ABSTRACT
We synthesized two series of bimetallic (zinc and cobalt) zeolitic imidazolate frameworks (ZIF-62) under different solvothermal conditions. It is found that the structure of the derived ZIF crystals is highly sensitive to synthesis conditions. One series possesses the standard ZIF-62 structure, whereas the other has a mixed structure composed of both the standard structure and an unknown one. The standard series exhibits a slight negative deviation from linearity of melting temperature (T m) and glass transition temperature (T g) with the substitution of Co for Zn. In contrast, the new series displays a stronger negative deviation. These negative deviations from linearity indicate the mixed metal node effect in bimetallic ZIF-62 due to the structural mismatch between Co2+ and Zn2+ and to the difference in their electronic configurations. The new series involves both cobalt-rich and zinc-rich phases, whereas the standard one shows one homogeneous phase. Density functional theory calculations predict that the substitution of Co for Zn increases the bulk modulus of the ZIF crystals. This work indicates that the structure, melting behaviour, and mechanical properties of ZIFs can be tuned by metal node substitution and by varying the synthetic conditions. Both series of ZIFs have higher glass forming abilities due to their higher T g/T m ratios (0.77-0.84) compared to most good glass formers.
ABSTRACT
We have investigated the voltage-tunable characteristics of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) homogeneity region, for which samples were prepared using a conventional solid-state reaction. The highest value of the relative tunability (n(r)) was obtained for the sample with 5 mol% of NaTaO(3), i.e., 47% at 1 MHz and a 70 kV/cm dc bias field. This sample also showed the highest value of the dielectric losses (tan delta) and temperature coefficient of the dielectric constant (tau(epsilon)), i.e., 0.05 and 4478 ppm/K, respectively. As the concentration of NaTaO(3) increased up to 90 mol% n(r), tan delta, and tau(epsilon) gradually decreased toward 22%, 0.0002 and -899 ppm/K, respectively. The dielectric constant of the samples varied in a similar manner between 662 and 130. At microwave frequencies, the dielectric losses of the samples substantially increased due to their relaxor-type nature. The lowest value was obtained for the samples with 90 mol% of NaTaO(3), i.e., 0.002. The tunable characteristics of the samples are related to the ferroelectric and dielectric properties, and it appears that the dielectric tunability of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) system originates from its relaxor-type behavior.
