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At least 181 records · Page 10

Catalytic Activation of Polyethylene Model Compounds Over Metal-Exchanged Beta Zeolites

Decomposition of polymers by heterogeneous catalysts presents a promising approach for reuse of waste plastics. Here, we demonstrated non-hydrogenative decomposition of model polyolefins over proton-form and metal (Cu, Ni) ion-exchanged beta zeolites at moderate temperatures (ca. 300 degrees C). Near complete polyolefin decomposition was observed in batch reactions monitored by thermogravimetric analysis, while decomposition at partial conversion was studied in flow reactions. Ni-exchanged zeolites produced H 2 at substantially higher rates (> 10x) than other catalysts while also uniquely resisting deactivation over time. Application of the delplot formalism offered insights into the reaction network for polyolefin decomposition over Ni/BEA, most notably that H 2 is solely a primary product. We deduce that H 2 production is catalyzed by activation of C-H bonds at ionic Ni sites, and H 2 prevents buildup of polyaromatic coke species in Ni-exchanged zeolites that deactivate Cu-exchanged and protonic zeolites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Municipal Solid Waste Decontamination

The project goals are to understand the current types of contamination and their impact on conversion yields, to develop decontamination strategies, and to understand the TEA/LCA tradeoffs for these proposed strategies.

09 BIOMASS FUELS↗

The Detectors of the Mu2e Experiment

The Mu2e experiment aims to test Charge Lepton Flavour Violation to an unprecedented level, enhancing the current sensitivity by four orders of magnitude for the neutrinoless conversion of muons into electrons. A series of graded solenoids convey an intense, pulsed muon beam to an aluminum target. The main detector components are a low mass straw drift tubes tracker, a pure Cesium Iodide calorimeter and an extruded plastic scintillator cosmic ray veto. Requirements, tests on prototypes and status of the production will be discussed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Effects of Polymer Morphology on Solvent and Catalyst Accessibility during Polyethylene and Polystyrene Autoxidation

Efficient catalytic deconstruction of plastics requires facile solvent and catalyst access to polymer substrates to minimize mass transfer effects. Autoxidation using Co(II) acetate, Mn(II) acetate, and a radical carrier in acetic acid is a promising strategy to deconstruct mixed plastic waste, yet the role of polymer morphology in governing solvent and catalyst accessibility remains poorly understood. Here, in situ simultaneous small- and wide-angle X-ray scattering (SAXS/WAXS), complemented by X-ray fluorescence (XRF) imaging and high-pressure differential scanning calorimetry (DSC), were used to elucidate interactions between acetic acid, a Co/Mn catalyst solution, and semicrystalline polyethylene (PE) and amorphous polystyrene (PS) from room temperature to 160 °C. In PE, acetic acid and catalyst access were confined to amorphous regions and cryomilled particle interfaces at room temperature, while crystalline lamellae remained intact after soaking for up to 34 h. Increasing temperature enabled solvent uptake into PE, followed by solvent-assisted softening above 100 °C, and a modest melting-point depression that removed lamellar transport barriers upon melting. Conversely for PS, acetic acid penetrated the glassy polymer without inducing chain mobility until the glass transition was reached, above which the observed structural changes were consistent with enhanced segmental mobility which enabled bulk penetration. These results suggest that polymer morphology and thermally activated physical transitions arising from diffusion and polymer–solvent interactions can influence whether autoxidation of plastics is transport-limited or kinetically controlled, providing a framework for aligning reaction conditions with reaction outcomes.

09 BIOMASS FUELS↗

Fluidized Bed Gasification For Conversion of Biomass and Waste Materials to Renewable Hydrogen

This project was undertaken in order to study the potential for hydrogen production, at low cost, from mixtures of biomass and municipal solid waste (MSW). This approach allows for the production of hydrogen with a very low fossil carbon burden, while taking advantage of tipping fees (associated with MSW) to improved process economics. The team sourced three primary feedstocks (wood, MSW, and waste plastics) and characterized them comprehensively using established techniques with a long track record in the field of gasification. All three primary feedstocks were highly reactive and lost most of their mass during initial devolatilization. The production of tars, including heavy tars, was quite high, and was most problematic in the case of the MSW and Waste Plastics feedstocks. Little practical difference was identified between the MSW and Waste Plastics materials, and the addition of bed-forming materials (dolomite and brown alumina) to the feedstocks was found to reduce production of tars during devolatilization under thermogravimetric analysis and/or Fischer Assay conditions. A series of four tests in a lab-scale bubbling-fluidized-bed gasifier, at 50 psig of pressure and about 825 C, confirmed these findings. Pellet feedstocks, broken into fragments, were used for these tests, and pellets comprised of 50% MSW and 50% biomass were found to be the best option in terms of fossil carbon burden, economic potential, and gasification characteristics. Tests were then undertaken in a pilot-scale gasifier facility based on the GTI U-Gas fluidized-bed gasification technology. The feedstock handling train of the 20 TPD U-Gas pilot-scale gasifier located in Des Plaines, IL, was operated under simulated gasification conditions, and the 50/50 pellets were found to be very robust and unproblematic. An improved design for the forward end of the feedstock injection screw of the gasifier was developed and installed. The design approach was based on improved passive cooling of the front-most shroud at the end of the screw, since this approach was found in comprehensive modeling studies to be more than sufficient to accomplish the project objectives associated with this phase of the work, while also avoiding thermal gradients that could have caused heat-stress-induced damage to the refractory around the feedstock inlet if an active cooling approach had been applied. Careful technoeconomic analysis (TEA) of two possible 1000 TPD facilities was carried out. The TEA of conversion of MSW with corn stover in one case, and MSW with woody feedstock in the other case, showed that both had the potential to provide hydrogen at about $1/kg (minimum selling price, 2018 dollar basis). Of the two TEA cases, the one that was based on the conversion of wood in the southeastern USA was found to have slightly better economic potential. The other TEA case was based on a real location in Nebraska and called for corn stover feedstock conversion along with MSW. An underserved communities outreach program plan was developed in cooperation with personnel from the Nebraska Public Power District.

08 HYDROGEN↗

Multilevel Analysis of Electrochemically Mediated Methanolysis of Poly(ethylene terephthalate) (PET)

Here, this study presents a multilevel analysis of electrochemically mediated methanolysis as a promising method for reducing the environmental impacts of plastic recycling, with a focus on depolymerizing poly(ethylene terephthalate) (PET) into dimethyl terephthalate (DMT). Instead of conventional chemical PET depolymerization, this electrochemical approach provides distinct technical advantages in process control and efficiency. At the process level, key operational parameters, including applied current and reaction time, were systematically investigated to optimize PET conversion and DMT selectivity. The electrochemical approach was directly compared to equivalent chemical methanolysis systems and demonstrated superior performance in terms of PET conversion and DMT selectivity. Building on these findings, a technoeconomic assessment identified the current economic bottlenecks and revealed that improvements in process design, DMT selectivity, PET conversion, and energy efficiency are key to reducing the overall process cost and enabling future implementation. While further optimization is required for market competitiveness, these results establish a performance baseline for the electrochemically mediated PET methanolysis process and underscore the importance of combining process-level innovation with systems-level evaluation in the development of sustainable recycling technologies.

chemical recycling↗

Disordered, Sub-Nanometer Ru Structures on CeO 2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

We report non-degradable polyolefin plastics pose severe environmental threats, and thus demand efficient upcycling technologies. In this work, we discovered that low-loading (= 0.25 wt%) Ru/CeO 2 exhibits remarkable catalytic performance in the hydrogenolysis of polypropylene (PP), polyethylene (PE), and n-C 16 H 34 that is superior to high-loading (= 0.5 wt%) Ru/CeO 2 . They possess high PP conversion efficiency (7-fold increase over current literature reports), low selectivity towards undesired CH 4 , and good isomerization ability. In the low-loading range, the intrinsic activity of Ru in PP hydrogenolysis increases as the particle size decreases, opposite of the trend in the high-loading range. Detailed characterization revealed that the abrupt changes in catalytic behaviors coincide with Ru species transitioning from well-defined to highly disordered structures in the low-loading domain. The disordered Ru species were shown to be sub-nanometer in size and cationic. Mechanistically, the regioselectivity and the rate dependence on hydrogen pressure of C-C bond cleavage are different on low- and high-loading Ru/CeO 2 , both explained by the higher coverage of adsorbed hydrogen (*H) on low-loading Ru/CeO 2 . This work uncovers the remarkable catalytic performance of highly disordered, sub-nanometer, cationic Ru species in polyolefin hydrogenolysis, opening immense opportunities to develop effective, selective, and versatile catalysts for plastic upcycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Zymogen and activated protein C have similar structural architecture

Activated protein C is a trypsin-like protease with anticoagulant and cytoprotective properties that is generated by thrombin from the zymogen precursor protein C in a reaction greatly accelerated by the cofactor thrombomodulin. The molecular details of this activation remain elusive due to the lack of structural information. We now fill this gap by providing information on the overall structural organization of these proteins using single molecule Förster resonance energy transfer and small angle X-ray scattering. Under physiological conditions, both zymogen and protease adopt a conformation with all domains vertically aligned along an axis 76 Å long and maximal particle size of 120 Å. This conformation is stabilized by binding of Ca 2+ to the Gla domain and is affected minimally by interaction with thrombin. Hence, the zymogen protein C likely interacts with the thrombin-thrombomodulin complex through a rigid body association that produces a protease with essentially the same structural architecture. This scenario stands in contrast to an analogous reaction in the coagulation cascade where conversion of the zymogen prothrombin to the protease meizothrombin by the prothrombinase complex is linked to a large conformational transition of the entire protein. The presence of rigid EGF domains in protein C as opposed to kringles in prothrombin likely accounts for the different conformational plasticity of the two zymogens. The new structural features reported here for protein C have general relevance to vitamin K-dependent clotting factors containing EGF domains, such as factors VII, IX, and X.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microgravity Experiments of Solid Waste Conversion into Useful Commodities

This Summer I participated in two projects at Kennedy Space Center in Cape Canaveral, Florida. The projects focus on the NASA's Deep Space Gateway applications for future Mars travel. All of these projects use recycling technology to use resources found on Earth and on other planets for fuel and other environmental applications. The first project I took the lead on is “Plasma Arc Gasification.” Plasma is a high temperature and very efficient way to process waste to create usable byproducts. The plasma chamber in temperature is comparable to that of the sun and this energy will help create an environment in which the waste can be recycled properly for not only plant support, but also for possible fuel application as well. I preformed the tests in a quartz tube, which is used to hold the waste (cotton, plastics, nylon, paper and a human waste simulant) and the waste is then combusted using O2 (present in air) into gases such as H2, H2O, CH4 and CO2. I determined which gases are present using a Fourier-transform infrared spectroscopy (FTIR) machine, which analyzes the peaks of the gases using liquid nitrogen. Problems arose in the beginning from the reactor emitting electromagnetic waves (EMI) that interfered with the technology of the experiment, specifically the thermocouples. This was solved through multiple tests with the positioning of the thermocouple power supply further away from the plasma reactor. I worked with another intern, Daniel Santander, who developed a space plant chamber which uses CO2 and H2O (harvested from the plasma reactor) to grow plants in space. The chamber possess a CO2 monitor, which controls the amount of gas that enters the chamber, along with a water integration system to supply the amount of water needed for proper plan growth. This technology will then be used for plant growth in space for the Astronauts on future space flights and possibly on the International Space Station (ISS). The second project I worked on is the “Orbital Syngas / Commodity Augmentation Reactor (OSCAR)” which focuses on the issues experienced in long-duration space flight regarding waste disposal. In previous space flight missions, waste was stored on board and returned to Earth for disposal. This technique is not applicable to long space flight missions to Mars due to the rocket being months away from Earth. OSCAR is using microgravity waste disposal techniques to produce fuels from the recycled waste. The waste is converted to syngas through a thermal degradation process. This process helps create an environmentally friendly way to dispose and reuse trash on board the space craft. Currently waste is being tested in the form of cotton and plastics. OSCAR is designed as a microgravity reactor that is currently being tested in a drop tower rig at Glenn Research Center. I helped design the 3D model for the insulation that will line the reactor. The first few trials, I dissolved the plastic of the mold in acetone. This method worked, but was very costly. I then received a silicone material to construct the mold from Swamp Works here at Kennedy. Through multiple trials with the silicone, this method worked best for developing the end pieces of the insulation for the chamber.

Plasma↗

Automated Laboratory Kilogram-Scale Graphene Production from Coal

The flash Joule heating (FJH) method converts many carbon feedstocks into graphene in milliseconds to seconds using an electrical pulse. This opens an opportunity for processing low or negative value resources, such as coal and plastic waste, into high value graphene. Here, in this work, a lab-scale automation FJH system that allows the synthesis of 1.1 kg of turbostratic flash graphene from coal-based metallurgical coke (MC) in 1.5 h is demonstrated. The process is based on the automated conversion of 5.7 g of MC per batch using an electrical pulse width modulation system to conduct the bottom-up upcycle of MC into flash graphene. This study then compare this method to two other scalable graphene synthesis techniques by both a life cycle assessment and a technoeconomic assessment.

01 COAL, LIGNITE, AND PEAT↗

Enhanced Production of Algae Lipids and Carbohydrates for Fuel and Polyurethane Precursors

This Final Technical Report summarizes the goals, approach, and outcomes of the project “Enhanced Production of Algae Lipids and Carbohydrates for Fuel and Polyurethane Precursors”. The project addressed the challenge of improving microalgae biomass productivity and simultaneously producing valuable polyurethane precursors (PUPs), from both lipids and carbohydrates, that can be converted into renewable biofuels and bio-based polyurethane (PU) products. By integrating advanced genetic engineering, traditional breeding, high-throughput screening, pilot cultivation, and chemical conversion technologies, the team achieved significant advancements in algae biotechnology.

09 BIOMASS FUELS↗

Planar rotational magnetic micromotors with integrated shaft encoder and magnetic rotor levitation

Deep x-ray lithography and electroplating may be combined to form a fabrication tool for micromechanical devices with large structural heights, to 500 micron, and extreme edge acuities, less than 0.1 micron-run-out per 100 micron of height. This process concept which originated in Germany as LIGA may be further extended by adding surface micromachining. This extension permits the fabrication of precision metal and plastic parts which may be assembled into three-dimensional micromechanical components and systems. The processing tool may be used to fabricate devices from ferromagnetic material such as nickel and nickel-iron alloys. These materials when properly heat treated exhibit acceptable magnetic behavior for current to flux conversion and marginal behavior for permanent magnet applications. The tool and materials have been tested via planar, magnetic, rotational micromotor fabrication. Three phase reluctance machines of the 6:4 configuration with 280 micron diameter rotors have been tested and analyzed. Stable rotational speeds to 34,000 rpm with output torques above 10 x 10(exp -9) N-m have been obtained. The behavior is monitored with integrated shaft encoders which are photodiodes which measure the rotor response. Magnetic levitation of the rotor via reluctance forces has been achieved and has reduced frictional torque losses to less than 1 percent of the available torque. The results indicate that high speed limits of these actuators are related to torque ripple. Hysteresis motors with magnetic bearings are under consideration and will produce high speed rotational machines with excellent sensor application potential.

Guckel, Henry↗

Development status of the PDC-1 Parabolic Dish Concentrator

The status of development of the 12 m diameter parabolic dish concentrator which is planned for use with the Small Community Solar Thermal Power System. The PDC-1 unit features the use of plastic reflector film bonded to structural plastic gores supported by front-bracing steel ribs. An elevation-over-azimuth mount arrangement is employed, with a conventional wheel-and-track arrangement; outboard trunnions permit the dish to be stored in the face down position, with the added advantage of easy access to the power conversion assembly. The control system is comprised of a central computer (LSI 1123), a manual control panel, a concentrator control unit, two motor controllers, a Sun sensor, and two angular position resolvers. The system is designed for the simultaneous control of several concentrators. The optical testing of reflective panels is described.

Thostesen, T.↗

Harnessing Carbon: A Review of Current Technologies for Transform-ing Methane into Value-added Products

The concern over greenhouse gases, methane (CH 4 ) and carbon dioxide (CO 2 ), is increasing rapidly. There have been strides to find solutions to this global issue but there is not a clear path to a successful end goal. The concentration of CH 4 and CO 2 in the atmosphere has increased significantly over the last 60 years, methane is a great source of concern due to its ability to trap a high amount of heat in the atmosphere. These greenhouse gases contribute to global warming which has caused changes in the environment, including the melting of ice caps, and altered weather patterns. This review investigates biotechnology that has promising potential to aid in the mitigation of the negative effects methane has on the environment by exploring microorganisms, specifically methanotrophs, for their ability to convert methane into secondary value-added products that can be used for a wide range of applications. Methane as a feedstock could provide financial benefits due to the vast amount of methane available from sources like landfills, wastewater treatment plants, and agricultural sites. Furthermore, this review will look at the prospects of bioreactor technology and the potential for more environmentally friendly plastics, such as polyhydroxyalkanoate (PHA), to shy away from traditional petroleum-based plastics. The continuous advancement of bioreactor technology is crucial to mitigating greenhouse gas emissions.

36 MATERIALS SCIENCE↗

Upcycling and urban mining for nanomaterial synthesis

Responsible processing of complex waste streams, especially through resource recovery and upgrading, is essential to lessen the environmental and societal impacts of materials production and disposal. Upcycling waste into materials that have higher value than their original form, and urban mining, the recovery of metals from electronic waste, are two recent strategies in waste management. Sustainable cradle-to-grave manufacturing means recovering resources that would otherwise contaminate the planet. Here, we discuss upcycling of plastic, rubber, and related carbon waste streams into graphene, as well as the recovery of precious metals and rare earth elements, while removing toxic heavy metals, all using flash Joule heating. Furthermore, this article provides a brief overview of the current state of upcycling and urban mining as it applies to materials conversion, recovery, or nanomaterial synthesis, with a concluding perspective highlighting the considerations, opportunities, and challenges that accompany upcycling and urban mining research.

01 COAL, LIGNITE, AND PEAT↗

Hydrogenolysis of Polypropylene and Mixed Polyolefin Plastic Waste over Ru/C to Produce Liquid Alkanes

Catalytic depolymerization of polyolefins is a promising chemical recycling strategy to create value-added products from waste plastics, which are accumulating in landfills and the natural environment at unsustainable rates. The cleavage of strong C–C bonds in polyolefins can be performed using a noble metal and hydrogen via a hydrogenolysis mechanism. Previously, we identified ruthenium nanoparticles supported on carbon (Ru/C) as a highly active heterogeneous catalyst for the conversion of polyethylene into liquid and gaseous n-alkanes under mild conditions. In the present study, we investigated the catalytic depolymerization of polypropylene (PP) under mild conditions (200–250 °C, 20–50 bar H 2 ). We demonstrate that Ru/C produces C 5 –C 32 iso-alkane yields above 68% in the absence of solvent and identify trade-offs between product yield and temperature, hydrogen pressure, and reaction time. We apply a rigorous analytical method to quantify all liquid and gaseous alkane products. The characterized catalyst was found to be recyclable after the complete depolymerization of high molecular weight PP (M w ~ 340,000 Da) to liquid and gaseous hydrocarbons and after depolymerization of a postconsumer PP centrifuge tube. Finally, the catalyst was shown to be effective in depolymerizing a mixture of high-density polyethylene and PP to produce a mixture of linear and branched liquid alkanes, demonstrating feasibility for the depolymerization of streams of mixed polyolefin waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion Behavior of Laser-Interference Structured AA2024 Coated with a Chromate-Containing Epoxy Primer

In this study, the corrosion behavior of laser-interference treated AA2024-T3 specimens, which are coated with a primer, is presented. The surface of as-received AA2024-T3 specimens were laser-interference structured by splitting the primary beam of a Q-switched Nd:YAG pulsed nanosecond laser into two beams and focusing them to the same spot on the specimen surface. After being stored in plastic cases for up to 70 d, without any additional cleaning, the specimens were spray painted with a chromate-containing epoxy primer, CA7233, compliant to MIL-PRF-23377 Type I Class C2 specification. The corrosion behavior of laser-interference specimens was assessed against that of specimens prepared by chromated conversion coating and sulfuric acid anodizing treatments. After the ASTM B117 corrosion exposure, it was found that the laser processed specimens exhibited only few blisters. On one hand, most specimens prepared at a laser fluence of 1.78 J/cm 2 , without any additional chemical cleaning, were found to develop one very small blister after only 96 h of exposure. However, the growth of these blisters was not significant even after 1,000 h of salt spray exposure. On the other hand, only a fraction of the specimens prepared at a laser fluence of 1.24 J/cm 2 and acetone wiped right after the laser structuring were found to develop several tiny blisters after 790 h and longer exposure. Overall, it was found that the corrosion damage was minimized at a laser rastering speed of 4 mm/s, a condition for which only 33% of specimens developed very minor corrosion damage. Furthermore, the ASTM D1654 creepage ratings, which was used to evaluate the corrosion damage along the scribe lines, were found to be at least nine for all coated panels. These results indicate that the laser-interference technique with the additional acetone wiping has the potential to be further developed as a nonchemical surface preparation technique for chromate-containing epoxy primers coating systems.

36 MATERIALS SCIENCE↗

Flexural fatigue life prediction of closed hat-section using materially nonlinear axial fatigue characteristics

Straight or curved hat-section members are often used as structural stiffeners in aircraft. For instance, they are employed as stiffeners for the dorsal skin as well as in the aerial refueling adjacent area structure in F-106 aircraft. The flanges of the hat-section are connected to the aircraft skin. Thus, the portion of the skin closing the hat-section interacts with the section itself when resisting the stresses due to service loads. The flexural fatigue life of such a closed section is estimated using materially nonlinear axial fatigue characteristics. It should be recognized that when a structural shape is subjected to bending, the fatigue life at the neutral axis is infinity since the normal stresses are zero at that location. Conversely, the fatigue life at the extreme fibers where the normal bending stresses are maximum can be expected to be finite. Thus, different fatigue life estimates can be visualized at various distances from the neural axis. The problem becomes compounded further when significant portions away from the neutral axis are stressed into plastic range. A theoretical analysis of the closed hat-section subjected to flexural cyclic loading is first conducted. The axial fatigue characteristics together with the related axial fatigue life formula and its inverted form given by Manson and Muralidharan are adopted for an aluminum alloy used in aircraft construction. A closed-form expression for predicting the flexural fatigue life is then derived for the closed hat-section including materially nonlinear action. A computer program is written to conduct a study of the variables such as the thicknesses of the hat-section and the skin, and the type of alloy used. The study has provided a fundamental understanding of the flexural fatigue life characteristics of a practical structural component used in aircraft when materially nonlinear action is present.

Razzaq, Zia↗