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 obe...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.展开更多
为探明长江中游河段悬沙垂向分布规律,在总结分析相关研究成果的基础上,进一步用实测资料对Rouse公式、张小峰公式、E M Laursen公式、莱恩-卡林斯基公式进行了对比研究及合理性分析,选择适用于长江中游各段悬沙垂向分布计算的合理公式...为探明长江中游河段悬沙垂向分布规律,在总结分析相关研究成果的基础上,进一步用实测资料对Rouse公式、张小峰公式、E M Laursen公式、莱恩-卡林斯基公式进行了对比研究及合理性分析,选择适用于长江中游各段悬沙垂向分布计算的合理公式。结果表明:当泥沙颗粒较细且含沙量较小(S<0.1 kg/m^3)时,Rouse公式、张小峰公式、E M Laursen公式、莱恩-卡林斯基公式的计算结果与实测资料都比较吻合;在含沙量较小、紊动较大的中泓处,张小峰公式和E M Laursen公式的计算精度高;在长江中游河段近两岸处,莱恩-卡林斯基公式的计算精度较高。展开更多
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).
文摘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.
文摘为探明长江中游河段悬沙垂向分布规律,在总结分析相关研究成果的基础上,进一步用实测资料对Rouse公式、张小峰公式、E M Laursen公式、莱恩-卡林斯基公式进行了对比研究及合理性分析,选择适用于长江中游各段悬沙垂向分布计算的合理公式。结果表明:当泥沙颗粒较细且含沙量较小(S<0.1 kg/m^3)时,Rouse公式、张小峰公式、E M Laursen公式、莱恩-卡林斯基公式的计算结果与实测资料都比较吻合;在含沙量较小、紊动较大的中泓处,张小峰公式和E M Laursen公式的计算精度高;在长江中游河段近两岸处,莱恩-卡林斯基公式的计算精度较高。
