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At least 235 records · Page 13

Reaction Optimization for Enzymatic Deconstruction of Industrially Relevant Nylon Composites

Plastics such as polyamides (PAs) possess unique physicochemical properties that make them indispensable in modern society. However, their energy‐intensive production and challenging end‐of‐life management highlight the urgent need for efficient recycling or remanufacturing solutions. Enzymatic depolymerization offers a promising route toward circular recycling, yet remains constrained by limited enzyme characterization, lack of validation under industrially relevant conditions and substrates, and overall performance. Here, we optimized the reaction conditions for three recently discovered nylon‐degrading enzymes. One of them, Nyl12, achieved product titers with PA6 and PA66 that exceed previously reported values, without enzyme engineering or substrate pretreatment. We further demonstrated the scalability of the process and its application to complex PA‐based materials used in microelectronic components. Analysis of substrate features, including surface area and particle size, revealed key parameters governing enzymatic activity and provided a framework for future pretreatment and process optimization efforts. In combination, these efforts provide a new benchmark for enzymatic nylon recycling.

nylon↗

Surface property modification of silicon

The main emphasis of this work has been to determine the wear rate of silicon in fluid environments and the parameters that influence wear. Three tests were carried out on single crystal Czochralski silicon wafers: circular and linear multiple-scratch tests in fluids by a pyramidal diamond simulated fixed-particle abrasion; microhardness and three-point bend tests were used to determine the hardness and fracture toughness of abraded silicon and the extent of damage induced by abrasion. The wear rate of (100) and (111) n and p-type single crystal Cz silicon abraded by a pyramidal diamond in ethanol, methanol, acetone and de-ionized water was determined by measuring the cross-sectional areas of grooves of the circular and linear multiple-scratch tests. The wear rate depends on the loads on the diamond and is highest for ethanol and lowest for de-ionized water. The surface morphology of the grooves showed lateral and median cracks as well as a plastically deformed region. The hardness and fracture toughness are critical parameters that influence the wear rate. Microhardness tests were conducted to determine the hardness as influenced by fluids. Median cracks and the damage zone surrounding the indentations were also related to the fluid properties.

Danyluk, S.↗

Response of 304L stainless steel and 6061-T651 aluminum alloy at -40 °C

The objective of this work is to extend the thermal-mechanical, elastic-plastic calibrations for 304L stainless steel [1] and and 6061-T651 aluminum alloy [2] to the regime between room temperature and -40 °C. The basis to extend the calibration consisted of new uniaxial tension tests conducted at -40 °C using the same plate material stocks, circular cylindrical specimen geometries and testing apparatus as previously, followed by attempts to fit power-law hardening functions to replicate the response observed in the specimens and then extend the yield, hardening constant, hardening exponent and rate constant functions in the calibrations to cover the new temperature regime.

36 MATERIALS SCIENCE↗

Advanced stress analysis methods applicable to turbine engine structures

The following tasks on the study of advanced stress analysis methods applicable to turbine engine structures are described: (1) constructions of special elements which contain traction-free circular boundaries; (2) formulation of new version of mixed variational principles and new version of hybrid stress elements; (3) establishment of methods for suppression of kinematic deformation modes; (4) construction of semiLoof plate and shell elements by assumed stress hybrid method; and (5) elastic-plastic analysis by viscoplasticity theory using the mechanical subelement model.

Pian, Theodore H. H.↗

Method for Forming Hollow Profile Non-Circular Extrusions Using Shear Assisted Processing and Extrusion (ShAPE)

A process for forming extruded products using a device having a scroll face configured to apply a rotational shearing force and an axial extrusion force to the same preselected location on material wherein a combination of the rotational shearing force and the axial extrusion force upon the same location cause a portion of the material to plasticize, flow and recombine in desired configurations. This process provides for a significant number of advantages and industrial applications, including but not limited to extruding tubes used for vehicle components with 50 to 100 percent greater ductility and energy absorption over conventional extrusion technologies, while dramatically reducing manufacturing costs.

Joshi, Vineet V.↗

Method for forming hollow profile non-circular extrusions using shear assisted processing and extrusion (ShAPE)

A process for forming extruded products using a device having a scroll face configured to apply a rotational shearing force and an axial extrusion force to the same preselected location on material wherein a combination of the rotational shearing force and the axial extrusion force upon the same location cause a portion of the material to plasticize, flow and recombine in desired configurations. This process provides for a significant number of advantages and industrial applications, including but not limited to extruding tubes used for vehicle components with 50 to 100 percent greater ductility and energy absorption over conventional extrusion technologies, while dramatically reducing manufacturing costs.

Joshi, Vineet V.↗

Technologies and policies to decarbonize global industry: Review and assessment of mitigation drivers through 2070

Fully decarbonizing global industry is essential to achieving climate stabilization, and reaching net zero greenhouse gas emissions by 2050–2070 is necessary to limit global warming to 2 °C. This paper assembles and evaluates technical and policy interventions, both on the supply side and on the demand side. It identifies measures that, employed together, can achieve net zero industrial emissions in the required timeframe. Key supply-side technologies include energy efficiency (especially at the system level), carbon capture, electrification, and zero-carbon hydrogen as a heat source and chemical feedstock. There are also promising technologies specific to each of the three top-emitting industries: cement, iron & steel, and chemicals & plastics. These include cement admixtures and alternative chemistries, several technological routes for zero-carbon steelmaking, and novel chemical catalysts and separation technologies. Crucial demand-side approaches include material-efficient design, reductions in material waste, substituting low-carbon for high-carbon materials, and circular economy interventions (such as improving product longevity, reusability, ease of refurbishment, and recyclability). Strategic, well-designed policy can accelerate innovation and provide incentives for technology deployment. High-value policies include carbon pricing with border adjustments or other price signals; robust government support for research, development, and deployment; and energy efficiency or emissions standards. These core policies should be supported by labeling and government procurement of low-carbon products, data collection and disclosure requirements, and recycling incentives. In implementing these policies, care must be taken to ensure a just transition for displaced workers and affected communities. Similarly, decarbonization must complement the human and economic development of low- and middle-income countries.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Near-surface seismic anisotropy in Antarctic glacial snow and ice revealed by high-frequency ambient noise

Ambient seismic recordings taken at broad locations across Ross Ice Shelf and a dense array near West Antarctic Ice Sheet (WAIS) Divide, Antarctica, show pervasive temporally variable resonance peaks associated with trapped seismic waves in near-surface firn layers. These resonance peaks feature splitting on the horizontal components, here interpreted as frequency-dependent anisotropy in the firn and underlying ice due to several overlapping mechanisms driven by ice flow. Frequency peak splitting magnitudes and fast/slow axes were systematically estimated at single stations using a novel algorithm and compared with good agreement with active source anisotropy measurements at WAIS Divide determined via active sources recorded on a 1 km circular array. The approach was further applied to the broad Ross Ice Shelf (RIS) array, where anisotropy axes were directly compared with visible surface features and ice shelf flow lines. The near-surface firn, depicted by anisotropy above 30 Hz, was shown to exhibit a novel plastic stretching mechanism of anisotropy, whereby the fast direction in snow aligns with accelerating ice shelf flow.

58 GEOSCIENCES↗

Biobased chemical recycling: aminolysis of PET using renewable reagents and monomers to synthesize new semi-aromatic polyamides

Chemical recycling of PET is a method of depolymerizing polymer chains to monomeric components enabling the synthesis of second-generation materials with virgin-like quality. Commercial chemical recycling techniques rely upon high pressure methanolysis to create precursors capable of synthesizing a second-generation PET resin. However, despite the circular approach of methanolysis, a product with a very short lifespan and similar value is created. The approach of the current study is to utilize aminolysis as an ambient pressure technique to create precursors for higher value materials with longer lifespans to address the current crisis in plastic waste. Semi-aromatic polyamides (SAP) are desired in this circumstance because of their high melting point and heat resistance combined with good melt-processability similar to aliphatic polyamides. In this study SAPs were synthesized using precursors recovered from the aminolysis of PET employing biobased diamines and dicarboxylic acids. While aminolysis has been explored in previous studies, this work investigated the use of biobased components from castor oil: decamethylene diamine during recycling and sebacic acid during polymerization. Polymer synthesis resulted in the formation of SAPs similar to polyphthalamides (PPA) with novel structures given the aromatic portion from terephthalic acid (TPA) and aliphatic portion from the diamines and diacids. The synthesized materials exhibited excellent thermal stability with high glass transition temperatures. Novel polymers were created with varying aliphatic chain length to understand fundamental parameters needed to produce a valuable polymer from post-consumer waste.

High performance Applications↗

Advances in catalytic production processes of biomass-derived vinyl monomers

Plastic industries currently source the majority of monomers from crude oil substances. Although we have witnessed a significant interest of companies in the utilization of sustainable feedstock materials for bio-based compound synthesis in the past decade, the transition to photosynthetic or chemosynthetic plant-based production in a circular carbon economy is largely slow due to complex biomass processing, costs and related reaction factors. The upgrade of the separated platform chemicals with a deeper supporting understanding of processes, models and a root–cause analysis about the underlying distribution challenges of engineered transformation mechanisms, catalyzed conversion pathways and selectivity would be beneficial to advance applied scientific development, bio-refining and manufacturing output amount. This review provides a summary, assessment and perspective for three important polymer-forming vinyl molecules, i.e. acrylic acid, methacrylic acid and styrene. These provide a backbone to produce acrylates, polystyrene, resins, rubbers, protective surface coatings, adhesives, textiles and other obtained copolymers. A succinct analytical overview on the thermo-catalytic intermediate routes for property-wise drop-in alternatives is presented. Sugars, acrolein, allyl alcohol, ethylbenzene, glycerol, 3-hydroxypropionic acid, isobutene, itaconic acid and lactic acid are considered as the main starting reactants. Catalysts span mixed metal oxides, silicates, native or impregnated zeolite frameworks (HBEA, HZSM, and MFI) and hetero-poly acids as well as homogeneous base hydroxides or platinum group metals, supported on carbon, alumina and sulfates. Finally, the article concludes with a brief state sum-up of the results, topics and opportunities for systematic future research or scaling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Depolymerization and Repolymerization Toward Repurposing Polymer Waste Into Valuable Chemicals & Materials

The versatility of synthetic polymers has led to their continual and escalating production that has accompanied mismanagement at their end-of-life. Exploring and understanding complementary avenues to repurpose plastic waste beyond traditional mechanical recycling can unlock new opportunities in providing feedstock flexibility, securing supply chains, recovering valuable materials, and enabling new valorization paths. Chemical recycling allows for the return to monomers, tailored oligomers, and polymers, even from mixed states of post-consumer waste plastics. This review article summarizes our research team's efforts on elucidating key insights surrounding plastic depolymerization and repolymerization into valorized products. We revealed organocatalyst design rules lead to highly effective and selective deconstruction of condensation polymers. The intricacies of tailoring the reaction environment to produce products of specific lengths and desired functionalities transform low-value waste feedstocks into high-performance materials with embedded circularity. Other types of polymers, including polyolefins and polyakenamers, have also been designed and converted into valuable products. There remain opportunities for further developments such as low-energy and precision depolymerization, adoption of cutting-edge small molecule transformation to access functionalized polymer scaffolds typically inaccessible otherwise, as well as precision design and understanding through the aid of advanced tools.

Galan, Nick [ORNL]↗

Dehydrogenated Polyethylene from Discarded Plastics as a Synthon for Functional Polyolefins

Many valuable specialty chemicals and drug candidates rely on synthesizing reactive intermediates to generate the final product(s). An approach that leverages C-H activation chemistry to achieve chemically active reactive handles for polymer diversification is desirable. Further, this report describes the synthesis and functionalization of dehydrogenated high-density polyethylene (HDPE) from discarded post-consumer plastic via acceptorless Ir-pincer-catalyzed non-oxidative dehydrogenation followed by acid-catalyzed hydroamination and hydroalkoxylation. The final products show significant material property changes with tunability and scalability through variation of the olefin content. This method highlights the potential value of dehydrogenated intermediates as platforms to enable carbon circularity and polyolefin end-of-life management strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Rotational Millimeter-Wave Shoe Scanner Using the Discrete Fourier Transform for Backprojection-Based Image Reconstruction

An active 3D microwave / millimeter-wave shoe scanner was previously developed at the Pacific Northwest National Laboratory (PNNL) using two linear arrays scanned over a rectilinear aperture. The radar system chirps a frequency sweep from 10-40 GHz. These frequencies allow imaging through optically opaque material such as leather, rubber, plastics, and other dielectrics. The system was designed to detect concealed items in the soles of shoes while allowing people to leave their shoes on through a security checkpoint. To shrink the footprint of the system, a new iteration of the design has been developed that scans the two linear arrays over a circular aperture. This new footprint opens the possibility of it being installed in the floor of a cylindrical millimeter-wave body scanner. The backprojection-based multilayer dielectric image reconstruction developed at PNNL can easily handle arbitrary spatial sampling, accommodating the new rotational shoe scanner design. Commonly, the fast Fourier transform (FFT) is used to efficiently compute the range response from the data collected by the system as a preprocessing step to the backprojection algorithm. It was found that converting to range using the discrete Fourier transform (DFT) directly has some advantages over the FFT. For example, nonlinear and non-uniform frequency sweeps can easily be compensated for during the computation of the DFT and only the range bins of interest need to be computed and their spacing can be chosen arbitrarily. Because the range conversion step of the image reconstruction is the fastest part of the process there is very little speed penalty for using the DFT over the FFT and it can even increase the speed of image reconstruction when the ranges of interest are fewer than the total span that is calculated in the FFT.

Millimeter-wave imaging, microwave imaging, shoe s↗

Flow in the Proximity of the Pin-Tool in Friction Stir Welding and Its Relation to Weld Homogeneity

In the Friction Stir Welding (FSW) process a rotating pin inserted into a seam literally stirs the metal from each side of the seam together. It is proposed that the flow in the vicinity of the pin-tool comprises a primary rapid shear over a cylindrical envelope covering the pin-tool and a relatively slow secondary flow taking the form of a ring vortex about the tool circumference. This model is consistent with a plastic characterization of metal flow, where discontinuities in shear flow are allowed but not viscous effects. It is consistent with experiments employing several different kinds of tracer: atomic markers, shot, and wire. If a rotating disc with angular velocity w is superposed on a translating continuum with linear velocity omega, the trajectories of tracer points become circular arcs centered upon a point displaced laterally a distance v/omega from the center of rotation of the disc in the direction of the advancing side of the disc. In the present model a stream of metal approaching the tool (taken as the coordinate system of observation) is sheared at the slip surface, rapidly rotated around the tool, sheared again on the opposite side of the tool, and deposited in the wake of the tool. Local shearing rates are high, comparable to metal cutting in this model. The flow patterns in the vicinity of the pin-tool determine the level of homogenization and dispersal of contaminants that occurs in the FSW process. The approaching metal streams enfold one another as they are rotated around the tool. Neglecting mixing they return to the same lateral position in the wake of the tool preserving lateral tracer positions as if the metal had flowed past the tool like an extrusion instead of being rotated around it. (The seam is, however, obliterated.) The metal stream of thickness approximately that of the tool diameter D is wiped past the tool at elevated temperatures drawn out to a thickness of v/2(omega) in the wiping zone. Mixing distances in the wiping zone are multiplied in the unfolded metal. Inhomogeneities on a smaller scale than the mixing length are obliterated, but structure on a larger scale may be transmitted to the wake of a FSW weld.

Nunes, Arthur C., Jr.↗

Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries

The circularity of current and future polymeric materials is a major focus of fundamental and applied research, as undesirable end-of-life outcomes and waste accumulation are global problems that impact our society. The recycling or repurposing of thermoplastics and thermosets is an attractive solution to these issues, yet both options are encumbered by poor property retention upon reuse, along with heterogeneities in common waste streams that limit property optimization. Dynamic covalent chemistry, when applied to polymeric materials, enables the targeted design of reversible bonds that can be tailored to specific reprocessing conditions to help address conventional recycling challenges. In this review, we highlight the key features of several dynamic covalent chemistries that can promote closed-loop recyclability and we discuss recent synthetic progress towards incorporating these chemistries into new polymers and existing commodity plastics. Next, we outline how dynamic covalent bonds and polymer network structure influence thermomechanical properties related to application and recyclability, with a focus on predictive physical models that describe network rearrangement. Finally, we examine the potential economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing using elements derived from techno-economic analysis and life-cycle assessment, including minimum selling prices and greenhouse gas emissions. Throughout each section, we discuss interdisciplinary obstacles that hinder the widespread adoption of dynamic polymers and present opportunities and new directions toward the realization of circularity in polymeric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of soft inclusions on the strength of wrought materials

The three dimensional soft particles (such as sulfides, silicates and voids) present in most materials are modelled by circular voids in sheet metal. Relationships are sought between the shape and orientation of a hole after rolling and testing in tension. Then, the effect of hole shape and size on mechanical properties is considered experimentally. The presence of voids has a negligible influence on the ultimate tensile stress of ductile materials based on the unperforated area because plastic flow neutralizes the stress intensification present in the elastic region. However, the shape and orientation of the defects are found to play an important role relative to strain at fracture. In certain engineering applications the strain at fracture is more important than the stress at fracture and in this sense the presence of voids are considered to influence the strength of a ductile material.

Pai, D. M.↗