Department of Chemical and Biomolecular Engineering and Center for Molecular and Engineering Thermodynamics, Allan P. Colburn Laboratory, University of Delaware, Newark, DE 19716, USA.
Proc Natl Acad Sci U S A. 2012 Oct 2;109(40):16023-8. doi: 10.1073/pnas.1206915109. Epub 2012 Sep 17.
Polarizable colloids are expected to form crystalline equilibrium phases when exposed to a steady, uniform field. However, when colloids become localized this field-induced phase transition arrests and the suspension persists indefinitely as a kinetically trapped, percolated structure. We anneal such gels formed from magneto-rheological fluids by toggling the field strength at varied frequencies. This processing allows the arrested structure to relax periodically to equilibrium--colloid-rich, cylindrical columns. Two distinct growth regimes are observed: one in which particle domains ripen through diffusive relaxation of the gel, and the other where the system-spanning structure collapses and columnar domains coalesce apparently through field-driven interactions. There is a stark boundary as a function of magnetic field strength and toggle frequency distinguishing the two regimes. These results demonstrate how kinetic barriers to a colloidal phase transition are subverted through measured, periodic variation of driving forces. Such directed assembly may be harnessed to create unique materials from dispersions of colloids.
当暴露在稳定、均匀的场中时,极化胶体有望形成结晶平衡相。然而,当胶体局部化时,这种场诱导的相转变会停止,悬浮液会无限期地保持为动力学捕获的、渗透的结构。我们通过在不同频率下切换场强来退火由磁流变液形成的这种凝胶。这种处理允许被捕获的结构周期性地弛豫到平衡——富含胶体的圆柱状柱。观察到两个不同的生长阶段:一个是通过凝胶的扩散弛豫使颗粒域成熟,另一个是跨越系统的结构崩溃,柱状域通过场驱动的相互作用明显合并。作为磁场强度和切换频率的函数,存在一个明显的边界,将两个区域区分开来。这些结果表明,如何通过测量、周期性地改变驱动力来克服胶体相变的动力学障碍。这种定向组装可以用来从胶体分散体中创造独特的材料。