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At least 793 records · Page 44

Concentration of HLLW from Future SNF Recycling for Efficient Immobilization in a CCIM

Sponsored by the Department of Energy Nuclear Energy’s Fuel Cycle Research and Development Program, the Cold Crucible Induction Melter is being developed as the next generation of melter technology for High Level Liquid Waste’s efficient immobilization in highly durable glass ceramic and ceramic forms. Concentration of the radioactive High Level Liquid Waste generated from the proposed future recycling of spent nuclear fuel, after the fuel’s dissolution in nitric acid, is necessary to take advantage of the inherent attributes of Cold Crucible Induction Melting technology. Based on a provided range of commercial spent nuclear fuel fission product composition data and its expected High Level Liquid Waste raffinate composition data as provided in oxide form, an analysis was completed to concentrate the waste. The analysis involved using nitric acid vapor liquid equilibrium data over a range of boiling temperatures and performing spreadsheet calculations to concentrate the High Level Liquid Waste through evaporation. The calculation results will provide a concentrated nonradioactive surrogate High Level Liquid Waste melter feed recipe for testing in Idaho National Laboratory’s Cold Crucible Induction Melter Pilot Plant. This testing will provide a quantifiable verification of the relatively high feed rates of Cold Crucible Induction Melters compared to those achievable with the current ceramic lined Joule Heated Melters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Li-ion Identification For the Next Generation of Cathode Recycling

OnTo’s end-to-end solution will demonstrate (in partnership/collaboration with relevant industries) collection of lithium-ion batteries through recycling of cathode material. The DISCC project will prototype 1) deactivation of batteries 2) identification 3) sorting using automated techniques, 4) cutting with waterjet technology and 5) Cathode-Healing™ to produce valuable cathodes from scrap batteries.

25 ENERGY STORAGE↗

DEVELOPMENT OF OIL FREE CENTRIFUGAL BLOWER AS ENABLING TECHNOLOGY FOR SOLID OXIDE FUEL CELL ANODE GAS RECYCLING

Broad commercialization of solid oxide fuel cells (SOFCs), requires anode offgas recycle blowers (AORB) that are specifically designed for handling the challenging operating conditions presented by the SOFC process gases. Otherwise, they can be susceptible to frequent maintenance, low reliability, and short life. This work presents details of the development and testing of an oil-free, low cost centrifugal AORB based on compliant foil bearing (CFB) technology for support of a 100 kW solid oxide fuel cell power plant. The advantages of this novel technology are discussed, particularly its long life and maintenance-free operation, which are derived from the use of CFBs. Also included are preliminary techno-economic analysis considerations for cost-effective deployment of the technology.

03 NATURAL GAS↗

Multi-Physics Modeling of Molten Salt Transport in Solid Oxide Membrane (SOM) Electrolysis and Recycling of Magnesium

Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.

36 MATERIALS SCIENCE↗

Lightweight, Flexible Electromagnetic Shielding Composite Films Reinforced with Recycled Carbon Fibers and Carbon Nanofillers

Lightweight, flexible polymer composites are widely adopted in modern electronic devices and systems for high-efficiency electromagnetic interference (EMI) shielding. Reinforcing polymer composites with conductive fillers offers a promising alternative to conventional metal-based shielding material thanks to their low density, tunable properties, and flexibility. Herein, lightweight, flexible ultra-high molecular weight polyethylene composite films reinforced with recycled carbon fibers (rCFs) and carbon-based nanofillers, including graphene nanoplatelets (GNPs) and carbon nanotubes, are reported for EMI shielding applications. The incorporation of these nanofillers significantly reduces the required content of rCFs and improves processability while maintaining comparable shielding effectiveness. The addition of these nanofillers with rCFs enhances the EMI shielding effectiveness by up to 15 dB. Incorporating 1 wt% GNPs can replace 5 wt% rCFs and achieve comparable EMI shielding performance, while 5 wt% of either nanofillers can substitute for 10 wt% rCFs. Numerical modeling of electromagnetic wave transmission reveals that increasing nanofiller concentrations enhances both reflection and absorption losses, with absorption consistently dominating across all levels. Furthermore, this study not only provides insight into the synergistic contributions of rCFs and carbon nanofillers to shielding effectiveness but also paves the way for the design of sustainable, lightweight EMI shielding composite films for applications in electric vehicles, medical equipment, and portable electronics.

carbon nanofiller↗

Cathode Upcycling for Direct Recycling of Lithium‐Ion Batteries Using a Precipitation Approach

With the increased production of electric vehicles to reduce carbon emissions, the lithium-ion battery market to supply those vehicles has grown dramatically. To enhance battery sustainability and circularity, direct recycling methods aim to recover intact cathode materials. However, end-of-life cathode materials are typically 15–20 years old and often have lower energy density compared to current cathode materials. To address this challenge, a rapid precipitation process is developed to boost energy density by converting low Ni-compositions, LiNi 0.33 Co 0.33 Mn 0.33 O 2 (NMC111), into higher Ni-compositions (NMC622). This process forms a Ni-rich coating on cathode particles that diffuses into the core upon high-temperature relithiation, increasing compositional homogeneity. The upcycling process leverages existing infrastructure, offering low capital cost and minimal additional chemical input. Through ex situ tomographic transmission X-ray microscopy (TXM), 3D Ni:Co elemental mixing is quantified, confirming that elemental content evens at the secondary particle level with a mean NMC622 composition upon relithiation. However, elemental gradients remain in the single crystalline primary particles. Ex situ high-resolution and in situ wide-angle X-ray diffraction reveals concurrent structural changes during the relithiation process. These findings provide key insights into the structural and chemical mechanisms of elemental diffusion to obtain further improvements of increased capacity and retention through compositional conversion of cathode materials.

Cathode Upcycling↗

Redesigned Nylon 6 Variants with Enhanced Recyclability, Ductility, and Transparency

Geminal (gem−) disubstitution in heterocyclic monomers is an effective strategy to enhance polymer chemical recyclability by lowering their ceiling temperatures. However, the effects of specific substitution patterns on the monomer's reactivity and the resulting polymer's properties are largely unexplored. Here we show that, by systematically installing gem-dimethyl groups onto ϵ-caprolactam (monomer of nylon 6) from the α to ϵ positions, both the redesigned lactam monomer's reactivity and the resulting gem-nylon 6’s properties are highly sensitive to the substitution position, with the monomers ranging from non-polymerizable to polymerizable and the gem-nylon properties ranging from inferior to far superior to the parent nylon 6. Remarkably, the nylon 6 with the gem-dimethyls substituted at the γ position is amorphous and optically transparent, with a higher T g (by 30 °C), yield stress (by 1.5 MPa), ductility (by 3×), and lower depolymerization temperature (by 60 °C) than conventional nylon 6.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Repurposing Post-Consumer Polyethylene to Access Cross-Linked Polyethylene with Reprocessabilty, Recyclability, and Tunable Properties

Polyethylene (PE) is the most widely produced plastic but accumulation and resistance to degradation has significantly contributed to the plastic waste crisis. Upcycling has presented promising solutions to transform PE waste into value-added products. In this study, mixed post-consumer PE was successfully repurposed into reprocessable and chemically recyclable cross-linked polyethylene (XLPE). This process involved converting PE into telechelic oligomers, followed by repolymerization using a hybrid cross-linking system consisting of a dynamic cross-linker 2,4,6-triethoxy-1,3,5-triazine (TETA) and non-dynamic cross-linker tris(6-isocyanatohexyl)isocyanurate (Tri-HDI). In the resulting XLPE, TETA facilitated iterative reprocessing with minimal property degradation across cycles, whereas Tri-HDI helped preserve functional performance throughout service life. Compared to PE, XLPE exhibited enhanced mechanical properties, reduced creep deformation under application-relevant temperatures, and high temperature structural stability. Notably, copolymerizing PE oligomers with commercial macrodiols was employed to create composite XLPEs, enabling tuning material properties. After use, XLPE can be efficiently and selectively depolymerized under mild conditions, even when mixed with commercial insulator cables. This depolymerization allows for the recovery of the constituent building blocks, enabling purification and subsequent repolymerization for reuse. This approach demonstrates the potential of repurposing plastic waste into sustainable materials and fostering the development of a circular economy.

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMI↗

Cobalt–Nickel Exchange in Exfoliated Battery Layered Cathode Sheets with Application to Recycling

With the emerging dominance of electric vehicles (EV) in the transportation sector, recycling or upcycling spent battery materials will be required to reduce EV costs, lessen waste, and ease critical material supply chain issues for EV batteries. Here, motivated by work in the literature describing the exfoliation of layered oxides, first‐principles calculations are performed to show that Li x CoO 2 , if exfoliated into nanosheets, can readily undergo transition metal cation exchange in aqueous media. The substitution of Co 3+ or Co 4+ cations inside the sheet by Ni 2+ is associated with modest reaction barriers (Δ G* ≈ 0.3–0.7 eV) and is at most mildly endothermic (Δ G ≈ 0.2–0.3 eV). In contrast, previous battery degradation studies have shown that Co 3+ diffusion is strongly inhibited inside bulk layered oxides. This suggests that processing spent layered oxides as nanosheets can provide a potentially low‐energy‐cost pathway to altering the transition metal and/or dopant stoichiometry, which can be used toward developing new room‐temperature upcycling routes for cathodes from end‐of‐life batteries.

battery recycling↗

The Triple Catalytic Action of Tertiary Nitrogen Catalysts in Recyclable Epoxy-Anhydride Thermosets

The thermosetting polymer matrix in fiber reinforced composites is an important component for energy related applications, such as the lightweighting of vehicles or their use in wind and waterpower turbine blades, due to their ability to provide superior adhesion, stiffness, and applicability to a wide range of manufacturing processes. Despite these benefits, today's thermosets are widely considered to be unrecyclable; thus, there is a large interest in redesigning these materials to be inherently recyclable so that energy intensive production of fibers and monomers can be circumvented, bolstering composite manufacture supply chains. Polyester covalent adaptable networks (PECANs) are one such promising alternative to the incumbent, nonrecyclable epoxy-amine thermosets. PECANs can be formed from the ring-opening co-polymerization (ROCOP) of epoxy-anhydride monomer mixtures and subsequent curing at mild temperatures to exhibit similar performance to conventional epoxies while also possessing unique dynamic chemistries along the ester-hydroxyl backbone that are capable of transesterification and thus reprocessability. While significant advancements have been made in formulating these materials for improved mechanical properties or optimizing solvolysis and reprocessing strategies, less attention has been placed on the impact of the residing amine catalyst used to generate the polyester network. In this work, we evaluated the triple-catalytic efficacy of 12 tertiary amines that act as a curing (bulk ROCOP), a transesterification (internal bond exchange), and a deconstruction (methanolysis) catalyst for PECAN thermosets. Specifically, we first distinguish between chain-growth and step-growth polymerization mechanisms for epoxy-amine and epoxy-anhydride mechanisms. We also utilized density functional theory (DFT) to estimate the basicity (pKb) of each catalyst. Of the tested catalysts, the ROCOP of the studied PECAN network can be completed between 95 and 247 min (at 80 degrees C), with variable gelation phenomena. Additionally, the stress relaxation (transesterification metric) efficiency of the tested PECAN networks with alternative embedded catalysts ranged from 95% to 15% reduction in stress after 5 h at 200 degrees C, and the depolymerization efficacy ranged from 2.5% to 9.8% deconstruction after 36 h at 130 degrees C. Overall, the nitrogen-based moieties were demonstrated to influence polymerization kinetics, catalyze the dynamic transesterification exchange mechanism, and aid in the solvolysis of the thermosets at end-of-life.

36 MATERIALS SCIENCE↗

Glass-Fiber Reinforcement as a Means of Recycling Polymers from Post-Consumer Applications

A major barrier to the recycling of post-consumer plastics is the commingled nature of these materials with consequent poor and variable mechanical, thermal and flow properties. Using polymers from end-of-life electronics, this comprehensive study demonstrates that glass-reinforcement is a viable method for reusing post-consumer plastics. In this work, a twin screw extruder was used to incorporate short glass fibers into polycarbonate containing varying amounts of polymeric impurities. The mechanical and melt flow properties of the compounded polycarbonate, having as much as 50% impurity, were studied. It was observed that, in the presence of 15 wt% short glass fibers, the measured mechanical and flow properties of the glass-reinforced material containing 25% impurity in the matrix phase, were indistinguishable from the corresponding properties of the virgin polymer and containing the same amount of glass reinforcement but no impurities. The effectiveness of this approach was confirmed by obtaining similar mechanical property data on a variety of other glass-filled thermoplastics.

36 MATERIALS SCIENCE↗

Titania-Containing Recycled Polypropylene Surfaces with Photo-Induced Reversible Switching Wettability

Creation of smart surfaces with reversible wettability has always fascinated researchers over the past years but complicated methods are still employed. This study reports a facile and environment-friendly fabrication of smart composite coatings from recycled polypropylene (PP) plastics in which titanium dioxide or titania particles are added to impart extreme anti-wettability with improved thermal stability. The method used is simple and economical as the utilization of used PP plastics can positively impact to the volume reduction of plastic waste in the environment. Titania, being photo-responsive, makes the wetting behavior switch reversibly (i.e. from being superhydrophobic to hydrophilic and vice versa) by employing ultraviolet light as a stimulus and storage in the dark for superhydrophobicity restoration. Combined with relatively high thermal stability, the PP/TiO{sub 2} composites are thought to be useful not only as smart coatings but also for a wide variety of barrier-related applications.

36 MATERIALS SCIENCE↗

Multiscale modeling of hydrogenolysis of ethane and propane on Ru(0001): Implications for plastics recycling

Plastic waste presents an environmental threat. Chemical recycling via hydrogenolysis can convert plastic waste into waxes, lubricants, and fuels. Among catalysts, Ru stands out for its superior activity and selectivity. The chemistry of light alkane hydrogenolysis can help understanding plastics deconstruction. Here, we perform first-principles calculations, develop descriptor-based relations, and conduct microkinetic modeling and analysis on ethane and propane. Predictions are in excellent agreement with experimental data. We identify a similar cracking pattern for both hydrocarbons entailing a deeply dehydrogenated species with the removal of four hydrogen atoms: CHCH*+* → 2CH* for ethane and CH 3 CCH*+2* → CH 3 C* + CH* for propane. We find that the rate-determining step is the C-C cracking for ethane and the first dehydrogenation from the terminal carbon (CH 3 CH 2 CH 3 *+* → CH 3 CH 2 CH 2 *+H*) for propane. The vinyl species CH 2 CH* produced from propane cracking is responsible for whether a single or multiple cracking events occur and effectively controls the selectivity. Specifically, ethane formation in propane hydrogenolysis is suppressed at elevated temperatures due to over-cracking via multiple (two here) cracking events being preferred over hydrogenation and desorption of ethane from the catalyst. Our workflow and models provide a baseline for future studies on heavier hydrocarbons. Insights into recent experimental studies of polyethylene over Ru-based catalysts are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic conversion of post-consumer recycled high-density polyethylene oil over Zn-impregnated ZSM-5 catalysts

The catalytic conversion of post-consumer recycled high-density polyethylene (PCR-HDPE) pyrolysis oil was investigated using modified ZSM-5 zeolites, prepared under different conditions. The PCR-HDPE oil, obtained through pyrolysis at 500 °C followed by distillation at 165 °C, contained a naphtha fraction hydrocarbons suitable for catalytic upgrading. H/ZSM-5 converts PCR-HDPE naphtha fraction oil primarily into BTX, along with light paraffins and olefins. Introducing mesoporosity led to increased propylene yield at the expense of BTX. Zn impregnation onto H/ZSM-5 and H-meso/ZSM-5 enhanced BTX yield by up to 13 %. However, Zn-meso/ZSM-5 exhibited a lower BTX yield than Zn/ZSM-5 with the same Zn loadings, especially after additional steam treatment at 700 °C. Spent catalysts revealed no noticeable increase in metal contaminants such as calcium and aluminum that were present in the PCR-HDPE. Here, the Zn/ZSM-5 catalyst was stable for more than 50 h time on stream and showed promising potential for upgrading PCR-HDPE naphtha fraction oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Techno-Economic Analysis of Recycling Strategies for Catalyst and Acid During Catalytic Graphitization

With the aim of meeting the urgent demand for active anode materials (AAM) in energy storage systems, bio-based graphite (biographite) emerges as an affordable solution to de-risk the turbulent supply chain of critical minerals. Anode grade biographite requires high crystallinity and purity, which can be achieved by catalytic graphitization with iron, followed by acid washing. Therefore, a well-conceived process integration that recycles catalyst can be the starting point to commercialization. This study evaluates closed-loop catalyst recovery, and byproducts valorization scenarios through a technoeconomic framework to help understand the scale-up potential of biographite. For the acid washing, three reactors in series meet the required biographite purity at 99.95%. Iron and acid recovery can reduce material consumption and waste generation by ~95%, albeit at the expense of ~80% increase in capital costs. Recovery scenarios present similar capital and operational expenses, yielding minimum selling prices (MSP) near $6 kg-1 of biographite. Monte Carlo methodology reveals that feedstock price accounts for ~60% of MSP variance, followed by plant capacity ~20%. The likelihood of reaching a competitive profit margin of 30% in the U.S. AAM market sits at 85% average for recovery scenarios, and 103% when iron oxide is sold as byproduct. Additionally, an IRR >= 15% can be achieved for half of Monte Carlo simulations, representing promising early-stage results. Biographite production offers a strategic pathway to stabilize the anode market beyond China by integrating established technologies for a scalable, economically viable, and sustainable process. The role of catalyst recovery and byproducts utilization is critical for advancing the biomaterials industry.

97 MATHEMATICS AND COMPUTING↗

Recycling of waste automotive laminated glass and valorization of polyvinyl butyral through mechanochemical separation

Due to strong binding, optical clarity, adhesion to many surfaces, toughness and flexibility polyvinyl butyral (PVB) resin films are commonly used in the automotive and architectural application as a protective interlayer in the laminated glass. Worldwide million tons of PVB waste generated from end-of-life automotive associated with various environmental issues. Stringent environmental directive, higher land cost eliminates land filling option, needs a study, we have developed a mechanochemical separation process to separate PVB resins from glass and characterized the separated PVB through various techniques, i.e., scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR). Commercial nonionic surfactants D201 used for the mechanochemical separation purpose. Through parameter optimization following conditions are considered to be the optimum condition; 30 vol% D201, stirring speed of 400 rpm, 35 °C temperature, operation time 1 h, and dilute D201 volume to waste automotive laminated glass weight ratio of ≈25. The technology developed in our laboratory is sustainable, environmentally friendly, techno-economical feasible process, capable of mass production (recycling). - Highlights: • Waste automotive laminated glass and polyvinyl butyral mechanochemically separated. • An economical total recovery and environment-friendly process has been developed. • It is a global problem rather than regional environmental issue has been addressed. • Without using hazardous chemical wastes are being converted to a wealth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new recycling technique for the waste tires reuse

In this series of laboratory experiments, the feasibility of using fixed bed biofilm carriers (FBBC) manufactured from existing reclaimed waste tires (RWTs) for wastewater treatment was evaluated. To assess polyamide yarn waste tires as a media, the fixed bed sequence batch reactor (FBSBR) was evaluated under different organic loading rate (OLRs). An experimental model was used to study the kinetics of substrate consumption in biofilm. Removal efficiency of soluble chemical oxygen demand (SCOD) ranged by 76–98% for the FBSBR compared to 71–96% in a sequencing batch reactor (SBR). Removal efficiency of FBBC was significantly increased by inoculating these RWTs carriers. The results revealed that the sludge production yield (Y{sub obs}) was significantly less in the FBSBR compared to the SBR (p < 0.01). It also produced less sludge and recorded a lower stabilization ratio (VSS/TSS). The findings show that the Stover-Kincannon model was the best fit (R{sup 2} > 99%) in a FBSBR. Results from this study suggest that RWTs to support biological activity for a variety of wastewater treatment applications as a biofilm carrier have high potential that better performance as COD and TSS removal and sludge settling properties and effluent quality supported these findings. - Highlights: • Introduced new recycling technique for reclaimed waste tire. • Fixed bed biofilm carriers (FBBC) are widely used for the clean-up of wastewaters. • FBBC were manufactured from existing reclaimed waste tire. • Stover-Kincannonmodel was selected as the best model for describing pollutant removal and FBSBR design in this study.

54 ENVIRONMENTAL SCIENCES↗