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Abstract: This study has been dedicated to the foaming of modified poly (lactic acid) with supercritical CO2. The first part of this work consisted in a rheological modification of neat PLA through chain extension. Improvement of the melt viscosity and elasticity has been achieved by the use of an epoxy additive during a reactive extrusion process. Rheological characterizations confirmed an increase of the melt strength due to this chain extension process. Foaming was then performed on the neat and modified PLAs using a batch process with supercritical CO2 as blowing agent. The investigation of the foaming temperature revealed an enlarged processing window for modified PLAs compared to neat PLA. Depending on the foaming parameters, foams with a cellular structure ranging from macro scale to micro scale have been obtained. A concomitant effect of the CO2-plasticization and the crystallisation on the melt rheology could explain this wide range of cellular morphologies. [Copyright &y& Elsevier]

Polycaprolactone/nano-hydroxylapatite (PCL/nHA) nanocomposites have found use in tissue engineering and drug delivery owing to their good biocompatibility with these types of applications in addition to their mechanical characteristics. Three-dimensional (3D) printing of PCL/nHA nanocomposites persists as a defiance mostly because of the lack of commercial filaments for the conventional fused deposition modeling (FDM) method. In addition, as the composites are prepared using FDM for the purpose of delivering pharmaceuticals, thermal energy can destroy the embedded drugs and biomolecules. In this report, we investigated 3D printing of PCL/nHA using a lab-developed solution-extrusion printer, which consists of an extrusion feeder, a syringe with a dispensing nozzle, a collection table, and a command port. The effects of distinct printing variables on the mechanical properties of nanocomposites were investigated. Drug-eluting nanocomposite screws were also prepared using solution-extrusion 3D printing. The empirical outcomes suggest that the tensile properties of the 3D-printed PCL/nHA nanocomposites increased with the PCL/nHA-to-dichloromethane (DCM) ratio, fill density, and print orientation but decreased with an increase in the moving speed of the dispensing tip. Furthermore, printed drug-eluting PCL/nHA screws eluted high levels of antimicrobial vancomycin and ceftazidime over a 14-day period. Solution-extrusion 3D printing demonstrated excellent capabilities for fabricating drug-loaded implants for various medical applications. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study has been to gain a fundamental understanding of the mechanisms and conditions governing thermal degradation of poly (lactic acid) (PLA), poly (butylene-adipate-co-terephtalate) (PBAT) and their blends upon processing conditions. Thermal degradation of biodegradable PLA and PBAT was investigated firstly by thermal analysis and size-exclusion chromatography (SEC). It is shown that neat polymers degrade upon processing hence the decrease of the molecular weight, rheological and mechanical properties. Secondly, the reactive extrusion of polymers was performed with various amounts of chain extension/branching agent, containing nine Glycidyl methacrylate (GMA) functions, named Joncryl. The incorporation of this multi-functional oligomer showed an improvement of their thermal stability. SEC and intrinsic viscosity measurements of these modified PLA and PBAT confirmed the increase of viscosity and molecular weight probably related to the formation of extended and branched chains. Rheological investigation of extended/branched PLA and PBAT as well as their modified PLA/PBAT (80/20) (wt/wt) blends with various concentrations of GMA reactive functions exhibited higher viscosity and storage modulus compared to the unmodified samples. This increase becomes more pronounced as the concentration of Joncryl increases. Viscoelastic properties were assessed and related to the molecular structure of modified polymers. Hence, the mechanisms of degradation, chain extending with GMA functions and their competition have been proposed. The effect of reactive compatibilization on the PLA/PBAT blends has been confirmed using transmission electron microscopy (TEM), scanning electron microscopy (SEM) observations and tensile tests by the improvement of phase dispersion and the increase of both Young''s modulus and strain at break. [Copyright &y& Elsevier]

The diffusion process in the molten state at a polymer/polymer interface of symmetrical and model bilayers has been investigated using a small-amplitude oscillatory shear measurement. The polymers employed in this study were poly (vinylidene fluoride) (PVDF) and poly (methyl methacrylate) (PMMA) of varying molecular weights and polydispersities. The measurements were conducted in the linear viscoelastic regime (small deformations) so as to decouple the effect of flow from the diffusion. The focus of this paper has been to investigate the effects of healing time, angular frequency ( ω), temperature, and molecular weight on the inter-diffusion and the triggered interphase between the neighboring layers. The kinetics of diffusion, based on the evolution of the apparent diffusion coefficient ( D) versus the healing time, was experimentally obtained. The transition from the non-Fickian to the normal Fickian region for the inter-diffusion at the interface was clearly observed, qualitatively consistent with the reptation model, but it occurred at a critical time greater than the reptation time ( τ). In non-Fickian region, effects of frequency and temperature were studied with regard to the ratio of the apparent diffusion coefficient to the self-diffusion coefficient ( D/ D). The D determined in the Fickian region was found to be consistent with Graessley's model as well as with the literatures. And the dependence of the D on the frequency agreed well with the Doi-Edwards theory, in particular, scaling as $D_{\rm s} \sim \omega^{1/2}$ at ω > 1/ τ and $D_{\rm s} \sim \omega^{0}$ at ω < 1/ τ. Our experimental results also confirmed that the dependence of the D on the temperature for PMMA and PVDF can be well described by the Arrhenius law. Moreover, blends of PMMAs have been proposed in order to be able to change the $\overline M_\emph{w} $. The rheological investigations of these corresponding bilayers rendered it possible to monitor the effect of $\overline M_\emph{w} $ on the diffusion process. The obtained results gave $D_{\rm s} \sim \overline M_\emph{w}^{-1}$, thus corroborating some earlier studies and some experimental results recently reported by Time-Resolved Neutron Reflectivity Measurements. Lastly, the thickness of the interphase and its corresponding viscoelastic properties could be theoretically determined as a function of the healing time. [ABSTRACT FROM AUTHOR]

The aim of the present work is to examine the effect of the rheological behaviour and surface properties on the sintering of various polymers. Model polymers, liquid at room temperature and commercials materials with different viscosities and structures are used. Zero-shear viscosities and relaxation times are extracted from rheological curves. The surface tension of the materials is measured by the sessile drop method when possible. The sintering of two particles put in close vicinity is recorded using a CCD camera at regular intervals time. Two substrates with different surface tension are employed. The effects of viscosity, surface tension and relaxation time on the sintering kinetics are discussed. [ABSTRACT FROM AUTHOR]

Abstract: This paper describes the experimental investigation of the interdiffusion/reaction mechanisms of asymmetric polymer–polymer interfaces. The study deals with the assessment of the chemical reactions occurring at the interface between two reactive polymers. A focal point of the investigation was to study these interfacial reactions by an array of techniques at very different space scales: from macroscopic viscoelastic investigations to IR and NMR spectroscopies at the molecular scale. The studied material pairs include PE-GMA/PA6 as the reactive system (RS) and PE/PA6 as the non-reactive one (NRS) – of coextruded multilayer polymers, i.e., after processing. The linear viscoelastic properties of the reactive multilayer systems were determined and the mechanisms were analyzed by NMR and FTIR measurements. Substantial reactions occurred during the rheological measurements and the results indicated the preferential formation of a copolymer at the interface, triggered by the neighboring layers. Moreover, the contribution of an interface/interphase effect was investigated along with the increase in the number of layers. The results showed that the variation in dynamic modulus of the multilayer system was a result of both diffusion and chemical reaction. Specific experiments were carried out to follow-up on the physicochemical phenomena, and the results were rationalized by comparing the obtained data with theoretical models. The effect of this interphase was quantified at a specific welding time and oscillation frequency thanks to rheological modeling. Because of the coupling between rheology and spectroscopical tools, potential reactions between the GMA functions and the amine/carboxylic polyamide chain ends were explored. The results highlighted that the main reaction mechanism was constituted by the crosslinking reaction between the GMA and carboxylic acid units, and not by that between GMA and amine end functions. [Copyright &y& Elsevier]

To increase the lifetime of metallic molds and protect their surface from wear, a fluorinated ethylene propylene (FEP) polymer was coated onto a stainless-steel (SS304) substrate, using an air spray process followed by a heat treatment. The microstructural properties of the coating were studied using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) as well as X-ray diffraction. The mechanical properties and adhesion behavior were analyzed via a nanoindentation test and progressive scratching. According to the results, the FEP coating had a smooth and dense microstructure. The mechanical properties of the coatings, i.e., the hardness and Young's modulus, were 57 ± 2.35 and 1.56 ± 0.07 GPa, respectively. During scratching, successive delamination stages (initiation, expansion, and propagation) were noticed, and the measured critical loads LC1 (3.36 N), LC2 (6.2 N), and LC3 (7.6 N) indicated a high adhesion of the FEP coating to SS304. The detailed wear behavior and related damage mechanisms of the FEP coating were investigated employing a multi-pass scratch test and SEM in various sliding conditions. It was found that the wear volume increased with an increase in applied load and sliding velocity. Moreover, the FEP coating revealed a low friction coefficient (around 0.13) and a low wear coefficient (3.1 × 10−4 mm3 N m−1). The investigation of the damage mechanisms of the FEP coating showed a viscoelastic plastic deformation related to FEP ductility. Finally, the coating's resistance to corrosion was examined using electrochemical measurements in a 3.5 wt% NaCl solution. The coating was found to provide satisfactory corrosion protection to the SS304 substrate, as no corrosion was observed after 60 days of immersion. [ABSTRACT FROM AUTHOR]

Abstract: The evolution of the coefficient of thermal expansion (CTE) of a thermosetting polymer during cure reaction is an important parameter for industrial applications such as composite processing since it influences the development of internal stresses in the material. The CTE being almost impossible to measure on a reacting thermoset, we propose to use an indirect method based on the modelling of ionic conductivity by a modified WLF equation, allowing to calculate the evolution of CTE from dielectric spectroscopy measurements. This method is applied to a dicyanate ester thermosetting polymer, leading to encouraging results both qualitatively and quantitatively. [Copyright &y& Elsevier]

In a previous paper, the kinetic behavior of a cyanate ester trimerization was studied. In this paper, the thermophysical properties (heat capacity, thermal conductivity) are measured and modeled (as a function of temperature and conversion) for the neat resin and for a glass fibers composite. These models (thermophysical and kinetics) are used to simulate the thermal transfers in an instrumented heated mold. The calculated local temperatures and surface heat fluxes appear to be in very good agreement with measurements, for both the neat resin and the composite. [Copyright &y& Elsevier]

The multilayer coextrusion process is known to be a reliable technique for the continuous fabrication of high-performance micro-/nanolayered polymeric products. Using laminar flow conditions to combine polymer pairs, one can produce multilayer films and composites with a large number of interfaces at the polymer-polymer boundary. Interfacial phenomena, including interlayer diffusion, interlayer reaction, interfacial instabilities, and interfacial geometrical confinement, are always present during multilayer coextrusion depending on the processed polymers. They are critical in defining the microstructural development and resulting macroscopic properties of multilayered products. This paper, therefore, presents a comprehensive review of these interfacial phenomena and illustrates systematically how these phenomena develop and influence the resulting physicochemical properties. This review will promote the understanding of interfacial evolution in the micro-/nanolayer coextrusion process while enabling the better control of the microstructure and end use properties. [ABSTRACT FROM AUTHOR]

This paper is dealing with the polyisobutylene (PIB) migration phenomenon through the post-consumer agricultural waste multilayer films based on four linear low-density polyethylene (LLDPE) matrices. Through this work, a bridge between shear, elongational rheology, and tack surface properties was revealed on both model and recycled blends. Hereto, effects of aging time and temperature were investigated and rationalized depending on the short- and long-chain branching in LLDPE matrices as well their polyethylene (PE) crystallization. The linear viscoelastic properties were influenced despite the small PIB amounts. This migration influenced also the slippage in steady flow regime. It was also demonstrated that transient uniaxial extensional properties are very sensitive in the presence of PIB, which seems to hold back the PE strain hardening properties. Therefore, the axial force and the surface friction coefficient were determined and discussed in correlation with bulk rheological findings. Hence, the obtained results contributed to unveiling new insights on the physical mechanisms governing the PIB migration with or without fillers to inhibit its migration in their recycled films. [ABSTRACT FROM AUTHOR]

Multilayered polymer films are increasingly used in the daily life, but their macroscopic properties are always limited by the layer–layer interfacial compatibility. In this work, the influence of interface modification through in situ layer–layer interfacial reaction during a multilayered assembly is revealed from micro‐ to nanolayer films, based on maleated poly(vinylidene fluoride) and polyamide‐6. In the presence of interfacial reaction and confinement, layer architecture and microstructure are highly dependent on the number of layers. Specifically, for nanolayer films having smaller layer thicknesses and higher reaction extent, layer integrity is reduced with the occurrence of interfacial instabilities. Depending on the microstructural evolution from multilayer assembly, those films exhibit quantitatively different extensional rheological and dielectric properties from micro‐ to nanolayers. More importantly, dielectric spectroscopy reveals the contribution of copolymer‐rich interphases to the dielectric performance of micro/nanolayered films. Additionally, charge transport dynamics in nanolayered films also differ significantly from their microlayered counterparts. They are attributed to the strong dependence of interfacial reaction extent and resulting microstructure on the number of layers and layer thicknesses. This work clearly illustrates how the control of layer–layer interfacial reaction in micro/nanolayer assembly can tune the interfacial, microstructure, and macroscopic properties of multilayered products. [ABSTRACT FROM AUTHOR]

[Display omitted] • Flexible polymer PENGs were prepared with interface-engineered PVDF/CNTs nanofibers. • PVDF- g -MA stabilized electrospinning flow to yield defect-free composite nanofibers. • Interfacial anchoring of PVDF- g -MA promoted electroactive β -phase in PVDF matrix. • A small amount of PVDF- g -MA boosted piezoelectric outputs (10.6 V, 3.15 µW/cm2) • Our strategy enhanced PENG with preserved flexibility avoiding excessive filler use. Polymeric piezoelectric nanogenerators (PENGs) hold great promise for flexible energy harvesters and self-powered sensors. However, achieving high piezoelectricity in inherently piezoelectric polymers while maintaining their flexibility remains a challenge. Herein, we propose a simple yet effective approach to fabricate flexible and cost-effective PENGs based on interface-engineered composite nanofibers of poly(vinylidene fluoride) (PVDF)/carbon nanotubes (CNTs) using electrospinning. Our strategy involves the incorporation of a tailor-made interfacial coupling agent, maleic anhydride grafted PVDF (PVDF- g -MA), onto PVDF/CNTs interfaces. This mild interface-engineering strategy not only promotes interfacial interactions within composites but also stabilizes electrospinning flow jets, yielding defect-free nanofibers. More importantly, the interfacial anchoring of PVDF- g -MA molecules promotes the preferential crystallization of electroactive β -phase within PVDF matrix. By incorporating a small quantity of PVDF- g -MA (up to 1.0 wt%), our approach significantly enhances piezoelectric outputs while preserving flexibility. This eliminates the need for excessive nanofiller usage that can sacrifice the flexibility associated with conventional methods. Remarkably, the resulting composite nanofiber-based PENGs exhibit excellent piezoelectric performance, generating high output voltages (10.6 V) and remarkable power density (3.15 µW/cm2) under tiny force stimuli. Our findings open new avenues for efficient and scalable fabrication of polymeric piezoelectric nanogenerators for flexible and wearable energy harvesting and self-powered sensing applications. [ABSTRACT FROM AUTHOR]

Abstract: The TEMPO-mediated oxidation of date palm lignocellulosic fibers (DPLF) from Phoenix dactylifera – i.e. cellulosic fibers still containing their initial lignin and hemicellulose components – was performed under conditions leading to a high degree of oxidation. The resulting carboxylated fibers were shown to still contain high residual contents of lignin (12%, w/w) and hemicelluloses (34%, w/w). The ultrastructure of the oxidized DPLF was revealed by scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopy. These techniques not only confirmed the surface carboxylation of the DPLF, but also gave some insight on the oxidation heterogeneity when going from the surface to the core of the fibers. Finally, in relation with the chemical data and the morphology of the substrate, it has been possible to propose a heterogeneous oxidation kinetic model, which was applied with success not only to DPLF but also to the cellulose whiskers extracted from the rachis of the palm from P. dactylifera. [Copyright &y& Elsevier]

Poly (lactic acid) is an industrially mature, bio-sourced and biodegradable polymer. However, current applications of this eco-friendly material are limited as a result of its brittleness and its poorly melt properties. One of the keys to extend its processing window is to melt strengthen the native material. This paper considers the chain extension as a valuable solution for reaching such an objective. An additive based on epoxy-functionalized PLA was employed during reactive extrusion. The reaction times as a function of chain extender ratios were determined by monitoring the melt pressure during recirculating micro-extrusions. Once residence times were optimized, reactive extrusion experiments were performed on a twin screw extruder. Size exclusion chromatography provided information about the molecular weight distributions (MWD) of the modified PLAs and revealed the creation of a high molecular weight shoulder. The rheological experiments highlighted the enhancement of the melt properties brought about by the chain extension. Shear rheology revealed some enlarged and bimodal relaxation time spectra for the extended materials which are in accordance with the MWD analysis. Such a modification directly amplified the shear sensitivity of modified PLAs. Regarding the rheological temperature sensitivity, it was found to be decreased when the chain extender content is raised as shown from the Arrhenius viscosity fit. The reduction of the polar interactions from neat to highly chain-extended PLAs is here proposed to explain this surprising result. Chain extension was also found to impact on the elongational melt properties where strain hardening occurred for modified PLAs. Investigation of the chain extension architecture was made from the rheological data and revealed a long-chain branched topology for the modified PLAs. [ABSTRACT FROM AUTHOR]

At the present time, the rheology of sheet moulding compounds (SMC) during forming is not well known. In order to provide better experimental data, an experimental program was carried out as a result of the development of a new rheometer especially dedicated to this kind of material. Homogeneous simple compression and simple shear tests are presented. They allow the evaluation of the influence of the main parameters on the SMC behaviour: strain rate, temperature and fibre fraction. It is shown that the SMC can be considered as a strongly anisotropic non-linear viscous medium. [Copyright &y& Elsevier]

The development of new interfacial rheological setup (IRS) for characterizing the interfacial viscoelastic properties of polymer systems is a subject of growing interest and constitutes a well-known challenge of high scientific and industrial application value. Recently, biconical and double-wall Ring (DWR) devices that can easily be attached to standard rheometers have been marketed for this purpose, but measurements must be made below 70 °C to ensure a stable homogeneous temperature at the interface. Meanwhile each device has its own limitation: the bicone has high inertia and a relatively low Boussinesq number, giving it a low signal-to-noise ratio, while the DWR is too fragile to probe the interfaces of high viscous systems in the molten state. Currently, to predict the dynamic interfacial properties of molten polymer systems, the interfacial rheology characterization is based mainly on indirect methods such as numerical modeling. In this study, a novel high temperature resistant interfacial rheology cell has been developed. This new setup allows direct interfacial rheology measurements up to 200 °C with temperature gradients of 1 °C at the polymer-polymer interface. To validate this new IRS device, the surface/interfacial properties of different model fluids having different well-known structure and viscoelastic characteristics have been investigated. To enable a more sensitive measurement of interfacial rheological properties, lightweight titanium based biconical geometry was newly designed. The effect of the molecular weight and the temperature was highlighted. Finally, the interfacial rheology testing of molten semicrystalline polymer systems has been achieved for the first time. The measured apparent interfacial shear properties in both oscillatory and steady flow modes were carefully corrected, considering the contribution of the bulk-subphases during processing of the numerical data. • Custom design of a lightweight biconical fixture enables a more sensitive measurement of interfacial rheological properties. • A novel interfacial rheology cell allows measurements up to 200 °C with temperature gradients of 1 °C at the sample interface. • At a constant temperature, the more the viscosity of the subphases increased, the more the interfacial viscosity increased. • For low-viscosity systems, the interfacial moduli (and the interfacial viscosity) decreased when the temperature increased. • For molten semi-crystalline polymer subphases, increasing temperature and viscosity allow the formation of an interphase. [ABSTRACT FROM AUTHOR]

Poly(l-lactide-co-d,l-lactide) PDLA/45S5 Bioglass® (BG) composites for medical devices were developed using an original approach based on a thermal treatment of BG prior to processing. The aim of the present work is to gain a fundamental understanding of the relationships between the morphology, processing conditions and final properties of these biomaterials. A rheological study was performed to evaluate and model the PDLA/BG degradation during processing. The filler contents, as well as their thermal treatments, were investigated. The degradation of PDLA was also investigated by Fourier transform infrared (FTIR) spectroscopy, size-exclusion chromatography (SEC) and mechanical characterization. The results highlight the value of thermally treating the BG in order to control the degradation of the polymer during the process. The present work provides a guideline for obtaining composites with a well-controlled particle dispersion, optimized mechanical properties and limited degradation of the PDLA matrix. [ABSTRACT FROM AUTHOR]

This paper describes a future-oriented approach for the valorization of polyethylene-based multilayer films. The method involves going from eco-design to mechanical recycling of multilayer films via forced assembly coextrusion. The originality of this study consists in limiting the number of constituents, reducing/controlling the thickness of the layers and avoiding the use of tie layers. The ultimate goal is to improve the manufacturing of new products from recycled multilayer materials by simplifying their recyclability. Within this framework, new structures were developed with two polymer systems: polyethylene/polypropylene and polyethylene/polystyrene, with nominal micro- and nanometric thicknesses. Hitherto, the effect of the multi-micro/nanolayer architecture as well as initial morphological and mechanical properties was evaluated. Several recycling processes were investigated, including steps such as: (i) grinding; (ii) monolayer cast film extrusion; or (iii) injection molding with or without an intermediate blending step by twin-screw extrusion. Subsequently, the induced morphological and mechanical properties were investigated depending on the recycling systems and the relationships between the chosen recycling processes or strategies, and structure and property control of the recycled systems was established accordingly. Based on the results obtained, a proof of concept was demonstrated with the eco-design of multi-micro/nanolayer films as a very promising solution for the industrial issues that arise with the valorization of recycled materials. [ABSTRACT FROM AUTHOR]

An understanding of the structural evolution in micro-/nano-layer co-extrusion process is essential to fabricate high-performance multilayered products. Therefore, in this work, we reveal systematically the multiscale structural development, involving both the layer architecture and microstructure within layers of micro-/nano-layer coextruded polymer films, as well as its relationship to dielectric properties, based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/polycarbonate (PC) system. Interestingly, layer architecture and morphology show strong dependences on the nominal layer thicknesses. Particularly, with layer thickness reduced to nanometer scale, interfacial instabilities triggered by viscoelastic differences between components emerge with the creation of micro-droplets and micro-sheets. Films show an enhanced crystallization with the formation of two-dimensional (2D) spherulites in microlayer coextruded systems and the oriented in-plane lamellae in nanolayer coextruded counterparts, where layer breakup in the thinner layers further changes the crystallization behaviors. These macro- and microscopic structures, developed from the co-extrusion process, substantially influence the dielectric properties of coextruded films. Mechanism responsible for dielectric performance is further proposed by considering these effects of multiscale structure on the dipole switching and charge hopping in the multilayered structures. This work clearly demonstrates how the multiscale structural evolution during the micro-/nano-layer coextrusion process can control the dielectric properties of multilayered products. [ABSTRACT FROM AUTHOR]

The present work has aimed at gaining a deeper understanding of the effects of shear flow on the behaviors of nano filler evolution inside linear and long chain branched polymer matrices. Accordingly, measurements consisting of transient start-up shear rheology coupled with small amplitude oscillatory sweep (SAOS) and dielectric tests were designed. Linear polypropylene (PPC) and polypropylene (PPH) with long chain branching (LCB) were chosen as the polymer matrices and carbon nanotubes (CNTs) as the nanofillers. The percolation threshold of the LCB PPH nanocomposites was found to be higher than for linear PPC, due to the high viscosity and elasticity of LCB PPH. A transient shear with different shear rates was imposed on the composites after which SAOS and electrical conductivity measurements were conducted. The liquid-solid transitions of the nanocomposites were found to be different and to depend on the shear flow conditions (shear rate). For the linear PPC, higher shear rates caused the filler network to break down while lower shear rates helped the nanofillers to agglomerate. Interestingly, for LCB PPH, both higher and lower pre-shear rates resulted in the breakup of the filler networks, which was due to the restricted mobility of the CNTs by the LCB. The confinement of the polymer chains to the CNTs and their aggregates made it difficult for the fillers to move thus causing the formed network to be easily destroyed even under slow and slight shears. Similarly, the trend was also found after shear flows as reflected by the increase and decrease of electrical conductivities.

The objective of the present study was to investigate multiphase systems based on polylactic acid (PLA) and polyamide 11 (PA11) from blends to multilayers. Firstly, PLA/PA11 blends compatibilized with a multifunctionalized epoxide, Joncryl, were obtained through reactive extrusion, and the thermal, morphological, rheological, and mechanical behaviors of these materials were investigated. The role of Joncryl as a compatibilizer for the PLA/PA11 system was demonstrated by the significant decrease in particle size and interfacial tension as well as by the tensile properties exhibiting a ductile behavior. Based on these findings, we were able to further clarify the effects of interdiffusion and diffuse interphase formation on the structure, rheology, and mechanics of compatible multilayered systems fabricated with forced-assembly multilayer coextrusion. The results presented herein aim to provide a deeper understanding of the interfacial properties, including the rheological, mechanical, and morphological behaviors, towards the control of the interface and confinement in multilayer polymers resulting from coextrusion, and also to permit their use in advanced applications.

This paper investigates the biaxial stretchability of polylactic acid (PLA)/poly (butylene adipate co-terephthalate) (PBAT)/thermoplastic cereal flour (TCF) ternary blends with a PLA/PBAT ratio close to 60/40 and a constant TCF content. A twin-screw extrusion process was used to gelatinize the starch and devolatilize the water in order to obtain a water-free TCF, which was then blended into a compatibilized or non-compatibilized PLA/PBAT matrix, introduced in the molten state. These blends were subsequently cast into sheets and biaxially drawn using a biaxial laboratory stretcher. The prepared ternary blends were found to present a typical ductile behavior. Scanning electron micrography highlighted dispersion and adhesion properties in the PLA/PBAT/TCF blends, where two different phases were observed. Moreover, the addition of the thermoplastic cereal flour did not significantly affect the biaxial stretchability of the PLA/PBAT blends but was found to lower the maximum stress before breaking. The modification of the interfacial tension between PLA and PBAT with the compatibilizer Joncryl before mixing with TCF had no effect on the durability of the PLA/PBAT/TCF sheet. Still, it slightly increased the maximum of nominal stress before failure.

The incorporation of bioactive and biocompatible fillers improve the bone cell adhesion, proliferation and differentiation, thus facilitating new bone tissue formation upon implantation. During these last 20 years, those biocomposites have been explored for making complex geometry devices likes screws or 3D porous scaffolds for the repair of bone defects. This review provides an overview of the current development of manufacturing process with synthetic biodegradable poly(α-ester)s reinforced with bioactive fillers for bone tissue engineering applications. Firstly, the properties of poly(α-ester), bioactive fillers, as well as their composites will be defined. Then, the different works based on these biocomposites will be classified according to their manufacturing process. New processing techniques, particularly additive manufacturing processes, open up a new range of possibilities. These techniques have shown the possibility to customize bone implants for each patient and even create scaffolds with a complex structure similar to bone. At the end of this manuscript, a contextualization exercise will be performed to identify the main issues of process/resorbable biocomposites combination identified in the literature and especially for resorbable load-bearing applications.

The purpose of the present work was to gain a fundamental understanding of how the composition and physico-chemical properties affect the rheology, morphology, miscibility, and thermal stability of poly(lactic acid) (PLA)-poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) biopolymer blends obtained by melt mixing. First, restricted processing conditions were chosen, due to the inherent thermal degradation of PHBV, as proven by rheological dynamic time sweep (DTS) measurements and size-exclusion chromatography (SEC). Based on this, the composition dependence of the blends was investigated using small-amplitude oscillatory shear rheology (SAOS), and the results were confirmed by scanning electron microscopy (SEM) analysis. Subsequently, the changes in glass transition temperatures (T g s) from the molten to the solid state, as observed by DMA and DSC, were verified by coupling SAOS to dielectric relaxation spectroscopy (DRS). Herein, the thermo-rheological complexity of PLA/PHBV blends in the melt was revealed, especially for PLA-rich blends. Irregularly structured morphologies, caused by highly mismatched viscoelastic properties, illustrated the degree of partial miscibility. Moreover, the thermo-rheological complexity appeared in the molten state of the asymmetric PLA-rich phases could be correlated to the crystal-amorphous interfacial MWS polarization, because of the locally-induced phase separation and heterogeneity, and owing to the differences in their crystallization properties during cooling. The miscibility also suffered from the lower thermal stability of PLA and the even more unstable PHBV. Nevertheless, the melt-induced degradation process of the PLA/PHBV blends seemed to be responsible for some of the in situ self-compatibilization and plasticization mechanisms. As a result, the miscibility and thermo-rheological simplicity were improved for the intermediate and PHBV-rich compositions at low temperatures, since their properties were, to a large extent, governed by the significant degradation of PHBV. The present findings should increase the understanding of morphological changes in PLA/PHBV blends and help control their micro/nanostructure.

This study proposed a 3D-printed PEEK with a specific design to restore the damaged orbit shape. Such printed personalized implants are greatly affected by the process parameters, wherefore the effects of the nozzle temperatures, printing speed and layer thickness on the tensile properties were investigated based on the Taguchi approach. The optimal mechanical properties, i.e., the tensile strength and Young's modulus, were found to be 54.97 MPa and 2.67 GPa, respectively. These properties were obtained by adjusting the nozzle temperature to its high level (450 °C), while the layer thickness (0.1 mm) and printing speed (20 mm/s) were set to their low levels. Secondly, the mechanical behavior of a personalized orbital implant with these optimized properties was evaluated via finite elements analysis with various infill patterns and densities, at three thicknesses: 0.3, 0.5 and 0.7 mm. It was found that all thicknesses were acceptable for the 100% filling. For the honeycomb pattern, the thicknesses 0.5 and 0.7 mm were satisfactory with a fill rate of 70% and 55% whereas only the thickness of 0.7 mm was suitable for the 40% filling. The honeycomb pattern with 40% filling and a maximum stress (7.186 MPa) and strain (0.00627 mm) should be beneficial for light-weight orbital implants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The study of the viscoelastic properties of polymer systems containing huge internal two-dimensional interfacial areas, such as blends, foams and multilayer films, is of growing interest and plays a significant role in a variety of industrial fields. Hence, interfacial rheology can represent a powerful tool to directly investigate these complex polymer-polymer interfaces. First, the current review summarizes the theoretical basics and fundamentals of interfacial shear rheology. Particular attention has been devoted to the double-wall ring (DWR), bicone, Du Noüy ring and oscillating needle (ISR) systems. The measurement of surface and interfacial rheological properties requires a consideration of the relative contributions of the surface stress arising from the bulk sub-phases. Here, the experimental procedures and methodologies used to correct the numerical data are described considering the viscoelastic nature of the interface. Second, the interfacial dilational rheology is discussed, starting with the theory and underlying principles. In particular, the Langmuir trough method, the oscillating spinning drop technique and the oscillating pendant drop technique are investigated. The major pioneering studies and latest innovations dedicated to interfacial rheology in both shear and dilatation-compression are highlighted. Finally, the major challenges and limits related to the development of high-temperature interfacial rheology at the molten state are presented. The latter shows great potential for assessing the interfaces of polymer systems encountered in many high-value applications.

In a circular economy context with the dual problems of depletion of natural resources and the environmental impact of a growing volume of wastes, it is of great importance to focus on the recycling process of multilayered plastic films. This review is dedicated first to the general concepts and summary of plastic waste management in general, making emphasis on the multilayer films recycling process. Then, in the second part, the focus is dealing with multilayer films manufacturing process, including the most common materials used for agricultural applications, their processing, and the challenges of their recycling, recyclability, and reuse. Hitherto, some prospects are discussed from eco-design to mechanical or chemical recycling approaches.

It is known that the macroscopic properties of multilayer polymer films are largely dominated by the diffuse interphase formed via interfacial diffusion between neighboring layers. However, not much is known about the origin of this effect. In this work, we reveal the role of interfacial diffusion and the diffuse interphase development in multilayer polymer films, based on a compatible poly(vinylidene fluoride)/poly(methyl methacrylate) system fabricated by forced-assembly micro-/nanolayer coextrusion. Interestingly, the layer morphology is found to prevail in all investigated multilayer films, even for the nanolayered system where the interdiffusion is substantial. It is also demonstrated that, in the presence of macromolecular and geometrical confinements, interfacial diffusion significantly alters the crystalline morphology and microstructure of the resulting micro-/nanolayered films, which leads to quantitatively different dielectric and rheological properties. More importantly, the combination of dielectric relaxation spectroscopy and energy-dispersive X-ray analysis further reveals that multiple diffuse interphases with various length scales exist in the multilayer structures. The presence of these multiple interphases is explained in terms of a proposed physical picture for the interdiffusion of fast-mode mechanism occurring in the coextrusion process, and their length scales (i.e., interphase thicknesses) are further mapped quantitatively. These findings provide new insights into the effects of interfacial diffusion and diffuse interphases toward tailoring interfaces/interphases in micro-/nanolayered polymer structures and for their advanced applications.

We provide rheological and dynamic insights into the role of an in situ reactive interphase with graft copolymers in multilayered polymer systems, using a polyamide-6 (PA6)/maleic anhydride grafted poly(vinylidene fluoride) (PVDF-g-MAH) bilayer as a model. Firstly, the influence of the reactive interphase on macroscopic melt flow behavior was studied. The in situ generated interphase from coupling reactions in bilayers significantly contributed to overall viscoelastic responses in both linear and nonlinear regimes. Specifically, under fast extensional flows, the reactively healed bilayer showed enhanced strain hardening mainly due to the formed graft copolymers in the interphase. Secondly, the evolution of a reactive interphase and its effects on microscopic dynamics and structural properties were further probed using dielectric relaxation spectroscopy (DRS). Interestingly, the reactive interphase drastically altered the dielectric responses of the bilayer upon healing, manifesting in the distinct interfacial relaxation/polarization. The relaxation strength of the interfacial polarization increased linearly as a function of reaction time, and was further improved by increasing the number of layers. In agreement with the rheology, DRS also demonstrated the retarded microscopic dynamics of a reactive interphase in healed bilayers. Using the dielectric molecular relaxation spectrum as a probe for the structure, the effects of the reactive interphase on charge dynamics and the resulting structural properties of bilayers were further evaluated. These findings are aimed at providing a better understanding of the effects of the reactive interphase on rheology, dynamics and dielectric properties, towards controlling the interface/interphase in multi micro-/nano-layered polymer structures and for further applications.

An effort was made to demonstrate the dynamic heterogeneity of poly(methyl methacrylate) (PMMA)/poly(vinylidene fluoride) (PVDF) blends, where its composition dependence and the role of interphase were probed. Firstly, the composition dependence of thermorheological complexity of PMMA/PVDF blends in the melt was revealed. The molecular entanglement state involving intra- and interchain entanglements was found to govern the scenario of thermorheological complexity. Intriguingly, local heterogeneity was further demonstrated to exist in the melt-state blends with intermediate compositions, and its origin was depicted to be the interphase. The interphase, coupled with unfavourable interchain entanglements in those blends, could explain the reduced viscosity and speed-up relaxations, contributing to the overall thermorheological complexity. Besides, two experimental glass transition temperatures of blends were resolved in view of segment motions in the miscible phase and the crystal-amorphous interphase, and further assessed via the "self-concentration" concept. The presence of a crystal-amorphous interphase, likely leading to three distinct dynamics of segments in blends, was supposed to contribute to the dynamic heterogeneity in segment relaxations for PMMA/PVDF blends in the solid state. Lastly, effects of dynamic heterogeneity on dynamic mechanical properties were also evaluated.

The objective of this study was to gain a deep understanding of composition and compatibilization effects on the properties of entirely sustainably sourced polymer blends based on polylactide (PLA) and polyamide 11 (PA11). Generally, PLA cannot challenge regular commodity polymers due to its weak thermo-mechanical properties and its poor elongation properties. With this work, however, we present a promising route to overcome these drawbacks in order to enhance the processability of PLA: blending the polymer with various compositions of other ductile biopolymers such as PA11, as well as mixing PLA/PA11 blends with various amounts of a chain extender, Joncryl ADR ® -4368, containing reactive epoxy functions, in a laboratory-scale twin-screw extruder. The effects on the rheological, morphological and mechanical properties were investigated. Results showed that a "self compatibilization" between PLA and PA11 chains can occur but it was found to be insufficient, contrary to recent work reported in the literature. The role of Joncryl as a compatibilizer for the PLA/PA11 system has been demonstrated by the significant decrease of particle size and interfacial tension as well as the improvement of ductile properties. Moreover, a new relaxation peak appeared in the relaxation spectrum, indicating the generation of a copolymer at the polymer-polymer interface.