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Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition

机译:多分散性对接近玻璃化转变时胶体硬球悬浮液结晶动力学的影响

摘要

We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to increase the duration of the induction stage, due to the requirement for local fractionation of particles of larger or smaller than average size. Near the glass transition, the nucleation process is entirely frustrated, and the sample is locked into a compressed crystal precursor structure. Interestingly, neither polydispersity nor volume fraction significantly influences the precursor stage, suggesting that the crystal precursors are present in all solidifying samples. We speculate that these precursors are related to the dynamical heterogeneities observed in a number of dynamical studies.
机译:我们提出了一种在胶态硬球悬浮液中凝固情况的综合研究,其在从接近冻结到接近玻璃化转变的体积分数范围内,三种多分散性介于4.8%和5.8%之间。根据这些结果,我们确定了结晶过程中的四个阶段:(i)观察到大量前体结构的诱导阶段,(ii)将前体转化为紧密堆积结构的转化阶段,(iii)成核阶段, (iv)成熟阶段。发现对于低于或高于熔融体积分数的体积分数,该行为在质量上是不同的。由于需要对大于或小于平均粒径的颗粒进行局部分级,因此增加多分散度的主要作用是增加诱导阶段的持续时间。在玻璃化转变附近,成核过程完全受挫,样品被锁定在压缩的晶体前体结构中。有趣的是,多分散性和体积分数都不会显着影响前体阶段,表明所有固化样品中都存在晶体前体。我们推测这些前体与在许多动力学研究中观察到的动力学异质性有关。

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