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Simplified Vicarious Radiometric Calibration

A measurement-based radiance estimation approach for vicarious radiometric calibration of spaceborne multispectral remote sensing systems has been developed. This simplified process eliminates the use of radiative transfer codes and reduces the number of atmospheric assumptions required to perform sensor calibrations. Like prior approaches, the simplified method involves the collection of ground truth data coincident with the overpass of the remote sensing system being calibrated, but this approach differs from the prior techniques in both the nature of the data collected and the manner in which the data are processed. In traditional vicarious radiometric calibration, ground truth data are gathered using ground-viewing spectroradiometers and one or more sun photometer( s), among other instruments, located at a ground target area. The measured data from the ground-based instruments are used in radiative transfer models to estimate the top-of-atmosphere (TOA) target radiances at the time of satellite overpass. These TOA radiances are compared with the satellite sensor readings to radiometrically calibrate the sensor. Traditional vicarious radiometric calibration methods require that an atmospheric model be defined such that the ground-based observations of solar transmission and diffuse-to-global ratios are in close agreement with the radiative transfer code estimation of these parameters. This process is labor-intensive and complex, and can be prone to errors. The errors can be compounded because of approximations in the model and inaccurate assumptions about the radiative coupling between the atmosphere and the terrain. The errors can increase the uncertainty of the TOA radiance estimates used to perform the radiometric calibration. In comparison, the simplified approach does not use atmospheric radiative transfer models and involves fewer assumptions concerning the radiative transfer properties of the atmosphere. This new technique uses two neighboring uniform ground target areas having different reflectance values. The target areas can be natural or artificial and must be large enough to minimize adjacent-pixel contamination effects. The radiative coupling between the atmosphere and the terrain needs to be approximately the same for the two targets. This condition can be met for relatively uniform backgrounds when the distance between the targets is within a few hundred meters. For each target area, the radiance leaving the ground in the direction of the satellite is measured with a radiometrically calibrated spectroradiometer. Using the radiance measurements from the two targets, atmospheric adjacency and atmospheric scattering effects can be subtracted, thereby eliminating many assumptions about the atmosphere and the radiative interaction between the atmosphere and the terrain. In addition, the radiometrically calibrated spectroradiometer can be used with a known reflectance target to estimate atmospheric transmission and diffuse- to-global ratios without the need for ancillary sun photometers. Several comparisons between the simplified method and traditional techniques were found to agree within a few percent. Hence, the simplified method reduces the overall complexity of performing vicarious calibrations and can serve as a method for validating traditional radiative transfer models

Stanley, Thomas↗

Advanced Sensor Platform to Evaluate Manloads For Exploration Suit Architectures

Space suit manloads are defined as the outer bounds of force that the human occupant of a suit is able to exert onto the suit during motion. They are defined on a suit-component basis as a unit of maximum force that the suit component in question must withstand without failure. Existing legacy manloads requirements are specific to the suit architecture of the EMU and were developed in an iterative fashion; however, future exploration needs dictate a new suit architecture with bearings, load paths, and entry capability not previously used in any flight suit. No capability currently exists to easily evaluate manloads imparted by a suited occupant, which would be required to develop requirements for a flight-rated design. However, sensor technology has now progressed to the point where an easily-deployable, repeatable and flexible manloads measuring technique could be developed leveraging recent advances in sensor technology. INNOVATION: This development positively impacts schedule, cost and safety risk associated with new suit exploration architectures. For a final flight design, a comprehensive and accurate man loads requirements set must be communicated to the contractor; failing that, a suit design which does not meet necessary manloads limits is prone to failure during testing or worse, during an EVA, which could cause catastrophic failure of the pressure garment posing risk to the crew. This work facilitates a viable means of developing manloads requirements using a range of human sizes & strengths. OUTCOME / RESULTS: Performed sensor market research. Highlighted three viable options (primary, secondary, and flexible packaging option). Designed/fabricated custom bracket to evaluate primary option on a single suit axial. Manned suited manload testing completed and general approach verified.

McFarland, Shane↗

Machine Learning-Based Prediction of Distribution Network Voltage and Sensors Allocation: Preprint

Increasing penetration of fast-varying energy resources may negatively affect power systems' operation. At the same time, sensor deployment throughout distribution networks improves system awareness and enables the development of new and advanced voltage control solutions. Such control techniques rely on accurate prediction in anticipation to voltage violation scenarios. This paper analyzes various approaches for voltage prediction in a distribution system; it is shown that combining multiple techniques into a single regressor improves its predictive power. Moreover, a two-step regressor is proposed, where initial predictions based on a global regressor are refined by local regressors; in this case, prediction errors decrease significantly. Additionally, a clustering approach is employed for performing sensor allocation, so that only the most influential buses are selected for monitoring without diminishing prediction accuracy.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Machine Learning-Based Prediction of Distribution Network Voltage and Sensor Allocation

Increasing penetration of fast-varying energy resources may negatively affect power systems' operation. At the same time, sensor deployment throughout distribution networks improves system awareness and enables the development of new and advanced voltage control solutions. Such control techniques rely on accurate prediction in anticipation to voltage violation scenarios. This paper analyzes various approaches for voltage prediction in a distribution system; it is shown that combining multiple techniques into a single regressor improves its predictive power. Moreover, a two-step regressor is proposed, where initial predictions based on a global regressor are refined by local regressors; in this case, prediction errors decrease significantly. Additionally, a clustering approach is employed for performing sensor allocation, so that only the most influential buses are selected for monitoring without diminishing prediction accuracy.

61 RADIATION PROTECTION AND DOSIMETRY↗

Machine Learning-Based Prediction of Distribution Network Voltage and Sensor Allocation

Increasing penetration levels of fast-varying energy resources might negatively affect power system operation. At the same time, sensor deployment throughout distribution networks improves system awareness and enables the development of new and advanced voltage control solutions. Such control techniques rely on accurate prediction in anticipation of voltage violation scenarios. This paper analyzes various approaches to voltage prediction in a distribution system, and it is shown that combining multiple techniques into a single regressor improves its predictive power. Moreover, a two-step regressor is proposed in which initial predictions based on a global regressor are refined by local regressors; in this case, prediction errors decrease significantly. Additionally, a clustering approach is employed to perform sensor allocation so that only the most influential buses are selected for monitoring without diminishing prediction accuracy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Autonomous Navigation, Guidance, and Control Software in a Low SWaP Box

Onboard autonomy is a necessity for responsive space operations. Autonomous navigation, guidance, and control (NGC) enables space missions to reduce their dependence on high demand ground assets and costly ground personnel. It also allows for in-situ decision making and higher return on mission data. A flight software and hardware system providing this capability, called “autoNGC,” is currently being developed at NASA Goddard Space Flight Center for infusion into multiple future missions. The autoNGC flight software is built on the plug-and-play architecture of the core Flight System (cFS) consisting of the standard cFS apps and newly developed autoNGC interface apps and libraries. The various apps cooperate through communication over the message-based software bus. With the plug-and-play architecture of autoNGC, cFS apps can easily be added and replaced to meet the needs of different missions, even after launch. The first flight software release of autoNGC is targeted for Summer 2024 to provide autonomous navigation at the Moon and beyond. It can perform sensor fusion of multiple measurement types including pseudo-range from a Global Navigation Satellite System (GNSS) receiver (including weak signal), 1-way and 2-way range and Doppler from ground stations (i.e., direct to Earth (DTE)), bearing and range from optical camera images, and accelerometer data. Accurate onboard navigation and timing is obtained through the Goddard Enhanced Onboard Navigation System (GEONS) software library which fuses different measurement types through an extended Kalman filter (EKF) framework. Optical measurements that are ingested in GEONS are first extracted from optical images by the cFS Goddard Image Analysis and Navigation Tool (cGIANT) app. If the imaged body is far enough away that it appears as a pixel or cluster of pixels, then bearing angles to the body centroid can be provided. If the body is close enough and the shape is known coarsely, then bearing angles and range to the body centroid can be derived from the limb. Bearing angles to individual surface features can also be extracted (i.e., terrain relative navigation (TRN)). Onboard guidance and control capabilities are being developed for a future release to perform autonomous station-keeping and trajectory correction maneuvers in multiple orbital regimes. Capabilities to enable distributed systems missions and constellations, such as crosslink measurements, and onboard time management are being developed as well. The first hardware implementation of autoNGC is a minimal size, weight, and power (SWaP) design allowing for inclusion into CubeSats and SmallSat-size buses. Advancements in miniaturized space processors, such as the SpaceCube 3.0 Mini and the SpaceCube Mini-Z are utilized for low SWaP while maintaining a high level of performance. The current enclosure design is 12 cm x 17 cm x 13.5 cm. The box mass is expected to be less than 2 kg, and the nominal power is 21 W. In order to accommodate a wide range of missions, the hardware interfaces are designed for flexibility with a variety of sensor inputs. Through comprehensive testing in the software-in-the-loop, processor-in-the-loop, and hardware-in-the-loop test beds that are concurrently being developed, autoNGC is expected to achieve TRL 6 by late 2024.

Sun Hur-Diaz↗

MEDLI2: MISP Inferred Aerothermal Environment and Flow Transition Assessment

The Mars Entry, Descent, and Landing Instrumentation 2 (MEDLI2) sensor suite on the Mars2020 mission contained multiple sensors on the aeroshell to measure the aerothermal environment during entry into the Martian atmosphere. These sensors performed superbly and successfully returned forebody and aftbody heating measurements. Analysis of MEDLI2 data indicated flow transitioning from a laminar to turbulent state on the heatshield. No evidence of flow transition was observed on the backshell. Two methods were used to estimate flow transition times on the heatshield: (1) temperature gradient of near-surface thermocouple data and (2) heat flux gradient from an inverse reconstruction approach using thermocouple data and material response modeling. Both methods produced similar transition times with an estimated accuracy of ±1 s. To assess various transition criteria, transition parameters were evaluated at each sensor location using flow field solutions from computational fluid dynamics (CFD) simulations. The idea was to use conservative values inferred from MEDLI2 data as transition criteria for other Mars missions. To test this hypothesis, MEDLI data from the Mars Science Laboratory (MSL) mission was used to compare predicted vs. actual flow transition times. The comparisons suggest smooth wall transition criteria are not well-suited in modeling the rapid progression of a turbulent transition front. Transition criteria containing a roughness element parameter agreed better with the flight data. In summary, critical transition values derived from MEDLI2 data may be used as a starting point in constructing a flow transition model for future Mars missions.

Chun Y Tang↗

Comparative assessment of neutron flux sensor technologies for advanced reactors

This report documents the comparative assessment of the rhodium-based self-powered neutron detectors (Rh-SPND), micro-pocket fission detectors (MPFD), and dosimetry wires in heated irradiations at the Neutron Radiography reactor facility at Idaho National Laboratory. The sensors performances are evaluated high-temperature environments (upwards of 850°C) during maximum reactor power to simulate use in advanced reactor applications. The performance of the Rh-SPNDs indicates the experiment cartridge heater power supply interferes with the SPND signals. This interference become increasingly significant at temperatures above 500°C with minimal interference observed for temperatures below 500°C. This work also demonstrated the fabrication process for the updated design of the MPFD, but issues related to the seal welds were identified and usable data was limited. Finally, the dosimetry measurements were within the expected range correlated with reactor power; thus, the dosimetry results were used to provide preliminary SPND calibration factors. The results from this experiment serves as a reference for developing and testing of flux sensors that are designed for high-temperature irradiations and advanced reactor deployments. This includes upcoming FY22 irradiations at the Massachusetts Institute of Technology Reactor and the Neutron Radiography (NRAD) reactor utilizing additional fission chambers from Photonis Technologies and fission chambers and SPNDs from The French Alternative Energies and Atomic Energy Commission.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Analytic Spacecraft Attitude and Rate Estimation Performance During Attitude Sensor Outages

Analytic expressions for spacecraft attitude and rate estimation performance of an attitude estimation filter in terms of sensor specifications are useful tools for spacecraft design. Farrenkopf (1978) famously found analytic expressions for steady-state pre-update and post-update attitude and gyro bias estimate error variances for an attitude estimation filter for a single-axis spacecraft with a Rate Output Gyro (ROG). Markley and Reynolds (2000) extended the analysis for a Rate-Integrating Gyro (RIG) with angle white noise. These expressions allow for the rapid evaluation of system performance during preliminary mission design phases. One contribution of this paper is the analytic calculation of the steady-state pre-update and post-update angular rate estimate uncertainty for both the ROG and RIG cases. The primary contribution of this paper is the extension of the results for both the ROG and the RIG cases to the situation of an attitude sensor outage. This situation arises frequently in practice; for example when a star sensor’s field of view is occluded, when a star sensor’s readings are unreliable during a thruster burn that vibrates the spacecraft, or during star sensor outages due to radiation upsets. Analytic expressions for the attitude estimate uncertainty, gyro bias estimate uncertainty, and angular rate estimate uncertainty are given in terms of the attitude sensor outage interval, the star tracker measurement noise, and gyro noise parameters. Validity of the analytic results is demonstrated via Monte Carlo simulation.

Galante, Joseph M.↗

Analytic Spacecraft Attitude and Rate Estimation Performance During Attitude Sensor Outages

Analytic expressions for spacecraft attitude and rate estimation performance of an attitude estimation filter in terms of sensor specifications are useful tools for spacecraft design. Farrenkopf (1978) famously found analytic expressions for steady-state pre-update and post-update attitude and gyro bias estimate error variances for an attitude estimation filter for a single-axis spacecraft with a Rate Output Gyro (ROG). Markley and Reynolds (2000) extended the analysis for a Rate-Integrating Gyro (RIG) with angle white noise. These expressions allow for the rapid evaluation of system performance during preliminary mission design phases. One contribution of this paper is the analytic calculation of the steady-state pre-update and post-update angular rate estimate uncertainty for both the ROG and RIG cases. The primary contribution of this paper is the extension of the results for both the ROG and the RIG cases to the situation of an attitude sensor outage. This situation arises frequently in practice; for example when a star sensor’s field of view is occluded, when a star sensor’s readings are unreliable during a thruster burn that vibrates the spacecraft, or during star sensor outages due to radiation upsets. Analytic expressions for the attitude estimate uncertainty, gyro bias estimate uncertainty, and angular rate estimate uncertainty are given in terms of the attitude sensor outage interval, the star tracker measurement noise, and gyro noise parameters. Validity of the analytic results is demonstrated via Monte Carlo simulation.

Galante, Joseph M.↗

Airborne Radar for sUAS Sense and Avoid

A primary challenge for the safe integration of small UAS operations into the National Airspace System (NAS) is traffic deconfliction, both from manned and unmanned aircraft. The UAS Traffic Management (UTM) project being conducted at the National Aeronautics and Space Administration (NASA) considers a layered approach to separation provision, ranging from segregation of operations through airspace volumes (geofences) to autonomous sense and avoid (SAA) technologies for higher risk, densely occupied airspace. Cooperative SAA systems, such as Automatic Dependent Surveillance-Broadcast (ADS-B) and/or vehicle-to-vehicle communication systems provide significant additional risk mitigation but they fail to adequately mitigate collision risks for non-cooperative (non-transponder equipped) airborne aircraft. The RAAVIN (Radar on Autonomous Aircraft to Verify ICAROUS Navigation) flight test being conducted by NASA and the Mid-Atlantic Aviation Partnership (MAAP) was designed to investigate the applicability and performance of a prototype, commercially available sUAS radar to detect and track non-cooperative airborne traffic, both manned and unmanned. The radar selected for this research was a Frequency Modulated Continuous Wave (FMCW) radar with 120 degree azimuth and 80 degree elevation field of view operating at 24.55GHz center frequency with a 200 MHz bandwidth. The radar transmits 2 watts of power thru a Metamaterial Electronically Scanning Array antenna in horizontal polarization. When the radar is transmitting, personnel must be at least 1 meter away from the active array to limit nonionizing radiation exposure. The radar physical dimensions are 18.7cm by 12.1cm by 4.1cm and it weighs less than 820 grams making it well suited for installation on small UASs. The onboard, SAA capability, known as ICAROUS, (Independent Configurable Architecture for Reliable Operations of Unmanned Systems), developed by NASA to support sUAS operations, will provide autonomous guidance using the traffic radar tracks from the onboard radar. The RAAVIN set of studies will be conducted in three phases. The first phase included outdoor, ground-based radar evaluations performed at the Virginia Tech’s Kentland Farm testing range in Blacksburg, VA. The test was designed to measure how well the radar could detect and track a small UAS flying in the radar’s field of view. The radar was used to monitor 5 test flights consisting of outbound, inbound and crossing routes at different ranges and altitudes. The UAS flown during the ground test was the Inspire 2, a quad copter weighing less than 4250 grams (10 pounds) at maximum payload. The radar was set up to scan and track targets over its full azimuthal field of view from 0 to 40 degrees in elevation. The radar was configured to eliminate tracks generated from any targets located beyond 2000 meters from the radar and moving at velocities under 1.45 meters per second. For subsequent phases of the study the radar will be integrated with a sUAS platform to evaluate its performance in flight for SAA applications ranging from sUAS to manned GA aircraft detections and tracking. Preliminary data analysis from the first outdoor ground tests showed the radar performed well at tracking the vehicle as it flew outbound and repeatedly maintained a track out to 1000 meters (maximum 1387 meters) until the vehicle slowed to a stop to reverse direction to fly inbound. As the Inspire flew inbound tracks from beyond 800 meters, a reacquisition time delay was consistently observed between when the Inspire exceeds a speed of 1.45 meters per second and when the radar indicated an inbound target was present and maintained its track. The time delay varied between 6 seconds to over 37 seconds for the inbound flights examined, and typically resulted in about a 200 meter closure distance before the Inspire track was maintained. The radar performed well at both acquiring and tracking the vehicle as it flew crossing routes out past 400 meters across the azimuthal field of view. The radar and ICAROUS software will be integrated and flown on a BFD-1400-SE8-E UAS during the next phase of the RAAVIN project. The main goal at the conclusion of this effort is to determine if this radar technology can reliably support minimum requirements for SAA applications of sUAS. In particular, the study will measure the range of vehicle detections, lateral and vertical angular errors, false and missed/late detections, and estimated distance at closest point of approach after an avoidance maneuver is executed. This last metric is directly impacted by sensor performance and indicates its suitability for the task.

Szatkowski, George N.↗

Fast Radiative Transfer Model and Retrieval Algorithm Development for Satellite Remote Sensing Applications

The radiative transfer model (RTM) has a wide range of applications in satellite remote sensing and atmospheric radiation studies. For example, it can be used as a forward model for an inversion algorithm and a satellite data assimilation system, or as a L1 data simulator for pre-launch end-to-end satellite sensor performance studies. However, millions of line-by-line (LBL) radiative transfer calculations at fine monochromatic frequencies are needed in order to properly calculate spectral contributions of water vapor and trace gases in the atmosphere in infrared and solar spectral regions. Therefore, fast, and accurate radiative transfer models are needed. A Principal Component-based radiative transfer model (PCRTM) was developed at NASA Langley to fulfil this need. The PCRTM can simulate the top-of-atmosphere (TOA) radiance or reflectance spectra from 250 nm to 2000 micrometers with several orders of magnitude faster speed as compared to a LBL RTM. It is also extremely accurate compared to LBL RTM benchmarks. The PCRTM model has been developed for hyperspectral sensors such as AIRS, CrIS, IASI, NAST-I, SHIS, CPF, TEMPO, EMIT, OMI, and SCIAMACHY. By using the PCRTM as forward model for an inversion algorithm, one can reduce the data dimension significantly while maintaining original information content by compressing the TOA radiance spectrum into PC-scores. The PCRTM can directly compute the PC-scores and their derivatives with respect to retrieved parameters. Examples of using various PCRTM inversion algorithms to retrieve atmospheric temperature, water vapor, and trace gas profiles, as well as cloud and surface properties from satellite hyperspectral remote sensors will be given. Some of the algorithms have been transitioned to NASA's Goddard Earth Sciences Data and Information Services Center (GES DISC) for public access of high-quality L2 and L3 data.

Xu Liu↗

Effects of trapped charge on the signal formation and detection efficiency for subsequent pulses in irradiated silicon sensors

Envisaged high energy physics experiments like the Future Circular Collider require unprecedented radiation hardness of the detectors, as well as short readout time due to high luminosity and occupancy. Silicon has proven to be extremely radiation hard. Sufficient signals can be recorded even at fluences close to 1 ∙ 1 0 16 n e q / cm 2 . Here, the signal formation was studied in silicon strip sensors, irradiated and annealed until the phenomenon of charge multiplication occurred. ATLAS12EC R0 mini sensors were tested by means of edge TCT measurements at temperatures around –20 °C. It was observed that the detection of subsequent signals separated up to several microseconds is altered by the charge trapped during the preceding pulses. The effects of trapped charge on the electrical configuration of a sensor are well known as a polarization or pumping effect in larger band-gap materials like diamond, but is often neglected for silicon at this relatively high temperature. The investigation of the effect created by trapped charges in silicon sensors using subsequent pulses allows to gain information on important parameters such as de-trapping times. Furthermore, it shows a severe impact on the sensor performance in a pile-up scenario. The irradiation fluence and hence the effective doping concentration, the temperature and the amount of initially created charge have a large impact on this phenomenon. The measurements presented help to characterize this phenomenon; particular attention was paid to the application point of view.

47 OTHER INSTRUMENTATION↗

MAS-CCD: New technique for measuring low-level charge content based on the multiple amplifier architecture

Low-noise detectors are a key technology for the next generation of astronomical instruments aimed at spectroscopy of faint objects and the search for exoplanets. In this context, the multiple-amplifier sensing charge-coupled device (MAS-CCD) emerges as a promising technology for future scientific instruments. A critical parameter affecting the performance of these devices is spurious charge, produced by the clocking of the gates. Its measurement is typically challenging with existing methods. In practice, the optimization of this parameter often relies on empirical procedures that require significant time and careful consideration of the trade-off with full-well capacity. In this work, we present a new technique to estimate spurious charge based on covariance analysis of the output amplifiers of the MAS-CCD, which measures the same charge packet in different amplifiers at different times. The method enables fast and precise measurements of spurious charge under operating conditions where conventional approaches are difficult to apply. We develop the theoretical framework of the method and validate the model through simulations. The results demonstrate the feasibility of this approach and suggest that it could serve as a basis for reliable large-scale characterization of sensor performance.

Gamero, Miqueas E. [Buenos Aires, CONICET; Fermila↗

Impact of Footprint Diameter and Off-Nadir Pointing on the Precision of Canopy Height Estimates from Spaceborne Lidar

A spaceborne lidar mission could serve multiple scientific purposes including remote sensing of ecosystem structure, carbon storage, terrestrial topography and ice sheet monitoring. The measurement requirements of these different goals will require compromises in sensor design. Footprint diameters that would be larger than optimal for vegetation studies have been proposed. Some spaceborne lidar mission designs include the possibility that a lidar sensor would share a platform with another sensor, which might require off-nadir pointing at angles of up to 16 . To resolve multiple mission goals and sensor requirements, detailed knowledge of the sensitivity of sensor performance to these aspects of mission design is required. This research used a radiative transfer model to investigate the sensitivity of forest height estimates to footprint diameter, off-nadir pointing and their interaction over a range of forest canopy properties. An individual-based forest model was used to simulate stands of mixed conifer forest in the Tahoe National Forest (Northern California, USA) and stands of deciduous forests in the Bartlett Experimental Forest (New Hampshire, USA). Waveforms were simulated for stands generated by a forest succession model using footprint diameters of 20 m to 70 m. Off-nadir angles of 0 to 16 were considered for a 25 m diameter footprint diameter. Footprint diameters in the range of 25 m to 30 m were optimal for estimates of maximum forest height (R(sup 2) of 0.95 and RMSE of 3 m). As expected, the contribution of vegetation height to the vertical extent of the waveform decreased with larger footprints, while the contribution of terrain slope increased. Precision of estimates decreased with an increasing off-nadir pointing angle, but off-nadir pointing had less impact on height estimates in deciduous forests than in coniferous forests. When pointing off-nadir, the decrease in precision was dependent on local incidence angle (the angle between the off-nadir beam and a line normal to the terrain surface) which is dependent on the off-nadir pointing angle, terrain slope, and the difference between the laser pointing azimuth and terrain aspect; the effect was larger when the sensor was aligned with the terrain azimuth but when aspect and azimuth are opposed, there was virtually no effect on R2 or RMSE. A second effect of off-nadir pointing is that the laser beam will intersect individual crowns and the canopy as a whole from a different angle which had a distinct effect on the precision of lidar estimates of height, decreasing R2 and increasing RMSE, although the effect was most pronounced for coniferous crowns.

Pang, Yong↗

Synthesis of CdZnTeSe single crystals for room temperature radiation detector fabrication: mitigation of hole trapping effects using a convolutional neural network

In this article, we report the growth of Cd 0.9 Zn 0.1 Te 0.97 Se 0.03 (CZTS) wide bandgap semiconductor single crystals for room temperature gamma-ray detection using a modified vertical Bridgman method. Charge transport properties measured in the radiation detectors, fabricated from the grown CZTS crystals, indicated signs of hole trapping. Hole traps inhibit high-resolution radiation detection especially for energetic gamma rays. Machine learning (ML) applications are gaining tremendous mpetus in improving device and sensor performance by compensating for limi tations arising from such intrinsic material properties. In this article, we describe a deep convolutional neural network (CNN) that has demonstrated remarkable efficiency in identifying the energy of a gamma photon detected by a CZTS detector. The CNN has been trained using simulated data that resemble output pulses from actual CZTS detectors when exposed to 662-keV gamma photons. The device properties required for the simulation have been derived from radiation detection measurements on a real Cd 0.9 Zn 0.1 Te 0.97 Se 0.03 detector fabricated in our laboratory. The CNN has been trained with detector pulses arising through photoelectric (PE) and Compton scattering (CS) separately. The percentage error in predicting the detected energies, within an extremely small duration of 0.28 ms, was found to be lower than 0.1% for gamma energies above 50 keV and for training datasets con taining PE and CS events separately. The CNN was also validated for a mixed PE and CS dataset to obtain a prediction error of 1%. Additionally, the effect of detector resolution on the efficiency of the CNN was also explored.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Raman Spectroscopic In Situ Monitoring of Highly Turbid Media

The ability to run chemical processing more efficiently and cost effectively is a need that spans critical materials recovery and legacy nuclear waste cleanup. Sensors integrated to provide online monitoring are essential to addressing this need by providing near-real time feedback on process conditions, which can improve efficiency, aid in decision making, and reduce the need for grab sample measurements. Optical spectroscopy is well-suited for providing online chemical composition information and has been widely applied in varied chemical systems. However, applications in turbid matrices continue to represent substantial challenges to sensor performance, where absorption or scattering of excitation light can cause significant signal interference. Here, in this study, close-focus Raman probes are investigated for use in turbid media as a way to overcome the signal loss from the scattering of the Raman excitation source. This, paired with advanced data science techniques, allowed for the development of chemometric models for the accurate quantification of several analytes of interest (NO 3 – , NO 2 – , and PO 4 3– ) in highly turbid solutions with solids loadings of up to 20 wt %. This work focuses on offline sample measurement and characterization as an initial step toward the development of online monitoring capabilities. Chemical systems of interest were focused on nuclear waste at the Hanford Site, which represents highly complex matrices that could realize significant processing benefits through the integration of online monitoring.

Felmy, Heather M. [Pacific Northwest National Labo↗

Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu 3 (BTC) 2

Confinement of guest molecules in porous materials such as metal organic frameworks (MOFs) promises to deliver emergent properties separate from those of the individual components. Understanding the confinement mechanism is therefore important for the development of new synthesis routes that adjust MOF properties for specific applications. In this work, we developed a new synthetic method to confine guest molecules into MOF pores through a stepwise thermal annealing process, wherein the confinement of 7,7,8,8-tetracyanoquinodimethane (TCNQ) guest molecules into Cu 3 (BTC) 2 (BTC = benzene-1,3,5-tricarboxylic acid) MOF host is used as an example of how novel materials can be created with new physical properties. The stepwise thermal annealing process includes 1) an activation process of pristine Cu 3 (BTC) 2 MOF to maximizes the TCNQ guest loading in the MOF host by effectively removing the residual solvents and 2) post-annealing of the TCNQ infiltrated MOF to enhances the interaction of the confined guest molecules with the MOF host. Obtained experimental results based on thermogravimetric analysis, N 2 gas adsorption, electron microscopy, X-ray diffraction and infrared absorption, combined with density functional theory calculations provide evidence that the use of a stepwise thermal annealing process yields enhancements in the guest loading, packing and interaction between the TCNQ guest and the MOF host. The new hybrid TCNQ@Cu 3 (BTC) 2 system is stable and shows no significant signs of structural degradation even after submersion in water. This is due to the presence of significantly stronger interactions of TCNQ with the frame-work metal ions compared to those of the water molecules competing for the same framework binding sites. It was also found that TCNQ@Cu 3 (BTC) 2 system maintains a significant CO 2 and CH 4 adsorption potential compared to the pristine MOF. The synthetic route developed in this work yields novel guest@MOF hybrid systems that will be useful for many MOF-based applications such as gas separations and chemical sensors performed under humid conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗