JP2012162445A - High-expansive crystalline glass composition - Google Patents

High-expansive crystalline glass composition Download PDF

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JP2012162445A
JP2012162445A JP2011267549A JP2011267549A JP2012162445A JP 2012162445 A JP2012162445 A JP 2012162445A JP 2011267549 A JP2011267549 A JP 2011267549A JP 2011267549 A JP2011267549 A JP 2011267549A JP 2012162445 A JP2012162445 A JP 2012162445A
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glass composition
glass
expansion
mgo
crystalline glass
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JP5928777B2 (en
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Shoji Shibata
昭治 柴田
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Nippon Electric Glass Co Ltd
日本電気硝子株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

PROBLEM TO BE SOLVED: To exhibit fluidity suitable for sealing and a high coefficient of thermal expansion after heat treatment, and even when exposed to a high temperature for a long period of time, the hermeticity and adhesiveness of the bonded portion are reduced, and the glass component is volatilized. It is an object of the present invention to provide a material having stable heat resistance, in which the power generation characteristics of the fuel cell are hardly deteriorated by the above.
A high expansion crystallizable glass composition of the present invention, in mol%, SiO 2 of less than 30 super ~50%, 10~50% MgO, BaO 5~40%, CaO 0~20%, SrO 0~ 10%, B 2 O 3 0~15 %, 0~15% ZnO, Al 2 O 3 0~6%, ZrO 2 0~3%, characterized by comprising the SnO 2 0 to 3%.
[Selection] Figure 1

Description

  The present invention relates to a high expansion crystalline glass composition, and more specifically to a high expansion crystalline glass composition used for the purpose of bonding metals such as SUS and Fe, and high expansion ceramics such as ferrite and zirconia. .

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 differs depending on what is used for the electrolyte, but those used in industrial applications include phosphoric acid type (PAFC), molten carbonate type (MCFC), solid oxide type (SOFC), and solid polymer type. There are four types (PEFC). Among them, the solid oxide fuel cell (SOFC) has the characteristics that the internal resistance of the cell is small, so that the power generation efficiency is the highest among the fuel cells, and it is not necessary to use a precious metal for the catalyst, so that the manufacturing cost can be suppressed. The system is applicable to a wide range of applications from small-scale applications such as home use to large-scale applications such as a power plant.

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 fuel gas passage (fuel channel 4a) is formed, and a first support substrate 4 in contact with the anode, and an air passage (air channel 5a) is formed and a second support substrate 5 in contact with the cathode are formed. Fixed to the top and bottom of the cell. The first support substrate 4 and the second support substrate 5 are fixed to the cells so that the gas passages are orthogonal to each other. The support substrates 4 and 5 are made of metal such as SUS.

The flat plate-type SOFC having the above structure allows various gases such as hydrogen (H 2 ), city gas, natural gas, biogas, and liquid fuel to flow through the fuel channel 4a of the first support substrate 4 at the same time. Air or oxygen (O 2 ) is allowed to flow through the air channel 5 a of the support substrate 5. At this time, 1 / 2O 2 + 2e → O 2− at the cathode.
The reaction of H 2 + O 2 − → H 2 O + 2e occurs at the anode.
Reaction occurs. By this electrochemical, chemical energy can be directly converted into electric energy to generate electricity. In order to obtain a high output, an actual flat-plate SOFC has a number of layers of the structure shown in FIG.

WO2009-0117173 JP 2006-56769 A Japanese Patent Laid-Open No. 2004-43297

  In producing the structure, an airtight seal between the support substrates, an adhesion between the solid electrolyte and the support substrate, or an airtight seal between the solid electrolytes is required. In the case of SOFC, it is necessary to hermetically seal each constituent member so that the gas flowing to the anode side and the cathode side does not mix.

  For that purpose, a method of hermetically sealing by sandwiching an inorganic sheet-shaped gasket such as mica, vermiculite, alumina, etc. has been proposed, but a small amount of gas leak occurs because it is only bonded and not bonded. However, a decrease in fuel use efficiency is a problem. Therefore, fusion bonding with a glass material has been studied.

  By the way, in the case of an adhesive material made of a glass material, a high expansion material such as metal or ceramic is bonded to each other, and therefore, it is necessary to have a thermal expansion coefficient adapted to these materials. Further, SOFC has a high temperature range (operation temperature range) where an electrochemical reaction occurs (600 to 800 ° C.), and is operated at this temperature for a long period of time. Therefore, even if glass materials are exposed to high temperatures for a long period of time, they have high heat resistance so that the airtightness and adhesiveness are not lowered due to melting of the bonded parts, and the power generation characteristics of the fuel cell are not deteriorated due to volatilization of glass components. Desired. Furthermore, since it is an adhesion between high expansion materials such as metals and ceramics, the fluidity and sealing properties of the glass at a moderate temperature rise rate are also required.

As a high-expansion glass material, as shown in Patent Document 1, a CaO—MgO—SiO 2 -based crystal is precipitated by heat treatment, and a SiO 2 —CaO—MgO-based crystalline glass composition having a high expansion coefficient is obtained. It is disclosed.

Patent Document 2 also discloses a SiO 2 —B 2 O 3 —SrO-based amorphous glass composition that has good denseness after sealing and provides stable gas sealing characteristics.

  Furthermore, Patent Document 3 discloses a crystalline glass composition containing a large amount of MgO having a high expansion coefficient by precipitation of MgO-based crystals upon heat treatment.

  However, the crystalline glass composition as disclosed in Patent Document 1 has a high glass viscosity at high temperature, so that a dense crystal cannot be obtained unless it is sealed at a high temperature for a long time. There is a problem that it is difficult to obtain a sealing property. In addition, the amorphous glass composition disclosed in Patent Document 2 does not precipitate crystals even after heat treatment, and the glass transition point is around 600 ° C. Under the environment, there is a problem that the bonded portion is melted, and the airtightness and adhesiveness of the bonded portion are easily lowered. Furthermore, when the crystalline glass composition disclosed in Patent Document 3 is exposed to a high temperature for a long period of time, the glass component tends to volatilize, and the power generation characteristics of the fuel cell may deteriorate due to the volatile component from the glass. was there.

  The object of the present invention is to exhibit fluidity suitable for sealing and a high coefficient of thermal expansion after heat treatment. It is an object of the present invention to provide a material having stable heat resistance, in which power generation characteristics of a fuel cell are hardly deteriorated due to volatilization of components.

  As a result of conducting various experiments, the present inventor has MgO and BaO, and by restricting the content of these components strictly, it has fluidity suitable for sealing at the time of sealing. It precipitates and shows a high thermal expansion coefficient, and also has high heat resistance, and proposes as this invention.

That is, high-expansion crystallizable glass composition of the present invention, in mol%, SiO 2 of less than 30 super ~50%, MgO 10~45%, BaO 5~40%, CaO 0~20%, SrO 0~10% , B 2 O 3 0-15%, ZnO 0-15%, Al 2 O 3 0-6%, ZrO 2 0-3%, SnO 2 0-3%.

  The high expansion crystalline glass composition of the present invention exhibits fluidity suitable for sealing and a high thermal expansion coefficient after heat treatment, and crystals are deposited even when exposed to a high temperature for a long period of time. The component is less likely to volatilize and high heat resistance can be obtained. Therefore, it is suitable as an adhesive material used for adhesion or coating of a high expansion material, particularly a fuel cell such as SOFC.

It is explanatory drawing which shows the basic structure of SOFC.

  The high expansion crystalline glass composition of the present invention contains 10 mol% or more of MgO and 5 mol% or more of BaO, which are components for precipitating crystals when heat-treated. Therefore, even if it is used at a high temperature for a long period of time, the bonded portion is difficult to melt, and it is possible to suppress a decrease in airtightness and adhesiveness of the bonded portion.

In addition, when the high-expansion crystalline glass composition of the present invention is heat-treated, MgO-based crystals having a high thermal expansion coefficient such as 2MgO · SiO 2 , BaO · 2MgO · 2SiO 2 , and 2MgO · B 2 O 3 tend to precipitate. . Therefore, it can be used for the purpose of adhesion or coating between high expansion materials such as metals and ceramics.

Furthermore, high-expansion crystallizable glass composition of the present invention, although improving the fluidity of the glass, also contain more volatile B 2 O 3 in the use of high temperature, the heat treatment, 2MgO · B 2 O 3 Since crystals precipitate, it is difficult for B 2 O 3 to volatilize, and stable power generation characteristics and high heat resistance can be obtained.

  In the present invention, “crystallinity” means the property of precipitating crystals from the glass matrix upon heat treatment.

  “Heat treatment” means heat treatment at a temperature of 800 ° C. or higher for 10 minutes or longer.

  The reason for limiting the glass composition as described above in the high expansion crystalline glass composition of the present invention will be described below.

SiO 2 is a component that widens the vitrification range to facilitate vitrification and improves the water resistance and heat resistance of the glass, and its content is more than 30 to less than 50%. When the content of SiO 2 is too small, vitrification range is too narrow, it becomes difficult to vitrify. On the other hand, if the content of SiO 2 is too large, crystals are difficult to precipitate even after heat treatment. Moreover, it becomes difficult to melt the glass. A preferable range of SiO 2 is 31 to 49%, and a more preferable range is 31 to 45%.

  MgO is a component for precipitating crystals by heat treatment, and its content is 10 to 45%. If the content of MgO is too small, the glass composition will not sufficiently crystallize even after heat treatment, and the heat resistance tends to decrease. On the other hand, when the content of MgO is too large, the vitrification range tends to be narrow, and it becomes difficult to obtain a homogeneous glass. A preferable range of MgO is 10 to 44%, and a more preferable range is 15 to 43%.

  BaO is a component for expanding the vitrification range, suppressing devitrification during melting and sealing, and obtaining fluidity suitable for sealing, and its content is 5 to 40%. When there is too little content of BaO, it will become easy to devitrify at the time of fusion | melting or sealing, and it will become difficult to obtain the fluidity | liquidity suitable for sealing. On the other hand, if the content of BaO is too large, the crystallinity is lowered, sufficient crystal precipitation is not obtained, and the heat resistance is likely to be lowered. A preferable range of BaO is 6 to 38%, and a more preferable range is 8 to 35%.

CaO is a component for increasing the thermal expansion coefficient, and its content is 0 to 20%. When the content of CaO is excessively large, the content of SiO 2 , MgO, and BaO is relatively decreased, so that it is difficult to obtain desired characteristics. The preferable range of CaO is 0 to 18%, and the more preferable range is 0 to 16%.

SrO is a component for increasing the thermal expansion coefficient, and its content is 0 to 10%. If the SrO content is too high, SrO.SiO 2 crystals are likely to precipitate, making it difficult to obtain highly expanded crystalline glass. A preferable range of SrO is 0 to 5%, and a more preferable range is 0 to 4%.

B 2 O 3 is a component for improving the fluidity of the glass, and its content is 0 to 15%. When B 2 O content of 3 is too large, 2MgO · B 2 O 3 crystals is hardly precipitated, by B 2 O 3 that has not been crystallized, water resistance and heat resistance or, at high temperatures decreases When used, B 2 O 3 volatilizes and power generation characteristics are likely to deteriorate. A preferable range of B 2 O 3 is 0 to 13%, and a more preferable range is 0 to 11%.

In the case of incorporating the B 2 O 3 is preferably made to be 2.0 or more MgO / B 2 O 3 molar ratio. By doing so, 2MgO · B 2 O 3 crystals are precipitated when used under a high temperature for a long period of time, and volatilization of B 2 O 3 is suppressed, so that stable power generation characteristics and high heat resistance are easily obtained. . A more preferable range of MgO / B 2 O 3 is 2.1 or more, and a more preferable range is 2.3 or more.

  ZnO is a component for widening the vitrification range to facilitate vitrification and lowering the softening point of the glass to enable adhesion at low temperature, and its content is 0 to 15%. If the ZnO content is too high, the heat resistance tends to decrease. The preferable range of ZnO is 0 to 13%, and the more preferable range is 0 to 11%.

Al 2 O 3 is a component for adjusting the viscosity of the glass, and its content is 0 to 6%. If the content of Al 2 O 3 is too large, 5SiO 2 .2Al 2 O 3 .2MgO crystals are likely to precipitate, making it difficult to obtain highly expanded crystalline glass. A preferable range of Al 2 O 3 is 0 to 5.5%, and a more preferable range is 0 to 5%.

ZrO 2 is a component for improving water resistance, and its content is 0 to 3%. When the content of ZrO 2 is too large, it becomes easy to devitrify during melting or sealing, and it becomes difficult to obtain fluidity suitable for sealing. A preferable range of ZrO 2 is 0 to 2.5%, and a more preferable range is 0 to 2%.

SnO 2 is a component for improving water resistance, and its content is 0 to 3%. When the content of ZrO 2 is too large, it becomes easy to devitrify during melting or sealing, and it becomes difficult to obtain fluidity suitable for sealing. A preferable range of SnO 2 is 0 to 2.5%, and a more preferable range is 0 to 2%.

Moreover, the high expansion crystalline glass composition of the present invention may add up to 2 mol% of TiO 2 , La 2 O 3 , Y 2 O 3 or the like as components other than those described above. However, it is preferable to avoid the substantial introduction of R 2 O (R represents an alkali metal) and P 2 O 5 that easily deteriorate electrical insulation or volatilize when used at high temperatures.

  In the present invention, “substantial introduction is avoided” refers to a level that is not actively used as a raw material but mixed as an impurity, and specifically, that the content is 0.1 mol% or less. means.

The crystalline glass composition having the above composition precipitates 2MgO · SiO 2 , BaO · 2MgO · 2SiO 2 , 2MgO · B 2 O 3 crystals upon heat treatment, and is 90 × in a temperature range of 30 to 700 ° C. The coefficient of thermal expansion is 10 −7 / ° C. or higher. Further, after the heat treatment, high crystallinity is obtained, so that the heat resistance is high, and even when the heat treatment is performed again, it does not flow. Thereby, heat resistance can be maintained over a long period of time.

Incidentally glass powder material formed of the above glass compositions, for the adjustment of the fluidity, which is part of magnesium phosphate precipitated crystals (3MgO · P 2 O 5) and magnesia (MgO), zinc oxide (ZnO), Powders such as zirconia (ZrO 2 ), titania (TiO 2 ), and alumina (Al 2 O 3 ) may be added as filler powders up to 10 parts by weight, preferably up to 8 parts by weight with respect to 100 parts by weight of the glass powder. . The reason why the addition amount is limited to the above range is that when the amount is more than 10 parts by weight, the decrease in fluidity becomes too large. In addition, it is preferable to use a filler powder having a d50 particle size of about 0.2 to 20 μm.

  Next, a method for using the high expansion crystalline glass composition of the present invention as an adhesive material will be described. In addition, the usage method of the glass composition of this invention is not restrict | limited to the following description.

  First, the glass raw material prepared so as to have the above composition is melted at 1400-1500 ° C. for 0.5-2 hours. Next, after the molten glass is formed into a film or the like, it is pulverized and classified to produce glass powder. In addition, it is preferable that the particle size (d50) of glass powder is about 2-20 micrometers.

  Further, various filler powders are added to the glass powder as necessary.

  Next, glass powder or a mixed powder of glass powder and filler powder is prepared into, for example, a glass paste. When used in a glass paste, it can contain a plasticizer, a dispersant and the like in addition to an organic solvent, a resin, and glass powder.

  The organic solvent is a material for pasting glass powder, such as terpineol (Ter), diethylene glycol monobutyl ether (BC), diethylene glycol monobutyl ether acetate (BCA), 2,2,4-trimethyl-1,3-pentadiol. Monoisobutyrate, dihydroterpineol, etc. can be used alone or in admixture. The content is preferably 10 to 40% by mass.

  The resin is a component that increases the film strength after drying and imparts flexibility, and the 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.

  The plasticizer is a component that controls the drying speed and imparts flexibility to the dry 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.

  As the dispersant, an ionic or nonionic dispersant can be used. As the ionic type, a carboxylic acid, a polycarboxylic acid type such as a dicarboxylic acid type, an amine type, etc., as a nonionic type, a polyester condensation type or A polyhydric alcohol ether type can be used. The amount used is 0 to 5% by mass.

  The paste can be produced by kneading the above materials at a predetermined ratio.

  Next, the paste is applied to the bonding location 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 900 ° C. By this heat treatment, the glass powder is once softened and fluidized to fix the first and second members. Crystal precipitation occurs when the glass powder flows to some extent.

  Since these crystals have a high melting point and a large amount of precipitation, it is possible to obtain an adhesive bonded body having high thermal stability of the material and excellent heat resistance.

  The highly expanded crystalline glass composition of the present invention can be used for purposes such as coating and filling in addition to adhesion. Moreover, it can be used in forms other than paste, specifically in a powdered state, a green sheet, a tablet, or the like. For example, the form which fills glass powder with a lead wire in the cylinder made from a metal or ceramics, heat-processes, and performs airtight sealing is mentioned. Moreover, a preform formed by green sheet molding, a tablet produced by powder press molding, or the like can be placed on a metal or ceramic member and coated by heat treatment.

  Hereinafter, the high expansion crystalline glass composition of the present invention will be described based on examples.

  Tables 1 and 2 show examples (sample Nos. 1 to 8) and comparative examples (samples No. 9 and 10) of the present invention.

  Each sample in the table was prepared as follows.

  The glass raw material prepared so as to have the composition in the table was melted at the temperature shown in the table for about 1 hour, and then formed into a film through a pair of rollers. Next, the obtained film-like molded product was pulverized with a ball mill and classified to obtain a sample having a particle size (d50) of about 10 μm.

  Next, for each sample, the presence / absence of devitrification material during molding, thermal expansion coefficient, transition point, softening point, fluidity, precipitated crystal, crystallization temperature, and crystal melting point are shown in the table.

As is apparent from the table, sample No. which is an example of the present invention is shown. In Nos. 1 to 8, devitrified materials were not recognized during molding, and molding was easy. The coefficient of thermal expansion was as high as 95 to 140 × 10 −7 / ° C. Furthermore, MgO-based crystals were precipitated and had high heat resistance.

  On the other hand, sample No. which is a comparative example. No. 9 was easily devitrified, difficult to vitrify, and poor in fluidity. Sample No. No. 10 did not cause crystallization and had poor heat resistance.

  In addition, the presence or absence of devitrified material at the time of molding was observed with the microscope (50 times) the film-like molded product, "no" if the devitrified material was not recognized, "Yes" what was recognized It was. If there is no devitrified material, it can be determined that the stability of the glass is high.

  Regarding the coefficient of thermal expansion of glass, each glass powder sample is powder press-molded, heat-treated at 850 to 1000 ° C. for 15 minutes using a temperature of crystallization temperature + 10 ° C. as a guide, and then into a cylindrical shape having a diameter of 4 mm and a length of 20 mm It grind | polished and measured based on JISR3102 and calculated | required the value in the temperature range of 30-700 degreeC.

  The glass transition point, softening point, crystallization temperature, and crystal melting point were transferred from the data obtained by measuring each glass powder sample up to 1050 ° C using a macro differential thermal analyzer. The value of the point and the fourth inflection point were the softening point, the strong exothermic peak was the crystallization temperature, and the endothermic peak obtained after crystallization was the crystal melting point. Note that the higher the melting point of the crystal, or the lower the melting point, the more stable the crystal exists even at high temperatures, and it can be determined that the heat resistance is high.

  The fluidity was evaluated as follows. A glass powder with a specific gravity is placed in a 20 mm diameter mold and pressed, and then heat-treated by holding it at 850 to 1000 ° C. for 15 minutes on a SUS430 plate. Those having a diameter are indicated by “◎”, those having a flow diameter of 16 to less than 18 mm are indicated by “◯”, and those having a flow diameter of less than 16 mm are indicated by “x”.

Precipitated crystals were measured by XRD and identified by comparison with JCPDS card. In the table, 2MgO · 2SiO 2 was identified as “A”, BaO · 2MgO · 2SiO 2 as “B”, and 2MgO · B 2 O 3 as “C” as the precipitated crystal seeds identified at this time.

  The high expansion 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. Further, it is suitable as an adhesive material for hermetically sealing a support substrate, an electrolyte, an electrode, and the like used when manufacturing an SOFC.

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 (7)

  1. In mole%, SiO 2 of less than 30 super ~50%, MgO 10~45%, BaO 5~40%, CaO 0~20%, SrO 0~10%, B 2 O 3 0~15%, ZnO 0~15 %, Al 2 O 3 0-6%, ZrO 2 0-3%, SnO 2 0-3%, a high expansion crystalline glass composition.
  2. Substantially R 2 O (R is an alkali metal) and high-expansion crystallizable glass composition according to claim 1, characterized in that do not contain P 2 O 5.
  3. In mole%, a B 2 O 3 0.1 to 15%, high-expansion crystalline according to claim 1 or 2, wherein the molar ratio of MgO / B 2 O 3 is 2.0 or more Glass composition.
  4.   The high expansion crystalline glass composition according to any one of claims 1 to 3, wherein MgO-based crystals are precipitated when heat-treated.
  5. 5. One or more crystals selected from any of 2MgO · SiO 2 , BaO · 2MgO · 2SiO 2 , and 2MgO · B 2 O 3 are precipitated when heat-treated. High expansion crystalline glass composition.
  6. The high expansion crystalline glass composition according to any one of claims 1 to 5, wherein a coefficient of thermal expansion in a temperature range of 30 to 700 ° C is 90 × 10 -7 / ° C or more.
  7.   The high expansion crystalline glass composition according to claim 1, which is used for bonding.
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JP2013203627A (en) * 2012-03-29 2013-10-07 Asahi Glass Co Ltd Glass composition
JP2014156377A (en) * 2013-02-18 2014-08-28 Nippon Electric Glass Co Ltd Crystalline glass composition
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
JP2015513512A (en) * 2012-02-17 2015-05-14 フラウンホッファー−ゲゼルシャフト・ツァー・フォデラング・デル・アンゲワンテン・フォーシュング・エー.ファウ. Composition for the production of glass solder for high temperature applications and its use
JP2016115554A (en) * 2014-12-16 2016-06-23 日本電気硝子株式会社 Seal glass for solid oxide fuel cell
US20160236967A1 (en) * 2013-09-30 2016-08-18 Nihon Yamamura Glass Co., Ltd. Glass composition for sealing
US9487433B2 (en) 2012-12-25 2016-11-08 Nihon Yamamura Glass Co., Ltd. Sealing glass composition
WO2016185511A1 (en) * 2015-05-15 2016-11-24 日本ケンブリッジフィルター株式会社 High-temperature filter
CN107108315A (en) * 2014-10-01 2017-08-29 圣戈本陶瓷及塑料股份有限公司 The method for forming glass composition
WO2018190056A1 (en) * 2017-04-13 2018-10-18 日本電気硝子株式会社 Crystalline glass composition
KR20200038024A (en) * 2018-10-02 2020-04-10 공주대학교 산학협력단 Composition of sealing glass for solid oxide fuel cell and sealing paste comprising the same
US10658684B2 (en) 2013-03-29 2020-05-19 Saint-Gobain Ceramics & Plastics, Inc. Sanbornite-based glass-ceramic seal for high-temperature applications

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