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Polymer, Vol.55, No.14, 3186-3194, 2014
Melting behaviors of polyethylene crystals: An application of fast-scan DSC
Melting behaviors of linear polyethylene (PE) have been experimentally examined by fast-scan and conventional differential scanning calorimetry (DSC). By fast-scan heating up to 10(4) K s(-1), the melting peak temperature, (T)peak, is free from the influences of re-organization and re-crystallization and follows the shift only with superheating, which has been evaluated by a power-law behavior. The melting point, M-T, of the chain-folded crystals has been determined as Tpeak extrapolated to zero heating rate without the influences of non-equilibrium effects. The Hoffman-Weeks plot of TM against crystallization temperature, (T)c, suggests the equilibrium melting point M-T0 = 141.1 degrees C of the linear PE having M-w = 52.0 x 10(3) and the doubling of lamellar thickness concluded from the linear relationship between TM and Tc with the slope close to 1/2. While the lamellar doubling is a well-known behavior of PE crystallized from the melt, the present results with Tc down to similar to 100 degrees C suggest the doubling completed in a quite short time interval. The value of TA = 140.4 C has also been obtained by the Gibbs-Thomson plot of TM against the inverse of lamellar thickness, (d(c))(-1), determined by small angle X-ray scattering. The agreement of the results within +/- 1 degrees C suggests the Hoffman-Weeks plot as an appropriate method for the melting point determination with fast-scan heating, only with which the determination procedure is free from re-organization and re-crystallization. The consistent behavior has also been confirmed in terms of the end-surface free energy, sigma(e), determined by the Gibbs-Thomson plot and by the growth kinetics of crystallization. (C) 2014 Elsevier Ltd. All rights reserved.