Surface grafting of polymers onto glass plate: Polymerization of vinyl monomers initiated by initiating groups introduced onto the surface

The surface grafting of polymers onto a glass plate surface was achieved by the polymerization of vinyl monomers initiated by initiating groups introduced onto the surface. Azo groups were introduced onto the glass plate surface by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with isocyanate groups, which were introduced by the treatment with tolylene-2,4-diisocyanate. The radical polymerization of various vinyl monomers was initiated by azo groups introduced onto the glass plate surface and the corresponding polymers were grafted from the surface: The surface grafting of polymers was confirmed by IR spectra, and the contact angle of surface, with water. The contact angle of the glass plate increased by the grafting of hydrophobic polymers, but decreased by the grafting of hydrophilic polymers. The radical postpolymerization was successfully initiated by the pendant peroxycarbonate groups of grafted polymer on the surface to give branched polymer-grafted glass plate. The cationic polymerization of vinyl monomers was also successfully initiated by benzylium perchlorate groups introduced onto the glass plate surface and the corresponding polymers were grafted onto the surface. The contact angle of the glass plate surface obtained from the cationic polymerization of styrene was larger than that obtained from the radical polymerization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2165–2172, 1997     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Ab initio study on plane defects in zirconium–hydrogen solid solution and zirconium hydride

Hydrogen embrittlement of zirconium alloys is one of the main causes of the mechanical degradation of the fuel cladding in light water reactors, and has therefore been extensively studied. Although various conjectures have been proposed as the origin of such embrittlement, it is not known which one plays the most important role: the brittle nature of the hydride, micro-crack nucleation by interaction of hydride precipitates with dislocations or void nucleation at the interface between hydride precipitates and zirconium matrix. The purpose of the present study was to elucidate the origin of the embrittlement by investigating the fracture properties of the hydride. We have evaluated the surface energy γ_S and unstable stacking energy γ_US of Zr–H systems by using ab initio calculations. The ductile/brittle behavior of the hydride is discussed based on the difference between γ_S and γ_US among the hydride, pure zirconium and hydrogen solid solution. For the solid solution at a H/Zr ratio less than 0.5 we obtained a monotonous decrease by 15–34% and 50–100% in γ_S and γ_US, respectively, from those in pure zirconium, indicating a reduction in both brittleness and ductility. Thus, hydrogen-induced embrittlement of the hcp Zr matrix was not confirmed. On the other hand, for the hydride we obtained a 25% smaller γ_S and a 200–300% larger γ_US than those in pure zirconium. This indicates that zirconium hydride has an extremely brittle nature due to the synergistic effect of a small γ_S, implying easy generation of a fracture surface, and large γ_US, implying a difficulty in dislocation motion, compared with pure zirconium. Furthermore, Rice’s ductile/brittle parameter D was 1.4 in the δ-hydride, indicating that it undergoes brittle fracture more easily than iridium, known as an extremely brittle material. These results seem sufficient to attribute hydrogen embrittlement of zirconium alloys substantially to the brittle nature of the hydride.     

Oxygen Uptake and Release Mechanism of Lithium Manganese Ferrite in the Low Temperature Range of 573–773 K

Oxygen uptake and release of (Li,Mn) ferrite [LMF; (Li_0.60Mn_1.20Fe_1.20)_1−δO₄; δ= 0.007 to 0.033] was investigated concerning the relations between redox reactions of ferrite and cation migration. Mössbauer spectroscopy and X-ray diffractometry showed that some of the Li⁺ and Fe³⁺ ions migrated from the A sites to the B sites of the spinel-type structure and Mn⁴⁺ ions migrated from the B sites to the A sites during oxygen uptake at 573 K. The cation-deficient LMF formed by the oxygen uptake released oxygen molecules in He gas only at 660 K. The cation migration during the oxygen release was in the opposite direction of the movement during oxygen uptake at 573 K.     

Transmission Electron Microscopy Characterization of Hot-Pressed ZrB2 with MoSi2 Additive

Microstructure of the hot-pressed ZrB₂ with MoSi₂ additive was investigated by transmission electron microscopy (TEM). The effect of MoSi₂ addition on the microstructure of the ceramic was assessed. For the pure ZrB₂, the microstructure consisted of the equiaxed ZrB₂ grains and a few elongated ZrB₂ grains. For the ZrB₂ with MoSi₂ additive, the microstructure consisted almost entirely of equiaxed ZrB₂ grains. A few dislocations were present in the ZrB₂ grains. In addition, high-resolution TEM observations showed that the intergranular amorphous phase was absent at two ZrB₂ grain boundaries in the ZrB₂ with MoSi₂ additive.     

Combustion Synthesis of the Titanium-Aluminum-Boron System

TiB₂ and Al base composite powders, which will offer a weight-saving improvement in stiffness, were produced by combustion synthesis of Ti, Al, and B ternary powder mixtures. Finely dispersed TiB₂ was synthesized by reacting a mixture of Ti, Al, and B in the molar ratio of 1:1:4. The grain size of the TiB₂ formed was <0.5 μm, which was much smaller than that obtained from the reaction of a mixture of Ti, Al, and B in the molar ratio 1:1:2. These results are discussed in light of the reaction propagating velocity and heat removal during the combustion synthesis process.     

Thermal Expansion Behavior of the Si3N4-Whisker-Reinforced Soda-Borosilicate Glass Matrix Composite

Thermal expansion behaviors of a Si₃N₄-whisker-reinforced sodaborosilicate glass matrix composite are studied. An abrupt increase of the coefficient of thermal expansion is observed and is attributed to formation of crystobalite in the sodaborosilicate glass matrix. This thermal expansion behavior is discussed with special reference to the phase transformation of the crystobalite.     

Development of anchored oligothiophenes on substrates for the application to the tunable transparent conductive films

Bis(triethoxysilyl)-substituted oligothiophene with a moderate π-conjugation length was newly synthesized and polymerized to give a polysilsesquioxane network having oligothiophene units dispersed homogeneously without phase separation. The polymer was fixed on glass or ITO substrate by spin-coating and annealing. The resulting film exhibited a high mechanical strength due to the covalent bonding with the substrates, and was electrochemically stable even after 300 redox cycles in electrolyte solution. Chemical oxidation of the polymer films yielded electrically conductive and almost transparent films.     

Size Controlled Synthesis of Gold Nanoparticles by Porphyrin with Four Sulfur Atoms

Tetradentate thioacetyl porphyrin ligand (1) was synthesized to protect gold nanoparticles. 1-protected gold nanoparticles were characterized by UV-vis spectroscopy and XPS. Analysis by XPS showed that all of four thioacetyl groups of 1 were dissociated and bound to the surface of gold nanoparticles in thiolate form. The size of 1-protected gold nanoparticles (GN:1) was controlled by thioacetyl group/HAuCl₄ molar ratio and approached to 2 nm. Compared with a protecting ligand without porphyrin plane (2) or dodecanethiol, 1 can control the size of gold nanoparticles efficiently probably due to the tetradentate ligation effect.