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At least 145 records · Page 8

Multi-material direct ink writing and co-sintering of gadolinium oxide – zirconium oxide components

Methods for fabrication of multi-material or functionally graded ceramic composite architectures are of interest for numerous applications. However, conventional co-sintering of multi-material ceramic parts is a challenge because differences in the sintering behavior of the two materials leads to interfacial strain and, ultimately, component failure. Direct ink writing (DIW) is an extrusion-based additive manufacturing process that excels at multi-material printing because multiple extrusion nozzles can be installed on the same gantry system. Furthermore, the use of DIW as a method to fabricate multi-material ceramic green bodies offers an additional variable for controlling and potentially matching sintering kinetics in the slurry formulation used for two dissimilar feedstocks. In the work documented in this manuscript, we explored two strategies to successfully co-sinter multi-material ceramic oxides: slurry optimization to match sintering kinetics and material gradients to step from one material to another. This manuscript also quantifies the allowable mismatch that avoids part cracking in solid solution forming multi-material systems and discusses best strategies to reduce mismatch during co-sintering. Inks composed of gadolinium oxide (Gd 2 O 3 ) and zirconium oxide (ZrO 2 ), a surrogate for uranium oxide (UO 2 ), were thermally matched, which resulted in a sintering mismatch reduction of over 10%. It was found that ~1% mismatch is tolerable during debind cycles and that ~5% mismatch is manageable during sintering cycles after slurry formulations are optimized to match the sintering behavior. Use of continuous gradients is shown to reduce sintering mismatch, although geometric resolution may be lost due to solid solution formation.

Snarr, Patrick L. [Oak Ridge National Laboratory (↗

CO 2 utilization in built environment via the P CO 2 swing carbonation of alkaline solid wastes with different mineralogy

Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO 2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO 2 utilization has multifaceted environmental benefits including CO 2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO 2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO 2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the P CO 2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO 2 bubbling could not provide a low enough pH condition for concrete–water–CO 2 systems. Furthermore, this study showed that the two-step carbon mineralization via P CO 2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO 2 utilization potential as an upcycled construction material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiphysics simulation of supercritical CO 2 gasification for hydrogen production

A bench-scale supercritical CO 2 gasifier is being considered by the U.S. Department of Energy’s National Energy Technology Laboratory (NETL). A reacting computational fluid dynamics (CFD) model was developed using ANSYS/Fluent in order to investigate the impact of various operating parameters on syngas composition. The model was validated using available data in the literature. Simulations were conducted over a range of coal-slurry loadings, reaction temperatures, system pressures, and oxygen mass flowrates with the goal of optimizing hydrogen production for the considered reactor. The results from the simulations identified a positive correlation between slurry loading and hydrogen production, while reactor temperature and pressure had a limited impact on H 2 production at the conditions of interest. Additionally, the simulations indicated that oxygen mass flowrate has less of an impact on hydrogen production at higher slurry loadings.

08 HYDROGEN↗

Analysis of DWPF Sludge Batch 6 (Macrobatch 7): Pour Stream Glass Samples

The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 6 (SB6), also referred to as Macrobatch 7 (MB7), in June 2010. SB6 is a blend of the heel of Tank 40 from Sludge Batch 5 (SB5), H-Canyon Np transfers and SB6 that was transferred to Tank 40 from Tank 51.1 SB6 was processed using Frit 418. Sludge is received into the DWPF Chemical Processing Cell (CPC) and is processed through the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator Tank (SME). The treated sludge slurry is then transferred to the Melter Feed Tank (MFT) and fed to the melter. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program (GPCP) and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. The DWPF requested various analyses of radioactive glass samples obtained from the melter pour stream during processing of SB6 as well as reduction/oxidation (REDOX) analysis of MFT samples to determine the impact of Argon bubbling. Sample analysis followed the Task Technical and Quality Assurance Plan (TTQAP) and an Analytical Study Plan (ASP). Four Pour Stream (PS) glass samples and two MFT slurry samples were delivered to the Savannah River National Laboratory (SRNL) from the DWPF. Table 1-1 lists the sample information for each pour stream glass sample. SB6 PS3 (S03472) was selected as the official pour stream sample for SB6 and full analysis was requested. This report details the visual observations of the as-received SB6 PS No.3 glass sample as well as results for the chemical composition, Product Consistency Test (PCT), radionuclide content, noble metals, and glass density. REDOX results will be provided for all four pour stream samples and vitrified samples of MFT-558 and MFT-568A. Where appropriate, data from other pour stream samples will be provided.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

The Savannah River National Laboratory (SRNL) was requested to develop a new antifoam control method for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). SRNL completed testing of both chemical and nonchemical foam controls. The nonchemical foam controls were either ineffective (or worse, created more foam) or impractical (a water spray can control foam, but excessive water is needed). As a result, the focus of this study was on finding a superwetter or commercial antifoam for controlling foam. Thirty potential antifoams were tested as part of this study. A series of tests were developed to help screen out ineffective alternatives including: 1. Spreading testing of superspreaders, 2. Foam column testing with physical simulants, 3. Boiling testing with physical and chemical simulants, 4. Days-only Sludge Receipt and Adjustment Tank (SRAT) process simulations with sludge (containing noble metals and mercury), Precipitate Reactor Feed Tank (PRFT), and Slurry Mix Evaporator Feed Tank (SEFT) simulants in the RC1 Reaction Calorimeter (purchased for antifoam testing), and 5. Around-the-clock SRAT and Slurry Mix Evaporator (SME) process simulations with sludge(containing noble metals and mercury), PRFT, and SEFT simulants in the RC1 Reaction Calorimeter. Evonik Surfynol® MD20, a commercially available defoamer, was relatively effective in controlling foam, while remaining chemically stable in SRAT and SME processing across the pH range of 4 to 13. No degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. In nitric-glycolic acid flowsheet testing, 250 mg/kg Evonik Surfynol® MD20 was needed for foam control compared to 1,625 mg/kg for Antifoam 747, DWPF’s current antifoam. In nitric-formic acid flowsheet testing, 1,125 mg/kg of Evonik Surfynol® MD20 was needed to control foam throughout the SRAT and SME cycles. The commercially available superspreader Momentive™ Y-17112 was even more effective than Evonik Surfynol® MD20 as both a defoamer and an antifoam. Not only was the foam destroyed upon addition but also was less persistent between additions. It was the most effective antifoam in testing using both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. In nitric-glycolic acid flowsheet testing, only 100 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. In nitric-formic acid flowsheet testing, 300 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. Momentive™ Y-17112 is also resistant to hydrolysis as demonstrated by its chemical stability in SRAT and SME processing across the pH range of 4 to 13 and lack of degradation products in offgas or condensate. Both candidates were effective as potential replacements for Antifoam 747, with Y-17112 demonstrating superior foam control. During nitric-glycolic flowsheet testing 50% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. During nitric-formic flowsheet testing 75% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. Foam remediated with Momentive™ Y-17112 was less persistent throughout testing. In addition, no degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. Based on this testing, Momentive™ Y-17112 is clearly superior to Evonik Surfynol® MD20 and Antifoam 747, especially for the nitric-formic acid flowsheet processing; it is recommended that Momentive™ Y-17112 replace Antifoam 747 in DWPF. An antifoam addition strategy is recommended for both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. Implementation of Momentive™ Y-17112 is expected to decrease SRAT and SME boiling times by up to 50%, eliminate the issues resulting from Antifoam 747 degradation products, and minimize foamovers. To validate the effectiveness of these defoaming agents, SRNL recommends irradiation of a SRAT or SME product simulant containing fresh antifoam. The goal of this testing is to determine whether the irradiation causes decomposition of the antifoam that would make it less effective or produce new species in the offgas or slurry. This testing began in April 2020. An evaluation should be completed to determine the thermolytic hydrogen and methane generation rate in downstream equipment, including the High-Level Waste evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Formulation via Resonant Acoustic Mixing at LANL

Discussions in the middle of 2014 led researchers at LANL to seek an alternate formulation method for making PBX based explosives. We began looking into the use of Resonant Acoustic Mixers (RAM) to formulate explosives and mocks. Acoustic mixing had been used in pharmaceutical plants for mixing medicines and coating materials, so we envisioned transitioning that same technology to the energetics world. Up until this time only the wet slurry formulation method that had been used was from the 1940’s. This wet slurry method had been and still was the standard for all explosive formulations. The possibility of an alternate method needed to be looked at to advance the process by expanding solvent choices, substrates, and reducing costs. Acoustic mixing had been shown to mix powders, slurries, pastes or even liquids. A Resodyn LabRAM was purchased in late 2014 to explore these possible applications to energetics. This LabRAM was in a remote configuration that met our need for explosive operations.

36 MATERIALS SCIENCE↗

Characterization of the SRNL-Washed Tank 51 Sludge Batch 10 Qualification Sample

Savannah River National Laboratory (SRNL) personnel have been requested to qualify the next sludge batch (Sludge Batch 10 – SB10) for processing at the Defense Waste Processing Facility (DWPF). To accomplish this task, Savannah River Remediation (SRR) sent SRNL two 3-L samples of Tank 51H slurry to be characterized, washed, and then used in a lab-scale demonstration of the DWPF flowsheet. Sample HTF-51-19-114 was received on January 28, 2020, and HTF-51-20-15 was received on February 4, 2020. SRNL washed the Tank 51H sample per the Tank Farm washing strategy. During washing, material from H Canyon Tanks 16.3 and 16.4 was also added to the Tank 51 samples to simulate canyon discharges subsequent to sampling. A part of the qualification process is extensive radionuclide and chemical characterization of the SRNL-washed Tank 51H slurry. This report documents the chemical characterization of the washed slurry; radiological characterization will be documented in a separate report. The major supernatant components, elements on a weight percent calcined basis, and the weight percent solids of the SRNL-washed sample were comparable to the Tank Farm projections, with the exception of free hydroxide and carbonate. Therefore, this SRNL-washed sample is suitable for further SB10 qualification activities and SRR planning for SB10.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enzyme-assisted liquefaction for different fractions of corn stover pellets

With an increase in population, the world will depend on renewable sources to meet the increasing energy needs. The use of lignocellulosic biomass as a renewable source has been proven efficient for conversion to cellulosic ethanol and capable of contributing to thresholds for energy demand while reducing greenhouse gases by 90% when compared with fossil fuels. However, limitations in feeding and flow within biorefineries are encountered when system plugging occurs due to biomass compaction and a high yield stress for slurries formed during its processing. Furthermore, differences in the biomass source present a challenge to the continuity of operations and reliability in the process. This work explores enzyme-assisted liquefaction for solid loadings up to 30% as an alternative for the creation of slurry from two different types of biomass (pelleted corn stover and cobs) that were liquefied in a fed-batch process using commercial enzymes Celluclast 1.5L or Ctec-2 at 1FPU/g or 3 FPU/g of dry solids in a 10 mM sodium citrate buffer solution (pH 4.8). Pellets were fed into a 1 L stirred bioreactor according to a predefined fed-batch protocol during the first 5 hours until 30% solid loading was reached. After 6, 24 and 96 hours, samples were taken and characterized with respect to their composition, rheology, and water absorption. Successful slurry creation with dramatically reduced yield stress was achieved for corn stover for both enzymes assessed. Yield stresses of 178±7 Pa (3 FPU, Celluclast 1.5L) and 79±6 Pa (3 FPU, Ctec-2) were measured for corn stover at 24 hours, compared to 6,000 Pa for samples without enzyme. Yield stress was 155± 29 Pa (3FPU, Ctec-2) and 257 ± 72 Pa (1 FPU, Celluclast 1.5L) for corn cobs at 24 hours. A profile for 6, 24 and 96h of yield stress measurements and sugar conversion is presented.

Gutierrez, Diana↗

Modeling of High Solids Biomass Liquefaction, Techno-economic Assessment and Life Cycle Assessment for Industrial Scale UP

Biomass liquefaction improves corn-stover slurry transport within a biorefinery, and reduces challenges associated with solids handling. Slurries, formed with yield stresses (i.e., viscosities) that are low enough to facilitate pumping from one unit operation to the next, and that enable mixing at reasonable power inputs in large fermentation vessels, enable scaling of cellulose fermentations. Three liquefaction methods: enzyme, enzyme mimetic, and a hybrid approach were analyzed by a combination of techno-economic and life-cycle analyses, resulting in an assessment of cost-effectiveness and environmental impact. Of the three scenarios, enzyme-based processes emerged as the most efficient, both in cost and emissions reduction (gCO2-equivalent/kg slurry).

Ramirez, Jorge↗

Renewable low-Z wall for fusion reactors with built-in tritium recovery (Final Technical Report)

This project pursued development of a novel renewable plasma-facing wall technology for fusion reactors. The technology is based on a slurry which can be easily delivered by delivery tubes to the reactor wall. The slurry dries at the hot reactor wall into pebble rods which are extruded out into the hot plasma, where the pebbles break off and fall along the reactor wall and can be recovered by gravity and re-used. The falling pebbles carry away heat and tritium and also protect the wall against large scale erosion or redeposition of material. The research focused on carbon-based pebble rods and demonstrated that pebble rods could be produced from slurry with tolerable levels of outgassing on a reactor-relevant timescale (< 5 minutes). Steady-state handling of reactor relevant (up to 50 MW/m 2 ) normal-incidence heat loads was demonstrated. Pebble release velocities were found to be sufficiently small (< 1 m/s) to allow recovery below the vacuum chamber. Tunability of the pebble rod breaking rate was demonstrated by changing the fill fraction of the interpebble matrix which binds the pebbles together. This work could benefit the public by helping move forward the design of commercially viable fusion energy reactors. Designing a first wall for magnetic fusion reactors which can handle the huge heat loads present and also avoid buildup of tritium-containing deposits is extremely challenging and requires novel approaches like the one being investigated here.

36 MATERIALS SCIENCE↗

BETO 2021 Peer Review - Bench Scale Integration WBS 2.4.1.100

Bench Scale Integration develops and optimizes fermentation processes to produce bio-based fuels and chemicals from biomass sugars. The project uses fermentation science to achieve high titers and production rates by, for example, manipulating how the microorganisms are fed biomass sugars and nutrients, modifying fermentation conditions (pH, temperature, aeration) or developing online control strategies that increase production rates. For this period of performance, we conducted small scale fermentation research using strategies mentioned to produce 2,3-butanediol (BDO) from biomass utilizing NREL's proprietary Zymomonas mobilis microorganism. BDO is a versatile chemical which can be catalytically upgraded to a variety of hydrocarbon fuels and chemicals. The 3-yr project goal was to increase BDO titers from 50 g/L (FY17 level) to 125 g/L on biomass sugars by 2020. This is a 150% increase in titer showing the commercial potential of Z. mobilis while reducing the cost to downstream processing. We successfully achieved this target. The project also showed yearly progress improvements to the process design case by using a whole biomass slurry. Future work will focus on procedures for scaling to produce large quantities of BDO broth for separations and upgrading R&D and improve the titer and rates from biomass whole slurry. Our goal is to produce 100 g/L BDO titer from whole slurry at >1000L by 2023 which will meet the technical targets set by our techno-economic analysis.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Apparatus and method for three-dimensional metal printing

An apparatus and device for building an article by additive manufacturing or 3-D printing. The method includes feeding a supply of particulate slurry to and through a nozzle, such as including an integrated pump, to form a plurality of beads and layers of the slurry on a deposition surface, and ultimately forming a desirable article from the layers of deposited material. The liquid phase of the slurry is desirably removed by heat, and the deposited layers can be sintered or otherwise fused as needed.

Klett, James W.↗

Multiphysics Simulation of Supercritical CO2 Gasification for Hydrogen Production

A bench-scale supercritical CO2 gasifier is being considered by the U.S. Department of Energy’s National Energy Technology Laboratory (NETL). A reacting computational fluid dynamics (CFD) model was developed using ANSYS/Fluent in order to investigate the impact of various operating parameters on syngas composition. The model was validated using available data in the literature. Simulations were conducted over a range of coal-slurry loadings, reaction temperatures, system pressures, and oxygen mass flowrates with the goal of optimizing hydrogen production for the considered reactor. The results from the simulations identified a positive correlation between slurry loading and hydrogen production, while reactor temperature and pressure had a limited impact on H2 production at the conditions of interest. Additionally, the simulations indicated that oxygen mass flowrate has less of an impact on hydrogen production at higher slurry loadings.

Prlina, Alexander↗

Methods and systems for liquid separations

Methods and systems for separating liquid components are disclosed. A vessel is provided containing a solids conveyance device. At least a first portion of the vessel acts as an indirect-contact heat exchanger and a second portion of the vessel contains a filter. A process liquid stream, containing a first component and a second component, is passed into the first portion of the vessel. A portion of the second component is frozen and entrained in the first portion of the vessel into the process liquid stream, resulting in a process slurry stream. The process slurry stream is passed into a second portion of the vessel by the solids conveyance device. The process slurry stream is separated into a solid product stream and a primary liquid product stream by passing the primary liquid product stream through the filter and out of the vessel while separately removing the solid product stream out of the vessel.

Baxter, Larry↗

Method and integrated process for the carboxylation of furan derived carboxylic acids to 2,5-furandicarboxylic acid

A process for carboxylation of a furoate slurry to produce FDCA, especially 2,5-FDCA, includes the steps of: feeding a slurry containing a suspension fluid, furoate, a surfactant and an alkali metal carbonate to a carboxylation reactor; and feeding a flow of CO 2 to the carboxylation reactor at flow conditions sufficient to suspend the slurry in the reactor and react the furoate with CO 2 to form 2,5-FDCA. A fully integrated process is also disclosed.

Kittrell, James R.↗

Developing a Novel Ultrafine Coal Dewatering Process

Dewatering fine coal is needed in many applications but has remained a great challenge. The hydrophobic-hydrophilic separation (HHS) method is a powerful technology to address this problem. However, organic solvents in solvent-coal slurries produced during HHS must be recovered for the method to be economically viable. Here, the experimental studies of recovering solvents from pentane-coal and hexane-coal slurries by combining liquid-solid filtration and in-situ vaporization and removing the solvent by a carrier gas (i.e., drying) are reported. The filtration behaviors are studied under different solid mass loading and filtration pressure. It is shown that using pressure filtration driven by 20 psig nitrogen, over 95% of solvents by mass in the slurries can be recovered, and filtration cakes can be formed in 60 s. The drying behavior was studied using nitrogen and steam at different temperatures and pressures. It is shown that residual solvents in filtration cakes can be reduced below 1400 ppm within 10 s by 15 psig steam superheated to 150 degree C, while other parameter combinations are far less effective in removing solvents. Physical processes involved in drying and the structure of solvent-laden filtration cakes are analyzed in light of these results.

01 COAL, LIGNITE, AND PEAT↗

Vessel and method for solid-liquid separation

Devices, systems, and methods for separating solids from liquids are disclosed. A vessel includes an inlet, a carrier liquid outlet, a product outlet, a purifying section, and a heater. The inlet directs a slurry into the purifying section. The slurry comprises particles of a solid and a carrier liquid. The purifying section preferentially drives the particles of the solid towards a heating zone of the purifying section versus the carrier liquid. This displaces a first portion of the carrier liquid away from the heating zone of the purifying section. The heater heats the slurry. The carrier liquid outlet drives a majority of the carrier liquid out of the vessel. The product outlet is adjacent to the heating zone of the purifying section.

Baxter, Larry↗

Industrial scale mesofluidic particle separation

Here we explore the potential of a mesofluidic separator that fits within industrial piping and is designed to remove large aspherical particles out of an abrasive slurry at fast flow rates. Mesofluidic separators have recently demonstrated separation of spherical particles at flow rates of ~1 gallon/min (gpm) (6.3.10 -5 m 3 /s). Yet, the performance of these separators at flow rates achievable within industrial piping have not been explored. Here we evaluate the permeate flowrate fraction, large particle mass fraction, and pressure drop from approximately 35-100 gpm (2.2.10-3-6.3.10-3 m 3 /s) in a three inch tube using an abrasive and modestly non-spherical slurry. Faster flow rates may be achieved with larger pumps and larger diameters. We find the permeate fraction and pressure drop both increase with flow rate, though the pressure drop remains modest. Only two feet of inserts removed 97.6±2.1% of large particles for conditions tested. Separation was demonstrated in both vertical and horizontal orientations with the horizontal orientation benefiting marginally from gravitational settling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗