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At least 1,549 records · Page 86

Investigation of methane and ethane pyrolysis with highly active and durable iron-alumina catalyst to produce hydrogen and valuable nano carbons: Continuous fluidized bed tests and reaction rate analysis

The goal of this research work was to evaluate a novel iron-alumina catalyst for methane and ethane pyrolysis with high conversion rates to H 2 with a long life time to address two major issues reported with previous catalysts. Fluidized bed tests demonstrated continuous hydrogen production while collecting carbon containing fines. During the 230 h fluid bed test the methane conversion rate to hydrogen at 700 °C remained above 80% for 160 h while creating valuable nano carbons. Similarly high catalyst lifetimes with high methane conversions have not been reported before. Ethane was more active than methane for pyrolysis with 100% conversion to H 2 . Transmission electron microscopy and Raman analysis of the carbon showed single and multiwall nanotubes and conglomerate nano-fibers. Ethane did not impact the allotrope of carbon formed. TGA was used to create a data array that was used for kinetic analysis and reaction model parametric regressions. Ethane had a higher rate of pyrolysis that was 2.3–2.8 times that of methane. Ethane pyrolysis was found to be more sensitive to temperature with a higher activation energy of 62 kJ/mol as compared to methane at 43 kJ/mol. The frequency factor, A i , was significantly higher for ethane at 0.73 [[kmol/m 3 -sec]/[N/m2] n ] compared to 0.03 for methane on the same basis. Both gases had a functional partial pressure order dependence of ~0.6 based on the regression analysis.

08 HYDROGEN↗

Critical Role of the Steric Factor in the Viscoelasticity of Vitrimers

Dynamic covalent networks (DCNs) are a promising solution to mitigate plastic-waste-related issues through improved recyclability enabled by dynamic bonds. However, our understanding of the mechanisms controlling their viscoelasticity, especially in vitrimers where bond exchange relies on associative reactions, remains limited. Here, in this study, we investigate the dynamics in model DCNs with boric ester functionalities, and the analysis of the temperature dependence of their terminal relaxation times revealed a puzzling result: extremely large Arrhenius prefactors associated with their dynamic bond rearrangement times. We ascribe this observation to the often-overlooked chemical steric factor that slows down chemical reactions, therefore decreasing the vitrimers’ bond exchange rate by many orders. The estimated steric factor of the bond exchange in our model DCNs is comparable to those observed in boronic ester exchange reactions between small molecules. Additional analysis of literature data revealed an overall low steric factor also for imine bond exchange, thus highlighting the role of this parameter in tremendously slowing down bond exchange in DCNs despite low activation energy barriers. We propose a general approach for designing vitrimers with desired viscoelastic and creep properties considering the critical role of the steric factor in bond rearrangement mechanisms, in addition to the traditionally considered activation energy and matrix properties.

Carden, Gregory P. [Univ. of Tennessee, Knoxville,↗

Data analytics approach to predict high-temperature cyclic oxidation kinetics of NiCr-based Alloys

Abstract Although of practical importance, there is no established modeling framework to accurately predict high-temperature cyclic oxidation kinetics of multi-component alloys due to the inherent complexity. We present a data analytics approach to predict the oxidation rate constant of NiCr-based alloys as a function of composition and temperature with a highly consistent and well-curated experimental dataset. Two characteristic oxidation models, i.e., a simple parabolic law and a statistical cyclic oxidation model, have been chosen to numerically represent the high-temperature oxidation kinetics of commercial and model NiCr-based alloys. We have successfully trained machine learning (ML) models using highly ranked key input features identified by correlation analysis to accurately predict experimental parabolic rate constants ( k p ). This study demonstrates the potential of ML approaches to predict oxidation kinetics of alloys over wide composition and temperature ranges. This approach can also serve as a basis for introducing more physically meaningful ML input features to predict the comprehensive cyclic oxidation behavior of multi-component high-temperature alloys with proper constraints based on the known underlying mechanisms.

36 MATERIALS SCIENCE↗

Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)

Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$T_c$$ T c ) is less than the average $$T_c$$ T c supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$_2\, \rightarrow$$ 2 → V $$_6$$ 6 O $$_{13} \, \rightarrow$$ 13 → V $$_2$$ 2 O $$_5$$ 5 .

Wilson, Catrina E. (ORCID:0000000173397318)↗

Bio-inspired gas sensing: boosting performance with sensor optimization guided by “machine learning”

The performance of existing gas sensors often degrades in field conditions because of the loss of measurement accuracy in the presence of interferences. Thus, new sensing approaches are required with improved sensor selectivity. We are developing a new generation of gas sensors, known as multivariable sensors, that have several independent responses for multi-gas detection with a single sensor. In this study, we analyze the capabilities of natural and fabricated photonic three-dimensional (3-D) nanostructures as sensors for the detection of different gaseous species, such as vapors and non-condensable gases. We employed bare Morpho butterfly wing scales to control their gas selectivity with different illumination angles. Next, we chemically functionalized Morpho butterfly wing scales with a fluorinated silane to boost the response of these nanostructures to the vapors of interest and to suppress the response to ambient humidity. Further, we followed our previously developed design rules for sensing nanostructures and fabricated bioinspired inorganic 3-D nanostructures to achieve functionality beyond natural Morpho scales. These fabricated nanostructures have embedded catalytically active gold nanoparticles to operate at high temperatures of ≈300 °C for the detection of gases for solid oxide fuel cell (SOFC) applications. Our performance advances in the detection of multiple gaseous species with specific nanostructure designs were achieved by coupling the spectral responses of these nanostructures with machine learning (a.k.a. multivariate analysis, chemometrics) tools. Our newly acquired knowledge from studies of these natural and fabricated inorganic nanostructures coupled with machine learning data analytics allowed us to advance our design rules for sensing nanostructures toward the required gas selectivity for numerous gas monitoring scenarios at room and high temperatures for industrial, environmental, and other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genome and time-of-day transcriptome of Wolffia australiana link morphological minimization with gene loss and less growth control

Rootless plants in the genus Wolffia are some of the fastest growing known plants on Earth. Wolffia have a reduced body plan, primarily multiplying through a budding type of asexual reproduction. Here, we generated draft reference genomes for Wolffia australiana (Benth.) Hartog & Plas, which has the smallest genome size in the genus at 357 Mb and has a reduced set of predicted protein-coding genes at about 15,000. Comparison between multiple high-quality draft genome sequences from W. australiana clones confirmed loss of several hundred genes that are highly conserved among flowering plants, including genes involved in root developmental and light signaling pathways. Wolffia has also lost most of the conserved nucleotide-binding leucine-rich repeat (NLR) genes that are known to be involved in innate immunity, as well as those involved in terpene biosynthesis, while having a significant overrepresentation of genes in the sphingolipid pathways that may signify an alternative defense system. Diurnal expression analysis revealed that only 13% of Wolffia genes are expressed in a time-of-day (TOD) fashion, which is less than the typical ~40% found in several model plants under the same condition. In contrast to the model plants Arabidopsis and rice, many of the pathways associated with multicellular and developmental processes are not under TOD control in W. australiana, where genes that cycle the conditions tested predominantly have carbon processing and chloroplast-related functions. The Wolffia genome and TOD expression data set thus provide insight into the interplay between a streamlined plant body plan and optimized growth.

59 BASIC BIOLOGICAL SCIENCES↗

Development of FRET clusters for CBRN Detection

Advanced sensor capabilities for the simultaneous on-site detection of specific chemical, biological, and radiological/nuclear (CBRN) threats is important to significantly limit the risk of exposure to personnel and allow the rapid collection of essential scientific data and critical evidence. Commercially available sensor capabilities are generally complex, and/or require highly specific and ultra-sensitive methods that are often power demanding or require offsite post-analysis for positive detection, leaving personnel vulnerable. The goal of this project is to develop a portable sensor capable of simultaneously detecting CBRN signatures using a multiplexed Förster Resonance Energy Transfer (FRET) based sensor. FRET sensors are tailorable, specific, and highly dependent on the donor-acceptor distance. In this project, nanoparticles were functionalized with aptamers that were designed for the detection of methylphosphonate, a sarin metabolite. FRET was measured between quantum dot donors and dye and metal nanoparticle acceptors using optical spectroscopy.

61 RADIATION PROTECTION AND DOSIMETRY↗

EDXplorer: A Utility for APA Analysis

The automated particle analysis (APA) method of scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy (EDS/EDX) is a useful tool for analyzing the elemental and morphological data of particulate samples. Often, such datasets have many thousands of particles, and it can be difficult to sift through the data to find meaningful trends. EDXplorer is a software utility for processing APA data. They enable the user to easily load data and determine the important components and aspects of the datasets using a powerful and versatile library of data plotting functions, mainly centered around scatter plots and histograms. These programs are intended to fill a void in the data processing of data from certain instruments, where often the user must rely on their own code or other software that is not user-friendly. EDXplorer is intended as a general plotting utility for browsing through data and discovering data trends.

Moseley, Duncan [ORNL] (ORCID:0000000343518347)↗

THE STRUCTURE FUNCTION OF THE FREE NEUTRON AT HIGH X-BJORKEN

Understanding the internal structure of nucleons is one of the primary goal of nuclear physicists. As protons and neutrons are only the bound state solution of the QCD lagrangian (at least inside atomic nuclei), studying protons and neutrons helps uncover nuclear struc ture. Due to its easy availability, many studies on protons have been done on a wide range of kinematics. However, free neutron targets are not readily achievable. So, any information on neutrons has to be extracted from neutron-rich nuclei, and some nuclear models have to be used to subtract the contributions from other nucleons to extract the information on neutrons. So, the Barely Off-shell Nucleon Structure (BONuS12) experiment at Jefferson Lab was conducted to overcome these challenges by using spectator tagging. The experiment effectively created a quasi-free neutron target by scattering electrons off a deuterium target and detecting low-momentum, backward-moving protons using a custom-built Radial Time Projection Chamber (RTPC). Selecting the low momentum and backward-moving spectators would enable us to minimize the model-dependent effects due to final state interactions and target fragmentation. The RTPC was a 40 cm-long cylindrical detector that works on the principle of gaseous ionization. It had three layers of Gas Electron Multipliers (GEMs) for charge amplification and a surrounding readout pad. The scattered electrons were measured using the CLAS12 detector, and data were collected using a 10.4 GeV electron beam dur ing Spring and Summer 2020. Using spectator tagging, we extracted the structure function ratio Fn 2 of the quasi-free neutron in the deep inelastic scattering at high x, upto x ~ 0.8. The result was extracted in the region with the invariant mass W > 1.8 GeV/c2, and Q2 in the range 1.3 to 11 GeV2. This dissertation presents the methodology, event selection criteria and refinements, estimation and subtraction of backgrounds, and complete analysis of extraction of Fn 2/Fp 2 in a model-independent way. Also, systematic uncertainties in our final analysis will be discussed in detail.

Pokhrel, Madhusudhan [Old Dominion Univ., Norfolk,↗

Reverse-mode differentiation in arbitrary tensor network format: with application to supervised learning.

This paper describes an efficient reverse-mode differentiation algorithm for contraction operations of tensor networks that may have arbitrary and unconventional network topologies. The approach leverages the tensor contraction tree of Evenbly and Pfeifer (2014), which provides an instruction set for the contraction sequence of a network. We show that this tree can be efficiently leveraged for differentiation of a full tensor network contraction using a recursive scheme that exploits (1) the bilinear property of contraction and (2) the property that trees have single path from root to leaves. While differentiation of tensor-tensor contraction is already possible in most automatic differentiation packages, we show that exploiting these two additional properties in the specific context of contraction sequences can improve efficiency. Following a description of the algorithm and computational complexity analysis, we investigate its utility for gradient-based supervised learning for low-rank function recovery and for fitting real-world unstructured datasets. We demonstrate improved performance over alternating least-squares optimization approaches and the capability to handle heterogeneous and arbitrary tensor network formats. When compared to alternating minimization algorithms, we find that the gradient-based approach requires a smaller oversampling ratio (number of samples compared to number model parameters) for recovery. This increased efficiency extends to fitting unstructured data of varying dimensionality and when employing a variety of tensor network formats. Here, we show improved learning using the hierarchical Tucker method over the tensor-train in high-dimensional settings on a number of benchmark problems.

97 MATHEMATICS AND COMPUTING↗

A Measurement of νe Appearance and νµ Disappearance Using 10 Years of Data from the NOvA Experiment

NOvA is a long baseline neutrino experiment with an 810 km baseline, using the NuMIbeam at Fermilab, and a functionally identical near and far detector operating at an angle14 mrad off axis from the beam. NOvA jointly measures muon neutrino (and antineutrino)disappearance and electron neutrino (and antineutrino) appearance to make a measurementof sin2θ23, δCP, and ∆m232, including its sign, the mass ordering.This dissertation reports a new measurement from NOvA, using 10 years of data, with a totalexposure of 26.6 ×1020 POT of neutrino beam and 12.5 ×1020 POT of antineutrino beam.This represents 95.6% more neutrino beam exposure since the last NOvA analysis. Aspects ofthe analysis are discussed in detail, including neutrino energy estimation, analysis systematicuncertainties, including the implementation of systematics new to the NOvA analysis, andthe Bayesian fit infrastructure using Markov Chain Monte Carlo (MCMC).The analysis yields the following credible intervals for the oscillation parameters assumingthe normal ordering: δCP = 0.930+0.210−0.290 π ∪0.150+0.150−0.110 π,∆m232 = 2.424+0.035−0.040 × 10−3eV2,and sin2θ23 = 0.55+0.02−0.06, with a 76% preference for normal ordering using a prior for sin2(2θ13)using Daya Bay’s measurement. If the Daya Bay sin2(2θ13) vs ∆m232 constraint is used as aprior instead, an 87% preference for normal ordering emerges.

43 PARTICLE ACCELERATORS↗

Hybrid Cooling and Water Treatment for Resilient, Water-Self-Sufficient Data Centers

The continued growth of data center infrastructure is intensifying demand for freshwater resources, particularly in water-stressed regions, and is increasingly limiting sustainable capacity expansion. This work investigates a conceptual hybrid system that integrates freeze desalination with ultrasonic-assisted ice separation to enable on-site production of pure water from diverse sources, including seawater, brackish groundwater, and reclaimed industrial or agricultural wastewater. Simultaneously, the system produces low-temperature cooling streams that enhance heat removal in high power density computing environments. A process-level thermodynamic analysis is performed across a range of boundary and operating conditions, including variations in feed concentration, freezing temperature, and mass flow rate. The results are presented as performance curves relating feedwater concentration and target purified water output to the corresponding intake flow requirements, enabling estimation of source water demand per unit of Information Technology Equipment (ITE) energy consumption (kWh) across varying data center scales and operational scenarios. The corresponding electrical energy consumption for integrated cooling and water treatment is also evaluated as a function of system operating parameters and target water production levels. These results provide a basis for evaluating system feasibility across different conditions and for identifying parameter ranges in which integrated water treatment and cooling improve resource efficiency, thermal performance, and operational flexibility in data centers.

Elhefny, Aly [ORNL] (ORCID:0000000284907923)↗

V1G Frequency Regulation: Algorithm Development, Validation & Analysis at Scale

Researchers at Argonne National Laboratory developed and validated a high-fidelity digital twin of a smart charging (V1G) ecosystem to model the participation of up to 1,000 unique electric vehicles (EVs) in the PJM frequency regulation market. Utilizing a discrete-event framework, the simulation models complex interactions, from dynamic grid signals (updated every 2 seconds) to individual EV charging dynamics. The simulation incorporates multiple EV models created from real-world lab test data. Researchers tested multiple control algorithms to balance the dual objectives of maximizing aggregator’s revenue and driver charging needs. Results demonstrate that aggregated EVs function as a controllable, highly effective grid resource, achieving high PJM Performance Scores (80–90%). Additionally, an optimized, market-aware bidding strategy was identified as key to profitability. The platform was shown to provide drivers with an average charging discount of nearly 50%. The algorithm was further validated in the lab using production EVs and charging stations to compare simulation results with real-world performance.

Manne, Nithin↗

A generalized power-law criterion for rocks based on Mohr failure theory

Nonlinearity of Mohr envelopes confirmed by past laboratory test data can be of considerable importance in theoretical interpretation of rock strength behaviors and many practical applications. Current nonlinear failure criteria are introduced with parameters to empirically fit test data, and the physical and mechanical meanings of these fitting parameters are often not known. Predicted strengths by theoretical criteria (e.g., Griffith criterion) generally do not agree well with test data. Considering the nonlinear properties of a Mohr envelope, a nonlinear failure criterion in a generalized power-law form is derived in this paper based on strength magnitude coefficient (a) and failure envelope curvature coefficient (n) which are expressed in terms of uniaxial tensile strength, uniaxial compressive strength, and angle of internal friction. Test data on granite, marble, dolomite, and andesite from published literature were chosen to test the performance of the proposed criterion along with Griffith and Hoek-Brown criteria. Statistical analysis was performed to evaluate the application of different criteria in predicting the strength of rocks. In addition, some Griffith-typed criteria are mathematically shown to be the special cases of the proposed criterion. The proposed and Hoek-Brown criteria have similar power-law forms with a significant difference in the coefficient functions that govern the shear strength magnitude of rock. The different tensile and compressive failure mechanisms are also investigated from the perspective of the relationship between the uniaxial tension Mohr circle and the proposed failure envelope.

58 GEOSCIENCES↗

Low-lying states and total internal partition sums of CH

The electronic structure and spin-orbit states of the CH radical have been systematically investigated using multi-reference configuration interaction (MRCI) and single-reference coupled-cluster (CC) methods. These calculations were performed in conjunction with large correlation-consistent basis sets of quadruple-, quintuple-, and sextuple-ζ quality. To achieve high accuracy, electronic energies for all states were extrapolated to the complete basis set (CBS) limit, enabling the detailed construction of potential energy curves and determination of reliable spectroscopic constants. Spin-orbit coupling effects were explicitly incorporated, and vibrational energy levels were computed via Numerov analysis. Furthermore, the resulting values exhibit good to excellent agreement with available experimental data. Dipole moment and transition dipole moment curves were evaluated to assess the opacity characteristics of CH, revealing that transitions such as Χ 2 Π (u′′ = 0) → Α 2 Δ (u′ = 0), Χ 2 Π (u′′ = 0) → Β 2 Σ − (u′ = 0), Χ 2 Π (u′′ = 0) → C 2 Σ + (u′ = 0), and Χ 2 Π (u′′ = 0) → D 2 Σ + (u′ = 3) are particularly probable. Finally, the total internal partition function sum (TIPS) of CH was computed over a broad temperature range (10–30,000 K) based on our high-accuracy ab initio results.

74 ATOMIC AND MOLECULAR PHYSICS↗

Unveiling X-ray absorption signatures of boron nitride via first-principles simulation and machine learning

Boron nitride (BN) allotropes hold great promise in many advanced applications ranging from optical and photonic devices to energy storage and battery systems to tribological components. The diverse functionalities of this material stem from BN’s highly tunable structural and electronic properties, which are governed by the versatile boron–nitrogen bonding configurations. Exploring the structural landscape of BN can unveil novel structures possessing unique properties suited for specific applications, therefore accelerating the design of next-generation advanced functional materials. In this work, we leverage boron K-edge X-ray absorption spectroscopy (XAS) as an effective probe for local structural features and chemical environments. A total of 210 BN crystal structures are generated via analogies to the extensive array of carbon allotropes, and XAS is simulated for each unique local motif within the resulting collection of structures. A mapping between structural features and spectral signatures was established by synergizing first-principle simulations with data-driven based post-analysis approaches. Specifically, we developed a neural network model that can satisfactorily predict spectra line shapes from local structural descriptors. Toward automatic spectroscopic interpretation of any new BN structures, supervised machine learning models, trained on this structure–spectrum dataset, can accurately infer local coordination environments from simulated XAS, highlighting the strength of this unique approach of combining high-fidelity first-principles simulation and machine-learning to accelerate target design of novel BN materials via rational understanding of local structure-spectrum correlations.

36 MATERIALS SCIENCE↗

Ambient and High Pressure CuNiSb 2 : Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides

The mineral Zlatogorite, CuNiSb 2 , was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb 2 -AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb 2 -AP crystallizes in the NiAs-derived structure ( P 3 m 1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb 6 and CuSb 6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure ( P 6 3 / mm c, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb 2 -AP. The magnetic measurement indicates that CuNiSb 2 -AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb 2 -AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb 2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb 2 -8 GPa) was prepared by pressing CuNiSb 2 -AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb 2 -8 GPa are best fit with a disordered metal structure in the P 3 m 1 space group, corroborated by transmission electron microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗