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The crystallization of semi-crystalline polymers is often analyzed by rheometry and calorimetry. By rheometry the viscosity evolution during crystallization can be followed, whereas from a calorimetric measurement, the evolution of the degree of crystallinity can be calculated. The time evolution of these material properties is valuable input for polymer processing simulation software and in order to combine the data in a reliable manner, hardening curves are used as a characterization tool. Such a hardening curve correlates the relative increase of the viscosity resulting from crystallization, to the advancing degree of crystallinity. In this study, these are extracted from simultaneous measurements on one sample using a RheoDSC device. The RheoDSC technique allows for the direct combination of the rheological and calorimetric signal without the need of combining separate stand-alone measurement results. In this study, isothermal crystallization experiments are used to discuss the benefits of this approach. This will lead to the recommendation that measuring the hardening effect in steady shear measurements at very low shear rates in a direct combined RheoDSC setup is the most reliable method to compile unambiguously a material specific hardening curve for semi-crystalline polymers.

RheoDSC Analysis of Hardening of Semi-Crystalline Polymers during Quiescent Isothermal Crystallization