Thermal analysis of poly(phenylene sulfide). II: Non‐isothermal crystallization

The non‐isothermal crystallization of Fortron poly(phenylene sulfide), PPS, was examined to better understand its behavior during injection molding. The nonisothermal Avrami formalism was applied to this system, but this method was found to be questionable because of the sometimes severe curvature that appears in the plots of the transformed data. A method of ranking crystallization rates at low cooling rates by plotting the peak in the crystallization exotherm versus the cube root of cooling rate has been considered and shown to have limitations at the higher cooling rates of interest. The growth rate expression developed by J. D. Hoffman for polymer crystallization of chain folded lamella in three dimensions has been used to simulate crystallization exotherms. It was found that this could only fit the data at low cooling rates. At high cooling rates it was necessary to use a growth rate expression developed by Calvert and Ulhmann for polymer crystallization without chain folding. When this is used to describe a two dimensional growth geometry, close agreement in the positions of high cooling rate exotherms could be obtained. The implication is that a change in crystallization mechanism is possible as the conditions go from low to high cooling rates.