结晶动力学和结晶热力学补充材料解析.ppt

徐军 地址：英士楼218 电话 手机Email：jun-xu@tsinghua.edu.cn Process of Polymer CrystallizationTwo steps: 1. Nucleation (成核) process Size DG 0 embryo super critic. size stable critical nucleus DG = Gcrystal – Gmelt , DG = DH – TDS Gcrystal = Gbulk + SAs DG = Gbulk - Gmelt + SAs =DGf + SAs A is the suface area and DGf is the bulk free energy change. a b c Schematic representation of the change in free energy as a function of size illustrating the nucleation process Types of crystal nuclei. (a) primary (初次), (b) secondary (二次), (c) tertiary (三次) nucleus. Homogeneous (均相) and heterogeneous (异相) nucleation Estimate the critical nucleus size For primary nucleus For secondary nucleus 平衡熔点Tm0的测定方法 Gibbs-Thomson方程： Hoffman-Weeks方程： Hoffman JD, Weeks JJ. J. Res. Natl. Bur. Std. (U. S.) 1962, 66A, 13-28. 熔融线 熔融线 结晶线 Hoffman-Weeks 和Gibbs-Thomson方程的联系 Hoffman-Weeks曲线的斜率?, 等于熔融线和结晶线的斜率之比。 Thermodynamics of Crystallization: 2. Melting point of Polymer mixture Chemical Potential of Polymer in amorphous phase Consider a system of Polymer/Impurity mixture: Chemical Potential of one monomer unit of polymer in amorphous phase Polymer is compatible with impurity but can’t co-crystallize with impurity Effects of “Impurities” on Tm Condition of Phase Equilibrium Superscript of C: Crystalline Phase Superscript of I: Amorphous Phase Effects of “Impurities” on Tm For x2??, x1=1 For end-group effects: ?1=2/N, ?=0 For copolymer alternating copolymer: PXA Random copolmer: P=XA Block Copolymer: PXA?1 P: Probability of crystalline unit with sequential connection Note: For polymer blends polymer/small molecule polymer/polymer 2. Linear Growth of Polymer Crystallization Temperature dependence of linear growth rate (线生长速度) Temperature dependence of the radial growth rate u of spherulites in isotactic polystyrene (left), polyamid 6 (center) and poly(tetramethl-p-silpheylene siloxane) (right). Tf?: equilibrium melting temperature. Surface nucleation on sub