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At least 37 records · Page 2

A Multicopper Oxidase from Paenibacillus Polyethylenelyticus JNU01 Oxidizes Polyethylene

Polyethylene (PE) is a widely used plastic that persists in the environment and resists breakdown via microbial degradation. In this work, we discovered a new bacterium, Paenibacillus polyethylenelyticus JNU01, that grows on a PE-like wax (PELW, 4 kDa) as its sole carbon source, causing chemical modifications to the substrate and releasing small-molecule products. Genomic and transcriptomic analyses identified a multicopper oxidase (PpMmcO) as a key enzyme candidate for this observed activity. PpMmcO promoted surface oxidation, increased hydrophilicity, and the release of small-molecule products such as ketones, alkanes, and alkenoic acids. Scanning electron microscopy confirmed surface damage on both PELW and post-use greenhouse PE films. Weight loss analysis showed mass losses of 5.2% for the PELW powder and 1.6% for the greenhouse PE film after treatment with wild-type PpMmcO. We propose a radical-mediated pathway catalyzed by PpMmcO. These findings identify a new bacterium and enzyme capable of promoting partial PE oxidation and provide insight into biological processes that may act on polyethylene.

36 MATERIALS SCIENCE

Polyethylene Upcycling to Liquid Alkanes in Molten Salts under Neat and External Hydrogen Source-Free Conditions

Development of facile approaches to convert plastic waste into liquid fuels under neat conditions is highly desired but challenging, particularly without noble metal catalysts and an external hydrogen source. Herein, highly efficient and selective polyethylene-to-gasoline oil (branched C 6 –C 12 alkanes) conversion was achieved under mild conditions (<170 °C) using commercially available AlCl 3 -containing molten salts as reaction media and to provide catalytic sites (no extra solvents, additives, or hydrogen feeding). The high catalytic efficiency and selectivity was ensured by the abundant active Al sites with strong Lewis acidity (comparable to the Al type in acidic zeolite) and highly ionic nature of the molten salts to stabilize the carbenium intermediates. Dynamic genesis of the Al sites was elucidated via time-resolved Al K-edge soft X-ray and 27 Al NMR, confirming the tricoordinated Al 3+ as active sites and its coordination with the as-generated alkene/aromatic intermediates. Further, the carbenium formation and polyethylene chain variation was illustrated by inelastic neutron scattering (INS) and an isotope-labeling experiment. Theoretical simulations further demonstrated the successive hydride abstraction, β-scission, isomerization, and internal hydrogen transfer reaction pathway with AlCl 3 as active sites. This facile catalytic system can further achieve the conversion of robust, densely assembled, and high molecular weight plastic model compounds to liquid alkane products in the diesel range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

STUDIES ON PIPELINE POLYETHYLENES IN HYDROGEN GAS ENVIRONMENTS USING IN-SITU AND EX-SITU CHARACTERIZATION METHODS

Polymeric materials are commonplace in the natural gas infrastructure as distribution pipes, coatings, seals, and gaskets. Under the auspices of the U.S. Department of Energy HyBlend program, one of the means to reduce greenhouse gas emissions is with replacing natural gas, either partially or completely, with hydrogen. This approach makes it imperative that we conduct near-term and long-term materials compatibility research in these relevant environments. Insights into the effects of hydrogen and hydrogen gas blends on polymer integrity can be gained through both ex-situ and in-situ analytical methods. Our work represented here highlights a study of the behavior of pipeline polyethylene (PE) materials, including HDPE (Dow 2490 and GDB50) and MDPE (Ineos and legacy Dupont Aldyl A), when exposed to hydrogen by means of in-situ X-ray scattering and ex-situ Raman spectroscopy techniques. Samples were tested in ex-situ hydrogen and argon gas environments and in-situ hydrogen environments to identify differences due to permeation and solubility of these gases. These methods complemented each other because Raman spectroscopy could capture permanent effects after materials were removed from gaseous environments, and in-situ X-ray scattering analysis collected real-time data to elucidate the impact of the gas environment on polymer microstructure. Data collected revealed that the aforementioned polymers did not show significant changes in crystallinity and microstructure under the exposure conditions tested. Our findings from these studies will help establish real-time effects caused by hydrogen gas transport through pipeline polyethylenes by way of its influence on polymer structure and chemistry, which is directly related to pipeline mechanical strength and longevity of service.

Hydrogen materials compatibility, Natural gas pipe

Comparison of Mechanical Properties of Lignin/High-Density Polyethylene (HDPE) Composites and Wood/HDPE Composites

Lignin is a plant-derived, the second most abundant natural polymer, and a waste byproduct of the pulp industry. Incorporation of lignin into plastic composites using scalable approaches is commercially favored and low carbon-cost. Potential end applications for lignin plastic composites (LPCs) could be found in buildings and furniture where wood plastic composites (WPCs) are used in various components. This study compares the mechanical properties of LPCs and WPCs, aiming at the examination of the viability of the use of LPCs as alternative materials to WPCs in the building industry. Sodium ligninsulfonate (SLS)-based LPC blended with high-density polyethylene (HDPE) (45 wt.%) and maleic anhydride grafted polyethylene (MAPE) as a compatibilizer (5 wt.%) reached flexural strength (35.17 and 30.92 MPa respectively) and moduli (2.87 and 1.79 GPa respectively) comparable to benchmarking WPCs. Lignin dealkaline (LD)-based LPC exhibited higher ultimate strain but lower strength than SLS-based LPC, probably due to fragmentation during the post-sulfite treatment steps.

cellulose and other wood products

Synthesis and Properties of Poly(vinyl chloride)- b -polyethylene Multiblock Copolymers through the Hydrodechlorination of PVC with Silylium Ions

Polymer compatibilizers stabilize the interface between two immiscible polymers to allow for a material that improves properties for additional use. Chlorinated polyethylene (CPE) is a common compatibilizer, yet there does not exist a synthetic pathway either from monomers or via the functionalization of polyethylene (PE) to yield a polymer that has a controlled chlorine amount and primary structure along the polymer chain. Herein, we report a series of novel block copolymers of poly(vinyl chloride) (PVC) and PE, synthesized through selective hydrodechlorination of PVC. Contrary to CPE, the full range of chlorination can be obtained and the block number can be altered. Interfacial adhesion studies reveal samples with competitive compatibilization of PVC/polyolefin elastomer blends (POE). In conclusion, this method shows that post-polymerization modification can be a strategic top-down synthesis to achieve high performance polymers.

Wood, Zachary A. [Univ. of Southern California, Lo

Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

Petroleum-derived polyolefins exhibit diverse properties and are the most important and largest volume class of plastics. However, polyolefins are difficult to efficiently recycle or break down and are now a persistent global contaminant. Broadly replacing polyolefins with bio-derived and degradable polyethylene-like materials is an important yet challenging endeavour towards sustainable plastics. Here, in this study, we report a solution for circular bio-based polyethylene-like materials synthesized by acceptorless dehydrogenative polymerization from linear and branched diols and their catalytic closed-loop recycling. The polymerization and depolymerization processes utilize earth-abundant manganese complexes as catalysts. These materials exhibit a wide range of mechanical properties, encompassing thermoplastics to plastomers to elastomers. The branched diols, produced through a thiol-ene click reaction, can be polymerized to plastics with significantly enhanced tensile properties, toughness and adhesive properties. These materials could be depolymerized back to monomers through hydrogenation and were separatable with a monomer recovery of up to 99%, unaffected by the presence of dyes and additives. Overall, this system establishes a route to more sustainable plastics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Upcycling Polyethylene Waste to Advanced Carbon Materials for Energy Storage Applications

Polyethylene is notoriously difficult to upcycle because it decomposes into light gases at approximately 350-400 °C which prevents processing it at higher temperatures to convert it into high-value carbon materials, such as graphene or graphite. We address this challenge by using an air-based, thermo-oxidation process, which heats polyethylene (PE) just below the decomposition point to initiate oxidation and cross-linking of PE alkyl chains. These molecular transformations allow PE to be further graphenized or graphitized at higher temperatures without decomposing. The PE-derived graphene has a specific surface area up to 1,800 m 2/g and Raman ID/IG ratio of 0.85, which enables it to be used as an electrode material for a symmetric supercapacitor with the 1 M H2SO4 electrolyte. The PE-derived graphene material has a comparable electrochemical capacitive performance, such as power density, specific capacitance, and long cycle stability, to the commercial state of art porous carbon electrode. The stabilized PE could also be converted into highly crystalline flake graphite via low-temperature catalytic graphitization. The PE-derived graphite is used for the lithium-ion battery anode, which showed comparable electrochemical battery performance, such as reversible rate performance and long-term cyclic stability, to the current use battery-grade graphite, thus providing a scalable method to upcycle PE plastic waste into high-value carbon material.

Gao, Yuan

Irradiation of linear polyethylene - Partitioning between sol and gel.

Investigation of the importance of chain-scission processes and of the applicability of the general theory of network formation to polyethylene with respect to critical conditions for gelation, using molecular weight fractions of linear polyethylene irradiated at 133 C. The partitioning between sol and gel was found to adhere to the theory just beyond the gel point. Deviations from theory occurred as the irradiation dosage was increased. It was concluded that main-chain scission at the temperatures concerned is not a significant process.

Rijke, A. M.

Method for casting polyethylene pipe

Short lengths of 7-cm ID polyethylene pipe are cast in a mold which has a core made of room-temperature-vulcanizable (RTV) silicone. Core expands during casting and shrinks on cooling to allow for contraction of the polyethylene.

Elam, R. M., Jr.

Upcycling Polyethylene Waste into Hybrid Graphitic Porous Carbon Materials Used in High‐Performance Zinc‐Ion Hybrid Capacitors

Polyethylene (PE) waste is a challenge to upcycle into useful materials because this plastic tends to decompose into volatile compounds when heated at relatively low temperatures. In this work, mixtures of PE wastes into a hybrid graphitic porous carbon (HGPC) by a thermal oxidation pretreatment step, with assistance of an inert solid additive (KCl), to functionalize, crosslink, and stabilize the PE waste followed by carbonization and catalytic graphitization steps with a potassium carbonate catalyst, are upcycled. The PE waste‐derived HGPC (PW‐HGPC) has a hybrid structure composed of graphene‐like carbon nanosheets grown on the surface of carbon particles, high porosity with specific surface area, up to 1,763 m 2 g −1 , and good graphitic degree with average Raman I 2D / I G ratios of 0.53. When used as cathode material for zinc‐ion hybrid capacitors, this PW‐HGPC exhibits an excellent specific capacity, up to 126.7 mAh g −1 , at high mass loading of 10 mg cm −2 . Moreover, PW‐HGPC exhibits remarkable cycling stability with capacity retention of >94% after 10 000 cycles. Additionally, the KCl is recycled and reused over five times. This method provides a new solution for upcycling PE wastes into high value‐added carbon materials, not only for zinc‐ion hybrid capacitors but also for other electrochemical energy storage device applications.

hybrid graphitic porous carbon

Investigating the Role of Acid Sites in the Hydrocracking of Polyethylene-EVOH Multilayer Film Waste over Pt/BEA Catalyst

Multilayer polymer films (MFs) containing poly(ethylene-co-vinyl alcohol) (EVOH) and polyolefins are ubiquitous in single-use food and medical packaging. MFs are currently landfilled or incinerated rather than mechanically recycled because of the processing difficulties associated with their form factor and complex multicomponent structures. Advanced chemical recycling is a promising solution. Prior reports have explored hydrogenolysis and hydrodeoxygenation to convert EVOH, but these technologies are limited by catalyst deactivation and slow apparent kinetics, respectively. Alternatively, in this work, we demonstrate the efficient hydrocracking of commercial MFs into naphtha range (C5-C12) alkanes over platinum (Pt) supported on acidic zeolites. Mixtures of low-density polyethylene (LDPE) and EVOH are utilized as MF surrogates to gain fundamental insights. Pt deposited on BEA supports with varying Lewis acid site (LAS) concentrations are synthesized and tested for hydrocracking. Surprisingly, Pt/BEA with high LAS concentrations demonstrate improved activity for LPDE/EVOH blends over LDPE alone. In contrast, LAS concentrations are shown to have no influence on LDPE hydrocracking. LAS and Brønsted acid sites (BAS) catalyze the dehydration of EVOH to form water, which improves LDPE hydrocracking. Polyaromatics formed primarily via EVOH thermal degradation lead to detrimental coke formation, which hinders hydrocracking activity. Reaction conditions and feed ratios of LDPE and EVOH are tuned to balance these competing effects. Reusability tests demonstrate that Pt/BEA maintains high activity (81% conversion in 2 h) and high selectivity towards naphtha (78%) over multiple reuse cycles. Furthermore, these findings position hydrocracking as a promising technology for the circularity of complex MF plastic waste.

36 MATERIALS SCIENCE

Effect of Specimen Thickness on Fracture Toughness and Plane Stress to Plane Strain Transition in Medium-Density Polyethylene

This study investigates the effect of specimen thickness on fracture toughness and the transition from plane stress to plane strain conditions in Medium-Density Polyethylene (MDPE) using Single Edge Notched Bend (SENB) specimens. Three thickness groups (7.5 mm, 9.0 mm, and 12.1 mm) were tested following ASTM D5045 protocol. Conditional stress intensity factors (KQ) increased from 2.2 MPavm to 2.8 MPavm with increasing thickness, demonstrating significant size dependency. Confocal microscopy revealed a 34% reduction in maximum crack tip opening displacement (CTOD) from 0.478 mm to 0.314 mm as thickness increased, with plastic zone lateral extent decreasing by 32%. This quantitative evidence validates Irwin's theoretical prediction of plastic zone size transition from plane stress r_y˜ (1/2p) (K_I/s_y )^2 to plane strain conditions r_y˜ (1/6p) (K_I/s_y )^2.Scanning electron microscopy confirmed progressive suppression of shear lips and evolution from ductile tearing with extensive polymer chain drawing in thin specimens to localized crazing in thick specimens. Despite all specimens satisfying the ASTM D5045 criterion (B = 2.5(KQ/s_y )^2 ) ,residual shear lips persisted even in the thickest specimens, demonstrating that nominal size requirements alone are insufficient for achieving complete plane strain conditions in highly ductile polymers. The findings emphasize the necessity of integrated analytical and morphological assessment for valid fracture toughness characterization, with critical implications for life assessment and integrity prediction in thick-section polymer components such as natural gas distribution pipelines.

Medium-Density Polyethylene

Hydrogen-rich syngas production from the steam co-gasification of low-density polyethylene and coal refuse

Gasification provides a promising pathway for transforming waste materials into valuable products, such as fuels and chemicals. Here, this study investigates the steam co-gasification of low-density polyethylene (LDPE) and compressed thickener underflow, representative of coal refuse (CR), in a drop tube reactor. The effects of feed blend ratio (0–100 wt% LDPE) and temperature (800–1000 °C) on syngas composition, tar formation, and process efficiency are examined. The high volatility of LDPE makes it more reactive than CR but also promotes the formation of 2–7 ring aromatic tars. Increasing temperature improves carbon conversion efficiency (CCE), cold gas efficiency (CGE), and syngas yield, although the lower heating value (LHV) of syngas decreases. Hydrogen is the dominant gas product, reaching 59 vol% with the H 2 /CO molar ratio ranging from 2.27 to 4.74. Synergistic effects from alkali and alkali earth metals (AAEMs), particularly K and Ca, in CR ash enhance syngas yield by catalyzing char gasification and tar cracking. Hematite (Fe 2 O 3 ) and ash from sub-bituminous/bituminous coals are explored as tar reforming catalysts. Fe 2 O 3 achieves 100 % tar reforming efficiency, while coal ash, with a lower Fe 2 O 3 content (15 wt%), is less effective at cracking polycyclic aromatic hydrocarbons, particularly naphthalene. These findings demonstrate the flexibility of co-gasification, allowing precise tuning of syngas characteristics for specific downstream applications. Further optimization of waste-derived catalysts could enhance the economic viability of gasification in waste-to-energy processes.

01 COAL, LIGNITE, AND PEAT

Elucidation of odd-chain dicarboxylate metabolism in Acinetobacter baylyi and application to polyethylene upcycling

Polyethylene (PE) is a versatile polymer, but its end-of-life management is challenging due to its recalcitrant structure. We present a promising approach combining chemical degradation and bio-upcycling to convert postconsumer PE waste into a value-added bioproduct. Specifically, PE was degraded into acetic acid and C 4 –C 7 dicarboxylic acids by nitric acid. We then elucidated the catabolic pathways for glutarate (C 5 ) and pimelate (C 7 ) in the nonmodel bacterium Acinetobacter baylyi ADP1 through RNA sequencing, phenotyping, and enzymatic assays. Whole-genome sequencing of evolved isolates also identified a crucial IclR family transcriptional regulator, DcaS, which acts as a repressor of dicarboxylate metabolism. The reverse-engineered strain exhibited enhanced substrate utilization compared to the wild-type strain. Using rational metabolic engineering, the PE deconstruction products were bioconverted into the valuable chemical lycopene, highlighting the potential of this microbial chassis to produce value-added bioproducts from postconsumer PE waste, thus promoting a circular economy for plastics.

metabolic engineering

Molecular Level Understanding of Polyethylene Terephthalate (PET) Depolymerization in Base/Alcohol Hybrid Systems

Polyethylene terephthalate (PET) depolymerization in base/alcohol hybrid systems represents a promising low-energy approach for chemically recycling PET waste into valuable monomers. This study investigates the mechanistic pathways of PET depolymerization in NaOH/alcohol solutions, emphasizing the competing roles of hydroxide and alkoxide species. Utilizing a combination of experimental techniques, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations, we explore how factors such as base concentration, alcohol chain length, and pKa values of alcohols influence PET depolymerization efficiency and pathways. Our findings indicate that alkoxide ions (RO⁻) exhibit notably higher reactivity than hydroxide ions (HO⁻), favoring an alcoholysis pathway in the base/alcohol hybrid system. Experimental results across a series of C1 to C5 alcohols show that longer-chain alcohols, particularly 1-butanol, achieve higher PET conversion, although this does not align solely with simple nucleophilicity trends of alkoxides. While DFT calculations reveal comparable activation energies for various alkoxides in PET depolymerization, MD simulations underscore the significant role of alcohol chain length, with longer-chain alcohols forming more stable or frequent interactions with PET. Additionally, the alkoxide concentration, influenced by the alcohol’s pK a , directly impacts PET conversion. These suggest that PET depolymerization is governed by a balance between alkoxide concentration and alkoxide-PET interactions, rather than activation energies or nucleophilicity alone. From a practical perspective, incorporating long-chain alcohols as cosolvents may enhance process efficiency but increases raw material costs by approximately 30%. However, long-chain alcohols present a safer and more sustainable alternative to hazardous cosolvents such as dichloromethane. This work offers a molecular-level understanding of PET depolymerization in base/alcohol systems and provides insights into optimizing these systems for more efficient and sustainable PET recycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH