Hierarchical Nanoporous Silica Films for Wear Resistant Antireflection Coatings.

High-performance antireflection (AR) layers were prepared by depositing hierarchical nanoporous silica films on glass substrates. We designed a composite layer consisting of mesoporous silica nanoparticles (MSNs) and a mesoporous silica matrix. The introduction of bimodal nanoporous structures, i.e., independent nanopore formation within the MSN and within the matrix, was achieved by using surface-protected MSNs and a polymeric nonionic surfactant template during the fabrication process. A porosity of more than 40% was achieved for composite AR materials. The protrusion of MSNs from the matrix led to spontaneous formation of nanoscale roughness on the surface of the coatings, which enhanced the AR properties. The solid bonding of the MSNs to the nanoporous matrices played an important role in the achievement of high mechanical durability. The optimal nanoporous coating, which contained ca. 50 wt % MSN, exhibited high transparency (91.5-97.5%) and low reflectance (<2.2%), over the whole range of visible light wavelengths, and sufficient wear resistance.

Enzyme-enabled responsive surfaces for anti-contamination materials.

Many real-life stains have origins from biological matters including proteins, lipids, and carbohydrates that act as gluing agents binding along with other particulates or microbes to exposed surfaces of automobiles, furniture, and fabrics. Mimicking naturally occurring self-defensive processes, we demonstrate in this work that a solid surface carrying partially exposed enzyme granules protected the surface in situ from contamination by biological stains and fingerprints. Attributed to the activities of enzymes which can be made compatible with a wide range of materials, such anti-contamination and self-cleaning functionalities are highly selective and efficient toward sticky chemicals. This observation promises a new mechanism in developing smart materials with desired anti-microbial, self-reporting, self-cleaning, or self-healing functions.

Biobased polymers: synthesis of graft copolymers and comb polymers using lactic acid macromonomer and properties of the product polymers.

For developing broader application of biobased polymers, graft copolymers and comb polymers having poly(lactic acid) (PLA) side chains have been synthesized by using a macromonomer technique. PLA macromonomers (MMm) having a methacryloyl polymerizable group with different PLA chain length with an average length m = 4, 6, 8, 12, 18, and 30 were prepared via ring-opening polymerization of l-lactide using hydroxyethyl methacrylate (HEMA) initiator catalyzed by Sn(Oct)(2). Radical polymerization behaviors of these macromonomers were examined. Radical copolymerization of MMm (m = 4, 6, and 8), with vinyl monomers like n-butyl methacrylate (BMA) and n-butyl acrylate (BA) in water as the reaction medium, gave stable miniemulsions of poly[n-butyl (meth)acrylate-graft-lactic acid]s [PB(M)A-g-PLAm]. MMm with m value higher than 12, however, gave aggregate products in a minor amount besides miniemulsions in a major amount, producing not a stable emulsion system of graft copolymers. The solution copolymerization, on the other hand, produced a wider variety of the graft copolymers, where a wider range of MMm (even m ≥ 12) can be employed. In a 1,4-dioxane solution, the radical copolymerization of MMm with BMA and methyl methacrylate (MMA) gave various graft copolymers [PB(M)MA-g-PLAm]. A new type of comb polymers (PMMm) having PLAm as pendant side chains were obtained by radical homopolymerization of MMm in a 1,4-dioxane solution. The graft copolymers and comb polymers obtained here are amorphous. Physical properties of the polymers from miniemulsions suggested them to be applicable for coatings or elastic materials which are environmentally desirable as a new class of biobased polymers. In addition, the present approach provided fundamental information on relationships between the length of PLA side chain and the bulk properties of the product polymers.

Artificial black opal fabricated from nanoporous carbon spheres.

A nanocasting method via chemical vapor deposition of acetonitrile was successfully employed to fabricate porous carbon colloidal crystal using colloidal crystal from monodispersed mesoporous silica spheres (MMSS) as a sacrificial scaffold. The mesostructure as well as periodic arrays within (111) plane of MMSS were replicated for the carbon colloidal crystal (black opal) with the length scale in the centimeter range. Brilliant iridescent colors were clearly observed for the first time on the black carbon colloidal crystal fabricated from porous carbon spheres, and they changed dramatically in accordance with the observation angle, like natural black opals. Reflection spectra measurements based on 2D surface diffraction and Bragg diffraction in the mirror mode were conducted for the fabricated carbon periodic arrays. The periodicity in the (111) plane as well as in the direction perpendicular to the (111) plane of the colloidal crystal was evaluated by comparing the results obtained from these two measurements. It was found that the periodicity in the direction perpendicular to the (111) surface is not high for the obtained black carbon opal. On the other hand, the relationship between the incident angles and the peak wavelengths of the reflection spectra, collected in the condition where the incident light and the reflected light pass through in the same direction, is governed by an approximation based on 2D surface diffraction. The results imply that the origin of the iridescent colors on the fabricated black carbon opal is derived from the periodicity not in the direction perpendicular to the (111) plane but within the (111) plane.

Biobased polymer system: miniemulsion of poly(alkyl methacrylate-graft-lactic acid)s.

To broaden the application scope of lactic acid polymers, a new miniemulsion of poly(alkyl methacrylate-graft-lactic acid)s has been developed. The graft copolymer synthesis was based on a poly(lactic acid) macromonomer having a methacryloyl polymerizable group. The macromonomer and a comonomer of n-butyl methacrylate together with a suitable surfactant formed a miniemulsion of the comonomers in water. A radical copolymerization of the comonomers took place to produce the graft copolymer as a stable miniemulsion. The copolymer showed elastic polymer properties. The miniemulsion system may find useful applications as a new biobased polymer material that is environmentally desirable.

Structural colored liquid membrane without angle dependence.

We have demonstrated for the first time that condensed gel particle suspensions in amorphous-like states display structural color with low angle dependence. This finding is in contrast to the common understanding that a periodic dielectric structure is fundamental to photonic band gap (PBG) production, and it validates the theory that a "tight bonding model" that is applicable to semiconductor systems can also be applied to photonic systems. More practically, this structural colored suspension represents a promising new material for the manufacture of reflective full-color displays with a wide viewing angle and nonfading color materials. This liquid system shows promise as a display material because electronic equipment used for display systems can easily be filled with the liquid in the same way that liquid crystals are currently used.

Transparent CoAl2O4 hybrid nano pigment by organic ligand-assisted supercritical water.

Transparent types of inorganic pigments are important as they can be used in a variety of applications, such as metallic finishing, contrast enhancing luminescent pigments, high-end optical filters, and so on. Currently, the difficulty in producing monodisperse and stable binary metal oxide nano pigments at low temperature hampers the applicability and realization of transparent blue nano pigments. Here, for the first time, we report organic ligand capped CoAl2O4 hybrid transparent nano pigment, which has a particle size less than 8 nm with well-stabilized single nanocrystals, using organic ligand-assisted supercritical water as the reaction medium. The organic ligand capping could effectively inhibit the particle growth and also control the size of nanocrystals. This helps to diminish the scattering effect of the nano blue pigment, realizing a transparent cobalt blue nano pigment without any postheat treatment.

Photonic band structures of colloidal crystals measured with angle-resolved reflection spectroscopy.

We acquired angle- and polarization-resolved reflection spectra from a colloidal crystal made of polystyrene spheres along the two perpendicular directions corresponding to the LU and LW directions in the first Brillouin zone of an fcc lattice. Dispersion relations between the reflection peak positions and the wave vectors of the incident light were obtained from the measured spectra and compared with calculated photonic band structures. For the first stop band region in the spectra, the behavior of the reflection peak due to Bragg diffraction agreed with the calculated band structure and revealed some differences induced by the polarization and crystalline orientations. The spectral features observed in the higher energy regions also revealed these differences. In addition, dispersion relationships between the peak positions and the wave vectors were obtained from the results of fitting each spectrum with several Gaussian curves, compared with the calculated photonic band structures. The relationships obtained for the LU direction almost matched the calculated band structure, while the relationships obtained for the LW direction revealed the features of the mixed band structure calculated for the two perpendicular directions. These results indicate that angle- and polarization-resolved reflection spectroscopy has the potential to experimentally analyze the photonic band structures of actual photonic crystals.

Optically induced melting of colloidal crystals and their recrystallization.

Colloidal crystals melt by applying focused light of optical tweezers and recrystallize after removing it. The disturbed zone by the light grows radially from the focus point and the ordering starts from the interface with the crystal. Although the larger disturbed zone is observed for the higher power optical tweezers, a master curve is extracted by normalization of the disturbed zone. The temporal changes of the normalized disturbed zone are well described with exponential functions, indicating that the melting and recrystallization process is governed by a simple relaxation mechanism.

In situ observations of the self-assembling process of colloidal crystalline arrays.

Growth processes of colloidal crystalline arrays in a fluidic glass cell were observed by confocal laser scanning microscopy. The results showed that the growth direction varied with the growth rate. At an extremely low growth rate, the array grew toward the 112 direction of the face-centered-cubic lattice. At a moderate growth rate, it grew toward the 110 direction. However, an extremely high growth rate induced random arrays of the spheres. Moreover, we were able to visualize the generation and/or annihilation processes of several kinds of defects. The variation of the growth direction with the growth rate is discussed in terms of the difference in water-flow resistance in the crystalline arrays.

Close-packed colloidal crystalline arrays composed of silica spheres coated with titania.

Titania coated monodisperse silica spheres have been synthesized and fabricated as a close-packed colloidal crystalline array. We have demonstrated that the coated colloidal sphere can be used to control the peak position of the optical stop band through variation of the coating thickness. The titania coated silica spheres were prepared by the layer-by-layer assembly coating process, which reciprocally laminates the cationic polyelectrolyte and the anionic titania nanosheets on a monodisperse silica spheres, and were sintered to change the titania nanosheets to anatase. The Bragg diffraction peak of the colloidal crystalline array shifted to the long wavelength region with an increase of thickness of the titania layer. Angle-resolved reflection spectra measurements clarified that the red shift was caused by increasing of the refractive index with increase of the thickness of the layer. The current work suggests new possibilities for the creation of advanced colloidal crystalline arrays with tunable optical properties from tailored colloidal spheres.

Effects of compression and shearing on the microstructure of polymer-immobilized non-close-packed colloidal crystalline arrays.

We have examined the changes in the optical properties and microstructure of polymer-immobilized non-close-packed colloidal crystalline arrays with compression and shearing stress. The optical properties and microstructures of the arrays were measured by angle-resolved reflection spectroscopy. The spectra indicate an increase in the refractive index and a decrease in the interplane spacing with compression, however, indicating an increase in the interplane spacing with shearing stress. These results show that compression decreases the interplane spacing without moving the inner-plane position, while shearing stress increases the interplane spacing by moving the position of the spheres in the same plane.

Close-packed colloidal crystalline arrays composed of polystyrene latex coated with titania nanosheets.

We have demonstrated that polystyrene latex coated with titania nanosheets can be fabricated into a close-packed colloidal crystalline array, and that these coated colloidal spheres can be used to control the peak position of optical stop bands through the coating. The titania-nanosheets-coated polystyrene latex was prepared by the layer-by-layer (LBL) assembly coating process, involving alternating lamination of cationic polyelectrolytes and anionic titania nanosheets on monodisperse polystyrene latex particles. The Bragg diffraction peak of the colloidal crystalline array shifted to longer wavelengths with the coating of titania nanosheets. This red shift was caused by an increase in refractive index upon coating, as revealed by angle-resolved reflection spectra measurements. The current work suggests new possibilities for the creation of advanced colloidal crystals having tunable optical properties from tailored colloidal spheres.

Stepwise controlled immobilization of colloidal crystals formed by polymer-grafted silica particles.

Colloidal crystals formed by polymer-grafted silica particles were immobilized by a stepwise procedure consisting of gelation by radical copolymerization followed by solidification by ring-opening radical polymerization. In the first step, the poly(methyl methacrylate) (PMMA)-grafted silica colloidal crystal suspension was incorporated into the gel without altering the crystal structure by copolymerization of cross-linker, 1,2-dimethylacryloyloxyethane (DME) and methyl methacrylate (MMA). In the second step, ring-opening radical polymerization was performed after substituting the solvent with vinylidene-1,3-dioxolane. By this two-step procedure, the silica particle array of colloidal crystals was immobilized and made into durable material.

Large-domain colloidal crystal films fabricated using a fluidic cell.

The growth of colloidal crystal films from a dispersion of monodispersed silica spheres using a simple cell with one opening was investigated. Colloidal crystal films with large domain sizes were successfully fabricated almost over the cell (approximately 10 cm2) without applying any external force at room temperature. During the drying process, three distinct conditions were observed, in each of which the films exhibited different optical properties. Films with high transmittance were formed in the first stage. Upon further solvent evaporation, the films entered a medium transmittance state via an extremely low transmittance state. Angle-resolved reflection spectroscopy, which was used to analyze the three conditions, revealed that close-packed arrays with water-filled spaces between were formed in the first stage. One-directional flow was generated in the cell because water evaporation occurred only at the opening. The flow caused the spheres to be arranged epitaxially, resulting in a large domain size.

Preparation and structure of novel siloxene nanosheets.

We demonstrate the two-dimensional silicon backbone structure of siloxene nanosheets, which produces relatively monodisperse nanosheets with a thickness of 0.7 nm and lengths in the range 100-200 nm; the thickness is an order of magnitude smaller than that of previously reported silicon nanoparticles prepared by a variety of other methods.