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At least 847 records · Page 47

Multilayered graphene acquires ferromagnetism in proximity with magnetite particles

Anisotropic diamagnetism of pristine graphite and graphene is well known. Here, evidence of significant induced ferromagnetism in multilayer graphene (MLG) decorated with ferrimagnetic Fe{sub 3}O{sub 4} particles is reported. This MLG-Fe{sub 3}O{sub 4} nano-composite was prepared by a one-step ultrasonic treatment at 75 °C in the surfactant sodium dodecyl-benzene-sulfonate. To verify the phase structure and morphology of the composite, X-ray diffraction, scanning and transmission electron microscopy, scanning tunneling electron microscopy, and Raman spectroscopy were employed. Room temperature data of magnetization versus magnetic field showed that the saturation magnetization M{sub S} = 58.6 emu/gm for pristine Fe{sub 3}O{sub 4} increased to M{sub S} = 158.4 emu/gm for a 1:1 composite of Fe{sub 3}O{sub 4} to MLG. These results lead to induced M{sub S} = 253 emu/gm in MLG resulting from its proximity to Fe{sub 3}O{sub 4}. Similar experiments on Fe{sub 3}O{sub 4} to single walled carbon nanotubes (SWNT) composite did not show any induced magnetism in SWNT.

36 MATERIALS SCIENCE↗

An Analysis of Simulated and Observed Global Mean Near-Surface Air Temperature Anomalies from 1979 to 1999: Trends and Attribution of Causes

The 1979 - 1999 response of the climate system to variations in solar spectral irradiance is estimated by comparing the global averaged surface temperature anomalies simulated by a 2D (two dimensional) energy balance climate model to observed temperature anomalies. We perform a multiple regression of southern oscillation index and the individual model responses to solar irradiance variations, stratospheric and tropospheric aerosol loading, stratospheric ozone trends, and greenhouse gases onto each of five near-surface temperature anomaly data sets. We estimate the observed difference in global mean near surface air temperature attributable to the solar irradiance difference between solar maximum and solar minimum to be between 0.06 and 0.11 K, and that 1.1 - 3.8% of the total variance in monthly mean near-surface air temperature data is attributable to nations in solar spectral irradiance. For the five temperature data sets used in our analysis, the trends in raw monthly mean temperature anomaly data have a large range, spanning a factor of 3 from 0.06 to 0.17 K/decade. However. our analysis suggests that trends in monthly temperature anomalies attributable to the combination of greenhouse gas, stratospheric ozone, and tropospheric sulfate aerosol variations are much more consistent among data sets, ranging from 0.16 to 0.24 K/decade. Our model results suggest that roughly half of the warming from greenhouse gases is cancelled by the cooling from changes in stratospheric ozone. Tropospheric sulfate aerosol loading in the present day atmospheric contributes significantly to the net radiative forcing of the present day climate system. However, because the change in magnitude and latitudinal distribution of tropospheric sulfate aerosol has been small over the past 20 years, the change in the direct radiative forcing attributable to changes in aerosol loading over this time is also small.

MacKay, R. M.↗

Granular Temperature Modeling with Large-Scale CFD-DEM Data

The granular temperature is a measure of solids-phase fluctuating kinetic energy in particle-laden gas-solid flows. This report focuses on reduced-order models of granular temperature in triply-periodic cluster induced turbulent flow. The granular temperature data was generated by post-processing large-scale CFD-DEM simulations that were carried out as part of an ALCC awarded study. The algebraic model of Tang et al, originally fit to DNS data, was found to be amenable to the present data. The results of several regression analyses are presented building on the original expression. This work was performed in part through the National Nuclear Security Administration (NNSA) Minority Serving Institutions Internship Program (MSIIP).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supervisory Control and Data Acquisition for Electrochemical Separation Experimentation

The Python-based program is a laboratory automation tool designed to control and monitor electrochemical systems. The tool was developed for capacitive deionization (CDI) experiments, but it can be used for any system that requires controlled voltage or current segments and multi-parameter monitoring. The program integrates hardware components to run user-defined experimental parameters, providing operational control of a programmable power supply, peristaltic pump, and data acquisition devices. Currently, the program is structured with a workflow that includes an initialization (or pre-run) phase, a main loop, and a post-experiment stabilization (or post-run) phase. The initialization phase prepares and stabilizes the cell, ensuring that the electrodes and solution reach a baseline state before the experiment begins. The main loop consists of multiple voltage segments that repeat, controlling the experiment while recording key parameters such as time, voltage, current, pH, and conductivity. Finally, the post-experiment stabilization phase allows the system to stabilize after the experiment, returning the cell and solution to equilibrium conditions before ending the sequence. The program is designed with four variations, each tailored to different experimental needs. All variations include both the initialization and post-experiment stabilization stages, which run for a set amount of time, voltage, current, and flow rate before and after the main experiment block. The main loop runs for a set number of cycles, as defined by the user input, and each cycle is composed of 2 or 4 segments. The 4 program variations are described as follows: Program 1: The main program includes 2 segments. Each segment is defined to have a set duration, flow rate, voltage, and current. This program measures conductivity, flow rate, voltage, and current. Program 2: The main program expands Program 1 to include 4 segments. Each segment has a specified duration, flow rate, voltage, and current. Like Program 1, it measures conductivity, flow rate, voltage, and current. Program 3: The main program consists of 2 segments, each defined by time, flow rate, voltage, and current. In addition to conductivity, flow rate, voltage, and current, Program 3 collects pH and temperature data through a 4-channel data acquisition device. Program 4: This program independently controls two channels of a multi-channel power supply simultaneously. While conductivity can only be measured for one cell at a time, the dual-channel control makes it possible to operate two cells simultaneously under different voltage/current conditions. The main program includes 2 segments.For each program, all measurements are automatically logged and integrated into a single Excel output file. Data are displayed in numerical format and plotted, both in real time, to track system performance. A key feature of the program is its ability to synchronize all outputs so that every measurement shares a single timestamp, ensuring accurate alignment of voltage, current, pH, conductivity, and pH data.By combining hardware control, real-time monitoring, and unified data collection, this program significantly reduces manual workload and minimizes errors, making it a reliable platform for researchers, engineers, and laboratory technicians conducting CDI experiments, among other electrochemical tests.

Valentino, Lauren [Argonne National Laboratory (AN↗

Evaluation of the Paratrend Multi-Analyte Sensor for Potential Utilization in Long-Duration Automated Cell Culture Monitoring

BACKGROUND: Compact and automated sensors are desired for assessing the health of cell cultures in biotechnology experiments. While several single-analyte sensors exist to measure culture health, a multi-analyte sensor would simplify the cell culture system. One such multi-analyte sensor, the Paratrend 7 manufactured by Diametrics Medical, consists of three optical fibers for measuring pH, dissolved carbon dioxide (pCO(2)), dissolved oxygen (pO(2)), and a thermocouple to measure temperature. The sensor bundle was designed for intra-vascular measurements in clinical settings, and can be used in bioreactors operated both on the ground and in NASA's Space Shuttle and International Space Station (ISS) experiments. METHODS: A Paratrend 7 sensor was placed at the outlet of a bioreactor inoculated with BHK-21 (baby hamster kidney) cells. The pH, pCO(2), pO(2), and temperature data were transferred continuously to an external computer. Cell culture medium, manually extracted from the bioreactor through a sampling port, was also assayed using a bench top blood gas analyzer (BGA). RESULTS: Two Paratrend 7 sensors were used over a single cell culture experiment (64 days). When compared to the manually obtained BGA samples, the sensor had good agreement for pH, pCO(2), and pO(2) with bias (and precision) 0.005(0.024), 8.0 mmHg (4.4 mmHg), and 11 mmHg (17 mmHg), respectively for the first two sensors. A third Paratrend sensor (operated for 141 days) had similar agreement (0.02+/-0.15 for pH, -4+/-8 mm Hg for pCO(2), and 24+/-18 mmHg for pO(2)). CONCLUSION: The resulting biases and precisions are com- parable to Paratrend sensor clinical results. Although the pO(2) differences may be acceptable for clinically relevant measurement ranges, the O(2) sensor in this bundle may not be reliable enough for the ranges of pO(2) in these cell culture studies without periodic calibration.

Validation Studies↗

NGEE Arctic Soil Micro-warming Experiment Temperature Profiles, Council Road Mile Marker 71, Seward Peninsula, Alaska, 2017-2019

The reported soil temperature profile measurements (24 locations - 2 probes with 5 and 6 thermistors, respectively - Fig. 1 and Fig. 2) were initiated as part of a soil micro-warming experiment at the Council Road Mile Marker 71 Site (CN_MM71) in September 2017. From 2017 through August 2019, these were measurements of ambient pre-treatment plot conditions. This tussock tundra site (with underlying permafrost) experiences annual frost heaving that causes a vertical movement of the ground surface, hence causing some of the upper most temperature thermistors to be at surface level or above ground and recorded therefore air temperatures near the surface and not below ground soil temperature (see section on Quality Assurance). After August 2019, these measurements ended in preparation for transitioning to the experimental warming of individual plots. The reported temperature data are nominally 3-hour averages of measurements made at varying frequencies (3-hour maximum) with frequencies that depended upon power (solar) availability to operate the sensors (see section in documentation on Methods). The number of values and the standard deviation for each 3-hour average (where appropriate) are also provided. These measurements are located near the NGEE-Arctic CO2 and CH4 eddy covariance tower at the Council Road Site (US-NGC: NGEE Arctic Council, https://ameriflux.lbl.gov/sites/siteinfo/US-NGC#overview) and auxiliary data at https://doi.org/10.5440/1526749. This dataset contains four *.csv files and one *.pdf file. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Use of Frit‐Disc Crucible Sets to Make Solution Growth More Quantitative and Versatile

The recent availability of step‐edge, frit‐disc crucible sets (generally sold as Canfield Crucible Sets or CCS) has led to multiple innovations associated with the group's use of solution growth. The use of CCS allows for the clean separation of liquid from solid phases during the growth process. This clean separation enables the reuse of the decanted liquid, either allowing for simple, economic, savings associated with recycling expensive precursor elements or allowing for the fractionation of a growth into multiple, small steps, revealing the progression of multiple solidifications. Clean separation of liquid from solid phases also allows for the determination of the liquidus line (or surface) and the creation, or correction, of composition–temperature phase diagrams. The reuse of clean decanted liquid has also allowed to prepare liquids ideally suited for the growth of large single crystals of specific phases by tuning the composition of the melt to the optimal composition for growth of the desired phase, often with reduced nucleation sites. Finally, it is discussed how solution growth and CCS use can be harnessed to provide a plethora of composition–temperature data points defining liquidus lines or surfaces with differing degrees of precision to either test or anchor artificial intelligence and/or machine‐learning‐based attempts to augment and extend the limited experimentally determined database.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling the effect of climate change on U.S. state-level buildings energy demands in an integrated assessment framework

As long-term socioeconomic transformation and energy service expansion show large spatial heterogeneity, advanced understanding of climate impact on building energy use at the sub-national level will offer useful insights into climate policy and regional energy system planning. In this study, we presented a detailed building energy model with a U.S. state-level representation, nested in the GCAM integrated assessment framework. We projected state-level building energy demand and its spatial pattern over the century, considering the impact of climate change based on the estimates of heating and cooling degree days derived from downscaled USGS CASCaDE temperature data. The result indicates that climate change has a large impact on heating and cooling building energy and fuel use at the state level, exhibiting large spatial heterogeneity across states (ranges from -10% to +10%). The sensitivity analysis reveals that the building energy demand is subject to multiple key factors, such as the magnitude of climate change, the choice of climate models, and the growth of population and GDP, and that their relative contributions vary greatly across the space. The scale impact in building energy use modeling highlights the importance of constructing a building energy model with the spatially-explicit representation of socioeconomics, energy system development, and climate change. These findings will help the climate-based policy decision and energy system, especially utility planning related to building sector at the U.S. state and regional level facing the potential climate change.

Building Energy Demand, Climate Change Impact, Sta↗

Critical heat flux on zircaloy and accident tolerant fuel cladding under prototypical conditions of pressurized and boiling water reactors

First of a kind high spatial and temporal resolution temperature measurements of Pressurized Water Reactor and Boiling Water Reactor simulated fuel pins (high heat flux cosine profile heaters) in annular rod type geometry during nucleate boiling, departure from nucleate boiling and re-wetting has been performed. Distributed fiber optic measurements of the cladding axial temperature with spatial resolutions down to 2.5 mm axially at up to three equally spaced azimuthal locations per rod have demonstrated the similarities and differences of the different accident tolerant fuel cladding materials. These experiments show the performance of accident tolerant cladding with a precise measurement of the location and evolution of dryout followed by the re-wetting phenomena (see supplementary time history of a critical heat flux event). Experimental parameters varied coolant mass fluxes from 1695 to 2712 kg/m 2 s, pressures from 10 to 20 MPa, and inlet subcooling from 10 to 55 °C. It was found that the coatings and different material have little effect on the value of the critical heat flux. Any discrepancies between the local critical heat flux verified among the cladding material are attributed to different departure from nucleate boiling phenomena captured during the experiment with the high-resolution optical fiber temperature data. Substantial differences in the performance of the different cladding material to survive a critical heat flux event were however observed by post-test X-ray and optical inspection. External evident damage and internal cracks to the simulated fuel pin having the bare zircaloy cladding were observed in regions associated with the occurrence of the critical heat flux for longer periods. Such damages were associated with zirconium oxidation, and not noticed on the Cr coated zircaloy or FeCrAl claddings. These results indicate that the use of FeCrAl or a Cr coated zircaloy as cladding in Pressurized Water Reactor and Boiling Water Reactor may increase the survivability of the cladding material for short transients.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

iMatTOUGH: An open-source Matlab-based graphical user interface for pre- and post-processing of TOUGH2 and iTOUGH2 models

TOUGH2 and iTOUGH2 are powerful models that simulate the heat and fluid flows in porous and fracture media, and perform parameter estimation, sensitivity analysis and uncertainty propagation analysis. However, setting up the input files is not only tedious, but error prone, and processing output files is time consuming. Here, we present an open source Matlab-based tool (iMatTOUGH) that supports the generation of all necessary inputs for both TOUGH2 and iTOUGH2 and visualize their outputs. The tool links the inputs of TOUGH2 and iTOUGH2, making sure the two input files are consistent. It supports the generation of rectangular computational mesh, i.e., it automatically generates the elements and connections as well as their properties as required by TOUGH2. The tool also allows the specification of initial and time-dependent boundary conditions for better subsurface heat and water flow simulations. The effectiveness of the tool is illustrated by an example that uses TOUGH2 and iTOUGH2 to estimate soil hydrological and thermal properties from soil temperature data and simulate the heat and water flows at the Rifle site in Colorado.

58 GEOSCIENCES↗

Reactions of Propyl Radicals: A Shock Tube - VUV Photoionization Mass Spectrometry Study

The pyrolytic reactions of n-propyl and i-propyl radicals and their precursors have been investigated at elevated temperatures and pressures (600 – 900 K and 5 – 8 bar). The studies were performed in a miniature high repetition rate shock tube with synchrotron vacuum ultraviolet photoionization mass spectrometry yielding comprehensive datasets of temporal and photoionization energy dependencies of reagents and products. The propyl radicals were generated by pyrolysis of alkyl nitrites. In addition to the main decomposition path, NO elimination, the mass spectra allowed an alternative minor path via HNO elimination to be identified and quantified. For the n-propyl precursor the HNO elimination route accounted for 9% of the alkyl nitrite while for the i-propyl precursor it was 2.5%. These values are in good agreement with a recent study on i-butyl radicals in the same apparatus at similar conditions. The ratio of disproportionation/recombination was obtained for n- propyl from the relative concentrations of n-hexane and propene and for i-propyl from 2,3-dimethyl butane and propene. For n-propyl the ratio is 0.3 and 1.2 for i-propyl, both are independent of temperature and pressure over the experimental range. The disproportionation/recombination ratios are about a factor of 2 higher than prior evaluations that are based mainly on room temperature data. The experimental results are some of the first from the apparatus used and comments are made about the technique, challenges encountered, and suggestions for future developments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-CMB fluctuations and the Hubble tension

We study the covariance in the angular power spectrum estimates of CMB fluctuations when the primordial fluctuations are non-Gaussian. The non-Gaussian covariance comes from a nonzero connected four-point correlation function -- or the trispectrum in Fourier space -- and can be large when long-wavelength (super-CMB) modes are strongly coupled to short-wavelength modes. The effect of such non-Gaussian covariance can be modeled through additional freedom in the theoretical CMB angular power spectrum and can lead to different inferred values of the standard cosmological parameters relative to those in ΛCDM. Taking the collapsed limit of the primordial trispectrum in the quasi-single field inflation model as an example, we study how the six standard ΛCDM parameters shift when two additional parameters describing the trispectrum are allowed. The reduced statistical significance of the Hubble tension in the extended model allows us to combine the {\it Planck} temperature data and the type Ia supernovae data from Panstarrs with the distance-ladder measurement of the Hubble constant. Here, this combination of data shows strong evidence for a primordial trispectrum-induced non-Gaussian covariance, with a likelihood improvement of Δχ 2 ≈ –15 (with two additional parameters) relative to ΛCDM.

79 ASTRONOMY AND ASTROPHYSICS↗

Discrete Green’s functions and spectral graph theory for computationally efficient thermal modeling

Here, this work concerns solutions of the heat equation with the spectral graph method, for which the temperature is defined at discrete points in the domain and the spatial relationship among the points is described by a graph. The heat equation on the graph is solved using matrix techniques involving the eigenvectors and eigenvalues of the Laplacian matrix. The spectral graph approach precludes the computationally intensive meshing and numerous time-integration steps of the finite element method. In the present work, the spectral graph method is extended to include heat loss at the boundaries with a generalized boundary condition, and physics-based edge weights are introduced which simplify the calibration process. From this approach a discrete Green’s function is defined which allows for solutions under a variety of heating conditions including: space-varying initial conditions; time-and-space varying internal heating; and, time-and-space-varying heating at boundaries of type 1 (Dirichlet), type 2 (Neumann) and type 3 (Robin). Results are provided for benchmark heat transfer problems in one spatial dimension and in three spatial dimensions, and verification is provided by comparison with exact analytical solutions and finite difference solutions. The spectral graph method converges within 0.4% error of the analytical solution. The practical utility of the approach is demonstrated by thermal simulation of a multilayer additive manufacturing process. The spectral graph results are compared to experimentally-obtained temperature data for two metal parts, with error less than 5% of the experimental measurements, with computation time less than one minute on a desktop computer.

36 MATERIALS SCIENCE↗

Parametric study of residual stress formation in Wire and Arc Additive Manufacturing

Here, a finite element model was created to simulate the Wire Arc Additive Manufacturing (WAAM) thermal and mechanical processes of Inconel 718 on a A36 steel substrate, as well as the effects of process parameters on Residual Stress (RS). The model was verified using temperature data obtained from three thermocouples attached to the upper surface of the build substrate and micro-strain measurements obtained from Neutron Diffraction (ND) measurement. The model was then used to study the effects of changing the torch travel speed and interlayer dwell time. The study found that travel speed has little effect on RS when maintaining the same heat input rate. As well, the interlayer dwell time has a strong effect on RS. Reducing the dwell time causes the stress profiles to become relatively uniform and a high-stress region extends deeper along the build direction. This study provides important insight into mechanical stresses inside large walls made by the WAAM method.

36 MATERIALS SCIENCE↗

Effects of cycling temperatures on the voltage fade phenomenon in 0.5Li 2 MnO 3 ·0.5LiNi 0.375 Mn 0.375 Co 0.25 O 2 cathodes

The rate of voltage fade in 0.5Li2MnO3•0.5LiNi0.375Mn0.375Co0.25O2 cathodes was measured in half-cells in a temperature range of 25 to 55°C. On the basis of the dependence of the values of the open-circuit potential with cycle count and temperature, the voltage fade phenomenon seems to consist of two chemical processes: one that can be described using a parabolic rate law and another that uses a linear-with-time law. As the cycling temperature increased, the relative contributions of the two processes changed. On the basis of the overall rate versus temperature data, we believe the two processes may be in competition with one another.

kinetics↗

Direct measurements of channel specific rate constants in OH + C 3 H 8 illuminates prompt dissociations of propyl radicals

OH + molecules are an important class of reactions in combustion and atmospheric chemistry. Consequently, numerous studies have measured rate constants for these processes over an extended temperature range. A large majority of these experimental studies have utilized the decay of [OH] profiles (monitored either by absorption or laser-induced fluorescence) to obtain total rate constants. However, there are limited direct measurements of channel specific rate constants in this important class of reactions, particularly at combustion relevant temperatures. In the present experiments, we have directly measured site-specific rate constants for abstraction of the secondary C–H bond in OH + C 3 H 8 at high temperatures. Atomic resonance absorption spectrometry (ARAS) was used to monitor the formation of H-atoms from shock-heated mixtures of tert-butylhydroperoxide and C 3 H 8 at high temperatures. Simulations for the experimental H-atom profiles are sensitive only to abstraction of the secondary C–H bond leading to unambiguous measurements of the rate constants for this reaction. Over the T-range, 921 K < T < 1146 K, rate constants from the present experiments for OH + C 3 H 8 →H 2 O + i-C 3 H 7 can be represented by the Arrhenius expression, k = (3.935 ± 1.387) × 10-11 exp(-1681 ± 362 K/T )cm 3 molecule -1 s -1 Simulations of the lower temperature data (T < 1000 K) indicate that the H-atom profiles are also influenced to a minor extent by the thermal dissociation of iso-propyl, i-C 3 H 7 →H + C 3 H 6 , at short time-scales.

Shock Tube, H-ARAS, Prompt Dissociation, Bimolecul↗