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.

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.

Special Issue "Investigation of Polymer Nanocomposites' Performance".

Through this editorial, we aim to present the main aspects related to the scientific contributions that can be found in the Special Issue dedicated to the topic "Investigation of Polymer Nanocomposites' Performance" [...].

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.

Characterization of Cyclic Olefin Copolymers for Insulin Reservoir in an Artificial Pancreas.

Type-1 diabetes is one of the most prevalent metabolic disorders worldwide. It results in a significant lack of insulin production by the pancreas and the ensuing hyperglycemia, which needs to be regulated through a tailored administration of insulin throughout the day. Recent studies have shown great advancements in developing an implantable artificial pancreas. However, some improvements are still required, including the optimal biomaterials and technologies to produce the implantable insulin reservoir. Here, we discuss the employment of two types of cyclic olefin copolymers (Topas 5013L-10 and Topas 8007S-04) for an insulin reservoir fabrication. After a preliminary thermomechanical analysis, Topas 8007S-04 was selected as the best material to fabricate a 3D-printed insulin reservoir due to its higher strength and lower glass transition temperature (Tg). Fiber deposition modeling was used to manufacture a reservoir-like structure, which was employed to assess the ability of the material to prevent insulin aggregation. Although the surface texture presents a localized roughness, the ultraviolet analysis did not detect any significant insulin aggregation over a timeframe of 14 days. These interesting results make Topas 8007S-04 cyclic olefin copolymer a potential candidate biomaterial for fabricating structural components in an implantable artificial pancreas.

Ladder-like Poly(methacryloxypropyl) silsesquioxane-Al2O3-polybutadiene Flexible Nanocomposites with High Thermal Conductivity.

Ladder-like poly(methacryloxypropyl)-silsesquioxanes (LPMASQ) are photocurable Si-based gels characterized by a double-stranded structure that ensures superior thermal stability and mechanical properties than common organic polymers. In this work, these attractive features were exploited to produce, in combination with alumina nanoparticles (NPs), both unmodified and functionalized with methacryloxypropyl-trimethoxysilane (MPTMS), LPMASQ/Al2O3 composites displaying remarkable thermal conductivity. Additionally, we combined LPMASQ with polybutadiene (PB) to produce hybrid nanocomposites with the addition of functionalized Al2O3 NPs. The materials underwent thermal stability, structural, and morphological evaluations via thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR). Both blending PB with LPMASQ and surface functionalization of nanoparticles proved to be effective strategies for incorporating a higher ceramic filler amount in the matrices, resulting in significant increases in thermal conductivity. Specifically, a 113.6% increase in comparison to the bare matrix was achieved at relatively low filler content (11.2 vol%) in the presence of 40 wt% LPMASQ. Results highlight the potential of ladder-like silsesquioxanes in the field of thermally conductive polymers and their applications in heat dissipation for flexible electronic devices.

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.

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 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.

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.

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.

Electrospun Shape-Stabilized Phase Change Materials Based on Photo-Crosslinked Polyethylene Oxide.

Phase change materials (PCMs) in the form of fibers or fibrous mats with exceptional thermal energy storage ability and tunable working temperature are of high interest to produce smart thermoregulating textiles, useful for increasing human thermal comfort while avoiding energy waste. Common organic PCMs suffer from instability in their molten state, which limits their applicability as highly performing fibrous systems. In this work, electrospun fibrous mats made of polyethylene oxide (PEO), a PCM with excellent thermal properties and biocompatibility, were fabricated and their shape instability in the molten state was improved through UV photo-crosslinking. The characterization aimed to assess the performance of these shape-stable electrospun mats as nanofibrous PCMs for thermal management applications. In addition to an enhanced resistance to water-based solvents, UV-cured electrospun PEO mats demonstrated a remarkable latent heat (≈112 J/g), maintained over 80 heating/cooling cycles across the phase change temperature. Moreover, their morphological stability above their melting point was demonstrated both macroscopically and microscopically, with the retention of the initial nanofibrous morphology. Tensile mechanical tests demonstrated that the UV crosslinking considerably enhanced the ultimate properties of the fibrous mat, with a five-fold increase in both the tensile strength (from 0.15 MPa to 0.74 MPa) and the strain at break (from 2.5% to 12.2%) compared to the uncrosslinked mat. In conclusion, the photo-crosslinked electrospun PEO material exhibited high thermal properties and good shape stability without displaying leakage; accordingly, in the proposed PCM system, the necessity for encapsulation or use of a supporting layer has been eliminated. Photo-crosslinking thus proved itself as an effective, fast, and environmentally friendly method to dramatically improve the shape-stability of nanofibrous PEO electrospun mats for smart thermoregulating textiles.

Mechanical and Functional Properties of Novel Biobased Poly(decylene-2,5-furanoate)/Carbon Nanotubes Nanocomposite Films.

The present work investigates the microstructural, thermo-mechanical, and electrical properties of a promising, but still not thoroughly studied, biobased polymer, i.e., poly(decylene furanoate) (PDeF), and its performance when multi-walled carbon nanotubes (CNTs) are added. After sample preparation by solution mixing and film casting, the microstructural investigation evidences that the fracture surface becomes smoother and more homogeneous with a small fraction of CNTs, and that the production process is suitable to achieve good disentanglement and dispersion of CNTs within the matrix, although some aggregates are still observable. CNTs act as nucleating agents for PDeF crystals, as evidenced by differential scanning calorimetry, as the crystallinity degree increases from 43.2% of neat PDeF to 55.0% with a CNT content of 2 phr, while the crystallization temperature increases from 68.4 °C of PDeF to 91.7 °C of PDeF-CNT-2. A similar trend in crystallinity is confirmed by X-ray diffraction, after detailed Rietveld analysis with a three-phase model. CNTs also remarkably improve the mechanical performance of the bioderived polymer, as the elastic modulus increases up to 123% and the stress at break up to 131%. The strain at break also increases by +71% when a small amount of 0.25 phr of CNTs are added, which is probably the consequence of a more homogeneous microstructure. The long-term mechanical performance is also improved upon CNT addition, as the creep compliance decreases considerably, which was observed for both the elastic and the viscoelastic component. Finally, the films become electrically dissipative for a CNT content of 1 phr and conductive for a CNT amount of 2 phr. This study contributes to highlight the properties of bioderived furan-based polymer PDeF and evidences the potential of CNTs as a promising nanofiller for this matrix.

Bioinspired Polydopamine Coating as an Adhesion Enhancer Between Paraffin Microcapsules and an Epoxy Matrix.

Microencapsulated phase change materials (PCMs) are attracting increasing attention as functional fillers in polymer matrices, to produce smart thermoregulating composites for applications in thermal energy storage (TES) and thermal management. In a polymer composite, the filler-matrix interfacial adhesion plays a fundamental role in the thermomechanical properties. Hence, this work aims to modify the surface of commercial PCM microcapsules through the formation of a layer of polydopamine (PDA), a bioinspired polymer that is emerging as a powerful tool to functionalize chemically inert surfaces due to its versatility and great adhesive potential in many different materials. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) evidenced that after PDA coating, the surface roughness increased from 9 to 86 nm, which is beneficial, as it allows a further increase in the interfacial interaction by mechanical interlocking. Spectroscopic techniques allowed investigating the surface chemistry and identifying reactive functional groups of the PDA layer and highlighted that, unlike the uncoated microcapsules, the PDA layer is able to react with oxirane groups, thereby forming a covalent bond with the epoxy matrix. Hot-stage optical microscopy and differential scanning calorimetry (DSC) highlighted that the PDA modification does not hinder the melting/crystallization process of the paraffinic core. Finally, SEM micrographs of the cryofracture surface of epoxy composites containing neat or PDA-modified microcapsules clearly evidenced improved adhesion between the capsule shell and the epoxy matrix. These results showed that PDA is a suitable coating material with considerable potential for increasing the interfacial adhesion between an epoxy matrix and polymer microcapsules with low surface reactivity. This is remarkably important not only for this specific application but also for other classes of composite materials. Future studies will investigate how the deposition parameters affect the morphology, roughness, and thickness of the PDA layer and how the layer properties influence the capsule-matrix adhesion.

Docosane-Organosilica Microcapsules for Structural Composites with Thermal Energy Storage/Release Capability.

Organic phase change materials (PCMs) represent an effective solution to manage intermittent energy sources as the solar thermal energy. This work aims at encapsulating docosane in organosilica shells and at dispersing the produced capsules in epoxy/carbon laminates to manufacture multifunctional structural composites for thermal energy storage (TES). Microcapsules of different sizes were prepared by hydrolysis-condensation of methyltriethoxysilane (MTES) in an oil-in-water emulsion. X-ray diffraction (XRD) highlighted the difference in the crystalline structure of pristine and microencapsulated docosane, and 13C solid-state nuclear magnetic resonance (NMR) evidenced the influence of microcapsules size on the shifts of the representative docosane signals, as a consequence of confinement effects, i.e., reduced chain mobility and interaction with the inner shell walls. A phase change enthalpy up to 143 J/g was determined via differential scanning calorimetry (DSC) on microcapsules, and tests at low scanning speed emphasized the differences in the crystallization behavior and allowed the calculation of the phase change activation energy of docosane, which increased upon encapsulation. Then, the possibility of embedding the microcapsules in an epoxy resin and in an epoxy/carbon laminate to produce a structural TES composite was investigated. The presence of microcapsules agglomerates and the poor capsule-epoxy adhesion, both evidenced by scanning electron microscopy (SEM), led to a decrease in the mechanical properties, as confirmed by three-point bending tests. Dynamic mechanical analysis (DMA) highlighted that the storage modulus decreased by 15% after docosane melting and that the glass transition temperature of the epoxy resin was not influenced by the PCM. The heat storage/release properties of the obtained laminates were proved through DSC and thermal camera imaging tests.