C. S. Dias

Nonequilibrium growth of patchy-colloid networks on substrates

Patchy colloids with highly directional interactions are ideal building blocks to control the local arrangements resulting from their spontaneous self-organization. Here we propose their use, combined with substrates and nonequilibrium conditions, to obtain structures, different from those of equilibrium thermodynamic phases. Specifically, we investigate numerically the irreversible adhesion of three-patch colloids near attractive substrates, and analyze the fractal network of connected particles that is formed. The network density profile exhibits three distinct regimes, with different structural and scaling properties, which we characterize in detail. The adsorption of a mixture of three- and two-patch colloids is also considered. An optimal fraction of two-patch colloids is found where the total density of the film is maximized, in contrast to the equilibrium gel structures where a monotonic decrease of the density has been reported.

Mixtures of functionalized colloids on substrates.

Patchy particles are a class of colloids with functionalized surfaces. Through surface functionalization, the strength and directionality of the colloidal interactions are tunable allowing control over coordination of the particle. Exquisite equilibrium phase diagrams of mixtures of coordination two and three have been reported. However, the kinetics of self-organization and the feasibility of the predicted structures are still largely unexplored. Here, we study the irreversible aggregation of these mixtures on a substrate, for different fractions of two-patch particles. Two mechanisms of mass transport are compared: diffusion and advection. In the diffusive case, an optimal fraction is found that maximizes the density of the aggregate. By contrast, for advective transport, the density decreases monotonically with the fraction of two-patch colloids, in line with the behavior of the liquid density on the spinodal of the equilibrium phase diagram.

Kinetic interfaces of patchy particles

We study the irreversible adsorption of patchy particles on substrates in the limit of advective mass transport. Recent numerical results show that the interface roughening depends strongly on the particle attributes, such as, patch-patch correlations, bond flexibility and strength of the interactions, uncovering new absorbing phase transitions. Here, we revisit these results and discuss in detail the transitions. In particular, we present new evidence that the tricritical point, observed in systems of particles with flexible patches, is in the tricritical directed percolation universality class. A scaling analysis of the time evolution of the correlation length for the aggregation of patchy particles with distinct bonding energies confirms that the critical regime is in the Kardar-Parisi-Zhang with quenched disorder universality class.

Effect of the number of patches on the growth of networks of patchy colloids on substrates

We investigate numerically the irreversible aggregation of patchy spherical colloids on a flat substrate. We consider n-patch particles and characterise the dependence of the irreversible aggregation kinetics on n. For all values of n considered in this study, the growing interface of the aggregate is in the Kardar–Parisi–Zhang universality class, although the bulk structure exhibits a rich dependence on n. In particular, the bulk density varies with n, and the network is more ordered for particles with fewer patches. Preferred orientations of the bonds are also observed for networks of particles with low n.

Kinetic roughening of aggregates of patchy colloids with strong and weak bonds

We study the irreversible aggregation of films of patchy spherical colloids with directional and selective interactions. We report a crossover of the interfacial roughening from the Kardar-Parisi-Zhang (KPZ) to the KPZ with quenched disorder (KPZQ) universality class when the difference between the strong and weak bonds is sufficiently large. We calculate the critical exponents and identify the crossover between the two regimes.

Non-equilibrium adsorption of 2AnB patchy colloids on substrates

We study the irreversible adsorption of spherical 2AnB patchy colloids (with two A-patches on the poles and n B-patches along the equator) on a substrate. In particular, we consider dissimilar AA, AB, and BB binding probabilities. We characterize the patch–colloid network and its dependence on n and on the binding probabilities. Two growth regimes are identified with different density profiles and we calculate a growth mode diagram as a function of the colloid parameters. We also find that, close to the substrate, the density of the network, which depends on the colloid parameters, is characterized by a depletion zone.

Nonequilibrium self-organization of colloidal particles on substrates: adsorption, relaxation, and annealing

Colloidal particles are considered ideal building blocks to produce materials with enhanced physical properties. The state-of-the-art techniques for synthesizing these particles provide control over shape, size, and directionality of the interactions. In spite of these advances, there is still a huge gap between the synthesis of individual components and the management of their spontaneous organization towards the desired structures. The main challenge is the control over the dynamics of self-organization. In their kinetic route towards thermodynamically stable structures, colloidal particles self-organize into intermediate (mesoscopic) structures that are much larger than the individual particles and become the relevant units for the dynamics. To follow the dynamics and identify kinetically trapped structures, one needs to develop new theoretical and numerical tools. Here we discuss the self-organization of functionalized colloids (also known as patchy colloids) on attractive substrates. We review our recent results on the adsorption and relaxation and explore the use of annealing cycles to overcome kinetic barriers and drive the relaxation towards the targeted structures.

Adsorbed films of three-patch colloids: continuous and discontinuous transitions between thick and thin films.

We investigate numerically the role of spatial arrangement of the patches on the irreversible adsorption of patchy colloids on a substrate. We consider spherical three-patch colloids and study the dependence of the kinetics on the opening angle between patches. We show that growth is suppressed below and above minimum and maximum opening angles, revealing two absorbing phase transitions between thick and thin film regimes. While the transition at the minimum angle is continuous, in the directed percolation class, that at the maximum angle is clearly discontinuous. For intermediate values of the opening angle, a rough colloidal network in the Kardar-Parisi-Zhang universality class grows indefinitely. The nature of the transitions was analyzed in detail by considering bond flexibility, defined as the dispersion of the angle between the bond and the center of the patch. For the range of flexibilities considered we always observe two phase transitions. However, the range of opening angles where growth is sustained increases with flexibility. At a tricritical flexibility, the discontinuous transition becomes continuous. The practical implications of our findings and the relation to other nonequilibrium transitions are discussed.

Dynamics of network fluids

Network fluids are structured fluids consisting of chains and branches. They are characterized by unusual physical properties, such as, exotic bulk phase diagrams, interfacial roughening and wetting transitions, and equilibrium and nonequilibrium gels. Here, we provide an overview of a selection of their equilibrium and dynamical properties. Recent research efforts towards bridging equilibrium and non-equilibrium studies are discussed, as well as several open questions.

Analytical and numerical study of particles with binary adsorption

Electro-oxidation of ethanol represents a key process in fuel-cell technology. We introduce a generalization of the random sequential adsorption model to study the long time scale and large length scale properties of the electro-oxidation process. We provide an analytical solution for one dimension and Monte Carlo results in two dimensions. We characterize the coverage and percolation properties of the jammed state and unveil the influence of quenched impurities in the selectivity of oxidation products.