Novel synthesis of poly(methyl methacrylate) brush encapsulated silica particles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter = 20 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. The particle sizes of such core–shell structures [number‐average particle diameter (D_n) = 35–40 nm] were controlled by the variation of the feed amounts of the monomers and surfactant, or emulsion system. The size distributions were relatively narrow (weight‐average particle diameter/D_n ≈ 1.05). These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brush encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics of Free-Radical Polymerization of Vinylbenzyl-Terminated Macromonomers

Vinylbenzyl-terminated polystyrene (PS) macromonomers were prepared by the direct reaction of living PS anions with p-chloro-methylstyrene (CMS). The propagation rate constant (k _p) was obtained from free-radical polymerization of PS macromonomers in the presence of 1-buten-3-ol as a degradative chain transfer agent by using gel permeation chromatography (GPC) analysis. In this condition, the polymer radicals were terminated by a unimoiecular mechanism. Subsequently, we studied the radical propagation step of vinylbenzyl-terminated diblock poly[styrene (S)-b-isoprene (I)] and poly[S-b-2-vinylpyridine (2VP)] macromonomers in benzene. The vinylbenzyl groups at the terminal ends of diblock macromonomers apparently take the concentrated state in micelles. These results are discussed from the point of view of polymer-polymer reactions.     

Ferroelectric and Magnetic Properties in Room‐Temperature Multiferroic GaxFe2−xO3 Epitaxial Thin Films

GaFeO₃‐type iron oxide is a promising room‐temperature multiferroic material due to its large magnetization. To expand its usability, controlling the ferroelectric and magnetic properties is crucial. In this study, high‐quality Ga_xFe_2–xO₃ (x = 0–1) epitaxial films are fabricated and their properties are systematically investigated. All films exhibit room‐temperature out‐of‐plane ferroelectricity, showing that the coercive electric field (E_c) decreases monotonically with x. Additionally, the films show in‐plane ferrimagnetism with a Curie temperature (T_C) >350 K at x = 0–0.6. The coercive magnetic field (H_c) decreases with x at x ≤ 0.6, but shows a constant value at x > 0.6, whereas the saturated magnetization (M_s) increases with x at x ≤ 0.6, but decreases with x at x > 0.6. X‐ray magnetic circular dichroism reveals that the large magnetization at x = 0.6 is derived from Fe³⁺ (3d⁵) at octahedral sites. The controllable range of the E_c, H_c, and M_s values at room temperature (400–800 kV cm^?1, 1–8 kOe, and 0.2–0.6 µ_B/f.u.) is very wide and differs from those of well‐known multiferroic BiFeO₃. Furthermore, the Ga_xFe_2?xO₃ films exhibit room‐temperature magnetocapacitance effects, indicating that adjusting T_C near room temperature is useful to achieve large room‐temperature magnetocapacitance behavior.     

Nonstoichiometric deep levels in Mg-doped GaP epitaxial layers: Effects of pre-annealing of substrates

The effects of substrate pre-annealing on deep level density in Mg-doped GaP liquid-phase epitaxy (LPE) layers were investigated by photocapacitance measurement. With annealing under optimum phosphorus-vapor pressure, concentration of deep donor at E_C — 1.9–2.1 eV increased in undoped GaP substrate. Deep level densities in Mg-doped layers were also affected by pre-annealing of the substrates. Densities of dominant deep levels at E_V + 0.85 eV and E_V + 1.5 eV were an order of magnitude reduced and, in contrast, the level at E_C − 2.1 eV in Mg-doped layer increased with long pre-annealing. This level at E_C − 2.1 eV is supposed to be involved with P-rich-type nonstoichiometric defects, such as phosphorus interstitial atoms diffused from the surface of the substrate.     

Direct observation of corrosion fatigue cracks in aluminum alloy using ultra-bright synchrotron radiation

Refraction contrast X-ray imaging using synchrotron source with ultra-bright light and highly directional beam is a unique method to diagnose non-destructively cracks or voids formed in materials, providing us in principle completely different information from conventional methods such as absorption contrast X-ray imaging. The authors have applied this imaging technique in SPring-8 to materials fracture study. We have also introduced home-made, in-situ observation facility system of crack formation and propagation in materials and the originally-designed 3D X-ray imaging systems to the experimental Hutch C of BL24XU (Hyogo BL) of SPring-8. Using these 3D X-ray imaging technique, in-situ observations of initiation and propagation of corrosion fatigue crack of Al-10%Mg alloy were conducted. The absorption contrast X-ray images were also obtained for comparison. It is concluded that the X-ray imaging method using ultra-bright synchrotron radiation is very useful for fracture research of materials and 3D X-ray contrast images are much more distinct than the conventional X-ray images to obtain information of the crack initiation and propagation behavior in the alloy.     

Steam reforming of CH4 over Ni-Ru catalysts supported on Mg-Al mixed oxide

Ni_0.5/Mg_2.5(Al)O catalyst prepared from hydrotalcite precursors showed high and stable activity in the CH₄ steam reforming, but was severely deactivated in the daily start-up and shut-down (DSS) operation under steam purging. The addition of Ru drastically improved the behavior of Ni_0.5/Mg_2.5(Al)O catalyst for the DSS operation. During the wet Ru loading on the Ni_0.5/Mg_2.5(Al)O catalyst, the reconstitution of hydrotalcite took place by “memory effect,” resulting in the formation of Ru-Ni alloy as well as the strong interaction between Ru and Ni after the calcination followed by reduction. This provided the catalyst with high sustainability probably by suppressing the oxidation of Ni metal by steam by hydrogen spillover from Ru. Only 0.05 wt% of Ru loading was enough to effectively suppress the deactivation.     

Two‐dimensional regular nanopatterning on block copolymer substrate having lamellar morphology using star‐hyperbranched nanospheres by electrostatic interaction

Hyperbranched polystyrenes (PS) were prepared by living radical photopolymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate as an inimer under UV irradiation. The star‐hyperbranched copolymers were derived by grafting from surface N,N‐diethyldithiocarbamate groups of hyperbranched macroinitiator with t‐butyl methacrylate in the presence of N,N‐tetraethylthiuram disulfide. We obtained poly(methacrylic acid) star‐hyperbranched PS nanospheres by hydrolysis of poly(t‐butyl methacrylate)‐grafted chains. We established two‐dimensional (2D) regular nanopatterning by aligning continuously such nanospheres on poly(2‐vinylpyridine) (P2VP) lamellar layers of PS‐block‐P2VP diblock copolymer film. Electrostatic interaction between nanosphere surface having negative charges (? COOCs) and P2VP lamellar layer acted effectively for the 2D nanopattern formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4206–4210, 2006     

Airborne freeboard measurements of sea ice and lake ice at the Sea of Okhotsk coast in 1993-95 by a laser altimeter

An airborne laser altimeter using a Nd:YAG laser was constructed to measure surface profiles of sea ice and frozen lakes. The measurements were conducted to develop a technique for estimating the ice amount of the sea ice in the Sea of Okhotsk off the northern shore of Hokkaido Island, Japan. Distributions of freeboards, mean elevations and ice concentrations were investigated from the data observed in 1993-95. Distribution functions of the ice freeboard changed considerably depending on ice concentrations in contrast with the decreasing function for the sea ice in the Arctic Ocean. The mean ice freeboard, however, correlated very well with the ice concentration, which is very important for estimating total ice amounts in regions of drifting ice. The surface roughness of a frozen lake was also observed and analysed.