturer recommended conditions. Comparison of harvested insulation compositions from multiple NPP sites and locations in a given NPP with respect to activation energy could provide some guidance on property sensitivity and insulation variations. To address the issue of material thickness, an initial assessment of the influence of the CPSE individual jacket was also done. This was motivated by the different combinations of EPR insulation and CSPE individual jacket thicknesses that were found in harvested cables and previous measurements. Accelerated thermal aging of BIW-manufactured EPR insulation with individual CSPE jackets removed did show that the CSPE layer affected insulation degradation, further comparison of the compositional make-up of the CSPE and EPR for both BIW and Okonite insulation, along with a limited amount of additional accelerated aging, is needed to increase the level of confidence regarding the influence of the CSPE.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Apparent Activation Energies in Complex Reaction Mechanisms: A Simple Relationship via Degrees of Rate Control

The apparent activation energy of chemical reactions previously played a central role in the field of chemical kinetics and has served as an important tool for analyzing and understanding reaction rates, mechanistic details of complex reaction mechanisms, elementary-step energetics, catalytic activity and reaction selectivity. In this work, we derive a general expression which shows that the apparent activation energy equals a weighted average of the standard-state enthalpies (relative to reactants) of all the species (intermediates, transition states and products) in the reaction mechanism, each weighted by its generalized degree of rate control (DRC). Since the DRC is zero for most of these species, even in very complex mechanisms, the weighted average includes only a few terms. This simplicity provides deep insight into the connection between the reaction energy diagram and the apparent activation energy. We prove both this and the quantitative validity of this equation by analysis of numerous reaction mechanisms. We also show the failures or weaknesses of previous equations for the apparent activation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2018

Activation Energy Determination for Photovoltaic Encapsulant Discoloration by Indoor Accelerated UV Testing

A novel methodology for determining the activation energy of photovoltaic encapsulant discoloration using an indoor accelerated ultraviolet (UV) stress test while simultaneously maintaining multiple module temperatures in a single weathering chamber is presented. The testing was performed on some fresh mini-modules with a glass/EVA/cell/EVA/backsheet construction. The short-circuit current degradation from individual cells was used to quantify transmittance losses due to discoloration. Activation energy determined using indoor accelerated UV test data and Modified Arrhenius model ranges from 26 to 44 kJ/mol (0.27 to 0.46 eV). Activation energy was also determined from the outdoor field degradation data by employing different physical models that consider the individual or combined effects of key environmental factors. The approach here is instrumental to evaluating the reliability studies on encapsulant degradation mechanisms using relatively less time and resources.

14 SOLAR ENERGY↗
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.↗