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At least 757 records · Page 42

Advanced Anode for Internal Reforming and Thermal Management in Solid Oxide Fuel Cells

Solid oxide fuel cell (SOFC) is an efficient and clean electrical power generation system compared to conventional combustion based technologies with energy efficiency reaching as high as 85-90% in co-generation mode (electricity and heat). Other advantages of SOFCs are hybridization, modularity of construction, small CO 2 foot print per kWh of generated electricity and fuel flexibility. Hydrocarbons present in the gaseous fuel is utilized in SOFCs by internal or external reforming. There are two different internal reforming concepts: Direct Internal Reforming (DIR) and Indirect Internal Reforming (IIR). For DIR operation, the endothermic reforming reaction and the exothermic reaction from the oxidation reaction are operated together in the single unit eliminating the requirement for a separate fuel reformer. This configuration also simplifies the overall system design, making SOFC more attractive and efficient means of producing electrical power. The main advantage of the DIR type of operation is that the H 2 or CO consumption by the electrochemical reaction could directly promote the conversion of methane at the anode side of the fuel cell resulting in high conversion and high efficiency. The DIR operation, however, requires an anode material that has desired dual catalytic (hetero and electro) properties for reforming reaction and electrochemical reactions. The anode materials also need to remain resistant to carbon formation at the operating temperature and atmosphere with stable cell performance. Another requirement is to match the reforming reactions and electrochemical reactions to avoid local cooling or overheating, which can result in mechanical failure due to thermally induced stresses. Direct internal reforming (DIR) of hydrocarbon fuels simplifies the overall SOFC system design making it more attractive and efficient for producing electrical power. Low cost alloy anodes for distributed internal reforming of methane and other hydrocarbon fuels offer increased fuel-flexibility, reliability, and long term performance stability of solid oxide fuel cells (SOFC). The research program examined modification of the chemical compositions and microstructure of high entropy alloy (HEA) anode materials using thermochemical calculations and process simulation and modeling to achieve distributed reforming over the entire anode to eliminate hot zones. Cell fabrication and testing of the HEA anodes using button cell configuration has been performed to demonstrate the advantages of new anode over traditional Ni-YSZ anodes for distributed reforming and carbon free operation. Technical accomplishments include identification and synthesis of HEA carbon-resistant anode, demonstration of reduction in reforming rate confirmed by GC and modelling data validating effectiveness for thermal management in cell/stacks, electrochemical testing of HEA anode in single cell (HEA-GDC||YSZ||LSM-YSZ) and Characterization of pretest and posttest anode materials by TEM and SEM-EDS confirming carbon-free operation.

30 DIRECT ENERGY CONVERSION↗

Dispenser Reliability: Materials R&D. A Hydrogen Fueling Infrastructure Research and Station Technology (H2FIRST) Report

Dispensers are the top cause of maintenance events and down-time at hydrogen fueling stations. In an effort to help characterize and enable improvements in dispenser reliability, an extensive accelerated lifetime testing set-up was designed and built at NREL involving components typically part of dispensing operations at fueling stations. Device Under Test (DUTs) included different components such as normally open valves, normally closed valves, fueling nozzles, breakaways devices and filters. Conditions of testing included pressures, and flow rates similar to light duty fuel cell electric vehicles fueling at -40°C, and -20°C for thousands of cycles in hydrogen. Tested components (failed and non-failed) were disassembled at SNL and polymeric O-rings were carefully retrieved and cataloged for chemical and physical characterization. Data collected was compared to similar O-rings from unexposed or non-tested components for hydrogen effects, and failure modes. Degradation analyses, based on select polymer chemistries common across all component types, their location within components, visual assessment of damage coupled with strong hydrogen effects from chemical characterization, was completed and presented to NREL and DOE. Overall, the failure rate amongst the components was not as high as expected for the test conditions. Among the component types tested, breakaways were the most susceptible to damage under these test conditions, with fueling nozzles a close second. The proper combination of selection of the right polymer and optimum component design was found to make a strong difference in component reliability under severe dispenser operating conditions. Physical degradation of polymers, rather than chemical changes due to low temperature hydrogen exposure, is more prevalent as failure mode for these test conditions. The nature and the extent of the degradation was much less at -20°C as compared to -40°C. The damage and failure rates were higher at lower temperatures than at higher test temperatures. As expected, increasing the number of cycles at the lowest test temperature (-40°C) increased damage. This indicates that cycling at the low temperature of -40°C required by SAE J2601 can reduce component life in fuel dispensing operations

08 HYDROGEN↗

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

The GNIRS instrument on the Gemini 8-­‐m telescope observed comet 103P/Hartley on 2010-­‐ Dec-­‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­‐absorbing C=C aromatic rings, and these rings have to be less than 50-­‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-­‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-­‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-­‐0012-­‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-­‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.

Stardust samples↗

Thin Current Sheets of Sub-Ion Scales Observed by MAVEN in the Martian Magnetotail

Current sheets (CSs) play a crucial role in the storage and conversion of magnetic energy in planetary magnetotails. Using high‐resolution magnetic field data from MAVEN spacecraft, we report the existence of super thin current sheets (STCSs) in the Martian magnetotail. The typical half‐thickness of the STCSs is ~5 km, and it is much less than the gyroradius of thermal protons (ρp). The STCSs are embedded into a thicker sheet with L ≥ ρp forming a multiscale current configuration. The formation of STCS does not depend on ion composition, but it is controlled by the small value of the normal component of the magnetic field at the neutral plane (BN). A number of the observed multiscale CSs are located in the parametric map close to the tearing‐unstable domain, and thus, the inner STCS can provide an additional free energy to excite ion tearing mode in the Martian magnetotail.

Martian↗

The northern Utah satellite (NUSAT) communications link

During the planning Stages of the NUSAT satellite, an obvious issue to be discussed was the method of communications to be used. The frequencies would have to be high enough to pass through the atmosphere relatively unattenuated but low enough that antennas and transmission lines would not be so critical in length and properties that unexperienced students would have difficulty with handling them. In conversations with the Federal Communications Commission (FCC) in Washington D.C., the frequencies of 450.000 MHz and 137.900 MHz were decided upon and applied for licensing. The 450.000 MHt up-link is used on a "non-interference" basis to control the satellite while the 137.900 MHz frequency down-links data from the satellite. A reasonable amount of time was spent discussing the mods of transmission to be used in communication with the satellite. Representatives of the amateur radio satellite organization, AMSAT, were contacted for ides. This organization seems to favor AM types of emissions such as CW to control their OSCAR series of satellites and also the current Phase 111 unit. NUSAT personnel felt, however, that there would be merit in the improved signal to noise ratio usually obtained in an FM mode. Doppler shift of the transmitted information on the NUSAT also had to be considered. The final decision WBS to use Audio Frequency Shift Keying (AFSK) modulated on an FM carrier. In this mode the audio tones used would not shift frequency with Doppler - only the carrier would shift in frequency. If necessary, the receivers could be fitted with a form of AFC control or simply have enough bandwidth to handle the Doppler shift with an acceptable increase in noise.

Lee Barrett↗

DROP DURABILITY ASSESSMENT OF ELECTRONIC ASSEMBLIES UNDER OFF-AXIS LOADING WITH SKEWED FIXTURES

This thesis studies drop durability of electronic assemblies when the acceleration vector is oriented at 45° to the out-of-plane direction of the circuit card. The off-axis drop tests are accomplished with a skewed fixture and are conducted as a proxy for multiaxial drop testing. Advanced shock testing and vibration test methods have been developed over the last few decades to better represent real-world field environments during ground-based laboratory testing. However, many of these test methods require expensive and specialized equipment not available in most laboratories. An alternative approach for approximating simultaneous loading along multiple axes on conventional equipment utilizes skewed fixtures which have seen use in off-axis random vibration and drop impact testing. These methods generally rely on the conversion of a uniaxial input load from the test equipment (using a uniaxial drop tower or shaker) into a multiaxial load when resolved in the reference frame of the test article (mounted on a skewed fixture). Skewed fixture design is presented and recommendations for conducting skewed angle drop testing are introduced based on local measurements along the skewed face of the fixture to accurately monitor the impact event. Characterization tests were performed with a skewed fixture, at simultaneous acceleration loads from 500 to 3,000 g in two (in-plane and out-of-plane) directions, while meeting standard time domain tolerances. Upon experimental characterization, drop shock durability tests were conducted on a printed circuit assembly (PCA). Mean drops-to-failure were measured and quantified with Weibull statistics. Dominant solder joint failure modes were identified via failure analysis. Prior work on inclined angle impact testing is limited, and the majority of solder joint interconnect level fatigue studies are conducted considering perpendicular loading normal the circuit card. Low-cycle fatigue curves are generated based on plastic strain and plastic work density within the solder joint. A multiscale nonlinear finite element model is used to relate board-level flexure to solder joint interconnect level plastic strain. A high strain rate solder constitutive model allows for accurate modeling of solder plasticity resulting from high-impact drop shock. Fatigue parameters are computed from the Coffin-Manson relation and Palmgren-Miner damage accumulation. This work serves to apply established low-cycle fatigue methods for conventional drop shock loading (impact normal to circuit card) to non-perpendicular loading with a skewed fixture.

Hower, Jonathan [Kansas City National Security Cam↗

Polarization angle requirements for CMB B-mode experiments. Application to the LiteBIRD satellite

A methodology to provide the polarization angle requirements for different sets of detectors, at a given frequency of a CMB polarization experiment, is presented. The uncertainties in the polarization angle of each detector set are related to a given bias on the tensor-to-scalar ratio r parameter. The approach is grounded in using a linear combination of the detector sets to obtain the CMB polarization signal. In addition, assuming that the uncertainties on the polarization angle are in the small angle limit (lower than a few degrees), it is possible to derive analytic expressions to establish the requirements. The methodology also accounts for possible correlations among detectors, that may originate from the optics, wafers, etc. The approach is applied to the LiteBIRD space mission. We show that, for the most restrictive case (i.e., full correlation of the polarization angle systematics among detector sets), the requirements on the polarization angle uncertainties are of around 1 arcmin at the most sensitive frequency bands (i.e., ≈ 150 GHz) and of few tens of arcmin at the lowest (i.e., ≈ 40 GHz) and highest (i.e., ≈ 400 GHz) observational bands. Conversely, for the least restrictive case (i.e., no correlation of the polarization angle systematics among detector sets), the requirements are ≈ 5 times less restrictive than for the previous scenario. At the global and the telescope levels, polarization angle knowledge of a few arcmins is sufficient for correlated global systematic errors and can be relaxed by a factor of two for fully uncorrelated errors in detector polarization angle. The reported uncertainty levels are needed in order to have the bias on r due to systematics below the limit established by the LiteBIRD collaboration.

79 ASTRONOMY AND ASTROPHYSICS↗

Nth-plant scenario for blended pellets of Miscanthus, Switchgrass, and Corn Stover using multi-modal transportation: Biorefineries and depots in the contiguous U.S.

The sustainability of the biofuel industry depends on the development of a mature conversion technology on a national level that can take advantage of the economies of scale: the nth-plant. Here, this study addresses the logistic challenge of mobilizing national cellulosic feedstock supplies for a sustainable bioenergy industry. A Mixed Integer Linear Programming (MILP) model was developed and updated to deliver on-spec biomass that considers both a desired quantity and quality at the biorefinery. Our supply chain analysis includes multi-modal transport (truck and rail), varying depot and biorefinery sizes, and feedstock blends of corn stover (harvested by either a two- or three-pass method), switchgrass, and miscanthus. The following US states: Illinois, Kansas, Missouri, North Carolina, Oklahoma, Georgia, and Texas were identified as key locations for producing accessible miscanthus. Based on our most optimistic scenario, using trucks as the only transportation mode in 2040 with a cost target of $\$$79/dt, corn stover, switchgrass, and miscanthus could help meet 48% of the EPA target, 173 million dry tons that translate into 7.8 billion GGE. The addition of rail transportation for biomass delivery to biorefineries could help meet 79% of the EPA target, 283 million dry tons that translate into 12.7 billion GGE.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

P/N In(Al) GaAs Multijunction Laser Power Converters

Eight In(Al)GaAs P/N junctions grown epitaxially on a semi-insulating wafer were monolithically integrated in series to boost the approx. 0.4 V photovoltage per typical In(Al)GaAs junction to over 3 volts for the 1 sq cm laser power converter (LPC) chip. This is the first report of a multijunction LPC for the 1.3 to 1.5 microns wavelength range. This wavelength range is optimum for laser power transmission over low- loss single-mode silica optical fiber, and is also useful with high efficiency 1.315 microns iodine lasers in free-space power transmission. Advantages of multijunction LPC designs include the need for less circuitry for power reconditioning and the potential for lower I(exp 2)R power loss. As an example, these LPCs have a responsivity of approx.1 amp/watt. With a single junction LPC, 100 watts/sq cm incident power would lead to about 100 A/sq cM short-circuit current at approx. 0.4 V open-circuit voltage. One disadvantage is the large current would lead to a large 1(exp 2)R loss which would lower the fill factor so that 40 wattS/sq cm output would not be obtained. Another is that few circuits are designed to work at 0.4 volts, so DC-DC power conversion circuitry would be necessary to raise the voltage to a reasonable level. The multijunction LPC being developed in this program is a step toward solving these problems. In the above example, an eight-junction LPC would have eight times the voltage, approx. 3 V, so that DC-DC power conversion may not be needed in many instances. In addition, the multijunction LPC would have 1/8 the current of a single-junction LPC, for only 1/64 the 1(exp 2)R loss if the series resistance is the same. Working monolithic multijunction laser power converters (LPCs) were made in two different compositions of the ln(x)Al(y)Ga(l-x-y)As semiconductor alloy, In(0.53)Ga(0.47)As (0.74 eV) and In(0.5)Al(0.1)Ga(0.4)As (0.87 eV). The final 0.8 sq cm LPCs had output voltages of about 3 volts and output currents up to about one-half amp. Maximum 1.3 microns power conversion efficiencies were approx. 22%. One key advantage of multijunction LPCs is that they have higher output voltages, so that less DC-DC power conversion circuitry is needed in applications.

Wojtczuk, Steven↗

A Two-Stage Biological Reactor for Treatment of Space Based Waste Waters

Previous works on Membrane Aerobic Biological Reactors (MABR) CoMANDR 1.0, CoMANDR 2.0, and R-CoMANDAR have demonstrated their ability to stabilize various space based waste streams over operating periods of ~1 year. Biological pretreatment by MABR systems can stabilize space based waste streams. Biological stabilization includes reducing the pH, conversion of organic N to NOx- and oxidation of dissolved organic matter to CO2. These processes produce a more stable waste product (brine), facilitate the distillation processes, and enable evaporative or membrane based systems. An alternative to aerobic operation would be to include anoxic operation to promote denitrification and production of N2 gas. This results in a reduced O2 demand and increases ammonia oxidation efficiency. Denitrifictaion can be accomplished in either a single reactor (Simultaneous Nitrification Denitrification) or in a two-stage system with separate aerobic and anoxic reactors. We evaluated the performance of both architectures in pilot scale systems (1-2 crew/d). Each system was continuously operated for over 2 years during which they processed a variety of habitation waste streams (ISS, Transit, and EPB) in both a continuous and on production feed mode. Here we report the results of the two stage system. Results indicate that the two stage system can successfully remove organic carbon, lower pH and convert organic N to N2 gas. Organic carbon and organic N oxidation reaction rates for the two stage system are similar to past studies for single stage aerobic systems. The two stage system is more complex and requires an additional pump. While no maintenance was required on the system during the nearly two year period of operation, the packed bed did produce N2 gas for many operational test points. The performance and comparison of operational conditions are detailed below

Water↗

Effects of an External Magnetic Field on Keyhole Mode Laser Melting of 316 Stainless Steel

Keyhole-mode laser melting is an efficient method for joining or cutting large, thick components, but controlling keyhole depth and fluctuations has remained challenging. Applying an external magnetic field can control melt pool flows and indirectly influence keyhole morphology and dynamics. The induced Lorentz force, comprising Seebeck and damping components, plays a crucial role in the melt pool dynamics, depending on temperature gradient, flow rates, and magnetic field orientation and magnitude. This research investigates the effects of an external magnetic field on keyhole behavior during laser spot melting of 316 stainless steel using synchronized high-speed synchrotron X-ray and thermal imaging. Findings revealed that a longitudinal magnetic field (120 mT) increased keyhole depth but exacerbated lateral fluctuations, resulted in a 20% increase in the melt pool temperature gradient and a 27% decrease in cooling rate. Conversely, a transverse magnetic field (760 mT) reduced keyhole depth and improved porosity formation. The findings suggest that a decrease in keyhole depth correlates with a decrease in fluctuations, and vice versa. These insights enhance understanding of external magnetic fields’ impact on laser melting, with implications for improving part quality.

Alamdari, Aslan Bafahm [The Ohio State Univ., Colu↗

Microscopic subsurface characterization of layered magnetic materials using magnetic resonance force microscopy

This project resulted in the following accomplishments: 1) The invention of scanned probe ferromagnetic resonance microscopy. Upon implementation and refinement this approach was used to measure static and dynamic magnetic resonance properties of ferromagnets with an unprecedented combination of spectral and spatial resolution. 2) Demonstration and study of spin pumping in a pristine ferromagnet across a boundary defined entirely by a magnetic field gradient, and so free of materials discontinuities. 3) First demonstrated highly efficient dynamic spin injection from Y 3 Fe 5 O 12 (YIG) into NiO, an antiferromagnetic (AF) insulator and robust spin propagation in AF NiO over distances up to 100-nm thickness; both spin injection and spin transport are mediated by the AF spin correlations. 4) Demonstration of exceptionally high efficiency conversion of spin current to charge current achieved in spin pumping from the dynamic magnetization of a ferromagnetic insulator into a variety of adjacent metal films. 5) Seminal study of the nature of spin-orbit coupling in d-electron metals that revealed the dominant sensitivity of the d-orbital moment to the d-electron count and revealing the important roles of both d-electron configuration and atomic number in the physics of the spin Hall effect. 6) Demonstration of observation of FMR by means of optically-detected NV diamond relaxometry that provided a highly sensitive, spatially resolved FMR detection method and revealed spin pumping across 100-nm length scales by means of dipolar coupling. 7) Using magnetic field localization, developed for FMR imaging, demonstrated a novel approach to discretizing spin wave modes to improve the characteristics of auto-oscillators driven by pure spin currents produced by the spin Hall effect. 8) We demonstrated large spin pumping signals from propagating high wavevector spinwaves in thin film YIG find that the spin pumping efficiency was insensitive to wavevector thus emphasizing the promise of thin YIG films for spinwave-based spintronics by allowing for predictable down-scaling of device dimensions and enabling a broad range of operational frequencies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interpretation of Lyman opacity measurements in JET with the ITER-like wall using a particle balance approach

Recent measurements of the Ly β /D α ratio in the JET ITER-like wall (ILW) divertor show comparatively more pronounced Ly β reabsorption relative to previous results in JET with the carbon wall (JET-C). At the outer horizontal target ion current rollover point a Ly β reabsorption rate of 60% is measured, increasing to 80% in more pronounced detachment, implying a Ly α reabsorption rate of 90%–98%. The radially resolved Ly β /D α measurements are used to constrain Lyman opacity corrections to atomic rate coefficients using the population escape factor technique in order to capture the local changes to the excited state population structure in the high Lyman opacity regions at and outboard of the outer strike point. To check the self-consistency of the Lyman opacity measurements, a detailed spectroscopic interpretation of the outer divertor particle balance is presented, in which the impact of opacity corrections to the Ly α inverse photon efficiency coefficients is assessed. A five-fold deficit in the estimated D + source rate obtained with optically thin plasma assumptions is reconciled once the opacity corrections are factored into the Ly α photon rate to ionization rate conversion. The experiment results are reproduced in EDGE2D-EIRENE density scan simulations in which an imposed ad hoc Lyman reabsorption rate is recovered spectroscopically using synthetic measurements, and a similar shortfall in the D + source rate estimates is reconciled using Lyman opacity corrected atomic data. The model limitations prevent a more detailed self-consistent analysis of the Lyman opacity impact on divertor parameters and detachment evolution, and hence motivate renewed efforts to re-establish routine exploitation of the photon transport modelling capabilities in the EIRENE code package. Lyman opacity corrections to atomic data coefficients are necessary for spectroscopic interpretation of the JET-ILW divertor plasma, with significant influence on the divertor plasma also a likely consequence of the presence of strong Ly α reabsorption. Finally, a scan of auxiliary heating powers spanning L-mode and H-mode conditions reveals a strong correlation of the measured Ly β opacity with the outer target temperature, suggesting new possibilities for using Lyman opacity measurements in establishing detachment scalings.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Compact Ti:Sapphire Laser With its Third Harmonic Generation (THG) for an Airborne Ozone Differential Absorption Lidar (DIAL) Transmitter

A compact and high-pulse-energy Ti:Sapphire laser with its Third Harmonic Generation (THG) has been developed for an airborne ozone differential absorption lidar (DIAL) to study the distributions and concentrations of the ozone throughout the troposphere. The Ti:Sapphire laser, pumped by a frequency-doubled Nd:YAG laser and seeded by a single mode diode laser, is operated either at 867 nm or at 900 nm with a pulse repetition frequency of 20 Hz. High energy laser pulses (more than 110 mJ/pulse) at 867 nm or 900 nm with a desired beam quality have been achieved and utilized to generate its third harmonic at 289nm or 300nm, which are on-line and off-line wavelengths of an airborne ozone DIAL. After being experimentally compared with Beta-Barium Borate (beta - BaB2O4 or BBO) nonlinear crystals, two Lithium Triborate (LBO) crystals (5 x 5 x 20 cu mm) are selected for the Third Harmonic Generation (THG). In this paper, we report the Ti:Sapphire laser at 900 nm and its third harmonic at 300 nm. The desired high ultraviolet (UV) output pulse energy is more than 30 mJ at 300 nm and the energy conversion efficiency from 900 nm to 300 nm is 30%.

Chen, Songsheng↗

Root Cause Analysis of Degradation in Protonic Ceramic Electrochemical Cell with Interfacial Electrical Sensors Using Data‐Driven Machine Learning

Abstract Protonic ceramic electrochemical cells (PCECs) offer promising paths for energy storage and conversion. Despite considerable achievements made, PCECs still face challenges such as physiochemical compatibility between componenets and suboptimal solid–solid contact at the interfaces between the electrolytes and electrodes. In this study, a novel approach is proposed that combines in situ electrochemical characterization of interfacial electrical sensor embedded PCECs and machine learning to quantify the contributions of different cell components to total degradation, as well as to predict the remaining useful life. The experimental results suggest that the overpotential induced by the oxygen electrode is 48% less than that of oxygen electrode/electrolyte interfacial contact for up to 1171 h. The data‐driven machine learning simulation predicts the RUL of up to 2132 h. The root cause of degradation is overpotential increase induced by oxygen electrode, which accounts for 82.9% of total cell degradation. The success of the failure diagnostic model is demonstrated by its consistency with degradation modes that do not manifest in electrolysis fade during early real operations. This synergistic approach provides valuable insights into practical failure diagnosis of PCECs and has the potential to revolutionize their development by enabling improved performance prediction and material selection for enhanced durability and efficiency.

25 ENERGY STORAGE↗

Critical research and advanced technology (CRT) support project

A critical technology base for utility and industrial gas turbines by planning the use of coal-derived fuels was studied. Development tasks were included in the following areas: (1) Combustion - investigate the combustion of coal-derived fuels and methods to minimize the conversion of fuel-bound nitrogen to NOx; (2) materials - understand and minimize hot corrosion; (3) system studies - integrate and focus the technological efforts. A literature survey of coal-derived fuels was completed and a NOx emissions model was developed. Flametube tests of a two-stage (rich-lean) combustor defined optimum equivalence ratios for minimizing NOx emissions. Sector combustor tests demonstrated variable air control to optimize equivalence ratios over a wide load range and steam cooling of the primary zone liner. The catalytic combustion of coal-derived fuels was demonstrated. The combustion of coal-derived gases is very promising. A hot-corrosion life prediction model was formulated and verified with laboratory testing of doped fuels. Fuel additives to control sulfur corrosion were studied. The intermittent application of barium proved effective. Advanced thermal barrier coatings were developed and tested. Coating failure modes were identified and new material formulations and fabrication parameters were specified. System studies in support of the thermal barrier coating development were accomplished.

Furman, E. R.↗

Mimicking Extradiol Dioxygenase Reactivity on Iridium

Extradiol dioxygenases catalyze the cleavage of benzenediol (catechol) or vicinal aminophenols via oxygen atom insertion into the 2,3- C–C bond. These reactions are most often proposed to proceed through the migratory rearrangement of a d6 alkylperoxide, generating the corresponding d 6 ring expanded product. However, regiospecific insertion remains a rare outcome among synthetic model complexes. Here, a dioxygenated Ir complex (2) converts to (a) the paramagnetic metallatrioxolane (3) and (b) oxygen atom inserted products (4) and (5); all three complexes are third-row metal analogues of enzymatic intermediates. The conversion of 2 to 3 was triggered by an H• abstraction, generating a third-row metallatrioxolane that is one electron reduced from the canonical d 6 alkylperoxide. Alternatively, photolysis of 2 (467 nm) results in ring-expanded product 4, from which an H• can be abstracted to generate 5. This latter complex is also one electron reduced relative to the canonical ring expansion product. Because extradiol mechanisms were largely defined using Fe(II) metallocofactors, 3 and 5 may be especially relevant to the known Co(II) accepting variants. We propose these states became synthetically accessible via the incorporation of a catechol-like substrate into the larger, multidentate ligand L1. This perturbation enhances the affinity of L1 (and related intermediates) to the metal. The same perturbation may have also been key in characterizing the first κ 2 -bound, dianionic ortho ester ligand – the observed binding mode in the x-ray structure of 5. Broadly, we propose through this case study that connecting abiological dioxygen complexes to non-heme oxygenase-like intermediates might be a “roadmap” towards regiospecific aerobic oxygenations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗