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At least 739 records · Page 41

Nanoparticle dynamics in the spatial afterglows of nonthermal plasma synthesis reactors

Nonthermal plasma flow tube reactors are industrially scalable systems for the production of nanocrystal (NC) based materials and coatings. One key advantage of nonthermal plasma synthesis is the ability to both synthesize NCs and deposit films in a single reactor, as at the reactor outlet, NCs can be inertially deposited onto a target substrate. The size and morphology of deposited particles can substantially influence the film structure and function. Though NCs are typically near-spherical and monodispersed as-produced in plasma synthesis reactors, NC charge and growth dynamics can be altered substantially when NCs are sampled out of the plasma and through the spatial afterglow region, affecting deposition. Experiments have demonstrated changes of NC size and charge in the spatial afterglow; however, these dynamics remain unexplored and unexplained via theory and simulation. To address this, we developed a constant number Monte Carlo (CNMC) simulation model to examine the mechanisms of NC decharging and growth in the spatial afterglow of plasma flow tube reactors. Collisions between NC and plasma species, diffusive deposition, and electron desorption from NCs are incorporated in the CNMC simulation. The simulation results are specifically compared with previous experiments on Si NCs synthesized from a low pressure Ar-SiH 4 nonthermal plasma reactor. Furthermore, the experiment-model comparison shows that CNMC models can be implemented which accurately model NC size distribution evolution in a spatial afterglow. Simultaneously, results show that improved collision models, energetic species diffusion models, and electron desorption models will be necessary to accurately depict NC dynamics in spatial afterglows.

42 ENGINEERING↗

Three-dimensional simulations of reshocked inclined Richtmyer-Meshkov instability: Effects of initial perturbations

The effect of initial perturbations on the evolution of the inclined Richtmyer-Meshkov turbulent mixing layer before and after reshock initiated by a shock wave with Mach number 1.55 is investigated through three-dimensional (3D) simulations using the flash code. The 3D simulations aim to reproduce both predominantly single-mode and multimode interfaces between light and heavy gases (N 2 -CO 2 , Atwood number, A≈0.22; amplitude to wavelength ratio of 0.088) which were created in an inclined shock tube facility to analyze the effects of initial conditions on mixing development in the entire flow field. The two-dimensional center slices of 3D simulations are compared with the experimental results to validate the computational code. Mixing width, mixed mass, mixed-mass thickness, and circulation in addition to concentration fields are shown to be in good agreement with the experimental data. The three-dimensional density and vorticity fields are first presented to qualitatively describe the flow behavior before and after reshock. Several measured density/velocity-related quantities indicate that the growth of the mixing material is strongly dependent on initial conditions. Before reshock and at early times after reshock, flow is clearly maintaining the memory of initial perturbations. However, at late time after reshock, although the large wavelength feature still dominates the flow motion, and the morphology of the two different interfaces indicates several differences, by breakdown of large-scale coherent structures to much finer scales, the memory of small scales of the multimode initial perturbation is not as clear as pre-reshock. Regarding three-dimensionality of the flow, before reshock in the multimode case, the baroclinic vorticity production, circulation, turbulent kinetic energy, and turbulent mass flux suggest that the small-scale roll-up features along the large inclined wavelength quickly evolves in all three dimensions. The coherent vortex tubes break down to smaller wormlike vortex structures, and turbulent fluctuations in the out-of-plane dimension are comparable to the spanwise direction. After reshock, this three-dimensionality of mixing growth was observed in the flow for both initial conditions. The results of this work represent a significant extension of previous computational studies performed on this specific topic. A different code with a different numerical method is validated through comparison with the experimental data. The initial perturbations are directly measured from the experimental results. Moreover, the entire three-dimensional experimental shock tube domain is simulated, and more quantities are investigated to understand the mixing mechanism and instability evolution in all three dimensions.

42 ENGINEERING↗

Component Identification of Solid Biomass Fuels Using Reflected Light Microscopy: Interlaboratory Study 2

As nations transition toward sustainable energy systems, biomass has become a vital component of global energy portfolios. Derived from organic materials such as wood, agricultural residues, forestry byproducts, and organic waste, biomass is a renewable energy source with significant environmental and economic benefits. Responsible biomass energy production can improve waste management, reduce emissions of greenhouse gases, and mitigate environmental pollution. However, as the diversity of biomass-derived fuels increases, robust quality assessment methods are essential to ensure their efficiency, safety, and minimal environmental impact. Reflected light microscopy (RLM) is one such technique with the potential to complement conventional physico-chemical analyses by enabling a rapid identification of material constituents and impurities. To refine this methodology and evaluate the reproducibility of solid biomass component identification using RLM, an interlaboratory study (ILS) was conducted. The study involved the recognition of 58 components across 45 photomicrographs, with the participation of 65 scientists and students from 25 countries. The participants faced high difficulty identifying some of the marked components, and as a result, the percentage of correct answers ranged from 19.0 % to 98.3 %, with an average correct identification rate of 62.7 %. The most challenging aspects of the identification process included distinguishing between woody and non-woody (agro) biomass, accurately identifying petroleum-derived materials, and differentiating agro biomass from inorganic matter. The results suggest that while RLM is an important tool for characterizing solid biomass, further development of methodology guidelines and training are necessary to enhance its effectiveness. Future research should prioritize preparing detailed, image-rich, microscopic morphological descriptions of biomass fuel components, which could improve the accuracy and reliability of using RLM in biomass fuel characterization.

09 BIOMASS FUELS↗

Surface enhanced performance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathodes by infiltration Pr-Ni-Mn-O progress

Herein the present study reports the enhancement of electrochemical oxygen reduction activity of porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathodes by coating a thin film of Pr-Ni-Mn oxide (PNM5) using a multi-step infiltration process. XRD examination reveals that PNM5 mainly contains a multiphase mixture of Pr 6 O 11 , PrNiO 3 , MnO and NiO. SEM morphology shows a thin PNM5 film and small particles are formed on the surface of LSCF backbone particles. Impedance spectrum analysis indicates that PNM5 infiltrated LSCF exhibits dramatically reduced polarization resistance (R p ), reaching R p of 0.244 Ω cm 2 at 973 K, which is one-half of the baseline LSCF cathode. The activation energy of LSCF cathodes infiltrated with PNM5 is 1.45 eV, slightly lower than the baseline LSCF cathode (1.77 eV). Distribution of relaxation time (DRT) function analysis shows PNM5 infiltration layer significantly promotes the oxygen reduction reaction (ORR) of cathode surface. With the increase in firing temperature, the total resistance increases and R p changes from ion transport to oxygen reduction reaction. Degradation rate of the PNM5-infiltrated LSCF is also lower, 0.02168% vs 0.07093% for the baseline LSCF over a 200-h period. A single cell testing indicated that the peak power density of the PNM5-infiltrated cell was increased by 140.66%. Overall, PNM5 could be a potential catalyst for boosting the performance of a commercial LSCF cathode for solid oxide fuel cells (SOFC).

36 MATERIALS SCIENCE↗

On the thermal coarsening and transformation of nanoscale oxide inclusions in 316L stainless steel manufactured by laser powder bed fusion and its influence on impact toughness

The thermal evolution of nanoscale oxide inclusions in 316L stainless steel (SS) manufactured by laser powder bed fusion additive manufacturing (AM) was explored. The size, chemical composition, morphology, and distribution of the oxides were characterized as the function of heat treatment conditions. The study revealed the mechanistic driving force of the rapid oxide coarsening during recrystallization. Ostwald ripening governs oxide coarsening. The active grain boundary-oxide interaction at the early stage of recrystallization accelerated oxide coarsening via enhanced solute diffusion along grain boundaries. Pipe diffusion along dislocation cellular boundaries has a negligible contribution to oxide coarsening. At high temperatures (T> 1065 °C), although lattice diffusion primarily controlled the oxide growth, the contribution from the grain-boundary diffusion was necessary. The transformation from MnSiO 3 to CrMn 2 O 4 took place in the un-recrystallized grains but was not observed when recrystallization started. The interaction of grain boundary and oxides during recrystallization resulted in a high fraction of oxides accumulated at grain boundaries. While oxide coarsening does not significantly alter the toughness value, grain-boundary oxides promote microvoid formation and intergranular fracture under Charpy impact in the recrystallized AM 316L SS.

36 MATERIALS SCIENCE↗

Applications of Hyporheic Zone Sampling for Assessing VOC Plume Engineered Remediation and Natural Attenuation Effectiveness - 20414

Determining the efficacy of engineered remedial actions and/or natural attenuation as an acceptable EPA Record of Decision (ROD) must address long-term temporal and spatial variability. Since final plume downslope destinations are aquifers and related surface streams and rivers, hyporheic zone sampling is essential. Comprehensive hyporheic sampling documents plume groundwater remediation prior to upwelling into stream benthic strata and natural attenuation within this dynamic zone itself. Our intensive sampling of the Savannah River Site (SRS) Chemical, Metals, and Pesticides (CMP) Pits VOC plume-fringe from 2005 to 2018 documented PCE natural attenuation and effectiveness of In Situ Thermal Treatment (ISTT). Most plume hyporheic upwelling was delimited to a 20 m inflow reach along Pen Branch. Our study utilized corroborative sampling methodologies: ambient hole-water grab samples: passive diffusion bags (PDB); and hole-core sediment samples to confirm station to station spatial and temporal trends. VOC hot spot detections were confirmed from both groundwater and soil core samples. VOC pathways through the Pen Branch hyporheic zone were assessed at hole-installation using sequential soil samples from augered cores and grab-samples of hole-bottom water. Longer term, composite water samples were collected from PDBs deployed for a minimum two-week equilibration period. Soil samples were collected from the 15 and 65 cm core levels in December 2017 and June 2018 at six stations. Additional core depths of 40 and 85 cm were sampled in June 2018 at the highest VOC station (5DB80). All samples were analyzed in an EPA certified lab by purge and trap GC-MS. Effectiveness of previous ISTT and soil vapor extraction (SVE) for this CMP Pits PCE plume, was clearly documented by significant downward trends in VOC at hyporheic zone stations prior to December 2015. Achieving final stage conversions of PCE daughter products to ethene and CO{sub 2} may be limited depending upon suitable interactions between hyporheic zone sediment morphology, hydrology, and redox conditions. Because declines in VOC daughter products at our hyporheic stations may also be caused by physical actions of dilution and dispersion rather than true biochemical dechlorination, full quantification of natural attenuation requires the use of compound-specific isotope ratio analysis (CSIA) and microbial 16S rRNA with qPCR. To assist these next-phase efforts, a natural attenuation index (NAI) was used to help produce quicker, more cost-effective decision making for locating CSIA and microbial sampling efforts. The NAI used natural logarithm transformed GC-MS results for station VOC degradation compounds versus VOC parent compounds. Wide differences were observed between stations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Comparison of Solidification Structures and Submicroscale Cellular Segregation in Rapidly Solidified Stainless Steels Produced via Two-Piston Splat Quenching and Laser Powder Bed Fusion

Fusion-based additive manufacturing techniques leverage rapid solidification (RS) conditions to create parts with complex geometries, unique microscale/nanoscale morphological features, and elemental segregation. Three custom composition stainless steel alloys with varying chromium equivalence to nickel equivalence ratio (Cr eq /Ni eq ) between 1.53 and 1.95 were processed using laser powder bed fusion (LPBF) and/or two-piston splat quenching (SQ) to produce solidification rates estimated between 0.4 and 0.8 m/s. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were utilized to collect high-resolution images, electron backscatter diffraction (EBSD) phase identification, and measure cellular segregation. Similar features were observed in both LPBF and SQ samples including phase and microstructure, nanoscale oxide particles, cell size, and segregation behavior. However, dislocation pileup was observed along the cell boundaries only in the LPBF austenite solidified microstructure. Targeted adjustment of the SQ feedstock Cr and Ni concentrations, within the ASTM A240 specification for 316L resulted in no observable impact on the cell size, oxide particle size, or magnitude of segregation. Also, the amount of Ni segregation in the ferrite solidified microstructures did not significantly differ, regardless of Cr/Ni eq or processing technique. Here, SQ is demonstrated as capable of simulating RS rates and microstructures similar to LPBF for use as an alternative screening tool for new RS alloy compositions.

42 ENGINEERING↗

Impact of carrier wafer on etch rate, selectivity, morphology, and passivation during GaN plasma etching

The choice of carrier wafer was found to significantly influence etch rates, selectivity, and morphology in GaN micropillar etching in a Cl 2 -Ar high-density inductively coupled plasma. 7 × 7 mm 2 GaN on sapphire chips with a plasma-enhanced chemical vapor deposition SiO 2 hard mask was etched on top of 4-in. fused silica, silicon carbide, silicon, sapphire, aluminum nitride, and high purity aluminum carriers. Silicon and silicon carbide carriers reduced GaN:SiO 2 selectivity because incidental SiCl x and CCl x etch products from the carriers attack the SiO 2 mask. Aluminum nitride and high-purity aluminum carriers yielded the highest GaN:SiO 2 selectivities due to the deposition of Al-based etched by-products, while the highest GaN etch rate was achieved using the sapphire carrier since it was the most inert carrier and did not sink any Cl 2 . Overall, results indicate that SiO 2 and Al may be used as passivation materials during GaN etching, as vertical profiles were achieved when SiO 2 or Al is redeposited from the fused silica and aluminum carriers, respectively. Floor pitting, trenching, sidewall roughness, and faceting were all influenced by carrier wafer type and will be discussed.

36 MATERIALS SCIENCE↗

Binder-jetted AISI M2 tool steel during hot isostatic pressing: Densification and carbide transformation

Binder jetting (BJ) enables fabrication of complex components from high-alloy steels such as AISI M2; however, residual porosity after sintering limits mechanical performance. This study investigates the coupled effects of binder chemistry, sintering conditions, cooling rate, and subsequent hot isostatic pressing (HIP) on densification, microstructure, and mechanical response in binder-jetted M2 tool steel. HIP increased relative density from ∼93 to 95% to >99% and improved compressive strength by ∼40-70%. Densification was governed by initial pore morphology, where closed porosity was effectively eliminated, while interconnected porosity limited full consolidation. Microstructural analysis (XRD, EBSD, SEM) shows that HIP promotes dissolution of metastable carbides and redistribution of alloying elements (W, Mo, V), transforming heterogeneous carbide networks into finer and more uniformly distributed M 2 C, MC, and M 6 C phases through diffusion-assisted homogenization. Among the investigated conditions, the FluidFuse binder combined with sintering at 1270 °C for 60 min and furnace cooling produced the most balanced response, achieving ∼99.7% density, ∼855 HV hardness, ∼4130 MPa compressive strength, and ∼24% strain. In contrast, higher sintering temperatures promoted carbide coarsening, reducing ductility despite high density. HIP reduces microstructural heterogeneity and drives the system toward a near-equilibrium state with reduced sensitivity to prior processing history. A comparative assessment with conventional and additive manufacturing routes (LPBF, DED, EBM, FFF) shows that the BJ-HIP approach achieves competitive densification and mechanical performance. These findings provide a mechanistic basis for controlling densification and microstructure in high-alloy steels processed via BJAM.

AISI M2 tool steel↗

Rapid macrovoid characterization in membranes prepared via nonsolvent-induced phase separation: A comparison between 2D and 3D techniques

Optimizing the performance of asymmetric membranes prepared via nonsolvent-induced phase separation (NIPS) requires a quantitative understanding of how processing variables influence membrane morphology. Presently, the most useful structural quantification techniques require 3D visualization of the membrane structure and are best suited for studies seeking detailed information on small datasets. This study proposes and validates a rapid and accurate technique for quantifying macroporosity (i.e., D m ), a simple descriptor of sublayer macrovoid content in asymmetric membranes D m . values measured from segmented cross-sectional imaging performed via X-ray computed tomography (XCT) and scanning electron microscopy (SEM) are presented and compared for three asymmetric membranes prepared from commercial polymers. Importantly, analyses of 3D XCT membrane reconstructions reveal that D m is described by a single, centralized mean, which demonstrates that macrovoid content is spatially homogenous. Thus, D m can be approximated from limited sampling of the 2D cross-sectional membrane structure via SEM. A proposed 2D SEM sampling method provides D m estimates within ±6% of corresponding 3D XCT values with 30 independent measurements for the three membranes. Further sensitivity is achieved using complementary descriptors such as macrovoid count density (i.e., C m ). This technique is thus a useful tool for characterizing macroporosity from a broad selection of membrane samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Wormholes Within: A Study of 1, 3, 5–Triamino–2, 4, 6–Trinitrobenzene Crystal Morphology by Micro and Nano–Scale X–Ray Computed Tomography and its Effects Upon the Shock Sensitivity of Detonation

We report that we understand heterogeneous-explosive detonation only to the extent that we can first measure the salient chemical and microstructural features. Barring an inordinate amount of trial and error, we can tailor the detonation properties of our HE formulations only to the extent that we understand (at least qualitatively) the same effects. As an insensitive high explosive, 1, 3, 5-triamino-2, 4, 6-trinitrobenzene (TATB) burns more heterogeneously than conventional high explosives, making its detonation properties sensitive to microstructure. The Benziger route can produce various grain morphologies depending on the amount of water used in the amination step. So-called dry-aminated (DA) TATB crystals are riddled with a void structure called wormholes, which are washed out ammonium chloride (NH4Cl) inclusions that form during synthesis. So-called wet-aminated (WA) TATB crystals do not contain NH 4 Cl inclusions but possess a very convoluted external structure. Using both micro and nano-scale CT, we explore three DA-TATB lots that reflect evolutionary processing changes, plus one WA-TATB material. Micro CT imaged crystal collections show the exterior grain structure, revealing its roughness and providing a crude particle size measurement. The DA-TATB lots that test most sensitively in the LANL ECOT corner-turning test are roughest, having the appearance of being “corroded”. Nano-scale CT reveals both internal NH 4 Cl inclusions and void structures. The DA-TATB lots that tested intermediate and high sensitivity in ECOT exhibited similar wormhole structures, which were more extensive than that of the low-sensitivity lot. The least sensitive DA-TATB lot also retained more NH 4 Cl, consistent with reduced connectivity of voids to the surface.

1, 3, 5-triamino-2,4↗

Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production

The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. Here, we investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ~110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.

36 MATERIALS SCIENCE↗

Recent Advancements in Modeling and Simulation of Entry Systems at NASA

This paper describes recent development of modeling and simulation technologies for entry systems in support of NASA’s exploration missions. Mission-tailored research and development in modeling of entry systems occurs across the Agency (e.g., within the Orion and Mars 2020 Programs), however the aim of this paper is to discuss the broad, cross-mission research conducted by NASA’s Entry Systems Modeling (ESM) Project, which serves as the Agency’s only concerted effort toward advancing entry systems across a range of technical disciplines. Technology development in ESM is organized and prioritized from a system-level perspective, resulting in four broad technical areas of investment: (1) Predictive material modeling, (2) Shock layer kinetics and radiation, (3) Computational and experimental aerosciences, and (4) Guidance, navigation, and control. Investments in thermal protection material modeling are geared toward high-fidelity, predictive models capable of handling complex structures, with an eye toward optimizing design performance and quantifying thermal protection system reliability. New computational tools have been developed to characterize material properties and behavior at the microstructural level, and experimental techniques (molecular beam scattering, micro-computed tomography, among others) have been developed to measure material kinetics, morphology, and other parameters needed to inform and validate detailed simulations. Advancements have also been made in macrostructural simulation capability to enable 3-D system-scale calculations of material response with complex topological features, including differential recession of tile gaps. Research and development in the area of shock layer kinetics has focused on air and CO2-based atmospheres. Capacity and capability of the NASA Ames Electric Arc Shock Tube (EAST) have been expanded in recent years and analysis of resulting data has led to several improvements in kinetic models, while simultaneously reducing uncertainties associated with radiative heat transfer predictions. First-principles calculations of fundamental kinetic, thermodynamic, and transport data, along with state-specificmodels for non-equilibrium flow regimes, have also yielded new insights and have the potential to vastly improve model fidelity. Aerosciences is a very broad area of interest in entry systems, yet a number of important challenges are being addressed: Coupled fluid-structure simulations of parachute inflation and dynamics; Experimental and computational studies of vehicle dynamics; Multi-phase flow with dust particles to simulate entry environments at Mars during dust storms; Studies of roughness-induced heating augmentation relevant to tiled and woven thermal protection systems; and Advanced numerical methods to optimize computational analyses for desired accuracy versus cost. Guidance and control in the context of entry systems has focused on development of methods for multi-axis control (i.e. pitch and yaw, rather than bank angle alone) of spacecraft during entry and descent. With precision landing requirements driven by Mars human exploration goals, recent efforts have yielded 6-DOF models of multi-axis control with propulsive descent of both inflatable and rigid ellipsled-like architectures. Results for both configurations have demonstrated the ability to land within the 50-meter precision requirement demanded by Mars human exploration missions, while also reducing propellant requirements by enabling more efficient control through entry and descent. Ongoing research in GN&C is developing mechanical specifications for the systems and establishing engineering feasibility.

aerothermodynamics↗

Water mediated growth of oriented single crystalline SrCO3 nanorod arrays on strontium compounds

Abstract Morphology-controlled strontianite nanostructures have attracted interest in various fields, such as electrocatalyst and photocatalysts. Basic additives in aqueous strontium solutions is commonly used in controlling strontianite nanostructures. Here, we show that trace water also serves an important role in forming and structuring vertically oriented strontianite nanorod arrays on strontium compounds. Using in situ Raman spectroscopy, we monitored the structural evolution from hydrated strontium to strontianite nanorods, demonstrating the epitaxial growth by vapor–liquid–solid mechanism. Water molecules cause not only the exsolution of Sr liquid droplets on the surface but also the uptake of airborne CO 2 followed by its ionization to CO 3 2− . The existence of intermediate SrHO + –OCO 2 2− phase indicates the interaction of CO 3 2− with SrOH + in Sr(OH) x (H 2 O) y cluster to orient strontianite crystals. X-ray diffraction simulation and transmission electron microscopy identify the preferred-orientation plane of the 1D nanostructures as the (002) plane, i.e., the growth along the c-axis. The anisotropic growth habit is found to be affected by the kinetics of carbonation. This study paves the way for designing and developing 1D architecture of alkaline earth metal carbonates by a simple method without external additives at room temperature.

36 MATERIALS SCIENCE↗

Multiscale and Multiphysics Modeling of Additive Manufacturing of Advanced Materials

The objective of this proposed project is to research and develop a prediction tool for advanced additive manufacturing (AAM) processes for advanced materials and develop experimental methods to provide fundamental properties and establish validation data. Aircraft structures and engines demand materials that are stronger, useable at much higher temperatures, provide less acoustic transmission, and enable more aeroelastic tailoring than those currently used. Significant improvements in properties can only be achieved by processing the materials under nonequilibrium conditions, such as AAM processes. AAM processes encompass a class of processes that use a focused heat source to create a melt pool on a substrate. Examples include Electron Beam Freeform Fabrication and Direct Metal Deposition. These types of additive processes enable fabrication of parts directly from CAD drawings. To achieve the desired material properties and geometries of the final structure, assessing the impact of process parameters and predicting optimized conditions with numerical modeling as an effective prediction tool is necessary. The targets for the processing are multiple and at different spatial scales, and the physical phenomena associated occur in multiphysics and multiscale. In this project, the research work has been developed to model AAM processes in a multiscale and multiphysics approach. A macroscale model was developed to investigate the residual stresses and distortion in AAM processes. A sequentially coupled, thermomechanical, finite element model was developed and validated experimentally. The results showed the temperature distribution, residual stress, and deformation within the formed deposits and substrates. A mesoscale model was developed to include heat transfer, phase change with mushy zone, incompressible free surface flow, solute redistribution, and surface tension. Because of excessive computing time needed, a parallel computing approach was also tested. In addition, after investigating various methods, a Smoothed Particle Hydrodynamics Model (SPH Model) was developed to model wire feeding process. Its computational efficiency and simple architecture makes it more robust and flexible than other models. More research on material properties may be needed to realistically model the AAM processes. A microscale model was developed to investigate heterogeneous nucleation, dendritic grain growth, epitaxial growth of columnar grains, columnar-to-equiaxed transition, grain transport in melt, and other properties. The orientations of the columnar grains were almost perpendicular to the laser motion's direction. Compared to the similar studies in the literature, the multiple grain morphology modeling result is in the same order of magnitude as optical morphologies in the experiment. Experimental work was conducted to validate different models. An infrared camera was incorporated as a process monitoring and validating tool to identify the solidus and mushy zones during deposition. The images were successfully processed to identify these regions. This research project has investigated multiscale and multiphysics of the complex AAM processes thus leading to advanced understanding of these processes. The project has also developed several modeling tools and experimental validation tools that will be very critical in the future of AAM process qualification and certification.

Liou, Frank↗

Investigating the Electromechanical Sensitivity of Carbon-Nanotube-Coated Microfibers

The piezoresistance of carbon nanotube (CNT)-coated microfibers is examined using diametric compression. Diverse CNT forest morphologies were studied by changing the CNT length, diameter, and areal density via synthesis time and fiber surface treatment prior to CNT synthesis. Large-diameter (30–60 nm) and relatively low-density CNTs were synthesized on as-received glass fibers. Small-diameter (5–30 nm) and-high density CNTs were synthesized on glass fibers coated with 10 nm of alumina. The CNT length was controlled by adjusting synthesis time. Electromechanical compression was performed by measuring the electrical resistance in the axial direction during diametric compression. Gauge factors exceeding three were measured for small-diameter (<25 μm) coated fibers, corresponding to as much as 35% resistance change per micrometer of compression. The gauge factor for high-density, small-diameter CNT forests was generally greater than those for low-density, large-diameter forests. A finite element simulation shows that the piezoresistive response originates from both the contact resistance and intrinsic resistance of the forest itself. The change in contact and intrinsic resistance are balanced for relatively short CNT forests, while the response is dominated by CNT electrode contact resistance for taller CNT forests. These results are expected to guide the design of piezoresistive flow and tactile sensors.

36 MATERIALS SCIENCE↗

Synthesis‐Related Nanoscale Defects in Mo‐Based Janus Monolayers Revealed by Cross‐Correlated AFM and TERS Imaging

2D Janus transition metal dichalcogenides (TMDs) are promising candidates for various applications including non-linear optics, energy harvesting, and catalysis. These materials are usually synthesized via chemical conversion of pristine TMDs. Nanometer-scale characterization of the obtained Janus materials’ morphology and local composition is crucial for both the synthesis optimization and the future device applications. In this work, we present the results of cross-correlated atomic force microscopy (AFM) and tip-enhanced Raman spectroscopy (TERS) study of Janus monolayers synthesized by the hydrogen plasma-assisted chemical conversion of MoSe 2 and MoS 2 . We demonstrate that the choice of both the growth substrate and the starting TMD influences the residual strain, thereby shaping the nanoscale morphology of the resulting Janus material. Furthermore, by employing TERS imaging, we show the presence of nanoscale islands (≈20 nm across) of MoSe 2 - ${\mathrm{Mo}}_{{\mathrm{Se}}}^{\mathrm{S}}$ (MoS 2 -${\mathrm{Mo}}_{\mathrm{S}}^{{\mathrm{Se}}}$) vertical heterostructures originating from the bilayer nanoislands in the precursor monolayer crystals. The understanding of the origins of nanoscale defects in Janus TMDs revealed in this study can help with further optimization of the Janus conversion process towards uniform and wrinkle-/crack-free Janus materials. Moreover, this work shows that cross-correlated AFM and TERS imaging is a powerful and accessible method for studying nanoscale composition and defects in Janus TMD monolayers.

2D materials↗

Grafting nanometer metal/oxide interface towards enhanced low-temperature acetylene semi-hydrogenation

Metal/oxide interface is of fundamental significance to heterogeneous catalysis because the seemingly “inert” oxide support can modulate the morphology, atomic and electronic structures of the metal catalyst through the interface. The interfacial effects are well studied over a bulk oxide support but remain elusive for nanometer-sized systems like clusters, arising from the challenges associated with chemical synthesis and structural elucidation of such hybrid clusters. We hereby demonstrate the essential catalytic roles of a nanometer metal/oxide interface constructed by a hybrid Pd/Bi 2 O 3 cluster ensemble, which is fabricated by a facile stepwise photochemical method. The Pd/Bi 2 O 3 cluster, of which the hybrid structure is elucidated by combined electron microscopy and microanalysis, features a small Pd-Pd coordination number and more importantly a Pd-Bi spatial correlation ascribed to the heterografting between Pd and Bi terminated Bi 2 O 3 clusters. The intra-cluster electron transfer towards Pd across the as-formed nanometer metal/oxide interface significantly weakens the ethylene adsorption without compromising the hydrogen activation. As a result, a 91% selectivity of ethylene and 90% conversion of acetylene can be achieved in a front-end hydrogenation process with a temperature as low as 44 °C.

36 MATERIALS SCIENCE↗