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Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da

Physical Modeling and Design of a Nonvolatile Optically Gated High‐Power Diamond Transistor

In this work, we present the theory and modeling framework of a diamond optically gated junction field‐effect transistor (DOGFET). The device utilizes nitrogen substitutional centers in type‐1b diamond to optically modulate a p‐ boron doped diamond channel. Using sub‐gap lasers with intensities as low as 100 W/cm 2 , electrons are optically excited from substitutional nitrogen sites to the conduction band of the diamond substrate, thus enabling the optical gate to exercise control on modulating the space‐charge region at the junction and therefore the channel conductivity. We show that the device can deliver a current of 7 μA/μm, or equivalently 1750 A/cm 2 , while switching at a frequency greater than 100 kHz, in a form factor of 5 μm 2 . The breakdown voltage is found to be greater than 1850 V, with a breakdown field strength of ~13 MV/cm. Moreover, the device supports nonvolatile operation with a “memory effect” enabling single transistor state retention. The presented simulation framework provides a physically grounded insight into the limits and opportunities of optoelectronic diamond systems.

Engineering - Electronic and electrical engineerin

Investigating Laser Beam Welding as an In-Space Joining Technique via Thermal Vacuum and Microgravity and Vacuum Experiments

In-space joining technologies are crucial for stimulating an in-space economy and for enabling sustained space exploration by in-space manufacturing and repair of metallic structures. Compared to brazing or soldering, in-space welding (ISW) can provide highly hermetic, strong, and complex joints, potentially without introducing additional material. However, the influence of extreme temperatures, reduced pressure, and reduced gravity on ISW is not yet fully elucidated. Several efforts at NASA are investigating laser beam welding (LBW) as a joining and repair method in both thermal vacuum (TVAC) and combined vacuum & reduced gravity environments. NASA Marshall Space Flight Center (MSFC) shepherded several ISW projects in its past, including the 1973 electron beam welding on Skylab, the 1989 low-power LBW on parabolic flights, and the unflown 1990s-era In-Space Welding Experiment. Recent parabolic flights and 3 degree-of-freedom ground testing build upon this heritage. A collaboration with the Ohio State University using NASA Langley Research Center (LaRC) hardware retrofitted for LBW achieved the first high-powered laser welds under vacuum and low gravity and developed a workforce capable developing such experimental hardware. A ground testing campaign at the MSFC Flat Floor simulated fit-up and welding representative of ISW in 3 degrees of freedom to emulate microgravity effects on inertial systems. One ongoing effort is a NASA Early Career Initiative project – Lunar Assembly and Servicing by Autonomous Robotics (LASAR). Ruggedized LBW components were developed by an external partner for use in TVAC. A TVAC-rated robotic arm was procured by MSFC and used in the first known robotic laser weld where all components save the laser generator were under vacuum. NASA Johnson Space Center (JSC) is advancing supervised autonomy of ISW. NASA LaRC continues to adapt their unique snowflake joint geometry, suitable for connecting segments in trusses and other structures, to LBW. Upcoming TVAC campaigns will focus on testing extreme temperatures, proving out autonomous operations, and demonstrating weld repair. Weld inspection will occur via a non-contact nondestructive evaluation (NDE) technique – electromagnetic acoustic transduction (EMAT). Another ongoing effort based at MSFC is the DISCMAN -- DIsk-Shaped Configurable and Modular vAcuum uNit – which seeks to development a compact, modular payload that can provide a vacuum environment while in a reduced gravity condition. This payload could support multiple in-space manufacturing developmental efforts, with the first demonstration technology being LBW. Currently, the design is targeting operations in the pressurized volume of a space station, but the payload could readily be adapted to other flight platforms such as parabolic or even suborbital vehicles. LASAR elucidates the effects of temperature and vacuum on LBW while DISCMAN probes those of vacuum and gravity. Through these complementary efforts, NASA is addressing the primary challenges of ISW across the space environment while simultaneously developing and maturing technologies including robotic systems and inspection methodologies for future practical implementation on the Moon and beyond. This approach is timely, as upcoming missions requiring sustained human presence in space will depend on reliable ISW capabilities to create robust metallic joints currently unproven in the space environment and to perform repairs in situ .

hypogravity

Radiation-Resistant Ti/BN Coatings: Insights From 171 Days Exposure to Space Radiation and Atomic Oxygen in Low Orbit

Atmospheric Plasma Spray (APS) and Vacuum Plasma Spray (VPS) techniques were used to develop Ti/2 vol.% hBN coatings, for extreme space environments and tested aboard the International Space Station as part of the MISSE-17 (Materials International Space Station Experiments) program. The coatings were exposed to atomic oxygen, space radiation, and low-orbit thermal cycling. VPS coatings showed a 56% increase in microhardness, a 26% rise in elastic modulus, minimal porosity and crack density changes compared to APS coatings. The change in mechanical properties is attributed to the formation of TiO, TiO₂ and TiN from nitrogen retention, alongside radiation-induced dislocations, which enhanced surface hardening. The oxidation of titanium led to the formation of TiO and TiO₂, while boron nitride was retained and underwent transmutation in VPS coatings. XPS and EDS analyses confirmed the enhanced space-environment resistance of VPS coatings, making them ideal for long-term spacecraft protection in lunar and Martian conditions.

Abhijith Kunneparambil Sukumaran

Nanoscopic Imaging of Self-Propelled Ultrasmall Catalytic Nanomotors

Ultrasmall nanomotors (<100 nm) are highly desirable nanomachines for their size-specific advantages over their larger counterparts in applications spanning nanomedicine, directed assembly, active sensing, and environmental remediation. While there are extensive studies on motors larger than 100 nm, the design and understanding of ultrasmall nanomotors have been scant due to the lack of high-resolution imaging of their propelled motions with orientation and shape details resolved. Here, we report the imaging of the propelled motions of catalytically powered ultrasmall nanomotors─hundreds of them─at the nanometer resolution using liquid-phase transmission electron microscopy. These nanomotors are Pt nanoparticles of asymmetric shapes (“tadpoles” and “boomerangs”), which are colloidally synthesized and observed to be fueled by the catalyzed decomposition of NaBH4 in solution. Statistical analysis of the orientation and position trajectories of fueled and unfueled motors, coupled with finite element simulation, reveals that the shape asymmetry alone is sufficient to induce local chemical concentration gradient and self-diffusiophoresis to act against random Brownian motion. Our work elucidates the colloidal design and fundamental forces involved in the motions of ultrasmall nanomotors, which hold promise as active nanomachines to perform tasks in confined environments such as drug delivery and chemical sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Elucidating the impact of stress states on grain boundary passivation in Ni-5Cr using the Rhines pack method

The oxidation behavior of a Ni–5Cr (at.%) alloy was evaluated at 420 ° C using the Rhines pack method and simultaneous tensile and compressive stress states via a miniature four-point bending fixture. At this moderate temperature, grain boundaries dominate mass transport and the resulting oxidation response. Oxidation produced approximately 1μ⁢m-wide protective Cr 2 O 3 films capping some grain boundaries and penetrative, intergranular Cr-rich oxides at other grain boundaries. Externally applied tensile and compressive stress during oxidation increased the prevalence of Cr 2 O 3 cap formation compared to no applied stress, with tensile stress resulting in more Cr 2 O 3 caps than compressive stress. The observed oxide cap morphology was similar across all test conditions. Regions under compressive stress showed an order of magnitude greater Cr depletion depth along the grain boundary. Chromium nitrides (CrN), likely from N contamination of the Rhines pack cell, were observed both at the oxide–metal interface and intergranularly within the alloy. Collectively these results demonstrate that applied stress promotes localized protective oxide cap formation over grain boundaries, with compressive stress additionally promoting deeper Cr depletion. Furthermore the experimental approach helped separate out the effects of stress on local oxide formation and grain boundary passivation.

4 point bend

The NASA Turbulent Heat Flux (THX) Experiments: Summary and Lessons Learned

The Turbulent Heat Flux (THX) experiments were conducted at NASA Glenn Research Center (GRC) in order to collect measurements of velocities and temperatures for computational fluid dynamics (CFD) validation of heated flows, with a focus on propulsion system components. The experiments spanned 5 phases; four of which were conducted in the GRC AeroAcoustic Propulsion Laboratory (AAPL) using the Small Hot Jet Flow Rig (SHJAR). In addition to making velocity measurements with Particle Image Velocimetry (PIV), the THX experiments introduced a new Raman-scattering based capability to measure temperatures. Computational studies were also conducted for each of the experimental configurations, in order to provide a baseline of expected CFD results and conduct an assessment of the capability of various CFD approaches for calculating flows where the turbulent transport of heat was important. Two of the collected sets of data were used for American Institute of Aeronautics and Astronautics (AIAA) Propulsion Aerodynamic Workshops (PAWs). The data set from the 5th phase, collected for heated supersonic jets, was also used to construct new validation cases for the NASA Turbulence Model Resource (TMR). This paper provides an overview of the experiments and associated computations for each of the 5 test phases. Key experimental findings are presented. Lessons learned are provided concerning the effect of computational modeling choice on accuracy of predicting turbulent flows where thermal transport is important. Emphasis is placed on comparing Reynolds-averaged Navier-Stokes approaches with large-eddy simulation approaches. The benefits of utilizing a conjugate heat transfer method in conjunction with CFD solver for film cooling is demonstrated.

RANS

The 60-MW Shuttle Interaction Heating Facility

An arc-heated wind-tunnel system described in the present paper will simulate aerodynamic heating in large-scale tests of the thermal protection system of the Shuttle Orbiter Vehicle during entry. The system provides for large-scale subsystem tests in high-enthalpy streams with boundary layer flows at high Reynolds numbers and for large test-body sizes in stagnation flows. The discussion covers the design concept of the arc-jet systems, the extensive hardware developments of the arc heater to provide reliable operation, and verification and performance measurements of the system's operating envelopes.

W Winovich

Advancing technologies for lignin-based jet fuel production in aqueous phase

Integrating lignin into a cellulosic ethanol plant for the co-production of lignin-based jet fuel (LJF) in aqueous phase offers a significant opportunity to boost operational efficiency, economic viability, carbon conversion, and the overall sustainability of biofuel and chemical production. LJF is lignin-structure-based jet fuel blendstocks primarily composed of alkyl-substituted mono-, bi-, and tri-cyclohexanes. It exhibits high energy density, potential for low emissions, and favourable blend characteristics that comply with drop-in specifications. An overview of lignin feedstock, catalytic processes, LJF chemical compositions, fuel properties tests, and techno-economic analysis (TEA) and life cycle assessment (LCA) indicate that (1) the reactivity of lignin plays a crucial role in its structure transformation to LJF molecules; (2) catalytic processing of lignin to LJF can occur through a simultaneous depolymerization and hydrodeoxygenation process, bypassing the intermediate step of producing and upgrading lignin-derived oil; (3) LJF's uniqueness molecules making it more promising for high energy content and low emission jet fuel properties for next generation sustainable aviation fuel (SAF); and (4) TEA and LCA demonstrate that LJF is not only potentially cost-effective but also offers favourable carbon footprint compared to other SAFs. In conclusion, this review highlights the most recent advancements in LJF technology, along with the challenges and opportunities that lie ahead in fulfilling its potential.

09 BIOMASS FUELS

Pressure Switch Is a Low Cost Battery Indicator

Conventional pressure switch, fabricated by printed-circuit manufacturing techniques, can indicate when charge on battery departs from preset level. Membrane on switch is exposed to internal pressure of battery, which varies according to stored charge. When pressure varies from preset level, switch can turn on a light-emitting diode or similar indicator to warn user that battery is low.

Abita, J. L.

An enzyme-based approach for highly efficient self-replication of DNA origami dimers

Self-replication and exponential growth are essential to all living things, the driving force for Darwinian evolution, and potentially useful in nanotechnology for large-scale production of nanoscopic materials. An artificial (nonliving) self-replication system has been shown to exhibit exponential growth and selection using DNA monomer origami tiles templated on a dimer seed. That system purposefully avoided the use of enzymes to get a hint of how self-replication might have evolved in a prebiotic world by using CNV K and UV light to crosslink complementary DNA single strands. For further investigations into competition and extinction and for potential applications involving biocompatibility, we wanted to investigate enzymatic ligation to replace the chemical photo crosslinking step. Here, we present a system which uses thermotolerant T4 DNA ligase and no UV. This system has several additional advantages including a much faster cycling time, yielding 2,000,000 amplifications in 12 h. We also introduce competition to study the possibility of Darwinian-like evolution. Two pairs of DNA origami tiles compete for the same connection strands and show different growth rates under different connection strand concentrations. This system has the potential to combine with other enzymes, such as RNA polymerase to support feedback, allowing us to fine-tune replication dynamics and achieve sophisticated, life-like behaviors. The highly efficient self-replication and exponential growth of DNA origami dimers demonstrated in this work not only enhances our understanding of Darwinian evolution in nature but also opens the door to applications ranging from synthetic biology to smart materials.

Science & Technology - Other Topics

Novel PtNi single-atom–nanocluster (SA–NC) ensembles promote Tafel kinetics and ampere-class AEM hydrogen evolution

The development of efficient, durable, and low-PGM electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is critical for next-generation electrolysis technologies. We report a facile two-step synthesis of highly dispersed PtNi and PtNi-nitride nanoclusters (NCs) (~2.3 nm) with ultralow Pt content (0.5 at.%) anchored on N-doped Vulcan carbon. Structural and compositional characterization via XAS, XPS, HAADF-STEM, HRTEM, and EDS mapping established key structure–activity relationships across varying Pt/Ni ratios and pyrolysis temperatures. The Pt0.5Ni0.5/C-750 catalyst, an ensemble of PtNi M-N-C type single-atom (SA) moieties with neighboring PtNi nanoclusters (NC), exhibited superior HER performance in alkaline media, achieving overpotentials of 30, 115, and 210 mV at 10, 100, and 500 mA cm−2, respectively. Despite at a lower Pt content, this novel SA–NC ensemble outperformed commercial Pt/C by ~36%. A standardized literature comparison with contemporary Pt- and Ru-doped analogues reveals the as-prepared Pt0.5Ni0.5/C-750 to sit at the apex of Tafel-limited kinetics and low overpotential at 100 mA cm−2. Tafel-limited Tafel slopes in both alkaline and acidic regimes confirm favorable proton recombination kinetics. Mass activities at 200 mV reached 13.8 and 18.84 A mgPt−1 in alkaline and acidic media, respectively. However, excessive nitridation (e.g., at 650 °C) adversely altered Pt electronic structure and HER kinetics. While Ni enhanced alkaline HER, acidic HER favored Ni-free analogues. Pt0.5Ni0.5/C-750 also demonstrated robust temperature responsiveness and 300-h operational stability at high current densities (0.5–1.0 A cm−2) in MEA tests. This work presents a scalable strategy for designing thermally responsive, durable, and compositionally tunable NC catalysts with neighboring SA moieties for alkaline electrolysis.

AEMWE

The Origin of Palimpsests

Palimpsests are the most enigmatic impact features observed on icy worlds of the Solar System. Palimpsests are large impact features which are bright, old, mostly flat, and roughly circular. They range from >150 to ~350 km in diameter and sometimes exhibit recognizable associated radial secondary ejecta crater strings beyond their rims. Curiously, among all the Solar System's icy worlds, palimpsests are exclusively seen on the icy Galilean moons. Palimpsests are obviously different than similarly sized impact features seen on other icy satellites. For example, Evander, a 350 km diameter peak-ring impact basin on Saturn’s moon Dione, has a very low depth/diameter ratio of 0.008, indicating significant viscous relaxation. Nevertheless, it still retains short wavelength topography including a prominent central peak, peak ring, and a continuous rim, none of which are seen at palimpsests. Palimpsests display an approximately circular, and dominating, expanse of undulating plains, which is level with surrounding terrain and shows no recognizable rim. At the center of palimpsests are smooth central plains that are enclosed by a low scarp. Central plains material superposes the surrounding undulating plains and is littered with small blocks reminiscent of “small chaos” on Europa. Palimpsests have yet to be explored using modern impact simulation tools. We have begun to investigate two competing hypotheses: (A) Palimpsests form on targets which have a preexisting near-subsurface layer that is liquid or solid but very weak, and is excavated as proximal ejecta; or (B) They form in a solid ice target underlain by a steep thermal gradient that strongly influences the resulting impact feature, including the production of impact-induced melting at depth that is then a major component of proximal ejecta. Our results will have profound implications for the early thermal history of the icy Galilean satellites. We will test our two hypotheses for the formation of palimpsests on Ganymede (where they are both best observed and preserved) by means of 2D iSALE hydrodynamic simulations of impacts into ice targets that will be structured according to the scenarios for each hypothesis, with select runs in 3D. We have already conducted a pilot study using 2D iSALE that has yielded promising results, which we will report out at the meeting.

palimpsests

The NASA Turbulent Heat Flux Experiments: Summary and Lessons Learned

The Turbulent Heat Flux (THX) experiments were conducted at NASA Glenn Research Center (GRC) in order to collect measurements of velocities and temperatures for computational fluid dynamics (CFD) validation of heated flows, with a focus on propulsion system components. The experiments spanned 5 phases; four of which were conducted in the GRC AeroAcoustic Propulsion Laboratory (AAPL) using the Small Hot Jet Flow Rig (SHJAR). In addition to making velocity measurements with Particle Image Velocimetry (PIV), the THX experiments introduced a new Raman-scattering based capability to measure temperatures. Computational studies were also conducted for each of the experimental configurations, in order to provide a baseline of expected CFD results and conduct an assessment of the capability of various CFD approaches for calculating flows where the turbulent transport of heat was important. Two of the collected sets of data were used for American Institute of Aeronautics and Astronautics (AIAA) Propulsion Aerodynamic Workshops (PAWs). The data set from the 5th phase, collected for heated supersonic jets, was also used to construct new validation cases for the NASA Turbulence Model Resource (TMR). This paper provides an overview of the experiments and associated computations for each of the 5 test phases. Key experimental findings are presented. Lessons learned are provided concerning the effect of computational modeling choice on accuracy of predicting turbulent flows where thermal transport is important. Emphasis is placed on comparing Reynolds- averaged Navier-Stokes approaches with large-eddy simulation approaches. The benefits of utilizing a conjugate heat transfer method in conjunction with CFD solver for film cooling is demonstrated.

RANS

Effects of Composition and Oxidation States on the Structures of Chromium-Containing Sodium Silicate Glasses: Molecular Dynamics Simulations using Machine Learning Interatomic Potentials

Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.

Puga, Christina L.