CN109797323A - A kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe and its production method - Google Patents
A kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe and its production method Download PDFInfo
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Abstract
The present invention relates to a kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe and its production methods, Rolling compund forms after being laminated in order by clad alloy 1, barrier layer alloy, core alloys and clad alloy 2, the barrier layer alloy is made of the element of following mass fraction: 0.5%~1.0% Si, 0.15%~0.7% Fe, 1.0%~2.0% Mn, 0.05%~0.2% Mg, 1.5%~3.5% Zn, 0~0.15% Cu, single content≤0.05% and total content≤0.15% other elements, surplus Al.Barrier layer is the Al-Mn alloy for adding the Zn element of certain content; the effect of sacrificing protection is provided, the Zn optimum content on barrier layer is 1.5%~3.5% mass fraction, and the potential difference with sandwich layer is 60~140mV; protective effect is provided for sandwich layer, keeps the corrosion resistance of material best.
Description
Technical field
The present invention relates to a kind of MULTILAYER COMPOSITE aluminium alloy pipe and its production methods, more particularly to a kind of aluminium that is suitable for radiate
Soldering highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe and its production method of Type B pipe, U-tube and the hourglass pipe of device etc..
Technical background
MULTILAYER COMPOSITE brazed aluminum alloy material is widely used in heat exchanger system, as automobile radiators, in it is cold
Device, air-conditioning condenser, evaporator etc..Carry out heat exchange carrier be usually such as water, freezing liquid, oil liquid, these liquid and
Automobile exhaust gas or refrigerant etc. circulate in heat exchanger materials in the tube after combining very big corrosiveness to material, and one
Denier materials in the tube because corrosion leaks, then scrap by product generation, so improving MULTILAYER COMPOSITE brazed aluminum alloy materials in the tube corrosion resistance
Have great importance to the service life for improving product.
China's automobile radiators heat exchanger tubing is by three layers of compound tubing with brazed aluminum alloy at present, and core material is
AA3003 alloy, pricker deposited strength is lower, and corrosion resistance is poor, is easy fatigue fracture, corrosion leakage etc. in use
Unfavorable condition.
The CN 101927588A for opening monarch et al. discloses a kind of car heat exchanger NEW TYPE OF COMPOSITE brazed aluminum alloy material
Material, which equally increases by one layer of barrier layer structure in one end of sandwich layer and clad, to improve the corrosion-resistant of material
Performance.But the barrier layer in the invention can drop low-alloyed intensity using AA7072 alloy in certain degree.Though and
The corrosion potential of right AA7072 alloy is relatively low, can play the role of to the core material of current potential calibration good " anodic protection ", still
The potential difference of barrier layer and sandwich layer is not that very greatly, cannot play a good protective effect under certain special environment.
The CN 103122427A of Zhang Bin et al. discloses a kind of soldering aluminum alloy composite board and its manufacturing method,
Center core layer contains higher Si element, can consume more waste materials in process of production, reduces the cost of raw material and the energy disappears
Consumption, but the problems such as being easy to happen serious corrode during slice welds is spent in high temperature.Its described barrier layer alloy using
AA1050 adds 0.5%~3.5% Zn, although barrier layer can play the role of preferable " anodic protection " core material, can drop
The intensity of low material entirety.
Summary of the invention
The object of the present invention is to provide a kind of soldering highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe and the aluminium-alloy pipes
The production method of material, to overcome the shortcomings of the prior art.
The first object of the present invention is to provide a kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe, by clad alloy 1, resistance
Rolling compund forms after barrier alloy, core alloys and clad alloy 2 are laminated in order, which is characterized in that the barrier layer
Alloy is made of the element of following mass fraction: 0.5%~1.0% silicon (Si), 0.15%~0.7% iron (Fe), 1.0%
~2.0% manganese (Mn), 0.05%~0.2% magnesium (Mg), 1.5%~3.5% zinc (Zn), 0~0.15% copper (Cu),
Other element impurities of single content≤0.05% and total content≤0.15%, surplus are aluminium (Al).
In highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention, the core alloys by following mass fraction member
Element composition: 0.1%~0.8% silicon (Si), 0.15%~0.8% iron (Fe), 0.15%~0.7% copper (Cu), 0.5%
~1.8% manganese (Mn), 0.1%~0.45% magnesium (Mg), 0.05%~0.3% titanium (Ti), single content≤0.05%
And the other element impurities of total content≤0.15 weight %, surplus are aluminium (Al).
In highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention, the clad alloy 1 and clad alloy 2 are
Conventional brazing layer alloy material, for example, by using commercially available AA4343, AA4045 aluminium alloy, the quality of conventional element composition
Score are as follows: 4%~13% Si, 0.1%~0.4% Fe, 0.05%~0.25% Cu, 0~0.1% Mn, 0~
Other element impurities of 0.1% Zn, single content≤0.05% and total content≤0.15%, surplus Al.
Further, in highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention, the barrier layer alloy it is compound
Ratio is 10%~25%, and the recombination rate of the clad alloy 1 is 5%~15%, and the clad alloy 2 is answered
Composition and division in a proportion rate is 6%~15%；The thickness hundred that the recombination rate is occupied in multilayer materials by a certain monolayer material
Divide ratio.
Further, highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention, overall thickness are 0.15~0.5mm.
A second object of the present invention is to provide a kind of preparation methods of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe, special
Sign is, comprising steps of
(1) milling face is respectively cut in the ingot casting of barrier layer alloy, clad alloy 1 and clad alloy 2,520~580
DEG C Homogenization Treatments, are then hot-rolled down to required thickness under the conditions of 470~500 DEG C；Core alloys ingot casting is cut into milling face；(2)
By recombination rate requirement, by step (1) treated clad alloy 2, core alloys, barrier layer alloy and clad alloy 1
It is laminated from the bottom up；By 4 layer materials connect combine, then hot rolling under the conditions of 470~500 DEG C, rolling thickness be 3~
5mm；(3) composite material for obtaining step (2) carries out cold rolling, 0.15~0.5mm of rolling thickness；After cold rolling finished product 240~
300 DEG C of 1~3h of annealing.
The barrier layer alloy is made of the element of following mass fraction: 0.5%~1.0% Si, 0.15%~0.7%
Fe, 1.0%~2.0% Mn, 0.05%~0.2% Mg, 1.5%~3.5% Zn, 0~0.15% Cu, single contain
Other elements of amount≤0.05% and total content≤0.15%, surplus Al.
The core alloys are made of the element of following mass fraction: 0.1%~0.8% Si, 0.15%~0.8%
Fe, 0.15%~0.7% Cu, 0.5%~1.8% Mn, 0.1%~0.45% Mg, 0.05%~0.3% Ti,
Single content≤0.05% and the other elements of total content≤0.15 weight %, surplus Al.
The clad alloy 1 and clad alloy 2 is conventional brazing layer alloy material, for example, by using commercially available
AA4343, AA4045 aluminium alloy, the mass fraction of conventional element composition are as follows: 4%~13% Si, 0.1%~0.4%
Fe, 0.05%~0.25% Cu, 0~0.1% Mn, 0~0.1% Zn, single content≤0.05% and total content≤
0.15% other element impurities, surplus Al.
The recombination rate of the barrier layer alloy is 10%~25%, and the recombination rate of the clad alloy 1 is
5%~15%, the recombination rate of the clad alloy 2 is 6%~15%；The recombination rate is a certain monolayer material
The percentage thickness occupied in multilayer materials.
Further, the preparation method of a kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention further includes stopping
The fusion process of laminated gold and core alloys: in selection aluminium, zinc material, magnesium material, silicon powder and Al-50%Cu, Al-10%Mn
Between alloy material be raw material, respectively according to barrier layer alloy, composition proportion melting in melting furnace of core alloys, casting temperature
It is 720~780 DEG C；Deslagging agent is added, skims；It is cast into barrier layer alloy cast ingot or core alloys ingot casting.
The aluminium is rafifinal (Al) material of mass fraction >=99.95%；The zinc material be mass fraction >=
99.7% high purity zinc (Zn) material；The magnesium material is high purity magnesium (Mg) material of mass fraction >=99.7%；The silicon powder is
HIGH-PURITY SILICON (Si) powder of mass fraction >=99.7%.
Highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention increases by one layer of blocking in traditional three-layer composite structure
Layer structure；Sandwich layer is that Al-Mn alloy adds a small amount of Mg element to be formulated with Si element by common 3, is provided for material main
Strength support forms the mechanical property that certain ageing strengthening effect improves material in the case where not influencing clad brazing conditions,
Yield strength and tensile strength respectively reach 55MPa and 165Mpa or more after soldering, the yield strength after two weeks natrual ageing
75MPa and 185Mpa or more are respectively reached with tensile strength；Barrier layer is the Al-Mn alloy for adding the Zn element of certain content,
Zn optimum content is 1.5%~3.5% mass fraction, and the poor 60~140mV of best corrosion potential between barrier layer and sandwich layer is
Sandwich layer provides good sacrificing protection effect, and the effect of " anodic protection " sandwich layer is generated by the potential difference of barrier layer and sandwich layer
To greatly promote the corrosion resistance of material；Moreover, a certain amount of Mg element is added on barrier layer, guarantee to increase by one layer of barrier layer
Do not reduce the integral strength of material afterwards, the clad of two sides is Al-Si alloy, to be connected with the material of other solderings
It connects, does not influence the brazing property of material.Therefore, highly corrosion resistant MULTILAYER COMPOSITE brazed aluminum alloy tubing of the invention, can not only
Anode loss protection is effectively generated, to improve the corrosion resistance of barrier layer side, moreover it is possible to stop sandwich layer element to clad
Diffusion improve the intensity of material under conditions of guaranteeing material brazing property.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe of the invention.
Wherein: 1- clad alloy 1, the barrier layer 2- alloy, 3- core alloys, 4- clad alloy 2.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, it should be noted that the embodiment of the present invention is only to the present invention
Content make an explanation explanation, do not constitute the limitation to technical solution of the present invention, common sense is pressed in unmentioned part in embodiment
And general technology processing.
In the embodiment of the present invention and comparative example, symbol "-" indicates that this element is not added with.
Embodiment A1~A4, B1, B2,5~A6 of comparative example A, B3, B4
Embodiment A1~A4, B1, B2 and 5~A6 of comparative example A, B3, B4 are alloy material melting embodiment.Select purity for
Rafifinal (Al) material of 99.99% (mass fraction, similarly hereinafter), zinc (Zn) material that purity is 99.9%, the magnesium that purity is 99.9%
(Mg) material, silicon (Si) powder and Al-50%Cu, Al-10%Mn intermediate alloy material that purity is 99.9% are raw material, respectively
It is matched according to alloy according to table 1 and the ingredient of barrier layer alloy listed in table 2 and core alloys, is melted in melting furnace
Refining, casting temperature are 720~780 DEG C；Deslagging agent is added, skims；Be cast into barrier layer alloy cast ingot, clad alloy cast ingot and
Core alloys ingot casting；Then to ingot casting at 550 DEG C homogenizing annealing 10h, obtain required core alloys ingot casting and barrier layer
Alloy cast ingot.
1 barrier layer alloying component of table forms (wt%)
| Number | Si | Fe | Mn | Cu | Mg | Zn | Al |
| Embodiment A1 | 0.71 | 0.21 | 1.48 | 0.1 | 0.15 | 3.08 | Surplus |
| Embodiment A2 | 0.74 | 0.33 | 1.24 | 0.08 | 0.06 | 2.45 | Surplus |
| Comparative example A 3 | 0.82 | 0.22 | 1.60 | 0.05 | 0.16 | 0.88 | Surplus |
| Comparative example A 4 | 0.84 | 0.40 | 1.70 | 0.11 | 0.11 | 4.64 | Surplus |
2 core alloys of table are at being grouped as (wt%)
Examples 1 to 6, comparative example 1~5
The core alloys ingot casting obtained in the barrier layer alloy cast ingot and B1~B6 that obtain in embodiment A1~A4 is carried out
The milling face of cutting, remove feeders and epidermis；It is heated to 480 DEG C of Homogenization Treatments in the lehr behind milling face, keeps the temperature 2~4h,
Hot rolling is carried out under the conditions of 470~500 DEG C, 340 DEG C of finishing temperature, is rolled according to different composite rate and is as thin as 10~40mm；By outsourcing
Clad alloy cast ingot carries out cutting milling face, remove feeders and epidermis；According to recombination rate listed in table 3, coated according to 1-
Laminated golden 1, the sequence stacking of the barrier layer 2- alloy, 3- core alloys and 4- clad alloy 2, after connection combination, in annealing furnace
In be heated to 480 DEG C, keep the temperature 2~4h, carry out hot rolling, 3~5mm of rolling thickness；Then cold rolling, final pass working modulus 80%~
95%, it rolls and is as thin as 0.15~0.5mm, finally in 240~300 DEG C of 1~3h of annealing to finished product state.
3 Finished Product Examples of table and comparative example composition (wt%)
Simulation soldering is carried out to the embodiment and comparative example material in table 3, and tests different time timeliness after soldering, is surveyed
Try its mechanical property, brazing property and corrosive nature: yield strength, tensile strength are using GB/T228-2002 metal material room temperature
Stretching test method detection；Corrosive nature is detected using OY water solution cycle experimental method, and etching time is 8 weeks.
The performance test results after table 4 embodiment and comparative examples, 603 DEG C × 3min soldering
3 weeks natrual ageing the performance test results after table 5 embodiment and comparative examples, 603 DEG C × 3min soldering
| Number | Yield strength Rp0.2 (MPa) | Tensile strength Rm (MPa) | Elongation percentage (%) |
| Embodiment 1 | 86.5 | 197.2 | 13.1 |
| Embodiment 2 | 79.1 | 190.1 | 14.7 |
| Embodiment 3 | 84.6 | 198.0 | 15.4 |
| Embodiment 4 | 82.8 | 193.7 | 13.5 |
| Embodiment 5 | 78.6 | 188.2 | 14.2 |
| Embodiment 6 | 79.5 | 186.6 | 15.0 |
| Comparative example 1 | 62.6 | 173.9 | 13.7 |
| Comparative example 2 | 95.0 | 206.6 | 11.4 |
| Comparative example 3 | 88.0 | 200.3 | 14.7 |
| Comparative example 4 | 80.7 | 185.8 | 13.5 |
| Comparative example 5 | 81.8 | 187.8 | 12.5 |
Table 4,5 as above is as it can be seen that the mechanical property with higher of the embodiment of the present invention 1~6, excellent corrosive nature and good
Brazing property.Mg element can be improved the mechanical property of material, and have ageing strengthening work with Si Element generation Mg2Si phase
With so the mechanical property of material is helped to improve in sandwich layer containing a certain amount of Mg element.1 sandwich layer of comparative example is without Mg member
Element, so its postwelding mechanical property is lower.But Mg constituent content is excessively high, the Mg element in sandwich layer can be spread in brazing process
Into clad, the defects of influencing the brazing property of material, will appear rosin joint such as comparative example 2, so sandwich layer Mg content is 0.1%
~0.45%.Zn element can reduce the corrosion potential of material, and Zn element is added in barrier layer can make the corrosion on barrier layer
Current potential is lower, generates cathode current by " sacrificial anode " and sandwich layer is protected not to be corroded.Comparative example 3 is 3 traditional layer materials, is not had
There is the presence on barrier layer, sandwich layer can be by directly etching, so poor corrosion resistance.Although comparative example 4 has the presence on barrier layer,
Zn content is very little, does not have good protective effect.Comparative example 5 is then Zn too high levels, and barrier layer excessive sacrifice is accelerated instead
The corrosion of itself, so barrier layer Zn element most preferably 1.5%~3.5%.
Claims (12)
1. a kind of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe, by clad alloy 1, barrier layer alloy, core alloys and cladding
Laminated golden 2 in order be laminated after Rolling compund form, which is characterized in that the barrier layer alloy by following mass fraction element
Composition: 0.5%~1.0% Si, 0.15%~0.7% Fe, 1.0%~2.0% Mn, 0.05%~0.2% Mg, 1.5%~3.5%
Zn, 0~0.15% Cu, single content≤0.05% and total content≤0.15% other elements, surplus Al.
2. highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe according to claim 1, which is characterized in that the core alloys
It is made of the element of following mass fraction: 0.1%~0.8% Si, 0.15%~0.8% Fe, 0.15%~0.7% Cu, 0.5%
~1.8% Mn, 0.1%~0.45% Mg, 0.05%~0.3% Ti, single content≤0.05% and total content≤0.15 weight %
Other elements, surplus Al.
3. highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe according to claim 1, which is characterized in that the cladding is laminated
Gold 1 and clad alloy 2 are brazing layer alloy material.
4. any highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe according to claim 1~3, which is characterized in that described
The recombination rate of barrier layer alloy is 10%~25%, and the recombination rate of the clad alloy 1 is 5%~15%, the packet
The recombination rate of coating alloy 2 is 6%~15%.
5. highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe according to claim 4, which is characterized in that the MULTILAYER COMPOSITE
The overall thickness of aluminium alloy pipe is 0.15~0.5mm.
6. a kind of preparation method of highly corrosion resistant MULTILAYER COMPOSITE aluminium alloy pipe, which is characterized in that comprising steps of (1) will stop
Milling face is respectively cut in the ingot casting of laminated gold, clad alloy 1 and clad alloy 2, in 520~580 DEG C of Homogenization Treatments, then
Required thickness is hot-rolled down under the conditions of 470~500 DEG C；Core alloys ingot casting is cut into milling face；It (2), will by recombination rate requirement
Treated that clad alloy 2, core alloys, barrier layer alloy and clad alloy 1 are laminated from the bottom up for step (1)；
4 layer materials are connected and are combined, then hot rolling under the conditions of 470~500 DEG C, rolling thickness is 3~5mm；(3) step (2) is obtained
The composite material obtained carries out cold rolling, 0.15~0.5mm of rolling thickness；Finished product is in 240~300 DEG C of 1~3h of annealing after cold rolling.
7. preparation method according to claim 6, which is characterized in that the barrier layer alloy by following mass fraction member
Element composition: 0.5%~1.0% Si, 0.15%~0.7% Fe, 1.0%~2.0% Mn, 0.05%~0.2% Mg, 1.5%~
3.5% Zn, 0~0.15% Cu, single content≤0.05% and total content≤0.15% other elements, surplus Al.
8. preparation method according to claim 6, which is characterized in that the core alloys by following mass fraction member
Element composition: 0.1%~0.8% Si, 0.15%~0.8% Fe, 0.15%~0.7% Cu, 0.5%~1.8% Mn, 0.1%~
The other elements of 0.45% Mg, 0.05%~0.3% Ti, single content≤0.05% and total content≤0.15 weight %, surplus are
Al。
9. preparation method according to claim 6, which is characterized in that the clad alloy 1 and clad alloy 2 be
Brazing layer alloy material.
10. according to any preparation method of claim 6~9, which is characterized in that the compound ratio of the barrier layer alloy
Rate is 10%~25%, and the recombination rate of the clad alloy 1 is 5%~15%, the recombination rate of the clad alloy 2
It is 6%~15%.
11. preparation method according to claim 6, which is characterized in that further include the molten of barrier layer alloy and core alloys
Refining process: selection aluminium, zinc material, magnesium material, silicon powder and Al-50%Cu, Al-10%Mn intermediate alloy material are raw material, are pressed respectively
According to barrier layer alloy, composition proportion melting in melting furnace of core alloys, casting temperature is 720~780 DEG C；Slagging-off is added
Agent is skimmed；It is cast into barrier layer alloy cast ingot or core alloys ingot casting.
12. preparation method according to claim 11, which is characterized in that the aluminium is mass fraction >=99.95%
High-purity aluminium；The zinc material is the high purity zinc material of mass fraction >=99.7%；The magnesium material is mass fraction >=99.7%
High purity magnesium material；The silicon powder is the high-purity silicon powder of mass fraction >=99.7%.
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| CN114771049A (en) * | 2022-04-29 | 2022-07-22 | 无锡金洋铝业有限公司 | Corrosion-resistant aluminum brazing composite plate and preparation method thereof |
| CN115537608A (en) * | 2021-11-18 | 2022-12-30 | 格朗吉斯铝业（上海）有限公司 | Aluminum pipe, manufacturing method thereof and all-aluminum heat exchanger |
| WO2023207757A1 (en) * | 2022-04-27 | 2023-11-02 | 杭州三花微通道换热器有限公司 | Heat exchange tube for heat exchanger, and heat exchanger |
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| CN114771049B (en) * | 2022-04-29 | 2024-04-09 | 无锡金洋铝业有限公司 | Corrosion-resistant aluminum brazing composite plate and preparation method thereof |
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| CN109797323B (en) | 2021-02-02 |
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