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At least 1,495 records · Page 83

High-throughput printing of combinatorial materials from aerosols

The development of new materials and their compositional and microstructural optimization are essential in regard to next-generation technologies such as clean energy and environmental sustainability. However, materials discovery and optimization have been a frustratingly slow process. The Edisonian trial-and-error process is time consuming and resource inefficient, particularly when contrasted with vast materials design spaces 1 . Whereas traditional combinatorial deposition methods can generate material libraries 2,3 , these suffer from limited material options and inability to leverage major breakthroughs in nanomaterial synthesis. Here we report a high-throughput combinatorial printing method capable of fabricating materials with compositional gradients at microscale spatial resolution. In situ mixing and printing in the aerosol phase allows instantaneous tuning of the mixing ratio of a broad range of materials on the fly, which is an important feature unobtainable in conventional multimaterials printing using feedstocks in liquid–liquid or solid–solid phases 4–6 . We demonstrate a variety of high-throughput printing strategies and applications in combinatorial doping, functional grading and chemical reaction, enabling materials exploration of doped chalcogenides and compositionally graded materials with gradient properties. The ability to combine the top-down design freedom of additive manufacturing with bottom-up control over local material compositions promises the development of compositionally complex materials inaccessible via conventional manufacturing approaches.

36 MATERIALS SCIENCE↗

A sessile drop setup for the time-resolved synchrotron study of solid-liquid interactions: Application to intermetallic formation in 55%Al-Zn alloys

We introduce a dedicated setup for measuring by synchrotron diffraction in-situ crystallographic and chemical information at the solid–liquid interface. This setup mostly consists of a double-heating furnace composed of a resistive heating for the solid surface and an inductive heating to produce a liquid droplet. The available high energy and high flux beams allow the rapid reaction kinetics to be investigated with very good time resolution down to 1 ms. An application of this setup is illustrated for the growth mechanisms of intermetallic phases during the hot-dipping of steel in a 55%Al-Zn bath. Results show that the three η-Al{sub 5}Fe{sub 2}, θ-Al{sub 13}Fe{sub 4}, and α-Al{sub 8}Fe{sub 2}Si phases grow at different times and rates during the dipping process, whereas the face-centered cubic AlFe{sub 3} phase is not formed.

36 MATERIALS SCIENCE↗

Crystallographic-orientation dependent Li ion migration and reactions in layered MoSe 2

The lithium ion migration dynamics and the fast lithiation pathways in electrode materials are quite vital to the rate capability of lithium ion batteries (LIBs). To reveal the relationship between lithiation behavior and crystallographic orientations in layered MoSe 2 , its dynamic electrochemical reactions are investigated with in situ microscopy technique. Here, we report the crystallographic-orientation dependent lithium ion migration and reaction in MoSe 2 , where the preferential lithium-ion migration is observed along the $\langle10\bar{1}0\rangle$ orientations. These oriented-lithiation tips further assisted the surface to interior lithiation of layered MoSe 2 . At the same time, a phase transition from pristine 2H-MoSe 2 to 1T-Li x MoSe 2 and the following conversion reaction with the formation of Li2Se and Mo are observed during the first lithiation process. The lithiation induced stress and orientation-dependent interfacial reaction rate might be the main factor leading to the orientation-dependent lithiation behavior. The experimentally revealed crystallographic-orientation dependent lithium ion migration and reaction in layered MoSe 2 will provide intuitive understanding of the structural evolution during the discharge/charge cycling process, give guidance for the design of anode materials and can broaden the promising application of MoSe 2 in solid electrochemical devices.

Lithium ion battery↗

Storage and Diffusion of Carbon and Nitrogen in Crustal Materials

Nitrogen is a primary constituent of Earth’s atmosphere and an essential component of many biological processes. Recent developments in understanding N incorporation into silicate minerals suggest that the solid earth and lithosphere could provide a substantial reservoir for the planetary N budget. Furthermore, determining the concentration and distribution of low abundances of N in silicates presents a significant challenge in microanalysis. We tested capabilities for high spatial resolution quantification of low levels of N using EPMA with the goal of developing standards to be used in coupled N and noble gas analyses of silicate minerals. We investigated the concentration and distribution of N in a suite of ammonium-bearing silicate minerals that reflect the dominant N-bearing phases of the lithosphere: tobelite, buddingtonite, ammonioleucite, tsaregorodtsevite, and hyalophane. These minerals form during NH 4 -rich alteration of K-bearing silicate minerals, and the bonding environment of N in each mineral is likely to differ based on crystal structure. Using an optimized analytical routine for N quantification enables sensitivity approaching 0.02 weight% N and high-resolution quantitative mapping of sub-micron variations in N contents.

58 GEOSCIENCES↗

Adaptation of EVIAVE methodology for monitoring and follow-up when evaluating the environmental impact of landfills

Treatment and final disposal of Municipal Solid Waste can have a significant role in the generation of negative environmental impacts. As a prevention strategy, such activities are subjected to the process of Environmental Impact Assessment (EIA). Still, the follow-up of Environmental Management Plans or mitigation measures is limited, for one due to a lack of methodological approaches. In searching for possibilities, the University of Granada (Spain) developed a diagnostic methodology named EVIAVE, which allows one to quantify, by means of indexes, the environmental impact of landfills in view of their location and the conditions of exploitation. EVIAVE is applicable within the legal framework of the European Union and can be adapted to the environmental and legal conditions of other countries. This study entails its adaptation in Colombia, for the follow-up and control of the EIA process for landfills. Modifications involved inclusion of the environmental elements flora and fauna, and the evaluation of the environmental descriptors in agreement with the concept of vulnerability. The application of the modified EVIAVE in Colombian landfills allowed us to identify the elements affected by the operating conditions and maintenance. It may be concluded that this methodology is viable and effective for the follow-up and environmental control of EIA processes for landfills, and to analyze the associated risks, as it takes into account related environmental threats and vulnerabilities. - Highlights: • A modified methodology is used to monitor and follow-up environmental impacts in landfills. • The improved methodology includes the Vulnerability of Flora and Fauna to evaluate environmental impact of landfills. • The methodology serves to identify and evaluate the sources of risk generated in the construction and siting of landfills. • Environmental vulnerability indicators improve effectiveness of the control and follow-up phases of landfill management. • The follow-up of environmental management plans may help diminish the implementation gap in Environmental Impact Assessment.

54 ENVIRONMENTAL SCIENCES↗

Liquid Secondary Waste Grout Formulation and Waste Form Qualification

This report describes the results from liquid secondary waste (LSW) grout formulation and waste form qualification tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate new formulations for preparing a grout waste form with high-sulfate secondary waste simulants and the release of key constituents from these grout monoliths. Specific objectives of the LSW grout formulation and waste form qualification tests described in this report focused on five activities: 1.preparing new formulations for the LSW grout waste form with high-sulfate LSW simulants and solid characterization of the cured LSW grout waste form; 2.conducting the U.S. Environmental Protection Agency (EPA) Method 1313 leach test (EPA 2012) on the grout prepared with the new formulations, which solidify sulfate-rich Hanford Tank Waste Treatment and Immobilization Plant (WTP) off-gas condensate secondary waste simulant, using deionized water (DIW); 3.conducting the EPA Method 1315 leach tests (EPA 2013) on the grout monoliths made with the new dry blend formulations and three LSW simulants (242-A evaporator condensate, Environmental Restoration Disposal Facility (ERDF) leachate, and WTP off-gas condensate) using two leachants, DIW and simulated Hanford Integrated Disposal Facility (IDF) Site vadose zone pore water (VZPW); 4.estimating the 99 Tc desorption K d (distribution coefficient) values for 99 Tc transport in oxidizing conditions to support the IDF performance assessment (PA); 5.estimating the solubility of 99 Tc(IV)-bearing solid phases for 99 Tc transport in reducing conditions to support the IDF PA.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhancement and Tunability of Near-Field Radiative Heat Transfer Mediated by Surface Plasmon Polaritons in Thin Plasmonic Films

The properties of thermal radiation exchange between hot and cold objects can be strongly modified if they interact in the near field where electromagnetic coupling occurs across gaps narrower than the dominant wavelength of thermal radiation. Using a rigorous fluctuational electrodynamics approach, we predict that ultra-thin films of plasmonic materials can be used to dramatically enhance near-field heat transfer. The total spectrally integrated film-to-film heat transfer is over an order of magnitude larger than between the same materials in bulk form and also exceeds the levels achievable with polar dielectrics such as SiC. We attribute this enhancement to the significant spectral broadening of radiative heat transfer due to coupling between surface plasmon polaritons (SPPs) on both sides of each thin film. We show that the radiative heat flux spectrum can be further shaped by the choice of the substrate onto which the thin film is deposited. In particular, substrates supporting surface phonon polaritons (SPhP) strongly modify the heat flux spectrum owing to the interactions between SPPs on thin films and SPhPs of the substrate. The use of thin film phase change materials on polar dielectric substrates allows for dynamic switching of the heat flux spectrum between SPP-mediated and SPhP-mediated peaks

42 ENGINEERING↗

High-Fidelity and High-Performance Computational Simulations for Rapid Design Optimization of Sulfur Thermal Energy Storage

Industrial process heating (IPH) accounts for approximately 70% of US manufacturing energy use and is primarily produced by fossil fuel combustion. Approximately 1500 TWht (approximately 60%) of IPH demand is in the temperature range of 100-300. Industrial applications in this temperature range include drying, hydrothermal processing, thermal enhanced oil recovery, food and beverage, bioethanol production, etc. Cost-effective thermal energy storage (TES) that increases the utilization of waste and renewable heat (solar, geothermal, etc.) could provide significant energy savings and reliable heat sources, decrease emissions, and increase US manufacturing competitiveness through reductions in fuel consumption. TES development has historically been dominated by technologies suitable for deployment with concentrating solar power (CSP). State-of-the-art thermal storage deployed commercially with power tower CSP plants uses a 60%/40% NaNO3/KNO3 molten salt and operates between temperatures of approximately 280 degrees Celsius and 570 degrees Celsius using a two-tank configuration. However, these nitrate salts are unsuitable for operation outside of this temperature range due to a high freezing point of approximately 220 degrees Celsius, and limits on high-temperature salt stability and corrosion resistance of containment alloys. Other materials being investigated for TES include those based on: (1) sensible energy storage (various molten salt compositions, inert solid particles, rocks or pebble beds, sulfur, water, concrete, graphite, etc.), (2) latent energy storage in materials that undergo solid-liquid phase change at relevant temperatures (organic materials for low-temperature applications, inorganic salts and/or metals for high-temperature applications), or (3) thermochemical energy storage (hydrides, hydroxides, carbonates, metal oxides, etc.). The application temperature and challenges pertaining to storage material and/or containment cost, energy density, long-term thermal and cyclic stability, and charge/discharge heat transfer effectiveness drive material selection for a given IPH or electricity generation application. Sulfur is a cheap commodity at $80/ton compared to $1100 - 1300/ton for conventional salts. When using a metric of storage cost per kWh, sulfur costs around 2-3 $/kWh. Previous sulfur TES development focused on high temperature (>600 degrees) concentrated solar power applications with sulfur encapsulated in pipes and flow of gaseous HTF (air) in the shell side. However, for lower-temperature IPH applications in the range of approximately 100-300 degrees Celsius Element 16 adopted a compact and scalable TES design with molten sulfur in the shell and HTF pipes submerged in the molten sulfur bath. The low-cost molten sulfur TES for dispatchable IPH has deployment potential for broad applications. The spatial and temporal evolution of the HTF and sulfur temperature is critical to the TES system performance, and thus detailed modeling can improve understanding of the performance and facilitate design improvements. Using high performance computing and computational fluid dynamics (CFD) a low-cost molten sulfur thermal energy storage (TES) system for industrial process heating (IPH) applications was developed. The unique challenges in CFD modeling of sulfur TES are the sharp property changes of sulfur relevant to the working temperatures. Above 159, liquid sulfur undergoes polymerization, and the viscosity of sulfur rapidly increases by several orders of magnitude between 159 degrees Celsius and 188 degrees Celsius, followed by a decrease in viscosity beyond 188 degrees Celsius due to thermal bound dissociation. In addition, various concentrations of H2S impurities can also modify sulfur viscosity. This numerical challenge is especially relevant to transient simulation of the sulfur TES charging and discharging processes as the extreme property variations limit the applicability of traditional heat transfer correlations. Transient CFD simulations including the temperature-dependent sulfur properties and geometric complexity of the TES design were used to predict the effect of natural convection during charging and discharging on the heat transfer process, sulfur temperature uniformity, charge/discharge rates, and performance of the storage devices. The CFD model was validated with experimental results for a full charge and discharge cycle. The work will show 3D and 2D simulation comparisons aimed to facilitate rapid design iterations and a machine learning based design optimization approach.

CFD↗

Classification of particle height in a hopper bin from limited discharge data using convolutional neural network models

Hopper bin discharge processes are ubiquitous in many industrial applications. The preponderance of previous studies of this system has been focused on the forward discharge process given an initial particle packing configuration. Motivated by the needs in reaction design and optimization, we develop here an inverse reconstruction procedure that enables one to obtain the particle height information in the initial packing configuration in the hopper bin from limited discharge dynamics data and particle characteristics. Our procedure is based on convolutional neural network (CNN) models, which take experimentally measurable particle residence time, diameter and density as input, and provide a classification of particle height in the initial packing as output. Using MFIX-DEM simulations with enhanced physical modeling capabilities, we generate extensive discharge data for hoppers containing two distinct solid phase particles with four distinct classes of initial packing geometries. The CNN reconstruction models are subsequently trained and tested using the discharge data. Here, we find that the reconstruction (i.e., particle height classification) accuracy strongly depends on the initial packing geometry. For hopper-specific CNN models exclusively trained using discharge data from a single hopper, the classification can attain an accuracy up to almost 90%. The accuracy decreases for generic reconstruction models trained using a collection of discharge data for multiple hoppers. Finally, we apply the CNN model to accurately reconstruct a hopper containing four distinct solid phases with a layered configuration to further demonstrate its utility.

42 ENGINEERING↗

DIRECT RF SAMPLING BASED LLRF CONTROL SYSTEM FOR C-BAND LINEAR ACCELERATOR

Low Level RF (LLRF) control systems of linear accel- erators (LINACs) are typically implemented with hetero- dyne based architectures, which have complex analog RF mixers for up and down conversion. The Gen 3 Radio Fre- quency System-on-Chip (RFSoC) device from AMD Xilinx integrates data converters with maximum RF frequency of 6 GHz. This enables direct RF sampling of C-band LLRF signal typically operated at 5.712 GHz without any analogue mixers, which can significantly simplify the system architec- ture. The data converters sample RF signals in higher order Nyquist zones and then up or down convert digitally by the integrated data path in RFSoC. The closed-loop feedback control firmware implemented in FPGA integrated in RF- SoC can process the base-band signal from the ADC data path and calculate the updated phase and amplitude to be up- mixed by the DAC data path. We have developed a C-band LLRF control RFSoC platform with direct RF sampling, which targets Cool Copper Collider (𝐶3) and other C or S band LINAC research and development projects. In this paper, the architecture of the platform will be described. We have optimized the configuration of the data converter and characterized performance of them with RF pulses. The test results for some of the key performance parameters for the LLRF platform with our custom solid-state amplifier, such as phase and amplitude stability, will be discussed in this paper.

Liu, C↗

Diffusion bonding of tungsten-vanadium-zirconium using vacuum hot pressing for the development of a low decay heat cladding solution for tungsten spallation targets

Tantalum has been used as cladding material for water-cooled solid tungsten targets at many leading spallation neutron production facilities thanks to its high neutron yield, manageable radiation damage behavior, and excellent corrosion/erosion resistance in radiation environments. However, from a safety hazard perspective, thermal neutron capture of tantalum in spallation environments causes a high specific decay heat in the target volume, which often becomes a limiting factor in increasing the beam power on the target. In this paper, we studied vacuum hot pressing (VHP) parameters to diffusion bond zirconium to tungsten to explore the feasibility of using zirconium alloys as an alternative cladding material to tantalum. Zirconium alloys have long been used as cladding material for early generation solid spallation targets, and nuclear fuel rods. In spallation environments zirconium has significantly lower decay heat with shorter decay time compared to tantalum. The hot isostatic pressing (HIP) of zirconium and tungsten is known to produce limited bonding quality due to the formation of the brittle ZrW2 intermetallic layer. To overcome this problem, placing a vanadium interlayer between tungsten and zirconium has been proposed by exploring parameter space in binary alloy phase diagrams. Under the VHP conditions, 860 ◦C at 70 MPa for 4 hours, Zr-V and V-W showed good diffusion bonding, which demonstrates the feasibility of a single step HIP process to make the zirconium alloy clad tungsten spallation volumes.

Lee, Yong Joong↗

Diffraction Measurement of Reaction Products in Shock Compressed TATB on the NIF

The shock-induced reaction of high explosives to gaseous and solid reaction products is a rapid, complex process. Understanding solid reaction product structure and formation kinetics is essential in determining the high-pressure equation of state of these multicomponent systems. We use the National Ignition Facility (NIF) to shock compress ~500-µm thick pressed powder high-explosive TATB samples to 70-135 GPa and collect in situ structural data on detonation byproducts using the TARDIS X-ray diffraction diagnostic. Velocimetry is used to record the transmitted compression wave profile, which is well described by Cheetah hydrocode simulations coupled with a reactive flow model, providing strong evidence of reaction in the TATB sample. While an unambiguous determination of the product phases was not possible owing to the low signal-to-noise quality of the diffraction signal, X-ray diffraction data of the product phases formed within the first 50 ns of the reaction is most consistent with a mixture of amorphous products and crystalline hexagonal diamond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromium Vaporization Reduction by Nickel Coatings For SOEC Interconnect Materials

The vaporization of Cr-rich volatile species from interconnect materials is a major source of degradation that limits the lifetime of planar solid oxide devices systems with metallic interconnects, including Solid Oxide Electrolysis Cells, or SOECs. Some metallic coatings (Ni, Co, and Cu) significantly reduce the Cr release from interconnects and slow down the oxide scale growth on the steel substrate. To shed additional light upon the mechanisms of such protection and find a suitable coating material for ferritic stainless steel materials, we used a combination of first-principles calculations, thermodynamics, and diffusion modeling to investigate which factors determine the quality of the Ni metallic coating at stainless steel interconnector. We found that the Cr migration in Ni coating is determined by a delicate combination of the nickel oxidation, Cr diffusion, and phase transformation processes. Although the formation of Cr2O3 oxide is more exothermic than that of NiO, the kinetic rate of the chromia formation in the coating layer and its surface is significantly reduced by the low mobility of Cr in nickel oxide and in NiCr2O4 spinel. These results are in a good agreement with diffusion modeling for Cr diffusion through Ni coating layer on the ferritic 441 steel substrate.

99 GENERAL AND MISCELLANEOUS↗

Ionic Conductive and Highly-Stable Interface for Alkali Metal Anodes

Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. Further, this approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

By using a combination of wide-angle X-ray diffraction (WAXD), mass density, and 13 C solid-state nuclear magnetic resonance (NMR) measurements, a quantification of the absolute degree of crystallinity in regioregular poly(3-hexylthiophene) (rr-P3HT) is presented. A regiorandom P3HT (rra-P3HT), lacking long-range order, was used to separate the crystalline contribution from the total scattering in WAXD, thus yielding degrees of crystallinity in the range of 47–56% at room temperature for three different rr-P3HTs. For the same rr-P3HT with identical processing history, NMR yields degrees of crystallinity that are consistently ~10% greater than that obtained by WAXD, which can only be explained by ordered chain segments in the amorphous phase. NMR results also suggest that rra-P3HT contains weakly ordered chain segments, which likely contribute to an underestimation of degree of crystallinity when determined from mass density measurements, if rra-P3HT is used to approximate a fully amorphous P3HT. The results shown in this study provide direct proof of three different types of P3HT chain segments: crystallites (i.e., long-range ordered chain packing), amorphous phase (i.e., disordered chain packing), and short-range ordered chain packing embedded in the amorphous phase. Here, the presence of the short-range ordered chain packing is particularly important when correlating the morphology to macroscopic charge transport properties in P3HT-based devices. In general, those locally ordered chain segments, though not constituting a distinct phase, are believed to be of critical importance in determining the transport characteristics of conjugated semiconducting polymers with or without a distinct crystalline phase present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing temperature-dependent phase stability in high entropy alloys

High entropy alloys (HEAs) contain near equimolar amounts of five or more elements and are a compelling space for materials design. In the design of HEAs, great emphasis is placed on identifying thermodynamic conditions for single-phase and multi-phase stability regions, but this process is hindered by the difficulty of navigating stability relationships in high-component spaces. Traditional phase diagrams use barycentric coordinates to represent composition axes, which require ( N – 1) spatial dimensions to represent an N -component system, meaning that HEA systems with N > 4 components cannot be readily visualized. Here, we propose forgoing barycentric composition axes in favor of two energy axes: a formation-energy axis and a ‘reaction energy’ axis. These Inverse Hull Webs offer an information-dense 2D representation that successfully captures complex phase stability relationships in N ≥ 5 component systems. We use our proposed diagrams to visualize the transition of HEA solid-solutions from high-temperature stability to metastability upon quenching, and identify important thermodynamic features that are correlated with the persistence or decomposition of metastable HEAs.

Chemistry↗

Elucidating the role of reactive nitrogen intermediates in hetero-cyclization during hydrothermal liquefaction of food waste

Hydrothermal liquefaction (HTL) has emerged as a promising strategy for converting abundant, water-rich organic streams into an energy-dense, sustainable, biocrude. Despite major strides in improving oil yields and process intensification, a key underlying challenge persists in relating the composition of the feedstock to the ultimate fate of nitrogen, which is especially important for biocrude quality. To elucidate how nitrogen partitions into the respective gas, aqueous, oil and solid hydrothermal products, food waste was treated under HTL conditions (15 wt% solids, 575 K reaction temperature, and 1 hour reaction time) and elemental, chromatographic and mass spectroscopy analyses were performed on the products to establish dominant product classes and to close mass, carbon, and nitrogen balances. Liquid products (aqueous and biocrude) were found to contain nearly 60% of the nitrogen, with a majority of the biocrude-phase nitrogen in the form of amides. Ab initio thermodynamic and kinetic simulations on model reactants were used to evaluate potential reaction pathways involving reactive nitrogen intermediates. A subsequent kinetic model was evaluated at reaction temperatures ranging 300–1000 K and for a range of feedstock compositions to identify primary reaction pathways. The Maillard reaction is revealed to be the dominant pathway for converting reactive nitrogen intermediates into observed products, especially those in which nitrogen is present as a heterocyclic aromatic. Subsequent product analysis by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) confirms strong agreement among the experimental data, kinetic model and proposed Maillard pathways.

09 BIOMASS FUELS↗