Correlation of Cooperatively Localized Rearrangement on the ＂Fluidized Domain＂ of Polymers to Their Nonexponentially Viscoelastic Behaviors at Double Aging Processes （I）： A Set of Reduced Universal Equations on the Stress Relaxation Modulus and Creep Comp  

双重老化下高聚物流动微区的关联性局部化重排同其非指数性粘弹行为间的相关性（I）：一组具有K-W-W伸展指数函数的应力松弛模量和蠕变柔量对比态普适方程

作　　者：刘颖[2] 宋名实[1] 金艳[2] 胡桂贤[1] 吴大鸣[2] 

机构地区：[1]北京化工大学材料科学与工程学院,北京100029 [2]北京化工大学机电工程学院,北京100029

出　　处：《Chinese Journal of Chemical Physics》2010年第1期45-64,I0001,共21页化学物理学报（英文）

基　　金：ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.50973007）.

摘　　要：Based on the structure of glass （or liquid） polymers consisting of α-domain, β-co-domain, and entanglement constituent chain networks, and the nonexponentially viscoelastic behavior, a “heterophase fluctuation” model was proposed. It was found that the dynamics of cooperative rearrangement on the “fluidized domain” has a great shear rate, domain size, and temperature dependences. When the shear rate, domain size, and temperature dependences were taken account into the cooperatively localized rearrangement on the fluidized domain by the degradation of primary α-domain and the reformation of secondary β-co-domain constituent chains. A new dynamic theory of cooperatively localized rearrangement on the fluidized domain constituent chains with different size and different network chain length during physical and mechanical aging was established. The total viscoelastic free en-ergy of deformation resulting from the change in conformations of α-domain, β-co-domain, crytallite, crosslinked, and trapped entanglement constituent chains during aging processes was calculated by the combining method of kinetics and statistical mechanics. The constitu- tive equations and reduced stress relaxation modulus and creep compliances for three types of polymers were also derived. Finally, two reduced universal equations on creep compliance and stress relaxation modulus with a non-linear and two nonexponential parameters α and β were theoretically derived from the dynamic theory and a statistically extended mode coupling theory for double aging effects of polymers was developed. Results show that the two reduced universal equations have the same form as Kohlraush-Williams-Watts （K-W-W） stretched exponential function. The nonlinearity and the nonexponentiality are, respectively, originated from the memory effects of nonthermal and thermal history. The correlation of nonlinearity, α and β to the aging time, aging temperature, and the mesomorphic structure of fluidized domains was also established.

关 键 词：Heterophrase fluctuation model Kinetics of aging Dynamics of de-aging Creep and stress relaxation K-W-W decay function Fluidized domain constituent chain 

分 类 号：O[理学]