Swelling and Collapse of Cylindrical Polyelectrolyte Microgels

被引:0
|
作者
Portnov, Ivan, V [1 ,2 ]
Larina, Alexandra A. [1 ]
Gumerov, Rustam A. [1 ]
Potemkin, Igor I. [1 ,3 ]
机构
[1] Lomonosov Moscow State Univ, Phys Dept, Moscow 119991, Russia
[2] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia
[3] Natl Res South Ural State Univ, Chelyabinsk 454080, Russia
基金
俄罗斯科学基金会;
关键词
cylindrical microgels; collapse; electrostatics; computer simulations; PNIPAM-BASED MICROGELS; FUNCTIONAL MICROGELS; DYNAMICS;
D O I
10.3390/polym14225031
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
In this study, we propose computer simulations of charged cylindrical microgels. The effects of cross-linking density, aspect ratio, and fraction of charged groups on the microgel swelling and collapse with a variation in the solvent quality were studied. The results were compared with those obtained for equivalent neutral cylindrical microgels. The study demonstrated that microgels' degree of swelling strongly depends on the fraction of charged groups. Polyelectrolyte microgels under adequate solvent conditions are characterized by a larger length and thickness than their neutral analogues: the higher the fraction of charged groups, the longer their length and greater their thickness. Microgels' collapse upon solvent quality decline is characterized by a decrease in length and non-monotonous behavior of its thickness. First, the thickness decreases due to the attraction of monomer units (beads) upon collapse. The further thickness increase is related to the surface tension, which tends to reduce the anisotropy of collapsed objects (the minimum surface energy is known to be achieved for the spherical objects). This reduction is opposed by the network elasticity. The microgels with a low cross-linking density and/or a low enough aspect ratio reveal a cylinder-to-sphere collapse. Otherwise, the cylindrical shape is preserved in the course of the collapse. Aspect ratio as a function of the solvent quality (interaction parameter) demonstrates the maximum, which is solely due to the electrostatics. Finally, we plotted radial concentration profiles for network segments, their charged groups, and counterions.
引用
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页数:13
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