Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “polyolefins”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Impact of Small-Alkane Solvents on Polyolefin Hydrogenolysis over a Ruthenium Catalyst

Selective catalytic hydrogenolysis of polyolefins is a promising route to convert plastic waste into valuable liquid products, such as lubricants, waxes, and surfactants. However, the high viscosity of polymer melts imposes mass transfer limitations on this reaction. Solvents can mitigate these challenges, but their effects on reaction kinetics and product selectivity remain underexplored. Here, we systematically explore the effects of small n-alkanes and cycloalkanes on the hydrogenolysis of polyethylene and polypropylene over a Ru/TiO 2 catalyst. Using kinetic measurements and isotopic labeling, we show that n-octane at high mass fractions alters the mechanism from direct hydrogenation to solvent-mediated hydrogen transfer, reducing the rate of C–C bond cleavage. Longer alkanes further inhibit reactivity due to stronger surface binding. 1,4-Dimethylcyclohexane suppresses methane formation, favoring heavier products, while decalin likely forms surface-bound aromatics that poison the catalyst. Overall, alkane solvents modulate product selectivity and reduce the yield of methane byproduct, allowing for ∼35–40% selectivity to valuable C 20 -C 30 alkane products. This work highlights the complex impact of polymer–alkane mixtures on hydrogenolysis kinetics relevant to the design of commercial-scale plastic waste valorization processes.

Catalysts↗
DOE OSTI2024

Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization

To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene-co-ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C=C bonds were subsequently hydrogenated. Here, the bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Large-Scale Compatibilization of Postconsumer Polyolefins in the Presence of Paraffin Wax as a Rheology Modifier

Postconsumer polyolefins (r-POs) are leading plastic waste contributors today. This study reports, for the first time, the compatibilization of r-POs at a 50 kilogram (kg) scale with a styrene block copolymer compatibilizer in the presence of paraffin waxes as rheology modifiers (RMs). The addition of the rheological modifier (RM) and compatibilizer enhances the melt flow indices (MFIs) and mechanical properties, respectively. One aspect of this study is to compare the effectiveness of low-cost paraffin wax to that of specialized and expensive RMs in r-POs. The mechanical and rheological properties such as the melt flow index (MFI) of r-POs were compared in the presence of two types of RMs. Next, the study explores the challenges encountered when scaling the compatibilization of r-POs in the presence of paraffin wax from a 10-g to a 50-kg scale. The mechanical properties were determined and compared for samples at different scales. The study further investigated the effect of the method used for blending paraffin wax with r-PO and its impact on the value of their MFI and mechanical properties. This at-scale validation could pave the way for the commercialization of r-POs.

crystallinity↗
DOE OSTI2025

Intrinsically Bifunctional and Tunable Tungsten Carbide Catalysts Enable Efficient PVC-Compatible Polyolefin Hydrocracking

Hydrocracking is a promising route for the chemical recycling of polyolefins (PO), converting them into short hydrocarbons over bifunctional catalysts with metal sites for hydrogenation and dehydrogenation, and Brønsted acid sites (BAS) for isomerization and C–C bond cleavage. However, PO feedstocks containing polyvinyl chloride (PVC) can release chlorine (Cl) under reaction conditions, deactivating conventional noble metal/zeolite catalysts. Moreover, the lack of site intimacy and the presence of micropores within conventional catalysts create challenges around the transport of high-molecular-weight, sterically encumbered polymer intermediates. Here, in this study, we report tungsten carbides (W x C) as a novel type of bifunctional catalysts that address these challenges. W/W 2 C phases on W x C offer “metal” sites, and −OH on WO x species introduces BAS in close proximity. The “metal”:BAS ratio can be tuned through carburization temperature, leading to a volcano-shaped activity trend reflecting the requirement for metal–BAS balance. Kinetic data demonstrate that each PO chain undergoes sequential cleavage, while trends in cracking ideality and selectivity follow those in short-alkane hydrocracking. On the per-BAS basis, W x C is more efficient than conventional bifunctional catalysts by more than an order of magnitude, due to enhanced polymer transport. They maintain or show increased activity with 10 wt % PVC in the substrate. This work establishes transition-metal carbides as earth-abundant bifunctional catalysts with unique site proximity and heteroatom compatibility. These features, along with the broad structure space for rational tuning, make them promising options to tackle specific challenges that polymer feedstocks present in hydrocracking.

Nwachukwu, Uchenna C. [Univ. of Akron, OH (United ↗
DOE OSTI2025

Vinylsilanes as Chain-Transfer Agents in Ethylene Polymerization: Direct Synthesis of Heterotelechelic Polyolefins

A single-step route to heterotelechelic polyethylene is enabled by palladium-diimine-catalyzed polymerization of ethylene using vinylsilanes as chain-transfer agents. The reaction affords α-alkenyl-ω-silyl end-capped heterotelechelic polymers whose molecular weights are controllable over a wide range by adjusting the [ethylene]/[vinylsilane] molar ratios. Notably, highly efficient end-capping with silanes carrying a variety of functionalities can be achieved under the optimized conditions. Furthermore, the alkenyl- and silyl-terminated telechelics serve as polymer precursors for further reactions and can be converted into additional telechelic functionalized polyolefins in good yields.

Chen, Zhi-Hao [University of Houston, TX (United S↗
DOE OSTI2026

A Mesopore-Confined and Graphene Oxide-Localized Ruthenium Catalyst Increases Rates of Mid-Chain Polyolefin Hydrogenolysis

A catalyst architecture with mesoporous silica coating Ru nanoparticles on reduced graphene oxide (mSiO 2 /Ru/rGO) localizes the 2 nm Ru solely at the closed bottoms of 2.9 nm diameter mesopores. mSiO 2 /Ru/rGO catalyzes the rapid, selective hydrogenolysis of polyolefins at wax formation rates (ν wax ) up to 1700 g wax ·g Ru –1 ·h –1 and a turnover frequency (TOF) for C–C bond cleavage of 130 ± 8 min –1 . The ν wax and TOF for mSiO 2 /Ru/rGO are 23× and 16× those of nonporous Ru/rGO, respectively, indicating that faster chain cleavage is also more selective inside mesopores. The methane yield from mSiO 2 /Ru/rGO is ca. 30% of the value obtained from Ru/rGO. Methane decreases, and wax selectivity improves with narrow-pore (2.3 nm) mSiO 2 /Ru/rGO. The reaction rate decreases at lower and higher H 2 pressures from its maximum at 37 bar. Log(TOF)-log(P H2 ) plots reveal rates ∝ [P H2 ] 2.8 or [P H2 ] −2.0 in the lower or higher pressure ranges, respectively. Corresponding plots for Ru/C give rates ∝ [P H2 ] 1 or [P H2 ] −2.4 . Ru is hydrocarbon-covered at low pressure; thus, the higher H 2 order for mSiO 2 /Ru/rGO indicates that mesopores increase the density of cleavable unsaturated moieties on the Ru surface. The lower H 2 order on Ru/C implies a lower density of cleavable groups because saturated segments occupy a larger fraction of the Ru surface. Higher surface occupancy by the hydrocarbon reactant correlates with more methane formation. Therefore, pore confinement, narrower pore diameter in mSiO 2 /Ru/rGO, or higher H 2 pressure leads to lower methane yields. Ru nanoparticles in mSiO 2 /Ru/rGO maintain equivalent activity and selectivity over five recycling tests.

Catalysts↗
DOE OSTI2026

Single-Atom Nickel Dispersed on Mo 2 TiC 2 T x MXene for Upcycling of Polyolefins via Catalytic Hydropyrolysis for Fuels and Lubricants

Plastic waste has been a major social and environmental problem. Chemical upcycling of plastic waste into transportation fuels or lubricant oil has emerged as an attractive and promising approach to convert plastic waste into valuable products. However, conventional catalyst systems often require high-pressure hydrogen, prolonged residence time, and the use of noble metal catalysts. Here, we present zero-valent nickel single atoms on Mo-based MXenes (Ni/Mo 2 TiC 2 T x ) for effective hydrogenation of polyolefins. In situ spectroscopic and microscopic characterizations demonstrate the formation of Ni–Mo and Ni–C bonds at a low Ni loading, resulting in the formation of dispersed intercalated Ni atoms. The catalysts were then employed to convert polyethylene into fuels and lubricant molecules under atmospheric hydrogen pressure, short vapor residence time (τ < 1 s), and mild reaction temperature (300 °C). We further demonstrated the possibility of tuning the Ni structure by changing the Ni loading, attributed to the strong metal–support interactions (MSIs) with the Mo 2 TiC 2 T x support. Under optimized conditions, 22.5 C% gasoline, 12.0 C% diesel, 19.2 C% jet fuel (JP-8), and 37.4 C% lubricant were produced over 0.5% Ni/Mo 2 TiC 2 T x . This work highlights the potential of utilizing MSIs of Mo 2 TiC 2 T x MXenes to synthesize single-atom catalysts (SACs) for upcycling plastic waste into higher-value products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Dual C–H functionalization of polyolefins for covalent adaptable network formation via cooperative electrolysis

The increasing demand for carbon fibre-reinforced polymer composites with polyolefin thermoset matrices will lead to the generation of large volumes of low molecular weight waste oligomers during the fibre recovery process. To address this challenge, we present a cooperative electrolytic dual C–H bond functionalization strategy for the one-step installation of two key functional groups essential for dynamic linkages of these deconstructed oligomers. Through direct competition studies, we reveal the predominance of tertiary allylic C–H activation along the complex, branched oligomer backbone. The resulting difunctionalized oligomers form covalently adaptable networks with exceptional circularity. By establishing a sustainable pathway for upcycling deconstructed oligomers from carbon fibre-reinforced polymer fibre recovery, this strategy introduces thermoset materials derived directly from waste. Here, it advances sustainable manufacturing practices, contributing to a net-zero waste synthetic ecosystem, and highlights the prospects of mediated electrolysis in macromolecular transformations.

Electrocatalysis↗
NASA NTRS1983

13C and 1H NMR (Nuclear Magnetic Resonance) studies of solid polyolefines

The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.

Cudby, M. E. A.↗
NASA NTRS2010

Polyolefin-based aerogels

The present invention relates to cross-linked polyolefin aerogels in simple and fiber-reinforced composite form. Of particular interest are polybutadiene aerogels. Especially aerogels derived from polybutadienes functionalized with anhydrides, amines, hydroxyls, thiols, epoxies, isocyanates or combinations thereof.

Lee, Je Kyun↗
DOE OSTI2025

Minimum GHG emissions and energy consumption of U.S. PET and polyolefin packaging supply chains in a circular economy

There is a wide agreement on the urgency of transforming linear management of plastics towards a circular economy model. However, no clear pathways exist as to required recycling technologies involved and system-wide environmental impacts. This study explores such pathways in the U.S. for the most commonly used packaging plastics through a combination of mechanical and emerging advanced recycling technologies. A system optimization model aimed at minimizing environmental impacts was developed to determine optimal end-of-life (EOL) management and locations of existing and emerging U.S. recycling infrastructures. Our study includes material flows from virgin resin production through semi-manufacturing processes to existing EOL disposal and recycling processes. An optimized circular plastics packaging system achieved greenhouse gas (GHG) emission savings of up to 28% and cumulative energy demand (CED) savings of up to 46%, compared to the linear economy. Moreover, these savings of GHG emissions and CED impacts represent a reduction of 0.16% and 0.49% compared to annual U.S. GHG emissions and energy consumption in 2022, respectively. The optimal recycling rates and systems-level circularity ranged from 78–99% and 57–75%, respectively. Increased energy savings led to increased GHG emissions showing a potential trade-off between GHG emissions and energy. Analysis of 40 scenarios showed the importance of material collection distances, blend limit of mechanically recycled resins, process yields, and mandated recycling rates for achieving a sustainable circular economy of plastics.

09 - BIOMASS FUELS↗
DOE OSTI2025

The role of the Pt-group dehydrogenation catalyst in alkane metathesis for polyolefin deconstruction

Recent proposed approaches in the depolymerization of waste plastics employ an olefin intermediate to produce alkanes or alkenes using olefin metathesis in tandem chemistry. Here, in this study, we investigated the role of the dehydrogenation catalyst on reaction rate, kinetics, and product distribution in heterogeneous tandem dehydrogenation and olefin metathesis (alkane metathesis) of three different alkane reactants, including polyethylene. We found that many properties to which alkane dehydrogenation rates were sensitive-including metal composition, nanoparticle size, and surface doping of Re species also controlled activity in Tandem D/OM. When comparing Pd, Pt, and Pt 3 Sn 1 , supported Pd in tandem with a Re 2 O 7 olefin metathesis catalyst showed four-fold higher activity (surface area basis) compared to Pt or Pt 3 Sn 1 catalysts on the same support, mainly due to differences in the rate of hydrogenation. Catalyst preparation resulted in metal nanoparticles partially covered by ReO x , as seen from elemental mapping. Co-location of Re 2 O 7 and Pd correlated with increased rates of hydrogenation (i.e., an increase in the rate of alkane formation and simultaneous lowering of the rate of alkene formation), with a reaction order in catalyst study that further supported this conclusion. The Pd and Re 2 O 7 system displayed marked improvement compared to Pt or Pt 3 Sn 1 with Re 2 O 7 , and previous work, in the depolymerization rate of a linear polyethylene feedstock, with over 94 % reduction in polymer molecular weight in 15 h at 190 °C using less catalyst and increased reactant loadings, while keeping solvent to polymer consumption below 2.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

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↗
DOE OSTI2025

Polyhalohydrins: Investigating Vicinal Functionalities by Ring-Opening of Epoxides on Polyolefins

Halohydrins are functional groups that are underexplored in polymer science. This study synthesized and examined structure–property relationships of halohydrin-functionalized polymers derived from polycyclooctene (PCOE), which was obtained via ring-opening metathesis polymerization (ROMP). The polyhalohydrins, including polychlorohydrin, polybromohydrin, and polyiodohydrin, were produced through a two-step process involving epoxidation of PCOE followed by epoxide ring-opening using hydrochloric, hydrobromic, or hydroiodic acid. These stereoirregular and regioirregular polymers are amorphous as measured by differential scanning calorimetry and X-ray scattering. Lap joint shear testing revealed an enhanced adhesive performance in polychlorohydrin and polybromohydrin, with the former demonstrating nearly three times the ultimate shear stress compared to a model polyethylene, hydrogenated PCOE. Additionally, contact angle measurements and surface free energy analysis showed an increase in hydrophilicity and polarity from iodine- to bromine- to chlorine-functionalized polyhalohydrins, aligning with trends in adhesion strength. Furthermore, these results underscore the potential of halohydrin functionalization as a versatile approach for tuning surface properties, offering new opportunities for polymer-to-polymer transformations.

Functional groups↗
DOE OSTI2024

Chain-length-controllable upcycling of polyolefins to sulfate detergents

Escalating global plastic pollution and the depletion of fossil-based resources underscore the urgent need for innovative end-of-life plastic management strategies in the context of a circular economy. Thermolysis is capable of upcycling end-of-life plastics to intermediate molecules suitable for downstream conversion to eventually high-value chemicals, but tuning the molar mass distribution of the products is challenging. Here, in this study, we report a temperature-gradient thermolysis strategy for the conversion of polyethylene and polypropylene into hydrocarbons with tunable molar mass distributions. The whole thermolysis process is catalyst- and hydrogen-free. The thermolysis of polyethylene and polyethylene/polypropylene mixtures with tailored temperature gradients generated oil with an average chain length of ~C 14 . The oil featured a high concentration of synthetically useful α-olefins. Computational fluid dynamics simulations revealed that regulating the reactor wall temperature was the key to tuning the hydrocarbon distributions. Subsequent oxidation of the obtained α-olefins by sulfuric acid and neutralization by potassium hydroxide afforded sulfate detergents with excellent foaming behaviour and emulsifying capacity and low critical micelle concentration. Overall, this work provides a viable approach to producing value-added chemicals from end-of-life plastics, improving the circularity of the anthropogenic carbon cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Effects of Polyolefin Structure and Source on Pyrolysis-Derived Plastic Oil Composition

Seven types of plastics were pyrolyzed in a fluidized bed reactor: post-consumer recycled (PCR) high-density polyethylene (HDPE), PCR polypropylene (PP), virgin resins of varying molecular weights of HDPE, virgin resins of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and (PP). Pyrolysis produced non-condensable gases (C1-C3), liquid phase products (C4-C40), and solids (C40+ and chars), with alkane, alkene, alkadiene, aromatic, and multi-cycloaromatics as the predominant compounds. Polymer structure had the greatest impact on product distribution, with minimal influence from molecular weight. Branches in polyethylene (PE) acted as thermal defects initiating degradation. Higher branch density in PE led to increased concentrations of aromatics, branched alkanes, and internal alkenes. PP and PE exhibited distinct degradation mechanisms, with PP requiring less energy for decomposition and yielding more oil. Here, pyrolysis oil from PCR HDPE and PCR PP contained a higher proportion of branched compounds. Additives in PCR plastics may promote isomerization during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗