Secchi Eleonora, Buzzaccaro Stefano, Piazza Roberto
CMIC, Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, 20133 Milano, Italy.
Soft Matter. 2014 Aug 7;10(29):5296-310. doi: 10.1039/c4sm00299g. Epub 2014 Jun 10.
By exploiting photon correlation imaging and ghost particle velocimetry, two novel optical correlation techniques particularly suited to the investigation of the microscopic dynamics of spatially heterogeneous samples, we investigate the settling and restructuring dynamics of colloidal gels generated by short-ranged depletion interactions. Three distinct regions can be clearly set apart within the liquid-liquid coexistence region of the phase diagram where gel formation is observed. When depletion forces are barely sufficient to drive the system within the metastable region, an initial disordered gel hosts the rapid nucleation of crystallites, which stress the gel structure until it fully collapses, leading to the formation of a macroscopic colloidal crystal. For stronger attractive forces, two distinct scenarios are observed, depending on the particle volume fraction ϕ0 of the original suspension. At low ϕ0, the gel breaks after a short delay time into separate clusters, which rapidly settle until they compact in a denser disordered phase. The latter eventually undergoes a slow compression, which is accounted for by a poroelastic model where the microscopic gel dynamics is fully ruled by its macroscopic deformation. Yet, it is the intermediate stage between cluster settling and final compaction which displays very peculiar features, evidenced by anomalous settling profiles which are not shared, to our knowledge, by any other sedimentation processes investigated so far. For larger values of ϕ0, gel breaking is conversely suppressed, the structure undergoes a continuous compression that cannot be explained by a poroelastic model, and the microscopic dynamics is characterized by logarithmic correlation functions resembling those found for attractive glasses.
通过利用光子相关成像和鬼粒子测速技术,这两种特别适合研究空间非均匀样品微观动力学的新型光学相关技术,我们研究了由短程耗尽相互作用产生的胶体凝胶的沉降和重组动力学。在观察到凝胶形成的相图的液 - 液共存区域内,可以清楚地划分出三个不同的区域。当耗尽力勉强足以将系统驱动到亚稳区域时,初始无序凝胶中微晶快速成核,这会对凝胶结构施加应力直至其完全坍塌,导致形成宏观胶体晶体。对于更强的吸引力,根据原始悬浮液的颗粒体积分数ϕ0,观察到两种不同的情况。在低ϕ0时,凝胶在短延迟时间后破裂成单独的团簇,这些团簇迅速沉降直至它们在更致密的无序相中压实。后者最终经历缓慢压缩,这可以由一个多孔弹性模型来解释,其中微观凝胶动力学完全由其宏观变形决定。然而,正是团簇沉降和最终压实之间的中间阶段表现出非常奇特的特征,据我们所知,由异常沉降曲线证明,这是迄今为止所研究的任何其他沉降过程都不具备的。对于较大的ϕ0值,相反地抑制了凝胶破裂,结构经历连续压缩,这无法用多孔弹性模型解释,并且微观动力学的特征是对数相关函数,类似于在吸引性玻璃中发现的那些。