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NASA NTRS1997

First Single-Crystal Mullite Fibers

Ceramic-matrix composites strengthened by suitable fiber additions are being developed for high-temperature use, particularly for aerospace applications. New oxide-based fibers, such as mullite, are particularly desirable because of their resistance to high-temperature oxidative environments. Mullite is a candidate material in both fiber and matrix form. The primary objective of this work was to determine the growth characteristics of single-crystal mullite fibers produced by the laser-heated floating zone method. Directionally solidified fibers with nominal mullite compositions of 3Al2O3 2SiO2 were grown by the laser-heated floating zone method at the NASA Lewis Research Center. SEM analysis revealed that the single-crystal fibers grown in this study were strongly faceted and that the facets act as critical flaws, limiting fiber strength. The average fiber tensile strength is 1.15 GPa at room temperature. The mullite fibers exhibit superior strength retention (80 percent of their room temperature tensile strength at 1450 C). Examined by transmission electron microscopy, these mullite single crystals are free of dislocations, low-angle boundaries, and voids. In addition, they show a high degree of oxygen vacancy ordering. High-resolution digital images from an optical microscope furnish evidence of the formation of a liquid-liquid miscibility gap during crystal growth. These images represent the first experimental evidence of liquid immiscibility for these compositions and temperatures. Continuing investigation with controlled seeding of mullite single crystals is planned.

Source record↗

NASA NTRS2005

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

NASA NTRS2010

Effect of Post-HALT Annealing on Leakage Currents in Solid Tantalum Capacitors

Degradation of leakage currents is often observed during life testing of tantalum capacitors and is sometimes attributed to the field-induced crystallization in amorphous anodic tantalum pentoxide dielectrics. However, degradation of leakage currents and the possibility of annealing of degraded capacitors have not been investigated yet. In this work the effect of annealing after highly accelerated life testing (HALT) on leakage currents in various types of solid tantalum capacitors was analyzed. Variations of leakage currents with time during annealing at temperatures from 125 oC to 180 oC, thermally stimulated depolarization (TSD) currents, and I-V characteristics were measured to understand the conduction mechanism and the reason for current degradation. Annealing resulted in a gradual decrease of leakage currents and restored their initial values. Repeat HALT after annealing resulted in reproducible degradation of leakage currents. The observed results are explained based on ionic charge instability (drift/diffusion of oxygen vacancies) in the tantalum pentoxide dielectrics using a modified Schottky conduction mechanism.

Teverovsky, Alexander↗

NASA NTRS2014

The Significance of Breakdown Voltages for Quality Assurance of Low-Voltage BME Ceramic Capacitors

Application of thin dielectric, base metal electrode (BME) ceramic capacitors for high-reliability applications requires development of testing procedures that can assure high quality and reliability of the parts. In this work, distributions of breakdown voltages (VBR) in variety of low-voltage BME multilayer ceramic capacitors (MLCCs) have been measured and analyzed. It has been shown that analysis of the distributions can indicate the proportion of defective parts in the lot and significance of the defects. Variations of the distributions after solder dip testing allow for an assessment of the robustness of capacitors to soldering-related stresses. The drawbacks of the existing screening and qualification methods to reveal defects in high-value, low-voltage MLCCs and the importance of VBR measurements are discussed. Analysis has shown that due to a larger concentration of oxygen vacancies, defect-related degradation of the insulation resistance (IR) and failures are more likely in BME compared to the precious metal electrode (PME) capacitors.

reliability↗

NASA NTRS2014

Evaluation of Commercial Automotive-Grade BME Capacitors

Three Ni-BaTiO3 ceramic capacitor lots with the same specification (chip size, capacitance, and rated voltage) and the same reliability level, made by three different manufacturers, were degraded using highly accelerated life stress testing (HALST) with the same temperature and applied voltage conditions. The reliability, as characterized by mean time to failure (MTTF), differed by more than one order of magnitude among the capacitor lots. A theoretical model based on the existence of depletion layers at grain boundaries and the entrapment of oxygen vacancies has been proposed to explain the MTTF difference among these BME capacitors. It is the conclusion of this model that reliability will not be improved simply by increasing the insulation resistance of a BME capacitor. Indeed, Ni-BaTiO3 ceramic capacitors with a smaller degradation rate constant K will always give rise to a longer reliability life

capacitor↗

NASA NTRS2014

A Reliability Model for Ni-BaTiO3-Based (BME) Ceramic Capacitors

The evaluation of multilayer ceramic capacitors (MLCCs) with base-metal electrodes (BMEs) for potential NASA space project applications requires an in-depth understanding of their reliability. The reliability of an MLCC is defined as the ability of the dielectric material to retain its insulating properties under stated environmental and operational conditions for a specified period of time t. In this presentation, a general mathematic expression of a reliability model for a BME MLCC is developed and discussed. The reliability model consists of three parts: (1) a statistical distribution that describes the individual variation of properties in a test group of samples (Weibull, log normal, normal, etc.), (2) an acceleration function that describes how a capacitors reliability responds to external stresses such as applied voltage and temperature (All units in the test group should follow the same acceleration function if they share the same failure mode, independent of individual units), and (3) the effect and contribution of the structural and constructional characteristics of a multilayer capacitor device, such as the number of dielectric layers N, dielectric thickness d, average grain size r, and capacitor chip size S. In general, a two-parameter Weibull statistical distribution model is used in the description of a BME capacitors reliability as a function of time. The acceleration function that relates a capacitors reliability to external stresses is dependent on the failure mode. Two failure modes have been identified in BME MLCCs: catastrophic and slow degradation. A catastrophic failure is characterized by a time-accelerating increase in leakage current that is mainly due to existing processing defects (voids, cracks, delamination, etc.), or the extrinsic defects. A slow degradation failure is characterized by a near-linear increase in leakage current against the stress time; this is caused by the electromigration of oxygen vacancies (intrinsic defects). The two identified failure modes follow different acceleration functions. Catastrophic failures follow the traditional power-law relationship to the applied voltage. Slow degradation failures fit well to an exponential law relationship to the applied electrical field. Finally, the impact of capacitor structure on the reliability of BME capacitors is discussed with respect to the number of dielectric layers in an MLCC unit, the number of BaTiO3 grains per dielectric layer, and the chip size of the capacitor device.

reliability↗

NASA NTRS2014

Evaluation of Commercial Automotive-Grade BME Capacitors

reliability↗

NASA NTRS2013

Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics

Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

Good, Brian↗

NASA NTRS2015

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

Silicon-based ceramic components for next-generation jet turbine engines offer potential weight savings, as well as higher operating temperatures, both of which lead to increased efficiency and lower fuel costs. Silicon carbide (SiC), in particular, offers low density, good strength at high temperatures, and good oxidation resistance in dry air. However, reaction of SiC with high-temperature water vapor, as found in the hot section of jet turbine engines in operation, can cause rapid surface recession, which limits the lifetime of such components. Environmental Barrier Coatings (EBCs) are therefore needed if long component lifetime is to be achieved. Rare earth silicates such as Yb2Si2O7 and Yb2SiO5 have been proposed for such applications; in an effort to better understand diffusion in such materials, we have performed kinetic Monte Carlo (kMC) simulations of oxygen diffusion in Ytterbium disilicate, Yb2- Si2O7. The diffusive process is assumed to take place via the thermally activated hopping of oxygen atoms among oxygen vacancy sites or among interstitial sites. Migration barrier energies are computed using density functional theory (DFT).

Computer Simulation↗

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 NTRSDate not supplied

Infant Mortality and Wear-Out Failures in Polymer and MnO2 Tantalum Capacitors

Reliability testing of modern tantalum capacitors shows the presence of both types, infant mortality (IM) and wearout (WO) failures. To assure reliable operation, the probability of IM failures should be reduced to below the specified level, and the time of WO inception should be greater than the required useful life of the parts at operation conditions. In this work, several types of MnO2 and polymer cathode tantalum capacitors have been tested at highly accelerated conditions to assess voltage acceleration factors, determine adequate burn-in conditions, and assess the useful life. A modified time dependent dielectric breakdown (TDDB) model has been suggested to explain both types of failure, and a physical mechanism of degradation that is based on migration and reactions of oxygen vacancies explains increase of the defect related, IM failures with the level of stress.

tantalum capacitors↗

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 NTRS2023

Oxidation of Silicon Particles Suspended in Mullite Matrix With Dual-Mode Vacancy Diffusion of Oxygen

Mullite bond coats filled with silicon particles have recently been proposed for the next generation of environmental barrier coatings (EBCs). The sacrificial oxidation of the silicon particles eliminates some of the environmental durability issues associated with traditional EBC designs. To investigate this novel design approach, a mathematical formulation and resulting numerical method have been developed for simulating the oxidation of silicon particles embedded in a mullite matrix. The focus is on the oxidation of the silicon in a dry oxygen environment where the oxidant is presumably oxygen. Oxygen transport from the exterior environment through the mullite is assumed to occur via two lattice defect diffusion mechanisms. As a result, the rate of oxygen transport is dictated by the self-diffusivity of the lattice defects. The numerical method is implemented using the COMSOL Multiphysics® program (COMSOL, Inc.). The method is applied to simulate the oxidation of silicon particles in a mullite pellet in recent oxidation experiments. Numerical results compare favorably with the oxidation behavior observed in the oxidation experiments. The numerical method is also used to investigate the effects of various features of the mullite-silicon particle system on the oxidation behavior.

silicon oxidation↗

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 NTRS1984

The effects of lithium counterdoping on radiation damage and annealing in n(+)p silicon solar cells

Boron-doped silicon n(+)p solar cells were counterdoped with lithium by ion implantation and the resultant n(+)p cells irradiated by 1 MeV electrons. Performance parameters were determined as a function of fluence and a deep level transient spectroscopy (DLTS) study was conducted. The lithium counterdoped cells exhibited significantly increased radiation resistance when compared to boron doped control cells. Isochronal annealing studies of cell performance indicate that significant annealing occurs at 100 C. Isochronal annealing of the deep level defects showed a correlation between a single defect at E sub v + 0.43 eV and the annealing behavior of short circuit current in the counterdoped cells. The annealing behavior was controlled by dissociation and recombination of this defect. The DLTS studies showed that counterdoping with lithium eliminated three deep level defects and resulted in three new defects. The increased radiation resistance of the counterdoped cells is due to the interaction of lithium with oxygen, single vacancies and divacancies. The lithium-oxygen interaction is the most effective in contributing to the increased radiation resistance.

Weinberg, I.↗

NASA NTRS1984

Radiation damage and defect behavior in ion-implanted, lithium counterdoped silicon solar cells

Boron doped silicon n+p solar cells were counterdoped with lithium by ion implanation and the resultant n+p cells irradiated by 1 MeV electrons. The function of fluence and a Deep Level Transient Spectroscopy (DLTS) was studied to correlate defect behavior with cell performance. It was found that the lithium counterdoped cells exhibited significantly increased radiation resistance when compared to boron doped control cells. It is concluded that the annealing behavior is controlled by dissociation and recombination of defects. The DLTS studies show that counterdoping with lithium eliminates at least three deep level defects and results in three new defects. It is speculated that the increased radiation resistance of the counterdoped cells is due primarily to the interaction of lithium with oxygen, single vacancies and divacancies and that the lithium-oxygen interaction is the most effective in contributing to the increased radiation resistance.

Weinberg, I.↗

NASA NTRS1972

Electron spin resonance of ultraviolet radiation induced defects in ZnO thermal control coating pigment.

Electron spin resonance measurements on variously treated zinc oxide powders reveal that the resonance signal at g = 1.956 is due to one electron trapped oxygen ion vacancy level, at a depth of (0.31 plus or minus 0.02) eV below the conduction band. The electrons at this level are delocalized. Schottky barrier influences nearly the entire bulk of the powder sample, and the bending of the bands caused by chemisorbed oxygen puts the vacancy level above the Fermi level almost through the entire bulk.

Mookherji, T.↗