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At least 1,027 records · Page 57

Revisiting Multi-Material Composite Structures with Homogenized Composite Properties

Composite structures inherently develop residual stresses during their curing process. Driven predominately by mismatched thermal strains between differing materials or ply orientations, but also affected by curing process phenomena like polymer shrinkage, these residual stresses can lead to failure within composite structures. There are several methods varying in complexity that can be used to model the development of residual stresses, all of which are capable of capturing sufficient detail to understand the residual stress state at the ply level. However, explicitly modeling all plies of a layup in a composite structure can be prohibitively expensive based on the number of plies, structure size, and required element size. The computational cost can be reduced through the homogenization of the composite layup without losing much fidelity of the overall response of the structure. The homogenization process reduces the many plies of a laminate to a single lamina that reduces complexity and increases the mesh size where a single element can span multiple plies. This report focuses on verification and validation efforts for a homogenization process using a suite of finite element simulations rather than an analytic solution derived from classical laminate theory. Initial verification using representative element volumes indicated there was minimal error in the homogenization process; however, this compounded to a small, but acceptable error in strip and split ring experimental composite structures. The error does under predict the residual stress state in the strip and split ring and should be accounted for when simulating composite structures with homogenized properties.

36 MATERIALS SCIENCE↗

Identification of engine oil-derived ash nanoparticles and ash formation process for a gasoline direct-injection engine

Engine oil-derived ash particles emitted from internal combustion (IC) engines are unwanted by-products, after oil is involved in in-cylinder combustion process. Since they typically come out together with particulate emissions, no detail has been reported about their early-stage particles other than agglomerated particles loaded on aftertreatment catalysts and filters. To better understand ash formation process during the combustion process, here differently formulated engine oils were dosed into a fuel system of a gasoline direct injection (GDI) engine that produces low soot mass emissions at normal operating conditions to increase the chances to find stand-alone ash particles separated from soot aggregates in the sub-20-nm size range. In addition to them, ash/soot aggregates in the larger size range were examined using scanning transmission electron microscopy (STEM)-X-ray electron dispersive spectroscopy (XEDS) to present elemental information at different sizes of particles from various oil formulations. The STEM-XEDS results showed that regardless of formulated oil type and particle size, Ca, P and C were always contained, while Zn was occasionally found on relatively large particles, suggesting that these elements get together from an early stage of particle formation. The S, Ca and P K-edge X-ray absorption near edge structure (XANES) analyses were performed for bulk soot containing raw ash. The linear combination approach & cross-checking among XANES results proposed that Ca 5 (OH)(PO 4 ) 2 , Ca 3 (PO 4 ) 2 and Zn 3 (PO 4 ) 2 are potentially major chemical compounds in raw ash particles, when combined with the STEM-XEDS results. Despite many reports that CaSO 4 is a major ash chemical when ash found in DPF/GFP systems was examined, it was observed to be rarely present in raw ashes using the S K-edge XANES analysis, suggesting ash transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent and Dynamic Small Polaron Delocalization in CuFeO 2

Small polarons remain a bottleneck in realizing efficient transition metal oxide devices. Routes to engineer small polaron coupling to electronic states and lattice modes to control carrier localization remain unclear. Here, we measure small polaron formation in CuFeO 2 using transient extreme ultraviolet reflection spectroscopy and compare to theoretical predictions in realistically parametrized Holstein models, demonstrating that polaron localization depends on coupling to high-frequency versus low-frequency phonon bath components. We measure small polaron formation on a comparable ∼100 fs timescale to other Fe(III) compounds. Dynamic delocalization of the polaron follows formation through a coherent lattice expansion between Fe–O layers and charge-sharing with surrounding Fe(IV) states. Simulations reveal two major factors dictate polaron formation timescales: phonon density and reorganization energy distributions between acoustic and optical modes, matching experimental findings. Our work shows how electronic-structural coupling in a polaron-host material can be leveraged to suppress polaronic effects for various applications.

Hematite↗

Spacecraft Charging as an Asset to Interplanetary Small Spacecraft

Small spacecraft operate on a far more limited power budget than their larger counterparts, a problem compounded for interplanetary spacecraft in the outer solar system. The reduced solar flux beyond Earth’s orbit makes solar panels less effective for spacecraft exploring the gas giants and they are susceptible to damage by intense radiation belts. Radioisotope thermoelectric generators are expensive and bulky compared to their power output. Interplanetary small satellite missions benefit from both alternative energy sources and low-power electronics to power their buses and scientific payloads. Traditionally, spacecraft engineers treat the space environment as a hazard, but it nevertheless offers a potential solution. Currents from space plasmas charge spacecraft to high potentials and can cause electrical arcing to occur between differentially charged surfaces. The spacecraft can harvest a small amount of power —<10 mW/m2at Jupiter — from the electric field between these surfaces to do useful work, either by charging a battery or directly powering an instrument or actuator. While using the energy directly has limited use due to the low electron density and temperature of most space plasmas, it can nevertheless be used in situations where solar panels are not desirable, such as high radiation environments. Two applications — a Langmuir probe and an attitude control actuator — exploit the disparate current-voltage characteristics between surfaces with different material properties and require minimal input power to operate.

spacecraft charging↗

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt. In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ~3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine Learning Algorithm Identifies an Antibiotic Vocabulary for Permeating Gram-Negative Bacteria

Drug discovery faces a crisis. The industry has used up the “obvious” space in which to find novel drugs for biomedical applications, and productivity is declining. One strategy to combat this is rational approaches to expand the search space without relying on chemical intuition, to avoid rediscovery of similar spaces. Here, we present proof of concept of an approach to rationally identify a “chemical vocabulary” related to a specific drug activity of interest without employing known rules. We focus on the pressing concern of multidrug resistance in Pseudomonas aeruginosa by searching for submolecules that promote compound entry into this bacterium. By synergizing theory, computation, and experiment, we validate our approach, explain the molecular mechanism behind identified fragments promoting compound entry, and select candidate compounds from an external library that display good permeation ability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kitaev physics in the two-dimensional magnet NiPSe 3

The Kitaev interaction, found in candidate materials such as α − RuCl 3 , occurs through the metal ( M )-ligand ( X )-metal ( M ) paths of the edge-sharing octahedra because the large spin-orbit coupling (SOC) on the metal atoms activates directional spin interactions. Here, we show that even in 3 d transition-metal compounds, where the SOC of the metal atom is negligible, heavy ligands can induce bond-dependent Kitaev interactions. In this work, we take as an example the 3 d transition-metal chalcogenophosphate NiPSe 3 and show that the key is found in the presence of a sizable SOC on the Se p orbital, one which mediates the super-exchange between the nearest-neighbor Ni sites. Our study provides a pathway for engineering enhanced Kitaev interactions through the interplay of SOC strength, lattice distortions, and chemical substitutions. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Switching it up: New mechanisms revealed in wurtzite-type ferroelectrics

Wurtzite-type ferroelectrics have drawn increasing attention due to the promise of better performance and integration than traditional oxide ferroelectrics with semiconductors such as Si, SiC, and III-V compounds. However, wurtzite-type ferroelectrics generally require enormous electric fields, approaching breakdown, to reverse their polarization. The underlying switching mechanism(s), especially for multinary compounds and alloys, remains elusive. Here, we examine the switching behaviors in Al 1-x Sc x N alloys and wurtzite-type multinary candidate compounds we recently computationally identified. We find that switching in these tetrahedrally coordinated materials proceeds via a variety of nonpolar intermediate structures and that switching barriers are dominated by the more-electronegative cations. For Al 1-x Sc x N alloys, we find that the switching pathway changes from a collective mechanism to a lower-barrier mechanism enabled by inversion of individual tetrahedra with increased Sc composition. Our findings provide insights for future engineering and realization of wurtzite-type materials and open a door to understanding domain motion.

36 MATERIALS SCIENCE↗

Spacecraft Charging as an Asset to Interplanetary Small Spacecraft

Small spacecraft operate on a far more limited power budget than their larger counterparts, a problem compounded for interplanetary spacecraft in the outer solar system. The reduced solar flux beyond Earth’s orbit makes solar panels less effective for spacecraft exploring the gas giants and can they are susceptible to damage by intense radiation belts. Radioisotope thermoelectric generators are expensive and bulky compared to their power output. Interplanetary small satellite missions benefit from both alternative energy sources and low-power electronics to power their buses and scientific payloads. Traditionally, spacecraft engineers treat the space environment as a hazard, but it nevertheless offers a potential solution. Currents from space plasmas charge spacecraft to high potentials and can cause electrical arcing to occur between differentially charged surfaces. The spacecraft can harvest a small amount of power —<10 mW/m2at Jupiter — from the electric field between these surfaces to do useful work, either by charging a battery or directly powering an instrument or actuator. While using the energy directly has limited use due to the low electron density and temperature of most space plasmas, it can nevertheless be used in situations where solar panels are not desirable, such as high radiation environments. Two applications — a Langmuir probe and an attitude control actuator — exploit the disparate current-voltage characteristics between surfaces with different material properties and require minimal input power to operate.

Spacecraft↗

Electrolytes and metal hydride batteries

A metal hydride battery comprising at least one negative electrode, at least one positive electrode, a casing having said electrodes positioned therein and an electrolyte composition, where the electrolyte composition comprises an ionic compound selected from the group consisting of protic acids, protic ammonium compounds, protic oxonium compounds, aprotic ammonium compounds, aprotic oxonium compounds, aprotic phosphonium compounds and alkali or alkali earth metal salts; or where the electrolyte composition comprises an ionic compound selected from the group consisting of alkali or alkali earth metal hydroxides and alkali or alkali earth metal alkoxides and an organic solvent; or where the electrolyte composition comprises an alkali metal hydroxide, water and one or more further components selected from the group consisting of organic solvents, further ionic compounds and additives; or where the electrolyte composition comprises an ionic compound selected from the group consisting of carboxylate compounds and carboxylic acids. Ionic compounds include ionic liquids and salts. Metal hydride batteries comprising certain electrolyte compositions have a nominal open-circuit voltage of from about 1.5 V to about 5.0 V.

25 ENERGY STORAGE↗

Development of an Optical Library for Coevaporated CdSe x Te 1– x

The conversion efficiency of CdTe solar cells may be improved by bandgap engineering, i.e., changing the bandgap value through the addition of Se in the absorber. The Se alloying enables a short-circuit current density improvement, as it leads to a bandgap energy value decrease. Furthermore, it has been associated with increased minority carrier lifetimes, assuring high open-circuit voltage values. An Se gradient profile control can further optimize the solar cell performance. Thus, an optical model baseline of the CdSe x Te 1–x (CST) compound was developed. Spectroscopic ellipsometry measurements were conducted to accurately extract the optical constants of ten CST layers deposited through coevaporation with x varying from 0 to 1. Using the measured dielectric function spectra from the discrete CST layers with varying x, and considering the composition-induced shift in the critical point energies, an energy-shift model was employed to develop the accurate optical library for the CST compound for any x value to provide data for future modeling and optimization. Furthermore, the library accuracy was validated through optical simulations of the quantum efficiency of a graded CST solar cell using the finite-difference time-domain method by replicating the Se profile in the absorber layer measured through secondary ion mass spectrometry.

14 SOLAR ENERGY↗

Control of Carbon Allocation in Phenylpropanoid Metabolism

Understanding the molecular mechanisms by which carbon flux is partitioned in plants, and how flux through the phenylpropanoid pathway in particular is regulated and allocated to different branches of the pathway is essential for the eventual rational manipulation of phenylpropanoid flux for bioenergy applications. The phenylpropanoid pathway is responsible for the biosynthesis of a diverse array of metabolites essential for structural integrity, water transport, UV protection, and defense against herbivores and pathogens. The products of the phenylpropanoid pathway, all of which are derived from phenylalanine, range from complex, insoluble polymers such as lignin and suberin, to soluble flavonoids and hydroxycinnamate esters, to volatile compounds used to attract pollinators. By far the most abundant of these is the complex heteropolymer lignin, which accounts for a significant portion of the dry weight of not only woody plants, but also of crop residues. Decreasing or altering lignin structure to provide increased cell wall digestibility could greatly increase the cost effectiveness of converting cell wall polysaccharides to ethanol or second-generation biofuels. On the other hand, it is also possible that plants engineered to accumulate higher levels of lignin could provide improved feedstock for direct combustion and electricity generation as part of a diverse bioenergy portfolio. Consistent with the enormous commitment of energy and carbon it requires, the synthesis of lignin is under tight regulatory control. In order to influence transcription, gene-specific activators and repressors must interact with basal transcription factors and the rest of the core transcriptional machinery. In eukaryotes, this interaction is bridged by the large, multi-subunit complex known as Mediator. Despite the clear importance of Mediator throughout the eukaryotes, the complex has only recently been studied in plants. We have shown that a pair of Mediator subunits, MED5a and MED5b are required for normal regulation of phenylpropanoid pathway product accumulation. Plants lacking these proteins show increased accumulation of phenylpropanoids in multiple tissues indicating that normally they directly or indirectly repress expression of phenylpropanoid pathway genes. Furthermore, we have recently shown that MED5 plays a role in dwarfing in some low lignin plants and feedback between and within metabolic pathways of secondary metabolism in Arabidopsis. Taken together with the established roles of Mediator in transcriptional regulation, and of MED5a and MED5b in the repression of phenylpropanoid metabolism, these observations suggest that MED5a and MED5b are key components of an active, transcriptional process by which phenylpropanoid homeostasis is maintained in wild-type plants. Our research focused on expanding our understanding of the role of Mediator, as well as elucidating the mechanisms by which these proteins influence phenylpropanoid biosynthesis and how metabolite accumulation within the pathway and between metabolic pathways is essential for feedback regulatory control. This research will inform future bioengineering efforts aimed at altering carbon allocation and cell wall engineering by contributing to our understanding of the role of Mediator in regulating lignin biosynthesis, a pathway of plant metabolism that is important on a global scale.

09 BIOMASS FUELS↗

Waste to worth: a circular solution through lignin engineering

The inefficient management of industrial waste threatens environmental sustainability, requiring scalable resource recovery solutions. To address these challenges, we propose a novel and sustainable in-situ one-step strategy for the simultaneous recovery and functionalization of lignin from industrial black liquor, using a sustainable organic acid system assisted by choline chloride. The functionalized lignin adsorbent material (FLAM) exhibited superior adsorption performance, effectively treating animal feedlot wastewater to recover ammonia. The ammonia enriched FLAM was subsequently repurposed as a slow-release fertilizer, enhancing plant growth and demonstrating a closed-loop pathway for waste valorization and nutrient recycling. Methylene blue was used as a model cationic compound to simulate the adsorption behavior and interactions. FLAM achieved a high adsorption capacity of 725.98 mg/g across a broad pH range, significantly outperforming commercial kraft lignin. This sustainable approach advances circular economy principles by integrating remediation and resource recovery, offering a scalable, eco-friendly solution for environmental applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Predictive Engineering Tools for Injection-Molded Long-Carbon-Fiber Thermoplastic Composites. Topical Report

This project aimed to integrate, optimize, and validate the fiber orientation and length distribution models previously developed and implemented in the Autodesk® Simulation Moldflow® Insight (ASMI) software package for injection-molded long-carbon-fiber (LCF) thermoplastic composite structures. The project was organized into two phases. Phase 1 demonstrated the ability of the advanced ASMI package to predict fiber orientation and length distributions in LCF/polypropylene (PP) and LCF/polyamide-6, 6 (PA66) plaques within 15% of experimental results. Phase 2 validated the advanced ASMI package by predicting fiber orientation and length distributions within 15% of experimental results for a complex three-dimensional (3D) Toyota automotive part injection-molded from LCF/PP and LCF/PA66 materials. Work under Phase 2 also included estimate of weight savings and cost impacts for a vehicle system using ASMI and structural analyses of the complex part. The present report summarizes the completion of Phases 1 and 2 work activities and accomplishments achieved by the team comprising Pacific Northwest National Laboratory (PNNL); Purdue University (Purdue); Virginia Polytechnic Institute and State University (Virginia Tech); Autodesk, Inc. (Autodesk); PlastiComp, Inc. (PlastiComp); Toyota Research Institute North America (Toyota); Magna Exteriors and Interiors Corp. (Magna); and University of Illinois. Figure 1 illustrates the technical approach adopted in this project that progressed from compounding LCF/PP and LCF/PA66 materials, to process model improvement and implementation, to molding and modeling LCF/PP and LCF/PA66 plaques. The lessons learned from the plaque study and the successful validation of improved process models for fiber orientation and length distributions for these plaques enabled the project to go to Phase 2 to mold, model, and optimize the 3D complex part.

42 ENGINEERING↗

Strain-induced gap transition and anisotropic Dirac-like cones in monolayer and bilayer phosphorene

The electronic properties of two-dimensional monolayer and bilayer phosphorene subjected to uniaxial and biaxial strains have been investigated using first-principles calculations based on density functional theory. Strain engineering has obvious influence on the electronic properties of monolayer and bilayer phosphorene. By comparison, we find that biaxial strain is more effective in tuning the band gap than uniaxial strain. Interestingly, we observe the emergence of Dirac-like cones by the application of zigzag tensile strain in the monolayer and bilayer systems. For bilayer phosphorene, we induce the anisotropic Dirac-like dispersion by the application of appropriate armchair or biaxial compressive strain. Our results present very interesting possibilities for engineering the electronic properties of phosphorene and pave a way for tuning the band gap of future electronic and optoelectronic devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Advanced Non-Tread Materials for Fuel-Efficient Tires

PPG Industries, Inc. proposes to develop a new silica filler that can increase fuel efficiency by 2% while maximizing key performance properties in non-tread tire components compared to current carbon black/silica filler blends. In this project PPG focused on a sidewall compound. The developed compounds/components will reduce energy losses by approximately 25%, with no more than a 5% loss of resistance to degradative forces (targeting better performance). PPG plans to achieve this goal by characterizing the impact the silica filler can have on rubber properties and then tuning the silica morphology and surface chemistry for this end use. PPG will also provide guidance in optimizing the compound formulation to make the best use of this new filler. A key aspect is to understand and maintain, if not improve, the aging performance as evaluated by crack growth resistance under ozone environment. Two key strategies were used to meet the rolling resistance goal while maintaining other performance properties. The first factor was understanding the surface treatments and chemical makeup of the silica and its effects on compound performance. The second factor was using the best performing silicas and determining the optimum compound modifications to achieve the final sidewall compound performance. Using statistical analysis throughout the optimization process, it was determined that changing the silica morphology played a role in improving the reduction of tear strength while reducing rolling resistance and the improvements observed varied depending on the CB type.

36 MATERIALS SCIENCE↗

Stable White Organic Light-emitting Diodes Enabled by New Materials with Reduced Excited State Lifetime

Through this program, novel blue-emitting molecules and layers based on wide-bandgap ambipolar hosts having a low energy difference between singlet and triplet excited-states were developed and their properties investigated using a wide variety of experimental and theoretical tools. We demonstrated that the efficient Förster resonant energy transfer from a novel host to a fluorescent guest leads to blue-emitting layers with a high photoluminescence quantum yield and reduced excited-state lifetime. Blue-emitting OLEDs having emissive layers with high IQE and improved device lifetime were demonstrated. Development of these novel hosts also yielded compounds that exhibited low concentration-dependent fluorescence quenching as well as high photoluminescence quantum yields, leading to the demonstration of highly efficient OLEDs using emissive layers using a single material - a significant advance towards the simplification of a device’s architecture.

36 MATERIALS SCIENCE↗

Erosion Coatings for High-Temperature Polymer Composites: A Collaborative Project With Allison Advanced Development Company

The advantages of replacing metals in aircraft turbine engines with high-temperature polymer matrix composites (PMC's) include weight savings accompanied by strength improvements, reduced part count, and lower manufacturing costs. Successfully integrating high-temperature PMC's into turbine engines requires several long-term characteristics. Resistance to surface erosion is one rarely reported property of PMC's in engine applications because PMC's are generally softer than metals and their erosion resistance suffers. Airflow rates in stationary turbine engine components typically exceed 2.3 kg/sec at elevated temperatures and pressures. In engine applications, as shown in the following photos, the survivability of PMC components is clearly a concern, especially when engine and component life-cycle requirements become longer. Although very few publications regarding the performance of erosion coatings on PMC's are available particularly in high-temperature applications the use of erosion-resistant coatings to significantly reduce wear on metallic substrates is well documented. In this study initiated by the NASA Glenn Research Center at Lewis Field, a low-cost (less than $140/kg) graphite-fiber-reinforced T650 35/PMR 15 sheet-molding compound was investigated with various coatings. This sheet-molding compound has been compression molded into many structurally complicated components, such as shrouds for gas turbine inlet housings and gearboxes. Erosion coatings developed for PMC s in this study consisted of a two-layered system: a bondcoat sprayed onto a cleaned PMC surface, followed by an erosion-resistant, hard topcoat sprayed onto the bondcoat as shown in following photomicrograph. Six erosion coating systems were evaluated for their ability to withstand harsh thermal cycles, erosion resistance (ASTM G76 83 "Standard Practice for Conducting Erosion Tests by Solid Particle Impingement Using Gas Jets") using Al2O3, and adhesion to the graphite fiber polyimide composite (ASTM D 4541 95 "Pull Off Strength of Coatings"). Glenn and Allison Advanced Development Company collaborated to optimize erosion coatings for gas turbine fan and compressor applications. All the coating systems survived aggressive thermal cycling without spalling. During erosion tests (see the final photo), the most promising coating systems tested had Cr3C2-NiCr and WC-Co as the hard topcoats. In all cases, these coating systems performed significantly better than that with a TiN hard topcoat. When material depth (thickness) loss is considered, the Cr3C2-NiCr and WC-Co coating systems provided, on average, an erosion resistance 8.5 times greater than that for the uncoated PMR 15/T650 35 composite. Similarly, Cr3C2-NiCr and WC-Co coating systems adhered to the PMC substrate during tensile tests significantly better than systems containing a TiN topcoat. Differences in topcoats of Cr3C2-NiCr and WC-Co were determined by considering issues such as cost and environmental impact. The preferred erosion-resistant coating system for PMR 15/T650 35 has WC-Co as the hard topcoat. This system provides the following benefits in comparison to the coating system with Cr3C2-NiCr topcoat: lower powder material cost (15 to 20 percent), environmentally friendly materials (Cr3C2-NiCr is hazardous), and higher deposition yield (10 to 15 percent), which results in less waste.

Sutter, James K.↗