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Estimation Of The Nucleation And Crystal Growth Contributions To The Overall Crystallization Energy Barrier

A. T. Lorenzo, A. Müller
Published 2008 · Chemistry

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Classical kinetic theories of polymer crystallization were applied to iso- thermal crystallization kinetics data obtained by polarized optical microscopy (PLOM) and differential scanning calorimetry (DSC). The fitted parameters that were proportional to the energy barriers obtained allow us to quantitatively estimate the nucleation and crystal growth contributions to the overall energy barrier associ- ated to the crystallization process. It was shown that the spherulitic growth rate energy barrier found by fitting PLOM data is almost identical to that obtained by fit- ting the isothermal DSC crystallization data of previously self-nucleated samples. Therefore, we demonstrated that by self-nucleating the material at the ideal self- nucleation (SN) temperature, the primary nucleation step can be entirely completed and the data obtained after subsequent isothermal crystallization by DSC contains only contributions from crystal growth or secondary nucleation. In this way, by employing SN followed by isothermal crystallization, we propose a simple method to obtain separate contributions of energy barriers for primary nucleation and for crys- tal growth, even in the case of polymers where PLOM data are very difficult to obtain (because they exhibit very small spherulites). Comparing the results obtained with poly(p-dioxanone), poly(e-caprolactone), and a high 1,4 model hydrogenated polybuta- diene, we have interpreted the differences in primary nucleation energy barriers as
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