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At least 109 records · Page 6

Techno-Economic and Life Cycle Assessment of Chemical Recycling and Upcycling of Mixed Plastics Waste Containing Poly-vinyl-chloride

Developing technologies that completely remove chlorine from plastic waste can allow its chemical recycling and upcycling with catalytic methods. Here, this study compares eight processes involving different dechlorination methods (absorption columns, adsorption in beds of zeolites, catalytic dechlorination, and dissolution in ionic liquids) and chemical conversion technologies (incineration, pyrolysis, hydrogenolysis) to upgrade mixed plastics waste to various products (e.g., electricity, fuels, virgin polymers, and lubricant oil). The analysis determines that the absorption of chlorine in columns with basic aqueous solutions is limited to plastics waste with PVC concentrations below 0.1%. Dissolution in ionic liquids is not cost-competitive. On the contrary, two-step processes with catalytic dechlorination followed by thermochemical catalytic depolymerization, either pyrolysis or hydrogenolysis, significantly improve process economics and emissions. The most economically viable alternative is hydrogenolysis for producing lubricants, while the technology with the lowest global warming potential is chemical recycling via catalytic pyrolysis.

circular economy↗

A two-stage strategy for upcycling chlorine-contaminated plastic waste

Abstract Chemical upcycling of polyolefin plastic waste to lubricant, wax and fuel-range hydrocarbons over metal-based catalysts is a crucial technological solution to the enormous environmental threat posed by plastic waste. However, currently available methods are incompatible with chlorine-contaminated feedstocks. Here we report a two-stage strategy for upcycling chlorine-contaminated polypropylene. First, magnesia–alumina mixed oxide at 30 bar H 2 and 250 °C serves as a chlorine trap by rapidly forming solid chloride, resulting in nearly complete chlorine extraction from the polyolefin melt. This enables the upcycling of plastic waste with up to 10% polyvinyl chloride content to lubricants over ruthenium-based catalysts, in the second stage. The strategy is also applicable to chlorinated aromatics and alkanes. The proposed strategy renders hydrocracking and hydrogenolysis catalysts less sensitive to the chlorine impurities in feedstocks while eliminating HCl emissions and chlorine contamination in products. It could incentivize further progress in plastics upcycling.

Environmental Sciences & Ecology↗

Structure and dynamics of hydrodynamically interacting finite-size Brownian particles in a spherical cavity: Spheres and cylinders

The structure and dynamics of confined suspensions of particles of arbitrary shape are of interest in multiple disciplines from biology to engineering. Theoretical studies are often limited by the complexity of long-range particle-particle and particle-wall forces, including many-body fluctuating hydrodynamic interactions. Here, we report a computational study on the diffusion of spherical and cylindrical particles confined in a spherical cavity. We rely on an immersed-boundary general geometry Ewald-like method to capture lubrication and long-range hydrodynamics and include appropriate non-slip conditions at the confining walls. A Chebyshev polynomial approximation is used to satisfy the fluctuation-dissipation theorem for the Brownian suspension. We explore how lubrication, long-range hydrodynamics, particle volume fraction, and shape affect the equilibrium structure and the diffusion of the particles. It is found that once the particle volume fraction is greater than 10%, the particles start to form layered aggregates that greatly influence particle dynamics. Hydrodynamic interactions strongly influence the particle diffusion by inducing spatially dependent short-time diffusion coefficients, stronger wall effects on the particle diffusion toward the walls, and a sub-diffusive regime-caused by crowding-in the long-time particle mobility. The level of asymmetry of the cylindrical particles considered here is enough to induce an orientational order in the layered structure, decreasing the diffusion rate and facilitating a transition to the crowded mobility regime at low particle concentrations. Our results offer fundamental insights into the diffusion and distribution of globular and fibrillar proteins inside cells.

36 MATERIALS SCIENCE↗

Investigations in the tape-to-tape contact resistance and contact composition in superconducting CORC ® wires

Conductor on Round Core (CORC®) wires and cables, constructed from multiple layers of helically wound REBa 2 Cu 3 O 7–δ tapes, are a promising cable technology for high field magnet applications. An important feature of high-temperature superconductor cables is the ability to share current between conductors, allowing current to bypass drops in I c and minimizing the risk of hot spot formation, which could lead to potential burnout in the superconductor. In contrast to stacked-tape cables, which have continuous contact between tapes, in CORC® the transfer points occur at discrete tape crossovers. The tape-to-tape contact resistance, R c , plays a critical role in the current sharing capabilities and current distribution in cables. For the work reported here, special CORC® wires were manufactured using different winding parameters to investigate variations in R c . Variations comprised inclusion of a lubricant, different lubricant conductivity, inclusion of pre-tinning, and heating briefly to melt the solder. Cables were first tested as straight lengths, followed by bending to a 10 cm diameter. In straight cables R c values ranged from 1 to over 1000 μΩ cm 2 , depending on cabling parameters, with the highest values being found for cables made by the present 'standard' process. Bending the cables to a 10 cm diameter decreased R c by a factor 2–5. Tinning with PbSn decreased R c by three orders of magnitude compared to standard CORC® wires, and heat treating wires with tinned conductor resulted in only a small further decrease in R c . Based on the measured R c at an electric field of 1 μV cm –1 the resulting current transfer length between layers can range from a few millimeters to a tens of centimeters. Examination of contacts with a laser confocal microscope showed plastic deformation of the copper at the edges of the contact overlap area, apparently caused by thicker plating at tape edges digging into the copper of neighboring layers. These images reveal that only a fraction of the total contact surface may actually be touching when there is nothing to compensate for height differential. Images of the PbSn coated tapes indicated that application of solder produces a much more uniform contact surface and higher contact area. Furthermore, imaging of CORC® cross-sections confirmed that in the non-tinned cables there are many regions where tapes are not in contact, while in contrast the PbSn cable shows significantly more contact between the tapes. These different imaging techniques reveal that tape surface morphology is a significant parameter in determining R c .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The surface stress of biomedical silicones is a stimulant of cellular response

Silicones are commonly used for lubrication of syringes, encapsulation of medical devices, and fabrication of surgical implants. While silicones are generally viewed as relatively inert to the cellular milieu, they can mediate a variety of inflammatory responses and other deleterious effects, but the mechanisms underlying the bioactivity of silicones remain unresolved. Here, we report that silicone liquids and gels have high surface stresses that can strongly resist deformation at cellular length scales. Biomedical silicones, including syringe lubricants and fillings from FDA-approved breast implants, readily adsorb matrix proteins and activate canonical rigidity sensing pathways through their surface stresses. In 3D culture models, liquid silicone droplets support robust cellular adhesion and the formation of multinucleated monocyte-derived cell masses that recapitulate phenotypic aspects of granuloma formation in the foreign body response. Together, our findings implicate surface stress as a cellular stimulant that should be considered in application of silicones for biomedical purposes.

60 APPLIED LIFE SCIENCES↗

Report of the Condition of a General Electric Transportation Systems Gearbox

Wind power plant operations and maintenance (O&M) costs remain an appreciable contributor to the overall cost of wind energy. Premature of wind turbine gearboxes failures are often a result of abrasive wear, micropitting, scuffing, white-etch cracks, and macropitting issues. Micropitting is a fatigue phenomenon that occurs in Hertzian contacts in both gears and rolling-element bearings that operate in mixed or micro elastohydrodynamic lubrication regimes. Micropitting is influenced by and manifests itself in many different ways depending on operating conditions such as load, speed and operating temperature, and on factors such as gear geometry and accuracy, tooth flank roughness, percentage of tooth sliding, and lubricant composition. Despite much research by many investigators, micropitting remains complex, unpredictable, and difficult to control and remains a problem in wind turbine gearboxes. The purpose of this report is to document and describe the micropitting damage observed in a wind turbine gearbox, thereby facilitating further analysis and examination in future reports.

17 WIND ENERGY↗

Evaluation of the Volatile Species Associated with the K-Area Complex Blend Cans (D5043)

In the K-Area Complex (KAC), blend cans are used to down blend plutonium oxide for future disposal at the Waste Isolation Pilot Plant (WIPP). The blend can is a thin walled screw lid container that is used to down blend a measured amount of plutonium oxide with adulterant to reduce the attractiveness of the plutonium. The oxide and adulterant are mixed within the blend can and the blend can is packaged into a thick walled outer container. The blend cans are procured from an offsite vendor that uses a lubricant in the can manufacturing process. A thin coating of the lubricant adheres to the outer surface of the blend can and both inner and outer surfaces of the blend can cap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Scale up, Field testing, and Optimization of Nontoxic, Durable, Economical Coatings for Control of Biofouling and Corrosion (Abstract Only)

The objective of this project is the technical maturation and demonstration of a durable, economical, and nontoxic coating, Superhydrophobic Lubricant Infused Composite (SLIC), that will prevent fouling organisms from growing on marine and hydrokinetic (MHK) structures and prevent invasive mussels from growing on hydropower structures. SLIC technology was developed and patented by PNNL. It combines multiple antifouling mechanisms to provide excellent antifouling performance, durability, and low hydrodynamic drag without using toxic materials. Advanced proof-of-concept testing and demonstrations completed during a Phase 1 TCF project attracted industry interest and partnerships for this Phase 2 effort focused on maturation of a commercial product. Specific tasks and tests will shift the development emphasis to optimizing formulations, validating antifouling performance to address specific application needs, explore compatibility with other paint systems, develop a product with useful shelf life (in can), and determine curing times and effective applications methodology. Phase 2 efforts will focus upon technology transfer and commercialization of the technology with the industrial team. Industrial partners now include a coatings development specialist (Lorama), hydrophobic material manufacturer and paint developer (Dry Surface Technologies), nontoxic biodegradable lubricants manufacturer (BioBlend), and aquatic applications specialists (Prometheus Innovations, River Connectivity Systems). Engagement with the MHK device developers, the PNNL Marine and Coastal Research Laboratory (MCRL) test site in Sequim WA, Bureau of Reclamation, and Taylor Shellfish throughout the project will provide topical expertise and field test sites that will deliver crucial real-world performance data. Through this Phase 2 effort, SLIC will transition from a Technical Readiness Level (TRL) 5 to TRL 6 and long-term performance data will be acquired through demonstrations. The field test data will allow optimization of SLIC formulation to enhance performance (e.g., durability) and packaging, which are key de-risking activities for technology transfer and ultimately to the production of a viable commercial product.

13 HYDRO ENERGY↗

Investigations on the Thermal Stability and Kinetics of Biolubricants Synthesized from Different Types of Vegetable Oils

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soybean oil (HOSOY), regular soybean oil (RSOY), and waste cooking oil (WCO) were subjected to chemical modification, where isopropyl groups were attached to the fatty acid chains of the oils to produce branched oils, i.e., b-HOSOY, b-RSOY, and b-WCO. The detailed kinetic study of each regular and modified sample was investigated using thermogravimetric analysis. The kinetic parameters, such as the activation energies, reaction rate, and pre-exponential factor, were generated via Friedman methods. The differential thermal gravimetric (DTG) analysis showed low volatilization at the onset temperature in each modified oil as compared with the unmodified samples under an oxidative environment. Furthermore, the comparative kinetic studies demonstrated the enhanced thermoxidative stability of the modified products relative to their unaltered counterparts. Among the tested oils, the b-RSOY showed an average activation energy of 325 kJ/mol, followed by the b-WCO: 300 kJ/mol and the b-HOSOY: 251 kJ/mol, indicating the most stable modified product under an oxidative environment. For all the samples, the pre-exponential factors were in good agreement with the activation energies, which validates that finding the pre-exponential components is crucial to the kinetic analysis.

Sarker, Majher I. (ORCID:0000000299509274)↗

Paper #50 Preliminary Sizing of Active Magnetic Bearings for sCO2 Waste-Heat Recovery Application

The team of Southwest Research Institute (SwRI) and GE Vernova (GE) is executing a project developing conceptual designs of high-temperature active magnetic bearings (AMBs) for sCO2 machinery applications. The goals of the project are to develop conceptual designs for radial and thrust AMBs capable of operating in sCO2 environments up to 1000°F. A waste-heat recovery (WHR) application with hermetic machinery is used as a reference case to apply AMBs. This application was previously investigated to compare hermetic machinery enabled by process-lubricated bearings and high-speed motors/generators with traditional machinery configurations using oil-lubricated bearings, gearboxes, and grid-frequency electric machines. In this paper, AMBs are sized for the WHR application machinery. Load capacity estimates are made using first-principle-derived formulas that consider operation at elevated temperatures. Estimates of linearized AMB system coefficients are also made to aid future controller development. Rotor models are developed that account for AMB rotor geometry and housing space requirements. Rotordynamics studies are performed to identify reasonable target values for closed-loop AMB stiffness and closed-loop AMB damping. These target values will be used in future control studies.

Lipham, Robert↗

Preferred orientation of calcium aluminosilicate hydrate compacts: Implications for creep and indentation

Nano/micro-indentation has been extensively used to examine elastic properties and creep of cement-based materials. However, there have been inconsistencies in the measured elastic moduli and debate on the creep mechanism of calcium (alumino) silicate hydrates (C-(A-)S-H). To bring new insights, we examined the deviatoric stress-induced preferred orientation of calcium aluminosilicate hydrate (C-A-S-H), portlandite, and ettringite compacts, using synchrotron-based X-ray diffraction. Intense preferred orientations were observed in C-A-S-H compacts, and the c-axis of unit cells is highly aligned with the compression direction; weaker c-axis related fiber-type texture formed in portlandite and ettringite. Higher humidity, greater compacting pressure, and/or increased duration of the pressure intensified the C-A-S-H preferred orientation, which is facilitated by gel-pore water lubrication. This pressure-induced time-dependent preferential re-orientation of crystallites can contribute to the creep of cement-based materials, and it may cause overrepresentation of the soft c-axis of C-(A-)S-H unit-cell in nanoindentation experiments and underestimation of Young's modulus.

36 MATERIALS SCIENCE↗

Bioinspired nonwetting surfaces for corrosion inhibition over a range of temperature and corrosivity

Applications of superhydrophobic (SHS) and lubricant infused surfaces (LIS) involve exposure to corrosive environments from the acidic to the basic, at a range of temperatures, that are not fully characterized. Here, we present for the first time a multifactorial study of the effects of surface fabrication method, surface modification, surface functionalization time, temperature and pH of the immersion medium on the corrosion performance of nonwetting copper surfaces. Bioinspired SHS and LIS fabricated using facile methods of etching and electrodeposition are systematically assessed using potentiodynamic polarization measurements for their corrosion resistance in saline solution (pH ≈7) over a temperature range 23–85°C. SHS and LIS are shown to exhibit diminished corrosion rate, by up to two orders of magnitude, compared to bare copper surface. An Arrhenius model is developed for the first time, describing the temperature- dependent corrosion rate of SHS and LIS. Electrochemical impedance spectroscopy is used to show that corrosion resistance of LIS is larger by three orders of magnitude in extremely acidic (pH = 1) and by an order magnitude in extremely alkaline (pH = 14) media compared to bare copper surface. Etched LIS are generally more resistant to corrosion compared to SHS at all temperatures with excellent microstructural durability.

42 ENGINEERING↗

Novel nonwetting solid-infused surfaces for superior fouling mitigation

Fouling is a ubiquitous issue in several environmental and energy applications. Here we introduce novel nonwetting solid-infused surfaces (SIS) with superior anti-fouling characteristics that are durable than conventional nonwetting surfaces in a dynamic flow environment. A systematic study is presented to elucidate the fouling mitigation performance of SIS in comparison to lubricant-infused surface (LIS) and conventional smooth surface. Copper tubes with SIS, LIS or smooth inner walls are fabricated and subjected to accelerated calcium sulfate fouling in a flow fouling experimental setup. Fouling on the various surface types is quantified in terms of asymptotic fouling resistance, and the fundamental morphological differences in the interactions of the foulant and the various surface types are analyzed. Based on a systematic sweep of the parameter combinations using design of experiments and Taguchi analysis, an analytical dependence of asymptotic fouling resistance on the governing parameters namely, Reynolds number, foulant concentration and temperature is derived. The analytical model is shown to predict the asymptotic fouling resistance to within 20% accuracy with a 95% confidence. In addition, for the first time, the effects of shear durability on the fouling mitigation performance of LIS vis-à-vis SIS are studied. It is shown that the novel nonwetting SIS offers a robust option for superior fouling mitigation over LIS in the long run.

42 ENGINEERING↗

Discrepant wear behavior of carbon nanotubes (CNTs) and dispersant in four-ball unidirectional and ball-on-flat reciprocating sliding tests

Carbon nanotubes (CNTs), basically rolled graphene sheets, have been studied lately as oil additives in the literature. However, we observed discrepant impact of CNTs on wear protection from two common tribological tests, four-ball unidirectional sliding and high frequency reciprocating rig (HFRR) ball-on-flat reciprocating sliding. To gain a stable suspension and dispersion of the CNTs in the oil, the CNT surface was functionalized with a phenyl ligand and a dispersant, polyisobutylene succinimide (PIBSI), was added. In the four-ball test, PIBSI alone failed to protect the surface but the CNTs effectively reduced the wear loss. The observations in the HFRR test however were the opposite: the PIBSI alone provided strong wear reduction but the CNTs had no positive impact. Here, such a discrepancy was hypothetically attributed to the different wear protection mechanisms by the PIBSI and CNTs which responded distinctively under different testing conditions. Additional unidirectional and reciprocating sliding tests with matching Hertzian contact pressures were able to validate the hypothesis. Worn surface morphological examination and tribofilm chemical analysis further supported the proposed wear mechanisms. Fundamental understanding gained in this study provides insights into the potential benefits and limitations of using CNTs in lubrication.

36 MATERIALS SCIENCE↗

USAMP Low-Cost Mg Sheet Component Development and Demonstration Project

The overarching objective of this USAMP project was to develop and demonstrate door panels made from magnesium (Mg) sheet with a cost penalty over conventional steel stampings of no more than $\$5.50$/kg saved. The technical approach integrated experiments with advanced computational tools based on Integrated Computational Materials Engineering (ICME) methods to develop new alloy chemistries and their thermomechanical processing that promise improved formability and lower forming temperatures. A penultimate task before finally forming the stampings was to incorporate actual microstructure into models that would enable formability simulations. This approach would, for the first time, account for individual magnesium grains moving in an anisotropic fashion unlike that for aluminum or steel that have isotropic properties upon which the current simulation tools are based. In separate activities, new coatings and lubricants to facilitate forming and improved corrosion protection and joining strategies, were developed to ensure that the door could be produced with stated product requirements. A technical cost model, which included parts production, assembly, and paint for a door specifically designed for Mg sheet, showed the cost penalty to be between $\$4.26$ to $\$6.60$/kg saved, which enveloped the project’s cost targets. The cost of the coated Mg sheet was identified as the key driver for the cost penalty. The mass of the Mg-intensive door was 7.9 kg, which was 54% less than the baseline steel door.

36 MATERIALS SCIENCE↗

Low-Cost Magnesium Alloy Sheet Component Development and Demonstration Project

The overarching objective of this USAMP project was to develop and demonstrate door panels made from magnesium (Mg) sheet with a cost penalty over conventional steel stampings of no more than $5.50/kg saved. The technical approach integrated experiments with advanced computational tools based on Integrated Computational Materials Engineering (ICME) methods to develop new alloy chemistries and their thermomechanical processing that promise improved formability and lower forming temperatures. A penultimate task before finally forming the stampings was to incorporate actual microstructure into models that would enable formability simulations. This approach would, for the first time, account for individual magnesium grains moving in an anisotropic fashion unlike that for aluminum or steel that have isotropic properties upon which the current simulation tools are based. In separate activities, new coatings and lubricants to facilitate forming and improved corrosion protection and joining strategies, were developed to ensure that the door could be produced with stated product requirements. A technical cost model, which included parts production, assembly, and paint for a door specifically designed for Mg sheet, showed the cost penalty to be between 4.26 USD to 6.60 USD/kg saved, which enveloped the project’s cost targets. The cost of the coated Mg sheet was identified as the key driver for the cost penalty. The mass of the Mg-intensive door was 7.9 kg, which was 54% less than the baseline steel door.

36 MATERIALS SCIENCE↗

Graphene oxide gluing layer enabling macroscale tribology applications of pristine graphene

In recent studies of two-dimensional (2D) nanomaterial-based solid lubricants, the importance of durability has been emerging for real engineering-scale applications. To achieve this, a transfer layer formation is essential to prevent the wear of the mechanical systems. However, it has been challenging for pristine graphene (PG) to induce a material transfer due to chemical inertness. In this study, we suggest an easy-to-process strategy to promote the huge material transfer of the PG onto the counterpart contacting material. We utilized graphene oxide (GO) as a gluing layer between the PG film and the counterpart contact surface to realize the superior tribological performance. The high interaction energy of the GO from its functional groups makes a contribution to the material transfer of PG, which is unveiled by a systematic analysis of the counterpart contact surface and the wear track. The huge solid transfer layer not only makes a wear-resistant contact interface between the transfer layer and the underlying film by densification and oxidation, but also reduces surface interaction energies, finally resulting in a significant improvement in durability.

graphene oxide (GO)↗

Rheological Properties of Small-Molecular Liquids at High Shear Strain Rates

Molecular-scale understanding of rheological properties of small-molecular liquids and polymers is critical to optimizing their performance in practical applications such as lubrication and hydraulic fracking. We combine nonequilibrium molecular dynamics simulations with two unsupervised machine learning methods: principal component analysis (PCA) and t-distributed stochastic neighbor embedding (t-SNE), to extract the correlation between the rheological properties and molecular structure of squalane sheared at high strain rates (10 6 –10 10 s -1 ) for which substantial shear thinning is observed under pressures P ϵ 0.1–955 MPa at 293 K. Intramolecular atom pair orientation tensors of 435 × 6 dimensions and the intermolecular atom pair orientation tensors of 61 × 6 dimensions are reduced and visualized using PCA and t-SNE to assess the changes in the orientation order during the shear thinning of squalane. Dimension reduction of intramolecular orientation tensors at low pressures P = 0.1,100 MPa reveals a strong correlation between changes in strain rate and the orientation of the side-backbone atom pairs, end-backbone atom pairs, short backbone-backbone atom pairs, and long backbone-backbone atom pairs associated with a squalane molecule. At high pressures P ≥ 400 MPa, the orientation tensors are better classified by these different pair types rather than strain rate, signaling an overall limited evolution of intramolecular orientation with changes in strain rate. Dimension reduction also finds no clear evidence of the link between shear thinning at high pressures and changes in the intermolecular orientation. The alignment of squalane molecules is found to be saturated over the entire range of rates during which squalane exhibits substantial shear thinning at high pressures.

36 MATERIALS SCIENCE↗