Journal of Polymer Science Part B: Polymer Physics, Vol.36, No.16, 2923-2930, 1998
Crystallization-induced composition inhomogeneities in PVDF/PMMA blends
Composition profiles develop around growing PVDF spherulites in a blend with PMMA. These profiles assume stationary courses after a certain crystallization time provided that the overall degree of crystallinity is not too high. The composition-dependent growth rate and the diffusion-controlled remove of the surplus PMMA from the spherulite surface are then in a stationary equilibrium. The internal structure of the spherulites will then be homogeneous, too. Upon isothermal crystallization of a PVDF/PMMA = 60/40 (wt %) blend at 160 degrees C for at least 4 h, the spherulites internal degree of crystallinity x(c) as related to the PVDF fraction obeys the inequality 55 wt % less than or equal to x(c) less than or equal to 84 wt %. The overall PMMA content within the spherulites as averaged over its whole inside has been determined by IR microscopy. It amounts to about 15 wt %. In contrast, the PMMA content of the amorphous phase within the spherulites (averaged again over its whole inside) ranges between 28 and 52 wt %. This composition jumps at the spherulite surface to 52 wt %. From the slope of the composition profiles outside the spherulites that have a width of more than 50 mu m, the effective chain diffusion coefficient in blends as averaged over both components can be calculated to amount to (250 +/- 100) mu m(2)h(-1).
Keywords:CRYSTAL AMORPHOUS INTERPHASE, POLYMER BLENDS, PHASE-SEPARATION;POLY(VINYLIDENE FLUORIDE), COMPETITION, METHACRYLATE);MORPHOLOGY, INTERFACE, BEHAVIOR, KINETICS