One of the (Bi1/2Na1/2)TiO3 (BNT)-based solid solutions, Ba-modified bismuth sodium titanate, (Bi1/2Na1/2)1-x
Ba
x
TiO3 (BNBT), is studied for its dielectric and piezoelectric properties as a new group of lead-free piezoelectric ceramics. A rhombohedral (Fα)-tetragonal (Fβ) morphotropic phase boundary (MPB) is shown to exist at x=0.06∼0.07 by X-ray data, and dielectric and piezoelectric properties. BNBT ceramics with the MPB composition are superior as piezoelectric ceramics in high-frequency ultrasonic applications or as piezoelectric actuator materials because of a lower free permittivity, ε33
T/ε0, and a high electromechanical coupling factor, k
t or k
33, along with high mechanical strength.
The effect of grain orientation on the dielectric properties of hot-forged ferroelectric Bi4Ti3O12 ceramics has been investigated and the properties are compared with ordinarily fired ones. The degree of grain orientation f calculated from X-ray diffraction patterns is found to be as large as 0.95. The temperature dependences of the dielectric constant εs and loss tangent tan δ are measured with a Q-meter at 12 MHz in the perpendicular [⊥] and parallel [//] directions to the forging axis, and considerable anisotropies, such as εs[⊥]/εs[//]=5 at the Curie temperature of about 680°C, are seen.
The remanent polarization Pr is calculated for both cases of perfect (f=1) and random (f=0) grain orientations. Observed Pr values from hysteresis loops are smaller than calculated ones, the ratio of the former to the latter being about 82% for the hot-forged ceramics.
A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.
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