CN115476012B - Application of high Cu atomic ratio Cu-Ti brazing filler metal in brazing of ceramic and metal - Google Patents
Application of high Cu atomic ratio Cu-Ti brazing filler metal in brazing of ceramic and metal Download PDFInfo
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- CN115476012B CN115476012B CN202211313813.7A CN202211313813A CN115476012B CN 115476012 B CN115476012 B CN 115476012B CN 202211313813 A CN202211313813 A CN 202211313813A CN 115476012 B CN115476012 B CN 115476012B
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- 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
- B23K1/008—Soldering within a furnace
-
- 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
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
-
- 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
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/206—Cleaning
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/18—Dissimilar materials
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- 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
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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Abstract
High Cu atomic ratio Cu-The application of Ti brazing filler metal in the brazing of ceramics and metals relates to the technical field of the application of Cu-Ti brazing filler metal with high Cu atomic ratio. The invention aims to solve the problem that Ti is carried out by adopting the prior eutectic component Cu-23Ti (wt.%) solder 3 SiC 2 When the ceramic is connected with Nb in a brazing manner, brittle CuTi compounds generated in the joint cause the problem of low shear strength of the joint. The method comprises the following steps: according to Ti 3 SiC 2 Sequentially assembling ceramic/Ti foil/Cu foil/Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace at a temperature of 5×10 ‑2 Preserving heat for 5-60 min at the vacuum degree of Pa and the brazing temperature of 950-1010 ℃, and cooling to room temperature after brazing. The invention can obtain the application of the Cu-Ti brazing filler metal with high Cu atomic ratio in the brazing of ceramics and metals.
Description
Technical Field
The invention relates to the technical field of application of high-Cu atomic ratio Cu-Ti brazing filler metal, in particular to application of high-Cu atomic ratio Cu-Ti brazing filler metal in ceramic and metal brazing.
Background
Ti 3 SiC 2 The ceramic has the advantages of good room temperature and high temperature strength, oxidation resistance, corrosion resistance, good machinability and the like, is hopeful to become a novel high-temperature structural material, and is used as kiln furniture materials, turbine blade parts, high-temperature parts of aeroengines and the like. Nb is used as a high-temperature material and a structural material, is widely applied to the fields of aerospace and the like, and is Ti 3 SiC 2 The ceramic and the metal Nb are reliably connected, so that the advantages of the ceramic and the metal Nb can be fully exerted, and the application field of the material is widened. Wherein, the eutectic component Cu-23Ti (wt.%) solder can realize Ti 3 SiC 2 Direct braze joining of ceramics to Nb, however, generates large amounts of brittle CuTi compounds in the joint, resulting in reduced shear strength of the braze joint.
Disclosure of Invention
The invention aims to solve the problem that Ti is carried out by adopting the prior eutectic component Cu-23Ti (wt.%) solder 3 SiC 2 When the ceramic is in braze joint with Nb, the brittle CuTi compound generated in the joint causes the problem of low shear strength of the joint, and the application of the Cu-Ti brazing filler metal with high Cu atomic ratio in the braze joint of the ceramic and the metal is provided.
The application of the high Cu atomic ratio Cu-Ti brazing filler metal in the brazing of ceramics and metals is characterized in that the high Cu atomic ratio Cu-Ti brazing filler metal is Cu-10Ti brazing filler metal, and the Cu-10Ti brazing filler metal is used for the contact reaction brazing of the ceramics and the metals.
The ceramic is Ti 3 SiC 2 And the metal is Nb.
The Cu-10Ti solder is used for Ti 3 SiC 2 The contact reaction brazing of the ceramic and the metal Nb is carried out according to the following steps:
1. ti (Ti) 3 SiC 2 Pre-welding treatment of ceramics and Nb: ti is mixed with 3 SiC 2 Cutting the ceramic and Nb to a predetermined size and cutting Ti 3 SiC 2 Polishing and cleaning the surface to be welded of the ceramics and Nb; said Ti is 3 SiC 2 The ceramic is solid-dissolved with 0.5 to 2.0 percent of Al element by mass percent;
2. preparation of Cu-10Ti solder: cutting Cu foil and Ti foil into a mixture with Ti 3 SiC 2 Polishing the thickness of the Cu foil and the Ti foil according to the standard that the mass fraction of Ti in the Cu-10Ti solder is 10%, then treating the Cu foil and the Ti foil until the surfaces are flat, and then cleaning;
3. assembling a test piece to be welded and performing vacuum contact reaction brazing: according to Ti 3 SiC 2 Sequentially assembling ceramic/Ti foil/Cu foil/Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace at a temperature of 5×10 -2 Preserving heat for 5-60 min at the vacuum degree of Pa and the brazing temperature of 950-1010 ℃, cooling to room temperature after brazing is finished, and finishing Ti 3 SiC 2 And (3) carrying out contact reaction brazing on the ceramic, the Cu-10Ti brazing filler metal and the metal Nb.
The invention has the beneficial effects that:
(1) The invention uses a high Cu atomic ratio with less Ti contentBecause of lower Ti content, cu with better plasticity exists in a large amount in the welding line 4 Ti, which effectively reduces the generation of CuTi brittle compounds in the welding line, has excellent mechanical property and brazes Ti 3 SiC 2 The shear strength of the ceramic and metal rear joint reaches more than 130 MPa.
(2) The invention uses the Cu foil and the Ti foil with smaller thickness to form the composite solder, and the high Cu atomic ratio solder in the non-eutectic component can be melted and liquid-phase expanded at a relatively low temperature by a contact reaction brazing method, thereby realizing the welding at a relatively low temperature.
The invention can obtain the application of the Cu-Ti brazing filler metal with high Cu atomic ratio in the brazing of ceramics and metals.
Drawings
FIG. 1 shows the use of a Cu-Ti brazing filler metal having a high Cu atomic ratio in example 1 3 SiC 2 Microstructure back-scattering pictures of braze joints after ceramic and Nb contact reaction braze welding;
FIG. 2 is a schematic diagram of a conventional Cu-Ti eutectic solder used in comparative example 1 3 SiC 2 Microstructure back-scattered pictures of braze joints after ceramic and Nb contact reaction braze.
Detailed Description
The first embodiment is as follows: the application of the high Cu atomic ratio Cu-Ti brazing filler metal in the brazing of ceramics and metals is characterized in that the high Cu atomic ratio Cu-Ti brazing filler metal is Cu-10Ti brazing filler metal, and the Cu-10Ti brazing filler metal is used for the contact reaction brazing of the ceramics and the metals.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the ceramic is Ti 3 SiC 2 And (3) ceramics.
The other steps are the same as in the first embodiment.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that: the metal is Nb.
Other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one or more of the present embodiments and the embodiments are not limited to the aboveThe same points are: the Cu-10Ti solder is used for Ti 3 SiC 2 The contact reaction brazing of the ceramic and the metal Nb is carried out according to the following steps:
1. ti (Ti) 3 SiC 2 Pre-welding treatment of ceramics and Nb: ti is mixed with 3 SiC 2 Cutting the ceramic and Nb to a predetermined size and cutting Ti 3 SiC 2 Polishing and cleaning the surface to be welded of the ceramics and Nb; said Ti is 3 SiC 2 The ceramic is solid-dissolved with 0.5 to 2.0 percent of Al element by mass percent;
2. preparation of Cu-10Ti solder: cutting Cu foil and Ti foil into a mixture with Ti 3 SiC 2 Polishing the thickness of the Cu foil and the Ti foil according to the standard that the mass fraction of Ti in the Cu-10Ti solder is 10%, then treating the Cu foil and the Ti foil until the surfaces are flat, and then cleaning;
3. assembling a test piece to be welded and performing vacuum contact reaction brazing: according to Ti 3 SiC 2 Sequentially assembling ceramic/Ti foil/Cu foil/Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace, and placing the assembly to be welded into a vacuum brazing furnace at a temperature of 3 multiplied by 10 -3 Pa～5×10 -2 Preserving heat for 5-60 min at the vacuum degree of Pa and the brazing temperature of 950-1010 ℃, cooling to room temperature after brazing is finished, and finishing Ti 3 SiC 2 And (3) carrying out contact reaction brazing on the ceramic, the Cu-10Ti brazing filler metal and the metal Nb.
Other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: in step one, ti is added 3 SiC 2 The surface to be welded of the ceramics and the Nb is polished step by adopting 240-600 mesh sand paper.
Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the cleaning process in the first step is as follows: ti after polishing 3 SiC 2 Placing the ceramic and Nb into a cleaning agent, and ultrasonically cleaning for 10-20 min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone.
Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: in the second step, the thicknesses of the Cu foil and the Ti foil are 50-500 mu m.
Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the polishing process in the second step is as follows: and polishing the two sides of the Cu foil and the Ti foil step by using 240-600 mesh sand paper.
Other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the cleaning process in the second step is as follows: placing the polished Cu foil and Ti foil into a cleaning agent, and ultrasonically cleaning for 10-20 min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone.
Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: and thirdly, cooling to room temperature at a cooling rate of 4-6 ℃/min after brazing is finished.
Other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the braze in this example was Cu-10Ti (wt.%); cu-10Ti solder for Ti 3 SiC 2 The contact reaction brazing of the ceramic and the metal Nb is carried out according to the following steps:
1. ti (Ti) 3 SiC 2 Pre-welding treatment of ceramics and Nb: ti is mixed with 3 SiC 2 Cutting the ceramic into 5X 5mm 3 Cutting Nb into 3X 10X 15mm 3 And Ti is combined with 3 SiC 2 Sequentially polishing the surface to be welded of the ceramics and the Nb by 240, 400 and 600-mesh sand paper step by step, and polishing the polished Ti 3 SiC 2 Placing the ceramic and Nb into a cleaning agent, and ultrasonically cleaning for 15min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone; said Ti is 3 SiC 2 The ceramic is solid-dissolved with 0.5 to 2.0 percent of Al element by mass percent;
2. preparation of Cu-10Ti solder: cutting Cu foil and Ti foil into 5.5X5.5 mm area with diamond wire cutting machine 2 Sequentially polishing two sides of a Cu foil and a Ti foil step by adopting 240, 400 and 600 meshes of sand paper according to the standard that the mass fraction of Ti in the Cu-10Ti solder is 10 percent, polishing the Cu foil to about 31mg and the Ti foil to about 7mg, clamping the solder foil by two flat surfaces, pressing the Cu foil and the Ti foil to be flat by applying pressure, and then putting the Cu foil and the Ti foil into alcohol for ultrasonic cleaning in an ultrasonic cleaner for 15min; the thickness ratio of Cu foil to Ti foil is about 10:1, a step of;
3. assembling a test piece to be welded and performing vacuum contact reaction brazing: according to Ti 3 SiC 2 The order ceramic/Ti foil/Cu foil/Nb, ti was applied using graphite blocks 3 SiC 2 Compacting the ceramic, the Ti foil, the Cu foil and the Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace at a temperature of 5×10 -2 Preserving the heat for 10min at the vacuum degree of Pa and the brazing temperature of 990 ℃, cooling to room temperature at a cooling rate of 5 ℃/min after the brazing is finished, and taking out the test piece to finish the process.
Comparative example 1: the brazing filler metal in this comparative example is Cu-23Ti (wt.%);
1. ti (Ti) 3 SiC 2 Pre-welding treatment of ceramics and Nb: ti is mixed with 3 SiC 2 Cutting the ceramic into 5X 5mm 3 Cutting Nb into 3X 10X 15mm 3 And Ti is combined with 3 SiC 2 Sequentially polishing the surface to be welded of the ceramics and the Nb by 240, 400 and 600 meshes of sand paper step by step, and polishing the polished Ti 3 SiC 2 Placing the ceramic and Nb into a cleaning agent, and ultrasonically cleaning for 15min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone; said Ti is 3 SiC 2 The ceramic is solid-dissolved with 0.5 to 2.0 percent of Al element by mass percent;
2. preparing a Cu and Ti composite solder foil: cutting Cu foil and Ti foil into 5.5X5.5 mm area with diamond wire cutting machine 2 Sequentially polishing two sides of the Cu foil and the Ti foil step by adopting 240, 400 and 600 meshes of sand paper, and polishing the Cu foil to the following pointPolishing about 11mg of the Ti foil to about 7mg, clamping the brazing filler metal foil with two flat surfaces, pressing the Cu foil and the Ti foil to be flat by applying pressure, putting the Cu foil and the Ti foil into alcohol, and ultrasonically cleaning for 15min in an ultrasonic cleaner;
3. assembling a test piece to be welded and performing vacuum contact reaction brazing: according to Ti 3 SiC 2 The order ceramic/Ti foil/Cu foil/Nb, ti was applied using graphite blocks 3 SiC 2 Compacting the ceramic, the Ti foil, the Cu foil and the Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace at a temperature of 5×10 -2 Preserving the heat for 10min at the vacuum degree of Pa and the brazing temperature of 990 ℃, cooling to room temperature at a cooling rate of 5 ℃/min after the brazing is finished, and taking out the test piece to finish the process.
FIG. 1 shows the use of a Cu-Ti brazing filler metal having a high Cu atomic ratio in example 1 3 SiC 2 Microstructure back-scattering pictures of braze joints after ceramic and Nb contact reaction braze welding; FIG. 2 is a schematic diagram of a conventional Cu-Ti eutectic solder used in comparative example 1 3 SiC 2 Microstructure back-scattered pictures of braze joints after ceramic and Nb contact reaction braze.
As can be seen by comparing FIG. 1 with FIG. 2, the dark gray CuTi brittle compound in the joint of FIG. 1 is significantly reduced, and the base phase is mainly Cu with better plasticity 4 Ti and Cu, it can be seen that the joint performance is effectively improved by using the Cu-Ti brazing filler metal with a high Cu atomic ratio in example 1.
And (3) performing shearing test by using an electronic universal tester, wherein the loading speed is 0.5mm/min. The test results show that: the room temperature shear strength of the joint obtained by the Cu-10Ti (wt.%) solder contact reaction brazing method used in example 1 reached 130MPa, whereas the room temperature shear strength of the joint obtained by the Cu-23Ti (wt.%) solder contact reaction brazing method used in comparative example 1 was only 70MPa under the same parameters.
Claims (7)
1. The application of the high Cu atomic ratio Cu-Ti brazing filler metal in the brazing of ceramics and metals is characterized in that the high Cu atomic ratio Cu-Ti brazing filler metal is Cu-10Ti brazing filler metal, and the Cu-10Ti brazing filler metal is used for the contact reaction brazing of ceramics and metals;
said Cu-10Ti solder for Ti 3 SiC 2 The contact reaction brazing of the ceramic and the metal Nb is carried out according to the following steps:
1. ti (Ti) 3 SiC 2 Pre-welding treatment of ceramics and Nb: ti is mixed with 3 SiC 2 Cutting the ceramic and Nb to a predetermined size and cutting Ti 3 SiC 2 Polishing and cleaning the surface to be welded of the ceramics and Nb; said Ti is 3 SiC 2 The ceramic is solid-dissolved with 0.5 to 2.0 percent of Al element by mass percent;
2. preparation of Cu-10Ti solder: cutting Cu foil and Ti foil into a mixture with Ti 3 SiC 2 Polishing the thickness of the Cu foil and the Ti foil according to the standard that the mass fraction of Ti in the Cu-10Ti solder is 10%, then treating the Cu foil and the Ti foil until the surfaces are flat, and then cleaning;
3. assembling a test piece to be welded and performing vacuum contact reaction brazing: according to Ti 3 SiC 2 Sequentially assembling ceramic/Ti foil/Cu foil/Nb to obtain a fitting to be welded; placing the assembly to be welded into a vacuum brazing furnace, and placing the assembly to be welded into a vacuum brazing furnace at a temperature of 3 multiplied by 10 -3 Pa～5×10 -2 Preserving heat for 5-60 min at the vacuum degree of Pa and the brazing temperature of 950-1010 ℃, cooling to room temperature after brazing is finished, and finishing Ti 3 SiC 2 And (3) carrying out contact reaction brazing on the ceramic, the Cu-10Ti brazing filler metal and the metal Nb.
2. The use of a high Cu atomic ratio Cu-Ti brazing filler metal as recited in claim 1, wherein in step one Ti is added to the brazing filler metal 3 SiC 2 The surface to be welded of the ceramics and the Nb is polished step by adopting 240-600 mesh sand paper.
3. The use of a cu—ti braze of high Cu atomic ratio in ceramic to metal brazing according to claim 1, characterized by the cleaning process in step one: ti after polishing 3 SiC 2 Placing the ceramic and Nb into a cleaning agent, and ultrasonically cleaning for 10-20 min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone.
4. The use of a cu—ti solder of high Cu atomic ratio in ceramic to metal brazing as claimed in claim 1, characterized in that in step two the Cu foil and Ti foil are both 50 to 500 μm thick.
5. The application of the high-Cu atomic ratio Cu-Ti brazing filler metal in the brazing of ceramics and metals according to claim 1, wherein the polishing process in the second step is as follows: and polishing the two sides of the Cu foil and the Ti foil step by using 240-600 mesh sand paper.
6. The use of a cu—ti braze of high Cu atomic ratio in ceramic to metal brazing according to claim 1, characterized by the cleaning process in step two: placing the polished Cu foil and Ti foil into a cleaning agent, and ultrasonically cleaning for 10-20 min in an ultrasonic cleaning machine; the cleaning agent is alcohol or acetone.
7. The use of a cu—ti braze of high Cu atomic ratio in the braze of ceramics and metals according to claim 1, characterized in that in step three, after the braze is finished, it is cooled to room temperature at a cooling rate of 4-6 ℃/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211313813.7A CN115476012B (en) | 2022-10-25 | 2022-10-25 | Application of high Cu atomic ratio Cu-Ti brazing filler metal in brazing of ceramic and metal |
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| CN202211313813.7A CN115476012B (en) | 2022-10-25 | 2022-10-25 | Application of high Cu atomic ratio Cu-Ti brazing filler metal in brazing of ceramic and metal |
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| CN115476012B true CN115476012B (en) | 2023-08-01 |
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| CN115991609A (en) * | 2023-01-09 | 2023-04-21 | 南京理工大学 | Ceramic-metal discharge plasma connection method |
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| GB817659A (en) * | 1955-02-28 | 1959-08-06 | Sylvania Electric Prod | Improvements in and relating to the metallizing of ceramic or cermet materials |
| DE68904214T2 (en) * | 1988-03-04 | 1993-05-19 | Toshiba Kawasaki Kk | HARD-LOCKING PASTE FOR CONNECTING METALS AND CERAMIC MATERIALS. |
| JP2804766B2 (en) * | 1988-10-31 | 1998-09-30 | 達雄 石川 | Joint of ceramic and metal |
| CN101987402B (en) * | 2010-11-30 | 2012-09-05 | 哈尔滨工业大学 | Method for brazing Ti2AlC ceramics and Cu with Cu-Sn-Ti solder |
| DE102014115839A1 (en) * | 2014-10-30 | 2016-05-04 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und -Prüfung (Bam) | Method for applying a solder material |
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