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Assessment of the use of space technology in the monitoring of oil spills and ocean pollution: Technical volume. Executive summary

The potential of space systems and technology for detecting and monitoring ocean oil spills and waste pollution was assessed as well as the impact of this application on communication and data handling systems. Agencies charged with responsibilities in this area were identified and their measurement requirements were ascertained in order to determine the spatial resolution needed to characterize operational and accidental discharges. Microwave and optical sensors and sensing techniques were evaluated as candidate system elements. Capabilities are described for the following: synthetic aperture radar, microwave scatterometer, passive microwave radiometer, microwave altimeter, electro-optical sensors currently used in airborne detection, existing space-based optical sensors, the thematic mapper, and the pointable optical linear array.

Alvarado, U. R.↗

NASA's Soil Moisture Active and Passive (SMAP) Mission

The Soil Moisture Active-Passive (SMAP) Mission is one of the first Earth observation satellites being formulated by NASA in response to the 2007 National Research Council s Decadal Survey. SMAP will make global measurements of soil moisture at the Earth's land surface and its freeze-thaw state. These measurements will allow significantly improved estimates of water, energy and carbon transfers between the land and atmosphere. Soil moisture measurements are also of great importance in assessing flooding and monitoring drought. Knowledge gained from SMAP observations can help mitigate these natural hazards, resulting in potentially great economic and social benefits. SMAP observations of soil moisture and freeze/thaw timing over the boreal latitudes will also reduce a major uncertainty in quantifying the global carbon balance and help to resolve an apparent missing carbon sink over land. The SMAP mission concept will utilize an L-band radar and radiometer sharing a rotating 6-meter mesh reflector antenna flying in a 680 km polar orbit with an 8-day exact ground track repeat aboard a 3-axis stabilized spacecraft to provide high-resolution and high-accuracy global maps of soil moisture and freeze/thaw state every two to three days. In addition, the SMAP project will use these surface observations with advanced modeling and data assimilation to provide estimates of deeper root-zone soil moisture and net ecosystem exchange of carbon. SMAP recently completed its Phase A Mission Concept Study Phase for NASA and transitioned into Phase B (Formulation and Detailed Design). A number of significant accomplishments occurred during this initial phase of mission development. The SMAP project held several open meetings to solicit community feedback on possible science algorithms, prepared preliminary draft Algorithm Theoretical Basis Documents (ATBDs) for each mission science product, and established a prototype algorithm testbed to enable testing and evaluation of the performance of candidate algorithms. SMAP conducted an Applications Workshop in September 2009 to coordinate with potential application users interested in the mission data. A draft Applications Plan describing the Project s planned outreach to potential applications users has been prepared and will be updated during Phase B. SMAP made a significant evaluation of the potential terrestrial radio frequency interference (RFI) source environment and established radiometer and radar flight hardware and ground processing mitigation approaches. SMAP finalized its science orbit and orbit injection approach to optimize launch mass and prepared launch and commissioning scenarios and timeline. A science data communications approach was developed to maximize available science data volume to improve science margins while maintaining moderately short data product latencies to support many potential applications using existing ground assets and with minimum impact to the flight system. SMAP developed rigid multi-body and flexible body dynamics and control models and system designs for the 6-meter rotating instrument reflector-boom assembly (RBA) and flight system to confirm pointing and control performance, and devised strategies to efficiently implement on-orbit balancing if needed. Industry partners were selected for the spin mechanism assembly (SMA) and RBA. Preliminary designs for the radar and radiometer were initiated, including constructing breadboards of key assemblies.

Kellogg, Kent↗

Tracking the Oxidation of Silicon Anodes Using Cryo-EELS upon Battery Cycling

Silicon is a high-capacity material for the anode of a rechargeable lithium-ion battery. One of the fundamental challenges for using Si in anodes is capacity fading, which has been revealed to be partially associated with the interfacial instability between the Si and liquid electrolyte due to the large volume swing of Si upon charging and discharging. Smart nanoscale design concepts, either pre-synthesized or formed in-situ, have led to the mitigation of the detrimental factors associated with the volume swing of Si. However, it has never been clear as how the chemical state of Si evolves and contributes to the capacity fading upon battery cycling. Here, we use cryo-electron energy loss spectroscopy (EELS) to directly monitor, at sub-nanometer scale, the chemical evolution of Si upon battery cycling. We discover that during the cycling process, Si particles are progressively oxidized to form SiO 2 , which is initiated from the particle surface and gradually penetrates toward the interior of the particle, directly contributing to the capacity fading. Possible mechanisms of Si oxidation are postulated. We further show how the cycling stability can be improved by an electrolyte additive to form an effective passivation layer, representatively, even a small concentration of fluoroethylene carbonate (FEC) causes the formation of an LiF layer on the Si nanoparticle surface that prevents Si oxidation and improves cycling stability. Furthermore, the present work unveils Si oxidation as a previously unrecognized factor that contributes to capacity fading, therefore providing insight into the design of anodes with Si based materials.

25 ENERGY STORAGE↗

Performance of MODIS Thermal Emissive Bands On-orbit Calibration Algorithms

Two nearly identical copies of the Moderate Resolution Imaging Spectroradiometer (MODIS) are currently operated on-board the Terra and Aqua spacecrafts, launched in December 1999 and May 2002, respectively. Together, they have produced an unprecedented amount of science data products, which are widely used for the studies of changes in the Earth's system of land, oceans, and atmosphere. MODIS is a cross-track scanning radiometer, which uses a two-sided scan mirror and collects data continuously over a wide scan angle range (+/-55 degree relative to the instrument nadir) each scan of 1.47 seconds. It has 36 spectral bands with wavelengths ranging from visible (VIS) to long-wave infrared (LWIR). MODIS bands 1-19 and 26 are the reflective solar bands (RSB) and bands 20-25 and 27-36 are the thermal emissive bands (TEB). MODIS was developed and designed with improvements made over its heritage sensors (such as AVHRR and Landsat) and, in particular, with more stringent calibration requirements. Because of this, MODIS was built with a set of state-of-art on-board calibrators (OBC), which include a solar diffuser (SD), a solar diffuser stability monitor (SDSM), a blackbody (BB), a spectroradiometric calibration assembly (SRCA), and a space view (SV) port. With the exception of view angle differences, MODIS OBC measurements and the Earth View (EV) observations are made via the same optical path. MODIS TEB have a total of 160 individual TEB detectors (10 per band), which are located on two cold focal plane assemblies (CFPA). For nominal on-orbit operation, the CFPA temperature is controlled at 83K via a passive radiative cooler. For the TEB, the calibration requirements at specified typical scene radiances are less than or equal to 1% with an exception for the fire detection (low gain) band. MODIS TEB on-orbit calibration is performed on a scan-by-scan basis using a quadratic calibration algorithm, and data collected from sensor responses to the onboard BB and SV. The BB serves as the thermal calibration source and the SV provides measurements for the sensor's background and offsets. MODIS on-board BB is a v-grooved plate with its temperature measured using 12 platinum resistive thermistors (PRT) uniformly embedded in the BB substrate. All the BB thermistors were characterized pre-launch with reference to the NIST temperature standards. Unlike typical BB operations in many heritage sensors, which have no temperature control capability, the MODIS on-board BB can be operated at any temperatures between instrument ambient (about 270K) and 315K and can also be varied continuously within this range. This feature has significantly enhanced the MODIS' capability of tracking and updating the TEB nonlinear calibration coefficients over its entire mission. Following a brief description of MODIS TEB on-orbit calibration methodologies and its onboard BB operational activities, this paper provides a comprehensive performance assessment of MODIS TEB quadratic calibration algorithm. It examines the scan-by-scan, orbit-by-orbit, daily, and seasonal variations of detector responses and associated impact due changes in the CFPA and instrument temperatures. Specifically, this paper will analyze the contribution by each individual thermal emissive source term (BB, scan cavity, and scan mirror), the impact on the Level 1 B data product quality due to pre-launch and on-orbit calibration uncertainties. A comparison of Terra and Aqua TEB on-orbit performance, lessons learned, and suggestions for future improvements will also be made.

Xiong, Xiaoxiong↗

Analysis of STS-134 Hail Event at Pad 39A, March 30, 2011

During the late afternoon of March 30, 2011 at approximately 21:25 - 21:30 GMT, hail monitor stations at Pad 39A recorded rice to pea size hail. The duration of the event was approximately 5 minutes. The maximum size detected by the three hail monitors was 10 - 12 mm. The 12 mm marble size value was measured by the active impact sensor at site #2, which experienced high winds. This 12 mm measurement may be artificially higher by one or two mm due to the extra hail kinetic energy resulting from the extreme horizontal winds. High winds from the west produced a few notable long streak-like dents in the hail pads. High winds were also responsible for damage to facilities near hail monitor site #2 on the west side of pad A (a dumpster was overturned, and a picnic table roof was demolished). NWS radar volume scan (see Figure I) showed 60-65 dBZ reflectivity values in the lowest 4 scan elevations around and over the pad 39A area. Since the lowest 0.5 degree scan showed a definite 65 dBZ signature, it is unlikely that hail had an opportunity to melt before reaching the ground. Some of the larger passive hail pad dents were shallower than what would be expected from solid frozen ice hydrometeor dents. Therefore, it is possible that the larger pea size hail may have been softer than the smaller rice size hail. This would be consistent with some melting before reaching the ground.

Lane, John E.↗

Effects of Uncertainty in TRMM Precipitation Radar Path Integrated Attenuation on Interannual Variations of Tropical Oceanic Rainfall

Considerable uncertainty surrounds the issue of whether precipitation over the tropical oceans (30 deg N/S) systematically changes with interannual sea-surface temperature (SST) anomalies that accompany El Nino (warm) and La Nina (cold) events. Time series of rainfall estimates from the Tropical Rainfall Measuring Mission (TRMM Precipitation Radar (PR) over the tropical oceans show marked differences with estimates from two TRMM Microwave Imager (TMI) passive microwave algorithms. We show that path-integrated attenuation derived from the effects of precipitation on the radar return from the ocean surface exhibits interannual variability that agrees closely with the TMI time series. Further analysis of the frequency distribution of PR (2A25 product) rain rates suggests that the algorithm incorporates the attenuation measurement in a very conservative fashion so as to optimize the instantaneous rain rates. Such an optimization appears to come at the expense of monitoring interannual climate variability.

Robertson, Franklin R.↗

Soil Moisture and Sea Surface Salinity Derived from Satellite-Borne Sensors

The monitoring of soil moisture and sea surface salinity over the Earth has been profoundly enhanced during the last thirteen years owing to new generation of satellite sensors. L-band radiometry is currently the only technology providing direct measurements of soil moisture, insensitive to surface roughness and distribution of elements in the soil, and the only technology that allows to measure sea surface salinity from space. The SMOS (Soil Moisture and Ocean Salinity) and SMAP (Soil Moisture Active Passive) satellite missions resolve global and local variability with a spatial resolution of approximately 43 km, a swath width close to 1000 km, and a sampling time, for each mission, of at least twice every 3 days. These resolutions and samplings can be increased by either merging data from the two sensors, and with complementary informations gathered with other passive or active sensors, or with in situ information at higher spatial resolution. Numerous scientific studies based on the use of this new type of measurement have led to a better understanding and constraint of the processes governing the variability of the water cycle, ocean circulation and the Earth's climate. The continuity of measurements, and the increased spatial and radiometric resolution is critical for fulfilling scientific needs. Future L-band radiometry missions currently being planned in Europe (the Copernicus Imaging Microwave Radiometer), and in China (the Ocean Salinity Mission) should provide better constraint on auxiliary parameters by combining multiple frequencies, but they will not have improved spatial resolution beyond SMOS and SMAP. The temporal continuity with SMOS and SMAP will most likely not be ensured. In parallel, new concepts are being developed to increase spatial resolution of both land and ocean parameters.

J. Boutin↗

James Webb Space Telescope Integrated Science Instrument Module Thermal Vacuum Thermal Balance Test Campaign at NASA's Goddard Space Flight Center

The James Webb Space Telescope is a large infrared telescope with a 6.5-meter primary mirror, designed as a successor to the Hubble Space Telescope when launched in 2018. Three of the four science instruments contained within the Integrated Science Instrument Module (ISIM) are passively cooled to their operational temperature range of 36K to 40K with radiators, and the fourth instrument is actively cooled to its operational temperature of approximately 6K. Thermal-vacuum testing of the flight science instruments at the ISIM element level has taken place in three separate highly challenging and extremely complex thermal tests within a gaseous helium-cooled shroud inside Goddard Space Flight Centers Space Environment Simulator. Special data acquisition software was developed for these tests to monitor over 1700 flight and test sensor measurements, track over 50 gradients, component rates, and temperature limits in real time against defined constraints and limitations, and guide the complex transition from ambient to final cryogenic temperatures and back. This extremely flexible system has proven highly successful in safeguarding the nearly $2B science payload during the 3.5-month-long thermal tests. Heat flow measurement instrumentation, or Q-meters, were also specially developed for these tests. These devices provide thermal boundaries o the flight hardware while measuring instrument heat loads up to 600 mW with an estimated uncertainty of 2 mW in test, enabling accurate thermal model correlation, hardware design validation, and workmanship verification. The high accuracy heat load measurements provided first evidence of a potentially serious hardware design issue that was subsequently corrected. This paper provides an overview of the ISIM-level thermal-vacuum tests and thermal objectives; explains the thermal test configuration and thermal balances; describes special measurement instrumentation and monitoring and control software; presents key test thermal results; lists problems encountered during testing and lessons learned.

JWST ISIM Thermal↗

Phase Identification in Real Distribution Networks with High PV Penetration Using Advanced Metering Infrastructure Data

Many distribution network monitoring and control applications - including state estimation, volt/VAR optimization, and network reconfiguration - rely on accurate network models; however, the network models maintained by utilities can become outdated because of restoration activities, network reconfiguration, and missing data. With the widespread deployment of advanced metering infrastructure (AMI), abundant measurement data from low-voltage secondary networks are available. The AMI measurement data can be used for phase identification to improve the network models. Although the existing phase identification techniques work well in passive distribution feeders that do not have photovoltaic (PV) generation, they can fail to accurately identify the phases in the presence of PV. This paper proposes a robust phase identification algorithm based on supervised machine learning that accurately identifies the AMI meter phase connectivity in the presence of significant PV generation. The proposed algorithm does not require network topology information or feeder head measurement data. The algorithm is validated using the AMI measurement data collected in the field and the field-validated phase connectivity database on two real distribution feeders from San Diego Gas & Electric Company that have significant PV generation.

advanced metering infrastructure↗

Phase Identification in Real Distribution Networks with High PV Penetration Using Advanced Metering Infrastructure Data: Preprint

Many distribution network monitoring and control applications - including state estimation, volt/VAR optimization, and network reconfiguration - rely on accurate network models; however, the network models maintained by utilities can become outdated because of restoration activities, network reconfiguration, and missing data. With the widespread deployment of advanced metering infrastructure (AMI), abundant measurement data from low-voltage secondary networks are available. The AMI measurement data can be used for phase identification to improve the network models. Although the existing phase identification techniques work well in passive distribution feeders that do not have photovoltaic (PV) generation, they can fail to accurately identify the phases in the presence of PV. This paper proposes a robust phase identification algorithm based on supervised machine learning that accurately identifies the AMI meter phase connectivity in the presence of significant PV generation. The proposed algorithm does not require network topology information or feeder head measurement data. The algorithm is validated using the AMI measurement data collected in the field and the field-validated phase connectivity database on two real distribution feeders from San Diego Gas & Electric Company that have significant PV generation.

advanced metering infrastructure↗

Phase Identification in Real Distribution Networks with High PV Penetration Using Advanced Metering Infrastructure Data

Many distribution network monitoring and control applications - including state estimation, Volt/VAr optimization, and network reconfiguration - rely on accurate network models; however, the network models maintained by utilities can become outdated because of restoration activities, network reconfiguration, and missing data. With the widespread deployment of advanced metering infrastructure (AMI), abundant measurement data from low-voltage secondary networks are available. The AMI measurement data can be used for phase identification to improve the network models. Although the existing phase identification techniques work well in passive distribution feeders that do not have photovoltaic (PV) generation, they can fail to accurately identify the phases in the presence of PV. This paper proposes a robust phase identification algorithm based on supervised machine learning that accurately identifies the AMI meter phase connectivity in the presence of significant PV generation. The proposed algorithm does not require network topology information or feeder-head measurement data. The algorithm is validated using the AMI measurement data collected in the field and the field-validated phase connectivity database on two real distribution feeders from San Diego Gas & Electric Company that have significant PV generation.

advanced metering infrastructure (AMI)↗

Surface Melting Over the Greenland Ice Sheet Derived From Enhanced Resolution Passive Microwave Brightness Temperatures (1979–2019)

Surface melting is a major component of the Greenland ice sheet surface mass balance, and it affects sea level rise through direct runoff and the modulation of ice dynamics and hydrological processes, supraglacially, englacially and subglacially. Passive microwave (PMW) brightness temperature observations are of paramount importance in studying the spatial and temporal evolution of surface melting due to their long temporal coverage (1979–present) and high temporal resolution (daily). However, a major limitation of PMW datasets has been the relatively coarse spatial resolution, which has historically been of the order of tens of kilometers. Here, we use a newly released PMW dataset (37 GHz, horizontal polarization) made available through a NASA “Making Earth System Data Records for Use in Research Environments” (MeASUREs) program to study the spatiotemporal evolution of surface melting over the Greenland ice sheet at an enhanced spatial resolution of 3.125 km. We assess the outputs of different detection algorithms using data collected by automatic weather stations (AWSs) and the outputs of the Modèle Atmosphérique Régional (MAR) regional climate model. We found that sporadic melting is well captured using a dynamic algorithm based on the outputs of the Microwave Emission Model of Layered Snowpack (MEMLS), whereas a fixed threshold of 245 K is capable of detecting persistent melt. Our results indicate that, during the reference period from 1979 to 2019 (from 1988 to 2019), surface melting over the ice sheet increased in terms of both duration, up to 4.5 (2.9) d per decade, and extension, up to 6.9 % (3.6 %) of the entire ice sheet surface extent per decade, according to the MEMLS algorithm. Furthermore, the melting season started up to 4.0 (2.5) d earlier and ended 7.0 (3.9) d later per decade. We also explored the information content of the enhanced-resolution dataset with respect to the one at 25 km and MAR outputs using a semi-variogram approach. We found that the enhanced product is more sensitive to local-scale processes, thereby confirming the potential of this new enhanced product for monitoring surface melting over Greenland at a higher spatial resolution than the historical products and for monitoring its impact on sea level rise. This offers the opportunity to improve our understanding of the processes driving melting, to validate modeled melt extent at high resolution and, potentially, to assimilate these data in climate models.

Surface melting↗

Uncovering the Role of Hole Traps in Promoting Hole Transfer from Multiexcitonic Quantum Dots to Molecular Acceptors

The understanding of electronic dynamics in multiexcitonic quantum dots (QDs) is important for designing efficient systems useful in high power scenarios, such as solar concentrators and multielectron charge transfer. The multiple charge carriers within a QD can undergo undesired Auger recombination events, which rapidly annihilate carriers on picosecond time scales and generate heat from absorbed photons instead of useful work. Compared to the transfer of multiple electrons, the transfer of multiple holes has proven to be more difficult due to slower hole transfer rates. To probe the competition between Auger recombination and hole transfer in CdSe, CdS, and CdSe/CdS QDs of varying sizes, we synthesized a phenothiazine derivative with optimized functionalities for binding to QDs as a hole accepting ligand and for spectroscopic observation of hole transfer. Transient absorption spectroscopy was used to monitor the photoinduced absorption features from both trapped holes and oxidized ligands under excitation fluences where the averaged initial number of excitons in a QD ranged from ~1 to 19. We observed fluence-dependent hole transfer kinetics that last around 100 ps longer than the predicted Auger recombination lifetimes, and the transfer of up to 3 holes per QD. Theoretical modeling of the kinetics suggests that binding of hole acceptors introduces trapping states significantly different from those in native QDs passivated with oleate ligands. Holes in these modified trap states have prolonged lifetimes, which promotes the hole transfer efficiency. These results highlight the beneficial role of hole-trapping states in devising hole transfer pathways in QD-based systems under multiexcitonic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Reference Ocean Surface Emission and Backscatter Model from Microwaves to Infrared

Satellite observations are vital for the initialization of Numerical Weather Prediction models, and very important for climate monitoring and prediction, as well as other applications such as hydrology and flood awareness prediction. Knowledge of radiative contributions from the Earth's surface is needed to sound the lower troposphere from space. The lack of a reference quality ocean emission and backscatter model is a major gap in our ability to provide absolute calibration of the satellite based observing system. Uncertainty in emissivity models is not well characterized and different models are used for different spectral bands, for active and passive instruments. An International Space Science Institute (ISSI) team was put together [4] to address these issues. The objectives of the team are to provide a reference model as a community software (i.e., documented and freely available code), that is maintained and supported, has traceable uncertainty estimations, and that enables new science from microwaves to infrared with bidirectional reflectance distribution function (BRDF) capability. We will present the model and its various components, discussing the choices between various parameterizations, building on the LOCEAN model of [2]. The model predictions will be evaluated at various frequencies, including comparisons to radiometric observations by SMAP, AMSR2 and GMI (e.g., [5]). We will discuss early model evaluation in the infrared and for active microwave sensors. Areas of ongoing research include improving the foam parametrization (coverage and emissivity) to provide consistent performances across frequencies, building on [1], and the azimuthal dependence of the active and passive signals. The model will be used to generate training data for fast models e.g., Fastem, [3], that are used in operational data assimilation and climate re-analysis.

Emmanuel Dinnat↗

Arctic Ocean Hydroacoustics

As the Arctic warms and loses its perennial ice cover, it is becoming more attractive for a variety of human uses. Hydroacoustic monitoring of this activity will grow in importance over the coming years and decades. Changes to the physical environment affect acoustic propagation and noise, with ramifications for our ability to detect and locate events and activities of interest. In this report, we use two long-term data sets from the Beaufort Sea, western Arctic Ocean, to determine how acoustic propagation conditions and seismic source detections are impacted by the changing environment: 1) oceanographic observations from ice-tethered profilers, and 2) passive acoustic recordings from a hydrophone. We find that changes to Beaufort Sea thermohaline stratification is stabilizing a subsurface duct, leading to more focused acoustic energy arrivals. Detections of catalogued submarine earthquakes show geographic differences in signal strength between seismic and acoustic waves. Signal strength increases with earthquake magnitude, but relationships to other source and path factors are less clear. Ambient noise also has clear seasonal patterns in the Arctic, with relatively low noise in the spring, higher noise near 1 Hz in summer, and higher noise near 10 Hz in winter. Climate change is expected to modify these seasonal noise patterns, impacting event detection. Future work will further investigate the mechanisms of ice effects on sound and couple acoustic modeling to an Earth System Model.

54 ENVIRONMENTAL SCIENCES↗

Crop moisture estimation over the southern Great Plains with dual polarization 1.66 centimeter passive microwave data from Nimbus 7

Moisture content of snow-free, unfrozen soil is inferred using passive microwave brightness temperatures from the scanning multichannel microwave radiometer (SMMR) on Nimbus-7. Investigation is restricted to the two polarizations of the 1.66 cm wavelength sensor. Passive microwave estimates of soil moisture are of two basic categories; those based upon soil emissivity and those based upon the polarization of soil emission. The two methods are compared and contrasted through the investigation of 54 potential functions of polarized brightness temperatures and, in some cases, ground-based temperature measurements. Of these indices, three are selected for the estimated emissivity, the difference between polarized brightness temperatures, and the normalized polarization difference. Each of these indices is about equally effective for monitoring soil moisture. Using an antecedent precipitation index (API) as ground control data, temporal and spatial analyses show that emissivity data consistently give slightly better soil moisture estimates than depolarization data. The difference, however, is not statistically significant. It is concluded that polarization data alone can provide estimates of soil moisture in areas where the emissivity cannot be inferred due to nonavailability of surface temperature data.

Mcfarland, M. J.↗

Degradation science: Integrating modeling and experiments to predict localized corrosion processes (Annual Progress Report)

Additively manufactured (AM) eutectic high-entropy alloys (EHEAs), such as nano-lamellar AlCoCrFeNi 2.1 , have excellent strength, ductility, and wear resistance even at elevated temperatures, but their corrosion behavior in aggressive acids at different length scales remain poorly understood. This work investigates the corrosion behavior of laser powder bed–fused (L-PBF) AlCoCrFeNi 2.1 as a function of annealing temperatures, probing degradation mechanisms from nanoscopic to macroscopic length scales. The alloy is dual phase consisting of a ductile FCC L1 2 phase and a high-strength BCC B2 phase. Rapid solidification during L-PBF produces a far-from-equilibrium nano-lamellar structure with nearly homogeneous elemental distribution, which tends to evolve upon annealing toward Cr/Co/Fe-enriched FCC and Al/Ni-enriched B2. Three conditions were studied: as-printed, 600 °C/5 h, and 1000 °C/1 h, over which B2 lamellae coarsen, lamellar spacing increases, and elemental segregation becomes more prominent. Microstructure and chemistry were characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), while in-situ electrochemical atomic force microscopy (EC-AFM) was used to link early (<5 h) local dissolution to microstructure after exposure in sulfuric acid. EC-AFM highlights preferential dissolution of the BCC/B2 phase where the surrounding matrix is Cr-depleted and directly quantifies the dissolution rates within individual phases, tracks the transition from early nano-scale attack to partial repassivation, to correlate height differences with current and impedance responses. To monitor longer-term behavior (up to 96 h), ex-situ AFM, SEM, and confocal imaging were combined with conventional bulk electrochemical tests, bridging nanoscale observations to micro/meso-scale damage morphologies. At the meso-scale, the deepest dissolution channels align with the build-direction lamellae and melt-pool boundaries, indicating that printing directionality guides the propagation of these localized corrosion sites. Annealing modifies corrosion by restructuring BCC/FCC phase fractions, lamellar spacing, and Cr/Al segregation, thereby changing the cathode/anode ratio and passive film stability. The results clarify how as-printed and annealed nano-lamellar architectures differ in their susceptibility to selective dissolution; how elemental segregation competes with residual stresses along the build direction. With these insights, future work will use CALPHAD-guided alloy modification to stabilize higher Cr contents in the B2 phase while retaining a dominant FCC+B2/BCC microstructure, with the goal of designing mechanically robust, corrosion-resistant EHEAs for safety-critical applications to leverage the LLNL’s broader national and global security mission.

36 MATERIALS SCIENCE↗

Passive films on magnesium anodes in primary batteries

The characteristics of the passive films over Mg anodes, which essentially govern the voltage delay of the latter, have been determined nondestructively from an analysis of the transient and steady-state response of the electrode potential to low amplitude galvanostatic polarization under various experimental conditions viz., with different corrosion inhibitor coatings on Mg, after various periods of ageing of anode in solutions containing corrosion inhibitors, at various low temperatures etc. Using these parameters, the kinetics of film build-up or dissolution under these conditions have been monitored. The morphology of the anode film has been verified with scanning electron microscopy. Similar transients at low temperatures point out a steep rise in the film resistivity which is essentially responsible for the severe voltage delay. Finally, possible application of this technique in secondary Li batteries to improve cycling characteristics of the Li anode has been pointed out.

Ratnakumar, B. V.↗