Nylon 66 nanofibers loaded with different Graphene (G) amounts were successfully produced with stable process and good fiber quality, using an optimized solvent system suitable both for electrospinning and for G-suspension. G addition is found to significantly affect diameter but not thermal behaviour. A new phenomenological model is proposed for the interpretation of mechanical behaviour of nanofibrous mat, trying to take into account the nanofibrous morphology. The model highlights a G contribution to mechanical properties that mainly affects the initial steps of deformation where fibers stretch, slide, twist and re-orient. Finally, the nanofibers were analysed after 20 months ageing, showing no significant alteration with respect to the pristine ones, thus the lack of detrimental ageing-effects due to G addition.
Nanofibrous nonwovens show high versatility and outstanding properties, with reduced weight. Porous morphology, high material flexibility and deformability challenge their mechanical testing, severely affecting results reliability. Still today, a specific technical standard method to carry out tensile testing of nonwoven nanofibrous mats is lacking, as well as studies concerning tensile test data reliability. In this work, an accurate, systematic, and critical study is presented concerning tensile testing of nonwovens, using electrospun Nylon 66 random nanofibrous mats as a case study. Nanofibers diameter and specimen geometry are investigated to thoroughly describe the nanomat tensile behavior, also considering the polymer thermal properties, and the nanofibers crossings number as a function of the nanofibers diameter. Below a threshold value, which lies between 150 and 250 nm, the overall mat mechanical behavior changes from ductile to brittle, showing enhanced elastic modulus for a high number of nanofibers crossings. While specimen geometry does not affect tensile results. Stress–strain data are analyzed using a phenomenological data fitting model to better interpret the tensile behavior. The experimental results demonstrate the high reliability of the proposed mass‐based load normalization, providing a simple, effective, and universally suitable method for obtaining high reproducible tensile stress–strain curves.
Still today, concerns regarding delamination limit the widespread use of high-performance composite laminates, such as carbon fiber-reinforced polymers (CFRPs), to replace metals. Nanofibrous mat interleaving is a well-established approach to reduce delamination. However, nanomodifications may strongly affect other laminate thermomechanical properties, especially if achieved by integrating soft materials. Here, this limitation is entirely avoided by using rubbery nitrile butadiene rubber (NBR)/Nomex mixed nanofibers: neither laminate stiffness nor glass-transition temperature ( T g ) lowering occurs upon CFRP nanomodification. Stable noncrosslinked nanofibers with up to 60% wt of NBR were produced via single-needle electrospinning, which were then morphologically, thermally, spectroscopically, and mechanically characterized. NBR and Nomex disposition in the nanofiber was investigated via selective removal of the sole rubber fraction, revealing the formation of particular self-assembled structures resembling quasi-core–shell nanofibers or fibril-like hierarchical structures, depending on the applied electrospinning conditions (1.10 and 0.20 mL/h, respectively). Mode I and Mode II loading tests show a significant improvement of the interlaminar fracture toughness of rubbery nanofiber-modified CFRPs, especially G I (up to +180%), while G II enhancement is less pronounced but still significant (+40% in the best case). The two nanofibrous morphologies (quasi-core–shell and fibril-like ones) improve the delamination resistance differently, also suggesting that the way the rubber is located in the nanofibers plays a role in the toughening action. The quasi-core–shell nanofiber morphology provides the best reinforcing action, besides the highest productivity. By contrast, pure Nomex nanofibers dramatically worsen the interlaminar fracture toughness (up to −70% in G I ), acting as a release film. The achieved delamination resistance improvements, combined with the retention of both the original laminate stiffness and T g , pave the way to the extensive and reliable application of NBR/Nomex rubbery nanofibrous mats in composite laminates.
Carbon Fiber Reinforced Polymers (CFRPs) are widely used where high mechanical performance and lightweight are required. However, they suffer from delamination and low damping, severely affecting laminate reliability during the service life of components. CFRP laminates modified by rubbery nanofibers interleaving is a recently introduced way to increase material damping and to improve delamination resistance. In this work, nitrile butadiene rubber/poly(ε-caprolactone) (NBR/PCL) blend rubbery nanofibrous mats with 60 wt% NBR were produced in three different mat grammages (5, 10 and 20 g/m2) via single-needle electrospinning and integrated into epoxy CFRP laminates. The investigation demonstrated that both mat grammage and positioning affect CFRP tanδ behaviour, evaluated by dynamic mechanical analysis (DMA) tests, as well as the number of nano-modified interleaves. Double cantilever beam (DCB) tests were carried out to assess the mat grammage effect on the interlaminar fracture toughness. Results show an outstanding improvement of GI,R for all the tested reinforced laminates regardless of the mat grammage (from +140% to +238%), while the effect on GI,C is more dependent on it (up to +140%). The obtained results disclose the great capability of NBR/PCL rubbery nanofibrous mats at improving CFRP damping and interlaminar fracture toughness. Moreover, CFRP damping can be tailored by choosing the number and positioning of the nano-modified interleaves, besides choosing the mat grammage.
In the present study, the separation performance of new self-standing polyvinylamine (PVAm) membranes loaded with few-layer graphene (G) and graphene oxide (GO) was evaluated, in view of their use in carbon capture applications. PVAm, provided by BASF as commercial product named LupaminTM, was purified obtaining PVAm films with two degrees of purification: Low Grade (PVAm-LG) and High Grade (PVAm-HG). These two-grade purified PVAm were loaded with 3 wt% of graphene and graphene oxide to improve mechanical stability: indeed, pristine tested materials proved to be brittle when dry, while highly susceptible to swelling in humid conditions. Purification performances were assessed through FTIR-ATR spectroscopy, DSC and TGA analysis, which were carried out to characterize the pristine polymer and its nanocomposites. In addition, the membranes′ fracture surfaces were observed through SEM analysis to evaluate the degree of dispersion. Water sorption and gas permeation tests were performed at 35 °C at different relative humidity (RH), ranging from 50% to 95%. Overall, composite membranes showed improved mechanical stability at high humidity, and higher glass transition temperature (Tg) with respect to neat PVAm. Ideal CO2/N2 selectivity up to 80 was measured, paired with a CO2 permeability of 70 Barrer. The membranes’ increased mechanical stability against swelling, even at high RH, without the need of any crosslinking, represents an interesting result in view of possible further development of new types of facilitated transport composite membranes.
Innovative nanofibrous membranes based on Pd/Au catalysts immobilized via electrospinning onto different polymers were engineered and tested in the selective oxidation of 5-(hydroxymethyl)furfural in an aqueous phase. The type of polymer and the method used to insert the active phases in the membrane were demonstrated to have a significant effect on catalytic performance. The hydrophilicity and the glass transition temperature of the polymeric component are key factors for producing active and selective materials. Nylon-based membranes loaded with unsupported metal nanoparticles were demonstrated to be more efficient than polyacrylonitrile-based membranes, displaying good stability and leading to high yield in 2,5-furandicarboxylic acid. These results underline the promising potential of large-scale applications of electrospinning for the preparation of catalytic nanofibrous membranes to be used in processes for the conversion of renewable molecules.
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