Dielectric ceramic composition

Abstract

Disclosed is a dielectric ceramic composition having a high dielectric constant, which can be fired along with silver and silver alloys at temperatures not higher than 1000.degree. C. To a two-component dielectric ceramic composition comprising a solid solution that consists essentially of lead nickel niobate Pb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 and lead titanate PbTiO.sub.3, added is at least one additive selected from the group consisting of the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 capable of forming a composition of a chemical formula Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3, and manganese oxide. The additives have the ability to promote the sintering of the two-component composition and to lower the firing temperature for the composition.

Description

FIELD OF THE INVENTION

The present invention relates to a ceramic composition, in particular, to a dielectric ceramic composition capable of being fired at relatively low temperatures.

BACKGROUND OF THE INVENTION

With the recent demand for small-sized, large-capacity devices in ceramic capacitors, monolithic ceramic capacitors have become increasingly popular. Monolithic ceramic capacitors are produced by alternately laminating inner electrode layers and dielectric ceramic layers followed by firing the resulting laminate. For the dielectric ceramic layers are used ceramic capacitor materials having a high dielectric constant. The monolithic ceramic capacitors thus produced have a large capacitance.

Heretofore, barium titanate-type materials have been widely used as such high dielectric ceramic capacitor materials. However, those materials must be fired at high temperatures of not lower than 1300.degree. C. Therefore, when they are used in producing monolithic ceramic capacitors, expensive noble metals such as platinum and palladium must be used to form the inner electrodes in the capacitors.

On the other hand, some recent reports have proposed the use of lead-containing composite perovskite compounds which can be fired at low temperatures and have a high dielectric constant as the materials for monolithic ceramic capacitors. For example, it is reported in JP-B-01-46471 that a two-component composition comprising lead nickel niobate Pb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 and lead titanate PbTiO.sub.3 has an extremely high dielectric constant.

However, the firing temperature for the conventional barium titanate-type materials is not less than 1300.degree. C. and that for the conventional lead-containing composite perovskite compounds is about 1100.degree. C. Therefore, all those conventional materials are problematic in that they could not be fired together with inexpensive silver and silver alloys. In particular, where the conventional barium titanate-type materials and lead-containing composite perovskite compounds are used to produce monolithic ceramic capacitors, inexpensive silver or silver alloys could not be employed to form the inner electrodes for those capacitors, making it is impossible to produce monolithic ceramic capacitors at a low production cost.

SUMMARY OF THE INVENTION

The object of the present invention is to solve the problems mentioned above and to provide a dielectric ceramic composition having a high dielectric constant and capable of being fired at a temperature of 1000.degree. C. or lower along with silver and silver alloys.

After having studied the firing condition for the two-component composition comprising lead nickel niobate Pb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 and lead titanate PbTiO.sub.3 and also various additives thereto capable of promoting the sintering of the composition, the present inventors have found that manganese oxide (MnO), and the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 capable of forming a composition of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 can promote the sintering of the two-component composition while lowering the firing temperature for the composition, and have completed the present invention.

Specifically, the invention provides a dielectric ceramic composition including a solid solution including lead nickel niobate Pb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 and lead titanate PbTiO.sub.3, and at least one additive selected from the group consisting of (a) Pb.sub.3 O.sub.4, CuO and WO.sub.3 and (b) MnO.

Preferably, the solid solution is represented by a formula, xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x) PbTiO.sub.3, in which x indicates a molar fraction of 0.57.ltoreq..times..ltoreq.0.87, in order to make the composition have a relatively high specific inductive capacity.

More preferably, the solid solution is represented by a formula, xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3, in which x indicates a molar fraction of 0.65.ltoreq..times..ltoreq.0.75.

Preferably, the amount of manganese oxide (MnO) in the dielectric ceramic composition is not larger than about 1% by weight, more preferably not larger than about 0.75%, relative to the solid solution, in order not to lower the specific inductive capacity of the composition.

Also preferably, the amount of compounds of Pb.sub.3 O.sub.4, CuO and WO.sub.3 in the dielectric ceramic composition is not larger than about 9% by weight, more preferably not larger than about 4.5%, in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the essential component of the composition, in order not to lower the specific inductive capacity of the composition.

More preferably, the dielectric ceramic composition of the invention contains both the group of compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 capable of forming Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3, and manganese oxide, in order to further lower the firing temperature for the composition, in which the amount of manganese oxide (MnO) is not larger than about 1% by weight relative to the essential component of the composition and that of the group of compounds of Pb.sub.3 O.sub.4, CuO and WO.sub.3 is not larger than about 9% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the solid solution, in order not to lower the specific inductive capacity of the composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart for one embodiment of producing the dielectric ceramic composition of the invention.

FIG. 2 is a sectional view of a monolithic ceramic capacitor in accordance with the present invention.

DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

Now, preferred embodiments of the dielectric ceramic composition of the invention are described hereinunder.

Embodiment 1

Embodiment 1 of the invention is the dielectric ceramic composition which consists essentially of a solid solution of the formula xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3, where x indicates the molar fraction, and which contains manganese oxide MnO that acts to lower the firing temperature for the solid solution.

In Embodiment 1, the amount of manganese oxide to be added to the composition is preferably not larger than about 1% by weight relative to the essential component, in order not to lower the high specific inductive capacity, .di-elect cons., of the essential component, solid solution.

The dielectric ceramic composition of Embodiment 1 having the constitution mentioned above can be fired at low temperatures of 1000.degree. C. or lower, while having a relatively high specific inductive capacity, .di-elect cons..

Embodiment 2

Embodiment 2 of the invention is the dielectric ceramic composition which consists essentially of a solid solution of the formula xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3, where x indicates the molar fraction, and which contains the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 which acts to lower the firing temperature for the solid solution. In this, the group of compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 can form a composition of the chemical formula Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3.

In Embodiment 2, the amount of the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 added to the dielectric ceramic composition is preferably not larger than about 9% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the essential component, in order not to lower the high specific inductive capacity, .di-elect cons., of the essential component, solid solution.

The dielectric ceramic composition of Embodiment 2 having the constitution mentioned above can be fired at low temperatures of 1000.degree. C. or lower, while having a relatively high specific inductive capacity, .di-elect cons..

Embodiment 3

Embodiment 3 of the invention is the dielectric ceramic composition which consists essentially of a solid solution of the formula xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3, where x indicates the molar fraction, and which contains both manganese oxide MnO and the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3, both of which act to lower the firing temperature for the solid solution. In this, the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 can form a composition of the chemical formula Pb(CU.sub.1/2 W.sub.1/2)O.sub.3.

In Embodiment 3, the amount of manganese oxide MnO added to the dielectric ceramic composition is preferably not larger than about 1% by weight relative to the essential component and that of the compounds Pb.sub.3 O.sub.4, CuO and WO.sub.3 added thereto is preferably not larger than about 9% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the essential component, in order not to lower the high specific inductive capacity, .di-elect cons., of the essential component, i.e., the solid solution.

The dielectric ceramic composition of Embodiment 3 having the constitution mentioned above can be fired at lower temperatures than that of Embodiment 1 and Embodiment 2, while having a relatively high specific inductive capacity, .di-elect cons..

In those Embodiments 1 to 3, the solid solution of the essential component of the formula xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3, where x indicates the molar fraction, is preferably so defined that x in that formula falls within the range of 0.57.ltoreq..times..ltoreq.0.87 in order to make the dielectric ceramic composition have a high specific inductive capacity, .di-elect cons., but is more preferably so defined that x therein falls within the range of 0.65.ltoreq..times..ltoreq.0.75 in order to make the composition have a higher specific inductive capacity, .di-elect cons..

Now, referring to FIG. 1, hereinunder described is a method for producing the dielectric ceramic composition of Embodiments 1 to 3. In this method, Pb.sub.3 O.sub.4, NiO, Nb.sub.2 O.sub.5, TiO.sub.2, MnO, CuO and WO.sub.3 are weighed to give the essential component and the additive in a predetermined ratio in the step S1. In the step S2, the thus-weighed materials are mixed in a wet or dry system. Then, in the step S3, the resulting mixture is pre-fired at a predetermined temperature to give a solid solution of a dielectric ceramic composition material. Next, in the step S4, this dielectric ceramic composition material is powdered to obtain a powder of the material. In the next step S5, the powder is shaped to have a predetermined configuration along with a resin binder or the like. Then, in the step S6, this is fired at a relatively low, predetermined temperature of not higher than 1000.degree. C., whereby the powdery composition is sintered into a dielectric ceramic composition.

For example, where the dielectric ceramic composition of the invention is used to produce a monolithic ceramic capacitor 1 whose sectional view is shown in FIG. 2, a resin binder such as polyvinyl alcohol is added to the powdery dielectric ceramic composition and the resulting mixture is shaped into green sheets in the step S5. Then, those green sheets are alternately laminated with electrode layers 4 made of silver or a silver alloy, the resulting laminate is cut to have a predetermined shape, an electrode paste is applied to the edges of the thus-shaped laminate to form edge electrodes 5 therearound, and finally the unitary laminate thus composed of the green sheets and the electrodes is fired to obtain a monolithic ceramic capacitor. If necessary, a first plating layer 6 and a second plating layer 7 may be applied on the electrodes 5.

In the monolithic ceramic capacitors comprising the dielectric ceramic composition of any of those Embodiments 1 to 3, the composition can be fired at low temperatures of not higher than 1000.degree. C. Therefore, inexpensive silver and silver alloys can be used to form the inner electrodes of those capacitors, in place of expensive noble metals such as platinum and palladium, and the capacitors can be produced at low cost.

Now, examples of the invention are described below with reference to Table 1.

EXAMPLES

In these examples, starting materials of Pb.sub.3 O.sub.4, NiO, Nb.sub.2 O.sub.5, TiO.sub.2, MnO, CuO and WO.sub.3 were wet-milled in a ball mill to give final compositions shown in Table 1, then vaporized and dried. The compositions in Table 1 are as fired. Next, each powdery mixture was pre-fired at 750.degree. C. for 2 hours to obtain a predetermined, powdery dielectric ceramic composition. This was next wet-milled along with 5 parts by weight of a vinyl acetate-type binder in a ball mill. Then, the wet mixture was vaporized, dried and pressed, and the resulting powdery mixture was shaped under a pressure of 2.5 tons/cm.sup.2 to give discs each having a diameter of 10 mm and a thickness of 1.2 mm. These discs were fired in an electric furnace having a Pb atmosphere at the different temperatures shown in Table 1. Next, an Ag paste intended to form an electrode was applied to each disc, and fired at 800.degree. C. to prepare samples. The specific inductive capacity, .di-elect cons., and the dielectric loss (tan .delta.) of each sample were measured at 1 KHz, 1 Vrms and 20.degree. C. To measure its specific resistance, .rho., a voltage of 250 V was applied to each sample at 25.degree. C. for 120 seconds.

To prepare the samples of the dielectric ceramic composition, the molar fraction x in the chemical formula xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3 representing the essential component constituting the composition was varied within the defined range, as in Table 1, while the amount, .alpha., the % by weight relative to the essential component of the manganese oxide additive (MnO) added to the essential component as well as the amount, .beta., the % by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the essential component of the additive of Pb.sub.3 O.sub.4, CuO and WO.sub.3 added thereto was varied within the defined range, as shown in Table 1. The firing temperatures for those samples, and also the specific inductive capacity .di-elect cons., the dielectric loss tan .delta., and the specific resistivity .rho. of each sample are shown in Table 1.

TABLE 1______________________________________xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 + (1 - x)PbTiO.sub.3 + .alpha.MnO +.beta.Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 Firing Tem- per-Sample ature tan .delta.Number x 1 - x .alpha. .beta. (.degree. C.) .epsilon. % .rho.______________________________________*1 0.87 0.13 0 0 1100 2940 0.5 7.52 .times. 10.sup.10*2 0.80 0.20 0 0 1100 6480 0.8 6.92 .times. 10.sup.10*3 0.70 0.30 0 0 1100 14200 1.6 2.88 .times. 10.sup.10*4 0.60 0.40 0 0 1100 4480 2.9 8.12 .times. 10.sup.9*5 0.57 0.43 0 0 1100 2870 4.6 3.47 .times. 10.sup.9 6 0.87 0.13 0.5 0 990 2060 0.3 2.57 .times. 10.sup.12 7 0.80 0.20 0.5 0 990 4540 0.4 1.02 .times. 10.sup.12 8 0.75 0.25 0.5 0 990 5340 0.5 8.73 .times. 10.sup.11 9 0.70 0.30 0.5 0 990 10800 0.9 7.54 .times. 10.sup.1110 0.65 0.35 0.5 0 990 5570 1.2 3.31 .times. 10.sup.1111 0.60 0.40 0.5 0 990 3450 1.7 1.74 .times. 10.sup.1112 0.57 0.43 0.5 0 990 2010 2.6 1.12 .times. 10.sup.1113 0.87 0.13 1 0 970 1760 0.4 2.42 .times. 10.sup.1114 0.80 0.20 1 0 970 3940 0.4 9.94 .times. 10.sup.1115 0.75 0.25 1 0 970 5250 0.5 8.77 .times. 10.sup.1116 0.70 0.30 1 0 970 8550 0.8 7.12 .times. 10.sup.1117 0.65 0.35 1 0 970 5060 1.0 3.96 .times. 10.sup.1118 0.60 0.40 1 0 970 2690 1.5 2.32 .times. 10.sup.1119 0.57 0.43 1 0 970 1720 2.1 1.89 .times. 10.sup.1120 0.87 0.13 0 3 960 2740 0.4 7.61 .times. 10.sup.1121 0.80 0.20 0 3 960 4830 0.9 6.72 .times. 10.sup.1122 0.75 0.25 0 3 960 5780 1.3 5.68 .times. 10.sup.1123 0.70 0.30 0 3 960 12790 1.5 3.93 .times. 10.sup.1124 0.65 0.35 0 3 960 5110 2.1 3.19 .times. 10.sup.1125 0.60 0.40 0 3 960 4040 3.1 2.55 .times. 10.sup.1126 0.57 0.43 0 3 960 2580 4.5 1.56 .times. 10.sup.1127 0.87 0.13 0 9 900 1860 1.0 6.83 .times. 10.sup.1128 0.80 0.20 0 9 900 4080 1.3 6.21 .times. 10.sup.1129 0.75 0.25 0 9 900 5490 1.7 4.93 .times. 10.sup.1130 0.70 0.30 0 9 900 8940 2.1 4.15 .times. 10.sup.1131 0.65 0.35 0 9 900 5210 2.9 4.08 .times. 10.sup.1132 0.60 0.40 0 9 900 2830 3.5 3.86 .times. 10.sup.1133 0.57 0.43 0 9 900 1800 5.1 2.03 .times. 10.sup.1134 0.87 0.13 0.5 3 950 1950 0.3 3.61 .times. 10.sup.1135 0.80 0.20 0.5 3 950 4310 0.4 1.36 .times. 10.sup.1136 0.70 0.30 0.5 3 950 10280 1.0 8.71 .times. 10.sup.1137 0.60 0.40 0.5 3 950 3280 1.9 2.34 .times. 10.sup.1138 0.57 0.43 0.5 3 950 1910 3.1 9.67 .times. 10.sup.11______________________________________ Samples with * are outside the scope of the invention.

As is obvious from Table 1, samples Nos. 1, 2, 3, 4 and 5, which contained none of the manganese oxide (MnO) additive or the group Pb.sub.3 O.sub.4, CuO and WO.sub.3 additive and which are outside the scope of the invention, all had a low specific resistivity, .rho.<10.sup.11 .OMEGA..multidot.cm, or that is, those samples all had relatively low insulation resistance, and, in addition, those samples required a high firing temperature of 1100.degree. C. As opposed to these, samples Nos. 6 to 30 which are within the scope of the invention all had a high specific resistivity, .rho.>10.sup.11 .OMEGA..multidot.cm, or that is, those samples all had high insulation resistance, and those samples were successfully fired at temperatures lower than 1000.degree. C. As is also obvious from Table 1, the samples that satisfy the requirement for 0.65.ltoreq..times..ltoreq.0.75 had a much higher specific inductive capacity .di-elect cons.. In particular, samples Nos. 9, 16, 23, 30 and 36 with x=0.7 had a highest specific inductive capacity .di-elect cons. relative to the varying x in the other samples. Though not shown in Table 1, samples with x<0.57 and those with 0.87<x could be fired at temperatures lower than 1000.degree. C., but their specific inductive capacity .di-elect cons. was low and not higher than 1700. Therefore, in the present invention, preferred is 0.57.ltoreq..times..ltoreq.0.87, more preferred is 0.65.ltoreq..times..ltoreq.0.75, and most preferred is x=about 0.7. Though not shown in Table 1, where 1<.alpha. or where 9<.beta., the specific inductive capacity .di-elect cons. of the dielectric ceramic composition of the invention is often significantly lowered. Therefore, in the invention, preferred is .alpha..ltoreq.1 or .beta..ltoreq.9 (provided that .alpha.+.beta..noteq.0).

As has been described hereinabove, the dielectric ceramic composition of the invention can be fired at temperatures lower than 1000.degree. C., while having a high specific inductive capacity .di-elect cons. and high insulation resistance. Therefore, when the dielectric ceramic composition of the invention is used, it is possible to provide monolithic ceramic capacitors having large capacitance and high insulation resistance and, in addition, inexpensive silver and silver alloys can be used to form the inner electrodes in those monolithic ceramic capacitors. Accordingly, using the composition of the invention, good monolithic ceramic capacitors can be produced at low costs.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

1. A dielectric ceramic composition comprising:

a solid solution of lead nickel niobate Pb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 and lead titanate PbTiO.sub.3 ; and

an additive of Pb.sub.3 O.sub.4, CuO and WO.sub.3 forming a composition represented by the formula Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3.

2. A dielectric ceramic composition according to claim 1 containing manganese oxide.

3. A dielectric ceramic composition according to claim 2, wherein the amount of said manganese oxide is not larger than about 1% by weight relative to the solid solution.

4. A dielectric ceramic composition according to claim 1, wherein the amount of said additive (a) is not larger than about 9% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the solid solution.

5. A dielectric ceramic composition according to claim 1, wherein the amount of additive is not larger than about 9% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the solid solution.

6. A dielectric ceramic composition according to claim 3, wherein said solid solution is represented by the formula:

xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3,

in which x represents a molar fraction of 0.57.ltoreq..times..ltoreq.0.87, the amount of manganese oxide is not larger than about 0.75% by weight relative to the solid solution and the amount of additive (a) is not larger than about 4.5% by weight in terms of Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3 and relative to the solid solution.

7. A dielectric ceramic composition according to claim 1, wherein said solid solution is represented by the formula:

xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -(1-x)PbTiO.sub.3,

wherein x represents a molar fraction of 0.57.ltoreq..times..ltoreq.0.87.

8. A dielectric ceramic according to claim 7, wherein x represents a molar fraction of 0.65.ltoreq..times..ltoreq.0.75.

9. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 1.

10. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 2.

11. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 3.

12. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 4.

13. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 5.

14. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 6.

15. A monolithic ceramic capacitor comprising a plurality of ceramic layers and a plurality of electrodes each of which is disposed between two adjacent ceramic layers, wherein said ceramic layers comprise a dielectric ceramic composition according to claim 7.

16. A method of producing a dielectric ceramic composition comprising the steps of:

providing a mixture of Pb.sub.3 O.sub.4, NiO, Nb.sub.2 O.sub.5, TiO.sub.2, CuO, WO.sub.3 and MnO in amounts to satisfy the formula

xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 +(1-x)PbTiO.sub.3 +.alpha.MnO+.beta.Pb(Cu.sub.1/2 W.sub.1/2)O.sub.3

wherein 0.57.ltoreq..times..ltoreq.0.87, .alpha. is not larger than about 1 wt %, .beta. is not larger than about 9 wt % and .alpha.+.beta..noteq.0; and

firing said mixture to form a solid solution of xPb(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 +(1-x)PbTiO.sub.3.