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At least 469 records · Page 26

Solidification and fcc to metastable hcp phase transition in krypton under variable compression rates

In this work, we present time-resolved synchrotron x-ray diffraction measurements to study kinetics associated with the liquid-solid and solid-solid high-pressure phase transitions in Kr under dynamic loading in a dynamic-diamond anvil cell. The results show a strong compression-rate dependence of the solidification/melting process in liquid Kr. The analysis of the compression-rate dependent melting/solidification, using an Avrami equation with the parameter n=1, indicates a spontaneous nucleation and one-dimensional growth mechanism. In contrast, the face-centered-cubic to metastable hexagonal close-packed transition in solid Kr occurs rapidly at ~0.8 GPa near the melting line, which has negligible compression-rate dependence within the range of compression rates studied (0.004–13 GPa/s).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Informed Critical Mineral Recovery from Fossil Energy Waste Feedstocks

Critical minerals (CM), such as rare earth elements (REE), cobalt, nickel, and lithium, have important uses in modern energy and technologies, yet are vulnerable to potential supply chain disruptions. One potential domestic CM source is fossil energy wastes, such as coal combustion ash, acid mine drainage (AMD) and treatment solids (AMD solids), and Oil and Gas (O&G) drilling wastes (drill cuttings and produced waters). CM recovery from these feedstocks is promising due to their abundant quantity and fast availability as waste products. To develop informed and effective CM recovery, DOE’s National Energy Technology Laboratory (NETL) have collected and analyzed CM data for aforementioned fossil energy wastes, and utilized advanced geochemical characterization (e.g., synchrotron microprobe, sequential extraction and geochemical modeling) to identify the CM speciation and binding environments. Novel methods that recover multiple CMs while co-producing other valuable byproducts from these feedstocks have been developed. Successful examples include: (1) the discovery of easily mobile REE phases in Ca-rich coal combustion ash resulted in a patented REE recovery process from the ash feedstock while producing zeolite sorbents from the extraction wastes; (2) the successful identification of REE/Co/Ni/Zn hosting phases in acid mine drainage treatment solids (AMD solids) has informed the sequential CM recovery from AMD solids and has inspired lithium sorbent development from the extraction wastes; (3) the recovery potential of Li and other CMs in O&G produced waters and drill cuttings has been explored while the extraction residuals have been demonstrated to support plant growth as soil supplements. The innovations driven by characterization information have the potential to maximize CM recovery revenue, offset the cost of waste management and wastewater treatments while reducing the cost and environmental footprint of CM extraction.

characterization and extraction of rare earth elem↗

Five Rules for Measuring Biomass Pyrolysis Rates: Pulse-Heated Analysis of Solid Reaction Kinetics of Lignocellulosic Biomass

Pyrolytic conversion of lignocellulosic biomass utilizes high temperatures to thermally fragment biopolymers to volatile organic compounds. The complexity of the degradation process includes thousands of reactions through multiple phases occurring in less than a second. In this work, the requirements are established for measuring the reaction kinetics of high temperature (>400 °C) biomass pyrolysis in the absence of heat and mass transfer limitations. Additionally, experimental techniques must heat and cool biomass samples sufficiently fast to elucidate the evolution of reaction products with time while also eliminating a substantial reaction during the heating and cooling phases, preferably by measuring the temperature of the reacting biomass sample directly. Furthermore, these requirements are described with the PHASR (pulse-heated analysis of solid reactions) technique and demonstrated by measuring the time-resolved evolution of six major chemical products from loblolly pine pyrolysis over a temperature range of 400 to 500 °C. Differential kinetics of loblolly pine pyrolysis are measured to determine the apparent activation energy for the formation of six major product compounds including levoglucosan, furfural, and 2-methoxyphenol.

08 HYDROGEN↗

Waste Management Approach for a Potential Future U.S. Closed Fuel Cycle - 16233

The U.S. Department of Energy, Office of Nuclear Energy has chartered an effort to develop technologies to enable safe and cost effective recycle of commercial used nuclear fuel (UNF) in the U.S. Part of this effort includes the evaluation of exiting waste management technologies for effective treatment of wastes in the context of current U.S. regulations and development of waste forms and processes with significant cost and/or performance benefits over those existing. This study summarizes the results of these ongoing efforts with a focus on the highly radioactive primary waste streams. The primary streams considered and the recommended waste forms include: •Tritium separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers. •Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals. •Carbon-14 separated from LWR fuel treatment off-gases and immobilized as a CaCO3 in a cement waste form. •Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. •An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased titanate ceramic [e.g., synthetic rock (Synroc)]. •An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or titanate ceramics. •Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative Zr purification and reuse (or disposal as low-level waste, LLW) by reactive gas separations. •Electrochemical process salt HLW which is immobilized in a glass bonded Sodalite waste form known as the ceramic waste form (CWF). •Electrochemical process UDS and SS cladding hulls which are melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported.

Fuel Cycle↗

Waste Management Approach for a Potential Future U.S. Closed Fuel Cycle - 16233

The U.S. Department of Energy, Office of Nuclear Energy has chartered an effort to develop technologies to enable safe and cost effective recycle of commercial used nuclear fuel (UNF) in the U.S. Part of this effort includes the evaluation of exiting waste management technologies for effective treatment of wastes in the context of current U.S. regulations and development of waste forms and processes with significant cost and/or performance benefits over those existing. This study summarizes the results of these ongoing efforts with a focus on the highly radioactive primary waste streams. The primary streams considered and the recommended waste forms include: - Tritium separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers. - Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals. - Carbon-14 separated from LWR fuel treatment off-gases and immobilized as a CaCO{sub 3} in a cement waste form. - Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. - An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased titanate ceramic [e.g., synthetic rock (Synroc)]. - An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or titanate ceramics. - Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative Zr purification and reuse (or disposal as low-level waste, LLW) by reactive gas separations. - Electrochemical process salt HLW which is immobilized in a glass bonded Sodalite waste form known as the ceramic waste form (CWF). - Electrochemical process UDS and SS cladding hulls which are melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development and Rigorous Validation of Modules for Predicting Organic Aerosol CCN Activity from Molecular Properties

The indirect interaction of anthropogenic aerosols with clouds (aerosol indirect forcing) represents one of the main uncertainties in climate projections, and reducing this uncertainty requires improved understanding of the aerosol life cycle, including atmospheric aging and the ability to nucleate cloud droplets or crystals. A key parameter that links the chemical properties of aerosol to its nucleating properties, and ultimately to aerosol indirect forcing, is its hygroscopicity (ability to uptake water). One way to compare and systematize the ability of various chemical compounds or particle types to nucleate cloud drops is via the hygroscopicity parameter κ, which can be used directly in global models to simulate aerosol indirect forcing. In this project we further investigated the relationships between the chemical composition of organic aerosol particles, which are known to be important components of atmospheric particulate matter, and their ability to serve as cloud condensation nuclei (CCN). In particular, we isolated the role of viscosity on κ by applying methods similar to those we used previously in our DOE/ASR research. Our motivation for the focus on viscosity was through its link to particle phase state. Particle phase affects water uptake on timescales relevant to the laboratory and also likely relevant to atmospheric processes, with reduced apparent hygroscopicities for semisolid and solid particles, compared with liquid particles. Water uptake itself affects viscosity, an important feedback that we explored in this project. The objectives of the project were as follows: (1) measure the effects of molecular structure, temperature, and relative humidity on the viscosity of organic aerosol formed via controlled laboratory experiments, (2) measure the effects of organic aerosol viscosity on water uptake and CCN activity above and below water saturation, (3) further develop the κ parameterization of organic aerosol hygroscopicity to include viscosity/phase, and (4) experimentally validate the κ parameterization for organic aerosol with chemical composition ranging from relatively simple to complex. It was proposed that particle viscosity exerts a kinetic control on equilibrium water uptake. High viscosity was expected to delay water uptake based on diffusional limitations. This would manifest itself in reduced observed CCN activity or κ. Understanding the interplay between water content and viscosity (composition control on particle viscosity) and between viscosity and equilibrium water content (diffusional control on water uptake) were the overall science objectives of this grant. Targeted experiments were carried out to test the kinetic control hypothesis. These experiments included studies that explicitly measured the equilibration time scale of water uptake, and experiments that tested the role of viscous particle coatings on the observed CCN activity. From the combined work, it is concluded that mass transfer limitations by glassy organic particles are unlikely to affect cloud droplet activation near laboratory temperatures. This implies that viscosity does not need to be included in parameterizations that link particle chemical composition and κ. A parameterization to predict κ through the UNIFAC group contribution method was developed with previous ASR funding. As planned, this computational module was further developed and validated here through targeted laboratory studies. The computational module has been made available as free software under the GNU public license. A database of κ-values to aid model development has been compiled and is available online via an open access model. In conducting this work, significant effort was made to understand how aerosol composition, including the associated aerosol water content, affects viscosity. This included a study detailing the influence of functional group composition on organic aerosol viscosity. We identified a strong link between volatility and viscosity. Functional groups responsible for low vapor pressure also promote high viscosity. Specifically, carboxylic acid and hydroxyl groups were identified as major contributors to high viscosity. Several studies were carried out to characterize the link between composition and the glass-to-liquid phase transition. Compositions tested include models of organic/inorganic particles and models of complex organic aerosol formed through secondary processes. A simple computational model to predict the amorphous phase diagram was developed and tested. Excellent agreement between model and measurements was obtained for organic/inorganic mixtures. The computational model is simple enough to be included in global model simulations. However, constraints of input parameters such as the Gordon-Taylor constant for binary mixtures for a wide range of complex mixtures have not yet been fully evaluated. Combined, the performed work provides new constraints on the amorphous phase state of organic aerosols.

54 ENVIRONMENTAL SCIENCES↗

Computational Methodology to Simulate Pyrometallurgical Processes in a Secondary Lead Furnace

Pyrometallurgical recovery of nonferrous metals involves a combination of thermally intensive transformations during exothermic gas-phase reactions, endothermic decomposition of solid charge, and melting of simpler solids. In the recovery of secondary lead, simultaneous thermal effects in a reverberatory-style furnace cause a melt pool to accumulate at the bottom, with lighter solids (slag) floating above and gaseous products from decomposition of the charge diffusing through the gas–slag interface. Species from oxy-fuel combustion of natural gas, species profiles from smelting reactions, and the formation of a melt pool consisting primarily of lead are simulated via a time-averaged formulation. Predictions of outflow are compared with preset inflow profiles to ensure conservation of mass. Thermal profiles for solid, liquid, and gas phases are presented by species. A novel method is implemented to model the latent heat of fusion using a heterogeneous chemical reaction. The simulation is conducted in Simcenter STAR-CCM+ v. 16.02.009-R8.

Rao, Vivek↗

MEUMAPPS (Microstructure Evolution Using Massively Parallel Phase-field Simulations)

The software “MEUMAPPS” is a h high-performance computing code used to simulate microstructure evolution associated with diffusional solid-state transformations in structural alloys. Understanding microstructure evolution during thermo-mechanical processing of structural alloys is the first step towards designing and processing alloys for specific applications by meeting property requirements demanded by the application. In this instance, the code is an important component in predicting processing-structure linkages during additive manufacturing of structural alloys as a function of processing parameters and alloy composition used in an additive manufacturing process. The code provides a detailed three-dimensional distribution of different types of phases / constituents and their morphologies, as well as the compositions of these phases that make up the microstructure. The microstructure is simulated by solving the governing partial differential equations using a Fourier Spectral Method.

Radhakrishnan, Balasubram↗

Accretion of solid materials onto circumplanetary disks from protoplanetary disks

We investigate the accretion of solid materials onto circumplanetary disks from heliocentric orbits rotating in protoplanetary disks, which is a key process for the formation of regular satellite systems. In the late stage of the gas-capturing phase of giant planet formation, the accreting gas from protoplanetary disks forms circumplanetary disks. Since the accretion flow toward the circumplanetary disks affects the particle motion through gas drag force, we use hydrodynamic simulation data for the gas drag term to calculate the motion of solid materials. We consider a wide range of size for the solid particles (10{sup –2}-10{sup 6} m), and find that the accretion efficiency of the solid particles peaks around 10 m sized particles because energy dissipation of drag with circum-planetary disk gas in this size regime is most effective. The efficiency for particles larger than 10 m becomes lower because gas drag becomes less effective. For particles smaller than 10 m, the efficiency is lower because the particles are strongly coupled with the background gas flow, which prevents particles from accretion. We also find that the distance from the planet where the particles are captured by the circumplanetary disks is in a narrow range and well described as a function of the particle size.

79 ASTRONOMY AND ASTROPHYSICS↗

Template-independent enzymatic synthesis of RNA oligonucleotides

Abstract RNA oligonucleotides have emerged as a powerful therapeutic modality to treat disease, yet current manufacturing methods may not be able to deliver on anticipated future demand. Here, we report the development and optimization of an aqueous-based, template-independent enzymatic RNA oligonucleotide synthesis platform as an alternative to traditional chemical methods. The enzymatic synthesis of RNA oligonucleotides is made possible by controlled incorporation of reversible terminator nucleotides with a common 3′-O-allyl ether blocking group using new CID1 poly(U) polymerase mutant variants. We achieved an average coupling efficiency of 95% and demonstrated ten full cycles of liquid phase synthesis to produce natural and therapeutically relevant modified sequences. We then qualitatively assessed the platform on a solid phase, performing enzymatic synthesis of severalN + 5 oligonucleotides on a controlled-pore glass support. Adoption of an aqueous-based process will offer key advantages including the reduction of solvent use and sustainable therapeutic oligonucleotide manufacturing.

Biotechnology & Applied Microbiology↗

Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH) 3 ) with sodium nitrite/nitrate

Despite widespread industrial importance, predicting metal solubilities in highly concentrated, multicomponent aqueous solutions is difficult due to poorly understood ion–ion and ion–solvent interactions. Aluminum hydroxide solid phase solubility in concentrated sodium hydroxide (NaOH) solutions is one such case, with major implications for ore refining, as well as processing of radioactive waste stored at U.S. Department of Energy legacy sites, such as the Hanford Site, Washington State. The solubility of gibbsite (α-Al(OH) 3 ) is often not well predicted because other ions affect the activity of hydroxide (OH – ) and aluminate (Al(OH) 4 – ) anions. In the study reported herein, we systematically examined the influence of key anions, nitrite (NO 2 – ) and nitrate (NO 3 – ), as sodium salts on the solubility of α-Al(OH) 3 in NaOH solutions taking care to establish equilibrium from both under- and oversaturation. Rapid equilibration was enabled by use of a highly pure and crystalline synthetic nano-gibbsite of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by an α-Al(OH) 3 solubility model derived for simple Al(OH) 4 – /OH – systems. Specific anion effects were expressed as an enhancement factor (Al enhc ) conveying the excess of dissolved aluminum. At 45 °C, NaNO 2 and NaNO 3 -containing systems exhibited Al enhc values of 2.70 and 1.88, respectively, indicating significant enhancement. The solutions were examined by Raman and high-field 27 Al NMR spectroscopy, indicating specific interactions including Al(OH) 4 – –Na + contact ion pairing and Al(OH) 4 – –NO 2 – /NO 3 – ion–ion interactions. Dynamic evolution of the α-Al(OH) 3 particles including growth and agglomeration was observed revealing the importance of dissolution/reprecipitation in establishing equilibrium. These studies indicate that incomplete ion hydration, as a result of the low water activity in these concentrated electrolytes, results in: (i) enhanced reactivity of the hydroxide ion with respect to α-Al(OH) 3 ; (ii) increased concentrations of Al(OH) 4 – in solution; and (iii) stronger ion–ion interactions that act to stabilize the supersaturated solutions. This information on the mechanisms by which α-Al(OH) 3 becomes supersaturated is essential for more energy-efficient aluminum processing technologies, including the treatment of millions of gallons of Al(OH) 4 – -rich high-level radioactive waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fiscal Year 2021 Filtration of Hanford Tank 241-AP-107 Supernatant Samples Obtained at Prototypic Tank Level and Filtered at 16 °C

Bench-scale filtration testing of 8.5 liters of supernatant from Hanford waste tank 241-AP-107, chilled to 16 °C, was conducted using a backpulse dead-end filter (BDEF) filtration system equipped with a feed vessel and a Mott inline filter Model 6610 (Media Grade 5) in the hot cells of the Radiochemical Processing Laboratory at Pacific Northwest National Laboratory. This was done to assess the impact of a lower sampling location within the tank as well the lowered filtration temperature on supernatant stability and fouling. The as-received samples were transferred to 1.5-liter poly bottles and held at 16 °C for approximately 1 week prior to filtration. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft 2 to match the prototypic operation of the TSCR system. During the initial period of filtration, the differential pressure required to effect filtration at 0.065 gpm/ft 2 increased until it reached 2 psid [the Tank Side Cesium Removal (TSCR) action limit] at 26 hours. After this, the filter was backpulsed to dislodge accumulated solids and reduce this pressure differential. An additional eight backpulses were conducted during the initial filtration period; each time, the target pressure was reached sooner than during the previous interval. Volume filtered decreased from 0.9 to 0.03 m 3 /m 2 over the course of 14 processing hours. After the ninth backpulse, the backpulse frequency had become unsustainable, and it was decided to perform an extensive filter cleaning. The filter was cleaned by draining the chilled AP-107 feed into chilled holding containers, introducing 0.1 M NaOH into the feed vessel, and recirculating the NaOH through the system for 20 minutes before allowing the system to soak for 2 hours without temperature control. A measurable decrease in filter resistance during this recirculation indicated that the 0.1 M NaOH was likely dissolving some of the solids that had deposited on the filter. Post cleaning, the filter resistance was effectively restored to initial conditions as the initial transmembrane pressure was restored to original levels. However, resumed processing of the AP-107 feed at 16 °C continued to result in an increased rate of filter resistance. An additional five backpulses were conducted (four during feed processing, one during subsequent cleaning) before the conclusion of the test. Solids concentrated from the backpulse solutions displayed sodium oxalate-type phases, Al-oxides and sodium Al-oxides/carbonates, iron oxides, and Ca-bearing phases (calcite). The scanning electron microscopy analyses also revealed a large distribution of particles, with some particles, notably sodium phosphate dodecahydrate, having diameters close to 0.5 mm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Innovations Driven by Advanced Characterization to Strategize Critical Mineral Production and Beneficial Reuse from Fossil Energy Waste

Critical minerals (CM), such as rare earth elements (REE), cobalt, nickel, and lithium, have important uses in modern electronics and advanced manufacturing, yet are vulnerable to potential supply chain disruptions. Relatively abundant and readily available fossil energy (FE) wastes, such as coal combustion ash, acid mine drainage (AMD) and treatment solids (AMD solids), and Oil and Gas (O&G) drilling wastes (drill cuttings and produced waters) are under consideration as CM feedstocks. The National Energy Technology Laboratory (NETL) has studied CM resources for various FE wastes as part of the U.S. Department of Energy’s mission of bolstering the domestic CM supply, and makes the data available to the public on EDX at sites such as the NEWTS group. Advanced characterization utilizing synchrotron x-ray techniques coupled with laboratory extractions has been performed to identify CM hosting phases in these FE wastes to inform CM recoverability mechanisms. Novel methods to selectively recover CMs while co-producing other valuable byproducts have been developed. Successful examples discussed here include: (1) The identification of REE/Co/Ni/Sc binding and hosting phases in select FE waste (coal combustion ash and AMD solids), resulting in the development of a patented CM step-extraction process, (2) coupled production of functional sorbents from these extraction wastes and for CM recovery. A pilot-scale testing to evaluate the patent’s technical feasibility for extracting REE from coal ash on a barrel scale has been successfully performed. Additionally, (3) evaluation and measurements of brine geochemistry from U.S. O&G produced waters has informed a high Li recovery potential from Marcellus Shale produced water. NETL researchers have been developing tailored pre-treatment processes, an innovative and highly durable lithium sorbent, and geochemical model guided precipitation to accelerate Li production from the Marcellus Shale produced waters. These innovations driven by characterization are integral for maximizing and advancing the potential for CM recovery while offsetting the cost and environmental footprint for FE waste management.

critical mineral processing↗

Global Simulations of Phase State and Equilibration Time Scales of Secondary Organic Aerosols with GEOS-Chem

The phase state of secondary organic aerosols (SOA) can range from liquid through amorphous semisolid to glassy solid, which is important to consider as it influences various multiphase processes including SOA formation and partitioning, multiphase chemistry, and cloud activation. In this study, we simulate the glass transition temperature and viscosity of SOA over the globe using the global chemical transport model, GEOS-Chem. The simulated spatial distributions show that SOA at the surface exist as liquid over equatorial regions and oceans, semisolid in the midlatitude continental regions, and glassy solid over lands with low relative humidity. The predicted SOA viscosities are mostly consistent with the available measurements. In the free troposphere, SOA particles are mostly predicted to be semisolid at 850 hPa and glassy solid at 500 hPa, except over tropical regions including Amazonia, where SOA are predicted to be low viscous. Phase state also exhibits seasonal variation with a higher frequency of semisolid and solid particles in winter compared to warmer seasons. We calculate equilibration time scales of SOA partitioning (τ eq ) and effective mass accommodation coefficient (α eff ), indicating that τ eq is shorter than the chemical time step of GEOS-Chem of 20 min and αeff is close to unity for most locations at the surface level, supporting the application of equilibrium SOA partitioning. However, τ eq is prolonged and α eff is lowered over drylands and most regions in the upper troposphere, suggesting that kinetically limited growth would need to be considered for these regions in future large-scale model studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the elastocaloric effect in CuAlBe shape memory alloys: A quantitative phase-field modeling approach

We report the reversible stress-induced phase transformation in shape memory alloys (SMAs) is a dissipative process during which heat is absorbed or released. The inherent temperature variations inside the material has an elastocaloric effect (eCE) with appealing applications in solid-state cooling technology such as compact and efficient on-board refrigeration system for eletronic devices. In this manuscript, we conduct the first study of eCE of CuAlBe SMAs utilizing phase-field modeling. For an applied stress of 500 MPa, the results for polycrystalline Cu-Al11-2Be (at. %) show a minimum adiabatic unloading temperature change of -10 K over a pseudoelastic window of 40 K. In the absence of plastic deformation, the material demonstrates good reproducibility of the eCE over a few loading–unloading cycles. The presence of plastic deformation is found to cause functional fatigue that deteriorates the cooling capacity; however, the coefficient of performance only decreases from 9.04 to 8.03, which is still a very good value. These results place CuAlBe as a frontrunner SMA for solid-state cooling compared to the expensive NiTi.

36 MATERIALS SCIENCE↗

Critical roles of pores and moisture in sustainable nanocellulose-based super-thermal insulators

In a recent report in Matter, Bergström and co-workers describe a novel thermal transport behavior that subverts this assumption of porous materials. In their work, the authors describe a nanocellulose-based foam that features ultrahigh porosity (> 99.6%) and aligned µm-scale pores (10–100 µm) whose radial thermal conductivity (i.e., perpendicular to the pore alignment) is close to that of free air in the dry state. Furthermore, the radial thermal conductivity of the cellulose-based foam can be reduced to ~14 mW/(m·K) when the relative humidity is ~35%. Super-thermal insulators, which demonstrate a thermal conductivity below that of stationary air (~ 25 mW/(m·K), 20 ºC, 1.0 atm), are needed to minimize heat loss in various applications (e.g., buildings, thermal energy storage tanks, cold chain packaging, etc.) to mitigate the energy crisis and reduce carbon emissions. Introducing pores into a material is a facile and effective way to achieve low thermal conductivity as pores can suppress thermal transport through solids by reducing the cross-sectional area and increasing the tortuosity of the heat transfer pathway. In porous structures there are two kinds of pores: open and closed. While increased porosity can reduce heat conduction through solids with an open porous structure, the improved gas conduction creates a competing effect that simultaneously elevates the heat transfer. Therefore, the thermal conductivity of a material with µm-scale open pores is usually larger than that of stationary air. Reducing the pore size to less than the mean free path of air (~ 70 nm, 20 ºC, 1.0 atm) can effectively reduce gas conduction, enabling the material to achieve a thermal conductivity below that of stationary air. However, high cost of the nanosized raw materials and time-consuming fabrication processes limit the large-scale applications of nanoporous thermal insulators. Meanwhile, closed pores can block heat transport only through the continuous gas phase. As a result, the thermal conductivity of a closed porous structure can theoretically be much smaller than that of stationary air if the solid conduction can also be suppressed by (1) lowering the solid content of the material, (2) reducing the thermal conductivity of the building blocks of the material, and/or (3) increasing interfacial thermal resistance between neighboring building blocks. Most processes used to generate porous structures (e.g., supercritical drying, freeze drying) involve a solvent that escapes the material. Therefore, it is difficult to create pores and isolate them simultaneously, preventing the fabrication of super-thermal insulators with closed pores.

36 MATERIALS SCIENCE↗

Direct-Write Printing Copper–Nickel (Cu/Ni) Alloy with Controlled Composition from a Single Electrolyte Using Co-Electrodeposition

Although various processes for metal printing at the micro- and mesoscale have been demonstrated, printing functional devices such as thermocouples, thermopiles, and heat flux sensors that function based on interfaces between an alloy and another alloy/metal demands processes for printing alloys. Furthermore, a high-quality and crystalline alloy is required for acceptable function of these devices. This article reports for the first time co-electrodeposition-based printing of single-phase solid solution nanocrystalline copper/nickel (Cu/Ni) alloy with various controllable compositions (Cu100Ni0 to Cu19Ni81) from a single electrolyte. Additionally, the printed alloy is nanocrystalline (<35 nm), continuous, and dense with no apparent porosity, with remarkable mechanical and magnetic properties, without any postprocessing annealing such as heat treatment. In addition, a functional thermocouple fabricated using this process is demonstrated. Such a process can not only be used for fabrication of functional devices, it may also facilitate fundamental studies on alloys by printing a continuous library of alloy composition for material characterization.

36 MATERIALS SCIENCE↗

Letter Report Documenting Progress of Second Generation ATF FeCrAl Alloy Fabrication

Development of the 2 nd generation ATF FeCrAl alloy has been initiated, and a candidate alloy was selected for trial tube fabrication through hot-extrusion and gun-drilling processes. Four alloys based on Fe-13Cr-4.5Al-0.15Y in weight percent were newly cast with minor alloying additions of Mo, Si, Nb, and C to promote solid-solution and second-phase precipitate strengthening. The alloy compositions were selected with guidance from computational thermodynamic tools. The lab-scale heats of ~ 600g were arc-melted and drop-cast, homogenized, hot-forged and -rolled, and then annealed producing plate shape samples. An alloy with Mo and Nb additions (C35MN) processed at 800°C exhibits very fine sub-grain structure with the sub-grain size of 1-3μm which exhibited more than 25% better yield and tensile strengths together with decent ductility compared to the other FeCrAl alloys at room temperature. It was found that the Nb addition was key to improving thermal stability of the fine sub-grain structure. Optimally, grains of less than 30 microns are desired, with grains up to and order of magnitude in desired produced through Nb addition. Scale-up effort of the C35MN alloy was made in collaboration with a commercial cast company who has a capability of vacuum induction melting. A 39lb columnar ingot with ~81mm diameter and ~305mm height (with hot-top) was commercially cast, homogenized, hot-extruded, and annealed providing 10mm-diameter bar-shape samples with the fine sub-grain structure. This commercial heat proved consistent with materials produced at ORNL at the lab-scale. Tubes and end caps were machined from the bar sample and provided to another work package for the ATF-1 irradiation campaign in the milestone M3FT-14OR0202251.

2nd generation ATF FeCrAl alloy↗