Isotactic Polypropylene (iPP) is a widely used polymer due to its excellent mechanical and thermal properties, as well as its chemical resistance. The crystallization behavior of polypropylene is influenced by several factors, such as temperature, cooling rate, and pressure. The effect of pressure is significant for both scientific and technological points of view, since in important industrial processing techniques the polymer solidifies under high pressures. In this paper, the study of the effect of pressure on the crystallization kinetics of iPP was conducted using a dilatometer in the pressure range from 100 to 600 bar and under two cooling rates: 0.1 and 1 °C/s. The morphology of the samples was characterized using DSC, optical microscopy, and X-ray diffraction. The results showed that pressure had a larger effect on specific volume changes at higher temperatures (in the melt state) than at lower temperatures (in the solid state). The polymer crystallization, which determined the transition between the melt and solid state, occurred at higher temperatures with increasing pressure. The cooling rate affected the crystallization process, with higher cooling rates leading to crystallization at lower temperatures. The size of the spherulites decreased with increasing cooling rates. The crystallinity evolution curves showed a linear relationship between the crystallization temperature and pressure. The study used a Kolmogoroff–Avrami–Evans model to describe the evolution into isotropic structures, and the predictions of the model accurately described the effect of pressure and cooling rates on the final spherulite radii.

It is generally recognized that high-temperature treatments, namely annealing, influence the microstructure and the morphology, which, in turn, determine the mechanical properties of polymeric parts. Therefore, annealing can be adopted to control the mechanical performance of the molded parts. This work aims to assess the effect of annealing on the morphology developed in isotactic polypropylene (iPP) injection-molded parts. In particular, a two-step annealing is adopted: the polymer is injected in a mold at a high temperature (413 or 433 K), which is kept for 5 min (first annealing step); afterward, the mold temperature is cooled down at 403 K and held at that temperature for a time compatible with the crystallization half-time at that temperature (second annealing step). The characterization of morphology is carried out by optical and electronic scanning microscopy. The temperature of the first annealing step does not influence the thickness of the fibrillar skin layer; however, such a layer is thinner than that found in the molded parts obtained without any annealing steps. The second annealing step does not influence the thickness of the fibrillar skin layer. The dimension of spherulites found in the core is strongly influenced by both annealing steps: the spherulite dimensions enlarge by the effect of annealing steps. A model that considers spherulite and fibril evolutions is adopted to describe the effect of molding conditions on the final morphology distribution along the part thickness. The model, which adopts as input the thermo-mechanical histories calculated by commercial software for injection molding simulation, consistently predicts the main effects of the molding conditions on the morphology distributions.

A part made of just one material (mono-material) is a new frontier in reducing environmental impact of plastic, being 100% recyclable. The focus of this work is on the possibility of controlling the properties of parts obtained by microinjection molding (𝝁IM). 𝝁IM tests in variothermal conditions are conducted on an isotactic polypropylene. Two variothermal steps are adopted: the filling and packing stages are conducted at one selected mold temperature, and subsequent annealing steps are conducted while the sample is still inside the mold. A comparison with the parts produced under constant mold temperature is also performed. Electronic microscopy is adopted for the characterization of morphology. Furthermore, atomic force microscopy coupled with HarmoniX (HMX) tool allows detecting simultaneously local morphology and mechanical properties. The part morphology is characterized by a fibrillar layer close to the sample walls and a spherulitic core; a transition zone is also detectable in between. Morphology significantly influences mechanical properties: the transition zone shows the minimum value of elastic modulus, additionally, the elastic modulus increases with spherulite dimensions. Eventually, the annealing step results to be crucial in determining the part properties and can be adopted as a robust method to tailor properties through the process.