Unifying Atoms and Colloids near the Glass Transition through Bond-Order Topology.

In this combined experimental and simulation study, we utilize bond-order topology to quantitatively match particle volume fraction in mechanically uniformly compressed colloidal suspensions with temperature in atomistic simulations. The obtained mapping temperature is above the dynamical glass transition temperature, indicating that the colloidal systems examined are structurally most like simulated undercooled liquids. Furthermore, the structural mapping procedure offers a unifying framework for quantifying relaxation in arrested colloidal systems.

Periodically microstructured composite films made by electric- and magnetic-directed colloidal assembly.

Living organisms often combine soft and hard anisotropic building blocks to fabricate composite materials with complex microstructures and outstanding mechanical properties. An optimum design and assembly of the anisotropic components reinforces the material in specific directions and sites to best accommodate multidirectional external loads. Here, we fabricate composite films with periodic modulation of the soft-hard microstructure by simultaneously using electric and magnetic fields. We exploit forefront directed-assembly approaches to realize highly demanded material microstructural designs and showcase a unique example of how one can bridge colloidal sciences and composite technology to fabricate next-generation advanced structural materials. In the proof-of-concept experiments, electric fields are used to dictate the position of the anisotropic particles through dielectrophoresis, whereas a rotating magnetic field is used to control the orientation of the particles. By using such unprecedented control over the colloidal assembly process, we managed to fabricate ordered composite microstructures with up to 2.3-fold enhancement in wear resistance and unusual site-specific hardness that can be locally modulated by a factor of up to 2.5.

Colloidal assembly and 3D shaping by dielectrophoretic confinement.

For decades, scientists and engineers have strived to design means of assembling colloids into ordered structures. By now, the literature is quite peppered with reports of colloidal assemblies. However, the available methods can assemble only a narrow range of structures or are applicable to specific types of colloids. There are still only few generic methods that would lead to arbitrary colloidal arrays or would shape colloidal assemblies into predesigned structures. Here, we first discuss in detail how to spatially control the assembly and crystallization of colloids through the balance of dielectrophoretic and dipolar forces. Furthermore, we demonstrate how to flexibly program and shape arrays of 3D microstructures that can be permanently affixed by in situ UV polymerization and calcination by using two facing similar or distinct micro-fabricated electrodes.

Colloidal analogues of charged and uncharged polymer chains with tunable stiffness.

Yanking the chain: a general method for the preparation of colloidal analogues of polymer chains was developed. The flexibility of these chains can be tuned by applying electric fields in combination with their subjection to simple linkage-forming procedures.

Seeded growth of titania colloids with refractive index tunability and fluorophore-free luminescence.

Titania is an important material in modern materials science, chemistry, and physics because of its special catalytic, electric, and optical properties. Here, we describe a novel method to synthesize colloidal particles with a crystalline titania, anatase core and an amorphous titania-shell structure. We demonstrate seeded growth of titania onto titania particles with accurate particle size tunability. The monodispersity is improved to such an extent so that colloidal crystallization of the grown microspheres becomes feasible. Furthermore, seeded growth provides separate manipulation of the core and shell. We tuned the refractive index of the amorphous shell between 1.55 and 2.3. In addition, the particles show luminescence when trace amounts of aminopropyl-triethoxysilane are incorporated into the titania matrix and are calcined at 450 °C. Our novel colloids may be useful for optical materials and technologies such as photonic crystals and optical trapping.

Phase behavior and structure of a new colloidal model system of bowl-shaped particles.

We study the phase behavior of bowl-shaped (nano)particles using confocal microscopy and computer simulations. Experimentally, we find the formation of a wormlike fluid phase in which the bowl-shaped particles have a strong tendency to stack on top of each other. However, using free energy calculations in computer simulations, we show that the wormlike phase is out-of-equilibrium and that the columnar phase is thermodynamically stable for sufficiently deep bowls and high densities. In addition, we employ a novel technique based on simulated annealing to predict the crystal structures for shallow bowls. We find four exotic new crystal structures and we determine their region of stability using free energy calculations. We discuss the implications of our results for the development of materials consisting of molecular mesogens or nanoparticles.

A general method to coat colloidal particles with titania.

We describe a general one-pot method for coating colloidal particles with amorphous titania. Various colloidal particles such as silica particles, large silver colloids, gibbsite platelets, and polystyrene spheres were successfully coated with a titania shell. Although there are several ways of coating different particles with titania in the literature, each of these methods is applicable to only one type of material. The present method is especially useful for giving the opportunity to cover many types of colloidal particles with titania and forgoes the use of a coupling agent or a precoating step. We can produce particles with a smooth titania layer of tunable thickness. The monodispersity, which improves during particle growth, and the high refractive index of titania make these particles potential candidates for photonic crystal applications. We also describe various ways of fabricating hollow titania shells, which have been intensively studied in the literature for their applications in electronics, catalysis, separations, and diagnostics. Note that our method initially produces amorphous shells on the particles, but these can be easily turned into crystalline titania by a calcination step. We also find that the growth of titania is a surface-reaction-limited process.

Directed self-assembly of colloidal dumbbells with an electric field.

We demonstrate the assembly of colloidal particles with the shape of diatomic molecules ("dumbbells") into crystals that we study with confocal microscopy. The literature on the preparation of nonspherical colloidal particles has grown steadily. Assembly of these particles into regular three-dimensional crystalline lattices, however, is rarely, if ever, achieved and has not yet been studied quantitatively in 3D real space. We find that, by application of an electric field, such particles assemble quite readily. By varying the particle aspect ratio, range of interactions, and electric field strength, we find several different crystal structures of which three have never before been observed. Moreover, the electric field can be used to switch between different structures and manipulate/switch the photonic properties. Moreover, our work sheds light on fundamental questions related to the self-assembly of nonspherical particles.

Colloidal Switches by Electric and Magnetic Fields.

External electric and magnetic fields have already been proven to be a versatile tool to control the particle assembly; however, the degree of control of the dynamics and versatility of the produced structures is expected to increase if both can be implemented simultaneously. For example, while micromagnets can rapidly assemble superparamagnetic particles, repeated, rapid disassembly or reassembly is not trivial because of the remanence and coercivity of metals used in such applications. Here, an interdigitated design of micromagnet and microfabricated electrodes enables rapid switching of colloids between their magnetic and electric potential minima. Active control over colloids between two such adjacent potential minima enables a fast on/off mechanism, which is potentially important for optical switches or display technologies. Moreover, we demonstrate that the response time of the colloids between these states is on the order of tens of milliseconds, which is tunable by electric field strength. By carefully designing the electrode pattern, our strategy enables the switchable assembly of single particles down to few microns and also hierarchical assemblies containing many particles. Our work on precise dynamic control over the particle position would open new avenues to find potential applications in optical switches and display technologies.

Magnetophoretic Assembly of Anisotropic Colloids for Spatial Control of Reinforcement in Composites.

Anisotropic particles have attracted interest for decades and have been studied for many aspects, ranging from fundamental phase behavior to photonic properties. In addition, magnetic fields have been heavily used for external manipulation of colloidal particles for separation, for assembly, and even for photonic applications. Here we use magnetic field microgradients established in a paramagnetic fluid to act as templates for the assembly of both nonmagnetic and magnetic anisotropic colloidal particles. We embed the assembled structure in a polymer matrix in order to obtain a composite where the spatial distribution of the reinforcing particles are preprogrammed. By using a mixture of paramagnetic and diamagnetic particles with different mechanical strengths, a periodical modulation of reinforcement by the variation of the particle type at different locations is achieved. Furthermore, we introduce a similar method for assembly of paramagnetic particles, where we use magnetic gradients of permanent magnet arrays to obtain field gradients and modulate spatially the particle concentration, and thus reinforcement, through the macroscopic samples in three dimensions.