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At least 217 records · Page 12

Transverse impact by RCCs on S-glass and Kevlar® FRC strips

This study aims to isolate interactions between plies and tows and reveal fundamental physics involved in transverse impact on fiber-reinforced composite (FRC) structures. Composite strips were sectioned from large panels and characterized by optical photography, three-dimensional synchrotron X-ray computed tomography, and scanning electron microscopy (SEM). Each strip was impacted perpendicularly by a right circular cylinder (RCC) projectile at a velocity ranging from ~ 150 to 600 m/s. The global strip behavior, as well as localized deformation and failure of the strip near the projectile corner, were both captured by high-speed optical imaging. S-Glass FRC strips were observed to fail in tension ahead of the RCC projectiles’ flat surfaces while Kevlar® FRC strips fractured at the projectile corners. The concept of critical velocity region previously used for impact on yarns was introduced to define different failure modes of each composite strip type. The strip damage extent was found to increase with the impact velocity and reach the maximum at the upper limit of the critical velocity region. Above the critical velocity region, the damage extent decreased with impact velocity. Wave propagations and load histories in the composite strips during impact were quantified and compared with Smith’s theory. Finally, critical velocities of single fibers, yarns, and composite strips and ballistic limits of single-ply and multi-ply composite panels were compared to provide insight into the design of impact-resistant fabrics and composites.

42 ENGINEERING↗

Editorial overview: Unlocking the secrets of nongenetic plasticity, one cell at a time

Cellular noise, the non-genetic variability observed among isogenic cells, arises from factors such as growth conditions, aging, and stochastic gene expression, influencing cell stress-response, metabolism, morphology, and size. Here, such plasticity, while critical for adaptation, often goes unnoticed with traditional population-averaging biotechnologies that inevitably mask cell-specific variations and prompting the question, "What else might we be missing". However, recent breakthroughs in optical imaging, microfluidics, and omics, are beginning to uncover the complexity of cellular plasticity. This special is-sue highlights some of these breakthroughs, with key contributions including innovations in multimodal chemical imaging, label-free microscopy, spatial and temporal omics, and droplet-based microfluidics. Collectively, these cutting-edge tools provide unprecedent-ed insights into non-genetic cell-to-cell variability, enhancing our understanding of cellu-lar plasticity and its implications for health, energy, and ecology.

59 BASIC BIOLOGICAL SCIENCES↗

3D optical diagnostics for explosively driven deformation and fragmentation

High-speed, optical imaging diagnostics are presented for three-dimensional (3D) quantification of explosively driven metal fragmentation. At early times after detonation, Digital Image Correlation (DIC) provides non-contact measures of 3D case velocities, strains, and strain rates, while a proposed stereo imaging configuration quantifies in-flight fragment masses and velocities at later times. Experiments are performed using commercially obtained RP-80 detonators from Teledyne RISI, which are shown to create a reproducible fragment field at the benchtop scale. DIC measurements are compared with 3D simulations, which have been ‘leveled’ to match the spatial resolution of DIC. Overall, results demonstrate improved ability to identify predicted quantities-of-interest that fall outside of measurement uncertainty and shot-to-shot variability. Similarly, video measures of fragment trajectories and masses allow rapid experimental repetition and provide correlated fragment size-velocity measurements. Measured and simulated fragment mass distributions are shown to agree within confidence bounds, while some statistically meaningful differences are observed between the measured and predicted conditionally averaged fragment velocities. Together these techniques demonstrate new opportunities to improve future model validation.

42 ENGINEERING↗

Short Communication: Observation of Initial Burst Release of Fission Gas from High-Burnup UO 2 Nuclear Fuel During Thermal Transient

A system was developed and tested to provide a deeper understanding of the fission gas release kinetics from nuclear fuel during thermal transients. Pressure, temperature, spectral data, and optical images were simultaneously collected during resistive sample heating, and all released gases were collected in liquid nitrogen-cooled charcoal traps. Standup testing was performed with a high-burnup nuclear fuel segment from rod section with an average local burnup of 77 GWd/tU. During heating, the segment released approximately 6 ± 2% of generated fission gas inventory after ramp heating to 460°C. Here, heating ceased when the sample ejected from the holder, as observed by constant imaging.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of corrosion coupons exposed to molten-chloride electrorefiner salts long term

Corrosion mitigation has long been considered a challenge in long-term service of both pyrochemical reprocessing and molten salt reactor applications. Corrosion coupons consisting of 2.25Cr 1Mo ASME SA387 Grade 22 Class 2 steel, were installed in a uranium electrorefiner containing molten chloride salt at 500°C. This electrorefiner went into service at Idaho National Laboratory in 1994. Seven of these coupons were removed in 2019 (i.e., submerged in molten salt for 25 years) for analysis and characterization including neutron imaging, optical microscopy, scanning electron microscopy, and wave/energy dispersive x-ray spectroscopy. The results showed that all seven coupons experienced between 30 to 175 µm of surface degradation without evidence of brittle fracture. Meaning there was no evidence of accelerated corrosion or fractures, and the average steel surface loss was of less than 5 µm per year. All indications were that the environmental conditions inside the electrorefiner were favorable for the steel alloy.

36 - MATERIALS SCIENCE↗

Structure–property relations in graphitic pebbles for nuclear applications

This work presents an analytical approach for holistically characterizing graphitic matrix pebbles for nuclear applications whereby the macrostructure, microstructure, and thermophysical properties of pebbles are determined. A systematic sectioning method was applied to several pebbles to describe the regional properties of the samples. Intact matrix-only spheres and sections of spheres fabricated by Kairos Power were characterized via optical imaging, x-ray computed tomography, x-ray diffraction, and ellipsometry to determine 2D and 3D macrostructure and anisotropy. The thermophysical properties of these materials were determined via measurements of density, specific heat, thermal expansion, and thermal diffusivity. The results of this study indicate that the pebble fabrication methods and their resultant effect on microstructure have a nontrivial effect on thermophysical properties, confirming the importance of robust characterization of these components. A discussion of the characterization approach and its applicability to nuclear fuel development activities is also included.

42 ENGINEERING↗

Shape-Controlled Synthesis of Copper Nanocrystals for Plasmonic, Biomedical, and Electrocatalytic Applications

As a metal that can occur in nature in the elemental form, copper (Cu) has been used by humans since ca. 8000 BC. With most properties matching those of Ag and Au, Cu has played a more significant role in commercial applications owing to its much higher (the 25th among all elements) abundance in Earth’s crust and thus more affordable price. In addition to its common use as a conductor of heat and electricity, it is a constituent of various metal alloys for hardware, coins, strain gauges, and thermocouples. Bulk Cu is also widely utilized as a building material. When downsized to the nanoscale, Cu and Cu-based structures have found widespread use in applications ranging from electronics to optoelectronics, plasmonics, catalysis, sensing, and biomedicine. Besides Ag and Au, for example, Cu is another metal known for its localized surface plasmon resonance (LSPR) in the visible and near-infrared regions when prepared as nanocrystals. As a potential replacement for indium–tin oxide (ITO) films, polymer coatings containing Cu nanowires are strong candidates for the fabrication of transparent and flexible electrodes key to touchscreen display and related applications. The commercial catalysts for water–gas shift and gas detoxification reactions are also based on Cu nanoparticles. Most recently, Cu nanocrystals have attracted considerable interest for their superior selectivity toward hydrocarbons and multicarbon species during the electrochemical reduction of CO 2 . The success of all these applications critically depends on our ability to control the shape and surface structure of the nanocrystals. Relative to Ag and Au, it is more challenging to generate Cu-based nanocrystals using colloidal methods due to its lower reduction potential and greater vulnerability to oxidation. Here, in this account, we discuss recent progress in the colloidal synthesis of Cu nanocrystals with controlled shapes for plasmonic, biomedical, and catalytic applications. With glucose serving as a reducing agent, Cu nanocrystals bearing a twinned or single-crystal structure can be synthesized using an aqueous system with the assistance of hexadecylamine (HDA). In this synthetic protocol, HDA not only passivates the surface to protect the nanocrystals from oxidation but also manipulates the reduction kinetics of Cu(II) precursor through coordination and an increase of solution pH. Typical products include nanocubes and penta-twinned nanowires whose surfaces are dominated by {100} facets. When seeds produced either in situ or ex situ are introduced, Cu-based nanocrystals featuring a singly twinned, core–shell, or Janus structure can be readily synthesized. Aside from segmented structures, Cu-based alloys with various noble metals can be synthesized through coreduction or a galvanic replacement reaction with preformed Cu nanocrystals. By controlling the size and/or shape of Cu nanocrystals, their LSPR peaks can be tuned into the near-infrared region, making them promising candidates for optical imaging contrast enhancement and photothermal treatment. The inclusion of the 64 Cu isotope makes them immediately useful in positron emission tomography and thus image-guided therapy. The surface structure, elemental distribution, and valence state of Cu-based nanocrystals can all be tailored to augment their electrocatalytic performance. It is hoped that this Account will inspire more studies into the development of rational methods capable of producing Cu-based nanocrystals with diverse and well-controlled shapes, internal structures, and compositions for a broader range of applications.

36 MATERIALS SCIENCE↗

Cage Molecules Stabilize Lead Halide Perovskite Thin Films

The environmental stability of hybrid organic-inorganic perovskite (HOIP) materials needs to increase to enable their widespread adoption in thin-film solar and optoelectronic devices. Molecular additives have recently emerged as an effective strategy for regulating HOIP crystal growth and passivating defects. However, to date the choice of additives is largely limited to a dozen or so materials under the design philosophy that high crystallinity is a prerequisite for stable HOIP thin films. Here, in this study, we incorporate porous organic cages (POCs) as functional additives into perovskite thin films for the first time and investigate the HOIP-POC interaction via a combined experimental and computational approach. POCs are significantly larger than the small-molecule additives explored for HOIP synthesis to date but much smaller than polymeric sealants. Partially amorphized composites of MAPbI 3 (methylammonium lead iodide, HOIP) and RCC3 (an amine POC) form a network-like surface topography and lead to an increase in the optical bandgap from 1.60 to 1.63 eV. Further in situ optical imaging suggests that RCC3 can delay the MAPbI 3 film degradation onset up to 50x under heat and humidity stresses, showing promise for improving reliability in HOIP-based solar-cell and light-emitting applications. Furthermore, there is evidence of molecular interactions between RCC3 and MAPbI 3 , as fingerprinted by the suppressed N-H stretching mode in MA + from Fourier transform infrared (FTIR) spectra and density functional theory (DFT) simulations that suggest strong hydrogen bonding between MA + and RCC3. Given the diversity of POCs and HOIPs, our work opens a new avenue to stabilize HOIPs via tailored molecular interactions with functional organic materials.

36 MATERIALS SCIENCE↗

Effects of Particle Mixing and Gravitational Settling on Charge Transport in Carbon Flow-Electrode Cells

Flowable carbon slurries are actively studied and under development for charge transport in various electrochemical systems including flow capacitors, capacitive deionization cells, semi-solid flow batteries, and lithium extraction. However, much less is known about in operando slurry flow dynamics and their corresponding effect on charge transport. We performed an experimental study of mixing and settling dynamics of slurry electrodes within an electrochemical flow cell during continuous operations. The electrochemical cell consisted of two horizontal co-flowing channels, separated by a cation-exchange membrane (CEM). Here we used high-speed optical imaging of planes parallel to gravity and simultaneous electrochemical measurements. At low flow rates, dense yet dynamic particle beds formed on the bottom electrode in each channel, which unexpectedly yielded the highest currents. This approach enables the operation of the flow cell at low system-average particle concentrations while leveraging gravity-driven particle settling to locally enhance carbon concentrations precisely at the current collector sites. Conversely, high flow rates were characterized by thin particle beds and well-mixed particle flows. In the latter case, the electrodes in closest proximity (located on either side of the CEM) achieved a current higher than the other electrode pairs. The observations have implications for slurry control and electrode designs in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering Surface Architectures for Improved Durability in III–V Photocathodes

GaInP2 has shown promise as the wide bandgap top junction in tandem absorber photoelectrochemical (PEC) water splitting devices. Among previously reported dual-junction PEC devices with a GaInP 2 top cell, those with the highest performance incorporate an AlInP 2 window layer (WL) to reduce surface recombination and a thin GaInP2 capping layer (CL) to protect the WL from corrosion in electrolytes. However, the stability of these III-V systems is limited, and durability continues to be a major challenge broadly in the field of PEC water splitting. This work provides a systematic investigation into the durability of GaInP 2 systems, examining the impacts of the window layer and capping layer among single junction pn-GaInP 2 photocathodes coated with an MoS 2 catalytic and protective layer. The photocathode with both a CL and WL demonstrates the highest PEC performance and longest lifetime, producing a significant current for >125 h. In situ optical imaging and post-test characterization illustrate the progression of macroscopic degradation and chemical state. The surface architecture combining an MoS 2 catalyst, CL, and WL can be translated to dual-junction PEC devices with GaInP 2 or other III-V top junctions to enable more efficient and stable PEC systems.

08 HYDROGEN↗

Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH 4 F (aqueous) have been investigated during either a linear potential sweep or a constant potential hold ( E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments reflected the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. Furthermore, the etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiO x F y on the surface. The two-dimensional fractal dimension, D f,2D , of the patterns increased with etching time to a maximum observed value of D f,2D = 1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Addressing the Stability Gap in Photoelectrochemistry: Molybdenum Disulfide Protective Catalysts for Tandem III–V Unassisted Solar Water Splitting

While photoelectrochemical (PEC) solar-to-hydrogen efficiencies have greatly improved over the past few decades, advances in PEC durability have lagged behind. Corrosion of semiconductor photoabsorbers in the aqueous conditions needed for water splitting is a major challenge that limits device stability. In addition, a precious-metal catalyst is often required to efficiently promote water splitting. In this work, we demonstrate unassisted water splitting using a nonprecious metal molybdenum disulfide nanomaterial catalytic protection layer paired with a GaInAsP/GaAs tandem device. This device was able to achieve stable unassisted water splitting for nearly 12 h, while a sibling sample with a PtRu catalyst was only stable for 2 h, highlighting the advantage of the nonprecious metal catalyst. In situ optical imaging illustrates the progression of macroscopic degradation that causes device failure. Furthermore, this work compares unassisted water splitting devices across the field in terms of the efficiency and stability, illustrating the need for improved stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the Role of Lithium Iodide in Stabilizing Solid Interfaces in All-Solid-State Li Metal Batteries

A critical challenge in all-solid-state lithium metal batteries (ASSLMBs) is achieving a stable interface between the lithium metal anode and the solid electrolyte. Leveraging its success in Li/I 2 batteries, lithium iodide has garnered significant attentions for its potential to enhance interfacial stability and overall cell performance in ASSLMBs. Here, we elucidate the role of lithium iodide in stabilizing the solid interface in all-solid-state Li metal batteries with a Li argyrodite electrolyte, particularly focusing on its influence on lithium deposition behavior and interfacial evolution. Through in situ optical imaging, we demonstrate more uniform lithium deposition on an iodide-contained argyrodite electrolyte compared to a chloride-based counterpart. Complementary density functional theory calculations attribute improved lithium plating behavior to the enhanced lithiophilicity and better ionic conductivity of lithium iodide at the solid interface, effectively reducing localized current density. In conclusion, these findings provide useful insights into the mechanisms through which lithium iodide enhances the interfacial stability in ASSLMBs.

Anions↗

Large-Area, Highly Crystalline DNA-Assembled Metasurfaces Exhibiting Widely Tunable Epsilon-Near-Zero Behavior

Metasurfaces prepared via bottom-up nanoparticle assembly enable the deliberate manipulation of light in the optical regime, resulting in media with unprecedented optical responses. Here, we report a scalable method to grow highly crystalline 2D metasurfaces comprised of colloidal gold nanocubes, over macroscopic areas, using DNA-mediated assembly under equilibrium conditions. Using an effective medium description, we predict that these plasmonic metasurfaces behave as dielectric media with high refractive indices that can be dynamically tuned by tuning DNA length. Furthermore, we predict that when coupled with an underlying thin gold film, the real permittivity of these metasurfaces exhibits a crossover region between positive and negative values, known as the epsilon-near-zero (ENZ) condition, which can be tuned between 1.5 - 2.6 μm by changing DNA length. Optical characterization performed on the DNA-assembled metasurfaces reveals that the predicted optical properties agree well with measured response. Overall, we propose an efficient method for realizing large-area plasmonic metasurfaces that enable dynamic control over unique optical characteristics. High-index and ENZ metasurfaces operating in the telecommunications regime could have significant implications in high-speed optical computing, optical communications, optical imaging, and other areas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Magnetic Genome of Two-Dimensional van der Waals Materials

Magnetism in two-dimensional (2D) van der Waals (vdW) materials has recently emerged as one of the most promising areas in condensed matter research, with many exciting emerging properties and significant potential for applications ranging from topological magnonics to low-power spintronics, quantum computing, and optical communications. In the brief time after their discovery, 2D magnets have blossomed into a rich area for investigation, where fundamental concepts in magnetism are challenged by the behavior of spins that can develop at the single layer limit. However, much effort is still needed in multiple fronts before 2D magnets can be routinely used for practical implementations. In this comprehensive review, prominent authors with expertise in complementary fields of 2D magnetism (i.e., synthesis, device engineering, magneto-optics, imaging, transport, mechanics, spin excitations, and theory and simulations) have joined together to provide a genome of current knowledge and a guideline for future developments in 2D magnetic materials research.

36 MATERIALS SCIENCE↗

Topological solitonic macromolecules

Being ubiquitous, solitons have particle-like properties, exhibiting behaviour often associated with atoms. Bound solitons emulate dynamics of molecules, though solitonic analogues of polymeric materials have not been considered yet. Here we experimentally create and model soliton polymers, which we call “polyskyrmionomers”, built of atom-like individual solitons characterized by the topological invariant representing the skyrmion number. With the help of nonlinear optical imaging and numerical modelling based on minimizing the free energy, we reveal how topological point defects bind the solitonic quasi-atoms into polyskyrmionomers, featuring linear, branched, and other macromolecule-resembling architectures, as well as allowing for encoding data by spatial distributions of the skyrmion number. Application of oscillating electric fields activates diverse modes of locomotion and internal vibrations of these self-assembled soliton structures, which depend on symmetry of the solitonic macromolecules. Our findings suggest new designs of soliton meta matter, with a potential for the use in fundamental research and technology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Visible-to-THz near-field nanoscopy

Optical microscopy has a key role in research, development and quality control across a wide range of scientific, technological and medical fields. However, diffraction limits the spatial resolution of conventional optical instruments to about half the illumination wavelength. A technique that surpasses the diffraction limit in the wide spectral range between visible and terahertz frequencies is scattering-type scanning near-field optical microscopy (s-SNOM). The basis of s-SNOM is an atomic force microscope in which the tip is illuminated with light from the visible to the terahertz spectral range. By recording the elastically tip-scattered light while scanning the sample below the tip, s-SNOM yields near-field optical images with a remarkable resolution of 10 nm, simultaneously with the standard atomic force microscopic topography image. This resolution is independent of the illumination wavelength, rendering s-SNOM a versatile nanoimaging and nanospectroscopy technique for fundamental and applied studies of materials, structures and phenomena. This Review presents an overview of the fundamental principles governing the measurement and interpretation of near-field contrasts and discusses key applications of s-SNOM. We also showcase emerging developments that enable s-SNOM to operate under various environmental conditions, including cryogenic temperatures, electric and magnetic fields, electrical currents, strain and liquid environments. Furthermore, all these recent developments broaden the applicability of s-SNOMs for exploring fundamental solid-state and quantum phenomena, biological matter, catalytic reactions and more.

Hillenbrand, Rainer [CIC nanoGUNE BRTA and Departm↗

3D nanolithography with metalens arrays and spatially adaptive illumination

The growing demand for advanced materials, miniaturized devices and integrated microsystems calls for the reliable fabrication of complex, multiscale, three-dimensional (3D) architectures, a need increasingly addressed through light-based and laser-based processes. However, owing to the field-of-view (FOV) limitations of conventional imaging optics, existing 3D laser nanofabrication techniques face fundamental challenges in throughput, proximity error and stitching defects on the path to scaling. Here, in this study, we present a scalable 3D nanofabrication platform that uses a metalens-generated focal spot array to parallelize two-photon lithography (TPL) beyond centimetre-scale write field areas. Metalenses are ideally suited for producing submicron-scale focal spots for high-throughput nanolithography, as they uniquely feature large numerical apertures (NAs), immersion media compatibility and large-scale manufacturability. We experimentally demonstrate a printing system that uses a 12-cm 2 metalens array to produce more than 120,000 cooperative focal spots, corresponding to a throughput exceeding 10 8 voxels s −1 . By programmatically patterning the focal spot array using a spatial light modulator (SLM), an adaptive parallel printing strategy is developed for precise greyscale linewidth modulation and choreographed printing of semiperiodic and fully aperiodic 3D geometries. We demonstrate parallel printing of replicated microstructures (>50 M microparticles per day), centimetre-scale 3D architectures with feature sizes down to 113 nm, and photonic and mechanical metamaterials. This work demonstrates the potential of 3D nanolithography towards wafer-scale production, showing how TPL could be used at scale for applications in microelectronics, biomedicine, quantum technology and high-energy laser targets.

Materials science↗