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At least 613 records · Page 34

Toward a NASA Deep Space Optical Communications System

As discussed at SpaceOps in 2016, we expect the data rates from deep space missions to increase approximately one order of magnitude per decade for the next 50 years. The first order of magnitude improvement will come from existing plans for radio frequency (RF) communications including enhancements to both spacecraft and Deep Space Network (DSN) facilities. The next two orders of magnitude are predicted to come from the introduction of deep space optical communications. Studies indicate that optical receive apertures of between 8m12m are desired. The large cost of dedicated receive telescopes makes this method unrealistic – at least in the near-term. The cost of large optical ground terminals is driven primarily by the cost of the optics and by the cost of a stable structure for the telescope. We propose a novel hybrid design in which existing DSN 34m beam waveguide (BWG) radio antennas can be modified to include an 8m equivalent optical primary. By utilizing a low-cost segmented spherical mirror optical design, pioneered by the optical astronomical community, and by exploiting the already existing extremely stable large radio aperture structures in the DSN, we can minimize both of these cost drivers for implementing large optical communications ground terminals. Two collocated hybrid RF/optical antennas could be arrayed to synthesize the performance of an 11.3m receive aperture to support more capable or more distant space missions or used separately to communicate with two optical spacecraft simultaneously. NASA is in the midst of building six new 34m BWG antennas in the DSN. The final two are planned to be built at the DSN Goldstone, California and Canberra complexes. We are now investigating building these last two antennas as RF/optical hybrids. By delaying their operational dates by two years, we would be able to add the 8m optical receive capability for these two antennas while fitting within existing budgetary constraints. This paper describes the hybrid antenna design, the technical challenges being addressed, and plan for using this concept, together with ongoing work on optical flight terminals, to infuse operation optical communications into deep space missions.

Cornwell, Donald M.↗

Toward Rational Design of Supported Vanadia Catalysts of Lignin Conversion to Phenol

In sustainable chemical engineering, catalytic upgrading of lignocellulosic biomass has recently gained attention for producing renewable platform chemicals. To achieve maximal biomass utilization, upgrading the underutilized lignin components is essential. Among various catalysts for lignin upgrading, supported vanadia (V2O5) catalysts are promising because of their cost-effectiveness and tunability of either dopant metals or catalyst supports. Here, computational studies are conducted to derive rational design guidelines of supported V2O5 catalysts for accomplishing the high catalytic activity of lignin upgrading to phenol, a key compound for producing bioplastics and biofuel blendstocks. Guaiacol was used as the model compound since it comprises the highest portion of depolymerized lignin. Computational mechanistic studies for the catalytic guaiacol conversion to phenol were performed for the V2O5 catalysts on Titania (TiO2) and silica (SiO2) to explain higher experimental phenol yields on V2O5/SiO2 than V2O5/TiO2. The hydrogen migration from the methoxy group to the aryl ring was identified as a rate-determining step, and the overall activation energies on the two catalysts were compared. A structural analysis was carried out for the catalysts and rate-determining transition states to gain further insights from mechanistic studies. It was concluded that the tilt angle of the aryl group in the hydrogen migration transition state is a key descriptor determining the catalytic activity of phenol formation. These features correlate well with activation energies and experimental phenol yields, indicating that they provide design guidelines for supported metal catalysts for lignin upgrading before experiments.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Review—Development of Highly Active and Durable Hybrid Compressive Platinum Lattice Catalysts for Polymer Electrolyte Membrane Fuel Cells: Mathematical Modeling and Experimental Work

This review provides a comprehensive overview on the development of highly active and durable platinum catalysts with ultra-low Pt loadings for polymer electrolyte membrane fuel cells (PEMFCs) through a combined mathematical modeling and experimental work. First, simulation techniques were applied to evaluate the validity of the Tafel approximation for the calculation of the mass activity (MA) and specific activity (SA). A one-dimensional agglomeration model was developed and solved to understand the effects of exchange current density, porosity, agglomerate size, Nafion ® film thickness, and Pt loading on the MA and SA. High porosity (> 60%) and agglomerations at high Pt loadings cause the loss of the Tafel approximation and consequently the decrease in MA and SA. A new structure parameter was introduced to estimate the real porous structure using the fractal theory. The volumetric catalyst density was corrected by the fractal dimension (measured by Hg porosimetry), which gave a good agreement with the experimental values. The loading-dependent Tafel equation was then derived, which contains both the utilization and the non-linear scaling factor. Second, activated carbon composite support (ACCS) with optimized surface area, porosity, pore size, and pore size distribution was developed. The hydrophilic/hydrophobic ratio, structural properties (amorphous/crystalline ratio), and the number of active sites were optimized through metal-catalyzed pyrolysis. Stability of ACCS and Pt/ACCS were evaluated using an accelerated stress test (AST). The results indicated that Pt/ACCS showed no significant loss of MA and power density after 5,000 cycles at 1.0–1.5 V, while the commercial Pt/C catalysts showed drastic losses of MA and power density. Finally, monolayers of compressed Pt (core–shell-type Pt 3 Co 1 ) catalysts were structured by diffusing Co atoms (previously embedded in ACCS) into Pt. Compressive Pt lattice (Pt * ) catalysts were synthesized through an annealing procedure developed at the University of South Carolina (USC). The Pt * /ACCS catalyst showed high initial power density (rated) of 0.174 g Pt kW −1 and high stability (24 mV loss) at 0.8 A cm −2 after 30,000 cycles (0.6–1.0 V). The outstanding performance of Pt * /ACCS is due to the synergistic effect of ACCS and compressive Pt * lattice.

25 ENERGY STORAGE↗

Minimizing Cr-Evaporation from Balance Of Plant Components By Utilizing Cost-Effective Alumina-Forming Austenitic Steels

A solid oxide fuel cell (SOFC) is a clean and efficient energy conversion device. The development of intermediate-temperature SOFCs has made it preferable to use metallic interconnects (MICs) to greatly reduce the cost and significantly increase the efficiency compared to ceramic interconnect materials. However, gaseous chromium species will evaporate from the chromium-containing layer formed on the surface of commonly used MICs and balance of plant (BoP) components. Volatile chromium species have been shown to form solid deposits which poison the cathodes of SOFCs, causing drastic cell performance degradation and thereby limiting commercialization. In order to alleviate the Cr poisoning and achieve long-term high performance of SOFC stacks, various Al 2 O 3 -forming austenitic (AFA) stainless steels applied at different temperatures are evaluated in this project. Based on our Phase I results (500 h operation), it is shown that on the AFAs, an alumina-based protective layer forms under high temperature that is invulnerable to water vapor effects and suppresses the diffusion of chromium and manganese which can prevent the generation of spinels on the alloy surface. Therefore, 310S, OC4 and OC5 at 800 °C and 625, OC11 and OC11LZ at 900 °C are selected to be tested in the Phase II long-term operation. From the results, we find that besides the lower Cr evaporation rates and better oxidation resistance of AFAs than benchmark alloys after short-term (500 h) operation, AFAs also possess the sturdy and compact alumina layer after a long-term operation (5000 h). A protective oxide layer is of great importance for the long-term high-temperature operation of structural materials. The high-temperature oxidation behavior of AFAs and commercial 310S and 625 alloys in Air + 10% H 2 O at 800 °C and 900 °C is systematically investigated. Severe breakaway oxidation and minor spallation are observed for the 310S and 625 after the long-term operation, while the AFAs show high oxidation resistance. It is found that the formation of a continuous alumina layer could greatly prevent the volatilization of chromium vapors. In addition, the corresponding evolving models are discussed. Chromium evaporation from BoP components in high-temperature environment could severely deteriorate the electrochemical performance of SOFC. Several methods were applied to evaluate the Cr evaporation rates of BoP after 500 h exposure at 800 °C to 900 °C in air with 10% H 2 O. An optimal method was designed to exclude the effect of silicon (Si) deposits from quartz tube and sodium (Na) deposits from the sodium carbonate on the oxidation process and the chemical interaction between Cr gaseous species and alumina tube which could provide further quantitative correlation of the evaporated Cr species quantities and degradation rates of SOFC. Based on the great performance of AFAs after long-term operation, AFAs are assembled with Anode-supported cells (ASC) to investigate the the Cr deposition of anode-supported cell under a constant current density of 0.5 A cm -2 at 800 °C with AFA alloys compared with commercial alloys. In addition, the anodic and cathodic processes are deconvoluted by distribution of relaxation times (DRT) method which are comprehensively discussed. It is found out that the voltage exhibited a slight decrease of 5.09 % and 1.54 % in the presence of OC11 and OC11LZA alloy, respectively. However, a considerable decrease of 22.14 % and 12.06 % was determined in the presence of 310S and 625 alloy, respectively. AFAs possessing the low-cost, low Cr evaporation rates and the high oxidation resistance will make it of great potential to replace the existing BoP components.

01 COAL, LIGNITE, AND PEAT↗

Low Regeneration Temperature Sorbents for Direct Air Capture of CO 2

Susteon Inc., in partnership with University of Wyoming and SoCalGas, successfully met all major technical objectives to (1) scale up the ionic liquid catalyst for amine-based sorbents for improved desorption and absorption kinetics, (2) evaluate the catalyzed amine-based sorbents for direct CO 2 capture process to determine CO 2 adsorption and desorption rates and energy requirements, and (3) based on the experimental results, develop a conceptual process design to perform a preliminary economic assessment to evaluate the potential for DAC process cost reduction using the catalyzed sorbents. Amine doped solid sorbents are effective for DAC applications and can be regenerated by heat or by a combination of heat, steam, and vacuum. The best sorbent composition identified was polyethyleneimine (PEI) on fumed silica with 200 ppm ionic liquid catalyst. This sorbent formulation was shown to have a CO 2 breakthrough capacity twice that of the non-catalyzed sorbent, in laboratory tests with air at 75% relative humidity (RH). The CO 2 adsorption rate was also 40% higher than that of the non-catalyzed sorbent. This type of sorbents has the attributes required for lowering the overall cost of DAC with high CO 2 capacity and high rate of adsorption. The combination of an industrially utilized amine-based sorbent with a highly active catalyst to form a new class of materials for DAC provides a technically viable pathway for reducing the cost of DAC to <$100/tonne of CO 2 . Laboratory measurements show that the silica/PEI (polyethyleneimine) sorbents with 100 ppm of ionic liquid catalyst have almost 100% higher CO 2 cyclic capacity and 40% higher adsorption rate. Generally, CO 2 desorption occurred at higher temperatures with a rate of desorption 10 times faster than adsorption (which occurred at ambient conditions). Therefore, adsorption rate is a much more important factor in the cost of DAC because it is directly linked to the CAPEX of the total system and the cycle time (i.e., sorbent productivity in ton/day of CO 2 captured per unit volume of the air contactor). An initial process design, coupled with techno-economic analysis, based on optimal experimental results and preliminary resulting from structured sorbent testing, showed a path to lower the DAC cost from the current cost of over $200/tonne CO 2 to less than $100/tonne with a scale-up, mature state of the technology, with projected material and process improvements. These results demonstrate the effectiveness of the catalyst in silica/PEI sorbents in enhancing sorbents’ CO 2 working capacity, in (a) increasing the rate of adsorption and desorption, and (b) in lowering the CAPEX and OPEX of the DAC system employing the ionic liquid catalyzed sorbents.

01 COAL, LIGNITE, AND PEAT↗

Strong temporal variation in treefall and branchfall rates in a tropical forest is related to extreme rainfall: results from 5 years of monthly drone data for a 50 ha plot

Abstract. A mechanistic understanding of how tropical-tree mortality responds to climate variation is urgently needed to predict how tropical-forest carbon pools will respond to anthropogenic global change, which is altering the frequency and intensity of storms, droughts, and other climate extremes in tropical forests. We used 5 years of approximately monthly drone-acquired RGB (red–green–blue) imagery for 50 ha of mature tropical forest on Barro Colorado Island, Panama, to quantify spatial structure; temporal variation; and climate correlates of canopy disturbances, i.e., sudden and major drops in canopy height due to treefalls, branchfalls, or the collapse of standing dead trees. Canopy disturbance rates varied strongly over time and were higher in the wet season, even though wind speeds were lower in the wet season. The strongest correlate of monthly variation in canopy disturbance rates was the frequency of extreme rainfall events. The size distribution of canopy disturbances was best fit by a Weibull function and was close to a power function for sizes above 25 m2. Treefalls accounted for 74 % of the total area and 52 % of the total number of canopy disturbances in treefalls and branchfalls combined. We hypothesize that extremely high rainfall is a good predictor because it is an indicator of storms having high wind speeds, as well as saturated soils that increase uprooting risk. These results demonstrate the utility of repeat drone-acquired data for quantifying forest canopy disturbance rates at fine temporal and spatial resolutions over large areas, thereby enabling robust tests of how temporal variation in disturbance relates to climate drivers. Further insights could be gained by integrating these canopy observations with high-frequency measurements of wind speed and soil moisture in mechanistic models to better evaluate proximate drivers and with focal tree observations to quantify the links to tree mortality and woody turnover.

54 ENVIRONMENTAL SCIENCES↗

An epitaxial surface heterostructure anchoring approach for high-performance Ni-rich layered cathodes

Nickel-rich (Ni≥90%) layered oxides materials have emerged as a promising candidate for next-generation high-energy-density lithium-ion batteries (LIBs). However, their widespread application is hindered by structural fatigue and lattice oxygen loss. In this work, an epitaxial surface rock-salt nanolayer is successfully developed on the LiNi 0.9 Co 0.1 O 2 sub-surface via heteroatom anchoring utilizing high-valence element molybdenum modification. This in-situ formed conformal buffer phase with a thickness of 1.2nm effectively suppresses the continuous interphase side-reactions, and thus maintains the excellent structure integrity at high voltage. Furthermore, theoretical calculations indicate that the lattice oxygen reversibility in the anion framework of the optimized sample is obviously enhanced due to the higher content of O 2p states near the Fermi level than that of the pristine one. Meanwhile, the stronger Mo–O bond further reduces cell volume alteration, which improves the bulk structure stability of modified materials. Besides, the detailed charge compensation mechanism suggests that the average oxidation state of Ni is reduced, which induces more active Li + participating in the redox reactions, boosting the cell energy density. As a result, the uniquely designed cathode materials exhibit an extraordinary discharge capacity of 245.4 mAh g −1 at 0.1 C, remarkable rate performance of 169.3 mAh g −1 at 10 C at 4.5V, and a high capacity retention of 70.5% after 1000 cycles in full cells at a high cut-off voltage of 4.4V. Further, this strategy provides an valuable insight into constructing distinctive heterostructure on high-performance Ni-rich layered cathodes for LIBs.

25 ENERGY STORAGE↗

Potential Evaporite Biomarkers from the Dead Sea

The Dead Sea is located on the northern branch of the African-Levant Rift systems. The rift system, according to one model, was formed by a series of strike slip faults, initially forming approximately two million years ago. The Dead Sea is an evaporite basin that receives freshwater from springs and from the Jordan River. The Dead Sea is different from other evaporite basins, such as the Great Salt Lake, in that it possesses high concentrations of magnesium and has an average pH of 6.1. The dominant cation in the Great Salt Lake is sodium, and the pH is 7.7. Calcium concentrations are also higher in the Dead Sea than in the Great Salt Lake. Both basins are similar in that the dominant anion is chlorine and the salinity levels are approximately 20 %. Other common cations that have been identified from the waters of the Dead Sea and the Great Salt Lake include sodium and potassium. A variety of Archea, Bacteria, and a single genus of a green algal, Dunaliella, has been described from the Dead Sea. Earlier studies concentrated on microbial identification and analysis of their unique physiology that allows them to survive in this type of extreme environment. Potential microbial fossilization processes, microbial fossils, and the metallic ions associated with fossilization have not been studied thoroughly. The present study is restricted to identifying probable microbial morphologies and associated metallic ions. XRD (X Ray Diffraction) analysis indicates the presence of halite, quartz, and orthoclase feldspar. In addition to these minerals, other workers have reported potassium chloride, magnesium bromide, magnesium chloride, calcium chloride, and calcium sulfate. Halite, calcium sulfate, and orthoclase were examined in this report for the presence of microbes, microbially induced deposits or microbial alteration. Neither the gypsum nor the orthoclase surfaces possesses any obvious indications of microbial life or fossilization. The sand-sized orthoclase particles are weathered with 122 extensive fan-shaped mineral deposits. The gypsum deposits are associated with halite minerals and also exhibit extensive weathering. Halite minerals represent the only substrates that have probable rod-shaped microbial structures with long, filamentous, apical extensions. EDS (energy dispersive x-ray) analysis of the putative microbes indicates elevated calcium levels that are enriched with magnesium. The rod-shaped structures exhibit possible fossilization stages. Rhombohedralshaped minerals of magnesium-enriched calcium carbonate are deposited on the microbial surfaces, and eventually coat the entire microbial surface. The sodium chloride continues to crystallize on nearby halite surface and even crystallizes on the fossilized microbial remains. The putative fossils are found exclusively on halite surfaces, and all contained elevated levels of calcium magnesium cations. Both of these metallic cations are associated with microbial activity and fossilization. Their morphological diversity is low in comparison with the reported living Dead Sea microbial population. If we examine the fossil record for multicellular organisms, fossilization rates are lower for soft-bodied organisms than for those possessing hard parts, i.e. shells, bones. For example, smaller, single celled organisms would have a smaller chance of fossilization; their fossilized shapes could be mistaken for abiotic products. Another consideration is that dead organisms in the water column are probably utilized as a food source by other microbes before fossilization processes are completed. This may be an important consideration as we attempt to model and interpret ancient microbial environments either on Earth or on Mars.

Morris, Penny A.↗

Viscoplastic Constitutive Theory Demonstrated for Monolithic Ceramic Materials

Development of accurate three-dimensional (multiaxial) inelastic stress-strain models is critical in utilizing advanced ceramics for challenging 21st century high-temperature structural applications. The current state of the art uses elastic stress fields as a basis for both subcritical crack growth and creep life prediction efforts aimed at predicting the time dependent reliability response of ceramic components subjected to elevated service temperatures. However, to successfully design components that will meet tomorrow's challenging requirements, design engineers must recognize that elastic predictions are inaccurate for these materials when subjected to high-temperature service conditions such as those encountered in advanced heat engine components. Analytical life prediction methodologies developed for advanced ceramics and other brittle materials must employ accurate constitutive models that capture the inelastic response exhibited by these materials at elevated service temperatures. A constitutive model recently developed at the NASA Lewis Research Center helps address this issue by accounting for the time-dependent (inelastic) material deformation phenomena (e.g., creep, rate sensitivity, and stress relaxation) exhibited by monolithic ceramics exposed to high-temperature service conditions. In addition, the proposed formulation is based on a threshold function that is sensitive to hydrostatic stress and allows different behavior in tension and compression, reflecting experimental observations obtained for these material systems.

Janosik, Lesley A.↗

Evaluation of Silicon-on-Insulator HTOP-01 Operational Amplifier for Wide Temperature Operation

Electronics capable of operation under extreme temperatures are required in many of NASA space exploration missions. Aerospace and military applications, as well as some terrestrial industries constitute environments where electronic systems are anticipated to be exposed to extreme temperatures and wide-range thermal swings. Electronics that are able to withstand and operate efficiently in such harsh environments would simplify, if not eliminate, traditional thermal control elements and their associated structures for proper ambient operation. As a result, overall system mass would be reduced, design would be simplified, and reliability would be improved. Electronic parts that are built utilizing silicon-on-insulator (SOI) technology are known to offer better radiation-tolerance compared to their conventional silicon counterparts, provide faster switching, and consume less power. They also exhibit reduced leakage current and, thus, they are often tailored for high temperature operation. These attributes make SOI-based devices suitable for use in harsh environments where extreme temperatures and wide thermal swings are anticipated. A new operational amplifier, based on silicon-on-insulator technology and geared for high temperature well-logging applications, was recently introduced by Honeywell Corporation. This HTOP-01 dual precision operational amplifier is a low power device, operates on a single supply, and has an internal oscillator and an external clocking option [1]. It is rated for operation from -55 C to +225 C with a maximum output current capability of 50 mA. The amplifier chip is designed as a 14-pin, hermetically-sealed device in a ceramic package. Table I shows some of the device manufacturer s specifications.

Patterson, Richard↗

Characterization of compositional variation and solidification condition on rapid solidification behavior of beta stabilized titanium

Rapid solidification (RS) is a field of study that has increased in importance due to the rise of additive manufacturing (AM) techniques. The breakdown of equilibrium at the solid-liquid interface results in an inability to use traditional solidification models that have been applied to great success in casting. As such, there is a current need for a high-throughput testing method to screen alloys at rapid solidification conditions without the significant cost for powder atomization. In this work, twin hammer splat quenching (SQ) is utilized and theoretically developed as a technique uniquely placed to test alloy systems for AM applications. Using analytical thermal spray models and numerical heat transfer simulations, the cooling rate and solidification conditions of splat quenching are compared across several parameters to evaluate the key parameters for generating cooling rates relevant to AM process. Once a framework for the cooling rates and relevancy of SQ are developed, SQ was used to process alloy compositions in the Ti5553 alloy space (AMS 7026) to study the formation of detrimental secondary phases occurring upon rapid quenching from the melt. A martensitic phase is found to occur at the lower end of the standard, but the composition listed in the standard were found to be safe. Finally, the rapid solidification behavior of Ti-5553 is evaluated by comparing splat quenching, laser welding, and plasma atomization that offer a wide window of solidification conditions. The segregation and solidification structure are analyzed and compared to models to provide a deeper understanding of the solidification behavior of beta stabilized titanium alloys.

Williamson, Christopher J.↗

Nitrogen-Doped PtNi Catalysts on Polybenzimidazole-Functionalized Carbon Support for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

PtM (M = 3d transition metals) alloys are known as the promising oxygen reduction reaction catalysts and have been considered as the replacement of pure Pt catalysts for the commercialization of proton exchange membrane fuel cells. Although great progress has been made in the past three decades, the performance and durability of PtM catalysts still face stringent challenges from practical applications. Functionalization of a catalyst carbon support with nitrogen-contained groups can add charges onto its surface, which can be utilized to build a more complete ionomer/catalyst interface, to reduce the catalyst particle size, and to improve particle size distribution. Nitriding of PtNi catalysts can effectively improve the catalyst activity and stability by the modification of lattice strain. Hereby, we propose a synergistic approach of combining polybenzimidazole-grafted Vulcan XC72 carbon as the catalyst carbon support and the nitriding of PtNi to develop PtNiN/XC72-polybenzimidazole catalysts. Such PtNiN/XC72-PBI catalysts exhibit the excellent performance of fuel cell membrane electrode assembly (i.e., mass activity, 440 mA mgPt –1 ; electrochemical surface area, 51 m 2 gPt –1 ; and rated power density, 836 mW cm –2 ) as well as promising catalyst stability. The developed PtNiN/XC72-PBI meets the US DOE 2020 targets of mass activity for the fuel cell catalysts. This work provides a novel approach and a promising pathway on the development of the catalyst using such a synergistic approach-modification of the catalyst structure by nitrogen doping and functionalization of carbon support by polybenzimidazole for both high performance and high durability.

25 ENERGY STORAGE↗

Design of a Multi-Chemistry Battery Pack System for Behind-the-Meter Storage Applications

Battery management systems (BMS) are essential for a battery pack's safe operation and longevity. This paper presents an active balancing method-based BMS for different cell chemistry structures to be used in behind-the-meter storage (BTMS) applications. The proposed system utilizes modular isolated dual active bridge (DAB) DC/DC converters to actively balance the battery pack through a low voltage (LV) bus. A supervisory controller monitors all the cell voltage, current, and state of charge (SOC) values. Based on the estimation of the SOCs, reference currents for the DAB converters are generated by the supervisory controller. Detailed modeling and the control approach of the modular DAB converters are presented in the paper. Moreover, the control strategy of the supervisory control is also analyzed. The proposed method and structure can be extended to any combination of the number of cells to design the battery pack. Simulation results are provided for a system consisting of three cells in parallel to form a cell block and three cell blocks in series to form the battery module. Experimental results are provided for three modular DAB converters operating with a LiFeMnPO4 prismatic cell with 3.2V, 20Ah rated values.

battery management systems↗

Optimal Recursive Digital Filters for Active Bending Stabilization

In the design of flight control systems for large flexible boosters, it is common practice to utilize active feedback control of the first lateral structural bending mode so as to suppress transients and reduce gust loading. Typically, active stabilization or phase stabilization is achieved by carefully shaping the loop transfer function in the frequency domain via the use of compensating filters combined with the frequency response characteristics of the nozzle/actuator system. In this paper we present a new approach for parameterizing and determining optimal low-order recursive linear digital filters so as to satisfy phase shaping constraints for bending and sloshing dynamics while simultaneously maximizing attenuation in other frequency bands of interest, e.g. near higher frequency parasitic structural modes. By parameterizing the filter directly in the z-plane with certain restrictions, the search space of candidate filter designs that satisfy the constraints is restricted to stable, minimum phase recursive low-pass filters with well-conditioned coefficients. Combined with optimal output feedback blending from multiple rate gyros, the present approach enables rapid and robust parametrization of autopilot bending filters to attain flight control performance objectives. Numerical results are presented that illustrate the application of the present technique to the development of rate gyro filters for an exploration-class multi-engined space launch vehicle.

Orr, Jeb S.↗

Surface Dynamics of Selective Hydration of Rutile TiO 2 : A Kinetic Monte Carlo Approach

The utility of atomic layer deposition (ALD) continues to expand beyond conformal thin-film fabrication to include area- or site-selective ALD. We previously identified a strategy for site-selective ALD (SS-ALD) via the evaluation of thermodynamically preferred hydration of rutile TiO 2 surfaces, as deduced from electronic structure calculations. Here, we report a novel kinetic Monte Carlo (KMC) model that allows for the investigation of surface dynamics and kinetics that improves our understanding of and intuition for the selective hydration strategy. Here we demonstrate the validity of the strategy with respect to step-edge defects for the lowest energy (110) facet as well as report results for the other common facets which agree with experimental STM observations. The results here indicate that the selective hydration strategy is feasible both thermodynamically (evaluated in our previous publication) and kinetically (from the KMC model). Because diffusion has a slower rate than others, we find that any proximity effects between terrace and defect sites are unlikely to affect the selective hydration strategy for rutile TiO 2 . The KMC model further provides relevant timescales for achieving selectivity experimentally and establishes the kinetic viability of the selective hydration approach to SS-ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoinitiator Selection and Concentration in Photopolymer Formulations towards Large-Format Additive Manufacturing

Photopolymers are an attractive option for large-format additive manufacturing (LFAM), because they can be formulated from structural thermosets and cure rapidly in ambient conditions under low-energy ultraviolet light-emitting diode (UV LED) lamps. Photopolymer cure is strongly influenced by the depth penetration of UV light, which can be limited in the 2–4 mm layer thicknesses typical of LFAM. Photoinitiator (PI) systems that exhibit photobleaching have proven useful in thick-section cure applications, because they generate a photoinitiation wavefront, but this effect is time-dependent. This study investigates the light transmission and through-thickness cure behavior in (meth)acrylate photopolymer formulations with the photobleaching initiator bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BAPO). Utilizing an optical model developed by Kenning et al., lower concentrations (0.1 wt% to 0.5 wt%) of BAPO were predicted to yield rapid onset of photoinitiation. In situ cure measurements under continuous UV LED irradiation of 380 mW/cm2 showed that a 0.1 wt% concentration of BAPO achieved peak polymerization rate within 2.5 s at a 3-mm depth. With only 1 s of irradiation at 1.7 W/cm2 intensity, the 0.1 wt% BAPO formulation also achieved the highest level of cure of the formulas tested. For an irradiation dose of 5.5 J/cm2 at a duration of 3.7 s, cured polymer specimens achieved a flexural strength of 108 MPa and a flexural modulus of 3.1 GPa. This study demonstrates the utility of optical modeling as a potential screening tool for new photopolymer formulations, primarily in identifying an upper limit to PI concentration for the desired cure depth. The results also show that photobleaching provides only a limited benefit for LFAM applications with short (1.0 s to 3.7 s) UV irradiation times and indicate that excess PI concentration can inhibit light transmission even under extended irradiation times up to 60 s.

36 MATERIALS SCIENCE↗

Multi-Scale Modeling of Global of Magnetospheric Dynamics

To understand the role of magnetic reconnection in global evolution of magnetosphere and to place spacecraft observations into global context it is essential to perform global simulations with physically motivated model of dissipation that is capable to reproduce reconnection rates predicted by kinetic models. In our efforts to bridge the gap between small scale kinetic modeling and global simulations we introduced an approach that allows to quantify the interaction between large-scale global magnetospheric dynamics and microphysical processes in diffusion regions near reconnection sites. We utilized the high resolution global MHD code BATSRUS and incorporate primary mechanism controlling the dissipation in the vicinity of reconnection sites in terms of kinetic corrections to induction and energy equations. One of the key elements of the multiscale modeling of magnetic reconnection is identification of reconnection sites and boundaries of surrounding diffusion regions where non-MHD corrections are required. Reconnection site search in the equatorial plane implemented in our previous studies is extended to cusp and magnetopause reconnection, as well as for magnetotail reconnection in realistic asymmetric configurations. The role of feedback between the non-ideal effects in diffusion regions and global magnetosphere structure and dynamics will be discussed.

Kuznetsova, M. M.↗

Highly Reversible Plating/Stripping of Porous Zinc Anodes for Multivalent Zinc Batteries

Zinc continues to garner immense interest due to its versatility as an anode material in several configurations utilizing either alkaline or mild-pH electrolytes. Current research on using mild-pH electrolytes has improved the rechargeability aspect of Zn-based batteries since Zn2+ is solely utilized for plating/stripping of Zn. Several studies have incorporated Zn metal foils, yet, dramatic improvements can be achieved by expressing Zn as a porous structure. Herein, we use a quasi-pulsed electrodeposition process to prepare a conformal Zn coating onto 3D porous copper foam. By tuning the electrodeposition parameters, we achieved an optimal Zn coating that undergoes reversible plating/stripping when tested in symmetric Zn cells, which supported a low overpotential of ~60 mV for up to 100 cycles. We further investigated changes in the surface morphology by studying the Zn surface of both foil and 3D structure using scanning electron microscopy and X-ray micro-computed tomography. Both techniques showed that the Zn foil undergoes dramatic alterations at the surface, which results in inhomogeneous deposition of Zn, whereas the 3D form exhibited minimal changes. Lastly, we paired both Zn foil and 3D Zn with vanadium oxide and demonstrated that the porous structure supports high rate capability and high specific capacity.

25 ENERGY STORAGE↗