Biocomposites based on poly(lactic acid) (PLA) and biochar (BC) particles derived from spent ground coffee were prepared using two different processing routes, namely melt mixing and solvent casting. The formulated biocomposites were characterized through rheological, thermal, and mechanical analyses, aiming at evaluating the effects of the filler content and of the processing method on their final properties. The rheological characterization demonstrated the effectiveness of both exploited strategies in achieving a good level of filler dispersion within the matrix, notwithstanding the occurrence of a remarkable decrease of the PLA molar mass during the processing at high temperature. Nevertheless, significant alterations of the PLA rheological behavior were observed in the composites obtained by melt mixing. Differential scanning calorimetry (DSC) measurements indicated a remarkable influence of the processing method on the thermal behavior of biocomposites. More specifically, melt mixing caused the appearance of two melting peaks, though the structure of the materials remained almost amorphous; conversely, a significant increase of the crystalline phase content was observed for solvent cast biocomposites containing low amounts of filler that acted as nucleating agents. Finally, thermogravimetric analyses suggested a catalytic effect of BC particles on the degradation of PLA; its biocomposites showed decreased thermal stability as compared with the neat PLA matrix.

The aim of this work is the investigation of the effect of ultrasound treatment on the structural characteristics of carbon nanotubes (CNTs) and the consequent influence that the shortening induced by sonication exerts on the morphology, rheological behaviour and thermo-oxidative resistance of ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites. First, CNTs have been subjected to sonication for different time intervals and the performed spectroscopic and morphological analyses reveal that a dramatic decrease of the CNT’s original length occurs with increased sonication time. The reduction of the initial length of CNTs strongly affects the nanocomposite rheological behaviour, which progressively changes from solid-like to liquid-like as the CNT sonication time increases. The study of the thermo-oxidative behaviour of the investigated nanocomposites reveals that the CNT sonication has a detrimental effect on the thermo-oxidative stability of nanocomposites, especially for long exposure times. The worsening of the thermo-oxidative resistance of sonicated CNT-containing nanocomposites could be attributed to the lower thermal conductivity of low-aspect-ratio CNTs, which causes the increase of the local temperature at the polymer/nanofillers interphase, with the consequent acceleration of the degradative phenomena.

Fused deposition modeling (FDM) is one of the most commonly used commercial technologies of materials extrusion-based additive manufacturing (AM), used for obtaining 3D-printed parts using thermoplastic polymers. Notwithstanding the great variety of applications for FDM-printed objects, the choice of materials suitable for processing using AM technology is still limited, likely due to the lack of rapid screening procedures allowing for an efficient selection of processable polymer-based formulations. In this work, the rheological behavior of several 3D-printable, commercially available poly(lactic acid)-based filaments was accurately characterized. In particular, each step of a typical FDM process was addressed, from the melt flowability through the printing nozzle, to the interlayer adhesion in the post-deposition stage, evaluating the ability of the considered materials to fulfill the criteria for successful 3D printing using FDM technology. Furthermore, the rheological features of the investigated materials were related to their composition and microstructure. Although an exhaustive and accurate evaluation of the 3D printability of thermoplastics must also consider their thermal behavior, the methodology proposed in this work aimed to offer a useful tool for designing thermoplastic-based formulations that are able to ensure an appropriate rheological performance in obtaining 3D-printed parts with the desired geometry and final properties.

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Diimidazolium-based organic salts, bearing peptides or amino acids as anions have been synthesised and tested for their gelling ability in biocompatible solvents. These low molecular weight salts were successfully used as gelators in phosphate buffered saline (PBS) solution and ionic liquids. Then, the properties of the obtained soft materials were analysed in terms of melting temperature and gel strength as accounted for by rheological investigations. The gel-phase formation was studied by using UV/Vis and resonance light scattering measurements, whereas the morphology of the soft materials was analysed by using polarised optical microscopy and scanning electron microscopy. To get information about the organisation of the gelator in the gelatinous matrix, X-ray diffraction measurements were performed both on the neat gelators and their gels. The results collected show that the properties of the gel phases, like the thermal stability, the self-repairing ability, the resistance to flow as well as the morphology, are dependent on the nature of the anion. Furthermore, bioassays revealed that the obtained diimidazolium organic salts possessed antimicrobial activity, against gram-negative and gram-positive tester strains. In particular and noteworthy, the diimidazolium organic salts exert a bactericidal capability, which was retained even if they are included in the gel phase. Thus, a novel kind of bioactive soft material was obtained that could be fruitfully employed as a non-covalent coating exerting antibacterial capability.

In this work, biochar (BC) derived from spent coffee grounds has been incorporated into high density polyethylene (PE) through melt mixing. The influence of the filler content on the rheological and thermal behavior of the obtained composites was assessed. In particular, a rheological study was performed systematically using different flow fields, including linear and nonlinear dynamic shear flow, revealing that the dynamics of PE macromolecules in the composite materials are slowed down because of the confinement of the polymer chains onto the filler surface and/or within the BC porous structure. Oscillatory amplitude sweep tests indicated that composites show weak strain overshoot behavior in the nonlinear regime: This finding clearly proves the formation of weak structural complexes, which cause a retardation of the macromolecular chains dynamics. Furthermore, the embedded BC particles were able to improve the thermo-oxidative stability of PE-based composites, remarkably increasing the PE decomposition temperatures.

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