Many experimental realizations of self-propelled particles exhibit a strong tendency to aggregate and form clusters, [1] [2] [3] [4] [5] whose dynamics are much richer than those of passive colloids. These aggregates of particles form for a variety of reasons, from chemical gradients to magnetic and ultrasonic fields. [6] [7] Self-propelled enzyme motors and synthetic nanomotors also exhibit clustering effects in the form of chemotaxis. [7] [8] Chemotaxis is a form of collective motion of biological or non-biological particles toward a fuel source or away from a threat, as observed experimentally in enzyme diffusion [9] [10] [11] and also synthetic chemotaxis [12] [13] [14] or phototaxis. [14] In addition to irreversible schooling, self-propelled particles also display reversible collective motion, such as predator–prey behavior and oscillatory clustering and dispersion. [15] [16] [17] [18] [19] [20]
This clustering behavior has been observed for self-propelled Janus particles, either platinum-coated gold particles [1] or carbon-coated silica beads, [2] and for magnetically or ultrasonically powered particles. [5] [6] Clustering has also been observed for colloidal particles composed of either an embedded hematite cube [3] or slowly-diffusing metal ions. [4] [15] [16] [17] [18] Autonomous aggregation has also been observed in anatase TiO2 (titanium dioxide) particles. [21] Clustering also occurs in enzyme molecule diffusion. [9] [10] [11] [22] Recently, enzymes such as hexokinase and alkaline phosphatase were found to aggregate in the presence of their substrates. [23] In all these experiments, the motion of particles takes place on a two-dimensional surface and clustering is seen for area fractions as low as 10%. For such low area fractions, the clusters have a finite mean size [1] while at larger area fractions (30% or higher), a complete phase separation has been reported. [2] The dynamics of the finite-size clusters are very rich, exhibiting either crystalline order or amorphous packing. The finite size of the clusters comes from a balance between attachment of new particles to pre-existing clusters and breakdown of large clusters into smaller ones, which has led to the term "living clusters". [3] [4] [15] [16] [17] [18]
The precise mechanism leading to the appearance of clusters is not completely elucidated and is a current field of research for many systems. [24] A few different mechanisms have been proposed, which could be at play in different experimental setups.
Self-propelled particles can accumulate in a region of space where they move with a decreased velocity. [25] After accumulation, in regions of high particle density, the particles move more slowly because of steric hindrance. A feedback between these two mechanisms can lead to the so-called motility induced phase separation. [26] This phase separation can, however, be arrested by chemically-mediated inter-particle torques [27] or hydrodynamic interactions, [28] [29] which could explain the formation of finite-size clusters. Self-propelled particles spinning at intermediate Reynolds numbers exhibit flocking, chiral active phases, and clustering, highlighting the role of fluid inertia and rotational motion in active matter behavior. [30]
Alternatively, clustering and phase-separation could be due to the presence of inter-particle attractive forces, as in equilibrium suspensions. Active forces would then oppose this phase separation by pulling apart the particles in the cluster, [31] [32] following two main processes. First, single particles can exist independently if their propulsion forces are sufficient to escape from the cluster. Secondly, a large cluster can break into smaller pieces due to the build-up of internal stress: as more and more particles enter the cluster, their propulsive forces add up until they break down its cohesion.
Diffusiophoresis is also a commonly cited mechanism for clustering and collective behavior, involving the attraction or repulsion of particles to each other in response to ion gradients. [4] [15] [16] [17] [18] Diffusiophoresis is a process involving the gradients of electrolyte or non-electrolyte concentrations interacting with charged (electrophoretic interactions) or neutral (chemophoretic interactions) particles in solution and with the double layer of any walls or surfaces (electroosmotic interactions). [17] [18]
In experiments, arguments have been put forward in favor of any of the above mechanisms. For carbon-coated silica beads, attractive interactions are seemingly negligible and phase-separation is indeed seen at large densities. [2] For other experimental systems, however, attractive forces often play a larger role. [1] [3] [17] [18]