ABSTRACT
Polyurethanes are gaining increasing interest for their use as structural components subjected to cyclic loads, such as leaf springs. Thermoset polyurethane (PUR) based technology offers some advantages, such as fatigue resistance, low viscosity, and fast curing. However, current PUR formulations present two major drawbacks: their petrochemical origin and high reactivity. The aim of this work was to develop a novel biobased PUR (BIO-PUR) with the required mechanical properties and processability for manufacturing structural composites by resin transfer moulding (RTM). For this purpose, a high functionality and high hydroxyl index castor-oil-based polyol was used combined with a biobased glycerol (BIO-Gly) to increase the crosslinking density and improve the final properties of the BIO-PUR. The viscosity and reactivity of the different systems were studied by means of rheology tests and differential scanning calorimetry (DSC). Thermal and mechanical properties were studied by dynamic mechanical analysis (DMA) and flexural tests. Furthermore, the RTM process of a representative part was simulated and validated through the manufacturing and testing of plates. The properties of the BIO-PUR resin systems were strongly influenced by the addition of biobased glycerol and its effect on the crosslinking density. The combination of a high functionality and hydroxyl index biobased polyol with the biobased glycerol resulted in a high-performance BIO-PUR with the required reactivity and final properties for structural applications.
ABSTRACT
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.
ABSTRACT
From an environmental and cost-effective perspective, a number of research challenges can be found for electronics, household, but especially in the automotive polymer parts industry. Reducing synthesis steps, parts coating and painting, or other solvent-assisted processes, have been identified as major constrains for the existing technologies. Therefore, simple polymer processing routes (mixing, extrusion, injection moulding) were used for obtaining PMMA/HNT nanocomposites. By these techniques, an automotive-grade polymethylmethacrylate (PMMA) was modified with halloysite nanotubes (HNT) and an eco-friendly additive N,N'-ethylenebis(stearamide) (EBS) to improve nanomechanical properties involved in scratch resistance, mechanical properties (balance between tensile strength and impact resistance) without diminishing other properties. The relationship between morphological/structural (XRD, TEM, FTIR) and tribological (friction) properties of PMMA nanocomposites were investigated. A synergistic effect was found between HNT and EBS in the PMMA matrix. The synergy was attained by the phase distribution resulted from the selective interaction between partners and favourable processing conditions. Modification of HNT with EBS improved the dispersion of nanoparticles in the polymer matrix by increasing their interfacial compatibility through hydrogen bonding established by amide groups with aluminol groups. The increased interfacial adhesion further improved the nanocomposite scratch resistance. The PMMA/HNT-EBS nanocomposite had a lower coefficient of friction and lower scratch penetration depth than PMMA/HNT nanocomposite.
