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At least 343 records · Page 19

Long-term stabilization of intensity-difference squeezing from four-wave mixing in rubidium vapor

Generation of quantum states of light through off-resonance four-wave mixing in rubidium vapor is a straightforward and well-established technique. However, achieving a sufficiently high and consistent level of intensity difference squeezing (IDS) and intrinsic quantum correlations between photon pairs over an extended timescale, necessary for quantum-light-based nonlinear optical spectroscopy and microscopy, remains challenging and largely unexplored. Here, we report a simple stabilization method combining an active periodic laser frequency retuning with an automatic control algorithm based on quantitatively assessing the factors affecting the IDS level and squeezed light intensity. Validation of our method was performed by acquiring data over a 5-hour period, and the results demonstrate a remarkably stable squeezing level of -7.8 dB in combination with a > 4× reduction of the standard deviation of IDS level from 0.46 dB to 0.10 dB. The achieved stabilization further enables us to quantitatively assess the IDS reduction due to the scattering in a polystyrene bead suspension as a function of sample transmission. Our approach should enable a variety of applications requiring an extended squeezing stability over multiple hours, especially for those following biological processes and chemical reactions in real time.

Allen, Christian Harry [Oak Ridge National Laborat↗

Circular Plastics Technologies: Depolymerization of Polymers Into Parent Monomers

While most commodity plastics were not designed to easily depolymerize, some common plastics can be broken down into their parent monomers in the presence of heat, pressure, catalysts, and/or solvent. Here, we provide a high-level overview of the depolymerization technologies that have been studied and/or scaled as promising monomer-loop recycling processes for selective plastic waste streams. Namely, commodity plastics that are considered unzippable/depolymerizable include polyethylene terephthalate, polyamides, polymethyl methacrylate, and polystyrene. Monomer-loop recycling technologies are one of several pathways toward a circular economy for plastics.

circularity↗

Industrial Scalable Additives for Enhanced Decomposition of Plastic Waste Through Photocatalysis

Polymer pollution is a dangerous environmental problem that can lead to the spread of toxic chemicals and microplastics throughout aquatic biomes. Commonly littered plastic from consumer goods and products with a limited or single use can be embedded with photocatalysts to avoid an increase in the amount of plastic present in Earth’s bodies of water. In this work, the photocatalyst nanoparticles, less than 100 nm particle size, were integrated into polyethylene terephthalate, high-density polyethylene, low-density polyethylene, and polystyrene and exposed under ultraviolet light over two independent experimental trials examining both the environmental factors impacting decay and the physical parameters required to implement this solution on a large scale. The plastics were chosen due to their prolific use in items such as grocery bags, bottles, and packaging. The first half of the project examined the effects of water and light frequency on polymer decay, and the second half of the project examined photodecomposition of polymer films. We report that low-density and high-density polyethylene films with titanium dioxide decayed approximately 11.7 and 9.6 faster than control samples, respectively. With an estimated price of less than half the cost of a shopping bag for titanium catalyst integration and a retention of the polymer’s tensile strength with a 2 wt% catalyst concentration, photocatalytic decomposition is a feasible, scalable method for the prevention and future reduction of polymer waste from realistic products littered in the environment.

36 MATERIALS SCIENCE↗

Safety Evaluation of Nitric Acid Reactions with Non-Polysaccharide Organic Materials

The hazards of non-polysaccharide materials in a transuranic (TRU) waste drum exposed to nitric acid (HNO 3 ) and metal nitrate salts have been evaluated, focusing on sorbents and on resins used in ion-exchange chromatography. The range of sorbent materials can be grouped into two general categories: 1) a variety of polyacrylate and polyacrylamide compounds that incorporate polar carbonyl functional groups designed to sorb protic (i.e., acidic) substrates and solutions; 2) hydrocarbon based polymers that include polystyrene, polybutadiene, and polyethylene derivatives, which are designed to sorb non-polar organic substrates and solutions. The ion-exchange resins are constructed of hydrocarbon based polymeric networks equipped with pendant ionizable functional groups designed to reversibly sorb/desorb ionic species that are targeted for separation from a mobile phase.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Experimental Study of the Fundamental Properties of Warm Dense Mixtures

The aim of the proposed research was to provide a multi-scale study of the properties of warm dense hydrocarbons, by studying the thermodynamic properties through the equation of state and the microscopic properties by x-ray scattering. Understanding the fundamental properties of warm dense mixtures is an intellectual challenge due to the complexity of the system. Unlike liquids or gases, where constituent particle interactions occur through collisions or bonding between valence electrons, in these strongly coupled systems the atoms will be partially ionized and compressed so tightly together that interactions between the inner core electrons can play a role in the systems chemistry. Advances in computational capabilities and development of new theoretical models have been used to predict the properties of mixtures but there is currently no experimental data of the fundamental interaction between the particles in mixtures to test these predictions against. The proposed research was to experimentally investigate the interaction of the different species in hydrocarbons by measuring the compressibility of substances with different carbon and hydrogen ratios and the complexity of the microscopic interactions through elastic and inelastic x-ray scattering. To study the bulk properties of warm dense hydrocarbons we established the Warm Dense Matter Research Laboratory (WDMRL) in the Institute for Shock Physics at Washington State University. The goal was for experiments in the WDMRL to determine shock loading conditions of interest in the hydrocarbon mixtures. We planned on using Hugoniot EOS measurements and a range of carbon and hydrogen concentrations to determine conditions when the EOS of the mixture varied significantly from that of the classical mixing model. Even though shock transit measurements through aluminum foils suggested pressures upto 400GPa, the experiments in the WDMRL were unsuccessful in getting usable shockwave compression data above 100GPa in polystyrene which was below the pressure of interest for hydrocarbon mixtures (>200GPa). To complete the project, we tested a technique using x-ray phase contrast imaging to map the location of tracer layers in a test sample of polycarbonate to record the material motion in dynamically compressed samples. A technique that will be useful for future warm dense matter experiments. These experiments used <200nm gold layers in polycarbonate samples to measure the material velocity and shock speed using x-ray phase contrast imaging. These results were compared to continuum surface measurements performed at ISP and show that the tracer layer technique can measure hydrodynamic properties accurately in dynamically compressed materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Chemical Recycling of Mixed Plastics and Valuable Metals in the Electronic Waste Using Solvent-Based Processing

Annually, 20-55 million tons of electronic waste (e-waste) is produced worldwide (5% of all municipal solid waste). Although e-waste embodies only 2% of America’s municipal waste, it accounts for a significantly larger proportion of the heavy metals and flame retardants present in the waste stream. Currently, less than 20% of all e-waste is recycled in the United States because the heterogeneity of the feedstock limits the opportunity for reuse in high value products and processing of the waste itself is often too costly to justify handling. To address this concern, the aims of this study are: 1) to identify the major plastic and metal compositions within electronic shredder residue (ESR), 2) to formulate solvents and processing conditions to separate 90% of the plastics targeted from consumer shred ESR, and 3) to develop a process design model to estimate the cost and energy efficiency of the proposed solvent-based processing. In this study, a pre-sorted heterogeneous ESR feedstock (one where aluminum, magnetic components, and hazardous battery materials removed by an e-waste recycling facility) was used, with the major compositions of the ESR characterized. It was found that 25 wt.% of the feedstock was composed of plastics, 6 wt.% rubber, 27 wt.% printed circuit boards, 23% wire, and the remainder metals and capacitors. Within the plastic portion, polystyrene (PS, 40 wt.%), acrylonitrile butadiene styrene (ABS, 25 wt.%), and styrene-acrylonitrile (SAN, 9wt.%) were identified to compose the majority of the screened plastics using Fourier transform infrared spectroscopy (FTIR). Next, selective solvents were screened using Hansen Solubility Parameter Theory (HSP) for dissolving PS and ABS. The pre-screening results show that methylene chloride (dichloromethane, DCM) and tetrahydrofuran (THF) are capable of dissolving the most PS and ABS, while methanol (MeOH) and ethylene glycol (EG) are capable of precipitating the most PS and ABS. These solvents were subsequently used to recover polymers and remove. flame retardants within the ESR feedstock. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%%) was achieved using DCM for 48 hr. Both pre-screened anti-solvents (MeOH and EG) showed the highest polymer precipitation yield (71 wt.%). In terms of flame retardant removal rate, EG was found to have a high phosphorus-containing flame retardant removal rate (up to 98%). Characterization shows that the proposed solvent-based processing can preserve a high molecular weight fraction of the polymers and effectively remove flame retardants. Cost analysis indicates that the amount of the solvent/anti-solvent recovered after the reaction would play a critical role in reducing the operating costs. The energy analysis shows that the proposed solvent-based processes can save up to 60% of the embodied energy used to manufacture plastics used in electronics (PS and ABS were used for calculations). The results from this project prove the potential of solvent-based processing to produce secondary materials (plastics and metals) from e-waste for cross-industry reuse.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Ames National Laboratory Annual Site Environmental Report for CY2021

The primary purpose of this report is to summarize the performance of Ames National Laboratory’s environmental programs, present highlights of significant environmental activities, and confirm compliance with environmental regulations and requirements for calendar year 2021. This report is a working requirement of Department of Energy Order 231.1B, Environment, Safety and Health Reporting. It includes descriptions of the Laboratory’s site, mission, the status of its compliance with applicable environmental regulations, its planning and activities to maintain compliance, and a comprehensive review of its environmental protection, surveillance and monitoring activities. Ames National Laboratory is located on the campus of Iowa State University (ISU) and occupies 13 buildings owned by the Department of Energy (DOE). See the Laboratory’s Web page for location and Laboratory overview. The Laboratory also leases space in ISU owned buildings. In 2021, the Laboratory accumulated and disposed of hazardous waste under a U.S. Environmental Protection Agency (EPA) issued generator number. All waste was handled according to applicable EPA, State, and local regulations and DOE Orders. The Laboratory operates as a Small Quantity Generator (SQG) of hazardous waste. There were no radiological air emissions or exposures to the general public due to Laboratory activities in 2021 (See U.S. Department of Energy Air Emissions Annual Report in Appendix A.) The Laboratory has an established Environmental Radiological Protection Program (Plan 10200.041) per DOE Order 458.1 requirements. Plans, policies, and procedures are in place to protect the public and the environment against undue risk from radiation associated with DOE radiological activities. As indicated in prior Site Environmental Reports, formal pollution prevention awareness, waste minimization and recycling programs have been in practice since 1990, with improvements implemented most recently in 2017 with Iowa State University’s shift toward single-stream recycling. Included in recycling efforts are items such as batteries, monitors, corrugated cardboard, lamps, miscellaneous electronic office equipment, mixed paper, newsprint, food/beverage containers, and laboratory glassware. Ames National Laboratory also recycles/reuses salvageable metal, used oil, and foamed polystyrene peanuts, and encourages chemical redistribution and sharing among research groups. Ames National Laboratory reported its contractual performance to DOE-Ames Site Office (AMSO) through the Laboratory’s Performance Evaluation Measurement Plan (PEMP), and a performance level of “B+” was achieved in 2021 for Sustain Excellence and Enhance Effectiveness of Integrated Safety, Health, and Environmental Protection As reported in Site Environmental Reports for prior years, the Laboratory’s Environmental Management System (EMS) has been integrated into the Laboratory’s Integrated Safety Management System (ISMS) since 2005. The integration of EMS into Laboratory business practices allows the Laboratory to systematically review, address and respond to environmental impacts. In addition to DOE-identified objectives and targets, the EMS Steering Committee recommends annual environmental goals for the Laboratory. Due to the COVID-19 pandemic and limited onsite work staff, goals of reducing water usage and travel/commuting to promote the reduction of scope 3 greenhouse gases were achieved. All contract deliverables and environmental compliance activities were still met during this time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of A Microsampler for Aerial Platform on Collection of Aerosol Particles

A microsampler for aerosol particles was designed and evaluated in the laboratory for dry (no condensed water) and wet (foggy, misty, or rainy) air conditions. Computational Fluid Dynamics (CFD) results suggested a design that provided a higher sampling efficiency with minimal inlet loss. The microsampler was experimentally evaluated using fluorescent Polystyrene Latex (PSL) particles at four nominal sizes. The experimental results at the four PSL particle sizes agree reasonably well with the collection efficiencies predicted by CFD. We found no impacts on the collection efficiency of the microsampler at conditions under 80% Relative Humidity (RH). However, when condensed water exists, significant biases on the collection efficiencies were found suggesting this microsampler should not be used in the condition where there was condensed water in the atmosphere, e.g., foggy, misty, and rainy conditions.

54 ENVIRONMENTAL SCIENCES↗

Thermal Cross Section Measurements At The RPI LINAC [Slides]

This presentation gives an overview of thermal cross section measurements at the RPI LINAC. Work discussed includes novel cold moderator capability for use in extending neutron flux down to 0.0005 eV and total thermal neutron cross section measurements performed for polyethylene, polystyrene, Plexiglas (Lucite), and yttrium hydride over the entire thermal region (0.0005 – 1 eV).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nondestructive Evaluation of Rexolite Insulators for the Purpose of Monitoring the Structural Health of Particle Accelerator

Rexolite is a cross-linked polystyrene plastic with stable electrical properties into the gigahertz frequency range. The ability to withstand high voltage makes Rexolite one of the most used materials as insulators for particle accelerators. Although, Rexolite’s poor outgassing performance relative to traditional vacuum materials such as stainless steel or aluminum deems the necessity to treat Rexolite prior to its use as insulators. Insulators are mandatory for an accelerator system because a uniform electric field is required to ensure the alignment of the accelerated particles. Furthermore, to operate properly, a particle accelerator is required to maintain a high vacuum or even an ultrahigh vacuum. Although, because outgassing is the major contributor to the gas load of a vacuum system, Rexolite insulators with uncontrolled outgassing characteristics can severely damage the particle accelerator. Disassembly and reassembly of a complex system like a particle accelerator is also time consuming.

36 MATERIALS SCIENCE↗

Thermal Neutron Cross Section Measurements at the RPI LINAC [Slides]

Cold polyethylene shows adequate capacity for enhancing sub-thermal neutron flux. Cold moderator system produced high quality thermal cross section measurements. Measurements were performed for polyethylene, polystyrene, Plexiglas, yttrium hydride and beryllium and compared with ENDF/B-VIII.0 TSL evaluations. All data reduction for all measurements was finalized. Future work includes completion of necessary journal publications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Thermal Characterization of Acid Treated Anion Exchange Resins

Anion exchange is a chemical separation and purification technique in which a solid phase ion exchanging material (i.e., anion exchange resin beads) interchanges its anions with the desired anions from a solution phase. Typical anion exchange resins (e.g., Bio-Rad AG 1-X8 strongly basic anion exchange resin) consist of a polymer resin bead of cross-linked polystyrene with quaternary ammonium functional groups (Figure 1). Anion exchange occurs at the resin functional groups by exchange of the counter ion of the quaternary ammonium (typically chloride or nitrate) for the anionic species of interest. Other resin polymers have been developed—such as cross-linked vinylpyridine/divinylbenzene utilized in Reillex HPQ anion exchange resin—to improve the resins’ resistance against degradation by oxidizing agents, strong acids, and radiation. Anion exchange is performed for the separation of transuranic (TRU) elements throughout the Department of Energy complex. At the Los Alamos National Laboratory (LANL), production scale quantities of these resins are handled at the Chemistry and Metallurgy Research Facility, the Plutonium Facility, and the Transuranic Waste Facility. Spent anion exchange resin will eventually be disposed of as TRU waste. This has prompted concerns regarding its safe disposal under potential hazard scenarios, in particular a thermal excursion of a TRU waste drum. There is a concern that a potential thermal excursion of a TRU waste drum containing anion exchange resin previously contacted with nitric acid may result in energetic side reactions and pressure buildup due to resin degradation by nitric acid and heat. Therefore, the objective of the experiments described in this report was to gather qualitative and quantitative data to support decisions regarding the thermal stability and safe disposal strategy of nitric acid treated anion exchange resins utilized in TRU processing operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Self-assembly of co-continuous nanostructured copolymer templates with compositional and architectural dispersity

In our previous DOE-supported project (DE-SC0016208), we demonstrated that a particular architecture dubbed ‘randomly end-linked copolymer networks’ (RECNs) led to especially robust self-assembly of disordered cocontinuous nanostructures. Such structures, wherein both microphases are fully percolating in three dimensions, are attractive for a wide-variety of energy-relevant applications including purification membranes, separators in batteries and fuel cells, catalyst supports, and high surface area electrodes. In the current project we sought to substantially extend our fundamental understanding of how different types of randomness in blocky copolymer architecture contribute to the robust formation of disordered cocontinuous nanostructures. To do so, we filled in the sizable gap between the previously studied cases of randomly linked linear multiblock copolymers and RECNs by studying two intermediate cases: (i) random miktoarm star polymers, which contain dispersity in the number of the two chemically-incompatible strands located at each junction and therefore the preferred interfacial curvature of each polymer, and (ii) randomly branched copolymers, which also possess bridging strands that stretch across domains and apply local ‘elastic’ forces to the interfaces. In addition, we studied a different network architecture, statistically crosslinked copolymer networks, that is more straightforward to prepare using chain growth polymerization methods, enabling more facile formation of cocontinuous nanostructures. Finally, we extended our approaches from model systems based on polystyrene and poly(lactic acid) to copolymer architectures containing either (i) polysulfone, an engineering polymer that provides excellent mechanical properties for membrane applications, or (ii) polyacrylonitrile, providing a convenient route to nanoporous carbon materials.

36 MATERIALS SCIENCE↗

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials (Final Report)

One of the current challenges in polymer physics and engineering is to understand the behavior of circular macromolecules. Though such molecules have been made by dilute solution ring closure methods in the past, such procedures have been limited to relatively small, unentangled rings as well as to small sample quantities. Initial studies were also hampered by issues surrounding purity of the rings, though this problem has been somewhat overcome by the use of liquid chromatography at critical conditions (LCCC) methods that separate rings and linear chains. Furthermore, in spite of the continued progress a full understanding of ring dynamics remains elusive. The present work has addressed multiple aspects of the behavior of ring molecules by using a novel synthetic route: reversible radical recombination redox polymerization (R3P) to produce poly(3,6-dioxa-1,8-octanedithiol) (PolyDODT) molecules. The synthesis conditions were chosen to produce linear (LDODT), cyclic (RDODT) and linear-cyclic mixtures (LRDODT) in order to investigate dilute solution and rheological responses of the materials. Importantly, the R3P synthesis makes larger quantities and higher molecular weights than do the dilute solution ring closure methods and also has the potential to be scaled to industrial quantities, thus becoming commercializable. We emphasize two important outcomes of the work. The first is that the rheological investigation shows that very large molecular weight the PolyDODT rings permitted the investigation of ring dynamics from glassy towards terminal flow for molecular sizes corresponding to approximately 300 entanglements of the linear counterpart. At the same time, these very large sized rings could be diluted in a solvent in order to reduce the molecular entanglement density to less than unity. The results demonstrate that ring viscosity follows a Rouse-like linear dependence on molecular weight or entanglement number to approximately 15 entanglements. This range of "Rouse-like" response is greater than what was achieved in all prior works where synthesis conditions have limited the molecular sizes achievable. After the entanglement number $Z_w$ increases beyond approximately 15, we find that the viscosity-molecular weight scaling undergoes a rapid change from the Rouse-like $η\sim{Z}^1_w$ to a very strong power-law scaling that is approximately $η\sim{Z}^{5.8}_w$. This aspect of the work strongly suggests that prior investigations on highly pure rings have invariably been performed on unentangled systems simply because ring molecules have very high entanglement thresholds. The results are further supported by plateau modulus measurements that show that in the "Rouse-like" viscosity regime, for the RDODT samples there is a corresponding lack of a rubbery entanglement plateau and once entanglement coupling is seen, the rubbery plateau also appears in the dynamic modulus data. Furthermore, upon appropriate scaling, we show that the unentangled polyDODT rings (i.e., the diluted high molecular weight rings) show virtually identical dynamics (upon appropriate scaling to account for the chain dilutions) to the dynamics of similarly unentangled LCCC fractionated polystyrene rings.

36 MATERIALS SCIENCE↗

Status Report of Joint RPI/ORNL NCSP Task for Thermal Neutron Total Cross Section Measurements

A new cold neutron moderator system was developed and constructed at the Rensselaer Polytechnic Institute (RPI) Gaerttner Linear Accelerator. This system was then used to measure the neutron total cross section in the thermal energy range for polyethylene, polystyrene, Lucite, and yttrium hydride. In tandem with these measurements, a fitting procedure was developed at Oak Ridge National Laboratory to vary computationally simulated phonon density of states until a fit with differential and integral data was achieved. This model, combined with the new RPI total cross section data, was used to generate thermal scattering law files for the materials measured at RPI.

36 MATERIALS SCIENCE↗

Climate Impact of Primary Plastic Production

Plastics show the strongest production growth of all bulk materials over the last decade. The industry’s current growth trajectory is exponential and plastic production is expected to double or triple by 2050. The rapidly increasing production of plastics and the continued reliance on fossil fuels for production, have contributed to numerous environmental problems and health harms. As a result, plastic pollution has become an increasing threat to natural ecosystems, human health and climate. However, there is a lack of granularity on the contribution of the primary plastics specifically to greenhouse gas (GHG) emissions and their impact on the remaining global carbon budget needed to stay below a 1.5°C or 2°C global average temperature rise. In this report, we explore the contribution of primary plastic production to climate change disaggregated by polymer and technology. To this end, we have developed comprehensive bottom-up modeling of GHG emissions from global primary plastic production, with a special focus on polymer value chains. We have analyzed the results under various growth scenarios in the context of carbon budgets compatible with a 1.5°C global trajectory. Modeling includes the material flows of all production stages, processes and technologies used in primary plastic production value chains, including from the extraction of fossil fuels required for production to shaping the final product. We specifically focus on nine major types of fossil fuelbased plastic polymers that are produced and consumed in large quantities: three types of polyethylene (PE) – low-density (LDPE), linear low-density (LLDPE), and high-density (HDPE) – as well as polypropylene (PP); polyethylene terephthalate (PET); polyvinyl chloride (PVC); polystyrene (PS) and other key styrene-based plastics such as styrene acrylonitrile (SAN) and acrylonitrile butadiene styrene (ABS), and polyurethane (PU). Together these account for about 80% of plastics production.

54 ENVIRONMENTAL SCIENCES↗

Climate Impact of Primary Plastic Production

Plastics show the strongest production growth of all bulk materials over the last decade. The industry’s current growth trajectory is exponential and plastic production is expected to double or triple by 2050. The rapidly increasing production of plastics and the continued reliance on fossil fuels for production, have contributed to numerous environmental problems and health harms. As a result, plastic pollution has become an increasing threat to natural ecosystems, human health and climate. However, there is a lack of granularity on the contribution of the primary plastics specifically to greenhouse gas (GHG) emissions and their impact on the remaining global carbon budget needed to stay below a 1.5°C or 2°C global average temperature rise. In this report, we explore the contribution of primary plastic production to climate change disaggregated by polymer and technology. To this end, we have developed comprehensive bottom-up modeling of GHG emissions from global primary plastic production, with a special focus on polymer value chains. We have analyzed the results under various growth scenarios in the context of carbon budgets compatible with a 1.5°C global trajectory. Modeling includes the material flows of all production stages, processes and technologies used in primary plastic production value chains, including from the extraction of fossil fuels required for production to shaping the final product. We specifically focus on nine major types of fossil fuel-based plastic polymers that are produced and consumed in large quantities: three types of polyethylene (PE) – low-density (LDPE), linear low-density (LLDPE), and high-density (HDPE) – as well as polypropylene (PP); polyethylene terephthalate (PET); polyvinyl chloride (PVC); polystyrene (PS) and other key styrene-based plastics such as styrene acrylonitrile (SAN) and acrylonitrile butadiene styrene (ABS), and polyurethane (PU). Together these account for about 80% of plastics production.

54 ENVIRONMENTAL SCIENCES↗

Oxidative Funneling of PVDC (CRADA Final Report)

Poly(vinylidene chloride) (PVDC) is a major polymer product from the Participant. PVDC-containing plastics are not commonly recycled. To overcome the challenges associated with recycling PVDC and multi-layer materials, we propose a tandem catalytic-biological process to convert PVDC containing waste to upcycled, tunable products such as polyhydroxyalkanoates (PHAs). PHAs are commercially relevant, biodegradable polymers that are useful in packaging, biomedical, and personal care applications. This technology, which the Contractor has named oxidative funneling (OxFun), uses a metal-promoted autoxidation step to depolymerize co-mingled polymers to a mixture of oxygenated compounds, which an engineered bacterium can funnel to a single bioproduct: here, medium chain length polyhydroxyalkanoates (mcl-PHAs). The proposed oxidation chemistry is amenable to inclusion of additional polymers, and the biocatalyst can be engineered to convert the deconstruction products to a variety of valuable chemicals, thus presenting a tunable system for both feedstock variability and target product. Pseudomonas putida KT2440 – a metabolically robust microbe that has been engineered and proven viable for upcycling deconstructed polystyrene (PS), high density polyethlene (HDPE), and polyethylene terephthalate (PET) – can be engineered with enzymes capable of de-chlorinating PVDC deconstruction products (e.g., 2,2-dichloroacetate) in addition to PE-derived substrates into mcl-PHAs.

36 MATERIALS SCIENCE↗