Patti Alessandro, Dijkstra Marjolein
Debye Institute for NanoMaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands.
Phys Rev Lett. 2009 Mar 27;102(12):128301. doi: 10.1103/PhysRevLett.102.128301. Epub 2009 Mar 24.
We study the isotropic-to-crystal transformation in a mixture of colloidal hard rods and nonabsorbing polymer using computer simulations. We determine the height of the nucleation barrier and find that the critical cluster consists of a single crystalline layer growing laterally for all polymer fugacities considered. At lower supersaturation, the free energy of a single hexagonally packed layer increases monotonically with size, while the nucleation barrier of a second crystalline layer is extremely high. Hence, the nucleation of multilayer crystals is never observed. Multilayer crystals form only in the spinodal decomposition regime, either where, in an intermediate stage, single crystalline membranes coalesce into multilayer clusters or where, at higher polymer fugacity, smaller clusters of rods stack on top of each other to form long filaments. Eventually, these transient structures evolve into a thermodynamically stable bulk crystal phase.
我们使用计算机模拟研究了胶体硬棒和非吸收性聚合物混合物中的各向同性到晶体的转变。我们确定了成核势垒的高度,并发现对于所考虑的所有聚合物逸度,临界团簇由横向生长的单晶层组成。在较低的过饱和度下,单个六方堆积层的自由能随尺寸单调增加,而第二晶层的成核势垒极高。因此,从未观察到多层晶体的成核。多层晶体仅在亚稳分解区域形成,要么在中间阶段,单晶膜合并成多层团簇,要么在较高的聚合物逸度下,较小的棒状团簇相互堆叠形成长丝。最终,这些瞬态结构演变成热力学稳定的块状晶体相。