Microscopic structural origin behind slowing down of colloidal phase separation approaching gelation

The gelation of colloidal particles interacting through a short-range attraction is widely recognized as a consequence of the dynamic arrest of phase separation into colloid-rich and solvent-rich phases. However, the microscopic origin behind the slowing down and dynamic arrest of phase separation remains elusive. In order to access microscopic structural changes through the entire process of gelation in a continuous fashion, we used core–shell fluorescent colloidal particles, laser scanning confocal microscopy, and a unique experimental protocol that allows us to initiate phase separation instantaneously and gently. Combining these enables us to track the trajectories of individual particles seamlessly during the whole phase-separation process from the early stage to the late arresting stage. We reveal that the enhancement of local packing and the resulting formation of locally stable rigid structures slow down the phase-separation process and arrest it to form a gel with an average coordination number of z = 6–7. This result supports a mechanical perspective on the dynamic arrest of sticky-sphere systems based on the microstructure, replacing conventional explanations based on the macroscopic vitrification of the colloid-rich phase. Our findings illuminate the microscopic mechanisms behind the dynamic arrest of colloidal phase separation, the emergence of mechanical rigidity, and the stability of colloidal gels.