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At least 595 records · Page 33

Recycling of Printed Circuit Boards to Recover Critical Materials

The printed circuit board (PCB), a central component of most electronic devices, represents a significant fraction of the electronic product waste stream. The complex composition of PCBs, consisting of metals, polymers, and fiberglass, requires specialized recovery steps to reclaim valuable and critical materials and the safe disposal of brominated compounds. In this review paper, we describe the current state of critical material recovery and traditional recycling technologies and identify key obstacles to large-scale implementation. Metals present at high concentrations, such as copper, lead, and iron, are conventionally recovered from PCBs using hydrometallurgical, pyrometallurgical, or electrometallurgical processes. Hydrometallurgical methods achieve high selectivity through chemical leaching but pose significant challenges for effluent and reagent recovery. Pyrometallurgical methods facilitate rapid metal separation through smelting but require substantial energy and may release harmful gases. Electrometallurgical techniques produce high-purity metals but are constrained by pretreatment requirements and the consumption of energy. The non-metallic fraction of PCB waste is recycled using thermochemical conversion, microwave-aided heating, and direct recycling of epoxy–fiberglass composites, enabling material or energy recovery. The recovered polymer from direct recycling may have reduced mechanical strength and poor compatibility with new polymer matrices, and the resulting products from the thermal conversion suffer from incomplete conversion, degradation of quality, and residual contamination, as compared to synthetic polymers. Recent process developments have focused on extracting rare earth and supply-critical materials present at lower concentrations in the waste stream. The literature on existing and emerging approaches for recycling PCB wastes is reviewed to identify sustainable, economically viable, and environmentally responsible strategies for the recovery and reuse of critical materials from waste streams.

36 MATERIALS SCIENCE↗

GDSA Framework Development and Process Model Integration FY2024

The Disposal Research & Development (Disposal R&D) Campaign of the U.S. Department of Energy (DOE) Office of Nuclear Energy (NE), Office of Spent Fuel & High-Level Waste Disposition is conducting research and development (R&D) on geologic disposal of spent nuclear fuel (SNF) and high-level nuclear waste (HLW). A high priority for Disposal R&D is disposal system modeling (Sassani et al. 2023). The Geologic Disposal Safety Assessment (GDSA) work package is charged with developing a disposal system modeling and analysis capability for evaluating generic disposal system performance for nuclear waste in geologic media.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High-Fidelity and High-Performance Computational Simulations for Rapid Design Optimization of Sulfur Thermal Energy Storage

Industrial process heating (IPH) accounts for approximately 70% of US manufacturing energy use and is primarily produced by fossil fuel combustion. Approximately 1500 TWht (approximately 60%) of IPH demand is in the temperature range of 100-300. Industrial applications in this temperature range include drying, hydrothermal processing, thermal enhanced oil recovery, food and beverage, bioethanol production, etc. Cost-effective thermal energy storage (TES) that increases the utilization of waste and renewable heat (solar, geothermal, etc.) could provide significant energy savings and reliable heat sources, decrease emissions, and increase US manufacturing competitiveness through reductions in fuel consumption. TES development has historically been dominated by technologies suitable for deployment with concentrating solar power (CSP). State-of-the-art thermal storage deployed commercially with power tower CSP plants uses a 60%/40% NaNO3/KNO3 molten salt and operates between temperatures of approximately 280 degrees Celsius and 570 degrees Celsius using a two-tank configuration. However, these nitrate salts are unsuitable for operation outside of this temperature range due to a high freezing point of approximately 220 degrees Celsius, and limits on high-temperature salt stability and corrosion resistance of containment alloys. Other materials being investigated for TES include those based on: (1) sensible energy storage (various molten salt compositions, inert solid particles, rocks or pebble beds, sulfur, water, concrete, graphite, etc.), (2) latent energy storage in materials that undergo solid-liquid phase change at relevant temperatures (organic materials for low-temperature applications, inorganic salts and/or metals for high-temperature applications), or (3) thermochemical energy storage (hydrides, hydroxides, carbonates, metal oxides, etc.). The application temperature and challenges pertaining to storage material and/or containment cost, energy density, long-term thermal and cyclic stability, and charge/discharge heat transfer effectiveness drive material selection for a given IPH or electricity generation application. Sulfur is a cheap commodity at $80/ton compared to $1100 - 1300/ton for conventional salts. When using a metric of storage cost per kWh, sulfur costs around 2-3 $/kWh. Previous sulfur TES development focused on high temperature (>600 degrees) concentrated solar power applications with sulfur encapsulated in pipes and flow of gaseous HTF (air) in the shell side. However, for lower-temperature IPH applications in the range of approximately 100-300 degrees Celsius Element 16 adopted a compact and scalable TES design with molten sulfur in the shell and HTF pipes submerged in the molten sulfur bath. The low-cost molten sulfur TES for dispatchable IPH has deployment potential for broad applications. The spatial and temporal evolution of the HTF and sulfur temperature is critical to the TES system performance, and thus detailed modeling can improve understanding of the performance and facilitate design improvements. Using high performance computing and computational fluid dynamics (CFD) a low-cost molten sulfur thermal energy storage (TES) system for industrial process heating (IPH) applications was developed. The unique challenges in CFD modeling of sulfur TES are the sharp property changes of sulfur relevant to the working temperatures. Above 159, liquid sulfur undergoes polymerization, and the viscosity of sulfur rapidly increases by several orders of magnitude between 159 degrees Celsius and 188 degrees Celsius, followed by a decrease in viscosity beyond 188 degrees Celsius due to thermal bound dissociation. In addition, various concentrations of H2S impurities can also modify sulfur viscosity. This numerical challenge is especially relevant to transient simulation of the sulfur TES charging and discharging processes as the extreme property variations limit the applicability of traditional heat transfer correlations. Transient CFD simulations including the temperature-dependent sulfur properties and geometric complexity of the TES design were used to predict the effect of natural convection during charging and discharging on the heat transfer process, sulfur temperature uniformity, charge/discharge rates, and performance of the storage devices. The CFD model was validated with experimental results for a full charge and discharge cycle. The work will show 3D and 2D simulation comparisons aimed to facilitate rapid design iterations and a machine learning based design optimization approach.

CFD↗

Employing MACS/ViBRANT as a Surrogate MARVEL Reactor for Startup Reactivity Tuning and Supervisory Control Processes

Advanced nuclear reactors are a key part of the future of nuclear energy both in the United States and globally. They offer unique benefits for various energy-demanding applications, including use in remote locations, compact size, modular manufacturing, remote monitoring, low and/or variable power rating operation, and reliance on novel technologies to enhance operational safety. To achieve economic feasibility, advanced reactors must significantly reduce their workforces in comparison with the current fleet. Achieving this reduction will occur through reducing staff workloads using technology to achieve autonomous or semi-autonomous operations, demonstrated by comprehensive testing and validation activities. These operations will require both software and hardware platforms during the design and testing phases. While simulations are useful during the design phase, their performance can significantly deviate during actual deployment on hardware. This report presents the outcomes of a collaborative technical initiative between the U.S. Department of Energy (DOE) Microreactor Program (MRP) and Advanced Sensors and Instrumentation (ASI) Program. The collaboration utilized the Microreactor Automated Control System (MACS) hardware platform to bridge the gap between theoretical reactor design and actual startup and control operations. Two key use cases were investigated: facilitating the startup testing period and demonstrating supervisory control. The first use case details the key Microreactor Applications Research Validation and Evaluation (MARVEL) reactor startup physics testing activities conducted using the MACS platform. These activities included drum worth measurements, shutdown margin assessment, temperature feedback analysis, and scram time evaluation, as well as unique testing that would apply to the MARVEL reactor to demonstrate the testing methodologies in a low-risk environment. The MACS platform, serving as a surrogate representation of the MARVEL reactor, proved instrumental in performing these tests. The exercise revealed aspects that led to optimized processes, refined hardware design, and enhanced base software capabilities. By maturing methods and technologies in this manner, the initiative promises to reduce wasted time in the actual on-site reactor deployment effort, thereby saving significant time and resources. The second use case focuses on the development and implementation of supervisory control methods aimed at managing core tilt, which can result from asymmetrical operations or manufacturing imperfections in fuel rods or reactivity control devices. A key objective was to assess and compare the use of artificial intelligence (AI) for supervisory control. The effort aimed to define the role of supervisory control to enhance performance without risking control instability. This effort explored three distinct approaches: rules-based (RB) methods, optimization techniques, and reinforcement learning (RL) algorithms. Each approach was evaluated for its ease of implementation, its usability, and its effectiveness in responding to asymmetries in neutron flux. Comparative analysis of these approaches provided valuable insights into their applicability and effectiveness, offering a robust framework for advanced reactor operations. Together, these two use cases highlight the potential of hardware test beds to help streamline the design, operation, and control of advanced nuclear reactors. This collaborative effort underscores the importance of continued innovation and experimentation in achieving the next generation of safe, reliable, and economically viable nuclear energy solutions.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

Nuclear Balance-of-Plant Analysis for Heat and Electricity Calculations in Several Advanced Nuclear Reactor Concepts

In addition to producing electricity, advanced nuclear reactors can also serve as a source of process heat for a wide range of industrial or residential applications. In cases where the heat application requires low-temperature heat, waste heat from the balance of plant (BOP) can be utilized with minimal impact on electricity generation. For applications requiring higher-temperature heat, heat can be extracted from the BOP, though this will reduce the amount of electricity generated. In either case, the optimal BOP design will be case-specific and depend on multiple factors, including the reactor type and the thermal requirements of the heat application.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Sustainable aviation fuels from biomass and biowaste via bio- and chemo-catalytic conversion: Catalysis, process challenges, and opportunities

Sustainable aviation fuel (SAF) production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector, one of the most-difficult-to-electrify transportation sectors. Despite ongoing commercialization efforts using ASTM-certified pathways (e.g., lipid conversion, Fischer-Tropsch synthesis), production capacities are still inadequate due to limited feedstock supply and high production costs. New conversion technologies that utilize lignocellulosic feedstocks are needed to meet these challenges and satisfy the rapidly growing market. Combining bio- and chemo-catalytic approaches can leverage advantages from both methods, i.e., high product selectivity via biological conversion, and the capability to build C-C chains more efficiently via chemical catalysis. Herein, conversion routes, catalysis, and processes for such pathways are discussed, while key challenges and meaningful R&D opportunities are identified to guide future research activities in the space. Bio and chemo-catalytic conversion primarily utilize the carbohydrate fraction of lignocellulose, leaving lignin as a waste product. This makes lignin conversion to SAF critical in order to utilize whole biomass, thereby lowering overall production costs while maximizing carbon efficiencies. Thus, lignin valorization strategies are also reviewed herein with vital research areas identified, such as facile lignin depolymerization approaches, highly integrated conversion systems, novel process configurations, and catalysts for the selective cleavage of aryl C–O bonds. The potential efficiency improvements available via integrated conversion steps, such as combined biological and chemo-catalytic routes, along with the use of different parallel pathways, are identified as key to producing all components of a cost-effective, 100% SAF.

09 BIOMASS FUELS↗

M3SF-25LL010302052 - Radionuclide Interaction with Hydrothermally Altered Repository Materials

This progress report (Level 3 Milestone Number M3SF-25LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Host Rock Properties & Processes - LLNL Number SF-25LL01030205. Observed changes in radionuclide sorption after bentonite/clay heating have implications for radionuclide diffusive transport through engineered barriers and must be considered when designing waste disposal repositories. Recent research performed at Los Alamos National Laboratory (LANL) has provided key insights regarding the hydrothermal alteration behavior of bentonite backfill in the presence of repository materials (steel, concrete, etc.). We are examining how this mineral alteration affects retardation behavior of a suite of radionuclides of interest to repository performance assessment. Sorption experiments and data analysis for 233 U were initiated in FY24 following earlier experiments performed on 243 Am, 90 Sr, 137 Cs. In FY25, we completed the 233 U study and initiated and completed a study of 237 Np sorption. Below, we summarize the results and potential impacts of hydrothermal alteration on radionuclide retardation and assess the importance of this process to radionuclide migration from a GHRDC. We also use statistical tools (i.e. PCA) to help us determine the major drivers in affecting changes in measured Kd values induced by hydrothermal alteration. These experiments also allow us to test the predictive ability of our component additivity approach to surface complexation and ion exchange. Our guiding hypothesis is that a robust surface complexation/ion exchange model and associated database can effectively predict changes in radionuclide sorption behavior resulting from the hydrothermal alteration of mineralogy in a repository near field. In November 2024 the paper “Selenium interaction with iron minerals: Quantitative comparison of sorption and coprecipitation impacts on mobility” was published in Applied Geochemistry. A short update of results to date is presented below. In FY25, we also actively supported the DITUSC project, which is part of the EURADII initiative, as associate partners. We are executing the Migration2025 conference and support associated the NEA-TDB and Thermochimie workshops that will provide critical international engagements and develop consensus and synergy in thermodynamics as it relates to supporting the US nuclear waste repository program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microbial inoculum effects on the rumen epithelial transcriptome and rumen epimural metatranscriptome in calves

Manipulation of the rumen microbial ecosystem in early life may affect ruminal fermentation and enhance the productive performance of dairy cows. The objective of this experiment was to evaluate the effects of dosing three different types of microbial inoculum on the rumen epithelium tissue (RE) transcriptome and the rumen epimural metatranscriptome (REM) in dairy calves. For this objective, 15 Holstein bull calves were enrolled in the study at birth and assigned to three different intraruminal inoculum treatments dosed orally once weekly from three to six weeks of age. The inoculum treatments were prepared from rumen contents collected from rumen fistulated lactating cows and were either autoclaved (control; ARF), processed by differential centrifugation to create the bacterial-enriched inoculum (BE), or through gravimetric separation to create the protozoal-enriched inoculum (PE). Calves were fed 2.5 L/d pasteurized waste milk 3x/d from 0 to 7 weeks of age and texturized starter until euthanasia at 9 weeks of age, when the RE tissues were collected for transcriptome and microbial metatranscriptome analyses, from four randomly selected calves from each treatment. The different types of inoculum altered the RE transcriptome and REM. Compared to ARF, 9 genes were upregulated in the RE of BE and 92 in PE, whereas between BE and PE there were 13 genes upregulated in BE and 114 in PE. Gene ontology analysis identified enriched GO terms in biological process category between PE and ARF, with no enrichment between BE and ARF. The RE functional signature showed different KEGG pathways related to BE and ARF, and no specific KEGG pathway for PE. We observed a lower alpha diversity index for RE microbiome in ARF (observed genera and Chao1 (p < 0.05)). Five microbial genera showed a significant correlation with the changes in host gene expression: Roseburia (25 genes), Entamoeba (two genes); Anaerosinus, Lachnospira, and Succiniclasticum were each related to one gene. sPLS-DA analysis showed that RE microbial communities differ among the treatments, although the taxonomic and functional microbial profiles show different distributions. Co-expression Differential Network Analysis indicated that both BE and PE had an impact on the abundance of KEGG modules related to acyl-CoA synthesis, type VI secretion, and methanogenesis, while PE had a significant impact on KEGGs related to ectoine biosynthesis and D-xylose transport. Our study indicated that artificial dosing with different microbial inocula in early life alters not only the RE transcriptome, but also affects the REM and its functions.

59 BASIC BIOLOGICAL SCIENCES↗

Delamination recycling of multilayer plastic films: Solvent-assisted separation pathways and recovery of solid polyolefins

Multilayer plastic films are excellent packaging materials due to the bound layers of multiple polymers, with each different polymer contributing to the film properties. Desirable properties lead to continuously growing demand for multilayer films. Multilayer plastic films are typically single-use and, as such, their increased production and disposal have led to waste management problems. Multilayer films are not currently recyclable primarily due to the multiple bound polymers. This work advances delamination as a recycling process to separate and sequester valuable polymers from multilayer films, facilitating the incorporation of these polymers into the circular economy. We effect delamination in a physical process that preserves targeted polymers as solid film, hence retaining their embodied energy. This work documents three different pathways of inducing delamination of multilayer films, with appropriate solvents disrupting adhesion between adjacent layers or dissolving a minor component of the film in less than an hour and at temperatures below 90°C, and where all initial polyethylene is maintained in its solid form throughout the process and is recovered at high purity. Solvent-based delamination is exemplified on commercial multilayer films with majority polyethylene (PE), and polyethylene terephthalate (PET) or ethylene vinyl alcohol copolymer (EVOH) or nylon also present. Solvent-based delamination is an energy-efficient and environmentally friendly recycling process that improves upon dissolution-precipitation recycling, since delamination involves very little dissolution and no precipitation, and is superior to pyrolysis which breaks down the polymers, while delamination keeps polymer chains intact. Furthermore, delamination recycling can contribute to the sustainable use of multilayer films as they continue to protect our food and medicine.

Chemical Recycling↗

From the bench to the reactor: engineered filamentous fungi for biochemical and biomaterial production

Filamentous fungi can convert a wide variety of naturally occurring chemical compounds, including organic biomass and waste streams, into a range of products. They have long been used for industrial organic acid production and food preparation. In this review, we will discuss production of products such as organic acids, lipids, small molecules, enzymes, materials, and foods, and highlight advances in metabolic and protein engineering, including CRISPR-Cas9-mediated strain improvements. We discuss to what extent these products are already being made on a commercial scale, as well as what is still required to make certain promising concepts industrially and commercially relevant. Despite significant progress, the systematic application of synthetic biology to filamentous fungi remains in its infancy, with many opportunities for discovery and innovation as new strains and genetic tools are developed. The integration of fungal biotechnology into circular and bio-based economies promises to address critical challenges in waste management, resource sustainability, and the development of new materials for terrestrial and extraterrestrial applications, but requires further developments in genetic engineering and process design.

09 BIOMASS FUELS↗

Direct Air Capture and Utilization System (DACUS): FEED Study of CarbonCapture Inc. DAC and CarbonCure Utilization Technologies Using United States Steel’s Gary Works Plant Waste Heat

The effects of climate change are drastically perceived through the alarming rates of severe events such as flooding, hurricanes, wildfires, global temperature rise, sea-level rise, and ocean acidification etc., which has prompted the nations across the globe to control & reduce greenhouse gas (GHG) emissions, by massive adoption of electric vehicles, switching to renewal energy sources and promoting sustainable green products. However, recent climate studies have shown that such efforts will not be enough to keep the global temperature rising under 1.5° Celsius by the year 2050, which lead to the development of multiple Direct Air Capture (DAC) technologies. A DAC system extracts CO2 directly from the atmosphere, which is either stored underground for long term or utilized in other processes. The DACUS proposed at U.S. Steel Corporation’s Gary Works Plant in Gary, Indiana, will include an innovative DAC technology from CarbonCapture Inc. (CCI), which will be collocated and powered by waste heat from the steel plant to capture CO2 from ambient air, and CarbonCure CO2 utilization technology- which is a commercial technology that is already installed and in use by early adopters in more than 150 concrete mixing plants across North America and Asia. The University of Illinois at Urbana Champaign spearheaded this Front-End Engineering Design (FEED) study project, which was funded by US Department of Energy (DOE), aimed at designing a state-of-the art DACU system that can remove minimum of 5,000 tonne/year net CO2 from air (based on cradle-to-gate LCA) and converting the captured CO2 into low carbon intensity products. The off takers of the low Carbon product produced by the DACUS have also been identified near the steel plant in the Indiana, Illinois & Wisconsin Region. This creates a full CO2 value chain and provides a means to assess the impact of this holistic approach on job creation, regional economic impact, and environmental justice. DACUS is a promising new technology for reducing greenhouse gas in the atmosphere. Operation costs are minimized by locating CCI’s innovative DAC collector at United States Steel's Gary Works site where waste heat is utilized. Carbon emissions are minimized in CO2 transportation. The captured CO2 will be permanently sequestered in concrete used as construction material. This DOE funded FEED study demonstrates a full CO2 value chain for a DACU system, supported by an industrial facility. If this project were constructed, it would have a very positive and lasting impact on both the environment and the community.

42 ENGINEERING↗

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↗

Fault Slip and Fluid Flow: Seismic Source Analysis to Assess Role of Multiple Slip Patches in Fault Permeability

The relationship between fault reactivation, microearthquakes (MEQs), and permeability evolution during fluid injection plays a critical role in energy harvesting and waste disposal. Recent studies have demonstrated the possibility of predicting fault permeability using cumulative seismic moments of MEQs quantitatively. To understand the underlying physical processes, we conduct fault reactivation experiments using Utah FORGE granitoid and analyze acoustic emission (AE) signals generated during stepwise increases in fluid injection pressure. Frequency analysis of thousands of calibrated AE signals reveals that fault reactivation produces multiple AE source patches with millimeter-scale radii—smaller than the sample fault radius. The cumulative area of the reactivated patches covers the fault multiple times over (∼10x–50x area) for each pressure step. These findings provide mechanistic insight that measured permeability enhancement is not driven by a single large slip event, but by the sequential and interacting activation of multiple slip patches that create a continuous flow pathway.

Nurshal, M. E. M. [Pennsylvania State University, ↗

Path Toward a Breeding, Proliferation-Resistant, Thermal-Spectrum Molten Salt Reactor

Liquid-fueled, thermal-spectrum molten salt breeder reactors (TS-MSBRs) offer the potential for affordable, safe, inexhaustible energy with minimal potential for nuclear material misuse and without significant actinide waste generation. Realizing the full set of TS-MSBR capabilities is only now becoming possible with the advent of advanced fuel-salt processing techniques, improved materials, and a more detailed understanding of fuel-salt properties. Additionally, modern higher-fidelity modeling and simulation methods enable a more detailed evaluation of TS-MSBR design options. TS-MSBRs, however, remain immature and will require substantial, sustained development resources.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Genome reduction improves octanoic acid production in scale down bioreactors

Microorganisms in large-scale bioreactors are exposed to heterogeneous environmental conditions due to physical mixing constraints. Nutritional gradients can lead to transient expression of energetically wasteful stress responses and as a result, can reduce the titres, rates and yields of a bioprocess at larger scales. To what extent these process parameters are impacted is often unknown and therefore bioprocess scale-up comes with major risk. Designing platform strains to account for these intermittent stresses before introducing synthesis pathways is one strategy for de-risking bioprocess development. For example, Escherichia coli strain RM214 is a derivative of wild-type MG1655 that has had several genes and whole operons removed from its genome based on their metabolic cost. In this study, we engineered E. coli strain RM214 (referred to as WG02) to produce octanoic acid from glycerol in batch-flask and fed-batch bioreactor cultivations and compared it to an octanoic acid-producing E. coli MG1655 (WG01). In batch flask cultivations, the two strains performed similarly. However, in carbon limited fed-batch bioreactor cultivations, WG02 provided a greater than 22% boost to biomass compared to WG01 while maintaining similar titres of octanoic acid. Reducing the biomass accumulation of WG02 with nitrogen limited fed-batch cultivation resulted in a 16% improvement in octanoic acid titre over WG01. Finally, in a scale-down system consisting of a stirred tank reactor (representing a well-mixed zone) and plug flow reactor (representing an intermittent carbon starvation zone), WG02 again improved octanoic acid titre by almost 18% while maintaining similar biomass concentrations as WG01.

59 BASIC BIOLOGICAL SCIENCES↗

Macromolecules & Manufacturing Science

Outline • SRNL Overview • Mission overview • Polymers enabling the mission • R&D Highlights • Polymers in radiation environments • Tooling in shielded cells • Packaging for nuclear material shipments • Polymers supporting tank waste remediation • Ref electrode • Epoxy and polymer grout • Polymers for fusion energy • Deuterium labelling • Polymers for additive manufacturing • Coalescence and blends: experimental and predictive • Process modelling and sorting through big data (peregrine and latticeJ)

Chatham, Camden [Savannah River National Laborator↗

Affinity and Treatment of LDR Organics in Low Activity Waste by Cementitious Materials – 26109

The physiochemical interactions between organic contaminants, minerals, and polymer additives in grout/cementitious materials are being identified. This research supports a proposed Resource Conservation and Recovery Act (RCRA) treatment variance relevant to the Land Disposal Restriction (LDR) organics present in Hanford tank waste. It provides the technical basis to address the aspects documented by the Environmental Protection Agency in a draft memo necessary to establish that organics can be immobilized/stabilized in a cementitious matrix. The organic species may interact with cementitious minerals, including slag, fly ash, cement, and other components/dopants like activated carbon. A list of 132 reasonably expected LDR organics associated with Hanford tank waste (RPP-RPT-63493, Rev 1a) was screened by functional groups, octanol-water partitioning coefficients, and detection frequency in Hanford tank waste samples. A subset of 15 compounds spanning the identified properties was tested using sorption and leachate tests. These compounds were subjected to traditional batch sorption tests and leaching tests on/from Cast Stone cementitious material with and without activated carbon (a potential organic adsorption additive). The interactions between organic compounds were observed in traditional batch sorption and modified TCLP leachate tests for surrogate Cast Stone material with and without activated carbon addition. Specifically, phthalic acid (negatively charged) and 4-chloroaniline (polar) sorbed strongly to unmodified Cast Stone, while a group of three phenolic compounds (2,4,6-Trichlorophenol, Pentachlorophenol, o-Cresol) sorbed to and were retained by Cast Stone with a 1% activated carbon amendment. Mixtures of these compounds demonstrated visible retention of the organics within the matrix with a quantifiable affinity of the organics to the cement. This novel testing supports the notion that organics within Hanford tank waste would be retained onto the cement phase with the addition of simple materials easily added to the formulation as part of the treatment process. To further provide additional support to this claim, models employing Flory-Huggins theory in conjunction with macromolecular and organic molecule solubility parameters and species activity coefficients are being utilized to better understand these interactions. Within this context, Van Krevelen (VK) and Hansen organic and polymer solubility parameters were used to inform the Flory-Huggins interaction parameter, allowing for a quantifiable method of evaluating polymer-solvent compatibility and, by extension, interactions with proposed binding additives (e.g., activated carbon). These models and measurement should test the hypothesis for our systems understanding and applicability of Flory-Huggins theory, and whether the prediction of organics in the polymer phase versus the aqueous phase can be confidently made using this strategy. The estimation of the organic molecular activity coefficient in these high salt-saturated aqueous systems is another factor that will be assessed. This project aims to predict and understand complicated organic interactions in these heterogenous systems, guiding optimal treatment and stabilization methodologies.

Jolin, Will [Savannah River National Laboratory (S↗

Upcycling of polyethylene terephthalate to high-value chemicals by carbonate-interchange deconstruction

Condensation thermoplastics have become ubiquitous. The emergence of chemical upcycling could transform them into valuable feedstocks for chemical manufacturing at their end-of-life. However, current solvolysis processes suffer equilibrium limitations due to the liberation of reactive byproducts. We report a carbonate interchange deconstruction (CID) methodology for poly(ethylene terephthalate) (PET), where carbonates act as both latent nucleophiles and byproduct sequestering agents. High product selectivity (>95%) is achieved regardless of the targeted terephthalate product, originating from removal of ethylene glycol from the reaction equilibrium via its conversion into various oligoethers. CID is robust to the impurities present in post-consumer waste plastics and significantly reduces solvent demand, with just 10 mL of dimethyl carbonate successfully converting ca. 5 g of mixed PET waste into highly pure dimethyl terephthalate in excellent isolated yield (92%). CID opens a new upcycling paradigm wherein CO2, embedded in carbonates, is leveraged to choreograph the selectivity of an otherwise equilibrium-controlled polymer upcycling process.

Galan, Nick [ORNL]↗