Effect of coagulation bath temperature on formation mechanism of poly(vinylidene fluoride) membrane

Effects of coagulation bath temperature on the membrane formation mechanism and the morphologies of the formed membranes were studied. The binodal and spinodal lines in the phase diagrams of water/DMAc/Poly(vinylidene fluoride) (PVDF) were calculated based on the thermodynamics equations of membrane formation, and the gel phase boundaries of the systems at 25°C and 60°C were determined via cloud point measurement. The obtained ternary phase diagrams of water/DMAc/PVDF contain three regions: the one‐phase region, the liquid–liquid two‐phase region, and the gel region. In the phase diagrams, the liquid–liquid demixing line (binodal) is located inside the gelation line. At low temperature, there exists a wide region between gelation line and binodal line. Gelation could occur in the absence of liquid–liquid demixing, and becomes the dominant membrane formation mechanism. At high temperatures (60°C), however, the gelation line approaches the binodal line, which results in a much smaller gelation zone. The kinetics of the solvent out‐flux and water influx were enhanced, liquid–liquid demixing is the dominant mechanism. The membrane formation mechanisms at different temperature were confirmed by the light transmission measurements during membrane forming process and the morphologies of the membranes examined by SEM imaging. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.