A kind of haptoreaction diffusion brazing method of attachment of magnesium alloy and steel
Technical field
The invention belongs to technical field of dissimilar material connection, and in particular to magnesium alloy connects with the haptoreaction diffusion brazing of steel
Connect method.
Background technology
Magnesium alloy is the most light structural metallic materials of quality of current practice, is referred to as " the green engineering of 21 century
Environment-friendly materials ".Because it has little (the only 1.74g/cm of density3), specific strength and specific stiffness are high, and damping property and diamagnetism are good,
It is easy to the series of advantages such as machining and recovery, leads in the industry such as automobile, electronics, electrical equipment, traffic, Aeronautics and Astronautics and national defence
Domain has extremely important using value and prospect.But the application of magnesium alloy inevitably runs into and is asked with the connection of steel
Topic, so develop the efficient welding technology of magnesium alloy and steel, especially for lightweight labyrinth and needs large area part
Connection seem particularly urgent.
The fusing point of magnesium alloy is relatively low, only 650 DEG C, very sensitive to welding temperature, easily occurs in traditional fusion process
The oxidation of magnesium alloy and Evaporation Phenomenon, or even at normal temperatures magnesium alloy is also easy to aoxidize.Magnesium steel belongs to foreign material, its
Physical and chemical performance difference is larger, and especially the fusing point of bi-material, linear expansion coefficient difference are notable, considerably increase and weld this
The difficulty of two kinds of metals.Be related to magnesium alloy at present mainly has fusion welding, laser welding-brazing, soldering, diffusion with the method for attachment of steel
Weldering and agitating friction weldering.The greatest problem of melting welding is difficult to realize the control to welding process that magnesium alloy is easily sent out under high temperature
Raw burn-off phenomenon, oxidation is serious, and larger stress concentration and a large amount of pores can be produced in welding process.Liu Liming is molten
Weldering magnesium alloy has done substantial amounts of research with steel aspect.Research shows, it is single with laser and electric arc as thermal source welding magnesium alloy with
The drawbacks of steel has a lot.Absorbance difference of the magnesium alloy to laser energy, single is easily caused with laser welding magnesium steel dissimilar metal
Not enough, easily there are the defects such as crackle and pore in the magnesium steel different-metal material welding joint of formation in fusion penetration, and mechanical property is poor.It is single
Arc welding process in, because electric arc energy itself compares diverging, therefore increase the model of the welding heat affected zone in welding
Enclose so that the performance of joint is reduced.Hereafter, Liu Liming etc. is welded using laser-arc hybrid welding process to magnesium steel again, is still failed
Effectively solve the problems, such as magnesium steel interfacial metal oxide.Because fusion welds temperature is higher, and magnesium alloy is a kind of very active
Metal, fusing point boiling point is all than relatively low, it is easy to oxidation occurs and generates brittlement phase MgO, cause to occur being mingled with weld seam.In high temperature
Also easily nitride is generated with N2 reactions down, further reduce the performance of welding point.
M.Wahba laser is thermal source welding magnesium alloy AZ31B/SP781 galvanized steels.Due to larger between magnesium alloy and steel
Physical property difference, its welding process very unstable (splash, fusion penetration is than unstable etc.), particularly when laser beam penetrates magnesium
Alloy into steel curved beam make steel side form the pattern of similar lockhole when, its stability is very poor.Wingceltis wealth is prosperous with magnesium weld line to fill material
Material, the molten Braze tests research of single, double beam laser is carried out to AZ31 magnesium alloys/zinc-plated steel dissimilar alloys of DP980.Using single, double
The light beam molten soldering that carries out filling silk can obtain relatively satisfactory appearance forming, but no matter single, double shear strength test result shows
It is relatively low that light beam carries out welding shear strength to magnesium alloy and steel, and points out that the presence of welding toe crackle is to cause joint fails
Main cause.
Conventional brazing method welds magnesium alloy with the general solder relatively low using fusing point, such as Al bases solder or Zn bases during steel
Solder.By heating and thermal insulation, soldered fitting is obtained using metallurgical reaction is instead given birth to mother metal after brazing filler metal melts wetting and spreading, due to magnesium
Alloy is easily aoxidized in welding process, typically needs to use brazing flux, postwelding to need to be cleared up in welding process, and
There is the weld defects such as pore, " big surround " and " little encirclement ", joint compactness is poor, it is difficult to realize high compactness connection.
Takahiro et al. is studied magnesium alloy AZ31 using diffusion welding (DW) from different steel plates (two kinds of models of SPCC and GI)
Zinc layers and impact of the aluminium element to magnesium steel dissimilar metal diffusion welding (DW).Result of study shows that SPCC steel is not realized with magnesium alloy
Effectively connection, this is because magnesium alloy there occurs oxidation in welding process, its Surface Creation oxide layer, hinder magnesium steel it
Between contact diffusion.On the other hand, the combination of GI steel and magnesium alloy is successfully realized using identical welding procedure.Additionally, passing through
EPMA analyses find that magnesium steel interface forms one layer very thin and discontinuous Fe-Al intermetallic compounds layers, exactly by this layer
Fe-Al compounds just cause both materials to form metallurgical binding.So strict control oxygen content is that have very much must in diffusion welding (DW)
Want.
Y.Abe and Watanabe et al. realize the docking connection of magnesium steel dissimilar metal using agitating friction weldering.Have studied and stir
The rotary speed of head is mixed with the side-play amount of stirring-head to the microstructure of magnesium steel dissimilar metal joint and the impact of mechanical property.Grind
Study carefully and find that the amount of plastic deformation of the magnesium at bead contact face is improved, so that joint with the increase of the rotary speed of stirring-head
Mechanical property be improved 70% or so of about magnesium alloy mother metal.But tension failure position is said in the interface of magnesium steel
The bond strength at bright interface is undesirable.S.JANA et al. is carried out using agitating friction welding technology welding magnesium alloy with steel dissimilar metal
Research, it is again seen that the Zn-Mg alloy-layers that should be generated of sending out of the Zn layers on galvanized steel plain sheet and magnesium alloy improve magnesium/steel joint
Mechanical property.
In sum, develop a kind of new magnesium alloy and seem particularly urgent with steel method of attachment.Haptoreaction spreads
Soldering is that (eutectic is anti-for a kind of metallurgical reaction relied at a lower temperature between mother metal or between mother metal and intermediate layer material
Should) produce liquid phase to realize the process of connection, it can be good at avoiding the macroscopic view of liquid solder in conventional brazing technique
" big to surround " and " little encirclement " phenomenon that joint filling is brought, and because whole welding process is carried out in vacuum brazing furnace, nothing
Brazing flux need to be used, is a kind of method of attachment of environmental protection.Can be good at adapting to complex precise structural member and large area portion
The connection of part.
The content of the invention
It is an object of the invention to the method for attachment of a kind of magnesium alloy and steel is proposed, using haptoreaction diffusion brazing work
Skill, realizes the law temperature joining of magnesium alloy and steel, and without using the environmental protection method of attachment of brazing flux.
The haptoreaction diffusion brazing method of attachment of magnesium alloy and steel, it is characterised in that carry out according to the following steps:
First, six surfaces of magnesium alloy are polished flat, removes its surface film oxide, with the method for differential arc oxidation in magnesium alloy
Surface prepares differential arc oxidation layer;
2nd, the magnesium alloy surface to be welded after differential arc oxidation is polished flat, exposes magnesium alloy metallic luster, adopted and treated in magnesium alloy
The face of weld prepares the cu coating that thickness is 10-50 μm;
3rd, the magnesium alloy surface to be welded for being prefixed cu coating is polished flat and obtains different coating layer thicknesses, it is molten in alcohol
Clean in agent, and be dried;
4th, steel surface to be welded is polished flat, exposes metallic luster, be placed in be cleaned by ultrasonic in acetone solvent and go to degrease, and
It is dried;
5th, the magnesium alloy for being prefixed pure Cu layers is combined into steel and is docked after braze-welded structure, be fixed and clamped in Clamp for welding,
In being placed in the vacuum chamber for spreading brazier, additionally, being pre-coated with solder resist on the contact surface of Clamp for welding and magnesium alloy and steel;
6th, apply the welding pressure of 0.0375~0.2MPa, treat that vacuum is less than 5 × 10-3After Pa, with the liter of 10 DEG C/min
Warm speed is warming up to 450~480 DEG C, is incubated 10~40min, then is warming up to 495~555 DEG C, after 20~100min of insulation, with stove
Less than 150 DEG C are cooled to, welded specimen is taken out, soldering is completed.
Further, described magnesium alloy is AZ31B, and steel is 08F cold-rolled steels.
Further, the magnesium alloy surface to be welded 1500# abrasive paper for metallograph for being prefixed pure Cu layers is polished in step 3, then will
Surface to be welded is cleaned with 100% spirit solvent, and is dried.
Further, steel surface to be welded is polished flat with 800# abrasive paper for metallograph in step 3, exposes metallic luster, be placed in acetone
It is cleaned by ultrasonic 5~10min in solvent, and is dried.
Further, the vacuum in step 6 in diffusion in vacuum stove is 9 × 10-4~5 × 10-3Pa。
Further, the vacuum in step 6 in diffusion in vacuum stove is 3 × 10-3Pa。
Further, differential arc oxidation state modulator voltage is 410~430V, and pulse frequency is 400Hz, and dutycycle is 3%, micro-
The arc time is 4~8min;It is 3~6g/L sodium metasilicate that electrolyte is ratio, and 6~9g/L potassium fluorides, 9~12g/L potassium hydroxide is remaining
Measure as deionized water.
Magnesium alloy in the inventive method described in step one is AZ31B, and steel is 08F cold-rolled steels;Prepare magnesium alloy differential arc oxygen
It is to prevent magnesium alloy from volatilizing in the environment of high vacuum to change layer.The magnesium alloy by differential arc oxidation described in step 2 is to be welded
Face is polishing to expose metallic luster, and the cu coating preset on its surface is prepared with the method for cold spraying, uses cold spraying
Method be to prevent magnesium alloy in prior surface processing procedure from oxygen occurring in the purpose that magnesium alloy surface to be welded prepares cu coating
Change, and cu coating surface prepared by cold spraying is more smooth and have certain bond strength with magnesium alloy, before welding
Phase is installed and has very big advantage for large-area welding part.The magnesium alloy for being prefixed cu coating is treated in step 3
Face of weld polishing purpose is to obtain the fine copper intermediate layer of different-thickness.
The present invention, as the intermediate layer of haptoreaction diffusion brazing, its object is to copper and magnesium alloy can using copper coating
There is eutectic reaction at relatively low temperature (eutectic temperature).At about 485 DEG C, there is eutectic reaction in magnesium, copper, generate eutectic
Point eutectic liquid phase Mg2Cu, temperature is further raised, and the Al elements in magnesium alloy are also assisted in send out and answered, and with magnesium and copper Mg-Cu- is generated
Al ternary compounds.Now magnesium steel different-metal material welding interface is liquid metal mixed phase, in certain temperature retention time, Cu
Fe sides are diffused on a small quantity with Al elements, and the Fe of a small amount of dissolving is also diffused in liquid metal, forms solid solution phase, and this is to a certain degree
On can strengthen the intensity of soldered fitting, finally, with the reduction of temperature, mixes liquid metal freezing forms soldered fitting.This
Bright middle welding temperature and temperature retention time affect maximum to soldered fitting, therefore in the present invention welding temperature is set in into 495~
555 DEG C (magnesium alloy fusion temperature is 650 DEG C or so).From Mg-Cu binary phase diagramls (accompanying drawing 1), temperature too low (≤485
DEG C), do not react between magnesium copper heterogenous metal, it is impossible to form eutectic liquid phase thus soldered fitting cannot be formed;Temperature is too high, by
It is very sensitive to temperature in magnesium alloy, it is unfavorable for the connection of magnesium alloy.Additionally, temperature is too high to easily cause magnesium alloy and interface generation
The burn-off phenomenon of phase, has a strong impact on the performance of soldered fitting.In the case where welding temperature is for 530 DEG C, interfacial reaction products are bulk Mg-
Cu-Al ternary phases, Mg solid solution and Mg2Cu eutectic structure phases, interfacial reaction products do not change with the change of temperature retention time.
The present invention is set in temperature retention time 20~100 minutes, and temperature retention time is too short, reacts incomplete between magnesium copper heterogenous metal, copper
Layer is also remained at interface, it is impossible to form good soldered fitting.Increase temperature retention time, magnesium copper heterogenous metal interfacial reaction is complete
Entirely, bulk Mg-Cu-Al ternary phases in interface are initially produced in magnesium alloy AZ31B sides, and size is less, with the increase of temperature retention time,
Block ternary phase becomes large-sized, and gradually migrates to 08F steel side;Mg2Cu eutectic structures have generation in magnesium steel both sides, with guarantor
The increase of warm time, in the Mg of 08F steel side2Cu eutectic structures fade away, and the eutectic structure of magnesium side does not substantially become
Change.In sum, welding temperature is low in the inventive method connection procedure, mother metal deforms little, environmental protection, postwelding high precision, fits
For the connection that high accuracy builds.The present invention is capable of achieving to the process of large area parts surface, and can well avoid magnesium alloy
Oxidation, and then reduce the oxygen content in follow-up welding process weld seam, effectively improve the shear strength of welding point.
Description of the drawings
Fig. 1:Mg-Cu binary phase diagramls;
Fig. 2:Be installed schematic diagram;
Fig. 3:The haptoreaction diffusion brass solder technique schematic diagram of magnesium alloy and steel in the present invention;
Fig. 4:With cold spraying in the preset cu coating in magnesium alloy AZ31B surfaces;
Fig. 5:530 DEG C of welding temperature, on-load pressure 0.0375MPa, 50 μm of cu coating thickness, under temperature retention time 60min
AZ31B/Cu/08F steel haptoreaction diffusion brazing Microstructure of Joint figures.
Specific embodiment
Specific embodiment
Embodiment one:
1) AZ31B magnesium alloys and 08F steel are cut into respectively the rectangle strip of 30 × 10 × 3mm, apart from magnesium alloy one
The aperture (preparing magnesium alloy differential arc oxidation layer) of a Φ 2.5mm is bored at the 2~3mm of end of end, by magnesium alloy outer surface 800#
Sand papering to surfacing has after metallic luster, is put in acetone solvent and is cleaned by ultrasonic 10min, and wiping is dried;
2) 08F steel is had after metallic luster with 800# sand paperings to surfacing, is put in acetone solvent and is cleaned by ultrasonic
10min, wiping is dried;
3) differential arc oxidation layer, concrete differential of the arc oxygen are prepared on six surfaces of the magnesium alloy polished with the method for differential arc oxidation
(control voltage is 415V, and pulse frequency is 400Hz, and dutycycle is 3%, and the differential of the arc time is 5min to change parameter;The electrolyte of configuration
For 15L, its concrete ratio is 4g/L sodium metasilicate, 8g/L potassium fluorides, 10g/L potassium hydroxide, balance of deionized water.
4) after is carried out with 800# sand paperings light on 30 × 10mm surface for obtaining the magnesium alloy of differential arc oxidation layer
It is prepared by the cu coating in one stage;
5) cu coating is prepared on magnesium alloy AZ31B surfaces with the method for cold spraying, and coating layer thickness is 50 μm.
6) magnesium alloy for being prefixed pure Cu layers is combined into steel and is docked after braze-welded structure, be fixed and clamped with fixture (as attached
Shown in Fig. 1), it is advance with the contact surface of AZ31B magnesium alloys and 08F steel in Clamp for welding in being placed in diffusion in vacuum stove vacuum chamber
Apply solder resist;
7) door for vacuum chamber is closed, applying welding pressure is 0.0375MPa, treats that vacuum reaches 5.0 × 10-3After below Pa with
The programming rate of 10 DEG C/min is warming up to 450 DEG C, is incubated 10min, then after being warming up to 530 DEG C, is incubated 20min, cold with stove afterwards
But to less than 150 DEG C, welding is completed.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 11.6MPa.
Embodiment two:
The present embodiment from step 7 unlike embodiment one after being warming up to 530 DEG C, be incubated 40min.Other and enforcement
Example one is identical.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 20.3MPa.
Embodiment three:
The present embodiment from step 7 unlike embodiment one after being warming up to 530 DEG C, be incubated 60min.Other and enforcement
Example one is identical.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 39.6MPa.
Example IV:
The present embodiment from step 7 unlike embodiment one after being warming up to 530 DEG C, be incubated 80min.Other and enforcement
Example one is identical.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 34.3MPa.
Embodiment five:
The present embodiment from step 7 unlike embodiment one after being warming up to 530 DEG C, be incubated 100min.Other and reality
Apply example one identical.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 29.6MPa.
Embodiment six:
The present embodiment is 0.2MPa from applying welding pressure in step 7 unlike embodiment one, treats that vacuum reaches 5.0
×10-3480 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 30min is incubated, then after being warming up to 495 DEG C, are incubated 20min,
Other are identical with embodiment one.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 12.5MPa.
Embodiment six:
The thickness of the present embodiment and copper coating in step 5 unlike embodiment one is with 1500# sand paperings to 10 μm;Step
It is 0.05MPa to apply welding pressure in rapid 7, treats that vacuum reaches 5.0 × 10-3It is warming up to the programming rate of 10 DEG C/min after Pa
450 DEG C, 10min is incubated, then is warming up to 495 DEG C, be incubated 15min, other are identical with embodiment one.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 12.5MPa.
Embodiment seven:
The thickness of the present embodiment and copper coating in step 5 unlike embodiment one is with 1500# sand paperings to 20 μm;Step
It is 0.1MPa to apply welding pressure in rapid 7, treats that vacuum reaches 5.0 × 10-3It is warming up to the programming rate of 10 DEG C/min after Pa
460 DEG C, 20min is incubated, then is warming up to 495 DEG C, be incubated 40min, other are identical with embodiment one.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 23.5MPa.
Embodiment eight:
The thickness of the present embodiment and copper coating in step 5 unlike embodiment one is with 1500# sand paperings to 30 μm;Step
It is 0.15MPa to apply welding pressure in rapid 7, treats that vacuum reaches 5.0 × 10-3It is warming up to the programming rate of 10 DEG C/min after Pa
470 DEG C, 25min is incubated, then is warming up to 495 DEG C, be incubated 60min, other are identical with embodiment one.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 16.0MPa.
Embodiment nine:
The thickness of the present embodiment and copper coating in step 5 unlike embodiment one is with 1500# sand paperings to 40 μm;Step
It is 0.2MPa to apply welding pressure in rapid 7, treats that vacuum reaches 5.0 × 10-3It is warming up to the programming rate of 10 DEG C/min after Pa
480 DEG C, 30min is incubated, then is warming up to 495 DEG C, be incubated 80min, other are identical with embodiment one.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 20.5MPa.
Specific embodiment ten:
The present embodiment is 0.1MPa from applying welding pressure in step 7 unlike embodiment six, treats that vacuum reaches 3.0
×10-3460 DEG C are warming up to after Pa with the programming rate of 10 DEG C/min, are incubated 20min, then be warming up to 515 DEG C, be incubated 60min, its
It is identical with embodiment six.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 18.7MPa.
Embodiment 11:
Present embodiment is 0.05MPa from applying welding pressure in step 7 unlike embodiment seven, treats that vacuum reaches
5.0×10-3450 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 15min is incubated, then are warming up to 515 DEG C, insulation
80min, other are identical with embodiment seven.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 32.0MPa.
Embodiment 12:
The present embodiment is 0.2MPa from applying welding pressure in step 7 unlike embodiment eight, treats that vacuum reaches 1.0
×10-3480 DEG C are warming up to after Pa with the programming rate of 10 DEG C/min, are incubated 30min, then be warming up to 515 DEG C, be incubated 20min, its
It is identical with embodiment eight.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 16.5MPa.
Embodiment 13:
The present embodiment is 0.05MPa from applying welding pressure in step 7 unlike embodiment nine, treats that vacuum reaches
5.0×10-3450 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 15min is incubated, then are warming up to 515 DEG C, insulation
40min, other are identical with embodiment nine.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 24.6MPa.
Embodiment 14:
The present embodiment is 0.15MPa from applying welding pressure in step 7 unlike embodiment six, treats that vacuum reaches
3.0×10-3470 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 25min is incubated, then are warming up to 535 DEG C, insulation
80min, other are identical with embodiment six.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 15.7MPa.
Embodiment 15:
The present embodiment is 0.2MPa from applying welding pressure in step 7 unlike embodiment seven, treats that vacuum reaches 3.0
×10-3480 DEG C are warming up to after Pa with the programming rate of 10 DEG C/min, are incubated 30min, then be warming up to 535 DEG C, be incubated 80min, its
It is identical with embodiment seven.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 26.3MPa.
Embodiment 16:
The present embodiment is 0.05MPa from applying welding pressure in step 7 unlike embodiment eight, treats that vacuum reaches
9.0×10-4450 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 15min is incubated, then are warming up to 535 DEG C, insulation
40min, other are identical with embodiment eight.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 29.8MPa.
Embodiment 17:
The present embodiment is 0.10MPa from applying welding pressure in step 7 unlike embodiment nine, treats that vacuum reaches
9.0×10-4460 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 20min is incubated, then are warming up to 535 DEG C, insulation
20min, other are identical with embodiment nine.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 36.1MPa.
Embodiment 18:
The present embodiment is 0.2MPa from applying welding pressure in step 7 unlike embodiment six, treats that vacuum reaches 2.0
×10-3480 DEG C are warming up to after Pa with the programming rate of 10 DEG C/min, are incubated 30min, then be warming up to 555 DEG C, be incubated 40min, its
It is identical with embodiment six.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 20.8MPa.
Embodiment 19:
The present embodiment is 0.15MPa from applying welding pressure in step 7 unlike embodiment seven, treats that vacuum reaches
3.0×10-3470 DEG C are warming up to the programming rate of 10 DEG C/min after Pa, 25min is incubated, then are warming up to 555 DEG C, insulation
20min, other are identical with embodiment seven.
AZ31B magnesium alloys/Cu/08F steel haptoreaction diffusion brazing joints are obtained, shear strength is up to 33.8MPa.