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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Simulation of DWPF Chemical Process Cell Using a Reaction Calorimeter

The Defense Waste Processing Facility (DWPF) converts liquid radioactive waste into glass using a Sludge Receipt Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) in addition to other processes. The SRAT and SME processes can be simulated on a small-scale using the Mettler-Toledo Reaction Calorimeter (RC1). This equipment is able to automate the execution and monitoring of experiments involving nonradioactive chemical simulants. During the chemical processing of sludge in the SRAT process, foam begins to form and can foam over the reaction vessel. The current antifoam used at DWPF creates a risk of increased flammability and has a limited pH range. Usually, mercury is circulated back into the reaction vessel during the SRAT process, making it difficult to remove. To combat foam over, novel antifoams will be tested during the boil-up process using the RC1. To improve mercury extraction, 3D-printed coalescer columns will be tested within the Mercury Water Wash Tank (MWWT) of the RC1. Testing of Simulant Sludge Batch 6 (SB6) was performed to ensure: the sludge would form a stable foam at boiling during full SRAT/SME runs; the antifoam would reduce the amount of foam within the vessel The sludge and a Precipitate Reactor Feed Tank (PRFT) simulant with monosodium titanate (MST) were mixed separately, combined, and then heated to boiling. As shown below, the antifoam used was able to eliminate the foam within the vessel, as expected. The FormLabs Form2 3D Printer can be used to create roughly 3-inch tall and 1-inch diameter columns from clear and ceramic resins. The columns will utilize chemical and physical forces to draw the mercury out of a condensed offgas stream leaving the RC1 reaction vessel. These columns will be tested during full SRAT/SME runs on the basis of how well they are able to collect elemental mercury. In preparation for full-scale runs, the RC1 equipment was assembled onto a custom table and tested with water runs. The software used to control automation, iControl, has a user-friendly interface that allows the experiment to be altered as needed. An example of the data recorded during an experimental run is represented in Figure 1 below. Water runs were utilized as a way to prove if the RC1 system was functioning in the following areas: Boil-up rates, Chemical additions using pumps, Temperature readings, Balance readings, Probe readings, Offgas system, Agitation. Future Plans: Five novel antifoams will be tested during full SRAT/SME runs. The most effective antifoam will be utilized in DWPF's Chemical Process Cell. The design of the Mercury Extraction Coalescer can be further manipulated to increase the extraction of not only elemental mercury, but other heavy metals in environmental remediation processes as well.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Processing and 3D printing of SiCN polymer-derived ceramics

Preceramic polymer resins are attractive for the 3D printing of net-shaped ceramic components. Recently various processes have been demonstrated for 3D printing of polymer-derived ceramics (PDCs). Ultimately in these processes, the process outcomes strongly depend on the process parameters. In particular, for PDCs the ceramic density, and ceramic yield are affected by the catalyst concentration and cross-linking duration. Here, we use thermal analysis and FTIR to quantify the interrelation of the process parameters on the process outcome for polysilazanes and demonstrate 3D printing of PDC components based on the best-identified process parameters. Furthermore, the results of this work can be used as guidelines for future additive manufacturing of PDCs.

36 MATERIALS SCIENCE↗

Refractive index matching base resin for extremely fine three-dimensional ceramic structures

An optically clear resin for additive manufacturing includes an optically clear ceramic precursor having a pre-defined refractive index. Each molecule of the ceramic precursor has at least two photopolymerizable functional groups, at least one of the photopolymerizable functional groups being functionalized with a refractive index-tuning group thereby causing the ceramic precursor to have the pre-defined refractive index.

Mettry, Magi↗

Corrosion-Resistant Coatings on Spent Nuclear Fuel Canisters to Mitigate and Repair Potential Stress Corrosion Cracking (FY22 Status)

This report summarizes the activities performed by Sandia National Laboratories in FY22 to identify and test coating materials for the prevention, mitigation, and/or repair of potential chloride-induced stress corrosion cracking in spent nuclear fuel dry storage canisters. This work continues efforts by Sandia National Laboratories that are summarized in previous reports in FY20 and FY21 on the same topic. The previous work detailed the specific coating properties desired for application and implementation to spent nuclear fuel canisters (FY20) and identified several potential coatings for evaluation (FY21). In FY22, Sandia National Laboratories, in collaboration with four industry partners through a Memorandum of Understanding, started evaluating the physical, mechanical, and corrosion-resistance properties of 6 different coating systems (11 total coating variants) to develop a baseline understanding of the viability of each coating type for use to prevent, mitigate, and/or repair potential stress corrosion on cracking on spent nuclear fuel canisters. This collaborative R&D program leverages the analytical and laboratory capabilities at Sandia National Laboratories and the material design and synthesis capabilities of the industry collaborators. The coating systems include organic (polyetherketoneketone, modified polyimide/polyurea, modified phenolic resin), organic/inorganic ceramic hybrids (silane-based polyurethane hybrid and a quasi-ceramic sol-gel polyurethane hybrid), and hybrid systems in conjuncture with a Zn-rich primer. These coatings were applied to stainless steel coupons (the same coupons were supplied to all vendors by SNL for direct comparison) and have undergone several physical, mechanical, and electrochemical tests. The results and implications of these tests are summarized in this report. These analyses will be used to identify the most effective coatings for potential use on spent nuclear fuel dry storage canisters, and also to identify specific needs for further optimization of coating technologies for their application on spent nuclear fuel canisters. In FY22, Sandia National Laboratories performed baseline testing and atmospheric exposure tests of the coating samples supplied by the vendors in accordance with the scope of work defined in the Memorandum of Understanding. In FY23, Sandia National Laboratories will continue evaluating coating performance with a focus on thermal and radiolytic stability.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Task 2.1: Adsorption-Based ISPR for BETO-Relevant Bioproducts

This task focuses on the development of adsorption-based in situ product recovery (ISPR) integrated with simulated moving bed chromatography for the recovery and purification of carboxylate products that are relevant to BETO. ISPR has been pursued previously in the Separations Consortium to recover carboxylic acids near or below their pKa values with liquid-liquid extraction coupled to downstream distillation. However, there are many acid products in the BETO portfolio that require neutralization well above their pKa values wherein ISPR could still be a major benefit to the bioprocess performance, including muconic acid, beta-ketoadipic acid, 3-hydroxypropionic acid, itaconic acid, butyric acid, and others. In this task, we are combining dynamic filtration with a rotating ceramic disk, resin capacity measurements, tailored resin synthesis, and simulated moving bed chromatography into an ISPR system that can be used to recover BETO-relevant carboxylates from bioreactor cultivations. We are working across process scales and using computational modeling where applicable alongside techno-economic analysis and life cycle assessment to understand major cost, energy, and GHG emissions drivers. The impact of this project will be a bench-scale integrated approach to recover carboxylate products in situ, which will reduce the waste generation from biological carboxylate production processes and improve the productivities of biological systems.

bio-based acid↗

Corrosion-Resistant Coatings on Spent Nuclear Fuel Canisters to Mitigate and Repair Potential Stress Corrosion Cracking (FY23 Status)

This report summarizes the activities performed by Sandia National Laboratories in FY23 to identify and test coating materials for the prevention, mitigation, and/or repair of potential chloride-induced stress corrosion cracking in spent nuclear fuel dry storage canisters. This work continues efforts by Sandia National Laboratories that are summarized in previous reports from FY20 through FY22 on the same topic. In FY23, Sandia National Laboratories, in collaboration with five industry partners through a memorandum of understanding, evaluated the physical, mechanical, and corrosion-resistance properties of eight different coating systems. The evaluation included thermal and radiation environments relevant to various time periods of storage for spent nuclear fuel canisters. The coating systems include polymeric (polyetherketoneketone, modified polyimide/polyurea, modified phenolic resin, epoxy), organic/inorganic ceramic hybrids (silane-based polyurethane hybrid and a quasi-ceramic sol-gel polyurethane hybrid), and coatings utilizing a Zn-rich primer applied to stainless steel coupons. The results and implications of these tests are summarized in this report. These analyses will be used to identify the most effective coatings for potential use on spent nuclear fuel dry storage canisters and to identify specific needs for further optimization of coating technologies for application on spent nuclear fuel canisters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Scalable, Infiltration-Free Ceramic Matrix Composite (SIF-CMC) manufacturing for Molten Salt Receiver: Investigation of particle-loaded preceramic resin

Due to their unique combination of high temperature, corrosion resistance, and toughness, Ceramic Matrix Composites (CMC) are the optimal materials to be used in the next generation of Concentrated Solar Power (CSP), which will operate at working temperatures up to 800 °C. However, today, CMC is too costly to be used in CSP applications due to its complex manufacturing process based on repeated infiltration-pyrolysis cycles. To solve this issue, PARC is developing a scalable, infiltration-free method (SIF) to manufacture CMC, which can reduce the production cost, increase batch consistency, and leverage all of the intrinsic advantages of current CMCs. The key to the SIF method is using a flowable preceramic resin with high loading of functional components. The formulation impregnates the fiber during curing and leads to high-density, low-shrinkage parts upon pyrolysis. In this paper, we demonstrate a proof-of-concept of the SIF process and report the relationships between key process parameters in the manufacturing process: functional material loading in the resin vs. resin’s flowability and morphology changes upon pyrolysis.

ceramic matrix composite, concentrated solar power↗

High Char Yield and Flowable Preceramic Resin Enabled with the Monomer Functionalized SiC Particle

Ceramic matrix composites (CMCs) are used in diverse high temperature applications; however, manufacturing CMCs is highly time consuming and costly. We address this challenge by introducing a methodology for fabricating CMCs using an innovative composite preceramic resin. This composite resin contains 40% mass loading of SiC particles, which are chemically functionalized with a resin monomer. The functionalization facilitates a homogenous dispersion of SiC particles within the resin matrix, resulting in high char yield (83.6%) and enhanced impregnation efficiency through reduced melt viscosity, ~10 Pa.s for relevant shear rates. This breakthrough represents a significant stride towards developing a more economically viable and efficient manufacturing process for CMCs.

14 SOLAR ENERGY↗

Surviving nanoscale interfacial stability in extreme thermal expansion contrast Zn(CN) 2 -epoxy resin matrix composites

Here, we report the remarkable stability at the nanoscale matrix-filler interface in a series of overall low coefficient of thermal expansion (CTE) zinc cyanide (ZC)/epoxy resin composites. These interfaces demonstrate the stability of highly contrasting materials. These composites are designed to optimize the properties of both materials: epoxy resins are valued for their high strength, superb chemical resistance, low dielectric properties, and adhesive abilities. ZC, a model flexible framework, exhibits negative thermal expansion (NTE) behavior and compensates for the epoxy resin’s detrimentally large thermal expansion values. Filled resins minimize the native 65 ppm/°C CTE values to 19 ppm/° C over a wide temperature range while maintaining linearity, yielding composites compatible with typical metal and ceramic substrates’—commonly bonded to the resin— 0–20 ppm/° C CTE values. Additionally, with significant intrinsic differences in the materials, we use wide-angle X-ray diffraction and atomic force microscopy to elucidate thermal movement. The ZC/epoxy interface is surprisingly resilient over 1,000 cycles between -55° C and 75° C, extremes typical to aerospace applications. Further, we show that the resin viscosity remains less than 21 Pa*s at up to 30 vol% ZC, an important consideration for workability. We also discuss settling distribution, glass transition temperature, flexural strength, and longevity. All results point favorably towards practical implementation in low thermal expansion application needs: filling the gap in component design.

42 ENGINEERING↗

High-Performance Coal-Based Commercial Facade Panels and Architectural Components (Phase I Final Report)

Semplastics has developed, tested, and documented the viability for commercialization of a new class of composite architectural panel materials that use coal as the primary constituent. This project produced sample panels using these novel materials that comprise 55% coal by mass (71% carbon by mass) and are comparable in dimensions to commercially available materials, while displaying superior mechanical strength, significant weight savings, and better insulating ability at a competitive cost. Phase I moved this coal-based composite materials technology from a Technology Readiness Level (TRL) of 3 to TRL 5. Semplastics’ new coal-based composite materials display an array of high-performance characteristics, including light weight, mechanical durability, temperature stability, and water resistance. These new materials require less energy to produce than comparable commercial products and could be manufactured on existing conventional plastic resin processing equipment in commercial quantities. The coal particles are completely encapsulated in ceramic from a polymer-derived ceramic (PDC) precursor, then bonded together by another inorganic resin. The material can be molded and cured to produce fireproof components such as ceiling panels, facades, and extruded underlayment, blocking, and backer boards, as well as other architectural design components such as moldings. The project included the production of sample panels for proof of concept, testing of the panels to show their improved characteristics, and development of a scale-up strategy to demonstrate the viability of the coal-based panels as a commercial alternative to existing building materials.

36 MATERIALS SCIENCE↗

Development of Additive Manufacturing for Ceramic Matrix Composite Vanes

This report discusses the development of additive manufacturing for polymer-derived ceramic materials to create novel cooled gas turbine airfoils made from ceramics. Gas turbine engines have extremely high temperatures in the hot section of the engine that exceed the melting point of nickel superalloy materials that the engine is made from. Advanced cooling technologies have been developed over decades for metallic parts. Ceramic materials have higher temperature capabilities than superalloys, but are difficult to shape in the complex designs used in modern turbines. Several thrusts were investigated during the project, including development of higher material strength resins, improvement of ultraviolet (UV) photopolymerization and post-processing techniques to increase survivability of ceramic parts, thermomechanical modeling of novel ceramic airfoil designs for higher cooling effectiveness, and experimental validation of the modeling and manufacturing in a turbine vane test facility at nondimensional conditions that are relevant to modern gas turbines. Some major findings of the work include a significant increase in ceramic survivability during pyrolysis (a high temperature process that converts the organic material to a ceramic) by adjusting the composition ratios of the resins, as well as a tolulene soak after printing to remove unreacted polymer material. Thermomechanical optimization of the internal cooling structure indicated that a high density pin fin array would enable an 80% increase in overall cooling effectiveness relative to a baseline geometry, which was later verified during experimental testing in a high speed linear cascade. Ceramic vanes were tested at Mach numbers of up to 0.9 which is relevant to modern gas turbines. High temperature capability of the ceramic vanes was not tested in this work.

36 MATERIALS SCIENCE↗

Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Technetium-99 (half-life of 2.1 × 10 5 yrs, β max = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO 4 – ), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Here, our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α 2 -[P 2 W 17 O 61 ] 10– ) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW 12 O 40 n – ) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO 4 – and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW 12 , SiW 12 , and AlW 12 promote the reduction of TcO 4 – to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of Tc IV {in the form of TcO 2 · 2H 2 O and Tc 2 (µ-O) 2 4+ } and Tc V , which is subsequently complexed into a POM defect as a Tc V =O species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resin chemistry and particle size influence on stereolithography with silicon carbide

Stereolithography (SLA) is an established process able to produce high resolution polymer parts with complex geometries. Silicon carbide (SiC) has uses in a variety of applications, but traditionally was difficult to manufacture into complex geometries. There have been advances in producing SiC through SLA using a SiC-derived ceramic such as silicon oxycarbide (SiOC). In this study, a slurry using a commercially available resin as the base material with additional modifiers was investigated to create a SiC slurry ready for pressureless sintering. The effects of photoinitiator, dispersant and a bimodal distribution of SiC particle sizes was studied using a design of experiments (DOE). A slurry with a bimodal distribution of 70 % coarse and 30 % fine SiC powder at 40 % solids loading by volume was prepared and successfully printed. Rheology measurements show the slurry to have viscoelastic shear thinning behavior below the recommended 1000 Pas necessary for printing. Printing parameters for the new material on a commercially available SLA printer were studied parametrically. The laser marking speeds found to print the slurry was 260 mm/s and 130 mm/s. A slurry and printing parameters were determined to produce a green part with a proposed debinding cycle.

Herd, Tien [ORNL]↗