Ivo Buttinoni

Dynamical clustering and phase separation in suspensions of self-propelled colloidal particles.

We study experimentally and numerically a (quasi-)two-dimensional colloidal suspension of self-propelled spherical particles. The particles are carbon-coated Janus particles, which are propelled due to diffusiophoresis in a near-critical water-lutidine mixture. At low densities, we find that the driving stabilizes small clusters. At higher densities, the suspension undergoes a phase separation into large clusters and a dilute gas phase. The same qualitative behavior is observed in simulations of a minimal model for repulsive self-propelled particles lacking any alignment interactions. The observed behavior is rationalized in terms of a dynamical instability due to the self-trapping of self-propelled particles.

Microswimmers in patterned environments

Tiny self-propelled swimmers capable of autonomous navigation through complex environments provide appealing opportunities for localization, pick-up and delivery of microscopic and nanoscopic objects. Inspired by motile cells and bacteria, man-made microswimmers have been created and their motion in homogeneous environments has been studied. As a first step towards more realistic conditions under which such microswimmers will be employed, here we study, experimentally and with numerical simulations, their behavior in patterned surroundings that present complex spatial features where frequent encounters with obstacles become important. To study the microswimmers as a function of their swimming behavior, we develop a novel species of microswimmers whose active motion is due to the local demixing of a critical binary liquid mixture and can be easily tuned by illumination. We show that, when microswimmers are confined to a single pore whose diameter is comparable with their swimming length, the probability of finding them at the confinement walls significantly increases compared to Brownian particles. Furthermore, in the presence of an array of periodically arranged obstacles, microswimmers can steer even perpendicularly to an applied force. Since such behavior is very sensitive to the details of their specific swimming style, it can be employed to develop advanced sorting, classification and dialysis techniques.

Circular motion of asymmetric self-propelling particles.

Micron-sized self-propelled (active) particles can be considered as model systems for characterizing more complex biological organisms like swimming bacteria or motile cells. We produce asymmetric microswimmers by soft lithography and study their circular motion on a substrate and near channel boundaries. Our experimental observations are in full agreement with a theory of Brownian dynamics for asymmetric self-propelled particles, which couples their translational and orientational motion.

Programmable colloidal molecules from sequential capillarity-assisted particle assembly.

Researchers produce tailor-made colloidal molecules from a variety of materials using a simple sequential assembly process. The assembly of artificial nanostructured and microstructured materials which display structures and functionalities that mimic nature’s complexity requires building blocks with specific and directional interactions, analogous to those displayed at the molecular level. Despite remarkable progress in synthesizing “patchy” particles encoding anisotropic interactions, most current methods are restricted to integrating up to two compositional patches on a single “molecule” and to objects with simple shapes. Currently, decoupling functionality and shape to achieve full compositional and geometrical programmability remains an elusive task. We use sequential capillarity-assisted particle assembly which uniquely fulfills the demands described above. This is a new method based on simple, yet essential, adaptations to the well-known capillary assembly of particles over topographical templates. Tuning the depth of the assembly sites (traps) and the surface tension of moving droplets of colloidal suspensions enables controlled stepwise filling of traps to “synthesize” colloidal molecules. After deposition and mechanical linkage, the colloidal molecules can be dispersed in a solvent. The template’s shape solely controls the molecule’s geometry, whereas the filling sequence independently determines its composition. No specific surface chemistry is required, and multifunctional molecules with organic and inorganic moieties can be fabricated. We demonstrate the “synthesis” of a library of structures, ranging from dumbbells and triangles to units resembling bar codes, block copolymers, surfactants, and three-dimensional chiral objects. The full programmability of our approach opens up new directions not only for assembling and studying complex materials with single-particle-level control but also for fabricating new microscale devices for sensing, patterning, and delivery applications.

Colloidal polycrystalline monolayers under oscillatory shear

In this paper we probe the structural response to oscillatory shear deformations of polycrystalline monolayers of soft repulsive colloids with varying area fraction over a broad range of frequencies and amplitudes. The particles are confined at a fluid interface, sheared using a magnetic microdisk, and imaged through optical microscopy. The structural and mechanical response of soft materials is highly dependent on their microstructure. If crystals are well understood and deform through the creation and mobilization of specific defects, the situation is much more complex for disordered jammed materials, where identifying structural motifs defining plastically rearranging regions remains an elusive task. Our materials fall between these two classes and allow the identification of clear pathways for structural evolution. In particular, we demonstrate that large enough strains are able to fluidize the system, identifying critical strains that fulfill a local Lindemann criterion. Conversely, smaller strains lead to localized and erratic irreversible particle rearrangements due to the motion of structural defects. In this regime, oscillatory shear promotes defect annealing and leads to the growth of large crystalline domains. Numerical simulations help identify the population of rearranging particles with those exhibiting the largest deviatoric stresses and indicate that structural evolution proceeds towards the minimization of the stress stored in the system. The particles showing high deviatoric stresses are localized around grain boundaries and defects, providing a simple criterion to spot regions likely to rearrange plastically under oscillatory shear.

Direct observation of impact propagation and absorption in dense colloidal monolayers

Significance Single-particle characterization of the impact response has unveiled design principles to focus and control stress propagation in macroscopic granular crystalline arrays. We demonstrate that similar principles apply to aqueous monolayers of microparticles excited by localized mechanical pulses. By inducing extreme local deformation rates and tracking the motion of each particle with velocities that reach up to few meters per second, we reveal that a regime of elastic collisions, typically forbidden due to overdamping, becomes accessible. This provides insights on the stress propagation and energy absorption of dense suspensions upon fast deformation rates. Dense colloidal suspensions can propagate and absorb large mechanical stresses, including impacts and shocks. The wave transport stems from the delicate interplay between the spatial arrangement of the structural units and solvent-mediated effects. For dynamic microscopic systems, elastic deformations of the colloids are usually disregarded due to the damping imposed by the surrounding fluid. Here, we study the propagation of localized mechanical pulses in aqueous monolayers of micron-sized particles of controlled microstructure. We generate extreme localized deformation rates by exciting a target particle via pulsed-laser ablation. In crystalline monolayers, stress propagation fronts take place, where fast-moving particles (V approximately a few meters per second) are aligned along the symmetry axes of the lattice. Conversely, more viscous solvents and disordered structures lead to faster and isotropic energy absorption. Our results demonstrate the accessibility of a regime where elastic collisions also become relevant for suspensions of microscopic particles, behaving as “billiard balls” in a liquid, in analogy with regular packings of macroscopic spheres. We furthermore quantify the scattering of an impact as a function of the local structural disorder.

Two-dimensional assemblies of soft repulsive colloids confined at fluid interfaces*

Colloidal systems are an excellent example of a materials class for which interrogating fundamental questions leads to answers of direct applied relevance. In our group, we in particular focus on two-dimensional assemblies of micro- and nano-particles confined at the interface between two fluids, e.g. , oil-water. Here, we review our work on systems interacting through soft repulsive forces of different origin, i.e. , electrostatic and steric. By starting from the paradigmatic case of charged colloids at an interface, we show how they are both offering great opportunities as model systems to investigate the structural and mechanical response of materials and as versatile patterning tools for surface nanostructuring. We then move to the case of deformable particles interacting via steric contacts. We first examine microgel particles, which we also demonstrate as very promising models for structural investigations and robust elements for tunable nanolithography. We conclude by briefly discussing the case of particles comprising a hard inorganic core and a deformable polymer shell, which maintain some of the advantageous features of microgel particles, but also enable the realization of two-dimensional functional materials. This article offers our perspective on a very active field of research, where many interesting developments are expected in the near future.

Reply to Comment on "Circular Motion of Asymmetric Self-Propelling Particles"

In a Comment [1] on our Letter on self-propelledasymmetric particles [2], Felderhof claims that our the-ory based on Langevin equations would be conceptuallywrong. In this Reply we show that our theory is appro-priate, consistent, and physically justified.The motion of a self-propelled particle (SPP) is force-and torque-free if external forces and torques are absent.Nevertheless, as stated in our Letter [2], effective forcesand torques [3–7] can be used together with the grand re-sistance matrix (GRM) [8] to describe the self-propulsionof force- and torque-free swimmers [9]. To prove this, weperform a hydrodynamic calculation based on slender-body theory for Stokes flow [10, 11]. This approach hasbeen applied successfully to model, e.g., flagellar loco-motion [12, 13] and avoids a general Fax´en’s theoremfor asymmetric particles. A key assumption of slender-body theory is that the width 2ǫ of the arms of the L-shaped particle is much smaller than the total arc lengthL = a +b, where a and b are the arm lengths.The centerline position of the slender particle is x(s) =r−r

Hybrid Colloids Produced by Sequential Capillarity-assisted Particle Assembly: A New Path for Complex Microparticles

Colloidal particles have long been under the spotlight of a very diverse research community, given their ubiquitous presence in a broad class of materials and processes, and their pivotal role as model systems. More recently, intense efforts have been devoted to the development of micro- and nanoparticles combining multiple materials in objects with a controlled architecture, hence introducing multiple functionalities and a prescribed symmetry for interactions. These particles are often called hybrid colloids or colloidal molecules, given the analogy with classical molecules presenting well defined structures and chemical compositions. Here, we review the recent progress made in our group to fabricate a broad library of hybrid colloids exploiting a novel assembly route, which uses capillary forces at the moving edge of an evaporating droplet for the sequential composition of colloidal clusters, whose geometry and chemistry can be independently programmed.

Kümmelet al.Reply

In a Comment [1] on our Letter on self-propelledasymmetric particles [2], Felderhof claims that our the-ory based on Langevin equations would be conceptuallywrong. In this Reply we show that our theory is appro-priate, consistent, and physically justified.The motion of a self-propelled particle (SPP) is force-and torque-free if external forces and torques are absent.Nevertheless, as stated in our Letter [2], effective forcesand torques [3–7] can be used together with the grand re-sistance matrix (GRM) [8] to describe the self-propulsionof force- and torque-free swimmers [9]. To prove this, weperform a hydrodynamic calculation based on slender-body theory for Stokes flow [10, 11]. This approach hasbeen applied successfully to model, e.g., flagellar loco-motion [12, 13] and avoids a general Fax´en’s theoremfor asymmetric particles. A key assumption of slender-body theory is that the width 2ǫ of the arms of the L-shaped particle is much smaller than the total arc lengthL = a +b, where a and b are the arm lengths.The centerline position of the slender particle is x(s) =r−r