Formation of two-dimensional diamond-like colloidal crystals using layer-by-layer electrostatic self-assembly.

We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 µm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.

Clustering of charged colloidal particles in the microgravity environment of space.

We conducted a charge-charge clustering experiment of positively and negatively charged colloidal particles in aqueous media under a microgravity environment at the International Space Station. A special setup was used to mix the colloid particles in microgravity and then these structures were immobilized in gel cured using ultraviolet (UV) light. The samples returned to the ground were observed by optical microscopy. The space sample of polystyrene particles with a specific gravity ρ (=1.05) close to the medium had an average association number of ~50% larger than the ground control and better structural symmetry. The effect of electrostatic interactions on the clustering was also confirmed for titania particles (ρ ~ 3), whose association structures were only possible in the microgravity environment without any sedimentation they generally suffer on the ground. This study suggests that even slight sedimentation and convection on the ground significantly affect the structure formation of colloids. Knowledge from this study will help us to develop a model which will be used to design photonic materials and better drugs.

Surface Plasmon Resonance of Two-Dimensional Gold Colloidal Crystals Formed on Gold Plates.

The free electrons inside precious metals such as Au vibrate when the surface of the metal is irradiated with an electromagnetic wave of an appropriate frequency. This oscillation is referred to as surface plasmon resonance (SPR), and the resonance frequency varies with permittivity of the medium around the metal. SPR sensors are widely applied in the fields of bioscience and pharmaceutical sciences, including biosensing for drug discovery, biomarker screening, virus detection, and testing for food safety. Here, we fabricated a metal-insulator-metal (MIM) SPR sensor by constructing two-dimensional (2D) regular array of Au colloidal particles (2D colloidal crystals) on an insulator layer over a thin Au film coated on a glass substrate surface. The 2D crystals were fabricated by electrostatically adsorbing negatively charged three-dimensional crystals onto a positively charged thin insulator formed on Au film. The plasmon peaks/dips from the MIM structure were measured in aqueous solutions of ethylene glycol (EG) at various concentrations. Multiple plasmon peaks/dips were observed due to the localized SPR (LSPR) of the Au particles and the Fano resonance between the Au particles and thin film. The plasmon peaks/dips shifted to higher wavelengths on increasing EG concentrations due to an increase in the refractive index of the media. The observed peak/dip shift was approximately twice that of LSPR from an isolated Au particle. We expect the present MIM substrate will be useful as a highly sensitive sensor in the pharmaceutical field.

Crystallization of charged gold particles mediated by nonadsorbing like-charged polyelectrolyte.

We report that the aqueous dispersions of negatively charged submicron-sized colloidal Au particles formed non-close-packed colloidal crystals by the addition of a like-charged linear polyelectrolyte, sodium polyacrylate (NaPAA). Au particles often form irregular aggregates in dispersions because of a strong van der Waals force acting between them. To prevent aggregation, we introduced negative electric charges on particle surfaces. By the addition of NaPAA, colloidal crystals were formed on the bottom of a sample cell because of the supply of Au particles by sedimentation and 2D diffusion even under very dilute conditions. Interparticle potential calculations demonstrated that the addition of NaPAA caused depletion attraction between the particles as well as a significant reduction in the interparticle repulsion because of the electrostatic screening effect. However, the electrostatic repulsion was strong enough to prevent the direct contact of particles in the excluded region between Au particles. Large-area crystals could be obtained by tilting the sample cell. By drying the sample, the Au particles came into contact and the non-space-filling crystals changed into closest packed crystals. These closest packed crystals exhibited a significant enhancement of Raman scattering intensity because of high hot-spot density.

Two-Dimensional Nonclose-Packed Colloidal Crystals by the Electrostatic Adsorption of Three-Dimensional Charged Colloidal Crystals.

We demonstrate that nonclose-packed two-dimensional (2D) colloidal crystals fixed on flat solid surfaces can be obtained by the electrostatic adsorption of three-dimensional (3D) charged colloidal crystals onto oppositely charged substrates. 3D colloidal crystals of negatively charged polystyrene (diameter d = 500 nm) and silica (d = 510 and 550 nm) particles were formed in their aqueous dispersions. Then, a single layer of the 3D crystals (the particle volume fraction = ∼0.07-0.3) was adsorbed onto a glass surface, which was earlier modified with 3-aminopropyltriethoxysilane (APTES), a cationic silane coupling reagent. Under salt-free conditions, the lowermost layer of the 3D crystals, which was oriented parallel to the substrate, was adsorbed onto the substrate surface, forming 2D crystals. Centimeter-sized, large 2D silica crystals were produced by combining a unidirectional 3D crystallization of the silica colloid under a base concentration gradient and a unidirectional adsorption under an acidic concentration gradient, which allowed tuning of the charge number on the APTES-modified substrate. The interparticle separations of the resulted 2D crystals did not vary greatly (within 5%) over a large area (length: 2 cm); however, the separations were smaller than the initial value because of gravitational sedimentation. We also produced 2D crystals of gold particles (d = 250 nm), which we expect to be applicable as plasmonic materials. The present study will provide a facile strategy to produce nonclose-packed 2D colloidal crystals of various types of particles, including large and high-density particles.

Mechanism of diffusiophoresis with chemical reaction on a colloidal particle.

A mechanism for diffusiophoresis of a charged colloidal particle undergoing surface chemical reaction is proposed. A theoretical model is constructed to describe the dynamics of the particle and the surrounding solution of a weak electrolyte. Theoretical analysis and numerical simulations of the model reveal that phoretic motion of the particle emerges in response to a concentration gradient of electrolyte. The concentration gradient breaks the spherical symmetry of the surface charge distribution, which gives rise to a net force on the particle and leads to directional motion of the particle.

Particle Adsorption on Hydrogel Surfaces in Aqueous Media due to van der Waals Attraction.

Particle adhesion onto hydrogels has recently attracted considerable attention because of the potential biomedical applications of the resultant materials. A variety of interactions have been taken advantage of for adsorption, including electrostatic forces, hydrophobic interactions and hydrogen bonding. In this study, we report significant adsorption of submicron-sized silica particles onto hydrogel surfaces in water, purely by van der Waals (vdW) attraction. The vdW forces enabled strong adhesions between dielectric materials in air. However, because the Hamaker constant decreases in water typically by a factor of approximately 1/100, it is not clear whether vdW attraction is the major driving force in aqueous settings. We investigated the adsorption of silica particles (diameter = 25-600 nm) on poly(acrylamide) and poly(dimethylacrylamide) gels using optical microscopy, under conditions where chemical and electrostatic adsorption is negligible. The quantity of adsorbed particles decreased on decreasing the Hamaker constant by varying the refractive indices of the particles and medium (ethyleneglycol/water), indicating that the adsorption is because of the vdW forces. The adsorption isotherm was discussed based on the adhesive contact model in consideration of the deformation of the gel surface. The present findings will advance the elucidation and development of adsorption in various types of soft materials.

Numerical study of cluster formation in binary charged colloids.

Cluster formation of oppositely charged colloidal particles is studied numerically. A simple Brownian dynamics method with a screened-Coulomb (Yukawa) potential is employed for numerical simulations. An equilibrium phase which consists of clusters and unassociated particles is obtained. It is shown that the equilibrium association number of clusters and their shapes are determined by charge numbers and charge ratio of the binary particles. The phase diagram of cluster formation for various charge numbers and their ratios is obtained. A simple relation between the association number and the charge ratio is found. It is demonstrated that in the case of high charge ratio the cluster takes a multilayer structure which is highly symmetric. It is also pointed out that the cluster-particle interaction changes dynamically in the cluster formation process, which is involved in the selection of final cluster structure.

Spontaneous Formation of Eutectic Crystal Structures in Binary and Ternary Charged Colloids due to Depletion Attraction.

Crystallization of colloids has extensively been studied for past few decades as models to study phase transition in general. Recently, complex crystal structures in multi-component colloids, including alloy and eutectic structures, have attracted considerable attention. However, the fabrication of 2D area-filling colloidal eutectics has not been reported till date. Here, we report formation of eutectic structures in binary and ternary aqueous colloids due to depletion attraction. We used charged particles + linear polyelectrolyte systems, in which the interparticle interaction could be represented as a sum of the electrostatic, depletion, and van der Waals forces. The interaction was tunable at a lengthscale accessible to direct observation by optical microscopy. The eutectic structures were formed because of interplay of crystallization of constituent components and accompanying fractionation. An observed binary phase diagram, defined by a mixing ratio and inverse area fraction of the particles, was analogous to that for atomic and molecular eutectic systems. This new method also allows the adjustment of both the number and wavelengths of Bragg diffraction peaks. Furthermore, these eutectic structures could be immobilized in polymer gel to produce self-standing materials. The present findings will be useful in the design of the optical properties of colloidal crystals.

Thermoreversible crystallization of charged colloids due to adsorption/desorption of ionic surfactants.

We report that charged colloids exhibit thermoreversible crystallization via the adsorption of ionic surfactants onto particle surfaces. Due to the temperature dependence of the adsorption quantity, the colloids crystallized upon cooling and melted upon heating. To clarify the influences of surfactant adsorption on the crystallization, polystyrene (PS) particles dispersed in ethylene glycol (EG)/water mixtures were employed, enabling continuous tuning of the adsorption quantity by changing the EG concentration. The thermoreversible crystallization/melting behavior was found to be mainly attributable to changes in the ionic strength of the medium resulting from variation in the concentration of the non-adsorbed ionic surfactant molecules with temperature. We expect that the present findings will be useful for fine control of colloidal crystallization and the further study of colloidal crystallization in low permittivity media.

Controlled Clustering in Binary Charged Colloids by Adsorption of Ionic Surfactants.

We report on the controlled clustering of oppositely charged colloidal particles by the adsorption of ionic surfactants, which tunes charge numbers Z of particles. In particular, we studied the heteroclustering of submicron-sized polystyrene (PS) and silica particles, both of which are negatively charged, in the presence of cetylpyridinium chloride (CPC), a cationic surfactant. The surfactant concentration Csurf was selected below the critical micelle concentration. As CPC molecules were adsorbed, Z values of the PS and silica particles decreased, inverting to positive when Csurf exceeded the isoelectric point Ciep. Hydrophobic PS particles exhibited much lower Ciep than hydrophilic silica particles. At Csurf valuess between their Ciep values, the particles were oppositely charged, and clustering was enabled. To explain the clustering behavior, we investigated adsorption isotherms of the CPC and screened-Coulomb-type pair potential. Expected applications of the present findings are the control of colloidal associations and construction of various particle types into heterogeneous colloidal clusters.

Dynamics of polyelectrolyte solutions under a constant gradient of base concentration.

Phase-separation dynamics of weakly charged polyacid solutions under a constant gradient of base concentration is studied both theoretically and numerically. The time-evolution equation of polymer volume fraction is derived by assuming that the chemical equilibrium of the dissociation reaction is locally established. Numerical simulations of the system in contact with two reservoirs in which the base concentrations differ are performed. The numerical results show that the polymer volume fraction can be transported by the concentration gradient of the base, which leads to the dynamic behavior of mesophase domain structures.

Mesoscopic simulation of phase behaviors and structures in an amphiphile-solvent system.

We have performed a three-dimensional simulation of mesoscopic structures in a mixture of AB amphiphilic molecule and C solvent by employing the density-functional theory under the conditions that (i) the size of the AB is much larger than C and (ii) the affinity between A and B is much larger than the affinity between B and C. First, we have calculated the free energy of five periodic structures, i.e., the lamellar phase, hexagonally packed cylinders, body-centered-cubic spheres, face-centered-cubic spheres, and gyroid phase for different sets of the concentration of AB (ϕ[over ¯]_{AB}) and the χ parameter (χ_{AC}). By comparing the free energies for these structures, the χ_{AC}-ϕ[over ¯]_{AB} phase diagram has been obtained. In addition to these periodic structures, it has been shown that nonperiodic structures such as spherical and rodlike micelles can be obtained although they might be metastable phase.

Exclusion of impurity particles in charged colloidal crystals.

Uniformly shaped, charged colloidal particles dispersed in water form ordered "crystal" structures when the interaction between the particles is sufficiently strong. Herein, we report the behavior of "impurity" particles, whose sizes and/or charge numbers are different from those of the bulk, on addition to the charged colloidal crystals. These impurities were excluded from the crystals during the homogeneous crystallization, crystal grain growth, and unidirectional crystallization processes. Such systems will be useful as models for studying the refinement of materials and crystal defects.

Recrystallization and zone melting of charged colloids by thermally induced crystallization.

We examined the application of recrystallization and zone-melting crystallization methods, which have been used widely to fabricate large, high-purity crystals of atomic and molecular systems, to charged colloidal crystals. Our samples were aqueous dispersions of colloidal silica (with particle diameters of d = 108 or 121 nm and particle volume fractions of ϕ = 0.035-0.05) containing the weak base pyridine. The samples crystallized upon heating because of increases in the particle charge numbers, and they melted reversibly on cooling. During the recrystallization experiments, the polycrystalline colloids were partially melted in a Peltier cooling device and then were crystallized by stopping the cooling and allowing the system to return to ambient temperature. The zone-melting crystallization was carried out by melting a narrow zone (millimeter-sized in width) of the polycrystalline colloid samples and then moving the sample slowly over a cooling device to recrystallize the molten region. Using both methods, we fabricated a few centimeter-sized crystals, starting from millimeter-sized original polycrystals when the crystallization rates were sufficiently slow (33 µm/s). Furthermore, the optical quality of the colloidal crystals, such as the half-band widths of the diffraction peaks, was significantly improved. These methods were also useful for refining. Small amounts of impurity particles (fluorescent polystyrene particles, d = 333 nm, ϕ = 5 × 10(-5)), added to the colloidal crystals, were excluded from the crystals when the crystallization rates were sufficiently slow (∼0.1 µm/s). We expect that the present findings will be useful for fabricating large, high-purity colloidal crystals.

Gravitational compression dynamics of charged colloidal crystals.

We examine the compression of charged colloidal crystals under the influence of gravitational force by monitoring the spatiotemporal variations of Bragg diffraction from the crystal lattice. We use the dilute aqueous dispersions of colloidal silica particles (diameter=216 nm, charge number=733, a particle volume fraction φ=0.06) in the presence of 5-15 µM sodium chloride. The sedimentation profiles of the colloidal crystals along the crystal height are determined by in situ fiber optics reflection spectroscopy. The time evolutions of the sedimentation profiles are calculated by numerical simulations based on a phenomenological continuum model that explicitly incorporates the electrostatic interparticle interactions. The simulation results correctly describe the experiments at sufficiently high ionic strength.

Exclusion of impurity particles during grain growth in charged colloidal crystals.

We examine the spatial distribution of fluorescent-labeled charged polystyrene (PS) particles (particle volume fraction ϕ = 0.0001 and 0.001, diameter d = 183 and 333 nm) added to colloidal crystals of charged silica particles (ϕ = ϕ(s) = 0.035-0.05, d = 118 nm). At ϕ(s) = 0.05, the PS particles were almost randomly distributed in the volume-filling polycrystal structures before the grain growth process. Time-resolved confocal laser scanning microscopy observations reveal that the PS particles are swept to the grain boundaries of the colloidal silica crystals owing to grain boundary migration. PS particles with d = 2420 nm are not excluded from the silica crystals. We also examine influences of the impurities on the grain growth laws, such as the power law growth, size distribution, and existence of a time-independent distribution function of the scaled grain size.

Controlling profiles of polymer dots by switching between evaporation and condensation.

We found that the profiles of the dots formed from the drying droplets of polymer solution can be modified by switching between the evaporation and condensation processes. When a polymer dot is exposed to solvent vapor during a certain time and is dried again, the dot profile changes from ringlike to flat. To obtain a flat dot, there exists an optimal exposure time. We conjecture that the change of the dot profile is due to the refluidization of the polymer film. Our results imply a new possibility for controlling the dot profile in inkjet printing technologies.

Controlling the drying and film formation processes of polymer solution droplets with addition of small amount of surfactants.

We studied how the addition of surfactants alters the drying and film formation processes of polymer solution droplets with contact lines strongly fixed by bank structures. We found that even if the amount of surfactant is quite small, it drastically changes the final profile of the polymer film from a ringlike profile to a flat profile. This property is observed commonly, irrespective of the polymer concentration, droplet volume, and type of solvent. We conjecture that the inhomogeneous distribution of the surfactant caused by the outward capillary flow induces the Marangoni flow directed toward the center of the droplet, which suppresses the outward flow. The present phenomenon implies an effective method for controlling the profile of the polymer film in inkjet printing technologies.