JP2000167688A - Aluminum alloy clad material for heat exchangers with excellent brazing and corrosion resistance - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To improve the brazing property and corrosion resistance, to improve the strength after brazing, to reduce the thickness of the working fluid passage material,
Provided is an aluminum alloy clad material for a heat exchanger that enables the weight reduction and long life of an aluminum heat exchanger to be achieved. SOLUTION: An aluminum alloy clad material in which a brazing material is clad on one or both surfaces of a core material, wherein the core material is Mn: 0.5% to 2.0%, Cu: 0.1% to 1.0%, Si:
0.1% or less, Fe: 0.3% or less, Ti: 0.06% to 0.35%, the content of Mg is regulated to 0.04% or less, and the remaining Al
The brazing material contains Si: 6% to 14%, Fe: 0.06% to 0.7%, the content of Mg is 0.04% or less, and the content of Ca is 0.1%.
It is characterized by being composed of an Al-Si based alloy restricted to 006% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy clad material for a heat exchanger having excellent brazing properties and corrosion resistance, and more particularly to a working fluid passage of a heat exchanger joined by brazing, such as an evaporator or a radiator of a car air conditioner. The present invention relates to an aluminum alloy clad material for a heat exchanger, which is used as a constituent material and has excellent brazing properties particularly in brazing in an inert gas atmosphere using a fluoride-based flux.

[0002]

2. Description of the Related Art Aluminum alloy heat exchangers are widely used as radiators, oil coolers, intercoolers, evaporators and condensers for heaters and air conditioners of automobiles, and heat exchangers for oil coolers of hydraulic equipment and industrial machines. . There are various types of aluminum alloy heat exchangers, but from the viewpoint of weight reduction, a working fluid passage is formed by superimposing aluminum alloy clad materials and forming a working fluid passage between them. Attention has been paid to a laminated heat exchanger (Drone cup type heat exchanger) manufactured by combining corrugated aluminum alloy fins and integrating them by brazing.

As shown in FIGS. 1 and 2, for example, a drone cup type evaporator 10 has core plates 11 and 1 made of press-formed aluminum alloy clad material.
2 and aluminum alloy fin 13 corrugated
And the core plates 11 and 12 are brazed.
The fins 13 are joined to the core plates 11 and 12 by melting the brazing material, and a working fluid passage 14 for a refrigerant or the like is formed between the core plates 11 and 12.

[0004] The core plates 11 and 12 are made of Al-Mn, Al-Mn-Cu, Al-Mn.
Aluminum alloys containing Mn, such as -Mg-based and Al-Mn-Cu-Mg-based alloys, for example, JIS A3003 alloy and 3005 alloy are used.
System, Al-Si-Mg system, Al-Si-Mg-Bi system,
Al-Si-Mg-Be system, Al-Si-Bi system, Al
Al- such as -Si-Be type, Al-Si-Bi-Be type
An Si alloy or the like is used, and an aluminum alloy clad material obtained by cladding the above brazing material on one or both surfaces of the above core material is used.

As the fins 13, an aluminum alloy obtained by adding Cu, Mg, Zn, Sn, In or the like to an Al-Mn alloy is used. A brazing method for the fins 13 and the core plates 11 and 12 is used. In general, a brazing method using a fluoride-based flux in an inert gas atmosphere is applied, but vacuum brazing may be applied in some cases.

In recent years, weight reduction and cost reduction of heat exchangers have been strongly demanded, and in order to achieve these demands, it is necessary to further reduce the thickness of the heat exchanger constituent materials such as working fluid passages. For example, in order to reduce the thickness of the aluminum alloy clad material constituting the working fluid passage, if various elements are added and the strength is increased, the corrosion resistance is reduced, and the brazing becomes difficult as the material becomes thinner, and heat exchange becomes difficult. Vessel manufacturability,
Since a problem arises in durability, there is a demand for the development of a clad material having further improved brazing properties and corrosion resistance.

The aluminum alloy clad material conventionally used as the core plates 11 and 12 of the drone cup type evaporator 10 has a core material of an aluminum alloy containing Mn as described above, and has a pitting corrosion resistance. For example, when applied to a working fluid passage material of a refrigerant, the penetration leakage accident due to pitting has been experienced.

In order to improve the pitting resistance of the working fluid passage material, the fins 13 are made of a material having a potential lower than that of the working fluid passage material, for example, Al-Mn-Zn, Al-M.
It is conceivable to apply an n-Sn-based alloy, an Al-Mn-In-based alloy, or the like, and to use the sacrificial anode effect of the fins 13 made of these materials to prevent corrosion of the working fluid passage material.
This anticorrosion method is effective only for the working fluid passage material near the joint with the fin 13, and the sacrifice anode effect of the fin 13 does not reach the working fluid passage material at a position away from the fin 13, and pitting occurs. Inevitable.

In order to improve the corrosion resistance of an aluminum alloy clad material for a working fluid passage, a clad material in which Cu, Ti, Cr, or Zr is added to a core material (Japanese Patent Publication No. 6-4)
No. 1621), the content of Fe, which constitutes a compound serving as a cathode among the core material components and degrades corrosion resistance, is set to 0.
Cladding material limited to 2% or less (JP-A-64-8339)
No. 6) or a clad material in which the contents of Fe and Si in the core material are respectively limited to improve intergranular corrosion resistance (Japanese Patent Publication No. 6-41621) has been proposed. The aluminum alloy clad material has some improvement in corrosion resistance, but has a problem that strength characteristics after brazing are not sufficiently improved and the pressure resistance of the heat exchanger is reduced.

As an effective means for improving the strength characteristics of the clad material, there is addition of Mg to the Al-Mn alloy core material, but a fluoride-based flux is used for the clad material comprising the Mg-containing core material. In the case of brazing, the Mg in the core material diffuses to the surface in the brazing process and reacts with F in the flux to form an MgF ₂ compound, and the amount of flux effectively acting in brazing decreases. In addition, there is a problem that the effect of removing the oxide film from the flux is reduced and the brazing property is impaired.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems particularly in the working fluid passage material and to obtain an aluminum alloy clad material which satisfies the demand for thinning the working fluid passage material. In particular, the composition of the core material on brazing properties and corrosion resistance, the composition of the brazing material clad on one or both sides, and the effect of their combination were made as a result of conducting multilateral experiments and studies. An object of the present invention is to provide an aluminum alloy clad material for a heat exchanger having good brazing properties and corrosion resistance and improved strength after brazing.

[0012]

According to a first aspect of the present invention, there is provided an aluminum alloy clad material for a heat exchanger, comprising a core material and a brazing material clad on one or both surfaces of a core material. The core material is composed of Mn: 0.5% to 2.0%, Cu: 0.1% to 1.0%, Si:
0.1% or less, Fe: 0.3% or less, Ti: 0.06% to 0.35%, the content of Mg is regulated to 0.04% or less, and the remaining Al
The brazing material contains Si: 6% to 14%, Fe: 0.06% to 0.7%, the content of Mg is 0.04% or less, and the content of Ca is 0.1%.
It is characterized by being composed of an Al-Si based alloy restricted to 006% or less.

According to a second aspect of the present invention, there is provided an aluminum alloy clad material for a heat exchanger, wherein the brazing material further contains 0.01 to 0.4% of Bi. The clad material according to claim 1 or 2, wherein the brazing material further comprises Zn: 0.3% to 4.0%, In:
It is characterized by containing one or more of 0.005% to 0.1% and Sn: 0.01% to 0.1%.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The significance of the alloy components in the aluminum alloy clad material for a heat exchanger of the present invention and the reasons for limiting the same will be described. (1) Components of core material Mn in the core material functions to improve the strength of the core material. Further, Mn forms a compound with Si and Fe as impurities, thereby confining the effect of reducing the corrosion resistance of Si and Fe, and improving the corrosion resistance. The preferred content range of Mn is 0.5% to 2.0%, and its effect is small when it is less than 0.5%, and when it exceeds 2.0%,
Coarse compounds are formed during casting, which impairs the rolling processability, making it difficult to obtain a sound clad material.

Cu in the core material functions to improve the strength of the core material, make the potential of the core material noble, increase the potential difference between the brazing material layer and the fin material, and enhance the anticorrosion effect. C
The preferable content range of u is 0.1% to 1.0%,
If the content is less than 1.0%, the effect is small. If the content exceeds 1.0%, the core material may be melted at the time of brazing, and in addition, the corrosion resistance of the core material itself deteriorates.

Both Si and Fe in the core material reduce the corrosion resistance as a cathode. The preferred content range is Si
Although it is 0.1% or less and Fe0.3% or less, a high-purity aluminum ingot with a small amount of Si and Fe is expensive and impractical.
0.1%, Fe 0.01% to 0.3%.

[0017] Ti acts to further improve the corrosion resistance of the core material. That is, Ti is divided into a high-concentration region and a low-concentration region, and these regions are alternately distributed in the plate thickness direction to form a layer, and a region with a low Ti concentration is preferentially corroded as compared with a region with a high concentration. As a result, the pitting resistance of the material is improved by preventing the progress of corrosion in the sheet thickness direction. The preferred content ranges from 0.06% to 0.35%,
If it is less than 0.06%, the effect is not sufficient, and if it exceeds 0.35%, a coarse compound is formed at the time of casting, so that rolling of the material becomes difficult and a sound clad material cannot be obtained.

In the case of brazing using a fluoride-based flux, Mg in the core material diffuses to the surface in the brazing step and reacts with F in the flux to form an MgF ₂ compound, and In the above, the amount of the flux effectively acting is reduced, and the effect of removing the oxide film of the flux is reduced, and the brazing property is inhibited. Therefore, the Mg content is
It is preferable to regulate it to 0.04% or less. More preferably
0.02% or less.

In addition, impurity elements such as Zn, Cr and Zr may be contained in the core material within a range that does not impair the effects of the present invention. However, Zn makes the potential of the core material low, reduces the potential difference with the fin material, and impairs the corrosion resistance.
It is preferable to set the following. Although Cr and Zr have the effect of making the structure finer, they impair workability. Therefore, each of them is preferably limited to 0.3% or less.

(2) Components of brazing filler metal The brazing filler metal differs depending on the brazing method. For example, in the case of vacuum brazing, an Al—Si—Mg alloy or Al—Si—
An Mg-Bi alloy is used. In the case of flux brazing, an Al-Si alloy is used.
The content of i is preferably in the range of 6% to 14%.

[0021] Fe has the effect of refining the structure of the brazing material and increasing the fluidity of the brazing material. The preferred content of Fe is
If the content is less than 0.06%, the effect is not sufficient. If the content exceeds 0.7%, the effect is saturated and A becomes a cathode with respect to the Al matrix.
The production amount of the l-Fe compound increases and the corrosion resistance decreases.

In the case of brazing using a fluoride-based flux, Mg is concentrated on the surface of the brazing material and reacts with fluorine (F) in the flux to form an MgF ₂ compound in the brazing step. Since the amount of flux that acts effectively in brazing is reduced and the effect of removing the oxide film of the flux is reduced and brazing properties are impaired, the use of Mg is preferably restricted to 0.04% or less, more preferably 0.02% or less. .

Since Ca in the brazing material constitutes a dense oxide on the surface of the brazing material, it lowers the wettability and spreadability of the brazing material and impairs the brazing property. The preferred content of Ca is in the range of 0.006% or less, and if it exceeds 0.006%, the brazing property is significantly reduced. The more preferred content of Ca is in the range of 0.004% or less.

Bi lowers the melting point of the wax and improves the wettability and flowability of the wax. The preferred content of Bi is 0.01
% To 0.4%, the effect is small when it is less than 0.01%, and when it exceeds 0.4%, the effect is saturated and the self-corrosion resistance is lowered.

Zn, In and Sn lower the potential of the brazing material, give a sacrificial anode effect to the core material, and improve the corrosion resistance of the clad material. The preferred content is Zn: 0.3%
4.0%, In: 0.005% to 0.1%, Sn: 0.01% to 0.1%
If the respective amounts are less than the lower limits, the effect is not sufficient. If the respective amounts exceed the upper limits, the corrosion and wear of the brazing material portion of the clad material is remarkable, and the sacrificial anode effect of the brazing material portion is not maintained for a long period of time. The self-corrosion resistance of the attached portion is also reduced.

In the brazing material, a small amount of, for example, 0.1% or less of Be, Sr, L
One or more of i and Na can be contained. Also, Mn, Cu, Ti, Cr, Zr, Ni
In order to improve the strength of the brazing material, a small amount of such an element may be contained in the brazing material as long as the effects of the present invention are not impaired. However, if the content of these elements increases, the self-corrosion resistance of the brazing filler metal decreases, so the total content of these elements is preferably suppressed to 1% or less.

The aluminum alloy clad material of the present invention comprises:
The aluminum alloy constituting the core material and the brazing material is ingot-formed by, for example, continuous casting, homogenized, or homogenized, and then hot-rolled to a predetermined thickness. According to the method, the clad material is formed by hot rolling, finally cold-rolled to a predetermined thickness, and finally subjected to annealing.

The aluminum alloy clad material of the present invention is
For example, as shown in FIGS. 1 and 2, the clad material is press-molded into core plates 11 and 12 to be used as a constituent member of a drone cup type evaporator. Then, a fin 13 made of aluminum alloy is brazed and joined to assemble a drone cup type evaporator. To make a tank material such as a radiator or a capacitor, the clad material is press-formed into a tank shape and brazed. It is preferable to apply an inert gas atmosphere brazing using a fluoride-based flux or a vacuum brazing to both brazing joints.

[0029]

Example 1 An aluminum alloy for a core material having the composition shown in Table 1 (compositions shown in core materials Nos. 1 to 9) and a composition shown in Table 2 (brazing material Nos. A to K) by continuous casting. An aluminum alloy for a brazing material having the following composition) was ingoted and the aluminum alloy for a core material was homogenized to a thickness of 21 mm.
In the case of aluminum alloy for brazing material, the ingot is hot-rolled and then hot-rolled to a 4.5 mm thick brazing material, and then the brazing material is laid on both sides of the core material. Then, hot rolling was performed to obtain a 3 mm-thick aluminum alloy clad material. Thereafter, cold rolling was performed, and final annealing was performed to produce a soft plate (temper 0) of a cladding material (brazing sheet) having a thickness of 0.5 mm (cladding materials No. 1 to 1).
8).

[0030]

[Table 1]

[0031]

[Table 2]

The clad material (clad material Nos. 1 to 18) obtained as described above was subjected to the following method.
(1) Strength after brazing, (2) Brazing property, and (3) Corrosion resistance were evaluated. (1) Strength after brazing The clad material was heated under the same brazing conditions, then cooled, and a tensile test was performed. That is, as a fluoride flux brazing heat treatment (NB), a cladding material is coated with a fluoride flux (concentration: 1%), heated in a nitrogen gas atmosphere at 600 ° C. (material temperature) for 5 minutes, and then cooled. Each of the test materials was subjected to a tensile test, and the tensile strength (MPa) was measured.

(2) Brazing performance As shown in FIG. 3, an aluminum alloy clad material 2 in which brazing materials 4 and 5 are clad on both surfaces of a core
mm and a length of 40 mm, placed on a 3003 alloy material (cut to a width of 25 mm, a length of 40 mm, and a thickness of 2 mm) 3 to form an inverted T-shaped joint 1 and brazing the above-mentioned fluoride flux. Heat treatment (NB) was performed. As shown in FIG. 4, fillet portions 7 and 8 are melt-formed at the corners of the inverted T-shaped joint 1 after the treatment, so that the cross-sectional areas of these fillet portions 7 and 8, A ₁ and A ₂ was measured, and from the ratio of the cross-sectional areas A ₁ and A ₂ to the cross-sectional areas of the brazing materials 4 and 5 before brazing and A ₀₁ and A ₀₂ , the flow coefficient K = (A ₁ + A ₂ ) / (A ₀₁ + _A02 ) is calculated. The larger the flow coefficient K, the higher the ratio of the molten brazing material, indicating that the flowability of the brazing material is good and the brazing property is excellent. The evaluation of the brazeability is such that the flow coefficient K is 0.
When the brazing property is 35 or more, the brazing property is good (○). When the brazing property is less than 0.35, poor brazing properties such as cut-out of the fillet are likely to occur. Insufficiency (x).

(3) Corrosion resistance Regarding the inverted T-shaped joint 1 after the above-mentioned brazing and heating, C
The ASS test was performed for 4 weeks based on JIS H8681, and the maximum corrosion depth of the general portion (the portion other than the fillet portion) of the clad material after the test was measured. Further, the corrosion state of the brazed joint fillet after the corrosion test was investigated, and the corrosion was less than 25% of the fillet area (レ ッ ト) and 2
Those having 5% or more and less than 50% (（) were regarded as having good corrosion resistance, and the test materials in which 50% or more of the fillet area disappeared due to corrosion were evaluated as having insufficient corrosion resistance (×).

Table 3 shows the evaluation results. As can be seen from Table 3, examples satisfying the conditions of the present invention (cladding material No.
1 to 18) all exhibited excellent brazing properties with a flow coefficient K of 0.41 or more. The maximum corrosion depth after the CASS test was 0.09 to 0.20 mm, indicating good corrosion resistance. The strength after brazing is 107MP
a Excellent strength was obtained. In addition, all the clad materials of this example were excellent in manufacturability without causing any problem in manufacturing.

[0036]

[Table 3]

Comparative Example 1 The compositions shown in Table 4 (core materials No. 10 to 1) were obtained by continuous casting.
9) and an aluminum alloy for a brazing material having the composition shown in Table 2 (compositions shown in brazing materials Nos. Q to Z) were ingots, and the same processes as in the above example were performed. A soft plate (temper 0) of an aluminum alloy clad material having a thickness of 0.5 mm was prepared (cladding material N
o. 19-38).

[0038]

[Table 4] << Table Note >> Core No.19 is 3003 alloy

[0039]

[Table 5]

With respect to the obtained aluminum alloy clad material (cladded materials No. 19 to 38), (1) strength after brazing,
(2) Brazing properties and (3) corrosion resistance were evaluated. Table 6 shows the evaluation results.

[0041]

[Table 6]

As shown in Table 6, the cladding materials (cladding materials Nos. 19 to 3) according to the comparative examples which did not satisfy the conditions of the present invention.
No. 8) does not have the required performance as an aluminum alloy clad material for a heat exchanger. That is, the clad material No. No. 19 has a low tensile strength because the content of Mn in the core material is small. Cladding material No. In No. 20, since the Mn content of the core material was too large, rolling was difficult and a sound plate material could not be produced. Cladding material No. 21 is the core material C
Since the content of u is small, the tensile strength is low, and after the CASS test, the maximum corrosion depth of the general portion is large and the corrosion resistance is poor. Cladding material No. 22 has a large content of Cu in the core material,
Local melting occurred due to heating during brazing. Cladding material N
o. 23 is CASS because of the high content of Si in the core material.
After the test, the maximum corrosion depth of the general part is large and the corrosion resistance is poor.

Clad material No. In No. 24, since the Fe content of the core material is large, the maximum corrosion depth of the general portion after the CASS test is large and the corrosion resistance is poor. Cladding material No. In No. 25, since the content of Ti in the core material is small, the maximum corrosion depth of the general portion after the CASS test is large and the corrosion resistance is poor. Cladding material N
o. In No. 26, since the content of Ti in the core material was large, rolling of the material was difficult and a sound clad material could not be produced.
Cladding material No. In No. 27, since the Mg content of the core material is large, a sufficient fillet portion is not formed, the fillet is cut off, and the brazing property is inferior. Cladding material No. 28 is
The core material was equivalent to JIS3003 alloy, and the content of Ti was small and the content of Si and Fe was large. Therefore, the corrosion resistance was poor, and a through hole was formed in the CASS test. Also Mg
, The brazing property was poor, sufficient fillets were not formed during brazing, and the fillets were cut.

Clad material No. 29 is Si in brazing material
, The flow coefficient K is small, and the brazing property is inferior. Cladding material No. In No. 30, since the content of Si in the brazing filler metal was too large, the rolling workability was poor and a sound clad material could not be produced. Cladding material No. 31 is
Since the content of Fe in the brazing material is small, the flow coefficient K is small, and the brazing property is inferior. Cladding material No. In No. 32, since the content of Fe in the brazing filler metal is large, the self-corrosion of the fillet portion after the CASS test is severe and the corrosion resistance is inferior. Cladding material No. 33 has a high Mg content in the brazing material,
Poor brazing properties were observed, and sufficient fillets were not formed during brazing, resulting in breakage of fillets.

Clad material No. In No. 34, since the Ca content of the brazing filler metal was large, the brazing properties were poor, and sufficient fillets were not formed during brazing, resulting in breakage of the fillets. Cladding material No. No. 35 has a large Bi content in the brazing material, and the clad material No. 35 has a high Bi content. No. 36 has a high Zn content in the brazing material, and the clad material No. No. 37 has a high In content in the brazing material, and clad material No. 37 has a high In content. 38 is S in brazing material
Since the content of n is large, in any case, the self-corrosion of the fillet portion is severe in the CASS test, and the corrosion resistance is poor.

[0046]

According to the present invention, there is provided an aluminum alloy clad material for a heat exchanger having particularly good brazing properties and corrosion resistance and having improved strength characteristics after brazing. According to the aluminum alloy clad material for a heat exchanger, the thickness of the working fluid passage material can be reduced, and the weight and life of an aluminum heat exchanger such as a radiator or a condenser can be reduced.

[Brief description of the drawings]

FIG. 1 is a perspective view of a drone cup type evaporator to which an aluminum alloy clad material for a heat exchanger according to an embodiment of the present invention can be applied.

FIG. 2 is a front view of FIG.

FIG. 3 is a cross-sectional view showing a state of a brazing property verification test (before brazing heating) of the aluminum alloy clad material for a heat exchanger according to the embodiment of the present invention.

FIG. 4 is a cross-sectional view showing a state of a brazing property verification test (after brazing heating) of the aluminum alloy clad material for a heat exchanger according to the embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Inverted T-shaped joint 2 Aluminum alloy clad material 3 3003 alloy material 4, 5 Brazing material 6 Core material 7, 8 Fillet part 10 Drone cup type evaporator 11, 12 Core plate 13 Aluminum alloy fin 14 Working fluid passage

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F28F 21/08 F28F 21/08 A

Claims (3)

[Claims] 1. An aluminum alloy clad material in which a brazing material is clad on one or both surfaces of a core material, wherein the core material has Mn: 0.5% (% by weight, the same applies hereinafter) to 2.0%, Cu: 0.1%.
1% to 1.0%, Si: 0.1% or less (excluding 0%, the same applies hereinafter) Fe: 0.3% or less, Ti: 0.06% to 0.35%,
The content of Mg is regulated to 0.04% or less, the balance is made of an aluminum alloy composed of Al and impurities, and the brazing material contains Si: 6% to 14%, Fe: 0.06% to 0.7%,
An aluminum alloy clad material for heat exchangers having excellent brazing properties and corrosion resistance, comprising an Al-Si alloy in which the content of Mg is regulated to 0.04% or less and the content of Ca is regulated to 0.006% or less. 2. The brazing material further comprises Bi: 0.01% to 0.4%.
The aluminum alloy clad material for a heat exchanger according to claim 1, which is excellent in brazing properties and corrosion resistance. 3. The brazing material further comprises Zn: 0.3% to 4.0%,
3. The heat excellent in brazing property and corrosion resistance according to claim 1 or 2, wherein one or more of In: 0.005% to 0.1% and Sn: 0.01% to 0.1% are contained. Aluminum alloy clad material for exchangers.