WO2018190056A1 - Crystalline glass composition - Google Patents

Crystalline glass composition Download PDF

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Publication number
WO2018190056A1
WO2018190056A1 PCT/JP2018/009606 JP2018009606W WO2018190056A1 WO 2018190056 A1 WO2018190056 A1 WO 2018190056A1 JP 2018009606 W JP2018009606 W JP 2018009606W WO 2018190056 A1 WO2018190056 A1 WO 2018190056A1
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Prior art keywords
glass composition
crystalline glass
heat treatment
content
mgo
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PCT/JP2018/009606
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French (fr)
Japanese (ja)
Inventor
聡子 此下
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日本電気硝子株式会社
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Priority claimed from JP2018037238A external-priority patent/JP2018177629A/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2018190056A1 publication Critical patent/WO2018190056A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc

Definitions

  • the present invention relates to a crystalline glass composition, and more specifically to a crystalline glass composition used for the purpose of bonding a metal such as SUS or Fe, or a high expansion ceramic such as ferrite or zirconia.
  • a fuel cell has been attracting attention as an effective technology that has high energy efficiency and can greatly reduce CO 2 emissions.
  • the type of fuel cell is classified according to the electrolyte used. For example, as used in industrial applications, phosphoric acid type (PAFC), molten carbonate type (MCFC), solid oxide type (SOFC), solid polymer type (PEFC) There are four types. Among them, the solid oxide fuel cell (SOFC) has the highest power generation efficiency among the fuel cells due to the low internal resistance of the cell, and it is not necessary to use a precious metal for the catalyst. Have. Therefore, it is a system that can be widely applied from a small-scale use such as home use to a large-scale use such as a power plant.
  • PAFC phosphoric acid type
  • MCFC molten carbonate type
  • SOFC solid oxide type
  • PEFC solid polymer type
  • a general plate-type SOFC is composed of an electrolyte 1 made of a ceramic material such as yttria stabilized zirconia (YSZ), an anode 2 made of Ni / YSZ, and (La, Ca) CrO 3 or the like.
  • the cathode 3 has a cell in which the layers are integrated. Further, a passage for fuel gas (fuel channel 4a) is formed, and a first support substrate 4 in contact with the anode 2 and a second support substrate 5 in which an air passage (air channel 5a) is formed and in contact with the cathode 3 are formed. Fixed to the top and bottom of the cell.
  • the first support substrate 4 and the second support substrate 5 are made of metal such as SUS, and are fixed to the cells so that the gas passages are orthogonal to each other.
  • the adhesive material to be used needs to have a thermal expansion coefficient compatible with these high expansion materials.
  • the SOFC has a high temperature range (operation temperature range) where an electrochemical reaction occurs (600 to 1000 ° C.), and is operated for a long time in the temperature range. Therefore, the adhesive material is required to have high heat resistance so that even if it is exposed to a high temperature for a long period of time, the hermeticity or adhesion deterioration due to melting of the bonded portion does not occur.
  • Patent Document 1 discloses a crystalline glass composition exhibiting high expansion characteristics by precipitating CaO—MgO—SiO 2 -based crystals upon heat treatment.
  • Patent Document 2 discloses a SiO 2 —B 2 O 3 —SrO-based amorphous glass composition capable of obtaining stable gas seal characteristics.
  • the crystalline glass composition described in Patent Document 1 has a high temperature viscosity, it is difficult to soften and flow during heat treatment, and it is difficult to obtain a dense sintered body. As a result, there is a problem that it is difficult to obtain a stable sealing property.
  • the amorphous glass composition disclosed in Patent Document 2 has a glass transition point of around 600 ° C., the bonded portion melts in a high-temperature operating environment of about 600 to 1000 ° C. There is a problem that adhesiveness cannot be secured.
  • an object of the present invention is to provide a crystalline glass composition having fluidity suitable for bonding, a high thermal expansion coefficient after heat treatment, and excellent heat resistance after bonding. .
  • the crystalline glass composition of the present invention comprises, in mol%, SiO 2 45 to 70%, MgO 5 to 40%, CaO + SrO 0.1 to 30%, BaO 5 to 40%, ZnO 5 to 40%, TiO 2 + ZrO. 2 0.1-10%, R 2 O (R is at least one selected from Li, Na, K, Cs) 0-5%, B 2 O 3 0-5%, Al 2 O 3 0-2% Less, La 2 O 3 0 to 15%.
  • “CaO + SrO” means the total amount of each content of CaO and SrO
  • TiO 2 + ZrO 2 means the total amount of each content of TiO 2 and ZrO 2 .
  • the “crystalline glass composition” refers to a glass composition having a property of precipitating crystals upon heat treatment. “Heat treatment” means heat treatment at a temperature of 800 ° C. or higher for 10 minutes or longer.
  • the crystalline glass composition of the present invention consists of crystals precipitated during heat treatment and residual glass not contained in the crystals after heat treatment.
  • TiO 2 and ZrO 2 are components that constitute the residual glass and increase the softening point of the residual glass.
  • the heat resistance of the bonded portion can be improved.
  • MgO, BaO and ZnO which are constituents of the high expansion crystal that precipitates during heat treatment, as described above, after heat treatment, the bonded portion has a high coefficient of thermal expansion and better heat resistance. It becomes. Therefore, even if it is used at a high temperature for a long period of time, the bonded portion is difficult to melt, and the deterioration of the airtightness and adhesiveness of the bonded portion can be suppressed.
  • SiO 2 , CaO and SrO are components that improve fluidity, and by defining their contents as described above, fluidity suitable for adhesion (sealing) can be obtained.
  • the crystalline glass composition of the present invention does not substantially contain P 2 O 5 and Bi 2 O 3 .
  • P 2 O 5 and Bi 2 O 3 are liable to volatilize by heat treatment and may adversely affect the power generation characteristics such as lowering the electrical insulation of the SOFC component. Therefore, by not containing these components substantially, it can suppress that an electric power generation characteristic falls unjustly.
  • “Substantially not contained” means not intentionally contained, and does not exclude inevitable contamination. Specifically, it means that the content of the corresponding component is less than 0.1 mol%.
  • the crystallizable glass composition of the present invention is selected MgO ⁇ SiO 2, BaO ⁇ 2MgO ⁇ 2SiO 2, 2SiO 2 ⁇ 2ZnO ⁇ BaO, from 4CaO ⁇ 6SiO 2 ⁇ 3La 2 O 3 and MgO ⁇ CaO ⁇ 2SiO 2 by heat treatment It is preferable to deposit at least one kind of crystal. With this configuration, it is possible to increase the bonding location and improve the heat resistance, and it is suitable for use in bonding or coating high expansion materials such as metals and ceramics.
  • the crystalline glass composition of the present invention preferably has a thermal expansion coefficient of 70 ⁇ 10 ⁇ 7 / ° C. or higher in the temperature range of 30 to 700 ° C.
  • the crystalline glass composition of the present invention is suitable for bonding.
  • the crystalline glass composition of the present invention has fluidity suitable for adhesion, has a high thermal expansion coefficient after heat treatment, and is excellent in heat resistance after adhesion. Therefore, even if it is used at a high temperature for a long period of time, the bonded portion is difficult to melt, and the deterioration of the airtightness and adhesiveness of the bonded portion can be suppressed.
  • the crystalline glass composition of the present invention comprises, in mol%, SiO 2 45 to 70%, MgO 5 to 40%, CaO + SrO 0.1 to 30%, BaO 5 to 40%, ZnO 5 to 40%, TiO 2 + ZrO. 2 0.1-10%, R 2 O (R is at least one selected from Li, Na, K, Cs) 0-5%, B 2 O 3 0-5%, Al 2 O 3 0-2% Less, La 2 O 3 0-15%.
  • R 2 O R is at least one selected from Li, Na, K, Cs
  • SiO 2 is a component of highly expanded crystals that are precipitated by heat treatment, and has the effect of improving water resistance and heat resistance in addition to improving fluidity.
  • the content of SiO 2 is 45 to 70%, preferably 46 to 69%, more preferably 47 to 65%.
  • fluidity suitable for bonding becomes difficult to obtain.
  • the content of SiO 2 is too large, high expansion crystal is less likely to precipitate during the heat treatment.
  • the melting temperature tends to be high and melting tends to be difficult.
  • MgO is a component of highly expanded crystals that are precipitated by heat treatment.
  • the content of MgO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%.
  • the content of MgO is too small, it becomes difficult for high-expansion crystals to precipitate during heat treatment, and the heat resistance tends to decrease.
  • there is too much content of MgO there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify. Moreover, fluidity tends to be lowered.
  • CaO and SrO are components for improving fluidity.
  • the content of CaO + SrO is 0.1-30%, preferably 1-25%, more preferably 1-20%. When there is too little content of CaO + SrO, it will become difficult to obtain the fluidity
  • the contents of CaO and SrO are each preferably 0 to 30%, more preferably 1 to 25%, and still more preferably 1 to 20%.
  • CaO is a constituent component of 4CaO.6SiO 2 .3La 2 O 3 , which is a kind of highly expanded crystal that is precipitated by heat treatment, and is preferable in that the effect of improving fluidity is particularly great.
  • the content of CaO is preferably larger than the content of MgO.
  • the CaO content is preferably 6% or more, 8% or more, and particularly preferably 10% or more.
  • BaO is a constituent component of a highly expanded crystal that is precipitated by heat treatment.
  • the content of BaO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%.
  • When there is too little content of BaO it will become difficult to precipitate a highly expanded crystal
  • when there is too much content of BaO there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify. Moreover, fluidity tends to be lowered.
  • ZnO is a constituent component of a highly expanded crystal that is precipitated by heat treatment.
  • the content of ZnO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%.
  • the content of ZnO is too small, it becomes difficult for highly expanded crystals to precipitate during the heat treatment, and the heat resistance tends to decrease.
  • the vitrification range tends to become narrow, and devitrification tends to occur.
  • TiO 2 and ZrO 2 are components that increase the softening point of the residual glass and improve heat resistance. It is also a component that improves fluidity.
  • the content of TiO 2 + ZrO 2 is 0.1 to 10%, preferably 0.1 to 8%, more preferably 0.5 to 6%.
  • the content of TiO 2 + ZrO 2 is too small, the softening point of the residual glass is lowered, the heat resistance tends to lower. Moreover, fluidity tends to be lowered. On the other hand, it tends to be devitrified when melted and the content of TiO 2 + ZrO 2 is too high. Moreover, fluidity tends to be lowered.
  • the contents of TiO 2 and ZrO 2 are each preferably 0 to 10%, more preferably 0.1 to 8%, and still more preferably 0.5 to 6%.
  • R 2 O (R is at least one selected from Li, Na, K, and Cs) is a component that widens the vitrification range and facilitates vitrification.
  • the content of R 2 O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%.
  • R 2 O volatilizes when used at a high temperature, and power generation characteristics are likely to deteriorate.
  • the contents of Li 2 O, Na 2 O, K 2 O, and Cs 2 O are each preferably 0 to 5%, more preferably 0 to 3%, and still more preferably 0 to 1%.
  • B 2 O 3 is a component for improving fluidity.
  • the content of B 2 O 3 is 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%. If the B 2 O 3 content is too large, water resistance and heat resistance tends to decrease. Further, when used as an adhesive material for constituent members of a fuel cell, B 2 O 3 volatilizes when used at a high temperature, and the power generation characteristics tend to deteriorate.
  • Al 2 O 3 is a component for adjusting the viscosity.
  • the content of Al 2 O 3 is 0 to less than 2%, preferably 0 to 1.5%, more preferably 0 to 1%.
  • heat treatment by 2SiO 2 ⁇ Al 2 O 3 ⁇ becomes low expansion crystal BaO or the like is likely to precipitate, hardly high expansion characteristics.
  • La 2 O 3 is a constituent component of the high expansion crystal precipitated by heat treatment, and is also a component for improving fluidity. Moreover, it is a component which expands the vitrification range and facilitates vitrification.
  • the content of La 2 O 3 is 0 to 15%, preferably 0 to 14%, more preferably 0.1 to 13%. When the content of La 2 O 3 is too large, easily devitrified when melted or during the heat treatment, the fluidity becomes difficult to obtain suitable adhesion.
  • the crystalline glass composition of the present invention may contain up to 2% of Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , SnO 2 , WO 3 and the like as components other than the above. it can.
  • P 2 O 5 and Bi 2 O 3 are preferably not substantially contained because they tend to volatilize by heat treatment and may adversely affect the power generation characteristics such as lowering the electrical insulation properties of the SOFC constituent members.
  • the crystalline glass composition having the above composition has the property of precipitating highly expanded crystals upon heat treatment.
  • the high expansion crystal include at least one selected MgO ⁇ SiO 2, BaO ⁇ 2MgO ⁇ 2SiO 2, 2SiO 2 ⁇ 2ZnO ⁇ BaO, from 4CaO ⁇ 6SiO 2 ⁇ 3La 2 O 3 and MgO ⁇ CaO ⁇ 2SiO 2 .
  • the thermal expansion coefficient of the crystalline glass composition after heat treatment in the temperature range of 30 to 700 ° C. is preferably 70 ⁇ 10 ⁇ 7 / ° C. or more, particularly preferably 80 ⁇ 10 ⁇ 7 / ° C. or more.
  • the upper limit is not particularly limited, but is practically 150 ⁇ 10 ⁇ 7 / ° C. or less.
  • the crystalline glass composition of the present invention tends to have a high crystallinity after heat treatment.
  • precipitated crystals have a high melting point and are difficult to flow even when heat-treated again, so that heat resistance can be maintained over a long period of time.
  • the crystalline glass composition of the present invention is prepared by adjusting magnesia (MgO), zinc white (ZnO), zirconia (ZrO 2 ), titania (TiO 2 ), alumina (Al 2 O) in order to adjust fluidity and thermal expansion coefficient.
  • the addition amount of the filler powder is preferably 0 to 10 parts by mass, 0.1 to 9 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the crystalline glass composition. When there is too much addition amount of filler powder, fluidity
  • the raw materials prepared to have the above composition are melted at 1400-1600 ° C. for about 0.5-2 hours until a homogeneous glass is obtained.
  • the molten glass is formed into a film or the like, and then pulverized and classified to produce a glass powder made of the crystalline glass composition of the present invention.
  • the particle size (d50) of the glass powder is preferably about 2 to 20 ⁇ m.
  • Various filler powders are added to the glass powder as necessary.
  • a glass paste is prepared by adding a vehicle to glass powder (or a mixed powder of glass powder and filler powder) and kneading.
  • the vehicle contains, for example, a plasticizer, a dispersant and the like in addition to an organic solvent and a resin.
  • the organic solvent is a material for pasting glass powder.
  • terpineol Te
  • diethylene glycol monobutyl ether BC
  • diethylene glycol monobutyl ether acetate BCA
  • 2,2,4-trimethyl-1,3-pentadiol Monoisobutyrate dihydroterpineol and the like
  • the content is preferably 10 to 40% by mass.
  • Resin is a component that increases the film strength after drying and imparts flexibility, and its content is generally about 0.1 to 20% by mass.
  • a thermoplastic resin specifically, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like can be used, and these are used alone or in combination.
  • the plasticizer is a component that controls the drying speed and imparts flexibility to the dried film, and the content thereof is generally about 0 to 10% by mass.
  • the plasticizer butylbenzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, dibutyl phthalate and the like can be used, and these are used alone or in combination.
  • an ionic or nonionic dispersant can be used as the dispersant.
  • a polyhydric alcohol ether type dispersant can be used. The amount used is generally 0 to 5% by mass.
  • the paste is applied to the bonding portion of the first member made of metal or ceramic and dried. Further, the second member made of metal or ceramic is fixed in a state where it is in contact with the dry paste film, and heat treated at 800 to 1050 ° C. By this heat treatment, the glass powder once softens and flows to fix the first and second members, and crystals precipitate. In this manner, a joined body can be obtained in which the first member and the second member are bonded by the sealing portion made of the crystalline glass composition of the present invention.
  • the crystalline glass composition of the present invention can be used for purposes such as coating and filling in addition to adhesion. Further, it can be used in a form other than paste, specifically in the form of powder, green sheet, tablet or the like.
  • a form which fills glass powder with a lead wire in the cylinder which consists of metal or ceramics, heat-processes, and performs airtight sealing is mentioned.
  • a green sheet molded preform, a tablet produced by powder press molding, or the like is placed on a member made of metal or ceramic, and can be coated by heat treatment and softening and flowing.
  • Tables 1 and 2 show examples (samples Nos. 1 to 12) and comparative examples (samples Nos. 13 and 14) of the present invention.
  • the raw materials prepared so as to have the respective compositions shown in the table were melted at 1400-1600 ° C. for about 2 hours, and then poured out between a pair of rollers to form a film.
  • the obtained film-like molded product was pulverized with a ball mill and classified to obtain a sample (crystalline glass composition powder) having a particle size (d50) of about 10 ⁇ m.
  • Examples No. Samples 1 to 12 were excellent in fluidity during heat treatment. Further, since the high expansion crystal was precipitated by the heat treatment, the thermal expansion coefficient was as high as 78 to 113 ⁇ 10 ⁇ 7 / ° C. Furthermore, it was found that the melting point of the precipitated crystals is high and the heat resistance is also excellent.
  • the coefficient of thermal expansion was determined by JIS using a measurement sample obtained by press-molding each glass powder sample, heat-treating it at 1000-1100 ° C. for 3 hours, and polishing it into a cylindrical shape having a diameter of 4 mm and a length of 20 mm. Based on R3102, a value in a temperature range of 30 to 700 ° C. was obtained.
  • Softening point, crystallization temperature, and crystal melting point were measured using a macro-type differential thermal analyzer. Specifically, for each glass powder sample, in the chart obtained by measuring up to 1050 ° C. using a macro-type differential thermal analyzer, the fourth inflection point value is the softening point and the strong exothermic peak is crystallized. The endothermic peak obtained after temperature and crystallization was defined as the crystalline melting point. Note that the higher the crystal melting point or if the crystal melting point is not confirmed, it means that the crystal exists stably even at a high temperature, and it can be determined that the heat resistance is high.
  • the fluidity was evaluated as follows. A glass powder sample having a specific gravity was put into a mold having a diameter of 20 mm, press-molded, and then heat-treated at 900 to 1100 ° C. for 15 minutes on a SUS430 plate. The molded product after the heat treatment having a flow diameter of 18 mm or more was evaluated as “ ⁇ ”, 16 mm or more and less than 18 mm as “ ⁇ ”, and less than 16 mm as “x”.
  • the precipitated crystal was identified by performing XRD measurement on a glass powder sample and comparing with a JCPDS card.
  • MgO ⁇ SiO 2 was identified as “A”
  • BaO ⁇ 2MgO ⁇ 2SiO 2 as “B”
  • 2SiO 2 ⁇ 2ZnO ⁇ BaO as “C”
  • 4CaO ⁇ 6SiO 2 ⁇ 3La 2 O 3 as the identified crystal seeds.
  • “D” showed the MgO ⁇ CaO ⁇ 2SiO 2 in the table as "E”.
  • the crystalline glass composition of the present invention is suitable as an adhesive material for metals such as SUS and Fe, and high expansion ceramics such as ferrite and zirconia.
  • metals such as SUS and Fe
  • high expansion ceramics such as ferrite and zirconia.
  • it is suitable as an adhesive material for hermetically sealing a support substrate, an electrode member, and the like used in manufacturing an SOFC.
  • the crystalline glass composition of the present invention can be used for purposes such as coating and filling in addition to adhesive applications. Specifically, it can be used for applications such as thermistors and hybrid ICs.

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Abstract

Provided is a crystalline glass composition that has a flowability suitable for adhesion, a high coefficient of thermal expansion after a heat treatment, and excellent heat resistance after adhesion. The crystalline glass composition is characterized by containing, in mol%, 45% to 70% of SiO2, 5% to 40% of MgO, 0.1% to 30% of CaO + SrO, 5% to 40% of BaO, 5% to 40%of ZnO, 0.1% to 10% of TiO2+ZrO2, 0% to 5% of R2O (R is at least one selected from Li, Na, K and Cs), 0% to 5% of B2O3, 0% to less than 2% of Al2O3 and 0% to 15% of La2O3.

Description

結晶性ガラス組成物Crystalline glass composition
　本発明は、結晶性ガラス組成物に関し、より具体的にはＳＵＳやＦｅといった金属や、フェライトやジルコニアといった高膨張なセラミックスを接着する目的で用いられる結晶性ガラス組成物に関するものである。 The present invention relates to a crystalline glass composition, and more specifically to a crystalline glass composition used for the purpose of bonding a metal such as SUS or Fe, or a high expansion ceramic such as ferrite or zirconia.
　近年、燃料電池（Ｆｕｅｌ　Ｃｅｌｌ）はエネルギー効率が高く、ＣＯ２の排出を大きく削減できる有力な技術として注目されてきている。燃料電池のタイプは使用する電解質によって分類され、例えば工業用途で用いられるものとして、リン酸型（ＰＡＦＣ）、溶融炭酸塩型（ＭＣＦＣ）、固体酸化物型（ＳＯＦＣ）、固体高分子型（ＰＥＦＣ）の４種類がある。中でも固体酸化物型燃料電池（ＳＯＦＣ）は、電池の内部抵抗が小さいため燃料電池の中では最も発電効率が高く、また触媒に貴金属を使用する必要がないため、製造コストが抑えられるといった特徴を有している。そのため、家庭用等の小規模用途から、発電所等の大規模用途まで幅広く適用可能なシステムであり、その将来性に期待が高まってきている。 In recent years, a fuel cell has been attracting attention as an effective technology that has high energy efficiency and can greatly reduce CO 2 emissions. The type of fuel cell is classified according to the electrolyte used. For example, as used in industrial applications, phosphoric acid type (PAFC), molten carbonate type (MCFC), solid oxide type (SOFC), solid polymer type (PEFC) There are four types. Among them, the solid oxide fuel cell (SOFC) has the highest power generation efficiency among the fuel cells due to the low internal resistance of the cell, and it is not necessary to use a precious metal for the catalyst. Have. Therefore, it is a system that can be widely applied from a small-scale use such as home use to a large-scale use such as a power plant.
　一般的な平板型ＳＯＦＣの構造を図１に示す。図１に示すように、一般的な平板型ＳＯＦＣは、イットリア安定化ジルコニア（ＹＳＺ）等のセラミック材料からなる電解質１、Ｎｉ／ＹＳＺ等からなるアノード２、及び（Ｌａ、Ｃａ）ＣｒＯ３等からなるカソード３が積層一体化されたセルを有している。さらに燃料ガスの通り道（燃料チャネル４ａ）が形成され、アノード２と接する第一の支持基板４と、空気の通り道（空気チャネル５ａ）が形成され、カソード３と接する第二の支持基板５とがセルの上下に固着されている。なお第一の支持基板４及び第二の支持基板５はＳＵＳ等の金属で構成されており、ガスの通り道が互いに直交するようにセルに固着される。 The structure of a general flat plate type SOFC is shown in FIG. As shown in FIG. 1, a general plate-type SOFC is composed of an electrolyte 1 made of a ceramic material such as yttria stabilized zirconia (YSZ), an anode 2 made of Ni / YSZ, and (La, Ca) CrO 3 or the like. The cathode 3 has a cell in which the layers are integrated. Further, a passage for fuel gas (fuel channel 4a) is formed, and a first support substrate 4 in contact with the anode 2 and a second support substrate 5 in which an air passage (air channel 5a) is formed and in contact with the cathode 3 are formed. Fixed to the top and bottom of the cell. The first support substrate 4 and the second support substrate 5 are made of metal such as SUS, and are fixed to the cells so that the gas passages are orthogonal to each other.
　上記構造を有する平板型ＳＯＦＣでは、燃料チャネル４ａに水素（Ｈ２）や、都市ガス、天然ガス、バイオガス、液体燃料といった様々なガスを流し、同時に空気チャネル５ａに空気または酸素（Ｏ２）を流す。このときカソードでは、１／２Ｏ２＋２ｅ－　→　Ｏ２－の反応が生じ、アノードでは、Ｈ２＋Ｏ２－　→　Ｈ２Ｏ　＋　２ｅ－の反応が起こる。この電気化学反応によって、化学エネルギーが直接電気エネルギーに変換され、発電することができる。なお高出力を得るために、実際の平板型ＳＯＦＣでは図１の構造体が何層も積層されている。 In the flat plate type SOFC having the above-described structure, various gases such as hydrogen (H 2 ), city gas, natural gas, biogas, and liquid fuel flow through the fuel channel 4a, and at the same time air or oxygen (O 2 ) flows through the air channel 5a. Shed. At this time, a reaction of 1 / 2O 2 + 2e − → O 2− occurs at the cathode, and a reaction of H 2 + O 2− → H 2 O + 2e − occurs at the anode. By this electrochemical reaction, chemical energy is directly converted into electric energy and can be generated. In order to obtain a high output, an actual flat plate type SOFC has a number of layers of the structure shown in FIG.
　上記構造体を作製するに当たっては、アノード側とカソード側に流すガスが交じり合わないように各構成部材を気密シールする必要がある。その目的で、マイカやバーミキュライト、アルミナといった無機質からなるシート形状のガスケットを挟み込んで気密シールする方法が提案されているが、当該方法では微量のガスリークが発生しやすく、燃料使用効率の低下が問題となっている。当該問題を解決するため、ガラスからなる接着材料を用いて構成部材同士を融解接着する方法が検討されている。 In manufacturing the structure, it is necessary to hermetically seal each component so that the gas flowing to the anode side and the cathode side does not mix. For this purpose, a method has been proposed in which an inorganic sheet-shaped gasket such as mica, vermiculite, or alumina is sandwiched and hermetically sealed, but this method is likely to cause a small amount of gas leak, resulting in a decrease in fuel use efficiency. It has become. In order to solve the problem, a method of melting and bonding constituent members using an adhesive material made of glass has been studied.
　上記構造体の構成部材としては金属やセラミックといった高膨張材料が使用されることから、使用する接着材料についても、これらの高膨張材料に適合する熱膨張係数を有する必要がある。また、ＳＯＦＣは電気化学反応が生じる温度域（作動温度域）が６００～１０００℃と高温であり、しかも当該温度域で長期間に亘って運転される。よって、接着材料には、長期間高温に晒されても、接着箇所の融解による気密性や接着性の低下が起こらないように高い耐熱性が求められる。 Since a high expansion material such as metal or ceramic is used as a constituent member of the structure, the adhesive material to be used needs to have a thermal expansion coefficient compatible with these high expansion materials. The SOFC has a high temperature range (operation temperature range) where an electrochemical reaction occurs (600 to 1000 ° C.), and is operated for a long time in the temperature range. Therefore, the adhesive material is required to have high heat resistance so that even if it is exposed to a high temperature for a long period of time, the hermeticity or adhesion deterioration due to melting of the bonded portion does not occur.
　ガラスからなる高膨張接着材料として、熱処理するとＣａＯ－ＭｇＯ－ＳｉＯ２系結晶が析出して高膨張特性を示す結晶性ガラス組成物が特許文献１に開示されている。また、特許文献２には、安定したガスシール特性が得られるＳｉＯ２－Ｂ２Ｏ３－ＳｒＯ系非晶質ガラス組成物が開示されている。 As a high expansion adhesive material made of glass, Patent Document 1 discloses a crystalline glass composition exhibiting high expansion characteristics by precipitating CaO—MgO—SiO 2 -based crystals upon heat treatment. Patent Document 2 discloses a SiO 2 —B 2 O 3 —SrO-based amorphous glass composition capable of obtaining stable gas seal characteristics.
国際公開第２００９／０１７１７３号公報International Publication No. 2009/0117173 特開２００６－５６７６９号公報JP 2006-56769 A
　特許文献１に記載されている結晶性ガラス組成物は、高温粘性が高いため、熱処理時に軟化流動しにくく、緻密な焼結体が得られにくい。結果として、安定したシール性が得られにくいという問題がある。また、特許文献２に開示されている非晶質ガラス組成物は、ガラス転移点が６００℃付近であるため、６００～１０００℃程度といった高温動作環境下では、接着箇所が融解し、気密性や接着性が確保できないという問題がある。 Since the crystalline glass composition described in Patent Document 1 has a high temperature viscosity, it is difficult to soften and flow during heat treatment, and it is difficult to obtain a dense sintered body. As a result, there is a problem that it is difficult to obtain a stable sealing property. In addition, since the amorphous glass composition disclosed in Patent Document 2 has a glass transition point of around 600 ° C., the bonded portion melts in a high-temperature operating environment of about 600 to 1000 ° C. There is a problem that adhesiveness cannot be secured.
　以上に鑑み、本発明は、接着に適した流動性を有するとともに、熱処理後に高い熱膨張係数を有し、かつ接着後の耐熱性にも優れる結晶性ガラス組成物を提供することを目的とする。 In view of the above, an object of the present invention is to provide a crystalline glass composition having fluidity suitable for bonding, a high thermal expansion coefficient after heat treatment, and excellent heat resistance after bonding. .
　本発明者が種々の実験を行った結果、特定組成を有するガラス組成物により上記課題を解決できることを見出した。 As a result of various experiments conducted by the inventor of the present invention, it has been found that the above problem can be solved by a glass composition having a specific composition.
　本発明の結晶性ガラス組成物は、モル％で、ＳｉＯ２　４５～７０％、ＭｇＯ　５～４０％、ＣａＯ＋ＳｒＯ　０．１～３０％、ＢａＯ　５～４０％、ＺｎＯ　５～４０％、ＴｉＯ２＋ＺｒＯ２　０．１～１０％、Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋ、Ｃｓから選択される少なくとも一種）　０～５％、Ｂ２Ｏ３　０～５％、Ａｌ２Ｏ３　０～２％未満、Ｌａ２Ｏ３　０～１５％を含有することを特徴とする。ここで、「ＣａＯ＋ＳｒＯ」はＣａＯ及びＳｒＯの各含有量の合量を意味し、「ＴｉＯ２＋ＺｒＯ２」はＴｉＯ２及びＺｒＯ２の各含有量の合量を意味する。なお、本発明において、「結晶性ガラス組成物」とは、熱処理すると結晶を析出する性質を有するガラス組成物をいう。また、「熱処理する」とは、８００℃以上の温度で１０分間以上の条件で熱処理することを意味する。 The crystalline glass composition of the present invention comprises, in mol%, SiO 2 45 to 70%, MgO 5 to 40%, CaO + SrO 0.1 to 30%, BaO 5 to 40%, ZnO 5 to 40%, TiO 2 + ZrO. 2 0.1-10%, R 2 O (R is at least one selected from Li, Na, K, Cs) 0-5%, B 2 O 3 0-5%, Al 2 O 3 0-2% Less, La 2 O 3 0 to 15%. Here, “CaO + SrO” means the total amount of each content of CaO and SrO, and “TiO 2 + ZrO 2 ” means the total amount of each content of TiO 2 and ZrO 2 . In the present invention, the “crystalline glass composition” refers to a glass composition having a property of precipitating crystals upon heat treatment. “Heat treatment” means heat treatment at a temperature of 800 ° C. or higher for 10 minutes or longer.
　本発明の結晶性ガラス組成物は、熱処理後において、熱処理時に析出した結晶及びその結晶に含有されない残留ガラスからなる。ＴｉＯ２及びＺｒＯ２は、残留ガラスを構成し、残留ガラスの軟化点を高める成分であり、これらの含有量を上記の通り規定することにより、接着箇所の耐熱性を向上させることができる。また、熱処理時に析出する高膨張結晶の構成成分であるＭｇＯ、ＢａＯ及びＺｎＯの含有量を上記の通り規制することで、熱処理後、接着箇所が高い熱膨張係数を有し、耐熱性もさらに良好となる。そのため、長期間に亘って高温下で使用しても、接着箇所が融解し難くなり、接着箇所の気密性や接着性の低下を抑制することができる。 The crystalline glass composition of the present invention consists of crystals precipitated during heat treatment and residual glass not contained in the crystals after heat treatment. TiO 2 and ZrO 2 are components that constitute the residual glass and increase the softening point of the residual glass. By specifying these contents as described above, the heat resistance of the bonded portion can be improved. In addition, by regulating the content of MgO, BaO and ZnO, which are constituents of the high expansion crystal that precipitates during heat treatment, as described above, after heat treatment, the bonded portion has a high coefficient of thermal expansion and better heat resistance. It becomes. Therefore, even if it is used at a high temperature for a long period of time, the bonded portion is difficult to melt, and the deterioration of the airtightness and adhesiveness of the bonded portion can be suppressed.
　ＳｉＯ２、ＣａＯ及びＳｒＯは流動性を向上させる成分であり、これらの含有量を上記の通り規定することにより、接着（封着）に適した流動性を得ることができる。 SiO 2 , CaO and SrO are components that improve fluidity, and by defining their contents as described above, fluidity suitable for adhesion (sealing) can be obtained.
　本発明の結晶性ガラス組成物は、Ｐ２Ｏ５及びＢｉ２Ｏ３を実質的に含有しないことが好ましい。Ｐ２Ｏ５及びＢｉ２Ｏ３は熱処理により揮発しやすく、ＳＯＦＣ構成部材の電気絶縁性を低下させる等、発電特性に悪影響を与えるおそれがある。そのため、これらの成分を実質的に含有しないことにより、不当に発電特性が低下することを抑制することができる。なお、「実質的に含有しない」とは意図的に含有させないことを意味し、不可避的不純物の混入を排除するものではない。具体的には、該当する成分の含有量が０．１モル％未満であることを意味する。 It is preferable that the crystalline glass composition of the present invention does not substantially contain P 2 O 5 and Bi 2 O 3 . P 2 O 5 and Bi 2 O 3 are liable to volatilize by heat treatment and may adversely affect the power generation characteristics such as lowering the electrical insulation of the SOFC component. Therefore, by not containing these components substantially, it can suppress that an electric power generation characteristic falls unjustly. “Substantially not contained” means not intentionally contained, and does not exclude inevitable contamination. Specifically, it means that the content of the corresponding component is less than 0.1 mol%.
　本発明の結晶性ガラス組成物は、熱処理によりＭｇＯ・ＳｉＯ２、ＢａＯ・２ＭｇＯ・２ＳｉＯ２、２ＳｉＯ２・２ＺｎＯ・ＢａＯ、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３及びＭｇＯ・ＣａＯ・２ＳｉＯ２から選択される少なくとも一種の結晶を析出することが好ましい。当該構成により、接着箇所の高膨張化及び耐熱性向上を図ることが可能となり、金属やセラミックといった高膨張材料同士の接着または被覆の用途に好適となる。 The crystallizable glass composition of the present invention is selected MgO · SiO 2, BaO · 2MgO · 2SiO 2, 2SiO 2 · 2ZnO · BaO, from 4CaO · 6SiO 2 · 3La 2 O 3 and MgO · CaO · 2SiO 2 by heat treatment It is preferable to deposit at least one kind of crystal. With this configuration, it is possible to increase the bonding location and improve the heat resistance, and it is suitable for use in bonding or coating high expansion materials such as metals and ceramics.
　本発明の結晶性ガラス組成物は、３０～７００℃の温度範囲における熱膨張係数が７０×１０－７／℃以上であることが好ましい。 The crystalline glass composition of the present invention preferably has a thermal expansion coefficient of 70 × 10 −7 / ° C. or higher in the temperature range of 30 to 700 ° C.
　本発明の結晶性ガラス組成物は、接着用として好適である。 The crystalline glass composition of the present invention is suitable for bonding.
　本発明の結晶性ガラス組成物は、接着に適した流動性を有するとともに、熱処理後に高い熱膨張係数を有し、かつ接着後の耐熱性にも優れる。そのため、長期間に亘って高温下で使用しても、接着箇所が融解し難くなり、接着箇所の気密性や接着性の低下を抑制することができる。 The crystalline glass composition of the present invention has fluidity suitable for adhesion, has a high thermal expansion coefficient after heat treatment, and is excellent in heat resistance after adhesion. Therefore, even if it is used at a high temperature for a long period of time, the bonded portion is difficult to melt, and the deterioration of the airtightness and adhesiveness of the bonded portion can be suppressed.
ＳＯＦＣの基本構造を示す模式的斜視図である。It is a typical perspective view which shows the basic structure of SOFC.
　本発明の結晶性ガラス組成物は、モル％で、ＳｉＯ２　４５～７０％、ＭｇＯ　５～４０％、ＣａＯ＋ＳｒＯ　０．１～３０％、ＢａＯ　５～４０％、ＺｎＯ　５～４０％、ＴｉＯ２＋ＺｒＯ２　０．１～１０％、Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋ、Ｃｓから選択される少なくとも一種）　０～５％、Ｂ２Ｏ３　０～５％、Ａｌ２Ｏ３　０～２％未満、Ｌａ２Ｏ３　０～１５％を含有する。ガラス組成を上記のように限定した理由を以下に説明する。なお、以下の各成分の含有量に関する説明において、特に断りのない限り、「％」は「モル％」を意味する。 The crystalline glass composition of the present invention comprises, in mol%, SiO 2 45 to 70%, MgO 5 to 40%, CaO + SrO 0.1 to 30%, BaO 5 to 40%, ZnO 5 to 40%, TiO 2 + ZrO. 2 0.1-10%, R 2 O (R is at least one selected from Li, Na, K, Cs) 0-5%, B 2 O 3 0-5%, Al 2 O 3 0-2% Less, La 2 O 3 0-15%. The reason for limiting the glass composition as described above will be described below. In the following description regarding the content of each component, “%” means “mol%” unless otherwise specified.
　ＳｉＯ２は、熱処理により析出する高膨張結晶の構成成分であり、流動性の向上以外に、耐水性や耐熱性を向上させる効果がある。ＳｉＯ２の含有量は４５～７０％であり、好ましくは４６～６９％、より好ましくは４７～６５％である。ＳｉＯ２の含有量が少なすぎると、接着に適した流動性が得にくくなる。一方、ＳｉＯ２の含有量が多すぎると、熱処理時に高膨張結晶が析出しにくくなる。また、溶融温度が高くなり、溶融が困難になる傾向がある。 SiO 2 is a component of highly expanded crystals that are precipitated by heat treatment, and has the effect of improving water resistance and heat resistance in addition to improving fluidity. The content of SiO 2 is 45 to 70%, preferably 46 to 69%, more preferably 47 to 65%. When the content of SiO 2 is too small, fluidity suitable for bonding becomes difficult to obtain. On the other hand, if the content of SiO 2 is too large, high expansion crystal is less likely to precipitate during the heat treatment. In addition, the melting temperature tends to be high and melting tends to be difficult.
　ＭｇＯは、熱処理により析出する高膨張結晶の構成成分である。ＭｇＯの含有量は５～４０％であり、好ましくは５～３９％、より好ましくは６～３８％である。ＭｇＯの含有量が少なすぎると、熱処理時に高膨張結晶が析出しにくくなり、耐熱性が低下しやすくなる。一方、ＭｇＯの含有量が多すぎると、ガラス化範囲が狭くなる傾向にあり、失透しやすくなる。また、流動性が低下しやすくなる。 MgO is a component of highly expanded crystals that are precipitated by heat treatment. The content of MgO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%. When the content of MgO is too small, it becomes difficult for high-expansion crystals to precipitate during heat treatment, and the heat resistance tends to decrease. On the other hand, when there is too much content of MgO, there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify. Moreover, fluidity tends to be lowered.
　ＣａＯ及びＳｒＯは流動性を向上させるための成分である。ＣａＯ＋ＳｒＯの含有量は０．１～３０％であり、好ましくは１～２５％、より好ましくは１～２０％である。ＣａＯ＋ＳｒＯの含有量が少なすぎると、接着に適した流動性が得にくくなる。一方、ＣａＯ＋ＳｒＯの含有量が多すぎると、熱処理によりＣａＯ・ＳｉＯ２、ＳｒＯ・ＳｉＯ２等の低膨張結晶が析出しやすくなり、高膨張特性が得られにくくなる。なお、ＣａＯ、ＳｒＯの含有量はそれぞれ、好ましくは０～３０％、より好ましくは１～２５％、さらに好ましくは１～２０％である。なかでもＣａＯは、熱処理により析出する高膨張結晶の一種である４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３の構成成分であり、流動性を向上させる効果が特に大きいという点で好ましい。さらに、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３を積極的に析出するためには、ＣａＯの含有量がＭｇＯの含有量より多いことが好ましい。具体的には、ＣａＯの含有量は６％以上、８％以上、特に１０％以上であることが好ましい。 CaO and SrO are components for improving fluidity. The content of CaO + SrO is 0.1-30%, preferably 1-25%, more preferably 1-20%. When there is too little content of CaO + SrO, it will become difficult to obtain the fluidity | liquidity suitable for adhesion | attachment. On the other hand, if the content of CaO + SrO is too large, low-expansion crystals such as CaO.SiO 2 and SrO.SiO 2 are likely to be precipitated by heat treatment, and high expansion characteristics are difficult to obtain. The contents of CaO and SrO are each preferably 0 to 30%, more preferably 1 to 25%, and still more preferably 1 to 20%. Among these, CaO is a constituent component of 4CaO.6SiO 2 .3La 2 O 3 , which is a kind of highly expanded crystal that is precipitated by heat treatment, and is preferable in that the effect of improving fluidity is particularly great. Furthermore, in order to actively precipitate 4CaO.6SiO 2 .3La 2 O 3 , the content of CaO is preferably larger than the content of MgO. Specifically, the CaO content is preferably 6% or more, 8% or more, and particularly preferably 10% or more.
　ＢａＯは、熱処理により析出する高膨張結晶の構成成分である。ＢａＯの含有量は５～４０％であり、好ましくは５～３９％、より好ましくは６～３８％である。ＢａＯの含有量が少なすぎると、熱処理時に高膨張結晶が析出しにくくなり、耐熱性が低下しやすくなる。一方、ＢａＯの含有量が多すぎると、ガラス化範囲が狭くなる傾向にあり、失透しやすくなる。また、流動性が低下しやすくなる。 BaO is a constituent component of a highly expanded crystal that is precipitated by heat treatment. The content of BaO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%. When there is too little content of BaO, it will become difficult to precipitate a highly expanded crystal | crystallization at the time of heat processing, and heat resistance will fall easily. On the other hand, when there is too much content of BaO, there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify. Moreover, fluidity tends to be lowered.
　ＺｎＯは、熱処理により析出する高膨張結晶の構成成分である。ＺｎＯの含有量は５～４０％であり、好ましくは５～３９％、より好ましくは６～３８％である。ＺｎＯの含有量が少なすぎると、熱処理時に高膨張結晶が析出しにくくなり、耐熱性が低下しやすくなる。一方、ＺｎＯの含有量が多すぎるとガラス化範囲が狭くなる傾向にあり、失透しやすくなる。 ZnO is a constituent component of a highly expanded crystal that is precipitated by heat treatment. The content of ZnO is 5 to 40%, preferably 5 to 39%, more preferably 6 to 38%. When the content of ZnO is too small, it becomes difficult for highly expanded crystals to precipitate during the heat treatment, and the heat resistance tends to decrease. On the other hand, when there is too much content of ZnO, the vitrification range tends to become narrow, and devitrification tends to occur.
　ＴｉＯ２及びＺｒＯ２は、残留ガラスの軟化点を高め、耐熱性を向上させる成分である。また、流動性を向上させる成分でもある。ＴｉＯ２＋ＺｒＯ２の含有量は０．１～１０％であり、好ましくは０．１～８％、より好ましくは０．５～６％である。ＴｉＯ２＋ＺｒＯ２の含有量が少なすぎると、残留ガラスの軟化点が低下し、耐熱性が低下しやすくなる。また、流動性が低下しやすくなる。一方、ＴｉＯ２＋ＺｒＯ２の含有量が多すぎると溶融時に失透しやすくなる。また、流動性が低下しやすくなる。なお、ＴｉＯ２、ＺｒＯ２の含有量はそれぞれ、好ましくは０～１０％、より好ましくは０．１～８％、さらに好ましくは０．５～６％である。 TiO 2 and ZrO 2 are components that increase the softening point of the residual glass and improve heat resistance. It is also a component that improves fluidity. The content of TiO 2 + ZrO 2 is 0.1 to 10%, preferably 0.1 to 8%, more preferably 0.5 to 6%. When the content of TiO 2 + ZrO 2 is too small, the softening point of the residual glass is lowered, the heat resistance tends to lower. Moreover, fluidity tends to be lowered. On the other hand, it tends to be devitrified when melted and the content of TiO 2 + ZrO 2 is too high. Moreover, fluidity tends to be lowered. The contents of TiO 2 and ZrO 2 are each preferably 0 to 10%, more preferably 0.1 to 8%, and still more preferably 0.5 to 6%.
　Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋ、Ｃｓから選択される少なくとも一種）は、ガラス化範囲を拡げてガラス化しやすくする成分である。Ｒ２Ｏの含有量は、０～５％であり、好ましくは０～３％、より好ましくは０～１％である。Ｒ２Ｏの含有量が多すぎると、燃料電池の構成部材の接着材料として使用した場合に、高温下の使用でＲ２Ｏが揮発し、発電特性が劣化しやすくなる。なお、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｃｓ２Ｏの含有量はそれぞれ、好ましくは０～５％、より好ましくは０～３％、さらに好ましくは０～１％である。 R 2 O (R is at least one selected from Li, Na, K, and Cs) is a component that widens the vitrification range and facilitates vitrification. The content of R 2 O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. When the content of R 2 O is too large, when it is used as an adhesive material for a constituent member of a fuel cell, R 2 O volatilizes when used at a high temperature, and power generation characteristics are likely to deteriorate. The contents of Li 2 O, Na 2 O, K 2 O, and Cs 2 O are each preferably 0 to 5%, more preferably 0 to 3%, and still more preferably 0 to 1%.
　Ｂ２Ｏ３は流動性を向上させるための成分である。Ｂ２Ｏ３の含有量は０～５％であり、好ましくは０～４％、より好ましくは０～３％である。Ｂ２Ｏ３の含有量が多すぎると、耐水性や耐熱性が低下しやすくなる。また、燃料電池の構成部材の接着材料として使用した場合に、高温下の使用でＢ２Ｏ３が揮発し、発電特性が劣化しやすくなる。 B 2 O 3 is a component for improving fluidity. The content of B 2 O 3 is 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%. If the B 2 O 3 content is too large, water resistance and heat resistance tends to decrease. Further, when used as an adhesive material for constituent members of a fuel cell, B 2 O 3 volatilizes when used at a high temperature, and the power generation characteristics tend to deteriorate.
　Ａｌ２Ｏ３は粘性を調整するための成分である。Ａｌ２Ｏ３の含有量は０～２％未満であり、好ましくは０～１．５％、より好ましくは０～１％である。Ａｌ２Ｏ３の含有量が多すぎると、熱処理により２ＳｉＯ２・Ａｌ２Ｏ３・ＢａＯ等の低膨張結晶が析出しやすくなり、高膨張特性が得られにくくなる。 Al 2 O 3 is a component for adjusting the viscosity. The content of Al 2 O 3 is 0 to less than 2%, preferably 0 to 1.5%, more preferably 0 to 1%. When the content of Al 2 O 3 is too large, heat treatment by 2SiO 2 · Al 2 O 3 · becomes low expansion crystal BaO or the like is likely to precipitate, hardly high expansion characteristics.
　Ｌａ２Ｏ３は熱処理により析出する高膨張結晶の構成成分であり、流動性を向上させるための成分でもある。また、ガラス化範囲を拡げてガラス化しやすくする成分である。Ｌａ２Ｏ３の含有量は０～１５％であり、好ましくは０～１４％、より好ましくは０．１～１３％である。Ｌａ２Ｏ３の含有量が多すぎると、溶融中や熱処理時に失透しやすくなり、接着に適した流動性が得られにくくなる。 La 2 O 3 is a constituent component of the high expansion crystal precipitated by heat treatment, and is also a component for improving fluidity. Moreover, it is a component which expands the vitrification range and facilitates vitrification. The content of La 2 O 3 is 0 to 15%, preferably 0 to 14%, more preferably 0.1 to 13%. When the content of La 2 O 3 is too large, easily devitrified when melted or during the heat treatment, the fluidity becomes difficult to obtain suitable adhesion.
　本発明の結晶性ガラス組成物は、上記以外の成分としてＹ２Ｏ３、Ｇｄ２Ｏ３、Ｎｂ２Ｏ５、Ｔａ２Ｏ５、ＳｎＯ２、ＷＯ３等をそれぞれ２％まで含有させることができる。ただし、Ｐ２Ｏ５及びＢｉ２Ｏ３は熱処理により揮発しやすく、ＳＯＦＣ構成部材の電気絶縁性を低下させる等、発電特性に悪影響を与えるおそれがあるため、実質的に含有しないことが好ましい。 The crystalline glass composition of the present invention may contain up to 2% of Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , SnO 2 , WO 3 and the like as components other than the above. it can. However, P 2 O 5 and Bi 2 O 3 are preferably not substantially contained because they tend to volatilize by heat treatment and may adversely affect the power generation characteristics such as lowering the electrical insulation properties of the SOFC constituent members.
　以上のような組成を有する結晶性ガラス組成物は、熱処理すると高膨張結晶を析出する性質を有する。高膨張結晶としては、ＭｇＯ・ＳｉＯ２、ＢａＯ・２ＭｇＯ・２ＳｉＯ２、２ＳｉＯ２・２ＺｎＯ・ＢａＯ、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３及びＭｇＯ・ＣａＯ・２ＳｉＯ２から選択される少なくとも一種が挙げられる。熱処理後の結晶性ガラス組成物の３０～７００℃の温度範囲における熱膨張係数は、７０×１０－７／℃以上、特に８０×１０－７／℃以上であることが好ましい。上限は特に限定されないが、現実的には１５０×１０－７／℃以下である。なお、本発明の結晶性ガラス組成物は、熱処理後に高い結晶化度が得られやすい。また、析出する結晶は融点が高く、再度熱処理を行っても流動しにくいため、長期に亘って耐熱性を維持することができる。 The crystalline glass composition having the above composition has the property of precipitating highly expanded crystals upon heat treatment. As the high expansion crystal include at least one selected MgO · SiO 2, BaO · 2MgO · 2SiO 2, 2SiO 2 · 2ZnO · BaO, from 4CaO · 6SiO 2 · 3La 2 O 3 and MgO · CaO · 2SiO 2 . The thermal expansion coefficient of the crystalline glass composition after heat treatment in the temperature range of 30 to 700 ° C. is preferably 70 × 10 −7 / ° C. or more, particularly preferably 80 × 10 −7 / ° C. or more. The upper limit is not particularly limited, but is practically 150 × 10 −7 / ° C. or less. Note that the crystalline glass composition of the present invention tends to have a high crystallinity after heat treatment. In addition, precipitated crystals have a high melting point and are difficult to flow even when heat-treated again, so that heat resistance can be maintained over a long period of time.
　ちなみに、熱処理時に４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３が析出すると、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３が結晶核となり他の高膨張結晶の析出を促進するため、結晶性ガラス組成物が熱処理後に高い結晶化度を有しやすくなる。 Incidentally, when 4CaO · 6SiO 2 · 3La 2 O 3 is deposited during the heat treatment, since the 4CaO · 6SiO 2 · 3La 2 O 3 to promote the precipitation of other high expansion crystal becomes crystal nuclei, crystalline glass composition after heat treatment It tends to have a high crystallinity.
　本発明の結晶性ガラス組成物は、流動性、熱膨張係数の調整のために、マグネシア（ＭｇＯ）、亜鉛華（ＺｎＯ）、ジルコニア（ＺｒＯ２）、チタニア（ＴｉＯ２）、アルミナ（Ａｌ２Ｏ３）等の粉末をフィラー粉末として添加して用いても良い。フィラー粉末の添加量は、結晶性ガラス組成物１００質量部に対して０～１０質量部、０．１～９質量部、特に１～８質量部であることが好ましい。フィラー粉末の添加量が多すぎると、流動性が低下しやすくなる。なおフィラー粉末の粒径はｄ５０で０．２～２０μｍ程度のものを使用することが好ましい。 The crystalline glass composition of the present invention is prepared by adjusting magnesia (MgO), zinc white (ZnO), zirconia (ZrO 2 ), titania (TiO 2 ), alumina (Al 2 O) in order to adjust fluidity and thermal expansion coefficient. You may add and use powders, such as 3 ), as a filler powder. The addition amount of the filler powder is preferably 0 to 10 parts by mass, 0.1 to 9 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the crystalline glass composition. When there is too much addition amount of filler powder, fluidity | liquidity will fall easily. It is preferable to use a filler powder having a d50 particle size of about 0.2 to 20 μm.
　次に本発明の結晶性ガラス組成物の製造方法、及び本発明の結晶性ガラス組成物を接着材料として使用する方法の一例について説明する。 Next, an example of a method for producing the crystalline glass composition of the present invention and a method of using the crystalline glass composition of the present invention as an adhesive material will be described.
　まず、上記組成を有するように調合した原料を１４００～１６００℃で０．５～２時間程度、均質なガラスが得られるまで溶融する。次いで、溶融ガラスをフィルム状等に成形した後、粉砕し、分級することにより本発明の結晶性ガラス組成物からなるガラス粉末を作製する。なお、ガラス粉末の粒径（ｄ５０）は２～２０μｍ程度であることが好ましい。必要に応じて、ガラス粉末に各種フィラー粉末を添加する。 First, the raw materials prepared to have the above composition are melted at 1400-1600 ° C. for about 0.5-2 hours until a homogeneous glass is obtained. Next, the molten glass is formed into a film or the like, and then pulverized and classified to produce a glass powder made of the crystalline glass composition of the present invention. The particle size (d50) of the glass powder is preferably about 2 to 20 μm. Various filler powders are added to the glass powder as necessary.
　次いで、ガラス粉末（あるいは、ガラス粉末とフィラー粉末との混合粉末）にビークルを添加して混練することによりガラスペーストを調製する。ビークルは例えば有機溶剤、樹脂の他、可塑剤、分散剤等を含有する。 Next, a glass paste is prepared by adding a vehicle to glass powder (or a mixed powder of glass powder and filler powder) and kneading. The vehicle contains, for example, a plasticizer, a dispersant and the like in addition to an organic solvent and a resin.
　有機溶剤はガラス粉末をペースト化するための材料であり、例えばターピネオール（Ｔｅｒ）、ジエチレングリコールモノブチルエーテル（ＢＣ）、ジエチレングリコールモノブチルエーテルアセテート（ＢＣＡ）、２，２，４－トリメチル－１，３－ペンタジオールモノイソブチレート、ジヒドロターピネオール等を単独または混合して使用することができる。その含有量は１０～４０質量％であることが好ましい。 The organic solvent is a material for pasting glass powder. For example, terpineol (Ter), diethylene glycol monobutyl ether (BC), diethylene glycol monobutyl ether acetate (BCA), 2,2,4-trimethyl-1,3-pentadiol Monoisobutyrate, dihydroterpineol and the like can be used alone or in combination. The content is preferably 10 to 40% by mass.
　樹脂は、乾燥後の膜強度を高め、また柔軟性を付与する成分であり、その含有量は、０．１～２０質量％程度が一般的である。樹脂は熱可塑性樹脂、具体的にはポリブチルメタアクリレート、ポリビニルブチラール、ポリメチルメタアクリレート、ポリエチルメタアクリレート、エチルセルロース等が使用可能であり、これらを単独あるいは混合して使用する。 Resin is a component that increases the film strength after drying and imparts flexibility, and its content is generally about 0.1 to 20% by mass. As the resin, a thermoplastic resin, specifically, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like can be used, and these are used alone or in combination.
　可塑剤は、乾燥速度をコントロールするとともに、乾燥膜に柔軟性を与える成分であり、その含有量は０～１０質量％程度が一般的である。可塑剤としてはブチルベンジルフタレート、ジオクチルフタレート、ジイソオクチルフタレート、ジカプリルフタレート、ジブチルフタレート等が使用可能であり、これらを単独あるいは混合して使用する。 The plasticizer is a component that controls the drying speed and imparts flexibility to the dried film, and the content thereof is generally about 0 to 10% by mass. As the plasticizer, butylbenzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, dibutyl phthalate and the like can be used, and these are used alone or in combination.
　分散剤としては、イオン系またはノニオン系の分散剤が使用可能であり、イオン系としてはカルボン酸、ジカルボン酸系等のポリカルボン酸系、アミン系等の分散剤、ノニオン系としてはポリエステル縮合型や多価アルコールエーテル型の分散剤が使用可能である。その使用量としては０～５質量％が一般的である。 As the dispersant, an ionic or nonionic dispersant can be used. As the ionic type, a carboxylic acid, a dicarboxylic acid type polycarboxylic acid type, an amine type dispersant, and the nonionic type as a polyester condensation type. Alternatively, a polyhydric alcohol ether type dispersant can be used. The amount used is generally 0 to 5% by mass.
　次いで、ペーストを金属やセラミックからなる第一の部材の接着箇所に塗布し、乾燥させる。さらに金属やセラミックからなる第二の部材をペースト乾燥膜に接触させた状態で固定して８００～１０５０℃で熱処理する。この熱処理により、ガラス粉末が一旦軟化流動して第一及び第二の部材を固着するとともに、結晶が析出する。このようにして、第一の部材及び第二の部材が本発明の結晶性ガラス組成物からなる封止部により接着してなる接合体を得ることができる。 Next, the paste is applied to the bonding portion of the first member made of metal or ceramic and dried. Further, the second member made of metal or ceramic is fixed in a state where it is in contact with the dry paste film, and heat treated at 800 to 1050 ° C. By this heat treatment, the glass powder once softens and flows to fix the first and second members, and crystals precipitate. In this manner, a joined body can be obtained in which the first member and the second member are bonded by the sealing portion made of the crystalline glass composition of the present invention.
　本発明の結晶性ガラス組成物は、接着以外にも被覆、充填等の目的で使用できる。またペースト以外の形態、具体的には粉末、グリーンシート、タブレット等の状態で使用することができる。例えば、金属やセラミックスからなる円筒内にリード線とともにガラス粉末を充填して熱処理し、気密封止を行う形態が挙げられる。またグリーンシート成形されたプリフォームや、粉末プレス成型により作製されたタブレット等を金属やセラミックからなる部材上に載置し、熱処理して軟化流動させることで被覆することもできる。 The crystalline glass composition of the present invention can be used for purposes such as coating and filling in addition to adhesion. Further, it can be used in a form other than paste, specifically in the form of powder, green sheet, tablet or the like. For example, the form which fills glass powder with a lead wire in the cylinder which consists of metal or ceramics, heat-processes, and performs airtight sealing is mentioned. Further, a green sheet molded preform, a tablet produced by powder press molding, or the like is placed on a member made of metal or ceramic, and can be coated by heat treatment and softening and flowing.
　以下に、本発明の結晶性ガラス組成物を実施例に基づいて説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the crystalline glass composition of the present invention will be described based on examples, but the present invention is not limited to these examples.
　表１及び２は、本発明の実施例（試料Ｎｏ．１～１２）及び比較例（試料Ｎｏ．１３、１４）を示している。 Tables 1 and 2 show examples (samples Nos. 1 to 12) and comparative examples (samples Nos. 13 and 14) of the present invention.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　各試料は次のようにして作製した。 Each sample was prepared as follows.
　表中の各組成になるように調合した原料を１４００～１６００℃で約２時間溶融した後、一対のローラー間に流し出してフィルム状に成形した。得られたフィルム状成形物をボールミルにて粉砕し、分級して、粒度（ｄ５０）が約１０μｍの試料（結晶性ガラス組成物粉末）を得た。 The raw materials prepared so as to have the respective compositions shown in the table were melted at 1400-1600 ° C. for about 2 hours, and then poured out between a pair of rollers to form a film. The obtained film-like molded product was pulverized with a ball mill and classified to obtain a sample (crystalline glass composition powder) having a particle size (d50) of about 10 μm.
　各試料について、熱膨張係数、軟化点、結晶化温度、結晶融点、析出結晶、流動性について、測定または評価した。結果を表１及び２に示す。 For each sample, the thermal expansion coefficient, softening point, crystallization temperature, crystal melting point, precipitated crystal, and fluidity were measured or evaluated. The results are shown in Tables 1 and 2.
　表から明らかなように、実施例であるＮｏ．１～１２の試料は、熱処理時の流動性に優れていた。また、熱処理により高膨張結晶が析出したため、熱膨張係数が７８～１１３×１０－７／℃と高かった。さらに、析出結晶の融点が高く、耐熱性にも優れていることが分かった。 As is apparent from the table, Examples No. Samples 1 to 12 were excellent in fluidity during heat treatment. Further, since the high expansion crystal was precipitated by the heat treatment, the thermal expansion coefficient was as high as 78 to 113 × 10 −7 / ° C. Furthermore, it was found that the melting point of the precipitated crystals is high and the heat resistance is also excellent.
　一方、比較例であるＮｏ．１３の試料は、熱処理時の流動性に劣っていた。Ｎｏ．１４の試料は熱処理により結晶が析出しなかったため、熱膨張係数が５８×１０－７／℃と低かった。 On the other hand, No. which is a comparative example. Sample 13 was inferior in fluidity during heat treatment. No. In the sample No. 14, no crystal was precipitated by the heat treatment, so the thermal expansion coefficient was as low as 58 × 10 −7 / ° C.
　なお、各特性の測定及び評価は以下のようにして行った。 In addition, measurement and evaluation of each characteristic were performed as follows.
　熱膨張係数は、各ガラス粉末試料をプレス成形し、１０００～１１００℃で３時間熱処理した後、直径４ｍｍ、長さ２０ｍｍの円柱状に研磨加工して得られた測定用試料を用いて、ＪＩＳ　Ｒ３１０２に基づき、３０～７００℃の温度範囲における値を求めた。 The coefficient of thermal expansion was determined by JIS using a measurement sample obtained by press-molding each glass powder sample, heat-treating it at 1000-1100 ° C. for 3 hours, and polishing it into a cylindrical shape having a diameter of 4 mm and a length of 20 mm. Based on R3102, a value in a temperature range of 30 to 700 ° C. was obtained.
　軟化点、結晶化温度、結晶融点はマクロ型示差熱分析計を用いて測定した。具体的には、各ガラス粉末試料につき、マクロ型示差熱分析計を用いて１０５０℃まで測定して得られたチャートにおいて、第四の変曲点の値を軟化点、強い発熱ピークを結晶化温度、結晶化後に得られた吸熱ピークを結晶融点とした。なお、結晶融点が高いほど、または、結晶融点が確認されなければ、高温下においても結晶が安定に存在していることを意味し、耐熱性が高いと判断することができる。 Softening point, crystallization temperature, and crystal melting point were measured using a macro-type differential thermal analyzer. Specifically, for each glass powder sample, in the chart obtained by measuring up to 1050 ° C. using a macro-type differential thermal analyzer, the fourth inflection point value is the softening point and the strong exothermic peak is crystallized. The endothermic peak obtained after temperature and crystallization was defined as the crystalline melting point. Note that the higher the crystal melting point or if the crystal melting point is not confirmed, it means that the crystal exists stably even at a high temperature, and it can be determined that the heat resistance is high.
　流動性は次のようにして評価した。比重分のガラス粉末試料を直径２０ｍｍの金型に入れてプレス成形した後に、ＳＵＳ４３０板上で９００～１１００℃にて１５分間熱処理した。熱処理後の成形体の流動径が１８ｍｍ以上であるものを「◎」、１６ｍｍ以上、１８ｍｍ未満のものを「○」、１６ｍｍ未満のものを「×」として評価した。 The fluidity was evaluated as follows. A glass powder sample having a specific gravity was put into a mold having a diameter of 20 mm, press-molded, and then heat-treated at 900 to 1100 ° C. for 15 minutes on a SUS430 plate. The molded product after the heat treatment having a flow diameter of 18 mm or more was evaluated as “◎”, 16 mm or more and less than 18 mm as “◯”, and less than 16 mm as “x”.
　析出結晶は、ガラス粉末試料についてＸＲＤ測定を行い、ＪＣＰＤＳカードとの対比にて同定した。このとき同定された析出結晶種としてＭｇＯ・ＳｉＯ２を「Ａ」、ＢａＯ・２ＭｇＯ・２ＳｉＯ２を「Ｂ」、２ＳｉＯ２・２ＺｎＯ・ＢａＯを「Ｃ」、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３を「Ｄ」、ＭｇＯ・ＣａＯ・２ＳｉＯ２を「Ｅ」として表中に示した。 The precipitated crystal was identified by performing XRD measurement on a glass powder sample and comparing with a JCPDS card. At this time, MgO · SiO 2 was identified as “A”, BaO · 2MgO · 2SiO 2 as “B”, 2SiO 2 · 2ZnO · BaO as “C”, and 4CaO · 6SiO 2 · 3La 2 O 3 as the identified crystal seeds. "D", showed the MgO · CaO · 2SiO 2 in the table as "E".
　本発明の結晶性ガラス組成物は、ＳＵＳやＦｅといった金属、フェライトやジルコニアといった高膨張セラミックスの接着材料として好適である。特に、ＳＯＦＣを作製する際に使用される支持体基板や、電極の部材等を気密封止するための接着材料として好適である。また、本発明の結晶性ガラス組成物は、接着用途以外にも被覆、充填等の目的で使用できる。具体的には、サーミスタ、ハイブリッドＩＣ等の用途に使用することができる。 The crystalline glass composition of the present invention is suitable as an adhesive material for metals such as SUS and Fe, and high expansion ceramics such as ferrite and zirconia. In particular, it is suitable as an adhesive material for hermetically sealing a support substrate, an electrode member, and the like used in manufacturing an SOFC. Moreover, the crystalline glass composition of the present invention can be used for purposes such as coating and filling in addition to adhesive applications. Specifically, it can be used for applications such as thermistors and hybrid ICs.
１　電解質
２　アノード
３　カソード
４　第一の支持体基板
４ａ　燃料チャネル４ａ
５　第二の支持体基板
５ａ　空気チャネル５ａ DESCRIPTION OF SYMBOLS 1 Electrolyte 2 Anode 3 Cathode 4 First support substrate 4a Fuel channel 4a
5 Second support substrate 5a Air channel 5a

Claims (5)

  1. 　モル％で、ＳｉＯ２　４５～７０％、ＭｇＯ　５～４０％、ＣａＯ＋ＳｒＯ　０．１～３０％、ＢａＯ　５～４０％、ＺｎＯ　５～４０％、ＴｉＯ２＋ＺｒＯ２　０．１～１０％、Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋ、Ｃｓから選択される少なくとも一種）　０～５％、Ｂ２Ｏ３　０～５％、Ａｌ２Ｏ３　０～２％未満、Ｌａ２Ｏ３　０～１５％を含有することを特徴とする結晶性ガラス組成物。 In mol%, SiO 2 45-70%, MgO 5-40%, CaO + SrO 0.1-30%, BaO 5-40%, ZnO 5-40%, TiO 2 + ZrO 2 0.1-10%, R 2 O (R is at least one selected from Li, Na, K, and Cs) 0 to 5%, B 2 O 3 0 to 5%, Al 2 O 3 0 to less than 2%, La 2 O 3 0 to 15% A crystalline glass composition comprising:
  2. 　Ｐ２Ｏ５及びＢｉ２Ｏ３を実質的に含有しないことを特徴とする請求項１に記載の結晶性ガラス組成物。 The crystalline glass composition according to claim 1, which is substantially free of P 2 O 5 and Bi 2 O 3 .
  3. 　熱処理により、ＭｇＯ・ＳｉＯ２、ＢａＯ・２ＭｇＯ・２ＳｉＯ２、２ＳｉＯ２・２ＺｎＯ・ＢａＯ、４ＣａＯ・６ＳｉＯ２・３Ｌａ２Ｏ３及びＭｇＯ・ＣａＯ・２ＳｉＯ２から選択される少なくとも一種の結晶を析出することを特徴とする請求項１または２に記載の結晶性ガラス組成物。 By heat treatment, to precipitate at least one crystal selected MgO · SiO 2, BaO · 2MgO · 2SiO 2, 2SiO 2 · 2ZnO · BaO, from 4CaO · 6SiO 2 · 3La 2 O 3 and MgO · CaO · 2SiO 2 The crystalline glass composition according to claim 1, wherein:
  4. 　３０～７００℃の温度範囲における熱膨張係数が７０×１０－７／℃以上であることを特徴とする請求項１～３のいずれか一項に記載の結晶性ガラス組成物。 The crystalline glass composition according to any one of claims 1 to 3, wherein a thermal expansion coefficient in a temperature range of 30 to 700 ° C is 70 × 10 -7 / ° C or more.
  5. 　接着用であることを特徴とする請求項１～４のいずれか一項に記載の結晶性ガラス組成物。 The crystalline glass composition according to any one of claims 1 to 4, which is used for adhesion.
PCT/JP2018/009606 2017-04-13 2018-03-13 Crystalline glass composition WO2018190056A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012162445A (en) * 2011-01-18 2012-08-30 Nippon Electric Glass Co Ltd High-expansive crystalline glass composition
JP2013056795A (en) * 2011-09-08 2013-03-28 Nippon Electric Glass Co Ltd Crystalline glass composition and adhesive material using the same
WO2014103973A1 (en) * 2012-12-25 2014-07-03 日本山村硝子株式会社 Glass composition for sealing
JP2014231469A (en) * 2013-05-28 2014-12-11 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ Vitreous or at least partially crystalline joining material and uses of the same
WO2015046195A1 (en) * 2013-09-30 2015-04-02 日本山村硝子株式会社 Glass composition for sealing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012162445A (en) * 2011-01-18 2012-08-30 Nippon Electric Glass Co Ltd High-expansive crystalline glass composition
JP2013056795A (en) * 2011-09-08 2013-03-28 Nippon Electric Glass Co Ltd Crystalline glass composition and adhesive material using the same
WO2014103973A1 (en) * 2012-12-25 2014-07-03 日本山村硝子株式会社 Glass composition for sealing
JP2014231469A (en) * 2013-05-28 2014-12-11 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ Vitreous or at least partially crystalline joining material and uses of the same
WO2015046195A1 (en) * 2013-09-30 2015-04-02 日本山村硝子株式会社 Glass composition for sealing

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