CN1104992C - Brazing aluminum alloy powder composition and brazing method using such powder composition - Google Patents
Brazing aluminum alloy powder composition and brazing method using such powder composition Download PDFInfo
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- CN1104992C CN1104992C CN98109401A CN98109401A CN1104992C CN 1104992 C CN1104992 C CN 1104992C CN 98109401 A CN98109401 A CN 98109401A CN 98109401 A CN98109401 A CN 98109401A CN 1104992 C CN1104992 C CN 1104992C
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Abstract
A brazing powder comprises a single powder or mixture powder that is composed of one or more type of elements consisting of Al, Si and Zn, having the composition of Al-Si-Zn hypereutectic alloy in terms of the total amount. The brazing powder comprises above 15% but up to 60% by weight of Si and 5% to 30% by weight of Zn. The brazing powder may also comprises a brazing flux, a binder resin and a solvent that are mixed with the above composition into a slurry form. A coating of the resulting mixture may be applied onto an object made of aluminum or aluminum alloy, such as mechanical assembly parts, etc., which is heated to allow the surface of the object to be melted, thereby forming a Zn-contained layer. The object is then brazed by soldering.
Description
Technical field
The present invention relates to a kind of brazing powder composition that is used to weld as article such as aluminium alloy or aluminum machine components, element, parts, and a kind ofly use this brazing powder composition to weld the method for this class part.A kind of possible application is to make heat exchanger assemblies.
Background technology
Connect the method for one or more aluminum or aluminum alloy system article as soldering, use pulverous cored solder, and cored solder is coated on the connection surface of article to be connected.Typical example is disclosed among the US3971501, brazing powder wherein can use, and be not subjected to or seldom be subjected to the restriction of the shape, form etc. at abutment, even can easily be applied to use in the prior art in all reluctant some article of any cored solder, as the object of complex configuration.In this respect, above-mentioned United States Patent (USP) causes extensive attention.
The disclosed brazing powder of above-mentioned patent has used the Al-Si eutectic alloy, and its fusing point is lower than the fusing point of the aluminum or aluminum alloy parts that connected by soldering.In order to improve the corrosion resistance at abutment, the brazing powder of a kind of Al-Si of containing eutectic alloy and a small amount of Zn is disclosed among another part patent documentation US5547517.Another patent US5251374 discloses the brazing powder of a kind of Al-Si of containing alloyed powder and Zn powder mixture.Brazing powder in US5547517 contains maximum 5% (weight) addings Zn wherein, and the brazing powder among the US5251374 contains the Zn that maximum 3% (weight) are mixed.Opposite with these two parts of patents is the flat 7-314177A of Japanese patent application (now open), and this application has proposed a kind of brazing powder by the Al-Si-Zn alloy composition that contains 10-50% (weight) Zn.The flat 7-88689A of another Japanese patent application discloses a kind of brazing composition that is not more than 20 weight portion Zn that contains.
Be to be noted that the fusing point of the Zn component in brazing composition is lower than the fusing point of Al-Si alloy compositions, thereby Zn can melt quickly in brazing process.Therefore, Zn tends to coating zone and flows to the zone that forms weld seam, and Zn enrichment herein.Therefore, Zn can not partly provide satisfied corrosion resistance to the coating zone that Zn has flowed away, because its Zn content is low.As another kind of method, can provide the brazing composition that contains more Zn.In this case, the content of Zn is high concentration greater than aequum in forming welded seam area.When this situation occurring, the effect of Zn is remarkable, and this may make Zn corrode weld seam and other.Therefore, corrosion resistance there is adverse effect.
As described, the brazing powder composition that contains Zn can not be put forward gratifying corrosion resistance.For example, in being installed on automobile and the heat exchanger that must satisfy the high corrosion-resistant needs, thermal spraying Zn is to form the Zn coating on the aluminium piece surface that connects in soldering in advance.Especially, among the open EP0140267A of european patent application a kind of technology that comprises form Zn sedimentary deposit is disclosed.But it should be noted that this technology comprises more step, has increased manufacturing cost.
In order between two parts with big space, to connect with method for welding, being connected between the pipe in the heat exchanger assemblies and the header box for example, perhaps form the connection of big weld seam for needs, the consumption that is used for the brazing powder of soldering obviously increases, therefore the also corresponding increase of brazing powder amount that is used to apply.For the coating that increases, need to apply several times, because the resulting coated weight of primary coating is limited (for example flow coat).Increase coating step like this and can increase manufacturing cost.Usually, brazing powder is valuable, so the increase of brazing powder consumption increases Material Cost.
The inventor of the present patent application has studied the problem relevant with the prior art brazing powder, and find when use comprises the brazing powder of hypereutectic Al-Si alloy, parent metal is etched (fusing) in brazing process, and the parent metal that is etched part provides the soldering effect with the brazing powder coating that applies.Afterwards, the inventor finds that the consumption of brazing powder can reduce, thereby applies number of times and also can reduce, and keeps good braze ability simultaneously.Two parts of international open WO94/29072 of disclosed patent application document PCT and Japan Patent disclose flat 8-511201A and disclose the cored solder composition that contains more Si, but unexposed this hypereutectic alloy can provide similar aforesaid result.
Be pointed out that also when the Al-Si hypereutectic alloy was used as cored solder, Si can crystallize out, the Si of crystallization can cause local corrosion or cause other corrosion that can form pit owing to cathodic process.This corrosion can reduce in the soldered joint point or apply corrosion resistance in the coating area of brazing powder.For avoiding this problem, must carry out a plurality of steps, to form described Zn coating.
Because these problems, conventional brazing powder is uneconomic.
In view of the above problems and for addressing these problems, an object of the present invention is to provide a kind of new brazing powder and a kind of improved method for welding, wherein the corrosion resistance of soldered joint point can improve, and does not need the too much step of any complexity.
Summary of the invention
Another object of the present invention provides a kind of new brazing powder and a kind of improved method, and wherein above-mentioned purpose can obtain and needn't increase the brazing powder consumption, and these soldering processes can carry out under the brazing powder consumption reducing.
The present invention includes a kind of brazed aluminum alloy powder composition.
Particularly, in first embodiment of this aluminium alloy brazing powder composition, it is made up of one or more powder material, this powder material is made up of the element that one or more are selected from Al, Si and Zn basically, and the total amount of described one or more powder material has the hypereutectic alloy composition of being made up of Al-Si-Zn.
In second embodiment of this brazed aluminum alloy powder composition, it comprises one or more powder material, wherein all the powder material basically by greater than 15 to forming up to 60% (weight) Si and 5-30% (weight) Zn.
In the 3rd embodiment of this brazed aluminum alloy powder composition, it comprises that one or more are selected from the powder material of Al-Si alloyed powder, Al-Si-Zn alloyed powder, Al-Zn alloyed powder, Si or Si alloyed powder and Zn or Zn alloyed powder.
In the 4th embodiment of this brazed aluminum alloy powder composition, it contains the different metal powder of two or more proportions, for the proportion ratio between the metal powder is 2 or bigger situation, and wherein the average particle size particle size of the metal powder that proportion is little is greater than the average particle size particle size of heavy metal powder.
In the 5th embodiment of this brazed aluminum alloy powder composition, it contains average particle size particle size is that the equal particle size of Si powder peace of 1-100 μ m is the Zn powder of 1-50 μ m, and wherein the average particle size particle size of Si powder is greater than Zn powder average particle size particle size.
In the 6th embodiment of this brazed aluminum alloy powder composition, it contains one or more powder material of being made up of Al-Si-Zn ternary hypereutectic alloy powder and Si powder mixture,
In the 7th embodiment of this brazed aluminum alloy powder composition, it contains one or more powder material, it is made up of hypereutectic powder of Al-Si-Zn ternary and Si powder mixture, and the composition of described Al-Si-Zn ternary hypereutectic alloy is the Al and the unavoidable impurities of 13-45% (weight) Si, 6-35% (weight) Zn and aequum.
In the 8th embodiment of this brazed aluminum alloy powder composition, it contains one or more powder material, it is made up of hypereutectic powder of Al-Si-Zn ternary and Si powder mixture, wherein the average particle size particle size of Al-Si-Zn ternary hypereutectic alloy powder is 5-100 μ m and Si powder average particle size particle size is 1-50 μ m, and the former average particle size particle size is greater than the latter's.
In the 9th embodiment of this brazed aluminum alloy powder composition, it contains one or more powder material, also contains the soldering auxiliary agent of adding.
The present invention also comprises a kind of method for welding, and this method uses any brazed aluminum alloy powder composition in the above-mentioned embodiment to carry out soldering.
Particularly, in an embodiment of this method, this method is used for soldering as analogs such as the aluminum or aluminum alloy part of article to be brazed, element, parts (below be called " aluminium article "), this method comprises that the coating with any above-mentioned brazing powder is coated in the surface of aluminum alloy article, with coating that applies and the aluminium article surface partial melting that scribbles this coating, the material of fusing is solidified, form the layer that contains Zn thus with the soldering of aluminium article and at this aluminium article surface.
In second embodiment of this method, also be included in coating brazed aluminum alloy powder coating and in the brazed aluminum alloy powder, add soldering auxiliary agent, resin glue and solvent before and it is mixed into the step of slurry form.
In the 3rd embodiment of this method, also be included in fine weldering and on the aluminium article surface, form the step that contains the Zn layer before.
The inventor finds can obviously to improve corrosion resistance by add Zn in the hypereutectic Al-Si alloy, and needn't increase the consumption of brazing powder, and this is with conventional to contain the Zn brazing powder different, and the Zn that routine contains in the Zn brazing powder does not have effect well to improving corrosion resistance.The present invention is based on this discovery.
It should be understood that this brazing powder must contain the Si as the scheduled volume of its total amount part, so that it becomes is hypereutectic.Because the eutectic point of Si is subjected to the influence of other constituent contents, this content is not well-determined.For example, containing specific Si greater than 15% (weight), that this brazing powder is become is hypereutectic.When this hypereutectic brazing powder contained excessive Si, Si tended to diffuse in brazing process in the aluminium article, and this has reduced the fusing point of these article and has made article part fusings (being etched) thus.The melt portions of article flows with the brazing powder coating of coating, fills the space of junction or forms weld seam.The part of these article can form the cored solder of the coating of part, and provides fine weldering required brazing powder amount together.Therefore, the brazing powder total amount that is used to apply can reduce.Yet be to be noted that if brazing powder contains the less Si that makes brazing powder eutectic or eutectic, the fusing effect of article can not be provided.
In order to provide above-mentioned fusing effect, Si content preferred 20% or more.Be more preferably 25% or more.
If brazing powder contains excessive Si, Si can more easily corrode the article depths, and removes some part from article, thereby makes these parts become extremely thin.This makes the intensity at abutment low.In addition, can corrode and cause perforation.This has caused relevant intensity and corrosion resistance problem.Especially, because brazing powder contains Zn, Zn is introduced the corrosion area of the article that caused by Si most ofly, also can promote corrosion function.If brazing powder contains 60% or more Si, the fusing point of this cored solder can be up to 1150 ℃.This can be difficult to make brazing powder.Reason for this reason, Si content be preferably 60% or below, more preferably 50% or below, most preferably 45% or below.
It should be noted, make the parent metal partial melting that scribbles brazing powder coating because hypereutectic powder works, the Zn that is contained in the brazing powder can more easily be diffused in the melt portions of parent metal.This increases the concentration of Zn in the parent metal part of fusing, and the result forms on brazing powder coated portion surface and contains the Zn layer, and this layer contains the Zn of high concentration, and little concentration difference is arranged.Be also noted that Zn diffuses into the parent metal more deeply from containing the Zn layer.The result is that the brazing powder coated portion comprises and contains Zn layer and Zn diffusion layer.This Zn diffusion layer can extend to certain degree of depth, is rich in Zn herein, is enough to resist any corrosion.This has eliminated the problem of conventional brazing powder, in conventional brazing powder, can obtain initial best corrosion resistance, but this reduces in time and gradually.
Should be noted also that the weld seam of the fusion of flowing with the form that forms weld seam also can corrode the new part of parent metal in flow process.Therefore, the Zn in the weld seam of fusion follows and reduces and diluted.Thereby the fusion weld seam that flows contains the Zn of low concentration, and the Zn concentration in weld seam is less than the Zn concentration in the brazing powder coated portion.According to prior art, the Zn concentration in weld seam is higher, and this easily is corroded weld seam.Final fin may be disassembled.According to the present invention, avoided this situation.When the Zn concentration in weldering is met was lower than Zn concentration in the brazing powder coated portion, it also can be as sacrificial anode, thereby improved the corrosion resistance of weld seam.
For the part that the brazing powder that contains q.s Zn applies, the corrosion type that is taken place is a general corrosion, can prevent that corrosion from developing into the depths.Therefore, the corrosion resistance of improvement can be provided.
Make part objects become the weld seam of fusion because soldering hypereutectic alloy powder acts on by the article of soldering, then the amount of fusion weld seam is greater than the amount of the powdery paints that applies.If Zn content is low, and when diluted, can not provide best corrosion resistance.Reason for this reason, total Zn amount is preferably more than 5%.
For same cause, the Zn amount is preferably 8% or more.More preferably 10% or more, most preferably be 15% or more.
If the Zn amount too much, the article of coating powders coating are etched at a relatively high speed, have reduced corrosion resistance.Therefore, preferably the total amount of Zn be 30% or below, more preferably 25% or below, by weight percentage.
The inventor has found can provide and use the single result who comes to the same thing that above-mentioned hypereutectic Al-Si-the Zn alloy is provided by the mixture of powders of two or more different elements and/or alloy composition.For total consumption, this mixture of powders can equal hypereutectic Al-Si-Zn alloy, and can use the content value of the Si and the Zn of above-mentioned qualification.This powder composition can comprise that two or more are selected from the material of the Al-Si alloy of powder type, Al-Si-Zn alloy, Al-Zn alloy, Si or Si alloy, Zn or Zn alloy.Be to be noted that the composition of metal or alloy and the blending ratio of various different materials all are hard-core, but can change when selecting specific metal or alloy from above-mentioned material.Importantly should equal to comprise the hypereutectic Al-Si-Zn alloy of any required composition, consider with total amount.For providing fusing effect and powder, the brazing powder coating that guarantees to apply to melt more equably.Desirable is that above-mentioned Al-Si alloy or Al-Si-Zn alloy are hypereutectic.Reason for this reason, when selecting above-mentioned material, desirable is to comprise at least a in these alloys.
It should be noted when Al-Si alloy or Al-Si-Zn alloy when being hypereutectic, can equal the determined Si content of above-mentioned Al-Si-Zn alloy at the Si content of these alloys in any.
Lower limit for Zn content, can equal the determined Zn content of hypereutectic Al-Si-Zn alloy, and to its upper limit, be preferably 30%, more preferably 20%, because when Zn content is higher when it dissolves the contained zinc of oxidation significantly, make it become zinc oxide, cause the solid solution capacity in the cored solder to reduce.This makes the production process difficulty.Can contain more Zn by Zn or the additional powder Zn amount that contains aequum.
Have from above-mentioned viewpoint and consider and the brazing powder composition of the composition determined can be by following method manufacturing, these methods are to utilize mechanical crushing method, water spray method, atomization, centrifugal atomization method and the materialization comminuting method of grinder etc. such as coagulation, thermal decomposition method, reducing process, sedimentation, displacement method, electrolysis, alloy decomposition method, organic solvent method etc.Then the gained powder is adjusted to suitable particle size (for example 1-100 μ m).If it is particle size is excessive, then easily inhomogeneous with the coating layer thickness of brazing powder composition coating.This makes product size produce too big change, and easily causes relatively poor braze ability.
In adjusting particle size, if this mix powder contains Si, the desirable particle size that is the Si powder particle size less than other element powders.This be because the Si powder corrode stronger by the aggressivity of soldering thing, and when the Si particle size hour, Si can diffuse in this mix powder equably, this can reduce the local erosion of Si powder to the soldering article.In this way, the erosion that causes of Si can be even and lighter.
Especially, when mixed powder comprised Si powder and other element powder, the average particle size particle size of other elements was preferably 5-100 μ m, and the average particle size particle size of Si powder is 1-50 μ m, and should be littler than the average particle size particle size of other powder.
More preferably, the average particle size particle size of other element powder is 10-70 μ m, and the average particle size particle size of Si powder is 1-30 μ m, and the average particle size particle size of Si powder is preferred less than the average particle size particle size of other powder.Most preferably, the average particle size particle size of other elements is 15-40 μ m, and the average particle size particle size of Si powder is less than the average particle size particle size of other powder.
Also be applicable to the mixture of forming by Al-Si-Zn ternary hypereutectic alloy powder and Si powder as above-mentioned determined average particle size particle size.
If in brazing powder composition, have the metal powder mixture with the form of mixtures of two or more powder, and the proportion of a kind of metal in this metal powder mixture is the twice of other metals or when bigger, preferably adjusts the particles of powder size to avoid following problems.Even multiple metal powder mixes with the preparation slurry mix, and fully mixed under stirring before applying, more specifically, the metal powder (as Zn) with big proportion easily precipitates, and the metal powder of little proportion (as Si) is easily floating, and this is because proportion changes according to the metal powder kind.Therefore, different metals is separated from one another, thus the easy layering of these metal powders, and vertically exist for inhomogeneous mode.If this mixture is coated in by on the soldering article, the little proportion metal powder that swims in the slurry mainly is coated in by on the soldering article.In addition, easily flow away when the proportion metal powder is on being coated in by the soldering article greatly, so little proportion metal powder (Si) mainly is retained on the coating surface.Therefore, be coated in by the composition of the powder composition on the soldering article surface different with predetermined composition as the starting powder mix ingredients, therefore then can not bring into play as expected desired effect of metal powder mixture such as corrosion resistance, this is disadvantageous.
Between metal powder, have in the metal powder mixture of 2 times or bigger difference of specific gravity, if these metal powders have different average particle size particle size, be the average particle size particle size of the average particle size particle size of little proportion metal powder, then can avoid above-mentioned phenomenon greater than big proportion metal powder.
It is 2 times or bigger situation that above-mentioned restriction is aimed at difference of specific gravity, its reason be if difference of specific gravity less than 2 times, the frequency that then this problem occurs is quite low.In this case, this restriction is not too necessary.Even, also may make this restriction below 2 times.If the difference of this particle size is stipulated greater than necessary degree, then owing to easily producing dense and coarse part is difficult to carry out even dispersion step.Therefore, preferably only difference of specific gravity is made above-mentioned restriction greater than 2 times or bigger metal powder.When the pre-adjustment metal dust made it have different average particle size particle size, relatively distinguishing between large scale and small size was feasible at least.Yet preferably, the average particle size particle size of little proportion metal powder is 1.1-4 with the relative ratio of the average particle size particle size (this dimension definitions is 1) of big proportion metal powder.This is because if ratio less than 1.1, then can not be brought into play the effect that addresses this problem fully, on the contrary, if greater than 4, then easily causes coarse and dense part.Reason for this reason, more preferably the relative ratio of these average particle size particle size is 1.2-3.
In addition, concerning particle size ratio, not only average particle size particle size is in above-mentioned scope, and actual particle size is also preferably in this scope.When containing proportion ratio in the composition less than 2 metal powder, for fear of coarse and dense part, the average particle size particle size relative ratio of two kinds of powder wherein is preferably less than 1.2, as mentioned above, the Si particle size preferably less than other proportion ratio less than the particle size of 2 metal powder.
Have proportion ratio and be 2 or bigger metal powder comprise Si powder and Zn powder.When the proportion of Si powder was compared with the proportion of Zn powder, the proportion of Zn was about 3 times of Si.According to the present invention, the average particle size particle size of Zn powder should be greater than the average particle size particle size of Si powder.In this case, preferably, the average particle size particle size of Si powder is 1-100 μ m, and the average particle size particle size of Zn powder is 1-50 μ m.The reason of particle size being made afore mentioned rules is to be difficult to prepare particle size less than 1 μ m or littler powder, and because too big particle size can cause the coating layer thickness that applies with the gained brazing composition inhomogeneous, the result causes product size to change greatly, easily causes ropy soldering.
When needs, can obtain brazing powder by in any single powder or mix powder, adding any suitable soldering auxiliary agent.Can select any proper mixture ratio.For example, the soldering auxiliary agent of 1-2 weight portion can be added in the Al alloy powder of the single of 20-1 weight portion or mixing.It should be understood that the present invention is not limited to above-mentioned specific mixing ratio.
Operable soldering auxiliary agent comprises fluoride such as KAlF
4, F
2AlF
55H
2O, K
3AlF
6, AlF
3, and chloride such as NaCl, KCl, LiCl, ZnCl
2But the present invention is not limited to this several auxiliary agents.
In the time of on the coating with any above-mentioned brazing powder is coated to by the soldering article, should comprise any suitable solvent and/or the adhesive that play cementation.Available solvent comprises water, alcohol (being preferably the aliphatic alcohol of 1-8 carbon atom) etc.
Available adhesive comprises bond powders preferably and to soldered joint point mass any binding agent of influence not, as carboxyl water-soluble polymer, acrylic resin, methacrylic resin etc.The mixing ratio of these solvents and binding agent can be selected as required.
Above-mentioned brazing powder composition is coated to by on the soldering article.In advance said composition is fully mixed and stirring together, be coated in then by on the soldering article.Mixing and stirring method are not particularly limited, still, are to use the mechanical mixing method of stirring vane as the method that exemplifies.Under this stirring, can prevent metal powder in the brazing powder composition uneven distribution and can make its even dispersion, no matter and the kind of metal dust what is, this is because adjusted the particle size of the metal dust of various different specific weights in advance.
The coating that obtains thus and contain any solvent and adhesive is coated in by on the soldering article.Available spraying process, spray process, flow coat method, rolling method, spread coating, dip coating etc. apply coating.It should be noted these methods that the invention is not restricted to.
Article with brazing powder welding of the present invention can comprise that at least one is to be made by aluminum or aluminum alloy.It should be noted that aluminium alloy is not limited to the alloy of special component.Be pointed out that also aluminum or aluminum alloy can any processing method make.Contain the Zn coating and can be formed on the aluminium article surface.Available any appropriate method forms this and contains the Zn coating, as metal spraying or cladding process and immersion plating.
But be coated in by the brazing powder composition air dry on the soldering article so that solvent seasoning.Consider that from the productivity ratio aspect said composition is preferably dry under heating.
After the brazing powder composition solidifies, will be welded thing by fibre according to a conventional method and carry out soldering.
Description of drawings
Fig. 1 is a perspective view of using heat exchanger assemblies of the present invention.
Fig. 2 is the schematic diagram that is illustrated in coating system used in the one embodiment of the invention.
Fig. 3 is the figure that is similar to Fig. 1, has represented the parts of heat exchanger assemblies enlargedly, and wherein a pipe has inserted in the header box before soldering.
Fig. 4 is the figure of similar Fig. 1, has represented the parts of heat exchanger assemblies enlargedly, wherein is welded in this header box after this Guan Zaiyu header box soldering.
Fig. 5 is the perspective view that carries out the parts of soldering test, and these parts assemble by the preferred embodiment of the invention.
Fig. 6 is the figure of similar Fig. 5, has illustrated the soldered joint point of parts enlargedly.
Fig. 7 is the figure of similar Fig. 5, and it is the amplification sectional view of parts soldered joint point.
Fig. 1 has shown the heat exchanger assemblies of using brazing composition of the present invention and method.In following description, there are some its possible application.Be understood that following explanation only is exemplary, the present invention is not limited to these application.
This heat exchanger assemblies comprises header box 1,1, pipe 2 ... 2, and waveform heat loss through radiation sheet 3 ... 3, these are all made by JIS A3003 aluminium alloy.This heat exchanger assemblies can be by assembling these individual components.When these independent elements of assembling, can provide corresponding each abutment of each interelement with brazing powder composition of the present invention and method, this describes in detail below.
The brazing powder composition all is prepared into the Al-Si-Zn hypereutectic alloy in advance, and atomized powder is broken into to hold and decides particle size then, is coated in joint afterwards.
The method of making this powder is not particularly limited, except atomizing, and available suitable method such as this powder of mechanical crushing manufactured.In addition, condition or the adjustment by adjusting the preparation method in advance by sieving every kind of particles of powder size is met the demands after the preparation.In this way, when the difference of specific gravity of these powder for example be twice or when bigger, prepared little proportion particles of powder size is bigger than big proportion particles of powder size.
If desired, with proper mixture ratio binding agent and solvent are sneaked in the powder with preparation brazing powder composition.
Can use coating system shown in Figure 2 that the brazing powder composition is coated on the pipe (by the soldering article) of heat exchanger assemblies.This coating system is equipped with a container that fills the brazing powder composition, to be introduced in this brazing powder composition by the soldering article for one, and the conveying device that these article are pulled out from the liquid surface of brazing powder composition, an and drying device that is used for dry soldering article surface that is installed in brazing powder composition liquid surface top again.
More specifically, export cylinder 11 and importing tube 21 are installed together, on export cylinder 11, be wound with aluminium alloy extruded flat tube (coated material) 10, import tube 21 and be used to reel and carry the extruding flat tube 10 of coming and apply the brazing powder composition from export cylinder 11 as pipe with coil form.Container 13 is installed in export cylinder 11 and imports between the tube 21, and the stirring vane 14a of agitating device 14 is installed in the container 13.
In addition, deflector roll 15 is installed between export cylinder 11 and the container 13 and is used for guiding extruding flat tube 10 into container 13, and deflector roll 16 is installed in and is used in the container 13 upwards carrying extruding flat tube 10, will manage 10 simultaneously and remain in the container 13.Above deflector roll 16, drier 18 is installed, flat tube 10 passes this drier 18 after passing little deflector roll 17, and little deflector roll 17,17 is used from deflector roll 19 1 flat tube 10 guiding is imported tube 21, supports flat tube 10 simultaneously.These deflector rolls 15,16,17 and 19 have been formed the conveying device of extruding flat tube 10 together.
The following describes the painting method that uses this coating system.
The stirring vane 14a of the brazing powder composition 25 usefulness mixers 14 in the container 13 of packing into stirs.No matter the difference of its proportion of various powder in this brazing powder composition and being evenly dispersed.At this state, the extruding flat tube of being carried by export cylinder 11 10 immerses in the brazing powder composition 25 along deflector roll 15,16, upwards pull out from the liquid surface of brazing powder composition 25 by pushing flat tube 10 subsequently, then brazing powder composition 25 is applied on flat tube 10 surfaces.By further flat tube 10 being passed roller 17,17 and after making coating equably on extruding flat tube 10 surfaces, the surface that scribbles brazing powder composition 25 is dry in 300-500 ℃ of thermal air current in drier 18, afterwards, to manage 10 and be wrapped in by deflector roll 19 and to import on the tube 21, thereby make soldering goods 20.
Pass through painting method, said composition can be coated on the surface of extruding flat tube 10 equably, in addition, can be coated on flat tube 10 surfaces as the brazing powder composition of various powders mixture, the constituent with design in advance is identical generally for this composition simultaneously.
This brazing powder composition applies and is fixed on the soldering goods 20 with its predetermined composition composition.Therefore, braze ability well can be got during soldering, in addition, required performance such as corrosion resistance can be reproduced utterly, because this depends on the constituent of brazing powder composition, or even after the soldering.
Once more soldering goods 20 are got around from roller, and assemble (not shown) with header box as pipe fitting.
Expressed the pipe 2 that has brazing powder 25 coatings on its surface and be inserted in the hole 4 of header box 1 in Fig. 3, the surface of this header box 1 also has brazing powder 25 coatings.
The assembly that will comprise the abutment of all as above handling then heats under suitable temperature in appropriate atmosphere, makes brazing powder 25 fusings of these junction points.Preferably in 580 ℃ of-620 ℃ of scopes, heat.At 580 ℃ or when following, powder 25 and all can not melted fully by self part such as soldering article such as header box (jointly being called " article ") then can not be realized welding.When being higher than 620 ℃, then can produce the erosion of certain degree.In this respect, the said temperature scope is desirable.This assembly preferably keeps in this temperature range 1-10 minute time of heating.
Fig. 4 has shown with the header box 1 of brazing powder 25 welding of the present invention and pipe 2.As seen from Figure 4, this abutment comprises the weld seam 6 that forms thus of q.s.Formed a solidification layer 1a and a 2a respectively on the surface separately that is coated with brazing powder 25 coatings of header box 1 and pipe 2, this solidification layer contains coating powders 25, and this powder 25 once was melted and had solidified now.
The part Zn that is contained in the above-mentioned coating powders 25 can enter in the above-mentioned abutment, and remainder is present among the solidification layer 1a and 2a that is formed by coating powders 25, and has suitable and equally distributed concentration.This can alleviate the general corrosion on solidification layer surface separately, the crystallization that easily produces Si, and this can prevent to form local corrosion or other corrosion of spot corrosion.The result has improved corrosion resistance.It should be noted that the concentration that is contained in the part Zn in the abutment separately is lower than the concentration of part Zn in coating.So can not observe the Zn partial coagulation.
It should be understood that parent metal can partly melt and enter in the weld seam, and the thickness of parent metal is reduced when applying powder of the present invention.Therefore, the present invention is particularly suitable for having the metallic plate of specific thicknesses, and for example thickness is 0.5mm or thicker.What however, it should be understood that is that the present invention is not limited to above-mentioned those specific metallic plates.Also have, the invention is not restricted to above-mentioned application, also can be used for other application.
Carry out following test to estimate the effect of following different embodiments of the present invention.
Embodiment
Embodiment 1
As shown in table 1, according to the invention provides several Al alloy powder samples, each all contains the Si and the Zn (their maximum particle size is 75 μ m, and average particle size particle size is 20-30 μ m) of different amounts.In addition, soldering auxiliary agent of forming by fluoride and the adhesive of forming by acrylic resin are also provided.By 10: 1: 1 weight ratio the three is mixed then and obtain brazing powder.For comparing with these samples of the present invention, non-sample of the present invention is provided, they contain Al-Si alloy or Al-Si-Zn alloy.
Use said sample to weld as shown in Figure 5 two metal parts with the configuration of falling T, method is that the coating with varying number is coated in the space between this two position, carries out this test to check how this space is filled.Concrete, metal parts 30 horizontal positioned, these parts are made by JIS A 3003 aluminium alloys as the butt welding metal, and it is of a size of the 30mm height, and 60mm is wide, and 1.5mm is thick.Another metal parts 31 also is to be made by the JISA3003 alloy as parent metal, high 30mm, wide 50mm, thick 1.0mm.With flow coat method the coating of sample of the present invention is coated in the both sides of parent metal 31 then.Subsequently, parent metal parts 31 are pushed down the T configuration be placed on the butt welding metal parts 30, the bar-shaped pad rod 32 of a diameter 2.0mm is crossed an end that is placed on metal parts 30.This pad rod 32 provides a little space 33 between butt welding metal parts 30 and parent metal parts 31.
With butt welding metal parts 30, parent metal parts 31 and pad rod 32 were in 600 ℃ of heating 5 minutes, and soldering under argon gas atmosphere.In brazing process, make the coating of coating and the parent metal and the butt welding metal molten of part, until length (L) little space 33 is filled along 30mm.Obtain soldered joint point 34 thus.At last, detect the coated brazing powder amount of soldering that is actually used in.Shown in Fig. 6 and 7, also detect the maximum depth of erosion (D) in brazing area.The results are shown in Table 1.
Then prepared assembly is carried out the CASS test, the test that wherein will contain the 0.26g/l copper chloride under 50 ℃ test temperature sprays to this assembly (480 hours) continuously with ackd salt (heat is to 50 ℃).Afterwards, check the corrosion depth of brazing powder coating zone, also detect corrosion type.Also detect weld seam to determine corrosion type.The result also lists in the table 1.
Table 1
| Test piece number (Test pc No.) | Brazing powder * | Coating content (g/m 2) | Be coated with the number of plies | Use the effect of soldering | The state of corrosion weld seam |
| Si wt％ Zn wt％ | Maximum depth of erosion (μ m) maximum corrosion depth (μ m) corrosion type | ||||
| 1234 samples 56789 10 11 12 of the | 16 5 16 30 25 10 25 16 25 25 30 20 40 22 45 24 50 16 50 25 60 5 60 30 | 200 200 125 125 125 100 70 65 60 60 55 55 | 2 2 1 1 1 1 1 1 1 1 1 1 | 160 150 comprehensive 160 90 comprehensive 180 120 comprehensive 180 80 comprehensive 180 80 comprehensive 200 70 comprehensive 230 76 comprehensive 250 72 comprehensive 270 80 comprehensive 270 80 comprehensive 300 150 comprehensive 300 90 is comprehensive | ◎ △ ○ ○ ○ ○ ○ ○ ○ ○ ◎ △ |
| 12 non-samples 345 of the present invention | 10 - 10 20 20 3 20 40 65 - | 350 350 150 150 50 | 3 3 1 1 1 | 100 350 spot corrosion, 100 70 comprehensive 180 300 spot corrosion, 180 250 comprehensive 400 400 spot corrosion | ◎ × ◎ × ◎ |
*Surplus: inevitable impurity and aluminium
(1) corrosion test: CASS (CASS test)
(2) state of corrosion weld seam
◎: do not have corrosion zero: slight △: corrosion but do not remove weld seam
*: seriously corroded and weld seam are removed
Can be clear that by table 1, for the sample that contains greater than 15% (weight) Si, use less to be coated with the soldered joint point that the number of plies and every layer of more a spot of powder of usefulness can provide (space fill better), and the parent metal amount (maximum depth of erosion) of fusing can be controlled to moderate.Especially, for other samples that contain 20-30% (weight) Si, maximum depth of erosion is quite shallow, and the soldered joint that can provide point.
Can find out that from table 1 for the sample that contains greater than 60% (weight) Si, maximum depth of erosion is bigger, it is darker to mean that parent metal is etched.Have good above-mentioned performance and do not contain or contain other samples of seldom measuring Zn for some, find that parent metal has the spot corrosion that corrosion produces, and means the darker of corrosion.
For other samples that contain moderate quatity Zn, corrosion depth shoals significantly.And for other samples that contain too many Zn, as contain greater than 30%Zn, general corrosion has taken place and has corroded to the depths of parent metal in them.
Will be understood that by above-mentioned explanation use contains the Si of moderate and the brazing powder of Zn can provide good corrosion resistance to the coating of coating with to the weld seam that forms.The soldered joint point that uses less powder also can provide.
In this embodiment, preparation has the Al-Si-Zn ternary alloy three-partalloy powder of the atomizing of composition shown in the table 2 and average particle size particle size, and it comprises fusion Al.This Al-Si-Zn ternary alloy three-partalloy also comprises the pure Si powder with average particle size particle size shown in the table 2.Obtain several brazing powder sample of the present invention thus.Label is that each of these samples of 1-10 all comprises the Si and the Zn of total amount respectively, and their ratio is listed in the table 2.These samples are called " sample of the present invention ".In order to compare, also prepare non-sample 1-5 of the present invention with these samples.These samples are called " non-sample of the present invention ".
The sample non-of the present invention that also provides another kind to be called " prior art sample ", it contains Al-Si bianry alloy powder.Soldering auxiliary agent and 1 part of binding agent of in every kind of sample 1-10 of the present invention of 10 weight portions, non-sample 1-5 of the present invention and prior art sample, adding 1 part then, all by weight.They are mixed into the slurry filling form.It should be noted that each among the non-sample 1-5 of the present invention all has the composition ratio of each element, any one of these ratios is not that the present invention limits.
As the step of embodiment 1, each sample all is coated on the article of testing.Carry out soldering then under the same conditions.The following SWAAT that carries out tests.The testing liquid that will comprise artificial sea water and acetate is ejected into this article last 30 minute in 50 ℃.Stop after 30 minutes spraying, article were placed 30 minutes under wet atmosphere.Same steps as is repeated 20 days.When off-test, the results are shown in Table 2 to detect corrosion depth and corrosion type.
Table 2
*: non-the present invention
| Test piece number (Test pc No.) | The mixing ratio of Al-Si-Zn powder and Si powder (wt%) | The amount of element (total amount) in the mix powder | Average particle size particle size (μ m) | Coating content (g/m 2) | Maximum depth of erosion (mm) | Corrosion type | Corrosion depth (μ m) |
| Si(wt％) Zn(wt％) | Al-Si-Zn Si | ||||||
| 1234 samples 56789 10 of the present invention | Al-13%Si-20%Zn powder: Si powder=40: 1 Al-13%Si-20%Zn powder: Si powder=11: 1 Al-13%Si-20%Zn powder: Si powder=6: 1 Al-20%Si-15%Zn powder: Si powder=7: 1 Al-20%Si-15%Zn powder: Si powder=4: 1 Al-20%Si-15%Zn powder: Si powder=3: 1 Al-20%Si-20%Zn powder: Si powder=7: 1 Al-30%Si-20%Zn powder: Si powder=4: 1 Al-30%Si-20%Zn powder: Si powder=3: 1 Al-40%Si-30%Zn powder: Si powder=3: 1 | 15.1 20 20 18 25 17 30 13 35 12 40 11 30 18 44 16 48 15 55 23 | 50 30 50 30 70 40 70 50 30 20 30 20 40 20 80 30 80 30 80 50 | 200 150 120 100 80 70 100 68 65 60 | 0.15 0.16 0.18 0.20 0.21 0.23 0.20 0.24 0.25 0.26 | Comprehensively | 95 90 90 90 90 90 90 90 90 100 |
| 12 non-the present invention's 3 samples 456 | Al-20%Si-15%Zn powder: Si powder=3: 1 Al-50%Si-30%Zn powder: Si powder=3: 1 Al-7.5%Si-20%Zn powder: Si powder=36: 1 Al-20%Si-3%Zn powder: Si powder=7: 1 Al-20%Si-40%Zn powder: Si powder=7: 1 Al-7.5%Si powder (prior art) | 30 13 *63 23 *10 19 40 *2 30 35 *7.5 - | 50 *100 80 50 70 50 30 20 70 50 50 - | 100 50 250 70 100 350 | 0.40 0.40 0.14 0.23 0.20 0.14 | The comprehensive spot corrosion of spot corrosion comprehensively | 90 100 90 350 350 350 |
The result of table 2 shows that concerning the abutment that obtains with each the institute's soldering among the sample 1-10 of the present invention, coated coating content and depth of erosion are significantly less than coating content and the depth of erosion with the contact point of No. 6 institutes of prior art sample soldering.Show that also according to sample 1-10 of the present invention, the abutment shows as general corrosion, and the sample of prior art, the coating consumption is more, and the abutment of soldering shows the corrosion type that produces spot corrosion thus, this means that this abutment is easier to be corroded.Show that also each any performance that non-the present invention tries among the 1-5 is all very poor, this is undesirable, these performances such as coating consumption, maximum depth of erosion and corrosion resistance.The weld seam that forms with every kind of sample of the present invention all has good corrosion resistance, as the weld seam in last embodiment.
Embodiment 3
Be prepared as follows brazing powder, at first prepare Al-Si powder (75wt% Al and 25wt%Si) with mechanical crushing method, the average particle size particle size of this powder is 40 μ m (actual particle size is 5-60 μ m), and prepare the Zn powder that average particle size particle size is 20 μ m (actual particle size is 3-35 μ m) with atomization, prepare fluoride-based soldering auxiliary agent, acrylic resin adhesive, isopropanol solvent subsequently, and with the Al-Si powder: Zn powder: auxiliary agent: adhesive: solvent is 4: 1: 10: 2: 25 weight ratio mixes them.
The brazing powder composition is placed the container 13 of the coating system of above-mentioned embodiment, use this coating system with this brazing powder composition with 20g/m
2Average speed be coated in by JIS A3003 aluminium alloy make as on the extruding flat tube surface of pipe.In order to compare, in addition, use the coating system of another same structure will contrast the brazing powder composition under the same conditions and be coated on the identical flat tube, difference is that the Al-Si alloyed powder in this contrast brazing powder composition and the average particle size particle size of Zn powder are 40 μ m.
After this brazing powder composition dries, will be fixed on the lip-deep brazing powder composition of flat tube and strip down, analyze its composition.The result is, the composition of the brazing powder composition of the present invention after the coating have almost with apply before the identical weight ratio of weight ratio, i.e. (Al-Si): Zn=4: 1; And the composition of the contrast brazing powder composition after applying has (Al-Si): Zn=8: 1 weight ratio, this amount that shows the Zn with big relatively proportion have reduced, and the result is that composition ratio is different with the ratio before the coating significantly.
Can draw from above stated specification, comprise that the brazed aluminum alloy powder composition of the present invention that contains the Zn hypereutectic alloy provides a superiority, it makes and contains the containing on the coating that the Zn layer is formed on brazing powder of appropriate amount Zn.Having the corrosion type that takes place on the article surface of this coating is general corrosion, and this prevents to corrode the depths of developing into article.Therefore, can provide good corrosion resistance.Compare with the powder of prior art, the amount of coated brazing powder can obviously reduce.Available braze ability is equal to or greater than the braze ability that the prior art powder is provided.Therefore, the present invention has industrial applicibility.
Although describe the present invention with reference to some particularly preferred embodiment, it should be understood that under the condition that does not break away from the spirit and scope of the present invention and can make various variations and change.
Claims (6)
1. the powder composition of a brazed aluminum alloy, it is characterized in that containing Al, Si or a kind of powder material of Zn or the mixed-powder material of Al, Si and Zn of forming Al-Si-Zn hypereutectic alloy composition, wherein Si amount in powder composition weight greater than 15 to up to 60% weight, be 5-30% weight with the Zn amount in powder composition weight, and the Al of aequum.
2. the powder composition of the brazed aluminum alloy of claim 1, wherein it comprises that one or more are selected from the powder material of Al-Si alloyed powder, Al-Si-Zn alloyed powder, Al-Zn alloyed powder, Si powder and Zn powder.
3. the powder composition of claim 1 or 2 brazed aluminum alloy, wherein this powder composition contains the powder of the different mixing of proportion, for the proportion ratio between the metal powder is 2 or bigger situation, and the average particle size particle size of the metal powder of its medium and small proportion is greater than the average particle size particle size of the metal powder of big proportion.
4. the powder composition of the brazed aluminum alloy of claim 3, the equal particle size of Si powder peace that contains average particle size particle size and be 1-100 μ m is the Zn powder of 1-50 μ m, wherein the average particle size particle size of Si powder is greater than the average particle size particle size of Zn powder.
5. the powder composition of the brazed aluminum alloy of claim 1, wherein it contains a kind of mixture of powders of being made up of Al-Si-Zn ternary hypereutectic alloy powder and Si powder, and described Al-Si-Zn ternary hypereutectic alloy powder is made up of the Al of 13-45% weight Si, 6-35% weight Zn and aequum and unavoidable impurities; Wherein said Al-Si-Zn ternary hypereutectic alloy powder has the average particle size particle size of 5-100 μ m, described Si powder has the average particle size particle size of 1-50 μ m, and the average particle size particle size of described Al-Si-Zn ternary hypereutectic alloy powder is relatively greater than the average particle size particle size of described Si powder.
6. the powder composition of each brazed aluminum alloy among the claim 1-5 also contains the soldering auxiliary agent of the powder type of one or more types.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP75358/1997 | 1997-03-27 | ||
| JP7535897 | 1997-03-27 | ||
| JP75358/97 | 1997-03-27 | ||
| JP296322/97 | 1997-10-14 | ||
| JP296322/1997 | 1997-10-14 | ||
| JP29632297A JP3212927B2 (en) | 1996-12-14 | 1997-10-14 | Aluminum alloy powder brazing material and brazing method using the same |
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| CN1211484A CN1211484A (en) | 1999-03-24 |
| CN1104992C true CN1104992C (en) | 2003-04-09 |
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| US20040251008A1 (en) * | 2003-05-30 | 2004-12-16 | O'neill Patrick S. | Method for making brazed heat exchanger and apparatus |
| CN100453243C (en) * | 2006-12-28 | 2009-01-21 | 山东建筑大学 | Grey cast iron welding process and self-fluxing homogeneous welding powder |
| MX2012002899A (en) | 2009-11-27 | 2012-04-02 | Nissan Motor | Si ALLOY NEGATIVE ELECTRODE ACTIVE MATERIAL FOR ELECTRICAL DEVICE. |
| CN105149597B (en) * | 2015-08-11 | 2018-09-11 | 利宝地工程有限公司 | The reparation of metal or alloy component or connecting method and component that is repaired or being coupled |
| JP6294537B1 (en) | 2017-01-20 | 2018-03-14 | 三菱アルミニウム株式会社 | Mixed composition paint for brazing |
| CN113369618B (en) * | 2021-07-08 | 2022-09-09 | 烟台市固光焊接材料有限责任公司 | Brazing process of ultrathin liquid cooling plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100048A (en) * | 1991-01-25 | 1992-03-31 | Alcan International Limited | Method of brazing aluminum |
| JPH0788689A (en) * | 1993-09-21 | 1995-04-04 | Mitsubishi Alum Co Ltd | Composition for brazing |
| US5547517A (en) * | 1991-12-27 | 1996-08-20 | Showa Aluminum Corporation | Brazing agent and a brazing sheet both comprising an aluminum alloy containing a flux |
| JPH1014177A (en) * | 1996-03-25 | 1998-01-16 | Xerox Corp | Motor |
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1998
- 1998-03-27 CN CN98109401A patent/CN1104992C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100048A (en) * | 1991-01-25 | 1992-03-31 | Alcan International Limited | Method of brazing aluminum |
| US5547517A (en) * | 1991-12-27 | 1996-08-20 | Showa Aluminum Corporation | Brazing agent and a brazing sheet both comprising an aluminum alloy containing a flux |
| JPH0788689A (en) * | 1993-09-21 | 1995-04-04 | Mitsubishi Alum Co Ltd | Composition for brazing |
| JPH1014177A (en) * | 1996-03-25 | 1998-01-16 | Xerox Corp | Motor |
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