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At least 595 records · Page 33

Loading direction dependence of asymmetric response of pyramidal slip in rolled AZ31 magnesium alloy

Textured magnesium alloys usually exhibit anisotropic mechanical behavior due to the asymmetric activation of different twinning and slipping modes. This work focuses on the pyramidal slip responses of rolled AZ31 magnesium alloy under two loading conditions, compressive and tensile loading along the normal direction. Under the condition where the compressive loading direction is closely parallel to the c-axis of the unit cell, tensile twinning and basal slips are prohibited, dislocations then active and tend to accumulate at grain boundaries and form dislocation walls. Meanwhile, these dislocations exhibit zigzag morphologies, which result from the cross-slip from {$10\bar{1}1$} first-order pyramidal plane to {$11\bar{2}2$} second-order pyramidal plane, then back to {$10\bar{1}1$} first-order pyramidal plane. Under the condition where tensile twins are prevalent, {$10\bar{1}1$} first-order and {$11\bar{2}2$} second-order pyramidal dislocations are favorable to be activated. Both types of dislocations behave climb-like dissociations onto the basal plane, forming zigzag dislocations. first-order pyramidal plane to second-order pyramidal plane, then back to first-order pyramidal plane. Under the condition where tensile twins are prevalent, first-order and second-order pyramidal dislocations are favorable to be activated. Both types of dislocations behave climb-like dissociations onto the basal plane, forming zigzag dislocations.

36 MATERIALS SCIENCE↗

A New Simultaneous Membrane Thickness and Catalyst Loading Measurement for Fuel Cell Proton-Exchange Assemblies by $\mathrm{IR}$ Transmission

Here, we present a study of mid-infrared (mid-IR) transmission through typical proton-exchange fuel cell and water electrolyzer catalyst-coated membrane materials, and the determination of membrane layer thickness, and catalyst layer loading, from the power of the transmitted beam. Measured membrane thicknesses lay in the range of 25-125 um, and catalyst areal loadings range from 0.05 to 0.35 mg/cm 2 . We show that the transmission spectrum correlated to membrane thickness and catalyst loading values separately, and also used a mathematical model to calculate both quantities simultaneously, from a single measurement of transmission. Measurements were carried out using a Fourier-transform infrared (FTIR) spectrometer, in specular transmission mode, in the wavelength range of 3-13 um (3333-770 cm -1 ). We discuss the potential application of this method to the development of roll-to-roll manufacturing full-area-scanning quality inspection of catalyst-coated membrane (CCM) materials.

30 DIRECT ENERGY CONVERSION↗

Dislocation generation in diamond under extreme loading

Diamond is, by virtue of its high bonding forces and Peierls-Nabarro barrier stresses, among the hardest materials on earth due to the difficulty of generating and moving dislocations. We demonstrate, using molecular dynamics and analytical calculations, that the generation of defects is dependent on loading orientation. Shock-loading single-crystal diamond along [001] and [011] to a stress of 137 GPa did not reveal dislocations, whereas loading along [111] generated profuse dislocations. The introduction of a void at the latter orientation generated dislocations at 72.6 GPa. Two slip systems were identified: <011>{100} and <112>{111}. The threshold for plastic deformation in diamond is orientation dependent and significantly lower than reported in previous studies: 0.14 G (shear modulus). The void collapse generated localized amorphization for [001]. In conclusion, these results on the anisotropy of plasticity and void effects have relevance for the improvement of symmetry in the collapse of diamond capsules in inertial fusion experiments.

36 MATERIALS SCIENCE↗

Nanocarrier-loaded block copolymer dual domain organogels

Loaded polymer gels are prevalent materials in the controlled release community and, fairly recently, have been formulated to include nanocarrier domains such as micelles and vesicles. One mechanism used to establish the solid-like characteristic of gels is block copolymer self-assembly, which can result in a system-spanning, physically-crosslinked network. Additionally, the combination of nanocarrier and crosslink domain presence offers gels with a rich nanoscale phase space capable of intricate macroscopic property tuning. The current manuscript provides an overview of nanocarrier-loaded block copolymer organogels wherein nanocarriers are reverse micelles formed by sodium dioctyl sulfosuccinate (AOT), the block copolymer is a styrenic ABA triblock copolymer, and the gel solvent is aliphatic mineral oil. This introductory overview starts by identifying the envelope in ternary phase space wherein nanocarrier-loaded block copolymer organogels form (2-49 wt% triblock copolymer and 8x10 -3 -1 wt% AOT). Next, a detailed nanostructural description of gels varying in AOT and triblock copolymer concentration is presented. The manuscript concludes with demonstration of AOT reverse micelle release and gel uniaxial tensile response for gels containing 0-1 wt% AOT and 5-40 wt% styrenic triblock copolymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of wind conditions and impact on wind loading at an operational parabolic trough concentrating solar power plant using LiDAR observations

Wind loading is a major factor influencing the structural design costs of Concentrating Solar Power (CSP) collector systems, including heliostats and parabolic troughs. Traditionally, these designs have been based on wind-tunnel data, which often fail to accurately represent the dynamic effects experienced at full scale. This study presents a first-of-its-kind experimental characterization of wind conditions within an operational parabolic-trough CSP power plant focusing specifically on using lidar observations. The lidar observations give a unique opportunity to provide insights into wind flow conditions deep within the trough arrays. Our results suggest that (1) after being blocked by the first few rows, the wind speed above the troughs recovers to 73% of its inflow magnitude as it flows further over the trough field due to enhanced turbulent mixing and (2) due to the wind speed recovery, troughs in the interior field will likely experience higher shear-induced turning moments compared those at the front. The conclusions from this work stress the importance of better understanding the wind patterns and interior wind loads when designing solar collectors and highlights the need for more interior load measurements in the future field campaigns.

17 WIND ENERGY↗

Amorphous Pd-Loaded Ti 4 O 7 Electrode for Direct Anodic Destruction of Perfluorooctanoic Acid

In this work we present a novel Ti 4 O 7 -based electrode loaded with amorphous Pd clusters that achieve efficient anodic destruction of perfluorooctanoic acid (PFOA), a persistent water pollutant with significant environmental and human health concerns. These amorphous Pd clusters were characterized by the disordered, noncrystalline arrangement of Pd single atoms in close proximity, in contrast to crystalline Pd nanoparticles that have been often employed to tailor the electronic properties of an electrode. We found that the Ti 4 O 7 electrode loaded with amorphous Pd clusters significantly outperformed the Ti 4 O 7 electrode loaded with crystalline Pd particles due to enhanced electron transfer through dominant Pd–O bonds. Combined with the efficient binding of PFOA and its degradation intermediates to the fluorinated electrode surface, this electrode was capable of mineralizing PFOA and releasing fluoride as F – . The reaction pathway was found to proceed without involving reactive oxygen species and therefore was not quenched by common anions in complex natural water systems such as chloride ions.

36 MATERIALS SCIENCE↗

Gaseous Iodine Sorbents: A Comparison between Ag-Loaded Aerogel and Xerogel Scaffolds

The general properties of aluminosilicate aerogels and xerogels with silver nanoparticles as sorbents for capturing iodine gas [I2(g)] were investigated. The structures, morphologies, compositions, and pore structures of aerogel and xerogel were compared using powder X-ray diffraction (PXRD), scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, as well as specific surface area (SSA) and pore size analyses. The as-made aerogels, xerogels, and heat-treated aerogels were impregnated with Ag by aqueous ion exchange using AgNO3 solutions, and PXRD patterns showed the presence of nanocrystalline Ag0 after Ag-impregnation. Iodine loadings of aerogels and xerogels were 0.33–0.41 g g-1. The Ag-impregnated aerogels without heat-treatment showed an 8 mass% higher iodine loading than Ag-impregnated xerogels and 3 mass% higher than heat-treated Ag-impregnated aerogels. All gels after iodine uptake showed the presence of AgI, indicating chemisorption of iodine to silver. The SSA values of the as-made gels were 419–598 m2 g-1 but decreased significantly to 34–120 m2 g-1 after Ag-impregnation and iodine uptake processes. Overall, changes in physical and chemical properties of aerogels and xerogels after iodine uptake were similar, and the difference in iodine loading capacities of the aerogels and xerogels was not significant while the synthesis process of xerogel is more practical because it does not require supercritical drying.

aerogel, xerogel, iodine capture↗

Silver-Loaded Xerogel Nanostructures for Iodine Capture: A Comparison of Thiolated versus Unthiolated Sorbents

Here this paper describes the development and provides comparisons of thiolated (-SH) and unthiolated Ag-Al-Si-O xerogels for iodine gas capture. These xerogels were produced from alkoxides and then heat-treated at 350 °C to provide mechanical strength for subsequent processing steps. Then, a portion of the xerogels was thiolated using (3-mercaptopropyl)trimethoxysilane. Next, thiolated and unthiolated batches were ion-exchanged in AgNO 3 solutions where Ag + replaced Na + in the gel network on a near 1:1 molar basis. Subsamples of the Ag-exchanged xerogels were subjected to a reduction step in H 2 /Ar to convert Ag + to Ag 0 where the rest of the Ag-exchanged (Ag + ) were not reduced. X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy revealed nanoscale Ag 0 in the Ag + samples despite no active reduction where actively reduced samples had bimodal Ag 0 distribution of ~2-3 nm hexagonal and ~6-7 nm cubic crystallites. Synchrotron X-ray absorption spectroscopy was used to assess the oxidization states of Ag, S, and I within the different xerogel samples. The specific surface areas of the base xerogels decreased as subsequent treatments were performed on the as-made samples, albeit the decreases were smaller than aerogel equivalents of these samples from a previous study. All iodine-loaded Ag-based samples showed a mixture of β-AgI and γ-AgI. Comparisons of iodine-loading results with other Ag-based iodine sorbents show that the thiolated Ag 0 -xerogels in this work have one of the highest iodine-loading capacities (q e ) reported to date in saturated conditions with the thiolated Ag 0 -xerogel showing 522 mg iodine per g of the sorbent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bulk vs Intrinsic Activity of NiFeO x Electrocatalysts in the Oxygen Evolution Reaction: The Influence of Catalyst Loading, Morphology, and Support Material

We used a combination of ultrahigh vacuum surface science techniques, X-ray spectroscopy, electrochemistry, and density functional theory (DFT), to characterize the influence of catalyst morphology, loading/coverage, and substrate material on the bulk (all atoms) and intrinsic (electrochemically accessible atoms) activity of NiFeO x electrocatalysts in the oxygen evolution reaction (OER). NiFeO x catalysts were grown on both Au(111) and highly oriented pyrolytic graphite (HOPG) electrodes. DFT predicted Fe edge-site atoms at the NiFeO x /Au(111) interface to be the most thermodynamically favorable reaction center, and X-ray absorption spectroscopy data indicated small NiFeO x catalyst particles on Au(111) contained a high population of OER active Fe edge-site atoms. However, restructuring of the Au(111) surface due to repeated oxidation and reduction cycles of the OER CV measurements encapsulated small NiFeO x nanoparticles at catalyst loadings below ~1.5 nmol metal /cm 2 , passivated catalyst edges and reduced bulk OER activity of Au-supported NiFeO x compared with HOPG-supported ones. Analysis of intrinsic activity revealed that the Au(111) support strongly benefited electrochemically accessible NiFeO x atoms, and we observed a 2–3 fold activity enhancement compared with HOPG-supported catalysts for loadings above ~1 nmol metal /cm 2 . Overall, evaluating bulk vs intrinsic activity and identifying loading/coverage-dependent support effects is important for accurately probing fundamental interfacial chemistry, choosing suitable catalyst loadings and supports, and optimizing system parameters to maximize the performance of electrocatalyst systems.

36 MATERIALS SCIENCE↗

Coordinatively and Spatially Coconfining High-Loading Atomic Sb in Sulfur-Rich 2D Carbon Matrix for Fast K + Diffusion and Storage

The atomically dispersed materials promise ultrafast redox kinetics for alkali-ion storage. However, their relatively low mass loading limits their application. In this work, well-dispersed Sb atoms with high-loading of 23.3 wt % anchored in sulfur-rich amorphous carbon-coated reduced graphene oxide matrix (SbSA/C) are prepared by a coordinative and spatial coconfinement methodology including freeze-casting the well-dissolved Sb-chelates (Sb-thioglycolate) within graphene oxide suspension and post heating-treatment. The reduced graphene oxide substrate features open two-dimensional spatial framework for loading atomically dispersive Sb species, and the pyrolyzed Sb-chelates would provide not only massive desirable heteroatoms (S, O) for coordinating the Sb atoms but also in situ pyrolytic carbon for further spatially separating those dispersive atoms. The coordinative and spatial coconfinement engineering also endows the SbSA/C composite with atomic-level Sb atoms against migration and agglomeration during electrochemical K-storage cycling. In situ TEM reveals the uniform potassiation behavior of the SbSA/C without obvious volume change; DFT calculation and electrochemical characterization suggest the significantly lower K-ion diffusion energy barrier. Therefore, on the basis of both the active Sb center and the coordinative heteroatom, the SbSA/C electrode delivers high fast-charging capacity, outstanding rate capability and long-lifespan performance in half/full K-ion batteries (e.g., a stable capacity of 331.3 mA h g –1 is maintained over 1100 cycles at 1.0 A g –1 for half-cell).

36 MATERIALS SCIENCE↗

Load‐Balancing Intense Physics Calculations to Embed Regionalized High‐Resolution Cloud Resolving Models in the E3SM and CESM Climate Models

Abstract We design a new strategy to load‐balance high‐intensity sub‐grid atmospheric physics calculations restricted to a small fraction of a global climate simulation's domain. We show why the current parallel load balancing infrastructure of Community Earth System Model (CESM) and Energy Exascale Earth Model (E3SM) cannot efficiently handle this scenario at large core counts. As an example, we study an unusual configuration of the E3SM Multiscale Modeling Framework (MMF) that embeds a binary mixture of two separate cloud‐resolving model grid structures that is attractive for low cloud feedback studies. Less than a third of the planet uses high‐resolution (MMF‐HR; sub‐km horizontal grid spacing) relative to standard low‐resolution (MMF‐LR) cloud superparameterization elsewhere. To enable MMF runs with Multi‐Domain cloud resolving models (CRMs), our load balancing theory predicts the most efficient computational scale as a function of the high‐intensity work's relative overhead and its fractional coverage. The scheme successfully maximizes model throughput and minimizes model cost relative to precursor infrastructure, effectively by devoting the vast majority of the processor pool to operate on the few high‐intensity (and rate‐limiting) high‐resolution (HR) grid columns. Two examples prove the concept, showing that minor artifacts can be introduced near the HR/low‐resolution CRM grid transition boundary on idealized aquaplanets, but are minimal in operationally relevant real‐geography settings. As intended, within the high (low) resolution area, our Multi‐Domain CRM simulations exhibit cloud fraction and shortwave reflection convergent to standard baseline tests that use globally homogenous MMF‐LR and MMF‐HR. We suggest this approach can open up a range of creative multi‐resolution climate experiments without requiring unduly large allocations of computational resources.

54 ENVIRONMENTAL SCIENCES↗

Global Barotropic Tide Modeling Using Inline Self‐Attraction and Loading in MPAS‐Ocean

Abstract We examine ocean tides in the barotropic version of the Model for Prediction Across Scales (MPAS‐Ocean), the ocean component of the Department of Energy Earth system model. We focus on four factors that affect tidal accuracy: self‐attraction and loading (SAL), model resolution, details of the underlying bathymetry, and parameterized topographic wave drag. The SAL term accounts for the tidal loading of Earth's crust and the self‐gravitation of the ocean and the load‐deformed Earth. A common method for calculating SAL is to decompose mass anomalies into their spherical harmonic constituents. Here, we compare a scalar SAL approximation versus an inline SAL using a fast spherical harmonic transform package. Wave drag accounts for energy lost by breaking internal tides that are produced by barotropic tidal flow over topographic features. We compare a series of successively finer quasi‐uniform resolution meshes (62.9, 31.5, 15.7, and 7.87 km) to a variable resolution (45 to 5 km) configuration. We ran MPAS‐Ocean in a single‐layer barotropic mode forced by five tidal constituents. The 45 to 5 km variable resolution mesh obtained the best total root‐mean‐square error (5.4 cm) for the deep ocean ( 1,000 m) tide compared to TPXO8 and ran twice as fast as the quasi‐uniform 8 km mesh, which had an error of 5.8 cm. This error is comparable to those found in other forward (non‐assimilative) ocean tide models. In future work, we plan to use MPAS‐Ocean to study tidal interactions with other Earth system components, and the tidal response to climate change.

54 ENVIRONMENTAL SCIENCES↗

Ultra-thermostable RNA nanoparticles for solubilizing and high-yield loading of paclitaxel for breast cancer therapy

Paclitaxel is widely used in cancer treatments, but poor water-solubility and toxicity raise serious concerns. Here we report an RNA four-way junction nanoparticle with ultra-thermodynamic stability to solubilize and load paclitaxel for targeted cancer therapy. Each RNA nanoparticle covalently loads twenty-four paclitaxel molecules as a prodrug. The RNA-paclitaxel complex is structurally rigid and stable, demonstrated by the sub-nanometer resolution imaging of cryo-EM. Using RNA nanoparticles as carriers increases the water-solubility of paclitaxel by 32,000-fold. Intravenous injections of RNA-paclitaxel nanoparticles with specific cancer-targeting ligand dramatically inhibit breast cancer growth, with nearly undetectable toxicity and immune responses in mice. No fatalities are observed at a paclitaxel dose equal to the reported LD 50 . The use of ultra-thermostable RNA nanoparticles to deliver chemical prodrugs addresses issues with RNA unfolding and nanoparticle dissociation after high-density drug loading. This finding provides a stable nano-platform for chemo-drug delivery as well as an efficient method to solubilize hydrophobic drugs.

60 APPLIED LIFE SCIENCES↗

Fifth-degree elastic energy for predictive continuum stress–strain relations and elastic instabilities under large strain and complex loading in silicon

Materials under complex loading develop large strains and often phase transformation via an elastic instability, as observed in both simple and complex systems. Here, we represent a material (exemplified for Si I) under large Lagrangian strains within a continuum description by a 5th-order elastic energy found by minimizing error relative to density functional theory (DFT) results. The Cauchy stress—Lagrangian strain curves for arbitrary complex loadings are in excellent correspondence with DFT results, including the elastic instability driving the Si I → II phase transformation (PT) and the shear instabilities. PT conditions for Si I → II under action of cubic axial stresses are linear in Cauchy stresses in agreement with DFT predictions. Such continuum elastic energy permits study of elastic instabilities and orientational dependence leading to different PTs, slip, twinning, or fracture, providing a fundamental basis for continuum physics simulations of crystal behavior under extreme loading.

36 MATERIALS SCIENCE↗

Electrochemical loading enhances deuterium fusion rates in a metal target

Nuclear fusion research for energy applications aims to create conditions that release more energy than required to initiate the fusion process1. To generate meaningful amounts of energy, fuels such as deuterium need to be spatially confined to increase the collision probability of particles2, 3–4. We therefore set out to investigate whether electrochemically loading a metal lattice with deuterium fuel could increase the probability of nuclear fusion events. Here we report a benchtop fusion reactor that enabled us to bombard a palladium metal target with deuterium ions. These deuterium ions undergo deuterium–deuterium fusion reactions within the palladium metal. We showed that the in situ electrochemical loading of deuterium into the palladium target resulted in a 15(2)% increase in deuterium–deuterium fusion rates. This experiment shows how the electrochemical loading of a metal target at the electronvolt energy scale can affect nuclear reactions at the megaelectronvolt energy scale.

Chen, Kuo-Yi↗

Fabrication, thermal analysis, and heavy ion irradiation resistance of epoxy matrix nanocomposites loaded with silane-functionalized ceria nanoparticles

This paper describes a detailed understanding of how nanofillers function as radiation barriers within the polymer matrix, and how their effectiveness is impacted by factors such as composition, size, loading, surface chemistry, and dispersion. Here, we designed a comprehensive investigation of heavy ion irradiation resistance in epoxy matrix composites loaded with surface-modified ceria nanofillers, utilizing tandem computational and experimental methods to elucidate radiolytic damage processes and relate them to chemical and structural changes observed through thermal analysis, vibrational spectroscopy, and electron microscopy. A detailed mechanistic examination supported by FTIR spectroscopy data identified the bisphenol A moiety as a primary target for degradation reactions. Results of computational modeling by the Stopping Range of Ions in Matter (SRIM) Monte Carlo simulation were in good agreement with damage analysis from surface and cross-sectional SEM imaging. All metrics indicated that ceria nanofillers reduce the damage area in polymer nanocomposites, and that nanofiller loading and homogeneity of dispersion are key to effective damage prevention. The results of this study represent a significant pathway for engineered irradiation tolerance in a diverse array of polymer nanocomposite materials. Numerous areas of materials science can benefit from utilizing this facile and effective method to extend the reliability of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

One-pot ethanol production under optimized pretreatment conditions using agave bagasse at high solids loading with low-cost biocompatible protic ionic liquid

Agave bagasse (AG) is a potential bioenergy feedstock due to its high biomass productivity, even in semiarid lands. In particular, ionic liquid (IL) pretreatment using aprotic ILs (AILs) has greatly reduced AG recalcitrance towards downstream processing by lowering lignin content and achieving high sugar yields. However, AIL's low biocompatibility towards enzymes and bacteria combined with the high initial cost has limited further development of this technology. In a wash-free one-pot (OP) ethanol conversion process, the evaluation of AG pretreatment with a biocompatible low-cost protic IL (PIL), 2-hydroxyethylammonium acetate ([2-HEA][OAc]) was achieved, where PIL pretreatment was followed by enzymatic saccharification, then ethanol fermentation in a single vessel. The pretreatment conditions were optimized using a central composite design to enable high sugar conversion at low PIL content. Under optimized pretreatment conditions (160 °C, 60% IL loading and 1.5 h), a yield of 132 kg of ethanol per Ton of untreated biomass was estimated using high solids loading (30% solids loading) under a PIL-OP scheme. High lignin removal (>50%), a decreased cellulose crystallinity, and high glucan conversion (>85%) were achieved with PIL-pretreated AG comparable to yields obtained in an AIL-AG pretreated sample using 1-ethyl-3-methyl-imidazolium acetate ([C 2 C 1 Im][OAc]). Here, these results using [2-HEA][OAc] demonstrate the potential of AG in an OP scheme with improved total ethanol yields paving the way towards a more feasible IL-based biorefinery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Higher loadings of Pt single atoms and clusters over reducible metal oxides: application to C–O bond activation

We develop higher loadings of isolated noble metal atoms and clusters on a mildly reducible metal oxide. Here we demonstrate the approach for Pt supported on TiO 2 and confirmed it by XRD, AC-HAADF-STEM, CO-FTIR, XAS, and XPS. Density functional theory calculations rationalize the experimental stability and the IR shifts using mixtures of CH 3 I and CO. The redispersed catalysts are thermally stable in inert gas or H 2 and afford enhanced selectivity and activity in hydrodeoxygenation reactions compared to metal nanoparticles by creating surface oxygen vacancies that promote C–O cleavage without side reactions. Higher metal loadings, e.g., 1%Pt/TiO 2 , on the oxide surface profoundly increase the activity of the bare oxide catalyst tenfold compared to ultra-low loadings typically used for single atom catalysis.

36 MATERIALS SCIENCE↗