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Poly(lactic acid) (PLA), as a biodegradable material, finds wide applications in packaging, automotive, and biological industries. However, achieving high strength, toughness, ultra-transparency, and heat resistance simultaneously in pure PLA through continuous one-step manufacturing remains a significant challenge. In this study, we addressed this challenge by utilizing the eccentric rotor extruder (ERE) in combination with cooling rolls to manufacture PLA sheets with outstanding mechanical performance. The ERE's elongational flow field combined with the cooling roller's weak stretching action induced orientation in the PLA molecular chains and promoted the formation of more mesophase, significantly improving mechanical properties. When the extrusion-stretch ratio (λ) value was 3.5, the tensile yield strength, Young's modulus, and elongation at break of ERE-fabricated samples ER-3.5 reached 86.2 MPa, 1777 MPa, and 57.9 %, respectively. Compared to the SE-3.5 samples manufactured with traditional methods, the increases were 38.8 %, 25.8 %, and 9.4 times, respectively. Additionally, the ERE manufactured samples maintained ultra-transparency and high heat resistance, making them suitable for food packaging, biomedicine, and other related fields. This methodology provides an efficient industrial-scale approach for manufacturing neat, biodegradable PLA with outstanding mechanical performance and ultra-transparency.

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Atomistic simulations of the linear, entangled polyethylene C1000H2002 melt undergoing steady-state and startup conditions of uniaxial elongational flow (UEF) over a wide range of flow strength were performed using a united-atom model for the atomic interactions between the methylene groups constituting the polymer macromolecules. Rheological, topological, and microstructural properties of these nonequilibrium viscoelastic materials were computed as functions of strain rate, focusing on regions of flow strength where flow-induced phase separation and flow-induced crystallization were evident. Results of the UEF simulations were compared with those of prior simulations of planar elongational flow, which revealed that uniaxial and planar flows exhibited essentially a universal behavior, although over strain rate ranges that were not completely equivalent. At intermediate flow strength, a purely configurational microphase separation was evident that manifested as a bicontinuous phase composed of regions of highly stretched molecules that enmeshed spheroidal domains of relatively coiled chains. At high flow strength, a flow-induced crystallization (FIC) occurred, producing a semicrystalline material possessing a high degree of crystallinity and primarily a monoclinic lattice structure. This FIC phase formed at a temperature (450 K) high above the quiescent melting point (≈400 K) and remained stable after cessation of flow for temperature at or below 435 K. Careful examination of the Kuhn segments constituting the polymer chains revealed that the FIC phase only formed once the Kuhn segments had become essentially fully extended under the UEF flow field. Thermodynamic properties such as the heat of fusion and heat capacity were estimated from the simulations and found to compare favorably with experimental values.

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TEMPO-oxidized cellulose nanofibril (CNF) hydrogels or cellulose nanocrystal (CNC) hydrogels can now be obtained at high concentrations (>10 wt%) and used to fabricate biobased materials and structures. Thus, it is required to control and model their rheology in process-induced multiaxial flow conditions using 3D tensorial models. For that purpose, it is necessary to investigate their elongational rheology. Thus, concentrated TEMPO-oxidized CNF and CNC hydrogels were subjected to monotonic and cyclic lubricated compression tests. These tests revealed for the first time that the complex compression rheology of these two electrostatically stabilised hydrogels combines viscoelasticity and viscoplasticity. The effect of their nanofibre content and aspect ratio on their compression response was clearly emphasised and discussed. The ability of a non-linear elasto-viscoplastic model to reproduce the experiments was assessed. Even if some discrepancies were observed at low or high strain rates, the model was consistent with the experiments.

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Computational fluid dynamics modeling was used to characterize the effect of the integration of constrictions defined by the vertices of hyperbolas on the flow structure in microfluidic serpentine channels. In the new topology, the Dean flows characteristic of the pressure-driven fluid motion along curved channels are combined with elongational flows and asymmetric longitudinal eddies that develop in the constriction region. The resulting complex flow structure is characterized by folding and stretching of the fluid volumes, which can promote enhanced mixing. Optimization of the geometrical parameters defining the constriction region allows for the development of an efficient micromixer topology that shows robust enhanced performance across a broad range of Reynolds numbers from Re = 1 to 100.

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Processing cellulose nanofibril (CNF) hydrogels with a high concentration is a solution to reduce logistics costs and drying energy and to produce CNF-based materials with good dimensional stability. However, the rheology of concentrated and highly concentrated CNF hydrogels is poorly understood due to the difficulties to characterise them using standard shear rheometers. In this study, enzymatic CNF hydrogels in the concentrated and highly concentrated regimes (3-13.6 wt%) were subjected to lubricated compression at various strain rates. At low strains, compression curves exhibited a linear regime. At higher strains and low strain rates, a heterogeneous and marked hardening of stress levels was observed and accompanied with a two-phase flow with significant fluid segregation and network consolidation. At high strain rates, a homogeneous and incompressible one-phase plateau-like regime progressively established. In this regime, a yield stress was measured and compared with literature data, showing a good agreement with them.

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The challenge of calculating nonequilibrium entropy in polymeric liquids undergoing flow was addressed from the perspective of extending equilibrium thermodynamics to include internal variables that quantify the internal microstructure of chain-like macromolecules and then applying these principles to nonequilibrium conditions under the presumption of an evolution of quasie equilibrium states in which the requisite internal variables relax on different time scales. The nonequilibrium entropy can be determined at various levels of coarse-graining of the polymer chains by statistical expressions involving nonequilibrium distribution functions that depend on the type of flow and the flow strength. Using nonequilibrium molecular dynamics simulations of a linear, monodisperse, entangled C1000H2002 polyethylene melt, nonequilibrium entropy was calculated directly from the nonequilibrium distribution functions, as well as from their second moments, and also using the radial distribution function at various levels of coarse-graining of the constituent macromolecular chains. Surprisingly, all these different methods of calculating the nonequilibrium entropy provide consistent values under both planar Couette and planar elongational flows. Combining the nonequilibrium entropy with the internal energy allows determination of the Helmholtz free energy, which is used as a generating function of flow dynamics in nonequilibrium thermodynamic theory.

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The emerging profile of blood flow and the cross-sectional distribution of blood cells have far reaching biological consequences in various diseases and vital internal processes, such as platelet adhesion. The effects of several essential blood flow parameters, such as red blood cell free layer width, wall shear rate, and hematocrit on platelet adhesion were previously explored to great lengths in straight geometries. In the current work, the effects of channel curvature on cellular blood flow are investigated by simulating the accurate cellular movement and interaction of red blood cells and platelets in a half-arc channel for multiple wall shear rate and hematocrit values. The results show significant differences in the emerging shear rate values and distributions between the inner and outer arc of the channel curve, while the cell distributions remain predominantly uninfluenced. The simulation predictions are also compared to experimental platelet adhesion in a similar curved geometry. The inner side of the arc shows elevated platelet adhesion intensity at high wall shear rate, which correlates with increased shear rate and shear rate gradient sites in the simulation. Furthermore, since the platelet availability for binding seems uninfluenced by the curvature, these effects might influence the binding mechanics rather than the probability. The presence of elongational flows is detected in the simulations and the link to increased platelet adhesion is discussed in the experimental results.

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Polymer-processing operations with dominating elongational flow have a great relevance, especially in several relevant industrial applications. Film blowing, fiber spinning and foaming are some examples in which the polymer melt is subjected to elongational flow during processing. To gain a thorough knowledge of the material-processing behavior, the evaluation of the rheological properties of the polymers experiencing this kind of flow is fundamental. This paper reviews the main achievements regarding the processing-structure-properties relationships of polymer-based materials processed through different operations with dominating elongational flow. In particular, after a brief discussion on the theoretical features associated with the elongational flow and the differences with other flow regimes, the attention is focused on the rheological properties in elongation of the most industrially relevant polymers. Finally, the evolution of the morphology of homogeneous polymers, as well as of multiphase polymer-based systems, such as blends and micro- and nano-composites, subjected to the elongational flow is discussed, highlighting the potential and the unique characteristics of the processing operations based on elongation flow, as compared to their shear-dominated counterparts.

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Fluid forces and their effects on cells have been researched for quite some time, especially in the realm of biology and medicine. Shear forces have been the primary emphasis, often attributed as being the main source of cell deformation/damage in devices like prosthetic heart valves and artificial organs. Less well understood and studied are extensional stresses which are often found in such devices, in bioreactors, and in normal blood circulation. Several microfluidic channels utilizing hyperbolic, abrupt, or tapered constrictions and cross-flow geometries, have been used to isolate the effects of extensional flow. Under such flow cell deformations, erythrocytes, leukocytes, and a variety of other cell types have been examined. Results suggest that extensional stresses cause larger deformation than shear stresses of the same magnitude. This has further implications in assessing cell injury from mechanical forces in artificial organs and bioreactors. The cells' greater sensitivity to extensional stress has found utility in mechanophenotyping devices, which have been successfully used to identify pathologies that affect cell deformability. Further application outside of biology includes disrupting cells for increased food product stability and harvesting macromolecules for biofuel. The effects of extensional stresses on cells remains an area meriting further study.

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von Willebrand Factor is a mechano-sensitive protein circulating in blood that mediates platelet adhesion to subendothelial collagen and platelet aggregation at high shear rates. Its hemostatic function and thrombogenic effect, as well as susceptibility to enzymatic cleavage, are regulated by a conformational change from a collapsed globular state to a stretched state. Therefore, it is essential to account for the conformation of the vWF multimers when modeling vWF-mediated thrombosis or vWF degradation. We introduce a continuum model of vWF unfolding that is developed within the framework of our multi-constituent model of platelet-mediated thrombosis. The model considers two interconvertible vWF species corresponding to the collapsed and stretched conformational states. vWF unfolding takes place via two regimes: tumbling in simple shear and strong unfolding in flows with dominant extensional component. These two regimes were demonstrated in a Couette flow between parallel plates and an extensional flow in a cross-slot geometry. The vWF unfolding model was then verified in several microfluidic systems designed for inducing high-shear vWF-mediated thrombosis and screening for von Willebrand Disease. The model predicted high concentration of stretched vWF in key regions where occlusive thrombosis was observed experimentally. Strong unfolding caused by the extensional flow was limited to the center axis or middle plane of the channels, whereas vWF unfolding near the channel walls relied upon the shear tumbling mechanism. The continuum model of vWF unfolding presented in this work can be employed in numerical simulations of vWF-mediated thrombosis or vWF degradation in complex geometries. However, extending the model to 3-D arbitrary flows and turbulent flows will pose considerable challenges.

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Improving the processability of ultrahigh molecular weight polyethylene (UHMWPE) and understanding the effect of the polymeric chain mobility has long been a challenging task. Herein, we show that UHMWPE without any processing aids can be processed at a lower temperature of 180 °C compared to conventional processing temperatures (~250 °C) under a continuous elongational flow (CEF) by using an eccentric rotor extruder (ERE). By probing the effect of the residence time of UHMWPE samples under a CEF on the morphology, rheological behavior and molecular orientation, we find that the long polymer chains of UHMWPE are apt to orientate under a consecutive volume elongational deformation, thereby leading to a higher residual stress for the extruded sample. Meanwhile, the residence time of samples can regulate the polymeric chain mobility, giving rise to the simultaneous decrease of the melting defects and residual stress as well as Hermans orientation function with increasing residence time from 0 to 60 s. This also engenders the enhanced diffusion of UHMWPE segments, resulting in a defect-free morphology and higher entanglement with lower crystallinity but without causing obvious thermal oxidative degradation of UHMWPE. This interesting result could originate from the fast chain entanglement and particle welding enabled by a desirably short residence time, which could be explained by the empirical, entropy-driven melting explosion mechanism.

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The continuous development of plasticizing conveying methods and devices has been carried out to meet the needs of the polymer processing industry. As compared to the conventional shear-flow-dominated plasticizing and conveying techniques, a new method for processing polymers based on elongational flow was proposed. This new method and the related devices such as vane extruders, eccentric rotor extruders and so on, exhibited multiple advantages including shorter processing time, higher mixing effectiveness, improved product performance and better adaptability to various material systems. The development of new techniques in the field of polymer material processing has opened up a broad space for the development of new plastic products, improved product performance and reduced processing costs. In this review, recent advances concerning the processing techniques based on elongational flow are summarized, and the broad applications in polymer processing as well as some future opportunities and challenges in this vibrant area are elucidated in detail.

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It is well known that the need for more environmentally friendly materials concerns, among other fields, the food packaging industry. This regards also, for instance, nets used for agricultural product (e.g., citrus fruits, potatoes) packaging. These nets are typically manufactured by film blowing technique, with subsequent slicing of the films and cold drawing of the obtained strips, made from traditional, non-biodegradable polymer systems. In this work, two biodegradable polymer systems were characterized from rheological, processability, and mechanical points of view, in order to evaluate their suitability to replace polyethylene-based polymer systems typically used for agricultural product net manufacturing. Furthermore, laboratory simulation of the above-mentioned processing operation paths was performed. The results indicated a good potential for biodegradable polymer systems to replace polyethylene-based systems for agricultural product packaging.

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INTRODUCTION: Pathological flows in patients with severe aortic stenosis are associated with acquired von Willebrand syndrome. This syndrome is characterized by excessive cleavage of von Willebrand factor by its main protease, A Disintegrin and Metalloproteinase with a Thrombospondin Type 1 Motif, Member 13 (ADAMTS13) leading to decreased VWF function and mucocutaneous bleeding. Aortic valve replacement and correction of the flow behavior to physiological levels reverses the syndrome, supporting the association between pathological flow and acquired von Willebrand syndrome. We investigated the effects of shear and elongational rates on von Willebrand factor cleavage in the presence of ADAMTS13. METHODS: We identified acquired von Willebrand syndrome in five patients with severe aortic stenosis. Doppler echography values from these patients were used to develop three computational fluid dynamic (CFD) aortic valve models (normal, mild and severe stenosis). Shear, elongational rates and exposure times identified in the CFD simulations were used as parameters for the design of microfluidic devices to test the effects of pathologic shear and elongational rates on the structure and function of von Willebrand factor. RESULTS: The shear rates (0-10,000s-1), elongational rates (0-1000 s-1) and exposure times (1-180 ms) tested in our microfluidic designs mimicked the flow features identified in patients with aortic stenosis. The shear and elongational rates tested in vitro did not lead to excessive cleavage or decreased function of von Willebrand factor in the presence of the protease. CONCLUSIONS: High shear and elongational rates in the presence of ADAMTS13 are not sufficient for excessive cleavage of von Willebrand Factor.

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Polyamide/polyolefin blends have gained attention from the academia and the industry for several years. However, in order to optimize their properties, some drawbacks such as chemical incompatibility must be adequately overcome. This can be done by adding suitable compatibilizers. On the other hand, it is less known that suitable processing techniques may also lead to significant results. In a previous work on a low-density polyethylene/polyamide 6 (LDPE/PA6) blend, we found that the orientation due to elongational flow processing conditions could lead to an unexpected brittle⁻ductile transition. In this work, this phenomenon was further investigated and the attention was mainly focused on the effects that processing can have on the morphology and, as a consequence, on the final properties of a polymer blends. With regard to LDPE/PA6 blend, an important result was found, i.e., the effects on the ductility induced by the elongational flow orientation are similar to those obtained by using an ethylene-glycidyl methacrylate compatibilizer.

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Despite the evolution of ventricular assist devices, ventricular assist device patients still suffer from complications due to the damage to blood by fluid dynamic stress. Since rotary ventricular assist devices are assumed to exert mainly shear stress, studies of blood damage are based on shear flow experiments. However, measurements and simulations of cell and protein deformation show normal and shear stresses deform, and potentially damage, cells and proteins differently. The aim was to use computational fluid dynamics to assess the prevalence of normal stress, in comparison with shear stress, in rotary ventricular assist devices. Our calculations showed normal stresses do occur in rotary ventricular assist devices: the fluid volumes experiencing normal stress above 10 Pa were 0.011 mL (0.092%) and 0.027 mL (0.39%) for the HeartWare HVAD and HeartMate II (HMII), and normal stresses over 100 Pa were present. However, the shear stress volumes were up to two orders of magnitude larger than the normal stress volumes. Considering thresholds for red blood cell and von Willebrand factor deformation by normal and shear stresses, the fluid volumes causing deformation by normal stress were between 2.5 and 5 times the size of those causing deformation by shear stress. The exposure times to the individual normal stress deformation regions were around 1 ms. The results clearly show, for the first time, that while blood within rotary ventricular assist devices experiences more shear stress at much higher magnitudes as compared with normal stress, there is sufficient normal stress exposure present to cause deformation of, and potentially damage to, the blood components. This study is the first to quantify the fluid stress components in real blood contacting devices.

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Graphene has been publicized as the game changing material of this millennium. To this day, scalable production leading to exceptional material properties has been difficult to attain. Most methods require harsh chemicals, which result in destroying the graphene surface. A method was developed, exploiting high speed elongational flow in a novel designed batch mixer; creating a distribution of pristine few to many layer graphene flakes. The method focuses on exfoliating in a molten polyamide 66 (PA66) matrix, creating a graphene reinforced polymer matrix composite (G-PMC). The process revealed that high speed elongational flow was able to create few layer graphene. Graphite exfoliation was found driven in part by diffusion, leading to intercalation of PA66 in graphite. The intercalated structure lead to increases in the hydrogen bonding domain, creating anisotropic crystal domains. The thermal stability of the G-PMC was found to be dependent to the degree of exfoliation, PA66 crystal structure and composite morphology. The aim of this research is to characterize uniquely produced graphene containing polymer matrix composites using a newly created elongational flow field. Using elongational flow, graphite will be directly exfoliated into graphene within a molten polymer.

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A simple theory of the unfolding kinetics of a semi-flexible polymer chain is presented in terms of a Kramers type picture for the energy of elongation. The hydrodynamic interactions are discussed in terms of slender body theory. It turns out that the elongation of the chain is basically linear in time and independent of the viscosity. The former prediction agrees with experiments on the stretching dynamics of DNA under planar elongational flow. Nevertheless, the theory overestimates the experimental rate by a significant amount for reasons that are unclear.

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The characterization of the extensional rheology of polymeric solutions is important in several applications and industrial processes. Filament stretching and capillary breakup rheometers have been developed to characterize the extensional properties of polymeric solutions, mostly for high-viscosity fluids. However, for low concentration polymer solutions, the measurements are difficult using available devices, in terms of the minimum viscosity and relaxation times that can be measured accurately. In addition, when the slow retraction method is used, solvent evaporation can affect the measurements for volatile solvents. In this work, a new setup was tested for filament breakup experiments using the slow retraction method, high-speed imaging techniques, and an immiscible oil bath to reduce solvent evaporation and facilitate particle tracking in the thinning filament. Extensional relaxation times above around 100 µs were measured with the device for dilute and semi-dilute polymer solutions. Particle tracking velocimetry was also used to measure the velocity in the filament and the corresponding elongation rate, and to compare with the values obtained from the measured exponential decay of the filament diameter.

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Remarkable combination of excellent gas barrier performance, high strength, and toughness was realized in polylactide (PLA) composite films by constructing the supernetworks of oriented and pyknotic crystals with the assistance of ductile in situ nanofibrils of poly(butylene adipate-co-terephthalate) (PBAT). On the basis that the permeation of gas molecules through polymer materials with anisotropic structure would be more frustrated, we believe that oriented crystalline textures cooperating with inerratic amorphism can be favorable for the enhancement of gas barrier property. By taking full advantage of intensively elongational flow field, the dispersed phase of PBAT in situ forms into nanofibrils, and simultaneously sufficient row-nuclei for PLA are induced. After appropriate thermal treatment with the acceleration effect of PBAT on PLA crystallization, oriented lamellae of PLA tend to be more perfect in a preferential direction and constitute into a kind of network interconnecting with each other. At the same time, the molecular chains between lamellae tend to be more extended. This unique structure manifests superior ability in ameliorating the performance of PLA film. The oxygen permeability coefficient can be achieved as low as 2 × 10(-15) cm(3) cm cm(-2) s(-1) Pa(-1), combining with the high strength, modulus, and ductility (104.5 MPa, 3484 MPa, and 110.6%, respectively). The methodology proposed in this work presents an industrially scalable processing method to fabricate super-robust PLA barrier films. It would indeed push the usability of biopolymers forward, and certainly prompt wider application of biodegradable polymers in the fields of environmental protection such as food packaging, medical packaging, and biodegradable mulch.

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