Toughening Effect of 2,5-Furandicaboxylate Polyesters on Polylactide-Based Renewable Fibers.

This work presents the successful preparation and characterization of polylactide/poly(propylene 2,5-furandicarboxylate) (PLA/PPF) and polylactide/poly(butylene 2,5-furandicarboxylate) (PLA/PBF) blends in form of bulk and fiber samples and investigates the influence of poly(alkylene furanoate) (PAF) concentration (0 to 20 wt%) and compatibilization on the physical, thermal, and mechanical properties. Both blend types, although immiscible, are successfully compatibilized by Joncryl (J), which improves the interfacial adhesion and reduces the size of PPF and PBF domains. Mechanical tests on bulk samples show that only PBF is able to effectively toughen PLA, as PLA/PBF blends with 5-10 wt% PBF showed a distinct yield point, remarkable necking propagation, and increased strain at break (up to 55%), while PPF did not show significant plasticizing effects. The toughening ability of PBF is attributed to its lower glass transition temperature and greater toughness than PPF. For fiber samples, increasing the PPF and PBF amount improves the elastic modulus and mechanical strength, particularly for PBF-containing fibers collected at higher take-up speeds. Remarkably, in fiber samples, plasticizing effects are observed for both PPF and PBF, with significantly higher strain at break values compared to neat PLA (up to 455%), likely due to a further microstructural homogenization, enhanced compatibility, and load transfer between PLA and PAF phases following the fiber spinning process. SEM analysis confirms the deformation of PPF domains, which is probably due to a "plastic-rubber" transition during tensile testing. The orientation and possible crystallization of PPF and PBF domains contribute to increased tensile strength and elastic modulus. This work showcases the potential of PPF and PBF in tailoring the thermo-mechanical properties of PLA in both bulk and fiber forms, expanding their applications in the packaging and textile industry.

A Green Treatment Mitigates the Limitations of Coffee Silver Skin as a Filler for PLA/PBSA Compatibilized Biocomposites.

The development of fully renewable and biodegradable composites for short-term applications was pursued by combining a compatibilized poly(lactic acid) (PLA)/poly(butylene succinate-co-adipate) (PBSA) (60:40 wt:wt) blend with coffee silver skin (CSS), an industrial byproduct from coffee processing. An epoxy-based reactive agent (Joncryl ADR-4468) was added as a compatibilizer. CSS was incorporated at 5, 10, and 20 wt% in the blend both in the as-received state and after a simple thermal treatment in boiling water, which was performed to mitigate the negative impact of this filler on the rheological and mechanical properties of the blend. The CSS treatment effectively increased the filler degradation temperature of 30-40 °C, enabling stable melt processing of the composites. It also improved filler-matrix adhesion, resulting in enhanced impact properties (up to +172% increase in impact energy compared to the untreated filler). Therefore, treated CSS demonstrated potential as an effective green reinforcement for PLA/PBSA blends for rigid packaging applications. Future works will focus on studying suitable surface modification of CSS to further increase the interfacial interaction and the tensile quasi-static properties, to fully exploit the capabilities of this renewable material toward the development of eco-friendly composites.

Development of Novel Polypropylene Syntactic Foams Containing Paraffin Microcapsules for Thermal Energy Storage Applications.

polypropylene (PP) syntactic foams (SFs) containing hollow glass microspheres (HGMs) possess low density and elevated mechanical properties, which can be tuned according to the specific application. A possible way to improve their multifunctionality could be the incorporation of organic Phase Change Materials (PCMs), widely used for thermal energy storage (TES) applications. In the present work, a PCM constituted by encapsulated paraffin, having a melting temperature of 57 °C, was embedded in a compatibilized polypropylene SF by melt compounding and hot pressing at different relative amounts. The rheological, morphological, thermal, and mechanical properties of the prepared materials were systematically investigated. Rheological properties in the molten state were strongly affected by the introduction of both PCMs and HGMs. As expected, the introduction of HGMs reduced both the foam density and thermal conductivity, while the enthalpy of fusion (representing the TES capability) was proportional to the PCM concentration. The mechanical properties of these foams were improved by the incorporation of HGMs, while they were reduced by addition of PCMs. Therefore, the combination of PCMs and HGMs in a PP matrix generated multifunctional materials with tunable thermo-mechanical properties, with a wide range of applications in the automotive, oil, textile, electronics, and aerospace fields.

Three Dimensional Printing of Multiscale Carbon Fiber-Reinforced Polymer Composites Containing Graphene or Carbon Nanotubes.

Three-dimensional printing offers a promising, challenging opportunity to manufacture component parts with ad hoc designed composite materials. In this study, the novelty of the research is the production of multiscale composites by means of a solvent-free process based on melt compounding of acrylonitrile-butadiene-styrene (ABS), with various amounts of microfillers, i.e., milled (M) carbon fibers (CFs) and nanofillers, i.e., carbon nanotubes (CNTs) or graphene nanoplatelets (GNPs). The compounded materials were processed into compression molded sheets and into extruded filaments. The latter were then used to print fused filament fabrication (FFF) specimens. The multiscale addition of the microfillers inside the ABS matrix caused a notable increase in rigidity and a slight increase in strength. However, it also brought about a significant reduction of the strain at break. Importantly, GNPs addition had a good impact on the rigidity of the materials, whereas CNTs favored/improved the composites' electrical conductivity. In particular, the addition of this nanofiller was very effective in improving the electrical conductivity compared to pure ABS and micro composites, even with the lowest CNT content. However, the filament extrusion and FFF process led to the creation of voids within the structure, causing a significant loss of mechanical properties and a slight improvement of the electrical conductivity of the printed multiscale composites. Selective parameters have been presented for the comparison and selection of compositions of multiscale nanocomposites.

Evaluating the Multifunctional Performance of Structural Composites for Thermal Energy Storage.

The simultaneous need for high specific mechanical properties and thermal energy storage (TES) function, present in several applications (e.g., electric vehicles), can be effectively addressed by multifunctional polymer-matrix composites containing a reinforcing agent and a phase change material (PCM). The PCMs generally decrease the mechanical properties of the host structural composites, but a multifunctional composite can still be beneficial in terms of mass saving, compared to two monofunctional units performing the structural and heat management functions individually. To quantify any possible advantages, this paper proposes an approach that determines the conditions for an effective mass saving at the system level and ranks the investigated structural TES composites with a parameter called multifunctional efficiency. It is found that the potential mass saving is higher when the volume fraction of the reinforcement is kept constant also when the PCM fraction increases or when the single phases (reinforcement, PCM) are themselves multifunctional.

Mechanical Behaviour of Multifunctional Epoxy/Hollow Glass Microspheres/Paraffin Microcapsules Syntactic Foams for Thermal Management.

Epoxy/hollow glass microsphere (HGM) syntactic foams (SFs) are peculiar materials developed to combine low density, low thermal conductivity, and elevated mechanical properties. In this work, multifunctional SFs endowed with both structural and thermal management properties were produced for the first time, by combining an epoxy matrix with HGM and a microencapsulated phase change material (PCM) having a melting temperature of 43 °C. Systems with a total filler content (HGM + PCM) up to 40 vol% were prepared and characterized from the mechanical point of view with a broad experimental campaign comprising quasi-static, impact, and fracture toughness tests. The experimental results were statistically treated and fitted with a linear model, to produce ternary phase diagrams to provide a comprehensive interpretation of the mechanical behaviour of the prepared foams. In quasi-static tests, HGM introduction helps to retain the specific tensile elastic modulus and to increase the specific compressive modulus. The brittle nature of HGMs decreases the Charpy impact properties of the SFs, while the PCM insertion improve their toughness. This result is confirmed in KIC and GIC tests, where the composition with 20 vol% of PCM shows an increase of 80% and 370% in KIC and GIC in to neat epoxy, respectively. The most promising compositions are those combining PCM and HGMs with a total particle volume fraction up to 40 vol%, thanks to their optimal combination of thermal management capability, lightness, thermal insulation, and mechanical properties. The ability to fine-tune the properties of the SFs, together with the acquired thermal energy storage (TES) capability, confirm the great potential of these multifunctional materials in automotive, electronics, and aerospace industries.

Thermophysical Properties of Multifunctional Syntactic Foams Containing Phase Change Microcapsules for Thermal Energy Storage.

Syntactic foams (SFs) combining an epoxy resin and hollow glass microspheres (HGM) feature a unique combination of low density, high mechanical properties, and low thermal conductivity which can be tuned according to specific applications. In this work, the versatility of epoxy/HGM SFs was further expanded by adding a microencapsulated phase change material (PCM) providing thermal energy storage (TES) ability at a phase change temperature of 43 °C. At this aim, fifteen epoxy (HGM/PCM) compositions with a total filler content (HGM + PCM) of up to 40 vol% were prepared and characterized. The experimental results were fitted with statistical models, which resulted in ternary diagrams that visually represented the properties of the ternary systems and simplified trend identification. Dynamic rheological tests showed that the PCM increased the viscosity of the epoxy resin more than HGM due to the smaller average size (20 µm vs. 60 µm) and that the systems containing both HGM and PCM showed lower viscosity than those containing only one filler type, due to the higher packing efficiency of bimodal filler distributions. HGM strongly reduced the gravimetric density and the thermal insulation properties. In fact, the sample with 40 vol% of HGM showed a density of 0.735 g/cm3 (-35% than neat epoxy) and a thermal conductivity of 0.12 W/(m∙K) (-40% than neat epoxy). Moreover, the increase in the PCM content increased the specific phase change enthalpy, which was up to 68 J/g for the sample with 40 vol% of PCM, with a consequent improvement in the thermal management ability that was also evidenced by temperature profiling tests in transient heating and cooling regimes. Finally, dynamical mechanical thermal analysis (DMTA) showed that both fillers decreased the storage modulus but generally increased the storage modulus normalized by density (E'/ρ) up to 2440 MPa/(g/cm3) at 25 °C with 40 vol% of HGM (+48% than neat epoxy). These results confirmed that the main asset of these ternary multifunctional syntactic foams is their versatility, as the composition can be tuned to reach the property set that best matches the application requirements in terms of TES ability, thermal insulation, and low density.

Graphene/Carbon Nanotube Hybrid Nanocomposites: Effect of Compression Molding and Fused Filament Fabrication on Properties.

The present work reports on the production and characterization of acrylonitrile butadiene styrene (ABS) hybrid nanocomposite filaments incorporating graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) suitable for fused filament fabrication (FFF). At first, nanocomposites with a total nanofiller content of GNP and/or CNT of 6 wt.% and a GNP/CNT relative percentage ratio of 0, 10, 30, 50, 70, and 100 were produced by melt compounding and compression molding. Their mechanical, electrical resistivity, and electromagnetic interference shielding effectiveness (EMI SE) properties were evaluated. The hybrid nanocomposites showed a linear increase in modulus and decrease in strength as a function of GNP content; on the other hand, the addition of CNT in hybrid nanocomposites determined a positive increase in electrical conductivity, but a potentially critical decrease of melt flow index. Due to the favorable compromise between processability and enhancement of performance (i.e., mechanical and electrical properties), the hybrid composition of 50:50 GNP/CNT was selected as the most suitable for the filament production of 6 wt.% carbonaceous nanocomposites. EMI SE of ABS-filled single CNT and hybrid GNP/CNT nanofillers obtained from compression molding reached the requirement for applications (higher than -20 dB), while slightly lower EMI SE values (in the range -12/-16 dB) were obtained for FFF parts dependent on the building conditions.

Effects of the Nanofillers on Physical Properties of Acrylonitrile-Butadiene-Styrene Nanocomposites: Comparison of Graphene Nanoplatelets and Multiwall Carbon Nanotubes.

The effects of carbonaceous nanoparticles, such as graphene (GNP) and multiwall carbon nanotube (CNT) on the mechanical and electrical properties of acrylonitrile⁻butadiene⁻styrene (ABS) nanocomposites have been investigated. Samples with various filler loadings were produced by solvent free process. Composites ABS/GNP showed higher stiffness, better creep stability and processability, but slightly lower tensile strength and electrical properties (low conductivity) when compared with ABS/CNT nanocomposites. Tensile modulus, tensile strength and creep stability of the nanocomposite, with 6 wt % of GNP, were increased by 47%, 1% and 42%, respectively, while analogous ABS/CNT nanocomposite showed respective values of 23%, 12% and 20%. The electrical percolation threshold was achieved at 7.3 wt % for GNP and 0.9 wt % for CNT. The peculiar behaviour of conductive CNT nanocomposites was also evidenced by the observation of the Joule's effect after application of voltages of 12 and 24 V. Moreover, comparative parameters encompassing stiffness, melt flow and resistivity were proposed for a comprehensive evaluation of the effects of the fillers.

Filaments Production and Fused Deposition Modelling of ABS/Carbon Nanotubes Composites.

Composite acrylonitrile-butadiene-styrene (ABS)/carbon nanotubes (CNT) filaments at 1, 2, 4, 6 and 8 wt %, suitable for fused deposition modelling (FDM) were obtained by using a completely solvent-free process based on direct melt compounding and extrusion. The optimal CNT content in the filaments for FDM was found to be 6 wt %; for this composite, a detailed investigation of the thermal, mechanical and electrical properties was performed. Presence of CNT in ABS filaments and 3D-printed parts resulted in a significant enhancement of the tensile modulus and strength, accompanied by a reduction of the elongation at break. As documented by dynamic mechanical thermal analysis, the stiffening effect of CNTs in ABS is particularly pronounced at high temperatures. Besides, the presence of CNT in 3D-printed parts accounts for better creep and thermal dimensional stabilities of 3D-printed parts, accompanied by a reduction of the coefficient of thermal expansion). 3D-printed nanocomposite samples with 6 wt % of CNT exhibited a good electrical conductivity, even if lower than pristine composite filaments.

Wax Confinement with Carbon Nanotubes for Phase Changing Epoxy Blends.

A paraffin wax was shape stabilized with 10 wt % of carbon nanotubes (CNTs) and dispersed in various concentrations in an epoxy resin to develop a novel blend with thermal energy storage capabilities. Thermogravimetric analysis showed that CNTs improve the thermal stability of paraffin, while differential scanning calorimetry showed that the paraffin kept its ability to melt and crystallize, with enthalpy values almost proportional to the paraffin fraction. In contrast, a noticeable loss of enthalpy was observed for epoxy/wax blends without CNTs, which was mainly attributed to the partial exudation of paraffin out of the epoxy matrix during the curing phase. Dynamic mechanical thermal analysis contributed to elucidate the effects of the melting of the paraffin phase on the viscoelastic properties of the epoxy blends. Flexural elastic modulus and strength of the blends decreased with the wax/CNT content according to a rule of mixtures, while flexural strain at break values deviate positively from it. These results show the potentialities of the investigated epoxy blends for the development of multifunctional structural composites.

Effects of Fumed Silica and Draw Ratio on Nanocomposite Polypropylene Fibers.

Hydrophylic fumed silica AR974 was tested as a potential nanofiller for the production of composite isotactic polypropylene filaments/fibers (containing 0.25⁻2 vol % of nanoparticles) via melt compounding and subsequent hot drawing. The objectives of this study were as follows: (i) to investigate the effects of the composition and the processing conditions on the microstructure and the thermal and mechanical properties of the produced fibers; (ii) to separate the effects of silica addition from those produced by fiber drawing; and (iii) to interpret the changes in the matrix molecular mobility (produced by silica and/or drawing). Scanning electron microscopy (SEM) evidenced a good dispersion of nanoparticles at fractions up to 0.5 vol % of the nanofiller. X-ray diffraction (XRD) analyses revealed the increase in crystallinity after drawing of both neat polypropylene (PP) and produced nanocomposite fibers. Consequently, tensile modulus and stress at break of the fibers were enhanced. Drawn fibers containing 0.25⁻0.5 vol % of nanofiller showed also a remarkable increase in the creep resistance. Loss modulus of drawn fibers showed a pronounced α-relaxation peak at about 65 °C; the higher the draw ratio, the higher the peak intensity. Thermal and mechanical properties of composite fibers were improved due to the combined effects of nanofiller reinforcement and fiber orientation produced during hot drawing. Both fumed silica and draw ratio were significantly effective on tensile modulus and tenacity of nanocomposite fibers up to 0.5 vol % of AR974.

Modeling of the devolatilization kinetics during pyrolysis of grape residues.

Thermo-gravimetric analysis (TGA) was performed on grape seeds, skins, stalks, marc, vine-branches, grape seed oil and grape seeds depleted of their oil. The TGA data was modeled through Gaussian, logistic and Miura-Maki distributed activation energy models (DAEMs) and a simpler two-parameter model. All DAEMs allowed an accurate prediction of the TGA data; however, the Miura-Maki model could not account for the complete range of conversion for some substrates, while the Gaussian and logistic DAEMs suffered from the interrelation between the pre-exponential factor k0 and the mean activation energy E0--an obstacle that can be overcome by fixing the value of k0 a priori. The results confirmed the capabilities of DAEMs but also highlighted some drawbacks in their application to certain thermodegradation experimental data.