Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
Instituto de Química Física Rocasolano, CSIC, C/ Serrano 119, 28006 Madrid, Spain.
Int J Mol Sci. 2021 Oct 13;22(20):11050. doi: 10.3390/ijms222011050.
Systems with short-range attractive and long-range repulsive interactions can form periodic modulated phases at low temperatures, such as cluster-crystal, hexagonal, lamellar and bicontinuous gyroid phases. These periodic microphases should be stable regardless of the physical origin of the interactions. However, they have not yet been experimentally observed in colloidal systems, where, in principle, the interactions can be tuned by modifying the colloidal solution. Our goal is to investigate whether the formation of some of these periodic microphases can be promoted by confinement in narrow slit pores. By performing simulations of a simple model with competing interactions, we find that both the cluster-crystal and lamellar phases can be stable up to higher temperatures than in the bulk system, whereas the hexagonal phase is destabilised at temperatures somewhat lower than in bulk. Besides, we observed that the internal ordering of the lamellar phase can be modified by changing the pore width. Interestingly, for sufficiently wide pores to host three lamellae, there is a range of temperatures for which the two lamellae close to the walls are internally ordered, whereas the one at the centre of the pore remains internally disordered. We also find that particle diffusion under confinement exhibits a complex dependence with the pore width and with the density, obtaining larger and smaller values of the diffusion coefficient than in the corresponding bulk system.
具有短程吸引和长程排斥相互作用的体系在低温下可以形成周期性调制相,如团簇-晶体、六方、层状和双连续的介晶相等。这些周期性微相应该是稳定的,无论相互作用的物理起源如何。然而,它们在胶体体系中尚未被实验观察到,在胶体体系中,原则上可以通过改变胶体溶液来调整相互作用。我们的目标是研究在狭窄的狭缝孔中受限是否可以促进这些周期性微相的形成。通过对具有竞争相互作用的简单模型进行模拟,我们发现,团簇-晶体相和层状相都可以在比体相系统更高的温度下稳定,而六方相在稍低于体相的温度下失稳。此外,我们观察到层状相的内部有序性可以通过改变孔径来改变。有趣的是,对于足以容纳三个层状相的足够宽的孔,存在一个温度范围,在该温度范围内,靠近孔壁的两个层状相内部有序,而孔中心的层状相内部无序。我们还发现,受限下的颗粒扩散与孔径和密度具有复杂的依赖性,得到的扩散系数值大于或小于相应的体相系统的值。