论文标题

联想聚合物溶液中凝胶化的普遍缩放和表征

Universal scaling and characterisation of gelation in associative polymer solutions

论文作者

Santra, Aritra, Dünweg, B., Prakash, J. Ravi

论文摘要

布朗动力学算法用于描述关联聚合物溶液的静态行为。对系统参数的函数(例如贴纸的数量,贴纸之间的单体数量,溶剂质量和浓度)的函数,对受链内和链间关联限制的贴纸分数进行预测。进行了与多布林蛋白平均场理论(Macromolecules,37,3881,2004)预测的缩放关系的系统比较。根据单体浓度,链上的贴纸密度以及主链单体的溶剂质量,确定了不同的缩放行为方式。模拟结果验证了所有缩放机制中均广泛参数值的平均场理论的预测。 Dobrynin对粘性聚合物溶液提出的DES氯济指数的值已显示导致此处考虑的所有缩放关系的仿真数据崩溃。确定了三个不同的胶凝表征的特征,每个特征导致溶液凝胶过渡时浓度的不同值。发现修改的烟螺旋体表达通过所有三个胶凝特征的模拟验证。仿真结果证实了当使用修改后的flory-stockmayer表达时,将胶质和凝胶相分开的胶凝线的缩放理论的预测。发现相位分离是随着主链单体处于theta-溶剂条件下的系统的增加而发生的,并且显示出与缩放理论预测的分解相吻合。

A Brownian dynamics algorithm is used to describe the static behaviour of associative polymer solutions. Predictions for the fractions of stickers bound by intra-chain and inter-chain association, as a function of system parameters, such as the number of stickers, the number of monomers between stickers, the solvent quality, and concentration are obtained. A systematic comparison with the scaling relations predicted by the mean-field theory of Dobrynin (Macromolecules, 37, 3881, 2004) is carried out. Different regimes of scaling behaviour are identified depending on the monomer concentration, the density of stickers on a chain, and the solvent quality for backbone monomers. Simulation results validate the predictions of the mean-field theory across a wide range of parameter values in all the scaling regimes. The value of the des Cloizeaux exponent proposed by Dobrynin for sticky polymer solutions, is shown to lead to a collapse of simulation data for all the scaling relations considered here. Three different signatures for the characterisation of gelation are identified, with each leading to a different value of the concentration at the sol-gel transition. The modified Flory-Stockmayer expression is found to be validated by simulations for all three gelation signatures. Simulation results confirm the prediction of scaling theory for the gelation line that separates sol and gel phases, when the modified Flory-Stockmayer expression is used. Phase separation is found to occur with increasing concentration for systems in which the backbone monomers are under theta-solvent conditions, and is shown to coincide with a breakdown in the predictions of scaling theory.

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