Detection and characterization of folded-chain clusters in the structured melt of isotactic polypropylene

Abstract

Despite ceaseless efforts in past decades, the memory effect of semi-crystalline polymers has not been elucidated completely yet. An important reason why is that residual lamellar crystals in the structured melt are difficult to characterize. Recently, we developed a new small-angle X-ray scattering (SAXS) theory [Li et al. (2019). IUCrJ, 6, 968–983] and Fourier transform method [Li et al. (2020). CrystEngComm, 22, 3042–3058] for lamellar crystals that could derive structural information from SAXS readily. In this study, we tried to employ the new theory and method to characterize residual lamellar crystals in the structured melt. It was found that although scattering peaks cannot be observed in raw scattering profiles, they actually exist. Subtracting free-melt scattering and multiplying by q4 benefit the observation of these weak scattering peaks. With the new Fourier transform method, it was found that indeed as proposed previously, thicker lamellar crystals exist in the structured melt. To determine the lateral size of residual lamellar crystal especially, a new method was developed under the guidance of the new theory. With the new method, it was found that although the crystallinity is very low (∼1% at 174°C), the lateral sizes in the structured melts are still large, e.g. 45.3 nm at 174°C, much greater than the critical nucleation size. This implies that these residual lamellar crystals can act as athermal nuclei after quenching to a lower temperature, as proposed by Ziabicki & Alfonso [(1994). Colloid Polym. Sci. 272, 1027–1042; (2002). Macromol. Symp. 185, 211–231] more than 20 years ago. The methodologies proposed here could also be applied to other polymer lamellar systems.

Keywords

• crystal engineering
• crystal morphology
• crystal-structure prediction
• folded-chain clusters
• lamellar systems
• structured melts
• isotactic polypropylene
• saxs