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At least 253 records · Page 14

Aerospace Fuels From Nonpetroleum Raw Materials

Recycling human metabolic and plastic wastes minimizes cost and increases efficiency by reducing the need to transport consumables and return trash, respectively, from orbit to support a space station crew. If the much larger costs of transporting consumables to the Moon and beyond are taken into account, developing waste recycling technologies becomes imperative and possibly mission enabling. Reduction of terrestrial waste streams while producing energy and/or valuable raw materials is an opportunity being realized by a new generation of visionary entrepreneurs; several relevant technologies are briefly compared, contrasted and assessed for space applications. A two-step approach to nonpetroleum raw materials utilization is presented; the first step involves production of supply or producer gas. This is akin to synthesis gas containing carbon oxides, hydrogen, and simple hydrocarbons. The second step involves production of fuel via the Sabatier process, a methanation reaction, or another gas-to-liquid technology, typically Fischer-Tropsch processing. Optimization to enhance the fraction of product stream relevant to transportation fuels via catalytic (process) development at NASA Glenn Research Center is described. Energy utilization is a concern for production of fuels whether for operation on the lunar or Martian surface, or beyond. The term green relates to not only mitigating excess carbon release but also to the efficiency of energy usage. For space, energy usage can be an essential concern. Another issue of great concern is minimizing impurities in the product stream(s), especially those that are potential health risks and/or could degrade operations through catalyst poisoning or equipment damage; technologies being developed to remove heteroatom impurities are discussed. Alternative technologies to utilize waste fluids, such as a propulsion option called the resistojet, are discussed. The resistojet is an electric propulsion technology with a powered thruster to vaporize and heat a propellant to high temperature, hot gases are subsequently passed through a converging-diverging nozzle expanding gases to supersonic velocities. A resistojet can accommodate many different fluids, including various reaction chamber (by-)products.

Palaszewski, Bryan A.↗

Aerospace Fuels from Nonpetroleum Raw Materials

Recycling human metabolic and plastic wastes minimizes cost and increases efficiency by reducing the need to transport consumables and return trash, respectively, from orbit to support a space station crew. If the much larger costs of transporting consumables to the Moon and beyond are taken into account, developing waste recycling technologies becomes imperative and possibly mission enabling. Reduction of terrestrial waste streams while producing energy and/or valuable raw materials is an opportunity being realized by a new generation of visionary entrepreneurs; several relevant technologies are briefly compared, contrasted and assessed for space applications. A two-step approach to nonpetroleum raw materials utilization is presented; the first step involves production of supply or producer gas. This is akin to synthesis gas containing carbon oxides, hydrogen, and simple hydrocarbons. The second step involves production of fuel via the Sabatier process, a methanation reaction, or another gas-to-liquid technology, typically Fischer- Tropsch processing. Optimization to enhance the fraction of product stream relevant to transportation fuels via catalytic (process) development at NASA GRC is described. Energy utilization is a concern for production of fuels whether for operation on the lunar or Martian surface, or beyond. The term "green" relates to not only mitigating excess carbon release but also to the efficiency of energy usage. For space, energy usage can be an essential concern. Other issues of great concern include minimizing impurities in the product stream(s), especially those that are potential health risks and/or could de-grade operations through catalyst poisoning or equipment damage; technologies being developed to remove heteroatom impurities are discussed. Alternative technologies to utilize waste fluids, such as a propulsion option called the resistojet, are discussed. The resistojet is an electric propulsion technology with a powered thruster to vaporize and heat a propellant to high temperature, hot gases are subsequently passed through a converging-diverging nozzle expanding gases to supersonic velocities. A resistojet can accommodate many different fluids, including various reaction chamber (by-)products.

Palaszewski, B. A.↗

Chemical Recycling Processes of Waste Polyethylene Terephthalate Using Solid Catalysts

Polyethylene terephthalate (PET) is a non-degradable single-use plastic and a major component of plastic waste in landfills. Chemical recycling is one of the most widely adopted methods to transform post-consumer PET into PET's building block chemicals. Non-catalytic depolymerization of PET is very slow and requires high temperatures and/or pressures. Recent advancements in the field of material science and catalysis have delivered several innovative strategies to promote PET depolymerization under mild reaction conditions. Particularly, heterogeneous catalysts assisted depolymerization of post-consumer PET to monomers and other value-added chemicals is the most industrially compatible method. Here, this review includes current progresses on the heterogeneously catalyzed chemical recycling of PET. It describes four key pathways for PET depolymerization including, glycolysis, pyrolysis, alcoholysis, and reductive depolymerization. The catalyst function, active sites and structure-activity correlations are briefly outlined in each section. An outlook for future development is also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Chemical Recycling of Post-Consumer Polyethylene

Among commercial plastics, polyolefins are the most widely produced worldwide but have limited recyclability. Here, we report a chemical recycling route for the conversion of post-consumer high-density polyethylene (HDPE) into telechelic macromonomers suitable for circular reprocessing. Unsaturation was introduced into HDPE by catalytic dehydrogenation using an Ir-POCOP catalyst without an alkene acceptor. Cross-metathesis with 2-hydroxyethyl acrylate followed by hydrogenation transformed the partially unsaturated HDPE into telechelic macromonomers. The direct repolymerization of the macromonomers gave a brittle material due to the low overall weight-average molecular weight. Aminolysis of telechelic macromonomers with a small amount of diethanolamine increased the overall functionality. The resulting macromonomers were repolymerized through transesterification to generate a polymer with comparable mechanical properties to the starting post-consumer HDPE waste. Finally, depolymerization of the repolymerized material catalyzed by an organic base regenerated the telechelic macromonomers, thereby allowing waste polyethylene materials to enter a chemical recycling pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Closing the Loop on Automotive Carbon Fiber Prepreg Manufacturing Scrap

The project demonstrated how to “close the loop” on carbon fiber by integrating industrial carbon fiber scrap into new functional components in an automotive lightweighting application. The project serves as a validation of discontinuous recycled carbon fiber in a commercial context, while generating comprehensive material data throughout the production chain. To this end, the project exhibited increasing complexity as material evaluation progressed from benchtop to commercial scale through full-scale part production, with key material properties thoroughly characterized throughout the process. Of particular focus was the form of the fiber that was fed into compounding, as recycled fiber has historically been problematic to feed at commercial-scale. Carbon fiber is energy-intensive to manufacture, so reuse of existing fiber material can reduce costs and increase sustainability. Additionally, by integrating recovered short fiber into a thermoplastic, regrind processes can be used to provide feedstock for later generations of product. While regrind plastics are not “infinitely recyclable”, reusing the manufacturing scrap over several generations of products can greatly increase material sustainability and lower the fractional embodied energy of each successive product. As such, this project supports the IACMI technical goals of (1) 25% lower carbon fiber-reinforced polymer (CFRP) cost, (2) 50% reduction in CFRP embodied energy, and (3) 80% composite recyclability into useful products. The initial stage of the project involved down selecting surface treatment (sizing) chemistries. Sizing evaluations were performed on Vartega’s chemically recycled intermediate modulus fiber along with standard modulus dry scrap which was oversized with sizing provided by Michelman. More dramatic improvements from sizing were found on the standard rather than the intermediate modulus fibers. The strength of the chemically recycled individual fibers were evaluated by Michelman and ORNL through single fiber testing and found to be comparable to similarly evaluated virgin fibers. UDRI’s mechanical testing on injection molded test specimens identified similar mechanical properties and fiber distribution relative to benchmark specimens. Additional surface chemistry tests and visualizations were performed by the Colorado School of Mines to confirm close conformance between the benchmark and recycled-fiber specimens. As the mechanical test results exceeded the 80% threshold established as the go/no-go(GNG), the project scale was increased to use commercial-scale equipment that would both better characterize the manufacturing utility of the target product format and allow qualitative assessment of a complex commercial part. An upscaled compounding evaluation was performed with a 27 mm twin-screw compounding extruding using oversized standard modulus fibers that were formatted to improve bulk solids transfer. The project team anticipated that milestone mechanical benchmarks could be achieved given the favorable performance of the sized standard modulus material identified in the initial micro-compounding trials. While the mechanical performance did meet the milestone target for that phase of the project, mechanical properties for this standard modulus-based compound were still less than those of the Ford specification. To compare the performance, the project team oversized intermediate modulus dry fibers and compounded them with the project resin at BASF using a 40 mm compounder. Test specimen mechanical performance exceeded the targets laid out in both the project milestone and the Ford specification. A series of prototype parts were successfully molded, albeit with instances of short shot components due to the high thermal conductivity of the carbon fiber compared to glass fiber for which the prototype tool was designed for. The project demonstrated that recycled carbon fiber is a viable option in fiber reinforced compound, providing greatly increased strength and modulus for applications that require them. The “agglomerated” format that facilitated effective bulk solids transfer of recovered fiber showed promise for industrial application.

36 MATERIALS SCIENCE↗

Tailoring the Properties of Chemically Recyclable Polyethylene‐Like Multiblock Polymers by Modulating the Branch Structure

Abstract Developing plastics that fill the need of polyolefins yet are more easily recyclable is a critical need to address the plastic waste crisis. However, most efforts in this vein have focused on high‐density polyethylene (PE), while many different types of PE exist. To create broadly sustainable PE with modular properties, we present the synthesis, characterization, and demonstration of materials applications for chemically recyclable PE‐like multiblock polymers prepared from distinct hard and soft blocks using ruthenium‐catalyzed dehydrogenative polymerization. By altering the branching pattern within the soft blocks, a series of PE‐like multiblock polymers were synthesized with tunable glass transition temperatures ( T g ) while maintaining consistent high melting temperatures ( T m ). A clear U‐shape trend between T g and mechanical properties was found, showcasing their potential as sustainable materials with tailored properties spanning commercial linear low‐density polyethylene (LLDPE) and low‐density polyethylene (LDPE). These materials offer adjustable adhesive strength to metal and demonstrate chemical recyclability and selective depolymerization in mixed plastic streams, promoting circularity and separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring the Properties of Chemically Recyclable Polyethylene‐Like Multiblock Polymers by Modulating the Branch Structure

Abstract Developing plastics that fill the need of polyolefins yet are more easily recyclable is a critical need to address the plastic waste crisis. However, most efforts in this vein have focused on high‐density polyethylene (PE), while many different types of PE exist. To create broadly sustainable PE with modular properties, we present the synthesis, characterization, and demonstration of materials applications for chemically recyclable PE‐like multiblock polymers prepared from distinct hard and soft blocks using ruthenium‐catalyzed dehydrogenative polymerization. By altering the branching pattern within the soft blocks, a series of PE‐like multiblock polymers were synthesized with tunable glass transition temperatures ( T g ) while maintaining consistent high melting temperatures ( T m ). A clear U‐shape trend between T g and mechanical properties was found, showcasing their potential as sustainable materials with tailored properties spanning commercial linear low‐density polyethylene (LLDPE) and low‐density polyethylene (LDPE). These materials offer adjustable adhesive strength to metal and demonstrate chemical recyclability and selective depolymerization in mixed plastic streams, promoting circularity and separation.

Zhao, Yucheng↗

Recovery of Glass and Silicon Solar Cells from Si-Modules Through Laser Processing

This study demonstrates an innovative and environmentally friendly laser-based approach for the efficient recovery of glass and silicon solar cells, allowing the recycling of photovoltaic modules. The methodology involves the use of a high-power pulsed laser beam focusing at various interfaces within the modules. Specifically, the delivery of ultra-short pulse laser energy at the interfaces of glass and polymeric encapsulants, as well as at the encapsulants and silicon solar cells, facilitates the debonding of polymers from both glass and silicon cell surfaces. The debonding occurs through photothermal, ablation, chemical modification, and localized heat generation. The research successfully demonstrates the recovery of glass from commercial mini solar modules of size 11.5 x 6.8 cm 2 and a silicon wafer of size 3.0x1.6 cm 2 . Ongoing efforts aim to extend the effectiveness of this laser-based methodology to comprehensively recycle larger-size components. This innovative approach holds promise for addressing environmental concerns associated with the disposal of solar modules, contributing to sustainable practices in the renewable energy sector.

glass↗

Low-velocity impact resistance and failure characteristics of all thermoplastic woven polymer-fiber-reinforced plastic composites

This study addresses the impact performances of recyclable composites made of all thermoplastic polymer-fiber-reinforced plastics (PFRPs), where the reinforcing fibers and matrix are made of thermoplastic polymers. Three woven PFRPs systems were evaluated, including polypropylene fibers, polypropylene matrix, and high-density polyethylene matrix. In low-velocity impact scenario with an impactor speed of less than 6 m/s, our results demonstrate the energy absorption capabilities of the flat laminate PFRPs compared to woven carbon fiber-reinforced plastics (CFRPs) and aluminum alloy 5052. For the systems studied, the PFRPs can reach the specific energy absorption 89% to 115% of the CFRPs. Even compared with the aluminum alloy 5052, the PFRPs can reach up to 97%. We investigate the failure morphologies of the PFRPs using X-ray µCT scans. They reveal the PFRPs’ unique ductile failure morphologies compared to common CFRPs. In addition, we heal the perforated region in the PFRPs by applying the manufacturing process identical to the initial curing process. The healed panels are perforated again, and they recovered 30% to 38% of their original specific energy absorption, a recovery not achievable with CFRPs. This study provides valuable experimental results, and concrete insights into the potential applications of recyclable PFRPs in various engineering fields. It emphasizes their excellent energy-absorbing capability and repairability.

CFRPs↗

Upcycling of post-consumer mixed polyolefin feedstock: An economic and technical evaluation

Here, this study reports techno-economic and life cycle analyses to evaluate the economic and environmental impacts of mechanically recycled PE/PP blends in the presence of rheology modifiers. Additionally, fiber-reinforced composites derived from the compatibilized blends were prepared and evaluated for their performance compared with virgin plastics. Results suggest that compatibilized PE/PP blends exhibit a 70% lower selling price compared to virgin PE. Furthermore, these blends achieved a 74% reduction in greenhouse gas emissions or climate change impact compared to the virgin counterpart. Fiber-reinforced composites from compatibilized PE/PP blends demonstrated improved or comparable mechanical properties relative to composites made from virgin PE/PP blends. Based on their favorable cost and environmental impact, along with performance comparable to virgin composites, compatibilized PP/PE composites made from post-consumer plastics can find applications in large-scale composite manufacturing.

Fiber reinforced plastics (FRP)↗

Molar-Mass-Dependent Partitioning of Polyethylene in Nanopores of Model Catalyst Supports from Small-Angle Neutron Scattering

Heterogeneous catalysis offers opportunities to enhance valorization of plastic waste via chemical recycling through control of the upcycled product distributions. Minimizing low-value light hydrocarbons is desired; however, fundamental insights into how to control selectivity are lacking. Here we use contrast variation with small-angle neutron scattering (SANS), model perdeuterated polyethylenes (dPEs), and a model liquid hydrocracking product (tetradecane) to quantify polymer partitioning within mesoporous silica (SBA-15). Polyethylene concentration within the mesopores is increased relative to the bulk solution, and this partitioning increases as the temperature increases. However, this polyethylene partitioning is maximized when the radius of gyration of the polymer chains is comparable to the SBA-15 pore size (10 nm). An increased partitioning at higher temperatures is attributed to entropically driven adsorption of PE within the mesopores. There is no observed preferential partitioning of hexatriacontane (a model oligomer) within the mesopores at the temperatures examined. Furthermore, these results suggest that pore size could promote the selective partitioning of polymer species into the mesopores by size. For plastic upcycling, pore-size-dependent partitioning should increase the probability for the reaction of long polymers over oligomeric and small-molecule polyolefin depolymerization products.

Adsorption↗

Blending Polyurethane Thermosets Using Dynamic Urethane Exchange

Recycling crosslinked polyurethanes (PUs) is accomplished through mechanical or chemical processes that are energy-intensive or produce plastics of lesser value. Polymer recycling processes are notably intolerant of polymer mixtures, yet the ability to reprocess and compatibilize two or more crosslinked PUs together will make this process more amenable to mixed waste streams while offering an opportunity to tune the properties of the recycled polymer products. Here, we blend a rigid polyester PU and a soft polyether PU using twin-screw extrusion to yield materials with tunable mechanical properties based on the feed composition. Their material properties were compared to those of compression-molded reprocessed blends and blends where the monomers were mixed prior to synthesis. The extruded materials showed similar mechanical and thermal properties to newly prepared blends and had higher-value mechanical properties compared to the samples reprocessed via compression molding. The morphologies of the blends were observed using phase imaging via atomic force microscopy to show that there is less phase separation in the extruded materials compared to compression-molded blends. The mechanical properties of these materials were tunable from soft to elastomeric to rigid based on the feed composition, and this tunability was demonstrated through four consecutive reprocessing cycles, through which the mechanical properties were steadily varied from rigid to soft by incorporating increasing amounts of soft polyether PU material. Here, this blending method for reprocessing mixed waste compatibilizes different PUs and provides a means to tune the mechanical properties of a PU product, even if starting from waste streams of varying compositions. As such, this process represents an intriguing new approach for polymer reprocessing.

Extrusion↗

Corrosion Engineering of Part‐Per‐Million Single Atom Pt 1 /Ni(OH) 2 Electrocatalyst for PET Upcycling at Ampere‐Level Current Density

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt 1 /Ni(OH) 2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000 mA cm −2 (1.444 V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500 h of continuous operation. In conclusion, this process allows valuable chemical production at high space-time yield and is highly profitable (588–700 $\$$ ton −1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

36 MATERIALS SCIENCE↗

Understanding Depolymerization and Repolymerization Toward Repurposing Polymer Waste Into Valuable Chemicals & Materials

The versatility of synthetic polymers has led to their continual and escalating production that has accompanied mismanagement at their end-of-life. Exploring and understanding complementary avenues to repurpose plastic waste beyond traditional mechanical recycling can unlock new opportunities in providing feedstock flexibility, securing supply chains, recovering valuable materials, and enabling new valorization paths. Chemical recycling allows for the return to monomers, tailored oligomers, and polymers, even from mixed states of post-consumer waste plastics. This review article summarizes our research team's efforts on elucidating key insights surrounding plastic depolymerization and repolymerization into valorized products. We revealed organocatalyst design rules lead to highly effective and selective deconstruction of condensation polymers. The intricacies of tailoring the reaction environment to produce products of specific lengths and desired functionalities transform low-value waste feedstocks into high-performance materials with embedded circularity. Other types of polymers, including polyolefins and polyakenamers, have also been designed and converted into valuable products. There remain opportunities for further developments such as low-energy and precision depolymerization, adoption of cutting-edge small molecule transformation to access functionalized polymer scaffolds typically inaccessible otherwise, as well as precision design and understanding through the aid of advanced tools.

Galan, Nick [ORNL]↗

Plastic waste upcycling toward a circular economy

Large amounts of plastics are discarded worldwide each year, leading to a significant mass of waste in landfills and pollution to soil, air, and waterways. Upcycling is an efficient way to transform plastic waste into high-value products and can significantly lessen the environmental impact of plastic production/consumption. In this article, current advances and future directions in plastic waste upcycling technologies are discussed. In particular, this review focuses on the production of high-value materials from plastic waste conversion methods, including pyrolysis, gasification, photoreforming, and mechanical reprocessing. Plastic waste compositions, conversion products, reaction mechanisms, catalyst selection, conversion efficiencies, polymer design, and polymer modification are also explored. Furthermore, the main challenges facing the adoption and scale-up of these technologies are highlighted. Suggestions are given for focusing future research and development to increase the efficiency of upcycling practices.

30 DIRECT ENERGY CONVERSION↗

Pyrolysis in Molten Salts Converts Plastics into a Mesoporous Electrocatalyst with a High Density of Atomic Fe–N–C Active Site

Upcycling plastic waste into value-added products is a promising strategy for both economic and environmental sustainability. However, achieving control over structure–property correlations during the upcycling process remains challenging. Here, in this study, we investigate the modulation of active site formation during pyrolytic conversion of plastics to carbon by composition-controlled molten salts. Using melamine formaldehyde (MF) foams as a precursor, we demonstrate that their pyrolysis in eutectic chloride molten salts with Fe 2+ , Na + , and K + ions directs the carbonization process toward the formation of mesoporous functional carbon enriched with atomically dispersed Fe–N–C sites, which are well-known for their catalytic activity in oxygen reduction reaction (ORR). Compared to pyrolysis in the FeCl 2 -only salt, the incorporation of alkali metal ions (Na + , K + ) in the eutectic mixture facilitates nitrogen retention in the carbon matrix and modulates iron speciation. This synergistic environment promotes a higher density and more uniform dispersion of Fe–N–C moieties within the carbon matrix. Consequently, the resulting catalyst exhibits a high surface area, hierarchical porosity, and improved electrochemical properties. When tested as an ORR catalyst, the Fe–N–C-enriched catalyst delivers a high half-wave potential (E 1/2 = 0.875 V vs RHE) with nearly exclusive 4e – pathway. These properties are comparable to those of commercial Pt/C catalysts, along with improved stability.

Fe−N−C active sites↗

Depolymerization of Vinyl Polymers

Depolymerization is a promising approach to reduce plastic waste by regenerating monomers from polymers, presenting a compelling solution to maintain a circular polymer economy. However, vinyl polymers with all-carbon backbones are especially difficult to depolymerize due to significant thermodynamic and kinetic barriers. Developments in reversible-deactivation radical polymerization and catalytic methods demonstrate how tuning polymer structure and reaction conditions can address these challenges. This Viewpoint revisits early studies on radical depolymerization and recent advances enabling monomer recovery at lower temperatures. Exciting current trends to utilize depolymerization as a strategy for tuning polymer material properties and upcycling waste polymer to high-value products are discussed. Finally, we outline key directions to make vinyl polymer depolymerization scalable, efficient, and economically viable.

depolymerization↗