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The present work provides a unique insight to reveal the long chain branching (LCB) influence to the nano‐fillers, that is via analyzing the conductivity evolution during the thermal annealing, fast shear flow and melt to solid cooling process. Meanwhile the crystallization behavior is also discussed. A linear polypropylene (PPC) and a long chain branched polypropylene (PPH) are chosen as the two polymer matrices with carbon nanotubes (CNTs) as the nanofillers. During the thermal annealing process, a more obvious growth of electrical conductivity of linear PPC nanocomposites are observed compared with LCB PPH nanocomposites. The harder movement of CNTs inside LCB PPH matrix may be the main reason. This also can be reflected by the conductivity evolution during slow cooling process where a decrease‐then‐increase (DTI) phenomenon is found for PPC/CNTs systems due to the rebuilding of CNTs conductivity network after crystallization. By contrast, this does not happen for PPH/CNTs systems. [ABSTRACT FROM AUTHOR]

For blending immiscible polymers, such as in the toughening modification of polylactide (PLA) via blending with rubbery materials, interfacial compatibilization is of great significance while the mechanism, especially the role of interfacial rheology, remains elusive. In this study, styrene-butadiene block copolymer elastomer (SBC) was employed to toughen PLA and a dumbbell-shaped Janus nanoparticle (JNP) consisting of polymethyl methacrylate and polystyrene spheres with equal size (∼80 nm) was used as the compatibilizer. Located at the interface, JNPs exhibited a great compatibilization efficiency in PLA/SBC blends, as demonstrated by the good morphology stabilization against droplet coalescence under static annealing and low shear flow conditions, as well as by the resistance against droplet breakup under high shear flow conditions. Moreover, as revealed from the linear viscoelasticity of JNP compatibilized blends, when JNP loading is more than 2 phr, aside from shape relaxation, an interfacial relaxation dominated by Marangoni stress was observed, indicating the possibility of particle redistribution on droplet surfaces. However, when loading is more than 4 phr, relaxations in the terminal zone no longer exist, implying the possible formation of a particle network on the droplet surface. This is consistent with the mechanical properties. The blend shows the greatest toughness at JNP loading around 3 phr, while the toughness is very poor when JNP loading is either too low or too high. This suggests interfacial relaxation to be crucial to guarantee a good toughening effect of SBC in PLA. [ABSTRACT FROM AUTHOR]

Biocomposites from polylactic acid (PLA) and olive solid waste (OSW) were melt-blended with core-shell acrylate rubber particles (ACR) in order to enhance the thermal stability upon melt processing and the mechanical performances of these biocomposites, thereby expanding their area of application. Dynamic mechanical analysis indicated that the ACR particles imparted more flexibility to the PLA/OSW biocomposites and thermal analysis showed that the incorporation of ACR significantly restrained the ability of the PLA chains to crystallize. The values of complex viscosity and storage modulus were significantly increased with the introduction of ACR. These results could be assigned to the entanglements between the PLA chains and those of the ACR shell, giving rise to a physical network that limited the segmental mobility of PLA and induced a high melt elasticity. Mechanical tests revealed that the elongation at break and the impact strength of the biocomposites were considerably improved. Moreover, morphological observations showed a clear adhesion enhancement between the PLA matrix and the OSW fillers in the presence of the ACR additive. POLYM. ENG. SCI., 58:894-902, 2018. [C] 2017 Society of Plastics Engineers, INTRODUCTION The current policies related to polymer materials are based on three principles: respecting the environment, reducing waste and pollutants and replacing materials derived from petroleum by renewable and sufficiently [...]

This paper deals with the study of new interfacial instabilities, called 'grainy' defects, in coextrusion process of reactive multilayer polymers. The main objective was to better understand this phenomenon since no help can be found in the literature. The fundamental approach from a micro-scale to a macro-scale involves the study of relationships between polymer structure, processing, and interfacial properties. The influence of these parameters on the generation of 'grainy' defects during coextrusion has been assessed in correlation with physicochemical properties. Through this work, rheological properties and the interfacial morphology between tie and barrier layers have been investigated by shear stress relaxation experiments and transmission electronic microscopy, respectively. Depending on the reactive polymers, the interfacial coupling was found to significantly alter the stress relaxation behavior by extending the relaxation time and generating an interfacial roughness. Hence, relations between the copolymer architecture, the relaxation process, and the interfacial morphology were established in correlation with the generation of grainy defects in coextrusion process., INTRODUCTION Coextrusion is a widely used industrial process to obtain multilayer films commonly employed in varied applications, such as food packaging, the medical area, and recently in microelectronic and nonlinear [...]

A novel way using a polarized optical microscopy and statistical image analysis techniques for direct investigation of the crystallization kinetics and spherulitic morphology of poly (lactic acid) induced by casting process has been proposed. DSC analyses were carried out to explore the effect of drawing in thermal properties of PLA. We found that the rate of cold crystallization was sharply increased with draw ratio. Isothermal calorimetric results reveal that thin films crystallize slowly compared to sheets. Moreover, thin films don't fit the Avrami model demonstrating that more stretching may modify the crystallization kinetics of films. A comparison was made between pure PLA and stretched materials using Hoffman theory and giving a compiled view on the details of crystallization behavior with relation to stretch effect. At draw ratio 167, the growth rate reach its maximum and the crystallization rate go up exponentially. POM experiments showed the existence of two different spherulitic populations in thin films and two nucleation mechanisms was identified. Accordingly, the growth rate was found to be not linear with time. Furthermore, the X-ray diffraction analyses showed the presence of α and α crystal form in thin films contrarily to sheets with α form., INTRODUCTION Poly (lactic acid) is a well-known biodegradable polymer because of his wide application in environmental friendly packaging. The monomer used in the polymerisation of PLA is produced metabolically in [...]

This work aims to investigate the growth and structural evolution of a diffuse interphase generated in a flow field and to highlight its importance on controlling the final properties of compatible multilayer materials. The model polymers chosen are poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVDF). Interdiffusion kinetics, geometrical, and rheological properties of the interphase decoupled and coupled to flow have been probed and quantified under fundamental conditions of rheological measurement and under real practical conditions of processing, respectively. Polymer chain orientation is shown to decelerate the interdiffusion coefficient. This phenomenon is demonstrated to be balanced by intermixing (i.e. flow effect) at the vicinity of the interface triggered from excess interfacial shear stress, thus favors development of the interphase. The diffuse interphase generated therein during the processing has been well characterized via scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) and transmission electron microscopy (TEM). Results indicate that the interphase is robust with a geometrical property of tens microns depending on processing conditions and the interfacial structure is shown to be smooth with continuous amorphous-crystallization transition between neighboring layers without causing any interfacial disturbances. Finally, experimental studies concerning the interfacial flow instability and encapsulation in coextrusion process have been performed, taking into account some key classical decisive parameters such as viscosity ratio, thickness ratio and elasticity ratio, etc. Different from severe flow instability observed in incompatible multilayer systems, presence of the interphase at PMMA/PVDF multilayers plays a vital role in weakening (or even eliminating) the viscous instabilities and elastic instabilities despite of the very high rheological contrast. POLYM. ENG. SCI., 55:771-791, 2015. [C] 2014 Society of Plastics Engineers, INTRODUCTION In general, owning the advantage of combining separate features of different individual polymers together in a facile way, technology of coextrusion has been widely used to fabricate multilayered composite [...]

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. [ABSTRACT FROM AUTHOR]

The blown extrusion of poly(lactic acid) (PLA) presents several challenges mainly due to the poor shear and elongation properties of this biopolymer. This article highlights some promising routes to enhance [...]

A semicrystalline poly(lactic acid) (PLA) was modified with the help of an epoxy-based chain extender (CE) during reactive extrusion. Different amounts of CE were used resulting in samples with increased and broadened molar mass distributions as revealed by size exclusion chromatography. Thermal properties were then investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). On one hand, the thermal ramps performed with DSC revealed that the glass transition was not modified by the chain extension process. On the other hand, the crystallization behavior was found to be highly impacted by this molecular modification. Decreases in the cold crystallization temperatures [T.sub.cc] and in the melting temperatures [T.sup.m] occurred when the CE content was raised. Isothermal crystallizations from the melt were performed using both DSC and POM. It revealed that the overall crystallization process was significantly faster for the chain-extended PLAs while crystalline ratios were lowered. An improvement of the nucleation process coupled with a reduced crystal growth was assumed to be responsible for this change. POLYM. ENG. SCI., 54:616-625, 2014. © 2013 Society of Plastics Engineers, INTRODUCTION Poly (lactic acid) (PLA) is a promising polymer as a biobased and biodggradable material. Current ecological concerns have confronted the plastic industry with the issue of sustainable production. Ideally, [...]