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Probe Rheology: A Simple Method to Test Tube Motion

机译:探针流变学:一种测试管运动的简单方法

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We investigate the relaxation dynamics in the melt of entangled binary mixtures comprising a small fraction of short polybutadiene, polyisoprene and polystyrene chains in a high molecular weight (MW) matrix. In this way, we create model environments of quasi-permanent entanglements for probe chains, where tube motions are suppressed at the time scale of the probe chains reptation, while contour length fluctuations remain unaffected. The relaxation of a probe in its matrix presents several important features, which are independent of polymer species. Because of the absence of tube motions, the probe chains terminal peak is narrower, with a G"(omega) approx omega~(-1/2) high-frequency slope, in agreement with the prediction of pure reptation theory. Moreover, the position of the G" peak, omega_(max) (rad/s), shifts to lower frequencies, which means that the longest relaxation time of the probe chains is increased, as compared to a melt of pure probe chains. Unambiguous and quantitative comparisons between the terminal times of probe chains in a matrix or self-melt environments are obtained with the help of an iso-free-volume correction. In this way, we clarify for the first time contributions from tube motions to the terminal relaxation. The retardation factor for the terminal relaxation time is independent of the number of entanglements Z above 100 but increases steadily below that threshold as Z~(0.3). The Z dependence of the retardation factor leads to different scalings for the terminal relaxation time of probe chains in self-melt or matrix environments. The observed scaling exponent of 3.1 in the matrix is very close to the prediction of the original reptation model. Our results hence indicate that the motions of surrounding chains have a dominant influence on the 3.4 exponent for terminal relaxation times and zero shear viscosity. This is in sharp contrast with the conventional view attributing the nonreptation scalings entirely to fluctuations but is in agreement with existing literature on tracer (probe) chains and self-diffusion.
机译:我们研究了在高分子量(MW)基质中纠缠的二元混合物的熔体中的弛豫动力学,该混合物包含一小部分短的聚丁二烯,聚异戊二烯和聚苯乙烯链。通过这种方式,我们为探针链创建了准永久缠结的模型环境,其中在探针链复制的时间尺度上抑制了管运动,而轮廓长度波动却不受影响。探针在其基质中的弛豫具有几个重要特征,这些特征与聚合物种类无关。由于没有管运动,探针链的末端峰较窄,具有大约GΩ(ω)〜(-1/2)的高频斜率,这与纯正复制理论的预测是一致的。 G“峰的位置omega_(max)(rad / s)移至较低频率,这意味着与纯探针链的熔体相比,探针链的最长弛豫时间增加了。借助等体积体积校正,可以在基质或自融环境中实现探针链末端时间的明确定量比较。这样,我们首次澄清了管运动对终端松弛的影响。最终弛豫时间的延迟因子与Z大于100的纠缠数无关,但在Z +(0.3)以下稳定增加。延迟因子的Z依赖性导致在自融或基质环境中探针链的末端弛豫时间具有不同的缩放比例。在矩阵中观察到的3.1的缩放指数非常接近原始副本模型的预测。因此,我们的结果表明,围绕链的运动对3.4指数的最终松弛时间和零剪切粘度具有主要影响。这与传统观点形成鲜明对比,传统观点将非重复缩放比例完全归因于波动,但与有关示踪剂(探针)链和自我扩散的现有文献相一致。

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