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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.

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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Motor scaling by viewing distance of early visual motion signals during smooth pursuit

The geometry of gaze stabilization during head translation requires eye movements to scale proportionally to the inverse of target distance. Such a scaling has indeed been demonstrated to exist for the translational vestibuloocular reflex (TVOR), as well as optic flow-selective translational visuomotor reflexes (e.g., ocular following, OFR). The similarities in this scaling by a neural estimate of target distance for both the TVOR and the OFR have been interpreted to suggest that the two reflexes share common premotor processing. Because the neural substrates of OFR are partly shared by those for the generation of pursuit eye movements, we wanted to know if the site of gain modulation for TVOR and OFR is also part of a major pathway for pursuit. Thus, in the present studies, we investigated in rhesus monkeys whether initial eye velocity and acceleration during the open-loop portion of step ramp pursuit scales with target distance. Specifically, with visual motion identical on the retina during tracking at different distances (12, 24, and 60 cm), we compared the first 80 ms of horizontal pursuit. We report that initial eye velocity and acceleration exhibits either no or a very small dependence on vergence angle that is at least an order of magnitude less than the corresponding dependence of the TVOR and OFR. The results suggest that the neural substrates for motor scaling by target distance remain largely distinct from the main pathway for pursuit.

Non-NASA Center↗
NASA NTRS1981

Solar cell development for the Power Extension Package

The Power Extension Package (PEP), a 32-kilowatt, flexible-substrate, retrievable solar array system for use on the Space Shuttle, is described. It is noted that solar cell costs will be reduced by increasing cell area and simplifying cell and coverglass fabrication processes and specifications. The tests that have been carried out on the cells are described, among them a unique radiation damage test and a side-by-side comparison of candidate cell types with pre- and post-irradiation airplane calibration of outer space short-circuit current

Baraona, C. R.↗
NASA NTRS1985

In vivo inhibition of polyamine biosynthesis and growth in tobacco ovary tissues

Post fertilization growth of tobacco ovary tissues treated with inhibitors of polyamine (PA) biosynthesis was examined in relation to endogenous PA titers and the activities of arginine decarboxylase (ADC, EC 4.1.1.19) and ornithine decarboxylase (ODC, EC 4.1.1.17). DL-alpha-Difluoromethylornithine (DFMO) and DL-alpha-difluoromethylarginine (DFMA), specific, irreversible ("suicide") inhibitors of ODC and ADC in vitro, were used to modulate PA biosynthesis in excised flowers. ODC represented >99% of the total decarboxylase activity in tobacco ovaries. In vivo inhibition of ODC with DFMO resulted in a significant decrease in PA titers, ovary fresh weight and protein content. Simultaneous inhibition of both decarboxylases by DFMO and DFMA produced only a marginally greater depression in growth and PA titers, indicating that ODC activity is rate-limiting for PA biosynthesis in these tissues. Paradoxically, DFMA alone inhibited PA biosynthesis, not as a result of a specific inhibition of ADC, but primarily through the inactivation of ODC. In vivo inhibition of ODC by DFMA appears to result from arginase-mediated hydrolysis of this inhibitor to urea and DFMO, the suicide substrate for ODC. Putrescine conjugates in tobacco appear to function as a storage form of this amine which, upon hydrolysis, may contribute to Put homeostasis during growth.

NASA Program Space Biology↗
NASA NTRS2008

Final Report on NASA Portable Laser Coating Removal Systems Field Demonstrations and Testing

Processes currently used throughout the National Aeronautics and Space Administration (NASA) to remove corrosion and coatings from structures, ground service equipment, small parts and flight components result in waste streams consisting of toxic chemicals, spent media blast materials, and waste water. When chemicals are used in these processes they are typically high in volatile organic compounds (VOC) and are considered hazardous air pollutants (HAP). When blast media is used, the volume of hazardous waste generated is increased significantly. Many of the coatings historically used within NASA contain toxic metals such as hexavalent chromium, and lead. These materials are highly regulated and restrictions on worker exposure continue to increase. Most recently the Occupational Safety and Health Administration (OSHA) reduced the permissible exposure limit (PEL) for hexavalent chromium (CrVI) from 52 to 5 micrograms per cubic meter of air as an 8-hour time-weighted average. Hexavalent chromium is found in numerous pretreatment and primer coatings used within the Space Shuttle Program. In response to the need to continue to protect assets within the agency and the growing concern over these new regulations, NASA is researching different ways to continue the required maintenance of both facility and flight equipment in a safe, efficient, and environmentally preferable manner. The use of laser energy to prepare surfaces for a variety of processes, such as corrosion and coating removal, weld preparation, and non destructive evaluation (NDE) is a relatively new application of the technology that has been proven to be environmentally preferable and in many cases less labor intensive than currently used removal methods. The novel process eliminates VOCs and blast media and captures the removed coatings with an integrated vacuum system. This means that the only waste generated are the coatings that are removed, resulting in an overall cleaner process. The development of a Portable Laser Coating Removal System (PLCRS) started as the goal of a Joint Group on Pollution Prevention (JG-PP) project, led by the Air Force, where several types of lasers in several configurations were thoroughly evaluated. Following this project, NASA decided to evaluate the best performers on processes and coatings specific to the agency. Laser systems used during this project were all of a similar design, between 40 and 500 Watts, most of which had integrated vacuum systems in order to collect materials removed from substrate surfaces during operation.

Rothgeb, Matthew J↗
DOE OSTI2026

Compressive strain turns 𝑠 ± - into 𝑑-wave pairing in a one-unit-cell La 3 ⁢Ni 2 ⁢O 7 thin film via substrate-induced hole doping

Motivated by recent reports of ambient-pressure superconductivity in La 3 ⁢Ni 2⁢ O 7 films grown on LaSrAlO 4 , we investigate the superconducting instability in a one-unit-cell (1UC) thin film using ab initio and random-phase approximation techniques. Compared to the high-pressure bulk system, the ratio of interlayer 𝑑 3⁢𝑧 2 −𝑟 2 hopping to intralayer 𝑑 𝑥 2 −𝑦 2 hopping is suppressed in the 1UC thin film, and the crystal-field splitting of the 𝑒 𝑔 orbitals is increased. Here, our calculation indicates that spin-fluctuation-driven pairing correlations are weak for the stoichiometric case at ambient pressure, but increase significantly under hole doping. The leading pairing symmetry is also found to change by hole doping. Specifically, we obtain a leading 𝑑 𝑥 2 −𝑦 2 pairing state at moderate hole doping, followed by a 𝑑 𝑥⁢𝑦 state at higher doping. These states are driven by intraband spin-fluctuation scattering within the 𝛾 hole pocket centered around the 𝑀 point, and arise primarily from states in the Ni layer farther from the substrate. These results strongly suggest that the thin-film superconducting samples are hole-doped and that pairing in this system predominantly arises in the layer, as opposed to the interlayer pairing in the pressurized bulk system.

Zhang, Yang [Oak Ridge National Laboratory (ORNL),↗
NASA NTRS2007

Toward a III-V Multijunction Space Cell Technology on Si

High efficiency compound semiconductor solar cells grown on Si substrates are of growing interest in the photovoltaics community for both terrestrial and space applications. As a potential substrate for III-V compound photovoltaics, Si has many advantages over traditional Ge and GaAs substrates that include higher thermal conductivity, lower weight, lower material costs, and the potential to leverage the extensive manufacturing base of the Si industry. Such a technology that would retain high solar conversion efficiency at reduced weight and cost would result in space solar cells that simultaneously possess high specific power (W/kg) and high power density (W/m2). For terrestrial solar cells this would result in high efficiency III-V concentrators with improved thermal conductivity, reduced cost, and via the use of SiGe graded interlayers as active component layers the possibility of integrating low bandgap sub-cells that could provide for extremely high conversion efficiency.1 In addition to photovoltaics, there has been an historical interest in III-V/Si integration to provide optical interconnects in Si electronics, which has become of even greater relevance recently due to impending bottlenecks in CMOS based circuitry. As a result, numerous strategies to integrate GaAs with Si have been explored with the primary issue being the approx.4% lattice mismatch between GaAs and Si. Among these efforts, relaxed, compositionally-graded SiGe buffer layers where the substrate lattice constant is effectively tuned from Si to that of Ge so that a close lattice match to subsequent GaAs overlayers have shown great promise. With this approach, threading dislocation densities (TDDs) of approx.1 x 10(exp 6)/sq cm have been uniformly achieved in relaxed Ge layers on Si,5 leading to GaAs on Si with minority carrier lifetimes greater than 10 ns,6 GaAs single junction solar cells on Si with efficiencies greater than 18%,7 InGaAs CW laser diodes on Si,8 and room temperature GaInP red laser diodes on Si.9 Here we report on the first high performance dual junction GaInP/GaAs solar cells grown on Si using this promising SiGe engineered substrate approach.

Ringel, S. A.↗
DOE OSTI2025

Architecture-Dependent Thin Film Self-Assembly of Star Polystyrene-poly(2-vinylpyridine) Block Copolymers

Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for their use in templating, transport, and pattern transfer. Conventional efforts mainly focus on adjusting enthalpic interactions between the blocks and interfaces, while entropic contributions are often overlooked. Here, we show that the morphology of BCP thin films can be precisely tuned by the architectural design of star BCPs. Specifically, we synthesized multiarm star BCPs with a polystyrene (PS) core and poly(2-vinylpyridine) (P2VP) corona, which exhibits a lamellar microdomain morphology. The entropic penalty associated with a parallel orientation of the microdomains to the substrate is controlled by varying the number of arms comprising the star BCPs, from 2-arms (triblock) to 3-arms and 4-arms. We systematically investigated the thin film morphology at different depths using grazing incidence small-angle X-ray and neutron scattering (GISAXS and GISANS), atomic force microscopy (AFM), water contact angle (WCA), and interference microscopy. The results show that 2-arm star BCPs show a parallel orientation, the 3-arm star BCPs form a uniform PS film at the air surface with a vertical orientation of the microdomains underneath, and the 4-arm star BCPs exhibit a parallel microdomain orientation at the air surface with mixed parallel and perpendicular microdomain orientation in the bulk. Additionally, we found that the inclination angle of microdomains at the edges of islands and holes, resulting from the incommensurability between film thickness and the characteristic period of the microdomain morphology, increases with a higher number of arms. This suggests a greater grain boundary tilt angle in the microdomains of star-shaped block copolymers (BCPs). When silicon substrates were modified with PS homopolymer, the selective interaction between substrate and core blocks promotes a parallel orientation for the 4-arm star BCPs. In conclusion, this work shows that control of arm number in star BCPs affords diverse BCP thin film morphologies, offering insights into the star BCP conformations in thin films across different depths.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

Tkachenko, Alexei V. (ORCID:000000031291243X)↗
NASA NTRS1999

Transmission Measurement of the Third-Order Susceptibility of Gold

Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

Smith, David D.↗
NASA NTRS2003

Crystal structures of pinoresinol-lariciresinol and phenylcoumaran benzylic ether reductases and their relationship to isoflavone reductases

Despite the importance of plant lignans and isoflavonoids in human health protection (e.g. for both treatment and prevention of onset of various cancers) as well as in plant biology (e.g. in defense functions and in heartwood development), systematic studies on the enzymes involved in their biosynthesis have only recently begun. In this investigation, three NADPH-dependent aromatic alcohol reductases were comprehensively studied, namely pinoresinol-lariciresinol reductase (PLR), phenylcoumaran benzylic ether reductase (PCBER), and isoflavone reductase (IFR), which are involved in central steps to the various important bioactive lignans and isoflavonoids. Of particular interest was in determining how differing regio- and enantiospecificities are achieved with the different enzymes, despite each apparently going through similar enone intermediates. Initially, the three-dimensional x-ray crystal structures of both PLR_Tp1 and PCBER_Pt1 were solved and refined to 2.5 and 2.2 A resolutions, respectively. Not only do they share high gene sequence similarity, but their structures are similar, having a continuous alpha/beta NADPH-binding domain and a smaller substrate-binding domain. IFR (whose crystal structure is not yet obtained) was also compared (modeled) with PLR and PCBER and was deduced to have the same overall basic structure. The basis for the distinct enantio-specific and regio-specific reactions of PCBER, PLR, and IFR, as well as the reaction mechanism and participating residues involved (as identified by site-directed mutagenesis), are discussed.

NASA Discipline Plant Biology↗
NASA NTRS1992

Nonenzymatic template-directed synthesis on hairpin oligonucleotides. 2. Templates containing cytidine and guanosine residues

We have prepared hairpin oligonucleotides in which a 5'-terminal single-stranded segment contains cytidylate (C) and guanylate (G) residues. When these hairpin substrates are incubated with a mixture of cytidine 5'-phosphoro(2-methly)imidazolide (2-MeImpC) and guanosine 5'-phosphoro(2-methyl)imidazolide (2-MeImpG), the 5'-terminal segment acts as a template to facilitate sequence-specific addition of G and C residues to the 3'-terminus of the hairpin. If an isolated G residue is present at the 3'-end of the template strand, it is copied regiospecifically in the presence of 2-MeImpC and 2-MeImpG to give a product containing an isolated C residue linked to its G neighbors by 3'-5'-internucleotide bonds. However, if only 2-MeImpC is present in the reaction mixture, very little reaction occurs. Thus, the presence of 2-MeImpG catalyzes the incorporation of C. If the template strand contains a short sequence of G residues, it is copied in the presence of a mixture of 2-MeImpC and 2-MeImpG. If only 2-MeImpC is present in the reaction mixture, efficient synthesis occurs to give a final product containing one fewer C residue than the number of G residues in the template.

NASA Program Exobiology↗
NASA NTRS2010

Advanced Flip Chips in Extreme Temperature Environments

The use of underfill materials is necessary with flip-chip interconnect technology to redistribute stresses due to mismatching coefficients of thermal expansion (CTEs) between dissimilar materials in the overall assembly. Underfills are formulated using organic polymers and possibly inorganic filler materials. There are a few ways to apply the underfills with flip-chip technology. Traditional capillary-flow underfill materials now possess high flow speed and reduced time to cure, but they still require additional processing steps beyond the typical surface-mount technology (SMT) assembly process. Studies were conducted using underfills in a temperature range of -190 to 85 C, which resulted in an increase of reliability by one to two orders of magnitude. Thermal shock of the flip-chip test articles was designed to induce failures at the interconnect sites (-40 to 100 C). The study on the reliability of flip chips using underfills in the extreme temperature region is of significant value for space applications. This technology is considered as an enabling technology for future space missions. Flip-chip interconnect technology is an advanced electrical interconnection approach where the silicon die or chip is electrically connected, face down, to the substrate by reflowing solder bumps on area-array metallized terminals on the die to matching footprints of solder-wettable pads on the chosen substrate. This advanced flip-chip interconnect technology will significantly improve the performance of high-speed systems, productivity enhancement over manual wire bonding, self-alignment during die joining, low lead inductances, and reduced need for attachment of precious metals. The use of commercially developed no-flow fluxing underfills provides a means of reducing the processing steps employed in the traditional capillary flow methods to enhance SMT compatibility. Reliability of flip chips may be significantly increased by matching/tailoring the CTEs of the substrate material and the silicon die or chip, and also the underfill materials. Advanced packaging interconnects technology such as flip-chip interconnect test boards have been subjected to various extreme temperature ranges that cover military specifications and extreme Mars and asteroid environments. The eventual goal of each process step and the entire process is to produce components with 100 percent interconnect and satisfy the reliability requirements. Underfill materials, in general, may possibly meet demanding end use requirements such as low warpage, low stress, fine pitch, high reliability, and high adhesion.

Ramesham, Rajeshuni↗
DOE OSTI2026

High Temperature High Vacuum Mechanical Property Assessment of Zirconium Nuclear Fuel Cladding

This report presents the mechanical characterization of a specific Zry-4 cladding batch serving as the foundation for a diverse range of fuel performance research at Oak Ridge National Laboratory (ORNL). This effort supports research needs for the U.S. Department of Energy (DOE), particularly regarding evaluating accident tolerant fuel (ATF) cladding coating concepts, expanding understanding of cladding response to loss-of-coolant accidents (LOCA) transients, refining post-critical heat flux (CHF) limits (t@T), and upcoming irradiation campaigns. The central objective was to define the baseline performance of the substrate Zircaloy-4 (Zry-4) material leveraged across ORNL Advanced Fuel Campaign (AFC) efforts through controlled high-temperature vacuum tensile testing. This work begins to address gaps in existing models where implementation based on nominal heat-treatment labels, such as stress relief annealed (SRA), often fail to capture the interplay of recovery, recrystallization, and grain growth. To quantify this, data was benchmarked against the Pacific Northwest National Laboratory (PNNL) stress strain model to determine where this material falls in comparison to assumed values for materials in the same heat treatment regime. Analysis of the tensile data revealed that this specific SRA batch exhibits a transitional microstructural state best described by an effective cold-work (CW) parameter of 0.09, diverging from the previous estimation of 0.5 for SRA materials. Additionally, comparative testing of Cr coated specimens demonstrated no distinct difference in axial strength relative to the bare substrate. This suggests that the strengthening benefits of Cr coatings observed in burst scenarios are driven by residual stress mechanisms acting solely in the hoop direction.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Genomics and physiology of Catenibacillus, human gut bacteria capable of polyphenol C-deglycosylation and flavonoid degradation

The genusCatenibacillus(familyLachnospiraceae, phylumBacillota) includes only one cultivated species so far,Catenibacillus scindens,isolated from human faeces and capable of deglycosylating dietary polyphenols and degrading flavonoid aglycones. Another human intestinalCatenibacillusstrain not taxonomically resolved at that time was recently genome-sequenced. We analysed the genome of this novel isolate, designatedCatenibacillus decagia, and showed its ability to deglycosylateC-coupled flavone and xanthone glucosides andO-coupled flavonoid glycosides. Most of the resulting aglycones were further degraded to the corresponding phenolic acids. Including the recently sequenced genome ofC. scindensand ten faecal metagenome-assembled genomes assigned to the genusCatenibacillus, we performed a comparative genome analysis and searched for genes encoding potentialC-glycosidases and other polyphenol-converting enzymes. According to genome data and physiological characterization, the core metabolism ofCatenibacillusstrains is based on a fermentative lifestyle with butyrate production and hydrogen evolution. BothC. scindensandC. decagiaencode a flavonoidO-glycosidase, a flavone reductase, a flavanone/flavanonol-cleaving reductase and a phloretin hydrolase. Several gene clusters encode enzymes similar to those of the flavonoidC-deglycosylation system ofDoreastrain PUE (DgpBC), while separately located genes encode putative polyphenol-glucoside oxidases (DgpA) required forC-deglycosylation. The diversity ofdgpAanddgpBCgene clusters might explain the broadC-glycoside substrate spectrum ofC. scindensandC. decagia. The otherCatenibacillusgenomes encode only a few potential flavonoid-converting enzymes. Our results indicate that severalCatenibacillusspecies are well-equipped to deglycosylate and degrade dietary plant polyphenols and might inhabit a corresponding, specific niche in the gut.

Genetics & Heredity↗
NASA NTRS1972

Infrared radiation of thin plastic films.

A combined analytical and experimental study is presented for infrared radiation characteristics of thin plastic films with and without a metal substrate. On the basis of the thin-film analysis, a simple analytical technique is developed for determining band-averaged optical constants of thin plastic films from spectral normal transmittance data for two different film thicknesses. Specifically, the band-averaged optical constants of polyethylene terephthalate and polyimide were obtained from transmittance measurements of films with thicknesses in the range of 0.25 to 3 mil. The spectral normal reflectance and total normal emittance of the film side of singly aluminized films are calculated by use of optical constants; the results compare favorably with measured values.

Tien, C. L.↗
NASA NTRS1981

Ohmic contacts to GaAs for high-temperature device applications

Ohmic contacts to n-type GaAs were developed for high temperature device applications up to 300 C. Refractory metallizations were used with epitaxial Ge layers to form the contacts: TiW/Ge/GaAs, Ta/Ge/GaAs, Mo/Ge/GaAs, and Ni/Ge/GaAs. Contacts with high dose Si or Se ion implantation of the Ge/GaAs interface were also investigated. The contacts were fabricated on epitaxial GaAs layer grown on N+ or semi-insulating GaAs substrates. Ohmic contact was formed by both thermal annealing (at temperatures up to 700 C) and laser annealing (pulsed Ruby). Examination of the Ge/GaAs interface revealed Ge migration into GaAs to form an N+ doping layer. The specific contact resistances of specimens annealed by both methods are given.

Anderson, W. T., Jr.↗
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 ↗