Combined Molecular Dynamics Simulation and Rouse Model Analysis of Static and Dynamic Properties of Unentangled Polymer Melts with Different Chain Architectures

作     者：Pu Yao Lu-Kun Feng Hong-Xia Guo Pu Yao;Lu-Kun Feng;Hong-Xia Guo

作者机构：Beijing National Laboratory for Molecular SciencesJoint Laboratory of Polymer Sciences and MaterialsState Key Laboratory of Polymer Physics and ChemistryInstitute of ChemistryChinese Academy of SciencesBeijing 100190China University of Chinese Academy of SciencesBeijing 100049China 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2021年第39卷第4期

页      面：512-524,I0008页

核心收录：

学科分类：08[工学] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.21790343,21574142,21174154) the National Key Research and Development Program of China(No.2016YFB1100800). 

主　　题：Rouse model Unentangled chains Architecture Excluded volume effects 

摘      要：Chain architecture effect on static and dynamic properties of unentangled polymers is explored by molecular dynamics simulation and Rouse mode analysis based on graph theory.For open chains,although they generally obey ideal scaling in chain dimensions,local structure exhibits nonideal behavior due to the incomplete excluded volume(EV)screening,the reduced mean square internal distance(MSID)can be well described by Wittmer theory for linear chains and the resulting chain swelling is architecture dependent,i.e.,the more branches a bit stronger swelling.For rings,unlike open chains they are compact in term of global sizes.Due to EV effect and nonconcatenated constraints their local structure exhibits a quite different non-Gaussian behavior from open chains,i.e.,reduced MSID curves do not collapse to a single master curve and fail to converge to a chain-length-independent constant,which makes the direct application of Wittmer s theory to rings quite questionable.Deviation from ideality is further evidenced by limited applicability of Rouse prediction to mode amplitude and relaxation time at high modes as well as the non-constant and mode-dependent scaled Rouse mode amplitudes,while the latter is architecture-dependent and even molecular weight dependent for rings.The chain relaxation time is architecture-dependent,but the same scaling dependence on chain dimensions does hold for all studied architectures.Despite mode orthogonality at static state,the role of cross-correlation in orientation relaxation increases with time and the time-dependent coupling parameter rises faster for rings than open chains even at short time scales it is lower for rings.