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Physical Modeling of Coupled Thermohydraulic Behavior of Compacted MX80 Bentonite during Heating
Abstract This paper describes a tank-scale test setup and experimental methodology used to investigate coupled heat transfer and water flow processes during heating of compacted MX80 bentonite to high temperatures. Specifically, a temperature of 200°C was maintained by a cylindrical heating element at the center of a compacted bentonite layer containing an array of temperature, dielectric, and relative humidity sensors. In addition to providing an evaluation of the spatiotemporal variations in temperature, relative humidity, degree of saturation, and global volume, the coupled thermohydraulic properties of the bentonite were assessed. A wetting front was initially observed to move away from the central heater, followed by a drying process until reaching thermohydraulic equilibrium. The soil–water retention curve (SWRC) of the bentonite followed a wetting scanning path before following the primary drying path exhibiting a shift in water retention with elevated temperature. Results from the tank-scale test can be used for validation of numerical simulations of drying processes in the engineered barrier system of a high-level radioactive waste geological disposal repository and confirm that a temperature-dependent hysteretic SWRC with scanning paths is required to accurately capture the bentonite response.
Production of synthesis gas from natural gas with copper—iron—manganese oxide oxygen carriers/catalysts via partial oxidation and dry reforming processes
Materials, methods of making, and methods of providing a trimetallic oxygen carrier for converting methane containing fuel to synthesis gas. The trimetallic oxygen carrier comprises CuxFeyMnzOt, where CuxFeyMnzOt is a chemical composition with 0 < x ≤ 3 and 0 < y ≤ 3 and 0 < z ≤ 3 and, 0 < t ≤ 5. For example, CuxFeyMnzOt may be one of CuMnFeO 4 , CuFe 0.5 Mn 1.5 O 4 , CuFeMn 2 O 4 , CuFe 2 MnO 4 , or Cu impregnated on FerMnsOu, Fe impregnated on CurMnsOu, Mn impregnated on CurFesOu where r > 0, s > 0 and u > 0 and combinations thereof. Reaction of trimetallic CuxFeyMnzOt with methane generates a product stream comprising at least 50 vol. % CO and H 2 .
Engineering Scale Drying of Aluminum-Clad Spent Nuclear Fuel: Experiment Report
Engineering-scale tests were performed to evaluate the relative effectiveness of forced gas and vacuum-drying processes on aluminum-clad spent nuclear fuel (ASNF) in preparation for extended dry storage. Drying models were developed to improve confidence in the likely range of conditions at the start of dry storage and to understand the factors most significant to each process. Testing was performed at the Holtec International Forced Helium Dehydration training facility in Camden, New Jersey, by students from the University of South Carolina in collaboration with Idaho National Laboratory. A full-size Type 1a basket, with a full-diameter vessel configuration (based on the Department of Energy standardized canister design), was used in combination with a 10 assembly surrogate ASNF arrangement to provide a proxy for geometry. A resistance heater incorporated in one assembly simulated the influence of 100 W decay heat. This instrumented chamber allowed testing of the removal of bulk water, physisorbed water, and chemisorbed water over a range of operating parameters with either drying process. Thick oxide films were grown on aluminum test plates to mimic the ASNF surface chemistry. These one-use test plates were housed within select assemblies during drying. Post-test analysis of these plates gave a measure of the moisture removed during each test, which was compared to a control. Instrumentation provided detailed thermal, humidity, and gas or pressure data relevant to each test. Model simulations generally compared favorably to instrument data for the tests. While both processes were able to remove bulk water, removal of chemisorbed water was shown to depend heavily on local temperature. To the disadvantage of vacuum drying, operations approaching or exceeding 220°C achieved consistently more dehydroxylation.
Reactions during conversion of simplified low-activity waste glass feeds
The mechanisms that affect the incorporation of 99Tc, a volatile radioactive component of concern, into glass melt during vitrification of low-activity waste (LAW) are being investigated to develop the method to increase the retention of 99Tc in glass waste form. Previous studies with simulated LAW glass feeds (slurry mixture of liquid waste and chemical/mineral additives) demonstrated that the early stage feed-to-glass conversion reactions below 800°C are critical for the Re (used as a nonradioactive surrogate of 99Tc) retention in glass. To examine the effect of feed composition on the feed-to-glass conversion reactions, simplified systems containing major LAW components (NaNO3 and NaOH) and representative additive components (SiO2 and H3BO3) were designed and tested. The ratio of H3BO3 to NaNO3 was varied in three-component system without NaOH and that of NaOH to NaNO3 was varied in the four-component system at a fixed H3BO3 to NaNO3 ratio. As a first step of testing with simplified feeds, this study applied thermal analyses and phase characterization of the reacting feeds, which were performed without the addition of Re, to investigate the evolution of salt phases during slurry drying process and upon heating of dried feeds.
Electrification of Boilers in U.S. Manufacturing
Decarbonization of the industrial heat demand through electrification where low/no-carbon electricity is used can contribute significantly to global greenhouse gas (GHG) reduction. In U.S. manufacturing, thermal processes account for approximately 75% of the total final energy demand, of which nearly 17% was consumed by conventional industrial boilers for steam generation in 2018 (this does not include boilers for combined heat and power – CHP). Steam is generally used in industry to regulate temperatures and pressures in industrial processes, dry products, strip impurities from process fluids, etc. Although all kinds of energy sources such as fossil fuels, renewables, nuclear, and electricity can generate steam, fossil fuels’-fired boilers are dominant in U.S. manufacturing. Electric boilers, which are a mature technology, have a small market share for steam generation in the global and U.S. industry (approximately 2% in U.S. manufacturing) due to several techno-economic reasons.
Review and Summary of Corrosion Behavior for Aluminum-Clad Spent Nuclear Fuel in Dry Storage
A description of the corrosion behavior of aluminum alloys used for cladding on aluminum-based, aluminum-clad nuclear fuel used in research reactors under potential dry storage conditions has been compiled. An evaluation is made of potential additional corrosion with water postulated to not be removed during drying. The relative humidity (RH) produced by typical dryness criteria for industrial spent nuclear fuel drying is expected to be low, particularly at high temperatures (17% RH at 20°C and lower at higher temperatures). Existing corrosion data suggests that negligible vapor-phase corrosion of aluminum is expected at such low humidity, even for nominally bare aluminum surfaces. That is, the predicted relative humidity from free water (e.g., 17% RH) is below the “critical” relative humidity (~40% RH at room temperature), below which no significant corrosion is observed for bare aluminum. Furthermore, reported room-temperature corrosion rates are very low even under saturated (100% RH) water vapor. Existing results showing significant vapor-phase corrosion corresponded specifically to conditions of high temper ed with high relative humidity. A relatively large reservoir of (chemically bound) water exists in the aluminum (oxy)hydroxide films on the SNF cladding surface. The estimated total could saturate the gas even at relatively high temperature if fully released; however, its release as molecular water is expected to only be plausible if the temperature during storage exceeds both the drying temperature and the threshold for thermal decomposition of the trihydroxides (~220°C). Therefore, the combination of high temperature and high relative humidity that could drive significant corrosion is considered implausible during sealed dry storage following an appropriate drying process, to include >220°C drying for canisters that may approach or exceed this temperature during storage. Vapor-phase testing of aluminum samples with an adherent (oxy)hydroxide layer, prepared in liquid water to resemble those on actual aluminum-clad spent nuclear fuel (ASNF), did not observe evidence of additional corrosion even at combined high-temperature (up to 180°C) and high-humidity (up to 100% RH) conditions. Instead, small net mass losses were observed for most specimens and attributed to dehydration of the samples, which had been air-dried only prior to testing. ASNF being moved to dry storage is expected to have an existing (oxy)hydroxide film, suggesting that the cladding will be less prone to additional corrosion than bare aluminum metal. If significant corrosion did occur during sealed storage, the overall extent and impact is expected to be small. Corrosion post-closure of a canister would not alter the total amount of hydrogen in the canister, so it would have no effect on the maximum H 2 release already assessed in existing bounding calculations. In addition, the total amount of water in a 25-µm dense bayerite film would consume a only ~8 µm additional aluminum metal on average, if fully consumed by oxidizing aluminum metal to Al 2 O 3 . These conclusions are consistent with ASNF-in-canister simulations to date, which included a reaction pathway for corrosion using kinetics from previous literature and believed to be conservative and predicted very low rates of corrosion.
Characterization of CNC Nanoparticles Prepared via Ultrasonic-Assisted Spray Drying and Their Application in Composite Films
The ultrasonic-assisted spray dryer, also known as a nano spray dryer and predominantly used on a lab scale in the pharmaceutical and food industries, enables the production of nanometer-sized particles. In this study, the nano spray dryer was applied to cellulosic materials, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). CNC suspensions were successfully dried, while the CNF suspensions could not be dried, attributable to their longer fibril lengths. The nano spray drying process was performed under different drying conditions, including nebulizer hole sizes, solid concentrations, and gas flow rates. It was confirmed that the individual particle size of nano spray-dried CNCs (nano SDCNCs) decreased as the nebulizer hole sizes and solid contents of the suspensions decreased. The production rate of the nano spray dryer increased with higher solid contents and lower gas flow rates. The resulting nano SDCNCs were added to a polyvinyl alcohol (PVA) matrix as a reinforcing material to evaluate their reinforcement behavior in a plastic matrix using solvent casting. After incorporating the 20 wt.% nano SDCNCs into the PVA matrix, the tensile strength and tensile modulus elasticity of the neat PVA nanocomposite film increased by 22% and 32%, respectively, while preserving the transparency of the films.
Sensor Development for Liquid Water Detection in Dry Storage Casks: FY 2023 Status
Modeling efforts were undertaken in fiscal year (FY) 2023 to evaluate the feasibility and capability for sensing of liquid water inside canister-based dry cask storage systems (DCSSs). The focus was on the development of full-scale finite element models (FEMs) of ultrasound propagation through DCSS canister components. For these initial investigations, simulation of the baseplate component was targeted, envisioning water collection at the bottom of a vertically oriented canister. The effects of internal canister components (i.e., fuel basket, fuel assemblies) on ultrasound propagation in the baseplate component were evaluated in these efforts. The environment inside a DCSS confinement is intended to be inert and free of water to prevent potential corrosion of used fuel cladding or other internal hardware. Spent fuel assemblies are dried, after storage in water pools, to make sure water has been removed from assembly cavities. However, there is some uncertainty about the amount of residual water potentially left behind in a DCSS after drying processes, because water can become trapped in cavities or other small crevices in the surfaces formed by the fuel cladding, fuel assemblies, and other internal hardware components. Considering the complex space- and time-dependent temperature profiles in DCSSs, water may be in a liquid or gas phase depending on its location in the cask and how long the cask has been in storage. Evacuating most water and oxidizing agents contained within a canister is recommended by NUREG-1536 (NRC 2010), which covers DCSSs. As summarized by Salazar et al. (2020), existing guidance typically relies on achievable vacuum pumping pressures sustained over a hold period as a signal of dryness and water removal. However, time series data about water removal from full-scale commercial drying procedures are lacking (Hanson and Alsaed 2019). A review of drying specifications from several vendors led to the conclusion that if the specifications are followed correctly, the residual moisture in DCSSs should present an insignificant risk of cladding degradation (Knoll and Gilbert 1987). A more recent analysis concluded that much larger quantities of residual water could remain in DCSSs, but the amount would still not be expected to lead to significant corrosion of fuel cladding or other internal components (Jung et al. 2013). Industry drying procedures are mostly prescriptive in nature, and operational issues arising during the process could result in incomplete drying. A summary of operational issues and potential negative effects of residual water is provided by Salazar et al. (2019). Experimental efforts are ongoing to validate the extent of water removal in a DCSS based on drying procedures used at nuclear power plants through well-designed investigations of drying process efficacy and water retention (Durbin et al. 2021; Pulido et al. 2022a, Pulido et al. 2022b). This has been approached by simulating limited portions of a DCSS internal volume and fuel assemblies. So far, these efforts have focused on the effects of potential water trapping in the dashpot region of control rod guide tubes but are expected to be expanded to include the effects of other internal hardware features and failed fuel rod cladding. A method for detection and measurement of liquid water (Meyer et al. 2022; Meyer et al. 2021), in tandem with the drying information gained through experimental investigations, provides comprehensive bases for understanding the internal conditions of DCSSs and provides technical information to support licensing decisions.
Next-Generation Desiccant-Based Gas Clothes Dryer Systems
The goal of the project is to develop an advanced gas clothes dryer system demonstrating significant improvements in fuel efficiency and drying performance compared to current gas clothes dryer technologies. The new system decouples latent and sensible loads to effectively utilize the latent heat associated with laundry moisture as an advantageous energy source. In other words, the system captures the waste latent heat from moisture produced during the fabric-drying process and reuses it to improve drying efficiency.
Solvent-free processing of lithium lanthanum zirconium oxide coated-cathodes
A dry process for coating Ni-rich cathode powder with cubic LLZO powder prepared by flame spray pyrolysis.
High Throughput Solvent-free Manufacturing of Battery Electrodes
The project goal is to develop and demonstrate an advanced solvent-free lithium-ion battery electrode process through proposed Advanced Dry Electrode Process (ADEP) equipment, which is expected to exhibit a better binder fibrillization and high throughput and suitable for high performance electrode manufacturing, and commonize the anode and cathode dry processing equipment, supply chain and operation for lithium-ion battery OEMs for replacing the solvent-based slurry casting. Our proposed approach will facilitate low-cost battery production by addressing the following gaps in present dry electrode processing: • Extend the dry electrode fabrication process to lithium-ion battery anode manufacturing • Increase the active material content for anodes and cathodes • Intensify the process through improved mixing, powder rheology and surface modifications • Enable processing of next-generation electrode materials that are not stable to solvent or ambient air exposure. The project objectives include the development of anode-compatible binder and binder fibrillization promoter for low irreversible capacity loss, low electrode binder content yet higher film mechanical strength, and the optimization of solvent-free anode and cathode process for low cost (>60% electrode cost reduction), high performance (10% increase in energy density without sacrificing cycle life) and high throughput to enable next generation lithium-ion battery electrode production. Solvent-free electrode manufacturing will also enable next-generation cell designs based on prelithiated anodes or solid-state electrolytes.
Spray Manufacturing Thermal Insulation Composites
Cellulose-based thermal insulation materials present significant potential for modern green building applications due to their inherent carbon sequestration properties. However, traditional manufacturing of composites often results in the limited thermal insulation performance and embodied carbon footprint due to an increased density from material shrinkage and higher energy consumption during the water-based slurry drying process. Here, we report solvent spraying coupled with dry powder feedstock to manufacture highly porous silica/straw insulation composites. The manufactured composite exhibits negligible shrinkage with the density of 0.08 g/cm 3 , thermal conductivity of 27.8 mW/(m·K), flexural modulus of 3.1 MPa, and compressive modulus of 0.89 MPa. Additionally, the prepared composite demonstrates fire retardancy (burning rate of 0.5 mm/min) and recyclability (99%). Furthermore, this solvent-spraying strategy opens up opportunities of energy-efficient insulation materials for carbon-sequestration building sectors.
Rare earth metals production using alternative feedstock that eliminates HF
This work reports the successful production of rare earth (RE) metal using Na-RE-F. Presently, RE metals are primarily produced using RE-fluoride due to its higher air and moisture stability compared to RE-chloride. However, its preparation requires the use of corrosive and hazardous chemicals, such as hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ). The present study demonstrates that Na-RE-F is an alternative salt to the typically used RE-fluoride. The Na-RE-F for this work is produced via a scalable hydrometallurgical approach using three different RE salts as feedstock, including acetate, nitrate, and chloride. HF is neither used nor generated during the salt preparation process. Furthermore, the Na-RE-F powder dries in air (without dry HF), and only water evolves during the drying process. Analyses of the Na-RE-F show that NaF liberates as a flux during the heating process, which lowers the salt reduction temperature to <900 °C, thus minimizing or eliminating the need for additional flux. Calciothermic reduction of the Na-RE-F salt is successfully employed to obtain RE metal. This work represents a safer, greener, and more widely deployable approach for producing the RE metals needed for permanent magnets which support the transition to a cleaner society through the decarbonization of the transportation industry.
In Situ Structure Characterization in Slot-Die-Printed All-Polymer Solar Cells with Efficiency Over 9%
Herein, high-performance printed all-polymer solar cells (all-PSCs) based on a bulk-heterojunction (BHJ) blend film are demonstrated using PTzBI as the donor and N2200 as the acceptor. A slot-die process is used to prepare the BHJ blend, which is a cost-effective, high-throughput approach to achieve large-area photovoltaic devices. The real-time crystallization of polymers in the film drying process is investigated by in situ grazing incidence wide-angle X-ray scattering characterization. Printing is found to significantly improve the crystallinity of the polymer blend in comparison with spin coating. Moreover, printing with 1,8-diiodooctane as the solvent additive enhances the polymer aggregation and crystallization during solvent evaporation, eventually leading to multi-length-scale phase separation, with PTzBI-rich domains in-between the N2200 crystalline fibers. This unique morphology achieved by printing fabrication results in an impressively high power conversion efficiency of 9.10%, which is the highest efficiency reported for printed all-PSCs. Finally, these findings provide important guidelines for controlling film drying dynamics for processing all-PSCs.
Drying of strawberries with airborne ultrasound and other integrated dehydration mechanisms
This article presents a comprehensive investigation into the drying of strawberries using multiple dehydration methods with an emphasis on energy efficiency and sustainability. Initially, an airborne ultrasonic transducer with a frequency of 21 kHz was employed in batch operations to examine the effects of controlling parameters, including applied power, distance from the transducer plate, sample thickness, and sample holder type. The Energy Ratio, defined as the ratio of thermal energy required to evaporate moisture to ultrasonic energy, was observed to reach up to 2.2, particularly during the initial stages of drying. Subsequently, the Smart Dryer integrated airborne ultrasound (US) dehydration, slot jet reattachment (SJR) nozzle convective drying, infrared (IR) drying, and their combinations, enabling a systematic exploration of various drying conditions on the drying time and quality of strawberries. The integration of airborne US with SJR nozzles and IR drying demonstrates a promising approach for optimizing drying processes. This method not only preserves the quality of dried strawberries but also improves the energy factor to 0.88, reducing drying time by 89% compared with other conditions. Key quality attributes of the dried strawberries, such as color and water activity, were evaluated to understand the influence of each drying method. The findings highlight the potential of these integrated drying techniques as sustainable solutions for efficient and high-quality strawberry dehydration.
Electrode manufacturing for lithium-ion batteries—Analysis of current and next generation processing
As modern energy storage needs become more demanding, the manufacturing of lithium-ion batteries (LIBs) represents a sizable area of growth of the technology. Specifically, wet processing of electrodes has matured such that it is a commonly employed industrial technique. Despite its widespread acceptance, wet processing of electrodes faces a number of problems, including expensive and dangerous solvent recovery, cut-off waste, coating inconsistencies, and microstructural defects due to the solvent drying process. This review considers each of these issues and discusses which electrode slurry properties should be considered when optimizing wet slurry fabrication. Simultaneously, methods to replace traditional wet processing of electrodes are being extensively researched. Some of these novel electrode manufacturing techniques prioritize solvent minimization, while others emphasize boosting energy and power density by thickening the electrode and, subsequently, creating an organized pore structure to permit faster ion diffusion. This review contemplates the advantages and disadvantages of each of these approaches and provides a comprehensive outlook on the future of electrode manufacturing.