The Effect of Biochar Addition on Thermal Stability and Decomposition Mechanism of Poly(butylene succinate) Bionanocomposites.

In the present study, poly(butylene succinate) (PBSu) and its bionanocomposites containing 1, 2.5, and 5 wt.% biochar (MSP700) were prepared via in situ melt polycondensation in order to investigate the thermal stability and decomposition mechanism of the materials. X-ray photoelectron spectroscopy (XPS) measurements were carried out to analyze the surface area of a biochar sample and PBSu/biochar nanocomposites. From XPS, it was found that only physical interactions were taking place between PBSu matrix and biochar nanoadditive. Thermal stability, decomposition kinetics, and the decomposition mechanism of the pristine PBSu and PBSu/biochar nanocomposites were thoroughly studied by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). TGA thermograms depicted that all materials had high thermal stability, since their decomposition started at around 300 °C. However, results indicated a slight reduction in the thermal stability of the PBSu biochar nanocomposites because of the potential catalytic impact of biochar. Py-GC/MS analysis was employed to examine, in more detail, the thermal degradation mechanism of PBSu nanocomposites filled with biochar. From the decomposition products identified by Py-GC/MS after pyrolysis at 450 °C, it was found that the decomposition pathway of the PBSu/biochar nanocomposites took place mainly via ß-hydrogen bond scission, which is similar to that which took place for neat PBSu. However, at higher biochar content (5 wt.%), some localized differences in the intensity of the peaks of some specific thermal degradation products could be recognized, indicating that α-hydrogen bond scission was also taking place. A study of the thermal stability and decomposition pathway of PBSu/biochar bionanocomposites is crucial to examine if the new materials fulfill the requirements for further investigation for mulch films in agriculture or in electronics as possible applications.

Non-Isothermal Crystallization Kinetics of PBSu/Biochar Composites Studied by Isoconversional and Model Fitting Methods.

Non-isothermal crystallization of Poly(butylene succinate) (PBSu)/biochar composites was studied at various constant cooling rates using differential scanning calorimetry. The analysis of the kinetics data revealed that the overall crystallization rate and activation energy of the PBSu polymer were significantly influenced by the addition of biochar. Specifically, the PBSu/5% biochar composite with a higher filler content was more effective as a nucleation agent in the polymer matrix, as indicated by the nucleation activity (ψ) value of 0.45. The activation energy of the PBSu/5% biochar composite was found to be higher than that of the other compositions, while the nucleation activity of the PBSu/biochar composites decreased as the biochar content increased. The Avrami equation, which is commonly used to describe the kinetics of crystallization, was found to be limited in accurately predicting the non-isothermal crystallization behavior of PBSu and PBSu/biochar composites. Although the Nakamura/Hoffman-Lauritzen model performed well overall, it may not have accurately predicted the crystallization rate at the end of the process due to the possibility of secondary crystallization. Finally, the combination of the Sesták-Berggren model with the Hoffman-Lauritzen theory was found to accurately predict the crystallization behavior of the PBSu/biochar composites, indicating a complex crystallization mechanism involving both nucleation and growth. The Kg parameter of neat PBSu was found to be 0.7099 K2, while the melting temperature and glass transition temperature of neat PBSu were found to be 114.91 °C and 35 °C, respectively, very close to the measured values. The Avrami nucleation dimension n was found to 2.65 for PBSu/5% biochar composite indicating that the crystallization process is complex in the composites.

Thermal Stability and Decomposition Mechanism of PLA Nanocomposites with Kraft Lignin and Tannin.

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.

Influence of Graphene Platelet Aspect Ratio on the Mechanical Properties of HDPE Nanocomposites: Microscopic Observation and Micromechanical Modeling.

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.

Thermal Decomposition Kinetics and Mechanism of In-Situ Prepared Bio-based Poly(propylene 2,5-furan dicarboxylate)/Graphene Nanocomposites.

Bio-based polyesters are a new class of materials that are expected to replace their fossil-based homologues in the near future. In this work, poly(propylene 2,5-furandicarboxylate) (PPF) nanocomposites with graphene nanoplatelets were prepared via the in-situ melt polycondensation method. The chemical structure of the resulting polymers was confirmed by 1H-NMR spectroscopy. Thermal stability, decomposition kinetics and the decomposition mechanism of the PPF nanocomposites were studied in detail. According to thermogravimetric analysis results, graphene nanoplatelets did nοt affect the thermal stability of PPF at levels of 0.5, 1.0 and 2.5 wt.%, but caused a slight increase in the activation energy values. Pyrolysis combined with gas chromatography and mass spectroscopy revealed that the decomposition mechanism of the polymer was not altered by the presence of graphene nanoplatelets but the extent of secondary homolytic degradation reactions was increased.

Kinetics of Crystallization and Thermal Degradation of an Isotactic Polypropylene Matrix Reinforced with Graphene/Glass-Fiber Filler.

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.