摘要
在高分子溶液理论中引入Gibbs分布 ,用统计物理学方法重新推导出了聚合物溶液的热力学公式 .将高分子溶液的自由能和熵分三部分进行了计算 ,无热平动部分 ,无热构象部分和构象有热部分 .无热平动自由能和无热构象自由能分别等于Flory Huggins混合自由能公式的前两项 ,构象有热部分引入了Gibbs分布 ,考虑了链段 溶剂分子相互作用对高分子构象的影响 .在分子间的相互作用足够小时 。
The Gibbs distribution is introduced into the theory of polymer solutions. The statistical mechanics method is used to deduce the thermodynamic theory of polymer solutions. The analytical expressions of thermodynamic quantities, including the free energy of mixing kind the entropy of mixing, are presented in the present theory. The free energy of mixing has three fundamentally different types of contributions, i.e. the translational free energy, the configurational free energy and the thermal correction free energy. The first two terms of the free energy of mixing are equal to the corresponding terms in the FH theory. The influence of interactions among chain units and solvent molecules on the configuration is included in the third term. In the case of small interactions among solvent molecules and chain units the expression of free energy of mixing in the present theory approximates that of the FH theory. An apparent Flory interaction parameter chi(AP) is introduced in this paper. It not only depends on temperature and the interaction energy as the Flory interaction parameter chi, but also depends on the concentration of polymer solutions. The difference between chi(AP) and chi increases,as the interaction energy increases or the concentration of the solution increases.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2003年第4期581-587,共7页
Acta Polymerica Sinica
基金
国家重点基础研究专项经费 (项目号G19990 64 80 8)
863项目高分子加工的科学基础及软件化资助项目
