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At least 487 records · Page 27

Nanomechanical testing of freestanding polymer films: in situ tensile testing and Tg measurement

Abstract A method for small-scale testing and imaging of freestanding, microtomed polymer films using a push-to-pull device is presented. Central to this method was the development of a sample preparation technique which utilized solvents at cryogenic temperatures to transfer and deposit delicate thin films onto the microfabricated push-to-pull devices. The preparation of focused ion beam (FIB)-milled tensile specimens enabled quantitative in situ TEM tensile testing, but artifacts associated with ion and electron beam irradiation motivated the development of a FIB-free specimen preparation method. The FIB-free method was enabled by the design and fabrication of oversized strain-locking push-to-pull devices. An adaptation for push-to-pull devices to be compatible with an instrumented nanoindenter expanded the testing capabilities to include in situ heating. These innovations provided quantitative mechanical testing, postmortem TEM imaging, and the ability to measure the glass transition temperature, via dynamic mechanical analysis, of freestanding polymer films. Results for each of these mentioned characterization methods are presented and discussed in terms of polymer nanomechanics. Graphic Abstract

36 MATERIALS SCIENCE↗

Selective Adsorption of Thiol-Containing Molecules on Copper Sulfide Surfaces via Molecule–Surface Disulfide Bridges

Recent results in the fields of nanoenhanced agriculture and expanding interest in prebiotic chemistry have placed increased emphasis on understanding the chemically selective interaction of small molecules with the surfaces of metal sulfides. Here, we present an integrated experimental and computational study of the interaction of thiol-containing molecules with copper sulfide (covellite) surfaces in aqueous media. In situ Fourier-transform infrared (FTIR) measurements and ex situ X-ray photoelectron spectroscopy (XPS) measurements show that molecules bearing free thiol groups, including glutathione and cysteine, bind strongly to CuS (covellite) nanoparticles and to CuS (001) single crystals, while control studies show that similar molecules lacking the free thiol group exhibit much less binding. Additional experiments show that these thiol-containing molecules interact transiently with CuO nanoparticle surfaces but are readily removed by rinsing. The FTIR and XPS experiments demonstrate that adsorption of molecular thiols to CuS surfaces occurs in a chemically selective manner. Further experimental studies and density functional calculations show that the preferred mode of binding is through the surface S atoms, forming a Solid–S–S–Molecule disulfide linkage. While the role of disulfide linkages in controlling structure and function of proteins and other biomolecules is widely known, the formation of surface disulfide linkages as a motif for covalent molecular binding at surfaces has not been established previously.

36 MATERIALS SCIENCE↗

Three-dimensional phenotyping of peach tree-crown architecture utilizing terrestrial laser scanning

Tree training systems for temperate fruit have been developed throughout history by pomologists to improve light interception, fruit yield, and fruit quality. These training systems direct crown and branch growth to specific configurations. Quantifying crown architecture could aid the selection of trees that require less pruning or that naturally excel in specific growing/training system conditions. Regarding peaches [Prunus persica (L.) Batsch], access tools such as branching indices have been developed to characterize tree-crown architecture. However, the required branching data (BD) to develop these indices are difficult to collect. Traditionally, BD have been collected manually, but this process is tedious, time-consuming, and prone to human error. These barriers can be circumnavigated by utilizing terrestrial laser scanning (TLS) to obtain a digital twin of the real tree. TLS generates three-dimensional (3D) point clouds of the tree crown, wherein every point contains 3D coordinates (x, y, z). To facilitate the use of these tools for peach, we selected 16 young peach trees scanned in 2021 and 2022. These 16 trees were then modeled and quantified using the open-source software TreeQSM. As a result, “in silico” branching and biometric data for the young peach trees were calculated to demonstrate the capabilities of TLS phenotyping of peach tree-crown architecture. The comparison and analysis of field measurements (in situ) and in silico BD, biometric data, and quantitative structural model branch uncertainty data were utilized to determine the reconstructive model’s reliability as a source substitute for field measurements. Mean average deviation when comparing young tree (YT) height was approx. 5.93%, with crown volume was approx. 13.26% across both 2021 and 2022. All point clouds of the YTs in 2022 showed residuals lower than 12 mm to cylinders fitted to all branches, and mean surface coverage greater than 40% for both the trunk and primary branching orders.

09 BIOMASS FUELS↗

Laboratory Evaluation of the Thermal Breakout Method for Maximum Horizontal Stress Measurement

Measuring in situ stress is essential for many problems in geomechanics, and the maximum horizontal stress is the most difficult to constrain. We are developing an extension of the breakout method to measure maximum horizontal stress in regions where natural breakouts do not occur. In the novel thermal breakout method, additional compression which leads to breakout development is induced by heating the borehole wall. In the present study, we validated the method experimentally in a true-triaxial apparatus on samples with predrilled boreholes. Two rocks were selected for laboratory testing: high-porosity Berea sandstone and low-porosity Niagaran dolomite. Prior to main true-triaxial tests, we carried out standard testing to characterize the strength, elasticity and thermal properties. The true-triaxial experiments consisted of: (1) room-temperature tests where samples were first loaded mechanically until the breakout formed, and (2) elevated-temperature tests where samples were loaded mechanically within the elastic range with additional compression induced thermally. Breakout initiation was monitored by acoustic emission sensors mounted on the pistons that applied horizontal stresses. Furthermore, the magnitude of induced thermal stress was calculated from temperature measurements around the borehole wall. In both rock types, we created thermally induced breakouts and examined analytical expressions to constrain maximum horizontal stress based on strength, elastic and thermal properties of the rocks.

58 GEOSCIENCES↗

Effect of particle size on thermodynamics and lithium ion transport in electrodes made of Ti 2 Nb 2 O 9 microparticles or nanoparticles

This study compares the charging mechanisms, thermodynamics, lithium ion transport, and operando isothermal calorimetry in lithium-ion battery electrodes made of Ti 2 Nb 2 O 9 microparticles or nanoparticles synthesized by solid-state or sol-gel methods, respectively. First, electrochemical testing showed that electrodes made of Ti 2 Nb 2 O 9 nanoparticles exhibited larger specific capacity, smaller polarization, and better capacity retention at large currents than those made of Ti 2 Nb 2 O 9 microparticles. Furthermore, potentiometric entropy measurements revealed that electrodes made of either Ti 2 Nb 2 O 9 microparticles or nanoparticles showed similar thermodynamics behavior governed by lithium intercalation in solid solution, as confirmed by in situ XRD measurements. However, electrodes made of Ti 2 Nb 2 O 9 nanoparticles featured smaller overpotential and faster lithium ion transport than those made of Ti 2 Nb 2 O 9 microparticles. In fact, operando isothermal calorimetry revealed smaller instantaneous and time-averaged irreversible heat generation rates at electrodes made of Ti 2 Nb 2 O 9 nanoparticles, highlighting their smaller resistive losses and larger electrical conductivity. Finally, the measured total heat generation over a charging/discharging cycle matched the measured net electrical energy loss. Overall, Ti 2 Nb 2 O 9 nanoparticles synthesized by the novel sol-gel method displayed excellent cycling performance and reduced heat generation as a fast-charging lithium-ion battery anode material. These features present major advantages for actual battery systems including larger energy and power densities, simpler thermal management, and enhanced safety.

25 ENERGY STORAGE↗

A roadmap to understanding and anticipating microbial gene transfer in soil communities

Engineered microbes are being programmed using synthetic DNA for applications in soil to overcome global challenges related to climate change, energy, food security, and pollution. However, we cannot yet predict gene transfer processes in soil to assess the frequency of unintentional transfer of engineered DNA to environmental microbes when applying synthetic biology technologies at scale. This challenge exists because of the complex and heterogeneous characteristics of soils, which contribute to the fitness and transport of cells and the exchange of genetic material within communities. Here, we describe knowledge gaps about gene transfer across soil microbiomes. Here, we propose strategies to improve our understanding of gene transfer across soil communities, highlight the need to benchmark the performance of biocontainment measures in situ, and discuss responsibly engaging community stakeholders. We highlight opportunities to address knowledge gaps, such as creating a set of soil standards for studying gene transfer across diverse soil types and measuring gene transfer host range across microbiomes using emerging technologies. By comparing gene transfer rates, host range, and persistence of engineered microbes across different soils, we posit that community-scale, environment-specific models can be built that anticipate biotechnology risks. Such studies will enable the design of safer biotechnologies that allow us to realize the benefits of synthetic biology and mitigate risks associated with the release of such technologies.

bioccontainment↗

Thermally Grown Oxide Stress in PS-PVD and EB-PVD Thermal Barrier Coatings Observed at Various Lifetimes Via Synchrotron X-ray Diffraction

The current standard application method for thermal barrier coatings (TBCs) on turbine blades for jet engines is electron-beam physical vapor deposition (EB-PVD) due to its high strain tolerance and low thermal conductivity. An emerging deposition method, plasma-spray physical vapor deposition (PS-PVD), presents an opportunity for a tailorable microstructure, and non-line-of-sight deposition that is faster and less expensive. To compare the lifetime behavior of both PS-PVD and EB-PVD coatings, samples subjected to 300 and 600 thermal cycles were measured during a 1 h thermal cycle to determine the strains, which were converted to stress, in the thermally grown oxide (TGO) layer of the TBCs using synchrotron X-ray diffraction (XRD). Room temperature XRD measurements indicated among samples that PS-PVD coatings experienced greater variation in in-plane room temperature strain in the TGO after cycling than the EB-PVD coatings. In-situ XRD measurements indicated similar high-temperature strain and no spallation after 600 thermal cycles for both coatings. Further, microscopy imaging after cycling showed greater rumpling in PS-PVD coatings that led to different failure modes between the two coatings’ TGO layers. The tailorability of PS-PVD coatings allows for adjustments in the processing parameters to improve their overall performance after aging and bridge the differences between the two deposition methods.

36 MATERIALS SCIENCE↗

Design Report on the MiniFuel Instrumented Test Apparatus for Understanding Radiation Effects

Most nuclear fuels irradiations at Oak Ridge National Laboratory (ORNL) over the past decade have been conducted using MiniFuel—a static capsule design employing subscale fuel specimens to collect separate-effects irradiated fuel performance data. Irradiation conditions for MiniFuel experiments are predicted pre-test using reactor physics, and thermal models are verified post-irradiation via SiC dilatometry and various spectrometry methods. Relevant fuel performance parameters are also observed post-irradiation in a hot cell, thereby providing a single data point for each parameter representing the cumulative effects of the irradiation conditions. Substantially more data can be harvested from a single test and within a shorter duration by instrumenting irradiation vehicles and measuring desired quantities in situ. This report presents the design and analysis of the MiniFuel INstrumented Irradiation Test Apparatus for Understanding Radiation Effects (MINITAURE)—an instrumented test rig based on the separate-effects MiniFuel concept that aims to capture fission gas release (FGR) and thermal conductivity degradation of fuel specimens during irradiation in the High Flux Isotope Reactor (HFIR). MINITAURE will be integrated with the Materials Irradiation Facility (MIF) located in the HFIR building outside the reactor containment. The MIF will act as the instrumentation and control center for the experiment, enabling real-time feedback from in situ sensors and control of irradiation temperatures via a gas delivery system. Two unique capsule designs were developed to capture each phenomenon: the thermal conductivity capsule, which uses a thermopile method to estimate fuel specimen thermal conductivity, and the fission gas release capsule, which will have continuous flowing gas communication to high-purity germanium detectors that are housed in the MIF for monitoring FGR. This report details the reactor physics and heat transfer modeling activities that were used to inform the experiment design and predict capsule performance. It also describes out-of-pile activities conducted to stand up this new capability and verify the measurement techniques. Modeling efforts to date have demonstrated the feasibility of the in situ measurement techniques and supported the development of the MINITAURE assembly configuration. Out-of-pile testing of the thermal conductivity measurement shows promise in capturing relative changes in thermal conductivity. However, significant errors exist in the measured absolute value, posing a need for further refinement.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-Pressure Sound Velocity Measurements of Liquids Using In Situ Ultrasonic Techniques in a Multianvil Apparatus

Sound velocity and equation of state of liquids provide important constraints on the generation, presence, and transport of silicate and metallic melts in the Earth’s interior. Unlike their solid counterparts, these properties of liquids pose great technical challenges to high-pressure measurements and are poorly constrained. Here we present the technical developments that have been made at the GSECARS beamline 13-ID-D of the Advanced Photon Source for the past several years for determination of sound velocity of liquids using the ultrasonic techniques in a 1000-ton Kawai-type multianvil apparatus. Temperature of the sound velocity measurements has been extended to ~2400 K at 4 GPa and ~2000 K at 8 GPa to enable studies of liquids with very high melting temperatures, such as the silicate liquids.

58 GEOSCIENCES↗

A Gapped Phase in Semimetallic T d -WTe 2 Induced by Lithium Intercalation

The Weyl semimetal WTe 2 has shown several correlated electronic behaviors, such as the quantum spin Hall effect, superconductivity, ferroelectricity, and a possible exciton insulator state, all of which can be tuned by various physical and chemical approaches. A new electronic phase in WTe 2 induced by lithium intercalation is discovered. The new phase exhibits an increasing resistivity with decreasing temperature and its carrier density is almost two orders of magnitude lower than the carrier density of the semimetallic T d phase, probed by in situ Hall measurements as a function of lithium intercalation. The theoretical calculations predict the new lithiated phase to be a potential charge density wave (CDW) phase with a bandgap of ≈0.14 eV, in good agreement with the in situ transport data. The new phase is structurally distinct from the initial T d phase, characterized by polarization-angle-dependent Raman spectroscopy, and large lattice distortions close to 6% are predicted in the new phase. This finding of a new gapped phase in a 2D semimetal demonstrates electrochemical intercalation as a powerful tuning knob for modulating electron density and phase stability in 2D materials.

36 MATERIALS SCIENCE↗

Measurement and modeling of methane diffusion in hydrocarbon mixtures

Methane (CH 4 ) dissolution and diffusive mass transfer in liquid hydrocarbon mixtures is of key interest in the context of enhanced oil recovery from tight shales. In this paper, we have studied CH 4 dissolution and diffusion in normal alkane mixtures at a temperature of 50 ⁰C and at pressures of ~8 MPa. For the measurement of CH 4 dissolution/diffusion in bulk liquid hydrocarbon mixtures, we have utilized a high pressure and temperature, constant-volume diffusion (CV-D) setup. Here, we have studied CH 4 diffusion in mixtures with three long-chain normal alkanes: decane (C 10 ), dodecane (C 12 ) and hexadecane (C 16 ). We have measured CH 4 solubility and diffusion in its binary mixtures with each of these three normal alkanes, as well as in ternary and quaternary mixtures. During the experiments, the swelling of the liquid mixture due to CH 4 dissolution was measured in situ via a cathetometer and was subsequently integrated into the data analysis. A key conclusion from this study is that the solubility and transport properties of the multicomponent mixtures can be predicted accurately from binary mixture measurements using an appropriate Equation of State (EOS) and Wilke’s simplification of the classical Maxwell-Stefan (MS) diffusion theory. This observation can facilitate accurate prediction of diffusive mass transfer in more complex liquid hydrocarbon mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Instrumented Capsule Design to Measure Thermal Conductivity in Miniature UO2 Specimens

Numerous separate effects irradiations of miniature nuclear fuel specimens have been conducted in the High Flux Isotope Reactor (HFIR) under the experimental platform designated as MiniFuel. MiniFuel is a static irradiation capability in which microstructural evolution and fuel performance phenomena are observed during postirradiation examination thereby offering a snapshot of the terminal fuel characteristics. This approach inherently requires fielding an irradiation where the experimental conditions are determined using predictive models and the pertinent outcomes are measured at the end of the test. Static irradiations can provide useful insights to the relationships between fuel performance and the pivotal irradiation conditions, namely temperature and burnup, but the ability to monitor fuel performance in situ would further support fuel development and qualification. To this end, an instrumented experiment design is being developed at Oak Ridge National Laboratory to capture thermal conductivity degradation and fission gas release during HFIR irradiation. These phenomena will be monitored using unique capsule designs that each target a different phenomenon. This paper details the thermal conductivity capsule (TCC) design and its expected performance envelope as determined using computer models. Each TCC will contain a miniature UO2 disc specimen (~0.5 mm thick × 5 mm diameter) sandwiched between metallic slugs with embedded thermocouples. The coupling of in situ temperature measurements, known thermal conductivity of the metallic components, and heat generation rates computed using high-fidelity neutronics models make the thermal conductivity measurement possible. This paper describes the reactor physics and heat transfer models used to predict the capsule’s performance and the methodology for calculating the fuel specimen’s thermal conductivity from the thermocouple measurements.

Gorton, Jacob [ORNL] (ORCID:0000000269806083)↗

Innovative laser-based methods for monitoring fuel retention in ITER

This paper addresses the challenge of tritium inventory management in ITER and future fusion reactors, highlighting the importance of accurate tritium measurement and its spatial distribution within the vacuum vessel. Given ITER’s operational constraints, especially the limit on tritium retention, precise measurement is essential for both safety and regulatory compliance. To tackle these questions, the paper presents the T-monitor diagnostic system developed by Forschungszentrum Jülich, which uses Laser-Induced Desorption (LID) in combination with Diagnostic Residual Gas Analysis (DRGA) to measure hydrogen isotope concentrations on the surface of divertor tiles. The system integrates a high-power laser, advanced optical components, and a Fast Scanning Mirror Unit (FSMU) for accurate laser spot positioning with rapid response. Designed to measure in situ tritium retention, the diagnostic provides high-resolution spatial mapping, vital for evaluating detritiation strategies. The laser heating process increases the divertor surface temperature to 1600 K within the laser spot, promoting hydrogen isotope desorption. Accurate measurements require the precise control of laser parameters, including pulse duration and spot size, with a target relative accuracy of 20%. The optical design includes both in-vessel and ex-vessel components, such as durable high-reflectivity mirrors made of gold and copper, selected not only for their infrared performance but also for their transmission of visible wavelengths for observation purposes. To protect optical components from contamination, a pneumatic shutter is used.

Hydrogen isotopes↗

Impacts of long-range transport of aerosols on marine-boundary-layer clouds in the eastern North Atlantic

Vertical profiles of aerosols are inadequately observed and poorly represented in climate models, contributing to the current large uncertainty associated with aerosol–cloud interactions. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) aircraft field campaign near the Azores islands provided ample observations of vertical distributions of aerosol and cloud properties. Here we utilize the in situ aircraft measurements from the ACE-ENA and ground-based remote-sensing data along with an aerosol-aware Weather Research and Forecast (WRF) model to characterize the aerosols due to long-range transport over a remote region and to assess their possible influence on marine-boundary-layer (MBL) clouds. The vertical profiles of aerosol and cloud properties measured via aircraft during the ACE-ENA campaign provide detailed information revealing the physical contact between transported aerosols and MBL clouds. The European Centre for Medium-Range Weather Forecasts Copernicus Atmosphere Monitoring Service (ECMWF-CAMS) aerosol reanalysis data can reproduce the key features of aerosol vertical profiles in the remote region. The cloud-resolving WRF sensitivity experiments with distinctive aerosol profiles suggest that the transported aerosols and MBL cloud interactions (ACIs) require not only aerosol plumes to get close to the marine-boundary-layer top but also large cloud top height variations. Based on those criteria, the observations show that the occurrence of ACIs involving the transport of aerosol over the eastern North Atlantic (ENA) is about 62 % in summer. For the case with noticeable long-range-transport aerosol effects on MBL clouds, the susceptibilities of droplet effective radius and liquid water content are -0.11 and +0.14, respectively. When varying by a similar magnitude, aerosols originating from the boundary layer exert larger microphysical influence on MBL clouds than those entrained from the free troposphere.

54 ENVIRONMENTAL SCIENCES↗

Assessing Simulations of Forest Hurricane Disturbance and Recovery in Puerto Rico by ELM-FATES Using Field Measurements

In the past three decades, Puerto Rico (PR) experienced five hurricanes that met or exceeded category three, and they caused severe forest structural damage and elevated tree mortality. To improve our mechanistic understanding of hurricane impacts on tropical forests and assess hurricane-affected forest dynamics in Earth system models, we use in situ forest measurements at the Bisley Experimental Watersheds in Northeast PR to evaluate the Functionally Assembled Terrestrial Ecosystem Simulator coupled with the Energy Exascale Earth System Model Land Model (ELM-FATES). The observations show that before Hurricane Hugo, 77.3% of the aboveground biomass (AGB) is from the shade-tolerant plant function type (PFT). The Hugo-induced mortality rates are over ~50%, and they induce a ~39% AGB reduction, which recovers to a level like the pre-Hugo condition in 2014, following a second, lower intensity hurricane, Georges. We perform numerical experiments that simulate damage from Hugo and Georges on the forests, including defoliation, sapwood and structural biomass damage, and hurricane-induced mortality. ELM-FATES can reasonably represent coexistence between the two PFTs–light-demanding and shade-tolerant–for both the pre-Hugo and post-Hugo conditions. The model represents a reasonable size distribution of mid-and large-sized trees although it underestimates AGB, likely due to the overestimated nonhurricane mortality. ELM-FATES temporarily stimulated leaf biomass and diameter increment after Georges, an effect that should be tested with observations of future hurricane defoliation events. This research indicates that addressing model-data mismatches in tree mortality and understory dynamics are essential to simulation of more extreme hurricane effects under climate change.

58 GEOSCIENCES↗

Earth System Model Aerosol–Cloud Diagnostics (ESMAC Diags) package, version 1: assessing E3SM aerosol predictions using aircraft, ship, and surface measurements

Abstract. An Earth system model (ESM) aerosol–cloud diagnostics package is developed to facilitate the routine evaluation of aerosols, clouds, and aerosol–cloud interactions simulated by the Energy Exascale Earth System Model (E3SM) from the US Department of Energy (DOE). The first version focuses on comparing simulated aerosol properties with aircraft, ship, and surface measurements, which are mostly measured in situ. The diagnostics currently cover six field campaigns in four geographical regions: eastern North Atlantic (ENA), central US (CUS), northeastern Pacific (NEP), and Southern Ocean (SO). These regions produce frequent liquid- or mixed-phase clouds, with extensive measurements available from the Atmospheric Radiation Measurement (ARM) program and other agencies. Various types of diagnostics and metrics are performed for aerosol number, size distribution, chemical composition, cloud condensation nuclei (CCN) concentration, and various meteorological quantities to assess how well E3SM represents observed aerosol properties across spatial scales. Overall, E3SM qualitatively reproduces the observed aerosol number concentration, size distribution, and chemical composition reasonably well, but it overestimates Aitken-mode aerosols and underestimates accumulation-mode aerosols over the CUS and ENA regions, suggesting that processes related to particle growth or coagulation might be too weak in the model. The current version of E3SM struggles to reproduce the new particle formation events frequently observed over both the CUS and ENA regions, indicating missing processes in current parameterizations. The diagnostics package is coded and organized in a way that can be extended to other field campaign datasets and adapted to higher-resolution model simulations.

54 ENVIRONMENTAL SCIENCES↗

In situ synchrotron X-ray total scattering measurements and analysis of colloidal CsPbX 3 nanocrystals during flow synthesis

In situ X-ray scattering measurements of CsPbX 3 (X = Cl, Br, I) nanocrystal formation and halide exchange at NSLS-II beamlines were performed in an automated flow reactor. Total scattering measurements were performed at the 28-ID-2 (XPD) beamline and small-angle X-ray scattering at the 16-ID (LiX) beamline. Nanocrystal structural parameters of interest, including size, size distribution and atomic structure, were extracted from modeling the total scattering data. The results highlight the potential of these beamlines and the measurement protocols described in this study for studying dynamic processes of colloidal nanocrystal synthesis in solution with timescales on the order of seconds.

nucleation↗