Ceramic powder and method for producing same

Abstract

The present invention provides a ceramic powder, in which -eucryptite or a -quartz solid solution is precipitated as a main crystal phase, and which includes TiO.sub.2 and/or ZrO.sub.2.

Claims

1. A ceramic powder, in which -eucryptite or a -quartz solid solution is precipitated as a main crystal phase, in which TiO.sub.2 and/or ZrO.sub.2 is solid solved, and which has an average particle diameter D.sub.50 of 7 m or less, wherein the ceramic powder is substantially free of a glass phase.

2. The ceramic powder according to claim 1, wherein the ceramic powder comprises as a composition, in terms of mol %, 10% to 35% of Li.sub.2O, 10% to 35% of Al.sub.2O.sub.3, 30% to 79.5% of SiO.sub.2, and 0.005% to 5% of TiO.sub.2+ZrO.sub.2.

3. The ceramic powder according to claim 1, wherein the ceramic powder has a negative thermal expansion coefficient in a range of from 30 C. to 300 C.

4. A sealing material, comprising a glass powder and a ceramic powder, wherein the ceramic powder comprises the ceramic powder of claim 1.

5. A laser sealing comprising the sealing material according to claim 4.

6. A method of producing a ceramic powder, comprising the steps of: firing a raw material batch to obtain, through a solid phase reaction, a sintered body in which -eucryptite or a -quartz solid solution is precipitated as a main crystal phase, and which comprises TiO.sub.2 and/or ZrO.sub.2, and pulverizing the sintered body to obtain a ceramic powder, wherein the ceramic powder has an average particle diameter D.sub.50 of 7 m or less; and wherein the ceramic powder is substantially free of a glass phase.

7. The method of producing a ceramic powder according to claim 6, comprising using a pulverized product of a pre-sintered body containing Li, Al, and Si as a whole or part of introduction raw materials for Li, Al, and Si.

8. The method of producing a ceramic powder according to claim 6, comprising using any one of an oxide raw material, a hydroxide raw material, and a carbonate raw material as a whole or part of introduction raw materials for Li, Al, and Si.

9. The method of producing a ceramic powder according to claim 6, wherein the firing a raw material batch provides, through the solid phase reaction, a sintered body comprising as a composition, in terms of mol %, 10% to 35% of Li.sub.2O, 10% to 35% of Al.sub.2O.sub.3, 30% to 79.5% of SiO.sub.2, and 0.005% to 5% of TiO.sub.2+ZrO.sub.2.

10. The method of producing a ceramic powder according to claim 6, wherein the firing a raw material batch is performed at from 1,000 C. to 1,450 C.

11. The method of producing a ceramic powder according to claim 6, wherein the pulverizing the sintered body is performed so that the ceramic powder obtained in the step of the pulverizing the sintered body has a size smaller than a size of a precipitated crystal grain.

12. The method of producing a ceramic powder according to claim 6, wherein the pulverizing the sintered body is performed so that a grain boundary between precipitated crystal grains is substantially free of microcracks.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an electron micrograph of Sample No. 1 (before pulverization) shown in Table 2.

(2) FIG. 2 is an electron micrograph of Sample No. 1 (after pulverization) shown in Table 2.

(3) FIG. 3 is an electron micrograph of Sample No. 2 (before pulverization) shown in Table 2.

(4) FIG. 4 is an electron micrograph of Sample No. 2 (after pulverization) shown in Table 2.

DESCRIPTION OF EMBODIMENTS

(5) In a ceramic powder of the present invention, it is preferred that -eucryptite or a -quartz solid solution be precipitated as a main crystal phase and no other crystal be precipitated, but as long as the effects of the present invention are not significantly impaired, the other crystal may be precipitated in a small amount.

(6) The ceramic powder of the present invention comprises TiO.sub.2 and/or ZrO.sub.2. The content thereof in terms of a total content is preferably from 0.005 mol % to 5 mol %, particularly preferably from 0.1 mol % to 4 mol %. Also the individual content thereof is preferably from 0.005 mol % to 5 mol %, particularly preferably from 0.1 mol % to 4 mol %. When the content of TiO.sub.2 and/or ZrO.sub.2 is too small, the amount of solid solved TiO.sub.2 and/or ZrO.sub.2 in a LAS-based crystal is reduced. As a result, the ceramic powder is difficult to maintain negative expansion characteristics when reduced in particle diameter. Meanwhile, when the content of TiO.sub.2 and/or ZrO.sub.2 is too large, TiO.sub.2 and/or ZrO.sub.2 is not entirely solid solved in the LAS-based crystal, and TiO.sub.2 and/or ZrO.sub.2 is liable to remain as an oxide. As a result, the ceramic powder is difficult to maintain the negative expansion characteristics.

(7) It is preferred that the ceramic powder of the present invention comprise, as a composition, in terms of mol %, 10% to 35% (preferably 16% to 30%) of Li.sub.2O, 10% to 35% (preferably 16% to 30%) of Al.sub.2O.sub.3, 30% to 79.5% (preferably 40% to 70%) of SiO.sub.2, and 0.005% to 5% (preferably 0.1% to 4%) of TiO.sub.2+ZrO.sub.2. When the composition of the ceramic powder deviates from the above-mentioned range, the precipitation of the -eucryptite or the -quartz solid solution as a main crystal phase becomes difficult. In addition, the ceramic powder is difficult to maintain the negative expansion characteristics when reduced in particle diameter. Any component other than the above-mentioned components, such as a sintering aid, may be introduced within a range of 10% or less.

(8) The ceramic powder of the present invention has an average particle diameter D.sub.50 of preferably 20 m or less, 10 m or less, 7 m or less, or 5 m or less, particularly preferably from 1 m to 3 m. As described above, the ceramic powder of the present invention can maintain the negative expansion characteristics even when having a small particle diameter. Therefore, the effects of the present invention are relatively increased as the particle diameter becomes smaller. The average particle diameter D.sub.50 refers to a value measured by laser diffractometry, and represents, in a cumulative particle size distribution curve on a volume basis measured by the laser diffractometry, a particle diameter at which the integration amount of particles from a smaller particle side is 50% in a cumulative manner.

(9) The ceramic powder of the present invention has a maximum particle diameter D.sub.max of preferably 50 m or less, 30 m or less, 20 m or less, or 15 m or less, particularly preferably from 2 m to 10 m. As described above, the ceramic powder of the present invention can maintain the negative expansion characteristics even when having a small particle diameter. Therefore, the effects of the present invention are relatively increased as the particle diameter becomes smaller. The maximum particle diameter D.sub.max refers to a value measured by the laser diffractometry, and represents, in the cumulative particle size distribution curve on a volume basis measured by the laser diffractometry, a particle diameter at which the integration amount of the particles from the smaller particle side is 99% in a cumulative manner.

(10) The ceramic powder of the present invention preferably has a negative thermal expansion coefficient (less than 010.sup.7/ C.) in a range of from 30 C. to 300 C. The thermal expansion coefficient is preferably 110.sup.7/ C. or less, 310.sup.7/ C. or less, or 610.sup.7/ C. or less, particularly preferably 2010/ C. or more and 910.sup.7/ C. or less. When the thermal expansion coefficient in a range of from 30 C. to 300 C. is too high, it becomes difficult to sufficiently reduce the thermal expansion coefficient of a sealing material.

(11) A sealing material of the present invention comprises a glass powder and a ceramic powder, and the ceramic powder is preferably the above-mentioned ceramic powder. The technical features of the sealing material of the present invention partially overlap the technical features of the ceramic powder of the present invention, and the detailed description of the overlapping portions is omitted.

(12) In the sealing material of the present invention, the content of the ceramic powder is from 1 vol % to 45 vol %, preferably from 10 vol % to 45 vol % or from 15 vol % to 40 volt, particularly preferably from 20 vol % to 35 volt. When the content of the ceramic powder is too large, the content of the glass powder is relatively reduced, and hence it becomes difficult to ensure desired flowability and thermal stability. When the content of a refractory filler powder is too small, an effect exhibited by the addition of the refractory filler powder becomes poor.

(13) A ceramic powder other than the ceramic powder of the present invention may be used as the ceramic powder. For example, one kind or two or more kinds selected from cordierite, zircon, alumina, mullite, willemite, zirconium phosphate, zirconium phosphate tungstate, and zircon tungstate may be included, but the content thereof is preferably from 0 vol % to 15 vol %, particularly preferably from 0 vol % to less than 10 vol % in terms of a total content.

(14) In the sealing material of the present invention, any of various glass powders may be used as the glass powder. For example, Bi.sub.2O.sub.3-based glass, V.sub.2O.sub.5-based glass, or SnO-based glass is suitable in view of a low melting point characteristic, and Bi.sub.2O.sub.3-based glass is particularly preferred in view of thermal stability and water resistance. As used herein, the term -based glass refers to glass which comprises the specified components as essential components and in which the total content of the specified components is 25 mol % or more, preferably 30 mol % or more, more preferably 35 mol % or more. The glass composition of the glass powder is preferably substantially free of PbO (less than 0.1 mol %) from an environmental point of view.

(15) The Bi.sub.2O.sub.3-based glass preferably comprises as a glass composition, in terms of mol %, 28% to 60% of Bi.sub.2O.sub.3, 15% to 37% of B.sub.2O.sub.3, and 1% to 30% of ZnO. The reasons why the content range of each component is limited as described above are described below. In the description of the glass composition range, the expression % means mol %.

(16) Bi.sub.2O.sub.3 is a main component for lowering a softening point, and its content is preferably from 28% to 60% or from 33% to 55%, particularly preferably from 35% to 45%. When the content of Bi.sub.2O.sub.3 is too small, the softening point becomes too high and hence flowability is liable to lower. Meanwhile, when the content of Bi.sub.2O.sub.3 is too large, the glass is liable to devitrify at the time of firing, and owing to the devitrification, the flowability is liable to lower.

(17) B.sub.2O.sub.3 is an essential component as a glass-forming component, and its content is preferably from 15% to 37% or from 20% to 33%, particularly preferably from 25% to 30%. When the content of B.sub.2O.sub.3 is too small, a glass network is hardly formed, and hence the glass is liable to devitrify at the time of firing. Meanwhile, when the content of B.sub.2O.sub.3 is too large, the glass has an increased viscosity, and hence the flowability is liable to lower.

(18) ZnO is a component which enhances devitrification resistance, and its content is preferably from 1% to 30%, from 3% to 25%, or from 5% to 22%, particularly preferably from 9% to 20%. When the content is less than 1%, or more than 30%, the glass composition loses its component balance, and hence the devitrification resistance is liable to lower.

(19) In addition to the above-mentioned components, for example, the following components may be added.

(20) SiO.sub.2 is a component which enhances water resistance, while having an action of increasing the softening point. Accordingly, the content of SiO.sub.2 is preferably from 0% to 5%, from 0% to 3%, or from 0% to 2%, particularly preferably from 0% to 1%. In addition, when the content of SiO.sub.2 is too large, the glass is liable to devitrify at the time of firing.

(21) Al.sub.2O.sub.3 is a component which enhances the water resistance. The content of Al.sub.2O.sub.3 is preferably from 0% to 10% or from 0% to 5%, particularly preferably from 0.1% to 2%. When the content of Al.sub.2O.sub.3 is too large, there is a risk in that the softening point is inappropriately increased.

(22) Li.sub.2O, Na.sub.2O, and K.sub.2O are each a component which reduces the devitrification resistance. Therefore, the content of each of Li.sub.2O, Na.sub.2O, and K.sub.2O is from 0% to 5% or from 0% to 3%, particularly preferably from 0% to less than 1%.

(23) MgO, CaO, SrO, and BaO are each a component which enhances the devitrification resistance, but are each a component which increases the softening point. Therefore, the content of each of MgO, CaO, SrO, and BaO is from 0% to 20% or from 0% to 10%, particularly preferably from 0% to 5%.

(24) In order to lower the softening point of Bi.sub.2O.sub.3-based glass, it is required to introduce a large amount of Bi.sub.2O.sub.3 into the glass composition, but when the content of Bi.sub.2O.sub.3 is increased, the glass is liable to devitrify at the time of firing, and owing to the devitrification, the flowability is liable to lower. This tendency is particularly remarkable when the content of Bi.sub.2O.sub.3 is 30% or more. As a countermeasure for this problem, the addition of CuO can effectively suppress the devitrification of the glass even when the content of Bi.sub.2O.sub.3 is 30% or more. Further, when CuO is added, laser absorption characteristics at the time of laser sealing can be enhanced. The content of CuO is preferably from 0% to 40%, from 5% to 35%, or from 10% to 30%, particularly preferably from 15% to 25%. When the content of CuO is too large, the glass composition loses its component balance, and hence the devitrification resistance is liable to lower to the worse.

(25) Fe.sub.2O.sub.3 is a component which enhances the devitrification resistance and the laser absorption characteristics, and its content is preferably from 0% to 10% or from 0.1% to 5%, particularly preferably from 0.5% to 3%. When the content of Fe.sub.2O.sub.3 is too large, the glass composition loses its component balance, and hence the devitrification resistance is liable to lower to the worse.

(26) Sb.sub.2O.sub.3 is a component which enhances the devitrification resistance, and its content is preferably from 0% to 5%, particularly preferably from 0% to 2%. When the content of Sb.sub.2O.sub.3 is too large, the glass composition loses its component balance, and hence the devitrification resistance is liable to lower to the worse.

(27) The glass powder preferably has an average particle diameter D.sub.50 of less than 15 m or from 0.5 m to 10 m, particularly preferably from 1 m to 5 m. As the average particle diameter D.sub.50 of the glass powder is smaller, the softening point of the glass powder lowers.

(28) Any powder material other than the glass powder and the ceramic powder may be introduced in the sealing material of the present invention. For example, in order to enhance the laser absorption characteristics, a laser absorbent, such as a MnFeAl-based oxide, carbon, or a MnFeCr-based oxide, may be included at from 1 vol % to 15 vol %. In addition, glass beads, a spacer, or the like may be introduced.

(29) The sealing material of the present invention may be used in a powdery state, but is preferably formed into a paste by being uniformly kneaded with a vehicle from the viewpoint of improving handleability. The vehicle generally comprises a solvent and a resin. The resin is added for the purpose of adjusting the viscosity of the paste. In addition, a surfactant, a thickener, or the like may also be added thereto as required. The produced paste is applied onto a surface of an object to be sealed by means of a coating machine, such as a dispenser or a screen printing machine.

(30) As the resin, there may be used an acrylic acid ester (acrylic resin), ethylcellulose, a polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, a methacrylic acid ester, and the like. In particular, an acrylic acid ester and nitrocellulose are preferred because of good thermolytic property.

(31) As the solvent, there may be used N,N-dimethyl formamide (DMF), -terpineol, a higher alcohol, -butyrolactone (-BL), tetralin, butylcarbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycolmonoethyl ether, diethylene glycol monoethylether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, and the like. In particular, -terpineol is preferred because of high viscosity and good solubility of a resin and the like.

(32) A method of producing a ceramic powder of the present invention comprises the steps of: firing a raw material batch to obtain, through a solid phase reaction, a sintered body in which -eucryptite or a -quartz solid solution is precipitated as a main crystal phase, and which comprises TiO.sub.2 and/or ZrO.sub.2; and pulverizing the sintered body to obtain a ceramic powder. The technical features of the method of producing a ceramic powder of the present invention partially overlap the technical features of the ceramic powder and the sealing material of the present invention, and the detailed description of the overlapping portions is omitted.

(33) Various raw materials may be used as introduction raw materials for Li, Al, and Si. Of those materials, a pulverized product of a pre-sintered body containing Li, Al, and Si is preferably used. When the whole or part of the introduction raw materials are pre-sintered, a precipitated crystal can be homogenized, and variations in characteristics of the ceramic powder can be reduced. In addition, other than the pulverized product of a pre-sintered body containing Li, Al, and Si, an oxide raw material, a hydroxide raw material, a carbonate raw material, or the like may be used.

(34) Various raw materials may be used as introduction raw materials for Ti and Zr. For example, a pulverized product of a pre-sintered body containing Ti and Zr, an oxide raw material, a hydroxide raw material, or a carbonate raw material may be used.

(35) The firing of the raw material batch may be performed with an electric furnace, a gas furnace, or the like. A firing temperature of the raw material batch is preferably from 1,000 C. to 1, 450 C., particularly preferably from 1,250 C. to 1,400 C. When the firing temperature is too low, the amount of the precipitated crystal in the ceramic powder is liable to be reduced. Meanwhile, when the firing temperature is too high, part of the sintered body is vitrified, and a glass phase is liable to remain in the sintered body. In addition, the degree of sintering of the sintered body is increased, and hence it becomes difficult to pulverize the sintered body. A firing time period of the raw material batch is preferably from 15 hours to 40 hours. When the firing time period is too short, the amount of the precipitated crystal in the ceramic powder is liable to be reduced. Meanwhile, when the firing time period is too long, the degree of sintering of the sintered body is increased, and hence it becomes difficult to pulverize the sintered body.

(36) The raw material batch is preferably wet pulverized and mixed with a ball mill or the like. With this, the homogeneity of the raw material batch is improved, and hence the solid phase reaction can be promoted.

(37) The pulverization of the sintered body may be performed with a ball mill, a jaw crusher, a jet mill, a disc mill, a spectro mill, a grinder, a mixer mill, or the like, but from the viewpoints of running cost and pulverization efficiency, dry or wet pulverization with a ball mill is preferred. A pulverized particle size of the sintered body is preferably smaller than the size of a precipitated crystal grain. In addition, the pulverized particle size of the sintered body is preferably adjusted to the extent that a grain boundary between the crystal grains is substantially free of microcracks. With this, the particle diameter of the ceramic powder is reduced, and hence the ceramic powder can be suitably applied to a hermetic package including a sealing layer having a small thickness.

(38) After the pulverization of the sintered body, the particle diameter of the sintered body is preferably controlled through sieve classification or air classification as required.

EXAMPLES

(39) Now, the present invention is described in detail based on Examples. The following Examples are merely illustrative. The present invention is by no means limited to the following Examples.

(40) (Production of Pulverized Product of Pre-Sintered Body)

(41) Raw materials shown in Table 1 were loaded into a pot made of alumina having an inner volume of 3.6 L and wet pulverized and mixed with each other for 12 hours. Thus, a raw material batch was produced. In the pulverization and mixing, 3,000 g of zirconia balls of 3.0 mm were used as pulverization balls, and 800 ml of an alcohol was used as a dispersion medium.

(42) TABLE-US-00001 TABLE 1 (Mass %) A B Aluminum hydroxide 44 33 Lithium carbonate 23 17 Silicon oxide 33 50

(43) Next, the raw material batch was dried, crushed, and retained at 800 C. for 8 hours and then fired at 1,335 C. for 16 hours in an electric furnace. A temperature increasing rate from room temperature to 800 C. was set to 5 C./min, a temperature increasing rate from 800 C. to 1,335 C. was set to 1 C./min, and a temperature decreasing rate from 1,335 C. was set to 1 C./min.

(44) Further, the resultant sintered body was pulverized through dry pulverization and wet pulverization until the sintered body achieved an average particle diameter D.sub.50 of 1.0 m, and then classified with a 350-mesh test sieve. Thus, pulverized products A and B of pre-sintered bodies were produced.

(45) (Production of Ceramic Powder)

(46) A raw material batch shown in Table 2 was loaded into a pot made of alumina having an inner volume of 3.6 L and wet pulverized and mixed for 12 hours. In the pulverization and mixing, 3,000 g of zirconia balls of 3.0 mm were used as pulverization balls, and 800 ml of an alcohol was used as a dispersion medium.

(47) TABLE-US-00002 TABLE 2 (Mass %) No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Pre-sintered body A 98 95 100 0 0 0 Pre-sintered body B 0 0 0 100 0 0 Aluminum hydroxide 0 0 0 0 44 33 Lithium carbonate 0 0 0 0 23 17 Silicon oxide 0 0 0 0 33 50 Titanium oxide 2 0 0 0 0 0 Zirconium oxide 0 2 0 0 0 0

(48) Next, the raw material batch was dried, crushed, and retained at 800 C. for 8 hours and then fired at 1,335 C. for 16 hours in an electric furnace. A temperature increasing rate from room temperature to 800 C. was set to 5 C./min, a temperature increasing rate from 800C to 1,335 C. was set to 1 C./min, and a temperature decreasing rate from 1,335 C. was set to 1 C./min.

(49) Further, the resultant sintered body was pulverized through dry pulverization and wet pulverization until the sintered body achieved an average particle diameter D.sub.50 of 1.0 m, and then classified with a 350-mesh test sieve. Thus, each of Sample Nos. 1 to 6 was obtained. The compositions of Sample Nos. 1 to 6 are shown in Table 3. In each of Sample Nos. 1 and 2, a main crystal was -eucryptite.

(50) TABLE-US-00003 TABLE 3 (Mol %) No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Li.sub.2O 25 25 25 17 25 17 Al.sub.2O.sub.3 25 25 25 17 25 17 SiO.sub.2 49 49 50 66 50 66 TiO.sub.2 1 0 0 0 0 0 ZrO.sub.2 0 1 0 0 0 0 30-300 (10.sup.7/ C.) 12 6 0 2 3 6

(51) (Production of Bi.sub.1O.sub.3-Based Glass Powder)

(52) A glass batch was prepared by blending raw materials, such as various oxides and carbonates, so that a glass powder comprising as a glass composition, in terms of mol %, 38% of Bi.sub.2O.sub.3, 27% of B.sub.2O.sub.3, 5% of ZnO, 4% of BaO, 24.35% of CuO, 0.7% of Fe.sub.2O.sub.3, and 1% of Al.sub.2O.sub.3 was obtained. The prepared glass batch was loaded into a platinum crucible and melted at from 1,000 C. to 1,100 C. for 2 hours. Next, the resultant molten glass was formed into a thin sheet shape with a water-cooling roller. Finally, the glass in the thin sheet shape was pulverized with a ball mill, and then subjected to air classification. Thus, a Bi.sub.2O.sub.3-based glass powder was obtained. The Bi.sub.2O.sub.3-based glass powder had an average particle diameter D of 2.5 m, a maximum particle diameter D.sub.max of 10 m, and a thermal expansion coefficient in a range of from 30 C. to 300 C. of 10410.sup.7/ C.

(53) (Production of Sealing Material)

(54) The Bi.sub.2O.sub.3-based glass powder described above and the ceramic powder shown in Table 3 were mixed at a volume ratio of 75:25. Thus, a sealing material was obtained.

(55) The resultant sealing material was fired at 500 C. to provide a dense fired body. After that, a measurement sample for push-rod type thermal expansion coefficient measurement (TMA) was produced by processing the fired body into a predetermined shape. TMA was performed in a temperature range of from 30 C. to 300 C. through use of the measurement sample. The thermal expansion coefficient of the ceramic powder shown in Table 3 was calculated based on the thermal expansion coefficient of the sealing material obtained.

(56) FIG. 1 is an electron micrograph of Sample No. 1 (before pulverization) shown in Tables 2 and 3. FIG. 2 is an electron micrograph of Sample No. 1 (after pulverization) shown in Tables 2 and 3. FIG. 3 is an electron micrograph of Sample No. 2 (before pulverization) shown in Tables 2 and 3. FIG. 4 is an electron micrograph of Sample No. 2 (after pulverization) shown in Tables 2 and 3. From FIGS. 1 to 4, it is revealed that each of Sample Nos. 1 and 2 has a crystal grain size of about 10 m, and through the pulverization, the particle diameter of each of Sample Nos. 1 and 2 becomes smaller than the crystal grain size. Moreover, it is also revealed that, in each of Sample Nos. 1 and 2, a grain boundary between crystal grains is substantially free of microcracks.

(57) As apparent from Table 3, each of Sample Nos. 1 and 2 exhibited negative expansion because of containing TiO.sub.z or ZrO.sub.2 in its composition. Meanwhile, each of Sample Nos. 3 to 6 exhibited positive expansion because of not containing TiO.sub.2 and ZrO.sub.2 in its composition.

(58) (Reference Example of Ceramic Powder Produced by Melting Method)

(59) A raw material batch shown in Table 4 was loaded into a pot made of alumina having an inner volume of 3.6 L and wet pulverized and mixed for 12 hours. In the pulverization and mixing, 3,000 g of zirconia balls of 3.0 mm were used as pulverization balls, and 800 ml of an alcohol was used as a dispersion medium.

(60) TABLE-US-00004 TABLE 4 (Mass %) Aluminum hydroxide 44 Lithium carbonate 23 Silicon oxide 33

(61) Next, the raw material batch was loaded into a platinum crucible and melted at 1,580 C. for 1 hour. After that, the resultant melt was poured between forming rollers (twin rollers) to cool and form the melt into a film shape. Subsequently, the resultant film was pulverized with a ball mill, classified with a 250-mesh pass sieve, and then retained at 800 C. for 12 hours in an electric furnace. A temperature increasing rate from room temperature to 800 C. was set to 5 C./min and a temperature decreasing rate from 800 C. was set to 1 C./min.

(62) Further, the resultant sintered body was pulverized through dry pulverization and wet pulverization until the sintered body achieved an average particle diameter D.sub.50 of 1.0 m, and then classified with a 350-mesh test sieve. Thus, Sample No. 7 was obtained.

(63) Finally, the Bi.sub.1O.sub.3-based glass powder described above and Sample No. 7 were mixed at a volume ratio of 75:25. Thus, a sealing material was obtained. The resultant sealing material was fired at 500 C. to provide a dense fired body. After that, a measurement sample for TMA was produced by processing the fired body into a predetermined shape. TMA was performed in a temperature range of from 30C to 300 C. through use of the measurement sample. The thermal expansion coefficient of Sample No. 7 was calculated based on the thermal expansion coefficient of the sealing material obtained. As a result, Sample No. 7 had a thermal expansion coefficient of 1010.sup.7/ C.