Ceramic dielectric composition

Abstract

A dielectric ceramic composition comprises as principle constituents, 86 - 99.6 mole % of barium titanate, 0.2 - 10 mole % of niobium pentaoxide and 0.2 - 4 mole % of cerium oxide.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a ceramic dielectric composition having a high dielectric constant and a small variation of its dielectric constant with temperature and which is easily formed into excellent ceramic devices.

2. Description of the Prior Art

Heretofore, it has been known that ceramic dielectric compositions having small temperature variations with changing temperature can be prepared by adding a bismuth compound to a dielectric, e.g., bismuth stannate is added to barium titanate to provide flat temperature characteristics in U.S. Pat. No. 2,908,579 and U.S. Pat. No. 3,410,705. In such compositions, a grain boundary is formed by the coating of the crystals of BaTiO.sub.3 with a bismuth compound having a low melting point. As a result, the Curie point of the BaTiO.sub.3 is changed such that a dielectric constant rather insensitive to temperature changes ensues.

In the past, there has been a need for a small ceramic capacitor having a large capacity and excellent characteristics for high frequency applications. The known compositions have not been satisfactory for such uses. It is advantageous for such a small ceramic capacitor with large capacity to have a high dielectric constant. However, a ceramic capacitor having a high dielectric constant usually has large variations of dielectric constant with temperature changes so that the size and the capacity have been limited.

Accordingly, in practice there have been attempts to decrease the thickness of the dielectric substrate and to increase its capacity. Dielectric substrates with thicknesses of 0.1 - 0.2 mm have been obtained. In the conventional technique of incorporating a bismuth compound in the composition, are several significant disadvantages: the bismuth compound can become vaporized; the substrate can become bent; or pin-holes can be formed making it difficult to produce a ceramic having high density. This is a deleterious factor for determining the maximum voltage of the capacitor. As a result, incorporation of an additive which is not vaporized by calcination is required. Additionally, the composition containing the bismuth compound has a disadvantageously high loss in high frequency operation. Moreover, bismuth is a toxic heavy metal so that use of a bismuth compound poses a serious problem from the viewpoint of heavy metal pollution.

Ceramic dielectric compositions having the formula BaTiO.sub.3 -Nb.sub.2 O.sub.5 -MgO are disclosed in U.S. Pat. No. 3,788,867 and Ceramic Bulletin Vol. 50, no. 5, pages 488-492 (1971). These compositions have .epsilon..sub.s values of less than 2000 and inferior temperature characteristics. When MgO of the composition is replaced by CeO.sub.2, the .epsilon..sub.s values of the compositions are about two times (about 4000) that of the conventional compositions.

As can be seen, it would be most desirable to have a dielectric ceramic composition which has a high dielectric constant which is insensitive to temperature variations.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a ceramic dielectric composition which has a high dielectric constant and a small variation of dielectric constant with temperature changes.

It is another object of this invention to provide a ceramic dielectric composition which is suitable for forming excellent ceramics having high density and which does not cause heavy metal pollution in its production.

These and other objects of this invention as will become clear by the ensuing discussion have been attained by providing a ceramic dielectric composition having a high dielectric constant, a small temperature dependence of the dielectric constant, an excellent capability for ceramic formation, and a low loss which comprises barium titanate, niobium pentaoxide and cerium oxide as main components.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention and many of the attendant advantages thereof will be readily attained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

FIG. 1 shows temperature characteristics of the dielectric constant and the dielectric tangent of Sample 15 below, and

FIG. 2 shows a ternary diagram of the three main components of barium titanate, cerium oxide and niobium pentaoxide depicting the compositions within the scope of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The ceramic dielectric composition of this invention comprises 86 - 99.6 mole%, preferably 92 - 99.6 mole %, of barium titanate, 0.2 - 10 mole %, preferably 0.2 - 6.0 mole%, of niobium pentaoxide and 0.2 - 4 mole%, preferably 0.2 - 2.0 mole %, of cerium oxide as main components.

A second embodiment of the ceramic dielectric composition of this invention comprises 86 - 99.6 mole% of barium titanate, 0.2 - 10 mole% of niobium pentaoxide and 0.2 - 4 mole% of cerium oxide as main components with at least one of calcium titanate or magnesium titanate added in an amount of less than 10 wt%, preferably 0.5 - 5.0 wt% relative to the amount of the main components.

A third embodiment of the ceramic dielectric composition of this invention comprises 86 - 99.6 mole% of barium titanate, 0.2 - 10 mole% of niobium pentaoxide and 0.2 - 4 mole% of cerium oxide as main components with the addition of at least one of the oxides of Mn, Cr, Fe, Ni or Co, clay or a rare earth element, preferably an oxide, in an amount of 0.01 - 0.5 wt%, preferably 0.05 - 0.3 wt%, relative to the amount of the main components.

A fourth embodiment of the ceramic dielectric composition of this invention comprises 86 - 99.6 mole% of barium titanate, 0.2 - 10 mole% of niobium pentaoxide and 0.2 - 4 mole% of cerium oxide as main components with the addition of at least one of calcium titanate or magnesium titanate in an amount of less than 10 wt%, preferably 0.5 - 5 wt% relative to the amount of the main components, and at least one of the oxides of Mn, Cr, Fe, Ni or Co, clay or a rare earth element, preferably as an oxide, in an amount of 0.01 - 0.5 wt%, preferably 0.05 - 0.3 wt%, relative to the amount of the main components.

The reasons for the above-described limitations on the amounts of the components of the composition will now be illustrated.

When more than 99.6 mole% of barium titanate is incorporated, the sintering temperature is increased to higher than 1400.degree. C, and ceramics having high density are not obtained. Both results are undesirable. When less than 86 mole% of barium titanate is incorporated, the dielectric constant is disadvantageously lower than about 900. When less than 0.2 mole% of niobium pentaoxide is incorporated, the sintering temperature is increased to higher than 1400.degree. C, and the temperature characteristics are inferior. When more than 10 mole% of niobium pentaoxide is incorporated, the dielectric constant is disadvantageously lower than about 900, and the product is not amenable to practical use. When less than 0.2 mole% of cerium oxide is incorporated, the effect on the temperature characteristics by the shift of the Curie point does not occur and tan .delta. is disadvantageously high. When more than 4 mole% of cerium oxide is incorporated, the Curie point is significantly lowered, thereby deteriorating the temperature characteristics to values higher than 30%.

The addition of calcium titanate or magnesium titanate is effective for improving the temperature characteristics, and also for decreasing the sintering temperature. When more than 10 wt% of calcium titanate or magnesium titanate is incorporated, the dielectric constant is disadvantageously decreased. When less than 0.01 wt% of calcium titanate or magnesium titanate is incorporated, the beneficial effects are unsubstantial. The sintering properties of the ceramic can be improved by adding 0.01 - 0.5 wt% or at least one of the oxides of Mn, Cr, Fe, Ni or Co, clay or a rare earth element, preferably as an oxide as a mineralizer.

In accordance with the compositions of this invention, ceramic dielectric compositions having high dielectric constants, excellent characteristics in high frequency operation, small temperature dependencies for their dielectric constants over a broad range, and low losses can be obtained. The compositions have substantially no pin-holes and are not bent by the sintering step. They can form thin plates having high density. The heavy metal pollution problem is not encountered and the compositions of the invention are industrially advantageous.

Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified.

EXAMPLE

Samples are prepared as follows. Barium carbonate (BaCO.sub.3) and titanium oxide (TiO.sub.2) in a ratio of 1 : 1; calcium carbonate (CaCO.sub.3) and titanium oxide ((TiO.sub.2) in a ratio of 1 : 1 and magnesium carbonate (MgCO.sub.3) and titanium oxide (TiO.sub.2) in a ratio of 1 : 1 were respectively mixed for 20 hours by a ball-mill in a wet process. The mixture was dried and calcined at 1100 - 1200.degree. C for 2 hrs. to form BaTiO.sub.3, CaTiO.sub.3 and MgTiO.sub.3. The products were respectively crushed to form fine powders having an average diameter of about 2.5.mu. m. These starting materials were measured out in the proportions as set forth in Table 1, and were mixed in a wet process in a ball-mill. Water was removed from the mixture and a binder of polyvinyl alcohol was added to each in a ratio of 10-15 wt parts to 100 wt parts of the fine powder. The mixtures were compressed in a mold having a diameter of 16 mm and a thickness of 0.6 mm under a pressure of 3 ton/cm.sup.2. The shaped mixtures were sintered at 1200.degree. - 1380.degree. C for 2 hours. Silver electrodes were formed on each surface of the sintered substrates and the electrical characteristics of the sintered substrates were measured. The particle sizes of the raw materials were as follows.

______________________________________BaCO.sub.3 particle size 1.5 - 2.5 .mu.mTiO.sub.2 particle size 0.3 - 0.7 .mu.mCaCO.sub.3 particle size 2 - 2.5 .mu.mMgCO.sub.3 particle size 1 4 .mu.m______________________________________ The results are shown in Table 1.

The measurements of the capacity and the dielectric tangent were conducted at 25.degree. C (room temperature) by using a Multi-purpose bridge model 4255A (manufactured by YEW), applying 5 volts of AC voltage for the measurement.

In Table 1, samples Nos. 8,9,10,11,13,20,28,29 and 30 are out of the scope of claims and are provided for reference only. The composition, H, is also for reference only. It incorporates 98.5 mole% of bismuth stannate. In the following tables, the meanings of the symbols are as follows.

______________________________________T.sub.2 : sintering temperature.epsilon.s: dielectric constanttan .delta.: dielectric tangentT.C.: temperature characteristics (standard of 20.degree. C)______________________________________ Table 1__________________________________________________________________________Sample (mole %) (mole %) (mole %) (wt. %) (wt. %) T.sub.2 .epsilon.s tan .delta. T. C. (%)No. BaTiO.sub.3 CeO.sub.2 Nb.sub.2 O.sub.5 CaTiO.sub.3 MgTiO.sub.3 (.degree. C) 1 KHz 1 KHz -25.degree. C +85.degree. C__________________________________________________________________________1 98 1 1 0 0 1320 5200 2.0 -29 -312 98.2 1 0.8 0 0 1320 5030 2.1 -35 -243 97.8 1 1.2 0 0 1320 5760 1.8 -31 -424 97.8 1.2 1.0 0 0 1320 6060 1.9 -35 -395 98 1.2 0.8 0 0 1320 5800 1.8 -37 -316 98 0.8 1.2 0 0 1320 5440 1.9 -31 -387 97 1 2 0 0 1300 3000 0.8 +11 -278 98 2 0 0 0 hard to be sintered (<1400.degree. C)9 98 0 2 0 0 1300 2500 2.2 -15 -1710 98.9 0.1 1 0 0 1300 2300 2.1 -15 -2211 94 5 1 0 0 1300 1200 0.8 +20 -3112 99.6 0.2 0.2 0 0 1370 2200 2.3 -23 +3213 88 1 11 0 0 1200 880 1.7 +42 -6014 98 0.8 1.2 1 0 1320 4311 1.6 -26 -2815 98 0.8 1.2 2 0 1320 4020 1.7 -28 -2316 98 0.8 1.2 3 0 1320 3585 1.8 -26 -1117 98 0.8 1.2 4 0 1300 3369 1.9 -25 - 418 98 0.8 1.2 5 0 1300 3200 1.9 -24 + 319 98 0.8 1.2 7 0 1280 3010 2.1 -23 +1720 98 0.8 1.2 11 0 1280 2430 2.6 -20 +2821 97.8 0.9 1.3 4 0 1300 3614 1.8 -23 -1522 96.8 0.2 3.0 0 0 1270 1930 1.0 +25 -34.523 97.6 1.4 1.0 0 0 1320 4600 1.3 -15 -4524 88.5 2.5 9.0 0 0 1220 930 0.5 +30 -4525 92.0 2.0 6.0 0 0 1250 1200 1.5 -10 -2226 98 0.8 1.2 0 1 1300 4305 1.5 -24.7 -2827 98 0.8 1.2 0 5 1300 3000 1.5 -23.8 -2628 98 0.8 1.2 0 12 1280 2300 1.1 -19.6 -2429 85.5 4.5 10 0 0 1220 800 0.5 +27 -3030 99.7 0.2 0.1 0 0 hard to be sintered (<1400.degree. C)31 98 0.8 1.2 0.5 0 1320 4800 1.8 -30 -3432 98 0.8 1.2 10 0 1280 2600 2.4 -20 +2533 98 0.8 1.2 0 0.5 1320 4750 1.6 -28 -3234 98 0.8 1.2 0 7.5 1280 2700 1.4 -24 -2535 98 0.8 1.2 0 10 1280 2530 1.2 -26.3 -2436 98 0.8 1.2 2 7 1280 2300 1.6 -25 -2337 98 0.8 1.2 4 4 1280 2600 1.6 -27 -1038 98 0.8 1.2 7 2 1280 2550 1.7 -28 - 5H 98.5 mole % Bi.sub.2 (SnO.sub.3).sub.3 1.5 mole % 1270 2400 2.3 + 7.8 - 9.5__________________________________________________________________________

The effects of the additives on the composition of Sample No. 1 of Table 1, are shown in Table 2.

Table 2______________________________________ tan .delta.Amount T.sub.2 .epsilon..sub.s (%) T. C.Additive (wt.%) (.degree. C) 1 KHz 1 KHz -25.degree. C +85.degree. C______________________________________none 0 1320 5200 2.0 -29 -31MnO 0.1 3900 1.0 -16 -28 0.3 1320 2950 0.7 - 2 -32CoO 0.1 1320 4300 1.9 -17 -30 0.3 1300 2600 1.6 - 5 - 7clay 0.1 1320 5050 2.0 -30 -31 0.3 1320 4450 1.9 -28 -33La.sub.2 O.sub.3 0.05 1320 5000 1.8 -28 -32 0.4 1320 3800 1.6 -15 -37______________________________________

The effects of the additives on the composition of Sample No. 7 of Table 1, are shown in Table 3.

Table 3______________________________________ tan .delta.Amount T.sub.2 .epsilon.s (%) T. C.Additive (wt %) (.degree. C) 1 KHz 1 KHz -25.degree. C +85.degree. C______________________________________none 0 1300 3000 0.8 +11 -27MnO 0.1 1320 2420 0.6 +15 -32 0.3 1320 1800 0.5 -17 -36CoO 0.1 1320 2750 0.8 + 8 -20 0.3 1280 2100 0.6 + 1 - 6clay 0.1 1320 2900 0.8 +12 -26 0.3 320 2400 0.7 +10 -25La.sub.2 O.sub.3 0.05 1320 2950 0.8 +12 -28 0.4 1320 2100 0.6 +22 -34______________________________________

The effects of the additives on the composition of Sample No. 15 of Table 1 are shown in Table 4.

Table 4______________________________________ tan .delta.Amount T.sub.2 .epsilon..sub.s (%) T. C.Additive (wt.%) (.degree. C) 1 KHz 1 KHz -25.degree. C +85.degree. C______________________________________none 0 1320 4020 1.7 -28 -23MnO 0.1 1320 3850 1.5 -26 -25 0.4 1320 2740 1.2 -20 -26CoO 0.1 1320 3450 1.6 -25 -18 0.4 1200 2050 1.5 - 1 - 3clay 0.1 1320 3900 1.7 -28 -24 0.2 1320 3600 1.6 -27 -26La.sub.2 O.sub.3 0.05 1320 3900 1.5 -28 -25 0.2 1320 3650 1.5 -20 -27______________________________________

The effects of the additives on the composition of Sample No. 18 of Table 1, are shown in Table 5.

Table 5______________________________________ tan .delta.Amount T.sub.2 .epsilon..sub.s (%) T. C.Additive (wt%) (.degree. C) 1 KHz 1 KHz -25.degree. C +85.degree. C______________________________________none 0 1300 3200 1.9 -24 + 3MnO 0.05 1300 3050 1.7 -23 + 2 0.2 1300 2700 1.4 -20 - 2CoO 0.1 1300 3050 1.8 -20 0 0.3 1280 2400 1.7 - 9 + 5clay 0.1 1300 3100 1.8 -24 + 2 0.3 1300 2800 1.8 -23 - 1La.sub.2 O.sub.3 0.05 1300 3050 1.8 -21 - 2 0.2 1300 2600 1.7 - 8 -15______________________________________

In accordance with the addition of the special additives discussed above, the inferiorities of the ceramic dielectric compositions in the sintering step can be avoided, enabling the formation of a dense ceramic. Additionally, bending and curving of the ceramic during sintering can be prevented. The amount of the additive employed is in the range necessary for maintaining the desired electrical characteristics of the ceramic.

Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.

Claims

1. A dielectric ceramic composition which comprises as principle constituents, 86-99.6 mole % of barium titanate, 0.2 - 10 mole% of niobium pentaoxide and 0.2 - 4 mole% of cerium oxide.

2. The dielectric ceramic composition of claim 1, which comprises as principle constituents, 92 - 99.6 mole% of barium titanate, 0.2 - 6.0 mole% of niobium pentaoxide and 0.2 - 2.0 mole% of cerium oxide.

3. The dielectric ceramic composition of claim 1, which further contains at least one of calcium titanate or magnesium titanate in an amount of less than 10 wt% relative to the total amount of the principle constituents.

4. The dielectric ceramic composition of claim 3, wherein at least one of calcium titanate or magnesium titanate is present in an amount of 0.5 - 5.0 wt% relative to the total amount of the principle constituents.

5. The dielectric ceramic composition of claim 1, which further comprises at least one of the oxides of Mn, Cr, Fe, Ni or Co, clay or a rare earth element in an amount of 0.01 - 0.5 wt% relative to the total amount of the principle constituents.

6. The dielectric ceramic composition of claim 5, wherein at least one of the oxides of Mn, Cr, Fe, Ni and Co, clay or a rare earth element is present in an amount of 0.05 - 0.3 wt% relative to the total amount of the principle constitutents.

7. The dielectric ceramic composition of claim 1, which further comprises at least one of calcium titanate or magnesium titanate in an amount of less than 10 wt% relative to the total amount of the principle constituents and at least one of the oxides of Mn, Cr, Fe, Ni and Co, clay or rare earth element in an amount of 0.01 - 0.5 wt% relative to the total amount of the principle constituents.

8. The dielectric ceramic composition of claim 5, wherein the rare earth element is present in the form of an oxide.

9. The dielectric ceramic composition of claim 1, comprising 98 mole% barium titanate, 1 mole% niobium pentaoxide and 1 mole% cerium oxide.

10. The dielectric ceramic composition of claim 7, comprising 0.05 wt% of MnO and 5 wt% of calcium titanate relative to the total amount of principle constituents in the composition of 98 mole% barium titanate, 0.8 mole% cerium oxide, and 1.2 mole% niobium pentaoxide.