当前的聚合物流动范式假设(i)大分子分子量的影响,M,和温度,T,关于聚合物熔体粘度的表达式;(ii)缠结的分子量,Mc,与T无关;(iii)通过对数粘度曲线相对于对数M的断裂来确定Mc明确地将未缠结的熔体与缠结的熔体区分开。我们使用从极低分子量(M/Mc=0.015)到相对较高分子量(M/Mc=34)的单分散聚苯乙烯样品的可靠流变学数据来测试M和T在粘度表达式中的分离;我们揭示了T和M分离有效性的总体错觉在数学上是可理解的,特别是在高温下,对于M>2Mc,但是,严格来说,M和T的分离无效,除了M的某些周期值等于Mc,2Mc,4Mc,8Mc,16Mc,等。(周期加倍)围绕“极点参考”值MR=4Mc组织。我们还透露,对于MTg:TgTLL,其中TLL是液-液温度。我们的结论是,聚合物熔体粘度的经典配方过于简化,以至于缺少重要的实验事实。例如T和M分离的周期加倍,TLL,M\'c,Mc,导致它无法理解纠缠的真正本质。我们在本文的讨论中提出了粘弹性行为的替代方法,二元一致性的“二元性和交叉二元性”,显示了该模型形式主义如何用于数学测试并使经典粘度公式中T和M的分离无效。
The current paradigm of polymer flow assumes that (i) the effect of the molecular weight of the macromolecules, M, and of the temperature, T, on the expression of the viscosity of polymer melts separate; (ii) the molecular weight for entanglement, Mc, is independent of T; and (iii) the determination of Mc by the break in the log viscosity curve against log M unequivocally differentiates un-entangled melts from entangled melts. We use reliable rheological data on monodispersed polystyrene samples from very low molecular weight (M/Mc = 0.015) to relatively high molecular weight (M/Mc = 34) to test the separation of M and T in the expression of the viscosity; we reveal that an overall illusion of the validity of the separation of T and M is mathematically comprehensible, especially at high temperature and for M > 2Mc, but that, strictly speaking, the separation of M and T is not valid, except for certain periodic values of M equal to Mc, 2Mc, 4Mc, 8Mc, 16Mc, etc. (period doubling) organized around a \"pole reference\" value MR = 4Mc. We also reveal, for M < Mc, the existence of a lower molecular weight limit, M\'c = Mc/8 for the onset of the macromolecular behavior (macro-coil). The discrete and periodic values of M that validate the separation of the effect of M and T on the viscosity generate the fragmentation of the molecular range into three rheological ranges. Likewise, we show that the effect of temperature is also fragmented into three rheological ranges for T > Tg: Tg < T< (Tg + 23°), (Tg + 23°) < T < TLL and T > TLL\' where TLL is the liquid-liquid temperature. Our conclusion is that the classical formulation of the viscosity of polymer melts is so overly simplified that it is missing important experimental facts, such as period doubling for the separation of T and M, TLL, M\'c, and Mc, resulting in its inability to understand the true nature of
entanglements. We present in the discussion of the paper the alternative approach to the viscoelastic behavior, \"the duality and cross-duality\" of the Dual-conformers, showing how this model formalism was used to test mathematically and invalidate the separation of T and M in the classical formulation of viscosity.