During sintering of Ni-electrode multi-layer ceramic capacitors (MLCCs), the Ni electrode often becomes discontinuous because of its lower sintering temperature relative to that of BaTiO3. In an attempt to retard the sintering of Ni, we introduced passivation of the Ni powder. To find the optimal passivation conditions, a thermogravimetric analysis (TGA) was conducted in air. After passivation at 250oC for 11 h in air, a nickel oxide shell with a thickness of 4- 5 nm was formed on nickel nanoparticles of 180 nm size. As anticipated, densification of the compacts of the passivated Ni/NiO core-shell powder was retarded: the starting temperature of densification increased from ~400oC to ~600oC in a 97N2-3H2 (vol %) atmosphere. Grain growth was also retarded during sintering at temperatures of 750 and 1000oC. When the sintering atmosphere was changed from wet 99.93N2-0.07H2 to wet 99.98N2-0.02H2, the average grain size decreased at the same sintering temperature. The conductivity of the passivated powder sample sintered at 1150oC for 8 h in wet 99.93N2-0.07H2 was measured to be 3.9 × 104 S/cm, which is comparable with that, 4.6 × 104 S/ cm, of the Ni powder compact without passivation. These results demonstrate that passivation of Ni is a viable means of retarding sintering of a Ni electrode and hence improving its continuity in the fabrication of BaTiO3-based multi-layer ceramic capacitors.

The ferroelectric properties of barium titanate strongly depend on its microstructure, in particular, grain size and distribution. During sintering, usually exhibits abnormal grain growth, which deteriorates considerably the ferroelectric properties. A typical technique to suppress the abnormal grain growth is the addition of dopants. Dopant addition, however, affects the ferroelectric properties and thus limits the application of . Here, we report a simple but novel technique to prevent the abnormal grain growth of and to overcome the limitation of dopant use. The technique consists of stepwise sintering in a reducing atmosphere and in an oxidizing atmosphere. The materials prepared by the present technique exhibit uniform grain size and high dielectric properties. The technique should provide opportunities of having -based materials with superior ferroelectric properties.