The melting-point depression of a random copolymer with comonomer exclusion from the crystalline phase is investigated. The analysis is based on simulation results obtained with an extended Sadler-Gilmer crystallization model. Apparent copolymer melting points T,p(l) of lamellae of finite thickness I are observed. Further thickening is entropically suppressed. It is shown that the average lamellar thickness and the minimum thermodynamically stable thickness converge at Tzp. The fine-grained nature of the model reveals an entropic contribution to the melting-point depression, which is due to the so-called blind attachment of chain segments to the growth face. Our new kinetic melting-point equation is compared with the equilibrium result by Flory and shows a considerably stronger melting-point depression.
Посилання на статтю:
On the melting-point depression of copolymer crystals / G. Goldbeck-Wood // Polymer. – 1992. – Vol 33. – P. 778-782.