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The direct observation of unidirectional solidification as a function of gravity level

A saturated solution of NH4 Cl-H2O was solidified unidirectionally on earth at 1 g and in a suborbital rocket at 0.001 g. In the 1 g experiment, extensive fluid flow was apparent, creating plumes which carry numerous crystallites vertically above the interface in a manner associated with freckling in castings. During growth the interface grew into the liquid at the same rate as the individual dendrites. When solidified in low g, the interface grew at a slower rate than the individual dendrites. No plumes of liquid carrying crystals were seen, but several crystals did appear and grow ahead of the interface. Growth rates, dendrite morphologies and preferred crystallographic orientations are compared for the two experiment conditions. Results indicate that solidification in low gravity produces more uniform dendrite arm spacings, and tends to be controlled by diffusion and crystallographic orientation.

Johnston, M. H.↗

The role of moisture in MgCl 2 salt: A multiscale approach to TES performance

This study presents a comprehensive multiscale analysis to evaluate the influence of moisture on the thermal performance of thermal energy storage systems using magnesium chloride (MgCl 2 ) as the phase-changing material. The system uses graphite foam with 90% relative density to enhance thermal conductivity. The analysis includes thermal conductivity calculations and specific heat capacity for different hydrate phases of MgCl 2 : Anhydrous, Mono, Di, Tetra, and Hexa. These properties were evaluated for the first time using the phonon density of states from Density Functional Theory simulations. Results showed that thermal conductivity decreased, while specific heat capacity increased by a factor of two as the phase changed from anhydrous to hexahydrate. Meso-scale models were created to account for the anisotropy of graphite foam and property variations of the MgCl 2 hydrate phases. Asymptotic Expansion homogenization simulations determined the anisotropic thermal conductivity for all phases. This unique methodology improved simulation accuracy, which matched experimental data for anhydrous MgCl 2 . A parametric study examined various operating conditions and their effect on TES performance. It revealed that higher charging temperatures did not enhance exergy efficiency, but increased discharge mass flow rates improved it due to better heat transfer. Thermal performance evaluated by the exergy efficiency remained consistent across hydrate systems under the tested conditions. Furthermore, the study suggests that this uniformity is linked to missing key data, particularly latent heat and melting point for different hydrates. Overall, it highlights the importance of multiscale effects and accurate material properties in designing and optimizing TES systems.

Molten salt degradation↗

NMR Studies of Block Copolymer-Based Supramolecules in Solution

Hierarchical assemblies from block copolymer (BCP)-based supramolecules have shown immense potential as programmable materials owing to their versatility for incorporating functional molecules and provide access to arrays of hierarchical structures. However, there remains a knowledge gap on the formation of the supramolecule in solution. Here, we applied NMR techniques to investigate the solution-phase behavior of the most studied supramolecular systems, polystyrene-block-poly(4-vinylpyridine)(3-pentadecylphenol) (PS-b-P4VP(PDP) r ). The results show that the supramolecule likely adopts a coil-comb conformation, despite the small molecule's (PDP) rapid exchange between the bonded and free states. The exchange rate (>10 4 s -1 ) exceeds the NMR time scale at the frequency of interest. The supramolecules form under dilute conditions (~2 vol %) and are attributed to the enthalpic gain of the hydrogen bonding between the PDP and 4VP. As the solute concentration increases (>10 vol %), the supramolecule forms micelle-like aggregates with PDP accumulated within the comb-block's pervaded volume based on analysis of the apparent molecular weight, viscosity, and chain dynamics. Overall, this work sheds light on the long-standing question regarding the evolution of the constituents in the BCP-based supramolecule in solution and provides valuable guidance toward their solution-based processing and morphological control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Band structure of the growth rate of the two-stream instability of an electron beam propagating in a bounded plasma

Our paper presents a study of the two-stream instability of an electron beam propagating in a finite-size plasma placed between two electrodes. It is shown that the growth rate in such a system is much smaller than that of an infinite plasma or a finite size plasma with periodic boundary conditions. Even if the width of the plasma matches the resonance condition for a standing wave, a spatially growing wave is excited instead with the growth rate small compared to that of the standing wave in a periodic system. Furthermore, the approximate expression for this growth rate is γ≈(1/13)ω pe (n b /n p )(Lω pe /v b )ln(Lω pe /v b )[1-0.18 cos (Lω pe /v b +π/2)], where ωpe is the electron plasma frequency, n b and n p are the beam and the plasma densities, respectively, v b is the beam velocity, and L is the plasma width. The frequency, wave number, and the spatial and temporal growth rates, as functions of the plasma size, exhibit band structure. Finally, the amplitude of saturation of the instability depends on the system length, not on the beam current. For short systems, the amplitude may exceed values predicted for infinite plasmas by more than an order of magnitude.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Performance parameters of a liquid filled ionization chamber array

Purpose: In this work, the properties of the two-dimensional liquid filled ionization chamber array Octavius 1000SRS (PTW-Freiburg, Germany) for use in clinical photon-beam dosimetry are investigated.Methods: Measurements were carried out at an Elekta Synergy and Siemens Primus accelerator. For measurements of stability, linearity, and saturation effects of the 1000SRS array a Semiflex 31013 ionization chamber (PTW-Freiburg, Germany) was used as a reference. The effective point of measurement was determined by TPR measurements of the array in comparison with a Roos chamber (type 31004, PTW-Freiburg, Germany). The response of the array with varying field size and depth of measurement was evaluated using a Semiflex 31010 ionization chamber as a reference. Output factor measurements were carried out with a Semiflex 31010 ionization chamber, a diode (type 60012, PTW-Freiburg, Germany), and the detector array under investigation. The dose response function for a single detector of the array was determined by measuring 1 cm wide slit-beam dose profiles and comparing them against diode-measured profiles. Theoretical aspects of the low pass properties and of the sampling frequency of the detector array were evaluated. Dose profiles measured with the array and the diode detector were compared, and an intensity modulated radiation therapy (IMRT) field was verified using the Gamma-Index method and the visualization of line dose profiles.Results: The array showed a short and long term stability better than 0.1% and 0.2%, respectively. Fluctuations in linearity were found to be within ±0.2% for the vendor specified dose range. Saturation effects were found to be similar to those reported in other studies for liquid-filled ionization chambers. The detector's relative response varied with field size and depth of measurement, showing a small energy dependence accounting for maximum signal deviations of ±2.6% from the reference condition for the setup used. The σ-values of the Gaussian dose response function for a single detector of the array were found to be (0.72 ± 0.25) mm at 6 MV and (0.74 ± 0.25) mm at 15 MV and the corresponding low pass cutoff frequencies are 0.22 and 0.21 mm{sup −1}, respectively. For the inner 5 × 5 cm{sup 2} region and the outer 11 × 11 cm{sup 2} region of the array the Nyquist theorem is fulfilled for maximum sampling frequencies of 0.2 and 0.1 mm{sup −1}, respectively. An IMRT field verification with a Gamma-Index analysis yielded a passing rate of 95.2% for a 3 mm/3% criterion with a TPS calculation as reference.Conclusions: This study shows the applicability of the Octavius 1000SRS in modern dosimetry. Output factor and dose profile measurements illustrated the applicability of the array in small field and stereotactic dosimetry. The high spatial resolution ensures adequate measurements of dose profiles in regular and intensity modulated photon-beam fields.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Implications of Galaxy Buildup for Putative IMF Variations in Massive Galaxies

Recent observational evidence for initial mass function (IMF) variations in massive quiescent galaxies at z = 0 challenges the long-established paradigm of a universal IMF. While a few theoretical models relate the IMF to birth cloud conditions, the physical driver underlying these putative IMF variations is still largely unclear. Here we use post-processing analysis of the Illustris cosmological hydrodynamical simulation to investigate possible physical origins of IMF variability with galactic properties. We do so by tagging stellar particles in the simulation (each representing a stellar population of ≈10{sup 6} M{sub ⊙}) with individual IMFs that depend on various physical conditions, such as velocity dispersion, metallicity, or star formation rate, at the time and place in which the stars are formed. We then follow the assembly of these populations throughout cosmic time and reconstruct the overall IMF of each z = 0 galaxy from the many distinct IMFs it is composed of. Our main result is that applying the observed relations between IMF and galactic properties to the conditions at the star formation sites does not result in strong enough IMF variations between z = 0 galaxies. Steeper physical IMF relations are required for reproducing the observed IMF trends, and some stellar populations must form with more extreme IMFs than those observed. The origin of this result is the hierarchical nature of massive galaxy assembly, and it has implications for the reliability of the strong observed trends, for the ability of cosmological simulations to capture certain physical conditions in galaxies, and for theories of star formation aiming to explain the physical origin of a variable IMF.

79 ASTRONOMY AND ASTROPHYSICS↗

Echocardiographic evaluation of Space Shuttle crewmembers

Echocardiographic measurements of left ventricular volume were obtained from 17 members of four Space Shuttle crews before and after 5- to 8-day space flights. Measurements obtained 1 h after landing indicated increases in the heart rate (HR), mean arterial pressure, and systemic vascular resistance values. On the other hand, the end-diastolic volume index (EDVI) fell 17 ml/sq m, and the stroke volume index (SVI) fell 15 ml/sq m. Measurements taken 1-2 weeks later demonstrated that the HR values returned to normal, but the EDVI and SVI values remained significantly below preflight levels, despite the ability of the subjects to ambulate and exercise. The results indicate that a space flight induces significant changes in heart volume affecting the left-ventricle function. It is suggested that the prolonged recovery period is related to the high level of aerobic conditioning in these subjects.

Bungo, M. W.↗

Effects of prolonged head-down bed rest on physiological responses to moderate hypoxia

To determine the effects of hypoxia on physiological responses to simulated zero-gravity cardiopulmonary and fluid balance measurements were made in 6 subjects before and during 5-degree head-down bed rest (HDBR) over 8 d at 10,678 ft and a second time at this altitude as controls (CON). The V-dot(O2)(max) increased by 9 percent after CON, but fell 3 percent after HDBR. This reduction in work capacity during HDBR could be accounted for by inactivity. The heart rate response to a head-up tilt was greatly enhanced following HDBR, while mean blood pressure was lower. No significant negative impact of HDBR was noted on the ability to acclimatize to hypoxia in terms of pulmonary mechanics, gas exchange, circulatory or mental function measurements. No evidence of pulmonary interstitial edema or congestion was noted during HDBR at the lower PIO2 and blood rheology properties were not negatively altered. Symptoms of altitude illness were more prevalent, but not marked, during HDBR and arterial blood gases and oxygenation were not seriously effected by simulated microgravity. Declines in base excess with altitude were similar in both conditions. The study demonstrated a minimal effect of HDBR on the ability to adjust to this level of hypoxia.

Loeppky, J. A.↗

A Multifunctional Coating for Autonomous Corrosion Control

This slide presentation reviews the effects of corrosion on various structures at the Kennedy Space Center, and the work to discover a corrosion control coating that will be autonomous and will indicate corrosion at an early point in the process. Kennedy Space Center has many environmental conditions that are corrosive: ocean salt spray, heat, humidity, sunlight and acidic exhaust from the Solid Rocket Boosters (SRBs). Presented is a chart which shows the corrosion rates of carbon steel at various locations. KSC has the highest corrosion rates with 42.0 mils/yr, leading the next highest Galeta Point Beach, in the Panama Canal Zone with 27 mils/yr corrosion. A chart shows the changes in corrosion rate with the distance from the ocean. The three types of corrosion protective coatings are described: barrier (passive), Barrier plus active corrosion inhibiting components, and smart. A smart coating will detect and respond actively to changes in its environment in a functional and predictable manner and is capable of adapting its properties dynamically. The smart coating uses microcapsules, particles or liquid drops coated in polymers, that can detect and control the corrosion caused by the environment. The mechanism for a pH sensitive microcapsule and the hydrophobic core microcapsule are demonstrated and the chemistry is reviewed. When corrosion begins, the microcapsule will release the contents of the core (indicator, inhibitor, and self healing agent) in close proximity to the corrosion. The response to a pH increase is demonstrated by a series of pictures that show the breakdown of the microcapsule and the contents release. An example of bolt corrosion is used, as an example of corrosion in places that are difficult to ascertain. A comparison of various coating systems is shown.

Calle, L. M.↗

A New GaAs Laser Radar for Atmospheric Measurements

A special GaAs lidar using fiber coupled diode lasers was constructed for the purpose of measuring the extinction coefficient distribution within a large atmospheric volume at a rate compatible with atmospheric kinematics. The technique is based on taking backscatter signature ratios over spatial increments after the returns are normalized by pulse integration. Essential aspects of the lidar design are beam pulse power, repetition rate, detection system dynamic range and decay linearity. It was necessary to preclude the possibility of eye hazard under any operating conditions, including directly viewing the emitting aperture at close distance with a night-adapted eye. The electronic signal processing and control circuits were built to allow versatile operations. Extinction coefficient measurements were made in fog and clouds using a low-power laboratory version of the lidar, demonstrating feasibility. Data are presented showing range squared corrected backscatter profiles converted to extinction coefficient profiles, temporal signal fluctuations, and solar induced background noise. These results aided in the design of the lidar which is described. Functional tests of this lidar and the implications relevant to the design of a prototype model are discussed. This work was jointly sponsored by Sperry Rand Corporation under its Independent Research and Development program; the Air Force Avionics Laboratory, Wright Field, Dayton, Ohio; and the Naval Ammunition Depot, Crane, Indiana.

Brown, R. T.↗

Particle Loading Tests on HEPA Flat Sheet Media at Sub-Ambient Pressures Using a Lunar Dust Simulant

When humans return to the moon under the NASA Artemis program, their activities on the lunar surface will inevitably lead to the intrusion of some level of lunar dust into the lander cabin. Therein the crew would be exposed to the potential hazards of lunar dust and the possibility of subsequent transfer into orbiting segments after docking. The spacecraft’s cabin filtration system will need to be effective at removing the airborne lunar dust to properly purify the breathable cabin air and minimize the spreading of the dust throughout the vehicle and orbital segments through the mission duration. The fine nature of the lunar dust will require high efficiency filtration, such as HEPA. A series of tests were performed in a specially designed recirculating sealed flow loop, for testing filter media and filter elements at the NASA Glenn Research Center. The flow loop was used to assess the performance and capacity of flat sheet filter media at representative cabin pressures using JSC-1AF lunar dust simulant and at high rates of particle loading. The pressure drop across the filter media was measured as a function of accumulated particle mass load at ambient pressure and at two sub-ambient pressures, 0.0703MPa and 0.0565MPa, and at a media velocity that was scaled relative to its pleated configuration. The challenge particle flows were generated by a custom designed particle generator that introduces dispersed particles of the lunar simulant at high concentrations. An optical particle counting instrument provided filter efficiency measurements within the sealed environment. The pressure drop was found to increase linearly with the amount of dust load on the media, for all test conditions, while the starting pressure drop was found to be lower at the lowest sub-ambient pressure case. High filter efficiency was maintained after high particle loads on the media.

Sub-ambient↗

Millimeter wave sensor for far-field standoff vibrometry

A millimeter wavelength (MMW) measurement system for remote detection of object characteristics and methods for detecting such characteristics. The MMW measurement system comprises a front-end and an optional signal conditioning component. The MMW front-end includes an oscillator, a transceiver portion, and an antenna for focusing a detection component comprising micrometer level wavelength electromagnetic radiation onto the object. A portion of the electromagnetic radiation reflected by the object is received by the MMW measurement system, which is indicative of a displacement of the object. The MMW system may be configured to detect micrometer level displacement of the object disposed tens of meters from the MMW measurement system. In various embodiments the object may be a natural object, including a human, and the displacement may be indicative of a heart rate and/or a respiratory function.

42 ENGINEERING↗

Machine Learning-Guided Identification of PET Hydrolases from Natural Diversity

The enzymatic depolymerization of poly(ethylene terephthalate) (PET) is emerging as a leading chemical recycling technology for waste polyester. As part of this endeavor, new candidate enzymes identified from natural diversity can serve as useful starting points for enzyme evolution and engineering. In this study, we improved upon HMM searches by applying an iterative machine learning strategy to identify 400 putative PET-degrading enzymes (PET hydrolases) from naturally occurring homologs. Using high-throughput (HTP) experimental techniques, we successfully expressed and purified >200 enzyme candidates and assayed them for PET hydrolysis activity as a function of pH, temperature, and substrate crystallinity. From this library, we discovered 91 previously unknown PET hydrolases, 35 of which retain activity at pH 4.5 on crystalline material, which are conditions relevant to developing more efficient commercial processes. Notably, four enzymes showed equal to or higher activity than LCC-ICCG, a benchmark PET hydrolase, at this challenging condition in our screening assay, and 11 of which have pH optima <7. Using these data, we identified regions of PETases statistically correlated to activity at lower pH. We additionally investigated the effect of condition-specific activity data on trained machine learning predictors and found a precision (putative hit rate) improvement of up to 30% compared to a Hidden Markov Model alone. Our findings show that by pointing enzyme discovery toward conditions of interest with multiple rounds of experimental and machine learning, we can discover large sets of active enzymes and explore factors associated with activity at those conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework

The Zr 6 -based metal–organic framework NU-1000 was successfully functionalized with candidate catalysts—MoS x units—via SIM (solvothermal deposition in MOFs) of molybdenum(VI), followed by reaction with H2S gas. The structure of the material, named MoS x - SIM, was characterized spectroscopically and through a single-crystal X-ray diffraction measurement. These measurements and others established that the catalyst is monometallic, with mixed oxygen and sulfur coordination, and that it forms from a MOF-node-supported molybdenum-based cluster featuring only oxy ligands. Notably, the formal potential for the MOF-grafted complex, like that for the metal–sulfur active site of hydrogenase, is nearly coincident with the formal potential for the hydrogen couple. Its effective concentration within the mesoporous MOF is several hundred millimolar, and its porous-framework-based immobilization/heterogenization obviates the need for aqueous solubility as a condition for use as a well-defined catalyst. MoS x - SIM was evaluated as an electrocatalyst for evolution of molecular hydrogen from aqueous acid. Although the MoS x - functionalized framework exhibits catalytic behavior, the highly insulating nature of the support inhibits high electrocatalytic performance. Introduction of an archetypal redox mediator (RM), methyl viologen (MV 2+ ), resulted in more than 20-fold enhancement in its catalytic performance on a turnover frequency basis, implying efficient RM-assisted electron transfer to otherwise electrochemically non-addressable MoS x moieties. Electrochemical kinetic studies with additional viologens as mediators reveal an unexpected square-root dependence of overall reaction rate on mediator concentration, as well as sensitivity to the strength of RM •+ as a reductant. These observations, together with observations of potential-dependent H/D isotope effects and potential-dependent pH effects, provide useful insights into the catalysis mechanism and help to explain how the MOF-affixed monometallic catalyst can effectively catalyze a two-electron reduction reaction, i.e., hydrogen evolution from acidified water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Acidolysis of α-O-4 Aryl-Ether Bonds in Lignin Model Compounds: A Modeling and Experimental Study

Lignocellulosic biomass offers a vast, renewable resource for the sustainable production of fuels and chemicals. To date, a commonly employed approach to depolymerize the polysaccharides in plant cell walls employs mineral acids, and upgrading strategies for the resulting sugars are under intense development. Although the behavior of cellulose and hemicellulose is reasonably well characterized, a more thorough understanding of lignin depolymerization mechanisms in acid environments is necessary to predict the fate of lignin under such conditions and ultimately to potentially make lignin a viable feedstock. To this end, dilute acid hydrolysis experiments were performed on two lignin model compounds containing the a-O-4 ether linkage at two temperatures concomitant with dilute acid pretreatment. Both primary and secondary products were tracked over time, giving insight into the reaction kinetics. The only difference between the two model compounds was the presence or absence of a methyl group on the a-carbon, with the former being typical of native lignin. It was found that methylation of the a-carbon increases the rate of reaction by an order of magnitude. Density functional theory calculations were performed on a proposed mechanism initiated by a nucleophilic attack on the a-carbon by water with a commensurate protonation of the ether oxygen. The values for the thermodynamics and kinetics derived from these calculations were used as the basis for a microkinetic model of the reaction. Results from this model are in good agreement with the experimental kinetic data for both lignin model compounds and provide useful insight into the primary pathways of a-O-4 scission reactions in acid-catalyzed lignin depolymerization. The distribution of primary and secondary products is interpreted as a function of two barriers of formation exhibiting opposite trends upon methylation of the a-carbon (one barrier is lowered while the other is increased). Such insights will be needed to construct a comprehensive model of how lignin behaves in a common deconstruction approach.

14 SOLAR ENERGY↗

Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reaction

Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.

08 HYDROGEN↗

Spatially programmed alignment and actuation in printed liquid crystal elastomers

Liquid crystal elastomers (LCEs) exhibit reversible shape morphing behavior when cycled above their nematic-to-isotropic transition temperature. During extrusion-based 3D printing, LCE inks are subjected to coupled shear and extensional flows that can be harnessed to spatially control the alignment of their nematic director along prescribed print paths. Here, we combine experiment and modeling to elucidate the effects of ink composition, nozzle geometry, and printing parameters on director alignment. From rheological measurements, we quantify the dimensionless Weissenberg number ( Wi ) for the flow field each ink experiences as a function of printing conditions and demonstrate that Wi is a strong predictor of LCE alignment. We find that director alignment in LCE filaments printed through a tapered nozzle varies radially when Wi < 1, while it is uniform when Wi ≫ 1. Based on COMSOL simulations and in operando X-ray measurements, we show that LCE inks printed through nozzles with an internal hyperbolic geometry exhibit a more uniform director alignment for a given Wi compared to those through tapered nozzles. Concomitantly, the stiffness along the print direction and actuation strain of printed LCEs increases substantially under such conditions. By varying Wi during printing through adjusting the flow rate “on the fly”, LCE architectures with uniform composition, yet locally encoded shape morphing transitions can be realized.

36 MATERIALS SCIENCE↗

Towards Mitigating Electron Beam-Induced Damage in MOFs Using Low Dose Electron Microscopy for In-Situ Room-Temperature Measurements

Metal-Organic Frameworks (MOFs) have emerged as a versatile class of materials with applications in gas storage and separation, catalysis, and drug delivery [1]. Understanding their damage mechanisms in under various environmental conditions is crucial for optimizing performance and stability [2]. This study employs a combination of Length Structural Coherence (LSC) analysis in electron scattering and Electron Energy Loss Spectroscopy (EELS) to elucidate the damage mechanisms in two representative MOFs. MIL101(Fe), and MIL101(Cr). Here, the primary objective is to reveal structural and chemical changes that occur under electron beam irradiation in Scanning Transmission Electron Microscopy (STEM), both in the pristine state and during in-situ CO and CO 2 adsorption. By combining LSC in Radial Distribution Function (RDF) analysis with EELS, comprehensive insights into the nanoscale alterations are obtained and correlated to the electron dose rate.

dos Santos, Gabriel T. [Northwestern University, E↗