On the Melting and Crystallization of Linear Polyethylene, Poly(ethylene oxide) and Metallocene Linear Low-Density Polyethylene

The crystallization and melting behaviors of an ethylene/1-hexene copolymer and series of narrow molecular weight linear polyethylene and poly(ethylene oxide) fractions were studied using a combination of ultra-fast and conventional differential scanning calorimetry, optical microscopy, small angle X-ray scattering, and wide angle X-ray diffraction.

In the case of linear polyethylene and poly(ethylene oxide), the zero-entropy production melting temperatures of initial lamellae of isothermally crystallized fractions were analyzed in the context of the non-linear Hoffman-Weeks method. Using the Huggins equation, limiting equilibrium melting temperatures of 141.4 ± 0.8oC and 81.4 ± 1.0oC were estimated for linear polyethylene and poly(ethylene oxide), respectively. The former and the latter are about 4oC lower and 12.5oC higher than these predicted by Flory/Vrij and Buckley/Kovacs, respectively. Accuracy of the non-linear Hoffman-Weeks method was also examined using initial lamellar thickness literature data for a linear polyethylene fraction at different crystallization temperatures. The equilibrium melting temperature obtained by the Gibbs-Thomson approach and the C2 value extracted from the initial lamellar thickness vs. reciprocal of undercooling plot were similar within the limits of experimental error to those obtained here through the non-linear Hoffman-Weeks method.

In the next step, the Lauritzen-Hoffman (LH) secondary nucleation theory was modified to account for the effect of stem length fluctuations, tilt angle of the crystallized stems, and temperature dependence of the lateral surface free energy. Analysis of spherulite growth rate and wide angle X-ray diffraction data for 26 linear polyethylene and 5 poly(ethylene oxide) fractions revealed that the undercooling at the regime I/II transition, the equilibrium fold surface free energy, the strength of the stem length fluctuations and the substrate length at the regime I/II transition are independent of chain length. The value of the equilibrium fold surface free energy derived from crystal growth rate data using the modified Lauritzen-Hoffman theory matches that calculated from lamellar thickness and melting data through the Gibbs-Thomson equation for both linear polyethylene and poly(ethylene oxide). Larger spherulitic growth rates for linear polyethylene than for poly(ethylene oxide) at low undercooling is explained by the higher secondary nucleation constant of poly(ethylene oxide). While the apparent friction coefficient of a crystallizing linear polyethylene chain is 2 to 8 times higher than that of a chain undergoing reptation in the melt state, the apparent friction coefficient of a crystallizing poly(ethylene oxide) chain is about two orders of magnitude lower. This observation suggests that segmental mobility on the crystal phase plays a significant role in the crystal growth process.

In case of the statistical ethylene/1-hexene copolymer, the fold surface free energies of the copolymer lamellae at the time of crystallization and melting increase with increasing undercooling, approaching the same magnitude at high undercooling. As a result of this temperature dependence, the experimental melting vs. crystallization temperature plot is parallel to the Tm = Tc line and the corresponding Gibbs-Thomson plot is non-linear. This behavior is attributed to the fact that longer ethylene sequences form a chain-folded structure with lower concentration of branch points on the lamellar surface at lower undercooling, while shorter ethylene sequences form lamellar structures at higher undercooling exhibiting a higher concentration of branch points on the lamellar surface. Branch points limit the ability of lamellar structures to relax their kinetic stem-length fluctuations during heating prior to melting.