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At least 181 records · Page 10

Mars Oxidant and Radical Detector

The Mars Oxidant and Radical Detector is an instrument designed to characterize the reactive nature of the martian surface environment. Using Electron Paramagnetic Resonance (EPR) techniques, this instrument can detect, identify, and quantify radical species in soil samples, including those inferred to be present by the Viking experiments. This instrument is currently funded by the Mars Instrument Development Program and is compatible with the Mars Science Laboratory mission.

Yen, A. S.↗

Evaluation of Oxygen Interactions with Materials 3: Mission and induced environments

The Evaluation of Oxygen Interactions with Materials 3 (EOIM-3) flight experiment was developed to obtain benchmark atomic oxygen/material reactivity data. The experiment was conducted during Space Shuttle mission 46 (STS-46), which flew July 31 to August 7, 1992. Quantitative interpretation of the materials reactivity measurements requires a complete and accurate definition of the space environment exposure, including the thermal history of the payload, the solar ultraviolet exposure, the atomic oxygen fluence, and any spacecraft outgassing contamination effects. The thermal history of the payload was measured using twelve thermocouple sensors placed behind selected samples and on the EOIM-3 payload structure. The solar ultraviolet exposure history of the EOIM-3 payload was determined by analysis of the as-flown orbit and vehicle attitude combined with daily average solar ultraviolet and vacuum ultraviolet (UV/VUV) fluxes. The atomic oxygen fluence was assessed in three different ways. First, the O-atom fluence was calculated using a program that incorporates the MSIS-86 atmospheric model, the as-flown Space Shuttle trajectory, and solar activity parameters. Second, the oxygen atom fluence was estimated directly from Kapton film erosion. Third, ambient oxygen atom measurements were made using the quadrupole mass spectrometer on the EOIM-3 payload. Our best estimate of the oxygen atom fluence as of this writing is 2.3 +/- 0.3 x 10(exp 20) atoms/sq cm. Finally, results of post-flight X-ray photoelectron spectroscopy (XPS) surface analyses of selected samples indicate low levels of contamination on the payload surface.

Koontz, Steven L.↗

The critical role of configurational flexibility in facilitating reversible reactive metal deposition from borohydride solutions

Development of calcium metal batteries has been historically frustrated by a lack of electrolytes capable of supporting reversible calcium electrodeposition. In this paper, we report the study of an electrolyte consisting of Ca(BH 4 ) 2 in tetrahydrofuran (THF) to gain important insight into the role of the liquid solvation environment in facilitating the reversible electrodeposition of this highly reactive, divalent metal. Through interrogation of the Ca 2+ solvation environment and comparison with Mg 2+ analogs, we show that an ability to reversibly electrodeposit metal at reasonable rates is strongly regulated by dication charge density and polarizability. Our results indicate that the greater polarizability of Ca 2+ over Mg 2+ confers greater configurational flexibility, enabling ionic cluster formation via neutral multimer intermediates. Increased concentration of the proposed electroactive species, CaBH 4 + , enables rapid and stable delivery of Ca 2+ to the electrode interface. Finally, this work helps set the stage for future progress in the development of electrolytes for calcium and other divalent metal batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The stability of Cl-, Br-, and I-passivated Si(100)-(2 × 1) in ambient environments for atomically-precise pattern preservation

Abstract Atomic precision advanced manufacturing (APAM) leverages the highly reactive nature of Si dangling bonds relative to H- or Cl-passivated Si to selectively adsorb precursor molecules into lithographically defined areas with sub-nanometer resolution. Due to the high reactivity of dangling bonds, this process is confined to ultra-high vacuum (UHV) environments, which currently limits its commercialization and broad-based appeal. In this work, we explore the use of halogen adatoms to preserve APAM-derived lithographic patterns outside of UHV to enable facile transfer into real-world commercial processes. Specifically, we examine the stability of H-, Cl-, Br-, and I-passivated Si(100) in inert N 2 and ambient environments. Characterization with scanning tunneling microscopy and x-ray photoelectron spectroscopy (XPS) confirmed that each of the fully passivated surfaces were resistant to oxidation in 1 atm of N 2 for up to 44 h. Varying levels of surface degradation and contamination were observed upon exposure to the laboratory ambient environment. Characterization by ex situ XPS after ambient exposures ranging from 15 min to 8 h indicated the Br– and I–passivated Si surfaces were highly resistant to degradation, while Cl–passivated Si showed signs of oxidation within minutes of ambient exposure. As a proof-of-principle demonstration of pattern preservation, a H–passivated Si sample patterned and passivated with independent Cl, Br, I, and bare Si regions was shown to maintain its integrity in all but the bare Si region post-exposure to an N 2 environment. The successful demonstration of the preservation of APAM patterns outside of UHV environments opens new possibilities for transporting atomically-precise devices outside of UHV for integrating with non-UHV processes, such as other chemistries and commercial semiconductor device processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Environmental stability of additively manufactured siliconized silicon carbide for applications in hybrid energy systems

A key consideration for the successful operation of hybrid energy systems will be the environmental stability of materials used for their construction, particularly when experiencing service environments containing water vapor at high temperatures. Here, we report results from the characterization of siliconized silicon carbide (Si-SiC) prepared via binder jet additive manufacturing and reactive silicon melt infiltration after being exposed to environments representative of those in solid oxide fuel cell (SOFC) anodes, and to exhaust gases inside a microturbine operating on natural gas. In both cases, it was found that oxide scales formed on the surface and that these scales were dense, continuous, and well-bonded to the substrates, although there was evidence of transverse and longitudinal cracking most likely as a result of mismatches in the thermal expansion of the scale and the substrate. Measured values of the thickness of the oxide scale were compared to those predicted by parabolic oxidation kinetics of silicon, but the potential effects of silica volatilization induced by water vapor, and silica reduction when exposed to hydrogen are discussed. The overall results showed that the oxide scale is expected to be protective under the conditions of hybrid power generation systems.

36 MATERIALS SCIENCE↗

A streamlined software environment for situated skills

This paper documents a powerful set of software tools used for developing situated skills. These situated skills form the reactive level of a three-tiered intelligent agent architecture. The architecture is designed to allow these skills to be manipulated by a task level engine which is monitoring the current situation and selecting skills necessary for the current task. The idea is to coordinate the dynamic activations and deactivations of these situated skills in order to configure the reactive layer for the task at hand. The heart of the skills environment is a data flow mechanism which pipelines the currently active skills for execution. A front end graphical interface serves as a debugging facility during skill development and testing. We are able to integrate skills developed in different languages into the skills environment. The power of the skills environment lies in the amount of time it saves for the programmer to develop code for the reactive layer of a robot.

Yu, Sophia T.↗

Bioinspired mineralizing microenvironments generated by liquid-liquid phase coexistence

Biominerals such as bones, teeth and shells exhibit improved mechanical properties and intricate morphologies not seen in nonbiologically-produced minerals of ostensibly the same composition. These remarkable properties of biogenic minerals are thought to arise due to precise local control over the mineral deposition process, including organic and inorganic inclusions. Understanding how Biology controls the local reaction environment during formation of these materials to control their composition, structure, and properties is a grand challenge that promises to enable new routes to high-performance materials. This project developed multi-compartment bioinspired microreactors as artificial mineralizing vesicles, and used them to understand and control formation of inorganic/organic composite solid materials. A major emphasis was on developing all-aqueous emulsions in which each droplet was a structured microreactor with two or more adjacent phases. This approach provided local control over reaction environment including availability of inclusions such as polypeptides and metal ions, while being sufficiently simple to produce large populations of essentially identical multiphase reactor droplets simultaneously within a batch. Organic/inorganic composite materials could be produced with very high organic content that stabilized the inorganic portions as amorphous materials (e.g., amorphous calcium carbonate) by preventing the typical conversion to more thermodynamically crystalline forms (e.g., calcite). These stabilized amorphous composites could be stored indefinitely and converted to crystalline forms later by removal of the organic inclusions via, for example, heating. Compositional gradients in the organic and inorganic components were embedded during synthesis due to the evolution of the reaction microenvironment, and despite the complexity of this process it occurred similarly across the population of reactive droplets and was hence encoded into the population of resulting composite particles. The approach developed here allows pre-structuring of reactive microenvironments to control the spatiotemporal reaction environment, which is an important step towards rational design and on-demand production of complex functional materials with desired composition, optical properties, and mechanical response.

36 MATERIALS SCIENCE↗

Metaoptics Enabled Multifunctional Imaging

Despite the fact that most microorganisms occupy two- and three-dimensional space in heterogeneous arrangements and in proximity to other microorganisms of different species, much of our current knowledge about their metabolic processes is derived from homogenizing, then analyzing, the chemical content of cultures containing a single microbial species. This project addressed this fundamental dichotomy by developing a set of optical imaging principles combining multiple new technologies. The imaging strategies developed in this project combine metaoptics structures with active in situ nanoscale control of the chemical environment and applied them to a microbial system, Myxococcus xanthus, with particular relevance to the DoE mission. The combination of metaoptical architectures and nanoscale control over the molecular environment enables: (a) precise control over the electromagnetic (EM) field at length scales smaller than the wavelength of light; (b) control of the interaction of the EM field with critical molecular systems in DOE relevant microbes; (c) control over the chemical environment – especially the presence and quantity of reactive oxygen species (ROS) that can affect redox homeostasis; and (d) the ability to ask new kinds of questions not accessible to ‘omics’ approaches or standard methods of biological imaging. These capabilities are applicable to detailed studies of metabolic pathways in microbes and to lignocellulosic biomass deconstruction. To accomplish these objectives, we pursued two over-arching technical goals: (1) the development of new metaoptics-enabled approaches to imaging and spectroscopic characterization; and (2) the development of tools to control the chemical environment of a microbial sample with nanometer-scale precision. Goal 1 was addressed through the design, fabrication, and characterization of new metasurfaces capable of super-resolution imaging through extreme confinement of the optical field. Goal 2 was addressed by controlling the redox potential on the nanoscale in microbial communities and characterizing their effect on intrinsic bacterial fluorophores which act as molecular sentinels and through characterization of soluble factors secreted by Myxococcus xanthus by confocal Raman imaging. The optical imaging/sensing approaches developed here make it possible to use these powerful new imaging and sensing modalities in metabolic studies by making it possible to visualize and track the spatial and temporal expression patterns of natural or engineered pathways in microorganisms.

09 BIOMASS FUELS↗

Heterometallic Ce IV / V V Oxo Clusters with Adjustable Catalytic Reactivities

Heterometallic Ce IV /M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce 12 V 6 oxo clusters with different capping ligands: Ce 12 V 6 -SO 4 , Ce 12 V 6 -OTs (OTs: toluenesulfonic acid), and Ce 12 V 6 -NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce 12 V 6 cubane core formulated [Ce 12 (VO) 6 O 24 ] 18+ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV–vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance ( 1 H NMR) proved the successful coordination of the organic ligands to the Ce 12 V 6 core, liquid phase 51 V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce 12 V 6 core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce 12 V 6 -OTs and Ce 12 V 6 -NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce 12 V 6 -SO 4 . Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). Furthermore, this work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep Reactive Ion Etching (DRIE) of High Aspect Ratio SiC Microstructures using a Time-Multiplexed Etch-Passivate Process

High aspect ratio silicon carbide (SiC) microstructures are needed for microengines and other harsh environment micro-electro-mechanical systems (MEMS). Previously, deep reactive ion etching (DRIE) of low aspect ratio (AR less than or = 1) deep (greater than 100 micron) trenches in SiC has been reported. However, existing DRIE processes for SiC are not well-suited for definition of high aspect ratio features because such simple etch-only processes provide insufficient control over sidewall roughness and slope. Therefore, we have investigated the use of a time-multiplexed etch-passivate (TMEP) process, which alternates etching with polymer passivation of the etch sidewalls. An optimized TMEP process was used to etch high aspect ratio (AR greater than 5) deep (less than 100 micron) trenches in 6H-SiC. Power MEMS structures (micro turbine blades) in 6H-SiC were also fabricated.

Evans, Laura J.↗

Latent Virus Reactivation in Astronauts and Shingles Patients

Spaceflight is a uniquely stressful environment with astronauts experiencing a variety of stressors including: isolation and confinement, psychosocial, noise, sleep deprivation, anxiety, variable gravitational forces, and increased radiation. These stressors are manifested through the HPA and SAM axes resulting in increased stress hormones. Diminished T-lymphocyte functions lead to reactivation of latent herpesviruses in astronauts during spaceflight. Herpes simplex virus reactivated with symptoms during spaceflight whereas Epstein-Barr virus (EBV), cytomegalovirus (CMV), and varicella zoster virus (VZV) reactivate and are shed without symptoms. EBV and VZV are shed in saliva and CMV in the urine. The levels of EBV shed in astronauts increased 10-fold during the flight; CMV and VZV are not typically shed in low stressed individuals, but both were shed in astronauts during spaceflight. All herpes viruses were detected by polymerase chain reaction (PCR) assay. Culturing revealed that VZV shed in saliva was infectious virus. The PCR technology was extended to test saliva of 54 shingles patients. All shingles patients shed VZV in their saliva, and the levels followed the course of the disease. Viremia was also found to be common during shingles. The technology may be used before zoster lesions appear allowing for prevention of disease. The technology may be used for rapid detection of VZV in doctors offices. These studies demonstrated the value of applying technologies designed for astronauts to people on Earth.

Mehta, Satish K.↗

Atomic cluster expansion potential for large scale simulations of hydrocarbons under shock compression

We present an Atomic Cluster Expansion (ACE) machine learned potential developed for high-fidelity atomistic simulations of hydrocarbons, targeting pressures and temperatures near and above supercritical fluid regimes for molecular fluids. A diverse set of stoichiometries were covered in training, including 1:0 (pure carbon), 1:4 (methane), and 1:1 (benzene), and rich bonding environments sampled at supercritical temperatures, hydrogen rich, reactive mixtures where metastable stoichiometries arise, including 1:2 (ethylene) and 1:3 (ethane). A high-fidelity training database was constructed by performing large-scale quantum molecular dynamic simulations [density functional theory (DFT) MD] of diamond, graphite, methane, and benzene. A novel approach to selecting structures from DFT MD is also presented, which allows for the rapid selection of unique DFT MD frames from complex trajectories. Comparisons to DFT and experimental data demonstrate that the presented ACE potential accurately reproduces isotherms, carbon melting curves, radial distribution functions, and shock Hugoniots for carbon and hydrocarbon systems for pressures up to 100 GPa and temperatures up to 6000 K for hydrocarbon systems and up to 9000 K for pure carbon systems. This work delivers a potential that can be used for accurate, large-scale simulations of shocked hydrocarbons and demonstrates a methodology for fitting and validating machine learning interatomic potentials to complex molecular environments, which can be applied to energetic materials in future works.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Overview of Experiments and Modeling of Polysiloxane-Coated Thermal Protection Systems for Missions to Mars, Titan, and Beyond.

Phenolic Impregnated Carbon Ablator (PICA) gained heritage during the historic Stardust mission, where it successfully returned samples from a comet’s tail and has since been instrumental in delivering payloads to the surface of Mars [1-3]. Most recently, PICA enabled the safe return of samples collected from asteroid Bennu as part of the OSIRIS-REx mission. This rich legacy underscores PICA’s critical role in allowing NASA’s most ambitious exploration missions. However, the friable nature of its phenolic phase presents challenges during handling and pre-launch activities. To mitigate this issue, PICA is coated with a polysiloxane resin system, which serves to suppress particulate dispersion and thereby safeguard spacecraft components. A comprehensive understanding of the polysiloxane resin’s behavior is imperative, as it profoundly shapes the material response of PICA during atmospheric entry by influencing its thermal and oxidative stability. This influence extends to thermocouple plugs embedded within thermal protection systems. These plugs have demonstrated their significance in missions such as Mars Science Laboratory (MSL) and Mars 2020, where the MEDLI and MEDLI2 instrumentation suites delivered in-valuable insights into the performance of thermal protection systems during entry into the Martian atmosphere [4]. Looking ahead, missions such as Dragonfly, set to descend into Titan’s dense atmosphere, aim to leverage advanced sensor technologies to further refine our understanding of thermal protection response [5]. Moreover, thermocouple plugs play an essential role in validating cutting-edge material response models, such as those pioneered under NASA’s Entry Systems Modeling Project (ESM), designed, in-part, to predict the operational integrity of thermal protection systems under the extreme stresses of atmospheric entry. To achieve these modeling goals, ground-based experiments are crucial to provide the foundational data necessary for developing and refining these predictive tools. To this end, an extensive test campaign was conducted at the Hypersonic Materials Environmental Test System (HyMETS) to investigate the high-temperature behavior of the polysiloxane resin in an air environment [6]. These experiments revealed critical phenomena, including the formation of a silicon oxycarbide layer that enhances oxidation resistance, moderates surface temperatures, and alters in-depth thermal response. Building on these findings, subsequent tests were designed to simulate atmospheric entry conditions in reactive gases, such as CO2 and N2, to mimic the environments of Mars and Titan, respectively, as well as non-reactive gases representing the atmospheres of the Ice Giants (Neptune and Uranus). A heating rate dependent decomposition mechanism has been identified for the polysiloxane resin under oxidizing conditions (Fig. 1). In the initial stage, the resin and the underlying thermal protection system undergo pyrolysis, rapidly generating a thin amorphous silicon oxycarbide interwoven with carbonaceous char and residual fibers from PICA. During the second stage, the nascent oxide layer establishes a robust, oxidation-resistant thermal barrier coating, which significantly impedes heat transfer to the underlying carbonaceous char, resulting in a stagnation of the surface temperature. A key factor contributing to this thermal resistance is the low recombination efficiency of atomic oxygen (γ), which further diminishes the heat load on the material’s interior layers [7]. Moreover, as the surface temperature stagnates, the silicon oxycarbide phase separates into distinct regions of silica and free graphite. Ultimately, when the heat flux reaches a critical threshold, a third stage is triggered, leading to the breakdown of the coating through carbothermal reduction, exposing the underlying char layer. This exposure leads to a dramatic surface temperature spike, driven by highly exothermic reactions between atomic oxygen and the char layer, further accelerating material degradation. A detailed mass and heat transfer model of PICA coated with polysiloxane resin was implemented in the Porous material Analysis Toolbox based on OpenFOAM, PATO [8]. The initial stage was considered negligible in this model because the resin decomposition occurs rapidly within a thin surface layer. Instead, the coating was directly considered as an oxygen-resistant thermal barrier coating. For the second stage, the thin amorphous silicon oxycarbide was treated as a pure silica surface to simplify the thermochemical behavior. The model ac-counts for surface equilibrium processes using representative elements of the coating-environment system. For the third stage, specific boundary conditions were developed to estimate the onset and progression of the coating removal. Two-dimensional material response simulations were conducted to compare uncoated and coated PICA using boundary conditions calibrated with HyMETS data. Fig. 2 illustrates that the simulations closely align with experimental data, successfully reproducing measured temperature profiles. This work will include the latest advancements in the coating model, including the calibration of recombination of atomic oxygen at the surface during the second phase. These simulated results will be further validated against additional CO2 data points from HyMETS, reinforcing the models’ predictive capabilities. These mechanisms and their effects on thermal protection systems, including thermochemical behavior and thermocouple probe performance in extreme environments, provide crucial insights for optimizing spacecraft designs that safeguard scientific payload and ensure mission success in future planetary exploration endeavors.

Active Oxidation↗

Metal–Organic Framework Nodes as a Supporting Platform for Tailoring the Activity of Metal Catalysts

Catalysis is a ubiquitous element of the modern economy, representing a cornerstone of many sectors including energy, materials, and pharmaceuticals. Within this realm, 80% of reactions are carried out by heterogeneous catalysts due to their advantageous physical and chemical characteristics. In some heterogeneous systems, the reaction rate can be optimized through rational catalyst design, in which support materials can be tailored structurally and stereoelectronically for targeted purposes to better facilitate the catalytic reaction. To this end, metal-organic frameworks (MOFs) have garnered recent attention due to their high porosity, crystallinity, and chemical tunability, which can be used to derive structure-activity relationships in the design of catalysts. In this Perspective, we survey examples of catalytically active guest metals on the inorganic nodes of MOFs. This is done with the intention of providing design guidelines for tailoring chemical reactivity and insights into the opportunities for future growth in this field. Strategies for rational design in MOF catalysis include electronic tuning of the metal node in the MOF support, installing promoter ions onto the node to effect the reactivity of grafted metals, modulation of the spatial environment around the transition metal using the metal node structure, and achieving site uniformity in supported catalysts. By highlighting these efforts, we seek to underscore the role of MOF nodes as nonspectator supports for catalytic metal complexes and provide future directions for rational catalyst design by tuning reactivity on these anchoring platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coatings in space environment

The behavior in space environment of evaporated Al uncoated and coated with reactively deposited silicon oxide (SiOx), electron beam evaporated SiO2 and Al2O3, and Al and Ag coated with double layers of Al2O3 + SiOx is compared with metallized Teflon and Kapton, anodized Al (Alzak), and white paints. Flight data from three calorimetric experiments and one reflectometer flown in different orbital environments are compared with laboratory test data. The results demonstrate that evaporated thin films are extremely versatile and stable coatings for space applications. Through the use of control samples studied in different laboratory tests and monitored for up to 12,000 hours of solar exposure in different orbits, a classification of orbital severity and an estimate of laboratory simulation accuracy is obtained.

Triolo, J. J.↗

Investigating the Effects of Exposure to Blue-Enriched Light or Peppermint Odor on Alertness, Mood, and Performance Upon Awakening from Deep Sleep at Night

Introduction: Sleep inertia refers the transient neurobehavioral impairments experienced immediately after waking from sleep. This period of reduced alertness and performance poses a significant safety risk to on-call workers who may be required to perform a safety-critical task immediately after waking (e.g., emergency services, health care, and military). In these operations, the need for a rapid return to full alertness is critical to mission safety and success. Several factors may exacerbate sleep inertia, resulting in greater impairment upon waking, including: waking from deep sleep, (i.e., slow wave sleep, SWS), waking at night, and waking following prior sleep loss. Awakenings under these conditions are common for on-call and extended shift workers who may need to perform safety-critical tasks soon after waking from unprotected sleep opportunities. Therefore, there is a need for evidence-based reactive countermeasures (i.e., used upon waking) to the cognitive consequences sleep inertia. Specifically, countermeasures that can rapidly restore alertness and performance immediately following sleep. A recent review of the literature on reactive countermeasures highlighted several research gaps and promising candidates for further investigation. The review also emphasized the need for countermeasures that are operationally viable and readily deployed in occupational settings. This study aims to address the identified gaps and limitations by assessing the efficacy of exposure to two known acute alerting stimuli - blue-enriched light and peppermint odor - to improve cognitive performance, alertness, and mood immediately after waking from SWS at night. Materials and Methods: Twelve participants completed a two-week within-subject, randomized, cross-over intervention study including two in-laboratory overnight visits. During each experimental week, the subjects experienced one intervention (light or peppermint) and a control condition upon awakening from SWS at night. The presentation order of the two conditions (intervention or control) at wake-up and the order of intervention (light or peppermint) by week was randomized by sex. Prior to each in-laboratory visit, participants maintained a sleep schedule of 8.5 h for 5 nights and 5 h for one night. Compliance with this sleep schedule was confirmed by actigraphy. In the laboratory, participants went to bed at their habitual bedtime and were monitored by standard polysomnography. After at least five minutes of continuous SWS, participants were awoken and exposed, in a randomized order, to either the control or intervention condition. During the hour after awakening from SWS (at 2, 17, 32, and 47 minutes after waking), participants completed a battery of tasks including a 5-minute psychomotor vigilance task (PVT), a subjective scale of alertness (Karolinska Sleepiness Scale, KSS), and visual analogue scales (VAS) of mood. Following this sleep inertia measurement period, all lights were turned off and participants were allowed to return to sleep. They were then awoken again from their subsequent SWS period and exposed to the alternative condition (control or intervention). Following this second awakening, participants were allowed to sleep until their habitual wake time and were then released from the laboratory. Participants then followed the at-home sleep schedule and returned to the laboratory for the second intervention (light or peppermint) following the procedures described above. The light intervention involved exposure to a blue-enriched light canvas illuminated for 1 hour at a distance of ~56 cm from the participant (~200 lux and ~60 melanopic lux at angle of gaze). For the peppermint intervention, peppermint oil was pipetted onto a mask, and participants inhaled the odor with the mask covering the nose and mouth for 1 minute. The control condition for both weeks involved a dim, red ambient light (<1 lux). An odorless mask, without any oil pipetted onto the mask, was also worn in the peppermint control condition. Results: Compared to the control condition, participants exposed to blue-enriched light had fewer PVT lapses (χ2 = 5.285, p = .022), reported feeling more alert (KSS: F1,77 = 4.955, p = .029; VASalert: F1,77 = 8.226, p = .005), and had improved mood (VAScheerful: F1,77 = 8.615, p = .004; VASdepressed: F1,77 = 4.649, p = .034; VASlethargic: F1,77 = 5.652, p = .020). Exposure to peppermint oil did not improve any outcome measures on any of the tasks compared to control condition (p > .05). Conclusions: We found that participants had fewer lapses of attention upon awakening when exposed to blue-enriched light compared to dim, red light. In addition, participants reported feeling more alert, more cheerful, less depressed, and less lethargic in the blue-enriched light condition. Brief exposure to a peppermint odor, however, did not appear to improve performance, alertness, or mood under the experimental conditions. Our null results in the peppermint condition may have been due to methodological limitations such as the duration and method of administration. Given the need to mitigate the potential impact of sleep inertia on safety-critical tasks in on-call operations, our findings suggest that blue-enriched light exposure upon awakening may help to improve performance and alertness during the sleep inertia period following awakening from deep, nocturnal sleep. We are currently exploring the potential mechanisms for the effect of light on cognitive performance upon awakening as well as investigating its application in real-world settings to explore the translational efficacy of this countermeasure to occupational environments. Continued exploration into light and other reactive countermeasures, and potentially their combination, is needed in order to provide evidence-based guidance on effective sleep inertia countermeasures to improve the alertness and performance of those required to perform safety-critical tasks soon after waking.

sleep inertia↗

On the Pressure Generated by Thermite Reactions Using Stress-Altered Aluminum Particles

Here we examine pressure build-up and decay in thermites upon impact ignition and interprets reactivity based on the holistic pressure history. The thermite is a mixture of aluminum (Al) combined with bismuth trioxide (Bi 2 O 3 ) powder. Four different Al particles sizes were examined that ranged from 100 nm to 18.5 μm mean diameter and for each size, two different Al powder treatments were examined: stress-altered compared to untreated, as-received Al powder. Stress-altered Al powders have been shown to be more reactive, such that the stress-altered Al powder thermites offer a metric for analyzing thermite reactivity in terms of pressure development compared to untreated Al powder. In a binary thermite system, multiple phase changes and interface chemistry influence the transient pressure response during reaction. Results reveal three key pressure metrics that need consideration specifically for thermite combustion: (1) delay time to peak pressure, (2) peak pressure, and (3) decay after peak pressure. Our experiments show that a lower peak pressure corresponds with higher thermite reactivity because aluminum consumption of oxygen generated by decomposing solid oxidizer reduces the peak pressure. Faster rates of reaction consume oxygen at higher rates such that pressure development becomes more limited than less reactive thermites and the result is a lower peak pressure. This conclusion is opposite of traditional studies using metal fuels with a gaseous environment that typically show higher peak pressures correspond with greater reactivity.

42 ENGINEERING↗

Multi–length scale characterization of point defects in thermally oxidized, proton irradiated iron oxides

A key for the success of safe nuclear power generation system is to consider structural materials that are economical, meet mechanical property needs, possess good corrosion resistance, and are radiation tolerant. Nevertheless, fundamental insights that elucidate the details of radiation damage on materials corrosion performance are lacking. This includes the behavior of surface oxides which often regulate corrosion. For example, it is unclear how non-equilibrium point defects, oxide structure, mass transport in oxides, and subsequent oxidation behavior are altered by the radiation. Here, in this work, some of the effects of proton irradiation on the attributes of point defects, iron oxide microstructures, and the physical nature of the oxidation product were correlated with corrosion behavior. Iron oxides, fabricated by thermal oxidation in air at 400°C and 800°C for 1 h, were subjected to 200 keV, 0.03 dpa (displacements per atom) of proton irradiation, and subjected to corrosion reactivity assessment using AC and DC electrochemical methods. Experimental methods that target materials information at different length scales, such as positron annihilation spectroscopy (atomistic), transmission electron microscopy (mesoscopic), and electrochemical methods (macroscopic), were coupled to shed light on the impact of radiation-induced defect modifications and structural changes in oxides on corrosion reactivity which ultimately affects durability in harsh environments.

36 MATERIALS SCIENCE↗