WO2011142262A1 - 大気接合用ろう材、接合体、および、集電材料 - Google Patents
大気接合用ろう材、接合体、および、集電材料 Download PDFInfo
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- WO2011142262A1 WO2011142262A1 PCT/JP2011/060251 JP2011060251W WO2011142262A1 WO 2011142262 A1 WO2011142262 A1 WO 2011142262A1 JP 2011060251 W JP2011060251 W JP 2011060251W WO 2011142262 A1 WO2011142262 A1 WO 2011142262A1
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- brazing material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3602—Carbonates, basic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12896—Ag-base component
Definitions
- the present invention relates to a brazing material for air bonding, a joined body joined by using the brazing material, and a current collecting material, and more particularly to improvement of a technique for lowering the melting point of a brazing material for air bonding.
- a joined body of metal members, a joined body of ceramic members, and a joined body of a ceramic member and a metal member are obtained by brazing.
- the joining method is actively researched.
- An active metal brazing method is usually used as a method for joining a ceramic member and a metal member.
- an active element such as Ti or Zr
- an active element such as Ti or Zr
- the brazing material is heated in a vacuum to form a reaction layer on the surface of the ceramic member.
- This improves the wettability and adhesion of the brazing material.
- TiN is generated in the first layer on the ceramic member side of the reaction layer, and when carbide is used, TiC is formed, and TiO is formed when the oxide is used.
- the active metal brazing method requires heating in a vacuum or in an inert gas atmosphere, which increases equipment costs and requires air supply / exhaust, so continuous production cannot be performed. . For this reason, manufacturing cost increases.
- a member that cannot be exposed in a vacuum and an active atmosphere or a member that cannot be held at a high temperature may be used. In this case, a manufacturing process is restricted.
- it is required to establish an air brazing technique capable of obtaining a good joined body in a relatively low temperature region not only in the manufacturing cost can be reduced, but also in an air atmosphere. Yes.
- a flux brazing method which is a general method for brazing in the air.
- a good bonded body is obtained by applying a flux to the bonding surface of the base material to obtain a reducing atmosphere at the bonded portion by the flux and blocking oxygen entry.
- a flux having a melting point lower than 780 ° C. which is the melting point of BAg-8 is used as the brazing material, and the flux is melted before the brazing material.
- a good joined body is obtained by activating the joint surface and preventing oxidation of the brazing material.
- bonding is usually performed by local heating using a torch or the like, and this method is effective for point bonding and line bonding, but is not suitable for surface bonding.
- the ceramic member may be broken by a thermal stress generated by local heating, which is not suitable for manufacturing a bonded body having a ceramic member.
- many of the fluxes themselves and their residues have a function of corroding metals, and in this case, a flux residue removal step is additionally required after joining.
- Patent Document 1 a reactive air brazing method (for example, Patent Document 1) as an air brazing technique that does not require flux.
- a reactive air brazing method for example, Patent Document 1
- the base materials are joined to the atmosphere by brazing.
- the main component of the brazing material is a noble metal component such as Ag, the flux is not necessary for brazing, and as a result, the above-mentioned problem due to the flux can be solved.
- Patent Document 2 proposes a brazing material made of an Ag—Ge—Si alloy.
- the Ag—Ge—Si brazing material of Patent Document 2 is difficult to obtain a good joined body because the brazing material itself oxidizes when heated to the joining temperature. From the viewpoint of productivity and quality improvement, it is required to provide a bonded body having good airtightness and bonding strength in the air without using a flux. It was difficult due to problems.
- Another object of the present invention is to provide a bonded body and a current collecting material that can have bonding strength.
- the brazing filler metal for air bonding of the present invention contains Ag (silver) and B (boron) as essential components, and Ag is in the range of 50% to less than 92% by volume ratio, and B is in the range of more than 8% and 50% or less. And the total of these is adjusted to 100% including inevitable impurities.
- Ag and B are essential components.
- Ag is a main component that is not easily oxidized even when melted in the atmosphere, and B is a low-melting-point material that oxidizes at about 300 ° C. or higher and has a relatively low melting point (about 577 ° C.).
- the volume ratio of these essential components is such that Ag is in the range of 50% or more and less than 92%, B is in the range of more than 8% and 50% or less, and the total is adjusted to 100% including inevitable impurities.
- the base material is oxidized even when brazing is performed in the air. Therefore, flux is not necessary. In this case, oxidation of the brazing material itself can also be prevented.
- the melting point of the brazing material can be lowered, and the joining temperature can be set to a melting point of Ag (about 961 ° C.) or lower.
- the bonding temperature is lower than that of the conventional Ag-based brazing filler metal, when the metal member is used as the base material, it is possible to suppress oxidation of the base material and prevent deterioration on the metal member side. can do.
- the joining temperature is low as described above, it is possible to reduce thermal stress due to a difference in thermal expansion coefficient between the two members.
- the air brazing filler metal of the present invention can have various configurations.
- joined bodies according to various purposes can be obtained by adding various elements as dispersing agents and active elements to the two components which are essential elements.
- Ge germanium
- Al aluminum
- Si silicon
- V vanadium
- Mo molecular weight
- W tungsten
- Mn manganese
- Ti titanium
- Zr zirconium
- the added element means all elements contained in the oxide.
- Ge oxide can be deposited on the ceramic by adding Ge. Since Ge has an action as an active metal, the wettability is improved. be able to. Further, for example, by adding Zr, ZrO 2 having a vapor pressure lower than that of B 2 O 3 is generated, so that durability can be improved.
- At least one selected from Si (silicon), Ca (calcium), Ti (titanium), Zr (zirconium), nitrides, carbides, and hydrides thereof is added, and B and the above It is possible to use a mode in which the total volume ratio of the added elements is in the range of more than 8% and 50% or less, and the total is adjusted to 100% including inevitable impurities.
- the added element means all elements contained in nitrides, carbides, and hydrides.
- the airtightness of the joined body obtained becomes favorable. Further, for example, by adding Zr, ZrO 2 having a vapor pressure lower than that of B 2 O 3 is generated, so that durability can be improved.
- the brazing filler metal for air bonding of the present invention can have a low melting point as described above, and can have a melting point of 650 ° C. or higher and 850 ° C. or lower, for example, in the air.
- the joined body of the present invention can be obtained by joining using the above brazing material for atmospheric joining. That is, the joined body of the present invention is characterized in that it consists of metal members joined together using the brazing material for atmospheric joining, ceramic members, or a metal member and a ceramic member, and has gas sealing properties. To do.
- Various structures can be used for the joined body of the present invention.
- the joined body can be used for a fuel cell or a solid oxide fuel cell.
- the current collecting material of the present invention is composed of metal members joined using the above brazing material for atmospheric bonding, ceramic members, or metal members and ceramic members, and has electrical conductivity. .
- Various configurations can be used for the current collecting material of the present invention.
- the current collecting material can be used for a fuel cell or a solid oxide fuel cell.
- the brazing material for air bonding of the present invention it is possible to prevent oxidation of the brazing material itself as well as eliminating the need for flux even in bonding in the air.
- B which is a low melting point material, as an essential component, it is possible to obtain effects such as the ability to lower the melting point of the brazing material.
- the joined body or current collecting material of the present invention it is obtained by using the brazing material for air bonding of the present invention, and can have good airtightness and bonding strength.
- FIG. 4 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of the main part of a bonding test piece according to Sample 1 shown in FIG. 3. It is a cross-sectional electron microscope figure (x30 time) of the joining test piece obtained by joining using the brazing material which concerns on the sample 2 of this invention.
- FIG. 4 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of the main part of a bonding test piece according to Sample 1 shown in FIG. 3. It is a cross-sectional electron microscope figure (x30 time) of the joining test piece obtained by joining using the brazing material which concerns on the sample 2 of this invention.
- FIG. 6 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of a main part of a bonding test piece according to Sample 2 shown in FIG. 5. It is a cross-sectional electron microscope figure of the joining test piece obtained by joining using the brazing material which concerns on the sample 3 of this invention.
- 7A and 7B show the element distribution analysis results of the bonding test piece according to the sample 3 shown in FIG. 7, where (A) is Ag, (B) is Ge, (C) is B, (D) is Zr, and (E) is O distribution. It is a figure showing an analysis result.
- FIG. 7A and 7B show the element distribution analysis results of the bonding test piece according to the sample 3 shown in FIG. 7, where (A) is Ag, (B) is Ge, (C) is B, (D) is Zr, and (E) is O distribution. It is a figure showing an analysis result.
- FIG. 4 is a cross-sectional electron micrograph ( ⁇ 500 times) of a joining test piece obtained by joining using a brazing material according to Samples 4A to 4C of the present invention
- A is Sample 4A in which the joining conditions are 650 ° C./1 hr.
- B is a cross-sectional electron micrograph of a bonded test piece in the case of sample 4B in which the bonding conditions are 750 ° C./1 hr
- (C) is the sample 4C in the case of sample 4C where the bonding conditions are 850 ° C./1 hr.
- It is a cross-sectional electron microscope figure (x500 times) of the joining test piece obtained by joining using the brazing material which concerns on the sample 6 of this invention.
- 2 is a cross-sectional electron micrograph ( ⁇ 300 times) of a bonding test piece obtained by bonding using a brazing filler metal according to Comparative Sample 1.
- FIG. 1 is a cross-sectional electron micrograph ( ⁇ 300 times) of
- a bonded specimen was prepared as a sample according to the present invention using a brazing material for atmospheric bonding within the scope of the present invention.
- the joining body test piece was produced as a comparative sample using the brazing material for atmospheric joining outside the scope of the present invention.
- a leak test was performed on all the specimens, and a joint portion was observed on some of the specimens.
- the brazing material for air bonding that can be used for the preparation of the sample of the present invention contains Ag and B as essential components, and Ag is in the range of 50% to less than 92% by volume ratio. Is within the range of more than 8% and not more than 50%, and the brazing material is adjusted so that the total of these is 100% including inevitable impurities.
- the brazing material is added so that the total volume ratio of B and the added element is in the range of more than 8% and 50% or less, and the total of these is 100% including inevitable impurities.
- Ag and B are contained as essential components, and at least one selected from Si, Ca, Ti, Zr, nitrides, carbides, and hydrides thereof is added, and B and the above are added.
- the brazing material is adjusted so that the total volume ratio of the elements is in the range of more than 8% and 50% or less, and the total of these elements is 100% including inevitable impurities.
- Examples of the form of the brazing material for air bonding that can be used in the sample preparation of the present invention include, for example, a form in which a metal mixed powder is pasted with an organic solvent, an organic binder, etc., various forms such as an alloy powder paste, foil, sol-gel, etc. There is no particular limitation.
- Examples of the metal member material that can be used in the sample preparation of the present invention include ferritic stainless steel, stainless steel, heat resistant stainless steel, FeCrAl alloy, FeCrSi alloy, Ni-based heat resistant alloy, and the like. Absent.
- Examples of the material of the ceramic member used in the sample preparation of the present invention include yttria-stabilized zirconia and oxide ceramics such as zirconia, alumina, magnesia, steatite, mullite, titania, silica, and sialon, and are particularly limited. It is not something.
- a mixed metal powder having a composition within the scope of the present invention shown in Table 1 was mixed with an organic binder to form a paste.
- a metal member according to each sample of the present invention a cylindrical member having an outer diameter of 14 mm and an inner diameter of 8 mm of ZMG232L (manufactured by Hitachi Metals), which is a ferritic alloy, was used.
- ZMG232L manufactured by Hitachi Metals
- a stabilized zirconia plate, a magnesia plate, an aluminum nitride plate, an alumina plate, or a silicon carbide plate was used as the ceramic member according to each sample of the present invention. In this case, the size of each plate was set to 20 mm ⁇ 20 mm.
- a mixed metal powder having a composition outside the range of the present invention shown in Table 1 and mixed with an organic binder to form a paste is used.
- a stabilized zirconia plate was used as the ceramic member.
- the ratio shown before the element indicates the content ratio (volume ratio) of the element.
- a paste-like air bonding brazing material was applied to one end face of a metal member, a ceramic member was placed on the applied surface, and the bonding conditions (temperature and time) shown in Table 1 in the atmosphere were used. By heating, the joining test piece which concerns on each sample and a comparative sample was produced.
- FIG. 1 is a schematic diagram showing the configuration of the produced joint test piece 10.
- Reference numeral 11 denotes a metal member that is a cylindrical member
- reference numeral 11A denotes an opening of the metal member
- reference numeral 12 denotes a ceramic member
- reference numeral 13 denotes a bonding layer.
- FIG. 2 is a schematic diagram of an observation cross-section of a joint including the joint layer 13 (a perspective view showing a side cross-sectional configuration in the arrow direction 1A of FIG. 1).
- FIG. 3 is a cross-sectional electron micrograph ( ⁇ 30 times) of the bonding test piece of sample 1
- FIG. 4 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of the main part of the bonding test piece of sample 1 shown in FIG. ).
- B powder hereinafter referred to as “B powder”, reference numeral 14
- melted Ag hereinafter referred to as “melted Ag”, reference numeral 15
- FIG. 5 is a cross-sectional electron micrograph ( ⁇ 30 times) of the bonding test piece of sample 1
- FIG. 6 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of the main part of the bonding test piece of sample 2 shown in FIG. ).
- B powder (symbol 14) and molten Ag (symbol 15) were observed in the bonding layer 13, no unmelted Ag and voids existed, and the brazing material for atmospheric bonding was melted. It was confirmed.
- FIG. 7 is a cross-sectional electron micrograph of a joint specimen of Sample 3.
- FIG. 8 shows the element distribution analysis results of the bonding test piece shown in FIG. 7, where (A) is Ag, (B) is Ge, (C) is B, (D) is Zr, and (E) is O distribution. It is a figure showing an analysis result.
- the area shown in FIG. 7 corresponds to the area shown in FIGS. 8A to 8E.
- FIG. 8 shows that the abundance of the element increases as it approaches red, and the abundance of the element decreases as it approaches blue.
- FIGS. 8 (B) and 8 (E) a large amount of Ge oxide was precipitated in the bonding specimen of Sample 3.
- an oxide of Ge can be precipitated.
- FIG. 9A is a cross-sectional electron micrograph ( ⁇ 500 times) of the bonding test piece of sample 4A
- FIG. 9B is a cross-sectional electron micrograph ( ⁇ 500 time) of the bonding test piece of sample 4B
- (C) is a cross-sectional electron micrograph ( ⁇ 500 times) of a bonding test piece of Sample 4C.
- the bonding layer 13 has no unmelted Ag and voids, and is a brazing material for atmospheric bonding. Melted. Thereby, it was confirmed that the brazing material for air bonding having a composition within the range of the present invention has a melting point of 650 ° C. or higher and 850 ° C. or lower.
- brazing material in the case of sample 5A, a brazing material having a composition of Ag-3% Ge-17% B-6% Al by volume ratio was used, and in the case of sample 5B, Ag-3% Ge-17% by volume ratio.
- sample 5C a brazing material having a composition of B-6% Si was used.
- a brazing material having a composition of Ag-3% Ge-17% B and 16% SiO 2 was used.
- a brazing material having a composition of Ag-3% Ge-17% B-3% ZrH 2 by volume ratio was used.
- a brazing material having a composition of Ag-3% Ge-17% B-3% V by volume is used, and in the case of Sample 5F, Ag-3% Ge-17% B-2% by volume
- a brazing material having a composition of Ag-3% Ge-17% B-1% W is used, and in the case of sample 5H, a volume ratio of Ag- A brazing material having a composition of 3% Ge-17% B-3% WO 3 was used.
- a brazing material having a composition of Ag-3% Ge-17% B-4% TiH 2 by volume ratio was used.
- a brazing material having a composition of Ag-3% Ge-17% B-5% SiC by volume was used.
- FIG. 10 is an enlarged cross-sectional electron micrograph ( ⁇ 500 times) of the main part of the bonding test piece of Sample 1.
- B powder reference numeral 14
- molten Ag reference numeral 15
- (G) Comparative sample 1 As shown in Table 1, in the production of the joint specimen of Comparative Sample 1, a stabilized zirconia plate was used as the ceramic member 12, a brazing material having a composition of Ag-18% Ge in volume ratio, and a heating temperature of 850 was used. Brazing set at ° C. was performed for 1 hr. In the helium leak test of the joint specimen of Comparative Sample 1, as shown in Table 1, a leak was observed. This confirmed that the brazing filler metal for air bonding did not melt.
- FIG. 11 is an enlarged cross-sectional electron micrograph ( ⁇ 300 magnification) of the main part of the bonded specimen of Comparative Sample 1.
- granular unmelted Ag reference numeral 16
- voids reference numeral 17
- I confirmed that I did not. From the above, it was confirmed that the Ag—Ge brazing material has a melting point higher than 850 ° C. and does not have a low melting point.
- (H) Comparative sample 2 As shown in Table 1, in the production of the joint specimen of Comparative Sample 2, a stabilized zirconia plate was used as the ceramic member 12, a brazing material having a composition of Ge-68% B by volume ratio, and a heating temperature of 850. Brazing set at ° C. was performed for 1 hr. In the helium leak test of the joint specimen of Comparative Sample 2, as shown in Table 1, a leak was observed. This confirmed that the brazing filler metal for air bonding did not melt. As a result, it was confirmed that the Ge—B brazing filler metal had a melting point higher than 850 ° C. and no low melting point.
- Comparative sample 3 In the production of the joint specimen of Comparative Sample 3, as shown in Table 1, a stabilized zirconia plate was used as the ceramic member 12, and a brazing material having a composition of Ag-4% Ge-8% B by volume was used. Brazing at a heating temperature set to 850 ° C. was performed for 1 hr. In the helium leak test of the joint specimen of Comparative Sample 3, as shown in Table 1, a leak was observed. This confirmed that the brazing filler metal for air bonding did not melt. From a comparison between Comparative Sample 3 and Samples 1 to 9, it was confirmed that the addition amount of B is preferably more than 8%.
- the composition ratio of the brazing filler for air bonding the lower limit value of the B addition amount needs to be more than 8% by volume as described above, and the upper limit value of the B addition amount is the volume ratio. It was confirmed that it was necessary to be 50% or less. As for the upper limit, if the amount of B added exceeds 50% by volume, the main component is B, so that the desired bonding strength, vapor pressure, and melting point cannot be obtained.
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Abstract
Description
本発明の試料作製に用いることができる大気接合用ろう材は、AgとBを必須成分とし、体積比でAgが50%以上92%未満の範囲内、Bが8%超50%以下の範囲内とし、これらの合計が不可避不純物を含めて100%となるように調整されているろう材である。
接合試験片10について、金属部材11の開口面11Aを閉塞し、金属部材11内部を真空排気して、ヘリウムリーク試験を行った。ヘリウムリーク試験結果について、表1では、ヘリウムが検出されなかったものをリークなし、ヘリウムが検出されたものをリークありと表記している。また、試料1~4,6および比較試料1については、図2に示すように、接合試験片10を中央部で切断し、接合層13を含む接合部を観察した。以下では、各試料および各比較試料の評価結果について説明する。
本発明の試料1の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-18%Bの組成を有するろう材を用い、加熱温度を750℃に設定したろう付を1hr行った。試料1の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料2の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-50%Bの組成を有するろう材を用い、加熱温度を750℃に設定したろう付を1hr行った。試料2の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料2の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-16%Ge-16%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。試料2の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料4A~4Cの接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-3%Ge-40%Bの組成を有するろう材を用いた。接合条件について、表1に示すように、試料4Aの場合、加熱温度を650℃に設定したろう付を1hr行い、試料4Bの場合、加熱温度を750℃に設定したろう付を1hr行い、試料4Cの場合、加熱温度を850℃に設定したろう付を1hr行った。試料4A~4Cの接合試験片のヘリウムリーク試験では、いずれの接合試験片についても、表1に示すように、リークは観察されなかった。
本発明の試料5A~5Jの接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、加熱温度を850℃に設定したろう付を1hr行った。
本発明の試料6の接合試験片の作製では、表1に示すように、セラミックス部材12としてマグネシア板を用い、体積比でAg-3%Ge-40%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。試料6の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料7の接合試験片の作製では、表1に示すように、セラミックス部材12として窒化アルミ板を用い、体積比でAg-3%Ge-40%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。試料7の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料8の接合試験片の作製では、表1に示すように、セラミックス部材12としてアルミナ板を用い、体積比でAg-3%Ge-40%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。試料8の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
本発明の試料9の接合試験片の作製では、表1に示すように、セラミックス部材12として炭化珪素板を用い、体積比でAg-3%Ge-40%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。試料9の接合試験片のヘリウムリーク試験では、表1に示すように、リークは観察されなかった。これにより、大気接合用ろう材が溶融したことを確認した。
比較試料1の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-18%Geの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。比較試料1の接合試験片のヘリウムリーク試験では、表1に示すように、リークが観察された。これにより、大気接合用ろう材が溶融しなかったことを確認した。
比較試料2の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でGe-68%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。比較試料2の接合試験片のヘリウムリーク試験では、表1に示すように、リークが観察された。これにより、大気接合用ろう材が溶融しなかったことを確認した。これによりGe-B系ろう材は、850℃よりも融点が高く、低融点を有しないことを確認した。
比較試料3の接合試験片の作製では、表1に示すように、セラミックス部材12として安定化ジルコニア板を用い、体積比でAg-4%Ge-8%Bの組成を有するろう材を用い、加熱温度を850℃に設定したろう付を1hr行った。比較試料3の接合試験片のヘリウムリーク試験では、表1に示すように、リークが観察された。これにより、大気接合用ろう材が溶融しなかったことを確認した。比較試料3と試料1~9との比較から、Bの添加量は8%超であることが好適であることを確認した。
Claims (8)
- AgとBを必須成分とし、体積比でAgが50%以上92%未満の範囲内、Bが8%超50%以下の範囲内とし、これらの合計が不可避不純物を含めて100%となるように調整されていることを特徴とする大気接合用ろう材。
- Ge、Al、Si、V、Mo、W、Mn、Ti、Zr、および、これらの酸化物の中から選択された少なくとも1種以上が添加され、Bと前記添加された元素の体積比の合計が8%超50%以下の範囲内とし、これらの合計が不可避不純物を含めて100%となるように調整されていることを特徴とする請求項1に記載の大気接合用ろう材。
- Si、Ca、Ti、Zr、これらの窒化物、炭化物、および、水素化物の中から選択された少なくとも1種以上が添加され、Bと前記添加された元素の体積比の合計が8%超50%以下の範囲内とし、これらの合計が不可避不純物を含めて100%となるように調整されていることを特徴とする請求項1に記載の大気接合用ろう材。
- 大気中において650℃以上850℃以下の融点を有することを特徴とする請求項1~3のいずれかに記載の大気接合用ろう材。
- 請求項1~4のいずれかに記載の大気接合用ろう材を用いて接合された金属部材同士、セラミックス部材同士、あるいは、金属部材とセラミックス部材とからなるとともに、ガスシール性を有することを特徴とする接合体。
- 燃料電池用あるいは固体酸化物型燃料電池用として使用されることを特徴とする請求項5に記載の接合体。
- 請求項1~4のいずれかに記載の大気接合用ろう材を用いて接合された金属部材同士、セラミックス部材同士、あるいは、金属部材とセラミックス部材とからなるとともに、電気伝導性を有することを特徴とする集電材料。
- 燃料電池用あるいは固体酸化物型燃料電池用として使用されることを特徴とする請求項7に記載の集電材料。
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CN201180023852.7A CN102883853B (zh) | 2010-05-13 | 2011-04-27 | 大气接合用钎料、接合体及集电材料 |
US13/642,770 US20130040226A1 (en) | 2010-05-13 | 2011-04-27 | Brazing material for bonding in atmosphere, bonded article, and current collecting material |
DE112011101640T DE112011101640T5 (de) | 2010-05-13 | 2011-04-27 | Lötmaterial für das Fügen an der Atmosphäre, gefügter Artikel und Strom-sammelndes Material |
KR1020127031608A KR101454983B1 (ko) | 2010-05-13 | 2011-04-27 | 대기 접합용 납재, 접합체, 및, 집전재료 |
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WO2014168704A1 (en) * | 2013-04-11 | 2014-10-16 | General Electric Company | Method of brazing two parts of a dynamoelectric machine with a non self fluxing braze alloy in air atmosphere |
US10293704B2 (en) | 2014-04-08 | 2019-05-21 | StoreDot Ltd. | Electric vehicles with adaptive fast-charging, utilizing supercapacitor-emulating batteries |
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US10367192B2 (en) | 2016-04-07 | 2019-07-30 | StoreDot Ltd. | Aluminum anode active material |
US10818919B2 (en) | 2016-04-07 | 2020-10-27 | StoreDot Ltd. | Polymer coatings and anode material pre-lithiation |
US10199677B2 (en) | 2016-04-07 | 2019-02-05 | StoreDot Ltd. | Electrolytes for lithium ion batteries |
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CN117586042A (zh) * | 2024-01-19 | 2024-02-23 | 成都飞机工业(集团)有限责任公司 | 一种陶瓷基复合材料的连接方法 |
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- 2011-04-27 CN CN201180023852.7A patent/CN102883853B/zh not_active Expired - Fee Related
- 2011-04-27 DE DE112011101640T patent/DE112011101640T5/de not_active Ceased
- 2011-04-27 US US13/642,770 patent/US20130040226A1/en not_active Abandoned
- 2011-04-27 KR KR1020127031608A patent/KR101454983B1/ko not_active IP Right Cessation
- 2011-04-27 WO PCT/JP2011/060251 patent/WO2011142262A1/ja active Application Filing
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JP2011235345A (ja) | 2011-11-24 |
US20130040226A1 (en) | 2013-02-14 |
CN102883853A (zh) | 2013-01-16 |
KR20130016348A (ko) | 2013-02-14 |
DE112011101640T5 (de) | 2013-03-21 |
CN102883853B (zh) | 2016-05-04 |
KR101454983B1 (ko) | 2014-10-27 |
JP5623783B2 (ja) | 2014-11-12 |
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