Crystallization of poly(vinyl alcohol) during solvent removal: Infrared characterization and mathematical modeling

Abstract

Crystallization of semicrystalline polymer films during drying has a significant effect on the rate of solvent removal. Understanding and controlling the crystallization kinetics is important in controlling residual solvent levels and drying kinetics. The degree of crystallinity of the poly(vinyl alcohol) films during multicomponent drying was investigated using Fourier transform infrared spectroscopy (FTIR). The 1141 cm-1 band is sensitive to the degree of crystallinity of the polymer and the growth of intensity of this band was monitored as drying progressed. The results from the FTIR studies were comparable to the results obtained from differential scanning calorimetry. Studies were conducted to test the effect of initial solvent composition (water-methanol mixture), drying temperature, and polymer molecular weight on the rate of crystallization and the final crystallinity of the films. An increase in initial methanol composition increased the crystallization rate but did not affect the final degree of crystallinity. An increase in drying temperature and decrease in polymer molecular weight increased the rate of crystallization as well as the final degree of crystallinity. Based on the experimental data, rate constants for crystallization kinetics were extracted from our previously developed model based on free volume theory. The experimental data and the simulation results showed good agreement. The ability of the free volume theory to illustrate the crystallization behavior validated the model and improved its capability.