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401 records · Page 22

SILICON CARBIDE THERMOMETRY USING RAMAN SPECTROSCOPY ON IRRADIATED TRISO PARTICLES

Silicon carbide (SiC) passive thermometry has emerged as a promising post-irradiation examination (PIE) technique for estimating irradiation temperature near the end of irradiation. While dilatometry techniques have been traditionally used to analyze prismatic samples after irradiation, Raman spectroscopy has recently been shown to provide comparable results by analyzing Raman-active phonon modes. In this work, Raman spectroscopy has been applied to the SiC layer of cross-sectioned irradiation tristructural isotropic (TRISO) particles from the AGR-5/6/7 experiment to evaluate the feasibility of particle-scale passive thermometry. Two-dimensional Raman mapping was used to measure the position of the SiC longitudinal optical (LO) phonon, which was then converted to an apparent irradiation temperature using a previously established empirical correlation. Particles from AGR-5/6/7 Compacts 2-2-1 and 5-1-3 were selected as their calculated time-averaged, volume-averaged (TAVA) temperatures (828°C and 706°C, respectively) fall within the range of the sensitivity of the experimental approach. The use of SiC thermometry was anticipated to confirm or highlight potential deviations from calculated end-of-life TAVA temperature across compacts. Four particles from Compact 2-2-1 and two particles from Compact 5-1-3 were selected based on 110mAg inventory (either some measurable activity or below the minimum detection limit) which is commonly used as an indicator of in-pile temperature variation of particles within the same compact. Across every particle selected it was determined that the average LO peak position was located around 968 cm-1 to 969 cm-1. Using the previously determined empirical correlation, this corresponds to an irradiation temperature around 950°C to 966°C, which does not align with the reported TAVA temperature values. This discrepancy in apparent irradiation temperatures likely reflects a combination of uncertainties in the calculated particle temperatures and differences in irradiation history between the present specimens and those used to establish the empirical Raman calibration such as neutron flux (damage rate) and SiC microstructure (as fabricated and irradiated).

Vawdrey, Josh [ORNL]

AC and DC Fault Management for Megawatt Electrified Aircraft Electrical Powertrains - Task 2: Power Quality Filtering Using Nanocrystalline Soft Magnetic Inductor

The NASA RTAPS program on AC and DC Fault Management for Megawatt Electrified Power Train is a multi-year joint project with Pratt & Whitney (P&W), Collins Aerospace (CA), and RTX Technology Research Center (RTRC). This research program focuses on the high-voltage distribution issues that present a significant technological obstacle in the adoption of Electrified Aviation Propulsion (EAP) systems. One challenge to the adoption of high-voltage distribution systems with power electronic converters is the need for filter elements to limit the generation and propagation of noise, protect the cable systems from premature aging and prevent against excessive heating within subcomponents due to high-frequency induced currents. While increased distribution voltages aide in reducing the cable mass for a fixed power system, the associated mass with the filtering elements for power electronic converter can grow with increasing distribution voltages – thereby mitigating any benefit associated with increasing the distribution system voltage. To enable high-voltage distribution systems with high system specific power densities, new magnetic materials must be developed. Therefore, the second task of the NASA RTAPS program is associated with the design and application of advanced soft magnetic components for Megawatt class electric propulsion systems, specifically the motor drive system. This report covers the collaborative work between NASA Glenn Research Center (GRC), RTRC, P&W and CA in the development of three types of magnetic components over the span of the three-year program. These critical magnetic components are the DC side EMI filter, which limits the propagation of harmful electromagnetic noise to the rise of the distribution system, and the AC side damping with the dv/dt filter, which limits the fast rise time of the power electronic converter output voltage to limit the degradation on the cable/motor insulation systems. Each of these components are investigated from component level design and are optimized at the system level with a combined modelling and testing effort. In the final experimental evaluation of the NASA developed soft magnetic material with a dv/dt filter, a commercial-off-the-shelf (COTS) magnetic core and the GRC magnetic core are optimized and loaded at 320Arms to evaluate their difference in performance. After a run time of 30 minutes in a MW-class motor driver at RTRC, the NASA GRC cores were found to not only offer a lower temperature rise of nearly 25°𝐶, but also a reduction in measured core loss of 25% (12.75W to 9.5W).

Elecrified Aircraft Propulsion

The Origin of Palimpsests

Palimpsests are the most enigmatic impact features observed on icy worlds of the Solar System. Palimpsests are large impact features which are bright, old, mostly flat, and roughly circular. They range from >150 to ~350 km in diameter and sometimes exhibit recognizable associated radial secondary ejecta crater strings beyond their rims. Curiously, among all the Solar System's icy worlds, palimpsests are exclusively seen on the icy Galilean moons. Palimpsests are obviously different than similarly sized impact features seen on other icy satellites. For example, Evander, a 350 km diameter peak-ring impact basin on Saturn’s moon Dione, has a very low depth/diameter ratio of 0.008, indicating significant viscous relaxation. Nevertheless, it still retains short wavelength topography including a prominent central peak, peak ring, and a continuous rim, none of which are seen at palimpsests. Palimpsests display an approximately circular, and dominating, expanse of undulating plains, which is level with surrounding terrain and shows no recognizable rim. At the center of palimpsests are smooth central plains that are enclosed by a low scarp. Central plains material superposes the surrounding undulating plains and is littered with small blocks reminiscent of “small chaos” on Europa. Palimpsests have yet to be explored using modern impact simulation tools. We have begun to investigate two competing hypotheses: (A) Palimpsests form on targets which have a preexisting near-subsurface layer that is liquid or solid but very weak, and is excavated as proximal ejecta; or (B) They form in a solid ice target underlain by a steep thermal gradient that strongly influences the resulting impact feature, including the production of impact-induced melting at depth that is then a major component of proximal ejecta. Our results will have profound implications for the early thermal history of the icy Galilean satellites. We will test our two hypotheses for the formation of palimpsests on Ganymede (where they are both best observed and preserved) by means of 2D iSALE hydrodynamic simulations of impacts into ice targets that will be structured according to the scenarios for each hypothesis, with select runs in 3D. We have already conducted a pilot study using 2D iSALE that has yielded promising results, which we will report out at the meeting.

palimpsests

Reduced instability growth and improved radiation trapping with optimized shock timing in double-shell inertial confinement fusion capsules

The double shell is a volume-burn inertial confinement fusion concept consisting of two concentric shells: a low-Z outer shell that collides with and transfers momentum to a high-Z inner shell which compresses and heats the thermonuclear fuel. The increased number of capsule interfaces and severe hydrodynamic instability of the high-density pusher during its acceleration phase provide challenges to the success of the double shell. Two-dimensional radiation-hydrodynamics simulations predict the hydrodynamic instability growth on the outer surface of the pusher can be greatly reduced through appropriate timing of two shocks that cross this interface. One of these shocks, unique to multi-shell designs, arises from radiation-driven ablation of the inner shell ahead of the main shock, the second shock of concern. The shock timing is optimized by increasing the thickness of a low-Z tamper layer exterior to the pusher, resulting in only minimal changes to the implosion timing. Reducing the instability growth on the outer surface of the high-Z pusher can dramatically decrease the modulations that feedthrough to the pusher inner surface, improving the efficacy of radiation trapping in the thermonuclear fuel and increasing the predicted thermonuclear yield by ≳20×.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Large moiré superstructure of stacked incommensurate charge density waves

This article reports how two different charge density waves with slightly different wavevectors can exist in the same crystal and create moiré superstructure. Advances in heterostructure fabrication have opened new frontiers in moiré physics. Here we extend moiré engineering from artificially assembled thin flakes with mismatched lattice parameters to materials that host incommensurate orders, presenting a long-period moiré superlattice in a layered charge-density-wave compound, EuTe 4 . Using high-momentum-resolution X-ray diffraction, we found two coexisting incommensurate charge density waves with slightly mismatched in-plane wavevectors. The interaction between these two charge density waves leads to joint commensuration with the lattice and a moiré superstructure with a period of ~13.6 nm, offering key insights into the unique properties of EuTe4, such as the temperature-invariant incommensurate wavevectors and unconventional in-gap states. Owing to interlayer phase shifts, the moiré superstructure exhibits a clear thermal hysteresis, accounting for the large hysteresis in electrical resistivity and numerous metastable states. Our findings open new directions for moiré engineering based on incommensurate lattices and highlight the important role of interlayer ordering in stacked structures.

36 MATERIALS SCIENCE

Interleaved bond frustration in a triangular lattice antiferromagnet

Frustration of long-range order via lattice geometry amplifies fluctuations and generates ground states that are highly sensitive to perturbations. Traditionally, geometric frustration is used to engineer unconventional magnetic states; however, the charge degree of freedom and bond order can be similarly frustrated. Finding materials that host both frustrated magnetic and bond networks holds promise for engineering structural and magnetic states with the potential of coupling to one another via either magnetic or strain fields. Here we identify an unusual instance of this coexistence in the triangular lattice antiferromagnets LnCd 3 P 3 (Ln = lanthanides). These compounds feature two-dimensional planes of unique trigonal planar CdP 3 units with an underlying bond instability that is frustrated via emergent kagome ice correlations. This bond instability is interleaved in between layers of frustrated magnetic moments. Furthermore, our results establish LnCd 3 P 3 as a rare materials class in which frustrated magnetism is embedded within a dopable semiconductor with a frustrated bond order instability.

Gomez Alvarado, S. J. [University of California, S

BISON analyses of TRISO fuel performance, its dependence on time-at-temperature, and possible implications for fuel design and qualification

The Advanced Gas Reactor Fuel Development and Qualification (AGR) program has established a substantial technical foundation to support private entry into the U.S. high-temperature gas-cooled reactor market. However, emerging tristructural isotropic (TRISO)-fueled reactor applications include small modular reactors and microreactors with longer fuel residence times, which may expose fuels to higher time-at-temperature (TAT) values than were explored by the AGR program. Increased TAT could affect diffusive and thermomechanical behaviors such as Pd penetration, fission gas release, creep, and fission product transport. In this work, we applied multiscale best-estimate BISON fuel performance modeling to assess these effects within a representative design space based on the AGR-5/6/7 experiment and analyzed trends in predicted particle and compact fuel performance metrics with possible implications for near-term fuel design and qualification. BISON unambiguously predicted that TRISO fuel performance is sensitive to TAT. Increasing TAT was not predicted to increase the magnitude of failure-inducing tangential stresses in particle coating layers. Predictions obtained using a mechanistic model for Pd penetration indicated that penetration depth does not depend strongly on TAT. While these observations suggest that AGR testing provides a conservative upper bound for the steady-state operation of TRISO particles at lower powers and higher residence times, BISON also predicted that the release of poorly retained Ag would increase with TAT. Because these analyses applied models to extrapolate beyond the available experimental data, the authors recommend performing targeted experiments to confirm these predictions. Nevertheless, these predictions may provide reactor developers with enough confidence to make near-term design decisions associated with the potential fuel performance trade-offs of increasing TAT.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Dynamic Analysis of Reynolds Number Effects on Trailing Edge Transonic Vortex Shedding and Its Impact on Turbine Blade Aerodynamic Performance

In this work, we will discuss observations from images acquired from a time-resolved, high-speed self-aligned focusing Schlieren campaign that was performed at the CW-22 facility at NASA Glenn Research Center to understand the dynamic behavior of thick trailing-edge high-pressure turbine blades simulating a ceramic matrix composite (CMC) construction at high inlet turbulence conditions. For the CMC-9 blade, which has a trailing edge thickness of 9% of the axial chord, we identified a regime where an excessive total pressure loss (loss anomaly) is observed only for a narrow range of Reynolds numbers at a fixed exit Mach number of 0.74. The loss anomaly is qualitatively explained by our images, which were taken at 10 distinct blade Reynolds numbers spanning a factor of 6. The images show a significant increase in energy related to the oscillations due to transonic vortex shedding at the Reynolds numbers related to the high loss conditions. This increased energy leads to the formation of strong acoustic waves that turn into shock waves at the highest loss conditions. From our observations stemming from Spectral POD analysis of the high-speed images, we see the acoustic waves produced by the trailing edge vortex shedding exist in all conditions tested; but the shedding frequency has a very slight trend upwards as the Reynolds number is increased, varying about 6% in the range tested. Considering this variation of shedding frequency as a function of Reynolds number, which is well-established for other bluff-body flows, we stipulate there may be a potential feedback mechanism involving an acoustic information transfer path across neighboring blades that may explain why only a narrow range of Reynolds numbers displays strong, shock-forming vortex shedding. We consider a few feedback paths and examine the timing based on the mean flow field from a high-resolution LES simulation. It appears that all feedback mechanisms are viable, presenting an integer number of delay cycles with respect to disturbances generated at the trailing edge. Most noteworthy, however, is the acoustic/shock-boundary layer interaction mechanism at the blade geometric throat. Based on our analysis, this mechanism likely plays an important role in realistic, curved turbine blade passages.

Aerodynamics

Emergent surface resonance from charge density wave symmetry breaking in TiSe 2

Surface confined electronic states provide a fertile ground for discovering emergent phenomena that have no counterpart in the bulk, offering new routes to manipulate correlations, symmetry breaking, and dimensionality at the atomic scale. Here, in this study, we show that charge density wave (CDW) symmetry breaking can yield surface states in 1⁢T−TiSe 2 . Micro–angle-resolved photoemission spectroscopy (µ-ARPES) resolves a sharp, two-dimensional surface resonant state (SRS) that emerges within the CDW reconstructed low energy spectrum. The SRS exhibits notable temperature dependence and its spectral weight collapses around ∼ 160 K, while CDW transition temperature 𝑇 CDW is commonly reported as ≈ 202 K. Slab DFT + 𝑈 calculations reproduce a surface localized resonance when CDW folding brings valence and conduction states into near degeneracy, suggesting a correlation tuned, surface selective origin. These results point to a form of correlation-tuned surface resonance in a layered CDW compound and suggest a framework for engineering low-dimensional quantum states in van der Waals materials via symmetry breaking and electronic structure tuning.

36 MATERIALS SCIENCE

Interwoven magnetic kagome metal overcomes geometric frustration

Magnetic kagome materials provide a platform for exploring magneto-transport phenomena, symmetry breaking and charge ordering driven by the intricate interplay among electronic structure, topology and magnetism. Yet geometric frustration in conventional kagome magnets limits their tunability. Here we propose a design strategy for interweaving quasi-one-dimensional magnetic Tb zigzag chains with non-magnetic Ti-based kagome bilayers in TbTi 3 Bi 4 . Comprehensive spectroscopic analyses reveal coexisting elliptical-spiral magnetic and spin-density-wave orders accompanied by a large ~90 meV band-folding gap. The combined magnetic and electronic state leads to a giant anomalous Hall conductivity of 10 5 Ω −1 cm −1 , which exceeds that observed in frustrated kagome analogues. These results establish TbTi 3 Bi 4 as a model system of magnetic kagome metals with strong electron–magnetism interactions and underscore the necessity of interweaving designed magnetic and charge layers separately to achieve tunable transport properties. This design strategy will enable the discovery of emergent quantum states and next-generation electronic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Identifying Strain Stacking Boundaries between Multiphase Domains in Atomically Thin Two-Dimensional Magnets

Stacking engineering of van der Waals materials is an important strategy to control the materials’ properties, such as electronic correlations, ferroelectricity, and layer-dependent two-dimensional magnetism. A timely testbed for the study of the latter is atomically thin chromium trihalides (CrX 3 , X = Cl, Br, I). Notably, by understanding the sliding mechanism between different stacking sequences, control of the stacking arrangement, and thus magnetic properties in CrX 3 , can be achieved. Such insight, however, is currently lacking. Here, in this study, advanced electron microscopy methods are used to identify multiple stacking sequences corresponding to different bulk phases in atomically thin CrX 3 (X = Cl and Br) down to bilayer thickness and with lateral domain sizes as small as tens of nanometers. Indications of nanometer scale transitions and interactions at the stacking boundaries are found, including a universally preferred sliding direction that is consistent with density functional theory calculations and the strain fields at lateral heterostructure boundaries. This study demonstrates the necessity to consider local stacking structures when interpreting averaged magnetic properties measured with macroscale probes. Additionally, the preferred sliding direction insight from this study provides a strategy to control stacking sequence in atomically thin CrX 3 samples during the exfoliation and sample fabrication process.

DFT calculations

Staged Z-pinch experiment at the double-EAGLE pulsed power facility

The staged Z-pinch is a potential high-energy gain fusion concept where a high atomic number liner implodes on a deuterium target using a pulsed multi-MA current source. Over the past several years this concept has been studied on 0.5–1.0 MA facilities using Ar and Kr gas puffs injected at R = 1.2 cm. Neutron yield up to (2.5 ± 0.34) x 10 10 was measured, Ruskov et al (2023 IEEE Trans. Plasma Sci. 51 3310–6). Here, in this study, we present experimental results from the 4 MA, 110 ns current rise time Double-EAGLE facility at L3Harris (currently, Fisica Inc.) where a larger radius nozzle created gas density profiles peaked at R = 2.5 cm. Modeling with the MACH2 and FLASH codes indicates that the larger radius allows stronger acceleration of the liner plasma and generation of shock waves that preheat a target plasma layer next to the liner to temperatures $T_i >$1 keV. The resulting counter thermal pressure on the liner plasma limits the growth of the Magneto-Rayleigh–Taylor (MRT) instability at the liner-vacuum boundary and the implosion proceeds in a relatively stable manner. Near bang time the enormous target plasma thermal pressure smoothens the MRT perturbations developed during the earlier implosion stages. Time integrated x-ray pinhole images with cutoff energy of 100 eV confirm that a long (∼3 cm), stable and uniform high energy density plasma column is formed in the final implosion stage. Consistent neutron yield in the 10 10 –10 11 range was measured for both Ar and Kr liners imploding on a deuterium target.

Physics - Plasma physics

Elimination of detrimental grain boundary segregation in garnets

Garnet Li 7 La 3 Zr 2 O 12 electrolyte is considered a key enabler of solid-state batteries with Li metal electrodes, but the grain boundaries impair its performance. To date, the understanding of grain boundary structures and its impact on performance remains elusive. Here, we show that element segregation at Li 7 La 3 Zr 2 O 12 grain boundaries critically governs Li transport and nucleation. During conventional sintering, Al, Ta, and La segregate at grain boundaries, locally depleting Li and creating space-charge layers that lower total ionic conductivity. Simultaneously, this segregation leads to higher electronic conductivity along grain boundaries, which promotes Li nucleation at grain boundary edges with increased risk of dendrite formation. The underlying mechanism of segregation is governed by both thermodynamic driving forces and diffusion kinetics. Building on this understanding, we develop a strategy to achieve segregation-free grain boundaries through a rapid sintering protocol that utilizes the onset of solid-state softening. This approach yields transparent, polycrystalline Li 7 La 3 Zr 2 O 12 with negligible grain boundary impedance and enhanced dendrite tolerance. By elucidating the structural origins and electrochemical consequences of grain boundary segregation, this work provides a guidance for the rational optimization of solid electrolytes.

Energy - Storage

Heterotrophic respiration by soil microbes in a changing climate

Soil microbes strongly influence the soil organic carbon (SOC) pool, which globally stores ~2,000 PgC. Specifically, the balance between microbial heterotrophic respiration (R H ), which degrades SOC, and plant–microbe interactions that stabilize SOC determines whether terrestrial ecosystems are a net source or sink of CO 2 to the atmosphere. Here, in this Review, we evaluate how climate change alters these competing processes. R H is approximately half of total soil respiration, at ~50 PgC yr −1 , with 70% occurring in topsoils. Warming accelerates microbial metabolism, with a 10 °C temperature increase estimated to raise R H by ~50%, an effect that is particularly strong in Arctic soils. Warming also reduces soil moisture, further modulating R H , which responds nonlinearly to soil moisture, being limited by saturation and desiccation and meeting a maximum at intermediate levels. Consequently, R H is highly sensitive to future precipitation changes and drought. However, soil management strategies could enhance SOC stocks and persistence under climate change. Bacterial and fungal inoculants can promote SOC production and stabilization, while deep-rooting plants increase SOC inputs to deeper layers that experience lower R H . Agricultural practices and biochar amendments can also enhance SOC and reduce R H . Expanding field trials across regions, climates and soil types would improve empirical understanding of these responses and support better representation of R H in predictive models, enabling more accurate assessments of climate impacts on SOC storage.

Jansson, Janet K. [Pacific Northwest National Labo

In-Situ Scanning Electron Microscope Experiments for Microscale Mechanical Testing and Validated Modeling of Fiber Reinforced Thermoplastics

A novel, in-situ, scanning electron microscope (SEM) mechanical testing capability for materials at the microscale which provides experimental validation to a machine learning (ML) toolset for full-field validation of physics-based micromechanics models is being developed by researchers at NASA Glenn Research Center. These are enabling technologies for the integration of multiscale digital twins for materials into system level models which will result in the improved performance, material discovery, reduced production cost and time, rapid characterization, and prognostic structural health monitoring (SHM) for materials and structures for extreme environments in support of NASA space exploration missions. In order to bridge the material structure-to-system gap for digital twins, physics-based models must be experimentally validated at multiple length scales. Seminal microscale experiments, conducted at the Air Force Research Laboratory (AFRL), were limited to transverse compression of single-layer, unidirectional thermoset polymer matrix composite (PMC) micropillar specimens [1]. The early phases of the current project followed those initial results and setup to reproduce the compression testing of PMC material on the custom-built piezoelectric actuated micromechanical testing rig built by MicroTesting Solutions LLC. In this work, samples of thermoplastic PMC material were first machined into 3 mm cubes, and then further machining and final milling was done using a Focused Ion Beam (FIB). The initial experiment was done on a pillar roughly 20 µm x 20 µm x 40 µm tall. Additional pillars were milled with final sizes ranging from 20 µm x 20 µm x 40 µm tall to 40 µm x 40 µm x 65 µm tall. A speckle pattern for in-situ full-field measurements using Digital Image Correlation (DIC) was applied with platinum, which was coated on the surface, and then the FIB was used to mill away some of the coating to produce an irregular pattern of Pt on the pillar surface. The samples were loaded into the custom testing rig and placed into the SEM and loaded under compression until failure. Images were collected in the SEM during testing. Post-processing of the images was conducted using DIC to obtain full-field displacement and strain measurements elucidating the role of the matrix as well as fiber-fiber interaction at the microscale within the composite subjected to compression loading well into the non-linear regime of the material. Moreover, the evolution of fiber-matrix debonding and matrix cracking is observed in-situ at the microscale. This data, along with images segmented with a newly developed ML toolset [2], was used to create and validate physics-based micromechanics models. An image of the failed micropillar is shown in Figure 1. The techniques developed in the initial compression experiment was tailored to the validation needs of the models and expanded to include different sized samples as well as possibly tension and fatigue.

Laura Wilson

Nitrile/Buna N Material Failure Assessment for an O-Ring used on the Gaseous Hydrogen Flow Control Valve (FCV) of the Space Shuttle Main Engine

After the rollout of Space Shuttle Discovery in April 2005 in preparation for return-to-flight, there was a failure of the Orbiter (OV-103) helium signature leak test in the gaseous hydrogen (GH2) system. Leakage was attributed to the Flow Control Valve (FCV) in Main Engine 3. The FCV determined to be the source of the leak for OV-103 is designated as LV-58. The nitrile/Buna N rubber O-ring seal was removed from LV-58, and failure analysis indicated radial cracks providing leak paths in one quadrant. Cracks were eventually found in 6 of 9 FCV O-rings among the three Shuttle Orbiters, though none were as severe as those for LV-58, OV-103. Testing by EM10 at MSFC on all 9 FCV O- rings included: laser dimensional, Shore A hardness and properties from a dynamic mechanical analyzer (DMA) and an Instron tensile machine. The following test data was obtained on the cracked quadrant of the LV-58, OV-103 O-ring: (1) the estimated compression set was only 9.5%, compared to none for the rest of the O-ring; (2) Shore A hardness for the O.D. was higher by almost 4 durometer points than for the rest of the O-ring; and (3) DMA data showed that the storage/elastic modulus E was almost 25% lower than for the rest of the O-ring. Of the 8 FCV O-rings tested on an Instron, 4 yielded tensile strengths that were below the MIL spec requirement of 1350 psi-a likely influence of rubber cracking. Comparisons were made between values of modulus determined by DNA (elastic) and Instron (Young s). Each nitrile/Buna N O-ring used in the FCV conforms to the MIL-P-25732C specification. A number of such O-rings taken from shelf storage at MSFC and Kennedy Space Center (KSC) were used to generate a reference curve of DMA glass transition temperature (Tg) vs. shelf storage time ranging from 8 to 26 years. A similar reference curve of TGA onset temperature (of rubber weight loss) vs. shelf storage time was also generated. The DMA and TGA data for the used FCV O-rings were compared to the reference curves. Correlations were also made between the DMA modulus (at 22 C) and Shore A hardness for all 9 of the FCV O-rings used among the three Shuttle Orbiters. The radial cracking in the FCV O-rings was determined to be due to ozone attack, as nitrile/Buna N rubber is susceptible to such attack. Nitrile/Buna N material under MIL-P25732C should be used in a hydraulic fluid environment to help protect it from cracking. However, the FCV O-rings were used in an air only environment. The FCV design has as much as a 9-mil gap that allows the O.D. of the O-ring to be directly exposed to ozone, pressurized air and some elevated temperatures, accelerating the weathering process that leads to O-ring cracking. Space Shuttle flights will likely not continue past 2010. Therefore, Shuttle management decided to continue using the nitrile/Buna N material for the FCVs, but have each O-ring replaced after 3 years to minimize any chances for crack initiation.

Doug Wingard

Aliovalent gallium dopants remove Ti 3+ defects and improve photocatalytic and photoelectrochemical water oxidation properties of LaTiO 2 N

LaTiO 2 N is a promising semiconductor for the water splitting reaction due to its 2.1 eV band gap and stability against corrosion. However, its solar energy conversion is limited by Ti 3+ recombination defects introduced during ammonolysis. Here we show for the first time that Ti 3+ defects in LaTiO 2 N can be suppressed with incorporation of 2, 5, and 10% aliovalent gallium (Ga 3+ ) dopants during synthesis via the layered La 2 Ti 2 O 7 intermediate. Electron paramagnetic resonance (EPR) spectroscopy on the solid powders confirms a reduction in the Ti 3+ donor density from 2.97 × 10 17 cm −3 for the non-doped material to ∼6.24 × 10 16 cm −3 for 5% Ga-doped LaTiO 2 N. The remaining Ti 3+ defects are concentrated near the LaTiO 2 N surface, according to X-ray photoelectron spectroscopy. The defect reduction shifts the optical absorption edge from 2.02 to 2.09 eV and eliminates a broad absorption band at 1050 nm from the optical absorption spectra. It also removes a 1.0–1.7 eV sub-band gap photovoltage signal from surface photovoltage spectra. This suggests that empty Ti 3+ d-orbitals are located 1.0–1.7 eV above the LaTiO 2 N valence band edge. Removing these recombination states with increasing Ga 3+ content enhances the photoconversion efficiency of LaTiO 2 N during water oxidation. The optimized 2 wt% CoO x -loaded 5% Ga-doped LaTi O2 N material has a 16% AQE (400 nm) for O 2 production from aqueous silver nitrate solution and a ∼2.1 mA cm −2 water oxidation photocurrent at 1.23 V under 100 mW cm −2 Xe arc lamp illumination. The water oxidation photocurrent is stable during a 50 min test, and the Faraday efficiency for O 2 generation is 97%, confirming short-term corrosion stability of LaTiO 2 N. Altogether, these results provide a better understanding of the distribution, concentration, and impact of Ti 3+ defects on the optical, photovoltage, and photoelectrochemical properties of LaTiO 2 N. In combination with other defect control strategies, aliovalent Ga 3+ doping can help bring the solar energy conversion efficiency of LaTiO 2 N closer to the theoretical limit.

Wang, Li [University of California, Davis, CA (Uni

Erosion Results of the MISSE 9-15 Polymers and Composites Experiment 1-4 (PCE 1-4)

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded from reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft it is important to know the extent of erosion that will occur during a mission. This can be determined by knowing the LEO AO erosion yield, E y (volume loss per incident oxygen atom), of materials susceptible to AO reaction. In addition, recent flight experiments have shown that the AO E y can vary with the AO fluence and/or solar exposure. Therefore, obtaining AO E y data for materials flown on various spaceflight missions is important. NASA Glenn Research Center has flown numerous experiments as part of the Materials International Space Station Experiment (MISSE) missions on the exterior of the International Space Station (ISS) to characterize the LEO E y of polymers, composites, protective coatings, and other spacecraft materials. Recently, four Glenn experiments with 365 flight (F) samples were flown on ISS’s MISSE-Flight Facility (MISSE-FF). These experiments are the Polymers and Composites Experiment-1 (PCE-1) flown as part of the MISSE-9 mission, the PCE-2 flown as part of the MISSE-10 mission, the PCE-3 flown as part of the MISSE-12 and MISSE-15 missions, and the PCE-4 flown as part of the MISSE-13 mission. Although each experiment had numerous sample objectives, the primary objective was to determine the LEO AO E y of various spacecraft materials as a function of solar irradiation and AO fluence. This paper provides a summary of the erosion data for the PCE 1-4 AO E y samples. The AO E y for 150 samples flown in either the LEO ram, wake, zenith or nadir directions are provided. The AO ram fluence varied from 2.97×10 20 atoms/cm 2 after 0.89 years of direct space exposure (with relatively high levels of Si contamination) on MISSE 12 to 3.93×10 20 atoms/cm 2 after 1.17 years of direct space exposure on MISSE-10. The ram AO E y values for uncoated polymers range from 3.81×10 –25 cm 3 /atom for polytetrafluoroethylene (M9R-C20 F) exposed to an AO fluence of 3.44×10 20 atoms/cm 2 on MISSE-9 to 4.43×10 –23 cm 3 /atom for AO etched low density polyimide aerogel (M12R-C21 F) exposed to an AO fluence of 2.97×10 21 atoms/cm 2 on MISSE-12. Because of the low AO fluence and relatively high Si contamination, a number of PCE-3 wake samples experienced mass gain. Thus, AO E y values are not provided for these samples. Although there are calculated AO E y values for the zenith, wake and nadir samples, the ram AO E y for a particular material is a more reliable value in terms of AO exposure because the zenith, wake and nadir directions were exposed to either no or very little AO fluence and thus other space environmental factors (i.e. vacuum, thermal extremes and thermal cycling, and/or various types of radiation) are responsible for the mass loss.

Erosion yield