CN102471836B - 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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- CN102471836B CN102471836B CN201080028399.4A CN201080028399A CN102471836B CN 102471836 B CN102471836 B CN 102471836B CN 201080028399 A CN201080028399 A CN 201080028399A CN 102471836 B CN102471836 B CN 102471836B
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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 manufacture method thereof, and use its high anti-corrosion heat exchanger, in detail, relate to high anti-corrosion aluminium alloy brazing sheet material and manufacture method thereof as the high temperature compressed air of the heat exchangers such as side cooler or the use of the passage constituent material of refrigeration agent, and use its high anti-corrosion heat exchanger.
Background technology
Aluminium alloy possesses light weight and high heat conductivity, can realize high anti-corrosion by suitable processing, therefore, and for vapour heat exchanger for vehicle, for example, scatterer, condenser, vaporizer, well heater, side cooler etc.As the tubing of vapour heat exchanger for vehicle, use using the Al-Mn of 3003 alloys etc. and be associated gold as heartwood, in one side, coated Al-Si is associated golden braze material or Al-Zn and is associated two layers of packaging material of golden sacrificial anode material, or further on another side coated Al-Si be associated three layers of packaging material etc. of golden braze material.Conventionally the radiator element of this packaging material of combination and corrugation passes through soldered joint under the high temperature of 600 ℃ of left and right.When making interior radiator element be bonded on occasion in the tubing that uses packaging material, need to, in the both sides of the inner face side of tubing, exterior side, invest soldering function.
If exist and there is corrosive liquid in the tubing of this heat exchanger, exist because origination point corrosion causes tubing and connect, or reduce because homogeneous corrosion causes tubing thickness, compressive strength reduces, the danger that tubing breaks.Its result, exists the air of internal recycling or water coolant, refrigeration agent that the danger of leaking occurs.In the past, corrosive liquid that has that what is called is present in tubing is the neutrality such as the water coolant of engine or the refrigeration agent of water cooler or weakly acidic liquid, under this corrosive environment, in order to meet 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, forms heat exchanger.
But in recent years, in order to meet the exhaust restriction of EU and the U.S., take the specific fuel consumption that improves automobile as object, exploitation Exhaust Gas is by the system of heat exchanger.Occasion in the tubing of Exhaust Gas by heat exchanger, if cooling tubing internal cause heat exchange and cooling, because dewfall generates the water of condensation (below, being called " exhaust water of condensation ") that comprises Exhaust Gas composition.This water of condensation is strongly-acid occasion, and the Al-Si of such use covering interpolation Zn was the soldering sheet material of braze material in the past, and solidity to corrosion is insufficient.
It is very large that the corrosion speed of aluminium is affected by pH value, and pH value is lower, and corrosion speed increases.If according to pH-Electric Potential value figure, in general, in pH value below 4, Al
3+stable, be difficult to use as the corrosion-resistant material of aluminium.Again, the Al-Si that soldering sheet surface is added Zn is 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 there is chloride ion in solution, chloride ion destroys passive film again, origination point corrosion.Exhaust water of condensation contains chloride ion, therefore, has the character that causes pitting attack.That is, Exhaust Gas, by occasion in the tubing of heat exchanger, needs to suppress because of the low corrosion causing of pH value, meanwhile, makes tubing also have the corrosion protection of sacrifice effect, needs the generation/growth of inhibition point corrosion.The composition of exhaust water of condensation because of various condition different, sometimes becoming pH value is the strongly-acid below 3, sometimes becomes more than chloride ion concentration becomes the 5ppm with bringing out property of pitting attack.
For making it have soldering function on tubing two sides on the one hand, making it have on the one hand than the Al-Si of in the past such covering interpolation Zn is the high corrosion proof problem of soldering sheet material of braze material, use Si addition than many 1.5～6.0% material in the past, as sacrificial anode material, the soldering sheet material by its covering in heartwood is documented in patent documentation 1～3.Like this, in sacrificial anode material, add the occasion of the Si of volume, when soldering heating, melt the part of sacrificial anode material, play as braze material effect, can with bare radiator (bare fin) soldering, on the other hand, a part keeps solid state remaining, and therefore, can obtain than the Al-Si of in the past such interpolation Zn is the solidity to corrosion that braze material is high.But, the soldering sheet material being obtained by above-mentioned technology, as the corrosive environment of tubing inside, the mobile neutrality that imagination scatterer, condenser, vaporizer are such or the device of weakly acidic liquid, under the corrosive environment existing at the extremely low liquid of the such pH value of exhaust water of condensation, solidity to corrosion is insufficient.
That is, in technology shown in patent documentation 1, although energy soldering sacrificial anode material and interior radiator element,, about Zn addition, be only set as, below 7%, not showing the opinion that limits its addition.As mentioned above, Zn promotes the melting of aluminium, therefore,, in order to suppress corrosion speed, must strictly limit Zn addition, but, about this problem, be not familiar with completely, be placed in the solution countermeasure of the liquid occasion problem that the such pH value of exhaust water of condensation is low for tubing, without any record, also without any hint.
On the other hand, in technology shown in patent documentation 2, in order to improve the solderability of sacrificial anode material, in sacrificial anode material, contain 15000～40000/mm of Si particle of 0.1～1.0 μ m
2.As mentioned above, Si particle becomes negative electrode in corrosion reaction, and corrosion speed is increased.The Si particle of 0.1～1.0 μ m melts in the time that soldering is heated, become braze material, can not make the corrosion speed that melts remaining sacrificial anode material increase, but, Si particles more than 1.0 μ m, melting in remaining sacrificial anode material also remainingly after soldering heating, increases corrosion speed.Therefore, for Si particles more than 1.0 μ m, need to limit its number density, still, in the technology of patent documentation 2, for this situation without any consideration.And be not recited as the manufacture method of the number density that obtains fixed Si particle yet.
In patent documentation 3, about size and the number density of Si particle, be documented, still, it relates to the distribution of fine particle, about the restriction of the number density of thick Si particles more than 1.0 μ m, without any record, also without any hint.
Patent documentation 1: TOHKEMY 2008-188616 communique
Patent documentation 2: TOHKEMY 2000-309837 communique
Patent documentation 3: TOHKEMY 2004-156108 communique
As mentioned above, the waste gas of for example automobile, by the inner occasion of tubing of heat exchanger, needs to suppress because of the low corrosion causing of pH value, meanwhile, also needs to make tubing to have the corrosion protection of sacrifice effect, the generation/growth of inhibition point corrosion.In the prior art, be difficult to obtain standing the solidity to corrosion using under this corrosive environment.
Summary of the invention
The present invention puts forward in order to address the above problem a little, the object of the invention is to, provide molten solder there is soldering in aluminium alloy brazing sheet material time after the good solderability of heartwood diffusion and soldering, not there is excellent corrosion proof aluminium alloy brazing sheet material for exhaust water of condensation, especially can be used as suitably the aluminium alloy brazing sheet material of the fluid channel constituent material of vapour heat exchanger for vehicle, and manufacture method.
The inventor furthers investigate result repeatedly in order to solve above-mentioned problem, discovery can make sacrificial anode material have specific alloy composition, make Si content, Zn content and cladding thickness meet characteristic relation, again, there is fixed Si particle and exists the clad material of density by use, can solve this problem, complete the present invention.
Specifically, the high anti-corrosion aluminium alloy brazing sheet material of claim 1 of the present invention comprises the heartwood of aluminium alloy, the sacrificial anode material of covering in the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be associated golden braze material, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy, 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 inevitable impurity, 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 aluminium alloy, and covering is at the sacrificial anode material on the two sides of this heartwood, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy, 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 inevitable impurity, 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 contains at least one that select 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 %.
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 the Si particle of suitable circular diameter more than 1.0 μ m is 5000/mm
2below, and the density that exists with the Si particle of suitable circular diameter more than 5.0 μ m be 500/mm
2below.
In claim 6 of the present invention, high anti-corrosion aluminium alloy brazing sheet material after soldering heating, the more than 80% of cladding thickness that the average crystallite particle diameter of the thickness direction of above-mentioned sacrificial anode material is this sacrificial anode material.
In claim 7 of the present invention, be used as the tubing of the heat exchanger of automobile exhaust gas inflow.
The high anti-corrosion heat exchanger of claim 8 of the present invention is characterised in that:
Right to use requires the high anti-corrosion aluminium alloy brazing sheet material described in 7, as the tubing that sacrificial anode material is made as to inner face, at this sacrificial anode material face configuration bare radiator, radiator element in forming, the above-mentioned sacrificial anode material of soldered joint and bare radiator form.
The manufacture method of the high anti-corrosion aluminium alloy brazing sheet material of claim 9 of the present invention, is the manufacture method of the high anti-corrosion aluminium alloy brazing sheet material described in any in 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 meets following formula (2):
V≥Sic/5(2)
In heating process after casting process, the ingot bar of sacrificial anode material is heated at 300～500 ℃ and keep 1～10 hour;
In hot-rolled process after heating process, the temperature of the sacrificial anode material during by end is made as below 350 ℃.
The manufacture method of the high anti-corrosion aluminium alloy brazing sheet material of claim 10 of the present invention, is the manufacture method of the high anti-corrosion aluminium alloy brazing sheet material described in any in claim 1-7, it is characterized in that, comprises following operation:
Laminated operation, sacrificial anode material, aluminium alloy heartwood, the Al-Si of method manufacture is associated golden braze material described in combination claim 9, as laminate;
Heating process after laminated operation, heats laminate and keeps 1～10 hour at 400～500 ℃;
Laminated hot-rolled process, after heating process, is made as the needed rolling laminate time below 40 minutes, and the temperature of laminate when rolling is finished is made as below 300 ℃.
The following describes effect of the present invention
According to the present invention, provide at for example automobile exhaust gas and pass through, under the environment of the tubing inside of heat exchanger, to there is sufficient corrosion proof aluminium alloy brazing sheet material.Under the state of the aluminium alloy brazing sheet material the present invention relates to after soldering heating, performance suppresses the effect of the homogeneous corrosion causing because corrosive fluid pH value is low, can also bring into play the effect of generation/growth that inhibition contains the pitting attack that chloride ion causes because of corrosive fluid simultaneously.Again, the radiator element joint rate of this soldering sheet material, the solderability excellence such as environment resistant, as for example vapour heat exchanger for vehicle, light weight and heat conductivity excellence, most suitable as the tubing of vapour heat exchanger for vehicle.Have again, use and there is the fin material of specific alloy ingredient, as interior radiator element, combine by the tubing forming with the aluminium alloy brazing sheet material by the present invention relates to, can manufacture for exhaust water of condensation and bring into play high corrosion proof heat exchanger.
Embodiment
The high anti-corrosion aluminium alloy brazing sheet material (brazing sheet, also referred to as " brazing sheet ") that detailed description the present invention relates to and the suitable example of manufacture method thereof.
A. the corrosive environment of heat exchanger
First, illustrate that effect of the present invention can obtain the corrosive environment of performance to the limit.The high anti-corrosion aluminium alloy brazing sheet material the present invention relates to, passing through the heat exchanger occasion of tubing inside for automobile exhaust gas etc., can be brought into play effect to greatest extent.As mentioned above, if 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 that the Al-Si of interpolation Zn is braze material occasion, and the Si particle on top layer becomes negative electrode, and Zn promotes the melting 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, the tubing use occasion of the heat exchanger of the waste gas as inside by automobile etc., and soldering sheet material of the present invention suppresses corrosion, can bring into play to greatest extent its effect.Do not pass through the tubing use occasion of the heat exchanger of waste gas as inside, corrosion speed is so not fast, can not effectively bring into play effect of the present invention.
Again, as mentioned above, if there is chloride ion in solution, because chloride ion destroys passive film, origination point corrosion.As inside by the tubing use occasion of the heat exchanger of the waste gas such as automobile, contain chloride ion at the inner exhaust water of condensation generating of tubing, there is bringing out property of pitting attack, therefore, generation/the growth of the soldering sheet material inhibition point corrosion the present invention relates to, can bring into play effect to greatest extent.Do not pass through the tubing use occasion of the heat exchanger of waste gas as inside, corrosive environment does not have bringing out property of pitting attack sometimes, can not effectively bring into play effect of the present invention.As the corrosive environment of bringing into play to greatest extent effect of the present invention, be preferably, pH value is below 3, more than chloride ion concentration 5ppm.
The sacrificial anode material, heartwood and the braze material that form the aluminium alloy brazing sheet material the present invention relates to are described below.
B. sacrificial anode material
B-1.Si
By adding Si, make the melting point depression of sacrificial anode material, produce liquid phase, make thus soldering possibility.The content of Si is 2.5～7.0 quality % (mass%, below brief note is " % ").Containing quantity not sufficient 2.5%, liquid phase produces few, therefore, is difficult to have outside soldering function.On the other hand, if exceed 7.0%, the amount of liquid phase producing when soldering heating is too much, and the sacrificial anode material existing 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, and the potential difference by formation with heartwood, because sacrificial anode effect can improve solidity to corrosion.The content of Zn is 1.0～5.5%.Containing quantity not sufficient 1.0%, because of the corrosion proof effect of raising that sacrificial anode effect causes insufficient.On the other hand, if exceed 5.5%, corrosion speed accelerates, and sacrificial anode material disappears in early days, and solidity to corrosion reduces.
B-3.Fe
Fe easily forms the compound of Al-Fe system and Al-Fe-Si system, and above-claimed cpd becomes negative electrode in aluminium, and solidity to corrosion is reduced.The content of Fe is 0.05～1.0%.Containing quantity not sufficient 0.05%, must use raffinal matrix metal, cause that cost is high.On the other hand, if exceed 1.0%, cathodic reaction sensitization, solidity to corrosion becomes insufficient.The preferred content of Fe is 0.1～0.5%.
B-4.Ti
Ti, by solution strengthening, improves intensity, and can improve solidity to corrosion.The content of Ti preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of Ti is 0.1～0.2%.
B-5.Zr
Zr, by solution strengthening, improves intensity, and separates out the intermetallics of Ai-Zr system, and the crystallization particle diameter coarsening after soldering is worked.The content of Zr preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of Zr is 0.1～0.2%.
B-6.Cr
Cr, by solution strengthening, improves intensity, and separates out the intermetallics of Ai-Cr system, and the crystallization particle diameter coarsening after soldering is worked.The content of Cr preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of Cr is 0.1～0.2%.
B-7.V
V, by solution strengthening, improves intensity, and can improve solidity to corrosion.The content of V preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of V is 0.1～0.2%.
Above-mentioned Ti, Zr, Cr and V can at least add a kind of in sacrificial anode material as required.
B-8.Si content, the relation of Zn content and covering (clad) thickness T
Have again, about Si content Sic (quality %), Zn content Znc (quality %), and the cladding thickness T of sacrificial anode material (μ m), not only be limited in scope separately, and making them meet above-mentioned formula (1), this is very suitable from solidity to corrosion viewpoint.X in formula (1) represents soldering when heating, do not melt as the Zn total amount in the remaining sacrificial anode material of solid.
; in sacrificial anode material; when soldering heating, determined by Si content Sic (quality %) as the remaining ratio of solid; with (1.1-0.1Sic) give with; be multiplied by Zn content Znc (quality %); as the T of cladding thickness, (μ m), obtains X value, and this X value becomes the index representing as the Zn total amount in the remaining sacrificial anode material of solid.The inventor finds through in detail test and result of study, in the time that this X value becomes below 150, is presented at and under exhaust water of condensation environment, has the solidity to corrosion of excellence especially.That is, mean when the Zn total amount in the sacrificial anode material remaining as solid be below certain level time, show excellent especially solidity to corrosion.Better the scope of X value is below 140.This X value is larger, 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 lower, and the difference change of the different corrosion speeds that cause of X value greatly.Therefore, the pH value of liquid is lower, and superiority of the present invention more can be brought into play.X value, than 150 large occasions, is becoming under the environment of the exhaust water of condensation of pH value below 3, and corrosion speed is fast, does not have sufficient solidity to corrosion.
B-9. the cladding thickness of sacrificial anode material
The cladding thickness that forms the sacrificial anode material of the aluminium alloy brazing sheet material 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 sacrifice corrosion protection result, and in the time that soldering is heated, one partial melting becomes braze material, plays a part and bare radiator soldered joint.The cladding thickness less than 25 μ m of sacrificial anode material, the Si composition of sacrificial anode material adds and hankers being diffused into heartwood from sacrificial anode material in soldering.Its result, the remaining Si quantitative change in sacrificial anode material when soldering is few, is difficult to guarantee the fused solution phasor for soldering.Again, if the cladding thickness of sacrificial anode material exceedes 80 μ m, mobile braze material surplus, the corrosion that produces solder erosion fin material.
B-10. the metal structure of raw sheet
Have again, about the metal structure of the sacrificial anode material of raw sheet, Si the particles more than suitable circular diameter 1.0 μ m in matrix (matrix) 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 Si particles more than 1.0 μ m is made as 5000/mm
2below.As mentioned above, Si particle becomes negative electrode in corrosion reaction, and corrosion speed is increased.The Si particle of 1.0 μ m deficiencies melts and becomes braze material in the time that soldering is heated, and therefore, can not make the corrosion speed of the remaining sacrificial anode material of melting increase.On the other hand, Si particles more than 1.0 μ m is in the remaining sacrificial anode material of melting, also remaining after soldering heating, therefore, corrosion speed is increased.The relative pH value of corrosion speed at the aluminium of acidic region becomes negative exponential function, and therefore, pH value is lower, because of the difference of the corrosion speed that quite Si particle density differences more than circular diameter 1.0 μ m causes larger.Therefore, the pH value of the liquid that is placed in is lower, and superiority of the present invention more can be brought into play.By the density that exists of Si particles more than 1.0 μ m is made as to 5000/mm
2below, can suppress the corrosion speed of sacrificial anode material, obtain sufficient solidity to corrosion.Quite Si particles more than circular diameter 1.0 μ m there is 5000/mm of density ratio
2large occasion, the corrosion speed of sacrificial anode material increases, and can not obtain sufficient solidity to corrosion.Quite the density that preferably exists of Si particles more than circular diameter 1.0 μ m is 3000/mm
2below.
In the present invention, above-mentioned " more than 1.0 μ m " comprise 1.0 μ m (below all like this), above-mentioned " 5000/mm
2below " comprise 5000/mm
2(below all like this).
Have, from solidity to corrosion viewpoint, be preferably, aluminium alloy brazing sheet material of the present invention is after heating for soldering, 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 more than 5.0 μ m Si particle there is preferably 500/mm of density
2below.Suitable circular diameter is the core that Si particles more than 5.0 μ m becomes recrystallize in the time that soldering is heated, therefore, so large occasion of Si particle density, the crystallization particle diameter after soldering becomes more small.Suitable circular diameter is that Si particles more than 5.0 μ m exceedes 500/mm
2occasion, the crystallization particle diameter ratio cladding thickness of the sacrificial anode material after soldering 80% little.Be more preferably, quite circular diameter is that Si particle densities more than 5.0 μ m is 400/mm
2below.From the above point of view, suitable circular diameter is that Si particle densities more than 5.0 μ m does not have lower limit, still, in the composition of the sacrificial anode material stipulating at soldering sheet material of the present invention, is difficult to be made as 10/mm
2below.
B-11. the metal structure after soldering heating
In aluminium alloy brazing sheet material of the present invention, after soldering heating, the average crystallite particle diameter of the thickness direction of sacrificial anode material is preferably the more than 80% of cladding thickness of above-mentioned sacrificial anode material.If aluminium alloy brazing sheet material of the present invention soldering, molten solder is created on the grain boundary of sacrificial anode material, therefore, if soldering is placed on corrosive environment, grain boundary local corrosion.After soldering, 80% above occasion of the cladding thickness that the average crystallite particle diameter of the thickness direction of sacrificial anode material is sacrificial anode material, be present in the centre of the sacrificial anode material of thickness direction, or the grain boundary at the interface of sacrificial anode material and heartwood is few, therefore the crystal grain that, inhibition causes because of grain boundary attack comes off.Therefore, sacrificial anode material needs long-time because corrosion disappears, can obtain sufficient solidity to corrosion.80% occasion of the cladding thickness of the not enough sacrificial anode material of average crystallite particle diameter of the thickness direction of the sacrificial anode material after soldering, be present in the centre of 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, Yi Fashengyin grain boundary attack causes comes off.Therefore, sacrificial anode material disappears in early days, can not obtain sufficient solidity to corrosion.Be more preferably, after soldering, the more than 90% of cladding thickness that the crystallization particle diameter of sacrificial anode material is sacrificial anode material.
C. heartwood
Adopt JIS 3000 to be associated gold for the aluminium alloy of heartwood of the present invention, it is very suitable that the Al-Mn of such as JIS 3003 alloys etc. is associated gold.The following describes major ingredient.
C-1.Si
Si forms the intermetallics of Al-Mn-Si system together with Mn, by dispersion-strengthened, or is solid-solubilized in aluminium parent phase, improves intensity by solution strengthening.The content of Si is 0.1～1.2%.Containing quantity not sufficient 0.1%, above-mentioned effect is insufficient, if exceed 1.2%, heartwood melting point depression, melting possibility occurs and uprise.The preferred content of Si is 0.1～1.0%.
C-2.Fe
Fe easily forms the intermetallics of the size that can become recrystallization nucleus, makes the crystallization particle diameter after soldering thick, suppresses the diffusion of solder from braze material to heartwood.Fe content is 0.05～1.0%.Containing quantity not sufficient 0.05%, must use raffinal matrix metal, cost is high, if exceed 1.0%, the crystallization particle diameter after soldering becomes small, has the danger that produces solder diffusion.The preferred content of Fe is 0.1～0.5%.
C-3.Cu
Cu, by solution strengthening, improves intensity.Cu content is 0.05～1.2%.Containing quantity not sufficient 0.05%, above-mentioned effect is insufficient, if exceed 1.2%, the possibility that when casting, aluminium alloy cracks uprises.The preferred content of Cu is 0.3～1.0%.
C-4.Mn
Mn forms the intermetallics of Al-Mn-Si system together with Si, by dispersion-strengthened, or is solid-solubilized in aluminium parent phase, improves intensity by solution strengthening.The content of Mn is 0.6～1.8%.Containing quantity not sufficient 0.6%, above-mentioned effect is insufficient, if exceed 1.8%, easily forms large intermetallics when casting, and plastic working reduces.The preferred content of Mn is 0.8～1.6%.
C-5.Mg
Mg is by separating out Mg
2si, improves intensity.The content of Mg preferably 0.05～0.5%.Containing quantity not sufficient 0.05%, above-mentioned effect is insufficient sometimes, if exceed 0.5%, soldering difficulty occurs sometimes.The better content of Mg is 0.15～0.4%.
C-6.Ti
Ti, by solution strengthening, improves intensity.The content of Ti preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, above-mentioned effect is insufficient sometimes, if exceed 0.3%, sometimes easily forms large intermetallics, and plastic working reduces.The better content of Ti is 0.1～0.2%.
C-7.Zr
Zr, by solution strengthening, improves intensity, and separates out the intermetallics of Al-Zr system, and the crystallization particle diameter coarsening after soldering is worked.The content of Zr preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect, if exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of Zr is 0.1～0.2%.
C-8.Cr
Cr, by solution strengthening, improves intensity, and separates out the intermetallics of Al-Cr system, and the crystallization particle diameter coarsening after soldering is worked.The content of Cr preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of Cr is 0.1～0.2%.
C-9.V
V, by solution strengthening, improves intensity, meanwhile, can also improve solidity to corrosion.The content of V preferably 0.05～0.3%.Containing quantity not sufficient 0.05%, sometimes can not obtain above-mentioned effect.If exceed 0.3%, sometimes easily form large intermetallics, plastic working reduces.The better content of V is 0.1～0.2%.
As heartwood, according to mentioned component, can use suitably aluminium alloy, 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 inevitable impurity.Can use the aluminium alloy that further contains at least one element of selecting from 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 % in this composition again.
D. braze material
Braze material can use normally used Al-Si to be associated gold.Alloying constituent is not particularly limited, and for example, can use suitably JIS4343,4045,4047 alloys (Al-7～13 quality %Si).
E. the manufacture method of high anti-corrosion aluminium alloy brazing sheet material
E-1. the manufacture of heartwood
The common semicontinuous casting method of heartwood that is used for the aluminium alloy brazing sheet material the present invention relates to is cast.Carry out the processing that homogenizes of 1～20 hour at 400～620 ℃ as required, after this, carry out the adjustment thickness such as face cutting, make the ingot bar of heartwood.
E-2. the manufacture of sacrificial anode material
The sacrificial anode material that the present invention uses comprises the casting process of semicontinuous casting, the operation of the heating ingot bar that obtains, and by the operation of its hot rolling.In order further to improve the solidity to corrosion of sacrificial anode material, be preferably, in matrix, the density that exists of the Si particle with suitable circular diameter more than 1.0 μ m is made as to 5000/mm
2be made as 500/mm below, and by the density that exists of the Si particle with suitable circular diameter more than 5.0 μ m
2below.Thus, prevent the coarsening of Si particle.For this reason, need to control the speed of cooling of the ingot bar of the casting process of sacrificial anode material, control Heating temperature and the heat-up time of the heating process after casting process, the temperature when hot rolling after control heating process finishes.
Speed of cooling when sacrificial anode material casting is larger, is more difficult to generate thick Si particle, and still, the speed of cooling necessitating exists with ... the amount of the Si that adds sacrificial anode material to.The inventor is for size and the density of Si particle, speed of cooling V when the 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 be related to occasion when meeting above-mentioned formula (2), can obtain better Si particle distribution.The speed of cooling control of sacrificial anode material be certain more than certain benchmark value, mean that Si amount is more, this benchmark value is higher.Speed of cooling when casting is the speed of cooling of slab central part while solidifying.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 meet following formula (3):
V≥Sic/4 (3)
The ingot bar of the sacrificial anode material being obtained by above-mentioned casting in hot-rolled process rolling until determine thickness of slab.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 is made as 1～10 hour.If ingot bar temperature exceedes 500 ℃, or the hold-time exceed 10 hours, the Si particle coarsening in sacrificial anode material, can not more suitably be distributed, solidity to corrosion reduce.On the other hand, 300 ℃ of ingot bar temperature less thaies, in the time of hot rolling resistance to deformation large, therefore, rolling difficulty sometimes, hold-time less than 1 hour, sometimes ingot bar temperature heterogeneity.
The ingot bar of sacrificial anode material imposes hot-rolled process after heating process.In the present invention, be preferably, when hot rolling finishes, ingot bar temperature is made as below 350 ℃.If ingot bar temperature exceedes 350 ℃ when hot rolling finishes, the Si particle coarsening in sacrificial anode material, can not more suitably be distributed, and solidity to corrosion reduces.The thickness of slab of the sacrificial anode material after hot rolling is determined by the covering rate of target and the ingot bar thickness of heartwood, is generally 10～100mm left and right.
E-3. the manufacture of braze material
Braze material, also by casting process and hot-rolled process manufacture, at this, there is no need to do special control, conventionally, and with 0.3 ℃/more than s speed of cooling casting, heating hot rolling afterwards 500 ℃ below, more than 1 hour.
E-4. the manufacture of laminate
The aluminium alloy brazing sheet material the present invention relates to comprises laminated operation, heating process and laminated hot-rolled process, described laminated operation is to use the heartwood of being manufactured by aforesaid method, sacrificial anode material and braze material, composite sacrificial anodes material in the one side of heartwood, on another side, combine braze material, or composite sacrificial anodes material on heartwood two sides, make it as laminate, the ingot bar of described heating process zone of heating condensation material, described laminated hot-rolled process is rolled the laminate of heating.Even in the manufacturing process of above-mentioned laminate, be preferably, the density that exists of controlling the Si particle with suitable circular diameter more than 1.0 μ m existing in the matrix of sacrificial anode material is made as 5000/mm
2below.Thus, prevent the coarsening 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 is made as 1～10 hour.Exceed 500 ℃ if ingot bar reaches temperature, or the hold-time exceed 10 hours, the Si particle coarsening in sacrificial anode material, can not obtain more suitably Si and distribute, 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, sometimes laminate temperature heterogeneity.
Through the laminate of heating process, be subjected to laminated hot-rolled process.In the present invention, be preferably, the needed laminated hot-rolled process time was made as below 40 minutes.Be preferably, the temperature of laminate when laminated hot-rolled process finishes is made as below 300 ℃.If rolling time exceedes 40 minutes, or the temperature of rolling while finishing exceed 300 ℃, and the Si particle coarsening in sacrificial anode material, can not obtain more suitably Si and distribute, and solidity to corrosion reduces.Be more preferably, the needed laminated hot-rolled process time is made as at least 10 minutes.Carry out 10 minutes occasions of laminated hot rolling deficiency of time, the crackle of material generation sometimes, or sacrificial anode material or braze material peel off, and guarantees that manufacturing is very difficult.Thickness of slab while end for laminated hot rolling is not particularly limited, and is generally 2～10mm left and right.
The aluminium alloy brazing sheet material being obtained by laminated hot rolling, after this by cold rolling until determine thickness of slab.After midway cold rolling or cold rolling, can be through the annealing operation of 1～2 left and right.Condition for cold rolling and annealing operation is not particularly limited, and conventionally, after cold rolling Process Annealing, applies the rolling of 5～80% left and right, becomes determined thickness of slab, is made as H1X modified, or rolling until determine after thickness of slab, anneal, be made as H2X modified.Annealing operation is used batch furnace at 200～500 ℃ conventionally, carries out, or use continuous furnace to carry out at 200～550 ℃ of temperature under the condition of 1～10 hour.
For the thickness of aluminium alloy brazing sheet material of the present invention, the covering rate of braze material layer is not particularly limited, conventionally,, as the tubing use occasion of the side cooler that the pressurized air of turbo-supercharger is circulated, can be made as the following thin-walled soldering sheet material in about 0.6mm left and right.But, be not defined as the thickness of slab within the scope of this, also can be used as the materials'use of the comparison heavy wall that 0.6mm left and right is above, 5mm left and right is following.The covering rate of braze material layer is generally 3～20% left and right.
F. heat exchanger
Under the state of the aluminium alloy brazing sheet material the present invention relates to after soldering heating, there is the effect suppressing because of the low homogeneous corrosion causing of pH value of corrosive fluid, and also there is the effect that suppresses the generation/growth because contain the pitting attack that chloride ion causes in corrosive fluid simultaneously, excellent strength, solderability is good, therefore, very suitable as the vapour heat exchanger for vehicle use of for example light weight.
F-1. interior fin material
The formation and the composition range that aluminium alloy brazing sheet material of the present invention are used in to the interior fin material of the heat exchanger occasion with interior radiator element are described below.
Interior radiator element uses bare radiator.As mentioned above, interior radiator element has braze material occasion, and under exhaust water of condensation environment, the Si particle in braze material becomes negative electrode, and corrosion speed increases.So, the bare radiator of use corrosion resistance excellent.
As the Al alloying constituent of interior fin material, be defined as below Cu0.1%, below Zn0.5%.Cu becomes negative electrode under the environment of exhaust water of condensation, because causing grain boundary attack, corrosion speed is increased, and therefore, if Cu content exceedes 0.1%, the strength decreased after corrosion becomes large, and the compressive strength of heat exchanger reduces.Zn promotes the melting of aluminium under the environment of exhaust water of condensation, increases corrosion speed, and therefore, if Zn content exceedes 0.5%, the strength decreased after corrosion is large, and the compressive strength of heat exchanger reduces.Be not particularly limited about composition beyond Cu, the Zn of interior radiator element, conventionally, use the alloy that pure Al is, Al-Fe is, Al-Mn is.
Manufacture method about the heat exchanger the present invention relates to is not particularly limited, and conventionally, after the part combinations such as forming tube, radiator element, collector, is heated to approximately 600 ℃ of soldering manufactures.
The heat exchanger obtaining like this has high voltage endurance, and has good solidity to corrosion, therefore, in the vapour heat exchanger for vehicle of the environment in waste gas passes through tubing etc., can bring into play good weather resistance.
[embodiment]
, further describe the present invention according to embodiment below, still, the present invention is not limited by the following examples.
There is the sacrificial anode material of alloying constituent shown in table 1 by the casting of DC castmethod respectively, and there is the heartwood alloy of alloying constituent shown in table 2, respectively surfacing processing is carried out in two sides.The ingot bar thickness of the heartwood in this moment and sacrificial anode material is all 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 from sacrificial anode material, as braze material, use JIS4045 alloy, above-mentioned sacrificial anode material and 4045 alloy brazed materials are applied to heating process and hot-rolled process, rolling is until desirable thickness respectively.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, the sacrificial anode material at the one side of heartwood as skin-material 1 combination table 1, sacrificial anode material or 4045 alloy brazed materials at another side as skin-material 2 combination table 1.Above-mentioned laminate is imposed to heating process and laminated 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 to process annealing (condition: keep 5 hours at 400 ℃ of temperature), 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 inventive 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 be illustrated in the process conditions of table 3.
Table 4
G. evaluate
Measure the sacrificial anode material of test portion and the thickness of braze material of above-mentioned making, calculate the X value being given by formula (1).Measure respectively the density that exists of the Si particle with the above and more than 5.0 μ m suitable circular diameter of 1.0 μ m in sacrificial anode material again.And then, above-mentioned test portion is carried out at 600 ℃ of temperature to the soldering heating of 3 minutes, evaluate 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
With grinding, the L-ST face of test portion is carried out to surperficial centering, carve with triumphant Le Shi liquid corrosion, the difference of the contrast causing because of alloying constituent difference by microscopic examination, the thickness of mensuration sacrificial anode material and 4045 alloy brazed materials.
The mensuration that has density of G-2.Si particle
Have the above and more than 5.0 μ m suitable circular diameter of 1.0 μ m Si particle there is density, by the cross section of the sacrificial anode material with the etched sample of the above-mentioned triumphant Le Shi liquid of observation by microscope, measure.For two bread crumb sacrificial anode material persons, using skin-material 1 as mensuration face.
G-3. the mensuration of the average crystallite particle diameter of the sacrificial anode material after soldering
After separately test portion soldering being heated with sheet material, with grinding, L-ST face is carried out to surperficial centering, use Pa Keshi (Barker, name) liquid to make anodic oxidation, by 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 average crystallite particle diameter.For two bread crumb sacrificial anode material persons, using skin-material 1 as mensuration face.
G-4. corrosion proof mensuration
Separately to after test portion soldering heating, cut out 50mm × 50mm with sheet material, shelter the face of skin-material 2 by resin, using the face of the covering sacrificial anode material of skin-material 1 as test face.In the aqueous solution of composition shown in table 5, carry out the dip test of 50 ℃, 1000 hours.After off-test, remove corrodibility biology with concentrated nitric acid, measure the depth of corrosion that occurs in sacrificial anode material face by depth of focus method, by the darkest person as depth of corrosion.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 "○", even if only have one to be the above occasion of 150 μ m, be made as defective "×".
Table 5
| Chloride ion concentration (ppm) | 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
3003 alloy corrugateds are shaped and obtain radiator element, with the sacrificial anode material face combination of test portion, be immersed in 5% the fluoride flux aqueous solution, carry out the 80 ℃ of solderings of 3 minutes heating.Be more than 95% by the radiator element joint rate of this test heartwood, and test portion do not produce melting occasion, as the qualified "○" of solderability, radiator element joint rate less than 95% and/or test portion produce melting occasion as the insufficient "×" of solderability.
Thickness, the X value of sacrificial anode material and braze material, the result with average crystallite particle diameter, depth of corrosion and the solderability of the thickness direction that has separately the sacrificial anode material after density, soldering of the Si particle of the above and more than 5.0 μ m suitable circular diameter of 1.0 μ m are illustrated in table 6.
Table 6
Wherein, symbolic significance is as follows:
M1: (μ is < skin-material 1> m) for sacrificial anode material thickness
M2: (μ is < skin-material 2> m) for sacrificial anode material or braze material thickness
Si particle density (individual/mm more than N1:1.0 μ m
2)
Si particle density (individual/mm more than N2:5.0 μ m
2)
D: (μ m) for the average crystallite particle diameter of the thickness direction of the sacrificial anode material after soldering
In the inventive example 1～14 and 22～31, meet defined terms of the present invention, solidity to corrosion and solderability are all qualified.Especially, in the inventive example that has separately density 1～8 and 22～24 of the Si particle of the suitable circular diameter more than meeting formula (1) and thering are 1.0 μ m and more than 5.0 μ m, the whole less than 100 μ m of 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 excessively thin, and therefore, solderability is poor.
In comparative example 21, the thickness of sacrificial anode material is blocked up, and therefore, solderability is poor.
The following describes the utilizability in industry
The aluminium alloy clad material the present invention relates to has the effect suppressing because of the low homogeneous corrosion causing of pH value of corrosive fluid, and also there is the effect that suppresses the generation/growth because contain the pitting attack that chloride ion causes in corrosive fluid 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 such as automobile etc. is used.
Claims (10)
1. a high anti-corrosion aluminium alloy brazing sheet material, comprises the heartwood of aluminium alloy, the sacrificial anode material of covering in the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be associated golden braze material, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy, and it contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %, and remainder is made up of Al and inevitable impurity;
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;
The cladding thickness of this sacrificial anode material is 25～80 μ m, and in the matrix of above-mentioned sacrificial anode material, the density that exists with the Si particle of suitable circular diameter more than 1.0 μ m is 5000/mm
2below, the density that exists that has a Si particle of suitable circular diameter more than 5.0 μ m is 500/mm
2below.
2. a high anti-corrosion aluminium alloy brazing sheet material, comprise the heartwood of aluminium alloy, and covering is at the sacrificial anode material on the two sides of this heartwood, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy, and it contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %, and remainder is made up of Al and inevitable impurity;
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;
The cladding thickness of above-mentioned each sacrificial anode material is 25～80 μ m, and in the matrix of above-mentioned sacrificial anode material, the density that exists with the Si particle of suitable circular diameter more than 1.0 μ m is 5000/mm
2below, the density that exists that has a Si particle of suitable circular diameter more than 5.0 μ m is 500/mm
2below.
3. a high anti-corrosion aluminium alloy brazing sheet material, comprises the heartwood of aluminium alloy, the sacrificial anode material of covering in the one side of this heartwood, and the Al-Si of covering on the another side of this heartwood be associated golden braze material, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy; it contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; and further contain at least one that select 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 %, remainder is made up of Al and inevitable impurity;
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;
The cladding thickness of this sacrificial anode material is 25～80 μ m, and in the matrix of above-mentioned sacrificial anode material, the density that exists with the Si particle of suitable circular diameter more than 1.0 μ m is 5000/mm
2below, the density that exists that has a Si particle of suitable circular diameter more than 5.0 μ m is 500/mm
2below.
4. a high anti-corrosion aluminium alloy brazing sheet material, comprise the heartwood of aluminium alloy, and covering is at the sacrificial anode material on the two sides of this heartwood, it is characterized in that:
Above-mentioned sacrificial anode material is aluminium alloy; it contains Si:2.5～7.0 quality %, Zn:1.0～5.5 quality %, Fe:0.05～1.0 quality %; and further contain at least one that select 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 %, remainder is made up of Al and inevitable impurity;
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;
The cladding thickness of above-mentioned each sacrificial anode material is 25～80 μ m, and in the matrix of above-mentioned sacrificial anode material, the density that exists with the Si particle of suitable circular diameter more than 1.0 μ m is 5000/mm
2below, the density that exists that has a Si particle of suitable circular diameter more than 5.0 μ m is 500/mm
2below.
5. according to the high anti-corrosion aluminium alloy brazing sheet material described in any in claim 1-4, it is characterized in that:
High anti-corrosion aluminium alloy brazing sheet material after soldering heating, the more than 80% of cladding thickness that the average crystallite particle diameter of the thickness direction of above-mentioned sacrificial anode material is this sacrificial anode material.
6. according to the high anti-corrosion aluminium alloy brazing sheet material described in any in claim 1-4, it is characterized in that:
Be used as the tubing of the heat exchanger of automobile exhaust gas inflow.
7. high anti-corrosion aluminium alloy brazing sheet material according to claim 6, is characterized in that:
Under environment in pH value below 3, more than chloride ion concentration 5ppm, use.
8. a manufacture method for high anti-corrosion aluminium alloy brazing sheet material, is the manufacture method of the high anti-corrosion aluminium alloy brazing sheet material described in claim 1 or 3, and it comprises:
Casting process, casts respectively above-mentioned heartwood, above-mentioned sacrificial anode material and above-mentioned Al-Si and is associated golden braze material, semicontinuous casting method casting for above-mentioned heartwood;
Heating process, heats above-mentioned sacrificial anode material and above-mentioned Al-Si is associated golden braze material;
Hot-rolled process, rolling above-mentioned sacrificial anode material and above-mentioned Al-Si is after this associated golden braze material;
Laminated operation, combines above-mentioned heartwood, above-mentioned sacrificial anode material and above-mentioned Al-Si and is associated golden braze material, as laminate;
Heating process, heats the ingot bar of above-mentioned laminate;
Laminated hot-rolled process, the laminate of the above-mentioned heating of rolling;
The cold rolling process of above-mentioned laminate after this; And
The annealing operation of laminate, above-mentioned midway cold rolling or cold rolling after, anneal;
The manufacture method of above-mentioned high anti-corrosion aluminium alloy brazing sheet material is characterised in that:
In the casting process of above-mentioned sacrificial anode material, 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 meets following formula (2):
V≥Sic/5 (2)
In the heating process of above-mentioned sacrificial anode material, the ingot bar of sacrificial anode material is heated at 300～500 ℃ and keep 1～10 hour;
In the hot-rolled process of above-mentioned sacrificial anode material, the temperature of the sacrificial anode material during by end is made as below 350 ℃; In the heating process of ingot bar that heats above-mentioned laminate, Heating temperature is made as to 400～500 ℃, the heating hold-time is made as 1～10 hour; In above-mentioned laminated hot-rolled process, the needed rolling laminate time was made as below 40 minutes, the temperature of laminate when rolling is finished is made as below 300 ℃.
9. a manufacture method for high anti-corrosion aluminium alloy brazing sheet material, is the manufacture method of the high anti-corrosion aluminium alloy brazing sheet material described in claim 2 or 4, and it comprises:
Casting process, casts respectively above-mentioned heartwood and above-mentioned sacrificial anode material, semicontinuous casting method casting for above-mentioned heartwood;
Heating process, heats above-mentioned sacrificial anode material;
Hot-rolled process, rolling above-mentioned sacrificial anode material after this;
Laminated operation, combines above-mentioned heartwood and above-mentioned sacrificial anode material, as laminate;
Heating process, heats the ingot bar of above-mentioned laminate;
Laminated hot-rolled process, the laminate of the above-mentioned heating of rolling;
The cold rolling process of above-mentioned laminate after this; And
The annealing operation of laminate, above-mentioned midway cold rolling or cold rolling after, anneal;
The manufacture method of above-mentioned high anti-corrosion aluminium alloy brazing sheet material is characterised in that:
In the casting process of above-mentioned sacrificial anode material, 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 meets following formula (2):
V≥Sic/5 (2)
In the heating process of above-mentioned sacrificial anode material, the ingot bar of sacrificial anode material is heated at 300～500 ℃ and keep 1～10 hour;
In the hot-rolled process of above-mentioned sacrificial anode material, the temperature of the sacrificial anode material during by end is made as below 350 ℃; In the heating process of ingot bar that heats above-mentioned laminate, Heating temperature is made as to 400～500 ℃, the heating hold-time is made as 1～10 hour; In above-mentioned laminated hot-rolled process, the needed rolling laminate time was made as below 40 minutes, the temperature of laminate when rolling is finished is made as below 300 ℃.
10. a high anti-corrosion heat exchanger, is characterized in that:
Right to use requires the high anti-corrosion aluminium alloy brazing sheet material described in 5, as the tubing that sacrificial anode material is made as to inner face, at this sacrificial anode material face configuration bare radiator, radiator element in forming, the above-mentioned sacrificial anode material of soldered joint and bare radiator form.
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| CN103567656A (en) * | 2013-10-28 | 2014-02-12 | 顾建 | Brazing material for aluminum alloy |
| EP3121301B1 (en) * | 2014-03-19 | 2018-10-17 | UACJ Corporation | Cladded aluminium-alloy material and production method therefor, and heat exchanger using said cladded aluminium-alloy material and production method therefor |
| US20180073118A1 (en) * | 2015-03-14 | 2018-03-15 | Uacj Corporation | Aluminum-alloy brazing sheet fin material for heat exchanger, and production process therefor |
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| JP2021063264A (en) * | 2019-10-11 | 2021-04-22 | パナソニックＩｐマネジメント株式会社 | Brazing sheet for heat exchanger and heat exchanger for air conditioner |
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