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聚合物胶束溶液剪切带流的临界现象分析。1. 理论方法。

Critical phenomenon analysis of shear-banding flow in polymer-like micellar solutions. 1. Theoretical approach.

机构信息

Departamento de Física, Universidad de Guadalajara, Boul. M. García-Barragán #1451 Guadalajara, Jal. 44430, Mexico.

出版信息

J Phys Chem B. 2009 Dec 17;113(50):16101-9. doi: 10.1021/jp906310k.

Abstract

The shear-banding flow in polymer-like micellar solutions is examined here with the generalized Bautista-Manero-Puig model. The coupling between flow and diffusion naturally arises in this model, which is derived from the extended irreversible thermodynamic formalism. The limit of an abrupt interface is treated here. The model predicts a dynamic master steady-flow diagram, in which all data collapse at low shear rates. Moreover, the model predicts that a nonequilibrium critical line is reached upon decreasing the shear-banding intensity parameter of the model, which corresponds to increasing temperature, increasing surfactant concentration, or varying salt-to-surfactant concentration ratio. By employing nonequilibrium critical theory and the concept of dissipated energy (or extended Gibbs free energy), a set of symmetrical reduced stress versus reduced shear-rate curves are obtained similar to gas-liquid transitions around the critical point. In addition, the nonequilibrium critical exponents are derived, which follow the extended Widom's rule and the extended Rushbroke relationship, but they are nonclassical.

摘要

这里采用广义 Bautista-Manero-Puig 模型研究类似聚合物胶束溶液的剪切带流。该模型源自扩展不可逆热力学形式,自然地出现了流与扩散的耦合。这里处理的是突然界面的极限。该模型预测了动态主稳态流图,在低剪切速率下所有数据都发生了崩塌。此外,该模型预测,随着模型的剪切带强度参数的降低,即随着温度的升高、表面活性剂浓度的增加或盐与表面活性剂浓度比的变化,达到非平衡临界线。通过采用非平衡临界理论和耗散能量(或扩展吉布斯自由能)的概念,得到了一组对称的简化应力与简化剪切速率曲线,类似于临界点附近的气-液转变。此外,推导出了非平衡临界指数,它们符合扩展的 Widom 法则和扩展的 Rushbroke 关系,但它们是非经典的。

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