CN114669816A - Alumina ceramic-metal brazing method - Google Patents
Alumina ceramic-metal brazing method Download PDFInfo
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- CN114669816A CN114669816A CN202210428575.8A CN202210428575A CN114669816A CN 114669816 A CN114669816 A CN 114669816A CN 202210428575 A CN202210428575 A CN 202210428575A CN 114669816 A CN114669816 A CN 114669816A
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- 238000005219 brazing Methods 0.000 title claims abstract description 71
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 58
- 239000006260 foam Substances 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001465 metallisation Methods 0.000 claims abstract description 14
- 229910000679 solder Inorganic materials 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000004544 sputter deposition Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 238000003466 welding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 5
- 235000019743 Choline chloride Nutrition 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229960003178 choline chloride Drugs 0.000 description 5
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 238000005477 sputtering target Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005304 joining Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 mechanical joining Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007660 shear property test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Products (AREA)
Abstract
The invention relates to the technical field of ceramic-metal processing, in particular to an alumina ceramic-metal brazing method, wherein after the alumina ceramic is subjected to metallization treatment, composite brazing filler metal is adopted to braze and connect the alumina ceramic and metal; the composite solder comprises the following components in parts by weight: 45-60 parts of silver powder, 8-15 parts of titanium powder, 5-10 parts of indium powder, 3-6 parts of molybdenum powder, 4-8 parts of nickel sulfide @ graphene/foam copper, 2-4 parts of titanium diboride and 2-3 parts of binder.
Description
Technical Field
The invention relates to the technical field of ceramic-metal processing, in particular to an alumina ceramic-metal brazing method.
Background
The ceramic has excellent performances of high strength, high hardness, high temperature resistance, wear resistance, corrosion resistance and the like, and is widely applied to the fields of aerospace, machinery, medical treatment, energy and the like. The inherent brittleness of ceramics makes them difficult to machine into large size or complex structure parts. The metal material has good room temperature strength, electrical conductivity and thermal conductivity, excellent plasticity and toughness and good machining performance, but has poor mechanical property at high temperature. Therefore, the ceramic and the metal are connected to form the composite member, so that good complementation in performance can be formed, and the composite member has important significance for meeting engineering application requirements and expanding the application range of materials.
Currently, various joining methods are available for joining ceramics to metals, such as mechanical joining, adhesive bonding, brazing, diffusion welding, laser welding, and the like. Among the connection methods, the brazing process is simple, the size and the shape of the joint are limited to a small extent, and the method is suitable for large-scale industrial production and has wide application in connection of ceramics and metals. However, because of the great differences in chemical bond type, physicochemical properties, microstructure and the like between ceramics and metals, common brazing filler metals are difficult to wet the ceramics and the metals at the same time. Secondly, the ceramic and metal create large residual stresses in the joint after brazing is complete, which can affect the joint performance.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problem, the invention provides an alumina ceramic-metal brazing method.
The adopted technical scheme is as follows:
an alumina ceramic-metal brazing method comprises the following steps:
after the aluminum oxide ceramic is subjected to metallization treatment, brazing connection is carried out on the aluminum oxide ceramic and the metal by adopting a composite brazing filler metal;
the composite brazing filler metal comprises the following components in parts by weight:
45-60 parts of silver powder, 8-15 parts of titanium powder, 5-10 parts of indium powder, 3-6 parts of molybdenum powder, 4-8 parts of nickel sulfide @ graphene/foamy copper, 2-4 parts of titanium diboride and 2-3 parts of a binder.
Further, the composite solder comprises the following components in parts by weight:
55 parts of silver powder, 12 parts of titanium powder, 8 parts of indium powder, 5 parts of molybdenum powder, 6 parts of nickel sulfide @ graphene/foam copper, 2 parts of titanium diboride and 3 parts of a binder.
Further, the preparation method of the nickel sulfide @ graphene/copper foam comprises the following steps:
s1: placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 950-4Keeping the temperature for 10-20min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper;
s2: and depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, and then placing the graphene/foam copper in a vulcanizing liquid for hydrothermal reaction at 160-180 ℃ for 24-36h to obtain the nickel sulfide @ graphene/foam copper.
Further, CH4The flow rate is 10-15cm3/min，N2The flow rate is 100-120cm3/min，H2The flow rate is 30-40cm3/min。
Further, the electrodeposition solution comprises the following components:
NiCl2·6H2115g/L of O100-.
Further, the vulcanizing liquid comprises the following components:
10-15g/L of thioacetamide, 8-10g/L of urea, 300-400g/L of ethanol and the balance of water.
Further, the binder is polyvinyl alcohol.
Further, the metallization method of the alumina ceramic is as follows:
and (3) sputtering titanium and molybdenum simultaneously by adopting a magnetron sputtering technology, and depositing a metallization layer on the surface of the alumina ceramic.
Further, the metal is any one of a TC4 titanium alloy, a TC5 titanium alloy and a TC6 titanium alloy.
Further, the temperature of the braze joint was 980-.
The invention has the beneficial effects that:
the invention provides an alumina ceramic-metal brazing method, which comprises the steps of firstly carrying out metallization treatment on alumina ceramic, wetting the alumina ceramic as a transition layer, forming a metalized layer with large adhesive force, good weldability and bright and compact surface, enabling a composite brazing filler metal to be better suitable for an alumina ceramic substrate, reducing residual stress at a brazed joint, improving joint shear strength, enabling the brazing quality to be more reliable and stable, enabling the joint to have no connection defects such as cracks, air holes and the like, further effectively eliminating the residual stress at an interface by adding nickel sulfide @ graphene/foam copper, improving the shear strength and the brazing quality, and testing the alumina ceramic-metal brazing connection joint has higher shear strength which is up to more than 90MPa and is improved in different degrees compared with the connection joint formed without metallization, the comparison shows that the shear strength of the connecting joint is obviously improved after the nickel sulfide @ graphene/copper foam is added.
Drawings
FIG. 1 is a schematic view showing a typical microstructure of a brazed joint in example 1 of the present invention;
wherein:
1-alumina ceramic, 2-metalized layer, 3-composite solder and 4-TC4 titanium alloy.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
an alumina ceramic-metal brazing method comprises the following steps:
performing magnetron sputtering on a magnetron sputtering film plating machine with a working cavity diameter of 800mm, controlling the pressure to be 0.6Pa and the sputtering current to be 60A by taking argon as working gas, performing sputtering for 5min, and performing sputtering on a titanium target (pure titanium target)The degree is not lower than 99.9 percent) and a molybdenum target (the purity is not lower than 99.9 percent) are used as sputtering targets, titanium and molybdenum are sputtered at the same time, a metallization layer is deposited on the surface of the alumina ceramic, then the alumina ceramic after metallization treatment is connected with TC4 titanium alloy in a brazing mode through composite solder, the composite solder is printed on one surface of the alumina ceramic during brazing, then the TC4 titanium alloy and the alumina ceramic are laminated to form a sandwich structure, the composite solder is positioned between the TC4 titanium alloy and the alumina ceramic and is placed in a vacuum brazing furnace, the vacuum degree of the brazing furnace is controlled to be 1 x 10- 3Pa, heating to 980 ℃ for braze welding connection for 20min, then cooling to 500 ℃ for heat preservation for 10min, and finally naturally cooling to room temperature along with the furnace;
the composite solder comprises the following components in parts by weight:
55 parts of silver powder, 12 parts of titanium powder, 5 parts of indium powder, 4 parts of molybdenum powder, 5 parts of nickel sulfide @ graphene/foam copper, 4 parts of titanium diboride and 2 parts of binder polyvinyl alcohol.
The preparation method of the nickel sulfide @ graphene/foam copper comprises the following steps:
placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 960 deg.C at a rate of 15 deg.C/min under the atmosphere, maintaining the temperature for 20min, and introducing CH4，CH4The flow rate is 15cm3/min，N2The flow rate is 120cm3/min，H2The flow rate was 35cm3Keeping the temperature for 20min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper, depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, adopting a three-electrode system on an electrochemical workstation, taking the graphene/foam copper as a working electrode, taking silver wires as a reference electrode, taking a graphite electrode as a counter electrode, and controlling the voltage at-0.90V (relative to Ag/Ag)+) Performing electrodeposition for 10min, wherein the electrodeposition solution comprises the following components: NiCl2·6H2O115 g/L, choline chloride 45g/L, sodium chloride 10g/L, boric acid 15g/L, sodium citrate 60g/L, ethylene glycol 120g/L and the balance of water, and then placing the mixture into a vulcanizing liquid for reaction in a hydrothermal reaction kettle at 180 ℃ for 24 timesh, the vulcanizing liquid comprises the following components: 15g/L of thioacetamide, 10g/L of urea, 300g/L of ethanol and the balance of water, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying in vacuum for 8 hours at 60 ℃ to obtain the nickel sulfide @ graphene/foamy copper.
Example 2:
an alumina ceramic-metal brazing method comprises the following steps:
performing magnetron sputtering on a magnetron sputtering film plating machine with a working cavity diameter of 800mm, using argon as working gas, controlling the air pressure to be 0.6Pa, sputtering current to be 60A, sputtering for 5min, using a titanium target (the purity is not lower than 99.9%) and a molybdenum target (the purity is not lower than 99.9%) as sputtering targets, simultaneously sputtering titanium elements and molybdenum elements, depositing a metallization layer on the surface of alumina ceramic, brazing and connecting the metallized alumina ceramic and TC4 titanium alloy by using a composite brazing filler metal, during brazing, firstly printing the composite brazing filler metal on one surface of the alumina ceramic, laminating the TC4 titanium alloy and the alumina ceramic to form a sandwich structure, wherein the composite brazing filler metal is positioned between the TC4 titanium alloy and the alumina ceramic, placing the composite brazing filler metal in a vacuum brazing furnace, and controlling the vacuum degree of the brazing furnace to be 1 × 10- 3Pa, heating to 990 ℃ for braze welding connection for 20min, then cooling to 500 ℃ for heat preservation for 10min, and finally naturally cooling to room temperature along with the furnace;
the composite solder comprises the following components in parts by weight:
60 parts of silver powder, 15 parts of titanium powder, 10 parts of indium powder, 6 parts of molybdenum powder, 8 parts of nickel sulfide @ graphene/foam copper, 4 parts of titanium diboride and 3 parts of binder polyvinyl alcohol.
The preparation method of the nickel sulfide @ graphene/foam copper comprises the following steps:
placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 980 deg.C at a rate of 15 deg.C/min under the above atmosphere, maintaining for 20min, and introducing CH4，CH4The flow rate is 15cm3/min，N2The flow rate is 120cm3/min，H2The flow rate was 40cm3Min, keeping the temperature for 20min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper, depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, adopting a three-electrode system on an electrochemical workstation, taking the graphene/foam copper as a working electrode, taking silver wires as a reference electrode, taking a graphite electrode as a counter electrode, and controlling the voltage at-0.90V (relative to Ag/Ag)+) Performing electrodeposition for 10min, wherein the electrodeposition solution comprises the following components: NiCl2·6H2O115 g/L, choline chloride 50g/L, sodium chloride 15g/L, boric acid 15g/L, sodium citrate 70g/L, ethylene glycol 200g/L and the balance of water, and then placing the mixture into a vulcanizing liquid for reaction for 36 hours in a hydrothermal reaction kettle at 180 ℃, wherein the vulcanizing liquid comprises the following components: 15g/L of thioacetamide, 10g/L of urea, 400g/L of ethanol and the balance of water, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying in vacuum for 8 hours at 60 ℃ to obtain the nickel sulfide @ graphene/foamy copper.
Example 3:
an alumina ceramic-metal brazing method comprises the following steps:
performing magnetron sputtering on a magnetron sputtering film plating machine with a working cavity diameter of 800mm, using argon as working gas, controlling the air pressure to be 0.6Pa, sputtering current to be 60A, sputtering for 5min, using a titanium target (the purity is not lower than 99.9%) and a molybdenum target (the purity is not lower than 99.9%) as sputtering targets, simultaneously sputtering titanium elements and molybdenum elements, depositing a metallization layer on the surface of alumina ceramic, brazing and connecting the metallized alumina ceramic and TC4 titanium alloy by using a composite brazing filler metal, during brazing, firstly printing the composite brazing filler metal on one surface of the alumina ceramic, laminating the TC4 titanium alloy and the alumina ceramic to form a sandwich structure, wherein the composite brazing filler metal is positioned between the TC4 titanium alloy and the alumina ceramic, placing the composite brazing filler metal in a vacuum brazing furnace, and controlling the vacuum degree of the brazing furnace to be 1 × 10- 3Pa, heating to 980 ℃ for braze welding connection for 20min, then cooling to 500 ℃ for heat preservation for 10min, and finally naturally cooling to room temperature along with the furnace;
the composite solder comprises the following components in parts by weight:
45 parts of silver powder, 8 parts of titanium powder, 5 parts of indium powder, 3 parts of molybdenum powder, 4 parts of nickel sulfide @ graphene/foam copper, 2 parts of titanium diboride and 2 parts of binder polyvinyl alcohol.
The preparation method of the nickel sulfide @ graphene/foam copper comprises the following steps:
placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 950 deg.C at a speed of 10 deg.C/min under the atmosphere, maintaining for 10min, and introducing CH4，CH4The flow rate is 10cm3/min，N2The flow rate is 100cm3/min，H2The flow rate was 30cm3Min, keeping the temperature for 10min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper, depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, adopting a three-electrode system on an electrochemical workstation, taking the graphene/foam copper as a working electrode, taking silver wires as a reference electrode, taking a graphite electrode as a counter electrode, and controlling the voltage at-0.90V (relative to Ag/Ag)+) Performing electrodeposition for 10min, wherein the electrodeposition solution comprises the following components: NiCl2·6H2100g/L of O, 40g/L of choline chloride, 10g/L of sodium chloride, 10g/L of boric acid, 50g/L of sodium citrate, 100g/L of ethylene glycol and the balance of water, and then placing the mixture into a vulcanizing liquid for reaction for 24 hours in a hydrothermal reaction kettle at 160 ℃, wherein the vulcanizing liquid comprises the following components: 10g/L of thioacetamide, 8g/L of urea, 300g/L of ethanol and the balance of water, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying in vacuum for 8 hours at 60 ℃ to obtain the nickel sulfide @ graphene/foamy copper.
Example 4:
an alumina ceramic-metal brazing method comprises the following steps:
performing magnetron sputtering on a magnetron sputtering film plating machine with a working cavity diameter of 800mm, controlling the air pressure to be 0.6Pa, the sputtering current to be 60A and the sputtering time to be 5min by taking argon as a working gas, taking a titanium target (the purity is not less than 99.9%) and a molybdenum target (the purity is not less than 99.9%) as sputtering targets, simultaneously sputtering titanium elements and molybdenum elements, depositing a metallization layer on the surface of alumina ceramic, then adopting a composite brazing filler metal to braze and connect the metallized alumina ceramic and TC4 titanium alloy, printing the composite brazing filler metal on one surface of the alumina ceramic during brazing, and then using the composite brazing filler metal to braze and connect the alumina ceramic and the TC4 titanium alloyThe TC4 titanium alloy and the alumina ceramic are laminated to form a sandwich structure, the composite solder is positioned between the TC4 titanium alloy and the alumina ceramic and is put into a vacuum brazing furnace, and the vacuum degree of the brazing furnace is controlled to be 1 multiplied by 10- 3Pa, heating to 980 ℃ for braze welding connection for 20min, then cooling to 500 ℃ for heat preservation for 10min, and finally naturally cooling to room temperature along with the furnace;
the composite solder comprises the following components in parts by weight:
60 parts of silver powder, 8 parts of titanium powder, 10 parts of indium powder, 3 parts of molybdenum powder, 8 parts of nickel sulfide @ graphene/foam copper, 2 parts of titanium diboride and 3 parts of binder polyvinyl alcohol.
The preparation method of the nickel sulfide @ graphene/foam copper comprises the following steps:
placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 980 deg.C at a speed of 10 deg.C/min under the atmosphere, maintaining for 10min, and introducing CH4，CH4The flow rate is 15cm3/min，N2The flow rate is 100cm3/min，H2The flow rate was 40cm3Min, keeping the temperature for 10min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper, depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, adopting a three-electrode system on an electrochemical workstation, taking the graphene/foam copper as a working electrode, taking silver wires as a reference electrode, taking a graphite electrode as a counter electrode, and controlling the voltage at-0.90V (relative to Ag/Ag)+) Performing electrodeposition for 10min, wherein the electrodeposition solution comprises the following components: NiCl2·6H2O115 g/L, choline chloride 40g/L, sodium chloride 15g/L, boric acid 10g/L, sodium citrate 70g/L, ethylene glycol 100g/L and the balance of water, and then placing the mixture into a vulcanizing liquid for reaction for 24 hours in a hydrothermal reaction kettle at 180 ℃, wherein the vulcanizing liquid comprises the following components: 15g/L of thioacetamide, 8g/L of urea, 400g/L of ethanol and the balance of water, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying in vacuum for 8 hours at 60 ℃ to obtain the nickel sulfide @ graphene/foamy copper.
Example 5:
an alumina ceramic-metal brazing method comprises the following steps:
performing magnetron sputtering on a magnetron sputtering film plating machine with a working cavity diameter of 800mm, using argon as working gas, controlling the air pressure to be 0.6Pa, sputtering current to be 60A, sputtering for 5min, using a titanium target (the purity is not lower than 99.9%) and a molybdenum target (the purity is not lower than 99.9%) as sputtering targets, simultaneously sputtering titanium elements and molybdenum elements, depositing a metallization layer on the surface of alumina ceramic, brazing and connecting the metallized alumina ceramic and TC4 titanium alloy by using a composite brazing filler metal, during brazing, firstly printing the composite brazing filler metal on one surface of the alumina ceramic, laminating the TC4 titanium alloy and the alumina ceramic to form a sandwich structure, wherein the composite brazing filler metal is positioned between the TC4 titanium alloy and the alumina ceramic, placing the composite brazing filler metal in a vacuum brazing furnace, and controlling the vacuum degree of the brazing furnace to be 1 × 10- 3Pa, heating to 980 ℃ for braze welding connection for 20min, then cooling to 500 ℃ for heat preservation for 10min, and finally naturally cooling to room temperature along with the furnace;
the composite solder comprises the following components in parts by weight:
45 parts of silver powder, 15 parts of titanium powder, 5 parts of indium powder, 6 parts of molybdenum powder, 4 parts of nickel sulfide @ graphene/foamy copper, 4 parts of titanium diboride and 2 parts of polyvinyl alcohol serving as a binder.
The preparation method of the nickel sulfide @ graphene/foamy copper comprises the following steps:
placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 950 deg.C at a rate of 15 deg.C/min under the atmosphere, maintaining for 20min, and introducing CH4，CH4The flow rate is 10cm3/min，N2The flow rate is 120cm3/min，H2The flow rate was 30cm3Min, keeping the temperature for 20min, stopping heating, and stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper, depositing a nickel layer on the surface of the graphene/foam copper by an electrodeposition method, and performing electrochemical work on an electrochemical workstation by adopting a three-electrode system, wherein the graphene/foam copper is used as a working electrode, silver wires are used as a reference electrode, the graphite electrode is used as a counter electrode, and the voltage of the counter electrode is-0.90V (relative to Ag/Ag)+) Performing electrodeposition for 10min, and performing electrodepositionThe solution comprises the following components: NiCl2·6H2100g/L of O, 50g/L of choline chloride, 10g/L of sodium chloride, 15g/L of boric acid, 50g/L of sodium citrate, 200g/L of ethylene glycol and the balance of water, and then placing the mixture into a vulcanizing liquid for reaction for 36 hours in a hydrothermal reaction kettle at 160 ℃, wherein the vulcanizing liquid comprises the following components: 10g/L of thioacetamide, 10g/L of urea, 300g/L of ethanol and the balance of water, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying in vacuum for 8 hours at 60 ℃ to obtain the nickel sulfide @ graphene/foamy copper.
Comparative example 1:
essentially the same as in example 1, except that the alumina ceramic was not metallized.
Comparative example 2:
essentially the same as example 1 except that the composite braze did not include nickel sulfide @ graphene/copper foam.
Comparative example 3:
essentially the same as in example 1, except that copper foam was used instead of nickel sulfide @ graphene/copper foam in the composite braze.
And (3) performance testing:
the soldered joints obtained in examples 1 to 5 of the present invention and comparative examples 1 to 3 were used as test samples, respectively, and the soldered joints were subjected to a shear property test using an electronic universal tester (Instron-1186) to evaluate the joining properties of the joints, and the test results are shown in table 1:
table 1:
as can be seen from table 1, the alumina ceramic-metal brazed joints in examples 1 to 5 of the present invention have higher shear strength, which is up to 90MPa or more, and the shear strength of the joints formed without metallization is improved to different degrees compared to comparative example 1, and the shear strength of the joints is also improved significantly compared to comparative examples 2 and 3 in which nickel sulfide @ graphene/copper foam is added.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An alumina ceramic-metal brazing method is characterized in that after the alumina ceramic is metallized, a composite brazing filler metal is adopted to braze and connect the alumina ceramic and metal;
the composite solder comprises the following components in parts by weight:
45-60 parts of silver powder, 8-15 parts of titanium powder, 5-10 parts of indium powder, 3-6 parts of molybdenum powder, 4-8 parts of nickel sulfide @ graphene/foam copper, 2-4 parts of titanium diboride and 2-3 parts of a binder.
2. The alumina ceramic-metal brazing method according to claim 1, wherein the composite brazing filler metal comprises the following components in parts by weight:
55 parts of silver powder, 12 parts of titanium powder, 8 parts of indium powder, 5 parts of molybdenum powder, 6 parts of nickel sulfide @ graphene/foam copper, 2 parts of titanium diboride and 3 parts of a binder.
3. The alumina ceramic-metal brazing method according to claim 1, wherein the nickel sulfide @ graphene/copper foam is prepared as follows:
s1: placing the foam copper in a tube furnace, and using N2After replacing the air in the tube furnace, keeping continuously introducing N2While introducing H2Heating to 950-4Keeping the temperature for 10-20min, and stoppingHeating, stopping introducing CH4Cooling the furnace to room temperature to obtain graphene/foam copper;
s2: and depositing a nickel layer on the surface of the graphene/foam copper by adopting an electrodeposition method, and then placing the graphene/foam copper in a vulcanizing liquid for hydrothermal reaction at 160-180 ℃ for 24-36h to obtain the nickel sulfide @ graphene/foam copper.
4. The alumina ceramic-metal brazing method according to claim 3, wherein CH4The flow rate is 10-15cm3/min，N2The flow rate is 100-120cm3/min，H2The flow rate is 30-40cm3/min。
5. The alumina ceramic-metal brazing process according to claim 3, wherein the electrodeposition solution comprises the following composition:
NiCl2·6H2115g/L of O100-.
6. The alumina ceramic-metal brazing process according to claim 3, wherein the sulfidizing solution comprises the following composition:
10-15g/L of thioacetamide, 8-10g/L of urea, 300-400g/L of ethanol and the balance of water.
7. The alumina ceramic-metal brazing method according to claim 1 wherein the binder is polyvinyl alcohol.
8. The alumina ceramic-to-metal brazing method according to claim 1, wherein the alumina ceramic is metallized as follows:
and (3) sputtering titanium and molybdenum simultaneously by adopting a magnetron sputtering technology, and depositing a metallization layer on the surface of the alumina ceramic.
9. The alumina ceramic-metal brazing method according to claim 1, wherein the metal is any one of a TC4 titanium alloy, a TC5 titanium alloy, and a TC6 titanium alloy.
10. The alumina ceramic-metal brazing method according to claim 1, wherein the temperature of the brazing connection is 980-.
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