Two-Steps Versus One-Step Solidification Pathways of Binary Metallic Nanodroplets.

The solidification of AgCo, AgNi, and AgCu nanodroplets is studied by molecular dynamics simulations in the size range of 2-8 nm. All these systems tend to phase separate in the bulk solid with surface segregation of Ag. Despite these similarities, the simulations reveal clear differences in the solidification pathways. AgCo and AgNi already separate in the liquid phase, and they solidify in configurations close to equilibrium. They can show a two-step solidification process in which Co-/Ni-rich parts solidify at higher temperatures than the Ag-rich part. AgCu does not separate in the liquid and solidifies in one step, thereby remaining in a kinetically trapped state down to room temperature. The solidification mechanisms and the size dependence of the solidification temperatures are analyzed, finding qualitatively different behaviors in AgCo/AgNi compared to AgCu. These differences are rationalized by an analytical model.

Brownian dynamics simulations of one-patch inverse patchy particles.

Inverse patchy particles are promising colloids to develop new architectures in ceramic materials based on their self-assembly. Nonetheless, a good understanding of their aggregation is required. Several previous studies have shown that the behavior of ceramic colloids can be well described by the DLVO interaction potential. In the present paper, we develop new coarse-grained Brownian dynamics simulations, where particles are represented by an assembly of beads interacting via DLVO interactions, whose parameters can be directly linked to experimental characterization. First, the validity of the simulations is proved by studying the heteroaggregation of homogeneously charged particles. Then, simulations are applied to one-patch inverse patchy particles to study the effect of the patch size. They show that the smaller the patch, the more elongated the aggregates. Simulations are also performed to understand the role of the Debye screening length in the particular case of large patches and they show that aggregation leads always to compact aggregates.

Computer simulations of heteroaggregation with large size asymmetric colloids.

HYPOTHESIS: Hetero-aggregation of inorganic colloids is influenced by numerous parameters, which dictate the suspension properties. When particles are different in size, the suspension can be either stable or unstable according to concentration of components, ionic strength, and pH. Experimentally, understanding the role of each parameter is sometimes difficult because parameters cannot easily be modified independently. Numerical simulations are thus very useful to discriminate between different effects. SIMULATIONS: Brownian dynamics simulations are used here to study the heteroaggregation of dilute suspensions composed of two populations of colloids with large size asymmetry. Special attention is paid to the effect of small-particle concentration, surface potentials, and ionic strength. FINDINGS: The simulation results show that hetero-aggregation can be tuned by modifying these different parameters, and that the resulting aggregate structures depend more on the surface properties of small particles than on those of large particles. The simulations shed light on a further parameter crucially influencing hetero-aggregation, i.e. the mobility of small particles when adsorbed on large ones. The present results rationalize numerous experimental observations reported in the literature and can be used as reference to explain future experimental observations.

Interdiffusion and crystallization of oppositely charged colloids.

The aggregation of oppositely charged colloids, usually denoted as heteroaggregation, is often used in colloidal processing, for which a precise control of the basic mechanisms of aggregate formation is of crucial importance. A promising way to achieve a better degree of control is to guide heteroaggregation by imposing geometric constraints. Here, we consider this possibility by simulating the heteroaggregation of two oppositely charged suspensions which are initially separated and then put into contact through a planar interface. Our Brownian dynamics simulations show that this type of heteroaggregation allows the formation of mixed films whose thickness can be controlled by tuning the interactions between the particles or by changing the colloidal concentration in the initial suspensions. The dependence of the type of crystalline order in these films on these parameters is also analyzed.