The two-domain Schmidt equation of state (EoS), which describes the pressure-specific volume–temperature (pvT) behavior of polymers in both the equilibrium molten/liquid state and non-equilibrium solid/glassy state, is often used in the simulation of polymer processing. However, this empirical model has a discontinuity problem and low fitting accuracy. This work derived a continuous two-domain pvT model with higher fitting accuracy compared with the Schmidt model. The cooling rate as an obvious influencing factor on the pvT behavior of polymers was also considered in the model. The interaction parameters of the equations were fitted with the experimental pvT data of an amorphous polymer, acrylonitrile-butadiene-styrene (ABS), and a semi-crystalline polymer, polypropylene (PP). The fitted results by the continuous two-domain EoS were in good agreement with the experimental data. The average absolute percentage deviations were 0.1% and 0.16% for the amorphous and semi-crystalline polymers, respectively. As a result, the present work provided a simple and useful model for the prediction of the specific volume of polymers as a function of temperature, pressure, and cooling rate.

The modelling of the correlation between pressure, specific volume and temperature (pvT) of polymers is highly important for applications in the polymer processing of semi-crystalline thermoplastics, especially in injection moulding. In injection moulding, the polymer experiences a wide range of cooling rates, for example, 60 °C/min near the centre of the part and up to 3000 °C/min near the mould walls. The cooling rate has a high influence on the pvT behaviour, as was shown in the continuous two-domain pvT model (CTD). This work examined the Hoffman–Lauritzen nucleation and growth theory used in the modified Hammami model for extremely high cooling rates (up to 300,000 °C/min) by means of Flash differential scanning calorimeter (DSC) measurements. The results were compared to those of the empirical continuous two-domain pvT model. It is shown that the Hammami model is not suitable to predict the crystallisation kinetics of polypropylene at cooling rates above 600 °C/min, but that the continuous two-domain pvT model is well able to predict crystallisation temperatures at high cooling rates.

The production of fibre-reinforced composites for use in applications such as type-4 pressure vessels for hydrogen storage is achieved through the use of a thermoset matrix. However, the recycling of thermosets presents a significant challenge due to the lack of established recycling methods. Epoxy-based vitrimers show thermoset characteristics during the manufacturing and utilisation phases but exhibit thermoplastic behaviour at elevated temperatures of 190 °C. This study investigates the industrial-scale production of carbon fibre reinforced vitrimers via a wet filament winding, as exemplified by a type-4 pressure vessel demonstrator. Processing conditions of industrial processes have yet to be applied to vitrimers; therefore, two vitrimer formulations are compared to a conventional epoxy thermoset. The processability and resulting composite quality of wound composites using these materials as matrices are compared. The mechanical properties of the composites are compared using an interlaminar shear strength test, demonstrating that the vitrimeric matrices exhibit 19.8% (23 °C) and 49.2% (140 °C) improved interlaminar strength. Consequently, the epoxy-based vitrimers investigated in this study can be employed as a direct replacement for the thermoset matrix in industrial-scale applications, with the potential for recycling the composite. To increase composite qualities, the winding process must be adapted for vitrimers, since a pore free composite could not be achieved.

Fibre-reinforced composites are facing new challenges in the context particular in sustainability and recyclability. Vitrimers could be useful as new matrices to support the increase in sustainability. Due to their high strength, which is comparable to that of thermosets often used in composites, and their covalent adaptive networks, which make them reshapeable for scaled-up manufacturing and recycling purposes, they are very useful. Orthogonal cutting is used for precise reshaping and functional integration into carbon fibre reinforced plastics. Vitrimers could improve processing results at the cutting edge as well as surface quality thanks to their self-healing properties compared to brittle matrices, as well as enabling the recycling of formed chips and scrap. This study showcases the manufacturing of a carbon fibre-reinforced vitrimer using 4-aminophenyl disulfide as a hardener, with vacuum-assisted resin infusion. The temperature of chip formation and the cutting parameters are then shown for different fibre orientations, cutting widths and speeds. The observed cutting forces are lower (less than 140 N) and more irregular for fibre orientations 45°/135°, increasing with cutting depth, and fluctuating periodically during machining. Despite varying cutting speeds, the forces remain relatively constant in range between 85 N and 175 N for 0°/90° fibre orientation and 50 N and 120 N for 45°/135° fibre orientation, with no significant tool wear observed and lower-damage depth and overhanging fibres observed for 0°/90° fibre orientation. Damage observation of the cutting tool shows promising results, with lower abrasion observed compared to thermoset matrices. Microscopic images of the broached surface also show good quality, which could be improved by self-healing of the matrix at higher temperatures. Temperature measurements of chip formation using a high-speed camera show a high temperature gradient as cutting speeds increase, but the temperature only ever exceeds 180 °C at cutting speeds of 150 m/min, ensuring reprocessability since this is below the degradation temperature. Therefore, orthogonal cutting of vitrimers can impact sustainable composite processing.