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Surface structure of water from soft X-ray second harmonic generation

The microscopic structure of water’s surface is crucial to many natural and industrial processes, but studying its hydrogen bond (H-bond) network directly remains challenging due to the required interfacial sensitivity of experimental techniques. By leveraging advances in flat liquid sheet microjets and terawatt-scale attosecond soft X-ray pulses from the LCLS X-ray free electron laser, we employed soft X-ray second harmonic generation (SXSHG) spectroscopy to examine the liquid water/vapor interface. SXSHG combines the elemental selectivity of X-ray spectroscopies with the surface selectivity of SHG and gives access to the electronic structure of interfacial species. Here, we show the SXSHG spectrum differs from bulk water’s X-ray absorption, with its peak shifted several eV, indicating a vastly different electronic environment at the interface as compared to the bulk. First-principles electronic structure calculations show the signal is highly sensitive to H-bond interactions, such as water molecules accepting a single H-bond, which are surface abundant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Herbaceous Feedstock 2022 State of Technology Report

The U.S. Department of Energy promotes production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the state of technology (SOT). As part of its involvement in this mission, Idaho National Laboratory completes an annual SOT report for nth-plant and 1st-plant herbaceous biomass feedstock logistics. The purpose of the SOT is to provide the status of feedstock supply system technology development for herbaceous biomass to biofuels relative to technical targets and cost goals from specific design cases, based on data and experimental results. Although conventional feedstock supply systems form the backbone of the emerging biofuels industry, they have limitations that restrict widespread implementation on a national scale. To meet the demands of the future industry, the feedstock supply system must shift from the conventional system to what has been termed “advanced” supply systems. In advanced designs, a distributed network of aggregation and processing centers, termed “depots,” are employed near the points of biomass production (i.e., the field or forest) to reduce feedstock variability and produce feedstocks of a uniform format, moving toward biomass commoditization. The 2022 Herbaceous SOT is part of a vision of achieving an implemented advanced feedstock supply system, which produces a stable, tradable commodity at the decentralized distributed depot. It utilizes feedstock fractionation by incorporating technologies that can separate the biomass into its anatomical fractions (leaves, husks, stems and cobs) to reduce impurities and produce fractions that satisfy downstream quality considerations. By using a series of air classification steps, this strategy can reduce the extrinsic ash in corn stover and produce enriched tissue fractions that can be blended to a conversion specification or converted individually in optimized biochemical conversion campaigns. Additionally, a majority of the leaves (which do not meet the quality specification) are separated out early and can be supplied to alternate markets. The 2022 Herbaceous SOT incorporates an advanced biomass fractionation and processing system to produce pellets enriched tissues from three-pass corn stover. The resulting enriched pellets are delivered to the biorefinery individually where they can be blended to a specification or converted in campaigns where the conditions are optimized for each tissue. Unused fractions can be sent to a a midstream market or to a different conversion process that is better suited to their properties to offset the cost of the delivered feedstock. The main benefits from the proposed system can be summarized as: (1) $6.86/dry ton (2016$) lower cost for the air classification due to elimination of the requirement to discard the high ash lights fraction; (2) $1.56/dry ton lower delivered cost by selling the unsuitable leaf fraction into the feed market as a midstream co-product (assuming a selling price that is 11% higher than their cost of production); (3) 0.98% increase in carbohydrate content (from 60.16% to 61.14%); and (4) 0.97% decrease in ash content (from 6.00% to 5.03%) compared to the 2021 Herbaceous SOT. Overall, the 2022 nth-plant Herbaceous SOT predicts a modeled delivered feedstock cost of $78.64/dry ton (2016$) if it is assumed that the enriched leaf fraction is sold at its production cost; this is a slight increase of $0.43/dry ton increase from the 2021 Herbaceous SOT nth-Supply case cost. The increased cost derived from a $0.38/dry ton increase in transportation and handling cost to procure more biomass (to replace the enriched leaf fraction that was not delivered to the biorefinery. The total preprocessing cost was $0.27/dry ton higher than the 2021 result because of updates to energy consumption, purchasing price and dry matter loss data for the rotary shear ($3.00/dry ton increase) and the pelleting mill ($4.52/dry ton increase). The data utilized were generated in pilot-scale tests in the Biomass Feedstock National User Facility (BFNUF) at INL and at Forest Concepts, including tests for rotary shear and pelleting of the air classified fractions. A greenhouse gas emissions analysis was performed by Argonne National Laboratory using the most up to date version of the Greenhouse Gases, Regulated Emissions, and Energy use in Transportation model (GREET®). The analysis showed an increase of 17.34 kg CO2e/dry ton from the 2021 SOT (67.71 kg CO2e/ton in the 2021 Herbaceous SOT to 85.05 kg CO2e/ton in the 2022 Herbaceous SOT). The net increase is primarily attributed to increased energy consumption in pelleting mill.

09 BIOMASS FUELS↗

Differential Radiometers Using Fabry-Perot Interferometric Technique for Remote Sensing Determination of Various Atmospheric Trace Gases

New type of remote sensing instrument based upon the Fabry-Perot inte rferometric technique has been developed at NASA's Goddard Space Flight Center. Fabry-Perot interferometry (FPI) is a well known, powerful spectroscopic technique and one of its many applications is to be use d to measure greenhouse gases and also some harmful species in the at mosphere. With this technique, absorption of particular species is me asured and related to its concentration. A solid Fabry-Perot etalon is used as a frequency filter to restrict the measurement to particular absorption bands of the gas of interest. With adjusting the thicknes s of the etalon that separation (in frequency) of the transmitted fri nges can be made equal to the almost constant separation of the gas a bsorption lines. By adjusting the temperature of the etalon, which changes the index of refi-action of its material, the transmission fring es can be brought into nearly exact correspondence with absorption li nes of the particular species. With this alignment between absorption lines and fringes, changes in the amount of a species in the atmosph ere strongly affect the amount of light transmitted by the etalon and can be related to gas concentration. The instrument that we have dev eloped detects the absorption of various atmospheric trace gases in d irect or reflected sunlight. Our instrument employing Fabry-Perot interferometer makes use of two features to achieve high sensitivity. The first is high spectral resolution enabling one to match the width of an atmospheric absorption feature by the instrumental band pass. The second is high optical throughput enabled by using multiple spectral lines simultaneously. For any species that one wishes to measure, thi s first feature is available while the use of multiple spectral features can be employed only for species with suitable spectra and freedom from interfering species in the same wavelength region. We have deve loped an instrument for use as ground based, airborne and satellite s ensor for gases such as carbon dioxide (1570 nm), oxygen (762 nm and 768 nm lines sensitive to changes in oxygen pressure and oxygen temper ature) and water vapor (940 nm). Our current goal is to develop an ul tra precise, inexpensive, ground based device suitable for wide deplo yment as a validation instrument for the Orbiting Carbon Observatory (OCO) satellite. We show sensitivity measurements for CO2, 02, and H2 O, compare our measurements to those obtained using other types of sensors and discuss some of the peculiarities that must be addressed in order to provide the very high quality column detection required for solving problems about global distribution of greenhouse gases and cl imatological models. In another area of research we are interested in developing a small-size channel for CO2 capable of doing simultaneous measurements with the AERONET (Aerosol Robotic Network) at NASA, God dard to study the hypothesis that atmospheric aerosols affect the reg ional terrestrial carbon cycle. We present recent data from our groun d based measurements of O2, CO2, H2O and (13)CO2 and discuss extensio n of the technique to new species and applications.

Georgieva, E. M.↗

Wireless Temperature-Monitoring System

A relatively inexpensive instrumentation system that includes units that are connected to thermocouples and that are parts of a radio-communication network has been developed to enable monitoring of temperatures at multiple locations. Because there is no need to string wires or cables for communication, the system is well suited for monitoring temperatures at remote locations and for applications in which frequent changes of monitored or monitoring locations are needed. The system can also be adapted to monitoring of slowly varying physical quantities, other than temperature, that can be transduced by solid-state electronic sensors. electronic sensors. The system comprises any number of transmitting units and a single receiving unit. Each transmitting unit includes connections for as many as four external thermocouples, a signal-conditioning module, a control module, and a radio-communication module. The signal-conditioning module acts as an interface between the thermocouples and the rest of the transmitting unit and includes a built-in solid ambient temperature sensor that is in addition to the external thermocouples. The control module is a system-on-chip embedded processor that includes analog-to-digital converters, serial and parallel data ports, and an interface for local connection to an analog meter that is used during installation to verify correct operation. The radio-communication module contains a commercial spread-spectrum transceiver that operates in the 900-MHz industrial, scientific, and medical (ISM) frequency band. This transceiver transmits data to the receiving unit at a rate of 19,200 baud. The receiving unit includes a transceiver like that of a transmitting unit, plus a control module that contains a system-on-chip processor that includes serial data port for output to a computer that runs monitoring and/or control software, a parallel data port for output to a printer, and a seven-segment light-emitting-diode display. Each transmitting unit is battery-powered and can operate for at least seven days continuously while reporting temperatures every half hour. The receiving unit is powered by a wall-mounted transformer source. The receiving unit responds to each transmitting unit and reports the readings of each of the four thermocouples and of the ambient-temperature sensor of the transmitting unit. The end-to-end accuracy of the system is plus or minus 0.2 C over the temperature range from 0 to 100 C. The radio-communication range between the receiving and transmitting units is approximately equal to 0.5 mile (approximately equal to 0.8 km).

Solano, Wanda↗

Wireless Temperature-Monitoring System

A relatively inexpensive instrumentation system that includes units that are connected to thermocouples and that are parts of a radio-communication network has been developed to enable monitoring of temperatures at multiple locations. Because there is no need to string wires or cables for communication, the system is well suited for monitoring temperatures at remote locations and for applications in which frequent changes of monitored or monitoring locations are needed. The system can also be adapted to monitoring of slowly varying physical quantities, other than temperature, that can be transduced by solid-state electronic sensors. The system comprises any number of transmitting units and a single receiving unit (see figure). Each transmitting unit includes connections for as many as four external thermocouples, a signal-conditioning module, a control module, and a radio-communication module. The signal- conditioning module acts as an interface between the thermocouples and the rest of the transmitting unit and includes a built-in solid ambient-temperature sensor that is in addition to the external thermocouples. The control module is a "system-on-chip" embedded processor that includes analog-to-digital converters, serial and parallel data ports, and an interface for local connection to an analog meter that is used during installation to verify correct operation. The radio-communication module contains a commercial spread-spectrum transceiver that operates in the 900-MHz industrial, scientific, and medical (ISM) frequency band. This transceiver transmits data to the receiving unit at a rate of 19,200 baud. The receiving unit includes a transceiver like that of a transmitting unit, plus a control module that contains a system-on-chip processor that includes serial data port for output to a computer that runs monitoring and/or control software, a parallel data port for output to a printer, and a seven-segment light-emitting-diode display.

Solano, Wanda↗

Spatial Predictive Modeling and Remote Sensing of Land Use Change in the Chesapeake Bay Watershed

This project was focused on modeling the processes by which increasing demand for developed land uses, brought about by changes in the regional economy and the socio-demographics of the region, are translated into a changing spatial pattern of land use. Our study focused on a portion of the Chesapeake Bay Watershed where the spatial patterns of sprawl represent a set of conditions generally prevalent in much of the U.S. Working in the region permitted us access to (i) a time-series of multi-scale and multi-temporal (including historical) satellite imagery and (ii) an established network of collaborating partners and agencies willing to share resources and to utilize developed techniques and model results. In addition, a unique parcel-level tax assessment database and linked parcel boundary maps exists for two counties in the Maryland portion of this region that made it possible to establish a historical cross-section time-series database of parcel level development decisions. Scenario analyses of future land use dynamics provided critical quantitative insight into the impact of alternative land management and policy decisions. These also have been specifically aimed at addressing growth control policies aimed at curbing exurban (sprawl) development. Our initial technical approach included three components: (i) spatial econometric modeling of the development decision, (ii) remote sensing of suburban change and residential land use density, including comparisons of past change from Landsat analyses and more traditional sources, and (iii) linkages between the two through variable initialization and supplementation of parcel level data. To these we added a fourth component, (iv) cellular automata modeling of urbanization, which proved to be a valuable addition to the project. This project has generated both remote sensing and spatially explicit socio-economic data to estimate and calibrate the parameters for two different types of land use change models and has undertaken analyses of these models. One (the CA model) is driven largely by observations on past patterns of land use change, while the other (the EC model) is driven by mechanisms of the land use change decision at the parcel level. Our project may be the first serious attempt at developing both types of models for the same area, using as much common data as possible. We have identified the strengths and weaknesses of the two approaches and plan to continue to revise each model in the light of new data and new lessons learned through continued collaboration. Questions, approaches, findings, publication and presentation lists concerning the research are also presented.

Goetz, Scott J.↗

Heat Integration Optimization and Dynamic Modeling Investigation for Advancing the Coal-Direct Chemical Looping Process

The purpose of the project is to address the optimization and startup operation of a modular coal direct chemical looping (CDCL) combustion system integrated with a steam cycle for power generation to reduce the risks involved in further scale-up of the technology. The modular reactor design of the CDCL process provides flexibility in the fabrication of the reactor and in its operating capacity (i.e. turndown ratio) at the cost of a more complex heat exchange network (HEN) design and integration. To address the technology gaps and advance the efficiency and economic feasibility of the CDCL technology, the project will perform a detailed and comprehensive analysis of the integration of a modular CDCL reactor system and a steam cycle system under both static and transient conditions via HEN process performance simulations and system dynamic modeling, respectively. The scope of work consists of 1) Experimental and computational studies of the CDCL combustor reactor 2) Comprehensive static (i.e. steady-state) system HEN design analysis in CDCL 550 MWe commercial unit for power generation and 3) Dynamic modeling of site specific design of 10MWe CDCL large pilot plant. The project team has successfully developed and validated a kinetic model for the oxidation of oxygen carriers in the combustor using the unreacted shrinking core model (UCSM). The model is capable of capturing the oxidation kinetics of fully or partially reduced oxygen carrier particles. A computational fluid dynamics (CFD) model is developed to simulate the hydrodynamics, heat transfer, and chemical reaction occurring in the CDCL combustor. The model is developed in MFIX and ANSYS Fluent. Key aspects of CDCL combustor operation, including heat transfer, oxygen carrier oxidation, and the transport of oxygen carrier particles, are simulated using this CFD model. The HEN for a commercial scale 550 MWe CDCL power plant is simulated and optimized using ASPEN Plus. Practical design considerations are incorporated based on industrial experiences. The performance and cost for the commercial CDCL plant is updated based on these analyses. A dynamic model for the 10 MWe CDCL pilot plant is developed in ProTRAX simulation software. The model is based on the pilot plant design developed in project DE-FE0027654 “10 MWe CDCL Large Pilot Plang – Pre-FEED Study” and the steam cycle data obtained from Dover Light & Power plant. The transient behaviors during pilot plant load variation are simulated using the dynamic model.

01 COAL, LIGNITE, AND PEAT↗

End-to-end jet classification of boosted top quarks with the CMS open data

Here we describe a novel application of the end-to-end deep learning technique to the task of discriminating top quark-initiated jets from those originating from the hadronization of a light quark or a gluon. The end-to-end deep learning technique uses low-level detector representation of high-energy collision event as inputs to deep learning algorithms. In this study, we use low-level detector information from the simulated Compact Muon Solenoid (CMS) open data samples to construct the top jet classifiers. To optimize classifier performance we progressively add low-level information from the CMS tracking detector, including pixel detector reconstructed hits and impact parameters, and demonstrate the value of additional tracking information even when no new spatial structures are added. Relying only on calorimeter energy deposits and reconstructed pixel detector hits, the end-to-end classifier achieves an area under the receiver operator curve (AUC) score of 0.975 ± 0.002 for the task of classifying boosted top quark jets. After adding derived track quantities, the classifier AUC score increases to 0.9824 ± 0.0013, serving as the first performance benchmark for these CMS open data samples.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis

Bismuth-oxocluster nodes for metal–organic frameworks (MOFs) and coordination networks/polymers are less prolific than other families featuring zinc, zirconium, titanium, lanthanides, etc. However, Bi 3+ is non-toxic, it readily forms polyoxocations, and its oxides are exploited in photocatalysis. This family of compounds provides opportunity in medicinal and energy applications. Here, we show that Bi node nuclearity depends on solvent polarity, leading to a family of Bi x -sulfonate/carboxylate coordination networks with x = 1–38. Larger nuclearity-node networks were obtained from polar and strongly coordinating solvents, and we attribute the solvent’s ability to stabilize larger species in solution. Here, the strong role of the solvent and the lesser role of the linker in defining node topologies differ from other MOF syntheses, and this is due to the Bi 3+ intrinsic lone pair that leads to weak node–linker interactions. We describe this family by single-crystal X-ray diffraction (eleven structures), obtained in pure forms and high yields. Ditopic linkers include NDS (1,5-naphthalenedisulfonate), DDBS (2,2'-[biphenyl-4,4'-diylchethane-2,1-diyl] dibenzenesulphonate), and NH 2 -benzendicarboxylate (BDC). While the BDC and NDS linkers yield more open-framework topologies that resemble those obtained by carboxylate linkers, topologies with DDBS linkers appear to be in part driven by association between DDBS molecules. An in situ small-angle X-ray scattering study of Bi 38 -DDBS reveals stepwise formation, including Bi 38 -assembly, pre-organization in solution, followed by crystallization, confirming the less important role of the linker. We demonstrate photocatalytic hydrogen (H 2 ) generation with select members of the synthesized materials without the benefit of a co-catalyst. Band gap determination from X-ray photoelectron spectroscopy (XPS) and UV–vis data suggest the DDBS linker effectively absorbs in the visible range with ligand-to-Bi-node charge transfer. In addition, materials containing more Bi (larger Bi 38 -nodes or Bi 6 inorganic chains) exhibit strong UV absorption, also contributing to effective photocatalysis by a different mechanism. All tested materials became black with extensive UV–vis exposure, and XPS, transmission electron microscopy, and X-ray scattering of the black Bi 38 -framework suggest that Bi o is formed in situ, without phase segregation. This evolution leads to enhanced photocatalytic performance, perhaps due to increased light absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Communications from Planetary Distances

Future planetary campaigns, including human missions, will require data rates difficult to realize by microwave links. Optical channels not only provide an abundance of bandwidth, they also allow for significant size, weight, and power reduction. Moreover, optical-based tracking may enhance spacecraft navigation with respect to microwave-based tracking. With all its advantages, optical communications from deep space is not without its challenges. Due to the extreme distance between the two ends of the link, specialized technologies are needed to enable communications in the deep space environment. Although some of the relevant technologies have been developed in the last decade, they remain to be validated in an appropriate domain. The required assets include efficient pulsed laser sources, modulators, transmitters, receivers, detectors, channel encoders, precise beam pointing technologies for the flight transceiver and large apertures for the ground receiver. Clearly, space qualification is required for the systems that are installed on a deep space probe. Another challenge is atmospheric effects on the optical beam. Typical candidate locations on the ground have a cloud-free line of sight only on the order of 60-70% of the time. Furthermore, atmospheric losses and background light can be problematic even during cloud-free periods. Lastly, operational methodologies are needed for efficient and cost effective management of optical links. For more than a decade, the National Aeronautics and Space Administration (NASA) has invested in relevant technologies and procedures to enable deep space optical communications capable of providing robust links with rates in the order of 1 Gb/s from Mars distance. A recent publication indicates that potential exists for 30-dB improvement in performance through technology development with respect to the state-of-the-art in the early years of this decade. The goal is to fulfill the deep space community needs from about 2020 to the foreseeable future. It is envisioned that, at least initially, optical links will be complemented by microwave assets for added robustness, especially for human missions. However, it is expected that as optical techniques mature, laser communications may be operated without conventional radio frequency links. The purpose of this paper is to briefly review the state-of-the-art in deep space laser communications and its challenges and discuss NASA-supported technology development efforts and plans for deep space optical communications at JPL.

Laser Communications↗

Feedback Augmented Sub-Ranging (FASR) Quantizer

This innovation is intended to reduce the size, power, and complexity of pipeline analog-to-digital converters (ADCs) that require high resolution and speed along with low power. Digitizers are important components in any application where analog signals (such as light, sound, temperature, etc.) need to be digitally processed. The innovation implements amplification of a sampled residual voltage in a switched capacitor amplifier stage that does not depend on charge redistribution. The result is less sensitive to capacitor mismatches that cause gain errors, which are the main limitation of such amplifiers in pipeline ADCs. The residual errors due to mismatch are reduced by at least a factor of 16, which is equivalent to at least 4 bits of improvement. The settling time is also faster because of a higher feedback factor. In traditional switched capacitor residue amplifiers, closed-loop amplification of a sampled and held residue signal is achieved by redistributing sampled charge onto a feedback capacitor around a high-gain transconductance amplifier. The residual charge that was sampled during the acquisition or sampling phase is stored on two or more capacitors, often equal in value or integral multiples of each other. During the hold or amplification phase, all of the charge is redistributed onto one capacitor in the feedback loop of the amplifier to produce an amplified voltage. The key error source is the non-ideal ratios of feedback and input capacitors caused by manufacturing tolerances, called mismatches. The mismatches cause non-ideal closed-loop gain, leading to higher differential non-linearity. Traditional solutions to the mismatch errors are to use larger capacitor values (than dictated by thermal noise requirements) and/or complex calibration schemes, both of which increase the die size and power dissipation. The key features of this innovation are (1) the elimination of the need for charge redistribution to achieve an accurate closed-loop gain of two, (2) a higher feedback factor in the amplifier stage giving a higher closed-loop bandwidth compared to the prior art, and (3) reduced requirement for calibration. The accuracy of the new amplifier is mainly limited by the sampling networks parasitic capacitances, which should be minimized in relation to the sampling capacitors.

Guilligan, Gerard↗

Supramolecular Control of Ionic Retention in Electrolyte-Gated Synaptic Transistors

Electrolyte-gated transistors with ion-trapping layers offer a promising platform for artificial synapses in neuromorphic computing, yet molecular mechanisms governing ionic retention remain poorly understood. Here, in this study, we present a supramolecular approach to modulate ion retention by incorporating a crown ether derivative-based polymer network as an ion-trapping layer on top of a semiconducting monolayer. We show that the balance between ion–host binding and ion–solvent interactions dictates the kinetics of ion capture and release, which in turn controls the memory characteristics of the device. By varying the solvent dielectric constant, we tune the ionic retention time from nearly permanent trapping to rapid relaxation. Intermediate solvent polarity enables programmable short- and long-term synaptic behaviors, including excitatory postsynaptic current, paired-pulse facilitation, and long-term potentiation and depression. These findings establish a direct link between supramolecular ion recognition and synaptic plasticity and provide a generalizable design strategy for ionic–electronic neuromorphic devices.

36 MATERIALS SCIENCE↗

Defect Properties, Anion Ordering, and Photochromic Mechanism in Yttrium Oxyhydride

Yttrium oxyhydride (YHO) undergoes a reversible photochromic transition when exposed to ultraviolet light. However, the mechanism for this transformation is not fully understood, and the structure and precise chemical composition of YHO remain under debate. Here, we use first-principles density functional theory calculations with a hybrid functional to study the structure, chemical stability, and point defect properties of YHO. As experiments have shown, we find that YHO prefers a cubic structure, with H and O anions present in equal concentrations and located on tetrahedral sites. Stoichiometric and ordered YHO is chemically stable, but it has a wide band gap of 5.01 eV, considerably larger than that measured in experiments (2.4–3.8 eV). On the other hand, Y4H10O has a smaller band gap of 2.97 eV and also has a region of chemical stability; thus, the actual material may include some fraction of this H-rich structure. The defect chemistry of YHO is dominated by anionic antisite species (H O and O H ), with hydrogen interstitials (H i ) and vacancies (V H ) also present in reasonably high concentrations. We show that antisite disorder lowers the band gap relative to the perfectly ordered structure, bringing the magnitude of the gap into closer agreement with experiment. Based on our calculations of defect migration and the positions of defect states relative to the band edges, we link the onset of photochromic behavior to the reaction H O – → V O 0 + H i – , which follows photoexcitation of a H O + defect. H i – can subsequently migrate away and be trapped by additional H O + defects, contributing to the persistence of the reaction, while the resultant oxygen vacancy, V O 0 , introduces an occupied defect state that leads to optical absorption at visible wavelengths. Our results can explain reported discrepancies between experimental and computational results for YHO, and they allow us to propose specific atomic-scale processes that can lead to photochromism. In conclusion, understanding these mechanisms is key for unlocking YHO’s application in devices ranging from smart windows and optoelectronics to electrochemical synapses for neural networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Is There an Optimal CO2 Partial Column for Flux Inversions?

The fidelity of flux estimates from an atmospheric inversion depends on the ability of atmospheric transport models to simulate the measured quantity. For species such as CO2, with surface fluxes and a large network of surface measurements, this means correctly simulating the dynamics of the planetary boundary layer (PBL), which is one of the most uncertain aspects of atmospheric transport modeling. In contrast, the simulated total column average mole fraction of CO2 (XCO2) is largely insensitive to simulated PBL dynamics. Therefore, measurements of XCO2 provided by current and future short wave infrared (SWIR) greenhouse gas (GHG) satellites such as GOSAT and the OCO family would seem to be more appropriate to flux inversions, as far as minimizing transport model errors (the "noise") is concerned. Unfortunately, the flux-induced variation of CO2 (the "signal") is the largest within the PBL and smallest in XCO2. Therefore, assimilating XCO2 as opposed to PBL CO2 need not give us the strongest "signal to noise" in flux inversions. Recent work on GOSAT and OCO2 retrievals suggest that SWIR satellite spectra may be used to estimate a lower partial column CO2, which could be assimilated in a flux inversion, instead of XCO2.Here we report on a study to assess whether there is an optimal partial column average CO2, intermediate between PBL CO2 and XCO2, whose assimilation might yield the best signal to noise in flux inversions, where (as before) "signal" is the flux-induced variation and "noise" is the error in transport modeling. We simulate atmospheric CO2 with five different global transport models and a common surface CO2 flux over ten years. We consider the spread across the five models to be a proxy for transport model error (the "noise"), and the common variation of CO2 in all five models to be a proxy for the "signal". We compare these signals and noises at different spatiotemporal scales for different partial column specifications to investigate whether there exists an optimal partial column that has large surface flux-driven variations and yet is relatively insensitive to errors in transport models. Finally, we comment on the feasibility of estimating such a partial column from current and future SWIR GHG satellites in the light of recent work on vertically resolved CO2 from current SWIR GHG satellites.

Basu, Sourish↗

NASA Tech Briefs, September 2006

Topics covered include: Improving Thermomechanical Properties of SiC/SiC Composites; Aerogel/Particle Composites for Thermoelectric Devices; Patches for Repairing Ceramics and Ceramic- Matrix Composites; Lower-Conductivity Ceramic Materials for Thermal-Barrier Coatings; An Alternative for Emergency Preemption of Traffic Lights; Vehicle Transponder for Preemption of Traffic Lights; Automated Announcements of Approaching Emergency Vehicles; Intersection Monitor for Traffic-Light-Preemption System; Full-Duplex Digital Communication on a Single Laser Beam; Stabilizing Microwave Frequency of a Photonic Oscillator; Microwave Oscillators Based on Nonlinear WGM Resonators; Pointing Reference Scheme for Free-Space Optical Communications Systems; High-Level Performance Modeling of SAR Systems; Spectral Analysis Tool 6.2 for Windows; Multi-Platform Avionics Simulator; Silicon-Based Optical Modulator with Ferroelectric Layer; Multiplexing Transducers Based on Tunnel-Diode Oscillators; Scheduling with Automated Resolution of Conflicts; Symbolic Constraint Maintenance Grid; Discerning Trends in Performance Across Multiple Events; Magnetic Field Solver; Computing for Aiming a Spaceborne Bistatic- Radar Transmitter; 4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells; Probabilistic Prediction of Lifetimes of Ceramic Parts; STRANAL-PMC Version 2.0; Micromechanics and Piezo Enhancements of HyperSizer; Single-Phase Rare-Earth Oxide/Aluminum Oxide Glasses; Tilt/Tip/Piston Manipulator with Base-Mounted Actuators; Measurement of Model Noise in a Hard-Wall Wind Tunnel; Loci-STREAM Version 0.9; The Synergistic Engineering Environment; Reconfigurable Software for Controlling Formation Flying; More About the Tetrahedral Unstructured Software System; Computing Flows Using Chimera and Unstructured Grids; Avoiding Obstructions in Aiming a High-Gain Antenna; Analyzing Aeroelastic Stability of a Tilt-Rotor Aircraft; Tracking Positions and Attitudes of Mars Rovers; Stochastic Evolutionary Algorithms for Planning Robot Paths; Compressible Flow Toolbox; Rapid Aeroelastic Analysis of Blade Flutter in Turbomachines; General Flow-Solver Code for Turbomachinery Applications; Code for Multiblock CFD and Heat-Transfer Computations; Rotating-Pump Design Code; Covering a Crucible with Metal Containing Channels; Repairing Fractured Bones by Use of Bioabsorbable Composites; Kalman Filter for Calibrating a Telescope Focal Plane; Electronic Absolute Cartesian Autocollimator; Fiber-Optic Gratings for Lidar Measurements of Water Vapor; Simulating Responses of Gravitational-Wave Instrumentation; SOFTC: A Software Correlator for VLBI; Progress in Computational Simulation of Earthquakes; Database of Properties of Meteors; Computing Spacecraft Solar-Cell Damage by Charged Particles; Thermal Model of a Current-Carrying Wire in a Vacuum; Program for Analyzing Flows in a Complex Network; Program Predicts Performance of Optical Parametric Oscillators; Processing TES Level-1B Data; Automated Camera Calibration; Tracking the Martian CO2 Polar Ice Caps in Infrared Images; Processing TES Level-2 Data; SmaggIce Version 1.8; Solving the Swath Segment Selection Problem; The Spatial Standard Observer; Less-Complex Method of Classifying MPSK; Improvement in Recursive Hierarchical Segmentation of Data; Using Heaps in Recursive Hierarchical Segmentation of Data; Tool for Statistical Analysis and Display of Landing Sites; Automated Assignment of Proposals to Reviewers; Array-Pattern-Match Compiler for Opportunistic Data Analysis; Pre-Processor for Compression of Multispectral Image Data; Compressing Image Data While Limiting the Effects of Data Losses; Flight Operations Analysis Tool; Improvement in Visual Target Tracking for a Mobile Robot; Software for Simulating Air Traffic; Automated Vectorization of Decision-Based Algorithms; Grayscale Optical Correlator Workbench; "One-Stop Shopping" for Ocean Remote-Sensing and Model Data; State Analysis Database Tool; Generating CAHV and CAHVOmages with Shadows in ROAMS; Improving UDP/IP Transmission Without Increasing Congestion; FORTRAN Versions of Reformulated HFGMC Codes; Program for Editing Spacecraft Command Sequences; Flight-Tested Prototype of BEAM Software; Mission Scenario Development Workbench; Marsviewer; Tool for Analysis and Reduction of Scientific Data; ASPEN Version 3.0; Secure Display of Space-Exploration Images; Digital Front End for Wide-Band VLBI Science Receiver; Multifunctional Tanks for Spacecraft; Lightweight, Segmented, Mostly Silicon Telescope Mirror; Assistant for Analyzing Tropical-Rain-Mapping Radar Data; and Anion-Intercalating Cathodes for High-Energy- Density Cells.

Source record↗

Machine Learning Framework for Characterizing Processing–Structure Relationship in Block Copolymer Thin Films

The morphology of block copolymers (BCPs) critically influences material properties and applications. This work introduces a machine learning (ML)-enabled, high-throughput framework for analyzing grazing incidence small-angle X-ray scattering (GISAXS) data and atomic force microscopy (AFM) images to characterize BCP thin film morphology. A convolutional neural network was trained to classify AFM images by surface features, achieving 97% testing accuracy. Classified images were then analyzed to extract 2D grain size measurements from the samples in a high-throughput manner. ML models were trained to predict domain orientation based on processing parameters such as solvent ratio, additive type, and additive ratio. GISAXS-based properties were predicted with strong performances (R 2 > 0.75), while AFM-based property predictions were less accurate (R 2 < 0.60), likely due to the localized nature of AFM measurements compared to the bulk information captured by GISAXS. Beyond model performance, interpretability was addressed using SHapley Additive exPlanations (SHAP). SHAP analysis revealed that the additive ratio had the largest impact on morphological predictions, where additive provides the BCP chains with increased volume to rearrange into thermodynamically favorable morphologies. This interpretability helps validate model predictions and offers insight into parameter importance. Altogether, the presented framework combining high-throughput characterization and interpretable ML offers an approach to exploring and optimizing BCP thin film morphology across a broad processing landscape.

36 MATERIALS SCIENCE↗

Autonomous Aerial Power Plant Inspection in GPS-denied Environments

Inspection of coal-fired power plants is frequently dangerous, includes difficult places to reach, and can turn expensive due to the downtimes and cost of inspection crew. Robotic systems have shown capabilities to address some of these issues, but most of the current robotic inspection technology in power plants is designed for specific components. Conversely, recent advances in machine vision have empowered aerial platforms for long-range, remotely-controlled, GPS-based inspections of industrial plants. This capability has led to wide spread utilization of aerial robots (commonly termed Drones, UVS or UAS) platforms for inspection in less challenging environments where both collision avoidance, and GPS reception are not significant issues. The challenge in adapting airborne technology for power plant inspection lies in internal structures and the complex network of piping, and distribution systems, which impose significant risks for collision and can hinder the reception and transmission of GPS signals. The current state of the art in aerial inspection technology within the energy sector is controlled via radio control, and utilizes GPS-based navigation, for inspection of large-scale plants such as offshore platforms and wind turbine parks. Nevertheless, close-range and autonomous inspection in the GPS-denied environments of power plants has not yet been achieved, as it requires precise guidance and navigation with real-time situational awareness and obstacle avoidance capabilities. This endeavor introduced the use of rotary wing flying robots, due to their station keeping and vertical take-off capabilities for power plant components inspection. To enable close quarter inspection two methods were used. One method uses the 3D CAD (Three-dimensional Computer-Aided Design) model of the asset to inspect to generate the UAV’s inspection path. To acquire, analyze and process the 3D model, first, the STL file is produced to obtain surface points and vectors normal to the surface. Later, by introducing other variables such as wall offset and a controlled trajectory between each outline and each subsequent layer, the flight path is generated. The proposed framework will generate a path that will pass as close as desired from the surface and navigate in intricate environments. A second method, use advanced manufacturing techniques such as CNC (Computer Numerical Control) and additive manufacturing. Once the inspection flight path is obtained, vision-based navigation systems are employed to have the UAV autonomously tracking the provided trajectory. Finally, Artificial Intelligence-enabled developments are in charge of detecting cracks and corrosion in structural components of power plants. The proposed methods are validated in simulations, laboratory and industrial setups, where it is shown that the developed systems acting together enable close-quarter autonomous aerial inspection and mapping in power plant assets. The system can be further improved by adding more sensors to navigate in different GPS-denied environments, with non-homogeneous lighting conditions, dust and in general situations where vision-based systems may fail.

01 COAL, LIGNITE, AND PEAT↗

Preshaping clear glass at low temperatures

Advances in available glass chemistries and glass processing methods have accompanied and enabled some of the biggest technology revolutions, from the development and mass production of light bulbs to low-loss fiber optics and durable smartphone touchscreens. An emerging generation of low-temperature processing technologies aims to continue this important trend and make a broader array of glass components mass producible. In the issue, Mader et al. (1) describe one such innovation in glass processing—the use of low-temperature injection molding to preshape silica particle–filled composites that can later be transformed into transparent fused silica glass objects. Traditionally, transparent glass objects are manufactured in high volume from molten or softened glass, which is floated, drawn, blown, cast, or blow-molded to a desired shape (see the figure, top). The glass composition and processing technique dictate the working temperature, which is usually quite high (near 1000°C) and often restricts the choice of compatible equipment or limits the choice of glass composition. Because geometry-specific capital investment is required for production, drastic or frequent component design changes or small batches may be cost prohibitive. Alternatively, transparent glass components can also be shaped at ambient temperature from solid glass by a series of subtractive processes, including cutting or multiple stages of grinding, followed by slower processing steps, such as polishing or etching. This approach is somewhat less amenable to mass production, and certain geometries containing tool-inaccessible regions cannot be fabricated in this way. Several emerging glass-shaping technologies aim to reduce the required manufacturing temperatures and still provide access to a broader range of glass compositions and component geometries (see the figure). These approaches use a three-step process. First, a desired shape is preformed at low temperature from a glass-forming, organic-inorganic composite. Next, the preform is dried, and organic materials used to bind particles are removed. Finally, the preform is heated (sintered) well below the glass-melting temperature to densify to transparent glass. Although the second and third steps do occur at increased temperatures, only standard, geometry-agnostic driers and furnaces are required. This strategy builds on the well-studied sol-gel approach to forming monolithic glass, where silica network–forming chemical solutions are poured into molds, slowly dried, and condensed into dense glass without melting (2). In a departure from the sol-gel process, these new technologies use solvents, cross-linkers, and polymers to formulate organic-inorganic composites tuned for compatibility with a particular shaping process, with formats ranging from photocurable liquids to shear-thickening pastes to solids. The composite inorganic loadings are also typically higher than those in the pure sol-gel approach, which drastically reduces shrinkage in comparison.

36 MATERIALS SCIENCE↗