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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 505 records · Page 28

Chromatin Structure and Radiation-Induced Intrachromosome Exchange

We have recently investigated the location of breaks involved in intrachromosomal type exchange events, using the multicolor banding in situ hybridization (mBAND) technique for human chromosome 3. In human epithelial cells exposed to both low- and high-LET radiations in vitro, intrachromosome exchanges were found to occur preferentially between a break in the 3p21 and one in the 3q11. Exchanges were also observed between a break in 3p21 and one in 3q26, but few exchanges were observed between breaks in 3q11 and 3q26, even though the two regions were on the same arm of the chromosome. To explore the relationships between intrachromosome exchanges and chromatin structure, we used probes that hybridize the three regions of 3p21, 3q11 and 3q26, and measured the distance between two of the three regions in interphase cells. We further analyzed fragile sites on the chromosome that have been identified in various types of cancers. Our results demonstrated that the distribution of breaks involved in radiation-induced intrachromosome aberrations depends upon both the location of fragile sites and the folding of chromatins

Mangala↗

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

Smart, Marshall C.↗

Tensile Behavior of As-Fabricated and Burner-Rig Exposed SiC/SiC Composites with Hi-Nicalon Type-S Fibers

Tensile stress-strain curves were measured at room temperature and 1315 C for 2D-woven SiC/BN/SiC ceramic matrix composites (CMC) reinforced by two variations of Hi-Nicalon Type-S SiC fibers. These fibers, which contained a thin continuous carbon-rich layer on their as-produced surface, provided the as-fabricated CMC with good composite behavior and an ultimate strength and strain of -350 MPa and -0.5%, respectively. However, after un-stressed burner-rig exposure at 815 C for -100 hrs, CMC tensile specimens with cut edges and exposed interphases showed a significant decrease in ultimate properties with effectively no composite behavior. Microstructural observations show that the degradation was caused by internal fiber-fiber oxide bonding after removal of the carbon-rich fiber surface layer by the high-velocity combustion gases. On the other hand, SiC/BN/SiC CMC with Sylramic-iBN fibers without carbon-rich surfaces showed higher as-fabricated strength and no loss in strength after the same burner rig exposure. Based on the strong role of the carbon layer in these observations, a process method was developed and demonstrated for achieving better strength retention of Hi-Nicalon Type-S CMC during burner rig exposure. Other general approaches for minimizing this current deficiency with as-produced Type-S fibers are discussed.

Yun, H. M.↗

Fundamental Investigation of Silicon Anode in Lithium-Ion Cells

Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is ~10 times of graphite and it is an abundant element on Earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. Understanding solid electrolyte interphase (SEI) formation along with the lithium ion insertion/de-insertion kinetics in silicon anodes will provide greater insight into overcoming these issues, thereby lead to better cycle performance. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of a Si anode during the first cycle; the lithium ion insertion and de-insertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes, and the combination of cyclic voltammetry with impedance spectroscopy provides a useful tool to evaluate the effectiveness of the design modifications on the Si anode performance.

Wu, James J.↗

mBAND Analysis of Early and Late Damages in the Chromosome of Human Lymphocytes after Exposures to Gamma Rays and Fe Ions

Stable type chromosome aberrations that survive multiple generations of cell division include translocation and inversions. An efficient method to detect an inversion is multi-color banding fluorescent in situ hybridization (mBAND) which allows identification of both inter- and intrachromosome aberrations simultaneously. Post irradiation, chromosome aberrations may also arise after multiple cell divisions as a result of genomic instability. To investigate the stable or late-arising chromosome aberrations induced after radiation exposure, we exposed human lymphocytes to gamma rays and Fe ions ex vivo, and cultured the cells for multiple generations. Chromosome aberrations were analyzed in cells collected at first mitosis and at several time intervals during the culture period post irradiation. With gamma irradiation, about half of the damages observed at first mitosis remained after 7 day- and 14 day- culture, suggesting the transmissibility of damages to the surviving progeny. At the doses that produced similar frequencies of gamma-induced chromosome aberrations as observed at first mitosis, a significantly lower yield of aberrations remained at the same population doublings after Fe ion exposure. At these equitoxic doses, more complex type aberrations were observed for Fe ions, indicating that Fe ion-induced initial chromosome damages are more severe and may lead to cell death. Detailed analysis of breaks participating in total chromosome exchanges within the first cell cycle post irradiation revealed a common hotspot located in the 3p21 region, which is a known fragile site corresponding to the band 6 in the mBand analysis. The breakpoint distribution in chromosomes collected at 7 days, but not at 14 days, post irradiation appeared similar to the distribution in cells collected within the first cell cycle post irradiation. The breakpoint distribution for human lymphocytes after radiation exposure was different from the previously published distribution for human mammary epithelial cells, indicating that interphase chromatin folding structures play a role in the distribution of radiation-induced breaks.

Sunagawa, Mayumi↗

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

Li-ion battery electrolytes↗

Physics Based Model for Online Fault Detection in Autonomous Cryogenic Loading System

We report the progress in the development of the chilldown model for rapid cryogenic loading system developed at KSC. The nontrivial characteristic feature of the analyzed chilldown regime is its active control by dump valves. The two-phase flow model of the chilldown is approximated as one-dimensional homogeneous fluid flow with no slip condition for the interphase velocity. The model is built using commercial SINDAFLUINT software. The results of numerical predictions are in good agreement with the experimental time traces. The obtained results pave the way to the application of the SINDAFLUINT model as a verification tool for the design and algorithm development required for autonomous loading operation.

Cryogenics↗

Methods for Producing High-Performance Silicon Carbide Fibers, Architectural Preforms, and High-Temperature Composite Structures

Methods are disclosed for producing architectural preforms and high-temperature composite structures containing high-strength ceramic fibers with reduced preforming stresses within each fiber, with an in-situ grown coating on each fiber surface, with reduced boron within the bulk of each fiber, and with improved tensile creep and rupture resistance properties tier each fiber. The methods include the steps of preparing an original sample of a preform formed from a pre-selected high-strength silicon carbide ceramic fiber type, placing the original sample in a processing furnace under a pre-selected preforming stress state and thermally treating the sample in the processing furnace at a pre-selected processing temperature and hold time in a processing gas having a pre-selected composition, pressure, and flow rate. For the high-temperature composite structures, the method includes additional steps of depositing a thin interphase coating on the surface of each fiber and forming a ceramic or carbon-based matrix within the sample.

DiCarlo, James A.↗

Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

Li-ion Battery↗

The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

High Temperture Resilience↗

Modeling of Different Fiber Type and Content SiC/SiC Minicomposites Creep Behavior

Silicon Carbide based Ceramic Matrix Composites (CMCs) are attractive materials for use in high-temperature applications in the aerospace and nuclear industries. However, creep damage mechanism in CMCs is the most dominant mechanism at elevated temperatures. Consequently, the tensile creep behavior of Hi-Nicalon, Hi-Nicalon Type S SiC fibers and Chemical vapor infiltrated Silicon Carbide matrix (CVI-SiC) were characterized and creep parameters were extracted from creep experiments. Some fiber creep tests were performed in inert environment at 1200 C on individual fibers. Creep behavior of different fiber content pristine and precracked Hi-Nicalon and Hi-Nicalon Type S reinforced minicomposites with BN interphases and CVI-SiC matrix were then modelled using the creep data found in this study and the literature and compared with creep experiments results for the pristine and precracked Hi-Nicalon and Hi-Nicalon Type S minicomposites. Finally, the effects of load-sharing and matrix cracking on CMC creep behavior will be discussed.

ceramic matrix minicomposites↗

Effect of Mechanical and Thermal Loading Histories on Residual Properties of SiCf/SiC Ceramic Matrix Composites

Silicon Carbide based Ceramic Matrix Composites (CMCs) are attractive materials for use in high-temperature structural applications in the aerospace and nuclear industries. Under high stresses and temperatures, creep degradation is the dominant damage mechanism in CMCs. Consequently, chemical vapor infiltration (CVI) SiCf/SiC ceramic matrix composites (CMC) incorporating SylramicTM-iBN SiC fibers coated with boron nitride (BN) interphase and CVI-SiC matrix were tested to examine creep behavior in air at a range of elevated temperatures of (2200 - 2700 F). Samples that survived creep tests were evaluated via RT fast fracture tensile tests to determine residual properties, with the use of acoustic emission (AE) to assess stress dependent damage initiation and progression. Microscopy of regions within the gage section of the tested specimens was performed. Observed material degradation mechanisms are discussed.

creep↗

SiC Fibers and SiCf/SiC Ceramic Matrix Minicomposites Damage Behavior

Silicon Carbide based Ceramic Matrix Composites (CMCs) are attractive materials for use in high-temperature applications in the aerospace industry. Performance and durability of CMCs depend on the properties of its constituents such as fibers and matrix. Therefore, CMCs constituents limitations and damage mechanisms are discussed and characterized in representative simulated application conditions and dominant damage mechanisms are identified at elevated temperatures. In this work, the initiation and evolution of damage in Hi-Nicalon type S fiber-reinforced minicomposites with different interphases thicknesses from different manufacturers were investigated employing several nondestructive evaluation techniques such as acoustic emission, electrical resistance and microscopy. Moreover, the tensile creep behavior of single Hi-Nicalon Type S SiC fibers were tested and characterized and creep parameters were extracted. Fibers creep tests were performed in air or vacuum at 1200-1482 C under high stresses. Creep parameters was then used in understanding load sharing and lifing of ceramic matrix minicomposites. Future work plans will be reviewed.

SiC fibers↗

Advanced Environmental Barrier Coating and SA Tyrannohex SiC Composites Integration for Improved Thermomechanical and Environmental Durability

The development of 2700 degF capable environmental barrier coating (EBC) systems, particularly, the Rare Earth "Hafnium" Silicon bond coat systems, have significantly improved the temperature capability and environmental stability of SiC/SiC Ceramic Matrix Composite Systems. We have specifically developed the advanced 2700 degF EBC systems, integrating the EBC to the high temperature SA Tyrannohex SiC fiber composites, for comprehensive performance and durability evaluations for potential turbine engine airfoil component applications. The fundamental mechanical properties, environmental stability and thermal gradient cyclic durability performance of the EBC - SA Tyrannohex composites were investigated. The paper will particularly emphasize the high pressure combustion rig recession, cyclic thermal stress resistance and thermomechanical low cycle fatigue testing of uncoated and environmental barrier coated Tyrannohex SiC SA composites in these simulated turbine engine combustion water vapor, thermal gradients, and mechanical loading conditions. We have also investigated high heat flux and flexural fatigue degradation mechanisms, determined the upper limits of operating temperature conditions for the coated SA composite material systems in thermomechanical fatigue conditions. Recent progress has also been made by using the self-healing rare earth-silicon based EBCs, thus enhancing the SA composite hexagonal fiber columns bonding for improved thermomechanical and environmental durability in turbine engine operation environments. More advanced EBC- composite systems based on the new EBC-Fiber Interphases will also be discussed.

Tyrannohex SiC Ceramics↗

Influence of Fiber Content, Thermal Cycles and Creep on Electrical Resistivity Measurements of SiCf/SiC Minicomposites

Fiber-reinforced Ceramic Matrix Composites (CMCs) are currently being used in high-temperature applications such as jet engine components. In such extreme environment applications, materials are exposed to many mechanical and thermal loading cycles during the life of the component. This exposure can degrade the component, and thus, components need to be monitored and inspected during service. The electrical resistivity nondestructive evaluation technique has been shown to be very sensitive to damage in CMCs, and although its performance is highly dependent on temperature, this temperature-dependence is still not well understood. Therefore, this current study aims to establish the influence of thermal cycles, creep, CVI-SiC matrix cracks and fiber volume fraction on the electrical resistance of Hi Nicalon and Hi-Nicalon Type S SiC fiber-reinforced minicomposites with BN interphases. Minicomposites with 97% CVI-SiC matrix volume fraction were used to characterize the electrical resistivity of the CVI-SiC matrix. Next, models were constructed to calculate fiber resistivity and onset and evolution of damage during tensile testing at room-temperature. The thermal cycles were achieved by heating as-received and precracked specimens to 1200°C and then cooling them to room temperature, with or without applied stress on fibers.

creep↗

Ionic Liquids at Electrified Interfaces: From Double Layers to Decomposition

Ionic liquids are versatile electrolytes whose properties at electrified interfaces have the potential to enable technologies such as supercapacitors and Li-metal battery anodes. At electrified carbon surfaces, ionic liquids form an electric double layer that stores energy and provides the foundation for supercapacitors. At electrified lithium surfaces, ionic liquids decompose to form a solid electrolyte interphase that has the potential to stabilize Li-metal anodes in rechargable batteries. The behavior of two ionic liquids of technological importance, [pyr14][TFSI] and [EMIM][BF4], are examined at these electrified interfaces through molecular dynamics and ab initio techniques.

Haskins, Justin B.↗

Ionic Liquids at Electrified Interfaces: from Double Layers to Decomposition

Ionic liquids are versatile electrolytes whose properties at electrified interfaces have the potential to enable technologies such as supercapacitors and Li-metal battery anodes. At electrified carbon surfaces, ionic liquids form an electric double layer that stores energy and provides the foundation for supercapacitors. At electrified lithium surfaces, ionic liquids decompose to form a solid electrolyte interphase that has the potential to stabilize Li-metal anodes in rechargable batteries. The behavior of two ionic liquids of technological importance, [pyr14][TFSI] and [EMIM][BF4], are examined at these electrified interfaces through molecular dynamics and ab initio techniques.

Haskins, Justin B.↗

Ionic Liquids at Electrified Interfaces: from Double Layers to Decomposition

Ionic liquids are versatile electrolytes whose properties at electrified interfaces have the potential to enable technologies such as supercapacitors and Li-metal battery anodes. At electrified carbon surfaces, ionic liquids form an electric double layer that stores energy and provides the foundation for supercapacitors. At electrified lithium surfaces, ionic liquids decompose to form a solid electrolyte interphase that has the potential to stabilize Li-metal anodes in rechargable batteries. The behavior of two ionic liquids of technological importance, [pyr14][TFSI] and [EMIM][BF4], are examined at these electrified interfaces through molecular dynamics and ab initio techniques.

Haskins, Justin B.↗