JP4236187B2 - Aluminum alloy clad material for automotive heat exchanger - Google Patents

Description

  The present invention relates to an aluminum alloy clad material for automobile heat exchangers, and in particular, aluminum alloys such as evaporators, capacitors, radiators and heater cores joined by brazing using a fluoride flux or a cesium fluoride flux in an inert gas atmosphere. The present invention relates to an aluminum alloy clad material for an automobile heat exchanger suitable as a tube material for an automobile heat exchanger or a piping material (extruded clad pipe) connected to the heat exchanger.

  An automobile heat exchanger, for example, a radiator, includes a tube and a header having fins on the outer surface and the inner surface serving as a passage for a working fluid (refrigerant). As a tube material and header plate material such as a radiator or a heater core of such an automobile, a two-layer in which an Al-Mn alloy alloy such as JIS A3003 is used as a core material and an Al-Si alloy brazing material is clad on one side of the core material. Aluminum alloy clad material with a three-layer structure in which a brazing material is clad on one surface of the core material and a sacrificial anode material of Al-Zn alloy or Al-Zn-Mg alloy is clad on the other surface A clad material is used.

  When manufacturing an aluminum alloy heat exchanger, the clad Al-Si brazing material is used when a tube is manufactured by joining a tube and a fin, joining a tube and a header plate, or brazing a clad plate. It is clad for brazing. In recent years, inert gas atmosphere brazing using a fluoride flux or a cesium fluoride flux is generally applied to these brazings. The sacrificial anode material is used, for example, on the inner surface side of the tube, and exerts a sacrificial anode action in contact with the working fluid to prevent the occurrence of pitting corrosion and crevice corrosion of the core material.

  In recent years, with the demand for lighter automobiles, automobile heat exchangers are also required to be made thinner from the viewpoint of energy saving and resource saving, and the tube materials are also becoming thinner. In the manufacture of various heat exchangers, conventionally, as shown in FIG. 1, an aluminum alloy clad material in which a sacrificial anode material 5 is clad on one surface of a core material 4 and a brazing material 6 is clad on the other surface is welded. The flat tube 1 was assembled to the header plate and integrally brazed, but recently, from the viewpoint of energy saving and work efficiency, both ends of the clad material are sacrificed as shown in FIG. By simply bending to be in contact with the anode material 5, a B-shaped tube shape 2 is formed, and after being assembled to the header plate, it is often brazed integrally, and as shown in FIG. A technique of increasing the rigidity of the tube by inserting a clad fin material (brazing material / core material / brazing material) 3 into the flat tube 1 and brazing is also performed.

  However, since the tube material and the fin material are thin, the amount of brazing material to be clad is small, and in the case where the sacrificial anode material is the brazing surface as shown in FIGS. In the case of FIG. 2, the brazing does not sufficiently occur, and it is not uncommon for poor bonding to occur at the abutting portion (dotted line enclosing portion-A portion) between both ends of the clad plate and the sacrificial anode material. Further, as shown in FIG. 3, when the clad fin material 3 is inserted into the tube 1 and brazed in an inert gas atmosphere, the air inside the tube is not completely replaced with the inert gas during brazing. Therefore, the brazing material of the clad fin material 3 does not sufficiently wet and spread in the joint portion, and the contact portion between the clad fin material 3 and the sacrificial anode material on the inner surface of the tube material 1 (the dotted line enclosed portion-B portion) is not bonded. May be sufficient.

  It is conceivable to solve the above problem by further brazing a brazing material on the inner surface side (sacrificial anode material 5 surface) of the tube and combining the brazing and brazing joints. When Si diffuses into the anode material and Zn diffuses from the sacrificial anode material into the brazing material, there is a problem that sufficient sacrificial anode effect is not exhibited and the corrosion resistance on the inner surface side is lowered.

As an aluminum alloy clad material excellent in erosion / corrosion resistance applied as a tube material, it contains Si: 3.0 to 12.0% as a sacrificial anode material on one side of an Al-Mn alloy core material, or Si : A material containing 3.0 to 12.0%, Zn: 1 to 10% and clad with an aluminum alloy composed of the balance Al and impurities has been proposed (see Patent Document 1). However, the sacrificial anode material is expected to solve the above problem by having a function as a brazing material. In this case, the sacrificial anode material flows due to the liquid phase generated in the sacrificial anode material during brazing heating. It is easy to do, and the function as a sacrificial anode material is often impaired.
JP 2000-190089 A

  In order to solve the above-mentioned conventional problems in the tube material, the inventors paid attention to the addition of Si to the sacrificial anode material, provided brazing properties to the sacrificial anode material surface, and improved the corrosion resistance of the sacrificial anode material surface. As a result of testing and examining the composition of the sacrificial anode material that can be maintained, the melting point is lowered by adding a very small amount of Si to the sacrificial anode material as compared with a normal Al-Si alloy brazing material. A slight liquid phase is generated in the sacrificial anode material during the application heating, and by adding Ni, an Al-Ni-Si compound is formed and the solid solubility of Si is lowered, and the liquid phase ratio is reduced. The brazing flow is suppressed, which improves the brazeability, and at the same time, the sacrificial anode material hardly flows, and the thickness of the sacrificial anode material is maintained and the corrosion resistance can be maintained. A large amount with Si and Ni It found that it is possible to further increase the corrosion resistance by the coexistence of n.

  The present invention has been made as a result of further investigation based on the above-mentioned knowledge, and the purpose thereof is, in particular, by brazing using a fluoride-based flux or a cesium-based flux in an inert gas atmosphere. Tube materials for aluminum heat exchangers made of aluminum alloys such as evaporators, condensers, radiators and heater cores to be joined (the clad plate is bent into a tube shape by welding, and other members are brazed to the sacrificial anode material, Bending to make both ends of the clad plate abut the sacrificial anode material into a B-shaped tube shape, and other members are assembled and brazed together), and piping material connected to the heat exchanger ( Aluminum alloy club for automotive heat exchangers with excellent formability suitable as an extruded clad tube), sacrificial sacrificial anode material surface, and excellent corrosion resistance To provide a de material.

  In order to achieve the above object, an aluminum alloy clad material for an automobile heat exchanger according to claim 1 is obtained by clad a sacrificial anode material on one surface of a core material and clad an Al-Si alloy brazing material on the other surface. An aluminum alloy clad material in which the sacrificial anode material is a brazed surface, the core material is an Al-Mn alloy containing 0.05 to 0.35% Ti, and the sacrificial anode material is 1.5% It is characterized by being an aluminum alloy containing more than 6.0% and less than 6.0% Si, 0.05 to 2.0% Ni, and the balance being Al and impurities.

  An aluminum alloy clad material for an automobile heat exchanger according to claim 2 is an aluminum alloy clad material in which a sacrificial anode material is clad on one surface of a core material and an Al—Si alloy brazing material is clad on the other surface. In the case where the material becomes a brazing surface, the core material is an Al-Mn alloy containing 0.05 to 0.35% Ti, and the sacrificial anode material is more than 1.5% and less than 6.0%. It is characterized by being an Al—Zn alloy containing Si and 0.05 to 2.0% Ni.

An aluminum alloy clad material for an automobile heat exchanger according to a third aspect is characterized in that, in the first aspect, the brazing material is an aluminum alloy containing Si: 6 to 13% and the balance being Al and impurities. An aluminum alloy clad material for an automobile heat exchanger according to claim 4 is characterized in that, in claim 2, the brazing material is an aluminum alloy containing Si: 6 to 13% and the balance being Al and impurities. .

An aluminum alloy clad material for automobile heat exchanger according to claim 5 is the aluminum alloy clad material according to claim 1 or 3 , wherein the brazing material is further Fe: 0.8-2.0%, Zn: 0.5-5.0%, Sr: It contains one or more of 0.005 to 0.1% . An aluminum alloy clad material for an automobile heat exchanger according to claim 6 is the aluminum alloy clad material according to claim 2 or 4, wherein the brazing material is further Fe: 0.8 to 2.0%, Zn: 0.5 to 5.0%, One or more of Sr: 0.005 to 0.1% is contained.

An aluminum alloy clad material for an automobile heat exchanger according to claim 7 is the aluminum alloy clad material according to any one of claims 1, 3, and 5 , wherein the brazing material is further Bi: 0.2% or less, Be: 0.1% or less. It contains seeds or two kinds . An aluminum alloy clad material for an automobile heat exchanger according to claim 8 is the aluminum alloy clad material according to any one of claims 2, 4, and 6, wherein the brazing material is further Bi: 0.2% or less, Be: 0.1% or less. It contains 1 type or 2 types of these.

The aluminum alloy clad material for an automobile heat exchanger according to claim 9 is the aluminum alloy clad material according to any one of claims 1, 3 , 5 , and 7 , wherein the brazing material is further In: 0.001-0.05%, Sn: 0.001- It is characterized by containing one or two of 0.05%. An aluminum alloy clad material for an automobile heat exchanger according to claim 10 is the aluminum alloy clad material according to any one of claims 2, 4, 6, and 8, wherein the brazing material further contains In: 0.001 to 0.05%, Sn: 0.00. It contains one or two of 001 to 0.05%.

An aluminum alloy clad material for an automobile heat exchanger according to claim 11 is an aluminum alloy clad material obtained by clad a sacrificial anode material on one surface of a core material, and the sacrificial anode material serves as a brazing surface. Al-Mn alloy containing 0.5 to 0.35% Ti, sacrificial anode material containing more than 1.5% and less than 6.0% Si, 0.05 to 2.0% Ni The aluminum alloy is composed of the remaining Al and impurities .

An aluminum alloy clad material for an automobile heat exchanger according to claim 12 is an aluminum alloy clad material obtained by clad a sacrificial anode material on one surface of a core material, and the sacrificial anode material serves as a brazing surface. Al-Mn alloy containing 0.5 to 0.35% Ti, sacrificial anode material containing more than 1.5% and less than 6.0% Si, 0.05 to 2.0% Ni It is an Al—Zn alloy .

The aluminum alloy clad material for an automobile heat exchanger according to claim 13 is the aluminum alloy clad material according to any one of claims 2 , 4 , 6 , 8 , 10 , and 12, wherein the sacrificial anode material exceeds Si: 1.5% and less than 6.0%. Ni: 0.05-2.0%, Zn: 3.0-10.0% is contained, It is the aluminum alloy which consists of remainder Al and an impurity, It is characterized by the above-mentioned.

The aluminum alloy clad material for an automobile heat exchanger according to claim 14 is any one of claims 1 to 13 , wherein the sacrificial anode material is further In: 0.001 to 0.05%, Sn: 0.001 to 0.05. % Of 1% or 2% .

The aluminum alloy clad material for automobile heat exchanger according to claim 15 is characterized in that in any one of claims 1 to 14 , the sacrificial anode material further contains Mg: 4.0% or less .

The aluminum alloy clad material for automobile heat exchanger according to claim 16 is the aluminum alloy clad material according to any one of claims 1 to 15 , wherein the sacrificial anode material is further Cu: 0.05% or less, Ti: 0.3% or less, Cr: 0.00. It is characterized by containing one or more of 2% or less and Zr: 0.3% or less .

The aluminum alloy clad material for automobile heat exchanger according to claim 17 is characterized in that in any one of claims 1 to 16 , the sacrificial anode material further contains Fe: 0.15 to 2.0% .

The aluminum alloy clad material for automobile heat exchanger according to claim 18 is characterized in that in any one of claims 1 to 17 , the sacrificial anode material further contains Sr: 0.005 to 0.1% .

The aluminum alloy clad material for an automobile heat exchanger according to claim 19 is the aluminum alloy clad material according to any one of claims 1 to 18 , wherein the core material exceeds Mn: 0.3% and is 2.0% or less, Ti: 0.05-0. It is an aluminum alloy containing 35%, the balance being Al and impurities .

The aluminum alloy clad material for an automobile heat exchanger according to claim 20 is any one of claims 1 to 19 , wherein the core material is further Cu: 0.1 to 1.0%, Si: 0.1 to 1.5% It contains 1 type or 2 types of these, It is characterized by the above-mentioned.

The aluminum alloy clad material for automobile heat exchanger according to claim 21 is characterized in that in any one of claims 1 to 20 , the core material further contains Mg: 0.5% or less .

Automotive heat exchanger aluminum alloy clad sheet according to claim 22, in any one of claims 1 to 21, wherein the core material further Cr: 0.5% or less, Zr: 1 kind of 0.3% or It contains two types.

  According to the present invention, a tube for an aluminum alloy automobile heat exchanger such as an evaporator, a condenser, a radiator, or a heater core, which is joined by brazing using a fluoride flux or a cesium fluoride flux in an inert gas atmosphere. Bending material (bending the clad plate into a tube by welding or brazing, brazing other members to the sacrificial anode material, bending so that both ends of the clad plate are in contact with the sacrificial anode material B Automobile heat exchange with excellent moldability suitable for piping material (extruded clad pipe) connected to a heat exchanger and brazing and corrosion resistance of the sacrificial anode material surface A dexterous aluminum alloy cladding material is provided.

The composition of the aluminum alloy clad material of the present invention and the reason for limitation will be described.
(Sacrificial anode material)
Si: more than 1.5% and less than 6.0% Si acts as a brazing by reducing the melting point of the sacrificial anode material and creating a very slight liquid phase during brazing. The preferable content of Si is in the range of more than 1.5% and less than 6.0%, and if it is 1.5% or less, it is difficult to act effectively as brazing, and if it is 6.0% or more, it tends to flow during brazing heating. Thus, the function as a sacrificial anode material is impaired. A more preferable content range of Si is more than 2.0% and less than 4.0%.

  Ni forms an Al-Si-Ni-based, Al-Zn-Ni-based or Al-Si-Zn-Ni-based compound, lowers the liquid phase ratio by lowering the solid solubility of Si and Zn, Suppresses the flow of wax. Moreover, the said compound becomes a starting point of corrosion, a pitting corrosion disperse | distributes, and corrosion resistance improves. The preferable content of Ni is in the range of 0.05 to 2.0%. If it is less than 0.05%, the effect is small, and if it exceeds 2.0%, the self-corrosion property of the sacrificial anode material increases. A more preferable content range of Ni is 0.5 to 1.2%.

Zn: 3.0 to 10.0%
Zn acts as a braze by lowering the melting point of the sacrificial anode material and creating a negligible liquid phase during brazing. Further, the potential of the sacrificial anode material is made lower, the sacrificial anode effect on the core material is exhibited, and the occurrence of pitting corrosion and crevice corrosion of the core material is prevented. In order to contain Si that makes the potential noble in the sacrificial anode material, it is necessary to contain a considerable amount of Zn. The preferable content of Zn is in the range of 3.0 to 10.0%. When the Zn content is less than 3.0%, the effect is small, and when the content exceeds 10.0%, the self-corrosion resistance of the sacrificial anode material. Decreases. The more preferable content range of Zn is 4.0 to 6.0%.

In: 0.001 to 0.05%
In adds a small amount to make the potential of the sacrificial anode material low, and reliably exert the sacrificial anode effect on the core material, thereby preventing the occurrence of pitting corrosion and crevice corrosion of the core material. The preferable content of In is in the range of 0.001 to 0.05%. If the content is less than 0.001%, the effect is not sufficient, and if it exceeds 0.05%, the self-corrosion resistance and the rolling workability are deteriorated. A more preferable content range of In is 0.01 to 0.03%.

Sn: 0.001 to 0.05%
Sn lowers the potential of the sacrificial anode material by adding a small amount, reliably exerts the sacrificial anode effect on the core material, and prevents the occurrence of pitting corrosion and crevice corrosion of the core material. The preferable content of Sn is in the range of 0.001 to 0.05%. If it is less than 0.001%, the effect is not sufficient, and if it exceeds 0.05%, the self-corrosion resistance and the rolling processability are deteriorated. The more preferable content range of Sn is 0.01 to 0.03%.

Mg: 4.0% or less Mg functions to diffuse into the core material during brazing heating during brazing assembly of a heat exchanger or the like and increase the strength together with Si and Cu in the core material. Mg remaining in the sacrificial anode material increases the strength of the sacrificial anode material together with Si, and improves the strength of the clad material by these effects. The preferable content of Mg is in the range of 4.0% or less. If it exceeds 4.0%, the rolling processability is lowered. A more preferable content range of Mg is 2.5% or less.

Cu: 0.05% or less Cu makes the potential of the sacrificial anode material noble and suppresses a decrease in self-corrosion resistance due to the addition of Zn to the sacrificial anode material. The preferable content of Cu is in the range of 0.05% or less, and if it exceeds 0.05%, a sufficient potential difference between the sacrificial anode material and the core material cannot be secured, and the sacrificial anode with respect to the core material. The effect is reduced.

Cr: 0.2% or less, Zr: 0.3% or less Cr and Zr increase the crystal grain size of the sacrificial anode material and suppress the Cu grain boundary diffusion of the core material during brazing heating. If Cr and Zr exceed 0.2% and 0.3%, respectively, huge crystallized products are generated during casting, and it becomes difficult to produce a sound plate material.

Ti: 0.3% or less Ti is divided into a high-concentration region and a low-concentration region in the thickness direction of the material. These regions are alternately distributed in layers, and a low-concentration region has priority over a high region. Corrosion has the effect of layering the corrosion form, and this effect prevents the progress of intergranular corrosion in the plate thickness direction and improves the pitting corrosion resistance of the material. The preferable content of Ti is in the range of 0.3% or less, and if it exceeds 0.3%, casting becomes difficult, and workability deteriorates, making it difficult to produce a sound material.

Fe: 0.15-2.0%
Fe forms an Al—Fe—Si-based compound, lowers the solid solubility of Si, lowers the liquid phase rate, and suppresses the flow of wax. Fe forms an Al-Fe-based or Al-Fe-Si-based compound, and these compounds serve as a starting point for corrosion to improve the corrosion resistance by dispersing pitting corrosion. The preferable content of Fe is in the range of 0.15 to 2.0%. If the content is less than 0.15%, the effect is small, and if it exceeds 2.0%, the self-corrosion resistance of the sacrificial anode material is lowered. A more preferable content range of Fe is more than 0.7% and 1.2% or less.

Sr: 0.005 to 0.1%
Sr functions to make the presence form of Si particles in the sacrificial anode material finer and uniform, and as a result, improves brazing properties. The preferable content of Sr is in the range of 0.005 to 0.1%. If the content is less than 0.005%, the effect is not sufficient, and even if the content exceeds 0.1%, the effect is saturated. In the present invention, even if Na: 1 to 100 ppm and Sb: 0.001 to 0.5% are added to the sacrificial anode material, the effect is not affected.

(Core material)
Mn: 0.3 to 2.0%
Mn functions to improve the corrosion resistance by improving the strength of the core material and making the potential of the core material noble and increasing the potential difference from the sacrificial anode material. The preferable content of Mn is in the range of 0.3 to 2.0%. If the content is less than 0.3%, the effect is small. If the content exceeds 2.0%, a coarse compound is produced during casting, and the rolling processability is low. It decreases and it becomes difficult to obtain a healthy plate (core material). A more preferable content range of Mn is 0.8 to 1.5%.

Ti: 0.05 to 0.35%
Ti is divided into a high concentration region and a low region in the thickness direction of the material, and these regions are alternately distributed in layers, and the low Ti concentration region corrodes preferentially compared to the high region, It has the effect of layering the corrosion form, and this effect prevents the progress of intergranular corrosion in the plate thickness direction and improves the pitting corrosion resistance of the material. The preferable content of Ti is in the range of 0.05 to 0.35%. If it is less than 0.05%, the effect is small, and if it exceeds 0.35%, casting becomes difficult and workability is reduced. It becomes difficult to produce sound materials. A more preferable content range of Ti is 0.1 to 0.2%.

Cu: 0.1 to 1.0%
Cu functions to improve the corrosion resistance by improving the strength of the core material, making the potential of the core material noble, and increasing the potential difference with the sacrificial anode material and the potential difference with the brazing material. In addition, it diffuses into the sacrificial anode material and the brazing material during brazing to form a gentle Cu concentration gradient in the thickness direction of the sacrificial anode material and brazing material. The potentials on the surface side of the anode material and the surface side of the brazing material become base, and a gentle potential gradient is formed in the thickness direction of the sacrificial anode material and the brazing material. The preferable content of Cu is in the range of 0.1 to 1.0%. If the content is less than 0.1%, the effect is small. If the content exceeds 1.0%, the corrosion resistance of the core material is lowered, and the melting point is lowered. Local melting tends to occur during brazing. The more preferable content range of Cu is 0.4 to 0.7%.

Si: 0.1 to 1.5%
Si has the effect of improving the strength of the core material. In particular, when Mg is contained in the sacrificial anode material, Si coexists with Mg diffusing from the sacrificial anode material during brazing, and bonds with Mg to form Mg ₂ Si, thereby age-hardening after brazing. And the strength is further improved. The preferable content of Si is in the range of 0.1 to 1.5%. If the content is less than 0.1%, the effect is small. If the content exceeds 1.5%, the corrosion resistance of the core material decreases, and The melting point is lowered, and local melting tends to occur during brazing. A more preferable content range of Si is 0.3 to 1.0%.

Mg: 0.5% or less Mg improves the strength of the core material. When the content exceeds 0.5%, when brazing is performed in an inert gas atmosphere using a fluoride-based flux, Mg reacts with the fluoride-based flux during brazing to produce Mg fluoride. While reducing brazing property, the external appearance of a brazing part worsens. A more preferable content range of Mg is 0.15% or less.

Cr: 0.5% or less, Zr: 0.3% or less Cr and Zr increase the crystal grain size of the core material and suppress the grain boundary diffusion of Si in the brazing material during brazing heating. When Cr and Zr exceed 0.5% and 0.3%, respectively, giant crystallized substances are generated during casting, and workability is lowered, making it difficult to produce a sound plate material.

(Brazing material)
As the brazing material, a commonly used Al—Si alloy, preferably an alloy containing Si: 6 to 13% is used. If Si is less than 6%, the fluidity is lowered and the effect as a brazing material is insufficient, and if Si exceeds 13%, it is difficult to produce a sound material.

Fe: 0.8 to 2.0%
Fe forms Al—Fe and Al—Fe—Si compounds, and these compounds serve as starting points for corrosion, so that pitting corrosion is dispersed and the corrosion resistance of the outer surface is improved. The preferable content range of Fe is 0.8 to 2.0%. If the content is less than 0.8%, the effect is small, and if it exceeds 2.0%, the corrosion resistance of the outer surface is lowered.

Zn: 0.5 to 5.0%
Even if Zn is contained in the above range, the effect of the present invention is not impaired. If the content exceeds 5.0%, the self-corrosion resistance decreases.

Sr: 0.005 to 0.1%
Sr has an effect of finely and uniformly dispersing Si particles in the brazing material. When the Si particles are finely and uniformly dispersed, the melting of the brazing becomes uniform and the brazing property is improved. The preferable content of Sr is in the range of 0.005 to 0.1%. If it is less than 0.005%, the effect is small, and if it exceeds 0.1%, the effect is saturated.

Bi: 0.2% or less, Be: 0.1% or less Even if Bi and Be are contained in the above ranges, the effect of the present invention is not impaired. When Bi and Be exceed 0.2% and 0.1%, the brazing property decreases.

In: 0.001-0.05%, Sn: 0.001-0.05%
Even if In and Sn are contained in the above ranges, the effects of the present invention are not impaired. When In and Sn exceed 0.05%, the self-corrosion resistance and rolling workability of the brazing material are lowered. In the present invention, even if Na: 1 to 100 ppm and Sb: 0.001 to 0.5% are contained, the effect of the present invention is not affected.

  The aluminum alloy clad material of the present invention comprises a core material, a sacrificial anode material, and an aluminum alloy constituting an Al—Si brazing material, for example, ingot by continuous casting, and after homogenization treatment as necessary, a sacrificial anode material The aluminum alloy ingots for solder and brazing material are each hot-rolled to a predetermined thickness, and then the aluminum alloy ingot for core material is combined with the aluminum alloy for sacrificial anode and the aluminum alloy for brazing material. Accordingly, the clad material is manufactured by hot rolling, and then is made to have a predetermined thickness by cold rolling, intermediate annealing, and cold rolling.

  The present invention relates to an aluminum alloy clad material 7 in which a sacrificial anode material 5 is clad on one surface of a core material 4 and the sacrificial anode material 5 serves as a brazing surface. Al alloy with sacrificial anode material containing more than 1.5% and less than 6.0% Si, 0.05-2.0% Ni, the balance Al and impurities, or 1.5% An aluminum alloy clad material for an automobile heat exchanger, which is an Al-Zn alloy containing less than 6.0% Si and 0.05 to 2.0% Ni, as shown in FIG. This is also effective when the clad fin material 3 is brazed to five surfaces.

  Examples of the present invention will be described below in comparison with comparative examples. These examples show one embodiment of the present invention, and the present invention is not limited to these examples.

Example 1
An ingot obtained by ingoting a core material alloy having the composition shown in Table 1, a sacrificial anode material alloy having the composition shown in Table 2, and a brazing alloy having the composition shown in Table 3 by continuous casting. Among these, the ingots of the core material alloy and the sacrificial anode material alloy were subjected to a homogenization treatment.

  Subsequently, the ingot of the sacrificial anode material alloy and the brazing material alloy is hot-rolled to a predetermined thickness, and the hot-rolled plate and the core alloy ingot are hot-rolled together to form a clad material. Got. Thereafter, a plate material (cladding material, tempered H14) having a thickness of 0.20 mm was obtained by cold rolling, intermediate annealing, and cold rolling. The structure of the clad material is 0.020 to 0.050 mm for the sacrificial anode material and 0.020 mm for the brazing material.

  Using the obtained clad material as a test material, (1) cladability (rollability), (2) brazeability, (3) corrosion resistance of the sacrificial anode material, and (5) corrosion resistance of the braze material were evaluated by the following methods. . The results are shown in Tables 4-7.

  Cladness (rollability): Sacrificial anode material, core material, brazing material production, or clad material production with poor rolling processability and failure to produce a sound material is regarded as poor cladability (x) The one obtained from the clad material is defined as good clad property (◯).

  Brazing property: The obtained clad material (test material) and 3003 alloy plate (thickness 1.0 mm) are combined as shown in FIG. 5 to produce an inverted T-shaped test piece, and a fluoride-based flux is applied. Then, the joining state was evaluated by heating to a brazing temperature of 600 ° C. (material temperature) in a nitrogen gas atmosphere. The case where the bonding state was good was marked with ◯, and the case where bonding failure or local melting occurred was marked with x.

Corrosion resistance of sacrificial anode material: The obtained clad material (test material) was applied as a single plate with fluoride-based flux and heated to a brazing temperature of 600 ° C. (material temperature) in a nitrogen gas atmosphere. A corrosion test was performed on the anode material surface under the following conditions.
Corrosion solution: Cl ⁻ : 195 ppm, SO ₄ ²⁻ : 60 ppm, Cu ²⁺ : 1 pm, Fe ³⁺ : 30 ppm
Specific liquid volume: 5 mL / cm ²
Seal: The brazing filler metal surface and the end surface were sealed with silicon resin.
Test method: After immersing in a corrosive liquid heated to 88 ° C. for 8 hours, a cycle of cooling and holding at 25 ° C. for 16 hours was repeated for 4 months, and the maximum corrosion depth was measured.

  Corrosion resistance of brazing material: The obtained clad material (test material) was applied as a single plate with a fluoride flux, heated to a brazing temperature of 600 ° C. (material temperature) in a nitrogen gas atmosphere, and then sacrificed anode The material surface and the end surface were sealed with silicon resin, and the CASS test of the brazing material surface was conducted for 2 weeks to measure the maximum corrosion depth.

  As seen in Tables 4-7, test material No. All of Nos. 1 to 121 have excellent cladability (rollability) and brazing properties, and the maximum corrosion depth is less than 0.1 mm in the corrosion test of the sacrificial anode material and the brazing material, and has good corrosion resistance. ing.

Comparative Example 1
An alloy for core material having the composition shown in Table 8 by continuous casting, an alloy for sacrificial anode material having the composition shown in Table 9, and an alloy for brazing material having the composition shown in Table 10 are obtained. The ingot of the sacrificial anode material alloy was homogenized.

  Next, the ingot of the alloy for sacrificial anode material and the ingot of the alloy for brazing material are hot-rolled to a predetermined thickness, and these hot-rolled plates and the ingot of the alloy for core material are used as a combined material for hot rolling. Thus, a clad material was obtained. Thereafter, a plate material (cladding material, tempered H14) having a thickness of 0.20 mm was obtained by cold rolling, intermediate annealing, and cold rolling. The structure of the clad material is 0.040 mm for the sacrificial anode material and 0.020 mm for the brazing material. In Tables 8 to 10, those outside the conditions of the present invention are underlined.

  The obtained clad material was used as a test material in the same manner as in Example 1. (1) Cladding property (rollability), (2) Brazing property, (3) Corrosion resistance of sacrificial anode material, (4) Corrosion resistance of brazing material Was evaluated. The results are shown in Table 11.

  As shown in Table 11, the test material No. Since 122 has a small amount of Mn in the core material, the sacrificial anode material has poor corrosion resistance. Test material No. Since 123 had a large amount of Mn in the core material, rolling workability was poor in the production of the core material, and as a result, it was difficult to produce a sound core material, resulting in poor cladness. Test material No. No. 124 is inferior in corrosion resistance (corrosion resistance of the brazing material surface) because the amount of Ti in the core material is small. Test material No. Since No. 125 has a large amount of Ti in the core material, rolling workability is poor in the production of the core material, and as a result, it became difficult to produce a sound core material, resulting in poor cladness. Test material No. Since 126 had a large amount of Cu in the core material, local melting occurred in the core material at the time of brazing, and the brazing performance was lowered. Test material No. Since 127 has a large amount of Si in the core material, local melting occurred in the core material at the time of brazing, and the brazing property was lowered. Test material No. Since 128 had a large amount of Mg in the core material, the brazeability was poor and poor bonding occurred.

  Test material No. Since 129 has a small amount of Si in the sacrificial anode material, the brazing property is inferior. Test material N. Since the sacrificial anode material 130 has a large amount of Si, the sacrificial anode material flows to lose its function as the sacrificial anode material, resulting in poor corrosion resistance. Test material No. 131 is inferior in corrosion resistance of the sacrificial anode material because the amount of Ni in the sacrificial anode material is small. Test material No. Since the sacrificial anode material 132 has a large amount of Ni, the sacrificial anode material undergoes self-corrosion and has poor corrosion resistance. Test material No. Since the sacrificial anode material 133 has a large amount of Zn, the sacrificial anode material is quickly consumed and the corrosion resistance is lowered. Test material No. Since 134 and 135 have large amounts of In and Sn in the sacrificial anode material, both of them have poor rolling processability in the production of the sacrificial anode material, and it is difficult to produce a sacrificial anode material, resulting in poor cladding properties. It was.

  Test material No. Since 136 has a large amount of Fe in the sacrificial anode material, self-corrosion is increased and corrosion resistance is inferior. Test material No. Since 137 had a large amount of Si in the brazing material, the rollability was inferior and a sound clad material could not be obtained.

It is sectional drawing which shows the conventional tube material manufactured from the aluminum alloy clad material. It is sectional drawing which shows the Example of the tube material (B type tube shape) manufactured from the aluminum alloy clad material by this invention. It is sectional drawing which shows the other Example of the tube material manufactured from the aluminum alloy clad material by this invention. It is sectional drawing which shows joining of the aluminum alloy clad material and clad fin by this invention. 3 is a diagram showing an inverted T-shaped test piece manufactured in Example 1. FIG.

Explanation of symbols

1 Tube material (flat tube)
2 B-shaped tube shape 3 Clad fin material 4 Core material 5 Sacrificial anode material 6 Brazing material 7 Two-layer clad material

Claims (22)

An aluminum alloy clad material in which a sacrificial anode material is clad on one surface of a core material and an Al—Si alloy brazing material is clad on the other surface, and the sacrificial anode material is a brazing surface. 0.05-0.35% (mass%, hereinafter the same) Ti-Mn alloy containing Ti, sacrificial anode material exceeding 1.5% and less than 6.0% Si, 0.05-2 An aluminum alloy clad material for an automobile heat exchanger, which is an aluminum alloy containing 0.0% Ni and the balance being Al and impurities. An aluminum alloy clad material in which a sacrificial anode material is clad on one surface of a core material and an Al—Si alloy brazing material is clad on the other surface, and the core material is 0 Al-Mn alloy containing 0.05 to 0.35% Ti, sacrificial anode material containing more than 1.5% and less than 6.0% Si, 0.05 to 2.0% Ni An aluminum alloy clad material for automobile heat exchangers, characterized in that the alloy is an Al-Zn alloy. The brazing material is Si: contains 6 to 13% automotive heat exchanger aluminum alloy clad sheet according to claim 1, characterized in that the aluminum alloy and the balance Al and impurities. 3. The aluminum alloy clad material for an automobile heat exchanger according to claim 2, wherein the brazing material is an aluminum alloy containing Si: 6 to 13%, and remaining Al and impurities. The brazing material further contains one or more of Fe: 0.8-2.0%, Zn: 0.5-5.0 % , Sr: 0.005-0.1%. The aluminum alloy clad material for an automotive heat exchanger according to claim 1 or 3 . The brazing material further contains one or more of Fe: 0.8-2.0%, Zn: 0.5-5.0 % , Sr: 0.005-0.1%. The aluminum alloy clad material for automobile heat exchanger according to claim 2 or 4 , characterized in that: 6. The automobile according to claim 1 , wherein the brazing material further contains one or two of Bi: 0.2% or less and Be: 0.1% or less. Aluminum alloy clad material for heat exchanger. The automobile according to any one of claims 2 , 4 , and 6 , wherein the brazing material further contains one or two of Bi: 0.2% or less and Be: 0.1% or less. Aluminum alloy clad material for heat exchanger. The brazing material further contains one or two of In: 0.001 to 0.05% and Sn: 0.001 to 0.05% . The aluminum alloy clad material for an automobile heat exchanger according to any one of 7 above. The brazing material further contains one or two of In: 0.001 to 0.05% and Sn: 0.001 to 0.05% . The aluminum alloy clad material for automobile heat exchanger according to any one of 8 . An aluminum alloy clad material in which a sacrificial anode material is clad on one surface of a core material, and the sacrificial anode material is a brazing surface, and the core material contains Al-Mn containing 0.05 to 0.35% Ti The sacrificial anode material is an aluminum alloy containing more than 1.5% and less than 6.0% Si, 0.05 to 2.0% Ni, the balance being Al and impurities. Aluminum alloy clad material for automotive heat exchanger. An aluminum alloy clad material in which a sacrificial anode material is clad on one surface of a core material, and the sacrificial anode material is a brazing surface, and the core material contains Al-Mn containing 0.05 to 0.35% Ti Automotive heat, characterized in that the sacrificial anode material is an Al—Zn alloy containing more than 1.5% and less than 6.0% Si and 0.05 to 2.0% Ni. Aluminum alloy clad material for exchangers. The sacrificial anode material contains Si: more than 1.5% and less than 6.0%, Ni: 0.05 to 2.0%, Zn: 3.0 to 10.0%, and the balance is Al and impurities. It is an aluminum alloy, The aluminum alloy clad material for motor vehicle heat exchangers in any one of Claim 2, 4, 6, 8, 10, 12 characterized by the above-mentioned. The sacrificial anode material is further an In: 0.001 to 0.05%, Sn: any of claims 1 to 13, characterized in that it contains 0.001 to 0.05% of one or two of An aluminum alloy clad material for an automobile heat exchanger according to claim 1. The aluminum alloy clad material for an automobile heat exchanger according to any one of claims 1 to 14 , wherein the sacrificial anode material further contains Mg: 4.0% or less. The sacrificial anode material further contains one or more of Cu: 0.05% or less, Ti: 0.3% or less, Cr: 0.2% or less, Zr: 0.3% or less. The aluminum alloy clad material for automobile heat exchanger according to any one of claims 1 to 15 . The aluminum alloy clad material for an automotive heat exchanger according to any one of claims 1 to 16 , wherein the sacrificial anode material further contains Fe: 0.15 to 2.0%. The aluminum alloy clad material for an automobile heat exchanger according to any one of claims 1 to 17 , wherein the sacrificial anode material further contains Sr: 0.005 to 0.1%. The core material is Mn: 2.0% exceeds 0.3% or less, Ti: contains 0.05 to 0.35%, claim, characterized in that an aluminum alloy and the balance Al and impurities 1 The aluminum alloy clad material for an automobile heat exchanger according to any one of -18 . The core further Cu: 0.1~1.0%, Si: any of claims 1 to 19, characterized in that it contains 0.1 to 1.5% of one or two of Aluminum alloy clad material for automobile heat exchanger as described in 1. The aluminum alloy clad material for an automobile heat exchanger according to any one of claims 1 to 20, wherein the core material further contains Mg: 0.5% or less. The automotive heat exchange according to any one of claims 1 to 21 , wherein the core material further contains one or two of Cr: 0.5% or less and Zr: 0.3% or less. Aluminum alloy clad material for equipment.

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