CN106001984B - Magnesium alloy brazing filler metal and preparation method and soldering processes based on magnesium-rare earth soldering - Google Patents

Magnesium alloy brazing filler metal and preparation method and soldering processes based on magnesium-rare earth soldering Download PDF

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Publication number
CN106001984B
CN106001984B CN201610420068.4A CN201610420068A CN106001984B CN 106001984 B CN106001984 B CN 106001984B CN 201610420068 A CN201610420068 A CN 201610420068A CN 106001984 B CN106001984 B CN 106001984B
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magnesium
rare earth
soldering
filler metal
magnesium alloy
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CN106001984A (en
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邹家生
杨骏
许祥平
黄晓龙
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JIANGSU YANGMING SHIP-EQUIPMENT MANUFACTURING TECHNOLOGY Co Ltd
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JIANGSU YANGMING SHIP-EQUIPMENT MANUFACTURING TECHNOLOGY Co Ltd
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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
    • 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
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/284—Mg 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/002—Soldering by means of induction heating
    • 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
    • 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
    • B23K35/0233—Sheets, foils
    • 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
    • B23K35/3603—Halide salts
    • 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
    • B23K35/362—Selection of compositions of fluxes

Abstract

The invention discloses a kind of magnesium alloy brazing filler metal based on magnesium-rare earth soldering and preparation method and soldering processes, the elemental composition of the solder by weight percentage includes：Zn8.8% 11.5%, Al8.2% 9.3%, Ni3.8% 5.5%, Ag1.0% 3.0%, Ti1.0% 2.0%, Cu0.8% 2.2%, Mn0.5% 1.0%, surplus Mg.The magnesium alloy brazing filler metal based on magnesium-rare earth soldering of the present invention, the brazing temperature of magnesium alloy brazing filler metal is at 425 DEG C 475 DEG C, brazing filler metal melts moderate temperature, and solder composition is uniform；The diffusion of each alloying element and interfacial reaction during soldering connection are may advantageously facilitate using magnesium alloy brazing filler metal paillon foil, improves solder in the wetting and spreading of magnesium-rare earth and gap filling, crystal grain thinning and reduces residual stress, improves the bond strength of joint.

Description

Magnesium alloy brazing filler metal and preparation method and soldering processes based on magnesium-rare earth soldering
Technical field
The present invention relates to a kind of magnesium alloy brazing filler metal based on magnesium-rare earth soldering and preparation method and soldering processes, belong to Soldering field.
Background technology
Magnesium and magnesium alloy are a kind of material (ρ=1.74g/cm most light in current structural metallic materials3), it has density It is low, specific strength is high, damping property is good, electromagnetic wave shielding is good, electrical and thermal conductivity is good, processability is good, hot formability is good, easy to be recycled The features such as and enjoy favor extensively.With developing by leaps and bounds for new and high technology, to realize the greens such as lightweight, low energy consumption, environment-friendly type Road for development, the application to metal material is there occurs significant change in the world, reduces the application of traditional metal materials, and with Magnesium alloy is the light metal material sustainable growth of representative.Whole world researcher pays much attention to the research and development of magnesium alloy, by it The green engineering environment-friendly materials of 21 century are described as, the grand strategy material as 21 century.Electronics, automobile, Aero-Space and The fields such as defence and military have extremely important an application value and vast potential for future development, therefore are ground on the connection of magnesium alloy Study carefully and also increasingly paid attention to by every field researcher.
Soldering can open up the application field of magnesium alloy well as a kind of interconnection technique.But current business application Magnesium alloy brazing filler metal kind it is considerably less.The U.S. BMg-1, BMg-2a (test material association of the U.S. trade mark be respectively AZ92A, AZ125A it is) currently used magnesium alloy brazing filler metal, brazing temperature range is respectively 604 DEG C -616 DEG C and 582 DEG C -610 DEG C, soldering Temperature is too high, and the brazing flux melting temperature being equipped with is also higher (more than 538 DEG C)；The MC3 standard magnesium alloy brazing filler metals of Japan, its composition The BMg-1 in the U.S. is in close proximity to, the temperature range of the solder is 605 DEG C -615 DEG C, and brazing temperature is also too high.Japan's research and development In-Mg-Zn-Al solders, its brazing filler metal melts temperature range are 449 DEG C -490 DEG C, although reducing brazing temperature, are contained in solder There is substantial amounts of noble metal In, greatly improve the cost of solder.Mg-Al-Zn solders start to be applied to the magnesium conjunction of AZ systems in recent years The welding of gold, but the intensity of welding point need further to improve.
The performance of magnesium alloy brazing joint is all relatively low at present, far below the performance (σ of magnesium alloy substrate material> 200MPa).Soldering obtained by a kind of Al-Mg-Zn magnesium alloy brazing solders soldering AZ31B magnesium alloys of the patent No. 201110000830.0 Lap joint shearing strength is 23MPa-28MPa, and the tensile strength of banjo fixing butt jointing is 39MPa-44MPa；Application number 200910092578.3 a kind of magnesium alloy brazing solder soldering AZ31B magnesium alloys containing rare earth, soldering lap joint shearing strength For 38MPa-39MPa, the tensile strength of banjo fixing butt jointing is 53MPa-62MPa；One kind of the invention of the patent No. 201110205638.5 Magnesium alloy containing rare earth element er, soldering lap joint shear strength obtained by soldering magnesium alloy is 40MPa-46MPa；Application number A kind of 200910092579.8 Zn-Mg magnesium alloy brazing solders, the lap joint shearing strength of soldering AZ31B magnesium alloys are 38MPa-43MPa, the tensile strength of banjo fixing butt jointing is 52MPa-53MPa；A kind of magnesium that is used for of application number 200910092580.0 closes Golden soldering Zn-Mg-Al solders, the lap joint shearing strength of soldering AZ31B magnesium alloys is 43MPa-45MPa, banjo fixing butt jointing Tensile strength is 59MPa-62MPa；Connect obtained by the Zinc-magnesium based brazing alloy soldering magnesium alloy of application number 200910184467.5 Head shearing strength is 53MPa-68MPa；The magnesium-based brazing filler metal alloy of application number 200910184466.0, soldering obtained by soldering magnesium alloy are taken It is 57MPa-70MPa to connect joint bending stiffness.Therefore, it is magnesium alloy brazing field to develop for the magnesium-based brazing filler metal of magnesium alloy brazing Urgent problem, especially develop one kind and be applied to magnesium-rare earth soldering packing material, its brazing temperature is relatively low, anti-corruption The benefit performances such as corrosion is good, improve the bulk strength and heat resistance of magnesium-rare earth matrix material.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention proposes that one kind is based on magnesium-rare earth pricker The magnesium alloy brazing filler metal and preparation method and soldering processes of weldering, solder intensity is high, heat resistance is preferable, brazing temperature 425 DEG C- 475 DEG C, brazing filler metal melts moderate temperature, solder composition is uniform.
Technical scheme：In order to solve the above technical problems, the magnesium alloy brazing filler metal based on magnesium-rare earth soldering of the present invention, institute The elemental composition of solder by weight percentage is selected to include：Zn8.8%-11.5%, Al8.2%-9.3%, Ni3.8%- 5.5%th, Ag1.0%-3.0%, Ti1.0%-2.0%, Cu0.8%-2.2%, Mn0.5%-1.0%, surplus Mg.
Preferably, the soldering materials consist of the following components in percentage by weight：Zn9.0%-11%, Al8.2%- 8.8%th, Ni3.8%-5.2%, Ag1.5%-2.5%, Ti1.0%-1.8%, Cu1.0%-2.0%, Mn0.6%-1.0%, Surplus is Mg.
Preferably, following components Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are mixed in proportion, mass percent Content is as follows：10%Zn, 8.5%Al, 4.5%Ni, 2.0%Ag, 1.4%Ti, 1.5%Cu, 0.8%Mn, surplus Mg.
Preferably, the solder is paillon foil banding, thickness 0.1-0.3mm.
A kind of preparation method of the above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 15-20min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 30-50 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to the spacing of copper roller surface is adjusted to 100-200 μm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of purity>99.99% high-purity Ar gas enters to 200-250mbar to whole cavity Row protection；
5) motor is opened, makes copper roller rotating speed us=30m/s-32m/s, is then turned on high frequency electric source, by quartz glass tube After metal mixture high-frequency induction heating melts to substantially uniformity, superheated melt 5s-10s is incubated；
6) Ar gas air pressure is modulated into P=20-40KPa, continuously sprayed the superheated melt in quartz glass with high pressure argon gas To the cooling copper roller surface of high speed rotation, liquid metal is formed foil shape by chilling, thick so as to obtain chilling solder foil strip Spend for 0.1-0.3mm.
Preferably, quartz ampoule nozzle is rectangle in the step 3, its length is 8-10mm, width 0.8- 1.2mm。
Preferably, copper roller diameter is 250mm in the step 6, copper roller width is 50mm.
A kind of soldering processes of the above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, it is characterised in that including following Step：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 15-20min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.02MPa-0.04MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.0L/min-1.5L/min, and heating rate is 20 DEG C -30 DEG C/min, brazing temperature for 425 DEG C - 475 DEG C, soaking time 10min-15min, room temperature is cooled to, taken out by weldering connector.
Preferably, step (2) the middle rare earth magnesium alloy brazing flux each component mass percentage content is as follows：3.0% ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12%NaCl, 35%LiCl, 34.5%KCl.
Beneficial effect：Compared with prior art, the present invention has advantages below：
(1) brazing temperature of magnesium alloy brazing filler metal of the present invention is at 425 DEG C -475 DEG C, brazing filler metal melts moderate temperature, solder composition Uniformly；The diffusion of each alloying element and interfacial reaction during soldering connection are may advantageously facilitate using magnesium alloy brazing filler metal paillon foil, is carried High solder crystal grain thinning and reduces residual stress in the wetting and spreading of magnesium-rare earth and gap filling, improves joint Bond strength；
(2) soldering processes using the solder connection magnesium-rare earth of the present invention are reliable and stable, utilize induction brazing, flame Soldering connects with resistance brazing, and component is in heating process phenomena such as non-oxidation, softening and burning, and whole component is without deformation, nothing Microfissure, stomata and the defects of be mingled with, its moistened surface is sprawled preferably, is sufficient filling with brazed seam, and the entirety for improving joint connects Intensity is connect, and possesses good plastic deformation ability, thus more reliable and stable soldered fitting can be obtained；
(3) solder of the present invention connection magnesium alloy, solder and matrix mother metal are sufficiently formed solid solution metallurgical reaction, tissue particle, Filling is uniform, embodies the excellent switching performance of solder of the present invention, has stronger bond strength, the application neck of magnesium alloy Domain；
(4) prepared by the magnesium alloy brazing filler metal that the present invention obtains and soldering processes are simple, and easy to implement quick, composition is easy to control System, impurity is few, is adapted to the batch production of high quality brazing filler metal alloy, the preparation of solder and the repeatable reproduction of soldering processes, is easy to wide General popularization and application.
Embodiment
Technical solution of the present invention is further elaborated with reference to specific embodiment, but the present invention and not only office It is limited to following examples.
Embodiment 1
The composition and mass percent of solder match：9.0%Zn, 8.8%Al, 3.8%Ni, 2.5%Ag, 1.0%Ti, 2.0%Cu, 0.6%Mn, Mg72.3%.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 20min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 30 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.2mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 200mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=31m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 8s is incubated；
6) Ar gas air pressure is modulated into P=30KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.3mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 20min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.04MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.5L/min, and heating rate is 30 DEG C/min, and brazing temperature is 475 DEG C, soaking time 10min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 125MPa.
Embodiment 2：
The composition and mass percent of solder match：10%Zn, 8.5%Al, 4.5%Ni, 2.0%Ag, 1.4%Ti, 1.5%Cu, 0.8%Mn, 71.3%Mg.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 15min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 40 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.1mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 250mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=31m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 8s is incubated；
6) Ar gas air pressure is modulated into P=20KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.2mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 20min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.03MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.0L/min, and heating rate is 25 DEG C/min, and brazing temperature is 450 DEG C, soaking time 10min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 132MPa.
Embodiment 3：
The composition and mass percent of solder match：11%Zn, 8.2%Al, 5.2%Ni, 1.5%Ag, 1.8%Ti, 1.0%Cu, 1.0%Mn, Mg70.3%.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 20min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 50 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.1mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 200mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=31m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 8s is incubated；
6) Ar gas air pressure is modulated into P=40KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.1mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 20min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.02MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.5L/min, and heating rate is 20 DEG C/min, and brazing temperature is 425 DEG C, soaking time 15min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 118MPa.
Embodiment 4
The composition and mass percent of solder match：8.8%Zn, 9.3%Al, 5.5%Ni, 3.0%Ag, 1.0%Ti, 2.2%Cu, 1.0%Mn, Mg69.2%.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 15min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 30 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.1mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 200mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=32m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 10s is incubated；
6) Ar gas air pressure is modulated into P=30KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.1mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 15min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.02MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.0L/min, and heating rate is 20 DEG C/min, and brazing temperature is 475 DEG C, soaking time 15min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 122MPa.
Embodiment 5：
The composition and mass percent of solder match：9.0%Zn, 8.2%Al, 5.2%Ni, 2.5%Ag, 1.8%Ti, 2.0%Cu, 0.6%Mn, 70.7%Mg.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 18min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 40 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.15mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 250mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=30m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 5s is incubated；
6) Ar gas air pressure is modulated into P=20KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.2mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 18min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.03MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.0L/min, and heating rate is 25 DEG C/min, and brazing temperature is 450 DEG C, soaking time 10min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 132MPa.
Embodiment 6：
The composition and mass percent of solder match：11.5%Zn, 9.3%Al, 5.5%Ni, 3.0%Ag, 2.0% Ti, 2.2%Cu, 1.0%Mn, Mg65.5%.
A kind of preparation method of above-mentioned magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprises the following steps：
1) the block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg of high-purity is weighed by mass percentage, is put into In container added with acetone, ultrasonic cleaning 20min is carried out at room temperature；
2) mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 50 DEG C, obtains dry mixture；
3) mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into proprietary quartz glass tube, mounted in getting rid of with machine In high-frequency induction heating circle, and its nozzle to copper roller surface spacing is adjusted to 0.1mm；
4) fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, high vacuum Degree is not less than 9 × 10-4Pa, then cavity be full of high-purity Ar gas (purity>99.99%) to 200mbar, whole cavity is protected Shield；
5) motor is opened, makes copper roller rotating speed us=31m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 8s is incubated；
6) Ar gas air pressure is modulated into P=40KPa, the superheated melt in quartz glass is continuously ejected into height with high pressure argon gas The cooling copper roller surface of speed rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.1mm。
Magnesium-rare earth (Nd0.010%, Ce0.264%, Mn1.74%, Pb0.014%, Ni0.003%, Zn0.004%, Sn0.004%, Si0.028%, La0.002%, surplus Mg) banjo fixing butt jointing high-frequency induction resistance brazing, examination Sample ruler cun is 20mm × 20mm × 6mm, and face to be brazed is 20mm × 6mm sections.
Brazing flux each component percent mass proportioning：3.0%ZnF2, 8.5%ZnCl2, 5.0%NaF, 2.0%LiF, 12% NaCl, 35%LiCl, 34.5%KCl.
A kind of soldering processes of the magnesium alloy brazing filler metal based on magnesium-rare earth soldering, comprise the following steps：
(1) preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, remove impurity, the greasy dirt on surface with And oxide-film, it is ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil is placed in third together In ketone, 20min is cleaned using ultrasonic wave, and carry out drying and processing；
(2) assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, at interface to be connected Surrounding adds magnesium-rare earth brazing flux, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture The pressure head of nominal-mass, produce 0.02MPa constant perpendicular pressure；
(3) the soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and enters Row protection, Ar throughputs be 1.5L/min, and heating rate is 20 DEG C/min, and brazing temperature is 425 DEG C, soaking time 15min, cold But to room temperature, take out by weldering connector.
As a result：The magnesium-rare earth jointing that soldering obtains is formed well, and metallographic observation finds that brazing area forms densification Interface cohesion, alloying component is evenly distributed, and room temperature shear strength is 128MPa.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (9)

  1. A kind of 1. magnesium alloy brazing filler metal based on magnesium-rare earth soldering, it is characterised in that：Selected solder is by weight percentage Elemental composition includes：Zn8.8%-11.5%、Al8.2%-9.3%、Ni3.8%-5.5%、Ag1.0%-3.0%、Ti1.0%-2.0%、 Cu0.8%-2.2%, Mn0.5%-1.0%, surplus Mg.
  2. 2. the magnesium alloy brazing filler metal according to claim 1 based on magnesium-rare earth soldering, it is characterised in that：The solder by Following components in percentage by weight forms：Zn9.0%-11%、Al8.2%-8.8%、Ni3.8%-5.2%、Ag1.5%-2.5%、 Ti1.0%-1.8%, Cu1.0%-2.0%, Mn0.6%-1.0%, surplus Mg.
  3. 3. the magnesium alloy brazing filler metal according to claim 2 based on magnesium-rare earth soldering, it is characterised in that：By following components Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are mixed in proportion, and mass percentage content is as follows： 10%Zn、8.5%Al、4.5% Ni, 2.0%Ag, 1.4%Ti, 1.5%Cu, 0.8%Mn, surplus Mg.
  4. 4. the magnesium alloy brazing filler metal according to claim 2 based on magnesium-rare earth soldering, it is characterised in that：The solder is Paillon foil banding, thickness 0.1-0.3mm.
  5. 5. a kind of preparation method of magnesium alloy brazing filler metal based on magnesium-rare earth soldering as described in any one of Claims 1-4, It is characterised in that it includes following steps：
    1）The block obtained mixture of Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg is weighed by mass percentage, is put into the appearance added with acetone In device, ultrasonic cleaning 15-20min is carried out at room temperature；
    2）Mixture after step 1 is cleaned by ultrasonic is dried at a temperature of 30-50 DEG C, obtains dry mixture；
    3）Mixture Zn, Al, Ni, Ag, Ti, Cu, Mn and Mg are fitted into quartz glass tube, added mounted in the high-frequency induction with machine is got rid of In gas ket, and its nozzle to the spacing of copper roller surface is adjusted to 100-200 μm；
    4）Fire door is closed, 1.5 × 10 are evacuated to using mechanical pump-1Pa, then using molecular pump pumping high vacuum, condition of high vacuum degree is not Less than 9 × 10-4Pa, then cavity full of Ar gas to 200-250mbar, whole cavity is protected；
    5）Motor is opened, makes copper roller rotating speed us=30m/s-32m/s, is then turned on high frequency electric source, and the metal in quartz glass tube is mixed After compound high-frequency induction heating melts to substantially uniformity, superheated melt 5s-10s is incubated；
    6）Ar gas air pressure is modulated into P=20-40KPa, is continuously ejected into the superheated melt in quartz glass at a high speed with high pressure argon gas The cooling copper roller surface of rotation, liquid metal are formed foil shape by chilling, and so as to obtain chilling solder foil strip, thickness is 0.1-0.3mm。
  6. 6. the preparation method of the magnesium alloy brazing filler metal according to claim 5 based on magnesium-rare earth soldering, it is characterised in that： Quartz ampoule nozzle is rectangle in the step 3, and its length is 8-10mm, width 0.8-1.2mm.
  7. 7. the preparation method of the magnesium alloy brazing filler metal according to claim 5 based on magnesium-rare earth soldering, it is characterised in that： Copper roller diameter is 250mm in the step 6, and copper roller width is 50mm.
  8. 8. a kind of soldering processes of magnesium alloy brazing filler metal based on magnesium-rare earth soldering as described in any one of Claims 1-4, It is characterised in that it includes following steps：
    （1）Preparatory stage：Magnesium-rare earth surface to be welded to be brazed is cleared up, removes the impurity, greasy dirt and oxygen on surface Change film, be ground using W28-W3.5 abrasive paper for metallograph smooth, magnesium-rare earth and solder paillon foil are placed in acetone together, 15-20min is cleaned using ultrasonic wave, and carries out drying and processing；
    （2）Assembling stage：Between solder paillon foil after cleaning is placed in into magnesium-rare earth welding surface, around interface to be connected Magnesium-rare earth brazing flux is added, and is close to be assemblied in special brazing jig, it is ensured that the precision of connection, is placed on fixture specified The pressure head of quality, produce 0.02MPa-0.04MPa constant perpendicular pressure；
    （3）The soldering connection stage：The fixture assembled is integrally placed in high-frequency induction resistance furnace apparatus, argon gas is filled with and is protected Shield, Ar throughputs are 1.0L/min-1.5L/min, and heating rate is 20 DEG C -30 DEG C/min, and brazing temperature is 425 DEG C -475 DEG C, Soaking time 10min-15min, is cooled to room temperature, takes out by weldering connector.
  9. 9. the soldering processes of the magnesium alloy brazing filler metal according to claim 8 based on magnesium-rare earth soldering, it is characterised in that： The step（2）Middle rare earth magnesium alloy brazing flux each component mass percentage content is as follows：3.0%ZnF2、8.5%ZnCl2、5.0% NaF、2.0%LiF、12%NaCl、35%LiCl、34.5%KCl。
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