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At least 1,135 records · Page 63

Estimating Material Properties Under Extreme Conditions by Using Bayesian Model Calibration with Functional Outputs

Summary Dynamic material properties experiments provide access to the most extreme temperatures and pressures attainable in a laboratory setting; the data from these experiments are often used to improve our understanding of material models at these extreme conditions. We apply Bayesian model calibration to dynamic material property applications where the experimental output is a function: velocity over time. This framework can accommodate more uncertainties and facilitate analysis of new types of experiments relative to techniques traditionally used to analyse dynamic material experiments. However, implementation of Bayesian model calibration requires more sophisticated statistical techniques, because of the functional nature of the output as well as parameter and model discrepancy identifiability. We propose a novel Bayesian model calibration process to simplify and improve the estimation of the material property calibration parameters. Specifically, we propose scaling the likelihood function by an effective sample size rather than modelling the auto-correlation function to accommodate the functional output. Additionally, we propose sensitivity analyses by using the notion of 'modularization' to assess the effect of experiment-specific nuisance input parameters on estimates of the physical parameters. The Bayesian model calibration framework proposed is applied to dynamic compression of tantalum to extreme pressures, and we conclude that the procedure results in simple, fast and valid inferences on the material properties for tantalum.

36 MATERIALS SCIENCE↗

Methods of electrophoretic deposition for functionally graded porous nanostructures and systems thereof

In one embodiment, an aerogel includes a layer of shaped particles having a particle packing density gradient in a thickness direction of the layer, wherein the shaped particles are characterized by being formed in an electrophoretic deposition (EPD) process using an impurity. In another embodiment, a method for forming a functionally graded porous nanostructure includes adding particles of an impurity and a solution to an EPD chamber, applying a voltage difference across the two electrodes of the EPD chamber to create an electric field in the EPD chamber, and depositing the material onto surfaces of the particles of the impurity to form shaped particles of the material. Other functionally graded materials and methods are described according to more embodiments.

36 MATERIALS SCIENCE↗

Efficient Reformulation of HOTFGM: Heat Conduction with Variable Thermal Conductivity

Functionally graded materials (FGMs) have become one of the major research topics in the mechanics of materials community during the past fifteen years. FGMs are heterogeneous materials, characterized by spatially variable microstructure, and thus spatially variable macroscopic properties, introduced to enhance material or structural performance. The spatially variable material properties make FGMs challenging to analyze. The review of the various techniques employed to analyze the thermodynamical response of FGMs reveals two distinct and fundamentally different computational strategies, called uncoupled macromechanical and coupled micromechanical approaches by some investigators. The uncoupled macromechanical approaches ignore the effect of microstructural gradation by employing specific spatial variations of material properties, which are either assumed or obtained by local homogenization, thereby resulting in erroneous results under certain circumstances. In contrast, the coupled approaches explicitly account for the micro-macrostructural interaction, albeit at a significantly higher computational cost. The higher-order theory for functionally graded materials (HOTFGM) developed by Aboudi et al. is representative of the coupled approach. However, despite its demonstrated utility in applications where micro-macrostructural coupling effects are important, the theory's full potential is yet to be realized because the original formulation of HOTFGM is computationally intensive. This, in turn, limits the size of problems that can be solved due to the large number of equations required to mimic realistic material microstructures. Therefore, a basis for an efficient reformulation of HOTFGM, referred to as user-friendly formulation, is developed herein, and subsequently employed in the construction of the efficient reformulation using the local/global conductivity matrix approach. In order to extend HOTFGM's range of applicability, spatially variable thermal conductivity capability at the local level is incorporated into the efficient reformulation. Analytical solutions to validate both the user-friendly and efficient reformulations am also developed. Volume discretization sensitivity and validation studies, as well as a practical application of the developed efficient reformulation are subsequently carried out. The presented results illustrate the accuracy and implementability of both the user-friendly formulation and the efficient reformulation of HOTFGM.

Zhong, Yi↗

High-throughput calculations of charged point defect properties with semi-local density functional theory—performance benchmarks for materials screening applications

Abstract Calculations of point defect energetics with Density Functional Theory (DFT) can provide valuable insight into several optoelectronic, thermodynamic, and kinetic properties. These calculations commonly use methods ranging from semi-local functionals with a-posteriori corrections to more computationally intensive hybrid functional approaches. For applications of DFT-based high-throughput computation for data-driven materials discovery, point defect properties are of interest, yet are currently excluded from available materials databases. This work presents a benchmark analysis of automated, semi-local point defect calculations with a-posteriori corrections, compared to 245 “gold standard” hybrid calculations previously published. We consider three different a-posteriori correction sets implemented in an automated workflow, and evaluate the qualitative and quantitative differences among four different categories of defect information: thermodynamic transition levels, formation energies, Fermi levels, and dopability limits. We highlight qualitative information that can be extracted from high-throughput calculations based on semi-local DFT methods, while also demonstrating the limits of quantitative accuracy.

36 MATERIALS SCIENCE↗

N-Doped Graphene (N-G)/MOF(ZIF-8)-Based/Derived Materials for Electrochemical Energy Applications: Synthesis, Characteristics, and Functionality

In recent years, graphene-type materials originating from metal–organic frameworks (MOFs) or integrated with MOFs have exhibited notable performances across various applications. However, a comprehensive understanding of these complex materials and their functionalities remains obscure. While some studies have reviewed graphene/MOF composites from different perspectives, due to their structural–functional intricacies, it is crucial to conduct more in-depth reviews focusing on specific sets of graphene/MOF composites designed for particular applications. In this review, we thoroughly investigate the syntheses, characteristics, and performances of N-G/MOF(ZIF-8)-based/derived materials employed in electrochemical energy conversion and storage systems. Special attention is given to realizing their fundamental functionalities. The discussions are divided into three segments based on the application of N-G/ZIF-8-based/derived materials as electrode materials for batteries, electrodes for electrochemical capacitors, and electrocatalysts. As electrodes for batteries, N-G/MOF(ZIF-8) materials can mitigate issues like an electrode volume expansion for Li-ion batteries and the ‘shuttle effect’ for Li-S batteries. As electrodes for electrochemical capacitors, these materials can considerably improve the ion transfer rate and electronic conductivity, thereby enhancing the specific capacitance while maintaining the structural stability. Also, it was observed that these materials could occasionally outperform standard platinum-based catalysts for the electrochemical oxygen reduction reaction (ORR). The reported electrochemical performances and structural parameters of these materials were carefully tabulated in uniform units and scales. Through a critical analysis of the present synthesis trends, characteristics, and functionalities of these materials, specific aspects were identified that required further exploration to fully utilize their inherent capabilities.

Electrochemistry↗

Fast Photoactuation Driven by Supramolecular Polymers Integrated into Covalent Networks

Abstract The design of robotic soft matter capable of emulating the complex movements of living organisms such as mechanical actuation, shape transformation, and autonomous translation remains a grand challenge in soft materials science. Functionalized hydrogels are excellent candidates for such materials since they can operate in water and are highly responsive to their environment, but their response times can be slow. This work investigates fast photoactuation of hybrid bonding hydrogels composed of peptide amphiphile (PA) supramolecular nanofibers bonded covalently to merocyanine‐based (MCH + ) photoresponsive networks. By incorporating ionizable acrylic acid (AA) co‐monomers in these networks, photoactuation at nearly neutral pH is observed, which in turn enables a new mechanism to accelerate the response by triggering the bundling of supramolecular nanofibers by rapid proton exchange reactions. Furthermore, this rapid response and its consequent large shape transformations lead to hydrogels capable of spontaneously tracking external light sources inspired by pedicellariae, defensive organs present in echinoderms like the starfish and the sea urchin. This work suggests that hybrid bonding polymers (HBPs), which leverage the interplay between supramolecular assemblies and covalent networks, offer novel strategies to design rapidly actuating soft robotic materials.

Cezan, S. Doruk↗

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host–guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru 2 nitride intermediate confined within the interstices of a Ru2-based metal–organic framework (MOF), Ru 3 (btc) 2 X 3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C–H functionalization of benzylic C–H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., k H /k D ) of C–H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru 2 nitride to the C–H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C–H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C–H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Virtually pure near-infrared electroluminescence from exciplexes at polyfluorene/hexaazatrinaphthylene interfaces

Electronic processes at the heterojunction between chemically different organic semiconductors are of special significance for devices such as light-emitting diodes (LEDs) and photovoltaic diodes. Here, we report the formation of an exciplex state at the heterojunction of an electron-transporting material, a functionalized hexaazatrinaphthylene, and a hole-transporting material, poly(9,9-dioctylfluorene-alt-N-(4-butylphenyl)diphenylamine) (TFB). The energetics of the exciplex state leads to a spectral shift of ∼1 eV between the exciton and the exciplex peak energies (at 2.58 eV and 1.58 eV, respectively). LEDs incorporating such bulk heterojunctions display complete quenching of the exciton luminescence, and a nearly pure near-infrared electroluminescence arising from the exciplex (at ∼1.52 eV) with >98% of the emission at wavelengths above 700 nm at any operational voltage.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic forming studies

Investigation of the tensile strength dependability on the characteristic time over which a pressure pulse is applied to a metal workpiece shows that the mechanical properties of these materials are functions of the rate at which the material is undergoing strain. These results and techniques are used in magnetomotive metal forming.

Furth, H. P.↗

Doping of GaN{sub 1-x}As{sub x} with high As content

Recent work has shown that GaN{sub 1-x}As{sub x} can be grown across the entire composition range by low temperature molecular beam epitaxy with intermediate compositions being amorphous, but control of the electrical properties through doping is critical for functionalizing this material. Here we report the bipolar doping of GaN{sub 1-x}As{sub x} with high As content to conductivities above 4 S/cm at room temperature using Mg or Te. The carrier type was confirmed by thermopower measurements. Doping requires an increase in Ga flux during growth resulting in a mixed phase material of polycrystalline GaAs:N embedded in amorphous GaN{sub 1-x}As{sub x}.

36 MATERIALS SCIENCE↗

Satellite Material Type and Phase Function Determination in Support of Orbital Debris Size Estimation

In performing debris surveys of deep-space orbital regions, the considerable volume of the area to be surveyed and the increased orbital altitude suggest optical telescopes as the most efficient survey instruments; but to proceed this way, methodologies for debris object size estimation using only optical tracking and photometric information are needed. Basic photometry theory indicates that size estimation should be possible if satellite albedo and shape are known. One method for estimating albedo is to try to determine the object's material type photometrically, as one can determine the albedos of common satellite materials in the laboratory. Examination of laboratory filter photometry (using Johnson BVRI filters) on a set of satellite material samples indicates that most material types can be separated at the 1-sigma level via B-R versus R-I color differences with a relatively small amount of required resampling, and objects that remain ambiguous can be resolved by B-R versus B-V color differences and solar radiation pressure differences. To estimate shape, a technique advanced by Hall et al. [1], based on phase-brightness density curves and not requiring any a priori knowledge of attitude, has been modified slightly to try to make it more resistant to the specular characteristics of different materials and to reduce the number of samples necessary to make robust shape determinations. Working from a gallery of idealized debris shapes, the modified technique identifies most shapes within this gallery correctly, also with a relatively small amount of resampling. These results are, of course, based on relatively small laboratory investigations and simulated data, and expanded laboratory experimentation and further investigation with in situ survey measurements will be required in order to assess their actual efficacy under survey conditions; but these techniques show sufficient promise to justify this next level of analysis.

Hejduk, M. D.↗

Defect Thermodynamics and Transport Properties of Proton Conducting Perovskite Electrode and Electrolyte Materials Evaluated Based on Density Functional Theory Modeling

Both electron-rich and electron-poor perovskite oxides have been used in solid oxide cell applications as electrode and electrolyte materials. The rich oxygen defect chemistry and its coupling to temperature, hydrogen-steam or oxygen-steam gas pressure, or to the applied potentials creates enormous complexities for modeling performance and degradation of the materials. Herein, density functional theory-based thermodynamic modeling was carried out to describe the defect chemistry and transport properties of the proton-conducting electrolyte BaZr1-xYxO3-δ (x≤0.1) and of the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr). The defect thermodynamics of intrinsic point defects and the hydrogen-related defect reactions were solved in integrated defect models and further used to predict the Brouwer diagram and the transport properties of the functional perovskites. For the electron-poor electrolytes BaZr0.9Y0.1O3-δ, the developed model has been used to describe the experimental transport properties in the SOC operating conditions. Specifically, the roles played by the acceptor-bound holes and the intrinsic and hydrogen point defects upon the conductivities of holes, protons, and oxygen vacancies under the hydrogen-rich and oxygen-rich conditions at various humidity levels were demonstrated. A defect modeling tool was also developed for the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr) to examine magnetic effects and hydride defects in defect equilibria.

defect thermodynamics↗

Propagation of atmospheric pressure plasmas through interconnected pores in dielectric materials

We report the propagation of atmospheric pressure plasmas (APPs) on and through porous dielectric materials is being investigated for plasma-catalysis and functionalizing biomedical materials for tissue scaffolding and bone regeneration. Such plasma functionalization improves wettability and cell attachment, and so uniformity of the treatment of the pore surfaces is important. The method of propagation of APPs through porous media is not well characterized. In this paper, we discuss results from a computational investigation of humid air APPs propagating through short fully interconnected pore-chains in a dielectric substrate. The properties of the dielectric and pores (diameter 150 μm) were chosen to resemble bone scaffolding. We found that photoionization is an important feature in plasma propagation through pore-chains to seed electrons in the following pore in the chain. This seeding of electrons in regions of high electric field allows for the formation of micro-streamers and surface ionization waves. This is particularly important when the openings between pores are small. The orientation of the pore-chain with respect to the applied electric field has a significant impact on plasma generation, mode of propagation, and fluences of short-lived, reactive species to the surfaces of the pores. The uniformity of fluences of charged and short-lived neutral species to the pore surfaces decreases as the angle of the pore chain deviates from being aligned with the applied electric field. Diffusion within pores

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

FUNCTIONALIZED SILICA AEROGELS: ADVANCED MATERIALS TO CAPTURE AND IMMOBILIZE RADIOACTIVE IODINE

To support the future expansion of nuclear energy, an effective method is needed to capture and safely store radiological iodine-129 released during reprocessing of spent nuclear fuel. Various materials have been investigated to capture and immobilize iodine. In most cases, however, the materials that are effective for capturing iodine cannot subsequently be sintered/densified to create a stable composite that could be a viable waste form. We have developed chemically modified, highly porous, silica aerogels that show sorption capacities higher than 440 mg of I2 per gram at 150 C. An iodine uptake test in dry air containing 4.2 ppm of iodine demonstrated no breakthrough after 3.5 h and indicated a decontamination factor in excess of 310. Preliminary densification tests showed that the I2-loaded aerogels retained more than 92 wt% of I2 after thermal sintering with pressure assistance at 1200 C for 30 min. These high capture and retention efficiencies for I2 can be further improved by optimizing the functionalization process and the chemistry as well as the sintering conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fabrication and microstructures of functional gradient SiBCN–Nb composite by hot pressing

A functional gradient material with five layers composed of SiBCN ceramic and niobium (Nb) was prepared successfully by hot pressing. The phase composition, morphology features and microstructures were investigated in each layer of the gradient material. The Nb-containing compounds involving NbC, Nb{sub 6}C{sub 5}, Nb{sub 4}C{sub 3}, Nb{sub 5}Si{sub 3} and NbN increase with the volume fraction of Nb increasing in the sub-layer. They are randomly scattered (≤ 25 vol.% Nb), then strip-like, and finally distribute continuously (≥ 75 vol.% Nb). The size of BN(C) and SiC grains in Nb-containing layers is larger than in 100% SiBCN layer due to the loss of the capsule-like structures. No distinct interfaces form in the transition regions indicating the gradual changes in phase composition and microstructures. - Highlights: • A functional gradient SiBCN–Nb material was prepared successfully by hot pressing. • Phase composition, morphology features and microstructures were investigated. • Thermodynamic calculation was used to aid in the phase analysis. • No distinct interfaces form typical of the functional gradient material.

36 MATERIALS SCIENCE↗

Visualization of Iron‐Binding Micelles in Acidic Recombinant Biomineralization Protein, MamC

Biological macromolecules are utilized in low‐temperature synthetic methods to exert precise control over nanoparticle nucleation and placement. They enable low‐temperature formation of a variety of functional nanostructured materials with properties often not achieved via conventional synthetic techniques. Here we report on the in situ visualization of a novel acidic bacterial recombinant protein, MamC, commonly present in the magnetosome membrane of several magnetotactic bacteria, including Magnetococcus marinus , strain MC‐1. Our findings provide an insight into the self‐assembly of MamC and point to formation of the extended protein surface, which is assumed to play an important role in the formation of biotemplated inorganic nanoparticles. The self‐organization of MamC is compared to the behavior of another acidic recombinant iron‐binding protein, Mms6.

Kashyap, Sanjay↗

Emergent Low-Symmetry Phases and Large Property Enhancements in Ferroelectric KNbO 3 Bulk Crystals [Emergent Low-Symmetry Phases with Large Property Enhancement in Ferroelectric KNbO 3 Bulk Crystals]

The design of new or enhanced functionality in materials is traditionally viewed as requiring the discovery of new chemical compositions through synthesis. Large property enhancements may however also be hidden within already well-known materials, when their structural symmetry is deviated from equilibrium through a small local strain or field. Here, the discovery of enhanced material properties associated with a new metastable phase of monoclinic symmetry within bulk KNbO 3 is reported. This phase is found to coexist with the nominal orthorhombic phase at room temperature, and is both induced by and stabilized with local strains generated by a network of ferroelectric domain walls. While the local microstructural shear strain involved is only ≈0.017%, the concurrent symmetry reduction results in an optical second harmonic generation response that is over 550% higher at room temperature. Moreover, the meandering walls of the low-symmetry domains also exhibit enhanced electrical conductivity on the order of 1 S m -1 . In conclusion, this discovery reveals a potential new route to local engineering of significant property enhancements and conductivity through symmetry lowering in ferroelectric crystals.

36 MATERIALS SCIENCE↗