This work is a comparative study of four different techniques to determine the crystallinity of high-density polyethylene (HDPE) nanocomposites filled with different diameter sizes (5, 15 and 25 μm) of graphene nanoplatelets (GNPs) at various amounts (0.5–5 wt%). The structure of HDPE/GNPs nanocomposites was extensively studied by using different experimental methods, such as X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. To further provide a complete comparison, differential scanning calorimetry measurements were utilized to calculate the crystallinity values, while temperature-modulated DSC was employed to investigate the possible mechanism of the different crystalline structures. It was found that these methods can be used to estimate the crystallinity, but the sample parameters and experimental conditions must be taken into consideration. All the techniques showed that the crystallinity depends on GNPs size and content. The distance between dispersed platelets was substantial at low concentrations of GNPs, making it comparatively easy for additional nucleation sites to incorporate the polymer matrix, and the crystal nucleus was simply formed. However, at high concentrations of GNPs, the diffusion of polymer chains to the growing crystallites was hindered by large GNPs particles, despite the formation of additional nucleation sites.
Vourlias, G. (2018). Insights into crystallization and melting of high density polyethylene/graphene nanocomposites studied by fast scanning calorimetry. Polymer Testing, 67,[349][350][351][352][353][354][355][356][357][358] AbstractGraphene nanoplatelets (5 wt.%) with different diameters (5 and 25 x 10 -6 m in diameter, 6 x 10 -9 m in thickness) filled high density polyethylene nanocomposites were prepared by the melt-mixing method and the effect of graphene nanoplatelets on the polymeric matrix are then investigated by X-ray diffraction, polarized light microscopy, differential scanning calorimetry, fast scanning calorimetry, and rheology. Polarized light microscopy revealed that graphene nanoplatelets of 5 x 10 -6 m promote the decrease in the size of the spherical aggregates during crystallization compared to larger nanoplatelets. From rheological measurements, it was found that even though the viscosity of the nanocomposites with increasing filler diameter was increased significantly compared to the neat polymer, the processability of these 2 materials was not affected. Several melting events for neat high-density polyethylene and graphene nanocomposites were observed by fast scanning calorimetry associated with the small imperfect crystals grown at large supercooling, the nucleation efficiency and the diameter size of the filler. The activation energy values versus the relative extent of crystallization revealed that graphene nanoplatelets block the movement of the molecular segments and make crystallization difficult, especially at the final stage of the process. Based on this work, it can be concluded that the nanocomposite with the smaller diameter showed the most enhanced crystallization kinetics as graphene increased the number of nucleation sites, while the larger ones hindered the melted molecules in reaching full isotropization above the melting temperature. determined by conventional DSC (filled symbols) and FSC (open symbols)
Poly(lactic acid) (PLA) nanocomposites with antimicrobial fillers have been increasingly explored as food packaging materials that are made of a biobased matrix and can minimize food loss due to spoilage. Some of the most commonly studied fillers are zinc oxide (ZnO), titanium dioxide (TiO2), and silver nanoparticles (AgNPs). In this work, nanocomposites with 1 wt.% of each filler were prepared by melt mixing. An extensive study of thermally stimulated processes such as crystallization, nucleation, degradation, and their kinetics was carried out using Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). In detail, non-isothermal cold crystallization studies were performed with DSC and polarized light microscopy (PLM), and kinetics were analyzed with multiple equations. The activation energy of the non-isothermal cold crystallization was calculated with the methods of Kissinger and Friedman. The latter was used to also determine the Hoffman–Lauritzen parameters (Kg and U*) by applying the Vyazovkin method. Additionally, effective activation energy and kinetic parameters of the thermal decomposition process were determined by applying the isoconversional differential method and multivariate non-linear regression method. According to TGA results, metal oxide nanofillers affected the thermal stability of PLA and caused a decrease in the activation energy values. Moreover, the fillers acted as heterogenous nucleating agents, accelerating the non-isothermal crystallization of PLA, thus reducing its activation energy. It can be concluded that metal oxide nanofillers catalytically affect the thermal degradation and crystallization of PLA samples.
Packaging applications cover approximately 40% of the total plastics production, whereas food packaging possesses a high proportion within this context. Due to several environmental concerns, petroleum-based polymers have been shifted to their biobased counterparts. Poly(lactic acid) (PLA) has been proved the most dynamic biobased candidate as a substitute of the conventional polymers. Despite its numerous merits, PLA exhibits some limitations, and thus reinforcing agents are commonly investigated as fillers to ameliorate several characteristics. In the present study, two series of PLA-based nanocomposites filled with biobased kraft-lignin (KL) and tannin (T) in different contents were prepared. A melt–extrusion method was pursued for nanocomposites preparation. The thermal stability of the prepared nanocomposites was examined by Thermogravimetric Analysis, while thermal degradation kinetics was applied to deepen this process. Pyrolysis–Gas Chromatography/Mass Spectrometry was employed to provide more details of the degradation process of PLA filled with the two polyphenolic fillers. It was found that the PLA/lignin nanocomposites show better thermostability than neat PLA, while tannin filler has a small catalytic effect that can reduce the thermal stability of PLA. The calculated Eα value of PLA-T nanocomposite was lower than that of PLA-KL resulting in a substantially higher decomposition rate constant, which accelerate the thermal degradation.
Polypropylene composites reinforced with a filler mixture of graphene nanoplatelet-glass fiber were prepared by melt mixing, while conventional composites containing graphene nanoplatelet and glass fiber were prepared for comparative reasons. An extensive study of thermally stimulated processes such as crystallization, nucleation, and kinetics was carried out using Differential Scanning Calorimetry and Thermogravimetric Analysis. Moreover, effective activation energy and kinetic parameters of the thermal decomposition process were determined by applying Friedman’s isoconversional differential method and multivariate non-linear regression method. It was found that the graphene nanoplatelets act positively towards the increase in crystallization rate and nucleation phenomena under isothermal conditions due to their large surface area, inherent nucleation activity, and high filler content. Concerning the thermal degradation kinetics of polypropylene graphene nanoplatelets/glass fibers composites, a change in the decomposition mechanism of the matrix was found due to the presence of graphene nanoplatelets. The effect of graphene nanoplatelets dominates that of the glass fibers, leading to an overall improvement in performance.
A series of high-density polyethylene nanocomposites filled with different diameter sizes (5, 15, and 25 μm) of graphene nanoplatelets at various amounts (0.5–5 wt.%) are prepared by the melt-mixing method. The effect of diameter size and filler content on the mechanical properties is reported, and the results are discussed in terms of morphology and the state of dispersion within the polymer matrix. The measured stiffness and strength of the nanocomposites were found to be mainly influenced by the filler aspect ratio and the filler-matrix adhesion. Fractography was utilized to study the embrittleness of the nanocomposites, and the observations revealed that a ductile to brittle transition is caused by a micro-deformation mechanism change in the nanocomposites. Several micromechanical models for the prediction of mechanical properties of nanocomposites, taking into consideration filler aspect ratio, percolation effect, and interphase regions, are considered. The three-phase model proposed by Ji accurately predicts the stiffness of graphene nanoplatelets with a higher diameter size, while Takayanagi modified model II was found to show good agreement with the experimental results of smaller ones at low filler content. This study demonstrates that the diameter size of the filler plays a central role in determining the mechanical properties.
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