CN102554509A - Vacuum brazing solder and process of Mo-Cu alloy and stainless steel - Google Patents
Vacuum brazing solder and process of Mo-Cu alloy and stainless steel Download PDFInfo
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- CN102554509A CN102554509A CN2012100433795A CN201210043379A CN102554509A CN 102554509 A CN102554509 A CN 102554509A CN 2012100433795 A CN2012100433795 A CN 2012100433795A CN 201210043379 A CN201210043379 A CN 201210043379A CN 102554509 A CN102554509 A CN 102554509A
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Abstract
The invention relates to a vacuum brazing solder and a process of Mo-Cu alloy and stainless steel. The process comprises the steps of placing BNi2 amorphous alloy solder between preprocessed Mo-Cu alloy and surface to be brazed of austenitic stainless steel, controlling the joint gap between 40-80mum, gently placing the assembled Mo-Cu alloy and the stainless steel at a uniform temperature zone in a vacuum brazing furnace, vacuumizing and brazing, wherein the BNi2 amorphous alloy solder comprises the components in percentage by mass: 6.5-7.5% of Cr, 3.0-5.0% of Si, 2.7-3.5% of B, 2.5-3.5% of Fe, less than or equal to 0.02% of C and the balance of Ni. The Mo-Cu alloy and stainless steel joint obtained by the process disclosed by the invention have the advantages of little impurity, high density, strong high temperature resisting ability and the like and can be used for manufacturing instrument and meter elements, electronic packaging and high temperature resisting devices.
Description
Technical field
The present invention relates to a kind of molybdenum-copper and stainless soldering processes, particularly a kind of amorphous filler metal that adopts belongs to the foreign material welding technology field with the method that molybdenum-copper and stainless steel carry out vacuum brazing.
Background technology
Molybdenum-copper has higher thermal conductivity factor and lower thermal coefficient of expansion and better heat-resisting performance, therefore is of use in many ways.Its high thermal conductivity factor has future preferably as high-power electronic device and radiating element; The low seal, sealing materials that can be used as of its coefficient of expansion; Its good heat resistance can be used as high-temperature component etc.But when molybdenum-copper and stainless steel welding, because between the two the thermal coefficient of expansion and the capacity of heat transmission differ bigger, the joint is prone to produce very big stress, increases the crackle tendency.And molybdenum-copper is responsive to gaseous impurity, and the joint is prone to produce pore, seam organization thick (200～500 μ m), and when joint cooled off fast, interstitial impurity also can form segregation on crystal boundary.Therefore, the pollution of gaseous impurity and seam organization alligatoring are the subject matter that molybdenum-copper and austenitic stainless steel welding face.
At present, in vacuum or protective atmosphere, welding is to suppress molybdenum-copper to be polluted approach preferably by gaseous impurity.Adopt molybdenum manganese metal method for brazing to Mo-Cu composite and Al like Beijing vacuum electronic technical research institute
2O
3Pottery carries out sealing-in, and the joint performance of acquisition meets the instructions for use of HIGH-POWERED MICROWAVES component vacuum tubulation; University of Science & Technology, Beijing adopts the Ag-Cu-Ti solder that Mo-Cu composite and AlN pottery are carried out brazing in controlled atmosphere, and solder and mother metal have wetability preferably; Shandong University adopts the tungsten argon arc soldering method that molybdenum-copper and austenitic stainless steel are welded.These methods can suppress the pollution of external gaseous impurity, obtain the higher seam organization of purity.But in order to obtain the welding point of high-compactness; Utilize that amorphous filler metals fusion temperature scope is extremely narrow, fusing time is extremely short, have mobile characteristics of good moment; Molybdenum-copper and stainless steel are carried out vacuum brazing, can obtain fine and close high-strength joint.The patent No. is that 2010105280034 Chinese patent discloses and a kind ofly carries out molybdenum-copper and stainless vacuum brazing technique with the Cu-Mn-Co brazing filler metal; Compare with amorphous filler metals; Cu-Mn-Co brazing filler metal fusion temperature wider range; The temperature retention time that needs is longer, is unfavorable for improving welding production efficiency.
Summary of the invention
The objective of the invention is deficiency to prior art; And a kind of molybdenum-copper and stainless vacuum brazing solder and technology are provided; This kind process using amorphous filler metals is carried out vacuum brazing with molybdenum-copper and austenitic stainless steel and is connected; The processing procedure of the molybdenum-copper nickel preplating of not only having avoided relating in other soldering processes need not to add brazing flux again.Therefore, these soldering processes have characteristics such as flexible operation is simple, cost is low, easy to utilize, are particularly useful for the welding of molybdenum-copper and austenitic stainless steel, also can be used for molybdenum-copper and other low-alloy steel, heat-resistant steel welding.
A kind of molybdenum-copper and stainless vacuum brazing solder, its mass percent consists of: Cr 6.5～7.5%, and Si 3.0～5.0%, and B 2.7～3.5%, and Fe 2.5～3.5%, C≤0.02%, Ni surplus.
A kind of molybdenum-copper and stainless vacuum brazing technique may further comprise the steps:
(1) molybdenum-copper and stainless steel are carried out surface treatment, remove oxide-film and foreign matter;
(2) be that the foil-like BNi2 amorphous filler metals of 50～80 μ m places between pretreated molybdenum-copper and the austenitic stainless steel welding surface with thickness, assemble then that the control play movement is between 40～80 μ m; The mass percent of BNi2 amorphous filler metals consists of: Cr 6.5～7.5%; Si 3.0～5.0%, and B 2.7～3.5%, and Fe 2.5～3.5%; C≤0.02%, the Ni surplus;
(3) place the uniform temperature zone in the vacuum brazing furnace to vacuumize soldering gently molybdenum-copper that assembles and stainless steel.
Molybdenum-copper and stainless steel carried out surface treatment step be described in the above-mentioned steps (1): earlier molybdenum-copper and stainless steel surfaces are adopted the SiC coated abrasive working of 800#, remove surperficial oxide-film; Then molybdenum-copper and stainless steel part are placed on ultrasonic cleaning 20～30min in the acetone, hot-air seasoning respectively.
Vacuumize soldering for molybdenum-copper that assembles and stainless steel are placed the uniform temperature zone in the vacuum brazing furnace gently described in the above-mentioned steps (3), shut the vacuum brazing stove evacuation, reach 1.33 * 10 to vacuum
-4～1.33 * 10
-3Heat during Pa, preferably follow these steps to soldering then:
1) makes the vacuum drying oven linear temperature increase, make furnace temperature at the uniform velocity be raised to 850 ℃ with 50min;
2) carry out phase I insulation 20min, the deflation course of workpiece mother metal and solder can fully be carried out, the hot stage soldering oven can be kept higher vacuum after being convenient to;
3) the phase I insulation is rapidly heated after finishing, and in 20min, furnace temperature at the uniform velocity is raised to 1030 ℃ from 850 ℃;
4) after furnace temperature reaches 1030 ℃, carry out second stage insulation 15min,, guarantee temperature-controlled precision so that avoid excessive thermal inertia;
5) after the second stage insulation finishes, in 15min, furnace temperature is at the uniform velocity risen to 1090 ℃ ± 10 ℃ from 1030 ℃;
6) when furnace temperature reaches 1090 ℃ ± 10 ℃, carry out phase III insulation 10min, so that guarantee the solder diffusion fully, and take into account the difference of Heating Zone Temperature;
7) after the phase III, insulation finished, vacuum brazing furnace stopped heating, cools off naturally with stove;
When 8) treating that the vacuum chamber temperature is cooled to below 100 ℃, take out weldment.
The present invention adopts directly fusing and wetting realization molybdenum-copper and the stainless vacuum brazing fast of BNi2 amorphous filler metals.Its soldering operation principle is: utilize the BNi2 amorphous filler metals of flash set technology preparation (rapid solidification preparation method is existing mature technology), have very big degree of supercooling and solid liquid interface fltting speed, enlarged solid solubility limit; Suppress the formation of equilibrium phase; Make the solder chemical composition even, segregation significantly reduces, and because the fusion temperature scope extremely narrow (970 ℃～1000 ℃) of BNi2 amorphous filler metals; Fusing time is extremely short; Thereby have good moment flowability, the capillary adsorption function can be given full play to, thereby fine and close molybdenum-copper and stainless steel high-strength joint can be obtained.In addition, the Ni element can be dissolved in Cu, can be dissolved in Mo again, and can increase the solubility of solid-state molybdenum in liquid copper, therefore in brazing process, can improve the wetability between liquid phase copper and the Mo preferably, and the increase molybdenum-copper combines with the stainless steel braze welding interface.
Compare with fusion welding method, adopt soldering processes of the present invention, not only can reduce cooling velocity, reduce the generation tendency of compound between brittle metal; And welding is to carry out in a vacuum, can reduce the pollution of gaseous impurity, improves the degree of purity of weld seam; Simultaneously, adopt the uniform BNi2 amorphous filler metals of chemical composition, can improve the density at soldering interface.The shear strength that obtains molybdenum-copper and stainless steel adapting piece reaches 200～230MPa.
Compare with the Cu-Mn-Co brazing filler metal, adopt soldering processes of the present invention, can reduce the high temperature retention time, help improving welding efficiency, and the strength of joint that obtains is also higher.
The vacuum brazing temperature curve that the present invention adopts is provided with three insulation platforms, and its effect is respectively: the one, and the deflation course of workpiece mother metal and solder can fully be carried out, be convenient to the hot stage soldering oven and can keep higher vacuum; The 2nd, make uniformity of temperature profile in the soldering oven, to guarantee accurately to control temperature; The 3rd, promote the abundant fusing and the diffusion of solder, improve strength of joint.
Adopt technology of the present invention, the molybdenum-copper of acquisition and stainless joint have advantages such as impurity is few, density is high, heat-resisting ability is strong, can be used for the manufacturing of instrument and meter element, Electronic Packaging, high temperature resistant device.
Description of drawings
Fig. 1 is molybdenum-copper of the present invention and stainless vacuum brazing technique temperature profile;
1. be warming up to 850 ℃; 2. be incubated 20min; 3. be warming up to 1030 ℃; 4. be incubated 15min; 5. be warming up to 1090 ℃ ± 10 ℃; 6. be incubated 10min; 7. cool off with stove.
The specific embodiment
Further specify below in conjunction with embodiment.
Embodiment 1:
The vacuum brazing of molybdenum-copper plate and 1Cr8Ni9Ti austenitic stainless steel banjo fixing butt jointing, molybdenum-copper consist of Mo60%-Cu40% (mass fraction), are of a size of 30mm * 8mm, and thickness is 2.5mm; Austenitic stainless steel is the 1Cr8Ni9Ti stainless steel, is of a size of 30mm * 10mm, and thickness is 3.0mm.
The first step, the stainless surface treatment of molybdenum-copper and 1Cr8Ni9Ti:
With the SiC coated abrasive working of molybdenum-copper and 1Cr8Ni9Ti stainless steel surfaces employing 800#, remove the oxide-film on surface earlier;
Put into acetone then, ultrasonic cleaning 30min, the taking-up oven dry is for use.
Second step, the stainless assembling of molybdenum-copper and 1Cr8Ni9Ti:
With thickness is that (chemical composition is: Cr 6.5%, and Si 5.0%, and B 2.7% for the foil-like BNi2 amorphous filler metals of 50 μ m; Fe 3.5%; C≤0.02%, the Ni surplus places between pretreated molybdenum-copper and the 1Cr8Ni9Ti stainless steel welding surface by percentage to the quality); Assemble control play movement 40～60 μ m then.
In the 3rd step, the molybdenum-copper that assembles and stainless steel are put into vacuum brazing furnace carry out soldering.Body of heater adopts tungsten bar to heat, and the working vacuum degree is 1.33 * 10
-5Pa, uniform temperature zone are of a size of 305mm * 305mm * 457mm, adopt heating in the digital process control stove, insulation and temperature-fall period.
Assembly parts are placed the uniform temperature zone in the vacuum brazing furnace gently, shut the vacuum brazing stove evacuation, reach 1.33 * 10 to vacuum
-3Heat during Pa.Brazing process temperature curve according to setting carries out soldering, and its process is following:
1) makes the vacuum drying oven linear temperature increase, make furnace temperature at the uniform velocity be raised to 850 ℃ with 50min;
2) carry out phase I insulation 20min, the deflation course of workpiece mother metal and solder can fully be carried out, the hot stage soldering oven can be kept higher vacuum after being convenient to;
3) the phase I insulation is rapidly heated after finishing, and in 20min, furnace temperature at the uniform velocity is raised to 1030 ℃ from 850 ℃;
4) after furnace temperature reaches 1030 ℃, carry out second stage insulation 15min,, guarantee temperature-controlled precision so that avoid excessive thermal inertia;
5) after the second stage insulation finishes, in 15min, furnace temperature is at the uniform velocity risen to 1100 ℃ from 1030 ℃;
6) when furnace temperature reaches 1100 ℃, carry out phase III insulation 10min, so that guarantee the solder diffusion fully, and take into account the difference of Heating Zone Temperature;
7) after the phase III, insulation finished, vacuum brazing furnace stopped heating, cools off naturally with stove;
When 8) treating that the vacuum chamber temperature is cooled to below 100 ℃, take out weldment.
The molybdenum-copper and the 1Cr8Ni9Ti stainless steel butt braze appearance of weld that obtain are attractive in appearance, and solder is good to molybdenum-copper and 1Cr8Ni9Ti stainless steel surfaces wetability.Do not find microfissure, defective such as be mingled with through the metallography microscope sem observation, it is good that the brazing area interface combines, and shearing strength of joint reaches 210MPa.
Embodiment 2
The vacuum brazing of molybdenum-copper plate and corrosion resistant plate lap joint, molybdenum-copper consist of Mo50%-Cu50% (mass fraction), are of a size of 30mm * 8mm, and thickness is 2.5mm; Austenitic stainless steel is the 1Cr8Ni9Ti stainless steel, is of a size of 30mm * 10mm, and thickness is 3.0mm.
The first step, molybdenum-copper and stainless surface treatment:
With the SiC coated abrasive working of molybdenum-copper and 1Cr8Ni9Ti stainless steel surfaces employing 800#, remove the oxide-film on surface earlier;
Put into acetone ultrasonic cleaning 25min then, hot-air seasoning.
Second step, molybdenum-copper and stainless assembling:
With thickness is that (chemical composition is: Cr 7.5%, and Si 3.0%, and B 3.5% for the foil-like BNi2 amorphous filler metals of 70 μ m; Fe 2.5%; C≤0.02%, the Ni surplus places between pretreated molybdenum-copper and the 1Cr8Ni9Ti stainless steel welding surface by percentage to the quality); Assemble control play movement 40～60 μ m then.
In the 3rd step, the molybdenum-copper that assembles and stainless steel are put into vacuum brazing furnace carry out soldering.Body of heater adopts tungsten bar to heat, and the working vacuum degree is 1.33 * 10
-5Pa, uniform temperature zone are of a size of 305mm * 305mm * 457mm, adopt heating in the digital process control stove, insulation and temperature-fall period.
Assembly parts are placed the uniform temperature zone in the vacuum brazing furnace gently, shut the vacuum brazing stove evacuation, reach 1.33 * 10 to vacuum
-3Heat during Pa.Brazing process temperature curve according to setting carries out soldering, and its process is following:
1) makes the vacuum drying oven linear temperature increase, make furnace temperature at the uniform velocity be raised to 850 ℃ with 50min;
2) carry out phase I insulation 20min, the deflation course of workpiece mother metal and solder can fully be carried out, the hot stage soldering oven can be kept higher vacuum after being convenient to;
3) the phase I insulation is rapidly heated after finishing, and in 20min, furnace temperature at the uniform velocity is raised to 1030 ℃ from 850 ℃;
4) after furnace temperature reaches 1030 ℃, carry out second stage insulation 15min,, guarantee temperature-controlled precision so that avoid excessive thermal inertia;
5) after the second stage insulation finishes, in 15min, furnace temperature is at the uniform velocity risen to 1090 ℃ from 1030 ℃;
6) when furnace temperature reaches 1090 ℃, carry out phase III insulation 10min, so that guarantee the solder diffusion fully, and take into account the difference of Heating Zone Temperature;
7) after the phase III, insulation finished, vacuum brazing furnace stopped heating, cools off naturally with stove;
When 8) treating that the vacuum chamber temperature is cooled to below 100 ℃, take out weldment.
The molybdenum-copper and the 1Cr8Ni9Ti stainless steel butt braze appearance of weld that obtain are attractive in appearance, and solder is good to molybdenum-copper and 1Cr8Ni9Ti stainless steel surfaces wetability.Do not find microfissure, defective such as be mingled with through the metallography microscope sem observation, it is good that the brazing area interface combines, and shearing strength of joint reaches 230MPa.
Embodiment 3
Step is with embodiment 1, and the mass percent of BNi2 amorphous filler metals that different is consists of: Cr 6.8%, and Si 3.8%, and B 2.9%, and Fe 3.1%, C≤0.02%, Ni surplus.
The molybdenum-copper and the 1Cr8Ni9Ti stainless steel butt braze appearance of weld that obtain are attractive in appearance, and solder is good to molybdenum-copper and 1Cr8Ni9Ti stainless steel surfaces wetability.Do not find microfissure, defective such as be mingled with through the metallography microscope sem observation, it is good that the brazing area interface combines, and shearing strength of joint reaches 225MPa.
Claims (4)
1. a molybdenum-copper and stainless vacuum brazing solder is characterized in that its mass percent consists of: Cr6.5～7.5%, and Si 3.0～5.0%, and B 2.7～3.5%, and Fe 2.5～3.5%, C≤0.02%, Ni surplus.
2. a molybdenum-copper and stainless vacuum brazing technique is characterized in that, may further comprise the steps:
(1) molybdenum-copper and stainless steel are carried out surface treatment, remove oxide-film and foreign matter;
(2) be that the foil-like BNi2 amorphous filler metals of 50～80 μ m places between pretreated molybdenum-copper and the austenitic stainless steel welding surface with thickness, assemble then that the control play movement is between 40～80 μ m; The mass percent of BNi2 amorphous filler metals consists of: Cr 6.5～7.5%; Si 3.0～5.0%, and B 2.7～3.5%, and Fe 2.5～3.5%; C≤0.02%, the Ni surplus;
(3) place the uniform temperature zone in the vacuum brazing furnace to vacuumize soldering gently molybdenum-copper that assembles and stainless steel.
3. a kind of molybdenum-copper according to claim 2 and stainless vacuum brazing technique; It is characterized in that; Molybdenum-copper and stainless steel carried out surface treatment step be described in the step (1): earlier molybdenum-copper and stainless steel surfaces are adopted the SiC coated abrasive working of 800#, remove surperficial oxide-film; Then molybdenum-copper and stainless steel part are placed on ultrasonic cleaning 20～30min in the acetone, hot-air seasoning respectively.
4. a kind of molybdenum-copper according to claim 2 and stainless vacuum brazing technique; It is characterized in that; Vacuumize soldering for molybdenum-copper that assembles and stainless steel are placed the uniform temperature zone in the vacuum brazing furnace gently described in the step (3); Shut the vacuum brazing stove evacuation, reach 1.33 * 10 to vacuum
-4～1.33 * 10
-3Heat during Pa, follow these steps to soldering then:
1) makes the vacuum drying oven linear temperature increase, make furnace temperature at the uniform velocity be raised to 850 ℃ with 50min;
2) carry out phase I insulation 20min, the deflation course of workpiece mother metal and solder can fully be carried out, the hot stage soldering oven can be kept higher vacuum after being convenient to;
3) the phase I insulation is rapidly heated after finishing, and in 20min, furnace temperature at the uniform velocity is raised to 1030 ℃ from 850 ℃;
4) after furnace temperature reaches 1030 ℃, carry out second stage insulation 15min,, guarantee temperature-controlled precision so that avoid excessive thermal inertia;
5) after the second stage insulation finishes, in 15min, furnace temperature is at the uniform velocity risen to 1090 ℃ ± 10 ℃ from 1030 ℃;
6) when furnace temperature reaches 1090 ℃ ± 10 ℃, carry out phase III insulation 10min, so that guarantee the solder diffusion fully, and take into account the difference of Heating Zone Temperature;
7) after the phase III, insulation finished, vacuum brazing furnace stopped heating, cools off naturally with stove;
When 8) treating that the vacuum chamber temperature is cooled to below 100 ℃, take out weldment.
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