Hlushak S P, Kalyuzhnyi Yu V, Cummings P T
Institute for Condensed Matter Physics, Lviv, Ukraine.
J Chem Phys. 2008 Apr 21;128(15):154907. doi: 10.1063/1.2907723.
A theoretical scheme developed earlier [Y. V. Kalyuzhnyi et al., Chem. Phys. Lett. 443, 243 (2007)] is used to calculate the full phase diagram of polydisperse athermal polymer-colloidal mixture with polydispersity in both colloidal and polymeric components. In the limiting case of bidisperse polymer-colloidal mixture, theoretical results are compared against computer simulation results. We present the cloud and shadow curves, critical binodals, and distribution functions of the coexisting phases and discuss the effects of polydispersity on their behavior. According to our analysis polydispersity extends the region of the phase instability, shifting the critical point to the lower values of the pressure and density. For the high values of the pressure polydispersity causes strong fractionation effects, with the large size colloidal particles preferring the low-density shadow phase and long chain length polymeric particles preferring the high-density shadow phase.
我们使用先前开发的理论方案[Y. V. 卡柳日尼等人,《化学物理快报》443, 243 (2007)]来计算在胶体和聚合物组分中均具有多分散性的多分散无热聚合物 - 胶体混合物的完整相图。在双分散聚合物 - 胶体混合物的极限情况下,将理论结果与计算机模拟结果进行比较。我们给出了共存相的云线和阴影曲线、临界双节线以及分布函数,并讨论了多分散性对其行为的影响。根据我们的分析,多分散性扩展了相不稳定区域,使临界点向压力和密度的较低值移动。对于高压力值,多分散性会导致强烈的分级效应,大尺寸胶体颗粒倾向于低密度阴影相,而长链长度的聚合物颗粒倾向于高密度阴影相。