Controlling the cooling rate experienced by a material during a manufacturing process is a challenge and a major issue. Industrial processing techniques are very diverse and may involve a whole range of cooling rates, which are sometimes extremely high for small and/or thin manufactured parts. For polymers, the cooling rate has consequences on both the microstructure and the time-dependent properties.
View Article and Find Full Text PDFThe kinetics of the glass transition and the characteristic size of the fluctuating spatio-temporal domains in supercooled glass-forming liquids, i.e., the Cooperatively Rearranging Regions (CRR), were measured upon cooling over a broad range of cooling rates using Differential Scanning Calorimetry (DSC) and chip-based Fast Scanning Calorimetry (FSC).
View Article and Find Full Text PDFThe blurring around the link between the isobaric fragility and the characteristic size of cooperative rearranging region for glass-forming liquids has been cleared up by considering volumetric and thermal contributions of the structural relaxation. The measurement of these contributions is carried out for three amorphous thermoplastic polymers using broadband dielectric spectroscopy under pressure, providing an understanding of the link between isobaric fragilities, glass transition temperatures, and microstructures. The cooperative rearranging region (CRR) volume is calculated as a function of pressure using the extended Donth's approach, and the values are compared with the activation volume at the glass transition under different isobaric conditions.
View Article and Find Full Text PDFThe present work aims at addressing the issue of molecular handedness in glassy and liquid states and its impact on heterogeneous equilibrium. For this purpose, we evaluated the glass forming ability (GFA), crystallization propensity, molecular mobility and hydrogen bonding structure of a chiral conglomerate forming system, -acetyl-α-methylbenzylamine (Nac-MBA), at various enantiomeric excesses (ees) using experimental and computational techniques. We revealed that the rich relaxational landscape (Debye (D), α, β and ϒ) and the temperature dependence of the time scale of each process were insensitive to chirality.
View Article and Find Full Text PDFNanomaterials have engaged response from the scientific world in recent decades due to their exceptional physical and chemical properties counter to their bulk. They have been widely used in a polymer matrix to improve mechanical, thermal, barrier, electronic and chemical properties. In rubber nanocomposites, nanofillers dispersion and the interfacial adhesion between polymer and fillers influences the composites factual properties.
View Article and Find Full Text PDFIn this paper, the calorimetric response of the amorphous phase was examined in hybrid nanocomposites which were prepared thanks to a facile synthetic route, by adding reduced graphene oxide (rGO), Cloisite 30B (C30B), or multiwalled carbon nanotubes (MWCNT) to lignin-filled poly(lactic acid) (PLA). The dispersion of both lignin and nanofillers was successful, according to a field-emission scanning-electron microscopy (FESEM) analysis. Lignin alone essentially acted as a crystallization retardant for PLA, and the nanocomposites shared this feature, except when MWCNT was used as nanofiller.
View Article and Find Full Text PDFUnderstanding the rheological behaviour of thermoplastic nanocomposites is important to obtain a concrete knowledge of their processability. The viscoelastic properties of nanocomposites are a reflection of their morphology. The study of flow and deformation of nanocomposites provides essential information related to prevalent interactions in the system as well as contribution from the dispersion of incorporated nanofillers.
View Article and Find Full Text PDFFast scanning calorimetry (FSC) experiments were performed to investigate physical aging in amorphous and semi-crystalline poly(l-lactic acid)s (PLLAs) that were thermally crystallized under conditions leading to the α'- or α-crystalline form, and either favouring or inhibiting the development of a rigid amorphous fraction (RAF). The enthalpy of recovery was calculated after two procedures of rescaling to the content of the whole amorphous phase and also to the only content of the mobile amorphous fraction (MAF), which helped in clarifying the contribution of the RAF. From the dependence of the structural relaxation rate on the aging temperature, two regimes were evidenced for all samples.
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