Aerov Artem A, Potemkin Igor I
Physics Department, Moscow State University, Moscow 119992.
J Phys Chem B. 2009 Feb 19;113(7):1883-90. doi: 10.1021/jp808349n.
We use a Flory-Huggins type approach to describe the swelling of a polymer microgel (a finite size network of polymer chains covalently bound with each other) with immobilized carbon nanotubes in an ionic liquid. The ionic liquid is modeled as a "two-component" solvent consisting of anions and cations. The anions and cations are assumed to have different affinities to the microgel. It is supposed that the carbon nanotubes form a conducting cluster interpenetrating the microgel. We show that if the difference of the Flory-Huggins parameters describing affinities of the anions and the cations to the microgel is high enough, the swelling ratio of the gel can depend on its size. The physical reason for the phenomenon is the violation of the cations and anions concentrations equality inside the gel that causes a shift of the free energy and can lead to a swelling-collapse transition. The segregation of cations and anions is different for microgels having different sizes because it is opposed by electrostatic field.
我们采用弗洛里-哈金斯(Flory-Huggins)类型的方法来描述在离子液体中含有固定化碳纳米管的聚合物微凝胶(由相互共价键合的聚合物链组成的有限尺寸网络)的溶胀情况。离子液体被建模为一种由阴离子和阳离子组成的“双组分”溶剂。假定阴离子和阳离子对微凝胶具有不同的亲和力。据推测,碳纳米管形成了一个贯穿微凝胶的导电簇。我们表明,如果描述阴离子和阳离子对微凝胶亲和力的弗洛里-哈金斯参数差异足够大,凝胶的溶胀率可能取决于其尺寸。该现象的物理原因是凝胶内部阳离子和阴离子浓度平衡的破坏,这会导致自由能的偏移,并可能引发溶胀-塌陷转变。对于不同尺寸的微凝胶,阳离子和阴离子的分离情况不同,因为这受到静电场的阻碍。