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At least 883 records · Page 49

Stereogenic-at-silicon hybrid conjugated polymers

Stereoregularity in carbon-based polymers impacts critical physical properties such as crystallinity, but achieving comparable precision in polysilanes remains challenging. Herein, we report the synthesis of hybrid σ,π-conjugated polysilanes with defined stereoregularity, derived from cis- and trans-cyclosilane building blocks. Using Kumada polycondensation, we accessed a series of atactic, trans-enriched, and cis-enriched polysilanes, enabling a systematic investigation of how tacticity influences thermal and optical properties. Differential scanning calorimetry revealed distinct glass transition behaviors for stereoregular polymers compared to their atactic counterpart, and UV-vis spectroscopy demonstrated enhanced spectral resolution upon annealing of stereoregular films. A linear silane-based analog further underscored the structural impact of cyclic stereogenic units. These findings highlight how stereochemical precision in silicon-containing backbones can modulate macromolecular properties, opening avenues for the rational design of stereoregular polysilanes.

36 MATERIALS SCIENCE↗

Understanding and tuning organocatalysts for versatile condensation polymer deconstruction

Plastics are widely used for their durability and versatility, but recycling remains a major challenge, especially for mixed or contaminated waste. Mechanical recycling works well for clean, single-polymer streams like PET but has limited efficiency for complex waste streams. Chemical recycling, particularly glycolysis, is often employed to selectively deconstruct condensation polymers under mild conditions. This study explores catalyst design for glycolysis using linear free energy (Hammett) analysis to evaluate how catalyst structure influences polymer deconstruction. Polycaprolactone (PCL) is used as a model polyester due to its solubility and low deconstruction temperature. Triazabicyclodecene (TBD) paired with benzoic acid derivatives depicts a clear linear trend in depolymerization rates with Hammett values. TBD with p-aminobenzoic acid (PABA) stands out for its catalytic efficiency, thermal stability, and scalability, along with PABA's commercial availability as vitamin B-10. The TBD : PABA catalyst not only effectively breaks down PCL but also enables sequential deconstruction of polycarbonate, PET, and Nylon in mixed waste streams. These results highlight the value of Hammett-guided catalyst design and establish TBD : PABA as a promising, scalable organocatalyst for mixed plastic recycling, enabling recovery of individual polymer building blocks from blended waste and offering a practical route toward circular plastics.

Zheng, Jackie [Univ. of Tennessee, Knoxville, TN (↗

Alkali triel chalcogenide nanocrystals: a molecular reactivity approach to ternary phase selectivity

Alkali-metal-based materials are promising building blocks for energy conversion and storage technologies. Here, we use a molecular reactivity-based solution-phase approach to selectively synthesize multiple phases and specific polymorphs of lithium- and sodium-containing triel chalcogenide nanocrystals, LiTrCh 2 , NaTrCh 2 , and NaTr 3 Ch 5 , where Tr = Ga and In and Ch = S, Se, and Te. Analogous to the case of binary II–VI and III–V tetrahedral semiconductors, where the two commonly isolated zinc blende and wurtzite polymorphs are separated by only 1–50 meV f.u. −1 , we find that LiTrCh 2 nanocrystals easily adopt tetragonal (chalcopyrite) and orthorhombic polymorphs separated by only 2.7–6.2 meV f.u. −1 Because of this small energy difference, soft colloidal synthesis succeeds in accessing either one of these polymorphs, depending on the specific dichalcogenide precursor used. Highly reactive diethyl diselenide favors the thermodynamically more stable tetragonal I$\bar{4}2$d phase, whereas mildly reactive diphenyl diselenide favors the kinetic, metastable orthorhombic Pna2 1 phase. Density functional theory calculations confirm the relative energies among multiple LiTrCh 2 polymorphs and also model the observed powder X-ray diffraction pattern of a new C2 NaIn 3 Te 5 phase. 7 Li, 69 Ga, and 77 Se solid-state NMR spectra are consistent with phase-pure ternary LiGaSe 2 nanocrystals. A majority of the nanocrystal compositions are visible-light emitters. This work opens the door to new Li/Na-based ternary triel chalcogenide nanostructures for energy storage and conversion applications.

Pavel, Md Riad Sarkar [Iowa State Univ., Ames, IA ↗

Upcycling waste PET into functional multiblock copolymers through controlled macromolecular design

Poly(ethylene terephthalate) (PET) oligomers derived from glycolysis depolymerization were converted into multiblock copolymers through diisocyanate-mediated coupling with dihydroxy-terminated oligomers, enabling precise control over copolymer sequence distribution, connectivity, and mechanical performance. Here, we demonstrate that telechelic PET oligomers isolated directly from depolymerized consumer waste can serve as reactive building blocks for the formation of segmented multiblock copolymers, eliminating the need to revert to monomeric feedstocks. Dihydroxy-terminated PET oligomers (Mw ≈ 8 kg mol−1) were coupled with poly(ethylene oxide) (PEO, Mw ≈ 4 kg mol−1) to form PET-PEO multiblock copolymers with high molar mass (Mw ≈ 160 kg mol−1). We further show that the timing of end-capping reactions provides a key control parameter that governs the competition between chain extension and termination, thereby dictating the resulting multiblock architecture and molecular-weight evolution. Evaluation of their mechanical properties reveals that virgin PET exhibits high modulus (∼3 GPa) and strength (43 MPa) but limited ductility (<10% elongation). In contrast, PET–PEO multiblock copolymers retain comparable tensile strength (44 MPa), albeit while exhibiting dramatically enhanced ductility (>90% elongation), forming tougher materials with efficient stress transfer between the rigid PET domains and the flexible PEO segments. When incorporated into PET/PEO blends at low loadings, the multiblock copolymers serve as effective compatibilizers, yielding materials with an intermediate modulus (1.1–1.2 GPa) and improved elongation compared to uncompatibilized blends. Furthermore, the presence of PEO blocks increases water uptake and gas permeability relative to virgin PET, reflecting the tunability of molecular transport through the copolymeric blocks. To our knowledge, this represents the first report of PET–PEO multiblock copolymers derived from post-consumer PET for gas transport applications. These results demonstrate that multiblock copolymer formation from telechelic PET oligomers provides a versatile platform for tailoring the mechanical and transport behavior of polyester-based materials through controlled macromolecular design and establishes a generalizable strategy for transforming consumer plastic waste into functional segmented polymers without requiring complete depolymerization to monomers.

Watson-Sanders, Shelby [Department of Chemistry, U↗

Co-templating of polyoxoniobates and silicate/germanate trimer-rings in crystals and inorganic gels

Polyoxometalate (POM) supramolecular gels are a growing family of materials, both for understanding fundamental self-assembly and fabricating flexible monolithic materials that retain the function of metal oxides. Here, we exploited the pH-dependent speciation of polyoxoniobates (PONbs), targeting the formation of PONb-containing supramolecular gels that contain other low molecular weight components (silicate, germanate, phosphate, and carbonate). The introduction of gaseous CO 2 into aqueous hexaniobate solutions resulted in the formation of both new crystalline phases and highly transparent gels. The crystalline phases, formulated Cs 24 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Si 3 O 9 )]·19.6H 2 O and Cs 21 Na 3 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Ge 3 O 9 )]·33.6H 2 O are templated by a rare planar [X 3 O 9 ] 6− (X = Si, Ge) ring. Crystalline phases were not obtained with phosphate; instead, the gels contain a mixture of phosphate-centred PONbs and network-forming phosphate. POM speciation within the gels, physical properties, and assembly mechanisms were benchmarked by solution and solid-state nuclear magnetic resonance (NMR) spectroscopy, vibrational spectroscopies, small-angle X-ray scattering (SAXS), and thermogravimetry-mass spectroscopy. Optical analysis and dielectric behavior of the gels confirmed that they are highly transparent ionic and electronic conductors. The alkali and hydroxide concentration controls the formation of crystalline materials or supramolecular gels while maintaining the same network building blocks, providing a rare opportunity to describe the molecular-level structure of inorganic amorphous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NEFTSec: Networked federation testbed for cyber-physical security of smart grid: Architecture, applications, and evaluation

As today's power grid is evolving into a densely interconnected cyber-physical system (CPS), a high fidelity and multifaceted testbed environment is needed to perform cybersecurity experiments in a realistic grid environment. Traditional standalone CPS testbeds lack the ability to emulate complex cyber-physical interdependencies between multiple smart grid domains in a real-time environment. Therefore, there are ongoing research and development (R&D) efforts to develop an interconnected CPS testbed by sharing geographically dispersed testbed resources to perform distributed simulation while analysing simulation fidelity. This paper presents a networked federation testbed for cybersecurity evaluation of today's and emerging smart grid environments. Specifically, it presents two novel testbed architectures, including cyber federation and cyber-physical federation, identifies R&D applications, and also describes testbed building blocks with experimental case studies. It also presents a novel co-simulation interface algorithm to facilitate distributed simulation within cyber-physical federation. The resources available at the PowerCyber CPS security testbed at Iowa State University (ISU) and the US Army Research Laboratory are utilised to develop this platform for performing multiple experimental case studies pertaining to wide-area protection and control applications in power system. Finally, experimental results are presented to analyse the simulation fidelity and real-time performance of the testbed federation.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗

Using OpenMP for HEP framework algorithm scheduling

The OpenMP standard is the primary mechanism used at high performance computing facilities to allow intra-process parallelization. In contrast, many HEP specific software packages (such as CMSSW, GaudiHive, and ROOT) make use of Intel’s Threading Building Blocks (TBB) library to accomplish the same goal. In these proceedings we will discuss our work to compare TBB and OpenMP when used for scheduling algorithms to be run by a HEP style data processing framework. This includes both scheduling of different interdependent algorithms to be run concurrently as well as scheduling concurrent work within one algorithm. As part of the discussion we present an overview of the OpenMP threading model. We also explain how we used OpenMP when creating a simplified HEP-like processing framework. Using that simplified framework, and a similar one written using TBB, we will present performance comparisons between TBB and different compiler versions of OpenMP.

97 MATHEMATICS AND COMPUTING↗

Bringing heterogeneity to the CMS software framework

The advent of computing resources with co-processors, for example Graphics Processing Units (GPU) or Field-Programmable Gate Arrays (FPGA), for use cases like the CMS High-Level Trigger (HLT) or data processing at leadership-class supercomputers imposes challenges for the current data processing frameworks. These challenges include developing a model for algorithms to offload their computations on the co-processors as well as keeping the traditional CPU busy doing other work. The CMS data processing framework, CMSSW, implements multithreading using the Intel Threading Building Blocks (TBB) library, that utilizes tasks as concurrent units of work. In this paper we will discuss a generic mechanism to interact effectively with non-CPU resources that has been implemented in CMSSW. In addition, configuring such a heterogeneous system is challenging. In CMSSW an application is configured with a configuration file written in the Python language. The algorithm types are part of the configuration. The challenge therefore is to unify the CPU and co-processor settings while allowing their implementations to be separate. We will explain how we solved these challenges while minimizing the necessary changes to the CMSSW framework. We will also discuss on a concrete example how algorithms would offload work to NVIDIA GPUs using directly the CUDA API.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ocean Energy for Ocean Worlds

Energy systems generating power from ocean waves, currents, tides, and thermal and salinity gradients are being developed to power oceanographic instrumentation and autonomous vehicles in Earth’s oceans. Exploration missions enabled or extended with in-situ energy harvesting on Earth may be similar to those on extra-terrestrial ocean worlds including mapping, biogeochemical sampling, acoustic monitoring, search for building blocks of life, and physical oceanographic characterization. With the addition of ocean energy available at the point of observation, data can be collected on larger spatial and temporal scales, enabling more comprehensive missions on other worlds. Power resource characteristics (e.g. current speed, variability) will similarly need to be assessed. Earth and extra-terrestrial ocean missions share vast technical challenges including high expense, need for advanced autonomy, ability to survive in the harshest environments, and limited communications or opportunities for intervention. Marine energy systems may be the only option for in-situ generation in certain scenarios (e.g., under a thick layer of ice) or advantageous over onboard energy storage options that may interfere with the natural environment (e.g., radioisotope thermoelectric generators). This work provides an overview of existing marine energy technology pertaining to ocean observations, highlights emerging research and development and new funding and program initiatives, explores similarities in mission requirements between terrestrial and extra-terrestrial applications, and suggests innovation pathways towards enabling high-value ocean world exploration powered by ocean energy.

Cavagnaro, Robert J.↗

Experimental characterization of a section of a spherically imploding plasma liner formed by merging hypersonic plasma jets

In this work, we report experimental results on merging of hypersonic plasma jets, which is the fundamental building block for forming spherically imploding plasma liners as a potential standoff compression driver for magneto-inertial fusion. Jets are formed and launched by contoured-gap coaxial plasma guns mounted at the six vertices and the center of a hexagon covering approximately one-tenth of the surface area of a 9-ft-diameter spherical chamber. First, from experiments with two and three merging jets of four different species (N, Ar, Kr, and Xe), we show that (1) density spatial non-uniformities can be large (with electron-density jumps ranging from 2.9 for N to 6.6 for Xe) when shocks form upon jet merging, but smaller (density jumps <2) when shocks do not form; (2) jet impurities (20% Ti in these experiments) can increase the level of density spatial non-uniformity by increasing the collisionality of jet merging, leading to shock formation rather than potentially more desirable shockless jet merging; and (3) the liner Mach number can remain high (≳10), as required for plasma liners to be an effective compression driver. Secondly, from experiments with six and seven merging jets using Ar, we present results with improved jet-to-jet mass balance of <2% across jets, including (1) evidence of substantially increased balance in the jet merging and symmetry of the liner structure and (2) potentially favorable changes in the jet-merging morphology with the addition of the seventh jet. Ultimately, for both experiments, we present comparisons between experimental and synthetic data from three-dimensional hydrodynamic codes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Nb 3 Sn multicell cavity coating system at Jefferson Lab

Superconducting radio frequency niobium cavities are the building blocks of modern accelerators for scientific applications. Lower surface resistance, higher fields, and high operating temperatures advance the reach of the future accelerators for scientific discovery as well as potentially enabling cost-effective industrial solutions. We describe the design and performance of an Nb 3 Sn coating system that converts the inner surface of niobium cavities to an Nb 3 Sn film. The niobium surface, heated by radiation from the niobium retort, is exposed to Sn and SnCl 2 vapor during the heat cycle, which results in about 2 μm Nb 3 Sn film on the niobium surface. Film composition and structure as well as radio frequency properties with 1-cell R&D cavities and 5-cell practical accelerator cavities are presented.

47 OTHER INSTRUMENTATION↗

Inverse methods for design of soft materials

Functional soft materials, comprising colloidal and molecular building blocks that self-organize into complex structures as a result of their tunable interactions, enable a wide array of technological applications. Inverse methods provide a systematic means for navigating their inherently high-dimensional design spaces to create materials with targeted properties. Furthermore, while multiple physically motivated inverse strategies have been successfully implemented in silico, their translation to guiding experimental materials discovery has thus far been limited to a handful of proof-of-concept studies. In this perspective, we discuss recent advances in inverse methods for design of soft materials that address two challenges: (1) methodological limitations that prevent such approaches from satisfying design constraints and (2) computational challenges that limit the size and complexity of systems that can be addressed. Strategies that leverage machine learning have proven particularly effective, including methods to discover order parameters that characterize complex structural motifs and schemes to efficiently compute macroscopic properties from the underlying structure. We also highlight promising opportunities to improve the experimental realizability of materials designed computationally, including discovery of materials with functionality at multiple thermodynamic states, design of externally directed assembly protocols that are simple to implement in experiments, and strategies to improve the accuracy and computational efficiency of experimentally relevant models.

36 MATERIALS SCIENCE↗

Superconducting neural networks with disordered Josephson junction array synaptic networks and leaky integrate-and-fire loop neurons

Fully coupled randomly disordered recurrent superconducting networks with additional open-ended channels for inputs and outputs are considered the basis to introduce a new architecture to neuromorphic computing in this work. Various building blocks of such a network are designed around disordered array synaptic networks using superconducting devices and circuits as an example, while emphasizing that a similar architectural approach may be compatible with several other materials and devices. A multiply coupled (interconnected) disordered array of superconducting loops containing Josephson junctions [equivalent to superconducting quantum interference devices (SQUIDs)] forms the aforementioned collective synaptic network that forms a fully recurrent network together with compatible neuron-like elements and feedback loops, enabling unsupervised learning. This approach aims to take advantage of superior power efficiency, propagation speed, and synchronizability of a small world or a random network over an ordered/regular network. Additionally, it offers a significant factor of increase in scalability. Here, a compatible leaky integrate-and-fire neuron made of superconducting loops with Josephson junctions is presented, along with circuit components for feedback loops as needed to complete the recurrent network. Several of these individual disordered array neural networks can further be coupled together in a similarly disordered way to form a hierarchical architecture of recurrent neural networks that is often suggested as similar to a biological brain.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Tailoring magnetization reversal of a single-domain bar nanomagnet via its end geometry

Nanoscale single-domain bar magnets are building blocks for a variety of fundamental and applied mesoscopic magnetic systems, such as artificial spin ices, magnetic shape-morphing microbots, and magnetic majority logic gates. The magnetization reversal switching field of the bar nanomagnets is a crucial parameter that determines the physical properties and functionalities of their constituted artificial systems. Previous methods on tuning the magnetization reversal switching field of a bar nanomagnet usually relied on modifying its aspect ratio, such as its length, width, and/or thickness. Here, we show that the switching field of a bar nanomagnet saturates when extending its length beyond a certain value, preventing further tailoring of the magnetization reversal via aspect ratios. We showcase a highly tunable switching field of a bar nanomagnet by tailoring its end geometry without altering its size. This provides an easy method to control the magnetization reversal of a single-domain bar nanomagnet. It would enable new research and/or applications, such as designing artificial spin ices with additional tuning parameters, engineering magnetic microbots with more flexibility, and developing magnetic quantum-dot cellular automata systems for low power computing.

36 MATERIALS SCIENCE↗

Self-interaction correction in water–ion clusters

We study the importance of self-interaction errors in density functional approximations for various water–ion clusters. We have employed the Fermi-Löwdin orbital self-interaction correction (FLOSIC) method in conjunction with LSDA, PBE, and SCAN to describe binding energies of hydrogen-bonded water–ion clusters, i.e., water–hydronium, water– hydroxide, water–halide, as well as non-hydrogen-bonded water–alkali clusters. In the hydrogen-bonded water–ion clusters, the building blocks are linked by hydrogen atoms, although the links are much stronger and longer-ranged than the normal hydrogen bonds between water molecules, because the monopole on the ion interacts with both permanent and induced dipoles on the water molecules. We find that self-interaction errors overbind the hydrogen-bonded water– ion clusters and that FLOSIC reduces the error and brings the binding energies into closer agreement with higher–level calculations. Here, the non-hydrogen-bonded water–alkali clusters are not significantly affected by self-interaction errors. Self-interaction corrected PBE predicts the lowest mean unsigned error in binding energies (≤ 50 meV/H 2 O) for hydrogen-bonded water–ion clusters. Self-interaction errors are also largely dependent on the cluster size, and FLOSIC does not accurately capture the subtle variation in all clusters, indicating the need for further refinement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The superatomic state beyond conventional magic numbers: Ligated metal chalcogenide superatoms

The field of cluster science is drawing increasing attention due to the strong size and composition-dependent properties of clusters and the exciting prospect of clusters serving as the building blocks for materials with tailored properties. However, identifying a unifying central paradigm that provides a framework for classifying and understanding the diverse behaviors is an outstanding challenge. One such central paradigm is the superatom concept that was developed for metallic and ligand-protected metallic clusters. The periodic electronic and geometric closed shells in clusters result in their properties being based on the stability they gain when they achieve closed shells. This stabilization results in the clusters having a well-defined valence allowing them to be classified as superatoms – thus, extending the periodic table to a third dimension. This perspective focuses on extending the superatomic concept to ligated metal-chalcogen clusters that have recently been synthesized in solutions and form assemblies with counterions that have wide-ranging applications. Here we illustrate that the periodic patterns emerge in the electronic structure of ligated metal-chalcogenide clusters. The stabilization gained by the closing of their electronic shells allows for the prediction of their redox properties. Further investigations reveal how the selection of ligands may control the redox properties of the superatoms. These ligated clusters may serve as chemical dopants for two-dimensional semiconductors to control their transport characteristics. Superatomic molecules of multiple metal-chalcogen superatoms allow for the formation of nano pn junctions ideal for directed transport and photon harvesting. As a result, the perspective outlines future developments, including the synthesis of magnetic superatoms.

36 MATERIALS SCIENCE↗

Magnetic field sensors for detection of trapped flux in superconducting radio frequency cavities

Superconducting radio-frequency (SRF) cavities are fundamental building block of modern particle accelerators. They operate at liquid helium temperatures 2-4 K to achieve very high quality factors 1e10-1e11. Trapping of magnetic flux within the superconductor is a significant contribution to the residual RF losses which limit the achievable quality factor. Suitable diagnostic tools are in high demand to understand the mechanisms of flux trapping in technical superconductors and the fundamental components of such diagnostic tool are magnetic field sensors. We have studied the performance of commercially available Hall probes, anisotropic magnetoresistive sensors and flux-gate magnetometers with respect to their sensitivity and capability to detect localized, low magnetic flux amplitudes, of the order of few tens of magnetic flux quantum at liquid helium temperature. Although Hall probes have the lowest magnetic field sensitivity (~96$ nV$/microT at 2 K), their physical dimensions are such that they have the ability to detect the lowest number of trapped vortices among the three type of sensors. Hall probes and anisotropic magnetoresistive sensors have been selected to be used in a setup to map regions of trapped flux on the surface of a single-cell SRF cavity.

47 OTHER INSTRUMENTATION↗