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Crystallization kinetics of suspensions of hard colloidal spheres

机译:硬胶体球悬浮液的结晶动力学

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摘要

The crystallization of suspensions of sterically stabilized polymer particles, with hard-sphere-like interactions, is studied by laser light scattering. Over the range of volume fractions examined, from just below melting to the glass transition, crystallization occurs by homogeneous nucleation. After the suspensions are shear melted, the intensity, position, and width of the main interlayer Bragg reflection are measured as functions of time. From these the amount of crystal, the average linear crystal dimension, the number of crystals, and the volume fraction of the crystal phase are obtained. No assumptions are made concerning the functional time dependence of nucleation or growth processes. Below the melting concentration the observed crystallization process is compatible with the classical picture of sequential nucleation and growth of isolated crystals. However, when the melting concentration is exceeded, nucleation events are correlated, nucleation is accelerated, and high nucleation rate densities suppress crystal growth. Above the melting concentration we infer, with the aid of the equations of state for the hard-sphere fluid and solid, that the first identifiable crystals are in mechanical equilibrium with the embedding fluid and, consequently, strongly compressed by it. Ensuing nucleation lags expansion of the crystal lattice.
机译:通过激光散射研究了具有硬球状相互作用的空间稳定化聚合物颗粒悬浮液的结晶。在所检测的体积分数范围内,从刚好低于熔融温度到玻璃化转变温度,均相成核会发生结晶。在悬浮液剪切熔融后,测量主层间布拉格反射的强度,位置和宽度,作为时间的函数。从这些晶体的量中,获得平均线性晶体尺寸,晶体的数目和晶体相的体积分数。没有关于成核或生长过程的功能时间依赖性的假设。在熔融浓度以下,观察到的结晶过程与相继成核和分离晶体生长的经典现象相吻合。然而,当超过熔融浓度时,成核事件相关,成核被促进,并且高成核速率密度抑制晶体生长。在高于熔化浓度的情况下,我们根据硬球流体和固体的状态方程推断出,第一个可识别的晶体与包埋的流体处于机械平衡状态,因此被包埋的流体强烈压缩。随后的成核滞后了晶格的膨胀。

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