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At least 919 records · Page 51

Instantiation of crystal plasticity simulations for micromechanical modelling with direct input from microstructural data collected at light sources

Novel non-destructive characterization techniques performed at light sources provide previously inaccessible 3-D mesoscopic information on the deformation of polycrystalline materials. One major difficulty for interpretation of these experiments through micromechanical modelling is the likelihood that processing and/or mounting the sample introduce residual stresses in the specimen. These stresses need to be incorporated into crystal plasticity formulations, for these models to operate directly from microstructural images and be predictive. To achieve this, the initial micromechanical state of each voxel needs to be specified. Here in this letter we present a method for incorporating grain-averaged residual stresses for instantiation of crystal plasticity simulations.

36 MATERIALS SCIENCE↗

MUTZ-3 derived Langerhans cells in human skin equivalents show differential migration and phenotypic plasticity after allergen or irritant exposure

After allergen or irritant exposure, Langerhans cells (LC) undergo phenotypic changes and exit the epidermis. In this study we describe the unique ability of MUTZ-3 derived Langerhans cells (MUTZ-LC) to display similar phenotypic plasticity as their primary counterparts when incorporated into a physiologically relevant full-thickness skin equivalent model (SE-LC). We describe differences and similarities in the mechanisms regulating LC migration and plasticity upon allergen or irritant exposure. The skin equivalent consisted of a reconstructed epidermis containing primary differentiated keratinocytes and CD1a{sup +} MUTZ-LC on a primary fibroblast-populated dermis. Skin equivalents were exposed to a panel of allergens and irritants. Topical exposure to sub-toxic concentrations of allergens (nickel sulfate, resorcinol, cinnamaldehyde) and irritants (Triton X-100, SDS, Tween 80) resulted in LC migration out of the epidermis and into the dermis. Neutralizing antibody to CXCL12 blocked allergen-induced migration, whereas anti-CCL5 blocked irritant-induced migration. In contrast to allergen exposure, irritant exposure resulted in cells within the dermis becoming CD1a{sup −}/CD14{sup +}/CD68{sup +} which is characteristic of a phenotypic switch of MUTZ-LC to a macrophage-like cell in the dermis. This phenotypic switch was blocked with anti-IL-10. Mechanisms previously identified as being involved in LC activation and migration in native human skin could thus be reproduced in the in vitro constructed skin equivalent model containing functional LC. This model therefore provides a unique and relevant research tool to study human LC biology in situ under controlled in vitro conditions, and will provide a powerful tool for hazard identification, testing novel therapeutics and identifying new drug targets. - Highlights: • MUTZ-3 derived Langerhans cells integrated into skin equivalents are fully functional. • Anti-CXCL12 blocks allergen-induced MUTZ-LC migration. • Anti-CCL5 blocks irritant-induced MUTZ-LC migration. • Irritant mediated MUTZ-LC trans-differentiation to macrophage-like cell in dermis. • Trans-differentiation of MUTZ-LC is IL-10 dependent.

60 APPLIED LIFE SCIENCES↗

Pyrolysis of municipal plastic wastes II: Influence of raw material composition under catalytic conditions

Highlights: > ZSM-5 zeolite catalytic pyrolysis transforms municipal plastic waste into liquids and gases useful as fuels or source of chemicals. > The composition of the waste sample plays an important role on the catalyst activity and the products obtained. > ZSM-5 zeolite is somehow deactivated when high proportions of fine inorganic materials are present in the sample. > When the sample contains cellulose-based materials, the formation of a two-phase liquid fraction can be avoided by a low temperature step. - Abstract: In this work, the results obtained in catalytic pyrolysis of three plastic waste streams which are the rejects of an industrial packing wastes sorting plant are presented. The samples have been pyrolysed in a 3.5 dm{sup 3} reactor under semi-batch conditions at 440 {sup o}C for 30 min in nitrogen atmosphere. Commercial ZSM-5 zeolite has been used as catalyst in liquid phase contact. In every case, high HHV gases and liquids which can be useful as fuels or source of chemicals are obtained. A solid fraction composed of the inorganic material contained in the raw materials and some char formed in the pyrolysis process is also obtained. The zeolite has shown to be very effective to produce liquids with great aromatics content and C3-C4 fraction rich gases, even though the raw material was mainly composed of polyolefins. The characteristics of the pyrolysis products as well as the effect of the catalyst vary depending on the composition of the raw material. When paper rich samples are pyrolysed, ZSM-5 zeolite increases water production and reduces CO and CO{sub 2} generation. If stepwise pyrolysis is applied to such sample, the aqueous liquid phase can be separated from the organic liquid fraction in a first low temperature step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recycling-oriented characterization of plastic frames and printed circuit boards from mobile phones by electronic and chemical imaging

Highlights: • A recycling oriented characterization of end-of-life mobile phones was carried out. • Characterization was developed in a zero-waste-perspective, aiming to recover all the mobile phone materials. • Plastic frames and printed circuit boards were analyzed by electronic and chemical imaging. • Suitable milling/classification strategies were set up to define specialized-pre-concentrated-streams. • The proposed approach can improve the recovery of polymers, base/precious metals, rare earths and critical raw materials. - Abstract: This study characterizes the composition of plastic frames and printed circuit boards from end-of-life mobile phones. This knowledge may help define an optimal processing strategy for using these items as potential raw materials. Correct handling of such a waste is essential for its further “sustainable” recovery, especially to maximize the extraction of base, rare and precious metals, minimizing the environmental impact of the entire process chain. A combination of electronic and chemical imaging techniques was thus examined, applied and critically evaluated in order to optimize the processing, through the identification and the topological assessment of the materials of interest and their quantitative distribution. To reach this goal, end-of-life mobile phone derived wastes have been systematically characterized adopting both “traditional” (e.g. scanning electronic microscopy combined with microanalysis and Raman spectroscopy) and innovative (e.g. hyperspectral imaging in short wave infrared field) techniques, with reference to frames and printed circuit boards. Results showed as the combination of both the approaches (i.e. traditional and classical) could dramatically improve recycling strategies set up, as well as final products recovery.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mechanical and chemical recycling of solid plastic waste

Highlights: • This paper reviews the current pathways for recycling of solid plastic waste, via both mechanical and chemical recycling. • The predominant industrial technologies, design strategies and recycling examples of specific waste streams are reviewed. • The main challenges and some potential remedies are discussed. - Abstract: This review presents a comprehensive description of the current pathways for recycling of polymers, via both mechanical and chemical recycling. The principles of these recycling pathways are framed against current-day industrial reality, by discussing predominant industrial technologies, design strategies and recycling examples of specific waste streams. Starting with an overview on types of solid plastic waste (SPW) and their origins, the manuscript continues with a discussion on the different valorisation options for SPW. The section on mechanical recycling contains an overview of current sorting technologies, specific challenges for mechanical recycling such as thermo-mechanical or lifetime degradation and the immiscibility of polymer blends. It also includes some industrial examples such as polyethylene terephthalate (PET) recycling, and SPW from post-consumer packaging, end-of-life vehicles or electr(on)ic devices. A separate section is dedicated to the relationship between design and recycling, emphasizing the role of concepts such as Design from Recycling. The section on chemical recycling collects a state-of-the-art on techniques such as chemolysis, pyrolysis, fluid catalytic cracking, hydrogen techniques and gasification. Additionally, this review discusses the main challenges (and some potential remedies) to these recycling strategies and ground them in the relevant polymer science, thus providing an academic angle as well as an applied one.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Superstructure Optimization of Waste Plastic Pyrolysis, Integrating Thermal, Catalytic, and Plasma Technologies with Machine Learning

Global plastic waste generation exceeds 430 million tonnes per year, yet fewer than 9% are recycled in the United States. Pyrolysis offers a chemical recycling route at scale, but existing techno-economic and life cycle assessments fix product yields to single pure polymers, producing economic and environmental outputs that break down when the feed composition changes. Here, we present a superstructure optimization framework that addresses this by embedding a composition-aware random forest yield predictor, trained on 566 pyrolysis experiments, within a full-scale process simulation. Product distributions update automatically as feed allocation shifts across four reactor chemistries: conventional thermal, catalytic (HZSM-5), thermal oxo-degradation, and nonequilibrium CO2 plasma. The optimal superstructure achieves minimum selling prices of −0.56 to −0.76/kg feed and global warming potentials of −0.276 to −0.322 kg CO2-eq/kg feed across four commodity price scenarios, confirming profitable, carbon-negative operation without tipping fees. Carbon abatement costs of $\$$0.46 to $\$$1.25/kg CO2-eq are competitive with direct air capture. Sensitivity analysis shows that the catalytic-plasma split fraction is the single largest driver of both economic and climate performance, while hydrocracking allocation in the wax upgrading stage is emission-neutral across the full variable range. Mixed plastic waste streams, evaluated as composition-variable feedstocks rather than pure resins, are profitable and carbon-negative across realistic market conditions. These results give a quantitative basis for reactor selection, circular economy investment, and policy design targeting chemical recycling on a large scale.

Life cycle assessment↗

Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids

Understanding the mechanisms controlling ionic conductivity is critical for the development of the next generation of batteries and supercapacitors. This paper discusses the significant role played by ionic correlations in conductivity of concentrated ionic systems. Our studies of an organic ionic plastic crystal reveal that correlations in ions dynamics suppress conductivity by 25–100 times in comparison to the expected uncorrelated ionic conductivity estimated from the Nernst–Einstein relationship. Furthermore, additional analysis also demonstrates that ionic correlations suppress conductivity in polymerized ionic liquids and gel by ~10 times. Thus, ionic correlations, usually neglected in many studies, play a very important role in conductivity of concentrated ionic systems. These results cannot be explained by a diffusion of ion pairs because all these systems are essentially single ion conductors. In contrast, strongly correlated motions of mobile ions with the same charge (cation–cation or anion–anion correlations) are the major mechanism suppressing the ionic conductivity in these systems. Finally, on the basis of these results, we emphasize that charge transport rather than ion diffusion is critical for electrolyte performance and suggest the potential design of plastic crystals and polymer electrolytes with enhanced ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Mechanisms Underlying Surfactant-Based Plastics De-Inking

Surfactant-mediated binder removal is critical for de-inking pretreatment in plastics recycling, yet the molecular mechanisms governing surfactant performance remain poorly understood. We used all-atom (AA) and coarse-grained (CG) molecular dynamics (MD) simulations alongside alkaline surfactant washing experiments to investigate interactions between a series of surfactants and a polyether urethane (PEU) binder in solution and on a polyethylene (PE) surface. Experiments reveal a range of de-inking efficiencies, ranging from <25 to >95% depending upon surfactant headgroup charge and tail length. AA simulations reveal that charged surfactants reach stable levels of surfactant coverage, while nonionic surfactants aggregate on the binder. CG umbrella sampling calculations quantify the thermodynamics of binder desorption in water. In ∼0.25 M surfactant solutions, up to a 52% reduction in the free energy barrier is computed, with trends in good agreement (R 2 = 0.92, Pearson’s r = –0.96, Spearman’s ρ = –0.83) with experimental de-inking efficiencies. We find that charged surfactants are more effective than nonionic surfactants for de-inking and propose three regimes of surfactant de-inking processes: good de-inking occurs in surfactants that promote PEU desorption with a low radius of gyration (R g ); moderate de-inking occurs when surfactants stabilize PEU but increase R g ; poor de-inking occurs in surfactants that aggregate on the binder and promote extensive anchoring to the surface. Overall, these molecular-level insights have the potential to guide the design of surfactant formulations for plastics recycling applications.

ink removal↗

Relationship between electromagnetic and acoustic emissions during plastic deformation of gamma-irradiated LiF monocrystals

Simultaneous measurements of acoustic emissions (AE) and electromagnetic emissions (EME) during plastic deformation and destruction under uniaxial compression along <001> direction are made on LiF monocrystals after gamma irradiation by {sup 60}Co source. The irradiation doses are 1, 2, and 10 Mrad. The EME measurements in the radio-frequency range are carried out using two types of electromagnetic sensors: (i) a simple electrical stub antenna and (ii) a toroidal inductance coil. Two checking experiments on unirradiated crystals are performed as the starting point to discover the effect of gamma irradiation on acoustic and electromagnetic emissive ability of plastically deformed ionic crystals. Unirradiated LiF monocrystals demonstrate high-intensive EME at easy glide and work hardening stages, as well as at the fracture during destruction of the sample. At radiation doses more than {approx}1 Mrad, in the active loading stage the EME of LiF monocrystals vanishes, except few individual electromagnetic pulses (only at 1 and 2 Mrad doses), which are time correlated with well-defined drop-jumps on the loading diagram and therefore can be associated with macroscopic crack openings. Moderate electromagnetic activity in irradiated crystals occurs only in the final stage of deformation at the complete fracture of the sample. Thus, after gamma irradiation the formation of polarization currents due to dynamic interaction between charged vacancies and moving dislocations is suppressed, and only EME connected with the redistribution of the free charge on the crack branches is observed. Acoustic emission diagrams of low-irradiated LiF are typical for the work hardening stage in crystals containing a great amount of strong point stoppers. At larger irradiation doses the AE diagram displays quite different behavior at low- and high-loading regions with a sharp boundary between them. The low-loading region shows poor AE activity, which changes sharply into high-active burst-like emission with an increase in loading. The boundary between two regions shifts to higher loadings with radiation dose. The higher is the radiation dose the lower is the relative intensity of AE in the high-stressed region. The physical mechanisms of EME and AE in gamma-irradiated ionic crystals are discussed.

36 MATERIALS SCIENCE↗

Determination of the structural changes by Raman and {sup 13}C CP/MAS NMR spectroscopy on native corn starch with plasticizers

The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and {sup 13}C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-scale observation of parallel development of super elasticity and reversible plasticity in GaAs nanowires

We report the atomic-scale observation of parallel development of super elasticity and reversible dislocation-based plasticity from an early stage of bending deformation until fracture in GaAs nanowires. While this phenomenon is in sharp contrast to the textbook knowledge, it is expected to occur widely in nanostructures. This work indicates that the super recoverable deformation in nanomaterials is not simple elastic or reversible plastic deformation in nature, but the coupling of both.

36 MATERIALS SCIENCE↗

Elementary model of severe plastic deformation by KoBo process

Self-consistent model of generation, interaction, and annihilation of point defects in the gradient of oscillating stresses is presented. This model describes the recently suggested method of severe plastic deformation by combination of pressure and oscillating rotations of the die along the billet axis (KoBo process). Model provides the existence of distinct zone of reduced viscosity with sharply increased concentration of point defects. This zone provides the high extrusion velocity. Presented model confirms that the Severe Plastic Deformation (SPD) in KoBo may be treated as non-equilibrium phase transition of abrupt drop of viscosity in rather well defined spatial zone. In this very zone, an intensive lateral rotational movement proceeds together with generation of point defects which in self-organized manner make rotation possible by the decrease of viscosity. The special properties of material under KoBo version of SPD can be described without using the concepts of nonequilibrium grain boundaries, ballistic jumps and amorphization. The model can be extended to include different SPD processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Changes in mobility of plastic crystal ethanol during its transformation into the monoclinic crystal state

Transformation of deuterated ethanol from the plastic crystal phase into the monoclinic one is investigated by means of a singular setup combining simultaneously dielectric spectroscopy with neutron diffraction. We postulate that a dynamic transition from plastic crystal to supercooled liquid-like configuration through a deep reorganization of the hydrogen-bonding network must take place as a previous step of the crystallization process. Once these precursor regions are formed, subsequent crystalline nucleation and growth develop with time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The M-band transmission flux of the plastic foil with a coated layer of silicon or germanium

Silicon (Si) and Germanium (Ge) can be used as the dopant in the ablator material for the purpose of reducing preheating in indirect-drive inertial confinement fusion. Their performances in reducing preheating are quite different. A method to evaluate the difference of these two kinds of dopants has been presented in this letter. In the Shenguang-II high power laser facility, the M-band (1.6–4.4 keV) transmission flux of Si-coated plastic (CH) and Ge-coated plastic (CH) has been measured by using the M-band x-ray diode. In the experiment, we find that the Si-coated CH can absorb more M-band x-rays and thus reduce the preheating of the fuel in our experiment condition. By using the radiation hydrodynamic code MULTI-1D, we got the simulation result which was well suited for the experiment. The comparison of their opacities (T{sub e} = 60–100 eV and ρ = 0.1–0.5 g/cm{sup 3}) also shows that the opacity of Si is higher than that of Ge almost in the whole range of 1.6–4.4 keV.

36 MATERIALS SCIENCE↗

Plasticity mechanisms in ultrafine grained freestanding aluminum thin films revealed by in-situ transmission electron microscopy nanomechanical testing

In-situ bright field transmission electron microscopy (TEM) nanomechanical tensile testing and in-situ automated crystallographic orientation mapping in TEM were combined to unravel the elementary mechanisms controlling the plasticity of ultrafine grained Aluminum freestanding thin films. The characterizations demonstrate that deformation proceeds with a transition from grain rotation to intragranular dislocation glide and starvation plasticity mechanism at about 1% deformation. The grain rotation is not affected by the character of the grain boundaries. No grain growth or twinning is detected.

36 MATERIALS SCIENCE↗

Terahertz inline wall thickness monitoring system for plastic pipe extrusion

Conventional and commercially available inline wall thickness monitoring systems for pipe extrusion are usually based on ultrasonic or x-ray technology. Disadvantages of ultrasonic systems are the usual need of water as a coupling media and the high damping in thick walled or foamed pipes. For x-ray systems special safety requirements have to be taken into account because of the ionizing radiation. The terahertz (THz) technology offers a novel approach to solve these problems. THz waves have many properties which are suitable for the non-destructive testing of plastics. The absorption of electrical isolators is typically very low and the radiation is non-ionizing in comparison to x-rays. Through the electromagnetic origin of the THz waves they can be used for contact free measurements. Foams show a much lower absorption in contrast to acoustic waves. The developed system uses THz pulses which are generated by stimulating photoconductive switches with femtosecond laser pulses. The time of flight of THz pulses can be determined with a resolution in the magnitude of several ten femtoseconds. Hence the thickness of an object like plastic pipes can be determined with a high accuracy by measuring the time delay between two reflections on materials interfaces e.g. at the pipe's inner and outer surface, similar to the ultrasonic technique. Knowing the refractive index of the sample the absolute layer thickness from the transit time difference can be calculated easily. This method in principle also allows the measurement of multilayer systems and the characterization of foamed pipes.

36 MATERIALS SCIENCE↗

High resolution transmission electron microscopic in-situ observations of plastic deformation of compressed nanocrystalline gold

Nanocrystalline (nc) metals possess extremely high strength, while their capability to deform plastically has been debated for decades. Low ductility has hitherto been considered an intrinsic behavior for most nc metals, due to the lack of five independent slip systems actively operating during deformation in each nanograin. Here we report in situ high resolution transmission electron microscopic (HRTEM) observations of deformation process of nc gold under compression, showing the excellent ductility of individual and aggregate nanograins. Compression causes permanent change in the profile of individual nanograins, which is mediated by dislocation slip and grain rotation. The high rate of grain boundary sliding and large extent of widely exited grain rotation may meet the boundary compatibility requirements during plastic deformation. The in situ HRTEM observations suggest that nc gold is not intrinsically brittle under compressive loading.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗