Kumar K Satheesh, Prakash J Ravi
Department of Chemical Engineering, Monash University, Clayton, Victoria-3168, Australia.
J Chem Phys. 2004 Aug 22;121(8):3886-97. doi: 10.1063/1.1775185.
The role of solvent quality in determining the universal material properties of dilute polymer solutions undergoing steady simple shear flow is examined. A bead-spring chain representation of the polymer molecule is used, and the influence of solvent molecules on polymer conformations is modelled by a narrow Gaussian excluded volume potential that acts pairwise between the beads of the chain. Brownian dynamics simulations data, acquired for chains of finite length, and extrapolated to the limit of infinite chain length, are shown to be model independent. This feature of the narrow Gaussian potential, which leads to results identical to a delta-function repulsive potential, enables the prediction of both universal crossover scaling functions and asymptotic behavior in the excluded volume limit. Universal viscometric functions, obtained by this procedure, are found to exhibit increased shear thinning with increasing solvent quality. In the excluded volume limit, they are found to obey power law scaling with the characteristic shear rate beta, in close agreement with previously obtained renormalization group results. The presence of excluded volume interactions is also shown to lead to a weakening of the alignment of the polymer chain with the flow direction.
研究了溶剂质量在确定经历稳定简单剪切流动的稀聚合物溶液的通用材料特性方面的作用。采用聚合物分子的珠簧链表示法,并通过在链的珠子之间成对作用的窄高斯排除体积势来模拟溶剂分子对聚合物构象的影响。为有限长度的链获取并外推到无限链长度极限的布朗动力学模拟数据显示与模型无关。窄高斯势的这一特性导致结果与δ函数排斥势相同,从而能够预测通用交叉标度函数以及排除体积极限下的渐近行为。通过该程序获得的通用粘度函数显示,随着溶剂质量的增加,剪切变稀程度增强。在排除体积极限下,发现它们遵循与特征剪切速率β的幂律标度,与先前获得的重整化群结果密切一致。还表明排除体积相互作用的存在会导致聚合物链与流动方向的排列减弱。