Adsorption, Desorption, Surface Diffusion, Lattice Defect Formation, and Kink Incorporation Processes of Particles on Growth Interfaces of Colloidal Crystals with Attractive Interactions

Good model systems are required in order to understand crystal growth processes because, in many cases, precise incorporation processes of atoms or molecules cannot be visualized easily at the atomic or molecular level. Using a transmission-type optical microscope, we have successfully observed in situ adsorption, desorption, surface diffusion, lattice defect formation, and kink incorporation of particles on growth interfaces of colloidal crystals of polystyrene particles in aqueous sodium polyacrylate solutions. Precise surface transportation and kink incorporation processes of the particles into the colloidal crystals with attractive interactions were observed in situ at the particle level. In particular, contrary to the conventional expectations, the diffusion of particles along steps around a two-dimensional island of the growth interface was not the main route for kink incorporation. This is probably due to the number of bonds between adsorbed particles and particles in a crystal; the number exceeds the limit at which a particle easily exchanges its position to the adjacent one along the step. We also found novel desorption processes of particles from steps to terraces, attributing them to the assistance of attractive forces from additionally adsorbing particles to the particles on the steps

Thermally Induced Unidirectional Crystallization of Charged Colloids(Poster session 1, New Frontiers in Colloidal Physics : A Bridge between Micro- and Macroscopic Concepts in Soft Matter)

この論文は国立情報学研究所の電子図書館事業により電子化されました。荷電コロイド粒子分散液は、粒子間の静電相互作用が十分大きいとき、粒子が規則配列した"結晶"構造を形成する。本研究では、昇温により粒子表面電荷数が増加して結晶化するコロイド系(ピリジン共存シリカ粒子/水分散液;粒径～100nm;粒子体積分率=0.035)を用い、加熱により結晶を一方向成長させた。大型(1mm×1cm×3cm)かつ試料セル壁面に良好に配列した、単一ドメイン結晶が生成した。結晶化機構および成長曲線について、試料温度分布の測定結果に基づいて議論する

Adsorption, Desorption, Surface Diffusion, Lattice Defect Formation, and Kink Incorporation Processes of Particles on Growth Interfaces of Colloidal Crystals with Attractive Interactions

Good model systems are required in order to understand crystal growth processes because, in many cases, precise incorporation processes of atoms or molecules cannot be visualized easily at the atomic or molecular level. Using a transmission-type optical microscope, we have successfully observed in situ adsorption, desorption, surface diffusion, lattice defect formation, and kink incorporation of particles on growth interfaces of colloidal crystals of polystyrene particles in aqueous sodium polyacrylate solutions. Precise surface transportation and kink incorporation processes of the particles into the colloidal crystals with attractive interactions were observed in situ at the particle level. In particular, contrary to the conventional expectations, the diffusion of particles along steps around a two-dimensional island of the growth interface was not the main route for kink incorporation. This is probably due to the number of bonds between adsorbed particles and particles in a crystal; the number exceeds the limit at which a particle easily exchanges its position to the adjacent one along the step. We also found novel desorption processes of particles from steps to terraces, attributing them to the assistance of attractive forces from additionally adsorbing particles to the particles on the steps

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 <i>Z</i> 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 <i>C</i>_surf was selected below the critical micelle concentration. As CPC molecules were adsorbed, <i>Z</i> values of the PS and silica particles decreased, inverting to positive when <i>C</i>_surf exceeded the isoelectric point <i>C</i>_iep. Hydrophobic PS particles exhibited much lower <i>C</i>_iep than hydrophilic silica particles. At <i>C</i>_surf valuess between their <i>C</i>_iep 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

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 <i>d</i> = 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, <i>d</i> = 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

Two-Dimensional Nucleation on the Terrace of Colloidal Crystals with Added Polymers

Understanding nucleation dynamics is important both fundamentally and technologically in materials science and other scientific fields. Two-dimensional (2D) nucleation is the predominant growth mechanism in colloidal crystallization, in which the particle interaction is attractive, and has recently been regarded as a promising method to fabricate varieties of complex nanostructures possessing innovative functionality. Here, polymers are added to a colloidal suspension to generate a depletion attractive force, and the detailed 2D nucleation process on the terrace of the colloidal crystals is investigated. In the system, we first measured the nucleation rate at various area fractions of particles on the terrace, ϕ_area. In situ observations at single-particle resolution revealed that nucleation behavior follows the framework of classical nucleation theory (CNT), such as single-step nucleation pathway and existence of critical size. Characteristic nucleation behavior is observed in that the nucleation and growth stage are clearly differentiated. When many nuclei form in a small area of the terrace, a high density of kink sites of once formed islands makes growth more likely to occur than further nucleation because nucleation has a higher energy barrier than growth. The steady-state homogeneous 2D nucleation rate, <i>J</i>, and the critical size of nuclei, <i>r</i>*, are measured by in situ observations based on the CNT, which enable us to obtain the step free energy, γ, which is an important parameter for characterizing the nucleation process. The γ value is found to change according to the strength of attraction, which is tuned by the concentration of the polymer as a depletant