Effect of miscible polymer diluents on the development of lamellar morphology in poly(oxymethylene) blends

The development of lamellar morphology in poly(oxymethylene) (POM) and its miscible blends was studied by synchrotron time-resolved small-angle X-ray scattering (SAXS), during primary and secondary crystallization at temperatures near 150°C. The blends contained two different diluents: poly(vinyl 4-hydroxy styrene) [common name poly(vinyl phenol), (PVP)], which had a high glass temperature (T_g = 150°C), and styrene-co-hydroxy styrene oligomer (PhSO), which had a low glass temperature (T_g = -37°C). The SAXS data were analyzed by correlation function analysis to extract several lamellar parameters: long period (L), lamellar crystalline thickness (lc), amorphous layer thickness (la), and invariant (Q). The variation in Q defined the region where spherulites quickly grew and filled the entire space, and was referred to as the primary crystallization dominant regime. A rapid drop in L and lc was observed at early times, and this can be explained by defective lamellar stacks filling in space between primary stacks, as secondary crystals form during the nominal primary crystallization dominant regime. Lamellar thickening with time in the long-time secondary crystallization region was observed in neat POM and the blend with 10% low T_g diluent, while this process was inhibited with the high T_g diluent due to the higher T_g of the interlamellar species. A decrease in la at long times confirmed the lamellar thickening. We refer to the lamellar thickening process as a type of secondary crystallization. Interlamellar inclusion or trapping was detected to different degrees with the high T_g diluent, while exclusion was found for the low T_g diluent.