Sommer J-U
Institut de Chimie des Surfaces et Interfaces (CNRS), 15 rue Jean Starcky, F-68057, Mulhouse Cedex, France.
Eur Phys J E Soft Matter. 2006 Apr;19(4):413-22. doi: 10.1140/epje/i2005-10055-1. Epub 2006 Apr 4.
The equilibrium state of polymer single crystals is considered by explicitly taking into account the amorphous fraction formed by loops and tails of the chains using a statistical model introduced by Muthukumar (Philos. Trans. R. Soc. London, Ser. A 361, 539 (2003)). We show that under realistic conditions below the equilibrium melting temperature, tight loops and close re-entries are favored, and that the amorphous fraction can be mapped into an excess surface free energy. The model is extended to many-chain crystals where it is shown that the lamellar thickness increases with the number of chains in the crystal and extended-chain conformations are thermodynamically favored if the number of chains in the crystal is sufficiently large. The number of chains necessary to form an extended-chain crystal in thermodynamic equilibrium scales with the square of the degree of polymerization of the chains. We discuss the temperature behavior of the equilibrium crystal thickness in the under-cooled state.
通过使用穆图库马尔提出的统计模型（《伦敦皇家学会哲学学报》A辑361卷，539页，2003年），明确考虑由链的环和尾形成的非晶部分，来研究聚合物单晶的平衡态。我们表明，在低于平衡熔点的实际条件下，紧密环和紧密再入是有利的，并且非晶部分可以映射为过量表面自由能。该模型扩展到多链晶体，结果表明层片厚度随晶体中链的数量增加而增加，并且如果晶体中的链数量足够大，伸展链构象在热力学上是有利的。在热力学平衡中形成伸展链晶体所需的链数量与链的聚合度的平方成比例。我们讨论了过冷状态下平衡晶体厚度的温度行为。
