CN109988946A - A kind of vacuum brazing fin material and preparation method thereof - Google Patents
A kind of vacuum brazing fin material and preparation method thereof Download PDFInfo
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- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
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Abstract
The present invention relates to a kind of Al alloy composite, it includes core alloy and composite layer alloy, the density for the particle that wherein equivalent circle diameter present in composite layer alloy and core alloy is 0.02 μm -0.2 μm is (with a/mm3Meter) ratio be 1.5 or more.Based on the core alloy, the core alloy includes: the Fe of the Mg of Mn, 0.1-0.9 weight % of Cu, 0.1-1.0 weight % of Si, 0.1-1.0 weight % of 0.3-1.5 weight % and≤0.35 weight %；The Cr of and at least one of (i)-(iii): (i) 0.05-0.25 weight % Ti, the Zr of (ii) 0.05-0.25 weight %, (iii) 0.02-0.25 weight %；And single content≤0.05 weight % and the other elements of total content≤0.15 weight %；Surplus is Al.The invention further relates to the preparation methods of the Al alloy composite.Al alloy composite of the invention with high intensity and has excellent resistance solder corrode ability, is suitable as fin material, the especially fin of the heat exchangers such as oil cooler, water tank as vacuum brazing.
Description
Technical field
The present invention relates to a kind of Al alloy composites, with high intensity and have excellent resistance solder corrode ability,
It is suitable as fin material, the especially fin of the heat exchangers such as oil cooler, water tank as vacuum brazing.The invention further relates to institute
State the preparation method of Al alloy composite.
Background technique
Aluminium alloy is widely used as application and preparation in various industries such as automobile, engineering machine due to light and high heat conductivity
The heat exchanger of tool, electric power etc..Heat exchanger passes through method for brazing (solder brazing) mainly to produce, and mainly includes vacuum brazing and controllable gas
Atmosphere soldering.Vacuum brazing is to carry out the connection of connector to the component heating of aluminium heater in the stove with vacuum condition.Very
The advantages of sky soldering, is since under vacuum condition, the content of oxygen is extremely low, will not when the component of aluminium heater is heated
Further oxidation, to make the thickness control of oxidation film in a certain range.Then under conditions of being warming up to close to 600 DEG C,
The fusing of Al-Si brazing filler metal alloy, the oxide film breakdown on surface flow to the solder of fusing at soldered fitting,
Form the soldered fitting of metallurgical bonding.Vacuum brazing does not need to add additional brazing flux (scaling powder) etc. to remove surface oxidation
Film, therefore the inner cavity of heat exchanger is very clean.The cleaning of inner cavity is very important certain heat exchangers, such as oil cooler.
Oil cooler is its engine lubrication system such as Hyundai Motor, engineering machinery or the indispensable heat exchanger of hydraulic system
Components.It is mainly used for the cooling of vehicle engine lubricating oil, hydraulic oil or fuel oil, the type of cooling can be cooling water or sky
Gas.There is oil cooler compact-sized, pressure-resistant and high temperature resistant to require height, corrosion resistance and good, heat transfer efficiency height, good reliability etc. special
Point.Vacuum brazing does not simultaneously use brazing flux, cleans oil cooler more, it is not easy to cause channel blockage because brazing flux remains
Or etching problem etc..But due in stove be vacuum environment, be only capable of in Process of Vacuum Brazing by radiation transmit heat,
So that heating rate is very slow when soldering, the holding time is very long, and corrode and softening transform etc. can occur at high temperature for aluminium soldering material
Problem.
With the continuous of emission regulation plus sternly, heat-exchanger products are also being kept updating, and new trend is more at present
Material is effectively utilized to reduce the weight of heat exchanger and cost.For oil cooler, pressure resistance and high temperature resistant requirement are higher,
And further to lightweight, densification, modular development.Also to vacuum brazing, with aluminium, more stringent requirements are proposed for this, it is desirable that
Material intensity itself, brazing property etc. reach higher target, and by using thinner material, reduce the weight of heat exchanger
It is possibly realized.And the material that existing vacuum brazing is also unable to satisfy heat exchanger loss of weight with fin material and proposes further is thinned
Requirement.For oil cooler, common vacuum brazing fin material is indeformable under its high temperature in order to guarantee, it is general using compared with
Thick fin material, thickness are generally higher than 0.25mm, and some even has 0.4mm.
CN102554585A discloses a kind of manufacturing method of aluminium alloy brazing plate, and this method includes successively executing down
State step: cast aluminium alloy gold ingot casting；The ingot casting is homogenized, is then cooled down, and carries out conventional milling face；The ingot casting is carried out
Single or double clad aluminum silicon solder layer, to form compound material；Heat the compound material；Heating described in hot rolling and cold rolling it is compound
Material, to form the cold rolling material with first thickness；Complete soft annealing is carried out to the cold rolling material；And to the soft annealing
Plate be pre-stretched, thus to obtain have less than the first thickness second thickness final aluminium alloy brazing sheet
Material.The material that the manufacturing method obtains has good elongation percentage and core material corrode residual thickness.CN 102357744A is disclosed
A kind of novel evacuated soldering 4A13 aluminium alloy, it is characterised in that: it includes the following materials that total weight number is 100 parts: silicon
(Si) greater than 8.2 parts -9 parts, 0 part -0.6 part of iron (Fe), 0 part -0.2 part of copper (Cu), 0 part -0.2 part of manganese (Mn), magnesium (Mg) 0.08
- 0.2 part of part, 0 part -0.2 part of zinc (Zn), 0 part -0.15 part of titanium (Ti), 0 part -0.15 part of other impurity microelements, remaining is aluminium
(Al)。
The present invention be in order to solve the above-mentioned vacuum brazing referred to fin material intensity it is not high or/and resist solder corrode
The exploitation that the problem of performance difference carries out, to obtain a kind of high-intensitive, preferably anti-solder corrode aluminium alloy compound fin material.This
Invention is recombinated by the composition to traditional fin material, and so that original monolayer material is become multilayer material, and optimize
The ingredient and accounting of layers of material realize the Al alloy composite while meeting thinned, and material has after brazing
Higher intensity, and the material has the preferable performance for resisting solder corrode in brazing process, particularly suitable for being used as
The fin material of vacuum brazing.Also, the present invention also provides a kind of manufacturing method of vacuum brazing aluminum alloy fin material,
The aluminum alloy fin material can obtain good soldered fitting under the conditions of prolonged vacuum brazing, and
There is excellent intensity, particularly suitable for the demanding heat-exchanger products of loss of weight after soldering.
The present inventor have studied aluminium soldering material obtain the various influences of high-intensitive and anti-solder corrode performance because
Element, as a result, it has been found that, by such as three layers of multilayer materials to replace traditional monolayer material and using with specific alloy
The aluminium alloy of composition and alloy structure, can obtain not only has fin material that is high-intensitive but also being resistant to solder corrode.Wherein, core material
(base material) can guarantee that material has very high intensity, and composite layer (clad) can be used to resist the corrosion of solder, two
The combination of person completes the present invention.
Summary of the invention
An aspect of of the present present invention is related to a kind of Al alloy composite, and it includes core alloys and composite layer alloy, wherein
The density for the particle that equivalent circle diameter present in composite layer alloy and core alloy is 0.02 μm -0.2 μm is (with a/mm3Meter)
Ratio be 1.5 or more；
It is wherein based on the core alloy, the core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %；
And
(i) at least one of-(iii):
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
In one embodiment, in Al alloy composite of the invention, it is based on the composite layer alloy, it is described compound
Laminated gold includes:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %；
And
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
In a preferred embodiment, in Al alloy composite of the invention, it is based on the core alloy, it is described
Core alloy includes the Mg of 0.2-0.6 weight %.
In another preferred embodiment, in Al alloy composite of the invention, the core alloy, institute are based on
State the Mn that core alloy includes 0.2-0.95 weight %.
In still another preferred embodiment, in Al alloy composite of the invention, it is based on the composite layer alloy,
The composite layer alloy includes the Si of 0.05-0.55 weight %.
In an also preferred embodiment, in Al alloy composite of the invention, it is based on the composite layer alloy,
The composite layer alloy includes the Mn of 0.8-1.8 weight %.
In yet another embodiment, Al alloy composite of the invention is characterized in that, in the core alloy
The composite layer alloy is coated on one face or two faces.
In a still further embodiment, Al alloy composite with a thickness of about 0.25mm or less.
Another aspect of the present invention relates to a kind of methods for preparing Al alloy composite comprising following steps:
A) ingot casting of core alloy and composite layer alloy is cast respectively；
B) composite layer alloy is heat-treated；
C) sawing, milling face；
D) the slab piece of composite layer alloy is prepared；
E) the slab piece of core alloy and composite layer alloy is carried out compound；
F) preheating and hot rolling；
G) cold rolling；
H) it anneals,
Wherein, the temperature being heat-treated in step b) is 400-540 DEG C.
In one embodiment, in the method for preparing Al alloy composite of the invention, it is based on the core alloy,
The core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %；
And
(i) at least one of-(iii):
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
In another embodiment, in the method for preparing Al alloy composite of the invention, it is based on the composite layer
Alloy, the composite layer alloy includes:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %；
And
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
In one embodiment, composite layer alloy and core in Al alloy composite prepared according to the methods of the invention
The density for the particle that equivalent circle diameter present in material alloy is 0.02 μm -0.2 μm is (with a/mm3Meter) ratio be 1.5 with
On.
In another embodiment, Al alloy composite prepared according to the methods of the invention with a thickness of 0.25mm
Below.
The aluminium that another aspect of the present invention further relates to Al alloy composite of the invention or prepared with method of the invention
Alloy composite materials are used as the purposes of the fin of vacuum brazing.
Brief description
Fig. 1: the structural schematic diagram of Al alloy composite of the invention；
Fig. 2: in the embodiment of the present invention 6 in composite layer alloy particle SEM pattern；
Fig. 3: in the embodiment of the present invention 6 in core alloy particle SEM pattern；
Fig. 4: the metallographic microscope of the soldered fitting of the fin and tubing of the Al alloy composite preparation of comparative example 2 is used
Photo；
Fig. 5: the gold of the soldered fitting of the fin and tubing of the Al alloy composite preparation of the embodiment of the present invention 6 is used
Phase microscope photo.
Specific embodiment
General definition and term
Unless otherwise defined, all technical and scientific terms used herein has and those skilled in the art of the invention
Normally understood identical meaning.Contradiction if it exists, then be subject to definition provided by the present application.
Unless otherwise stated, all percentage, number, ratio etc. herein are by weight.
When stating some in the form of range, preferred scope or preferred numerical upper limits and preferred numerical lower limits
When amount, concentration or other values or parameter, it should be understood that be equivalent to specifically disclose by by any pair of range limit or
Any range that preferred value combines with any range lower limit or preferred value, without considering whether the range specifically takes off
Show.Unless otherwise noted, numberical range listed herein is intended to include the endpoint of range, and all integers within the scope of this
And score.Such as any sub-range that " 1-8 " is covered 1,2,3,4,5,6,7,8 and be made of any two of them value, such as
2-6、3-5。
Statement "comprising" or with its synonymous similar statement " comprising ", " containing " and " having " etc. be it is open, do not arrange
Except additional unlisted element, step or ingredient.State " Consists of " exclude unspecified any element, step or at
Point.Statement "consisting essentially of ..." how is limited in specified element, step or ingredient, in addition what is be optionally present will not be real
Element, step or the ingredient of the basic and new feature of theme claimed are influenced in matter.It should be appreciated that statement "comprising"
Cover statement "consisting essentially of ..." and " Consists of ".
Within the scope of the present invention, the alloy substantially free refers in the manufacturing process of the alloy do not have
The component is intentionally added or contains, which is only the possibility to introduce as inevitable impurity.
Term as used herein " about " allows a degree of variation of value or range, such as in defined value or rule
The range of definite limitation and including exact value or range 10% within, within 5% or within 1%.
Term as used herein " optional " " optionally " refers to that the event then described or situation may occur or can
It can not occur, which includes that the event or situation occurs and the event or situation does not occur.
Term as used herein " at least one (a) " indicates 1,2,3,4,5,6,7,8,9,10 kind (a) or more.
Term as used herein " equivalent circle diameter " refers to be converted into and its area according to the area of irregularly shaped particles
Diameter when equal circular granular.
Term as used herein " other elements " refers to inevitable impurity, such as Zn, V, Ni etc. in aluminium alloy.
Material, method and the embodiment of this paper is exemplary, and unless stated otherwise, should not be construed as restricted
's.
Al alloy composite described in detail below and the method for preparing the Al alloy composite.
The present invention relates to a kind of Al alloy composites, and it includes core alloys and composite layer alloy.In an embodiment
In, the density for the particle that equivalent circle diameter present in composite layer alloy and core alloy is 0.02 μm -0.2 μm is (with a/mm3
Meter) ratio be 1.5 or more.
Core alloy
In Al alloy composite of the invention, it is based on the core alloy, the core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %.
In one embodiment, it is based on the core alloy, the core alloy also includes at least one in (i)-(iii)
Kind:
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %.
In another embodiment, it is based on the core alloy, the core alloy also includes single content≤0.05 weight
Measure % and the other elements of total content≤0.15 weight %.
In the above-described embodiment, surplus Al.
In core material of the invention, Si is very important element.Si and Fe, Mn are formed together AlFeMnSi system chemical combination
Object plays the role of dispersion-strengtherning, or by reacting to form Mg with Mg2Si compound improves intensity, or is solid-solution in matrix
In intensity improved by solution strengthening.Based on core alloy of the invention, Si content is below about 0.3 weight %, can weaken it
Bring effect is answered, Si content is more than about 1.5 weight %, and it will lead to the fusing point of core material and got higher a possibility that reducing, cause melting,
The eutectic phase of low melting point may be will form.Based on core alloy of the invention, the content of Si is about 0.3-1.5 weight in core material
Measure %, preferably from about 0.5-1.0 weight %, more preferably from about 0.7-1.0 weight %.
Mn, which has, improves intensity and soldering property, corrosion resistance, and improves the effect of current potential.The content of Mn is below about 0.1 weight
When measuring %, bring effect is small.When the content of Mn is more than about 1.0 weight %, a large amount of particle containing Mn will form, influence is tied again
Brilliant process simultaneously influences slump resistance energy, and a large amount of particle containing Mn will affect Mg2The effect of Si precipitation strength.Based on of the invention
Core alloy, the content of Mn is about 0.1-1.0 weight %, preferably from about 0.2-0.95 weight %, more preferably from about 0.5- in core material
0.95 weight %.
Mg has the effect of significantly improving alloy strength, solution strengthening or by the way that Mg is precipitated2Si improves intensity.Based on this
The core alloy of invention, when the content of Mg is below about 0.1 weight %, bring effect is not significant.The content of Mg is more than about 0.9
When weight %, the fusing point of core material is caused to reduce, is also easy to that grain boundary corrosion occurs.The content of Mg is about 0.1-0.9 weight %, preferably
About 0.2-0.6 weight %, more preferably from about 0.2-0.4 weight %.
Fe is impurity element generally existing in aluminium alloy.Fe, which has to be easily formed to become, recrystallizes crystalline core size
Intermetallic compound, the effect for reducing recrystallization temperature.Based on core alloy of the invention, the content of Fe is about 0.35 weight
Amount % or less can guarantee that material has mouldability and corrosion sex expression, and the too Fe of high-content can reduce formability and corrosive nature.
In order to guarantee the intensity after material soldering, the content of Fe is about 0.35 weight % hereinafter, preferably from about 0.25 weight % or less.
Cu improves intensity by solution strengthening, and can improve current potential.Based on core alloy of the invention, the content of Cu is low
When about 0.1 weight %, the effect generated is smaller.When the content of Cu is more than about 1.0 weight %, the possibility of intercrystalline corrosion occurs
Property is got higher, and fusing point also has large effect.Based on core alloy of the invention, the content of Cu is about 0.1-1.0 weight
Measure %, preferably from about 0.3-0.8 weight %, more preferably from about 0.5-0.7 weight %.
Ti improves intensity by solution strengthening, and improves corrosion resisting property.Based on core alloy of the invention, the content of Ti
When lower than 0.05, due effect can not be obtained.When the content of Ti is more than 0.25, huge intermetallic compound easy to form,
Make plastic processing reduction.Based on core alloy of the invention, the content of Ti is about 0.05-0.25 weight %.Preferably from about 0.1-
0.2 weight %, more preferably from about 0.1-0.15 weight %.
Zr is brilliant in order to further increase alloy intensity after brazing and control recrystallization as the addition of alloying element
The size of grain.Based on core alloy of the invention, the content of Zr is about 0.05-0.25 weight %, preferably from about 0.07-0.15 weight
Measure %, more preferably from about 0.07-0.12 weight %.
Cr can further improve alloy intensity after brazing and corrosion resistance as the addition of alloying element.Based on this
The core alloy of invention, the content of Cr are about 0.02-0.25 weight %, preferably from about 0.02-0.2 weight %, more preferably from about
0.02-0.1 weight %.
Composite layer alloy
In Al alloy composite of the invention, it is based on the composite layer alloy, the composite layer alloy includes:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %.
In one embodiment, it is based on the composite layer alloy, the composite layer alloy also includes
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %.
In another embodiment, be based on the composite layer alloy, the composite layer alloy also include single content≤
0.05 weight % and the other elements of total content≤0.15 weight %.
In the above-described embodiment, surplus Al.
In composite layer of the invention, Si can be formed together AlMnSi disperse phase particle with Mn, play dispersion-strengtherning
Effect, the particle of small and dispersed can control the process of recrystallization, and can influence the size of recrystal grain, to influence alloy
Resist the ability of solder corrode.For composite layer, based on composite layer alloy of the invention, the content of Si is below about 0.05 weight
When measuring %, effect is small.A possibility that when more than about 0.6 weight %, fusing point can be reduced, and cause melting gets higher.Based on the present invention
Composite layer, the content of Si is about 0.05-0.6 weight %, preferably from about 0.05-0.55 weight %.
Mn, which has, improves intensity and soldering property, corrosion resistance, and improves the effect of current potential.In addition, Mn can be formed largely
Diffusing particle containing Mn, these particles can control the recrystallization process of crystal grain in brazing process, be beneficial to control slump resistance
It can and resist solder corrode performance.Based on composite layer alloy of the invention, Mn content is about 0.5-2.0 weight %, preferably from about
0.8-1.8 weight %, more preferably from about 1.0-1.6 weight %.
Fe is impurity element generally existing in aluminium alloy.Similar with its effect in core material, Fe, which has, to be easily formed
The intermetallic compound of recrystallization crystalline core size, the effect for reducing recrystallization temperature can be become.In order to guarantee that material is brazed
When the energy of resistance to erosion, based on composite layer of the invention, the content of Fe is about 0.25 weight % or less.
Cu element strengthens in composite layer alloy as one or the component of hardening improves intensity by solution strengthening, and
Current potential can be improved.For composite layer, based on composite layer alloy of the invention, if the content of Cu is more than about 0.5 weight %
When, the fusing point of alloy reduces, and is easy to happen intercrystalline corrosion.Based on composite layer alloy of the invention, the content of Cu is about≤0.5
Weight %, preferably from about≤0.3 weight %, more preferably from about≤0.1 weight %, particularly preferably≤0.05 weight %.
Ti, Zr and Cr rise recrystallization temperature by generating small particle, are easy to obtain in brazing process good
Resistance solder corrode grain structure.When these elements are respectively below about 0.01 weight %, its effect can not be obtained well,
When more than about 0.25 weight %, huge intermetallic compound easy to form makes plastic processing reduction.It is answered based on of the invention
Laminated gold is closed, the content of Ti is about 0.01-0.25 weight %, and preferred content is about 0.01-0.15 weight %, even more preferably about
0.01-0.1 weight %.The content of Zr is about 0.05-0.25 weight %, and preferred content is about 0.1-0.15 weight %.Cr's
Content is about 0.02-0.25 weight %, and preferred content is about 0.02-0.15 weight %, more preferably from about 0.02-0.1 weight %.
Al alloy composite
In embodiments of the invention, equivalent circle diameter present in composite layer alloy and core alloy be 0.2 μm with
Under grain density (with a/mm3Meter) ratio be about 1.5 or more.In preferred embodiments, composite layer alloy and core material
The grain density that equivalent circle diameter present in alloy is 0.02 μm -0.2 μm is (with a/mm3Meter) ratio be about 1.5 or more,
Preferably from about 1.8 or more, about 2.0 or more, about 3.0 or more, about 4.5 or more, about 6 or more, for example, about 2.1, about 4.4, about 5.9.
In another preferred embodiment, equivalent circle present in composite layer alloy and core alloy of the invention is straight
The grain density that diameter is 0.02 μm -0.2 μm is (with a/mm3Meter) ratio be no more than 10.In another preferred embodiment
In, the grain density in composite layer and core alloy is respectively about 1 × 104A/mm3More than, preferably from about 1 × 106A/mm3With
On.
The particle that the equivalent circle diameter existing for the composite layer alloy and core alloy is 0.02 μm -0.2 μm density (it is a/
mm3) ratio be 1.5 or more when, the special tissue of available one kind, wherein composite layer as and melt solder contacted
Layer, start fusion temperature or less in solder and recrystallized, and since there are the obstructions of a large amount of fine particle, and make again
The grain structure of crystallization is coarse uniformly, so as to resist solder to the corrode further expansion of composite layer.And core material is by multiple
That closes layer is protected against the corrode of solder, so that core alloy be made to keep its very high intensity.
Al alloy composite of the invention with a thickness of about 0.25mm hereinafter, preferably from about 0.2mm is hereinafter, for example, about
0.15mm or less.
In one embodiment, it is coated on a side of core alloy of the invention certain thickness of the invention
Composite layer alloy.In another embodiment, Al alloy composite of the invention consists of three layers.In core material of the invention
Upper certain thickness composite layer alloy of the invention is respectively coated on two sides of alloy forms aluminium alloy compound material of the invention
Material.Al alloy composite of the present invention for example can have structure as shown in Figure 1, i.e., two-sided composite material.
The percentage that the thickness of unilateral composite layer accounts for material overall thickness is expressed as compound ratio.Aluminium alloy compound material of the invention
The compound ratio of composite layer is not particularly limited in material, but should make the Al alloy composite that can get target thickness.This hair
The compound ratio of composite layer is about 5-15% in bright Al alloy composite.
Preparation method
The present invention also provides the preparation methods of Al alloy composite.
The manufacturing method of Al alloy composite of the invention the following steps are included:
A) ingot casting of core alloy and composite layer alloy is cast respectively；
B) composite layer alloy is heat-treated；
C) sawing, milling face；
D) the slab piece of composite layer alloy is prepared；
E) the slab piece of core alloy and composite layer alloy is carried out compound；
F) preheating and hot rolling；
G) cold rolling；
H) it anneals,
Wherein, the temperature being heat-treated in step b) is about 400-540 DEG C.
The method described in detail below for producing the core alloy, composite layer alloy and Al alloy composite.
A) ingot casting of core alloy and composite layer alloy is cast respectively
The manufacture of core alloy and composite layer alloy
Composite layer aluminium ingot is manufactured by water cooling semi-continuous casting method comprising following steps: technical pure aluminium ingot is added
Smelting furnace fusing, 730-760 DEG C of smelting temperature, skim, sampling analysis, respectively according to core alloy of the present invention and compound
The composition of laminated gold stands after alloying element is added, stirs, refines, skimming, and standing furnace is poured into after adjusting component, be again stirring for,
It refines, skim, enter casting machine by online Metamorphism treatment, degasification, filtering and carry out being cast as ingot casting.
The composition of core alloy is as described above.Such as based on the core alloy, the core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %；
And
(i) at least one of-(iii):
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
The composition of composite layer alloy is as described above.Such as based on the composite layer alloy, the group of the composite layer alloy
Become:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %；
And
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
B) composite layer alloy is heat-treated
The amounts of particles in control composite layer alloy and size are the most key to the corrode for resisting solder in the present invention.It closes
Disperse phase particle of the equivalent diameter less than 0.2 μm can hinder the movement of dislocation, sub boundary and crystal boundary in gold, to generate obvious
Particle strengthening effect；And disperse phase particle of the equivalent diameter in 0.2-0.5 μ m is then to dislocation, sub boundary and crystal boundary
Inhibition obviously weakens, and particle strengthening effect is unobvious；Disperse phase particle of the equivalent diameter greater than 0.5 μm generally plays again
Crystalline can make crystal grain refinement at the effect of core, improve forming property.And the equivalent circle diameter in alloy is less than 0.2 μm
Movement of the particle due to hindering dislocation or sub boundary, crystal boundary, have the function of postponing recrystallizing.Therefore, equivalent circle diameter is small
It is more in the quantity of 0.2 μm of particle, it is not easy to recrystallize in brazing process.On the other hand, in order to resist the molten of molten solder
Erosion, the layer (composite layer) contacted with solder must be completed to recrystallize before solder melt starting temperature.This is because melting
Solder can quickly be spread along sub boundary etc., generate serious corrode.
In various embodiments, composite layer alloy is being lower than 550 DEG C, preferably at 400-540 DEG C, more preferably in 430-
530 DEG C, particularly preferably 450-520 DEG C at a temperature of be heat-treated.It can control composite layer under such heat treatment temperature
The quantity and size of particle are precipitated in alloy.Treatment temperature cannot be at 550 DEG C or more, to avoid causing the particle in ingot casting thick
Change, leads to the reduction of recrystallization temperature.
Small particle can be formed in core material ingot casting to the heat treatment of core alloy in 400 DEG C or more of temperature, this
To improve core material recrystallization temperature be play the role of it is positive.In one embodiment, in step b) also optionally to core material
Alloy is heat-treated.The temperature of heat treatment is about 450-550 DEG C.In another embodiment, heat is not carried out to core alloy
Processing.
The inventors found that working as equivalent circle diameter existing for composite layer alloy and core alloy is 0.02 μm of -0.2 μ
Density (a/mm of the particle of m3) ratio when being 1.5 or more, finds the special tissue of available one kind, wherein composite layer work
For the layer contacted with the solder of melting, start fusion temperature or less in solder and recrystallized, and is a large amount of due to existing
Fine particle obstruction, and make recrystallization grain structure it is coarse uniformly, so as to resist solder to the corrode of composite layer
Further expansion.And core material is protected against the corrode of solder by composite layer, so that core alloy be made to keep its very high
Intensity.In embodiments of the invention, equivalent circle diameter present in composite layer alloy and core alloy is 0.2 μm below
Grain density is (with a/mm3Meter) ratio be about 1.5 or more.In preferred embodiments, composite layer alloy and core alloy
Present in equivalent circle diameter be 0.02 μm -0.2 μm of grain density (with a/mm3Meter) ratio be about 1.5 or more, preferably
About 1.8 or more, about 2.0 or more, about 3.0 or more, about 4.5 or more, about 6 or more, for example, about 2.1, about 4.4, about 5.9.Another
In one preferred embodiment, equivalent circle diameter present in composite layer alloy of the invention and core alloy be 0.02 μm-
0.2 μm of grain density is (with a/mm3Meter) ratio be no more than 10.In still another preferred embodiment, composite layer and core
Grain density in material alloy is respectively about 1 × 104A/mm3More than, preferably from about 1 × 106A/mm3More than.In the present invention,
Method measurement commonly used in the art can be used in granule number in core alloy and composite layer alloy, such as passes through scanning electricity
Sub- microscope count to the particle of certain area in the visual field and be measured.
C) sawing, milling face
Sawing
The bottom of composite layer alloy prepared above, core alloy ingot casting is amputated into 200-500mm.Milling face
By each mill off 5-20mm in two sides of the core alloy, composite layer alloy cast ingot after sawing.
D) the slab piece of composite layer alloy is prepared
Composite layer alloy cast ingot behind two facing cut faces is put into furnace and is heated, specific thickness is rolled by milling train later
Slab piece.
E) core alloy and composite layer alloy plate piece are carried out compound
In the slab piece of the compound certain thickness composite layer alloy in the one or both sides of core alloy, compound ratio is about 5-
15%.And it is welded end to end with argon arc welding machine.
F) preheating and hot rolling
The composite ingot of core alloy and one or both sides composite layer alloy prepares heat after heating between 470-550 DEG C
It rolls.
Composite ingot after heating is subjected to hot rolling by hot-rolling mill, makes MULTILAYER COMPOSITE aluminium.By multistage hot deformation,
Composite ingot is hot-rolled down to 2 to 6mm, such as 3.5mm from original depth, and crimps coiled.
G) cold rolling
After cooling, hot rolled coil is rolled on cold-rolling mill with a thickness of 0.25mm hereinafter, it is preferred that 0.20mm is below cold
Rolling compound coiled material.Cold rolling overall reduction at least 80% or more, preferably 90% or more.In one embodiment, in cold-rolled process
It can carry out 350 DEG C of intermediate annealings below.
H) it anneals
Cold rolling composite sheet material is placed in annealing furnace and carries out finished products, annealing temperature is about 200-360 DEG C, preferably from about
240-320 DEG C, annealing time about 1-3 hours.Product after annealing can be used as Al alloy composite of the invention, have
The performance of the final condition of delivery.
The usual thickness about 0.25mm of Al alloy composite of the invention hereinafter, preferably from about 0.20mm hereinafter, for example, about
0.15mm or less.
Al alloy composite of the invention or Al alloy composite prepared by the method for the present invention can be used as very
The fin of sky soldering.In one embodiment, Al alloy composite can be used as the fin of vacuum brazing heat exchanger.Another
In a embodiment, Al alloy composite can be used as heat exchanger, such as the fin material of plate-fin heat exchanger.Preferred real
It applies in scheme, in the use process of fin material, soldering cooling procedure, which uses, is greater than 0.5 DEG C/s, and preferably greater than 1 DEG C/s is cooling
Speed.Such cooling velocity is more conducive to the promotion of the postwelding fin material intensity, to further extend heat exchanger
Service life.
Beneficial effect
The present invention is based on monolayer material is replaced using multilayer material in process, and adjust heterogeneous microstructure with
And particle size and distribution, it realizes required deposited strength and resists solder corrode performance, after especially realizing high soldering
Intensity and resistance solder corrode performance, and there is preferable forming property in finned blade forming.
When the MULTILAYER COMPOSITE aluminum alloy materials are used as vacuum brazing fin material, compared to traditional fin material, width is thinned
Degree is more than 40%, and excellent strength, resists the very capable of corrode, and material is not easy temperature distortion in brazing process, embodies
Good brazing property out.Since the fin material is substantially thinned, when as heat exchanger or heat exchanger, can have obvious
Lightweight advantage, and its intensity can also continue to enhance in use, can further extend heat exchanger or change
The service life of hot device.
Embodiment
The present invention described in further detail referring to following Examples, but its model for being not intended to be limiting of the invention
It encloses.
Sample preparation
To have core alloy shown in table 1, table 2 and composite layer alloy to cast (direct-cooled semicontinuous casting by DC respectively
Make), to composite layer 520 DEG C at a temperature of be heat-treated, after carrying out milling face to the two sides of core material and composite layer respectively, pass through hot rolling
Composite layer alloy is rolled into defined thickness respectively.According to combination shown in table 3, by two sides of core alloy point
The other laminated gold of covered composite yarn, is pressed by hot rolling at 500 DEG C, the 3-layer composite material of 3.5mm is made.It is carried out in cold rolling
The metal material cold rolling is later final plate thickness 0.15mm, and carries out final annealing by the middle intermediate annealing for carrying out 1 time.
Table 1
Table 2
Table 3
Sample particle morphology observations and size statistic
The composite layer alloy component of composite material in embodiment 6 and core alloy part is separately sampled, it is scanned electricity
The micro- sem observation of son, as shown in Figures 2 and 3.20 are chosen having a size of 85 μm2Region, be to wherein equivalent circle diameter respectively
0.02 μm -0.2 μm of granule number is counted.The density of the particle of composite layer alloy can be obtained (with a/mm3Meter) it is 1.1 × 109,
The density of the particle of core alloy is (with a/mm3Meter) it is 5.2 × 108.Composite layer alloy is with equivalent circle diameter in core alloy
The ratio of the density of 0.02 μm -0.2 μm of particle is 2.1.
With same method by the composite material of embodiment 3,8 composite layer alloy and core alloy Subsampling carry out
Scanning electron microscope analysis, the particle for being respectively 0.02 μm -0.2 μm to its equivalent circle diameter are counted, are obtained compound in embodiment 3
The density of the particle of laminated gold is (with a/mm3Meter) it is 2.2 × 109, the density of the particle of core alloy is (with a/mm3Meter) it is 3.7
×108.The ratio of the density for the particle that equivalent circle diameter is 0.02 μm -0.2 μm in composite layer alloy and core alloy is 5.9.
The density of the particle of composite layer alloy is (with a/mm in embodiment 83Meter) it is 2.0 × 109, the particle of core alloy density (with
A/mm3Meter) it is 4.5 × 108.The density for the particle that equivalent circle diameter is 0.02 μm -0.2 μm in composite layer alloy and core alloy
Ratio be 4.4.
Ionization meter after soldering
(1) vacuum simulation soldering
With vacuum brazing furnace, test sample was warming up to 600 DEG C by about 3 hours from room temperature, and keeps the temperature 15 minutes, in furnace
It is air-cooled to take out sample progress for opening fire door after being inside cooled to 500 DEG C.
(2) extension test
Prepare tensile testing samples according to EN10002-1 standard, gauge length be 50mm then, and drawn in room temperature with 20mm/min
It stretches speed and carries out stretching experiment.The sample of extension test includes: to be placed at room temperature for 7 days with after being brazed after soldering is simulated.
(3) corrode scale evaluation
Fin is made in fin material, and combine with tubing carry out soldering simulation after form soldered fitting, prepare gold later
Phase sample carries out corrode scale evaluation by metallographic microscope.Tensile strength and corrode degree are as shown in Table 4.
Table 4
By table 4 it can be concluded that, the tensile strength of the Al alloy composite of embodiment 1-8 after brazing be up to 130MPa with
On.
In contrast, the tensile strength of the Al alloy composite of comparative example 1 after brazing is lower than 120MPa, with the present invention
Embodiment is compared, hence it is evident that relatively low.For comparative example 2, deposited strength is also slightly below material of the invention.In addition, of the invention
Vacuum brazing fin material resists the functional of solder corrode, resists the performance of corrode much higher than comparative example.Such as Fig. 4 and Fig. 5
Shown, fin is by the serious corrode of solder in comparative example 2, and the fin of embodiment 6 is resisted solder corrode and had excellent performance.
Describe the present invention in detail in embodiments.But those skilled in the art can significantly modifications and changes it is real
Scheme is applied without departing from spirit of the invention.All modifications and change both fall within the range of the application the attached claims
It is interior.
Claims (14)
1. a kind of Al alloy composite, it includes core alloy and composite layer alloy,
The particle that wherein equivalent circle diameter present in composite layer alloy and core alloy is 0.02 μm -0.2 μm density (with
A/mm3Meter) ratio be 1.5 or more；
It is wherein based on the core alloy, the core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %；
And
(i) at least one of-(iii):
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
2. the Al alloy composite of claim 1, wherein being based on the composite layer alloy, the composite layer alloy includes:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %；
And
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
3. the Al alloy composite of claims 1 or 2, wherein being based on the core alloy, the core alloy includes 0.2-
The Mg of 0.6 weight %.
4. the Al alloy composite of one of claim 1-3, wherein being based on the core alloy, the core alloy includes
The Mn of 0.2-0.95 weight %.
5. the Al alloy composite of one of claim 1-4, wherein being based on the composite layer alloy, the composite layer alloy packet
The Si of the % of weight containing 0.05-0.55.
6. the Al alloy composite of one of claim 1-5, wherein being based on the composite layer alloy, the composite layer alloy packet
The Mn of the % of weight containing 0.8-1.8.
7. the Al alloy composite of one of claim 1-6, which is characterized in that in a face of the core alloy or two
The composite layer alloy is coated on face.
8. the Al alloy composite of one of claim 1-7, wherein the Al alloy composite with a thickness of 0.25mm with
Under.
9. a kind of method for preparing Al alloy composite comprising following steps:
A) ingot casting of core alloy and composite layer alloy is cast respectively；
B) the composite layer alloy is heat-treated；
C) sawing, milling face；
D) the slab piece of the composite layer alloy is prepared；
E) the slab piece of the core alloy and the composite layer alloy is carried out compound；
F) preheating and hot rolling；
G) cold rolling；
H) it anneals,
Wherein, the temperature being heat-treated in step b) is 400-540 DEG C.
10. method for claim 9, which is characterized in that be based on the core alloy, the core alloy includes:
The Si of 0.3-1.5 weight %,
The Cu of 0.1-1.0 weight %,
The Mn of 0.1-1.0 weight %,
The Mg of 0.1-0.9 weight % and
The Fe of≤0.35 weight %；
And
(i) at least one of-(iii):
(i) Ti of 0.05-0.25 weight %,
(ii) Zr of 0.05-0.25 weight %,
(iii) Cr of 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
11. the method for claim 9 or 10, which is characterized in that be based on the composite layer alloy, the composite layer alloy includes:
The Si of 0.05-0.6 weight %,
The Fe of≤0.25 weight % and
The Mn of 0.5-2.0 weight %；
And
At least one of (i ')-(iv ') for being optionally present:
The Cu of (i ')≤0.5 weight %,
The Ti of (ii ') 0.01-0.25 weight %,
The Zr of (iii ') 0.05-0.25 weight %,
The Cr of (iv ') 0.02-0.25 weight %；
And
Single content≤0.05 weight % and the other elements of total content≤0.15 weight %；
Surplus is Al.
12. the method for one of claim 9-11, which is characterized in that composite layer alloy and core material in the Al alloy composite
The density for the particle that equivalent circle diameter present in alloy is 0.02 μm -0.2 μm is (with a/mm3Meter) ratio be 1.5 or more.
13. the method for one of claim 9-12, wherein the Al alloy composite with a thickness of 0.25mm or less.
14. the aluminium of the method preparation of one of one of -8 Al alloy composite or claim 9-13 closes according to claim 1
Metal/composite material is used as the purposes of the fin of vacuum brazing.
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| CN114752829B (en) * | 2022-05-05 | 2022-10-04 | 银邦金属复合材料股份有限公司 | Composite aluminum alloy plate for new energy power battery liquid cooling plate and preparation method thereof |
| CN115771311A (en) * | 2022-12-23 | 2023-03-10 | 格朗吉斯铝业（上海）有限公司 | Aluminum alloy composite material for brazing and manufacturing method thereof |
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