Up to now, fiber-reinforced composites with thermoplastic matrix have seen limited fields of use in the structural scope due to their high viscosity in the molten state, which results in poor impregnability of the reinforcement, leading to mechanical properties of the finished product that are not comparable to those of thermosets. Although the latter still dominate the various sectors of automotive, aerospace, transportation and construction, new applications involving the production of thermoplastic composites are growing rapidly, offering new approaches to the solution of this problem. The aim of this work is to study and evaluate the state of the art on the manufacturing processes of thermoplastic matrix composite, analyzing the parameters that come into play and that most influence the process and material performance. The advantages of film stacking and powder impregnation techniques are contrasted by the versatility of hybrid fabrics and, at the same time, parameters such as pressure and temperature must be carefully considered. A description of different thermoplastic composite processes such as powder impregnation, film stacking molding, hybrid woven fabric, hybrid yarn and products follows, which represent the current possibilities to move from a thermosetting matrix composite to a thermoplastic one, upon which the concept of sustainability is based. This article wants to present an overview of research that has been done in manufacturing thermoplastic reinforced composites and will serve as a baseline and aid for further research and development efforts.

To move toward eco-sustainable and circular composites, one of the most effective solutions is to create thermoplastic composites. The strong commitment of world organizations in the field of safeguarding the planet has directed the research of these materials toward production processes with a lower environmental impact and a strong propensity to recycle the polymeric part. Under its chemical properties, Nylon 6 is the polymer that best satisfies this specific trade-off. The most common production processes that use a thermosetting matrix are described. Subsequently, the work aimed at investigating the use of thermoplastics in the same processes to obtain comparable performances with the materials that are currently used. Particular attention was given to the in situ anionic polymerization process of Nylon 6, starting from the ε-caprolactam monomer. The dependencies of the process parameters, such as temperature, time, pressure, humidity, and concentration of initiators and activators, were therefore investigated with reference to the vacuum infusion technique, currently optimized only to produce thermosetting matrix composites, but promising for the realization of thermoplastic matrix composite; this is the reason why we chose to focus our attention on the vacuum infusion. Finally, three production processes of the polymeric matrix and glass fiber composites were compared in terms of carbon footprint and cumulative energy demand (CED) through life-cycle assessment (LCA).

With a view to achieving sustainable development and a circular economy, this work focused on the possibility to valorize a secondary waste stream of recycled carbon fiber (rCF) to produce a 3D printing usable material with a PA6,6 polymer matrix. The reinforcing fibers implemented in the research are the result of a double-recovery action: starting with pyrolysis, long fibers are obtained, which are used to produce non-woven fabrics, and subsequently, fiber agglomerate wastes obtained from this last process are ground in a ball mill. The effect of different amounts of reinforcement at 5% and 10% by weight on the mechanical properties of 3D-printed thermoplastic composites was investigated. Although the recycled fraction was successfully integrated in the production of filaments for 3D printing and therefore in the production of specimens via the fused deposition modeling technique, the results showed that fibers did not improve the mechanical properties as expected, due to an unsuitable average size distribution and the presence of a predominant dusty fraction ascribed to the non-optimized ball milling process. PA6,6 + 10 wt.% rCF composites exhibited a tensile strength of 59.53 MPa and a tensile modulus of 2.24 GPa, which correspond to an improvement in mechanical behavior of 5% and 21% compared to the neat PA6,6 specimens, respectively. The printed composite specimens loaded with the lowest content of rCF provided the greatest improvement in strength (+9% over the neat sample). Next, a prediction of the “optimum” critical length of carbon fibers was proposed that could be used for future optimization of recycled fiber processing.

Cleavable bio-based epoxy resin systems are emerging, eco-friendly, and promising alternatives to the common thermoset ones, providing quite comparable thermo-mechanical properties while enabling a circular and green end-of-life scenario of the composite materials. In addition to being designed to incorporate a bio-based resin greener than the conventional fully fossil-based epoxies, these formulations involve cleaving hardeners that enable, under mild thermo-chemical conditions, the total recycling of the composite material through the recovery of the fiber and matrix as a thermoplastic. This research addressed the characterization, processability, and recyclability of a new commercial cleavable bio-resin formulation (designed by the R-Concept company) that can be used in the fabrication of fully recyclable polymer composites. The resin was first studied to investigate the influence of the different post-curing regimes (room temperature, 100 °C, and 140 °C) on its thermal stability and glass transition temperature. According to the results obtained, the non-post-cured resin displayed the highest T_g (i.e., 76.6 °C). The same post-curing treatments were also probed on the composite laminates (glass and carbon) produced via a lab-scale vacuum-assisted resin transfer molding system, evaluating flexural behavior, microstructure, and dynamic-mechanical characteristics. The post-curing at 100 °C would enhance the crosslinking of polymer chains, improving the mechanical strength of composites. With respect to the non-post-cured laminates, the flexural strength improved by 3% and 12% in carbon and glass-based composites, respectively. The post-curing at 140 °C was instead detrimental to the mechanical performance. Finally, on the laminates produced, a chemical recycling procedure was implemented, demonstrating the feasibility of recovering both thermoplastic-based resin and fibers.

Cleavable bio-based epoxy resin systems are emerging, eco-friendly, and promising alternatives to the common thermoset ones, providing quite comparable thermo-mechanical properties while enabling a circular and green end-of-life scenario of the composite materials. In addition to being designed to incorporate a bio-based resin greener than the conventional fully fossil-based epoxies, these formulations involve cleaving hardeners that enable, under mild thermo-chemical conditions, the total recycling of the composite material through the recovery of the fiber and matrix as a thermoplastic. This research addressed the characterization, processability, and recyclability of a new commercial cleavable bio-resin formulation (designed by R-Concept company) that can be use in the fabrication of fully recyclable polymer composites. The resin was first studied to investigate the influence different post-curing regime (room temperature, 100°C, and 140°C) on its thermal stability and glass transition temperature. According to the results obtained, the non-post-cured resin displayed the highest Tg (i.e., 76.6°C). The same post-curing treatments were also probed on the composite laminates (glass and carbon) produced via a lab-scale vacuum-assisted resin transfer molding system evaluating the flexural behavior, microstructure and dynamic-mechanical characteristics. The post-curing at 100°C would enhances the crosslinking of polymer chains, improving the mechanical strength of composites. With respect the non-post-cured laminates, the flexural strength improved by 3% and 12% in carbon and glass-based composites, respectively. The post-curing at 140°C was instead detrimental for the mechanical performance Finally, on the produced laminates, a chemical recycling procedure was implemented, demonstrating the feasibility of recovering both thermoplastic-based resin and fibers.

With a view to sustainable development and circular economy, this work focused on the possibility to valorize a secondary waste stream of recycled carbon fiber (rCF) to produce a 3D printing usable material with PA6,6 polymer matrix. The reinforcing fibers implemented in the present research are the result of a double recovery action: starting with pyrolysis from which long fibers are obtained, used to produce non-woven fabrics and, subsequently, fiber agglomerate wastes obtained from this last process are ground in a ball mill. The effect of a different amount of reinforcement at 5% and 10% by weight on the mechanical properties of 3D printed thermoplastic composites was investigated. Although the recycled fraction was successfully integrated in the production of filaments for 3D printing and therefore in the production of specimens via Fused Deposition Modeling technique, the results showed that fibers did not improve the mechanical properties as expected, due to an unsuitable average size distribution and the presence of a predominant dusty fraction ascribed to the non-optimized ball milling process. PA6,6 + 10 wt.% rCF composites exhibited a tensile strength of 59.53 MPa and a tensile modulus of 2.24 GPa, which correspond to an improvement in mechanical behavior of 21 5 % and 5 21 % compared to the neat PA6,6 specimens, respectively. The printed composite specimens loaded with the lowest content of rCF provided the greatest improvement in strength (+ 9% over the neat sample). Then, a prediction of the “optimum” critical length of carbon fibers was proposed that could be used for future optimizations of the recycled fiber processing.