结晶动力学和结晶热力学补充材料.pptVIP

优选结晶动力学和结晶热力学补充材料当前第1页\共有15页\编于星期三\10点 Process of Polymer CrystallizationTwo steps: 1. Nucleation (成核) processSizeDG0embryosuper critic. sizestablecritical nucleusDG = Gcrystal – Gmelt , DG = DH – TDSGcrystal = Gbulk + SAsDG = Gbulk - Gmelt + SAs =DGf + SAsA is the suface area and DGf is the bulk free energy change.abcSchematic representation of the change in free energy as a function of size illustrating the nucleation processTypes of crystal nuclei. (a) primary (初次), (b) secondary (二次), (c) tertiary (三次) nucleus. Homogeneous (均相) and heterogeneous (异相) nucleation当前第2页\共有15页\编于星期三\10点 Estimate the critical nucleus size For primary nucleus For secondary nucleus当前第3页\共有15页\编于星期三\10点 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.熔融线当前第4页\共有15页\编于星期三\10点 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。当前第5页\共有15页\编于星期三\10点 Thermodynamics of Crystallization: 2. Melting point of Polymer mixtureChemical Potential of Polymer in amorphous phaseConsider a system of Polymer/Impurity mixture:Chemical Potential of one monomer unit of polymer in amorphous phasePolymer is compatible with impurity but can’t co-crystallize with impurity当前第6页\共有15页\编于星期三\10点 Effects of “Impurities” on TmCondition of Phase EquilibriumSuperscript of C: Crystalline PhaseSuperscript of I: Amorphous Phase当前第7页\共有15页\编于星期三\10点 Effects of “Impurities” on TmFor x2??, x1=1For end-group effects: ?1=2/N, ?=0For copolymeralternating copolymer: PXARandom copolmer: P=XABlock Copolymer: PXA?1P: Probability of crystalline unit with sequential connection Note:For polymer blendspolymer/small moleculepolymer/polymer当前第8页\共有15页\编于星期三\10点 2. Linear Growth of Polymer CrystallizationTemperature 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 melti