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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Lithium-ion drifting: Application to the study of point defects in floating-zone silicon

The use of lithium-ion (Li(+)) drifting to study the properties of point defects in p-type Floating-Zone (FZ) silicon crystals is reported. The Li(+) drift technique is used to detect the presence of vacancy-related defects (D defects) in certain p-type FZ silicon crystals. SUPREM-IV modeling suggests that the silicon point defect diffusivities are considerably higher than those commonly accepted, but are in reasonable agreement with values recently proposed. These results demonstrate the utility of Li(+) drifting in the study of silicon point defect properties in p-type FZ crystals. Finally, a straightforward measurement of the Li(+) compensation depth is shown to yield estimates of the vacancy-related defect concentration in p-type FZ crystals.

Silicon↗
NASA NTRS2003

Atomic-scale Modeling of the Structure and Dynamics of Dislocations in Complex Alloys at High Temperatures

We report on the progress made during the first year of the project. Most of the progress at this point has been on the theoretical and computational side. Here are the highlights: (1) A new code, tailored for high-end desktop computing, now combines modern Accelerated Dynamics (AD) with the well-tested Embedded Atom Method (EAM); (2) The new Accelerated Dynamics allows the study of relatively slow, thermally-activated processes, such as diffusion, which are much too slow for traditional Molecular Dynamics; (3) We have benchmarked the new AD code on a rather simple and well-known process: vacancy diffusion in copper; and (4) We have begun application of the AD code to the diffusion of vacancies in ordered intermetallics.

Daw, Murray S.↗
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 NTRS2005

Comparative Planetary Mineralogy: Valence State Partitioning of Cr, Fe, Ti, and V Among Crystallographic Sites in Olivine, Pyroxene, and Spinel from Planetary Basalts

We have considered the valence-state partitioning of Cr, Fe, Ti, and V over crystallographic sites in olivine, pyroxene, and spinel from planetary basalts. The sites that accommodate these cations are the M2 site (6-8 coordinated) and M1 site (6 coordinated) in pyroxene, the M2 site (6-8 coordinated) and M1 site (6 coordinated) in olivine, and the tetrahedral and octahedral sites in spinel. The samples we studied are basalts from Earth, Moon, and Mars, which have fO2 conditions that range from IW-2 (Moon) to IW+6 (Earth) with Mars somewhere between at IW to IW+2. In this range of fO2 the significant elemental valences are (from low to high fO2) Ti4+, V3+, Fe2+, Cr2+, Cr3+, V3+, V4+, and Fe3+. V2+ and Ti3+ play a minor role in the phases considered for the Moon, and are probably in very low concentrations. V5+ plays a minor role in these phases in terrestrial basalts because it is probably in lower abundance than V4+ and it has an ionic radii that is so small (0.054 nm, 6- coordinated,[1]) that it is almost at the lower limit for octahedral coordination. The role of Cr2+ in the Moon is significant, as Sutton et al. [2] found that lunar olivine contains mostly Cr2+ while coexisting pyroxene contains mostly Cr3+. Hanson one vacancy only accommodates one V4+. Thus more vacancies are required in V4+ substitutions into olivine. In the Moon V3+ is much more abundant than V4+ [7, 8]. Thus in lunar chromite V3+ follows Cr3+, whereas in Earth V4+ (which is much greater in abundance than V3+) follows Ti4+ (eg in ulv spinel). We could go on in this vein for some time but space limitations do not permit us to do so.

Papike, J. J.↗
NASA NTRS2005

Compression and Tensile Creep of Binary NiAl

Compression creep and long term tensile creep studies were conducted on cast and extruded 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 in both compression and tension creep depending on stress and temperature although an asymmetrical response was observed under these two stress states. It was concluded that the primary creep of NiAl is limited by dislocation mobility. The stress exponents, n, for compression and tensile creep were similar varying between about 5 and 14. However, there were significant differences in the stress dependence of the activation energies for compression and tensile creep. The true activation energy for tensile creep, Q(sub c), was constant and equal to about 400 kJ/mol between 20 and 50 MPa but decreased to a constant value of 250 kJ/mol between 50 and 110 MPa. The activation energy was observed to be inversely stress dependent above 110 MPa. In contrast, Q(sub c) = 300 kJ/mol for compression creep was constant between 25 and 70 MPa and inversely dependent on the true stress above 70 MPa. 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 natures 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 NTRS2006

Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (~1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

Jones, John↗
NASA NTRS2011

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Good, Brian↗
NASA NTRS2010

Degradation of Leakage Currents in Solid Tantalum Capacitors Under Steady-State Bias Conditions

Degradation of leakage currents in various types of solid tantalum capacitors under steady-state bias conditions was investigated at temperatures from 105 oC to 170 oC and voltages up to two times the rated voltage. Variations of leakage currents with time under highly accelerated life testing (HALT) and annealing, thermally stimulated depolarization currents, and I-V characteristics were measured to understand the conduction mechanism and the reason for current degradation. During HALT the currents increase gradually up to three orders of magnitude in some cases, and then stabilize with time. This degradation is reversible and annealing can restore the initial levels of leakage currents. The results are attributed to migration of positively charged oxygen vacancies in tantalum pentoxide films that diminish the Schottky barrier at the MnO2/Ta2O5 interface and increase electron injection. A simple model allows for estimation of concentration and mobility of oxygen vacancies based on the level of current degradation.

Teverovsky, Alexander A.↗
NASA NTRS2015

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

Insulation resistance (IR) degradation in NiBaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure (TTF) and direct current leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current time dependence data fit well to an exponential form, and a characteristic growth time tau (sub SD) can be determined. A greater value of tau (sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in NiBaTiO3 capacitors. The reduction of barrier height as a function oftime follows an exponential relation of phi (t ) = phi (0) e (exp -2Kt), where 13 the degradation rate constant K Koe (Ek/kT) is inversely proportional to the mean TTF (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi (0) will favor a slow IR degradation process, but a lower phi (0) will also promote electronic carrier conduction across the barrier and decrease the IR. As a result, a moderate barrier height phi (0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant K) will result in a minimized IR degradation process and the most improved reliability in NiBaTiO3 multilayer ceramic capacitors.

reliability↗
NASA NTRS2015

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

Insulation resistance (IR) degradation in Ni-BaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure and direct-current (DC) leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current-time dependence data fit well to an exponential form, and a characteristic growth time SD can be determined. A greater value of tau(sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in Ni-BaTiO3 capacitors. The reduction of barrier height as a function of time follows an exponential relation of phi (𝑡)=phi (0)e(exp -2Κt), where the degradation rate constant 𝐾=𝐾o𝑒(𝐸𝑘/𝑘𝑇) is inversely proportional to the mean time to failure (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi(0) will favor a slow IR degradation process, but a lower phi(0) will also promote electronic carrier conduction across the barrier and decrease the insulation resistance. As a result, a moderate barrier height phi(0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant 𝐾) will result in a minimized IR degradation process and the most improved reliability in Ni-BaTiO3 multilayer ceramic capacitors.

dielectric degradation↗
NASA NTRS2016

Degradation of Leakage Currents and Reliability Prediction for Tantalum Capacitors

Two types of failures in solid tantalum capacitors, catastrophic and parametric, and their mechanisms are described. Analysis of voltage and temperature reliability acceleration factors reported in literature shows a wide spread of results and requires more investigation. In this work, leakage currents in two types of chip tantalum capacitors were monitored during highly accelerated life testing (HALT) at different temperatures and voltages. Distributions of degradation rates were approximated using a general log-linear Weibull model and yielded voltage acceleration constants B = 9.8 +/- 0.5 and 5.5. The activation energies were Ea = 1.65 eV and 1.42 eV. The model allows for conservative estimations of times to failure and was validated by long-term life test data. Parametric degradation and failures are reversible and can be annealed at high temperatures. The process is attributed to migration of charged oxygen vacancies that reduce the barrier height at the MnO2/Ta2O5 interface and increase injection of electrons from the MnO2 cathode. Analysis showed that the activation energy of the vacancies' migration is ~ 1.1 eV.

acceleration factors↗
NASA NTRS2020

On the Oxidation of the Silicon Bond Coat in Environmental Barrier Coatings

Deal and Grove’s formulation is applied to model the oxidation of the silicon bond coat in environmental barrier coatings. The approach is similar to the author’s previous study, except now the oxidant is assumed to flow through the coating as oxygen ions via vacancies on the oxygen sublattice. The use of an “effective permeability” of the oxidant in the coating is required under the vacancy diffusion assumption. It is found that the linear-parabolic growth equation from Deal and Grove, 2 xox + Axox = Bt , is still applicable for the oxidation of the silicon bond coat, but the equation for the parameter A must be modified to account for the coating. The expression for B is the same as that obtained by Deal and Grove and thus is unaffected by the presence of a coating. The modified expression for A is a linear function of the coating thickness and includes the ratio of the oxidant permeability in the oxide to its effective permeability in the coating

Roy M Sullivan↗
NASA NTRS2021

On the Oxidation of the Silicon Bond Coat in Environmental Barrier Coatings

Deal and Grove’s formulation is applied to model the oxidation of the silicon bond coat in environmental barrier coatings. The approach is similar to the author’s previous study, except now the oxidant is assumed to flow through the coating as oxygen ions via vacancies on the oxygen sublattice. The use of an “effective permeability” of the oxidant in the coating is required under the vacancy diffusion assumption. It is found that the linear-parabolic growth equation from Deal and Grove, , is still applicable for the oxidation of the silicon bond coat, but the equation for the parameter A must be modified to account for the coating. The expression for B is the same as that obtained by Deal and Grove and thus is unaffected by the presence of a coating. The modified expression for A is a linear function of the coating thickness and includes the ratio of the oxidant permeability in the oxide to its effective permeability in the coating.

silicon oxidation, ionic diffusion, permeation, li↗
NASA NTRSDate not supplied

Refractory Carbides for Hydrogen Erosion Resistance in Carbon Tubes for Nuclear Thermal Propulsion

As crewed travel becomes more common to the Moon and beyond, space nuclear propulsion-based craft offer reduced travel times and double the specific impulse compared to conventional chemical rockets. The nuclear core and its integral hydrogen propellant channels will require advanced refractory carbide coatings over a carbon/carbon substrate for hydrogen resistance. Using ab initio and other computational techniques, we studied select (Zr/Ta/Nb)C mixed carbide systems for erosion resistance and hydrogen diffusion using realistic levels of carbon vacancies and experimentally obtainable stoichiometries. Various contributions to the formation and hydrogen erosion free energies were calculated, including configurational, electronic, and vibrational terms. Our calculations indicate that ZrC is less likely to lose carbon than NbC or TaC, providing an explanation for heritage NERVA data on ZrC and NbC mass loss performance. Additionally, binary mixtures show compositions that are more stable than their end-member counterparts. Hydrogen diffusion in stoichiometric ZrC was found to be slightly higher than previously theorized, with the caveat that hydrogen saturation of carbon vacancies will hinder further hydrogen diffusion through the bulk, while hydrogen diffusion in ZrNbC is slightly enhanced over ZrC. And finally, we show that as carbon is depleted, the deformation mechanism of ZrC changes from brittle to ductile. Though many questions still remain as to the bulk performance of these materials, these trends and results are important in terms of materials selection efforts for hydrogen-resistant coatings on carbon/carbon substrates.

William C Tucker↗
NASA NTRSDate not supplied

Refractory Carbides for Hydrogen Erosion Resistance in Carbon Tubes for Nuclear Thermal Propulsion

As crewed travel becomes more common to the Moon and beyond, space nuclear propulsion-based craft offer reduced travel times and double the specific impulse compared to conventional chemical rockets. The nuclear core and its integral hydrogen propellant channels will require advanced refractory carbide coatings over a carbon/carbon substrate for hydrogen resistance. Using \textit{ab initio} and other computational techniques, we studied select (Zr/Ta/Nb)C mixed carbide systems for erosion resistance and hydrogen diffusion using realistic levels of carbon vacancies and experimentally obtainable stoichiometries. Various contributions to the formation and hydrogen erosion free energies were calculated, including configurational, electronic, and vibrational terms. Our calculations indicate that ZrC is less likely to lose carbon than NbC or TaC, providing an explanation for heritage NERVA data on ZrC and NbC mass loss performance. Additionally, binary mixtures show compositions that are more stable than their end-member counterparts. Hydrogen diffusion in stoichiometric ZrC was found to be slightly higher than previously theorized, with the caveat that hydrogen saturation of carbon vacancies will hinder further hydrogen diffusion through the bulk, while hydrogen diffusion in ZrNbC is slightly enhanced over ZrC. And finally, we show that as carbon is depleted, the deformation mechanism of ZrC changes from brittle to ductile. Though many questions still remain as to the bulk performance of these materials, these trends and results are important in terms of materials selection efforts for hydrogen-resistant coatings on carbon/carbon substrates.

William C. Tucker↗
NASA NTRSDate not supplied

Refractory Carbides for Hydrogen Erosion Resistance in Carbon Tubes for Nuclear Thermal Propulsion

As crewed travel becomes more common to the Moon and beyond, space nuclear propulsion-based craft offer reduced travel times and double the specific impulse compared to conventional chemical rockets. The nuclear core and its integral hydrogen propellant channels will require advanced refractory carbide coatings over a carbon/carbon substrate for hydrogen resistance. Using ab initio and other computational techniques, we studied select (Zr/Ta/Nb)C mixed carbide systems for erosion resistance and hydrogen diffusion using realistic levels of carbon vacancies and experimentally obtainable stoichiometries. Various contributions to the formation and hydrogen erosion free energies were calculated, including configurational, electronic, and vibrational terms. Our calculations indicate that ZrC is less likely to lose carbon than NbC or TaC, providing an explanation for heritage NERVA data on ZrC and NbC mass loss performance. Additionally, binary mixtures show compositions that are more stable than their end-member counterparts. Hydrogen diffusion in stoichiometric ZrC was found to be slightly higher than previously theorized, with the caveat that hydrogen saturation of carbon vacancies will hinder further hydrogen diffusion through the bulk, while hydrogen diffusion in ZrNbC is slightly enhanced over ZrC. And finally, we show that as carbon is depleted, the deformation mechanism of ZrC changes from brittle to ductile. Though many questions still remain as to the bulk performance of these materials, these trends and results are important in terms of materials selection efforts for hydrogen-resistant coatings on carbon/carbon substrates.

William C Tucker↗