JP5049536B2 - Aluminum piping material for automotive heat exchangers - Google Patents

Description

  The present invention relates to an aluminum piping material excellent in corrosion resistance suitable for piping of heat exchangers such as automobile air conditioners, oil coolers, radiators and heaters.

Conventionally, JIS 1000 series alloys, JIS 3000 series alloys, JIS 6000 series alloys and the like are often used as piping materials for this type of heat exchanger. For example, as a JIS 6000 series alloy, Mg is 0.35 to 1.5% by mass (hereinafter simply referred to as%), Si is 0.2 to 0.8%, and Zn is 0.1 to 0.3%. An aluminum alloy excellent in intergranular corrosion resistance and pitting corrosion resistance characterized by containing 0.02 to 0.1% Sn and 0.15 to 0.4% Cu is known. (For example, refer to Patent Document 1).
Further, as a JIS 3000 series alloy, it contains 0.5 to 2.0% Mn, 0.25 to 0.75% Cu, Mg: 0.05 to 0.2%, Si: 0.05 -1.0%, Fe: 0.5-1.2%, Ti: 0.05-0.2%, Zr: 0.05-0.2%, Cr: 0.05-0.15%, V: The manufacturing method of the tube material for heat exchangers excellent in the tube formability characterized by containing 1 type (s) or 2 or more types among 0.05-0.15% is disclosed (for example, patent document) 2). However, this is a plate material and is of a type that is piped by electro-sealing welding or the like.

Aluminum brazing sheet used as a tube material, clad with Al-Si alloy brazing material on one side of the core material and sacrificial anode material such as Al-Zn or Al-Zn-Mg alloy on the other side Has been proposed (see, for example, Patent Document 3). However, the casting method and the manufacturing process are completely different between the plate type tube material and the piping material.
Japanese Examined Patent Publication No. 61-36577 JP 2001-26850 A Japanese Patent Laid-Open No. 06-73480

As described above, JIS 3003 alloy having excellent strength, workability, weldability, and corrosion resistance is used for the conventional automobile piping material, but the corrosion resistance is insufficient under severe conditions. For example, when used in an engine room of a car with a poor environment or when used in a hot and humid environment such as Southeast Asia, penetration corrosion may occur. If even one point of penetration piping occurs in the installed piping, refrigerant (cooling water) in the piping leaks, the cooling function is lost in the air conditioner, and the engine burns in the radiator. Therefore, from the viewpoint of corrosion resistance, a core material such as JIS 3003 alloy is clad on the inner and outer surfaces and one side with JIS 7072 alloy, etc., as described above, but the manufacturing cost is high. There was a problem.
Therefore, an object of the present invention is to develop an aluminum alloy material having a single layer and better corrosion resistance than JIS 3003 alloy without being clad, and to provide an excellent aluminum piping material for an automobile heat exchanger.

As a result of intensive investigations to solve this problem, the present inventors have found that corrosion resistance is improved by simultaneously adding Ti and V to an Al-Mn alloy, and the present invention is based on this finding. It came to make.
That is, the present invention
( 1 ) 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, Ti 0.05 to 0.3% by mass and 0.05 to 0.3% by mass of V, and further 0.05 to 0.4% by mass of Mg, 0.05 to 0.2% by mass of Cr and Aluminum piping material for automobile heat exchanger excellent in corrosion resistance, characterized in that it contains at least one of 0.05 to 0.2% by mass of Zr, and the balance consists of Al and inevitable impurities,
(2) 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, Ti 0.05 to 0.3% by mass and 0.2 to 0.3% by mass of V, and further 0.05 to 0.4% by mass of Mg, 0.05 to 0.2% by mass of Cr and Aluminum piping material for automobile heat exchanger excellent in corrosion resistance, characterized in that it contains at least one of 0.05 to 0.2% by mass of Zr, and the balance consists of Al and inevitable impurities,
(3) The aluminum piping material for automobile heat exchangers with excellent corrosion resistance according to (1) or (2), wherein the Cu content is 0.05% by mass or less (4) 3) It is manufactured by extruding an aluminum alloy ingot having the composition described in any one of 3) by hot extrusion to obtain an extruded raw tube, and by using a draw bench type drawing process or a continuous drawing process as a pipe material. Aluminum piping materials for automobile heat exchangers with excellent corrosion resistance, and
(5) 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, and Ti 0.05 to 0.3% by mass and 0.05 to 0.3% by mass of V, and further 0.05 to 0.4% by mass of Mg, 0.05 to 0.2% by mass of Cr and An aluminum alloy ingot containing at least one of 0.05 to 0.2% by mass of Zr, with the balance being composed of Al and inevitable impurities, is hot-extruded to form an extruded element tube, and a draw bench The present invention provides a method for producing an aluminum pipe material for automobile heat exchangers having excellent corrosion resistance, characterized by being produced by forming a pipe material by a system drawing process or a continuous drawing process .

  As described above, according to the present invention, even if the aluminum alloy piping material of the automotive heat exchanger is not a clad material but a single-layer bare material, a heat exchanger piping material having excellent corrosion resistance can be obtained. And, it is not necessary to make a pipe from the plate material by electro-sealing welding, etc., and it is possible to process by an easy extrusion and drawing process, and the cost of the heat exchanger can be reduced.

The present invention will be described in detail below.
First, the components of the aluminum alloy constituting the aluminum piping material of the present invention will be described.

  In the present invention, Si is an essential component, and the Si content is 0.05 to 0.4 mass% (hereinafter simply referred to as%). Si has the effect of improving the strength after brazing by forming a solid solution in the matrix of the aluminum alloy structure or forming an Al—Mn—Si compound, and is an essential component. In order to acquire this effect, 0.05% or more needs to be contained. When the upper limit is exceeded, the corrosion resistance and extrudability (die life) are reduced. Therefore, the upper limit of Si addition is set to 0.4%. The content of Si is more preferably 0.05 to 0.2%.

  In the present invention, Fe is an essential component, and the Fe content is 0.05 to 0.4%. Fe has an effect of improving the strength by crystallization or precipitation as an Al—Fe-based intermetallic compound. In order to acquire this effect, 0.05% or more needs to be contained. On the other hand, the excessive Fe content is crystallized on the surface and increases the corrosion rate, so 0.4% is made the upper limit. The content of Fe is more preferably 0.05 to 0.2%.

  In the present invention, the Cu content is 0.6% or less, which is an optional additive component. Cu has the effect of improving the strength by solid solution. In order to obtain this effect, it may be added up to an upper limit of 0.6% as necessary. However, if the upper limit is exceeded, the corrosion resistance is significantly reduced. Among the characteristics, when the corrosion resistance is most important, Cu is more preferably 0.05% or less.

  The Mn content is 0.15 to 1.5%, and Mn is an essential component in the present invention. Mn is added in an amount of 0.15 to 1.5% in order to improve the strength. If the content is less than 0.15%, the effect cannot be obtained sufficiently. If the content exceeds 1.5%, the extrudability and the drawability are inferior. A more preferable Mn content is 0.8 to 1.2%.

  The content of Ti and the content of V are both 0.05 to 0.3%. In the present invention, Ti and V are essential components. Ti and V have the effect of further improving the corrosion resistance. That is, Ti and V are divided into a high concentration region and a low concentration region, and they are alternately distributed in the thickness direction to form a layer, and corrosion is preferentially compared to a region where the Ti concentration and V concentration are low. As a result, the corrosion form becomes lamellar, so that the progress of corrosion in the thickness direction is hindered and the pitting corrosion resistance is improved. By adding Ti and V simultaneously, this effect is more prominent. Moreover, Ti and V contribute to strength improvement, and further effects can be obtained by adding them in combination. In order to obtain these sufficient effects, both Ti and V must contain 0.05% or more. When the upper limit of 0.3% is exceeded, coarse intermetallic compounds are produced during casting, which adversely affects extrudability and drawing workability. A more preferable content is 0.1 to 0.2% for both Ti and V.

In the present invention , 0 . At least one of 0.05 to 0.4% Mg, 0.05 to 0.2% Cr, and 0.05 to 0.2% Zr can be contained. These components are dispersed as a solid solution or a fine intermetallic compound by a homogenization treatment, and contribute to improving the strength of the alloy. Therefore, the inclusion of one even without low. In order to sufficiently obtain the above action, the content of each element is preferably 0.05% or more. On the other hand, if it is contained excessively, the extrudability and the drawability are deteriorated, so the upper limit is determined as described above. These more preferable contents are 0.15 to 0.3% for Mg and 0.05 to 0.15% for Cr and Zr.

  The aluminum alloy piping material for an automobile heat exchanger according to the present invention can be manufactured by processing an aluminum alloy having the above composition by the following process.

The aluminum alloy of the present invention can be melted by a conventional method with the aforementioned components as targets, and the production method is not particularly limited. When manufacturing an extrusion element pipe using this alloy, it is desirable to homogenize the molten aluminum alloy.
The homogenization treatment is a step in which dispersed particles such as Si and Mn are uniformly and densely precipitated in the matrix, and is a conventional method such as 550 to 620 ° C., preferably 590 to 620 ° C., and 1 to 10 hours. It is preferably carried out under the condition of holding for 2 to 4 hours. Thereafter, it is heated to 450 to 550 ° C. at least before extrusion and subjected to a soaking treatment, followed by hot extrusion. In addition, it does not specifically limit about the heating method, heating furnace, etc. in the said homogenization process and soaking process.

The obtained extruded element tube is stretched by draw bench drawing or continuous drawing and processed into a product size, and then annealed at, for example, 300 to 520 ° C. for 1 to 10 hours to obtain a product.
The extruded material is used as a material for a heat exchanger, and is usually used for a piping material for circulating a heat medium, a piping material for circulating water such as a radiator and a heater core. Further, the use place of the heat exchanger is not particularly limited.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
Example 1
A billet having a diameter of 219 mm is manufactured by melting and casting an Al alloy having the component composition shown in Table 1 (the numerical value represents mass%), and this billet is homogenized under conditions of holding at 610 ° C. for 4 hours. The extruded billet was cut into a length of 300 mm. This was heated again to 450 to 500 ° C., and a tube with a diameter of 36 mm (outer diameter) and 3 mm (thickness) was extruded by a mandrel die. Thereafter, continuous drawing was performed several times in the cold to a final size of φ17 mm (outer diameter) and 1 mm (wall thickness) to obtain a tube material. Then, annealing was performed at 360 ° C. for 2 hours, and the product was allowed to cool and each No. 1 was cooled. The test material was obtained.
Conventional example No. 1 is a JIS 3003 alloy.

In order to evaluate the internal corrosion resistance of these test materials, a cycle test in which the pipes of the test materials are connected to a commercially available aqueous coolant using a circulation test apparatus, held at 88 ° C. for 8 hours, and held at room temperature for 16 hours is 1 I went for a year. The surface corrosion products of each test material were removed, and the corrosion status of the material was evaluated. In the evaluation, the maximum pitting depth was measured by a focal depth method with an optical microscope, and the results are shown in Table 1.
In addition, the tensile strength cut | disconnected the pipe | tube of the test material, created the JIS No. 11 test piece with circular arc shape, and tested it on the conditions of the tensile speed of 10 mm / min based on JISH4080.

As can be seen from Table 1, the samples of Comparative Examples 1 and 2 cannot be manufactured as products because they cannot be extruded or drawn because the components of Ti, V, and Mn are out of the scope of the present invention. It was. In the sample of Comparative Example 3, since Ti and V were below the specified range of the present invention, the corrosion resistance was not improved and the corrosion resistance was inferior to the conventional example. The samples of Comparative Examples 4 and 5 were inferior in corrosion resistance to the conventional examples because Cu or Fe exceeded the specified range of the present invention. In the sample of Comparative Example 6, since Si exceeded the specified range of the inventive example, the corrosion resistance was inferior to that of the conventional example, and the extrudability was also deteriorated.
It can be seen that the examples of the present invention have extremely excellent corrosion resistance inside the piping as compared with the comparative example and the conventional example.
Further, it can be seen that the present invention example is substantially equal to or better than the conventional example in terms of tensile strength.

(Example 2)
A billet having a diameter of 219 mm is manufactured by melting and casting an Al alloy having the component composition shown in Table 2 (numerical values represent mass%), and this billet is homogenized under conditions of holding at 610 ° C. for 4 hours. The extruded billet was cut into a length of 300 mm. This was heated again to 450 to 500 ° C., and a tube with a diameter of 36 mm (outer diameter) and 3 mm (thickness) was extruded by a mandrel die. Thereafter, continuous drawing was performed several times in the cold to a final size of φ17 mm (outer diameter) and 1 mm (wall thickness) to obtain a tube material. Then, annealing was performed at 360 ° C. for 2 hours, and the product was allowed to cool and each No. 1 was cooled. The test material was obtained.

In order to evaluate the external corrosion resistance of these test materials, a CASS test according to JIS H8601 was performed for 1500 hours on each test material. After the test, the surface corrosion products of the test material were removed, and the corrosion status of the material was evaluated. In the evaluation, the maximum pitting depth was measured by the depth of focus method using an optical microscope, and the results are shown in Table 2.
For the tensile strength, a test sample was prepared in the same manner as in Example 1, and the test was performed under the same conditions as in Example 1 in accordance with JIS H4080.

As can be seen from Table 2, the samples of Comparative Examples 1 and 2 cannot be manufactured as products without extrusion or drawing because the components of Ti, V, and Mn deviate from the prescribed range of the present invention. It was. In the sample of Comparative Example 3, since Ti and V were below the specified range of the present invention, the corrosion resistance was not improved and the corrosion resistance was inferior to the conventional example. The samples of Comparative Examples 4 and 5 were inferior in corrosion resistance to the conventional examples because Cu or Fe exceeded the specified range of the present invention. In the sample of Comparative Example 6, since Si exceeded the specified range of the present invention, the corrosion resistance was inferior to that of the conventional example, and the extrudability was also deteriorated.
It can be seen that the examples of the present invention are extremely excellent in corrosion resistance outside the pipe as compared with the comparative example and the conventional example. It can be seen that the tensile strength is substantially the same as or better than that of the conventional example.

Claims (5)

0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, and 0.05 of Ti -0.3% by mass and 0.05-0.3% by mass of V, and further 0.05-0.4% by mass of Mg, 0.05-0.2% by mass of Cr and 0.05 An aluminum piping material for an automotive heat exchanger having excellent corrosion resistance, comprising at least one of Zr of 0.2 mass% , and the balance being made of Al and inevitable impurities.   0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, and 0.05 of Ti -0.3 mass% and V is contained in 0.2-0.3 mass%, and further 0.05-0.4 mass% Mg, 0.05-0.2 mass% Cr, and 0.05 An aluminum piping material for an automotive heat exchanger having excellent corrosion resistance, comprising at least one of Zr of 0.2 mass%, and the balance being made of Al and inevitable impurities.   The aluminum piping material for an automobile heat exchanger having excellent corrosion resistance according to claim 1 or 2, wherein the Cu content is 0.05 mass% or less.   Manufactured by hot extruding an aluminum alloy ingot having the composition according to any one of claims 1 to 3 to form an extruded element tube, and forming a tube material by a draw bench type drawing process or a continuous drawing process. Aluminum piping material for automobile heat exchangers, which is characterized by having excellent corrosion resistance. 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.1 mass% or less of Cu, 0.15 to 1.5 mass% of Mn, and 0.05 of Ti -0.3% by mass and 0.05-0.3% by mass of V, and further 0.05-0.4% by mass of Mg, 0.05-0.2% by mass of Cr and 0.05 An aluminum alloy ingot containing at least one of Zr of 0.2 mass% with the balance consisting of Al and inevitable impurities is hot-extruded to form an extruded element tube, and a draw bench type drawing process Or the manufacturing method of the aluminum piping material for motor vehicle heat exchangers excellent in corrosion resistance characterized by manufacturing by making it into a pipe material by a continuous drawing process.