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The incorporation of poly(d-lactide) (PDLA) to form stereocomplex crystallites (SCs) within a poly(l-lactide) (PLLA) matrix is among the most effective strategies in overcoming PLLA's numerous drawbacks. However, high concentrations of PDLA (>3 wt%) are required to improve PLLA's crystallization kinetics and melt strength, which is undesirable owing to PDLA's high cost. In this study, we use chain alignment as a levier to tune stereocomplex superstructure morphology to overcome these limitations. Herein, PLLA/PDLA blends were manufactured using an environmentally friendly and low-cost single step spunbond fibrillation process, yielding microfibers stretched to diameters of 5-20 µm. During this stretching process, PLLA and PDLA chains are aligned along the flow direction. SCs subsequently formed in situ upon heating, dramatically improving crystallization kinetics, melt elasticity, and tensile performance compared with neat PLLA and non-stretched blend analogues, even with low PDLA content (<3 wt%). These improvements were attributed to topological variations in SC superstructures caused by alignment of PLLA and PDLA chains. The application of chain alignment in tuning SC superstructure morphology is ubiquitous in fibrillation processes.

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Polylactide (PLA) resins are among the most desirable biopolymers due to their biobased and compostable nature, excellent stiffness, and tensile strength. However, the widespread application of PLA has long been hindered by its inherent brittleness. While multiple routes have been successfully developed for the toughening of PLA, this toughening has always come at the cost of compromising the stiffness and strength of the matrix. In this work, we report a robust and scalable method for the development of PLA nanocomposites with an unprecedented combination of stiffness and toughness. Using the in situ nanofibrillation technique, we generated PLA composites containing nanofibrils of thermoplastic polyester elastomer (TPEE). Due to the high aspect ratio of these nanofibrils, they form physically percolated networks at low weight fractions (∼2.8 wt %) which dramatically change the mechanical behavior of the material. We found that, upon network formation, the material transitions from brittle to ductile behavior, dramatically increasing its toughness with only a marginal decrease in Young's modulus. We investigate the peculiar rheological behavior and crystallization kinetics of these blends, and propose an extension of the critical ligament thickness mechanism, wherein intrinsic toughening arises at the fiber-matrix interface in the presence of entangled elastomer networks.

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The bead foaming of semicrystalline polymers is a complex thermal process involving the formation of multiple crystalline populations, which serve the dual purposes of ensuring the structural integrity of beads while also allowing bead sintering at the interface. The quality of this "double melting peak" structure is determined by the temperature and duration of the isothermal treatment of the beads as well as the quenching rate following the isotherm. Currently, the intricacies of the quenching process are not very well-known due to the challenge of replicating these rapid cooling rates in a laboratory setting. Fast-scanning calorimetry was used to reproduce these conditions for isotactic polypropylene (iPP), revealing optimal quenching rates for the bead foaming of iPP. We further probed these thermal features using two-dimensional correlation analysis as a tool to understand the dynamics, interdependence, and relative contributions of multiple thermal events such as glass transition, mesophase formation, cold crystallization, and melting in response to the perturbation of the quenching rate.

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The physical properties of biocarbon vary widely with the biomass used, and the temperature and duration of pyrolysis. This study identifies the effects of feedstock characteristics and pyrolysis conditions on the production of biocarbon and the corresponding properties for industrial applications. For coffee chaff and soy hulls, ash content and carbon content increased with pyrolysis temperature and duration. Ash content increased thermal conductivity and specific heat, and decreased electrical conductivity. Change in surface area with pyrolysis conditions was dependent on type of feedstock. Increased surface area corresponded with increased thermal and electrical conductivity. Increased carbon content corresponded with increased graphitization and thermal stability and decreased surface functionality. Properties of soy hull biocarbons were found to be similar to the properties of other biocarbons with industrial applications such as incorporation into polymer composites.

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In this paper, the interaction between nylon 6 (PA6), polypropylene (PP) and poly(lactic acid) (PLA) is reported. To improve the compatibility between these immiscible polymers, a reactive compatibilization approach was used through extrusion with maleic anhydride grafted polypropylene (PP-g-MA). To further improve the compatibility of the phases, PLA was selected as a semi-polar polymer and a low molecular weight was used to assure a good droplet dispersion. All the blends were twin-screw extruded in the melt at different compositions. The morphologies of binary and ternary blends were investigated using microscopic techniques by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The PP-g-MA grafting process was observed to have a dramatic effect on the compatibility of both the binary and ternary blends and while a drastic reduction of the PP dispersed phases particle size was observed, the affinity between PLA and PP was also highlighted. The surface tension of the homopolymers and the interfacial tension of the pairs of polymers were measured to characterize the interaction at their interfaces. The interaction of PA6/PLA appeared preferable to PLA/PP, explaining the thinner dispersion obtained for PLA phase. The morphologies observed were compared to the predictions of spreading coefficient and minimum free energy models. While both models predicted the encapsulation of PP by the PLA phase, disagreeing with the morphological results, the rheological measurement gave an explanation for this phase separation. Using rheology measurements, the interaction between the phases was further investigated and the viscosity ratios were measured for the different pairs of polymers, stressing the high interaction between PA6 and PLA with and without compatibilizer. The droplet size of the dispersed phases appeared to substantially influence the chain relaxations in the melt.

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This paper presents an investigation into the behavior and performance of blends of Nylon 6 (PA6), polypropylene (PP), and poly(lactic acid) (PLA), compatibilized with maleic anhydride-grafted PP (PP-g-MA). The mechanical performance of ternary PA6/PP/PLA blends was superior to that of binary PA6/PP blends because of the addition of PLA. Through blending with PLA, the tensile and flexural strength and modulus were enhanced, maintaining performance similar to that of neat PA6. Tensile performance was further enhanced through reactive compatibilization of the blends with PP-g-MA due to the improved homogeneity of the materials. Impact behavior of the blends was found to be highly dependent on morphology, and the toughening behavior was observed at certain blending ratios. In PA6/PP blends, fractionated crystallization behavior was investigated through differential scanning calorimetry, in which both PA6 and PP droplets were crystallized at supercooled states. This effect was highly influenced by the presence of the compatibilizing agent and its effect on the morphology of the dispersed phase. As the droplet size of the dispersed phase was decreased to submicron levels, the efficiency of heterogeneous nucleation was limited. Crystallization of PLA in the blend was poor, but PP-g-MA was found to have an impact on its rate of crystallization.

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A fused deposition modeling method was used in this research to investigate the possibility of improving the mechanical properties of poly(lactic acid) by changing the thermal conditions of the printing process. Sample models were prepared while varying a wide range of printing parameters, including bed temperature, melt temperature, and raster angle. Certain samples were also thermally treated by annealing. The prepared materials were subjected to a detailed thermomechanical analysis (differential scanning calorimetry, dynamic mechanical analysis, heat deflection temperature (HDT)), which allowed the formulation of several conclusions. For all prepared samples, the key changes in mechanical properties are related to the content of the poly(lactic acid) crystalline phase, which led to superior properties in annealed samples. The results also indicate the highly beneficial effect of increased bed temperature, where the best results were obtained for the samples printed at 105 °C. Compared to the reference samples printed at a bed temperature of 60 °C, these samples showed the impact strength increased by 80% (from 35 to 63 J/m), HDT increased by 20 °C (from 55 to 75 °C), and also a significant increase in strength and modulus. Scanning electron microscopy observations confirmed the increased level of diffusion between the individual layers of the printed filament.

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Oxidative acid treatments of biochar produced from Miscanthus were performed in this study using nitric acid, sulfuric acid, and a mixture of both. The structural and morphological changes of the acid-treated biochar were investigated using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Raman spectroscopy, organic elemental analysis and energy-dispersive X-ray spectroscopy (EDS). Improved surface functionality of the treated biochars was observed in their respective FT-IR spectra through the presence of nitro and carboxylic acid functional groups. SEM-EDS and elemental analysis revealed a large increase in the oxygen to carbon ratio in the biochar, which was evidence of chemical oxidation from the acid treatment. Further, TGA study showed the reduced thermal stability of acid-treated biochar over 200°C due to the increased oxygen content. Acid treatments also influenced the graphitic structure of the biochar, as observed in the Raman spectra. The results suggest that biochar can be successfully functionalized for composite applications and provide a sustainable alternative to petroleum-based carbon additives.

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