Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)−3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by 1H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2394–2402

Thermoplastic resin transfer molding (T-RTM) is attracting much attention due to the need for recyclable alternatives to thermoset materials. In this work, we have prepared polyamide-6 (PA6) and PA6/fiber composites by T-RTM of caprolactam. Glass and carbon fibers were employed in a fixed amount of 60 and 47 wt.%, respectively. Neat PA6 and PA6 matrices (of PA6-GF and PA6-CF) of approximately 200 kg/mol were obtained with conversion ratios exceeding 95%. Both carbon fibers (CF) and glass fibers (GF) were able to nucleate PA6, with efficiencies of 44% and 26%, respectively. The α crystal polymorph of PA6 was present in all samples. The lamellar spacing, lamellar thickness and crystallinity degree did not show significant variations in the samples with or without fibers as result of the slow cooling process applied during T-RTM. The overall isothermal crystallization rate decreased in the order: PA6-CF > PA6-GF > neat PA6, as a consequence of the different nucleation efficiencies. The overall crystallization kinetics data were successfully described by the Avrami equation. The lamellar stack morphology observed by atomic force microscopy (AFM) is consistent with 2D superstructural aggregates (n = 2) for all samples. Finally, the reinforcement effect of fibers was larger than one order of magnitude in the values of elastic modulus and tensile strength.

Currently, the vast majority of composite waste is either landfilled or incinerated, causing a massive burden on the environment and resulting in the loss of potentially valuable raw material. Here, conventional pyrolysis and reactive pyrolysis were used to reclaim carbon fibers from aeronautical scrap material, and to evaluate the feasibility of using reclaimed carbon fibers in structural components for the automotive sector. The need for fiber sizing was investigated as well as the behavior of the fiber material in macroscopic impact testing. The fibers were characterized with the single fiber tensile test, scanning electron microscopy, and the microbond test. Critical fiber length was estimated in both polypropylene and polyamide matrices. Tensile strength of the fiber material was better preserved with the reactive pyrolysis compared to the conventional pyrolysis, but in both cases the interfacial shear strength was retained or even improved. The impact testing revealed that the components made of these fibers fulfilled all required deformation limits set for the components with virgin fibers. These results indicate that recycled carbon fibers can be a viable option even in structural components, resulting in lower production costs and greener composites.

The mechanical performance of a composite is greatly related to the load transfer capability of the interface between the matrix and the reinforcing fibers, i.e. the fiber/matrix adhesion, which is enhanced by a surface treatment called sizing. The original sizing of reinforcing fibers is removed during recycling process, which is recognized to contribute in typical issues of recycled fibers, namely uneven fiber properties and poor fiber/matrix adhesion. Applying a new sizing, a process denoted here as resizing, can help mitigate the issues. Furthermore, the sizing has a major role in improving the processability of the fibers as it contributes to the distribution of the fibers in the matrix. Proper distribution, along with the fiber fraction, are highly important for the composite performance. These properties are ensured by proper compounding. Here we demonstrate and validate the process steps to resize and compound recycled glass and carbon fibers with thermoplastic matrices. We found that at a relatively high sizing concentration, the compounding of all tested material combinations was possible. The resizing of the recycled fibers improved the compatibility at the fiber/matrix interface. It was concluded that recycled fibers can be used to replace virgin fibers in automotive industry to allow weight reductions and to promote circularity.

The possibility of recycling glass (GF) and carbon fibers (CF) from fiber-reinforced composites by using pyrolysis was studied. Different fibers from composite waste were recovered with thermal treatment. The recycled fibers were evaluated as a reinforcement for new materials or applications. The main objective was to evaluate the fibers obtained from the different types of industrial composite waste considering the format obtained, the cleanliness and the amount of inorganic fillers and finally, the fibers quality. These characteristics defined the processes, sectors and applications in which recycled fibers can replace virgin fibers. These fibers were also evaluated and validated with tensile testing and compared to the tensile strength of virgin GF and CF.