Rheological behavior of a semi-crystalline polymer during isothermal crystallization

Abstract

The theological behavior of a molten semi-crystalline polymer, namely, a high density polyethylene (HDPE), was investigated during isothermal crystallization from the melt, using dynamic oscillatory experiments at 1 tad/s in a parallel plates rheometer. The theological results were compared with those obtained from differential scanning calorimetry in the same conditions. During the crystallization, the molten and crystallizing polymer provides a useful model for filled polymers, the crystalline phase being the filler and the liquid phase being the matrix. In most cases, the filler can be considered to be spherical shaped (spherulites). Owing to the amorphous phase linking liquid and crystallites, the adhesion between matrix and filler in this system is perfect. The filler content increases continuously during the crystallization. This model might be used to test laws relating the theological parameters to the volume fraction of filler. Problems related to the rheometry for such systems are discussed and the key parameters insuring reproducibility and accuracy in the measurements are pointed out. The relative sensitivity of the various theological parameters (storage and loss moduli, loss angle) to structural changes of the liquid has been out forward. Some preliminary equations relating the variation of these parameters to the volume fraction of filler, through the use of simple fractal exponents have been derived and discussed in comparison with laws provided by various authors.