CN102676884A - High-sag-resistance brazing composite aluminum alloy foil for heat exchanger - Google Patents
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Abstract
The invention discloses high-sag-resistance brazing composite aluminum alloy foil for a heat exchanger, which consists of a core and a clad. The thickness of the clad accounts for 8-15% of the total thickness of the composite aluminum alloy foil. The core comprises the following components by weight: 1.4-1.6% of manganese, 0.4-0.6% of silicon, 0.50-0.90% of iron, 1.00-1.60% of zinc, 0.10-0.50% of vanadium, 0.05-0.30% of zirconium, 0.05-0.30% of titanium, and the balance of aluminum and inevitable impurities, wherein the contents of copper and magnesium in the impurities are both smaller than 0.05%. The alloy provided by the invention can be rolled into controlled atmosphere brazing (CAB) composite aluminum alloy foils for heat exchangers. The composite aluminum alloy foil disclosed by the invention has reasonable component ratio, easy manufacturing, good corrosion resistance, and high sag resistance after brazing, and is suitable for large-scale industrial production.
Description
Technical field
The invention discloses a kind of high sagging resistance heat exchanger aluminium alloy composite insulating foil for brazing.Belong to duraluminum and Technology of Plastic Processing field thereof.
Background technology
For the efficient that improves heat exchanger with alleviate engineering machinery weight such as automobile; Aluminium heat exchanger is by the mechanical type assembling in past; Developed into and generally adopted soldering processes now, it is to utilize lower melting point soldering Al-Si alloy layer that aluminium alloy pipe and aluminum alloy strip foil are formed by connecting.3003 duraluminums of common employing standard, this alloy has good forming property and mechanical property, and acceptable corrosion resisting property.In recent years, along with updating of aluminium heat exchanger structure design aspect, the thickness of brazed aluminum alloy foil will gradually become below the 0.07mm.Therefore, constantly development with developed some aluminum alloy materials based on Al-Mn system, bring the corresponding raising of sagging resistance behind the alloy brazed to satisfy because of reduced thickness, but the performance requriements that its corrosion resisting property can not reduce again etc. is necessary fully.
3XXX is that alloy is through in aluminium, adding Mn; Form the solution strengthening duraluminum; Improve the intensity of alloy; And keep good anti-corrosion, conduction, heat conductivility, and have good welding property and plastic deformation ability etc., be widely used in making in the industries such as automobile, refrigeration, chemical industry the radiating pipe and the radiator element of heat exchanger at present.Most widely used in the world at present Al-Mn alloy is 3003 duraluminums; But because the content of Mn is higher in the alloy; As easy as rolling off a log generation segregation in the casting process of cooling causes the corrosive nature of alloy and processing characteristics to reduce, and has limited the application of 3003 duraluminums at air-conditioning and refrigeration industry.In order to address these problems; American-European countries has registered the X800 that receives multinomial patent protection, K319, duraluminums such as 3190 and 3532; Through the content of elements such as the Mn of adjustment in the alloy, Fe, Mg, Cu, Zn, Ti, optimize its complete processing, guarantee alloy in brazing process because the diffusion of Si and form the galvanic anode protection sheath on its top layer; Thereby improved the corrosion resistance of alloy greatly, guaranteed that simultaneously alloy has good mechanical property, processing characteristics and welding property.Conventional 3003 duraluminums are realized solution strengthening through increasing constituent contents such as Mn, Cu often; And through adding the content crystal grain thinning of Ti element; So only can improve the preceding intensity of alloy brazed; But after scatterer assembling high temperature (the about 600-630 ℃) processing through soldering oven, aluminum alloy materials is softening fully, causes the intensity after its soldering to reduce greatly.The process characteristic of CAB nitrogen-protective soldering has limited the use of the heat-treatable strengthened alloy that contains Mg again.Fe and the increase of Cu content also can reduce corrosion resistance of alloy widely.The problem that sagging value was high when therefore present composite brazing aluminium alloy foil material also existed soldering, brazing property is low.
Patent of invention CN101433910 relates to the method that improves sink-resistance performance of aluminium alloy composite insulating foil for brazing; The middle Mg 0.3-0.6% that adds; Cu0.05-0.3%; The aluminium alloy composite insulating foil of preparing has good sink-resistance performance on the basis that keeps characteristics such as excellent mechanical performances, corrosion resistance nature, solderability and processibility, better satisfy all performance requriements of heat exchanger to aluminium alloy composite insulating foil; But Cu, Mg have certain influence to the CAB solderability, and it is not suitable for only being applicable to vacuum brazing as CAB (controlled atmosphere soldering) nitrogen-protective soldering.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of reasonable mixture ratio of components is provided; Processing and manufacturing is easy, and the alloy of preparation has the good high sagging resistance heat exchanger aluminium alloy composite insulating foil for brazing that shapes sink-resistance performance good after performance, good corrosion resisting property, the soldering.
A kind of high sagging resistance heat exchanger of the present invention aluminium alloy composite insulating foil for brazing is made up of core and coating layer, and said coating thickness accounts for the 8-15% of aluminium alloy composite insulating foil total thickness; Said core comprises that following component forms by mass percentage:
Mn 1.4-1.6, Si 0.4-0.6, Fe 0.50-0.90, Zn 1.00-1.60, V 0.10-0.50, Zr 0.05-0.30, Ti 0.05-0.30, all the other are aluminium and unavoidable impurities, Cu, Mg content are all less than 0.05% in the said impurity; Said coating layer is a silumin, and wherein to account for the mass percent of said silumin be 6.80-8.20 to silicon, and all the other are aluminium and unavoidable impurities.
The preparation method of a kind of high sagging resistance heat exchanger of the present invention aluminium alloy composite insulating foil for brazing comprises the steps:
The first step: the preparation of core, silumin coating layer
Core set of dispense ratio by designing is got each component, after melting, refining, casts, and teeming temperature 700-720 ℃, cast back ingot casting is incubated 18-36 hour down at 580-620 ℃ and carries out the homogenizing processing, obtains the core ingot casting;
Silumin coating layer set of dispense ratio by design is got each component, after melting, refining, casts, and teeming temperature 690-710 ℃, obtains the silumin ingot casting;
Second step: rolling
Get core ingot casting and silumin ingot casting that the first step obtains, account for the ratio of the 8-15% of aluminium alloy composite insulating foil total thickness, be combined into three layers of compound ingot blank by coating layer/core/coating layer after the blanking respectively in coating thickness in the aluminium alloy composite insulating foil; Said three layers of compound ingot blank are heated to 500-540 ℃ of samming, hot rolling, reduction in pass 5-35%, control hot rolling total deformation is 85-95%, the control finishing temperature is not less than 350 ℃; Then, cold roughing, reduction in pass is 15-35%, when cumulative deformation reaches 75-85%, carries out process annealing, annealing temperature 350-480 ℃, soaking time 2-6 hour, when controlling cold roughing total deformation and reaching 90-98%, stops cold roughing; Three layers of compound ingot blank that cold roughing is obtained be heated to 350-480 ℃ down insulation carried out second annealing in 2-6 hour, control pass deformation 20-35% then, pinch pass is to the aluminium alloy composite insulating foil thickness of design.
Mechanism of the present invention is sketched in following:
Study according to the inventor: for the Al-Mn line aluminium alloy; The content of adjustment Mn, Si, Fe and Zn; Elements such as compound interpolation V, Zr and Ti; When improving alloy strength, can not influence the non-uniform corrosion that alloy produces because of spot corrosion, and in the processing and preparing process, make it form multiple complex intensifying to stop crystal grain alligatoring and obtain stable fine grained texture's structure in the high temperature brazing process mutually.It is to reduce Cu content that the present invention intends the technical scheme of taking, the content of adjustment Mn, Si, Fe and Zn, elements such as compound interpolation V, Zr and Ti.Simultaneously; Guarantee that through controlled rolling and annealing process foil obtains stable thin crystal fiber weave construction; And form the combined high temperature strengthening phase that even dispersion distributes at intracrystalline and crystal boundary; Thereby stop crystal grain alligatoring in the high temperature brazing process, make alloy material have higher sink-resistance performance, and keep solidity to corrosion preferably.
The present invention has the following advantages and positively effect owing to adopt said components proportioning and preparation method:
1, utilize Mn and Al to form Al
6Mn is as the main strengthening phase of alloy, and the obstruction soldering forms the generation of the recrystallization process of the big crystal grain of recrystallize between heating period.But Mn content is higher than the performance that shapes that can form thick phase after 1.8% and have a strong impact on alloy.The optimum range of Mn content is between 1.40% to 1.60%.
2, Si can reduce the solvability of Mn; Si, Mn combine to produce the high-density dispersoid particle that contains Mn; Alloy strength there is certain effect and improves the flowability of alloy casting process, also can become superfine high-temperature stable Al (Fe, V) Si mutually simultaneously with Fe, V-arrangement; Sink-resistance performance behind the raising alloy brazed, and effectively reduce because of reinforced alloys improves Fe content and bring the corrosion proof disadvantageous effect of alloy.Some Si also is present in the sosoloid, no matter in sosoloid or dispersoid particle, Si gains in strength.Meeting reduces the fusing point of alloy and influences brazing property after 1.2% but be higher than.The optimum range of silicone content is between 0.40% to 0.60%.
3, Fe can improve the intensity of Al-Mn alloy, but is higher than 0.8%, in alloy, is easy to form intermetallic compounds such as a large amount of thick Al-Fe and Al-Fe-Si, and that reduces alloy greatly shapes performance and corrosion resisting property.The optimum range of iron level is between 0.50% to 0.60%.
4, the alloy compositions of the present invention's design does not contain Cu, Mg; And the content that in inevitable impurity, limits Cu, Mg is all less than 0.05%; Owing to do not contain Cu in the alloy or Cu content is extremely low, can effectively reduce corrosion potential positive in the alloy, improve alloy anti intercrystalline corrosion performance; Particularly, in the CAB soldering, can effectively improve the soldering Weldability between alloy and the other materials to effective control of Mg content.
5, it is limited that Zn adds in the aluminium raising to alloy strength separately.But zinc can improve the electropotential of aluminium, adds the Zn of 1.0-2.0%, can be used as the sacrificial anode effect, and pitting attack is become the face corrosion, improves the corrosion resistance nature of integral Al-alloy.The optimum range of zinc content is between 1.40% to 1.60%.
6, V generates Al in duraluminum
11Compound between the V insoluble metal, crystal grain thinning in melting and castingprocesses; Especially when high Fe and Si exist, can form superfine Al (Fe, V) Si high-temperature stable phase improves recrystallization temperature in thermal distortion and heat treatment process, refinement recrystallized structure improves the sink-resistance performance behind the alloy brazed.Can form compound between thick insoluble metal but surpass 0.5% content, reduce alloy and shape performance.The optimum range of content of vanadium is between 0.15% to 0.25%.
7, the general add-on of Zr is 0.1-0.3%, forms Al
3The Zr intermetallic compound hinders recrystallization process, the refinement recrystal grain.Zirconium content optimum range is between 0.10% to 0.20%.
8, but the main refinement cast structure of Ti improves the alloy processing characteristics.The more important thing is that Ti forms high density and lower concentration along thickness direction and intersects shape distribution once in alloy, low concentration region is corroded than area with high mercury is preferential, so another layer corrosion obstructed, and alloy corrosion resistance can improve greatly.Too high levels can form compound between thick insoluble metal, reduces alloy and shapes performance.The optimum range of titanium content is between 0.10% to 0.15%.
The present invention is through strict control Cu, Mg content; The content of adjustment Mn, Si, Fe and Zn; The optimization of compound interpolation V, Zr and Ti and rolling and annealing process is guaranteed that foil obtains stable thin crystal fiber weave construction, and is formed the combined high temperature strengthening phase that even dispersion distributes at intracrystalline and crystal boundary; Thereby stop crystal grain alligatoring in the high temperature brazing process, make alloy material have higher sink-resistance performance.The soldering foil and existing 3003 alloy phases ratio of preparation are guaranteeing that the sink-resistance performance after its soldering is that 3003 aluminium alloy composite insulating foils improve more than 20% than existing Al-Mn under the situation that its corrosion resisting property does not reduce.Solved the key technical problem that heat exchanger requires to improve sagging resistance behind the alloy brazed with CAB (controlled atmosphere soldering) brazed aluminum alloy material because of reduced thickness and keeps good corrosion resistance.
In sum, reasonable mixture ratio of components of the present invention, processing and manufacturing is easy, and the alloy of preparation has the good good sink-resistance performance after performance, good corrosion resisting property, the soldering that shapes.Solve the key technical problem that heat exchanger requires to improve sagging resistance behind the alloy brazed with CAB brazed aluminum alloy material because of reduced thickness and keeps good corrosion resistance, be suitable for large-scale industrial production.
Description of drawings
Accompanying drawing 1 is 0.1s for the alloy of the embodiment of the invention 1,2,3 and Comparative Examples preparation in strain rate
-1, the elevated temperature heat compression set process when texturing temperature is 550 ℃ the flow stress curve.
Among the figure: the flow stress curve of the alloy of 1-embodiment 1 preparation, the flow stress curve of the alloy of 2-embodiment 2 preparations, the flow stress curve of the alloy of 3-embodiment 3 preparations, the flow stress curve of the alloy of 4-Comparative Examples preparation.
As can be seen from the figure, the high temperature thermal deformation flow stress of the alloy of embodiment 1,2,3 preparations shows that than the height of Comparative Examples existing 3003 alloys of high high-temp stability of alloy material of the present invention improve greatly.
Embodiment
The alloy ingredient scope of design according to the present invention adopts 99.7Al ingot, Zn ingot and Mn, Si, Fe agent and Al
10Zr and Al
5The V master alloy is respectively according to core alloy, clad alloy and Comparative Examples core alloy standard 3003 alloys of the part by weight preparation embodiment of the invention 1,2,3.In capacity is the reflection fuel-oil melting furnace of 4T, after melting, refining, adopt semicontinuous casting to become ingot casting.
Actual measurement set of dispense ratio is in the core ingot casting:
| Si | Fe | Mn | Zn | Cu | V | Zr | Ti |
| 0.412 | 0.578 | 1.589 | 1.582 | 0.004 | 0.168 | 0.106 | 0.122 |
700 ℃ of teeming temperatures, cast back ingot casting are incubated 36 hours down at 580 ℃ and carry out the homogenizing processing;
Actual measurement set of dispense ratio is in the coating layer silumin ingot casting:
| Si | Al | Inevitable impurity |
| 6.80 | 92.8 | 0.04 |
690 ℃ of teeming temperatures;
Second step: rolling
Get core ingot casting and silumin ingot casting that the first step obtains, account for 8% ratio of aluminium alloy composite insulating foil total thickness, be combined into three layers of compound ingot blank by coating layer/core/coating layer after the blanking respectively in coating thickness in the aluminium alloy composite insulating foil; Said three layers of compound ingot blank are heated to 500 ℃ of sammings, hot rolling, reduction in pass 5-15%, control hot rolling total deformation is 85-95%, 360 ℃ of control finishing temperatures; Then, cold roughing, reduction in pass is 15-20%, when cumulative deformation reaches 75-85%, carries out process annealing, 350 ℃ of annealing temperatures, soaking time 6 hours; When controlling cold roughing total deformation and reaching 90-98%, stop cold roughing; Three layers of compound ingot blank that cold roughing is obtained be heated to 350 ℃ down insulation carried out second annealing in 6 hours, control pass deformation 20-25% then, pinch pass to thickness is the aluminium alloy composite insulating foil of 0.10mm.
Embodiment 2
Actual measurement set of dispense ratio is in the core ingot casting:
| Si | Fe | Mn | Zn | Cu | V | Zr | Ti |
| 0.503 | 0.532 | 1.566 | 1.511 | 0.004 | 0.191 | 0.192 | 0.129 |
710 ℃ of teeming temperatures, cast back ingot casting are incubated 24 hours down at 600 ℃ and carry out the homogenizing processing;
Actual measurement set of dispense ratio is in the coating layer silumin ingot casting:
| Si | Al | Inevitable impurity |
| 7.60 | 92.0 | 0.04 |
700 ℃ of teeming temperatures;
Second step: rolling
Get core ingot casting and silumin ingot casting that the first step obtains, account for 10% ratio of aluminium alloy composite insulating foil total thickness, be combined into three layers of compound ingot blank by coating layer/core/coating layer after the blanking respectively in coating thickness in the aluminium alloy composite insulating foil; Said three layers of compound ingot blank are heated to 520 ℃ of sammings, hot rolling, reduction in pass 10-25%, control hot rolling total deformation is 85-95%, 370 ℃ of control finishing temperatures; Then, cold roughing, reduction in pass is 20-25%, when cumulative deformation reaches 75-85%, carries out process annealing, 400 ℃ of annealing temperatures, soaking time 4 hours; When controlling cold roughing total deformation and reaching 90-98%, stop cold roughing; Three layers of compound ingot blank that cold roughing is obtained be heated to 400 ℃ down insulation carried out second annealing in 4 hours, control pass deformation 25-30% then, pinch pass to thickness is the aluminium alloy composite insulating foil of 0.10mm.
Embodiment 3
Actual measurement set of dispense ratio is in the core ingot casting:
| Si | Fe | Mn | Zn | Cu | V | Zr | Ti |
| 0.594 | 0.591 | 1.501 | 1.411 | 0.005 | 0.239 | 0.195 | 0.125 |
720 ℃ of teeming temperatures, cast back ingot casting are incubated 18 hours down at 620 ℃ and carry out the homogenizing processing;
Actual measurement set of dispense ratio is in the coating layer silumin ingot casting:
| Si | Al | Inevitable impurity |
| 8.20 | 91.4 | 0.04 |
710 ℃ of teeming temperatures;
Second step: rolling
Get core ingot casting and silumin ingot casting that the first step obtains, account for 15% ratio of aluminium alloy composite insulating foil total thickness, be combined into three layers of compound ingot blank by coating layer/core/coating layer after the blanking respectively in coating thickness in the aluminium alloy composite insulating foil; Said three layers of compound ingot blank are heated to 540 ℃ of sammings, hot rolling, reduction in pass 25-35%, control hot rolling total deformation is 85-95%, 380 ℃ of control finishing temperatures; Then, cold roughing, reduction in pass is 25-35%, when cumulative deformation reaches 75-85%, carries out process annealing, 480 ℃ of annealing temperatures, soaking time 2 hours; When controlling cold roughing total deformation and reaching 90-98%, stop cold roughing; Three layers of compound ingot blank that cold roughing is obtained be heated to 480 ℃ down insulation carried out second annealing in 2 hours, control pass deformation 30-35% then, pinch pass to thickness is the aluminium alloy composite insulating foil of 0.10mm.
Comparative Examples
Actual measurement set of dispense ratio is in the core ingot casting:
| Si | Fe | Mn | Zn | Cu | V | Zr | Ti |
| 0.386 | 0.451 | 1.364 | 0.042 | 0.182 | - | - | 0.072 |
700 ℃ of teeming temperatures, cast back ingot casting are incubated 20 hours down at 610 ℃ and carry out the homogenizing processing;
Actual measurement set of dispense ratio is in the coating layer silumin ingot casting:
| Si | Al | Inevitable impurity |
| 8.20 | 91.4 | 0.04 |
710 ℃ of teeming temperatures;
The rolling step and the processing parameter of Comparative Examples are identical with embodiment 3.
Aluminium alloy composite insulating foil to embodiment 1,2,3 and Comparative Examples acquisition carries out the DSC DTA; The fusing point data of alloy are seen table 1; Aluminium alloy composite insulating foil to embodiment 1,2,3 and Comparative Examples acquisition carries out the test of thermo compression deformation simulative, and its flow stress curve is seen accompanying drawing 1.It is thus clear that the alloy of the embodiment of the invention 1,2,3 preparations is along with the increase of Si, Fe, V content; Fusing point improves accordingly; High temperature thermal deformation flow stress (hot strength) is also along with raising; And the over-all properties of three embodiment, all be higher than Comparative Examples standard 3003 alloys, show that the high high-temp stability of its alloy material of the present invention improves greatly.
Aluminium alloy compound foil dynamic performance to embodiment 1,2,3 and Comparative Examples acquisition is measured the σ of alloy by " metallic substance tensile test at room temperature method " GB/T 228-2002
b/ MPa, δ/% data are seen table 1;
Anti-sagging value is to weigh the anti-main performance index that stays ability of soldering aluminium foil, and the more little sagging resistance of its value is good more, but because the mensuration of anti-sagging value does not have correlation standard.Therefore; The present invention adopts the aluminium alloy composite insulating foil that embodiment 1,2,3 and Comparative Examples are obtained to rise to 605 ± 3 ℃ from room temperature with 1 ℃/s heat-up rate; Be incubated air cooling simulation soldering processes process after 10 minutes; Measure the vertical naturally curved maximum height down of front end, as weighing its anti-sagging performance index, the sink-resistance performance achievement data is seen table 1.
Can find out that from table 1 sagging resistance and the mechanical property of the aluminium alloy composite insulating foil of the embodiment of the invention 1,2,3 preparations all obviously are superior to Comparative Examples standard 3003 alloys.
Table 1
Claims (3)
1. a high sagging resistance heat exchanger aluminium alloy composite insulating foil for brazing is made up of core and coating layer, and said coating thickness accounts for the 8-15% of aluminium alloy composite insulating foil total thickness; Said core comprises that following component forms by mass percentage:
Mn 1.4-1.6, Si 0.4-0.6, Fe 0.50-0.90, Zn 1.00-1.60, V 0.10-0.50, Zr 0.05-0.30, Ti 0.05-0.30, all the other are aluminium and unavoidable impurities, Cu, Mg content are all less than 0.05% in the said impurity; Said coating layer is a silumin, and wherein to account for the mass percent of said silumin be 6.80-8.20 to silicon, and all the other are aluminium and unavoidable impurities.
2. a kind of high sagging resistance heat exchanger aluminium alloy composite insulating foil for brazing according to claim 1 is characterized in that: said core comprises that following component forms by mass percentage:
Mn 1.4-1.6, Si 0.5-0.6, Fe 0.50-0.60, Zn 1.40-1.60, V 0.15-0.25, Zr 0.1-0.20, Ti 0.1-0.15, all the other are aluminium and unavoidable impurities, Cu, Mg content are all less than 0.05% in the said impurity.
3. the method for preparation a kind of high sagging resistance heat exchanger aluminium alloy composite insulating foil for brazing according to claim 1 or claim 2 comprises the steps:
The first step: the preparation of core, silumin coating layer
Core set of dispense ratio by designing is got each component, after melting, refining, casts, and teeming temperature 700-720 ℃, cast back ingot casting is incubated 18-36 hour down at 580-620 ℃ and carries out the homogenizing processing, obtains the core ingot casting;
Silumin coating layer set of dispense ratio by design is got each component, after melting, refining, casts, and teeming temperature 690-710 ℃, obtains the silumin ingot casting;
Second step: rolling
Get core ingot casting and silumin ingot casting that the first step obtains, account for the ratio of the 8-15% of aluminium alloy composite insulating foil total thickness, be combined into three layers of compound ingot blank by coating layer/core/coating layer after the blanking respectively in coating thickness in the aluminium alloy composite insulating foil; Said three layers of compound ingot blank are heated to 500-540 ℃ of samming, hot rolling, reduction in pass 5-35%, control hot rolling total deformation is 85-95%, the control finishing temperature is not less than 350 ℃; Then, cold roughing, reduction in pass is 15-35%, when cumulative deformation reaches 75-85%, carries out process annealing, annealing temperature 350-480 ℃, soaking time 2-6 hour, when controlling cold roughing total deformation and reaching 90-98%, stops cold roughing; Three layers of compound ingot blank that cold roughing is obtained be heated to 350-480 ℃ down insulation carried out second annealing in 2-6 hour, control pass deformation 20-35% then, pinch pass is to the aluminium alloy composite insulating foil thickness of design.
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| CN107245680A (en) * | 2017-06-05 | 2017-10-13 | 北京工业大学 | A kind of Technology for Heating Processing for improving Composite Brazing Aluminium Foil sink-resistance performance |
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Application publication date: 20120919 |