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At least 991 records · Page 55

Experimental Calibration of a Numerical Model of Prepreg Tack for Predicting AFP Process Related Defects

Wrinkles, puckers, and fiber bridging are among the major defects encountered in the Automated Fiber Placement (AFP) process, and are all different manifestations of fiber misalignment. The main driver for these defects are the residual stresses introduced in the tow during the deposition stage by the AFP head. In contrast, the tack between the deposited tape and the substrate is the resisting force against the formation of such defects. Tack may be defined as the ability of a material to form a bond immediately on contact with another surface. Tack is a very complex phenomenon that is influenced by a variety of process parameters including temperature, head pressure and speed, as well as degree of cure, moisture content, and surface roughness A physics-based modeling framework for simulation of tack was developed in this study that allows for prediction of tack response. The developed tack model is incorporated in the AFP placement modelling framework developed to simulate AFP defects.

Forghani, Alireza↗

Black carbon enriches short-range-order ferrihydrite in Amazonian Dark Earth: Interplay mechanism and environmental implications

Our study underpins the mechanism of organo-mineral interaction between black carbon (BC, biochar) and associated minerals in the historical BC-rich Amazonian Dark Earth (ADE) by using synchrotron-based microscopic (TXM), microspectroscopic (μFTIR) and spectroscopic (XAS and μ-diffraction) approaches. The BC-rich ADE contained over 100% more poorly crystalline minerals than the adjacent tropical soil. Linear combination fitting of k-spacing in the X-ray Absorption Spectra (XAS) revealed that ferrihydrite contributed to 81.1% of the Fe-minerals in BC. A small but distinct peak was observed at 5.7 Å –1 in the extended X-ray absorption fine structure k oscillation of BC, revealing the presence of Fe—C (including Fe-O-C) covalent bonds. No Fe—C path was yielded by the XAS fitting when an obvious peak downshift of the first (Fe—Fe 1 ) shell was observed, suggesting that the availability of inner-sphere Fe—C complexation was limited to the BC surface and interphase region. In this study, the main minerals for organo-mineral complexation were short-range-order (SRO) ferrihydrite on BC instead of corner-sharing FeO 6 octahedra. Compared to ADE, the coordination number of the first (Fe—Fe 1 ) and second (Fe—Fe 2 ) shell was higher in BC, revealing a higher degree of order in coordination between the neighboring Fe mineral crystals. Black C limited the progressive aging of amorphous Fe phases and greatly enriched SRO ferrihydrite in the redox-fluctuating and high-leaching environment. The transformation of SRO ferrihydrite into the more crystalline Fe oxides was controlled by the local pH environment. A strong signal from the complexed phenolic group (aryl-OH, 1241 cm –1 ) and a distinct band of inner-sphere complexation (Fe-aryl C, 1380–1384 cm –1 ) were identified in the FTIR spectra. The enrichment of poorly crystalline minerals can have positive feedback on the long-term stabilization of BC. The scale-up application of biochar to agricultural and ecological systems may have a long-lasting impact on the enrichment and transformation of the SRO minerals in the soil.

54 ENVIRONMENTAL SCIENCES↗

Corrosion Resistance and Durability of Superhydrophobic Copper Surface in Corrosive NaCl Aqueous Solution

Artificial superhydrophobic copper surfaces play an important role in modern applications such as self-cleaning and dropwise condensation; however, corrosion resistance and durability often present as major concerns in such applications. In this study, the anti-corrosion properties and mechanical durability of superhydrophobic copper surface have been investigated. The superhydrophobic copper surfaces were achieved with wet chemical etching and an immersion method to reduce the complexity of the fabrication process. The surface structures and materials were characterized using scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectrometer (FTIR). The corrosion resistance and mechanical properties of the superhydrophobic copper surface were characterized after immersing surfaces in a 3.5 wt % NaCl solution. The chemical stability of the superhydrophobic copper surface in the NaCl solution for a short period of time was also evaluated. An abrasion test and an ultrasound oscillation were conducted to confirm that the copper surface contained durable superhydrophobic properties. In addition, an atomic force microscope was employed to study the surface mechanical property in the corrosion conditions. The present study shows that the resulting superhydrophobic copper surface exhibit enhanced corrosion resistance and durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Verification Suite for the Application of the Limiting Surface Density Method to Arrays of 9975 Packages

Criticality Safety Engineering at the Savannah River Site’s K-Area Complex seeks to reduce the computational burden of analysis for the K-Area Complex. By applying an adapted Limiting Surface Density hand calculation method, the need for lengthy detailed Monte Carlo models of the storage arrays may be reduced or eliminated. After promising initial results using models of idealized but heterogeneous packages, application of the method to large arrays of highly heterogeneous 9975 shipping packages is attempted. A SCALE KENO-VI model of the 9975 package, with true dimensions and radial and axial heterogeneity is developed. A suite of array arrangements representing both arrays with equal number of packages per side (package-cubic) and arrays with unequal number of packages per side (non-cubic) are evaluated in SCALE. The cubic arrangements are used to derive the 9975-specific material and geometry constants for the LSD method. These constants are then used to implement the LSD method and compare the LSD- predicted critical mass per package to SCALE-predicted critical mass per package. Sensitivities to certain material and geometric nuances are evaluated for inclusion in the verification suite. Finally, the ability of the method to predict neutron multiplication changes induced by fissile mass changes is examined as a segue for evaluating credible abnormal conditions with the LSD method.

42 ENGINEERING↗

Verification suite for the application of the limiting surface density method to arrays of 9975 packages

Criticality Safety Engineering at the Savannah River Site's K-Area Complex seeks to reduce the computational burden of analysis for the K-Area Complex. By applying an adapted Limiting Surface Density hand calculation method, the need for lengthy detailed Monte Carlo models of the storage arrays may be reduced or eliminated. After promising initial results using models of idealized but heterogeneous packages, application of the method to large arrays of highly heterogeneous 9975 shipping packages is attempted. A SCALE KENO-VI model of the 9975 package, with true dimensions and radial and axial heterogeneity is developed. A suite of array arrangements representing both arrays with equal number of packages per side (package-cubic) and arrays with unequal number of packages per side (non-cubic) are evaluated in SCALE. The cubic arrangements are used to derive the 9975-specific material and geometry constants for the LSD method. These constants are then used to implement the LSD method and compare the LSD- predicted critical mass per package to SCALE-predicted critical mass per package. Sensitivities to certain material and geometric nuances are evaluated for inclusion in the verification suite. Finally, the ability of the method to predict neutron multiplication changes induced by fissile mass changes is examined as a segue for evaluating credible abnormal conditions with the LSD method. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Practical Considerations for Understanding Surface Reaction Mechanisms Involved in Heterogeneous Catalysis

Acquiring useful knowledge about the active site(s) of a catalyst, nature of reactant–catalyst interactions, nature of reactive intermediates, rate-determining step, reaction rate orders that affect various process parameters, and reaction mechanism as a whole is exceedingly challenging. This is especially true in the case of heterogeneous catalysts due to the complexity of the nature of surface active sites and their nonstatic behavior. Here, we present our perspective on differentiating between various surface reaction mechanisms in light of pioneering studies by leaders in the field, with the aim of clarifying some of the confusion associated with these complex mechanisms, especially the Eley–Rideal mechanism. Using bibliometric analysis, we identify and discuss the following four reactions that most commonly invoke the Eley– Rideal mechanism: H 2 activation, CO oxidation, esterification of alcohols by acids, and selective catalytic reduction (SCR) of NO x with NH 3 . Our analysis of studies utilizing well-suited experimental and computational methodologies for differentiating surface reaction mechanisms suggests that the above-mentioned four reactions do not occur via the Eley–Rideal mechanism. Instead, each reaction occurs via the Langmuir–Hinshelwood mechanism with nonidealities present. Lastly, we highlight practical considerations regarding select experimental (characterization methods and differential kinetics) and computational modeling that we believe can provide useful insights to accurately discern between the various possible reaction mechanisms in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alternating chempolishing and electropolishing for interior and exterior surface finishing of additively manufactured (AM) metal components

Additively manufactured (AM) components’ surface finishing is crucial in adopting them for intended applications in challenging environments involving fatigue, corrosion, high temperature, and nuclear radiation. In our prior research, chempolishing (C) was utilized as an electroless etching process that uniformly smoothens complex AM components’ accessible interior and exterior surfaces (Tyagi et al. Additive Manufacturing, 25:32–38, 22). A wide range of electropolishing (E) has been demonstrated for AM surface finishing. However, electropolishing can impact a surface that can be juxtaposed to counter electrode and can yield a very smooth surface to sub-micrometer level roughness. However, a knowledge gap exists about the impact of applying both approaches on the same surface one after another and what new advantages may arise because of combining two methods. This paper uses dual-stage liquid-based surface finishing strategies produced by alternating the chempolishing (C) and electropolishing (E) steps. Two dual-stage surface finishing approaches, i.e., chempolishing followed by electropolishing (CE) and electropolishing followed by chempolishing (EC), were performed on the 316 stainless AM steel component. Impacts of EC and CE approaches were compared with single-stage C and E surface finishing approaches. An optical microscope and mechanical profilometer were utilized to investigate the wide range of surface roughness parameters. CE and EC produced Ra ~ 1.4 µm and ~ 1.6 µm, respectively. Surface roughness on CE- and EC-treated AM samples was lower than those individually treated by C and E approaches. Scanning electron microscopy provided further insights into the microstructural difference between CE- and EC-treated AM samples. This paper reports a liquid contact angle study on CE- and EC-treated AM samples to provide insights into the relative difference in surface energy that is crucial for making coatings on AM parts. A spectroscopic reflectance study was also employed to register the difference in physical properties of AM components treated with CE and EC approaches. Further, this study reveals industrially practicable interior and exterior surface finishing approaches for complex AM metal components that require minimum tooling and real-time process monitoring.

36 MATERIALS SCIENCE↗

New experimental approach to understanding the chemical reactivity of oxide surfaces

Metal oxides have been an attractive option for a range of applications, including hydrogen sensors, microelectronics, and catalysis, due to their reactivity and tunability. The properties of metal oxides can vary greatly on their precise surface structure; however, few surface science techniques can achieve atomistic-level determinations of surface structure, and fewer yet can do so for insulator surfaces. Low energy ion beam analysis offers a potential insulator-compatible solution to characterizing the surface structure of metal oxides. As a feasibility study, we apply low energy ion beam analysis to investigate the surface structure of a magnetite single crystal, Fe 3 O 4 (100). We obtain multi-angle maps using both forward-scattering low energy ion scattering (LEIS) and backscattering impact-collision ion scattering spectroscopy (ICISS). Both sets of experimental maps have intensity patterns that reflect the symmetries of the Fe 3 O 4 (100) surface structure. However, analytical interpretation of these intensity patterns to extract details of the surface structure is significantly more complex than previous LEIS and ICISS structural studies of one-component metal crystals, which had far more symmetries to exploit. To gain further insight into the surface structure, we model our experimental measurements with ion-trajectory tracing simulations using molecular dynamics. Our simulations provide a qualitative indication that our experimental measurements agree better with a subsurface cation vacancy model than a distorted bulk model.

36 MATERIALS SCIENCE↗

Plasma interactions and surface/material effects

A discussion on plasma interactions and surface/material effects is summarized. The key issues in this area were: (1) the lack of data on the material properties of common spacecraft surface materials; (2) lack of understanding of the contamination and decontamination processes; and (3) insufficient analytical tools to model synergistic phenomena related to plasma interactions. Without an adequate database of material properties, accurate system performance predictions cannot be made. The interdisciplinary nature of the surface-plasma interactions area makes it difficult to plan and maintain a coherent theoretical and experimental program. The shuttle glow phenomenon is an excellent example of an unanticipated, complex interaction involving synergism between surface and plasma effects. Building an adequate technology base for understanding and predicting surface-plasma interactions will require the coordinated efforts of engineers, chemists, and physicists. An interdisciplinary R and D program should be organized to deal with similar problems that the space systems of the 21st century may encounter.

Mandel, M.↗

Centaur: A Mobile Dexterous Humanoid for Surface Operations

Future human and robotic planetary expeditions could benefit greatly from expanded Extra-Vehicular Activity (EVA) capabilities supporting a broad range of multiple, concurrent surface operations. Risky, expensive and complex, conventional EVAs are restricted in both duration and scope by consumables and available manpower, creating a resource management problem. A mobile, highly dexterous Extra-Vehicular Robotic (EVR) system called Centaur is proposed to cost-effectively augment human astronauts on surface excursions. The Centaur design combines a highly capable wheeled mobility platform with an anthropomorphic upper body mounted on a three degree-of-freedom waist. Able to use many ordinary handheld tools, the robot could conserve EVA hours by relieving humans of many routine inspection and maintenance chores and assisting them in more complex tasks, such as repairing other robots. As an astronaut surrogate, Centaur could take risks unacceptable to humans, respond more quickly to EVA emergencies and work much longer shifts. Though originally conceived as a system for planetary surface exploration, the Centaur concept could easily be adapted for terrestrial military applications such as de-Gig, surveillance and other hazardous duties.

Rehnmark, Fredrik↗

Elucidating the Nanoparticle–Metal Organic Framework Interface of Pt@ZIF-8 Catalysts

Composites of metal nanoparticles encapsulated in metal–organic frameworks (NP@MOFs) have emerged as heterogeneous catalysts for regioselective reactions. While numerous NP@MOF composite combinations have been synthesized, characterization of the nanoparticle–MOF interface and the encapsulated nanoparticle surface have yet to be determined. In this work, Pt@ZIF-8 synthesized by the controlled encapsulation method was chosen as a representative NP@MOF, and in situ characterization methods coupled with density functional theory (DFT) calculations were used to probe the nanoparticle surface. CO adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed that Pt@ZIF-8 exhibits red-shifted linear- and bridge-bound CO peaks and a linear peak associated with cationic Pt. DFT calculations and 1H NMR suggest that these sites arise from the binding and electronic donation of the MOF linker, 2-methylimidazole, to the Pt surface. DRIFTS under argon reveals that linker fragments may be present on the Pt nanoparticle surface, suggesting a reaction between the nanoparticle and the MOF linker during controlled encapsulation synthesis. Finally, CO oxidation reveals via DRIFTS that the red-shifted linear CO and bridging CO sites are active sites, while the cationic Pt is not. Overall, these results show that Pt@ZIF-8 contains unique Pt surface sites and indicate that the nanoparticle–MOF interface contains a heterogeneous mixture of framework 2-methylimidazole, free-standing 2-methylimidazole, and linker fragments. These findings expose the complex nature of the nanoparticle surface in NP@MOF composites and demonstrate the importance of characterizing their surface to understand their catalytic behavior.

Whitford, Cassandra L. (ORCID:0000000282237516)↗

Techniques and Applications of SAR interferometry for ERS-1: Topographic Mapping, Change Detection, and Slope Measurement

SAR (Synthetic Aperture Radar) interferometry allows the measurement of high resolution topography of terrain from repeat orbit SAR data sets obtained by the ERS-1 AMI (Active Microwave Instrument). The system parameters which affect the accuracy of the topographic maps are errors in determination of the interferometric baseline, non parallel orbit tracks, decorrelation caused by baseline length, thermal noise, and surface change. Surface change can be observed in the interferograms either through decorrelation of the interferometric phase, or coherent phase shifts caused by locally uniform surface displacements. Phase gradient maps can be derived directly from the complex interferograms and can be transformed into surface slopes mapped onto a geometrically corrected grid.

Charles L Werner↗

Using Machine Learning to Estimate Surface-Level SO2 Concentrations from Satellite-Based Measurements

Sulfur dioxide (SO2) is a criteria air pollutant due to its contributions to aerosol formation, rainfall acidification, and harm to human health. The placement of air quality monitoring sites is typically biased towards urban areas, leaving large areas with very limited monitoring data. The Ozone Monitoring Instrument (OMI) has been used to provide estimates of SO2 vertical column densities (VCDs) globally at spatial resolution of 10s of kms once per day. OMI SO2 VCDs have been previously used to estimate surface SO2 concentrations using chemical transport model (CTM) simulations. The CTMs use estimated emissions and assimilated meteorological data, and simulate the chemical and physical processes that determine the vertical profile of SO2, which can be used to derive a ratio between the surface concentrations and VCDs. These models are complex, computationally expensive, and have large uncertainties in the simulated surface-to-VCD ratio due to biases in emissions and relatively coarse resolution. Machine learning techniques are comparatively easier to use, much less computationally expensive to use after training, and can produce more accurate estimations of surface concentrations than the CTM-based method. The interpretation of machine learning models often poses challenges, and in some cases, non-physical variables unrelated to SO2 are used as predictors. In this work, we create an artificial neural network (ANN) to relate OMI retrievals and archived GEOS-FP boundary layer heights to surface SO2 concentrations from the ChinaHighAirPollutants ChinaHighSO2 dataset (CHAP; Wei et al., 2023) on a seasonal average timescale from 2013-2018. Our model only utilizes five variables that are directly relevant to the satellite retrieval, lifetime, and spatial distribution of SO2. The model was trained on 16 seasons (four of each) with independent validation (one of each season) and testing datasets (one of each season) to avoid overfitting. Our ANN generates surface SO2 concentrations that are sensitive (slope = 0.51) and consistent (r = 0.74) with the CHAP data, but are underpredicted by an average of 1.2 ppbv with a mean absolute error of 2.2 ppbv. These results are better than recent studies utilizing the CTM method. To our knowledge, this is the best performing machine learning model that only uses physical variables to predict surface SO2. Our work demonstrates that a carefully constructed, simple ML model can accurately estimate surface-based SO2 concentrations from satellite VCD measurements, and this technique has future promise to expend to newer, higher resolution satellites and other air pollutants.

SO2, air quality, OMI, machine learning↗

Ion solvation as a predictor of lanthanide adsorption structures and energetics in alumina nanopores

Adsorption reactions at solid-water interfaces define elemental fate and transport and enable contaminant clean-up, water purification, and chemical separations. For nanoparticles and nanopores, nanoconfinement may lead to unexpected and hard-to-predict products and energetics of adsorption, compared to analogous unconfined surfaces. Here we use X-ray absorption fine structure spectroscopy and operando flow microcalorimetry to determine nanoconfinement effects on the energetics and local coordination environment of trivalent lanthanides adsorbed on Al 2 O 3 surfaces. We show that the nanoconfinement effects on adsorption become more pronounced as the hydration free energy, ΔG hydr , of a lanthanide decreases. Neodymium (Nd 3+ ) has the least exothermic ΔG hydr (-3336 kJ·mol -1 ) and forms mostly outer-sphere complexes on unconfined Al 2 O 3 surfaces but shifts to inner-sphere complexes within the 4 nm Al 2 O 3 pores. Lutetium (Lu 3+ ) has the most exothermic ΔG hydr (-3589 kJ·mol -1 ) and forms inner-sphere adsorption complexes regardless of whether Al 2 O 3 surfaces are nanoconfined. Importantly, the energetics of adsorption is exothermic in nanopores only, and becomes endothermic with increasing surface coverage. Changes to the energetics and products of adsorption in nanopores are ion-specific, even within chemically similar trivalent lanthanide series, and can be predicted by considering the hydration energies of adsorbing ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Icy Satellites of the Planets, and the Work of V.I. Moroz

The satellites of the giant planets are highly varied in size and density, indicating a wide range of compositions. The principal components of these satellites are ices of many different compositions (with H2O the most abundant) and varying amounts of silicate rocky material. Many different ices have been found by spectroscopic techniques both from Earth-based observatories and from planetary spacecraft. Three of the Galilean satellites of Jupiter exhibit H2O ice on their surfaces, while small amounts of CO2 are present on Ganymede and Callisto. The volcanic satellite Io has abundant SO2 ice and frost deposits. Saturn s satellites have surfaces dominated by H2O ice, but CO2 is also present on most of them, and in the cases of the low-albedo satellites Iapetus and Phoebe, there is evidence of complex hydrocarbons mixed with the surface materials. The large Uranian satellites also have H2O-dominated surfaces, but CO2 has also been discovered on two of them. Neptune s largest satellite, Triton, show spectroscopic evidence for six different ices, including N2, CH4, CO, CO2, H2O, and C2H6. The latter ice is a photochemical product from the action of sunlight on Triton's atmosphere. Pluto is similar to Triton, although CO2 has not been found. Pluto s large satellite, Charon, shows evidence for an ammonia hydrate on part of its surface. V. I. Moroz was a pioneer in the application of near-infrared detectors to astronomical sources. Using a prism spectrometer he measured the spectra of the Galilean satellites of Jupiter, and in 1966 he published the first near-infrared spectra, noting the appearance of H2O ice as a major component of Europa and Ganymede. This discovery, and the techniques of Moroz measurements help set the stage for the broad extension of the study of planetary, satellite, and asteroid surfaces through reflectance spectroscopy in the near-infrared.

Cruikshank, Dale P.↗

Single Pass Laser Process for Super-Hydrophobic Flexible Surfaces with Micro/Nano Hierarchical Structures

Wetting has been studied in various fields: chemical industry, automobile manufacturing, food companies, and even life sciences. In these studies, super-hydrophobic surfaces have been achieved through complex steps and processes. To realize super-hydrophobicity, however, we demonstrated a simple and single pass laser process for the fabrication of micro/nano hierarchical structures on the flexible polytetrafluoroethylene (PTFE, Teflon) surface. The fabricated hierarchical structures helped increase the hydrophobicity by augmenting the surface roughness and promoting air-trapping. In addition, we employed a low-cost and high-throughput replication process producing numerous polydimethylsiloxane (PDMS) replicas from the laser-processed PTFE film. Thanks to the anti-adhesive characteristics of PTFE and the elasticity of PDMS, the structure perfectly transferred to the replica without any mechanical failure. Moreover, our designed mesh patterns offered the possibility of large area applications through varying the process parameters (pitch, beam spot size, laser fluence, and scan speed). Even though mesh patterns had relatively large pitch (190 μm), we were able to achieve high contact angle (>150°). Through pneumatically deformed structure, we clearly showed that the shape of the droplets on our laser-processed super-hydrophobic surface was spherical. Based on these outcomes, we can expect our single laser pulse exposure process can overcome many drawbacks and offer opportunities for advancing applications of the wetting phenomena.

36 MATERIALS SCIENCE↗

Kinetically versus thermodynamically controlled factors governing elementary pathways of GaP(111) surface oxidation

GaP and related III-V semiconductors have attracted interest as high-efficiency photoelectrochemical electrodes for solar water splitting. However, their efficacy is linked to the presence, identity, and integrity of native surface oxides, which are structurally and chemically complex and evolve during operation. Using ambient pressure X-ray photoelectron spectroscopy (APXPS) coupled with ab initio simulations, we track key chemical motifs expressed during evolution of GaP(111) surface oxides, their associated reaction kinetics, and their correlations with electronic properties. We identify two distinct thermal regimes corresponding to kinetically and thermodynamically controlled oxidation. Below 600 K, exposure to O2 generates kinetically facile Ga-O-Ga configurations, whereas higher temperatures cause activated oxygen to insert into Ga–P bonds as part of a thermodynamically driven transformation into a complex, heterogeneous 3D network of surface POx (1≤x ≤ 4) groups and Ga2O3 species, the latter of which eventually dominates upon depletion of surface phosphorus. Here our study highlights the critical competition between kinetic and thermodynamic factors during GaP oxidation, yielding insights for fabricating stable III-P-based photoelectrodes with precisely engineered surface properties.

08 HYDROGEN↗

Software Surface Modeling and Grid Generation Steering Committee

It is a NASA objective to promote improvements in the capability and efficiency of computational fluid dynamics. Grid generation, the creation of a discrete representation of the solution domain, is an essential part of computational fluid dynamics. However, grid generation about complex boundaries requires sophisticated surface-model descriptions of the boundaries. The surface modeling and the associated computation of surface grids consume an extremely large percentage of the total time required for volume grid generation. Efficient and user friendly software systems for surface modeling and grid generation are critical for computational fluid dynamics to reach its potential. The papers presented here represent the state-of-the-art in software systems for surface modeling and grid generation. Several papers describe improved techniques for grid generation.

Smith, Robert E.↗