A thermodynamic multiphase scheme treating polymer crystallization and melting.

A comparison of transition and melting temperatures of n-alkanes with experimentally determined ticknesses and melting points of polyethylene lamellae shows that the variation of the thickness with the crystallization temperature virtually agrees with the chain length dependence of the crystalline-mesomorphic phase transition in n-alkanes. Mesomorphic polyethylene layers are stable objects up to the thickness set by this phase transition. The findings lend further support to the view that polymer crystallization generally uses a route which includes a passage via a mesomorphic phase. We construct a thermodynamic scheme dealing with the transitions between melt, mesomorphic layers and lamellar crystallites, assuming for the latter ones that they exist both in an initial "native" and a final "stabilized" form. Application of the scheme in a reconsideration and quantitative evaluation of SAXS and DSC results previously obtained for PE, sPP, iPS and P(epsilonCL) yields the equilibrium transition temperatures between the various phases, latent heats of transition and surface free energies. According to the results the mesomorphic phases are not liquid-like, but have thermodynamic properties which place them truly intermediate between melt and crystals.