Time evolution of the inner structure of antimony phosphate nanosheet suspension developing structural colouration.

Structural colouration observed in antimony phosphate nanosheet suspensions has been known for two decades, but the stability of their inner structures has not been a topic in colloidal nanosheet systems. In this study, we investigate the time evolution of structures in suspension using UV-visible spectrometry and small-angle X-ray scattering. Here, we report that antimony phosphate nanosheet systems re-organise their inner structures, especially at lower concentrations (isotropic or biphasic region), and that the basal spacing decreases with time after sample preparation, although the evolution speed depends on the sample concentration. The stability of the inner structure of the suspension is essential for their application as structural colour materials in sensors and colourants.

Swelling and delamination of inorganic homoionic montmorillonite clay in water-polar organic mixed solvents.

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM.

Impacts of negatively charged colloidal clay particles on photoisomerization of both anionic and cationic azobenzene molecules.

Although smectite-type clays are used as heterogeneous media for photofunctional guest molecules, the guest species are limited to cationic or polar molecules because of the intrinsic negative electric charges of clay particles. Nevertheless, in this study, aqueous clay colloids are reported to affect the photoisomerization kinetics of anionic and cationic azobenzene molecules dissolved in the colloids. Under UV-light irradiation, the clay colloids decelerate trans-to-cis isomerization, while under visible-light irradiation, the clay colloids accelerate cis-to-trans isomerization. In addition, the sol-gel transition of clay colloids affects the kinetics. The results considerably expand the applicability of clay colloids as matrixes for functional organic species.

Electrically Induced Alignment of Semiconductor Nanosheets in Niobate-Clay Binary Nanosheet Colloids toward Significantly Enhanced Photocatalysis.

Aqueous binary colloids of niobate and clay nanosheets, prepared by the exfoliation of their mother layered crystals, are unique colloidal systems characterized by the separation of niobate and clay nanosheet phases, where niobate nanosheets form liquid crystalline domains with the size of several tens of micrometers among isotropically dispersed clay nanosheets. The binary colloids show unusual photocatalytic reactions because of the spatial separation of photocatalytically active niobate and photochemically inert clay nanosheets. The present study shows structural conversion of the binary colloids with an external electric field, resulting in the onsite alignment of colloidal nanosheets to improve the photocatalytic performance of the system. The colloidal structure is reshaped by the growth of liquid crystalline domains of photocatalytic niobate nanosheets and by their electric alignment. Niobate nanosheets are assembled by the domain growth process and then aligned by AC voltage, although clay nanosheets do not respond to the electric field. Photocatalytic decomposition of the cationic rhodamine 6G dye, which is selectively adsorbed on clay nanosheets, is examined for the niobate-clay binary nanosheet colloids with or without domain growth and electric field. The fastest decomposition is observed for the electrically aligned colloid without the domain growth, whereas the sample with the domain growth and without the electric alignment shows the slowest decomposition. The results demonstrate the improvement of the photocatalytic performance by changing the colloidal structure, even though the sample composition is the same.

Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System.

Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (∼several tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

Electric-Alignment Immobilization of Liquid Crystalline Colloidal Nanosheets with the Aid of a Natural Organic Polymer.

Inorganic nanosheets obtained by exfoliation of a layered crystal in water form colloidal liquid crystals, and their alignment can be controlled by an electric field. In order to realize the immobilization of the electrically aligned niobate nanosheets without external forces, an aqueous gelator, agar, is introduced to the niobate nanosheet system to utilize the thermosensitive sol-gel transition property of agar. Alignment of nanosheets in a niobate-agar system is performed by applying an electric field above the sol-gel transition temperature, and then, the sample is cooled down, followed by cooling below the transition temperature with the electric field turned off. The aligned structure is kept for more than 24 h after the removal of the electric field. The concentration of agar is a key parameter for both the orientation of nanosheets and the retention of the orientation.

pH-Sensitive Adsorption Behavior of Polymer Particles at the Air-Water Interface.

pH-Sensitive adsorption of polymer particles bearing poly[2-(dimethylamino)ethyl methacrylate] hairs at the air-water interface was investigated using a surface tensiometer, a Langmuir-Blodgett trough, and an X-ray reflectometer. We clarified that the particles are adsorbed at the interface at basic pH; by contrast, at acidic pH, only a small number of particles are adsorbed, whereas the majority are dispersed in the water phase. X-ray reflectometry analysis revealed that a particle monolayer was formed at the air-water interface, which was packed densely under increasing surface pressure, as determined by the electron density profile change. The contact angles of the particles at the air-water interface were estimated to be 29° and 34° at pH 3 and 10, respectively, by direct visualization of the air-water interface position of the particles using a polycyanoacrylate trapping method.

Flow-Induced Assembly of Colloidal Liquid Crystalline Nanosheets Toward Unidirectional Macroscopic Structures.

Multiscale structures of anisotropic nanoparticles up to macroscopic scales are important in order to produce practical materials through nanotechnology. As an example of such structures, hierarchical organization of colloidal liquid crystals of niobium oxide nanosheets yields stripe textures observable by naked eyes. The stripes are generated by the growth of liquid crystalline domains (tactoids) and the alignment of the tactoids under an electric field and gravity applied in the directions orthogonal to each other. The nanosheets forming the tactoids are unidirectionally aligned along the flow induced by gravity, and the aligned tactoids are stretched to be connected each other to form the stripes. Time evolution of the stripes indicates that they are generated during the settlement of the nanosheets. The nanosheets are debundled with the settlement, and thus the stripes are gradually degenerated during the settlement. Larger tactoids cause faster nanosheet settlement and stripe degeneration. The electric field applied orthogonally to gravity has roles of pinning the nanosheets to slow down their settlement and retains the stripes for several hours.

Synergistic photocatalytic hydrogen evolution over oxide nanosheets combined with photochemically inert additives.

Photocatalytic hydrogen evolution over semiconducting niobate nanosheets is synergistically improved by coexisting photochemically inactive additives of clay particles and sodium chloride without precise nanoscopic structural regulation. In addition, the Pt cocatalyst loaded on the clay particles works better than that photodeposited on the photocatalytic nanosheets.

Multiphase coexistence and destabilization of liquid crystalline binary nanosheet colloids of titanate and clay.

A plate-plate binary colloid system of photocatalytically active titanate and inert clay nanosheets shows macroscopically separated multiphase coexistence. Two liquid crystalline phases and one isotropic phase coexist at high titanate and low clay concentrations whereas the colloids are destabilized at high clay concentrations.

Panoscopic organization of anisotropic colloidal structures from photofunctional inorganic nanosheet liquid crystals.

Colloidal liquid crystals of inorganic nanosheets with thickness of around 1 nm and lateral dimensions of several micrometers prepared by exfoliation of a layered niobate are converted to hierarchically organized arrays whose structures are controlled from the nano to macroscopic length scale through the growth of liquid crystalline domains called tactoids as the secondary building blocks followed by controlled application of external fields. Growth of the tactoids is attained by incubation of the liquid crystals at room temperature. The tactoids are then assembled into higher-order structures with characteristic lengths of sub-mm to mm under the simultaneous application of an ac electric field and gravity, whose directions determine the final textural motif of the arrays. Whereas a net-like texture is observed when applying the electric and gravitational forces in the same direction, a striped texture where the nanosheets are unidirectionally aligned is observed when the electric field is applied in the direction perpendicular to gravity. The use of well-grown tactoids is key to the macroscopic structural control. Since the niobate nanosheets have wide band-gap semiconducting nature, the nanosheet stripe arrays exhibit photocatalysis that reflected the alignment of the nanosheets with respect to the polarized direction of impinging light.

Pickering emulsions prepared by layered niobate K4Nb6O17 intercalated with organic cations and photocatalytic dye decomposition in the emulsions.

We investigated emulsions stabilized with particles of layered hexaniobate, known as a semiconductor photocatalyst, and photocatalytic degradation of dyes in the emulsions. Hydrophobicity of the niobate particles was adjusted with the intercalation of alkylammonium ions into the interlayer spaces to enable emulsification in a toluene-water system. After the modification of interlayer space with hexylammonium ions, the niobate stabilized water-in-oil (w/o) emulsions in a broad composition range. Optical microscopy showed that the niobate particles covered the surfaces of emulsion droplets and played a role of emulsifying agents. The niobate particles also enabled the generation of oil-in-water (o/w) emulsions in a limited composition range. Modification with dodecylammonium ions, which turned the niobate particles more hydrophobic, only gave w/o emulsions, and the particles were located not only at the toluene-water interface but also inside the toluene continuous phase. On the other hand, interlayer modification with butylammonium ions led to the formation of o/w emulsions. When porphyrin dyes were added to the system, the cationic dye was adsorbed on niobate particles at the emulsion droplets whereas the lipophilic dye was dissolved in toluene. Upon UV irradiation, both of the dyes were degraded photocatalytically. When the cationic and lipophilic porphyrin molecules were simultaneously added to the emulsions, both of the dyes were photodecomposed nonselectively.

Effect of grafted polymer species on particle monolayer structure at the air-water interface.

We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass substrate.

Particle monolayer formation with arrayed structure by PMMA-grafted polystyrene Latex at the air-water interface.

The structure of the particle monolayer formed by the polymer-grafted latex particle at the air-water interface was estimated mainly by pi--A isotherm measurement and SEM observation to examine the effect of core particle characteristics and to generalize the key factors in determining the polymer-grafted particle monolayer structure. Methyl methacrylate (MMA) was polymerized from the polystyrene latex (PSL) surface by atom transfer radical polymerization to give a PMMA-grafted PSL (PSL-PMMA) with a relatively high graft density of about 0.2 nm-2. We obtained PSL-PMMA with PMMA of different molecular weights but almost the same graft density. The onset area of increasing surface pressure in pi-A isotherm was in agreement with the value of effective radius of PSL-PMMA with quite extended PMMA chains. The particle monolayer structure deposited on the substrate was strongly dependent on the molecular weight of the grafted PMMA. The aggregation size was reduced with increasing molecular weight and a lattice-like structure was observed for PSL-PMMA monolayer with a high molecular weight PMMA. The interparticle distance was decreased and structure becomes ordered with increasing surface pressure. The monolayer structure obtained here was consistent with that of the PMMA-grafted silica particle system. We also synthesized polystyrene (PS)-grafted PMMA latex (PML-PS) and compared the two systems. We confirmed that the lattice-like structure depended on the nature of the grafted PMMA chain, not the core particle characteristics.

X-ray reflectometry confirms polymer-grafted silica particle monolayer formation at the air-water interface.

We examined the air-water interface of the poly(methyl methacrylate)-grafted silica particle monolayer by X-ray reflectometry to obtain in situ information on the particle monolayer structure suggested by pi-A isotherm measurement and SEM observation. We confirmed the monolayer formation of polymethylmethacrylate-grafted silica particle at the air-water interface by interesting XR profile. We obtained XR profile with many tooth-shaped fringes for one of the PMMA-grafted silica particle monolayer. By the model fitting of this profile, we confirmed monolayer formation at the air-water interface. Furthermore, we found that the interface roughness became large at the plateau region in the pi-A isotherm, which provides insight into the origin of the plateau region. We confirmed the reproducibility of XR profiles at same surface pressure after surface compression. This indicates the structually-reversible nature of the particle monolayer, which is the unique nature of the polymer-grafted particle monolayer.

Colloidal crystallization of colloidal silica modified with ferrocenyl group-contained polymers in organic solvents.

Surface modification of colloidal silica with ferrocenyl-grafted polymer and colloidal crystallization of the particles in organic solvent were studied. Poly(methyl methacrylate-co-vinylferrocene)-grafted silica never formed colloidal crystals in polar solvent, such as acetone, acetonitrile, ethanol and N,N-dimethylformamide (DMF), while poly(methyl methacrylate-co-ferrocenyl acrylate)-grafted silica gave colloidal crystallization in DMF. The particles prepared by grafting of poly(N,N-dimethylacrylamide-co-vinylferrocene), with vinylferrocene (Vfc) mole fraction of 1/13 and 1/23, were observed to give the crystallization in ethanol and DMF over particle volume fraction of 0.058. Further, silica modified with copolymer of Vfc and N-vinyl-2-pyrrolidone, N-vinylcarbazole or N-isopropylacrylamide formed colloidal crystals in ethanol and DMF. Especially, poly(N-isopropylacrylamide-co-Vfc)-grafted silica, which was composed of the highest mole fraction of vinylferrocene, 1/3, afforded colloidal crystallization in ethanol over particle volume fraction of 0.053. Relatively high polar vinylferrocene copolymer grafting of silica resulted in colloidal polymerization in organic solvents.

Structural and morphological changes of monolayers of a block copolymer with dendron and perfluoroalkyl side chains by mixing a perfluorooctadecanoic acid.

Hybrid Langmuir and Langmuir-Blodgett monolayers of a perfluorooctadecanoic acid mixed with a rigid block copolymer, poly(3,5-bis(3,5-bis(benzyloxy)benzyloxy)benzyl methacrylate-randommethacrylic acid)-block-poly(2-perfluorooctylethyl acrylate), which is composed of benzyloxy dendron side chains and perfluorinated side chains, were prepared and characterized by surface pressure-surface area isotherms, atomic force microscopic images and neutron and X-ray reflectometries. The two-dimensionally phase-separated structures of monolayer films and their morphologies with plateau and terrace were confirmed. The monolayers were separated into a dendron layer, a perfluorinated layer, and a carboxyl layer. The layer formation is originated not only in the intermolecular interaction between a perfluorooctadecanoic acid and a block copolymer but also in the geometry of the molecules. Especially, the amphiphilicity of perfluorinated surfactant plays a role to the ordered array of the block copolymers.

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.

Critical brush density for the transition between carpet-only and carpet/brush double-layered structures.

The critical brush density, where transition from carpet-only structure to carpet/brush double-layered structure occurs, was estimated for a weakly ionic amphiphilic diblock copolymer, (diethylsilacyclobutane)34-b-(methacrylic acid)50, monolayer on water by an in situ X-ray reflectivity technique. The brush density in the monolayer was controlled from 0.11 to 0.60 brush chain/nm2 by changing surface pressure and mixing a poly(diethylsilacyclobutane) homopolymer separately synthesized. Only a carpet layer was formed at a low brush density condition, but a carpet and brush double layer was found for a higher brush density of more than 0.48/nm2. This brush density, which is fairly high, would be valuable for discussing the polyelectrolyte brush nanostructure.

Nanostructure of a "carpet"-like dense layer/polyelectrolyte brush layer in a block copolymer monolayer at the air-water interface.

The "carpet"/brush double layer structure in the polyelectrolyte layer in the amphiphilic diblock copolymer monolayer at the air-water interface was quantitatively studied by in situ neutron reflectometry in addition to X-ray reflectivity measurements. As a result of the higher contrast between polyelectrolyte [poly(methacrylic acid)] and solvent (D(2)O) for the neutron, the brush structure could be estimated more accurately as a function of surface pressure, that is, brush density. The thickness of the carpet layer, which is thought to be formed to reduce the interfacial free energy between water and the hydrophobic layer, was almost constant at 10-20 A at any surface pressure studied. Growth was clearly observed in the whole brush length with increasing surface pressure, and it was estimated to be almost 60% of the full-stretch length of the ionic polymer chain. Furthermore, by the comparison of density profiles by neutron and X-ray reflectometry, an anomalous hydration was suggested.