Biosourced Multiphase Systems Based on Poly(Lactic Acid) and Polyamide 11 from Blends to Multi-Micro/Nanolayer Polymers Fabricated with Forced-Assembly Multilayer Coextrusion.

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.

Unveiling the restricted mobility of carbon nanotubes inside a long chain branched polymer matrix via probing the shear flow effects on the rheological and electrical properties of the filled systems.

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.

Biaxial Orientation of PLA/PBAT/Thermoplastic Cereal Flour Sheets: Structure-Processing-Property Relationships.

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.

A Review on Manufacturing Processes of Biocomposites Based on Poly(α-Esters) and Bioactive Glass Fillers for Bone Regeneration.

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.

Study of Morphology, Rheology, and Dynamic Properties toward Unveiling the Partial Miscibility in Poly(lactic acid)-Poly(hydroxybutyrate-co-hydroxyvalerate) Blends.

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 (Tgs) 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.

Mechanical behavior of 3D-printed PEEK and its application for personalized orbital implants with various infill patterns and densities.

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.

A Journey from Processing to Recycling of Multilayer Waste Films: A Review of Main Challenges and Prospects.

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.

Rheology and Processing of Polymers.

I am so glad to share with you our Special Issue entitled 'Rheology and Processing of Polymers', which covers the latest developments in the field of rheology and polymer processing, highlighting cutting-edge research focusing on the processing of advanced polymers and their composites [...].

Fluorinated Ethylene Propylene Coatings Deposited by a Spray Process: Mechanical Properties, Scratch and Wear Behavior.

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.

Model Composites Based on Poly(lactic acid) and Bioactive Glass Fillers for Bone Regeneration.

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.

Multi-Micro/Nanolayer Films Based on Polyolefins: New Approaches from Eco-Design to Recycling.

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.

Interfacial Phenomena in Multi-Micro-/Nanolayered Polymer Coextrusion: A Review of Fundamental and Engineering Aspects.

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.

Zwitterionic Silicone Materials Derived from Aza-Michael Reaction of Amino-Functional PDMS with Acrylic Acid.

Supramolecular zwitterionic silicones are synthesized by aza-Michael reaction between acrylic acid and amine-functional polydimethylsiloxanes. The in-depth characterization of this chemistry, applied for the first time to silicones, is investigated first with model alkylamines (hexylamine, 2-ethylhexylamine and N-propylethylenediamine), a model oligosiloxane (3-aminopropylmethyl bis(trimethylsiloxy)silane), and finally various amino-polysiloxanes. It is shown that after a first acid-base reaction resulting in ionic pairing, aza-Michael addition proceeds smoothly in mild conditions (50 °C, 1-week reaction). Both monoadducts and di-adducts, together with residual amine, are observed by NMR. The supramolecular assembly of the thus-created zwitterionic moieties is highlighted by a concomitant increase in viscosity and phase separation, as observed by transmission electron microscopy, bringing an additional glass transition at -40 °C assigned to highly polar ionic clusters. Below the stoichiometry in acrylic acid, all zwitterionic silicones follow the same classical behavior of nonentangled polymers according to the Rouse model, whereas upon introducing an excess of acrylic acid to amino groups, an enhancement of the elasticity is observed. Finally, silicone elastomers with solid-like behavior and elastomeric mechanical properties are obtained using a high molar mass polymer bearing bifunctional N-(2-aminoethyl)-3-aminopropyl units that favor a high degree of physical crosslinking.

Multiscale Structural Evolution and Its Relationship to Dielectric Properties of Micro-/Nano-Layer Coextruded PVDF-HFP/PC Films.

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.

Effects of Hydrothermal Aging of Carbon Fiber Reinforced Polycarbonate Composites on Mechanical Performance and Sand Erosion Resistance.

Carbon fiber reinforced polycarbonate (CF/PC) composites have attracted attention for their excellent performances. However, their performances are greatly affected by environmental factors. In this work, the composites were exposed to hydrothermal aging to investigate the effects of a hot and humid environment. The mechanical properties of CF/PC composites with different aging times (0, 7, 14, 21, 28, 35, and 42 days) were analyzed. It was demonstrated that the storage modulus of CF/PC composites with hot water aged for seven days has the highest value in this sampling period and frequency. Through the solid particle erosion experiment, it was found that the hydrothermal aging causes the deviation of the maximum erosion angle of composites, indicating the composites underwent ductile-brittle transformation. Furthermore, the crack and cavity resulting from the absorption of water was observed via the scanning electron microscope (SEM). This suggested that the hydrothermal aging leads to the plasticization and degradation of CF/PC composites, resulting in a reduction of corrosion resistance.

Critical Role of Interfacial Diffusion and Diffuse Interphases Formed in Multi-Micro-/Nanolayered Polymer Films Based on Poly(vinylidene fluoride) and Poly(methyl methacrylate).

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.

Rheological and dynamic insights into an in situ reactive interphase with graft copolymers in multilayered polymer systems.

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.

Correction: Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties.

Correction for 'Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties' by Bo Lu et al., Soft Matter, 2016, DOI: .

Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties.

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.

Rheological, Morphological and Mechanical Studies of Sustainably Sourced Polymer Blends Based on Poly(Lactic Acid) and Polyamide 11.

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.