CN101405105A - Joint product between steel product and aluminum material, spot welding method for the joint product, and electrode chip for use in the joint product - Google Patents

Joint product between steel product and aluminum material, spot welding method for the joint product, and electrode chip for use in the joint product Download PDF

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CN101405105A
CN101405105A CNA2007800062345A CN200780006234A CN101405105A CN 101405105 A CN101405105 A CN 101405105A CN A2007800062345 A CNA2007800062345 A CN A2007800062345A CN 200780006234 A CN200780006234 A CN 200780006234A CN 101405105 A CN101405105 A CN 101405105A
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aluminium
steel
thickness
spot welding
layer
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CN101405105B (en
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漆原亘
武田实佳子
松本克史
加藤淳
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Kobe Steel Ltd
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Kobe Steel Ltd
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Abstract

The present invention provides a joint product of a steel product and an aluminum material, and a spot welding method for the joint product, ensuring that spot welding with high bonding strength can be performed. In one embodiment, a steel product 1 having a sheet thickness t 1 of 0.3 to 3.0 mm and an aluminum material 2 having a sheet thickness t 2 of 0.5 to 4.0 mm are joined together by spot welding to form a joint product of a steel product and an aluminum produce. In this joint product, the nugget area in the joint part is from 20 t 2 0.5 to 100 t 2 0.5 mm 2 , the area of a portion where the thickness of the interface reaction layer is from 0.5 to 3 [mu]m is 10 t 2 0.5 mm 2 or more, and the difference between the interface, reaction layer thickness at the joint part center and the interface reaction layer thickness at a point distant from the joint part center by a distance of one-fourth of the joint diameter D c is 5 [mu]m or less. According to this construction, there can be provided a dissimilar material joint product with excellent bonding strength, which can be formed by an existing spot welding apparatus at a low cost without newly using other materials such as clad material or without newly adding a separate step, and a spot welding method for the dissimilar material joint product.

Description

The conjugant of steel and aluminium alloy, spot welding method and be used for the electrode tip of this method
Technical field
The present invention relates to the technology that the steel that will need by spot welding and aluminium engage in the assembling procedure of haulage vehicles such as automobile, rail truck, machine components, building structure etc.
Background technology
Spot welding normally engages congener hardware each other.But, if for example can be applied to ferrous material (below, be called for short steel) and the joint (different material conjugant) of the hardware of the such xenogenesis of aluminium based material (be the general name of fine aluminium and aluminium alloy, be designated hereinafter simply as aluminium), then can help very much lightweight etc.
But, under situation, be easy to generate crisp intermetallic compound at the junction surface with steel and aluminium joint, therefore, be difficult to obtain having the high-intensity junction surface (bond strength) of certain reliability.Therefore, the joint that adopts bolt or rivet etc. to carry out to the joint of these different material conjugants (dissimilar metal member engages body) at present, but have the problem of the reliability, air-tightness, cost etc. of junction joint.
So the spot welding method to these xenogenesis conjugants has carried out a large amount of research all the time.For example motion a kind of method, this method is to embed aluminium-steel clad material (with reference to patent documentation 1,2) between aluminium and steel.In addition, also motion a kind of method, this method is at steel side plating or embed the low metal (with reference to patent documentation 3,4,5) of melting point.And, gone back motion and between aluminium and steel, pressed from both sides the method (with reference to patent documentation 6) of insulator particle or in advance member is carried out concavo-convex method for processing (with reference to patent documentation 7) etc.
But these any methods are not simple spot welding, but need be in the spot welding or the other operation such as plating or processing of multilayer, and existence must be organized the problem of going into new equipment on existing welding production line, and welding cost is also high.In addition, also exist these any methods all welding condition to be had problem in the operation of a lot of qualifications etc.
As the method by being different from these methods steel are implemented the method for the epithelium of plating etc., patent documentation 8～11 motions such as grade.If in these patent documentations, put down in writing in advance steel or aluminium implemented plating, just can directly weld, so versatility height, in addition, between steel-aluminum, form the film of low melting point, thus, be purpose to reduce interfacial reaction layer and to form concavo-convex at the interface, obtain respectively directly engaging higher intensity than steel and aluminum.In addition, according to the kind of plating, can be suppressed at the differential metals contact corrosion that produces between steel and the aluminium.Form Mg in the patent documentation 8, form film in the patent documentation 9 than the low melting point of aluminium, form film in the patent documentation 10 than the low melting point of steel, form in the patent documentation 11 than more than the temperature of low 300 ℃ of the melting point of aluminium and the temperature lower than the melting point of aluminium become the film of melting point.
But in patent documentation 8, concerning the mother metal fracture, the intensity of 80kgf is insufficient.In addition, in patent documentation 9, can access the disconnected tensile strength of sufficient line, but can not form nugget.The fixed effect of the combination by these microcosmic only though can guarantee the line tensile strength of break, can not keep cross tensile strength (peel strength), and its purposes is defined in and only produces the break specific use of tension of line.
In patent documentation 10, need further embedded resistor body, therefore exist and must in above-mentioned existing welding production line, organize the problem of going into new equipment, and cost is also high.In the patent documentation 11, obtain the mother metal fracture by cross tensile strength, but do not form interfacial reaction layer, above situation is put down in writing as high-intensity effect.Really, the intermetallic compound of steel and aluminium is that interfacial reaction layer is more crisp, according to inventors' opinion as can be known, shown in patent documentation 10, if there is not interfacial reaction layer fully, does not just have the adhesive layer of phase counterdiffusion, so bond strength is low.Therefore, the same with patent documentation 9, only by the combination of microcosmic, can not keep sufficient cross tensile strength, can not realize the more hope of high strength conjugant.
In addition, present inventors turn to the structure that target continues the interfacial reaction layer at the junction surface that research forms by spot welding with optimum, find thickness by suppressing interfacial reaction layer and area, structure, can produce the different material conjugant with high bond strength.
Present inventors' motion a kind of technology, this technology also has nugget size, interfacial reaction layer thickness by suppressing the thickness and the melting point of the plating epithelium in the patent documentation 12～15, can access the above peel strength of 0.9kN/spot thus.
(Japan) patent documentation 1: day disclosure special permission communique: 6-63763 number
(Japan) patent documentation 2: day disclosure special permission communique: 7-178563 number
(Japan) patent documentation 3: day disclosure special permission communique: 4-251676 number
(Japan) patent documentation 4: day disclosure special permission communique: 7-24581 number
(Japan) patent documentation 5: day disclosure special permission communique: 4-143083 number
(Japan) patent documentation 6: day disclosure special permission communique: 5-228643 number
(Japan) patent documentation 7: day disclosure special permission communique: 9-174249 number
(Japan) patent documentation 8: day disclosure special permission communique: 4-143088 number
(Japan) patent documentation 9: day disclosure special permission communique: 4-251676 number
(Japan) patent documentation 10: day disclosure special permission communique: 7-24581 number
(Japan) patent documentation 11: day disclosure special permission communique: 7-178565 number
(Japan) patent documentation 12: day disclosure special permission communique: 2005-305504 number
(Japan) patent documentation 13: day disclosure special permission communique: 2005-152958 number
(Japan) patent documentation 14: day disclosure special permission communique: 2005-152959 number
(Japan) patent documentation 15: day disclosure special permission communique: 9-174249 number
(Japan) patent documentation 8: day disclosure special permission communique: 2006-167801 number
But,, seek to finish the spot-welding technology that obtains higher bond strength for the hope of the further increase of the intensity that realizes parts, the minimizing of counting out.
Even utilize patent documentation 12～15, the limit is also arranged in order further to improve bond strength.In addition, between the dissimilar metal of steel and aluminium, be known as the contact corrosion of galvanic corrosion especially easily, even be the different material conjugant of steel and aluminium joint is no exception by spot welding.In the use as the different material conjugant of automobile component etc., under the situation that such galvanic corrosion takes place, the bond strength of different material conjugant also descends.
Therefore, be applied to suppress such contact corrosion in the middle of the reality as automobile component etc. in order steel and aluminium to be engaged the different material conjugant that forms by spot welding.In order to suppress such contact corrosion, effectively by organic resin epithelium etc. with steel and aluminium insulation.But under the situation of utilizing organic resin epithelium etc. with steel and aluminium insulation, though can suppress contact corrosion, the spot welding self of welding by these energisings between the two becomes difficulty.The problem that the bond strength of the different material conjugant when therefore, producing spot welding on the contrary descends.
So actual conditions are that raising can suppress the effective method of contact corrosion simultaneously by the bond strength of spot welding with the different material conjugant of steel and the formation of aluminium joint, does not also have motion up to now.
In addition, also there are the following problems: for the different material conjugant of steel and aluminium, the galvanized steel plain sheet that is widely used in the steel aspect of present body of a motor car panel etc. is compared the spot weldability variation with naked steel plate.
This is owing to except that the described crisp intermetallic compound that the junction surface that engages at different material generates, when the different material of galvanized steel plain sheet (galvanized steel) and aluminium engages, must generate the cause that comes from zinc-plated, crisp Zn-Fe based compound.Because this Zn-Fe based compound is crisp, so be reduced to the bond strength that destroys starting point significantly.
Summary of the invention
The present invention develops in view of solving above-mentioned various problems.Its purpose is, the conjugant and the spot welding method thereof of steel and aluminium are provided, the bond strength of the conjugant of these steel and aluminium is good, when steel and aluminium being engaged by spot welding, shown in above-mentioned present technology, other materials such as clad be can not reuse by existing spot welding device, other operation and formation at low cost also do not increased again.
In addition, the objective of the invention is to, different material conjugant and spot welding method thereof are provided, this different material conjugant can suppress contact corrosion in the bond strength that improves when by spot welding steel and aluminium being engaged.
And, the present invention also aims to, even provide to galvanized steel plain sheet (steel), also can form the conjugant high spot welding of bond strength, steel and aluminium.
As described below, present inventors have done further research for solving above-mentioned problem, up to having finished the present application.
As can be known, for steel each other or aluminium wait material of the same race to carry out to high strength spot welding each other each other, usually, as long as can promote a little formation, it is big more to put area, shearing strength and cross tensile strength are also high more.
In addition, nugget area (diameter) with advance heat and have close dependency relation, the magnitude of current is high more, the time is long more, it is big more, therefore, advances heat control point area during usually by spot welding, obtains the high conjugant of bond strength thus.Certainly, when the nugget area was excessive, the portion of dissolving reached and is engaged the material reversal connection and closes surface (surface of the opposition side on composition surface), produced dust, so it is very important to obtain suitable nugget area.
But, under the situation that steel and the so different material of aluminium are engaged, steel are compared with aluminium, and melting point, resistance are all high, and pyroconductivity is little, therefore, compare with the aluminium side, steel side one side's heating is big, therefore, the surface from joining with steel at first, the aluminium of low melting point dissolves.Then, the surface that joins with aluminium of steel dissolves, and consequently, forms the crisp intermetallic compounds layer (below, claim " interfacial reaction layer ") of Al-Fe system at joint interface, so can not get high bond strength.
As can be known, by the spot welding of steel and aluminium engage the intermetallic compound that forms roughly be divided into two-layer, at steel side formation Al 5Fe 2Based compound (the intermetallic compound Al of definition such as table 10 described later 5Fe 2The meaning), form Al in the aluminium side 3Fe based compound (the intermetallic compound Al of definition such as table 10 described later 3The meaning of Fe).Because these intermetallic compounds are very crisp, so all can not get high bond strength all the time.
And, fashionable at galvanized steel plain sheet (galvanized steel) and aluminium means of spot welds, as mentioned above, generate and come from zinc-plated Zn-Fe based compound (the intermetallic compound Fe of definition such as table 10 described later 3Zn 7The meaning) layer, and must be contained in the above-claimed cpd layer.Because this Zn-Fe based compound layer is crisp, so be reduced to the bond strength that destroys starting point significantly.
In addition, close the surface when producing dust when dissolving the reversal connection that reaches aluminium, the reduction of aluminium increases, and still can not get high bond strength.
That is, under situation about the different material of steel and aluminium being engaged,, need to add form a certain size nugget size high and advance heat in order to obtain high bond strength by spot welding.But, according to opinion of the present invention,, compare with the control nugget size in order to obtain higher bond strength, more need to control the formation area and the thickness distribution of interfacial reaction.
That is, under situation about steel and the so different material of aluminium being engaged,, only need apply the heat that advances of the nugget area that forms regulation in order to obtain high bond strength by spot welding.In order to suppress the formation of interfacial reaction layer at joint interface, require dissolving of steel is suppressed to irreducible minimum, and the generating capacity of dust is suppressed to minimum.
Therefore, think, at first for the spot welding condition, if can under high electric current, obtain big nugget area, and suppress the heating of steel and aluminium, and steel are suppressed then just can approach and form interfacial reaction layer on a large scale, thereby obtain high bond strength for the same and few dissolving as far as possible of joint interface.
But, when applying high electric current by present spot welding method, the current density height of junction surface central part, the heating of steel dissolves and dissolving also of aluminium increases, and therefore forms thick interfacial reaction layer at the junction surface central part.By increasing the front end R of electrode tip, alleviate electric current to the concentrating of junction surface central part, can carry out large tracts of land and engage, still, the interfacial reaction layer of junction surface central part is still thick, according to welding condition, at the junction surface central part, on aluminium defective will take place.
Present studies show that, why to determine bond strength, what consider is not the central part at junction surface, but periphery, the interfacial reaction layer thickness thickening of central part is little accounted of, when resolving in more detail, even periphery is the interfacial reaction layer thickness of identical size, when the interfacial reaction layer of central part is more than a certain size when thick, bond strength also can descend, in addition, because the generation of dust not only makes appearance damage, and the thickness distribution of the interfacial reaction layer of periphery also changes, and becomes the unbalanced main cause of bond strength.
Promptly, as can be known, all the time in order further to improve bond strength, suppress the heating of steel and aluminium, scattered current density and engaging by high electric current as far as possible, the junction surface central part also contains the interfacial reaction layer of engaged different material conjugant, and large tracts of land is controlled in the optimum thickness range, and this point is very important.
In addition, based on above-mentioned opinion, finished following invention.
The main idea that is used to realize different material conjugant above-mentioned purpose, steel of the present invention and aluminium is with thickness of slab t by spot welding 1Be steel and the thickness of slab t of 0.3～3.0mm 2Be that the fine aluminium material of 0.5～4.0mm or aluminium alloy material (below, fine aluminium material or aluminium alloy material are called " aluminium ") engage and form, it is characterized in that the nugget area at junction surface is 20 * t 2 0.5～100 * t 2 0.5Mm 2, the thickness of interfacial reaction layer is that the area of 0.5～3 μ m part is 10 * t 2 0.5Mm 2More than, and the center, junction surface is with the difference for the thickness of the interfacial reaction layer of the point of 1/4 the distance that engages diameter is in the 5 μ m from the center, junction surface.
At this, the maximum ga(u)ge of preferred described interfacial reaction layer is the scope of 0.5～10 μ m.
In addition, the electrode tip that uses in the spot welding of the conjugant that is used to form described main idea is preferably it and is engaged the contacting by more than 2 o'clock or wire or the planar electrode tip that carries out of material.
Preferred described electrode tip forms recess more than the diameter 2mm in the central authorities of described leading section when leading section forms dome type.
In addition, at least one side who is used to form in the preferred pair of electrodes head of spot welding method of conjugant of described main idea uses described electrode tip.
In addition, described spot welding method preferably is cooled at least one side in described steel and the described aluminium carry out below 5 ℃ spot welding again.
The main idea that is used to realize different material conjugant above-mentioned purpose, steel of the present invention and aluminium is with thickness of slab t by spot welding 1Be steel and the thickness of slab t of 0.3～3.0mm 2The aluminium joint that is 0.5～4.0mm forms, it is characterized in that, between the composition surface each other of these engaged steel and aluminium, under the state of the Zn that is preset with 350～1000 ℃ of melting points, average thickness 3～19 μ m or Zn alloy or Al or Al alloy coating and organic resin bonding agent epithelium or phosphate coating, carry out spot welding, and the thickness of the interfacial reaction layer of the weld part of some postwelding is that 0.5～5 μ m area partly is 10 * t 2 0.5Mm 2More than.
At this, in order to improve the bond strength of different material conjugant, the thickness of preferred described interfacial reaction layer is that the area of 0.5～5 mu m range part is 50 * t 2 0.5Mm 2More than.
In addition, in order to improve the bond strength of different material conjugant, preferred described Zn or Zn alloy coating are the plating epithelium that contains the Zn more than 88% quality that the surface of steel side is implemented equally.
In addition, same in order to improve the bond strength of different material conjugant, the average thickness of preferred described phosphate coating is 0.1～5 μ m.Also preferred described phosphate coating contains the Mg of 0.01～10% quality.
The main idea that is used to realize the spot welding method of different material conjugant above-mentioned purpose, steel of the present invention and aluminium is that it is thickness of slab t 1Be steel and the thickness of slab t of 0.3～3.0mm 2It is the spot welding method of different material conjugant of the aluminium of 0.5～4.0mm, it is characterized in that, have between the composition surface each other of these engaged steel and aluminium, under the state of the metal epithelium of Zn that is preset with 350～1000 ℃ of melting points, average thickness 3～19 μ m or Al and organic resin bonding agent epithelium, carry out spot welding, the point diameter of establishing simultaneously the electrode tip of aluminium side in this spot welding is more than the φ 7mm, and apply the plus-pressure of electrode tip, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05, and make 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec, and, carry out spot welding by the current-mode that does not have the operation that flows through the electric current higher than this operation.
At this, in order to improve the bond strength of different material conjugant, the thickness of preferred described interfacial reaction layer is that the area of the part of 0.5～5 mu m range is 50 * t 2 0.5Mm 2More than.
The main idea that is used to realize the spot welding method of different material conjugant above-mentioned purpose, steel of the present invention and aluminium is that it is thickness of slab t 1Be steel and the thickness of slab t of 0.3～3.0mm 2It is the spot welding method of different material conjugant of the aluminium of 0.5～4.0mm, it is characterized in that, have between the composition surface each other of these engaged steel and aluminium, at the Zn that is preset with 350～1000 ℃ of melting points, average thickness 3～19 μ m or Zn alloy coating, also have under the state of phosphate coating and carry out spot welding, the point diameter of establishing simultaneously the electrode tip of aluminium side in this spot welding is more than the φ 7mm, and apply the plus-pressure of electrode tip, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05, and make 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec, and, carry out spot welding by the current-mode that does not have the operation that flows through the electric current higher than this operation.
In addition, same, in order to improve the bond strength of different material conjugant, preferably make described 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5In the operation after the operation of msec, make 1 * t by having 2 0.5～10 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The current-mode of the operation of msec carries out spot welding.
The main idea that is used to realize different material conjugant above-mentioned purpose, steel of the present invention and aluminium is with thickness of slab t by spot welding 1The average thickness that is 0.3～3.0mm, zinc coat is galvanized steel and the thickness of slab t of 3～19 μ m 2The aluminium that is 0.5～4.0mm engages, and it is characterized in that, at the joint interface of this different material conjugant, has Al in the steel side respectively 5Fe 2Based compound has Al in the aluminium side 3The Fe based compound, the total average thickness of the nugget depth direction that this is two-layer is the ratio more than 50% part, account for the shared area of the in-plane at the joint interface of aluminium side of nugget at the shared total area of in-plane of the joint interface of aluminium side of 0.5～10 μ m, and, by SEM to described Al 5Fe 2Based compound layer and Al 3This two-layer total average thickness of the nugget depth direction of Fe based compound layer is that the cross section of the joint interface part of 0.5～10 μ m is observed, be contained in respectively this Zn-Fe based compound layer in two-layer in the ratio 10% below in the total of cross-wise direction shared total area at cross-wise direction shared area and Zn-Fe based compound layer of the shared total area of cross-wise direction for this two-layer total average thickness part that is 0.5～10 μ m.
At this, in order further to improve bond strength, on the basis of described main idea, preferred described nugget is more than the 7mm in the average diameter of the joint interface of aluminium side, the Zn layer of the joint interface that joins with this nugget be that nugget is at below 30% of the shared area of the in-plane of the joint interface of aluminium side at the shared total area of in-plane.
In addition, the minimum remaining thickness of slab of the described aluminium side at same preferred different material junction surface is initial more than 50% of aluminium thickness of slab.
And, the thickness ratio t of same preferred described steel and aluminium 1/ t 2Be more than 1.
The present invention's formation as implied above when the different material by spot welding steel and aluminium engages, can access bigger nugget area, and large tracts of land forms the interfacial reaction layer of optimum thickness range, thereby improves the bond strength of different material conjugant.Consequently, when forming the different material conjugant of steel and aluminium by spot welding, shown in present technology, do not reuse other material, not needing in addition increases new other operation, can utilize existing mash welder, therefore can realize reducing significantly cost.
Consequently, conjugant of the present invention is as various structural elements particularly suitables such as haulage vehicles such as automobile, rail truck, machine components, building structures.Therefore, according to the present invention, can enlarge the purposes of the different material conjugant of steel and aluminium greatly.
In addition, present inventors find under situation about the different material of steel and aluminium being engaged by spot welding, in order to control the formation area and the thickness distribution of interfacial reaction layer, and obtain high bond strength, suppress to be controlled at the time that forms interfacial reaction layer between steel and the aluminium, this point is very important.In addition, find also that it is very important to form the inhibition layer in advance on material in order to suppress to control this interfacial reaction layer formation time.
In the present invention, suppress layer, it is characterized in that, only do not suppress control and be used for the formation time of interfacial reaction layer, and selected to suppress the inhibition layer of differential metals contact corrosion as this.And in the present invention, the inhibition layer as such is characterized in that, sets in advance epithelium two-layer of the metal epithelium of the Zn of particular range or Al and organic resin bonding agent.
In order to control the inhibition of interfacial reaction layer formation time, and obtain high bond strength, need the approaching metal epithelium of melting point and aluminium, contact with the aluminium that has dissolved making it, and become the intermediate layer with steel.About this point, its melting point of metal epithelium and the aluminium of the Zn of particular range of the present invention or Al are approaching, and have interfacial reaction layer formation time when suppressing control spot welding, obtain the function of high bond strength.
In addition, in order to suppress differential metals contact corrosion, suppressing layer must be at a postwelding on a large scale or comprehensively between steel and aluminium, and becomes the insulating barrier of electricity.But, on the other hand, in order to carry out spot welding, and obtaining the high bond strength of spot-welding part, this inhibition layer must make steel and aluminium conduct when spot welding.About this point, the epithelium of organic resin bonding agent suppresses control interfacial reaction layer formation time as the insulating barrier of electricity when spot welding, and, have the function that suppresses differential metals contact corrosion at a postwelding.
For example, the epithelium that is provided with the machine resin adhesive is a thermosetting resin etc., under the situation of stress application when spot welding (plus-pressure), when easily the peripherad part of its welding portion from steel and aluminium being discharged or getting rid of, steel and aluminium is conducted.
And, carrying out the some postwelding, this organic resin bonding agent epithelium or comprehensively between steel and aluminium, becomes the insulator of electricity on a large scale only except that the spot-welding part that has been removed, suppresses the differential metals contact corrosion of different material conjugant.
Certainly, each suppresses layer in order to bring into play such function, as described later, has the condition of only composition or leather film thickness scope etc. on the epithelium of metal epithelium and organic resin bonding agent, when spot welding, has the optimum condition of plus-pressure or current-mode etc.
At this, usually during each other welding of the metalloid of the same race that waits each other at steel, known have, with bonding agent after between steel, the welding bonding way that steel are welded each other.But, under the situation that the different material that steel and aluminium is carried out by spot welding engages,, as mentioned above, compare with metalloid of the same race welding each other in order to obtain high bond strength, need apply the high heat that advances.Pin engages in the different material of steel that undertaken by spot welding and aluminium, gets involved bonding agent, about this point, can predict certainly and bring adverse effect with interfacial reaction layer being formed control.In addition, also can predict and to influence spot welding self.
In fact, under the situation that the different material that naked (not carrying out surface treatment) steel and aluminium is carried out by spot welding engages, when Jie had bonding agent, spot welding self and interfacial reaction layer formed the control difficulty, can not obtain high bond strength.
To this, under situation about being provided with in advance between the composition surface each other of engaged steel and aluminium as the metal epithelium of the Zn of another layer that suppresses layer or Al, even there is the epithelium of organic resin adhesive, it is not difficult that spot welding self and interfacial reaction layer form control yet, thus the function of the epithelium aspect of performance organic resin bonding agent.
This is to infer that the temperature of the interface temperature of steel and aluminium, especially steel is high significantly to the cause that dissolves temperature above aluminium because (Jie has) the resistance heating amount when causing spot welding that exists of the metal epithelium of Zn or Al increases.In addition, when inferring the resistance heating amount increase when spot welding, accelerate significantly in the diffusion velocity with interface steel aluminium, aluminium is guaranteed good engagement state rapidly to the diffusion of steel side.
As mentioned above, the invention is characterized in that when the different material that is undertaken by spot welding engaged, between the composition surface each other of engaged steel and aluminium, the metal epithelium of default Zn or Al and the epithelium of organic resin bonding agent were two-layer.
Thus, opposite with present general knowledge, suppress the time that the interfacial reaction layer between control steel and the aluminium forms, improve the bond strength of different material conjugant.In addition, as with the welding of the corresponding current-mode of spot welding condition, guarantee the raising of bond strength.
In addition, the invention is characterized in, not only do not influence the formation area of this interfacial reaction layer and the control of thickness distribution, and selected to suppress the inhibition layer (corrosion-inhibiting layer) of differential metals contact corrosion (galvanic corrosion).The inhibition of the differential metals contact corrosion during this different material conjugant uses is related to the decline of the bond strength that suppresses the different material conjugant that this corrosion causes, and keeps bond strength.In addition, feature of the present invention also is, as such inhibition layer, and between the composition surface each other of these engaged steel and aluminium, the Zn of default particular range or Zn alloy coating and phosphate coating two-layer.
For the formation area that do not influence interfacial reaction layer and the control of thickness distribution, and suppress differential metals contact corrosion (galvanic corrosion), need have the two-layer epithelium of various characteristics.That is,, contact with molten aluminium making it, and become intermediate layer with steel for the former needs melting point and the approaching metal epithelium of aluminium.For the latter, need have the natural potential lower and higher, have the natural potential lower, the epithelium that corrosion protection result is sacrificed in performance than the epithelium of the potential difference that reduces steel-aluminium or aluminium than aluminium than steel.
On this point, the characteristic of the Zn of particular range of the present invention or Zn alloy coating is, when spot welding,, do not hinder time control and the thickness range of interfacial reaction layer and the control that distributes of the interfacial reaction layer of the intermetallic compound that forms steel and aluminium even there is phosphate coating yet.In addition, have the natural potential lower and higher than aluminium than steel, not only reduce the potential difference of steel-aluminium, and become than the low natural potential of aluminium that forms oxide scale film according to environment, and the epithelium of corrosion protection result is sacrificed in performance, even therefore under corrosive environment, also have the function that obtains high bond strength.
On the other hand; in order more effectively to suppress differential metals contact corrosion; suppressing layer need be at a postwelding on a large scale or comprehensively between steel and aluminium; cut off the influence that is not subjected to corrosive environments such as moisture or oxygen between steel and the aluminium, or utilize and sacrifice the corrosion-inhibiting layer that the corrosion protection effect forms the protection base material.But, on the other hand, in order to carry out spot welding, and obtaining the high bond strength of spot-welding part, this inhibition layer must have the characteristic that when spot welding steel and aluminium is conducted.
On this point, under the situation of the Zn of phosphate coating and particular range of the present invention or the coexistence of Zn alloy coating, when spot welding, only the part of spot-welding part is destroyed, conducts steel and aluminium by this spot-welding part.Although phosphate self is present in any side, do not have Zn of the present invention or Zn alloy coating, when its alone between steel and aluminium the time, when welding, in addition the part of spot-welding part also be difficult to destroyed, thereby influence spot weldability.In addition, influence the formation area and the thickness distribution control of the interfacial reaction layer of conjugant.Therefore, can not get the high bond strength of different material conjugant.This is in congener metal nonevent phenomenon each other and when being situated between spot welding when phosphate is arranged, can be described as the distinctive problem of different material conjugant of steel and aluminium.
Suitable and when relatively thin at phosphate coating thickness, under the situation of stress application when spot welding (plus-pressure), can steel and aluminium be conducted by the hole of phosphate coating.In addition, with the situation of the Zn of particular range of the present invention or the coexistence of Zn alloy coating under, stress during by spot welding and resistance, phosphate coating is destroyed, even stripping also can make steel and aluminium conduct fully on a large scale in molten aluminium
Thus, the boiling point of phosphate (zinc) epithelium is approximately 1075 ℃ the higher high temperature of ratio.But, when spot welding,, under the situation of the Zn of particular range of the present invention or the coexistence of Zn alloy coating, above-mentioned phosphate coating is also produced destruction, thereby steel and aluminium are conducted even be the following temperature of this boiling point.
And, carrying out the some postwelding, this phosphate coating is except that the spot-welding part of having removed epithelium, on a large scale or comprehensively between steel and aluminium, cut off the influence that is not subjected to corrosive environments such as moisture or oxygen between steel and the aluminium, or utilize and sacrifice the corrosion-inhibiting layer that corrosion protection effect formation comprises base material, suppress the differential metals contact corrosion of different material conjugant.
But, owing on phosphate coating, have described hole, so can not cut off the corrosion factor of moisture or oxygen etc. fully.Therefore, the control epitheliums such as Mg that have the natural potential lower than aluminium described later by interpolation become to be grouped into, and strengthen sacrificing the corrosion protection effect, thus, can further bring into play the function that suppresses differential metals contact corrosion.
Much less, in order to bring into play such function that each suppresses layer, as described later, the condition that on metal epithelium and phosphate coating, has the scope etc. of only composition or leather film thickness, in addition, when spot welding, has the optimum condition of plus-pressure or current-mode etc.
As implied above, the invention is characterized in that carrying out different material by spot welding when engaging, the metal epithelium of default Zn or Zn alloy and phosphate coating is two-layer between engaged steel and aluminium.
Thus, do not hinder the formation area of the interfacial reaction layer between steel and the aluminium and the control of thickness distribution, in addition, suppress different material conjugant differential metals contact corrosion in use, can keep high bond strength.In other words, suppress the decline of the bond strength that causes because of differential metals contact corrosion.
Consequently, the xenogenesis conjugant of steel and aluminium has does not reuse as described the other material shown in the technology at present, does not need new other operation in addition, just obtains bond strength effect high, by the different material conjugant under spot welding this year.And, at a postwelding, have the effect of the different material conjugant of the differential metals contact corrosion that is inhibited.
In addition, the thickness of the interfacial reaction layer of the galvanized steel that present inventors are especially at length undertaken by spot welding influence and the different material bond strength of aluminium is investigated, it found that, the movement of interfacial reaction layer and present thin more good more opinion have very big-difference.That is, if discovery will constitute the Al of the steel side of interfacial reaction layer 5Fe 3The Al of based compound layer and aluminium side 3The thickness of Fe based compound layer and the relation of area are controlled at optimum scope, though then for example interfacial reaction layer constitute by this two-layer intermetallic compound, bond strength also can be brought up to practical level.
In addition, when the different material of galvanized steel that is undertaken by spot welding and aluminium engages, be on the one hand, come from zinc-plated and distinctive crisp Zn-Fe based compound layer that generate is suppressed, improve bond strength.
Thus, even galvanized steel plain sheet (galvanized steel) also can improve the different material zygosity or the spot weldability of itself and aluminium.Therefore, when the spot welding that most continuous is got ready, obtain the sufficient strength of joint or the bond strength of different material conjugant.And the contact condition of electrode of at every turn getting ready and steel and aluminium is stable, and significantly improve electrode life, guarantees that the efficient of the spot welding that most continuous is got ready is good.
In addition, also have following effect, do not reuse other the material shown in the above-mentioned present technology, also do not need new other operation, galvanized steel plain sheet (galvanized steel) and aluminium just can access the bond strength height, can engage by the different material that spot welding forms.
Description of drawings
Fig. 1 is the cross-section photograph of state in the cross section of expression different material conjugant of the present invention;
Fig. 2 is the sectional view of expression xenogenesis conjugant of the present invention;
Fig. 3 is the key diagram that expression is used to obtain the spot welding mode of xenogenesis conjugant;
Fig. 4 is the sectional view at the interface, junction surface of the different material conjugant of expression the present invention;
Fig. 5 is the key diagram of section structure (Fig. 6) that enlarges the interface, junction surface of the different material conjugant of signal the present invention;
Fig. 6 is the SEM photo that the replacement drawing of section structure at the interface, junction surface of expression the present invention different material conjugant is used;
Fig. 7 is the TEM photo that the replacement drawing of section structure at the interface, junction surface of expression the present invention different material conjugant is used;
Fig. 8 is the key diagram of thickness distribution of the junction surface interfacial reaction layer of expression the present invention different material conjugant;
Fig. 9 is the key diagram that the certain thickness of in-plane of the junction surface interfacial reaction layer of expression the present invention different material conjugant distributes;
Figure 10 is the key diagram of certain thickness distribution of in-plane of the junction surface interfacial reaction layer of expression comparative example different material conjugant;
Figure 11 is the key diagram that expression is used to obtain the spot welding mode of different material conjugant;
Figure 12 is the replacement drawing TEM photo of section structure at the interface, junction surface of expression comparative example different material conjugant.
Description of drawings
1 steel
2 aluminium alloys
3 nuggets
4 interfacial reaction layers
Center, 5 junction surface
D NNugget size
D CEngage diameter
11 steel plates
12 aluminium alloy plates
13 xenogenesis conjugants
14 suppress layer
15 nuggets
16 interfacial reaction layers
17,18 electrodes
21 steel plates
22 aluminium alloy plates
23 different material conjugants
24 oxide scale films
25 nuggets
26 interfacial reaction layers
27,28 electrodes
The specific embodiment
Below, the qualification reason and the effect thereof of each important document of embodiment of the present invention described.
In addition, below be described more specifically the present invention for example, much less, the present invention is not limited by following embodiment.Self-evident, also can in can being suitable for the scope of aforementioned, main idea described later, suitably change, these all are contained in technical scope of the present invention.
[1]
(formation of conjugant)
For the formation of conjugant that an embodiment of the present invention is described, Fig. 1 represents the cross-section photograph at the junction surface of conjugant of the present invention.In figure, 1 expression steel, 2 expression aluminiums, 3 expression nuggets, 4 expression cross section conversion zones, 5 expression centers, junction surface.
(steel)
The thickness of slab t of the steel that use among the present invention 1Be made as 0.3～3.0mm.Under the situation of not enough 0.3mm, structural elements or structural material as assembly can not be guaranteed necessary strength of parent or rigidity, on the other hand, surpassing under the situation of 3.0mm, as structural elements or structural material, usually adopt other joint method, this is because the few cause of necessity of utilizing spot welding to engage.
In addition, there is no particular limitation to the shape of the steel that use or material in the present invention, can be according to as each structure requiring characteristic suitablely to select general sheet material, section bar, forging material, cast material with member.
(aluminium)
The thickness of slab t of the aluminium that uses among the present invention 2Be made as the scope of 0.5～4.0mm.At aluminium thickness of slab t 2Under the situation of not enough 0.5mm, as structural material strength of parent deficiency not only, and can not get the nugget area of prescribed level, and be molten to the opposite composition surface of aluminium easily, therefore can not get high bond strength.On the other hand, at aluminium thickness of slab t 2Surpass under the situation of 4mm, adopt other joint method as structural elements or structural material, this is because the few cause of necessity of utilizing spot welding to engage.
In addition, among the present invention, there is no particular limitation to the aluminium shape used or material (kind of alloy), can be according to as each structure requiring characteristic suitablely to select general sheet material, section bar, forging material, cast material with member.In addition, the distortion that the pressurization when suppressing spot welding causes it is desirable to the high side of intensity of aluminium.On this point, preferably use in aluminium alloy intensity also high, and as this kind structure with the general A5000 system of member, A6000 system etc.
(nugget area)
The area of the nugget 3 that forms by spot welding shown in Figure 1 is made as the thickness of slab t by aluminium 2 2The regulation, 20 * t 2 0.5～100 * t 2 0.5Mm 2Scope.In other words, necessary Chosen Point welding rod spare is so that the nugget area becomes 20 * t 2 0.5～100 * t 2 0.5Mm 2Scope.
All the time, when spot welding hardware of the same race, the area of establishing the nugget that forms by spot welding with respect to the thickness of hardware is 20 * t 2 0.5Mm 2Size, no matter it is from the bond strength aspect,, all optimum still from processability and economy aspect.
To this, the invention is characterized in that dissimilar metal member joint each other is than the bigger nugget area of above-mentioned congener hardware joint each other.That is, carry out spot welding, so that the area of the nugget 3 that forms by spot welding becomes the thickness of slab t by aluminium 2 220 * t of regulation 2 0.5～100 * t 2 0.5Mm 2Scope, thus, even the conjugant of different material also can obtain sufficient joint strength, and processability, economy are also good.
Under situation about being engaged with each other as different metal materials of the present invention, only nugget area is characterised in that it exists with ... the thickness of slab t of aluminium 2 sides 2, the thickness of slab t of steel 1 1Influence little of negligible degree.
At this, at nugget area less than 20 * t 2 0.5Mm 2, less than 30 * t more strictly speaking 2 0.5Mm 2The time, the nugget area is too small, and bond strength is insufficient.Work as the nugget area on the other hand and surpass 1000 * t 2 0.5Mm 2The time, the bond strength that obtains is very abundant, but needs the high magnitude of current, therefore can not use existing spot welding device, needs device especially.So establishing the nugget area is 20 * t 2 0.5～100 * t 2 0.5Mm 2Scope, preferred 30 * t 2 0.5～100 * t 2 0.5Mm 2Scope.
Nugget area of the present invention obtains by the area of the joint interface of mensuration steel 1 and aluminium 2.The assay method of the area of joint interface is to separate conjugant at joint interface by peeling off or cutting off, and aluminium 2 sides are carried out image analysis, measures the area of nugget 3, tries to achieve therefrom.Nugget be shaped as circular the time, also can be at the center, junction surface 5 vertical (thickness of slab directions) cut off the junction surface by the observation by light microscope section, measure diameter (nugget size) D of the joint interface of nugget 3 NObtain area.At this moment, for example in the vertical section of two directions of quadrature, measure nugget size D NCalculating is the area of the ellipse of major diameter and minor axis with it, with it as the nugget area.
(thickness of interfacial reaction layer)
Interfacial reaction layer 4 shown in Figure 1, establishing its only thickness is 0.5～3 μ m, the area of establishing the part with this optimum thickness is 10 * t 2 0.5Mm 2More than.
Like this, why stipulate to have the area of the interfacial reaction layer 4 of optimum thickness, be based on as mentioned above,, enlarge this technological thought that forms interfacial reaction layer as far as possible with optimum thickness for the raising of bond strength.
That is, the thickness at interfacial reaction layer 4 is the area less than 10 * t of 0.5～3 μ m part 2 0.5Mm 2, less than 25 * t more strictly speaking 2 0.5Mm 2Situation under, have the narrow range that the interfacial reaction layer 4 of optimum thickness forms, bond strength descends.In addition, the diffusion of its steel aluminium of part of the thickness less than 0.5 μ m of interfacial reaction layer 4 is insufficient, and bond strength reduces.On the other hand, the part that the thickness of interfacial reaction layer 4 surpasses 3 μ m becomes fragile, and bond strength reduces.Thereby in order to improve the bond strength as junction surface integral body, the thickness that must establish interfacial reaction layer 4 is that the area of 0.5～3 μ m part is 10 * t 2 0.5Mm 2More than, preferred 25 * t 2 0.5Mm 2More than.
Also must establish center, junction surface 5 and 5 differences for the thickness of the interfacial reaction layer of the point of 1/4 the distance that engages diameter Dc are in the 5 μ m from the center, junction surface, it is desirable in the 3 μ m.At this, the so-called diameter Dc that engages is meant the diameter that forms interfacial reaction layer 4 scopes.When using the joint of common dome type electrode tip (also " electrode tip " can be abbreviated as " joint "), the center, junction surface (below, also can abbreviate as " " center ") 5; be the thickest position of interfacial reaction layer 4; relative therewith, decentre 5 is the interfacial reaction layer attenuation of the point of 1/4 the distance that engages diameter Dc.When the difference of above-mentioned thickness during greater than 5 μ m, the interfacial reaction layer 4 at center 5 is compared excessively with the interfacial reaction layer 4 of periphery and is thickened, bond strength descends, and, not only the generation owing to dust diminishes outward appearance, and the thickness distribution of the interfacial reaction layer 4 of periphery also changes, thereby becomes the unbalanced main cause of intensity.
In addition, it is desirable to, the maximum ga(u)ge of interfacial reaction layer 4 is 0.5～10 μ m, and better is the scope of 1.5～5 μ m.When using the joint of common dome type joint, center, junction surface 5 is equivalent to become the position of above-mentioned maximum ga(u)ge.When above-mentioned maximum ga(u)ge surpassed 10 μ m, not only the intensity of this part was low, and whole bond strength descends, and, because the generation of dust, the thickness distribution of the interfacial reaction layer 4 of periphery is also produced harmful effect, thereby become the uneven main cause of intensity.On the other hand, under the situation of above-mentioned maximum ga(u)ge less than 0.5 μ m, can not obtain the only thickness of above-mentioned 0.5～3 μ m.
The thickness of this interfacial reaction layer 4 is also the same with above-mentioned nugget area, and the area of joint interface that can be by measuring steel 1 and aluminium 2 obtains, and can try to achieve by the image analysis or the observation by light microscope of aluminium 2 sides.
Below, the important document of spot welding is described.
(electrode tip)
The relevant electrode tip that is used for spot welding it is desirable to, and is contacting with more than 2 o'clock or wire or planar carrying out of plate with being engaged material.Shown at present, with the very big pressurization part of plate be not a bit, and be more than 2, or use and be wire or planar street corner, can access the above-mentioned bigger only nugget area and the optimum structure of above-mentioned interfacial reaction layer thus.At this, so-called wire is defined as the above continuous lines of 3mm, the so-called planar 5mm that is defined as 2Above continuous face, what do not satisfy these is point.
In order to confirm the very big pressurization part of joint, the platen of selling on the market that adds is added between plate and the joint, add with the plus-pressure of 0.1kN, thus as long as adding the residual vestige of affirmation on the platen.Common dome type joint, only some vestiges of residual contact.
As an example of above-mentioned desirable electrode tip, the central authorities' (on axle of joint) that are recommended in the leading section of dome type joint are formed with the electrode tip of the above recess of diameter 2mm.Consume leading section owing to getting ready continuously when the spot welding, thus must be regularly by pouncing paper, grind butt joint leading sections such as cutting device and keep in repair, but this moment, the shape that is difficult to leading section is not that axisymmetric joint keeps in repair.By on the axle of joint (that is, concentric) with axle recess is set, thus, the handling ease of joint not only, and can make pouncing paper or grind and cut device and along the circumferential direction rotate and be easy to keep in repair.In addition, the butt joint leading section is entirely the plane joint on plane, because with respect to the planar butt of plate, so can reduce current density, like this, under situation with respect to the planar butt of plate, the joint rugosity is big to the influence of electric current pathway, needs to improve the maintenance frequency of butt joint.Therefore, for the maintenance frequency that satisfies joint simultaneously and the equalization effect of interfacial reaction layer 4, the leading section that is preferably in the dome type joint is provided with recess, and the diameter that it is desirable to recess is more than the 2mm.During not enough 2mm, can not fully suppress electric current to the concentrating of central part, the equalization effect of interfacial reaction layer 4 is little.In addition, do not establish the upper limit of recess diameter, when the size of considering joint and maintainability, consider that 15～20mm is maximum.Although concave depth is shallow, it is desirable to more than the 0.5mm.In addition, when concave depth was dark, joint was elongated, and the cooling effectiveness of cooling water descends, and therefore there is no need greater than 3mm.In addition, do not have especially point diameter, the front end R of dome type joint are stipulated, but in order to ensure the nugget area, it is desirable to point diameter is more than the 7mm, and front end R is more than the 75mm.
In addition, using under the situation of such joint, needing to confirm by pressure-sensitive paper in advance, and safeguard, contacting fully making it.
And; at least one side at the electrode tip of a pair of (two) that are used for spot welding uses the joint that is provided with recess at above-mentioned leading section; thus; if it is a plurality of by the welding current pathway in the plate; thereby suppress concentrating of electric current; when preventing that dust or defective from taking place, can make the thickness of interfacial reaction layer 4 even.Only use under the situation of joint a side, the method that is used for steel 1 side can further suppress heating, and two Fang Jun use the method for joint can also suppress concentrating of electric current, and can make the thickness homogenising of interfacial reaction layer 4 more reliably.
(welding temperature)
In addition,, also can suppress the heating of two members even at least one side of steel 1 and aluminium 2 is cooled to below 5 ℃, the generation of anti-dust or flaw, and make the interfacial reaction layer thickness even.Under the situation that the either party cools off, the method that steel is cooled off can further suppress heating, and the method that two sides are cooled off more can suppress to generate heat, and more can make the thickness homogenising of interfacial reaction layer 4 reliably.Suppress effect in order to give full play to this heating, it is desirable to, establishing welding temperature (plate temperature) is below 5 ℃.Can suppress heating more because welding temperature is low more, thus do not set lower limit, but when considering processability, suitable more than-5 ℃.
As the cooling means of plate, no matter be the method for welding again after by liquid or gaseous coolant plate being cooled off in advance, the method for cooling off by gaseous coolant when still welding can.In addition, under situation about in advance plate being cooled off, must after adhering to onboard frost etc., eliminating weld again.
In addition; by using the joint and two kinds of ways cooling off above-mentioned plate after use is studied above-mentioned leading section shape, can suppress concentrating of electric current, can prevent that plate from generating heat simultaneously more reliably; and can also suppress the generation of dust or flaw, more can make the thickness of interfacial reaction layer 4 even.
(engaging condition)
The engaging condition of the spot welding of using among the present invention is not particularly limited plus-pressure and current-mode, can be according to the material of steel 1 or aluminium 2 or thickness of slab, surface-treated difference, also have suitable selection such as joint leading section shape.But, the structure of nugget area and interfacial reaction layer 4 must satisfy the scope of the present invention's regulation, in order to ensure the nugget area, need for the thickness that suppresses interfacial reaction layer 4 increases, not exist under the situation of surface-treated layer onboard than the higher plus-pressure and the magnitude of current, ask for the welding of short time, have under the situation of surface-treated layer, after the surface-treated layer at same discharge junction surface, asking for the welding of short time as far as possible.
[embodiment]
As steel, use the steel plate that obtains as follows.That is, casting is as chemical composition, and containing 0.06%C-0.5%Si-1.2%Mn qualitatively, except that the unavoidable impurities of P, S etc., nubbin is essentially the confession examination steel ingot of Fe, and it is rolled down to the thickness of slab of 1.2mm, obtains sheet metal.And, in continuous annealing, after 500～1000 ℃ annealing, carry out oil wash or washing, obtain the high-tensile strength steel plate of 590MPa level thereafter by tempering.
In addition, as aluminium, use A6022 (6000 are) aluminium alloy plate of selling on two kinds of markets of thickness of slab 1.0mm and 1.6mm.
On the basis of the cross tensile test plate shape that these steel plates (steel) and aluminium alloy plate (aluminium) is processed into JIS A 3137 records, weld, thereby be made into the xenogenesis conjugant.Utilize water or frozen water in advance steel plate and aluminium alloy plate to be cooled off, before engaging, be adjusted to each test temperature, weld afterwards.In all soldering tests, the temperature of steel plate is identical with the temperature of aluminium alloy plate.In addition, before welding, wipe attached to lip-deep liquid of plate or frost.
When spot welding, use D.C. resistance soldering test machine.Electrode tip uses all the dome type joint (point diameter 12mm, front end R150mm) by the Cu-Cr alloy composition, and use unprocessed (joint A, comparative example :), carry out wide 5mm at joint leading section center by some butts, (joint B :) that the groove of dark 1mm is processed by 2 butts, process the joint of five shapes of (joint C, D, E :) of the recess of dark 1mm respectively at circumference wire butt with diameter 1mm, 2mm, 5mm at the joint leading section.If anode is aluminium alloy plate, negative electrode is steel plate, in all soldering tests, two sides' of pair of electrodes head shape is identical.Under the situation of using joint B, the direction that makes working groove is in the certain orientation unanimity.
[table 1]
Figure A20078000623400241
Figure A20078000623400251
Table 1 expression experimental condition (the thick t of aluminium sheet 2, plate temperature, kind, plus-pressure and the current-mode [welding current, weld interval] of electrode tip before the welding).
The nugget area by at the conjugant sample that will put postwelding after the center at junction surface slit shearing is imbedded resin and is ground, utilize the observation by light microscope section, measure the nugget that forms joint interface diameter and obtain.Measure the nugget size of two directions of quadrature, and calculate the area that these is made as the ellipse of major diameter and minor axis, and with it as the nugget area.
The thickness of interfacial reaction layer is by butt joint A, C, D and E, and each condition is made the conjugant sample of three spot welding, and respectively after the center at junction surface slit shearing is imbedded resin and ground, and observes by SEM and obtains.The thickness of interfacial reaction layer be under the situation more than the 1 μ m with 2000 times visual field, instrumentation is carried out in the visual field with 10000 times under the situation of not enough 1mm.And the maximum ga(u)ge during three samples are measured is made as the maximum ga(u)ge of interfacial reaction layer.In addition, measure the thickness at center, junction surface respectively, and divide the thickness take leave of about the center, junction surface to the interfacial reaction layer of 2 points (intermediate point) of 1/4 the distance that engages diameter, and obtain thickness poor of center and intermediate point, will average the value of 6 of each totals of 2 of per three samples the value that obtains as the center, junction surface and from the center, junction surface poor for the thickness of the interfacial reaction layer of the point of 1/4 the distance that engages diameter.Concerning the thickness of interfacial reaction layer is the area of 0.5～3 μ m part, calculates the area of graph that the line segment of 0.5～3 μ m part that makes each cross section was drawn around one week of center, junction surface, and three sample means are obtained this area.
In addition, because the shape of the recess of joint B is not the circle shape, can not utilize above-mentioned method to measure, so make the conjugant sample of six means of spot welds under each condition, and at the center at junction surface along with respect to linking the straight line that joint is connected to the point-to-point transmission of plate, tilt the respectively direction slit shearings of 0 degree, 15 degree, 30 degree, 45 degree, 60 degree, 75 degree, 90 degree after imbedding resin and grinding, carry out SEM and observe.Under the thickness of layer is situation more than the 1 μ m, under the situation with 2000 times visual fields, less than 1 μ m, carry out instrumentation with 10000 times visual fields.And the maximum ga(u)ge of establishing in the mensuration of each angle direction of six samples is the maximum ga(u)ge of interfacial reaction layer.In addition, for each sample, measure the center, junction surface thickness, divide the thickness of taking leave of about the center, junction surface to the interfacial reaction layer of 2 points (intermediate point) of 1/4 the length that engages diameter, obtain thickness poor of center and intermediate point, value maximum in these the difference is made as the junction surface and from the center, junction surface is thickness poor of interfacial reaction layer of point that engages 1/4 distance of diameter.In addition, when measuring, be maximum difference by the cross sections of joint B inclination 90 degree.In addition, in the scope of 0.5～3 μ m of each angle of 0～90 degree, the thickness of drawing interfacial reaction layer at each each angle direction is the curve of the area of 0.5～3 μ m part, links curve by straight line between each angle direction, calculates 0.5～3 μ m area partly of the scope of 0～90 degree thus.With the center is the object axle, can obtain the area of two 90 degree scopes, therefore with two area additions of obtaining 0.5～3 μ m part of the 90 degree scopes of coming, again it be multiply by 2, thereby calculates the area of whole 0.5～3 μ m part.
As the evaluation of bond strength, different material conjugant has been implemented the cross tensile test.In the cross tensile test, if bond strength is more than the 1.5kN or disrumpent feelings mode is that aluminum mother plate is disrumpent feelings, then be designated as ◎, if bond strength is 1.0～1.5kN then is designated as zero, if bond strength is 0.5～1.0kN then is designated as △, if the not enough 0.5kN of bond strength then be designated as *.
In addition, in the present embodiment, why the evaluation of bond strength not being adopted and cut off tensile test and adopt the cross tensile test, is because the relative different of the bond strength of cross tensile test one side between experimental condition is big, therefore, it is more suitable for the good cause of not judging.Cut off the tendency of tensile test and cross tensile test result and coincide, in the cross tensile test, obtain zero, the different material conjugant of the evaluation of ◎ all can access the high shearing strength more than the 2.5kN.
[table 2]
Test No Nugget area (* t 2 0.5mm 2) Area (* t with interfacial reaction layer of optimum thickness 2 0.5mm 2) The center, junction surface be poor (the μ m) of the thickness of the interfacial reaction layer of 1/4 the range points that engages diameter from the center, junction surface The maximum ga(u)ge of interfacial reaction layer (μ m) Cross tensile test result Remarks
1 45 22 14.5 18.2 × Comparative example
2 50 20 14.8 17.5 × Comparative example
3 47 21 15.0 18.1 × Comparative example
4 46 26 4.7 9.0 ○ Embodiment
5 45 25 4.9 8.3 ○ Embodiment
6 52 27 4.2 7.7 ○ Embodiment
7 54 26 5.0 10.0 ○ Embodiment
8 47 28 4.4 9.1 ○ Embodiment
9 49 32 2.9 4.9 ◎ Embodiment
10 51 35 1.3 4.1 ◎ Embodiment
11 55 36 2.4 5.0 ◎ Embodiment
12 50 38 2.2 3.3 ◎ Embodiment
13 56 39 1.8 4.1 ◎ Embodiment
14 19 11 3.9 5.2 × Comparative example
15 105 48 7.3 9.8 × Comparative example
16 76 33 5.5 10.3 △ Comparative example
Table 2 is illustrated under each experimental condition shown in the table 1, the cross tensile test result of the different material conjugant that obtains by spot welding.
When to test No.1～6 when comparing as can be known, compare in test No.1～3 that are higher than 5 ℃ with the temperature of plate, the temperature of plate is that its area for the optimum thickness range of interfacial reaction layer (0.5～3 μ m) part of test No.4～6 that is lower than below 5 ℃ is big, and, the center, junction surface is little with difference from the thickness of the interfacial reaction layer of the point of the length that engages diameter 1/4, the bond strength height of xenogenesis conjugant.
In addition, when to test No.1,2 and test No.7～11 when comparing as can be known, test No.1,2 at the unreal worker's of applying of leading section common dome type joint compares with use, be suitable for the present invention's regulation joint test No.7～11 its be that optimum thickness range (0.5～3 μ m) area partly of interfacial reaction layer is big, and, the center, junction surface is little with difference from the thickness of the interfacial reaction layer of the point of the distance that engages diameter 1/4, the bond strength height of different material conjugant.Especially, use is formed with test No.9～11 of the electrode tip of the recess more than the diameter 2mm in the leading section central authorities of dome type joint, can with for the area of the optimum thickness range (0.5～3 μ m) of interfacial reaction layer part, and the center, junction surface be controlled at better scope with difference from the thickness of the interfacial reaction layer of the point of the distance that engages diameter 1/4, so the bond strength of different material conjugant is high.And, the test No.12,13 of temperature reduction below 5 ℃ with plate, can be controlled at better scope with for poor with from the thickness of the interfacial reaction layer of the point of the distance that engages diameter 1/4 of the area of the optimum thickness range (0.5～3 μ m) of interfacial reaction layer part and center, junction surface.
Therefore, by the result of the foregoing description critical meaning of each important document of the present invention's regulation as can be known.
But, use the joint of regulation as the preferred joint of the present invention, even use the member of the low temperature below 5 ℃, the also unaccommodated test of engaging condition No.14～16, the area of the optimum thickness range of its nugget area or interfacial reaction layer (0.5～3 μ m) part, maximum interfacial reaction layer thickness, center, junction surface with in the difference of the thickness of the interfacial reaction layer of the point of the length that engages diameter 1/4 more than one not in prescribed limit, the bond strength reduction.
Promptly, material or thickness of slab, surface-treated difference that must be by steel plate or aluminium alloy plate, also have that joint geometry is suitable to be selected between optimum amount of money welding rod (plus-pressure, current-mode), so that the structure of nugget area, interfacial reaction layer satisfies the scope of the present invention's regulation.
[2]
(xenogenesis conjugant)
Fig. 2 represents the xenogenesis conjugant of one embodiment of the present invention regulation by sectional view.Among Fig. 2,13 different material conjugants for steel (steel plate) 11 and aluminium (aluminium alloy plate) 12 being engaged by spot welding.15 is the nugget with interfacial reaction layer 16 of spot welding, and horizontal direction has the diameter shown in the arrow among the figure.19 is the joint portion, dizzy district around the nugget.t 1Thickness of slab, t for steel 2For thickness of slab, the Δ t of aluminium is the remaining thickness of slab of the minimum of the aluminium after engaging by spot welding.
At this, 14 for suppressing layer, and between the composition surface each other that is preset in these engaged steel 11 and aluminium 12, the duplexer of the epithelium of the metal epithelium of Zn or Al and organic resin bonding agent.Fig. 2 represents not distinguish respectively ground whole expression Zn or the metal epithelium of Al and the epithelium of organic resin bonding agent, implements plating Zn on the engage side surface of steel 11, applies organic resin adhesive thereon, thereby makes the mode that suppresses layer 14.
And, that the junction surface that Fig. 2 is illustrated in the xenogenesis conjugant of a postwelding is got rid of is default before spot welding, for the duplexer of the epithelium of the metal epithelium of Zn or Al and organic resin bonding agent promptly suppresses layer 14, and steel 11 and aluminium 12 directly engages, the good engagement state of xenogenesis conjugant.In addition, Fig. 2 also is illustrated in the states that preformed these inhibition layers 14 of xenogenesis conjugant interface zone in addition exist in the same old way.
(thicknesss of slab of steel)
The present invention must be that the thickness of slab of steel is the conjugant of 0.3～3.0mm.Thickness of slab t at steel 1Under the situation of not enough 0.3mm, as said structure member or structural material, can not guarantee necessary strength or rigidity, this is inappropriate.In addition, in addition, because the pressurization that spot welding is carried out strengthens deformation of steel, oxide scale film is destroyed easily, therefore promotes the reaction of steel and aluminium.Consequently, form intermetallic compound easily.
On the other hand, surpass under the situation of 3.0mm at thickness of slab, as said structure member or structural material, adopt other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with steel 1Thickening surpasses 3.0mm.
(steel)
The present invention does not have especially the shape or the material of the steel that use are limited, and can use suitable shape, the material that is common to structural elements or the steel plate of selecting according to the structural elements purposes, steel profile, steel pipe etc.But for the high-strength structure member (different material conjugant) of the light weight that obtains automobile component etc., the tensile strength of preferred steel is the above common high tension steel (high strength steel) of 400MPa.
The low-intensity steel of the not enough 400MPa of tensile strength mostly is low-alloy steel usually, and oxide scale film is made up of ferriferous oxide, so Fe and Al diffusion are easily, form crisp intermetallic compound easily.Therefore, same preferred tensile strength is more than the 400MPa, and ideal is the above high tension steel (high strength steel) of 500MPa.
(aluminium)
Be used for aluminium of the present invention the kind and the shape of its alloy is not particularly limited, can be according to the characteristic that requires as each structural elements, suitable general sheet material, section bar, forging material, the casting material etc. selected.But the intensity of the aluminium also situation with above-mentioned steel is the same, the distortion that the pressurization during for inhibition spot welding causes, and a high side is desirable.On this point, preferably use intensity in the aluminium alloy also high and as this kind structure with the general A5000 system of member, A6000 system etc.
But, the thickness of slab t of these aluminiums that use among the present invention 2It is the scope of 0.5～4.0mm.Thickness of slab t at aluminium 2Under the situation of not enough 0.5mm, as the undercapacity of structural material, this is inappropriate.In addition, owing to can not get nugget size, and dissolve easy arrival aluminum surface and form dust easily, so can not obtain high bond strength.On the other hand, at the thickness of slab t of aluminium 2Surpass under the situation of 4.0mm, the same with the situation of the thickness of slab of above-mentioned steel, as said structure member or structural material, adopts other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with aluminium 2Thickening surpasses 4.0mm.
(suppressing layer)
The present invention when spot welding, controls the formation area and the thickness distribution of the interfacial reaction layer between steel and the aluminium in order to obtain higher bond strength.Therefore, the present invention suppresses to be controlled at the time that forms interfacial reaction layer between steel and the aluminium.And in order to suppress to control this conversion zone formation time, (material) forms the inhibition layer between steel and aluminium in advance.
Suppress layer as this, in order to suppress to control the interfacial reaction layer formation time and suppress differential metals contact corrosion, Zn or the metal epithelium of Al and the epithelium of organic resin bonding agent of the present invention's default two-layer particular range between these engaged steel and aluminium composition surface each other.Therefore, as described later, at the stacked epithelium that metal epithelium and organic resin bonding agent are set of arbitrary composition surface of steel side or aluminium side side.Though it can be arbitrarily that the order of (carrying out stacked) is set,, be provided with the epithelium that metal epithelium one side is provided with the machine resin adhesive easily earlier.
(the metal epithelium of Zn or Al)
Below, at first to describing as the Zn of the particular range that suppresses one of layer or the metal epithelium of Al.In the present invention, owing under the state of the metal epithelium that is preset with Zn or Al between engaged steel and aluminium composition surface each other, carry out spot welding, preset the metal epithelium of Zn or Al on the surface of the composition surface at least of steel or aluminium side.Shown in the specific as described later melting point scope of the metal epithelium of this Zn or Al, because its melting point with the aluminium that engages is approaching, so when spot welding, the intermetallic compound that can control steel and aluminium is the time that interfacial reaction layer forms, and can control the thickness range and the distribution of interfacial reaction layer.
In the present spot welding of steel that use metal epithelium naked or that do not have Zn or Al and aluminium, resistance heating amount during spot welding is fewer, therefore, because the interface temperature of steel and aluminium, especially the temperature of steel is not high significantly to the temperature that dissolves that surpasses aluminium, so can not obtain high bond strength.Like this, as the spot welding mode, Jie has under the situation of organic resin bond layer at joint interface, and more restive spot welding self or interfacial reaction layer form, thereby can not obtain high bond strength.
Relative with it, between engaged steel and aluminium composition surface each other, under the situation of the metal epithelium that is preset with Zn or Al as the inhibition layer, even between the composition surface, get involved the epithelium of organic resin bonding agent, it is not difficult that spot welding self and interfacial reaction layer form control yet, thus the function of performance organic resin bonding agent epithelium aspect.
As mentioned above, this is because the existing of the metal epithelium by Zn or Al (be situated between and exist), and the resistance heating amount during spot welding increases, and the temperature of the interface temperature of steel and aluminium, especially steel is high significantly to the cause that dissolves temperature above aluminium.By the increase of this resistance heating amount, the epithelium of organic resin bonding agent is discharged or eliminating from the peripherad part of the welding portion of steel and aluminium easily, thereby can conduct steel and aluminium.
In addition, as described above, when because the resistance heating amount when the existing of the metal epithelium of Zn or Al (be situated between and exist) and spot welding when increasing, aluminium is being accelerated significantly with the diffusion velocity at the interface of steel, aluminium spreads in the steel side, thereby can guarantee good engagement state rapidly.In addition, infer under the situation of galvanized steel plain sheet that utilize the difference of melting point, zinc coat dissolves in advance, consequently, also has the effect of the heat distribution homogenising that makes the interface.Be speculated as composite effect,, also can improve spot weldability even the intervention of the epithelium of organic resin bonding agent is opposite with present general knowledge by the metal epithelium of these Zn or Al.
In order to bring into play these effect, the melting point of establishing the metal epithelium of Zn or Al is 350～1000 ℃, preferred 400～950 ℃ narrow temperature scope.In addition, the melting point of more preferably establishing the metal epithelium of Zn or Al is the above narrower temperature range below 900 ℃ of aluminium melting point.The melting point of aluminium is (melting point of pure Al) about 660 ℃, and the melting point of pure Zn is about 420 ℃.As mentioned above, so-called melting point is approaching with the aluminium that engages, and for example is meant with respect to 660 ℃ of the melting points of pure Al, allows to have above-mentioned a certain size the meaning of amplitude.
In addition, the thickness of establishing the metal epithelium of Zn or Al is the thickness (average film thickness) of 3～19 μ m, more preferably the narrow thickness scope of 5～15 μ m.The thickness of the metal epithelium of relevant Zn or Al, the steel after these epitheliums are formed or the test portion of aluminium cut off, and imbed resin and grind, and the SEM that carries out the thickness of slab direction of metal epithelium observes.This SEM observes and utilizes 2000 times visual field to measure three dot thickness, and the thickness of metal epithelium is by obtaining these averaging.
The thickness of the metal epithelium of Zn or Al cross thin or situation that its melting point is low excessively under, at the joint initial stage of the metal epithelium of Zn or Al when spot welding, will dissolve discharge from the junction surface, thereby can not suppress the formation of interfacial reaction layer.
On the other hand,, need engaged steel and aluminium to be in direct contact with one another, when spot welding, must dissolve discharge from the junction surface between the Zn at junction surface or the metal epithelium of Al in advance on mutual composition surface in order to improve the bond strength of different material conjugant.To this, under the situation that thickness is blocked up or melting point is too high of the metal epithelium of Zn or Al,, need the big heat that advances for the metal epithelium with Zn or Al dissolves discharge from the junction surface.When this advances heat when excessive,, pretend to structural elements and can not use different material conjugant because the reduction that causes aluminium of dust strengthens.
The metal epithelium of Zn or Al can from the suitable pure Al of selection of above-mentioned melting point scope or Al, Zn alloy or Al alloy etc., use alloy composition.In addition, in the surface coverage of the composition surface at least of steel or aluminium side or the also suitable general known method of using plating, coating etc. of method of formation metal epithelium.In addition,, be at least the surface of composition surface side, much less,,, also can cover or form the metal epithelium of Zn or Al in the steel or the aluminium material surface side that are not the composition surface for corrosion protection to the covering or the formation of these steel or aluminium material surface.
But when considering practicality and efficient, the metal epithelium of preferred Zn or Al covers or forms as coating at Zn or the general steel side of Al plating.Usually, steel are implemented coating use, even in coating, damage, also preferentially corrode Zn or Al, so can protect steel.And, by reducing the potential difference of steel and aluminium, also can suppress the differential metals contact corrosion of one of problem for the xenogenesis conjugant.Have at plating under the situation of Zn or Al, guarantee the corrosion resistance of steel, in addition, to steel might as well, to aluminium might as well, all be easy to carry out plating.
With the plating is prerequisite, brings into play above-mentioned interfacial reaction layer and forms inhibit feature, even in order to bring into play to be situated between organic resin bonding agent epithelium is arranged, also makes to be welded into possible function the preferred pure Zn of the plating epithelium of Zn or Al, pure Al.In addition, even be Zn alloy or Al alloy, what also preferably contain above Zn of 80% quality or Al respectively is the alloy of main component with Zn or Al respectively at alloys such as Al-Zn, Al-Si, Zn-Fe.Carry out under the situation of alloying at plating epithelium,, make it not exceed above-mentioned molten point range, and corrosion resistance is worsened by adding alloying element and content thereof to Zn or Al.
Special recommendation also contains pure Zn or the Zn alloy plating epithelium of the Zn more than 88% quality in these plating epitheliums.When steel surface is implemented to contain the Zn plating epithelium of the above Zn of 88% quality, can improve the corrosion resistance of steel especially, in addition, this Zn plating epithelium is controlled at melting point above-mentioned 350～1000 ℃ scope easily.And corrosion resistance is also high, and also can suppress differential metals contact corrosion.From the viewpoint that this kind differential metals contact corrosion prevents, be preferably pure Zn plating epithelium.
About method for plating, the present invention does not limit, and can use existing wet type, dry type plating.Particularly when zinc-plated, recommend to electroplate or dissolve plating, dissolve the method for carrying out Alloying Treatment after the plating etc.
(epithelium of organic resin bonding agent)
Then, the epithelium inhibition layer, the organic resin bonding agent as another is described following.
As mentioned above, the epithelium of organic resin bonding agent is as electric insulation layer, suppresses control interfacial reaction layer formation time when spot welding, and, the some postwelding its on a large scale or comprehensively between steel and aluminium, have the function that suppresses differential metals contact corrosion.
The present invention implements spot welding after being applied to the epithelium that forms organic resin adhesive on (surface, composition surface of any) between the mutual composition surface of steel and aluminium.Therefore, the epithelium of organic resin bonding agent has the function of so-called welding binding agent when spot welding.That is, increase the contact resistance at the interface of steel-aluminium, evenly improve the caloric value at interface on a large scale, can form interfacial reaction layer on a large scale thus, thereby control the thickness of interfacial reaction layer easily.
Weight or applied thickness to the organic resin bonding agent are not particularly limited, usually, in the car body of automobile is made general frankincense bonding agent, welding with bonding agent, tape edge with bonding agent, spot welding with the back cover agent etc., its kind and applied thickness all can be suitable for.
The kind of illustration organic resin bonding agent.If bonding agent is a water solution system, then can use urea system, carbolic acid system, PVA etc.If bonding agent is a solution system, then can use CR system, acrylonitrile-butadiene rubber system, vinyl acetate, nitrocellulose etc.If bonding agent is a latex system, then can use vinyl acetate, propylene, EVA system, CR system, SBR system, nitrile rubber system etc.If bonding agent is solvent-free system, then can use epoxy, acrylate, polyester etc.In addition, according to different situations, also can use the organic resin bonding agent of shapes such as solid type or band.
In welding, steel and aluminium are conducted go forward side by side spot welding to engage.In order to improve bond strength, preferably means of spot welds fashionable with bonding agent to external compression, reduce the remaining quantity of the bonding agent at junction surface.But, though be not do not have bonding agent fully remaining at the junction surface,, bonding agent also can remain in the junction surface does not influence the degree that spot welding engages, for example not cambial degree.
About this point, if be the thermosetting resin bonding agent epithelium of epoxy, propylene etc., then when spot welding, under the situation of two electrode tip stress applications (plus-pressure) by clamping steel and aluminium, because the character softness, so it has the characteristic of discharging or getting rid of from the peripherad part of the welding portion of steel and aluminium easily.If use the thermosetting resin bonding agent, then utilize this characteristic, fashionable in means of spot welds, steel and aluminium can be conducted.
In addition, even be thermoplastic resin bonding agent epithelium, if when spot welding, heat, then owing to the character softness, so it also has the characteristic of being discharged or being got rid of by welding portion part around it of steel and aluminium easily.And, even heating or pressurization are not discharged this thermoplastic resin bonding agent epithelium or get rid of from the peripherad part of the welding portion of steel and aluminium like this,, steel and aluminium are conducted if the heating during because of spot welding is dispersed or burnt.
At a postwelding, organic resin bonding agent epithelium is only except that the spot-welding part that has been excluded, and it on a large scale or all sidedly between steel and aluminium, becomes the insulating barrier of electricity, thereby suppress the differential metals contact corrosion of different material conjugant.
In addition, the organic resin bonding agent thickness of coating does not have substantial influence to spot weldability.This be since the organic resin bonding agent thickness of weld part because of the composition of organic resin bonding agent or kind is different that some differences are also arranged, and the contact-making surface when being subjected to spot welding is in fact pressed the cause of domination.Therefore, as described later, the control contact-making surface is pressed very important.The organic resin bonding agent thickness of coating needs coating thinly for as long as pin hole is difficult to exist, more than anti-corrosion 0.1 μ m, and the pressure during by joint is extruded the degree of bonding agent.In addition, the final bonding agent thickness after spot welding engages is in order to suppress corrosion, if after the adhesive hardens or the target after the thermmohardening be the thickness of 0.1～10 μ m size.
Relative with it, between the mutual composition surface of engaged steel and aluminium, be preset with under the situation as the metal epithelium of the Zn of another layer that suppresses layer or Al, even there is the epithelium of organic resin adhesive, it is not difficult that spot welding self or interfacial reaction layer form control yet, thus the function of the epithelium aspect of performance organic resin bonding agent.
This be since be speculated as because of the existing of the metal epithelium of Zn or Al (Jie has) the resistance heating amount when the spot welding increase, the temperature of the interface temperature of steel and aluminium, especially steel will significantly increase and surpass the cause that dissolves temperature of aluminium.By the increase of this resistance heating amount, the epithelium of organic resin bonding agent is discharged or eliminating from the peripherad part of the welding portion of steel and aluminium easily, thereby steel and aluminium are conducted.
In addition, when the resistance heating amount when there is (Jie has) spot welding in the metal epithelium because of Zn or Al of being speculated as increased, aluminium was being accelerated significantly with the diffusion velocity at the interface of steel, and aluminium can be guaranteed good engagement state rapidly to the diffusion of steel side.In addition, under the situation that is galvanized steel plain sheet, infer that zinc coat dissolves owing to the difference of melting point in advance, consequently, also have the effect of the heat distribution homogenising that makes the interface.Be speculated as, utilize the composite effect of the metal epithelium of these Zn or Al, even the intervention of organic resin bonding agent is opposite with present general knowledge, the cause that spot weldability also improves.
(interfacial reaction layer)
The thickness that the present invention establishes different material conjugant interfacial reaction layer is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2The pass be 10 * t 2 0.5Mm 2More than.The present general knowledge that the area of the interfacial reaction layer of this optimum thickness regulation and interfacial reaction layer thin more (not having) are good more is different, is controlled at optimum scope, as the direction of guiding, not as also be the direction of positive existence.And, be based on following technological thought, that is, for the raising of bond strength, large tracts of land forms the interfacial reaction layer of optimum thickness range, in other words exists on a large scale.
Therefore, the thickness of this interfacial reaction layer is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2Relation do not satisfy 10 * t 2 0.5Mm 2More than, be lower than 50 * t more strictly speaking 2 0.5Mm 2, the interfacial reaction layer of optimum thickness range does not reach on a large scale, thereby bond strength descends.In the part of the thickness less than 0.5 μ m of interfacial reaction layer, the diffusion of steel-aluminium is insufficient, and bond strength reduces.Otherwise the thickness of interfacial reaction layer is thick more crisp more, and particularly, the thickness of interfacial reaction layer is crisp above the part of 5 μ m, and bond strength reduces.Thus, the area of such interfacial reaction layer is big more, and is low more as the bond strength of bond strength integral body.
Thereby in order to improve the bond strength as junction surface integral body, the thickness of interfacial reaction layer is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2Relation be necessary for 10 * t 2 0.5Mm 2More than, preferred 50 * t 2 0.5Mm 2More than.
In addition, usually be used under the situation of joint of dome type of electrode tip in use, central part is the thickest interfacial reaction layer, and decentre is far away more, and the thickness of interfacial reaction layer is more little.Therefore, even surpassing 5 μ m, the thickness of the interfacial reaction layer of this central part also has no relations.Image analysis or SEM area, the aluminium side, 2000 times that the thickness of this interfacial reaction layer can pass through the interface of steel-aluminium joint observe mensuration.
(spot welding)
Below, each important document of the spot welding method that is used to obtain the xenogenesis conjugant is described.Fig. 3 illustration is to be used to obtain the mode that the xenogenesis conjugant is the spot welding of prerequisite.The basic mode of spot welding method of the present invention is identical with the mode of common spot welding.Among Fig. 3,11 is that steel plate, 12 is that aluminium alloy plate, 15 is that nugget, 17 and 18 electrodes, 13 are the xenogenesis conjugant.
Spot welding method of the present invention is obtaining above-mentioned thickness of slab t by spot welding 1Steel and thickness of slab t 2The different material conjugant of aluminium the time, under the state of the epithelium of metal epithelium that is preset with Zn or Al between the mutual composition surface of these engaged steel and aluminium and organic resin bonding agent, carry out spot welding.
At this moment, as implied above, side applies organic resin adhesive on the composition surface of steel-aluminium, carry out spot welding, make the organic resin adhesive hardens of coating thereafter, from two viewpoints of the inhibition of the THICKNESS CONTROL of interfacial reaction layer and differential metals contact corrosion, more satisfactory.
(plus-pressure)
In such spot welding, the point diameter of establishing the electrode tip 18 of aluminium 12 sides is more than the φ 7mm, and applies the plus-pressure of electrode tip 17,18, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05.It is desirable to, the also big side of this plus-pressure further extrudes bonding agent, so preferably, but, in fact arrive 10kN from the capacity limit of spot welding.
The contact-making surface of some contact is pressed and (R * W) 1/3/ R roughly is directly proportional, and the contact-making surface at junction surface is pressed too small, and then bonding agent is remaining many, influences the growth of interfacial reaction layer, only therefore is necessary for bonding agent is pressed to the contact-making surface of outside extrusion.(R * W) 1/3/ R is that then bonding agent is remaining as layer below 0.05, and interfacial reaction layer is not grown up.
In addition, by applying bigger plus-pressure like this, the shape by electrode tip etc. not, just can make between foreign material, electrode and storeroom electrically contact stabilisation, and by the molten metal in the portion's of not dissolving support nugget of nugget periphery, thereby can access the above-mentioned bigger required area of nugget and the required area of above-mentioned optimum interfacial reaction layer.In addition, can suppress the generation of dust.When plus-pressure is too small, can not get such effect.
(electrode tip)
In order to form the interfacial reaction layer of above-mentioned optimum ranges of thicknesses on a large scale, establish the joint of the R type shape of point diameter is more than the φ 7mm, the front end radius of curvature R is big dome type etc. especially in the aluminium side.In addition, also the same with the steel side, the big side of radius of curvature R is desirable, but from the capacity limit of spot welding, R is to 250mm in the reality.
In addition, though to electrode shape regulation not, electrode improves the current efficiency at energising initial stage, thus preferably it.In addition, polarity is not stipulated yet, but under the situation of using dc spot welding, it is desirable to establish aluminium is that anode, steel are negative electrode.
(electric current)
Electric current during relevant spot welding in order to obtain the bigger nugget area and the required area of above-mentioned optimum interfacial reaction layer, has the thickness of slab t that makes it with above-mentioned aluminium 2The pass be 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec, and need be the current-mode of the operation that do not have the electric current higher than this operation.
By being set as such current-mode, when being pre-formed inhibition layer of the present invention, obtain a large amount of heats that advances, as mentioned above, and the interfacial reaction layer on the composition surface of control steel and aluminium, thus can access high bond strength.In addition, make between foreign material, electrode and storeroom electrically contact stabilisation, and support molten metal in the nugget, thereby can access required area of above-mentioned bigger nugget and the required area of above-mentioned optimum interfacial reaction layer by the portion of not dissolving of nugget periphery.In addition, can suppress the generation of dust.
In the above-mentioned operation of current-mode, at less than 15 * t 2 0.5KA or less than 100 * t 2 0.5Under the situation of msec, not dissolving of surface-treated layer and aluminium carried out on a large scale, and the area of the interfacial reaction layer of optimum ranges of thicknesses is little.On the other hand, surpass 30 * t 2 0.5KA or surpass 1000 * t 2 0.5Msec is then because the interfacial reaction layer growth is thick, so the area of the interfacial reaction layer of optimum ranges of thicknesses reduces.
The operation of this current range also can be a plurality of, and the total ascent time of these operations is 100 * t 2 0.5～1000 * t 2 0.5The scope of msec, this point is very important.In addition, when metal bond of the same race,, also can access close connected structure as long as it is identical to advance heat.When the joint of steel and aluminium, for example, according to surpassing 30 * t 2 0.5KA and less than 100 * t 2 0.5The current-mode of msec or less than 15 * t 2 0.5KA and surpass 1000 * t 2 0.5Msec current-mode, can not obtain the area of the interfacial reaction layer of optimum ranges of thicknesses on a large scale.In the front and back operation under this current condition, also can apply other current-mode, and as the current-mode in a plurality of stages, but since interfacial reaction layer become to look thick, so need there not be the operation of the electric current higher than this operation.
And, as desirable current-mode, preferably make 1 * t 2 0.5～10 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec suppresses the nugget cracking.
[embodiment]
To be the high-tensile strength steel plate of the 590MPa level of selling on the market and be that A6061 (6000 are) aluminium alloy plate sold on the market is overlapping as steel as aluminium, carried out spot welding afterwards, be made into different material conjugant, and bond strength, corrosion resistance are estimated.
[table 3] (thickness of slab t of aluminium 1: 1mm)
Figure A20078000623400381
[table 4] (thickness of slab t of aluminium 2: 2mm)
Figure A20078000623400382
(the welding point material after the change spot welding condition)
To the above-mentioned steel plate of pure Zn plating and above-mentioned aluminium sheet have been implemented to dissolve with average thickness 10 μ m as the welding point material that after the coating epoxy is thermmohardening type bonding agent between the composition surface, overlaps in engage side, carry out spot welding, table 3,4 expressions are made into the result of different material combination.
The thickness of slab of table 3 expression aluminium sheet is the situation of 1mm, and the thickness of slab of table 4 expression aluminium sheet is the situation of 2mm.In table 3,4, the plating condition and the thermmohardening type bonding agent condition of establishing the composition surface side of steel plate are certain, and the electrode condition and the current condition of spot welding are carried out many variations, are made into different material conjugant.In addition, in table 3,4 example, each example is all common, and all utilizing hairbrush to apply epoxy equably thinly is thermmohardening type bonding agent, reaches 0.5～1 μ m size (not extruding the degree of bonding agent by the fashionable pressure of means of spot welds) to make it thickness.
[table 5]
Figure A20078000623400391
(having changed the weld bond material of plating condition and thermmohardening type bonding agent condition)
In addition, table 5 also represents to make the electrode conditioned disjunction current condition of spot welding certain, plating conditioned disjunction thermmohardening type bonding agent condition to the composition surface side of steel plate or aluminium alloy plate is carried out various variations, is made into the result of different material conjugant by the welding point material of steel plate and aluminium sheet.In table 5, each example that is coated with the situation of bonding agent utilizes hairbrush to be coated with the bonding agent that epoxy is or polyurethane is equably thinly equally between the composition surface, so that thickness reaches 0.5～1 μ m size.
(use raw material)
As raw material, prepared: steel plate, its thickness of slab 1mm and contain composition, the A6061 aluminium alloy plate of 0.07% quality C-1.8% mass M n, its thickness of slab is 1mm and 2mm, these steel plates, aluminium alloy plate all are processed into the cross tensile test plate shape of JIS A 3137 records, and have carried out spot welding.
(bonding agent)
It is thermmohardening type structure bonding agent (the skill development ペ of Sunstar company Application ギ Application #1086) that epoxy system has used the epoxy of selling on the market.It is thermmohardening type structure bonding agent (the skill development ペ of Sunstar company Application ギ Application fluid sealant 980) that polyurethane system has used the polyurethane of selling on the market.
(plating)
When steel are implemented plating, all be after having carried out being undertaken 5 minutes the pre-treatment of pickling activate by 10% sulfuric acid, carry out various platings.When plating Zn, in zinc sulfate 400g/l, aluminum sulfate 30g/l, sodium chloride 15g/l, boric acid 30g/l, add sulfuric acid, flow through 20A/dm in the bath after pH is 3 2Electric current, implemented the pure Zn plating of 10 μ m thus.It is being made as under the situation of Zn-10%Ni alloy plating, in pure Zn plating is bathed, is being added with in the bath of nickelous sulfate, nickel chloride and flows through 10A/dm 2Electric current, implemented the Zn-10%Ni plating of 10 μ m thus.
Dissolve plating and only steel are carried out, utilize various molten metals to implement the Al plating of 10 μ m, Al-9% quality Si plating, zinc plating, Zn-Fe plating (the Fe amount is respectively 5,10,12,16% quality) respectively.In dissolving plating Zn,, thickness is adjusted to 1,3,10,15,19,20 μ m by changing temperature, promoting temperature.
In addition, the Ni of (comparative example 3 of table 5) plating utilizes watt to bathe as a comparative example, flows through 10A/dm 2Electric current, implemented 10 μ m thus.
Aluminium is being implemented under the situation of plating, utilize 10% nitric acid acidwashing 30 seconds, after in the treatment fluid of sodium hydride 500g/l, zinc oxide 100g/l, the chlorination second iron 1g/l, roscherite 10g/l, carrying out 30 seconds zinc replacement Treatment, carried out Zn or Zn-and electroplated.In addition, in this zinc-plated bath, added in the bath of nickelous sulfate, nickel chloride and flow through 10A/dm 2Electric current, implement the Zn-10%Ni plating of 10 μ m thus.
(mensuration thickness)
About the thickness of plating epithelium, by cutting off the sample behind the plating, imbed resin and grind, the joint interface of the state before the spot welding is carried out SEM observe.Measure three dot thickness by 2000 times visual field, average then and obtain.
(spot welding)
D.C. resistance soldering test machine is used in spot welding, and uses the electrode of the dome type of Cu-Cr alloy composition, and anode is made as aluminium, negative electrode is made as steel and engages.In the table 3,4, according to the electrode tip condition shown in the table 3,4 [leading section, front end radius of curvature R, plus-pressure W and (R * W) 1/3/ R], current-mode [ welding sequence 1 and 2 welding current, weld interval] welds, and is made into the cross tensile test body of different material conjugant.
At this moment, the point diameter that table 3, each example of 4 are established the electrode tip of aluminium side is more than the φ 7mm, and applies the plus-pressure of electrode tip, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05, and make 15 * t according to having 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The current-mode of the operation of msec carries out spot welding.
In addition, each example is all identical in the table 5, and the spot welding condition that makes the example shown in the N of table 3 is made into cross tensile test body for necessarily welding.
Under these each conditions, be made into 5 test bodies do the bond strength evaluation with, 3 test bodies do the joint interface evaluation with, 3 test bodies and make corrosion test usefulness.In this test, use identical shaped electrode tip in steel, aluminium side.Wherein, the sample that interface rating is used carries out 30 minutes heat treatment at a postwelding under 180 ℃, thereby bonding agent is hardened fully.
(interfacial reaction layer Determination of thickness)
About the thickness measurement of interfacial reaction layer, with the sample of a postwelding central cutout, imbed resin and grind from weld part, carried out the SEM observation.Under the thickness of layer is situation more than the 1 μ m, utilize 2000 times visual field to carry out instrumentation, utilize 10000 times visual field to carry out instrumentation under the situation of less than 1 μ m.In addition, at this, so-called interfacial reaction layer is meant the compound layer that contains Fe and Al simultaneously, by FDX, detects Fe and Al and is the above layer of 1wt%.That is, detecting Fe and Al is plating layer or residual bonding agent less than the layer more than the 1wt%, does not form interfacial reaction layer.
In addition, in this test, the interfacial reaction layer of central part is the thickest, end (circumference) interfacial reaction layer is thin more, therefore, obtain the diameter of interfacial reaction layer of diameter, the above thickness of 0.5 μ m of the interfacial reaction layer that surpasses 10 μ m thickness, be converted into area.Be determined on 3 conjugants and carry out, measure the nugget size of 2 directions of quadrature, and with its equalization.
(bond strength evaluation)
For the intensity that the measuring point welding is closed, under the state before adhesive hardens, 5 test sample of each condition have been implemented the cross tensile test, and to its averaging, as the evaluation to bond strength.If bond strength is more than the 1.5kN or disrumpent feelings mode is that aluminum mother plate is disrumpent feelings, then be designated as ◎, if bond strength is 1.0～1.5kN, then be designated as zero, if bond strength is 0.5～1.0kN, then be designated as △, if the not enough 0.5kN of bond strength, then be designated as *.At this, if bond strength not more than 1.0～1.5kN (zero), then can not use as the structural material of automobile etc.
(evaluation of differential metals contact corrosion system)
In addition, the conjugant after engaging is under various conditions carried out alkali degreasing, 0.1% aqueous solution of the サ one Off Off ア イ Application 5N-10 of Nippon Paint Co., Ltd.'s system is used in the washing back, the surface has been carried out regulating in 30 seconds handled.Thereafter, in zinc ion 1.0g/l, nickel ion 1.0g/l, manganese ion 0.8g/l, phosphate ion 15.0g/l, nitrate ion 15.0g/l, nitrite ion 0.12g/l, toner value 2.5pt, full acidity 22pt, free acidity 0.3～0.5pt, 50 ℃ bath, carried out 2 minutes trbasic zinc phosphates and handled., by cation electrodeposition coating (Nippon Paint Co., Ltd. system パ ワ one ト Star プ) apply,, formed the epithelium of 30 μ m 170 ℃ of following sintering 25 minutes thereafter.
, carry out composite corrosion test, preventing property of different metal contact corrosion is estimated thereafter.In corrosion test, establish A: chlorine water spraying (35 degree, 5%NaCl) 2hr; B: dry (60 ℃, 20-30%RH) 4hr; C: humidity (50 ℃, more than the 95%RH) 2hr is a circulation, and 90 circulations have been carried out in this test.After this test, peel off and observe the junction surface, corrosion resistance (maximum corrosion depth of Al) is estimated.
The maximum corrosion depth that corrosion resistance is measured the aluminium of three different material conjugants also averages, if not enough 0.01mm then is designated as ◎, if be 0.01～0.02mm then be designated as zero, and if be 0.02～0.1mm then be designated as △, if more than the 0.1mm then be designated as *.If maximum corrosion less than 0.01～0.02mm (zero) then can not use as the structural material of automobile etc.
(table 3,4 result)
From table 3,4 as can be known, the different material conjugant that carries out the example I～P of spot welding in preferred range can access very high corrosion resistance.This is the zinc-plated and effect of being located between composition surface thermmohardening type bonding agent of dissolving.But it is also identical with example to engage the Comparative examples A～H that carries out spot welding outside the condition and range in preferred spot welding, is provided with zinc-plated between the composition surface and thermmohardening type bonding agent, and corrosion resistance is high equally.
On the other hand, relevant bond strength removes the preferred spot welding joint condition and range, in the Comparative examples A～C of the little grade that plus-pressure is low aspect the relation front end radius of curvature of point diameter of electrode tip, can not obtain high bond strength.In addition, the bond strength of the Comparative Example D～H of the also discontented unabridged version invention scope of current condition is also low.
Comparative examples A～G except that the Comparative Example H of carrying out welding sequence 2, only by welding sequence 1, do not carry out welding sequence 2 and carry out spot welding.Wherein, the point diameter of its electrode tip of Comparative examples A is too small.Its plus-pressure relevant with the front end radius of curvature of comparative example B, comparative example C is low excessively.
In addition, the welding current of its welding sequence 1 of Comparative Example D is relevant with the thickness of slab of aluminium and low excessively.The weld interval of its welding sequence 1 of Comparative Example E is relevant and too short with the thickness of slab of aluminium.The welding current of its welding sequence 1 of Comparative Example F is relevant with the thickness of slab of aluminium too high.The weld interval of its welding sequence 1 of comparative example G is relevant and long with the thickness of slab of aluminium.There is the welding sequence 2 flow through the electric current significantly higher than welding sequence 1 in Comparative Example H.
That is, example I～P is when this spot welding, and the point diameter of the electrode tip by establishing the aluminium side is more than the φ 7mm, and applies the plus-pressure of electrode tip, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05, and make 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The preferred welding sequence of msec carries out spot welding.In addition, example I, K only by this welding sequence 1, do not carry out welding sequence 2 ground and carry out spot welding and engage.Therefore, each example can be controlled the interfacial reaction layer of optimum thickness, thus the bond strength height.
In these examples, example N, the O, the P that have above-mentioned welding sequence 1 and carry out spot welding by the non-existent current-mode of welding sequence that flows through the electric current higher than this welding sequence 1 also make 1 * t for the welding sequence 2 of back 2 0.5～10 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0. 5The optimum condition of msec, bond strength is the highest.To this, example L, M that the current-mode that exists by the welding sequence 2 that flows through the electric current higher than this welding sequence 1 carries out spot welding, its bond strength is lower than the routine N of foregoing invention, O, P.
(result of table 5)
As shown in Table 5, do not have the comparative example 1,10,14 of resin adhesive, its corrosion resistance is poor.In addition, the comparative example 2 of no coating, exceed a comparative example 3,4,5 of plating condition (melting point) scope, its cross tensile test is poor as a result, bond strength is low.In addition, under this condition, do not have plating, have in the comparative example 2 of bonding agent, cross tensile test result also is poor result on the contrary.Though the blocked up comparative example 21 of plating thickness is pure zinc coat, cross tensile test result also is poor result on the contrary.
Relative with it, having resin adhesive, spot welding condition (melting point), can to control interfacial reaction layer for the example 6～9,11～13,15,18,19,20,22 in the scope be optimum thickness, thereby corrosion resistance is good and bond strength is high.Wherein, it is the highest to implement pure zinc-plated example 6～7,11,18,19,20,22 its bond strengths.From this result as can be known, be optimum thickness by coating being controlled to composition of the present invention, melting point, thickness, can controlling interfacial reaction layer thus, thereby can access high bond strength and corrosion resistance.In addition, especially under the situation of the welding point that forms thickness 5～15 μ m by pure Zn spot welding, can obtain very high bond strength and corrosion resistance simultaneously.
By the result of above embodiment as can be known, by improving different material conjugant intensity and can suppressing the critical meaning of each important document of the present invention's regulation of contact corrosion.
[3]
(xenogenesis conjugant)
Fig. 2 represents the xenogenesis conjugant of one embodiment of the present invention regulation by sectional view.In Fig. 2,13 different material conjugants for steel (steel plate) 11 and aluminium (aluminium alloy plate) being engaged by spot welding.15 is the nugget with interfacial reaction layer 16 of spot welding, has the nugget size shown in the arrow among the figure in the horizontal direction.19 is the joint portion, dizzy district around the nugget.t 1Thickness of slab, the t of expression steel 2The thickness of slab of expression aluminium 12, Δ t represent to carry out the minimum remaining thickness of slab of the aluminium behind the joint of spot welding.
At this, 14 for suppressing layer (corrosion-inhibiting layer), and between the mutual composition surface that defaults in these engaged steel 11 and aluminium 12, Zn (meaning of pure Zn) or the metal epithelium of Zn alloy and the laminate of phosphate coating.Fig. 2 does not distinguish Zn or Zn alloy coating and phosphate coating respectively and one is represented, the engage side surface of steel 11 is located at Zn or Zn alloy coating by plating etc. in expression, and implement zinc phosphate coat thereon, thereby form the mode that suppresses layer 14 (corrosion-inhibiting layers).
And, that remove at the junction surface that Fig. 2 is illustrated in the xenogenesis conjugant of a postwelding is default before spot welding, be the inhibition layer (corrosion-inhibiting layer) 14 of the laminate of Zn or Zn alloy coating and zinc phosphate coat, makes the good juncture of the xenogenesis conjugant that steel 11 and aluminium 12 directly engage.And preformed these of interface zone that Fig. 2 also is illustrated in outside the junction surface of xenogenesis conjugant suppress the mode that layer (corrosion-inhibiting layer) 14 exist always.
(thickness of steel)
The present invention must be the thickness of slab t of steel 1It is the conjugant of 0.3～3.0mm.Under the situation of the not enough 0.3mm of the thickness of slab of steel, as said structure member or structural material, can not guarantee necessary strength or rigidity, this is inappropriate.In addition, in addition, because the pressurization that spot welding is carried out strengthens deformation of steel, oxide scale film is destroyed easily, therefore promotes the reaction of steel and aluminium.Consequently, form intermetallic compound easily.
On the other hand, surpass under the situation of 3.0mm at thickness of slab, as said structure member or structural material, adopt other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with steel 1Thickening surpasses 3.0mm.
(steel)
The present invention does not have especially the shape or the material of the steel that use are limited, and can use suitable shape, the material that is common to structural elements or the steel plate of selecting according to the structural elements purposes, steel profile, steel pipe etc.But for the high-strength structure member (different material conjugant) of the light weight that obtains automobile component etc., the tensile strength of preferred steel is the above common high tension steel (high strength steel) of 400MPa.
The low-intensity steel of the not enough 400MPa of tensile strength mostly is low-alloy steel usually, and oxide scale film is made up of ferriferous oxide, so Fe and Al diffusion are easily, form crisp intermetallic compound easily.Therefore, also preferred tensile strength is more than the 400MPa, and ideal is the above steel pulling force steel (high strength steel) of 500MPa.
(aluminium)
Be used for aluminium of the present invention the kind and the shape of its alloy do not limited especially, can be according to the characteristic that requires as each structural elements, suitable general sheet material, section bar, forging material, the casting material etc. selected.But the intensity of the aluminium also situation with above-mentioned steel is the same, the distortion that the pressurization when suppressing spot welding causes, and a high side is desirable.On this point, preferably use intensity in the aluminium alloy also high and as this kind structure with the general A5000 system of member, A6000 system etc.
But, the thickness of slab t of these aluminiums that use among the present invention 2It is the scope of 0.5～4.0mm.Thickness of slab t at aluminium 2Under the situation of not enough 0.5mm, as the undercapacity of structural material, this is inappropriate, and, owing to can not get nugget size, and dissolve easy arrival aluminum surface and form dust easily, so can not obtain high bond strength.On the other hand, at the thickness of slab t of aluminium 2Surpass under the situation of 4.0mm, the same with the situation of the thickness of slab of above-mentioned steel, as structural elements or structural material, adopts other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with aluminium 2Thickening surpasses 4.0mm.
(suppressing layer)
The present invention is corroded in order to suppress the dissimilar metal turnover, and is prevented the decline of bond strength in order to obtain higher bond strength, and (material) forms inhibition layer (corrosion-inhibiting layer) between steel and aluminium in advance.In addition, this inhibition layer must not damage the formation area of the interfacial reaction layer between steel and the aluminium and the control of distribution.
In the present invention, as the inhibition layer (corrosion-inhibiting layer) with such function, the metal epithelium and the zinc phosphate coat of default Zn or Zn alloy are two-layer between the mutual composition surface of these engaged steel and aluminium.Therefore, as described later, on the composition surface of the either side of steel side or aluminium side, lamination is provided with metal epithelium and phosphoric acid epithelium.(carrying out lamination) order is set also can be any, still, is provided with metal epithelium one side earlier zinc phosphate coat is set easily.
(the metal epithelium of Zn or Al)
Below, as suppressing one of layer (corrosion-inhibiting layer), at first the metal epithelium to Zn (pure Zn) or Zn alloy describes.Because being preset with between face being bonded with each other of engaged steel and aluminium under the state of metal epithelium of Zn or Zn alloy, the present invention carries out spot welding, so at the metal epithelium of default Zn in the surface of the composition surface at least of steel or aluminium side or Zn alloy.This Zn or Zn alloy coating have following characteristic: its melting point and aluminium are approaching, when spot welding, even there is phosphate coating, the intermetallic compound that does not also influence steel and aluminium is the control of interfacial reaction layer formation time, reaches the thickness range of interfacial reaction layer and distribute and control.
In the present spot welding of using steel naked or that do not have Zn or Zn alloy coating and aluminium, when when there is phosphatic epithelium in joint interface, spot welding self or interfacial reaction layer form the control difficulty, can not obtain high bond strength.
Relative with it, be preset with between face under the situation of Zn or Zn alloy coating being bonded with each other of engaged steel and aluminium as suppressing layer, even also have a phosphate coating between between the composition surface as suppressing layer, it is not difficult that spot welding self or interfacial reaction layer form control yet, and can bring into play the above-mentioned functions of phosphate coating.This is exist (Jie has of inferring because of Zn or Zn alloy coating), and the resistance heating amount during spot welding increases, and the temperature of the interface temperature of steel and aluminium, especially steel is high significantly to the cause that dissolves temperature that surpasses aluminium.Because of the increase of this resistance heating amount, phosphate coating is destroyed, easily on the aluminium that has dissolved liquate takes place, thereby can conduct steel and aluminium.
In other words, under the situation of the phosphate layer of another existence and this Zn or the coexistence of Zn alloy coating, when spot welding, only the spot-welding part part is destroyed, thereby can conduct steel and aluminium by this spot-welding part.No matter be present in which side,, and separately phosphate coating between steel and aluminium the time, as mentioned above, all influenced the formation area and the thickness distribution control of the interfacial reaction layer of conjugant when Zn that does not have particular range of the present invention or Zn alloy coating.
In addition, as implied above, when the existing of Zn or Zn alloy coating (be situated between and exist), the resistance heating amount when causing spot welding increased, aluminium was being accelerated significantly with the diffusion velocity at the interface of steel, and aluminium spreads to the steel side, can guarantee good engagement state rapidly.In addition, infer that because of the difference of melting point, zinc coat dissolves in advance, consequently, also has the effect of the heat distribution homogenising that makes the interface under the situation that is galvanized steel plain sheet.Infer composite effect, phosphate coating is arranged, also do not influence spot weldability even be situated between by these Zn or Zn alloy coating.
In order to bring into play these effect, the melting point of establishing Zn or Zn alloy coating is 350～1000 ℃, preferred 400～950 ℃ narrow temperature scope.In addition, more preferably establish the above narrower temperature range below 900 ℃ of melting point of aluminium.The melting point of fine aluminium is about 660 ℃, and the melting point of pure Zn is about 420 ℃.As mentioned above, so-called melting point is approaching with the aluminium that engages, and for example is meant with respect to 660 ℃ of the melting points of pure Al, allows to have above-mentioned a certain size the meaning of amplitude.
In addition, the thickness of establishing Zn or Zn alloy coating is the thickness (average film thickness) of 3～19 μ m, more preferably the thickness scope of 5～15 μ m.The thickness of relevant these Zn or Zn alloy coating, the steel after these epitheliums are formed or the test portion of aluminium cut off, and imbed resin and grind, and the SEM that carries out the thickness of slab direction of metal epithelium observes.This SEM observes and utilizes 2000 times visual field to measure three dot thickness, and the thickness of metal epithelium is by on average obtaining the observed result at five different positions of position.
The thickness of Zn or Zn alloy coating cross thin or situation that its melting point is low excessively under, Zn or the Zn alloy coating joint initial stage when spot welding, dissolve discharge from the junction surface, can not suppress the formation of interfacial reaction layer.In addition, reduce the increase of resistance heating amount, be difficult to destroy phosphate coating, be difficult to conduct steel and aluminium by spot-welding part.
On the other hand, in order to improve the bond strength of different material conjugant, need engaged steel and aluminium to be in direct contact with one another on mutual composition surface, when spot welding, Zn or the Zn alloy coating between the junction surface must dissolve discharge from the junction surface in advance.To this, under the situation that thickness is blocked up or melting point is too high of Zn or Zn alloy coating,, need the big heat that advances for Zn or Zn alloy coating are dissolved discharge from the junction surface.When this advances heat when excessive, the amount of dissolving of aluminium increases, because the reduction that causes aluminium of dust strengthens, pretends to structural elements and can not use different material conjugant.
Zn or Zn alloy coating can suit to select pure Zn, Zn alloy of above-mentioned melting point scope etc.The metal epithelium is in the surface coverage of the composition surface at least of steel or aluminium side or the also suitable general known method of using plating, coating etc. of method of formation.In addition, to the covering or the formation of these steel or aluminium material surface, be at least the surface of composition surface side, much less, for corrosion protection, steel or aluminium material surface side not being the composition surface also can cover or form Zn or Zn alloy coating.
But when considering practicality and efficient, preferred Zn or Zn alloy coating cover or form as coating at Zn or the general steel side of Zn alloy plating.Usually, steel are implemented the coating back use, even in coating, damage, also preferentially corrode Zn or Zn alloy, so can protect steel.And, by reducing the potential difference of steel and aluminium, also can suppress the differential metals contact corrosion of one of problem for the xenogenesis conjugant.Have at plating under the situation of Zn or Zn alloy, guarantee the corrosivity of steel, in addition, to steel might as well, to aluminium might as well, all be easy to carry out plating.
With the plating is prerequisite, bring into play above-mentioned interfacial reaction layer and form inhibit feature, even phosphate coating is arranged in order to bring into play to be situated between, and the also function that can weld, the preferred pure Zn of the plating epithelium of Zn or Zn alloy.In addition, preferably,, in alloys such as Al-Zn, Zn-Fe, be main component also to be respectively the Zn that contains the Zn more than 80% quality even be the Zn alloy.Carry out under the situation of alloying at plating epithelium,, make it not exceed above-mentioned molten point range thus, and do not reduce corrosion resistance by adding alloying element and content thereof to Zn or Zn alloy.
Special recommendation also contains pure Zn or the Zn alloy plating epithelium of the Zn more than 88% quality in these plating epitheliums.When steel surface is implemented to contain the Zn alloy plating epithelium of the Zn more than 88% quality, can improve the corrosion resistance of steel especially.In addition, this Zn plating epithelium is controlled at melting point above-mentioned 350～1000 ℃ scope easily.And corrosion resistance is also high, and also can suppress differential metals contact corrosion.From the viewpoint that this kind differential metals contact corrosion prevents, be preferably pure Zn plating epithelium.
About method for plating, in the present invention without limits, can use existing wet type, dry type plating.Particularly aspect zinc-plated, recommend to electroplate or dissolve plating, after dissolving plating, carry out the method for Alloying Treatment etc.
(phosphate coating)
Then, to as another the inhibition layer, phosphate coating describes following.As mentioned above, at phosphate coating by through hole, or with the situation of the Zn of particular range of the present invention or the coexistence of Zn alloy coating under, resistance destroys epithelium, steel and aluminium are conducted, when spot welding, can control the formation area and the thickness distribution of the interfacial reaction layer of conjugant.But, for making steel and aluminium, the junction surface in spot welding conducts, there is no need the phosphoric acid film is all removed from the junction surface.In other words, if conduct steel and aluminium, also can be at the junction surface of spot welding residual have a phosphate coating.
In addition, as mentioned above, phosphate coating has the part of only removing the ruined spot-welding part of epithelium at a postwelding, and being situated between on a large scale or comprehensively between steel and aluminium has, and blocks the function of corrosive environment, the contact corrosion of inhibition different metal.
This phosphate coating not only has above-mentioned action effect, and, also have the selection meaning from the viewpoint of practicality.For example, so long as film is not limited to phosphate coating,,, or, as if steel and aluminium are conducted by resistance destruction epithelium also by the hole even be phosphate epithelium in addition.But,,, make use (manufacturing) on the line at representative existing body of a motor car as panel for the different material conjugant that carries out spot welding of object of the present invention.In addition, the phosphate treated that steel or aluminium are implemented also as the based process of the vehicle body coating of this automobile, has at the vehicle body of above-mentioned automobile and makes the effect of using on the line.About this point has following advantage: even phosphate coating or comprehensively between steel and aluminium, does not influence desired other all characteristics such as the different material conjugant of processability or screening characteristics etc. on a large scale yet, other epithelium does not have.And phosphate treated also has following advantage: comprise spot welding yet, can implement in the vehicle body of above-mentioned automobile is made the condition of the existing equipment of line etc. or device, other epithelium does not have.And phosphate coating (processing) is as the based process of above-mentioned coating, can improve the screening characteristics of the cohesive of filming etc. of different material conjugant.
(forming a side of phosphate coating)
The present invention implements spot welding and engages after (surface, personnel composition surface) between the mutual composition surface of steel and aluminium forms phosphate coating.In order to improve the bond strength of different material conjugant, preferably form phosphate coating, and form phosphate coating on the surface of above-mentioned Zn that is located at the steel side surface or Zn alloy coating at the steel side surface.
But aluminium is compared with steel, has the low problem of phosphate treated, even different material conjugant is being carried out in the aluminium side this problem taking place also under the parkerized situation.But, as shown in the present,,, form phosphate coating as long as implement phosphate treated in advance in the side of aluminium at least of different material conjugant, then the aluminium side is also the same with the steel side, also has the advantage that can improve phosphate treated as the based process that applies.At this moment, as long as not only in the aluminium side of different material conjugant, and implement phosphate treated in advance in the steel side, form phosphate coating, then body of a motor car is made the based process of the conduct coating on the line, also has and can omit parkerized advantage.
(thickness of phosphate coating)
The average thickness of acid rain epithelium in forming preferably is made as the scope of 0.1～5 μ m.In this scope, can bring into play the effect of above-mentioned phosphate coating well.When the thickness less than 0.1 μ m of phosphate coating crosses when thin, the epithelium defective that mostly occurs big greatly, thus can not fully block corrosive environment, can not suppress differential metals contact corrosion etc., can not bring into play the effect of above-mentioned phosphate coating.On the other hand, the thickness thickening of phosphate coating need not be surpassed 5 μ m.And when thickening the thickness of above-mentioned phosphate coating, the resistance during spot welding is excessive, and dust takes place too far, and especially the thickness of slab at aluminium junction surface reduces increasing, and instead bond strength descends.In addition, be difficult to destroy phosphate coating, be difficult to conduct steel and aluminium by spot-welding part.
The average thickness of phosphate coating is after carrying out phosphate treated formation epithelium, to will from the test portion cross section that the steel after the air dry and aluminium are chosen imbed resin and grind after test portion, utilize the visual field of 2000 times or 10000 times in the thickness of slab direction in this phosphate coating cross section, observe by SEM (sweep type resistance microscope), measure three dot thickness thus, by the observed result at five different positions of position is on average obtained.
(phosphatic kind)
About phosphatic kind, as coating (film) based process of automobile, form the easy degree of (processings) etc. according to epithelium with galvanized steel plain sheet etc., preferably the most general trbasic zinc phosphate etc., be the zinc phosphate coat of main component with zinc.For the crystallinity of controlling this zinc phosphate coat or regiospecific etc., recommend to dezincify (Zn) in addition, also can contain Fe, Ni, Mn, Ca etc., and add Ni according to its purpose.In addition, the epithelium structure of trbasic zinc phosphate both can be zinc orthophosphate (ホ パ イ ト), also can be phosphophyllite, can also be these mixed structure.As phosphate coating, except that this trbasic zinc phosphate, also can be with these known parkerized calcium phosphate, ferric phosphate, manganese phosphate etc., separately or mixing, compound use.
(the formation method of phosphate coating)
As the formation method of phosphate coating, can adopt known method as above-mentioned coating based process.That is, in the phosphate aqueous solution of the metal of the salt that adds promising zinc, calcium, iron, manganese etc. or Mg etc., steel or aluminium are carried out impregnation process.Regulating the concentration of phosphate aqueous solution or the immersion condition of temperature, dip time etc. is the average thickness that reaches above-mentioned phosphate coating.
(the sacrifice corrosion protection effect of phosphate coating)
As mentioned above, phosphate coating has the blocking-up corrosive environment, suppresses the function of differential metals contact corrosion, but owing to has hole, the corrosive environment of blocks moisture or oxygen etc. fully.To this, between the mutual composition surface of engaged steel and aluminium, under the situation that suppresses default again one deck Zn of layer or Zn alloy coating, alleviate preferential corrosion to aluminium alloy by above-mentioned hole.Therefore, the effect of the potential difference by reducing Zn or Zn alloy coating can suppress differential metals contact corrosion.
Phosphate coating suppresses effect to differential metals contact corrosion, by strengthen containing sacrifice corrosion protection effect Mg etc., phosphate coating self in phosphate coating, is further enhanced.In order to strengthen the sacrifice corrosion protection effect of this phosphate coating, preferably in phosphate coating, contain the Mg of 0.01～10% quality.Mg in epithelium contains under the very few situation of quantity not sufficient 0.01% quality, can not bring into play the effect of Mg.On the other hand, be difficult to make the Mg content in the epithelium to contain above 10% quality.Therefore, establish that optionally to contain the Mg content that there is something special in phosphate be 0.01～10% quality.
Mg content in the phosphate coating is identical with the thickness measurement of above-mentioned phosphate coating, after carrying out phosphate treated formation epithelium, to will from the test portion cross section that the steel after the air dry and aluminium are chosen imbed resin and grind after test portion, obtain Mg intensity in the phosphate coating by fluorescent x-ray, be converted into the % quality.And, by the measurement result at different five positions, position is on average obtained.
(interfacial reaction layer)
The thickness that the present invention establishes interface body interface conversion zone is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2The pass be 10 * t 2 0.5Mm 2More than.The area regulation of the interfacial reaction layer of this optimum thickness is different with good more this present general knowledge of interfacial reaction layer thin more (not having), is controlled at optimum scope, as the direction of pointing to, much less also is the direction that lamination exists.And, in order to improve bond strength, form the interfacial reaction layer of optimum thickness range based on large tracts of land, in other words, this technological thought of Cun Zaiing on a large scale.
Therefore, the thickness at this interfacial reaction layer is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2Concern less than 10 * t 2 0.5Mm 2, less than 50 * t more strictly speaking 2 0.5Mm 2Situation under, the interfacial reaction layer of optimum thickness range does not form scope, so bond strength descends.The diffusion of part steel-aluminium of the thickness less than 0.5 μ m of interfacial reaction layer is insufficient, and bond strength reduces.Otherwise the thickness of interfacial reaction layer is thick more fragile more, and especially, the thickness of interfacial reaction layer surpasses the part fragility of 5 μ m, and bond strength reduces.Therefore, the area of such interfacial reaction layer is big more, and is low more as the bond strength of conjugant integral body.
Thereby in order to improve the bond strength as junction surface integral body, the thickness of interfacial reaction layer is the area of 0.5～5 μ m part and the thickness of slab t of aluminium 2Relation be necessary for 10 * t 2 0.5Mm 2More than, preferred 50 * t 2 0.5Mm 2More than.
In addition, be generally used in use under the situation of joint of dome type of electrode tip, central part is the thickest interfacial reaction layer, and decentre is far away more, and the thickness of interfacial reaction layer is more little.Therefore, even surpassing 5 μ m, the thickness of the interfacial reaction layer of this central part also has no relations.Area, the aluminium side, 2000 times the image analysis at the interface that the thickness of this interfacial reaction layer can engage by steel-aluminium or SEM observe and measure.
(spot welding)
Below, each important document of the spot welding method that is used to obtain the xenogenesis conjugant is described.Fig. 3 illustration is used to obtain a mode of the solder joint that becomes prerequisite of xenogenesis conjugant.The basic mode of spot welding method of the present invention is identical with the mode of common spot welding.Among Fig. 3,11 is that steel plate, 12 is that aluminium alloy plate, 13 is that xenogenesis conjugant, 15 is that nugget, 17 and 18 is electrode.
Spot welding method of the present invention is obtaining above-mentioned thickness of slab t by spot welding 1Steel and thickness of slab t 2The different material conjugant of aluminium the time, under the state that is preset with Zn or Zn alloy coating and phosphate coating between the mutual composition surface of these engaged steel and aluminium, carry out spot welding.
(plus-pressure)
In such spot welding, the point diameter of establishing the electrode tip 18 of aluminium 12 sides is more than the φ 7mm, and applies the plus-pressure of electrode tip 17,18, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05.The side that this plus-pressure is also big more can extrude bonding agent, thus preferred it, but, in fact arrive 10kN from the energy limit of spot welding.
The contact-making surface of some contact is pressed and (R * W) 1/3/ R approximately is directly proportional, and the contact-making surface at junction surface is pressed too small, and then bonding agent is remaining many, influences the growth of interfacial reaction layer, therefore must be only bonding agent to be pressed to the contact-making surface that the outside extrudes.(R * W) 1/3/ R is that then bonding agent is remaining as layer below 0.05, and interfacial reaction layer is not grown up.
In addition, by applying bigger plus-pressure like this, the shape by electrode tip etc. not, just can make between foreign material, electrode and storeroom electrically contact stabilisation, and by the molten metal in the portion's of not dissolving support nugget of nugget periphery, thereby can access the above-mentioned bigger required area of nugget and the required area of above-mentioned optimum interfacial reaction layer.In addition, can suppress the generation of dust.When plus-pressure is too small, can not get such effect.
(electrode tip)
In order to form the interfacial reaction layer of above-mentioned optimum ranges of thicknesses on a large scale, establishing point diameter in the aluminium side especially is more than the φ 7mm, and the joint of the R type shape of the big dome type of front end radius of curvature R etc.In addition, also the same with the steel side, the big side of radius of curvature R is desirable, but from the capacity limit of spot welding, R is to 250mm in the reality.
In addition, though to electrode shape regulation not, electrode improves the current efficiency at energising initial stage, thus preferably it.In addition, polarity is not stipulated yet, but be it is desirable under the situation of using dc spot welding that establishing aluminium is that anode, steel are negative electrode.
(electric current)
Electric current during relevant spot welding in order to obtain the bigger nugget area and the required area of above-mentioned optimum interfacial reaction layer, has the thickness of slab t that makes it with above-mentioned aluminium 2The pass be 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec, and be necessary for the non-existent current-mode of operation of the electric current higher than this operation.
By being set as such current-mode, when being pre-formed inhibition layer of the present invention, obtain a large amount of heats that advances, as mentioned above, and the interfacial reaction layer on the composition surface of control steel and aluminium, thus can access high bond strength.In addition, make between foreign material, electrode and storeroom electrically contact stabilisation, and support molten metal in the nugget, thereby can access required area of above-mentioned bigger nugget and the required area of above-mentioned optimum interfacial reaction layer by the portion of not dissolving of nugget periphery.In addition, can suppress the generation of dust.
In the above-mentioned operation of current-mode, at less than 15 * t 2 0.5KA or less than 100 * t 2 0.5Under the situation of msec, not dissolving of surface-treated layer and aluminium carried out on a large scale, and the area of the interfacial reaction layer of optimum ranges of thicknesses is little.On the other hand, surpass 30 * t 2 0.5KA or surpass 1000 * t 2 0.5Msec is then because the interfacial reaction layer growth is thick, so the area of the interfacial reaction layer of optimum ranges of thicknesses reduces.
The operation of this current range also can be a plurality of, and the total ascent time of these operations is 100 * t 2 0.5～1000 * t 2 0.5The scope of msec, this point is very important.In addition, when metal bond of the same race,, also can access close connected structure as long as it is identical to advance heat.When the joint of steel and aluminium, for example, according to surpassing 30 * t 2 0.5KA and less than 100 * t 2 0.5The current-mode of msec or less than 15 * t 2 0.5KA and surpass 1000 * t 2 0.5Msec current-mode, can not obtain the area of the interfacial reaction layer of optimum ranges of thicknesses on a large scale.In the operation of the front and back of this current condition, also can increase other current-mode, and as the current-mode in a plurality of stages, but since interfacial reaction layer become to look thick, so must not exist in the operation of the electric current higher than this operation.
And, as desirable current-mode, preferably make 1 * t 2 0.5～10 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The operation of msec suppresses the nugget cracking.
[embodiment]
[table 6] (thickness of slab t of aluminium 2: 1mm)
[table 7] (thickness of slab t of aluminium 2: 2mm)
Figure A20078000623400542
Will be as steel the high-tensile strength steel plate of the 590MPa level of selling on the market and as aluminium be A6061 (6000 are) aluminium alloy plate sold on the market stacked after, carry out spot welding, be made into different material conjugant, then bond strength, corrosion resistance estimated.Table 6,7 ecbatics.
In the composition surface of above-mentioned high science and engineering steel plate side, implemented the pure Zn plating that dissolves of average thickness 10 μ m in advance, and, implemented the phosphate coating that contains 1.0% mass M g of average thickness 2 μ m thereon.
The thickness of slab of table 6 expression aluminium sheet is the situation of 1mm, and the thickness of slab of table 7 expression aluminium sheet is the situation of 2mm.In the table 6,7, make the plating condition and the phosphate coating condition of composition surface side of steel plate certain, the electrode condition and the current condition of spot welding are carried out various variations, thereby be made into different material conjugant.
[table 8]
Figure A20078000623400551
In addition, table 8 also represents to make the electrode condition and the current condition of spot welding certain, and the plating condition and the phosphate coating condition of the composition surface side of steel plate or aluminium alloy plate are carried out various variations, is made into the result of the different material conjugant of steel plate and aluminium sheet.
(raw material of use)
As raw material, prepare respectively: high-tensile strength steel plate, its thickness of slab 1mm and for containing the composition of 0.07% quality C-1.8% mass M n; A6061 aluminium alloy plate, its thickness of slab are 1mm and 2mm.These steel plates, aluminium alloy plate all are processed into the cross tensile test plate shape of JIS A 3137 records, and have carried out spot welding.
(Zn or Zn alloy coating: the plating epithelium)
Under the situation that steel implement are electroplated, all be after utilizing 10% sulfuric acid to carry out 5 minutes the pre-treatment of pickling activate, carried out various plating.When the Zn plating, in zinc sulfate 400g/l, aluminum sulfate 30g/l, sodium chloride 15g/l, boric acid 30g/l, add sulfuric acid, flow through 20A/dm in 3 the bath establishing pH 2Electric current, implemented the pure Zn plating of 10 μ m thus.It is being made as under the situation of Zn-10%Ni alloy plating, in pure Zn plating is bathed, is being added with in the bath of nickelous sulfate, nickel chloride and flows through 10A/dm 2Electric current, implemented the Zn-10%Ni plating of 10 μ m thus.In addition, pure Ni plating as a comparative example utilizes watt to bathe and flows through 10A/dm 2Electric current, implemented 10 μ m thus.
Dissolve plating and only steel are carried out, utilize various molten metals to implement the Zn plating of 10 μ m, Zn-Fe plating (the Fe amount is each quality of 5,10,12,16%) respectively.When dissolving plating Zn,, thickness is adjusted to 1,3,10,15,19,20 μ m by changing the temperature of humidity, lifting.As a comparative example, steel have also been implemented to dissolve Al-10%Si alloy plating.
Aluminium is being implemented utilize 10% nitric acid acidwashing 30 seconds under the situation of plating, in the treatment fluid of sodium hydride 500g/l, zinc oxide 100g/l, the chlorination second iron 1g/l, roscherite 10g/l, carried out 30 seconds zinc replacement Treatment or plating.In addition, in this zinc-plated bath, added in the bath of nickelous sulfate, nickel chloride and flow through 10A/dm 2Electric current, implement the Zn-10%Ni plating of 10 μ m thus.
The thickness of relevant plating epithelium as mentioned above, to the sample of air dry behind the plating is cut off, and is imbedded resin and is ground, and the SEM observation has been carried out at the plating interface before spot welding.SEM observes and utilizes 2000 times visual field to measure three dot thickness, by the observed result at five different positions of position is on average obtained.
(phosphate coating)
Phosphate coating impregnation process steel or aluminium and form in 40 ℃ the aqueous solution of each concentration of zinc ion 1g/l, phosphate ion 15g/l, Ni ion 2g/l, F ion 0.2g/l, Mg ion 0～30g/l.Mg content in the phosphate coating is regulated by the Mg ionic weight in the above-mentioned aqueous solution, and phosphate coating thickness is regulated by changed dip time between 1～300 second.
The average thickness of relevant phosphate coating, as mentioned above, sample with air dry after the phosphate treated is cut off, and the test portion of imbedding resin and grinding, the thickness of slab direction in the phosphate coating cross section (interface) before spot welding, utilize 2000 times visual field, observe by SEM and measure three dot thickness, by the observed result at five different positions of position is on average obtained.
Mg content in the relevant phosphate coating, the average thickness of analyzing above-mentioned phosphate coating by fluorescent x-ray is measured the grinding test portion of usefulness, obtains the Mg intensity in the phosphate coating, is converted into the % quality.And, on average obtain by the observed result at five different positions of position.
(spot welding)
D.C. resistance soldering test machine is used in spot welding, and uses the electrode of the dome type of Cu-Cr alloy composition, and anode is made as aluminium, negative electrode is made as steel and engages.In the table 6,7, according to the electrode tip condition shown in the table 6,7 [leading section, front end radius of curvature R, plus-pressure W and (R * W) 1/3/ R], current-mode [ welding sequence 1 and 2 welding current, weld interval] welds, and is made into the cross tensile test body of different material conjugant.
At this moment, the point diameter that table 6, each example of 7 are established the electrode tip of aluminium side is more than the φ 7mm, and applies the plus-pressure of electrode tip, so that the relation of front end radius of curvature R mm and plus-pressure WkN becomes (R * W) 1/3/ R, and make 15 * t according to having 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The current-mode of the operation of msec carries out spot welding.In this test, electrode tip uses identical shaped electrode tip in steel side, aluminium side.
In addition, each example is all identical in the table 8, and the spot welding condition of the example shown in the N of table 6 is necessarily welded, and is made into cross tensile test body.
Under these each conditions, be made into 10 test bodies and do the bond strength evaluation and make joint interface evaluation usefulness with, 3 test bodies.
(measuring the thickness of interfacial reaction layer)
About the thickness measurement of interfacial reaction layer, with the sample of a postwelding central cutout, imbed resin and grind at weld part, carried out the SEM observation.Under the thickness of layer is situation more than the 1 μ m, utilize 2000 times visual field to carry out instrumentation, under the situation of less than 1 μ m, utilize 10000 times visual field to carry out instrumentation.In addition, at this, so-called interfacial reaction layer is meant the compound layer that contains Fe and Al simultaneously, by FDX, detects Fe and Al and is the above layer of 1wt%.That is, detecting Fe and Al all is not that the above layer of 1wt% is plating layer or residual bonding agent, does not form interfacial reaction layer.
In addition, in this test, the interfacial reaction layer of central part is the thickest, and more end (circumference) interfacial reaction layer is thin more, therefore, obtains the diameter of interfacial reaction layer of diameter, the above thickness of 0.5 μ m of the interfacial reaction layer that surpasses 10 μ m thickness, is converted into area.Mensuration is measured the nugget size of the both direction of quadrature to carrying out on 3 conjugants, and to its averaging.
(evaluation of differential metals contact corrosion system)
In addition, after the different material conjugant that is bonded under various conditions applied, carried out the differential metals contact corrosion evaluation test.Different material conjugant uses 0.1% aqueous solution of the サ one Off Off ア イ Application 5N-10 of Nippon Paint Co., Ltd.'s system after the test film of choosing being carried out alkali degreasing, washing, carry out 30 stopwatch faces and regulate processing.Thereafter, in zinc ion 1.0g/l, nickel ion 1.0g/l, manganese ion 0.8g/l, phosphate ion 15.0g/l, nitrate ion 6.0g/l, nitrite ion 0.12g/l, toner value 2.5pt, full acidity 22pt, free acidity 0.3～0.5pt, 50 ℃ bath, carry out 2 minutes trbasic zinc phosphates and handle.Thereafter, apply by cation electrodeposition coating (Nippon Paint Co., Ltd. system パ ワ one ト Star プ), 170 ℃ of sintering 25 minutes form the epithelium of 30 μ m.
These applied different material conjugant test film carry out composite corrosion test, and different metal contact corrosion preventing property estimated thereafter.In corrosion test, establish A: chlorine water spraying (35 degree, 5%NaCl) 2hr, B: dry (60 ℃, 20-30%RH) 4hr, C: humidity (50 ℃, more than the 95%RH) 2hr is a circulation, this test has been carried out the quantity of regulation circulation.5 different material conjugant test films of coating are 45 circulations, and 5 different material conjugant test films of coating are 90 circulations in addition.
(bond strength evaluation)
The evaluation of the bond strength of the different material conjugant test film of relevant coating is as follows, in order to measure the intensity of the spot welding behind the above-mentioned composite corrosion test, respectively each 5 test sample behind the composite corrosion test of above-mentioned 45 circulations and 90 circulations have been implemented the cross tensile test, it has been carried out on average.
The result of cross tensile test is, if bond strength is more than the 1.5kN or disrumpent feelings mode is that aluminum mother plate is disrumpent feelings, then be designated as ◎, if bond strength is 0.8～1.0kN then is designated as zero, if bond strength is 0.5～0.8kN then is designated as △, if the not enough 0.5kN of bond strength then be designated as *.At this,, then can not use as the structural material of automobile etc. if fly bond strength after the above-mentioned corrosion test not more than 0.8kN (zero).
(table 6,7 result)
From table 6,7 as can be known, the intensity height that engages of the spot welding after preferred range is carried out very high, the above-mentioned composite corrosion test of different material conjugant corrosion resistance of example I～P of spot welding.This is the zinc-plated and effect of being located between composition surface phosphate coating of dissolving.
Relative therewith, exceed preferred range and carry out among the Comparative examples A～H of spot welding joint, because the bond strength when spot welding originally is low, so the bond strength behind the above-mentioned composite corrosion test is also low.In Comparative examples A～C, the point diameter of electrode tip is little, and the plus-pressure relevant with the front end radius of curvature is low etc., has exceeded preferred spot welding and has engaged condition and range.In addition, the also discontented unabridged version scope of invention of the current condition of Comparative Example D～H.
Comparative examples A～G except that the Comparative Example H of carrying out welding sequence 2, all the other only by welding sequence 1, do not carry out welding sequence 2 ground and carry out spot welding and engage.Wherein, the point diameter of the electrode tip of Comparative examples A is too small.The plus-pressure relevant with the front end radius of curvature of comparative example B, comparative example C is low excessively.
In addition, the welding current of its welding sequence 1 of Comparative Example D is relevant with the thickness of slab of aluminium and low excessively.The weld interval of its welding sequence 1 of Comparative Example E is relevant and too short with the thickness of slab of aluminium.The welding current of its welding sequence 1 of Comparative Example F is relevant and too high with the thickness of slab of aluminium.The weld interval of its welding sequence 1 of comparative example G is relevant and long with the thickness of slab of aluminium.There is the welding sequence 2 flow through the electric current significantly higher than welding sequence 1 in Comparative Example H.
That is, example I～P is when spot welding, and the point diameter of the electrode tip by establishing the aluminium side is more than the φ 7mm, and applies the plus-pressure of electrode tip, so that the pass of front end radius of curvature R mm and plus-pressure WkN is (R * W) 1/3/ R＞0.05, and make 15 * t 2 0.5～30 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The preferred welding sequence of msec carries out spot welding.In addition, example I, K only by this welding sequence 1, do not carry out welding sequence 2 ground and carry out spot welding and engage.Therefore, each example can be controlled the interfacial reaction layer of optimum thickness, thus the bond strength height.
In these examples, have above-mentioned welding sequence 1, and, also make 1 * t for the welding sequence 2 of back sometimes by example N, O, P that the non-existent current-mode of welding sequence that flows through the electric current higher than this welding sequence 1 carries out spot welding 2 0.5～10 * t 2 0.5The electric current of kA flows through 100 * t 2 0.5～1000 * t 2 0.5The optimum condition of msec, bond strength is the highest.
To this, example L, M that the current-mode that exists by the welding sequence 2 that flows through the electric current higher than this welding sequence 1 carries out spot welding, its bond strength is lower than the routine N of foregoing invention, O, P.
(result of table 8)
As shown in Table 8, there is not the comparative example 1,2 of plating, though there is not the comparative example 1,8,12 of phosphate coating when spot welding, to form the interfacial reaction layer of optimum thickness, because corrosion resistance is poor, so the bond strength behind the above-mentioned composite corrosion test is low.
Comparative example 3,4,14 outside metal epithelium condition (kind and melting point) goes beyond the scope almost can not form the interfacial reaction layer of optimum thickness.Therefore, original bond strength when spot welding is low, so the bond strength behind the above-mentioned composite corrosion test is also low.
In the comparative example 7 of the Al-10%Si alloy plating that Zn or Zn alloy coating do not have, though be formed with the interfacial reaction layer of suitable thickness, because corrosion resistance is poor, so the bond strength behind the above-mentioned composite corrosion test is all low.
In addition, even Zn or Zn alloy coating are arranged,, also can not form the interfacial reaction layer of optimum thickness though the thin excessively comparative example 15 of plating layer, blocked up comparative example 19 are pure zinc-plated.Therefore original bond strength when spot welding is low, so the bond strength behind the above-mentioned composite corrosion test is also low.
In addition, even the Zn alloy coating is arranged, though the thin excessively comparative example 20 of phosphate coating forms the interfacial reaction layer of optimum thickness when spot welding, because corrosion resistance is poor, so the bond strength behind the above-mentioned composite corrosion test is low.Otherwise the blocked up comparative example 23 of phosphate coating also can not form the interfacial reaction layer of optimum thickness.Therefore original bond strength when spot welding is low, so the bond strength behind the above-mentioned composite corrosion test is also low.
Relative with it, have phosphate coating, plating condition (melting point, composition) as can be known and can control the interfacial reaction layer of optimum thickness for the example 5,6,9～11,13,16～18,21,22,24～27 in the scope, and corrosion resistance is very high, so the bond strength height behind the above-mentioned composite corrosion test.This is the zinc-plated and effect of being located between composition surface phosphate coating of dissolving.
Wherein, implementing 5,6,9,17,21,24～27 in the pure zinc-plated example as can be known can be controlled to be the area of the interfacial reaction layer of optimum thickness up to 50 * t 2 0.5Mm 2More than.And, example 5,6,9,17,22,26,27 corrosion resistances that Mg content 0.1% quality that pure as can be known zinc-plated thickness is 5～15 μ m and phosphate coating is above, thickness 1 μ m is above are also high in the extreme, so the intensity height that the spot welding behind the above-mentioned composite corrosion test engages.From this result as can be known,, the interfacial reaction layer of optimum thickness be can control, thereby high bond strength and corrosion resistance obtained by plating being controlled to composition of the present invention, melting point, thickness.
By the result of above embodiment as can be known, the bond strength by improving different material conjugant and can suppress contact corrosion and the critical meaning of each important document of the present invention's regulation of the decline of the bond strength that causes thus.
[4]
(different material conjugant)
Fig. 4 represents the different material conjugant (junction surface) of one embodiment of the present invention regulation by sectional view.In Fig. 4,23 different material conjugants for galvanized steel (galvanized steel plain sheet) 21 and aluminium (aluminium alloy plate) 22 being engaged by spot welding.24 is the zinc-plated epithelium or the oxide scale film on steel 21 surfaces.
25 of junction surface central authorities are the nugget with joint interface (interfacial reaction layer) 26 of spot welding, and horizontal direction has the nugget size shown in the arrow in the drawings.In addition, this nugget 25 has the shared area of in-plane (left and right directions of figure) (below, abbreviate nugget area S as) on the composition surface of the represented aluminium side of S.
t 1Thickness of slab, the t of expression galvanized steel 21 2The thickness of slab of expression aluminium 22, Δ t represent to carry out the minimum remaining thickness of slab of the aluminium after spot welding engages.29 is the joint portion, dizzy district around the nugget.
This Fig. 4 represents to guarantee nugget size, suppress simultaneously dust generation, keep the minimum remaining thickness of slab of aluminium, and dissolving of steel is suppressed to the engagement state of irreducible minimum, conjugant of the present invention also is the engagement state as this figure.
Below, the qualification reason and the effect thereof of each important document of the present invention described.
(thickness of slab of galvanized steel plain sheet)
In the present invention, the thickness of slab t of the galvanized steel of joint 1Must select thicker thickness of slab from the scope of 0.3～3.0mm according to the thickness of slab of aluminium side.The thickness of slab that simply adds steel plate, or with the direct each other thickness of slab that adds thick steel products 21 sides such as stacked of steel thus, although do not increase the current value or the conduction time of spot welding condition, also increases the heat of advancing that the resistance heating of steel causes.And the heat distribution of advancing of the radial direction of nugget also changes, and by these composite effect, can prevent the minimizing of the remaining thickness of slab Δ t of aluminium 22, also causes that the temperature of nugget end side increases simultaneously easily.Therefore, the zinc-plated Zn floor 30 that causes of the joint interface portion that contacts with nugget 25 (dizzy district in conjunction with) 29 dissolves discharge and can carry out effectively.Consequently, suppress the zinc-plated distinctive crisp Zn-Fe based compound layer that causes generation.And the ratio of remaining Zn layer 30 also descends.So the direct engaging zones of steel 21 and aluminium 22 increases, bond strength improves.
In addition, at the thickness of slab t of steel 1Under the situation of not enough 0.3mm, as said structure member or structural material, can not guarantee necessary strength or rigidity, this is inappropriate.In addition, in addition, because the pressurization that spot welding is carried out strengthens deformation of steel, oxide scale film is destroyed easily, therefore promotes the reaction of steel and aluminium.Consequently, form intermetallic compound easily.On the other hand, surpass under the situation of 3.0mm at thickness of slab, as said structure member or structural material, adopt other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with steel 1Thickening surpasses 3.0mm.
(thickness ratio of steel and aluminium)
At this, in order further to improve bond strength, the steel 21 of preferred Fig. 4 and the thickness ratio of aluminium 22 are t 1/ t 2Be more than 1.By adding the thickness of slab of thick steel products 21 sides, although can not increase the heat that advances of spot welding condition, the heat that advances that the resistance heating of steel causes increases.And the heat distribution of advancing of the radial direction of nugget also changes, as mentioned above, by these composite effect, the direct engaging zones of steel 21 and aluminium 22 increases, and thus, guarantees the total area S into the Zn layer 30 of the joint interface portion that contacts with nugget 25 of optimum condition of the present invention 4Below 30% of area S for nugget 25.Consequently, can improve bond strength.
To this, the steel 21 of Fig. 4 and the thickness ratio t of aluminium 22 1/ t 2Under the situation of less than 1,, increase the direct engaging zones of steel 21 and aluminium 22, need to increase the heat that advances of spot welding condition in order to reduce the ratio of remaining Zn layer 30.Thus, promptly allow to reduce the ratio of remaining Zn layer 30, can not prevent the minimizing of the remaining thickness of slab Δ of aluminium t.Consequently, the remaining thickness of slab Δ of aluminium t significantly reduces, and thereupon, bond strength descends.
About this point, the minimum remaining thickness of slab Δ t of the aluminium side at different material junction surface is preferably original aluminium thickness of slab t 2More than 50%.
(galvanized steel)
In the present invention, the average thickness with zinc coat is that the two sides of 3～19 μ m or the galvanized steel of single face are the object of conjugant.In addition, under the situation that is the one side zinc coating steel, also can partly cut in the engage side of spot welding and not carry out zinc-plated face.In the present invention, that galvanized layer thickness is not thin than it or the steel that do not have a zinc coat are as object.
(zinc coat)
In addition, no matter dissolve plating, plating, the zinc coat of steel self both can be zinc-plated, also can be the alloy plating with iron.Wherein, the average thickness of establishing zinc coat is 3～19 μ m.The average thickness less than 3 μ m of zinc coat can not bring into play the effect of the anticorrosion grade of zinc coat self, do not have big difference with naked steel, and are nonsensical.In addition, surpass under the situation of 19 μ m, can not suppress to come from zinc-plated and the crisp Zn-Fe based compound layer that generates or the generation of Zn layer, be difficult to these areas are controlled in the prescribed limit of the present invention at the average thickness of zinc coat.Consequently, a little less than the bond strength.
(tensile strength of steel)
The present invention is not particularly limited the shape or the material of the steel that use, can use suitable shape, the material of steel plate general or that select according to the structural elements purposes, steel profile, steel pipe etc. in the structural elements.Wherein, require under the situation of high strength steel in structural elements uses, the tensile strength of preferred steel is the above high-tensile strength steel of 400MPa.
Usually, low-intensity steel middle-low alloy steel is many, and oxide scale film is roughly ferriferous oxide, so the diffusion of Fe and Al is easy, forms crisp intermetallic compound easily.Therefore, more than the also preferred tensile strength 400MPa, it is desirable to more than the 500MPa.
The present invention is unqualified to the composition of steel, but in order to obtain the intensity of above-mentioned steel, preferred high tension steel (high strength steel).In addition, in order to improve hardenability, carry out precipitation-hardening, also the composition that can use steel also selectively contains the steel of Cr, Mo, Nb, V, Ti etc. except that C.Cr, Mo, Nb improve hardenability, improve intensity, and V, Ti improve intensity by precipitation-hardening.But, add the toughness that these elements reduce the weld part axial region in a large number, and the nugget cracking take place easily.
So, composition as steel, preferably containing C:0.05～0.5%, Mn:0.1～2.5%, Si:0.001～1.5% qualitatively basically, in addition, also optionally contain one or more of Cr:0～1%, Mo:0～0.4%, Nb:0～0.1%, V:0～0.1%, Ti:0～0.1% as required.And the remnants of defeated troops of these steel form preferred Fe and unavoidable impurities is formed.
(aluminium)
Be used for aluminium of the present invention the kind and the shape of its alloy do not limited especially,, can suit to select general sheet material, section bar, forging material, casting material etc. according to the characteristic that requires as each structural elements.But the intensity of the aluminium also situation with above-mentioned steel is the same, and the distortion that the pressurization when suppressing spot welding causes it is desirable to high-intensity aluminium.On this point, preferably use intensity in the aluminium alloy also high and as this kind structure with the general A5000 system of member, A6000 system etc.
But, the thickness of slab t of these aluminiums that use among the present invention 2It is the scope of 0.5～4.0mm.Thickness of slab t at aluminium 2Under the situation of not enough 0.5mm, as the undercapacity of structural material, this is inappropriate, and, owing to can not get nugget size, and dissolve easy arrival aluminum surface and form dust easily, so can not obtain high bond strength.On the other hand, at the thickness of slab t of aluminium 2Surpass under the situation of 4.0mm, the same with the situation of the thickness of slab of above-mentioned steel, as structural elements or structural material, adopts other joint method, the necessity of therefore carrying out the spot welding joint is few.So, there is no need thickness of slab t with aluminium 2Thickening surpasses 4.0mm.
(compound of interfacial reaction layer)
At the different material conjugant with above steel and aluminium is on the basis of prerequisite, and the present invention stipulates the intermetallic compound of the different material conjugant (joint interface 26 of Fig. 4) of a postwelding.
Fig. 5,6,7 represents intermetallic compound that the present invention the stipulates cross section at the joint interface of the nugget of different material junction body respectively.Fig. 5 is 5000 times the SEM photo that schematically shows the joint interface 26 of Fig. 6.In addition, Fig. 7 is 5000 times a TEM photo of same joint interface 26.Fig. 6, the 7th, the example 8 of embodiment described later.
Shown in these figure represent respectively, on joint interface 26, has the Al of stratiform respectively in the steel side 5Fe 2Based compound layer, the Al that has chock shape (or bar-shaped or needle-like) in the aluminium side 3Fe based compound layer.
(compound layer regulation of the present invention)
When describing based on Fig. 4,5, the regulation main idea of compound layer of the present invention is, on the joint interface 26 of the different material conjugant 23 of the precondition with above-mentioned zinc coat or thickness of slab etc., has (generation) Al in steel 21 sides at first respectively 5Fe 2The based compound layer, has Al in aluminium 22 sides 3Fe based compound layer.
(thickness of compound layer)
In Fig. 5, the average thickness l of the total of the nugget depth direction of the two-layer compound layer of these joint interfaces (above-below direction of joint interface cross-wise direction, figure) is the Al of steel 21 sides 5Fe 2The average thickness l of the nugget depth direction of each measuring point of based compound layer 2Al with aluminium 22 sides 3The average thickness l of the nugget depth direction of each measuring point of Fe based compound layer 1Total.
(the area regulation-in-plane of compound layer part)
At this,, describe to the nugget area of in-plane of the present invention with in the area regulation that joint interface has a certain thickness compound layer part at first with reference to Fig. 4.As shown in Figure 4, with the Al of steel 21 sides 5Fe 2The Al of based compound layer and aluminium 22 sides 3Average thickness (the l of Fe based compound layer 1+ l 2) be that the shared total area of in-plane of joint interfaces compound layer part, aluminium 22 sides of 0.5～10 μ m is defined as S 1(mm 2).Shown in Fig. 9,10, be S (mm at the shared nugget area of the in-plane of the joint interface of aluminium 22 sides as described later when establishing nugget 25 2) time, obtain have this certain joint interface compound layer part, at the shared total area S of in-plane of the joint interface of aluminium 22 sides 1Area ratio with respect to nugget area S.In the present invention, stipulate this total area S 1Account for the ratio more than 50% of nugget area S.
(the area regulation-cross-wise direction of compound layer part)
In addition, with reference to Fig. 5,7, the area regulation to the cross-wise direction of Zn-Fe based compound layer of the present invention describes especially.Fig. 5,7 partly represents the above-mentioned Al that the SEM by 5000 times observes 5Fe 2Based compound layer and Al 3The total average thickness of Fe based compound layer is the cross-section result of the joint interface part of 0.5～10 μ m.
At this, be located at these above-mentioned Al 5Fe 2Based compound layer and Al 3Contain (generation) in Fe based compound layer two-layer respectively, be S at the shared total area of cross-wise direction (above-below direction of figure) of Zn-Fe based compound layer 3(μ m 2).In addition, the average thickness of establishing this two-layer total is that the shared area of cross-wise direction of the compound layer part of 0.5～10 μ m is S 2(μ m 2).In the present invention, stipulate the total area S of this Zn-Fe based compound layer 3Be the specific thicknesses shared area S of cross-wise direction partly at these compound layers of three layers 2+ S 3The ratio below 10%.
(Zn layer)
Then, when explanation Zn layer plating, the Zn layer is the remnant of the zinc coat of steel surface.Therefore, as shown in Figure 4, under the remaining situation of Zn layer, it is present in the joint interface 26 of nugget end (circumference).This Zn layer is for the thickness identical with the thicker zinc coat that is present in this circumference or than its thin thickness.When this Zn layer remained in joint interface 26 when remaining (), this part was represented the meaning that steel 21 and aluminium 22 directly do not engage.Therefore, the shared total area S of in-plane of the Zn layer 30 of the joint interface 26 that contacts with nugget of regulation 4(mm 2) be the shared area S (mm of in-plane of above-mentioned nugget 2) below 30%.The total area S that the in-plane of Zn layer 30 is shared 4The same with nugget area S described later etc., be the shared area of in-plane at the joint interface of aluminium 22 sides.
(Al 3Fe based compound layer)
In the present invention, in order to improve bond strength, preferably establish the Al of aluminium 22 sides of Fig. 5 3The average thickness t of the nugget depth direction of the nugget central part of Fe based compound layer 1It is the scope of 0.5～10 μ m.
Shown in Fig. 5,6,7, be formed at the intermetallic compound Al of aluminium 22 sides 3Fe forms the shape of wedge-like.At central portion (nugget central part), the size of compound grain separately (or length of wedge-like, spiculation compound grain) is big, and thickness (specification and the distribution of grain, pin) slowly reduces along with towards the end of nugget (Fig. 5,6,7 left and right directions).
Such Al 3Fe based compound layer also comprises the effect of above-mentioned shape, has wedge (fixing) effect, and improves aluminium 22 and Al 3The cohesive of Fe based compound layer improves bond strength.If this effect is Al 3Fe based compound layer is thin excessively, can not bring into play.Especially l 1Under the situation of less than 0.20 μ m, above-mentioned wedge effect is insufficient, with Al 5Fe 2The poor adhesion of based compound layer, easy disrumpent feelings between genetic horizon, and might be disrumpent feelings at level and smooth interface.Therefore, preferably establish the Al of aluminium 22 sides 3The average thickness l of the nugget depth direction of the nugget central part of Fe based compound layer 1Be more than the 0.20 μ m.
On the other hand, work as Al 3When Fe based compound layer was too grown up blocked up formation layer, compound grain separately became the starting point of destruction on the contrary.Especially at l 1Surpassed under the situation of 10 μ m, this is inclined to significantly.Therefore, preferred Al 3The average thickness l of the nugget depth direction of the nugget central part of Fe based compound layer 1On be limited to below the 10 μ m.
(Al 5Fe 2The based compound layer)
In the present invention, in order further to improve bond strength, be preferably the intermetallic compound Al of steel 21 sides 5Fe 2, Al 5Fe 2The average thickness l based compound layer, the nugget depth direction 2It also is the scope of 0.20～5 μ m.This Al 5Fe 2The based compound layer is also along with towards the end of nugget (Fig. 5,6,7 left and right directions), and its thickness (specification and the distribution of grain, pin) reduces gradually.This Al 5Fe 2The average thickness l of based compound layer 2Compared thinly or blocked up with this scope, all might reduce bond strength, the Al of its reason and above-mentioned aluminium 22 sides 3The situation of Fe based compound layer is identical.
(areas of two compound layers)
In Fig. 4, above Shuo Ming Al 3The average thickness l of the nugget depth direction of Fe based compound layer 1With Al 5Fe 2The average thickness l of the nugget depth direction of based compound layer 2The total average thickness be the average thickness of this two-layer total of nugget depth direction.
As shown in Figure 9, the present invention is in order to improve bond strength, the above-mentioned area S of the part that to strengthen this total average thickness be 0.5～10 μ m 1(the area S that the in-plane of the joint interface of aluminium 22 sides is shared 1).That is regulation S, 1Be more than 50% of nugget area S (the shared area S of in-plane of the joint interface of aluminium 22 sides of Fig. 4 record).
That is Al, 3Fe based compound layer and Al 5Fe 2The area S of the in-plane at the interface, junction surface of the specific thicknesses part of based compound layer 1Big more bond strength is high more.As shown in figure 10, at this area S 150% o'clock of little and not enough nugget area S, under the situation that is same intensity, nugget area S is big more, and the possibility that the Breaking load at junction surface (bond strength) descends is high more.On the other hand, under the little situation of nugget area S, the junction surface is same disrumpent feelings with lower load easily.
As shown in Figure 9, at Al 3Fe based compound layer and Al 5Fe 2The area S of based compound layer 1Under the big situation, the junction surface that engaging force is high (joint interface) area is fully big, therefore can bear bigger breaking load.Consequently, joint interface is compared with aluminium base, and breaking load is very high, and therefore, the interface is not disrumpent feelings and the aluminium side is disrumpent feelings.
From the viewpoint of bond strength, the area of the interfacial reaction layer of above-mentioned optimum thickness there is regulation, the compound layer of aluminium side and the compound layer of steel side are controlled at optimum scope.Therefore, the direction as the present invention points to different as thin more good more present general knowledge, much less, is the direction of lamination existence.And, in order to improve bond strength, form the interfacial reaction layer of optimum thickness range based on large tracts of land, in other words, there is this technological thought on a large scale.
(Zn-Fe based compound)
On the other hand, in the present invention, be impurity as compound or compound layer, in order not influence bond strength, the restriction intermetallic compound is the Zn-Fe based compound.Specifically, be limited in these Al 3Fe based compound layer and Al 5Fe 2The Zn-Fe based compound that contains (generation) in based compound layer two-layer respectively.
As shown in Figure 5, be located at Al 5Fe 2Based compound layer and Al 3The Zn-Fe based compound layer that contains (generation) in Fe based compound layer two-layer respectively is S at the shared total area of cross-wise direction (above-below direction of figure) 3In addition, the average thickness of establishing this two-layer total is that the compound layer part of 0.5～10 μ m is S at the shared area of cross-wise direction 2In the present invention, stipulate the total area S of this Zn-Fe based compound layer 3For the specific thicknesses part of above-mentioned two-layer compound layer at the shared area S of cross-wise direction 2The ratio below 10%.
Total area S at crisp Zn-Fe based compound layer 3Surpassed above-mentioned area S 2With this S 3Total S 2+ S 310% situation under, the bond strength at junction surface descends significantly.In addition, the Zn-Fe based compound also can be said to the Fe-Zn based compound.
(area of Zn layer)
In addition, in the present invention, as preferred condition as mentioned above, the shared total area S of in-plane of the Zn layer 30 of the joint interface 26 that regulation contacts with nugget 4Below 30% of in-plane area occupied S for above-mentioned nugget.
As mentioned above, the Zn layer is the remnant of the zinc coat of steel surface, as shown in Figure 4, remains at the Zn layer under the situation of joint interface 26 of nugget end (circumference), just means that this part does not directly engage with steel 21 and aluminium 22.Total area S at this crisp Zn layer 4Surpassed under 30% the situation of nugget area S of in-plane of above-mentioned observation the possibility height that connect and the intensity at junction surface descends significantly.
The shared total area S of in-plane about the Zn layer 30 of the joint interface 26 that joins with nugget 4Mensuration, shown in Fig. 4 and 9, according to the observed result of the light microscope by 200 times, can be assumed to be Zn layer 30 and exist and measure in the circumferencial direction symmetry of nugget at the joint interface 26 that joins with nugget in the cross-wise direction at each position that Zn layer 30 exists.
(bond strength and disrumpent feelings mode)
The present invention is under the high situation of bond strength, and joint interface is not disrumpent feelings, and junction surface plug shape is disrumpent feelings (at Al 3The outside of the scope that Fe based compound layer exists, aluminium is disrumpent feelings in the thickness of slab direction of inside).In other words, the disrumpent feelings mode at such junction surface is represented the height of bond strength of the present invention.
On the other hand, disrumpent feelings at joint interface under the low situation of bond strength shown at present, at Al 5Fe 2Based compound layer and Al 3Between the Fe based compound layer or arbitrary compound layer inside is disrumpent feelings.In other words, the disrumpent feelings mode at such junction surface is represented the minuent of bond strength.
(ad hoc approach of intermetallic compound)
Al of the present invention 5Fe 2Based compound layer and Al 3The particular implementation of Fe based compound layer carries out the semi-quantitative analysis of EDX (Energy Dispersive X-ray spectroscopr) point analysis with fixed to the cross section at junction surface by HAADF-STEM image (5000 times～10000 times).In other words, also we can say the HAADF-STEM method of utilizing following explanation,, the intermetallic compound of the present invention's regulation is discerned or the thickness and the area of intermetallic compounds layer carried out correct mensuration with regard to being difficult to as long as do not measure the interface, junction surface.
The difference (identification) each other of these intermetallic compounds in above-mentioned semi-quantitative analysis, is measured the composition of (as much as possible) measuring point of the majority at interface, junction surface, by carrying out with Fe, Al, composition when Zn (at%) is percentage.That is, as shown in table 10, establish " Al 5Fe 2Based compound " the Fe amount of consisting of: 18.0～24.0at%, Al amount: the scope of 74.5～81.0at%.And that the composition of Zn-Fe based compound is representative is Fe 3Zn 7Composition, be the Fe amount: 31.0～40.0at%, Zn amount: the scope of 60.0～69.0at%.
At this, the judgement of the composition of above-mentioned each interfacial reaction layer (identification) benchmark is as follows.That is " Al, 5Fe 2Based compound " or " Al 3The Fe based compound " become and detect Fe and Al by the EDX point analysis and be layer more than 10% quality.In other words, the layer of equal less than 10% quality of Fe and Al is not in the present invention as specific interfacial reaction layer.
In addition, the Zn-Fe based compound passes through the EDX point analysis equally, becomes to detect the layer that the Fe:27.7% quality is above and the Zn:72.3% quality is following.Though detect Zn, the layer that does not detect Fe and be 27.7% quality is differentiated and is unborn Zn plating layer or Zn layer 30, does not form interfacial reaction layer.
Consisting of of Zn-Fe based compound is representative Fe 3Zn 7The composition of [Fe27.7～36.3% quality (Fe31.0～40.0at%)] is different from other the phase that is contained in the Zn plating layer.So-called other be meant ζ phase [FeZn13:Fe5.8～6.2% quality (Fe6.7～7.2at%)], δ 1 phase [FeZn mutually 7: Fe7.3～11.3% quality (Fe8.5～13.0at%)], Г 1 phase [Fe 5Zn 21: Fe16.2～20.8% quality (Fe18.5～23.5at%)], Г phase [Fe 3Zn 10: Fe21.2～27.7% quality (Fe24～31.0at%)] (with reference to exhibiting of the composition of relevant Zn coating: civic organization Japan iron steel association compiles, the 138th, 139 time Western Hills commemorate lectures " progress of process for treating surface and trend from now on " P.15 (putting down on May 1st, 3 issues)).
In addition, as the phase of interfacial reaction layer, approval has Al 5Fe 2, Al 3Fe, Fe 3Zn 7, its composition has and may not be made up of chemistry two opinions, and has a certain size composition width.To this, according to the same phasing of crystalline texture of the electronics line diffraction of TEM, and to separately the mensuration that EDX has carried out Fe, Al, Si, Mn, Zn element of passing through.Consequently, distinguished in fact Al 5Fe 2, Al 3A side, Fe that the ratios of forming than chemistry two opinions at Fe of Fe are lacked 3Zn 7The ratios of forming than chemistry two opinions at Fe one side of Duoing, the composition of phase is variant.Based on these result, what the ratio of judgement Fe, Al, Zn satisfied the scope shown in the table 10 is the phase of conversion zone separately mutually.
In addition, above-mentioned HAADF-STEM method (High Angle Annular Dark Field-Scanning Transmission Electron Microscope) is for obtaining the method for picture signal at high corner side elasticity at random electronics at random by circular detectors set.The HAADF-STEM image is characterised in that, is subjected to the influence of diffraction contrast hardly, and contrast roughly takes advantage of 2 times to be directly proportional with atom sequence number (Z), and the image that obtains is the original image with two dimension of original composition information.Owing to also can sensitivity detect trace element well, the fine structure of joint interface is resolved effectively.
More particularly, the nugget central portion at conjugant is cut off, imbed resin and carry out mirror ultrafinish, measure the average thickness of each compound layer of interfacial reaction layer by the SEM summary can observe the conjugant in cross section.Utilize Hitachi system boundling ion irradiation processing unit (plant) (FB-2000A) contrast regard as nugget central part and Al thereafter, 5Fe 2Based compound the layer the part that has the boundary inside, regard as Al 3The inside and outside part that has boundary of the layer of Fe based compound, the length of depth direction of regarding as the layer of each compound surpass the inside and outside part at the position of the upper limit and implement FIB processing, up to the thickness that can carry out TEM, the skiving test portion provides with test portion as observation analysis thus.
And, utilization possesses the JEOL system electric field radioactive TEM (JEM-2010F) of HAADF, by accelerating potential 200kV, observes with the scope (5000 times～10000 times) of visual field 100 μ m, and to each, homophase does not all carry out the EDX point analysis, to Al 3Fe based compound layer and Al 5Fe 2The based compound layer carries out with fixed.
The Al of Fig. 4 3Thickness (length) l of the depth direction of Fe based compound layer 2By the HAADF-STEM image of the visual field 100 μ m that obtain, measure and average all with being decided to be Al 3The length of the depth direction of the grain pin of Fe based compound.
The Al of Fig. 5 5Fe 2The thickness of the depth direction of based compound layer (length) l 2By same image, measure and average five dot thickness.Whole observation analysis have been implemented above mensuration with test portion.
(assay method of intermetallic compound in-plane area)
By these mensuration, obtain Al 5Fe 2Based compound layer and Al 3The total average thickness of the two-layer nugget depth direction of Fe based compound layer is the shared total area S of in-plane of the joint interface of 0.5～10 μ m aluminium side partly 1In addition, equally also obtain the shared nugget area S of in-plane at the joint interface of aluminium side.That is, shown in Fig. 9,10, be assumed to these layers symmetry on the nugget circumferencial direction, and be assumed to concentric circles from the location of the radial direction in cross section and calculate area on the in-plane.In addition, be the total area S that calculates the in-plane of Zn layer 30 too 4Method.Promptly as above-mentioned shown in Figure 4, under the situation that Zn layer 30 exists, its circumference along nugget (periphery) exists.Therefore, confirming to suppose Zn layer 30 along nugget circumferencial direction symmetry under the situation that Zn layer 30 exists, and be assumed to concentric circles from the location of the radial direction in cross section and calculate area on the in-plane.
(assay method of intermetallic compound cross-wise direction area)
Like this, undertaken with Al fixed, that determine by the EDX point analysis 3Fe based compound or Al 5Fe 2The total average thickness of the two-layer nugget depth direction of based compound is the total area S of the cross-wise direction of 0.5～10 μ m part 2, be contained in the total area S of the cross-wise direction of above-mentioned Zn-Fe based compound layer in two-layer respectively 3Deng mensuration, by to carry out with the position of the joint interface after fixed carry out above-mentioned SEM observe, 2000 times～10000 times (average thickness be 1 μ m when above with 2000 times, during average thickness less than 1 μ m with 2000 times) the SEM observation of multiplying power obtain.Specifically, on radial direction apart from each position of the 500 μ m of nugget center of radius portion, measure the area of the cross-wise direction of each conversion zone with visual field width 100 μ m, and this instrumentation is proceeded to the position that conversion zone exists along the nugget radial direction, by these totals are obtained.
In addition, same, also can carry out the tem observation of 2000 times～10000 times multiplying power and verify these results.For example, part shown in the dotted line is a joint interface in 5000 times the TEM photo of 5000 times SEM photo of joint interface shown in Figure 6, identical joint interface shown in Figure 7, and TEM photo one side of this joint interface is easy to visual differentiation.
(size of nugget)
The average diameter t of the joint interface of the aluminium side of the nugget 25 of the spot-welding part of Fig. 4 is in order to ensure more than the preferred 7mm of bond strength.In other words, preferred Chosen Point welding rod spare is so that the average diameter of nugget 25 is more than the 7mm.
Under the situation of the not enough 7mm of the average diameter of nugget 25, the nugget area is too small, the inadequate possibility height of bond strength.On the other hand, the average diameter of nugget 25 is preferably below the 12mm.When the average diameter of nugget 25 surpassed 12mm, it was abundant to obtain bond strength, but easily dust takes place, and the reduction of aluminium is many, so bond strength descends on the contrary.
At present, when metalloid material of the same race was carried out spot welding, with respect to the thickness of metal material, the area of establishing the nugget 25 of spot-welding part was 20 * t 2 0.5Mm 2Size, no matter such intensity is from the processability aspect, or see all be optimum from the economy aspect.
But, in the present invention, relevant different metal materials joint each other, it is bigger than above-mentioned metalloid material of the same race to establish the nugget area.The average diameter of the nugget 3 of the synthetic spot-welding part of means of spot welds is more than the 7mm, thus, obtains sufficient joint strength, and processability, economy are also good.
(mensuration of nugget area)
Nugget 25 of the present invention is at the shared area S of the in-plane of the joint interface of aluminium 22 sides, and the shared area S of cross-wise direction of nugget 25 5, nugget average diameter (at the shared diameter of in-plane of the joint interface of aluminium 22 sides) mensuration, for example can measure by 200 times observation by light microscope.That is, the nugget of the aluminium side that joint interface peels off or cut off and separate is resolved and be determined to a plurality of Sample Images, ask it average.At this moment, sightingpiston is by being that carry out in the cross section at center with the nugget center.Under the situation of shape of nugget circular shape, also can cut off the junction surface, utilize light microscope to observe, and measure the diameter of the nugget of formation at aluminium side engagement interface by a plurality of samples by the cross section, ask it average.At this moment, measure the nugget size of the both direction of quadrature at least.
(reduction of aluminium)
Guarantee the meaning of bond strength, it is desirable to reduce as much as possible reduction by the aluminium behind the spot welding joint.As this target, it is desirable to minimum remaining thickness of slab Δ t is initial thickness t 2More than 50%.Better is that minimum remaining thickness of slab Δ t is initial thickness t 2More than 90%.The minimum remaining thickness of slab Δ t of this aluminium can observe from joint interface by 200 times light microscope, measures thickness of slab and reduces length, gets with the difference of original thickness of slab and obtains.
(spot welding)
Figure 11 illustration is as a mode of the spot welding of the prerequisite that is used to obtain the xenogenesis conjugant.The basic mode of spot welding method of the present invention is identical with the mode of common spot welding.In Figure 11,21 is that steel plate, 22 is that aluminium alloy plate, 23 is that xenogenesis conjugant, 25 is that nugget, 27 and 28 is electrode.
Below, each condition of the spot welding that is used to obtain the different material conjugant of the present invention is described.
(plus-pressure)
Plus-pressure during relevant spot welding for the necessary area that obtains above-mentioned bigger nugget and the necessary area of above-mentioned optimum interfacial reaction layer, also in the optimum scope that becomes the invention described above regulation, must apply than higher plus-pressure.
Specifically, the thickness of slab t (t of Fig. 4 of plus-pressure and junction surface integral body 1+ t 2) relation, from 1 * t 2 0.5KN～2.5 * t 2 0.5The higher stressed scope of the ratio of kN is selected.But even in this higher stressed scope, the generation method of above-claimed cpd also because of raw material or other welding condition difference difference, is decided to be in the optimum scope of the invention described above regulation so differ.Therefore, must be according to the welding condition of raw material and other, the optimum plus-pressure in the above-mentioned optimum scope that is chosen as the invention described above regulation than higher stressed scope.
On the other hand, by applying the bigger plus-pressure of above-mentioned scope, the shape by electrode tip etc. not, just can make between foreign material, electrode and storeroom electrically contact stable, and by the molten metal in the portion's of not dissolving support nugget of nugget periphery, thereby can access required area of above-mentioned bigger nugget and the required area of above-mentioned optimum interfacial reaction layer.In addition, can suppress the generation of dust.
At plus-pressure less than 1 * t 2 0.5During kN, plus-pressure is low excessively, can not get such effect.Especially, R is positioned at the joint of front end, and its contact area descends, thereby causes the decline of nugget area, the increase of current density (increase of=interfacial reaction layer), so bond strength descends, in addition, can not obtain Al 3The average thickness l of Fe based compound layer 1, Al 5Fe 2The average thickness l of based compound layer 2, also have the possibility height of this two-layer total average thickness l.
On the other hand, when increasing plus-pressure, the tendency that exists the nugget area to reduce surpasses 2.5 * t at plus-pressure 2 0.5During kN, if obtain desirable nugget area, need to surpass the electric current of following optimum electric current, and cause the generation of dust and the growth of interfacial reaction layer, so bond strength reduces.In addition, the distortion of aluminium is big, and joint mark becomes big recess, so from undesirable in appearance.
(electric current)
In order to obtain the required area of required area of bigger nugget and above-mentioned optimum interfacial reaction layer, the electric current in the time of must be to spot welding is controlled, and the short time is flow through than higher electric current.
Specifically, need make the thickness of slab t of the steel integral body at electric current and above-mentioned junction surface 1(the t of Fig. 4 1, wherein more than two pieces during steel, be the thickness of slab of this steel integral body in lamination) the pass be 12 * t 2 0.5～35 * t 2 0.5The higher electric current of ratio of kA flows through 320 * t 2 0.5The short time that msec is following.But, even in this scope than higher electric current and time, even in this scope than higher electric current and time, also because of raw material or other welding condition difference difference, differ is decided to be in the optimum scope of the invention described above regulation the generation method of above-claimed cpd.Therefore, must be according to raw material or other welding condition, be chosen as optimum electric current and time in the optimum scope of the invention described above regulation from above-mentioned scope than higher electric current and time.
In addition, flow through like this than higher electric current by the short time, make between foreign material, electrode and storeroom electrically contact stabilisation, and by the molten metal in the portion's of not dissolving support nugget of nugget periphery, thereby can access required area of above-mentioned bigger nugget and the required area of above-mentioned optimum interfacial reaction layer.In addition, can suppress the generation of dust.
At undercurrent 12 * t 1 0.5KA, less than 15 * t strictly speaking 1 0.5Under the situation of the low current of kA, what can not get that nugget forms, grows up advances heat fully.Therefore, can not get the above-mentioned bigger required area of nugget and the required area of above-mentioned optimum interfacial reaction layer.In addition, can not obtain Al 3Fe based compound and Al 10Fe 4Si 2The average thickness l of Mn based compound layer 1, Al 5Fe 2The average thickness l of the nugget depth direction in the scope of the nugget center ± 0.1mm of based compound layer 2Deng the possibility height.
On the other hand, surpassing 35 * t 2 0.5Under the situation of the high electric current of kA, need extra equipment, unfavorable to the operating cost aspect.Therefore, from these viewpoints, establishing electric current is 35 * t 2 0.5Below the kA.Therefore, using electric current is 12 * t 2 0.5～35 * t 2 0.5The kA scope, preferred 15 * t 2 0.5～35 * t 2 0. 5The scope of kA.
(conduction time)
Be the thickness of slab t with above-mentioned steel integral body conduction time 1The pass be 320 * t 1 0.5The short time that msec is following.Surpass 320 * t in conduction time 1 0.5Under the long situation of msec, can guarantee nugget size, but cause the generation of dust and the growth of interfacial reaction layer, so bond strength is low.As mentioned above, in order to control interfacial reaction layer, establishing conduction time is 320 * t 1 0.5Below the msec, preferred 100 * t 1 0.5Msec～280 * t 1 0.5Msec.But, as mentioned above, must be according to raw material and other welding condition, according to the relation of above-mentioned electric current, select the compound of the invention described above regulation to be controlled to be optimum time in the optimum scope.
(two sections energisings)
For the conversion zone that makes joint interface forms the compound layer that the present invention stipulates,, carry out in two sections energisings or two stages spot welding mode preferably with one section common no power.Like this, the energising of the weldering of setting up an office was two stages, particularly, made second section the energising value of energising value than first section low, removed the zinc coat (removing) of steel surface thus, thereby steel and aluminium are directly engaged easily.
In addition, the easier compound layer that obtains The compounds of this invention layer regulation.That is,, generate Al easily in the steel side respectively at the joint interface of different material conjugant 5Fe 2The based compound layer generates Al easily in the aluminium side 3Fe based compound layer.In addition, the area S of this two-layer specific thicknesses part 1Form more than 50% of nugget area S easily.And, area S that easily will this Zn-Fe based compound layer that contains respectively in two-layer 3Be controlled at the compound area S of cross-wise direction 2+ S 3Below 10%.The also total area S of the Zn layer of the joint interface portion that will contact with nugget easily 4Be controlled at below 30% of nugget area.
Energising in the weldering of setting up an office is under this two stage situation, except that the above-mentioned energising value of second section energising value than first section is low, first section with second section also to establish plus-pressure identical, and preferred plus-pressure, current value, total are in the above-mentioned preferable range conduction time.Thus, can not influence spot welding efficient ground and carry out different material joint.
(electrode shape)
As long as the shape of the electrode tip of spot welding can access above-mentioned nugget area and interfacial reaction layer, no matter what shape can, although the electrode tip of steel material, aluminium side is different shapes, different sizes, have no relations.But all preferred front end as shown in Figure 5 in the both sides of steel side, aluminium side is the electrode tip of R " dome type ".Under the situation of such dome type, in order to reduce above-mentioned current density simultaneously and to increase the nugget area, the point diameter of electrode tip, front end R are necessary for more than the φ 7mm, more than the R100mm.In addition, utilize under the situation of dc spot welding in specified polarity not, preferably establishing the aluminium side is anode, and establishing the steel side is negative electrode.
In addition, especially by with more than the point diameter φ 7mm, and front end R is that the above electrode tip of 120mmR is used for two sides, above-mentioned current density reduced and put the area increase to reach optimum.Use under the situation of this joint, preferably apply and above-mentioned steel thickness of slab t 1The pass be 1.5 * t 1 0.5KN～2.5 * t 1 0.5The plus-pressure of kN, and make 15 * t 1 0.5～35 * t 1 0.5The electric current of kA flows through 0 * t three times 1 0.5Below the msec.
Optimum engaging condition is the balance of these each conditions of above explanation, for example, need increase joint diameter and joint R, plus-pressure, and reduce under the situation of current density, increases the magnitude of current thereupon, and interfacial reaction layer is controlled at optimum thickness.
[embodiment]
[table 9]
Figure A20078000623400751
[table 10]
Figure A20078000623400752
[table 11] (980Mpa level high-tensile strength GA steel)
Figure A20078000623400761
[table 12] (980Mpa level high-tensile strength GA steel)
*Among the cross tensile test result, * expression does not have the meaning (following table is also identical) of joint.
[table 13] (780Mpa level high-tensile strength GA steel)
Figure A20078000623400781
Figure A20078000623400791
*32～39 steel thickness of slab t 10.9mm be equivalent to the thickness of slab (two pieces total thickness of slab 1.8mm) of one piece of steel
[table 14] (780Mpa level high-tensile strength GA steel)
[table 15] (270-980MPa level GA steel plate: zinc-plated thickness 10 μ m)
Figure A20078000623400801
*42～57 steel thickness of slab t 1Thickness of slab (two pieces the total thickness of slab t that is equivalent to one piece of steel respectively 1* 2)
[table 16] (270-980MPa level GA steel plate: zinc-plated thickness 10 μ m)
Figure A20078000623400811
Be made into different material conjugant according to each condition shown in the table 11,13,15.Each conjugant that these are made into to each has been measured the area ratio of each compound by above-mentioned assay method, and the reduction (minimum remaining thickness of slab) of bond strength, aluminium is estimated.As gathering of these, table 12 is illustrated in the joint result of the spot welding under the condition of table 11, and table 14 is illustrated in the joint result of the spot welding under the condition of table 13, and table 16 is illustrated in the joint result of the spot welding under the condition of table 15.
(steel condition)
Casting contains the confession examination steel of four kinds of the chemical composition shown in the table 9 (% quality), is rolled the thickness of slab of 0.8～1.2mm, obtains sheet metal.After to of the annealing of this sheet metal, carry out oil wash or washing, thereafter, obtain the steel plate of each intensity (MPa) of four kinds shown in the table 9 by tempering by 50～1000 ℃ of continuous annealings.
(aluminium condition)
In addition, relevant aluminium uses the A60227 aluminium alloy plate of selling on the market of thickness of slab 1.0mm (Al-0.6% quality-1.0% quality Si-0.08% mass M n-0.17% quality Fe) all.
(spot welding condition)
After these steel plates (steel) and aluminium alloy plate (aluminium) are processed into the cross tensile test plate shape of JIS A3137 record, carry out spot welding under the conditions shown in Table 10, thereby be made into different material conjugant.
D.C. resistance soldering test machine is used in spot welding, and in advance conditions such as plus-pressure, welding current, time and the dependency relation that the average thickness and the area of the compound of the invention described above regulation are controlled is studied.Thereafter, according to the thickness of slab t of aluminium 2Set plus-pressure, welding current, time respectively, carrying out the welding of any with the condition shown in each table.
Plus-pressure, welding current, conduction time change in the pass with the following electrode tip that uses is each preferred range of above-mentioned paragraph 0395 record.
And, energising in the weldering of setting up an office is under the two stage situation, except that the energising value of energising value than first section that makes second section is low, first section with second section all to establish plus-pressure all identical, and to establish plus-pressure, current value, total be in the above-mentioned preferable range conduction time.
Electrode tip all is the dome type by the φ 12mm of Cu-Cr alloy composition, and the curvature of establishing the electrode front end is R150mm, and establishing anode is that aluminium, negative electrode are steel.
The mensuration of the minimum remaining thickness of slab of relevant nugget size, aluminium, the remaining ratio of Zn coating at the sample of the central cutout point postwelding of weld part, is imbedded resin, and is implemented grinding, chemical etching, observes by 200 times light microscope.
Relevant interfacial reaction layer Determination of thickness is used cross section sample same as described above, is undertaken by above-mentioned assay method respectively.
(evaluation of bond strength)
As the evaluation of the bond strength of each conjugant, implemented the cross tensile test of different material conjugant.The cross tensile test is a benchmark with A6022 material bond strength=1.0kN each other, if bond strength is more than the 1.5kN or disrumpent feelings mode is that aluminum mother plate is disrumpent feelings, then be designated as ◎, if bond strength is 1.0～1.5kN then is designated as zero, if bond strength is 0.5～1.0kN then is designated as △, if the not enough 0.5kN of bond strength then be designated as *.
In addition, in the present embodiment, why adopting the cross tensile test that bond strength is estimated, is because this cross tensile test is compared the cause that the diversity ratio between experimental condition is big with cutting off tensile test.But, also from example, selecting several tensile tests of trying to have carried out cutting off, its result and this cross tensile test result match, and obtain zero in the cross tensile test, the evaluation of ◎ is the high shearing strength more than the 2.5kN.
In the joint result who carries out table 12,14,16 spot welding, each example has the shared total area S of in-plane of certain thickness joint interface compound layer part 1The area ratio of nugget area S is more than 50% relatively.In addition, Zn-Fe based compound layer and other two-layer total area S 2+ S 3Ratio with respect to the shared area S of cross-wise direction with certain thickness joint interface compound layer part 2Be more than 10%.And as optimum condition, the Zn layer of the joint interface that joins with nugget is at the shared total area S of in-plane 4Be below 80% of nugget area S, the nugget average diameter is more than the 7.0mm.
Consequently, shown in table 12,14,16, in each example, different material conjugant obtains high bond strength.And in example, it is more to have certain thickness joint interface compound layer part, or the situation of the less example of Zn-Fe based compound layer segment, and the bond strength of its different material conjugant is also high.In addition, for the nugget average diameter of optimum condition is big more, the total area S that the in-plane of Zn layer is shared 4Few more, the bond strength of different material conjugant is high more.
On the other hand, in the joint result of table 12,14,16 spot welding, in each comparative example, at the shared total area S of in-plane 1The area ratio less than 50% of nugget area S, or Zn-Fe based compound layer relatively and other two-layer total area S 2+ S 3Ratio with respect to having certain thickness joint interface compound layer part at the shared area S of cross-wise direction 2Surpass 10%.That is it is very few or Zn-Fe based compound layer segment is too much, to have a certain thickness joint interface compound layer part.Therefore, the example corresponding with each compares, and the bond strength of different material conjugant is low significantly.
At this, the example 8 of his-and-hers watches 12 and the joint interface tissue of comparative example 7 carry out concrete comparison.Fig. 6,7 is the joint interface tissue of example 8, and Fig. 6 is 5000 times a SEM photo of joint interface.Fig. 7 is 5000 times a TEM photo of identical joint interface.By Fig. 6,7 as can be known, in the joint interface tissue of example 8, has Al in the steel side respectively 5Fe 2The based compound layer, has Al in the aluminium side 3Fe based compound layer.
On the other hand, Figure 12 is expressed as the joint interface tissue of comparative example 7, i.e. 5000 of joint interface times TEM photo.As shown in Figure 12, though the joint interface tissue of comparative example 7 has Al respectively at the aluminium layer 3Fe based compound layer, but do not have Al in the steel side 5Fe 2The based compound layer.
Fig. 8 represent these examples 8 and comparative example 7, Al 5Fe 2Based compound layer and Al 3The average thickness of the two-layer total of Fe based compound layer is apart from the distribution of nugget central part distance.Fig. 8 represents that the average thickness of the total that this is two-layer is that the part of 0.5～10 μ m is in the scope of two dotted lines.
Example 8 shown in the black triangle is except that the blocked up nugget central part of average thickness, and the part of its average thickness 0.5～10 μ m extends to apart from the part of the distance 4000 μ m of nugget central part.When its joint interface plane earth in the aluminium side is represented, as shown in Figure 9.Promptly, the area of the part of example 8 its average thickness 0.5～10 μ m is 80% with respect to nugget at the area ratio of the shared area S of the in-plane on the composition surface of aluminium side, except that nugget central part and nugget circumference, almost with nugget (area S) approximate (repetition).
Relative therewith, the part of comparative example 7 its average thickness 0.5～10 μ m of the black circle expression in the below of example 8 is the part apart from the distance of nugget central part to 2000 μ m.When its joint interface plane earth in the aluminium side is represented, as shown in figure 10.That is, the area of the part of comparative example 7 its average thickness 0.5～10 μ m is 36% with respect to nugget at the area ratio of the shared area S of the in-plane on the composition surface of aluminium side, promptly just in nugget central part and circumference and nugget (area S) repetition.
So from above embodiment as can be known, the thickness that is used to obtain the interfacial reaction layer high bond strength, joint interface of the present invention of different material conjugant has the meaning of the limit of structure regulation.
Industrial utilizability
According to the present invention, when forming the different material conjugant of steel and aluminium by spot welding, shown in present technology, do not reuse other material, in addition, do not need to increase newly other operation, can utilize existing mash welder, therefore can realize that cost greatly reduces.
In addition, according to the present invention, can provide different material conjugant and spot welding method thereof, this different material conjugant can suppress contact corrosion and the decline of the bond strength that causes thus in the bond strength that improves when by spot welding steel and aluminium being engaged.
In addition, according to the present invention, the different material conjugant of steel and aluminium can be provided, this conjugant need not add the other material of clad material etc., also need not increase other operation, and need not carry out large change to steel side and aluminium side or spot welding side slat spare, just can realize the spot welding that bond strength is high.
Such conjugant is as the various structural elements particularly suitables of the transport field of automobile, rail truck etc., machine components, building structure etc.
Therefore, the present invention is the invention of the purposes of the different material conjugant of expansion steel and aluminium.

Claims (15)

1, the conjugant of a kind of steel and aluminium, its by spot welding with thickness of slab t 1Be steel and the thickness of slab t of 0.3～3.0mm 2Be that the fine aluminium material of 0.5～4.0mm or aluminium alloy material (below, fine aluminium material or aluminium alloy material are called " aluminium ") engage and form, it is characterized in that the nugget area in the junction surface is 20 * t 2 0.5～100 * t 2 0.5Mm 2, the thickness of interfacial reaction layer is that the area of 0.5～3 μ m part is 10 * t 2 0.5Mm 2More than, and the difference of center, junction surface and the thickness of the interfacial reaction layer of the point that leaves 1/4 distance that engages diameter from the center, junction surface is in the 5 μ m.
2, the conjugant of steel as claimed in claim 1 and aluminium, wherein, the maximum ga(u)ge of described interfacial reaction layer is the scope of 0.5～10 μ m.
3, a kind of electrode tip, it uses in the spot welding that is used to form claim 1 or 2 described conjugants, wherein, and is engaged the contacting with more than 2 o'clock or wire or planar carrying out of material.
4, electrode tip as claimed in claim 3, it uses in the spot welding that is used to form claim 1 or 2 described conjugants, and wherein, leading section forms dome type, and to be formed with diameter in the central authorities of described leading section be recess more than the 2mm.
5, the spot welding method of a kind of steel and aluminium is used to form claim 1 or 2 described conjugants, it is characterized in that, at least one side in the pair of electrodes head uses claim 3 or 4 described electrode tips.
6, the spot welding method of a kind of steel and aluminium is used to form claim 1 or 2 described conjugants, it is characterized in that, at least one side in described steel and the described aluminium is cooled to carry out below 5 ℃ spot welding.
7, the different material conjugant of a kind of steel and aluminium, its by spot welding with thickness of slab t 1Be steel and the thickness of slab t of 0.3～3.0mm 2The aluminium joint that is 0.5～4.0mm forms, it is characterized in that, between the composition surface each other of these engaged steel and aluminium, with default melting point is that 350～1000 ℃, average thickness are that the Zn of 3～19 μ m or the epithelium of Zn alloy or Al or Al alloy and the state of organic resin bonding agent epithelium or phosphate coating carry out spot welding, and the thickness of the interfacial reaction layer of the weld part of some postwelding is that the area of the part of 0.5～5 mu m range is 10 * t 2 0.5Mm 2More than.
8, the different material conjugant of steel as claimed in claim 7 and aluminium, wherein, the thickness of described interfacial reaction layer is that the area of part of the scope of 0.5～5 μ m is 50 * t 2 0.5Mm 2More than.
9, as the different material conjugant of claim 7 or 8 described steel and aluminium, wherein, described Zn epithelium is to contain the plating epithelium that implements the Zn more than the 88 quality % on the surface of steel side.
10, a kind of spot welding method of different material conjugant is thickness of slab t 1Be steel and the thickness of slab t of 0.3～3.0mm 2It is the spot welding method of different material conjugant of the aluminium of 0.5～4.0mm, it is characterized in that, has following operation: between the composition surface each other of these engaged steel and aluminium, with default melting point is 350～1000 ℃, average thickness is the Zn of 3～19 μ m or the metal or alloy epithelium of Al, carry out spot welding with the state of organic resin bonding agent epithelium or phosphate coating, and the point diameter with the electrode tip of aluminium side in this spot welding is decided to be more than the φ 7mm, and apply the plus-pressure that electrode tip brings, make the pass of front end radius of curvature R mm and plus-pressure WkN be (R * W) 1/3/ R＞0.05, and make 15 * t 2 0.5～30 * t 2 0.5Current flowing 100 * t of kA 2 0.5～1000 * t 2 0.5Msec, and, carry out spot welding by the current-mode that does not have the operation that flows through the electric current higher than this operation.
11, the spot welding method of different material conjugant as claimed in claim 10 wherein, makes described 15 * t 2 0.5～30 * t 2 0.5Current flowing 100 * t of kA 2 0.5～1000 * t 2 0.5In the operation after the operation of msec, by making circulation 1 * t 2 0.5～10 * t 2 0.5Electric current 100 * t of kA 2 0.5～1000 * t 2 0. 5The current-mode that the operation of msec exists carries out spot welding.
12, the different material conjugant of a kind of steel and aluminium, its by spot welding with thickness of slab t 1The average thickness that is 0.3～3.0mm, zinc coat is galvanized steel and the thickness of slab t of 3～19 μ m 2The aluminium joint that is 0.5～4.0mm forms, it is characterized in that,
In the joint interface of this different material conjugant,
Has Al in the steel side 5Fe 2The based compound layer has Al in the aluminium side 3Fe based compound layer,
The total average thickness of the nugget depth direction that this is two-layer be 0.5～10 μ m part, in the joint interface of aluminium side the shared total area of in-plane account for nugget in the joint interface of aluminium side in the ratio more than 50% of the shared area of in-plane, and
By SEM to described Al 5Fe 2Based compound layer and Al 3This two-layer total average thickness of the nugget depth direction of Fe based compound layer is in the joint interface of 0.5～10 μ m cross-section of partly carrying out,
Be contained in respectively this Zn-Fe based compound layer in two-layer the shared total area of cross-wise direction for this two-layer total average thickness part that is 0.5～10 μ m in the shared area of cross-wise direction and Zn-Fe based compound layer the ratio below 10% in the total of the shared total area of cross-wise direction.
13, the different material conjugant of steel as claimed in claim 12 and aluminium, wherein, the average diameter of described nugget in the joint interface of aluminium side is more than the 7mm, the Zn layer in the joint interface that joins with this nugget the shared total area of in-plane be nugget in the joint interface of aluminium side at below 30% of the shared area of in-plane.
14, as the different material conjugant of claim 12 or 13 described steel and aluminium, wherein, the minimum remaining thickness of slab of the described aluminium side in the different material junction surface is initial more than 50% of aluminium thickness of slab.
15, as the different material conjugant of each described steel and aluminium in the claim 12～14, wherein, the thickness ratio t of described steel and aluminium 1/ t 2Be more than 1.
CN2007800062345A 2006-02-23 2007-02-21 Joint product between steel product and aluminum material, spot welding method for the joint product, and electrode chip for use in the joint product Expired - Fee Related CN101405105B (en)

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