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Viscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution

机译:纠缠不对称精确梳状聚合物溶液的粘弹性和非线性简单剪切流动行为

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We report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.
机译:我们报告了使用机械流变仪(标准锥和平板以及锥分隔板)和光学流变仪(具有流动双折射)的稳态剪切应力和第一法向应力差异随剪切速率变化的特征。设置)的不对称精确梳的纠缠解。梳子是聚丁二烯(1,4-加成),由一个H骨架和一个在骨架上的偏心分支组成。我们选择研究一种解决方案,以便使用两种不同的技术在重叠的动态区域中获得可靠的非线性剪切数据。圆锥隔板的瞬态测量表明,在启动剪切流期间,剪切应力和第一法向应力差均出现过冲。有趣的是,启动主应力差中的过冲仅在高于主干的反向拉伸时间的速率下才开始发生,这时,主干的拉伸时间与线性链(包括分支的动态稀释作用)类似地进行了估算但忽略了支点摩擦的影响,与线性聚合物的情况极为吻合。在Couette几何形状中进行流动双折射测量,发现提取的稳态剪切力和第一法向应力差与机械数据吻合得很好,但仅限于在骨架反向拉伸时间以下的相对较低的速率。最后,当支链被视为溶剂时,发现稳态特性与基于针对线性聚合物开发的非线性多模管模型的模型预测非常吻合。

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