Pairing-specific microstructure in depletion gels of bidisperse colloids

We report the ensemble-averaged and pairing-specific network microstructure formed by short-range depletion attractions in hard sphere-like colloidal systems. Gelation is induced by adding polystyrene molecules at a fixed concentration to colloids with different colloid bidispersity ratios (α = 1, 0.72, and 0.60) across a range of volume fractions (0.10 ≤ ϕ ≤ 0.40). 3D confocal microscopy imaging combined with a scale-invariant feature transform algorithm show that monodisperse colloids pack more efficiently, whereas increasing the size disparity leads to looser, more disordered, and sub-isostatic packings. Categorizing the structures formed by small and large particles reveal that certain cluster configurations may be favored due to the complex interplay between the differences in particle surface areas and attractive potentials. These pairwise bonds assemble to affect the density of tetrahedral and poly-tetrahedral clusters in bidisperse systems. With the exception of non-percolating samples at ϕ = 0.10, increasing the gel volume fraction leads to an increase in the number of nearest neighbors. However, the internal density within each cluster decreases, possibly due to kinetic arrest from the deeper potential wells of tetrahedral clusters at low volume fractions in which vertices are primarily made out of larger particles.