Dielectric ceramic composition

Abstract: Dislcosed herein is a dielectric ceramic composition based on a lead-based perovskite-type complex compound containing nickel, characterized in that the amount of nickel is smaller than the stoichiometric amount. A dielectric ceramic composition which contains α mol% (0 < α ≤ 100) of lead-based perovskite-type complex compound represented by the formula below Pb[Ni (1-x)/3 B +5 2/3 ] a [Ni (1-y)/2 B +6 1/2 ] (1-a) O 3 (where B +5 denotes at least one element selected from elements having a valance of +5, B +6 denotes at least one element selected from elements having a valance of +6, 0 < x < 1, 0 < y < 1, and 0 ≤ a ≤ 1.) with the amount of nickel being γ mol% (0 < γ ≤ 20) which is smaller than the stoichiometric amount (where γ = α x (a x χ x 1/3 + (1 - a) x y x 1/2) ). The dielectric ceramic composition which has a high dielectric constant and yet has nearly constant capacity-temperature characteristics.

Description: The present invention relates to a dielectric ceramic composition, more particularly, relates to a dielectric ceramic composition based on a lead-based perovskite-type complex compound containing nickel. Barium titanate series ceramics have been in general use as a high dielectric material for ceramic capacitors (as electronic parts). Unfortunately, they have such a high firing temperature (1300-1400°C) that their laminated ceramic capacitors need internal electrodes of expensive platinum or palladium. Although there have been available materials having nearly temperature-independent properties, they are not suitable for capacitors because of their low dielectric constant (about 2000 at the highest). There has recently been reported lead-based perovskite-type complex compounds as a high dielectric material capable of sintering at low temperatures. They include a ternary one which is composed of lead magnesium-niobate Pb(Mg 1/3 Nb 2/3 )O 3 , lead nickel-niobate Pb(Ni 1/3 Nb 2/3 )O 3 , and lead titanate PbTiO 3 . It has an extremely high dielectric constant but suffers the disadvantage of fluctuating somewhat in its value with temperature. From JP-A-62272403 a high permittivity ceramic composition laminate capacitor is known which comprises lead niobate, lead titanate and lead nickel tungsten. The JP-A-61155246 teaches a high dielectric constant ceramic composition comprising lead titanium, nickel niobium, nickel tungsten complex oxide. The present invention was completed in view of the foregoing. It is an object of the present invention to provide a dielectric ceramic composition which has nearly constant capacity-temperature characteristics despite its high dielectric constant. The present invention provides a dielectric ceramic composition of above mentioned kind which is characterized in that the lead-based perovskite-type complex compound containing nickel is represented by the following formula Pb[Ni (1-x)/3 B +5 2/3 ] a [Ni (1-y)/2 B +6 1/2 ] (1-a) O 3 (where B +5 denotes at least one element selected from elements having a valance of +5, B +6 denotes at least one element selected from elements having a valance of +6, 0 < x < 1, 0 < y < 1, and 0 ≤ a ≤ 1.) Preferably, the above described dielectric ceramic composition contains α mol% (0 < α ≤ 100) of said lead-based perovskite-type complex compound containing nickel, with the amount of the nickel being γ mol% (0 < γ ≤ 20) which is smaller than the stoichiometric amount (where γ = α x (a x χ x 1/3 + (1 - a) x y x 1/2) ). More preferably, the amount of the nickel is γ mol% (0 < γ ≤ 10). EXAMPLES The dielectric ceramic composition of the present invention is based on a lead-based perovskite-type complex compound containing nickel which is characterized in that the amount of nickel is smaller than the stoichiometric amount. In a preferred embodiment of the present invention, the dielectric ceramic composition contains α mol% (0 < α ≤ 100) of lead-based perovskite-type complex compound represented by the following formula Pb[Ni (1-x)/3 B +5 2/3 ] a [Ni (1-y)/2 B +6 1/2 ] (1-a) O 3 (where B +5 denotes at least one element selected from elements having a valance of +5, B +6 denotes at least one element selected from elements having a valance of +6, 0 < x < 1, 0 < y < 1, and 0 ≤ a ≤ 1.) with the amount of nickel being g mol% (0 < γ ≤ 20) which is smaller than the stoichiometric amount (where γ = α x (a x χ x 1/3 + (1 - a) x y x 1/2) ). In what follows, the embodiments of the present invention are explained. The dielectric ceramic composition of the present invention is based on a lead-based perovskite-type complex compound containing nickel which is characterized in that the amount of nickel is smaller than the stoichiometric amount. The fact that the amount of nickel is smaller than the stoichiometric amount required to form the perovskite structure is responsible for the dielectric ceramic composition which has nearly constant capacity-temperature characteristics despite its high dielectric constant. An example of the dielectric ceramic composition according to the present invention is one which is based on a lead-based perovskite-type complex compound represented by the following formula Pb[Ni (1-x)/3 B +5 2/3 ] a [Ni (1-y)/2 B +6 1/2 ] (1-a) O 3 (where B +5 denotes at least one element selected from elements having a valance of +5, B +6 denotes at least one element selected from elements having a valance of +6, 0 < x < 1, 0 < y < 1, and 0 ≤ a ≤ 1.) B +5 and B +6 in the formula above are exemplified by Nb and Ta, and W, respectively. The dielectric ceramic composition may contain the above-mentioned lead-based perovskite-type complex compound in an amount of α mol% (0 < α ≤ 100), in which case the amount of nickel should be γ mol% (0 < γ ≤ 20) which is smaller than the stoichiometric amount (where γ = α x (a x χ x 1/3 + (1 - a) x y x 1/2) ). If the amount of nickel exceeds 20 mol%, the resulting composition would have a dielectric constant lower than 3000. To have a higher dielectric constant, the amount of nickel should preferably be γ mol%, with γ in the range of 0 < γ ≤ 10. The invention will be described in more detail with reference to the following examples which are not intended to restrict the scope of the invention. Samples of the dielectric ceramic composition of the present invention were prepared according to different formulations. Each sample was prepared from Pb 3 O 4 , NiO, Nb 2 O 5 , TiO 2 , MnO, CuO, and WO 3 , whose amounts were so selected as to establish the desired composition. These starting materials were mixed by wet ball-milling. The resulting mixture was dried and then calcined at 750°C for 2 hours. The resulting powder (100 pbw) was mixed with vinyl acetate (5 pbw) as a binder by wet ball-milling (pbw = parts by weight).The resulting mixture was dried and crushed into powder. The powder was formed into a disk, 10 mm in diameter and 1.2 mm thick, by compression under a pressure of 2.5 t/cm 2 . The disk was fired in an atmosphere of Pb by using an electric furnace. The fired disk was provided with an electrode formed from Ag paste by baking. The thus prepared sample was measured for dielectric constant (ε) and dielectric loss ( tan δ ) at 1 kHz, 1 V, and 20°C. The sample was also measured for resistivity, with a voltage of 250 V applied for 2 minutes. The sample was tested for capacity-temperature characteristics at 1 kHz and 1 V. The capacity-temperature characteristics is expressed as a change (%) in capacity that occurs when the temperature is raised or lowered by 50°C from the reference temperature at which the capacity is maximum. The expression in this manner is more convenient for comparison of samples than the rate of change in capacity at -25°C and +85°C, because some samples have the transition point away from normal temperature. The samples vary in the amounts of principal and auxiliary components, the firing temperature, and the electrical properties as shown in Tables 1 to 8. Incidentally, the amount (wt%) of auxiliary components is based on the amount (as 100%) of principal components. In Table 1 to 8, α denotes the lead-based perovskite-type complex compound containing nickel and β1 and β2 denote the lead-based perovskite-type complex compound not containing nickel. Each amount (in mol%) of α, β1, and β2 should be such that their total amount is 100 mol%, although their ratio is arbitrary. In Tables 1 to 8, comparative samples are marked with an asterisk (*). Comparative samples Nos. 1 and 2 correspond to samples Nos. 3 to 11. Comparative sample No. 12 corresponds to sample No. 13. Comparative sample No. 14 corresponds to samples Nos. 15 to 19. Comparative sample No. 20 corresponds to samples Nos. 21 to 25. Comparative sample No. 26 corresponds to sample No. 27. Comparative sample No. 28 corresponds to sample No. 29. Comparative sample No. 32 corresponds to samples Nos. 33 to 35. Comparative sample No. 36 corresponds to samples Nos. 37 and 38. Comparative sample No. 30 corresponds to samples Nos. 31 and 32. Comparative sample No. 35 corresponds to samples Nos. 36 to 38. Comparative sample No. 39 corresponds to sample No. 40. Comparative sample No. 41 corresponds to samples Nos. 42 to 44. Comparative sample No. 45 corresponds to samples Nos. 46 to 48. Comparative sample No. 49 corresponds to sample No. 50. Comparative sample No. 51 corresponds to sample No. 52. It is apparent from Tables 2, 4, 6, and 8 that the samples decrease in the temperature dependence of capacity while keeping the dielectric constant as the amount of nickel deviates from the stoichiometric amount. All the samples excel their corresponding comparative samples. The dielectric ceramic composition of the present invention is based on a lead-based perovskite-type complex compound containing nickel which is characterized in that the amount of nickel is smaller than the stoichiometric amount. Therefore, it has a high dielectric constant and yet has nearly constant capacity-temperature characteristics.

Claims: A dielectric ceramic composition based on a lead-based perovskite-type complex compound containing nickel, characterized in that said lead-based perovskite-type complex compound containing nickel is represented by the following formula Pb[Ni (1-x)/3 B +5 2/3 ] a [Ni (1-y)/2 B +6 1/2 ] (1-a) ) 3 (where B +5 denotes at least one element selected from elements having a valance of +5, B +6 denotes at least one element selected from elements having a valance of +6, 0 < x < 1, 0 < y < 1, and 0 ≤ a ≤ 1.) A dielectric ceramic composition according to Claim 1, characterized in that said dielectric ceramic composition contains α mol% (0 <α ≤ 100) of said lead-based perovskite-type complex compound containing nickel, with the amount of the nickel being γ mol% (0 < γ ≤ 20) which is smaller than the stoichiometric amount (where γ = α x (a x χ x 1/3 + (1 - a) x y x 1/2) ). A dielectric ceramic composition according to Claim 2, characterized in that the amount of the nickel is γ mol% (0 < γ ≤ 10).

Inventors: MATOBA HIROAKI, MATOBA, HIROAKI
Applicants: MURATA MANUFACTURING CO, MURATA MANUFACTURING CO., LTD.
Application year: 1997
Main classification: C04B35
IPC codes: C04B35, H01B3, H01G4