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Bio-based poly(l-lactide)/poly(amide-11) blends (PLA/PA11, 80/20 w/w) and poly(l-lactide)/poly(amide-6) blends (PLA/PA6, 80/20 w/w) are processed by twin-screw extrusion followed by injection-moulding and key rheological parameters controlling their morphologie are investigated. The same work is done using the same PLA modified by a multi-step reactive extrusion route with an epoxy-based chain extender to obtain modified poly(lactide)/poly(amide-11) (PLA-j/PA11 80/20 w/w) blends. The morphologies of the extruded materials and of the injection moulded parts are characterized by SEM and their formation is deeply discussed via rheological investigation to highlight the contribution of viscosity, elasticity and interfacial tension. The existence of a critical shear rate related to the transition from nodular to fibrillar morphology is highlighted and the results are in good agreement with the condition of fibrillation Ca/Ca(crit) ≥ 4. Interestingly, with the exception of PLA/PA6 specimens, all blends obviously display uniform thin-thread fibrillar morphologies after injection-moulding. Compared with pure PLA, a drastic increase of the ductility was observed in the blends exhibiting a fiberlike structure without meanwhile sacrificing the stiffness. This study confirms that, through the appropriate choice of blend components (viscosity and elasticity ratio, flow conditions, interfacial tensions) the in situ fibrillation concept provides access, at a reasonable cost, to new materials with improved thermomechanical performances, without sacrificing weight and ability to be recycled.

RESUMEN

Starch was combined with plasticizers such as glycerol, sorbitol, glycerol/sorbitol and urea/ethanolamine blends by means of high shear extrusion process to prepare thermoplastic starch (TPS). Effect of storage time and plasticizers on the structural stability of melt processed TPS was investigated. Morphological observation, X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy reveal that melt extrusion process is efficient in transforming granular starch into a plasticized starch for all plasticizer compositions. XRD analysis highlights major changes in the microstructure of plasticized starch, and dependence of crystalline type and degree of crystallinity mainly on the plasticizer composition and storage time. Dynamical mechanical analysis (DMA) yields a decrease of the peak intensity of loss factor with aging time. The effect of ageing on tensile strength also appears to be highly dependent on the plasticizer composition. Thus, through different plasticizer combinations and ageing, starch-based materials with significant differences in tensile properties can be obtained, which may be tuned to meet the requirements of a wide range of applications.

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RESUMEN

The aim of this paper is to understand the influence of plasticizer and plasticizer amount on the mechanical and deformation behaviors of plasticized starch. Glycerol, sorbitol and mannitol have been used as plasticizers. After extrusion of the various samples, dynamic mechanical analyses and video-controlled tensile tests have been performed. It was found that the nature of plasticizer, its amount as well as the aging of the material has an impact on the involved deformation mechanism. The variations of volume deformation could be explained by an antiplasticization effect (low plasticizer amount), a phase-separation phenomenon (excess of plasticizer) and/or by the retrogradation of starch.

RESUMEN

Novel bionanocomposites based on halloysite nanotubes as nanofillers and plasticized starch as polymeric matrix were successfully prepared by melt-extrusion for the first time. Both modified and non modified halloysites were added at different weight contents. The structural, morphological, thermal and mechanical properties of plasticized starch/halloysites nanocomposites were investigated. Melt-compounding appears to be a suitable process to uniformly disperse nanotubes in the plasticized starch matrix. Interactions between plasticized starch and halloysites in the nanocomposites and microstructure modifications were monitored using Fourier transfer infrared spectroscopy, X-ray diffraction and dynamic mechanical analysis. Addition of halloysite nanotubes slightly enhances the thermal stability of starch (onset temperature of degradation delayed to higher temperatures). The tensile mechanical properties of starch are also significantly improved (up to +144% for Young's modulus and up to +29% for strength) upon addition of both modified and unmodified halloysites, interestingly without loss of ductility. Modified halloysites lead to significantly higher Young's modulus than unmodified halloysites.

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