WO2017169308A1 - Composition de verre cristallin - Google Patents

Composition de verre cristallin Download PDF

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Publication number
WO2017169308A1
WO2017169308A1 PCT/JP2017/006417 JP2017006417W WO2017169308A1 WO 2017169308 A1 WO2017169308 A1 WO 2017169308A1 JP 2017006417 W JP2017006417 W JP 2017006417W WO 2017169308 A1 WO2017169308 A1 WO 2017169308A1
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WO
WIPO (PCT)
Prior art keywords
glass composition
crystalline glass
bao
sio
heat treatment
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PCT/JP2017/006417
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English (en)
Japanese (ja)
Inventor
高山佳久
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日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016116785A external-priority patent/JP6709502B2/ja
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
Priority to KR1020187016179A priority Critical patent/KR102651661B1/ko
Priority to CN201780020090.2A priority patent/CN108883972B/zh
Priority to US16/062,670 priority patent/US20180370845A1/en
Publication of WO2017169308A1 publication Critical patent/WO2017169308A1/fr

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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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders

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 characteristics that the power generation efficiency is the highest among the fuel cells because the internal resistance of the cell is small, and the production cost can be reduced because 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 950 ° 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 under a high-temperature operating environment of about 600 to 800 ° 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 contains, in mol%, SiO 2 + CaO 57 to 80%, MgO + BaO 0 to 40%, ZnO 10 to 40%, La 2 O 3 0 to 15%. It is characterized by doing.
  • SiO 2 + CaO means the total amount of each content of SiO 2 and CaO
  • MgO + BaO means the total amount of each content of MgO and BaO.
  • SiO 2 and CaO are components that improve fluidity, and by defining the total amount thereof as described above, fluidity suitable for adhesion (sealing) is obtained. Can do.
  • MgO, BaO, ZnO and La 2 O 3 which are high-expansion crystal components that precipitate during heat treatment as described above, the adhesion location after heat treatment has a high coefficient of thermal expansion, The property is also good. 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.
  • Crystallity 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 crystalline glass composition of the present invention preferably contains substantially no R 2 O (R represents an alkali metal) and P 2 O 5 .
  • R 2 O and P 2 O 5 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 to deposit at least one crystal selected from MgO ⁇ SiO 2, BaO ⁇ 2MgO ⁇ 2SiO 2, 2SiO 2 ⁇ 2ZnO ⁇ BaO and La 2 O 3 ⁇ 2SiO 2 by heat treatment Is preferred.
  • MgO ⁇ SiO 2, BaO ⁇ 2MgO ⁇ 2SiO 2, 2SiO 2 ⁇ 2ZnO ⁇ BaO and La 2 O 3 ⁇ 2SiO 2 by heat treatment
  • the crystalline glass composition of the present invention preferably has a thermal expansion coefficient of 85 ⁇ 10 ⁇ 7 / ° C. or higher in a temperature range of 30 to 950 ° C.
  • the crystalline glass composition of the present invention preferably has a difference between the softening point and the crystallization temperature of 85 ° C or higher. If the difference between the softening point and the crystallization temperature is large, crystallization is difficult to start before flowing, so that fluidity suitable for adhesion can be easily obtained.
  • the crystalline glass composition of the present invention comprises, in mol%, SiO 2 40-70%, MgO 5-40%, BaO 5-40%, ZnO over 10-40%, CaO 3-30%, La 2 O 3 It is preferable to contain more than 0 to 15%.
  • 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 contains, in mol%, SiO 2 + CaO 57 to 80%, MgO + BaO 0 to 40%, ZnO 10 to 40%, La 2 O 3 0 to 15%.
  • the reason for limiting the glass composition as described above is shown below. In the following description regarding the content of each component, “%” means “mol%” unless otherwise specified.
  • SiO 2 and CaO are components for improving fluidity.
  • the content of SiO 2 + CaO is more than 57 to 80%, preferably 57.1 to 78%, particularly preferably 57.2 to 76%.
  • the content of SiO 2 + CaO is too small, fluidity suitable for bonding becomes difficult to obtain.
  • the content of SiO 2 + CaO is too large, it is difficult for high expansion crystals to precipitate during heat treatment, the melting temperature becomes high and melting becomes difficult, or defects such as devitrification easily occur during melting. become.
  • SiO 2 is a component for precipitating highly expanded crystals by heat treatment, and has the effect of improving water resistance and heat resistance in addition to improving fluidity.
  • the SiO 2 content is preferably 40 to 70%, 41 to 69%, particularly 41 to 65%.
  • fluidity suitable for bonding becomes difficult to obtain.
  • crystals are hardly precipitated even after heat treatment. In addition, the meltability tends to decrease.
  • the CaO content is preferably 3 to 30%, 3 to 29%, and particularly preferably 3 to 28%.
  • the CaO content is preferably 3 to 30%, 3 to 29%, and particularly preferably 3 to 28%.
  • MgO and BaO are components for precipitating highly expanded crystals by heat treatment.
  • the content of MgO + BaO is more than 0 to 40%, preferably 1 to 39%, 2 to 38%, 3 to 37%, 5 to 37%, particularly preferably 7 to 37%.
  • MgO + BaO When there is too little content of MgO + BaO, it will become difficult to precipitate a highly expanded crystal
  • there is too much content of MgO + BaO there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify. In addition, the difference between the softening point and the crystallization temperature becomes small, and the fluidity tends to decrease.
  • the MgO content is preferably 5 to 40%, 5 to 39%, particularly 6 to 38%.
  • the BaO content is preferably 5 to 40%, 5 to 39%, particularly 6 to 38%.
  • ZnO is a component for precipitating highly expanded crystals by heat treatment.
  • the content of ZnO is more than 10 to 40%, preferably 10.2 to 38%, 10.5 to 36%, particularly preferably 10.5 to 34%.
  • 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.
  • there is too much content of ZnO there exists a tendency for the vitrification range to become narrow and it becomes easy to devitrify.
  • the difference between the softening point and the crystallization temperature becomes small, and the fluidity tends to decrease.
  • La 2 O 3 is a component for precipitating highly expanded crystals by heat treatment. Moreover, it is a component which expands the vitrification range and facilitates vitrification.
  • the content of La 2 O 3 is more than 0 to 15%, preferably 0.5 to 14%, particularly preferably 1 to 13%. When the content of La 2 O 3 is too small, the effect is difficult to obtain. On the other hand, when the content of La 2 O 3 is too large, it easily devitrified during or heat treatment in the melt flowability becomes difficult to obtain suitable adhesion.
  • TiO 2 , ZrO 2 , SnO 2 , WO 3 or the like may be added up to 2% as components other than those described above.
  • R 2 O represents an alkali metal
  • P 2 O 5 are liable to be volatilized by heat treatment and may adversely affect the power generation characteristics such as reducing the electrical insulation of the SOFC component, It is preferable not to contain it.
  • the crystalline glass composition of the present invention having the above composition precipitates highly expanded crystals by heat treatment.
  • the high expansion crystal include at least one selected from MgO ⁇ SiO 2, BaO ⁇ 2MgO ⁇ 2SiO 2, 2SiO 2 ⁇ 2ZnO ⁇ BaO and La 2 O 3 ⁇ 2SiO 2.
  • the thermal expansion coefficient of the crystalline glass composition after the heat treatment is 85 ⁇ 10 ⁇ 7 / ° C. or higher, 86 ⁇ 10 ⁇ 7 / ° C. or higher, 87 ⁇ 10 ⁇ 7 / ° C. or higher, particularly 88 ⁇ 10 ⁇ 7 / ° C. or higher.
  • the crystal glass of the present invention tends to have a high degree of 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 difference between the softening point and the crystallization temperature is preferably 85 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 95 ° C. or higher. If the difference between the softening point and the crystallization temperature is small, crystallization starts before flowing, and fluidity decreases.
  • the crystalline glass composition of the present invention is made of magnesia (MgO), zinc white (ZnO), zirconia (ZrO 2 ), titania (TiO 2 ), alumina (Al 2 O 3 ), etc. for fluidity adjustment.
  • 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 material powder prepared so as to have the above composition is melted at about 1400 to 1600 ° C. for about 0.5 to 2 hours until a homogeneous glass is obtained.
  • the molten glass is formed into a film or the like, it is 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, such as terpineol (Ter), diethylene glycol monobutyl ether (BC), diethylene glycol monobutyl ether acetate (BCA), 2,2,4-trimethyl-1,3-pentadiol.
  • Te terpineol
  • BC diethylene glycol monobutyl ether
  • BCA diethylene glycol monobutyl ether acetate
  • Monoisobutyrate, dihydroterpineol and the like can be used alone or in combination.
  • 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, and the first and second members are fixed, and crystals are precipitated. 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 (Sample Nos. 1 to 9) and Comparative Examples (Sample Nos. 10 to 11) of the present invention.
  • the raw materials prepared so as to have the respective compositions in the table were melted at 1400-1600 ° C. for about 1 hour, 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 further classified to obtain a sample (crystalline glass composition powder) having a particle size (d50) of about 10 ⁇ m.
  • the coefficient of thermal expansion is based on JIS R3102 using a measurement sample obtained by press-molding each sample, heat-treating at 1000 ° C. for 3 hours, and polishing into a cylindrical shape having a diameter of 4 mm and a length of 20 mm. Values in a temperature range of 30 to 950 ° C. were 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. In addition, it means that it means that it means that the crystal
  • 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 fired on a SUS430 plate at 850 to 1050 ° C. for 15 minutes. Evaluations were made as “ ⁇ ” when the flow diameter of the molded body after firing was 18 mm or more, “ ⁇ ” when it was less than 16 to 18 mm, and “X” if it was less than 16 mm.
  • Precipitated crystals were identified by performing XRD (X-ray diffraction) measurement for each sample and comparing with JCPDS card.
  • MgO ⁇ SiO 2 is “A”
  • BaO ⁇ 2MgO ⁇ 2SiO 2 is “B”
  • 2SiO 2 ⁇ 2ZnO ⁇ BaO is “C”
  • La 2 O 3 ⁇ 2SiO 2 is “D”. As shown in the table.
  • No. 1 as an example of the present invention.
  • Samples 1 to 9 had a large difference between the softening point and the crystallization temperature of 90 ° C. or more, and were excellent in fluidity during firing. Further, since the high expansion crystal was precipitated by the heat treatment, the thermal expansion coefficient was as high as 88 to 114 ⁇ 10 ⁇ 7 / ° C. Further, it can be seen that the melting point of the precipitated crystal is high and the heat resistance is also excellent.
  • No. as a comparative example.
  • Sample No. 10 had a small difference between the softening point and the crystallization temperature of 10 ° C., and was inferior in fluidity during firing. No. Since the sample No. 11 did not precipitate highly expanded crystals by heat treatment, the coefficient of thermal expansion is as low as 56 ⁇ 10 ⁇ 7 / ° C., and it is considered that the sample is inferior in heat resistance.
  • 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 when 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une composition de verre cristallin qui possède une fluidité appropriée pour l'adhésion, un coefficient élevé de dilatation thermique après traitement thermique, et une excellente résistance à la chaleur après adhésion. La composition de verre cristallin est caractérisée en ce qu'elle comprend, en % en moles, plus de 57 à 80 % de SiO2+CaO, plus de 0 à 40 % de MgO + BaO, plus de 10 à 40 % de ZnO, et plus de 0 à 15 % de La2O3.
PCT/JP2017/006417 2016-03-28 2017-02-21 Composition de verre cristallin WO2017169308A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187016179A KR102651661B1 (ko) 2016-03-28 2017-02-21 결정성 유리 조성물
CN201780020090.2A CN108883972B (zh) 2016-03-28 2017-02-21 结晶性玻璃组合物
US16/062,670 US20180370845A1 (en) 2016-03-28 2017-02-21 Crystalline glass composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-063227 2016-03-28
JP2016063227 2016-03-28
JP2016-116785 2016-06-13
JP2016116785A JP6709502B2 (ja) 2016-03-28 2016-06-13 結晶性ガラス組成物

Publications (1)

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WO2017169308A1 true WO2017169308A1 (fr) 2017-10-05

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PCT/JP2017/006417 WO2017169308A1 (fr) 2016-03-28 2017-02-21 Composition de verre cristallin

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0597472A (ja) * 1991-02-08 1993-04-20 E I Du Pont De Nemours & Co 部分的に結晶性のガラス組成物
JP2013241323A (ja) * 2012-04-24 2013-12-05 Nippon Electric Glass Co Ltd 結晶性ガラス組成物
JP2014156377A (ja) * 2013-02-18 2014-08-28 Nippon Electric Glass Co Ltd 結晶性ガラス組成物
WO2015046195A1 (fr) * 2013-09-30 2015-04-02 日本山村硝子株式会社 Composition de verre pour scellement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0597472A (ja) * 1991-02-08 1993-04-20 E I Du Pont De Nemours & Co 部分的に結晶性のガラス組成物
JP2013241323A (ja) * 2012-04-24 2013-12-05 Nippon Electric Glass Co Ltd 結晶性ガラス組成物
JP2014156377A (ja) * 2013-02-18 2014-08-28 Nippon Electric Glass Co Ltd 結晶性ガラス組成物
WO2015046195A1 (fr) * 2013-09-30 2015-04-02 日本山村硝子株式会社 Composition de verre pour scellement

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