Development of a Xanthan Gum Based Superabsorbent and Water Retaining Composites for Agricultural and Forestry Applications.

In this work, bio-based hydrogel composites of xanthan gum and cellulose fibers were developed to be used both as soil conditioners and topsoil covers, to promote plant growth and forest protection. The rheological, morphological, and water absorption properties of produced hydrogels were comprehensively investigated, together with the analysis of the effect of hydrogel addition to the soil. Specifically, the moisture absorption capability of these hydrogels was above 1000%, even after multiple dewatering/rehydration cycles. Moreover, the soil treated with 1.8 wt% of these materials increased the water absorption capacity by approximately 60% and reduced the water evaporation rate, due to the formation of a physical network between the soil, xanthan gum and cellulose fibers. Practical experiments on the growth of herbaceous and tomato plants were also performed, showing that the addition of less than 2 wt% of hydrogels into the soil resulted in higher growth rate values than untreated soil. Furthermore, it has been demonstrated that the use of the produced topsoil covers helped promote plant growth. The exceptional water-regulating properties of the investigated materials could allow for the development of a simple, inexpensive and scalable technology to be extensively applied in forestry and/or agricultural applications, to improve plant resilience and face the challenges related to climate change.

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.

Barium Titanate Functionalization with Organosilanes: Effect on Particle Compatibility and Permittivity in Nanocomposites.

Barium titanate (BT) recently gained new interest in the preparation of dielectric and piezoelectric lead-free materials for applications in sensors, electronics, energy harvesting and storage fields. Barium titanate nanocomposites can achieve attractive performance, provided that the compatibility between ceramic particles and polymeric matrices is enhanced to the benefit of the physical properties of the final composite. Tuning the particle-matrix interface through particle functionalization represents a viable solution. In this work, surface functionalization of BT nanoparticles (NPs), obtained by hydrothermal synthesis, with 3-glycidyloxypropyltrimethoxysilane, 2-[(acetoxy(polyethyleneoxy)propyl]triethoxysilane and triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, was performed after optimizing the hydroxylation process of the NPs to improve their surface reactivity and increase the yield of grafting. Solid-state nuclear magnetic resonance and thermogravimetric analysis were used to quantify the molecules grafted onto the ceramic nanoparticles. Both bare and functionalized particles were employed in the realization of epoxy- and polydimethylsiloxane (PDMS)-based nanocomposites. Functionalization was proven to be beneficial for particle dispersibility and effective for particle alignment in the PDMS matrix. Moreover, the dielectric constant measurements revealed the potential of PDMS-based nanocomposites for applications in the field of dielectric elastomers.

Compatibilization of Polylactide/Poly(ethylene 2,5-furanoate) (PLA/PEF) Blends for Sustainable and Bioderived Packaging.

Despite the advantages of polylactide (PLA), its inadequate UV-shielding and gas-barrier properties undermine its wide application as a flexible packaging film for perishable items. These issues are addressed in this work by investigating the properties of melt-mixed, fully bioderived blends of polylactide (PLA) and poly(ethylene furanoate) (PEF), as a function of the PEF weight fraction (1-30 wt %) and the amount of the commercial compatibilizer/chain extender Joncryl ADR 4468 (J, 0.25-1 phr). J mitigates the immiscibility of the two polymer phases by decreasing and homogenizing the PEF domain size; for the blend containing 10 wt % of PEF, the PEF domain size drops from 0.67 ± 0.46 µm of the uncompatibilized blend to 0.26 ± 0.14 with 1 phr of J. Moreover, the increase in the complex viscosity of PLA and PLA/PEF blends with the J content evidences the effectiveness of J as a chain extender. This dual positive contribution of J is reflected in the mechanical properties of PLA/PEF blends. Whereas the uncompatibilized blend with 10 wt % of PEF shows lower mechanical performance than neat PLA, all the compatibilized blends show higher tensile strength and strain at break, while retaining their high elastic moduli. The effects of PEF on the UV- and oxygen-barrier properties of PLA are also remarkable. Adding only 1 wt % of PEF makes the blend an excellent barrier for UV rays, with the transmittance at 320 nm dropping from 52.8% of neat PLA to 0.4% of the sample with 1 wt % PEF, while keeping good transparency in the visible region. PEF is also responsible for a sensible decrease in the oxygen transmission rate, which decreases from 189 cc/m2·day for neat PLA to 144 cc/m2·day with only 1 wt % of PEF. This work emphasizes the synergistic effects of PEF and J in enhancing the thermal, mechanical, UV-shielding, and gas-barrier properties of PLA, which results in bioderived blends that are very promising for packaging applications.

Multifunctionality of Reduced Graphene Oxide in Bioderived Polylactide/Poly(Dodecylene Furanoate) Nanocomposite Films.

This work reports on the first attempt to prepare bioderived polymer films by blending polylactic acid (PLA) and poly(dodecylene furanoate) (PDoF). This blend, containing 10 wt% PDoF, was filled with reduced graphene oxide (rGO) in variable weight fractions (from 0.25 to 2 phr), and the resulting nanocomposites were characterized to assess their microstructural, thermal, mechanical, optical, electrical, and gas barrier properties. The PLA/PDoF blend resulted as immiscible, and the addition of rGO, which preferentially segregated in the PDoF phase, resulted in smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and in a higher PLA/PDoF interfacial interaction, which suggests the role of rGO as a blend compatibilizer. rGO also increased PLA crystallinity, and this phenomenon was more pronounced when PDoF was also present, thus evidencing a synergism between PDoF and rGO in accelerating the crystallization kinetics of PLA. Dynamic mechanical thermal analysis (DMTA) showed that the glass transition of PDoF, observed at approx. 5 °C, shifted to a higher temperature upon rGO addition. The addition of 10 wt% PDoF in PLA increased the strain at break from 5.3% to 13.0% (+145%), and the addition of 0.25 phr of rGO increased the tensile strength from 35.6 MPa to 40.2 MPa (+13%), without significantly modifying the strain at break. Moreover, rGO decreased the electrical resistivity of the films, and the relatively high percolation threshold (between 1 and 2 phr) was probably linked to the low aspect ratio of rGO nanosheets and their preferential distribution inside PDoF domains. PDoF and rGO also modified the optical transparency of PLA, resulting in a continuous decrease in transmittance in the visible/NIR range. Finally, rGO strongly modified the gas barrier properties, with a remarkable decrease in diffusivity and permeability to gases such as O2, N2, and CO2. Overall, the presented results highlighted the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and functional properties of PLA, with simultaneous enhancement of ductility, crystallization kinetics, and gas barrier performance, and these novel polymer nanocomposites could thus be promising for packaging applications.

Cyclic Olefin Copolymer Interleaves for Thermally Mendable Carbon/Epoxy Laminates.

Thin cyclic olefin copolymer (COC) foils were used as intrinsic thermoplastic healing agents in carbon fiber (CF)-reinforced epoxy laminates. COC films were produced by hot pressing and were interleaved in the interlaminar regions between each EP/CF lamina, during the hand layup fabrication of the laminates. Three samples were produced, i.e., the neat EP/CF laminate without COC, and two laminates containing COC layers with a thickness of 44 µm and 77 µm, respectively. It was observed that the fiber volume fraction decreased, and the porosity increased with the introduction of COC layers, and this effect was more evident when thick films were used. These two effects, combined with the sub-optimal adhesion between COC and EP, caused a decrease in the mechanical properties (i.e., the elastic modulus, flexural strength, interlaminar shear strength and interlaminar fracture toughness) of the laminates. Specimens subjected to mode I interlaminar fracture toughness test were then thermally mended under pressure by resistive heating, through the Joule effect of conductive CFs. A temperature of approximately 190 °C was reached during the healing treatment. The healing efficiency was evaluated as the ratio of critical strain energy release rate (GIC) of the healed and virgin specimens. Healed specimens containing COC layers of 44 µm and 77 µm exhibited a healing efficiency of 164% and 100%, respectively. As expected, the healing treatment was not beneficial for the neat EP/CF laminate without COC, which experienced a healing efficiency of only 2%. This result proved the efficacy of COC layers as a healing agent for EP/CF laminates, and the effectiveness of resistive heating as a way to activate the intrinsic healing mechanism.

Compatibilization of Polyamide 6/Cyclic Olefinic Copolymer Blends for the Development of Multifunctional Thermoplastic Composites with Self-Healing Capability.

This study investigated the self-healing properties of PA6/COC blends, in particular, the impact of three compatibilizers on the rheological, microstructural, and thermomechanical properties. Dynamic rheological analysis revealed that ethylene glycidyl methacrylate (E-GMA) played a crucial role in reducing interfacial tension and promoting PA6 chain entanglement with COC domains. Mechanical tests showed that poly(ethylene)-graft-maleic anhydride (PE-g-MAH) and polyolefin elastomer-graft-maleic anhydride (POE-g-MAH) compatibilizers enhanced elongation at break, while E-GMA had a milder effect. A thermal healing process at 140 °C for 1 h was carried out on specimens broken in fracture toughness tests, performed under quasi-static and impact conditions, and healing efficiency (HE) was evaluated as the ratio of critical stress intensity factors of healed and virgin samples. All the compatibilizers increased HE, especially E-GMA, achieving 28.5% and 68% in quasi-static and impact conditions, respectively. SEM images of specimens tested in quasi-static conditions showed that all the compatibilizers induced PA6 plasticization and crack corrugation, thus hindering COC flow in the crack zone. Conversely, under impact conditions, E-GMA led to the formation of brittle fractures with planar surfaces, promoting COC flow and thus higher HE values. This study demonstrated that compatibilizers, loading mode, and fracture surface morphologies strongly influenced self-healing performance.

Evaluation of the Physical and Shape Memory Properties of Fully Biodegradable Poly(lactic acid) (PLA)/Poly(butylene adipate terephthalate) (PBAT) Blends.

Biodegradable polymers have recently become popular; in particular, blends of poly(lactic acid) (PLA) and poly(butylene adipate terephthalate) (PBAT) have recently attracted significant attention due to their potential application in the packaging field. However, there is little information about the thermomechanical properties of these blends and especially the effect induced by the addition of PBAT on the shape memory properties of PLA. This work, therefore, aims at producing and investigating the microstructural, thermomechanical and shape memory properties of PLA/PBAT blends prepared by melt compounding. More specifically, PLA and PBAT were melt-blended in a wide range of relative concentrations (from 85/15 to 25/75 wt%). A microstructural investigation was carried out, evidencing the immiscibility and the low interfacial adhesion between the PLA and PBAT phases. The immiscibility was also confirmed by differential scanning calorimetry (DSC). A thermogravimetric analysis (TGA) revealed that the addition of PBAT slightly improved the thermal stability of PLA. The stiffness and strength of the blends decreased with the PBAT amount, while the elongation at break remained comparable to that of neat PLA up to a PBAT content of 45 wt%, while a significant increment in ductility was observed only for higher PBAT concentrations. The shape memory performance of PLA was impaired by the addition of PBAT, probably due to the low interfacial adhesion observed in the blends. These results constitute a basis for future research on these innovative biodegradable polymer blends, and their physical properties might be further enhanced by adding suitable compatibilizers.

Effect of Different Cellulose Fillers on the Properties of Xanthan-Based Composites for Soil Conditioning Applications.

The aim of this study was to investigate the effect of different types of natural cellulose-based fillers on the properties of Xanthan gum (XG) in order to develop novel bio-based soil conditioners (SCs) that could be used in forestry and agricultural applications. Rheological measurements highlighted that SCs with cellulose fillers characterized by a high aspect ratio and low oxide ash content exhibited an average increase of 21% in yield stress compared to neat Xanthan gum. The presence of cellulose fillers in the composites resulted in a slower water release than that of neat XG, limiting the volumetric shrinkage during the drying process. Furthermore, an analysis of the water absorption and water retention capacity of soils treated with the different SCs was carried out, demonstrating that the addition of 1.8 wt.% of SC with optimized composition to the soil led to an increase in water absorption capacity from 34% up to 69%. From the soil water retention curves, it was observed that the addition of SCs significantly increased the amount of water effectively available for plants in the area between field capacity and permanent wilting point (100-1000 kPa). From practical experiments on grass growth, it was observed that these SCs improved the water regulation of the soil, thus increasing the probability of plant survival under drought conditions.

High Temperature Performance of Concrete Confinement by MWCNT Modified Epoxy Based Fiber Reinforced Composites.

The conventional method of fiber reinforced polymer (FRP) wrapping around concrete columns uses epoxy as the binder along with synthetic or natural fibers such as carbon, glass, basalt, jute, sisal etc. as the reinforcement. However, the thermal stability of epoxy is a major issue in application areas prone to fire exposure. The current work addressed this major drawback of epoxy by modifying it with a nanofiller, such as multiwalled carbon nanotubes (MWCNT), and reinforcing it using basalt and sisal fibers. The effect of exposure to elevated temperature on the behavior of concrete cylinders externally confined with these FRP systems was analyzed. Three types of specimens were considered: unconfined; confined with sisal fiber reinforced polymer (SFRP); and confined with hybrid sisal basalt fiber reinforced polymer (HSBFRP) specimens. The test samples were exposed to elevated temperature regimes of 100 °C, 200 °C, 300 °C and 400 °C for a period of 2 h. The compressive strengths of unconfined specimens were compared with various confined specimens, and from the test results, it was evident that the mechanical and thermal durability of the FRP systems was substantially enhanced by MWCNT incorporation. The reduction in the compressive strength of the FRP-confined specimens varied depending on the type of the confinement. After two hours of exposure at 400 °C, the compressive strength corresponding to the epoxy-HSBFRP-confined specimens were improved by 15%, whereas a 50% increase in strength corresponding to MWCNT-incorporated epoxy-HSBFRP-confined specimens was observed with respect to unconfined unexposed specimens. The MWCNT-modified epoxy-incorporated FRP-confined systems demonstrated superior performance even at elevated temperatures in comparison to unconfined specimens at ambient temperatures.

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.

Thermo-Mechanical Behavior of Novel EPDM Foams Containing a Phase Change Material for Thermal Energy Storage Applications.

In this paper Ethylene Propylene Diene Monomer rubber (EPDM) foams were filled with different amounts of paraffin, a common phase change material (PCM) having a melting temperature at about 70 °C, to develop novel rubber foams with thermal energy storage (TES) capabilities. Samples were prepared by melt compounding and hot pressing, and the effects of three foaming methods were investigated. In particular, two series of samples were produced through conventional foaming techniques, involving physical (Micropearl® F82, MP, Lehvoss Italia s.r.l. Saronno, Italia) and chemical (Hostatron® P0168, H, Clariant GmbH, Ahrensburg, Germany) blowing agents, while the salt leaching method was adopted to produce another series of foams. Scanning electron microscopy (SEM) and density measurements showed that MP led to the formation of a closed-cell porosity, while a mixed closed-cell/open-cell morphology was detected for the H foamed samples. On the other hand, foams produced through salt leaching were mainly characterized by an open-cell porosity. The qualitative analysis of paraffin leakage revealed that at 90 °C only the foams produced through salt leaching suffered from significant PCM leakage. Consequently, the thermo-mechanical properties were investigated only in samples produced with H and MP. Differential Scanning Calorimetry (DSC) analysis revealed that EPDM/paraffin foams were endowed by good TES properties, especially at higher PCM contents (up to 145 J/g with a paraffin amount of 60 wt%). Tensile and compressive tests demonstrated the addition of the PCM increased the stiffness at 25 °C, while the opposite effect was observed above the melting temperature of paraffin. These results suggest that the EPDM foams produced with H and MP show an interesting potential for thermal management of electronic devices.

Thermotropic Optical Response of Silicone-Paraffin Flexible Blends.

Organic phase change materials, e.g., paraffins, are attracting increasing attention in thermal energy storage (TES) and thermal management applications. However, they also manifest interesting optical properties such as thermotropism, as they can switch from optically opaque to transparent reversibly and promptly at the melting temperature. This work aims at exploiting this feature to produce flexible silicone-based blends with thermotropic properties for applications in glazed windows or thermal sensors. Blends are produced by adding paraffin (Tm = 44 °C, up to 10 phr) to a silicone bicomponent mixture, and, for the first time, cetyltrimethylammonium bromide (CTAB) is also added to promote paraffin dispersion and avoid its exudation. CTAB is proven effective in preventing paraffin exudation both in the solid and in the liquid state when added in a fraction above 3 phr with respect to paraffin. Rheological results show that paraffin decreases the complex viscosity, but neither paraffin nor CTAB modifies the curing behavior of silicone, which indicates uniform processability across the investigated compositions. On the other hand, paraffin causes a decrease in the stress and strain at break at 60 °C, and this effect is amplified by CTAB, which acts as a defect and stress concentrator. Conversely, at room temperature, solid paraffin only slightly impairs the mechanical properties, while CTAB increases both the elastic modulus and tensile strength, as also highlighted with ANOVA. Finally, optical transmittance results suggest that the maximum transmittance difference below and above the melting temperature (65-70 percentage points) is reached for paraffin amounts of 3 to 5 phr and a CTAB amount of max. 0.15 phr.

Improving the Thermomechanical Properties of Poly(lactic acid) via Reduced Graphene Oxide and Bioderived Poly(decamethylene 2,5-furandicarboxylate).

Polylactide (PLA) is the most widely used biopolymer, but its poor ductility and scarce gas barrier properties limit its applications in the packaging field. In this work, for the first time, the properties of PLA solvent-cast films are improved by the addition of a second biopolymer, i.e., poly(decamethylene 2,5-furandicarboxylate) (PDeF), added in a weight fraction of 10 wt%, and a carbon-based nanofiller, i.e., reduced graphene oxide (rGO), added in concentrations of 0.25-2 phr. PLA and PDeF are immiscible, as evidenced by scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy, with PDeF spheroidal domains showing poor adhesion to PLA. The addition of 0.25 phr of rGO, which preferentially segregates in the PDeF domains, makes them smaller and considerably rougher and improves the interfacial interaction. Differential scanning calorimetry (DSC) confirms the immiscibility of the two polymer phases and highlights that rGO enhances the crystallinity of both polymer phases (especially of PDeF). Thermogravimetric analysis (TGA) highlights the positive impact of rGO and PDeF on the thermal degradation resistance of PLA. Quasi-static tensile tests evidence that adding 10 wt% of PDeF and a small fraction of rGO (0.25 phr) to PLA considerably enhances the strain at break, which raises from 5.3% of neat PLA to 10.0% by adding 10 wt% of PDeF, up to 75.8% by adding also 0.25 phr of rGO, thereby highlighting the compatibilizing role of rGO on this blend. On the other hand, a further increase in rGO concentration decreases the strain at break due to agglomeration but enhances the mechanical stiffness and strength up to an rGO concentration of 1 phr. Overall, these results highlight the positive and synergistic contribution of PDeF and rGO in enhancing the thermomechanical properties of PLA, and the resulting nanocomposites are promising for packaging applications.

Statistical Modeling and Optimization of the Drawing Process of Bioderived Polylactide/Poly(dodecylene furanoate) Wet-Spun Fibers.

Drawing is a well-established method to improve the mechanical properties of wet-spun fibers, as it orients the polymer chains, increases the chain density, and homogenizes the microstructure. This work aims to investigate how drawing variables, such as the draw ratio, drawing speed, and temperature affect the elastic modulus (E) and the strain at break (εB) of biobased wet-spun fibers constituted by neat polylactic acid (PLA) and a PLA/poly(dodecamethylene 2,5-furandicarboxylate) (PDoF) (80/20 wt/wt) blend. Drawing experiments were conducted with a design of experiment (DOE) approach following a 24 full factorial design. The results of the quasi-static tensile tests on the drawn fibers, analyzed by the analysis of variance (ANOVA) and modeled through the response surface methodology (RSM), highlight that the presence of PDoF significantly lowers E, which instead is maximized if the temperature and draw ratio are both low. On the other hand, εB is enhanced when the drawing is performed at a high temperature. Finally, a genetic algorithm was implemented to find the optimal combination of drawing parameters that maximize both E and εB. The resulting Pareto curve highlights that the temperature influences the mechanical results only for neat PLA fibers, as the stiffness increases by drawing at lower temperatures, while optimal Pareto points for PLA/PDoF fibers are mainly determined by the draw ratio and the draw rate.

Improving the Wet-Spinning and Drawing Processes of Poly(lactide)/Poly(ethylene furanoate) and Polylactide/Poly(dodecamethylene furanoate) Fiber Blends.

This work aims to produce poly(lactic acid) (PLA)/poly(alkylene furanoate)s (PAF)s fiber blends for textile applications and evaluates their microstructural, chemical, thermal, and mechanical properties. The work focuses on two PAFs with very different alkyl chain lengths, i.e., poly(ethylene 2,5-furandicarboxylate) (PEF) and poly(dodecamethylene 2,5-furandicarboxylate) (PDoF), which were blended in solution at various concentrations (in the range 2.5-10 wt %) with PLA, wet spun, and subsequently drawn. Light optical micrographs highlight that PLA/PEF blends present large and concentrate PEF domains, whereas PLA/PDoF blends show small and homogeneously distributed PDoF domains. The blends appear to be immiscible, which is confirmed also by scanning electron microscopy (SEM), Fourier-Transform Infrared (FT-IR) spectroscopy, and differential scanning calorimetry (DSC). Thermogravimetric analysis (TGA) highlights that the addition of the PAFs improves the thermal stability of the fibers. The drawing process, which was carried out at 80 °C with a heat setting step at 95 °C and at three draw ratios, improves the mechanical properties of the fibers upon the addition of the PAFs. The results obtained in this study are promising and may serve as a basis for future investigations on these novel bio-based fiber blends, which can contribute to increase the environmental sustainability of industrial textiles.

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.

Thermal Mending of Electroactive Carbon/Epoxy Laminates Using a Porous Poly(ε-caprolactone) Electrospun Mesh.

For the first time, a porous mesh of poly(ε-caprolactone) (PCL) was electrospun directly onto carbon fiber (CF) plies and used to develop novel structural epoxy (EP) composites with electro-activated self-healing properties. Three samples, i.e., the neat EP/CF composite and two laminates containing a limited amount of PCL (i.e., 5 wt.% and 10 wt.%), were prepared and characterized from a microstructural and thermo-mechanical point of view. The introduction of the PCL mesh led to a reduction in the flexural stress at break (by 17%), of the interlaminar shear strength (by 15%), and of the interlaminar shear strength (by 39%). The interlaminar fracture toughness of the prepared laminates was evaluated under mode I, and broken samples were thermally mended at 80 °C (i.e., above the melting temperature of PCL) by resistive heating generated by a current flow within the samples through Joule's effect. It was demonstrated that, thanks to the presence of the electrospun PCL mesh, the laminate with a PCL of 10 wt.% showed healing efficiency values up to 31%.

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.

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.