CN102471836A - Highly corrosion-resistant aluminum alloy brazing sheet, process for production of the brazing sheet, and highly corrosion-resistant heat exchanger equipped with the brazing sheet - Google Patents
Highly corrosion-resistant aluminum alloy brazing sheet, process for production of the brazing sheet, and highly corrosion-resistant heat exchanger equipped with the brazing sheet Download PDFInfo
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- CN102471836A CN102471836A CN2010800283994A CN201080028399A CN102471836A CN 102471836 A CN102471836 A CN 102471836A CN 2010800283994 A CN2010800283994 A CN 2010800283994A CN 201080028399 A CN201080028399 A CN 201080028399A CN 102471836 A CN102471836 A CN 102471836A
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Abstract
Disclosed are: an aluminum alloy brazing sheet which does not undergo the diffusion of a molten brazing filler material into a core material during brazing and therefore has good brazing properties, and has excellent corrosion resistance against an exhaust gas condensate after brazing; a process for producing the aluminum alloy brazing sheet; and a highly corrosion-resistant heat exchanger utilizing the aluminum alloy brazing sheet. Specifically disclosed is a highly corrosion-resistant aluminum alloy brazing sheet which comprises: an aluminum alloy core material; a galvanic anode material that is cladded on one surface of the core material; and an Al-Si-based alloy brazing filler material that is cladded on the other surface of the core material.; The brazing sheet is characterized in that the galvanic anode material contains 2.5-7.0 mass% of Si, 1.0-5.5 mass% of Zn and 0.05-1.0 mass% of Fe, with the remainder being Al and unavoidable impurities. The brazing sheet is also characterized in that the clad thickness of the galvanic anode material is 25-80 [mu]m.
Description
Technical field
The present invention relates to high anti-corrosion aluminium alloy brazing sheet material and method of manufacture thereof; And the high anti-corrosion heat exchanger that uses it; At length say; Relate to high anti-corrosion aluminium alloy brazing sheet material and method of manufacture thereof that the passage constituent material as the high temperature compressed air of heat exchangers such as side cooler or refrigeration agent uses, and the high anti-corrosion heat exchanger that uses it.
Background technology
Duraluminum possesses light weight and high heat conductivity, can realize high anti-corrosion through suitable processing, and therefore, be used for automobile and use heat exchanger, for example, scatterer, condensing surface, vaporizer, well heater, side cooler etc.As the tubing of automobile with heat exchanger; Use is that alloy is as heartwood with the Al-Mn of 3003 alloys etc.; On one side, coating Al-Si is that alloy brazed material or Al-Zn are two layers of packaging material of the sacrificial anode material of alloy, or further on another side, coats three layers of packaging material etc. that Al-Si is the alloy brazed material.Usually the radiator element of this packaging material of combination and corrugation passes through soldered joint under the high temperature about 600 ℃.Radiator element is bonded on occasion in the tubing that uses packaging material in making, need invest the soldering function in the inner face side of tubing, the both sides of exterior side.
Have corrosive liquid if in the tubing of this heat exchanger, exist, then exist because of origination point corrosion causing tubing connects, or because of homogeneous corrosion causing tubing thickness reduces, compressive strength reduces, the tubing disruptive is dangerous.Its result exists air or water coolant, the refrigeration agent of circulating inside that the danger of leaking takes place.In the past; What is called is present in neutral or weakly acidic liquid such as interior the having of the tubing water coolant that corrosive liquid is mover or the refrigeration agent of water cooler; Under this corrosive environment; In order to satisfy outside soldering function and tubing solidity to corrosion two aspects, the Al-Si that uses covering to add Zn is the soldering sheet material of braze material, constitutes heat exchanger.
But, in recent years,, be purpose with the specific fuel consumption that improves automobile in order to satisfy the exhaust restriction of the EU and the U.S., the system of gas through heat exchanger discharged in exploitation.Discharge gas through occasion in the tubing of heat exchanger, if cooling tubing internal cause heat exchange and cooling off, comprise the water of condensation of discharging gas ingredients (below, be called " exhaust water of condensation ") because of dewfall generates.This water of condensation is the strongly-acid occasion, and the Al-Si that such in the past use covering adds Zn is the soldering sheet material of braze material, and solidity to corrosion is insufficient.
It is very big that the corrosion speed of aluminium is influenced by the pH value, and the pH value is low more, and corrosion speed increases.If according to pH-Electric Potential value figure, generally speaking, in the pH value below 4, Al
3+Stable, be difficult to use as the corrosion-resistant material of aluminium.Again, the Al-Si that the soldering sheet surface is added Zn is the braze material occasion, and the Si particle on top layer becomes negative electrode, and the dissolving of Zn promotion Al, and corrosion speed further increases.Have, if having chloride ion in the solution, then chloride ion destroys passive film again, the origination point corrosion.The exhaust water of condensation contains chloride ion, therefore, has the character that causes pitting attack.That is, discharge gas, need to suppress, simultaneously, make tubing also have the corrosion protection of sacrifice effect, need the generation/growth of inhibition point corrosive because of the low corrosion that causes of pH value through occasion in the tubing of heat exchanger.The composition of exhaust water of condensation is different because of various condition, and becoming the pH value sometimes is the strongly-acid below 3, and becoming chloride ion concentration sometimes becomes more than the 5ppm with bringing out property of pitting attack.
For making it have the soldering function on the tubing two sides on the one hand; Making its Al-Si that has than such in the past covering interpolation Zn on the one hand is the high corrosion proof problem of soldering sheet material of braze material; Use the Si addition than Duoed 1.5～6.0% material in the past; As sacrificial anode material, the soldering sheet material of its covering on heartwood is documented in the patent documentation 1～3.Like this, in sacrificial anode material, add the occasion of the Si of volume, during the soldering heating; The fusion sacrificial anode material a part, play as the braze material effect, can with bare radiator (bare fin) soldering; On the other hand; A part keeps solid state remaining, and therefore, the Al-Si that can obtain than such in the past interpolation Zn is the high solidity to corrosion of braze material.But; By the soldering sheet material that above-mentioned technology obtains,, imagine scatterer, condensing surface, the mobile neutrality of vaporizer that kind or the device of weakly acidic liquid as the corrosive environment of tubing inside; Under the corrosive environment that the extremely low liquid of the such pH value of exhaust water of condensation exists, solidity to corrosion is insufficient.
That is, in technology shown in the patent documentation 1, though ability soldering sacrificial anode material and interior radiator element,, about the Zn addition, only be set at below 7%, show the opinion that limits its addition.As stated, Zn promotes the fusion of aluminium, therefore; In order to suppress corrosion speed, the Zn addition must strictly be limited, still; About this problem, be not familiar with fully, place the solution countermeasure of the low liquid occasion problem of the such pH value of exhaust water of condensation for tubing; Have no record, also have no hint.
On the other hand, in technology shown in the patent documentation 2,, in sacrificial anode material, contain 15000～40000/mm of Si particle of 0.1～1.0 μ m in order to improve the solderability of sacrificial anode material
2As stated, the Si particle becomes negative electrode in corrosion reaction, makes corrosion speed increase.0.1 the Si particle of～1.0 μ m fuses when soldering is heated; Become braze material; Can not make the corrosion speed of the sacrificial anode material that fusion is remaining increase; But the Si particle more than the 1.0 μ m is also remaining after the soldering heating in fusing remaining sacrificial anode material, makes corrosion speed increase.Therefore, the Si particle for more than the 1.0 μ m need limit its number density, still, in the technology of patent documentation 2, has no consideration for this situation.And be not recited as yet obtain the method for manufacture of number density of fixed Si particle.
In patent documentation 3, size and number density about the Si particle have write up, and still, it relates to the distribution of fine particle, and the restriction about the number density of the thick Si particle more than the 1.0 μ m has no record, also has no hint.
Patent documentation 1: TOHKEMY 2008-188616 communique
Patent documentation 2: TOHKEMY 2000-309837 communique
Patent documentation 3: TOHKEMY 2004-156108 communique
As stated, for example the waste gas of automobile needs to suppress because of the low corrosion that causes of pH value through the inner occasion of the tubing of heat exchanger, simultaneously, also need make tubing have the corrosion protection of sacrifice effect, the generation/growth of inhibition point corrosive.In technology in the past, be difficult to obtain to stand the solidity to corrosion of under this corrosive environment, using.
Summary of the invention
The present invention puts forward in order to address the above problem a little; The objective of the invention is to; Be provided at molten solder when having soldering in the aluminium alloy brazing sheet material and after the good solderability of heartwood diffusion and soldering, do not have excellent corrosion proof aluminium alloy brazing sheet material for the exhaust water of condensation; Especially can use suitably as the aluminium alloy brazing sheet material of automobile with the fluid channel constituent material of heat exchanger, and method of manufacture.
The inventor furthers investigate the result repeatedly in order to solve above-mentioned problem; Discovery can be so that sacrificial anode material has specific alloy composition; Make Si content, Zn content and cladding thickness satisfy characteristic relation, again, through use have fixed Si particle have the clad material of density; Can solve this problem, accomplish the present invention.
Specifically; The high anti-corrosion aluminium alloy brazing sheet material of claim 1 of the present invention comprises the heartwood of duraluminum; The sacrificial anode material of covering on the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be the braze material of alloy, it is characterized in that:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of this sacrificial anode material is 25～80 μ m.
The high anti-corrosion aluminium alloy brazing sheet material of claim 2 of the present invention comprises the heartwood of duraluminum, and covering is characterized in that at the sacrificial anode material on the two sides of this heartwood:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of above-mentioned each sacrificial anode material is 25～80 μ m.
In claim 3 of the present invention, above-mentioned sacrificial anode material further contain from Ti:0.05～0.3 quality %, Zr:0.05～0.3 quality %, Cr:0.05～0.3 quality % and V:0.05～0.3 quality % select at least a.
In claim 4 of the present invention, the Si content of above-mentioned sacrificial anode material is made as Sic quality %, and Zn content is made as Znc quality %, and cladding thickness is made as T μ m, is determined the value of X by following formula (1):
X＝(1.1-0.1×Sic)×Znc×T (1)
Above-mentioned X value is below 150.
In claim 5 of the present invention, in the matrix of above-mentioned sacrificial anode material, the density that exists with Si particle of the above suitable circular diameter of 1.0 μ m is 5000/mm
2Below, and the density that exists with Si particle of the above suitable circular diameter of 5.0 μ m is 500/mm
2Below.
In claim 6 of the present invention, high anti-corrosion aluminium alloy brazing sheet material is after the soldering heating, and the average crystallite particle diameter of the thickness direction of above-mentioned sacrificial anode material is more than 80% of cladding thickness of this sacrificial anode material.
In claim 7 of the present invention, use the tubing of the heat exchanger that flows into as automobile exhaust gas.
The high anti-corrosion heat exchanger of claim 8 of the present invention is characterised in that:
Use the described high anti-corrosion aluminium alloy brazing of claim 7 sheet material; As the tubing that sacrificial anode material is made as inner face; At this sacrificial anode material face configuration bare radiator, radiator element in constituting, above-mentioned sacrificial anode material of soldered joint and bare radiator form.
The method of manufacture of the high anti-corrosion aluminium alloy brazing sheet material of claim 9 of the present invention is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-7, it is characterized in that:
The manufacturing process of above-mentioned sacrificial anode material comprises casting process, heating process, and hot-rolled process;
In casting process, the Si content Sic quality % of the speed of cooling V of the ingot bar of above-mentioned sacrificial anode material ℃/s and sacrificial anode material satisfies following formula (2):
V≥Sic/5(2)
In the heating process behind casting process, with the ingot bar of sacrificial anode material 300～500 ℃ down heating kept 1～10 hour;
In the hot-rolled process after heating process, the temperature of the sacrificial anode material during with end is made as below 350 ℃.
The method of manufacture of the high anti-corrosion aluminium alloy brazing sheet material of claim 10 of the present invention is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-7, it is characterized in that, comprises following operation:
Layer closes operation, and sacrificial anode material, duraluminum heartwood, the Al-Si of the said method manufacturing of combination claim 9 are the braze material of alloy, as laminate;
Heating process after layer closes operation, heats maintenance 1～10 hour with laminate down at 400～500 ℃;
Layer closes hot-rolled process, after heating process, the needed time of rolling laminate is made as below 40 minutes, and the temperature of the laminate during with rolling the end is made as below 300 ℃.
Effect of the present invention is described below
According to the present invention, for example being provided at, automobile exhaust gas has sufficient corrosion proof aluminium alloy brazing sheet material through under the inner environment of the tubing of heat exchanger.The aluminium alloy brazing sheet material that the present invention relates to is under the state after the soldering heating; Performance suppresses because of the low homogeneous corrosive effect that causes of corrosive fluid pH value, and the while can also be brought into play inhibition contains the generation/growth of the pitting attack that chloride ion causes because of corrosive fluid effect.Again, the radiator element joint rate of this soldering sheet material, solderability such as environment resistant are excellent, use heat exchanger as for example automobile, and light weight and heat conductivity excellence are most suitable with the tubing of heat exchanger as automobile.Have again, use fin material,,, can make for the high corrosion proof heat exchanger of exhaust water of condensation performance through making up with the tubing that forms by the aluminium alloy brazing sheet material that the present invention relates to as interior radiator element with specific alloy ingredient.
Embodiment
The suitable example of high anti-corrosion aluminium alloy brazing sheet material that detailed description the present invention relates to (brazing sheet is also referred to as " brazing sheet ") and method of manufacture thereof.
A. the corrosive environment of heat exchanger
At first, explain that effect of the present invention can get the corrosive environment of performance to the limit.The high anti-corrosion aluminium alloy brazing sheet material that the present invention relates to can be brought into play effect to greatest extent being used for automobile exhaust gas etc. through the inner heat exchanger occasion of tubing.As stated, if the pH value is low, in liquid, there are a lot of H+, therefore; Corrosion speed is fast, and the surface of soldering sheet material is the braze material occasion for the Al-Si that adds Zn, and the Si particle on top layer becomes negative electrode; And Zn promotes the fusion of aluminium, and therefore, corrosion speed further increases.The soldering sheet material that the present invention relates to solves distinctive problem points in this exhaust water of condensation, and as the tubing use occasion of the heat exchanger of the waste gas of inside through automobile etc., soldering sheet material of the present invention suppresses corrosion, can bring into play its effect to greatest extent.The tubing use occasion of the heat exchanger through waste gas as inside, corrosion speed is so not fast, can not bring into play effect of the present invention effectively.
Again, as stated, if in solution, there is chloride ion, then because of chloride ion destroys passive film, the origination point corrosion.As the tubing use occasion of inside through the heat exchanger of waste gas such as automobile; Contain chloride ion at the inner exhaust water of condensation that generates of tubing, have bringing out property of pitting attack, therefore; The soldering sheet material inhibition point corrosive generation/growth that the present invention relates to can be brought into play effect to greatest extent.The tubing use occasion of the heat exchanger through waste gas as inside, corrosive environment does not have bringing out property of pitting attack sometimes, can not bring into play effect of the present invention effectively.Corrosive environment as bringing into play effect of the present invention to greatest extent is preferably, and the pH value is below 3, more than the chloride ion concentration 5ppm.
Below, the sacrificial anode material, heartwood and the braze material that constitute the aluminium alloy brazing sheet material that the present invention relates to are described.
B. sacrificial anode material
B-1.Si
Through adding Si, make the fusing point of sacrificial anode material reduce, produce liquid phase, make that thus soldering maybe.The content of Si is 2.5～7.0 quality % (mass%, below brief note is " % ").Contain quantity not sufficient 2.5%, liquid-phase generating is few, therefore, is difficult to have outside soldering function.On the other hand, if surpass 7.0%, the amount of liquid phase that produces during the soldering heating is too much, and the sacrificial anode material that exists as residual solid tails off, and reduces solidity to corrosion.The preferred content of Si is 3.0～6.0%.
B-2.Zn
Zn can make current potential low, through the potential difference of formation with heartwood, because of the sacrificial anode effect can improve solidity to corrosion.The content of Zn is 1.0～5.5%.Contain quantity not sufficient 1.0%, because of the corrosion proof effect of raising that the sacrificial anode effect causes insufficient.On the other hand, if surpass 5.5%, then corrosion speed accelerates, and sacrificial anode material disappears in early days, and solidity to corrosion reduces.
B-3.Fe
Fe is prone to form the compound of Al-Fe system and Al-Fe-Si system, and above-claimed cpd becomes negative electrode in aluminium, makes solidity to corrosion reduce.The content of Fe is 0.05～1.0%.Contain quantity not sufficient 0.05%, must use the raffinal matrix metal, cause that cost is high.On the other hand, if surpass 1.0%, then cathodic reaction sensitization, solidity to corrosion becomes insufficient.The preferred content of Fe is 0.1～0.5%.
B-4.Ti
Ti improves intensity, and can improve solidity to corrosion through solution strengthening.The content of Ti preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of Ti is 0.1～0.2%.
B-5.Zr
Zr improves intensity through solution strengthening, and separates out the intermetallics of Ai-Zr system, and thickization of crystallization particle diameter after the soldering worked.The content of Zr preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of Zr is 0.1～0.2%.
B-6.Cr
Cr improves intensity through solution strengthening, and separates out the intermetallics of Ai-Cr system, and thickization of crystallization particle diameter after the soldering worked.The content of Cr preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of Cr is 0.1～0.2%.
B-7.V
V improves intensity, and can improve solidity to corrosion through solution strengthening.The content of V preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of V is 0.1～0.2%.
Above-mentioned Ti, Zr, Cr and V can add a kind of in sacrificial anode material as required at least.
B-8.Si content, the relation of Zn content and covering (clad) thickness T
Have, about Si content Sic (quality %), Zn content Znc (quality %), and the cladding thickness T of sacrificial anode material (μ m) not only are limited in the scope separately, and make them satisfy above-mentioned formula (1) again, and this sees from the solidity to corrosion viewpoint, and is very suitable.X in the formula (1) representes soldering when heating, do not fuse as the Zn total amount in the remaining sacrificial anode material of solid.
Promptly; In sacrificial anode material, soldering when heating as the remaining ratio of solid by Si content Sic (quality %) decision, with (1.1-0.1Sic) give with; It multiply by Zn content Znc (quality %); T (μ m) as cladding thickness obtains the X value, and this X value becomes the index of expression as the Zn total amount in the remaining sacrificial anode material of solid.The inventor finds through in detail test and result of study, when this X value becomes 150 when following, is presented to have the solidity to corrosion of excellence especially under the exhaust water of condensation environment.That is, mean when the Zn total amount in the sacrificial anode material remaining as solid be certain level when following, show excellent especially solidity to corrosion.Better the scope of X value is below 140.This X value is big more, and corrosion speed increases, but becomes negative exponential function in the relative pH value of corrosion speed of the aluminium of acidic region, and therefore, pH value is low more, and the poor change of the different corrosion speeds that cause of X value greatly.Therefore, the pH value of liquid is low more, and meliority of the present invention can be brought into play more.The X value is than 150 big occasions, and under the environment that becomes the exhaust water of condensation of pH value below 3, corrosion speed is fast, does not have sufficient solidity to corrosion.
B-9. the cladding thickness of sacrificial anode material
The cladding thickness that constitutes the sacrificial anode material of the aluminium alloy brazing sheet material that the present invention relates to is defined as 25～80 μ m, and its reason is described.The sacrificial anode material that the present invention uses not only has the sacrifice corrosion protection result, and when soldering was heated, the one of which partial melting became braze material, played a part and the bare radiator soldered joint.The cladding thickness less than 25 μ m of sacrificial anode material, the Si composition of sacrificial anode material adds in soldering to be pined for being diffused into the heartwood from sacrificial anode material.Its result, the remaining Si quantitative change in the sacrificial anode material during soldering is few, is difficult to guarantee to be used for the fused solution phasor of soldering.Again, the cladding thickness of sacrificial anode material is if surpass 80 μ m, and then the mobile braze material is superfluous, produces the corrosion that solder corrodes fin material.
B-10. the metal structure of raw sheet
Have again, about the metal structure of the sacrificial anode material of raw sheet, the Si particle that the suitable circular diameter 1.0 μ m in the matrix (matrix) are above exist density very important.That is, be preferably, the suitable circular diameter in the matrix of sacrificial anode material is that the density that exists of the above Si particle of 1.0 μ m is made as 5000/mm
2Below.As stated, the Si particle becomes negative electrode in corrosion reaction, makes corrosion speed increase.Become braze material 1.0 the insufficient Si particle of μ m fuses when soldering is heated, therefore, can not make the corrosion speed of the sacrificial anode material that fusion is remaining increase.On the other hand, the above Si particle of 1.0 μ m is in the remaining sacrificial anode material of fusion, and is also remaining after the soldering heating, therefore, makes corrosion speed increase.The relative pH value of corrosion speed at the aluminium of acidic region becomes negative exponential function, and therefore, the pH value is low more, and the difference of the corrosion speed that causes because of the suitable above Si particle density difference of circular diameter 1.0 μ m is big more.Therefore, the pH value of the liquid that places is low more, and superiority of the present invention can be brought into play more.The density that exists through with the Si particle more than the 1.0 μ m is made as 5000/mm
2Below, can suppress the corrosion speed of sacrificial anode material, obtain sufficient solidity to corrosion.Quite the Si particle more than the circular diameter 1.0 μ m exists density than 5000/mm
2Big occasion, the corrosion speed of sacrificial anode material increases, and can not obtain sufficient solidity to corrosion.Quite the density that preferably exists of the Si particle more than the circular diameter 1.0 μ m is 3000/mm
2Below.
In the present invention, above-mentioned " more than the 1.0 μ m " comprise 1.0 μ m (hereinafter is all like this), above-mentioned " 5000/mm
2Below " comprise 5000/mm
2(hereinafter is all like this).
Have, see from the solidity to corrosion viewpoint, be preferably, aluminium alloy brazing sheet material of the present invention is after supplying the soldering heating, and the crystallization particle diameter of sacrificial anode material is thick.For this reason, as the metal structure of the sacrificial anode material of raw sheet, the suitable circular diameter in the matrix of sacrificial anode material be the above Si particle of 5.0 μ m have preferred 500 a/mm of density
2Below.Quite circular diameter is the above Si particle of 5.0 μ m becomes recrystallize when soldering is heated a nuclear, therefore, so big occasion of Si particle density, the crystallization particle diameter after the soldering becomes more small.Quite circular diameter is that the above Si particle of 5.0 μ m surpasses 500/mm
2Occasion, the crystallization particle diameter ratio cladding thickness of the sacrificial anode material after the soldering 80% little.Be more preferably, quite circular diameter is that the above Si particle density of 5.0 μ m is 400/mm
2Below.See that from the viewpoint of above that kind quite circular diameter is that the above Si particle density of 5.0 μ m does not have lower limit, still, in the composition of the sacrificial anode material that soldering sheet material of the present invention is stipulated, is difficult to be made as 10/mm
2Below.
B-11. the metal structure after soldering is heated
In aluminium alloy brazing sheet material of the present invention, after the soldering heating, the average crystallite particle diameter of the thickness direction of sacrificial anode material is preferably more than 80% of cladding thickness of above-mentioned sacrificial anode material.Aluminium alloy brazing sheet material of the present invention is as if soldering, and then molten solder is created on the grain boundary of sacrificial anode material, therefore, is placed on corrosive environment as if soldering, then the grain boundary local corrosion.After the soldering; The average crystallite particle diameter of the thickness direction of sacrificial anode material is 80% an above occasion of the cladding thickness of sacrificial anode material; The centre that is present in the sacrificial anode material of thickness direction; Or the grain boundary at the interface of sacrificial anode material and heartwood is few, and therefore, the crystal grain that suppresses to cause because of grain boundary attack comes off.Therefore, sacrificial anode material needs long-time because of corrosion disappears, can obtain sufficient solidity to corrosion.80% occasion of the cladding thickness of the not enough sacrificial anode material of the average crystallite particle diameter of the thickness direction of the sacrificial anode material after the soldering; The centre that is present in the sacrificial anode material of thickness direction; Or the grain boundary at the interface of sacrificial anode material and heartwood is many; Therefore, the crystal grain that causes of Yi Fashengyin grain boundary attack comes off.Therefore, sacrificial anode material disappears in early days, can not obtain sufficient solidity to corrosion.Be more preferably, after the soldering, the crystallization particle diameter of sacrificial anode material is more than 90% of cladding thickness of sacrificial anode material.
C. heartwood
It is alloy that the duraluminum that is used for heartwood of the present invention adopts JIS 3000, and for example the Al-Mn of JIS 3003 alloys etc. is that alloy is very suitable.Major ingredient is described below.
C-1.Si
Si and Mn form the intermetallics of Al-Mn-Si system together, through dispersion-strengthened, or are solid-solubilized in the aluminium parent phase, improve intensity through solution strengthening.The content of Si is 0.1～1.2%.Contain quantity not sufficient 0.1%, above-mentioned effect is insufficient, if surpass 1.2%, the heartwood fusing point reduces, and the fusion possibility takes place uprise.The preferred content of Si is 0.1～1.0%.
C-2.Fe
Fe is prone to the intermetallics that formation can become the size of recrystallization nucleus, makes that the crystallization particle diameter after the soldering is thick, suppresses solder from the diffusion of braze material to heartwood.Fe content is 0.05～1.0%.Contain quantity not sufficient 0.05%, must use the raffinal matrix metal, cost is high, if surpass 1.0%, the crystallization particle diameter after the soldering becomes small, has the danger that produces the solder diffusion.The preferred content of Fe is 0.1～0.5%.
C-3.Cu
Cu makes intensity improve through solution strengthening.Cu content is 0.05～1.2%.Contain quantity not sufficient 0.05%, above-mentioned effect is insufficient, if surpass 1.2%, the possibility that duraluminum cracks during casting uprises.The preferred content of Cu is 0.3～1.0%.
C-4.Mn
Mn and Si form the intermetallics of Al-Mn-Si system together, through dispersion-strengthened, or are solid-solubilized in the aluminium parent phase, improve intensity through solution strengthening.The content of Mn is 0.6～1.8%.Contain quantity not sufficient 0.6%, above-mentioned effect is insufficient, if surpass 1.8%, is prone to form big intermetallics, the reduction of plastic working property during casting.The preferred content of Mn is 0.8～1.6%.
C-5.Mg
Mg is through separating out Mg
2Si improves intensity.The content of Mg preferred 0.05～0.5%.Contain quantity not sufficient 0.05%, above-mentioned sometimes effect is insufficient, if surpass 0.5%, the soldering difficulty takes place sometimes.The better content of Mg is 0.15～0.4%.
C-6.Ti
Ti improves intensity through solution strengthening.The content of Ti preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, above-mentioned sometimes effect is insufficient, if surpass 0.3%, is prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of Ti is 0.1～0.2%.
C-7.Zr
Zr improves intensity through solution strengthening, and separates out the intermetallics of Al-Zr system, and thickization of crystallization particle diameter after the soldering worked.The content of Zr preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes,, be prone to form big intermetallics, the reduction of plastic working property sometimes if surpass 0.3%.The better content of Zr is 0.1～0.2%.
C-8.Cr
Cr improves intensity through solution strengthening, and separates out the intermetallics of Al-Cr system, and thickization of crystallization particle diameter after the soldering worked.The content of Cr preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of Cr is 0.1～0.2%.
C-9.V
V improves intensity through solution strengthening, simultaneously, can also improve solidity to corrosion.The content of V preferred 0.05～0.3%.Contain quantity not sufficient 0.05%, can not obtain above-mentioned effect sometimes.If surpass 0.3%, be prone to form big intermetallics, the reduction of plastic working property sometimes.The better content of V is 0.1～0.2%.
As heartwood; According to mentioned component; Can use duraluminum suitably, it contains Si:0.1～1.2 quality %, Fe:0.05～1.0 quality %, Cu:0.05～1.2 quality %, Mn:0.6～1.8 quality %, and remainder is made up of Al and unavoidable impurities.Can use the duraluminum that in this composition, further contains from least a element of Mg:0.05～0.5 quality %, Ti:0.05～0.3 quality %, Zr:0.05～0.3 quality %, Cr:0.05～0.3 quality % and V:0.05～0.3 quality % selection again.
D. braze material
It is alloy that braze material can use normally used Al-Si.The not special restriction of alloying constituent for example, can be used JIS4343,4045,4047 alloys (Al-7～13 quality %Si) suitably.
E. the method for manufacture of high anti-corrosion aluminium alloy brazing sheet material
E-1. the manufacturing of heartwood
The heartwood of the aluminium alloy brazing sheet material that is used to the present invention relates to is with common semicontinuous casting method casting.400～620 ℃ of processing that homogenize of carrying out 1～20 hour, after this, carry out adjustment thickness such as face cutting as required, make the ingot bar of heartwood.
E-2. the manufacturing of sacrificial anode material
The sacrificial anode material that the present invention uses comprises the casting process of semicontinuous casting, heats the operation of resultant ingot bar, and with its hot rolled operation.In order further to improve the solidity to corrosion of sacrificial anode material, be preferably, in matrix, the density that exists that will have the Si particle of the above suitable circular diameter of 1.0 μ m is made as 5000/mm
2Below, and the density that exists that will have a Si particle of the above suitable circular diameter of 5.0 μ m is made as 500/mm
2Below.Thus, prevent thickization of Si particle.For this reason, need the speed of cooling of ingot bar of the casting process of control sacrificial anode material, the Heating temperature and the heat-up time of the heating process behind the control casting process, the temperature the when hot rolling after the control heating process finishes.
Speed of cooling during the sacrificial anode material casting is big more, is difficult to generate thick Si particle more, and still, the speed of cooling that necessitates exists with ... the amount of the Si that adds sacrificial anode material to.The inventor is for the size and the density of Si particle, the speed of cooling V the during casting of sacrificial anode material (℃/s), and the relation of the Si amount (Sic) of sacrificial anode material, carry out detailed test/research.Its result finds to concern occasion when satisfying above-mentioned formula (2), can obtain better Si particle distribution.The speed of cooling of sacrificial anode material is controlled to be certain more than certain benchmark value, means that the Si amount is many more, and this benchmark value is high more.Speed of cooling when the speed of cooling during casting is solidified for the slab central part.Be more preferably, the speed of cooling (V) in sacrificial anode material when casting and the Si amount (Sic) that adds sacrificial anode material to satisfy following formula (3):
V≥Sic/4 (3)
Ingot bar by the resulting sacrificial anode material of above-mentioned casting is rolling until deciding thickness of slab in hot-rolled process.In the present invention, be preferably, the ingot bar temperature of the heating process before this hot-rolled process is 300～500 ℃, and the hold-time was made as 1～10 hour.If the ingot bar temperature surpasses 500 ℃, or the hold-time surpass 10 hours, then thickization of Si particle in the sacrificial anode material can not more suitably be distributed, solidity to corrosion reduces.On the other hand, 300 ℃ of ingot bar temperature less thaies, when hot rolling resistance to deformation big, therefore, rolling sometimes difficulty, hold-time less than 1 hour, ingot bar temperature heterogeneity sometimes.
The ingot bar of sacrificial anode material imposes hot-rolled process after heating process.In the present invention, be preferably, the ingot bar temperature was made as below 350 ℃ when hot rolling finished.If the ingot bar temperature surpassed 350 ℃ when hot rolling finished, then thickization of Si particle in the sacrificial anode material can not more suitably be distributed, and solidity to corrosion reduces.The thickness of slab of the sacrificial anode material after the hot rolling is generally about 10～100mm by the ingot bar thickness decision of the covering rate and the heartwood of target.
E-3. the manufacturing of braze material
Braze material also through casting process and hot-rolled process manufacturing, at this, there is no need to do special control, usually, and with the above speed of cooling casting of 0.3 ℃/s, in heating back hot rolling below 500 ℃, more than 1 hour.
E-4. the manufacturing of laminate
The aluminium alloy brazing sheet material that the present invention relates to comprises that layer closes operation, heating process and layer and closes hot-rolled process; Said layer closes operation system and uses the heartwood of being made by aforesaid method; Sacrificial anode material and braze material, composite sacrificial anodes material on the one side of heartwood makes up braze material on another side; Perhaps composite sacrificial anodes material on the heartwood two sides; Make it as laminate, the ingot bar of said heating process zone of heating condensation material, said layer closes hot-rolled process the laminate that heats is rolled.Even in the manufacturing process of above-mentioned laminate, be preferably, the density that exists of the Si particle with the above suitable circular diameter of 1.0 μ m that exists in the matrix of control sacrificial anode material is made as 5000/mm
2Below.Thus, prevent thickization of Si particle, further improve solidity to corrosion.
In the present invention, be preferably, the ingot bar of heating process reaches 400～500 ℃ of temperature, and the hold-time was made as 1～10 hour.Surpass 500 ℃ if ingot bar reaches temperature, or the hold-time surpass 10 hours, thickization of Si particle in the sacrificial anode material then can not obtain more suitably that Si distributes, solidity to corrosion reduces.On the other hand, ingot bar reaches 400 ℃ of temperature less thaies, and heartwood and sacrificial anode material, braze material can not melts combine sometimes, hold-time less than 1 hour, laminate temperature heterogeneity sometimes.
Through the laminate of heating process, imposed layer and closed hot-rolled process.In the present invention, be preferably, layer closed the needed time of hot-rolled process be made as below 40 minutes.Be preferably, the temperature of the laminate when layer closes the hot-rolled process end is made as below 300 ℃.If rolling time surpasses 40 minutes, or the temperature during rolling the end surpasses 300 ℃, and thickization of Si particle in the sacrificial anode material then can not obtain more suitably that Si distributes, and solidity to corrosion reduces.Be more preferably, layer closed the needed time of hot-rolled process be made as at least 10 minutes.Carry out layer and close 10 minutes occasions of hot rolling deficiency of time, the crackle of material generation sometimes, or sacrificial anode material or braze material peel off, and guarantees very difficulty of the property made.The not special restriction of the hot rolling end of thickness of slab when closing to(for) layer is generally about 2～10mm.
Close the resulting aluminium alloy brazing sheet material of hot rolling by layer, after this pass through cold rolling up to deciding thickness of slab.After midway cold rolling or cold rolling, can be through the annealing operation about 1～2 time.For the not special restriction of the condition of cold rolling and annealing operation, usually, behind cold rolling Process Annealing, apply rolling about 5～80%, become decide thickness of slab, it is modified to be made as H1X, or rollingly behind deciding thickness of slab, anneals, it is modified to be made as H2X.Annealing operation uses batch furnace at 200～500 ℃ usually, carries out under 1～10 hour the condition, or uses continuous furnace under 200～550 ℃ of temperature, to carry out.
Thickness for aluminium alloy brazing sheet material of the present invention; The covering rate of braze material layer is not special to be limited; Usually, as making the tubing use occasion of pressurized air round-robin side cooler of turbo-supercharger, the thin-walled soldering sheet material below can being made as about about 0.6mm.But, not being defined as the thickness of slab in this scope, the comparison heavy-walled material below also can be used as about above about 0.6mm, 5mm uses.The covering rate of braze material layer is generally about 3～20%.
F. heat exchanger
The aluminium alloy brazing sheet material that the present invention relates to is under the state after the soldering heating; Have the pH value low homogeneous corrosive effect that cause of inhibition because of corrosive fluid; And also have the effect that suppresses because of the generation/growth that in corrosive fluid, contains the pitting attack that chloride ion causes simultaneously, excellent strength, solderability is good; Therefore, the automobile as for example light weight is very suitable with the heat exchanger use.
F-1. interior fin material
Below, the formation and the composition range that aluminium alloy brazing sheet material of the present invention are used in the interior fin material of the heat exchanger occasion with interior radiator element are described.
Interior radiator element uses bare radiator.As stated, interior radiator element has the braze material occasion, and under exhaust water of condensation environment, the Si particle in the braze material becomes negative electrode, and corrosion speed increases.So, the bare radiator of use corrosion resistance excellent.
Al alloying constituent as interior fin material is defined as below the Cu0.1%, below the Zn0.5%.Cu becomes negative electrode under the environment of exhaust water of condensation, because of causing grain boundary attack, make corrosion speed increase, and therefore, if Cu content surpasses 0.1%, then strength after corrosion reduces and becomes big, and the compressive strength of heat exchanger reduces.Zn promotes the fusion of aluminium under the environment of exhaust water of condensation, increase corrosion speed, and therefore, if Zn content surpasses 0.5%, then strength after corrosion reduces greatly, and the compressive strength of heat exchanger reduces.Do not do special qualification about composition beyond the Cu of interior radiator element, the Zn, usually, use the alloy of pure Al system, Al-Fe system, Al-Mn system.
Do not limit about the method for manufacture of the heat exchanger that the present invention relates to is special, usually, after the combination of parts such as forming tube, radiator element, collector, be heated to about 600 ℃ of soldering manufacturings.
The heat exchanger that obtains like this has high voltage endurance, and has good solidity to corrosion, therefore, can bring into play favorable durability at the automobile of waste gas through the environment in the tubing in heat exchanger etc.
[embodiment]
Below, according to embodiment further explain the present invention, still, the present invention is not limited by following examples.
Have the sacrificial anode material of alloying constituent shown in the table 1 through the casting of DC castmethod respectively, and the heartwood alloy with alloying constituent shown in the table 2, respectively surfacing processing is carried out on the two sides.The heartwood in this moment and the ingot bar thickness of sacrificial anode material all are 500mm.The speed of cooling of the sacrificial anode material of casting process and the value representation of Sic/5 are in table 1.Again, different with sacrificial anode material, as braze material, use the JIS4045 alloy, above-mentioned sacrificial anode material and 4045 alloy brazed materials are applied heating process and hot-rolled process, rolling respectively up to desirable thickness.The heating process of sacrificial anode material and the condition of hot-rolled process are illustrated in table 3.
Table 1
Table 2
Table 3
Use above-mentioned alloy, at the single face of heartwood sacrificial anode material, at sacrificial anode material or the 4045 alloy brazed materials of another side as skin-material 2 combination table 1 as skin-material 1 combination table 1.Above-mentioned laminate is imposed heating process and layer closes hot-rolled process, make three layers of clad material of 3.5mm.The heating process of laminate and the condition of hot-rolled process are illustrated in table 3.Above-mentioned clad material is imposed process annealing (condition: under 400 ℃ of temperature keep 5 hours), finally cold rolling, become the sheet material test portion of the modified thickness of slab 0.5mm of H1n.
As shown in table 4; In the present invention's example and comparative example, combination is as the sacrificial anode material that is illustrated in table 1 of skin-material 1, as the sacrificial anode material that is illustrated in table 1 or the 4045 alloy brazed materials of skin-material 2; Be illustrated in the heartwood of table 2, and the process conditions that is illustrated in table 3.
Table 4
G. estimate
Measure sacrificial anode material and the thickness of braze material of the test portion of above-mentioned making, calculate the X value that gives by formula (1).Measure the density that exists of Si particle in the sacrificial anode material respectively with the above and suitable circular diameter that 5.0 μ m are above of 1.0 μ m again.And then, above-mentioned test portion is carried out 3 minutes soldering heating under 600 ℃ of temperature, estimate the average crystallite particle diameter of the thickness direction of sacrificial anode material, solidity to corrosion, solderability.
G-1. the thickness measurement of sacrificial anode material and braze material
L-ST face with grinding test portion carries out surperficial centering, carves the difference of the contrast that causes because of the alloying constituent difference through microscopic examination, the thickness of mensuration sacrificial anode material and 4045 alloy brazed materials with triumphant Le Shi liquid corrosion.
The mensuration that has density of G-2.Si particle
Have the above and suitable circular diameter that 5.0 μ m are above of 1.0 μ m the Si particle have density, through cross section, measure with the sacrificial anode material of the etched sample of the above-mentioned triumphant Le Shi liquid of observation by microscope.For two bread crumb sacrificial anode material persons, with skin-material 1 as the mensuration face.
G-3. the mensuration of the average crystallite particle diameter of the sacrificial anode material after the soldering
With sheet material separately to after the test portion soldering heating; With grinding the L-ST face carried out surperficial centering, to use Pa Keshi (Barker, name) liquid to make anodic oxidation; Through applying the microscopic examination of deflection, measure the average crystallite particle diameter of the thickness direction of sacrificial anode material.Observe multiplying power and be made as 100 times, whole crystallization particle diameters of sacrificial anode material of obtaining three visuals field are average, as the average crystallite particle diameter.For two bread crumb sacrificial anode material persons, with skin-material 1 as the mensuration face.
G-4. corrosion proof mensuration
Separately to after the test portion soldering heating, cut out 50mm * 50mm with sheet material, shelter the face of skin-material 2 through resin, with the face of the covering sacrificial anode material of skin-material 1 as test face.In the aqueous solution of composition shown in the table 5, carry out 50 ℃, 1000 hours dip test.After the off-test, remove the corrodibility biology with concentrated nitric acid, measure the depth of corrosion that occurs in the sacrificial anode material face through depth of focus method, the person is as depth of corrosion the most deeply.In the evaluation of water solution A, B, C, D, will in whole aqueous solution, depth of corrosion less than 150 μ m occasions be made as qualified " zero ", even have only one to be the above occasions of 150 μ m, be made as defective " * ".
Table 5
| Chloride ion concentration (ppm) | The pH value | |
| Water solution A | ?10 | 2.3 |
| Aqueous solution B | ?300 | 1.8 |
| Aqueous solution C | ?2 | 2.3 |
| Aqueous solution D | ?10 | 4.0 |
G-5. the evaluation of solderability
Make 3003 alloy corrugations obtain radiator element,, be immersed in 5% the fluoride flux aqueous solution, carry out 80 ℃ of 3 minutes solderings heating with the combination of the sacrificial anode material face of test portion.With the radiator element joint rate of this test heartwood is more than 95%, and test portion do not produce the fusion occasion, as solderability qualified " zero ", radiator element joint rate less than 95% with and/or test portion produce the fusion occasion as solderability insufficient " * ".
The thickness of sacrificial anode material and braze material, X value, the result of average crystallite particle diameter, depth of corrosion and solderability of the thickness direction that has the sacrificial anode material after density, the soldering separately with Si particle of the above and suitable circular diameter that 5.0 μ m are above of 1.0 μ m are illustrated in the table 6.
Table 6
Wherein, symbolic significance is following:
M1: sacrificial anode material thickness (μ m) < skin-material 1 >
M2: sacrificial anode material or braze material thickness (μ m) < skin-material 2 >
Si particle density more than the N1:1.0 μ m is (individual/mm
2)
Si particle density more than the N2:5.0 μ m is (individual/mm
2)
D: the average crystallite particle diameter of the thickness direction of the sacrificial anode material after the soldering (μ m)
In the present invention's example 1～14 and 22～31, satisfy defined terms of the present invention, solidity to corrosion and solderability are all qualified.Especially, satisfying formula (1) and having in the present invention's example 1～8 and 22～24 that has density separately of the Si particle that reaches the suitable circular diameter more than the 5.0 μ m more than the 1.0 μ m, the whole less than 100 μ m of the depth of corrosion of corrosion test, solidity to corrosion is very good.
In comparative example 15, the Si composition of sacrificial anode material is too much, and therefore, solidity to corrosion is poor.
In comparative example 16, the Zn composition of sacrificial anode material is too much, and therefore, solidity to corrosion is poor.
In comparative example 17, the Zn composition of sacrificial anode material is very few, and therefore, solidity to corrosion is poor.
In comparative example 18, the Fe composition of sacrificial anode material is too much, and therefore, solidity to corrosion is poor.
In comparative example 19, the Si composition of sacrificial anode material is very few, and therefore, solderability is poor.
In comparative example 20, the thickness of sacrificial anode material is thin excessively, and therefore, solderability is poor.
In comparative example 21, the thickness of sacrificial anode material is blocked up, and therefore, solderability is poor.
Below utilizability on the explanation industry
The duraluminum clad material that the present invention relates to has the pH value low homogeneous corrosive effect that cause of inhibition because of corrosive fluid; And also has the effect that suppresses because of the generation/growth that in corrosive fluid, contains the pitting attack that chloride ion causes simultaneously; It is very suitable that the corrosion resistant material of the fluid channel constituent material of the heat exchanger of therefore, using etc. as for example automobile etc. is used.
Claims (according to the modification of the 19th of treaty)
1. high anti-corrosion aluminium alloy brazing sheet material comprises the heartwood of duraluminum, the sacrificial anode material of covering on the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be the braze material of alloy, it is characterized in that:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of this sacrificial anode material is 25～80 μ m.
2. high anti-corrosion aluminium alloy brazing sheet material comprise the heartwood of duraluminum, and covering is characterized in that at the sacrificial anode material on the two sides of this heartwood:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of above-mentioned each sacrificial anode material is 25～80 μ m.
3. high anti-corrosion aluminium alloy brazing sheet material according to claim 1 and 2 is characterized in that:
Above-mentioned sacrificial anode material further contain from Ti:0.05～0.3 quality %, Zr:0.05～0.3 quality %, Cr:0.05～0.3 quality % and V:0.05～00.3 quality % select at least a.
4. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-3, it is characterized in that:
The Si content of above-mentioned sacrificial anode material is made as Sic quality %, and Zn content is made as Znc quality %, and cladding thickness is made as T μ m, is determined the value of X by following formula (1):
X＝(1.1-0.1×Sic)×Znc×T (1)
Above-mentioned X value is below 150.
5. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-4, it is characterized in that:
In the matrix of above-mentioned sacrificial anode material, the density that exists with Si particle of the above suitable circular diameter of 1.0 μ m is 5000/mm
2Below.
6. high anti-corrosion aluminium alloy brazing sheet material according to claim 5 is characterized in that:
In the matrix of above-mentioned sacrificial anode material, the density that exists with Si particle of the above suitable circular diameter of 5.0 μ m is 500/mm
2Below.
7. according to claim 5 or 6 described high anti-corrosion aluminium alloy brazing sheet materials, it is characterized in that:
Under the environment of pH value below 3, more than the chloride ion concentration 5ppm, use.
8. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 5-7, it is characterized in that:
High anti-corrosion aluminium alloy brazing sheet material is after the soldering heating, and the average crystallite particle diameter of the thickness direction of above-mentioned sacrificial anode material is more than 80% of cladding thickness of this sacrificial anode material.
9. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-8, it is characterized in that:
Use is as the tubing of the heat exchanger of automobile exhaust gas inflow.
10. high anti-corrosion heat exchanger is characterized in that:
Use the described high anti-corrosion aluminium alloy brazing of claim 9 sheet material; As the tubing that sacrificial anode material is made as inner face; At this sacrificial anode material face configuration bare radiator, radiator element in constituting, above-mentioned sacrificial anode material of soldered joint and bare radiator form.
11. the method for manufacture of a high anti-corrosion aluminium alloy brazing sheet material is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material in the claim 1～9, it is characterized in that:
The manufacturing process of above-mentioned sacrificial anode material comprises casting process, heating process, and hot-rolled process;
In casting process, the Si content Sic quality % of the speed of cooling V of the ingot bar of above-mentioned sacrificial anode material ℃/s and sacrificial anode material satisfies following formula (2):
V≥Sic/5(2)
In the heating process behind casting process, with the ingot bar of sacrificial anode material 300～500 ℃ down heating kept 1～10 hour;
In the hot-rolled process after heating process, the temperature of the sacrificial anode material during with end is made as below 350 ℃.
12. the method for manufacture of a high anti-corrosion aluminium alloy brazing sheet material is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material in the claim 1～9, it is characterized in that, comprises following operation:
Layer closes operation, and sacrificial anode material, duraluminum heartwood, the Al-Si of the said method manufacturing of combination claim 11 are the braze material of alloy, as laminate;
Heating process after layer closes operation, heats maintenance 1～10 hour with laminate down at 400～500 ℃;
Layer closes hot-rolled process, after heating process, the needed time of rolling laminate is made as below 40 minutes, and the temperature of the laminate during with rolling the end is made as below 300 ℃.
Explain or state (according to the modification of the 19th of treaty)
About explanation according to the correction of PCT treaty the 19th (1)
The later half separation of preceding half-sum of the claim 5 of claims during with application, respectively as revised claim 5,6 append, along with above-mentioned modification, former claim 5 deletion.
The technological item that original right requirement book does not have is appended as revised claim 7.The 6th page of 4-5 of specification sheets was capable when the technological item of being appended was documented in application.In addition, this technology item is documented in the claim 1 of claims of the JP2009-218234 of one of two days application of the present invention as basis for priority.
Follow above-mentioned modification, claim numbering and the subordinate relation of former claim 6-10 have been carried out corresponding modification.
Not change of the claim 1-4 of claims during application.
Claims (10)
1. high anti-corrosion aluminium alloy brazing sheet material comprises the heartwood of duraluminum, the sacrificial anode material of covering on the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be the braze material of alloy, it is characterized in that:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of this sacrificial anode material is 25～80 μ m.
2. high anti-corrosion aluminium alloy brazing sheet material comprise the heartwood of duraluminum, and covering is characterized in that at the sacrificial anode material on the two sides of this heartwood:
Above-mentioned sacrificial anode material is a duraluminum; It contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; Remainder is made up of Al and unavoidable impurities, and the cladding thickness of above-mentioned each sacrificial anode material is 25～80 μ m.
3. high anti-corrosion aluminium alloy brazing sheet material according to claim 1 and 2 is characterized in that:
Above-mentioned sacrificial anode material further contain from Ti:0.05～0.3 quality %, Zr:0.05～0.3 quality %, Cr:0.05～0.3 quality % and V:0.05～0.3 quality % select at least a.
4. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-3, it is characterized in that:
The Si content of above-mentioned sacrificial anode material is made as Sic quality %, and Zn content is made as Znc quality %, and cladding thickness is made as T μ m, is determined the value of X by following formula (1):
X＝(1.1-0.1×Sic)×Znc×T (1)
Above-mentioned X value is below 150.
5. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-4, it is characterized in that:
In the matrix of above-mentioned sacrificial anode material, the density that exists with Si particle of the above suitable circular diameter of 1.0 μ m is 5000/mm
2Below, and the density that exists with Si particle of the above suitable circular diameter of 5.0 μ m is 500/mm
2Below.
6. high anti-corrosion aluminium alloy brazing sheet material according to claim 5 is characterized in that:
High anti-corrosion aluminium alloy brazing sheet material is after the soldering heating, and the average crystallite particle diameter of the thickness direction of above-mentioned sacrificial anode material is more than 80% of cladding thickness of this sacrificial anode material.
7. according to any described high anti-corrosion aluminium alloy brazing sheet material among the claim 1-6, it is characterized in that:
Use is as the tubing of the heat exchanger of automobile exhaust gas inflow.
8. high anti-corrosion heat exchanger is characterized in that:
Use the described high anti-corrosion aluminium alloy brazing of claim 7 sheet material; As the tubing that sacrificial anode material is made as inner face; At this sacrificial anode material face configuration bare radiator, radiator element in constituting, above-mentioned sacrificial anode material of soldered joint and bare radiator form.
9. the method for manufacture of a high anti-corrosion aluminium alloy brazing sheet material is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material in the claim 1～7, it is characterized in that:
The manufacturing process of above-mentioned sacrificial anode material comprises casting process, heating process, and hot-rolled process;
In casting process, the Si content Sic quality % of the speed of cooling V of the ingot bar of above-mentioned sacrificial anode material ℃/s and sacrificial anode material satisfies following formula (2):
V≥Sic/5(2)
In the heating process behind casting process, with the ingot bar of sacrificial anode material 300～500 ℃ down heating kept 1～10 hour;
In the hot-rolled process after heating process, the temperature of the sacrificial anode material during with end is made as below 350 ℃.
10. the method for manufacture of a high anti-corrosion aluminium alloy brazing sheet material is the method for manufacture of any described high anti-corrosion aluminium alloy brazing sheet material in the claim 1～7, it is characterized in that, comprises following operation:
Layer closes operation, and sacrificial anode material, duraluminum heartwood, the Al-Si of the said method manufacturing of combination claim 9 are the braze material of alloy, as laminate;
Heating process after layer closes operation, heats maintenance 1～10 hour with laminate down at 400～500 ℃;
Layer closes hot-rolled process, after heating process, the needed time of rolling laminate is made as below 40 minutes, and the temperature of the laminate during with rolling the end is made as below 300 ℃.
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| PCT/JP2010/065968 WO2011034102A1 (en) | 2009-09-21 | 2010-09-15 | Highly corrosion-resistant aluminum alloy brazing sheet, process for production of the brazing sheet, and highly corrosion-resistant heat exchanger equipped with the brazing sheet |
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| CN103567656A (en) * | 2013-10-28 | 2014-02-12 | 顾建 | Brazing material for aluminum alloy |
| CN105378126A (en) * | 2013-07-29 | 2016-03-02 | 株式会社Uacj | Aluminum-alloy clad member, method for producing same, and heat exchanger using aluminum-alloy clad member |
| CN105829558A (en) * | 2014-03-19 | 2016-08-03 | 株式会社Uacj | Cladded aluminium-alloy material and production method therefor, and heat exchanger using said cladded aluminium-alloy material and production method therefor |
| CN107406920A (en) * | 2015-03-14 | 2017-11-28 | 株式会社Uacj | The aluminium alloy soldering lug fin material and its manufacture method of heat exchanger |
| CN108699637A (en) * | 2016-02-17 | 2018-10-23 | 株式会社Uacj | Aluminium alloy brazing piece and its manufacturing method and the manufacturing method for using the automobile heat exchanger for working as the soldering lug |
| CN113453839A (en) * | 2019-10-11 | 2021-09-28 | 松下知识产权经营株式会社 | Brazing sheet for heat exchanger and heat exchanger for air conditioning device |
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| JP2005307252A (en) * | 2004-04-20 | 2005-11-04 | Sumitomo Light Metal Ind Ltd | Aluminum alloy clad material for automobile heat exchanger |
| JP2009183980A (en) * | 2008-02-06 | 2009-08-20 | Furukawa-Sky Aluminum Corp | Brazing method for aluminum alloy, and aluminum alloy cladding material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005307252A (en) * | 2004-04-20 | 2005-11-04 | Sumitomo Light Metal Ind Ltd | Aluminum alloy clad material for automobile heat exchanger |
| JP2009183980A (en) * | 2008-02-06 | 2009-08-20 | Furukawa-Sky Aluminum Corp | Brazing method for aluminum alloy, and aluminum alloy cladding material |
Cited By (7)
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|---|---|---|---|---|
| CN105378126A (en) * | 2013-07-29 | 2016-03-02 | 株式会社Uacj | Aluminum-alloy clad member, method for producing same, and heat exchanger using aluminum-alloy clad member |
| CN105378126B (en) * | 2013-07-29 | 2018-02-06 | 株式会社Uacj | Aluminium, Al alloy clad material and its manufacture method and the heat exchanger using the aluminium, Al alloy clad material |
| CN103567656A (en) * | 2013-10-28 | 2014-02-12 | 顾建 | Brazing material for aluminum alloy |
| CN105829558A (en) * | 2014-03-19 | 2016-08-03 | 株式会社Uacj | Cladded aluminium-alloy material and production method therefor, and heat exchanger using said cladded aluminium-alloy material and production method therefor |
| CN107406920A (en) * | 2015-03-14 | 2017-11-28 | 株式会社Uacj | The aluminium alloy soldering lug fin material and its manufacture method of heat exchanger |
| CN108699637A (en) * | 2016-02-17 | 2018-10-23 | 株式会社Uacj | Aluminium alloy brazing piece and its manufacturing method and the manufacturing method for using the automobile heat exchanger for working as the soldering lug |
| CN113453839A (en) * | 2019-10-11 | 2021-09-28 | 松下知识产权经营株式会社 | Brazing sheet for heat exchanger and heat exchanger for air conditioning device |
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| Publication number | Publication date |
|---|---|
| CN102471836B (en) | 2014-06-18 |
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