Daiki Murakami

Wettability and Antifouling Behavior on the Surfaces of Superhydrophilic Polymer Brushes

The surface wettabilities of polymer brushes with hydrophobic and hydrophilic functional groups were discussed on the basis of conventional static and dynamic contact angle measurements of water and hexadecane in air and captive bubble measurements in water. Various types of high-density polymer brushes with nonionic and ionic functional groups were prepared on a silicon wafer by surface-initiated atom-transfer radical polymerization. The surface free energies of the brushes were estimated by Owens-Wendt equation using the contact angles of various probe liquids with different polarities. The decrease in the water contact angle corresponded to the polarity of fluoroalkyl, hydroxy, ethylene oxide, amino, carboxylic acid, ammonium salt, sulfonate, carboxybetaine, sulfobetaine, and phosphobetaine functional groups. The poly(2-perfluorooctylethyl acrylate) brush had a low surface free energy of approximately 8.7 mN/m, but the polyelectrolyte brushes revealed much higher surface free energies of 70-74 mN/m, close to the value for water. Polyelectrolyte brushes repelled both air bubbles and hexadecane in water. Even when the silicone oil was spread on the polyelectrolyte brush surfaces in air, once they were immersed in water, the oil quickly rolled up and detached from the brush surface. The oil detachment behavior observed on the superhydrophilic polyelectrolyte brush in water was explained by the low adhesion force between the brush and the oil, which could contribute to its excellent antifouling and self-cleaning properties.

Wetting Transition from the Cassie–Baxter State to the Wenzel State on Textured Polymer Surfaces

The wetting transition from the Cassie-Baxter state to the Wenzel state on textured surfaces was investigated. Nano- to microscale hexagonal pillared lattices were prepared by nanoimprint lithography on fluorinated cycloolefin polymer substrates. The transition was clearly observed for water and some ionic liquids through contact angle measurements and optical microscopy. A simple model clearly demonstrated that the energy barrier in the wetting transition from the Cassie-Baxter state to the Wenzel state was dominated by the competition between the energy barrier and external forces, particularly the Laplace pressure in the present case.

Measurement of the Electrostatic Interaction between Polyelectrolyte Brush Surfaces by Optical Tweezers

We demonstrated an optical tweezers method to measure the electrostatic interaction between the strong polyelectrolyte brushes, poly(2-(methacryloyloxy)ethyltrimethylammonium chloride) (PMTAC), grafted on silica particles in aqueous media. The weak electrostatic interaction was successfully detected with a resolution of less than 0.1 μN m(-1). The apparent Debye length, including the charge distribution in the polymer brush and the surface potential, decreased as the salt concentration in the medium increased. The experimentally obtained surface charge density was much smaller than that estimated from the amount of polyelectrolyte on the surface. Furthermore, the dissociation of ionic groups was enhanced by decreasing the grafting density of the polyelectrolyte brush. The results suggest that the majority of chloride counterions was immobilized in the dense polyelectrolyte brush layer to neutralize the high charge density.

X-ray photon correlation spectroscopy using a fast pixel array detector with a grid mask resolution enhancer

The performance of a fast pixel array detector with a grid mask resolution enhancer has been demonstrated for X-ray photon correlation spectroscopy experiments.

Spreading and Structuring of Water on Superhydrophilic Polyelectrolyte Brush Surfaces

The wetting behavior of superhydrophilic polyelectrolyte brushes was investigated. Reflection interference contrast microscopy demonstrated that the contact angles of water on the polyelectrolyte brushes were extremely low but remained finite in the range of <3°. The presence of water molecules was evident, even outside the macroscopic water droplet. These water molecules were confined to the thin brush layers and contained a highly ordered hydrogen bond network, which was identified as structural water. The presence of the thin film and the structural water changed the surface energies, which prevented the complete wetting of the surface.

Characterization of Surface Microstructures on Bio-based Polymer Film Fabricated with Nano-imprint Lithography by Synchrotron Radiation Small Angle X-ray Scattering

Nano-imprint lithography (NIL) is a simple, low cost and high-resolution patterning method. However the precise evaluation method of nano-imprinted structure has not been established. Synchrotron radiation small angle X-ray scattering (SR-SAXS) measurement is a nondestructive and high resolution characterization method. In this study, we attempt to fabricate nanostructures on the poly(lactic acid) (PLA) film by NIL and evaluated with microscopic and scattering techniques. The mold with line/space pattern was used for NIL. Scanning electron microscope observation confirmed the formation of surface nano-structure in large areas. Also, nano-imprinted PLA film was evaluated using SR-SAXS measurement. The scattering patterns obtained from nano-imprinted PLA films were clearly observed up to higher order scattering spots. These results suggested that highly regular structure was fabricated on the surface of PLA films.

Fluorinated Langmuir monolayers are more viscous than non-fluorinated monolayers.

The surface shear viscosity of the liquid expanded phase in Langmuir monolayers of fluorinated alcohols differs by orders of magnitude from the corresponding surface shear viscosity of Langmuir monolayers of their non-fluorinated counterparts. The line tension between the liquid expanded and the gaseous phase on the other hand is of similar magnitude for both fluorinated and non-fluorinated surfactants. The difference of fluorinated versus non-fluorinated monolayers is measured by active microrheology and by observing the shape relaxation of distorted liquid expanded domains toward a circular shape. Our microrheology measurements are supported by measurements of the relaxation rates of distortions, which in fluorinated liquid expanded phases are proportional to the deviation of the curvature from the mean curvature, whereas they are proportional to the square of the deviation of the curvature from the mean curvature in non-fluorinated monolayers.

Phase Transition and Domain Formation in the Gibbs Adsorbed Films of Long-Chain Alcohols

The adsorption behavior of 1,1,2,2,-tetrahydroheptadecafluorodecanol (FC10OH), 1-eicosanol (C20OH), and their mixtures at the hexane solution/water interface is summarized briefly and examined from the viewpoints of interfacial tensions in the presence of domains, domain formation, and the correlation between the phase transition and the miscibility of film forming substances in the adsorbed films. The two-dimensional analogue of the Laplace equation showed that the interfacial tension is always higher in the presence of domains than that in the absence of them. The higher tendency of domain formation of FC10OH compared to C20OH is mainly ascribed to the excess Gibbs energy of mixing of fluorocarbon chains and hydrocarbon solvent being positive and to the interaction energy between domains being more stable against cohesion for FC10OH than for C20OH. The thermodynamic equations derived here suggested the heteroazeotropy in the phase diagram of adsorption and the temperature dependence of interfacial tension at the phase transition points, which are in accord with the experimental findings qualitatively.

X-ray Photon Correlation Spectroscopy of Silica Particles Grafted with Polymer Brush in Polystyrene Matrix

X-ray photon correlation spectroscopy system was setup at SPring-8, BL19LXU, and the partial coherence scattering data from the silica particles grafted with polymer brush in polystyrene matrix were measured. Firstly, the static speckle patterns were checked. Below the glass transition temperature of polystyrene (Tg), speckles were clearly observed, on the other hand, above Tg, the scattering patterns became smooth and speckles were hardly observed. These variances of the speckle patterns result from the particle motion. Secondly, from the time variance of the speckle data, time autocorrelation functions g2(q,t) are calculated. While the flat behaviour of g2(q,t) without relaxation were observed below Tg, the relaxation behavior with relaxation time~100–101 were observed above Tg

Molecular orientation and multilayer formation of 1H,1H,8H,8H-perfluorooctane-1,8-diol at the air/water interface.

The surface tension of the aqueous solution of 1H,1H,8H,8H-perfluorooctane-1,8-diol (FC(8)diol) was measured as a function of temperature and concentration under atmospheric pressure. The interfacial density and the entropy and energy of adsorption were evaluated and compared to those obtained for the adsorption of 1H,1H,10H,10H-perfluorodecane-1,10-diol (FC(10)diol) at the hexane solution/water interface. The surface tension curves show a break point corresponding to a phase transition of the adsorbed FC(8)diol film. The value of mean area per adsorbed molecule A just below the phase transition indicated the formation of a parallel condensed monolayer, and that above the phase transition suggested the spontaneous formation of a multilayer. The multilayer of FC(8)diol is less compressible and shows a smaller increase in layering with pi compared to FC(10)diol. This is probably because the surface force is repulsive for the hexane/FC/water interface, while it is attractive for the air/FC/water interface. The partial molar entropy change of adsorption is positive in the condensed FC(8)diol film, while it is negative in the condensed FC(10)diol film, which is reasonably explained in terms of the difference in entropy change accompanied by desolvation around the hydrophobic chain. From the viewpoints of the energetic stabilization accompanied by adsorption for the FC(8)diol system, the contribution from the replacement of air/water contact with air/fluorocarbon and fluorocarbon/water contacts and that from the molecular ordering in the adsorbed film is almost equal in case of the condensed monolayer, while in the multilayer the latter is comparatively larger than the former due to the hydrogen bonding between hydroxyl groups and the dispersion interaction among the ordered hydrophobic chains.