JP2018028127A - Aluminum alloy-made clad plate for heat exchangers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum alloy-made clad plate for heat exchangers having excellent corrosion resistance.SOLUTION: An aluminum alloy-made clad plate for heat exchangers 1 has a core material 2 composed of an aluminum alloy, an intermediate layer 3 and a sacrificial material layer 4, and a first principal face 21 of the core material 2 is coated with a sacrificial material layer 4 via the intermediate layer 3. The core material 2 contains Mn: 0.4% (mass%, hereinafter the same) or more and 2.0% or less with the balance being Al and inevitable impurities. The intermediate layer 3 contains Mn: 0.2% or more and 1.8% or less with the balance being Al and inevitable impurities, with the Mn content being lower than that of the core material 2 by at least 0.2%. The sacrificial material layer 4 contains Mn: 0.05% or more and 1.6% or less, Mg: 0.1% or more and 2.0% or less, Si: 0.1% or more and 1.5% or less with the balance being Al and inevitable impurities, with the Mn content being lower than that of the intermediate layer 3 by at least 0.2%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an aluminum alloy clad plate for a heat exchanger.

  For example, in an automobile heat exchanger, a clad plate made of an aluminum alloy is used as a tube material constituting a flow path of a medium such as cooling water. As an aluminum alloy clad plate, for example, one surface of a core material made of an Al—Mn alloy or the like is formed of a brazing material layer made of an Al—Si alloy or the like, or an Al—Zn alloy or the like. A clad plate having a two-layer structure in which a sacrificial anode material layer (hereinafter referred to as a sacrificial material layer) is coated (clad), a brazing material layer on one side of the core material, and a three layer in which the sacrificial material layer is coated on the other side There are clad plates etc. of structure.

  In recent years, in order to improve the reliability and durability of heat exchangers, an aluminum alloy clad plate having excellent corrosion resistance has been demanded. In addition, in order to reduce the weight and size of the heat exchanger, it is required to reduce the thickness of the aluminum alloy clad plate, and accordingly, further improvement of the corrosion resistance of the aluminum alloy clad plate is required.

  In the conventional sacrificial corrosion prevention by Zn, the anticorrosion effect is acquired by adding Zn to a sacrificial material layer and making the electric potential of a sacrificial material layer lower than the electric potential of a core material. However, since the sacrificial material layer to which Zn is added has a high corrosion rate, the sacrificial material layer is consumed at an early stage when the aluminum alloy clad plate is thinned, and sufficient corrosion resistance cannot be obtained. In addition, with the recent increase in global demand for Zn, there is a concern that Zn resources will be depleted and prices soar in the future, and establishment of anticorrosion methods that do not use Zn is required.

  For this reason, for example, in Patent Document 1, a sacrificial material layer composed of an Al—Mg—Si alloy is coated on one surface of the core material, and Mg—Si crystal precipitates in the sacrificial material layer are covered. An aluminum alloy clad plate having a controlled size and number has been proposed. Patent Document 2 discloses a clad made of an aluminum alloy in which a sacrificial material layer is coated on one surface of a core material through an intermediate layer, and the potential becomes a monument in the order of the core material, the intermediate layer, and the sacrificial material layer. A board has been proposed.

JP 2014-55338 A JP-A-60-230987

  However, as in Patent Document 1, using a sacrificial material layer composed of an Al-Mg-Si alloy, just controlling the size and number of Mg-Si crystal precipitates in the sacrificial material layer, The corrosion resistance that can cope with the thinning of the clad plate made of aluminum alloy cannot be obtained sufficiently. In addition, precise process management is required to control the size and number of Mg—Si based crystal precipitates in the sacrificial material layer. In addition, as in Patent Document 2, simply providing an intermediate layer with a different potential is essentially the same as when the sacrificial material layer is thickened without providing an intermediate layer, and a significant improvement in corrosion resistance is achieved. I can't hope.

  This invention is made | formed in view of this background, and provides the clad board made from the aluminum alloy for heat exchangers excellent in corrosion resistance.

  An aluminum alloy clad plate for a heat exchanger according to one aspect of the present invention includes a core material, an intermediate layer, and a sacrificial material layer made of an aluminum alloy, and the sacrificial material is provided on at least one surface of the core material via the intermediate layer. The layer is coated. The core material contains Mn: 0.4% (mass%, the same applies hereinafter) and 2.0% or less, and the balance is made of an aluminum alloy composed of Al and inevitable impurities. The intermediate layer contains Mn: 0.2% or more and 1.8% or less, the balance is made of aluminum and inevitable impurities, and the Mn content is made of an aluminum alloy that is 0.2% or less less than the core material. ing. The sacrificial material layer contains Mn: 0.05% to 1.6%, Mg: 0.1% to 2.0%, Si: 0.1% to 1.5%, with the balance being Al And an inevitable impurity, and Mn content is 0.2% or less less than that of the intermediate layer, or Mg: 0.1% or more and 2.0% or less, Si: 0.00. The aluminum alloy contains 1% or more and 1.5% or less, the balance is made of Al and inevitable impurities, and Mn is contained only as an inevitable impurity.

  In the aluminum alloy clad plate for the heat exchanger, the specific intermediate layer is provided between the core material and the sacrificial material layer. Therefore, the corrosion resistance can be dramatically improved. Thereby, the outstanding corrosion resistance is securable without containing Zn conventionally used for sacrificial corrosion prevention. Moreover, even if it is a case where it thins, it can exhibit favorable corrosion resistance with respect to various severe environments.

  In the aluminum alloy clad plate for the heat exchanger, the core material is further Mg: 0.05% or more and 2.0% or less, Si: 0.05% or more and 1.5% or less, Cu: 0.05% or more 3.0% or less, Fe: 0.1% to 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05 % Or more and 0.3% or less, Ti: 0.05% or more and 0.3% or less, V: 0.05% or more and 0.3% or more may be contained.

  The intermediate layer further includes Mg: 0.05% to 2.0%, Si: 0.05% to 1.5%, Fe: 0.1% to 1.0%, Ni: 0 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05% to 0.3%, Ti: 0.05% to 0.3%, V : Containing one or more selected from 0.05% or more and 0.3% or less, and further containing Cu: 0.05% or more and 2.8% or less, and the Cu content is less than that of the core material. It may contain less than 2% or Cu only as an inevitable impurity.

  The sacrificial material layer further includes Fe: 0.05% to 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0 0.05% or more and 0.3% or less, Ti: 0.05% or more and 0.3% or less, V: One or more selected from 0.05% or more and 0.3% or less, and further Cu : It contains 0.05% or more and 1.5% or less, and Cu content may be 0.2% or less less than an intermediate | middle layer, or you may contain Cu only as an unavoidable impurity.

  Further, the sacrificial material layer may be coated on one surface of the core material through an intermediate layer, and the brazing material layer may be coated on the other surface of the core material.

It is sectional drawing which shows the structure of an aluminum alloy clad board.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment, It cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from the summary of this invention.

<Configuration of clad plate made of aluminum alloy>
As shown in FIG. 1, the aluminum alloy clad plate 1 includes a core material 2, an intermediate layer 3, and a sacrificial material layer 4 made of an aluminum alloy. The core material 2 is formed in a plate shape. The core material 2 has a first main surface 21 that is a main surface on one side in the thickness direction, and a second main surface 22 that is a main surface on the other side in the thickness direction.

  The first main surface 21 of the core material 2 is coated (clad) with the intermediate layer 3. The surface of the intermediate layer 3 is covered with a sacrificial material layer 4. The brazing material layer 5 is covered on the second main surface 22 of the core material 2. That is, in the aluminum alloy clad plate 1, the sacrificial material layer 4 is coated on the first main surface 21 of the core material 2 via the intermediate layer 3, and the brazing material layer 5 is coated on the second main surface 22 of the core material 2. Yes.

<Aluminum alloy composition of aluminum alloy clad plate>
In an aluminum alloy clad plate (hereinafter, simply referred to simply as a clad plate), the core material contains Mn: 0.4% (mass%, the same shall apply hereinafter) to 2.0%, with the balance being Al and inevitable impurities It is comprised with the aluminum alloy which consists of.

  The intermediate layer contains Mn: 0.2% or more and 1.8% or less, the balance is made of aluminum and inevitable impurities, and the Mn content is made of an aluminum alloy that is 0.2% or less less than the core material. ing.

  The sacrificial material layer contains Mn: 0.05% to 1.6%, Mg: 0.1% to 2.0%, Si: 0.1% to 1.5%, with the balance being Al And an inevitable impurity, and Mn content is 0.2% or less less than that of the intermediate layer, or Mg: 0.1% or more and 2.0% or less, Si: 0.00. The aluminum alloy contains 1% or more and 1.5% or less, the balance is made of Al and inevitable impurities, and Mn is contained only as an inevitable impurity.

  That is, in the clad plate, the aluminum alloy constituting the core material, the intermediate layer, and the sacrificial material layer contains Mn. Specifically, the aluminum alloy constituting the core material contains Mn: 0.4% or more and 2.0% or less. The aluminum alloy constituting the intermediate layer contains Mn: 0.2% or more and 1.8% or less, and the Mn content is 0.2% or less less than the core material. The aluminum alloy constituting the sacrificial material layer contains Mn: 0.05% or more and 1.6% or less, and the Mn content is 0.2% or less less than the intermediate layer, or Mn is only an inevitable impurity. Contains.

Next, the role of Mn contained in the aluminum alloy constituting each layer (core material, intermediate layer, sacrificial material layer) will be described.
Since Mn contributes to the potential of the metal, it greatly affects the sacrificial corrosion resistance. In a layer containing a large amount of Mn, the potential becomes more noble, so that more Mn is contained in the intermediate layer than in the sacrificial material layer and in the core material than in the intermediate layer. Accordingly, a layer having a relatively low Mn content sacrifices and protects a layer having a higher Mn content. In order to obtain such sacrificial anticorrosive effect, the difference in Mn content between the layers needs to be at least 0.2%, preferably 0.4% or more, more preferably 0.5% or more. . Note that the potential is not affected even if Mn is contained in an inevitable impurity level.

  Therefore, in order to make the difference in Mn content between the layers 0.2% or more, the core material needs to contain at least 0.4% Mn, and the intermediate layer similarly contains at least 0.2% Mn. Need to include. However, if the Mn content of each layer exceeds 2.0%, the productivity may be lowered. Therefore, the upper limit of the Mn content of the core material having the largest Mn content is set to 2.0%. Similarly, the Mn content of the intermediate layer is set so that the Mn content of the core material does not exceed 2.0% and to ensure a 0.2% Mn content difference between the core material and the intermediate layer. The upper limit was 1.8%.

  How much potential difference between each layer should be set is an individual design matter and varies depending on the use environment, the configuration of each layer, the composition of the material constituting each layer, etc. Preferably, it is more preferable to set it as 30-170 mV. When the potential difference between the layers is less than 20 mV, there is a possibility that the sacrificial corrosion resistance cannot be sufficiently ensured. On the other hand, when the potential difference between the layers exceeds 200 mV, the corrosion rate of the layer having a relatively low potential may be rapidly increased.

  Furthermore, the diffusion coefficient of Mn is very small and is one hundredth compared with other elements added to the aluminum alloy (for example, Zn, Cu, Si, Mg, etc.). Therefore, for example, it may be considered that Mn does not substantially diffuse in processes such as heat treatment and brazing heating after covering (cladding) the intermediate layer and the sacrificial material layer. Therefore, regardless of the thermal history of the manufacturing process, even if the thickness of the clad plate (hereinafter simply referred to as plate thickness) is reduced, the difference in the Mn content between the respective layers is maintained. In other words, the potential difference between the layers is maintained. Therefore, the progress of the corrosion generated in the sacrificial material layer is suppressed by the potential difference between the sacrificial material layer and the intermediate layer when reaching the intermediate layer, and the progress of the corrosion in the thickness direction is sufficiently suppressed.

  On the other hand, when Zn used for conventional sacrificial protection becomes thin, it diffuses throughout the clad plate and no potential difference is generated inside the clad plate, so that sacrificial protection does not work. Even when the plate is thick to some extent, a gentle gradient of Zn concentration (Zn content) occurs in the adjacent layer due to brazing heating or the like, and the potential difference gradually changes accordingly. Therefore, the boundary between the sacrificial material layer and the other portions becomes unclear, in other words, the sacrificial material layer is substantially thickened. Therefore, since the effect | action which suppresses the progress of corrosion does not work between each layer, the progress of the corrosion which arose in the sacrificial material layer is not suppressed until it bites into a part of intermediate | middle layer or a core material. Therefore, the corrosion reaches a considerable depth before the progress of the corrosion is suppressed by the sacrificial anticorrosive action (the corrosion depth at this time is referred to as “initial corrosion depth”), and various harmful effects are caused. Will cause.

  The adverse effect of the deep initial corrosion depth is first a reduction in the strength of the material. When corrosion progresses in the thickness direction, the strength naturally decreases accordingly. Moreover, since stress concentration is likely to occur at the corrosion location, it becomes extremely vulnerable to pressure from the inside or outside. Furthermore, it is not desirable that the initial corrosion depth is deep from the viewpoint of the corrosion mechanism. The corrosion form of aluminum is known to be pitting corrosion except for environments such as strong acidity and strong alkalinity, but pitting corrosion is known to have autocatalytic properties. It is known that once pitting corrosion begins to grow, pitting corrosion-inducing ions (such as chloride ions) are concentrated inside the pitting corrosion from the outside and further strongly acidify. That is, as the pitting corrosion grows, the inside of the pitting corrosion becomes a more corrosive environment, and further a vicious circle is caused in which the pitting corrosion growth becomes faster. This is the pitting corrosion autocatalytic property. Therefore, when the initial corrosion depth is deep, the inside of the corrosion is more isolated from the external environment and forms a site where the solution is likely to be concentrated. On the other hand, when the initial corrosion depth is shallow, the internal solution of the corrosion easily flows out to the outside due to water flow or convection from the outside, so that the concentration of the solution hardly occurs. Thus, increasing the initial corrosion depth is undesirable because it promotes the self-catalytic property of pitting corrosion, leading to a decrease in corrosion resistance.

  Therefore, paying attention to Mn having a very small diffusion coefficient, by providing an intermediate layer between the sacrificial material layer and the core material so that the difference in Mn content between each layer becomes a certain value or more, the initial corrosion depth Can be made shallower and a longer life can be realized. Also, if the initial corrosion depth is to be reduced, it is only necessary to provide a difference in Mn content between the core material and the sacrificial material layer without providing an intermediate layer, but in order to reduce the initial corrosion depth. It is not desirable to make the sacrificial material layer too thick. On the other hand, if the thickness of the sacrificial material layer is too thin, the sacrificial material layer is consumed in a short period of time, and the core material is exposed early. For this reason, by providing a large potential difference between the sacrificial material layer and the intermediate layer and between the intermediate layer and the core material by the intermediate layer, the progress of corrosion in the thickness direction between each layer is strongly suppressed. The

  Furthermore, from the viewpoint of improving the strength of the clad plate, as described later, the core material may contain a large amount of easily diffusing elements such as Cu, which diffuses by brazing heating or the like and greatly affects the potential difference between the layers. Sometimes. Therefore, the potential difference between each layer can be maintained by providing a specific intermediate layer whose composition is controlled between the sacrificial material layer and the core material. A plurality of intermediate layers may be provided between the sacrificial material layer and the core material as long as the difference in Mn content between adjacent layers is 0.2% or more, preferably 0.4% or more.

  As described above, the effects of Mn contained in the aluminum alloy constituting each layer (heart material, intermediate layer, sacrificial material layer) can be summarized as follows. That is, by using Mn that does not substantially diffuse and providing a difference in the Mn content between the layers, the progress of corrosion can be reliably suppressed between the layers regardless of the plate thickness. As a result, the initial corrosion depth can be reduced, and adverse effects caused by the large initial corrosion depth can be suppressed.

<Aluminum alloy composition of each layer>
1. Intermediate layer The intermediate layer is made of an aluminum alloy containing Mn: 0.2% or more and 1.8% or less, the balance being Al and inevitable impurities, and the Mn content being 0.2% or more less than the core material. It is configured. Mn crystallizes or precipitates as an Al—Mn intermetallic compound and contributes to the improvement of strength. Furthermore, since the Al—Mn intermetallic compound incorporates Fe, it has an effect of suppressing an increase in corrosion rate due to Fe as an additive or an inevitable impurity. However, Mn crystallizes out as a huge Al—Mn intermetallic compound depending on the production conditions, and the manufacturability may be reduced. Therefore, the Mn content in the intermediate layer is preferably 1.5% or less, and more preferably 1.0% or less.

  The intermediate layer further includes Mg: 0.05% to 2.0%, Si: 0.05% to 1.5%, Fe: 0.1% to 1.0%, Ni: 0 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05% to 0.3%, Ti: 0.05% to 0.3%, V : Containing one or more selected from 0.05% or more and 0.3% or less, and further containing Cu: 0.05% or more and 2.8% or less, and the Cu content is less than that of the core material. It may be less than 2% or contain Cu only as an inevitable impurity. In this case, the strength can be improved while sufficiently securing the corrosion resistance. Hereinafter, the effect obtained by containing each element, the reasons for defining the composition range, and the like will be described.

Mg, Si:
Mg and Si contribute to the strength improvement by being dissolved in the matrix (Al) or existing as Mg—Si based crystal precipitates. When considering the effect of improving the strength, each content of Mg and Si is preferably 0.05% or more. When the Mg content or the Si content is less than 0.05%, the strength improvement effect may not be sufficiently obtained. Moreover, when Mg content exceeds 2.0%, since a thick oxide layer is formed in the surface at the time of manufacture, there exists a possibility that manufacturability may fall. When the Si content exceeds 1.5%, the melting point of the material (aluminum alloy) constituting the intermediate layer is greatly reduced, and part or all of the intermediate layer may be melted during heating such as brazing. is there. Therefore, the Mg content is preferably 2.0% or less, and the Si content is preferably 1.5% or less.

Cu:
Cu contributes to strength improvement in the same manner as Mg and Si described above. However, since Cu has a great influence on the potential distribution of each layer, the Cu content of the intermediate layer is reduced by 0.2% or more than the core material. Moreover, it is preferable to make the Cu content of the intermediate layer 0.4% or less less than the core material. When the difference in Cu content between the intermediate layer and the core material is less than 0.2%, there is a possibility that a sufficient potential difference between the intermediate layer and the core material cannot be ensured. Further, as will be described later, if the Cu content of the core exceeds 3.0%, casting cracking is likely to occur, and the productivity may be lowered. Therefore, the Cu content of the intermediate layer is 2.8% or less. It is preferable that That is, in order to set the Cu content of the core material to 3.0% or less and further to set the difference in Cu content between the intermediate layer and the core material to 0.2% or more, the Cu content of the intermediate layer is set to 2.8%. The following is preferable. However, if the Cu content is about an inevitable impurity with a content of less than 0.05%, the influence on the potential of each layer is very small. Therefore, the intermediate layer may contain Cu only as an inevitable impurity. In addition, when it is not necessary to contain Cu in the intermediate layer and obtain the effect of improving the strength, the effect of improving the corrosion resistance can be enhanced by reducing the Cu content of the intermediate layer as much as possible.

Fe:
Fe refines coarse intermetallic compounds and crystal grains, and contributes to improving moldability and workability. If the Fe content is less than 0.1%, the effect of improving moldability and workability may not be sufficiently obtained. If the Fe content exceeds 1.0%, the corrosion resistance of the intermediate layer itself may be reduced. Therefore, the Fe content is preferably 0.1% or more and 1.0% or less.

Ni:
Ni contributes to improving corrosion resistance because Ni-based compounds are finely and uniformly distributed and have the effect of dispersing corrosion. If the Ni content is less than 0.05%, the corrosion resistance improvement effect may not be sufficiently obtained. If the Ni content exceeds 0.3%, the corrosion rate may increase. Therefore, the Ni content is preferably 0.05% or more and 0.3% or less.

Cr, Zr, Ti, V:
Cr, Zr, Ti and V contribute to improvement of corrosion resistance, particularly pitting corrosion resistance. When Cr, Zr, Ti, and V are added to the aluminum alloy, high concentration regions and low concentration regions of each element are alternately distributed in the thickness direction along the plate thickness direction. Here, since the low concentration region of each element is preferentially corroded over the high concentration region, the form of corrosion is layered. As a result, the progress of corrosion in the plate thickness direction is suppressed, and the pitting corrosion resistance is improved. When the content of any one of Cr, Zr, Ti and V is less than 0.05%, the pitting corrosion resistance improving effect may not be sufficiently obtained. When the content of any one of Cr, Zr, Ti and V exceeds 0.30%, a coarse compound is produced during casting, which may reduce the productivity. Therefore, it is preferable that the contents of Cr, Zr, Ti, and V are 0.05% or more and 0.30% or less.

2. Sacrificial material layer The sacrificial material layer is a layer composed of a sacrificial anode material. The sacrificial material layer contains Mg: 0.1% to 2.0%, Si: 0.1% to 1.5%, Mn: 0.05% to 1.6%, the balance being Al And an inevitable impurity, and Mn content is 0.2% or less less than that of the intermediate layer, or Mg: 0.1% or more and 2.0% or less, Si: 0.00. The aluminum alloy contains 1% or more and 1.5% or less, the balance is made of Al and inevitable impurities, and Mn is contained only as an inevitable impurity.

  As the sacrificial material layer, a layer having smaller self-corrosion is desirable. Self-corrosion is the amount of corrosion of the sacrificial material layer that does not contribute to sacrificial protection. That is, (the amount of self-corrosion of the sacrificial material layer) + (the amount of consumption of the sacrificial material layer due to sacrificial protection) = (the total amount of corrosion of the sacrificial material layer). The amount of corrosion of the entire layer can be suppressed.

  Therefore, by configuring the sacrificial material layer with an Al-Mg-Si alloy, Mg-Si crystal precipitates unavoidably present in the Al-Mg-Si alloy contribute to improving the corrosion resistance, and the heat exchanger Excellent corrosion resistance can be obtained in the use environment. That is, heat exchangers are exposed to high temperatures during operation due to their nature. At this time, a hydrated oxide film having excellent corrosion resistance is formed on the portion in contact with water. For example, since a water-based refrigerant or the like circulates inside the tube material of the heat exchanger, a hydrated oxide film is formed on the surface of the tube material. At this time, Mg elutes preferentially from the Mg—Si based crystal precipitates present on the surface of the sacrificial material layer, but Si also elutes at the same time, and the eluted Si is taken into the hydrated oxide film. Si taken into the hydrated oxide film is considered to repair defects of the hydrated oxide film and contribute to improvement of corrosion resistance. For this reason, a hydrated oxide film having better corrosion resistance is formed, and the self-corrosion of the sacrificial material layer is suppressed. In addition, Mg-Si-based crystal precipitates from which Mg is eluted will concentrate Si, and an effect of suppressing the progress of corrosion can be obtained. Further, since the potential of the Mg—Si based crystal precipitates is very low, the potential on the surface of the sacrificial material layer having a relatively large amount of Mg—Si based crystal precipitates is also more effective. Thus, by comprising a sacrificial material layer with an Al-Mg-Si type-alloy, the high anticorrosion effect is acquired irrespective of Zn conventionally used for sacrificial anticorrosion.

  In order to acquire said effect, Mg content of a sacrificial material layer shall be 0.1% or more and 2.0% or less, and Si content shall be 0.1% or more and 1.5% or less. Further, from the viewpoint of improving corrosion resistance, it is preferable that the content of Mg and Si in the sacrificial material layer is 0.15% or more and 1.0% or less. When each content of Mg and Si is less than 0.1%, the amount of Mg—Si based crystal precipitates is small, so that the above effect cannot be obtained sufficiently. On the other hand, when the Mg content exceeds 2.0%, the sacrificial material layer has a thick oxide film on the surface during production, and it becomes difficult to obtain a good clad plate. When the Si content exceeds 1.5%, the melting point of the material (aluminum alloy) constituting the sacrificial material layer decreases, so that part or all of the sacrificial material layer melts during heating such as brazing. End up.

  The sacrificial material layer further includes Fe: 0.05% to 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0 0.05% or more and 0.3% or less, Ti: 0.05% or more and 0.3% or less, V: One or more selected from 0.05% or more and 0.3% or less, and further Cu : It contains 0.05% or more and 1.5% or less, and Cu content may be 0.2% or less less than an intermediate | middle layer, or you may contain Cu only as an unavoidable impurity. In this case, the strength can be improved while sufficiently securing the corrosion resistance. The effect obtained by containing Fe, Ni, Cr, Zr, Ti and V and the reason for defining the composition range are the same as those of the above-described intermediate layer.

  When the thickness of the clad plate is particularly thin, it may be necessary to add Cu to the sacrificial material layer in order to improve the strength. In order to obtain a sufficient strength improvement effect, the sacrificial material layer preferably has a Cu content of 0.05% or more. However, when the sacrificial material layer has a Cu content of more than 1.5%, The corrosion rate of the material layer may be increased. Moreover, in order to ensure corrosion resistance, it is preferable to reduce the Cu content of the sacrificial material layer by 0.2% or more, and more preferably by 0.4% or more than the intermediate layer. However, if the Cu content is about an inevitable impurity with a content of less than 0.05%, the influence on the potential of each layer is very small. Therefore, the intermediate layer may contain Cu only as an inevitable impurity. In addition, when it is not necessary to contain Cu in a sacrificial material layer and to obtain the strength improvement effect, the corrosion resistance improvement effect can be enhanced by reducing the Cu content of the sacrificial material layer as much as possible.

3. Core Material The core material contains Mn: 0.4% or more and 2.0% or less, and the balance is made of an aluminum alloy composed of Al and inevitable impurities. Mn crystallizes or precipitates as an Al—Mn intermetallic compound and contributes to the improvement of strength. Furthermore, since the Al—Mn intermetallic compound incorporates Fe, it has an effect of suppressing an increase in corrosion rate due to Fe as an additive or an inevitable impurity. However, Mn crystallizes out as a huge Al—Mn intermetallic compound depending on the production conditions, and the manufacturability may be reduced. Therefore, the Mn content of the core material is preferably 1.50% or less, and more preferably 1.0% or less.

  Further, the core material further includes Mg: 0.05% to 2.0%, Si: 0.05% to 1.5%, Cu: 0.05% to 3.0%, Fe: 0.00%. 1% to 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05% to 0.3%, Ti: It may contain one or more selected from 0.05% to 0.3% and V: 0.05% to 0.3%. In this case, the strength can be improved while sufficiently securing the corrosion resistance. The effect obtained by containing Mg, Si, Fe, Ni, Cr, Zr, Ti and V and the reason for defining the composition range are the same as those of the above-described intermediate layer.

  Moreover, when Cu is added to the core material, in addition to the strength improvement effect, there is an effect that the potential of the core material becomes relatively noble than the intermediate layer and the sacrificial material layer, and the sacrificial anticorrosive effect on the core material of the intermediate layer and the sacrificial material layer Becomes higher. When the Cu content of the core material is less than 0.05%, the influence on the potential of each layer is very small, but there is a possibility that the effect of improving the strength cannot be obtained sufficiently. On the other hand, when the Cu content of the core exceeds 3.0%, casting cracks are likely to occur, and the productivity may be reduced.

4). Brazing material layer The aluminum material used for the brazing material layer is not particularly limited. As the aluminum material used for the brazing material layer, an Al—Si alloy brazing material used in normal brazing can be used. % Si) or the like.

<Others>
In the aluminum alloy clad plate, the aluminum alloy constituting the core material, the intermediate layer, and the sacrificial material layer may contain an element other than the elements described above as long as the characteristics such as corrosion resistance are not impaired. For example, as inevitable impurities, Na, Ca, or the like may be contained alone by 0.05% or more and 0.15% or less in total.

  The thickness of the intermediate layer is preferably 3 to 200 μm. If the thickness of the intermediate layer is less than 3 μm, it may be difficult to manufacture, and further, the intermediate layer cannot sufficiently prevent the initial corrosion, and the corrosion easily reaches the core material. There is a fear. On the other hand, when the thickness of the intermediate layer exceeds 200 μm, the thickness of the intermediate layer occupying the entire plate thickness becomes too thick compared to the thickness of the core material, and the mechanical properties of the entire clad plate may be deteriorated. .

  The thickness of the sacrificial material layer is preferably 2 to 100 μm, and more preferably 5 to 50 μm, from the viewpoint of reducing the initial corrosion depth in the sacrificial material layer. If the thickness of the sacrificial material layer is less than 2 μm, it may be difficult to manufacture, and the sacrificial material layer will be consumed in a short time, and the effect of reducing the initial corrosion depth can be sufficiently obtained. There is a risk of not. On the other hand, when the thickness of the sacrificial material layer exceeds 100 μm, the initial corrosion depth becomes too large, which may reduce the corrosion resistance.

  The clad rate of the intermediate layer is preferably 2 to 30%, more preferably 5 to 20% from the viewpoint of manufacturability. If the clad rate of the intermediate layer is less than 2% or exceeds 30%, it may be difficult to produce a clad plate. Here, the cladding ratio of the intermediate layer is a ratio of the thickness of the intermediate layer to the thickness of the entire cladding plate.

  The clad rate of the sacrificial material layer is preferably 2 to 30%, more preferably 5 to 20% from the viewpoint of manufacturability, like the intermediate layer. When the clad rate of the sacrificial material layer is less than 2% or more than 30%, it may be difficult to manufacture the clad plate. Here, the clad rate of the sacrificial material layer is a ratio of the thickness of the sacrificial material layer to the thickness of the entire clad plate.

  In the aluminum alloy clad plate, the sacrificial material layer may be coated on one surface of the core material through an intermediate layer, and the brazing material layer may be coated on the other surface of the core material. In this case, the clad plate can be easily brazed. For example, it becomes easy to produce a tube material for a heat exchanger by bending a clad plate and brazing and joining the overlapping portions of both ends thereof.

  The thickness of the brazing material layer is not particularly limited, but is preferably 10 to 50 μm, for example. The single-sided cladding rate of the brazing material layer is preferably 5 to 30%. Here, the single-sided cladding rate of the brazing material layer is the ratio of the thickness of the brazing material layer provided on one side of the clad plate to the thickness of the entire clad plate. The thickness of the entire clad plate is preferably 50 to 250 μm, and more preferably 70 to 220 μm.

  The said aluminum alloy clad board provided with a core material, an intermediate | middle layer, and a sacrificial material layer is manufactured by a normal manufacturing method. The aluminum alloy clad plate is used as a heat exchanger member such as a tube material, a fin material, or a header plate. In particular, it is suitably used as a tube material that requires thinning.

  Examples of the aluminum alloy clad plate (hereinafter, simply referred to as a clad plate as appropriate) will be described using Tables 1 to 8 in comparison with Comparative Examples. The following examples show one embodiment of the present invention, and the present invention is not limited to these.

<Production of aluminum alloy clad plate>
As the core material, alloys having compositions shown in Tables 1 to 4 were used. The core material alloy was cast by a semi-continuous casting method to obtain a core material ingot. Thereafter, the ingot for the core material was subjected to a homogenization treatment at 520 ° C. for 6 hours, and faced so as to have a predetermined thickness.

  Alloys having compositions shown in Tables 1 to 4 were used for the intermediate layer and the sacrificial material layer. The intermediate layer alloy and the sacrificial material layer alloy were cast by a semi-continuous casting method to obtain the intermediate layer ingot and the sacrificial material layer ingot. Thereafter, the ingot for the intermediate layer and the ingot for the sacrificial material layer were chamfered and hot-rolled at 500 ° C. to obtain a plate shape having a predetermined thickness. In addition, you may perform a homogenization process with respect to the ingot for intermediate | middle layers, and the ingot for sacrificial material layers before hot rolling.

  In addition, the alloy composition shown to Tables 1-4 is what measured the ingot after casting using the emission-spectral-analysis apparatus. Further, the thickness of the ingot for the core material after chamfering, the thickness of the ingot for the intermediate layer and the sacrificial material layer ingot after hot rolling are 5% for each cladding ratio of the intermediate layer and the sacrificial material layer. It adjusted so that it might become. Here, the cladding ratio of the intermediate layer or the sacrificial material layer is the ratio of the thickness of the intermediate layer or the sacrificial material layer to the thickness of the clad plate to be produced.

Subsequently, the ingot for intermediate | middle layer was accumulated on the single side | surface of the ingot for core materials, and also the ingot for sacrificial material layers was accumulated on the ingot for intermediate | middle layers. This laminated material was hot-rolled at 520 ° C. according to a normal method for producing a clad plate to obtain a three-layer clad plate having a thickness of 3.5 mm. Then, the three-layer clad plate was cold-rolled until the plate thickness became 0.20 mm, further annealed at 360 ° C. for 3 hours, and then cold-rolled. As a result, a three-layer clad plate having an overall thickness of 0.15 mm and a clad ratio of 5% for the intermediate layer and the sacrificial material layer (that is, each thickness of the intermediate layer and the sacrificial material layer was 7.5 μm) was obtained. Thereafter, the three-layer clad plate was subjected to brazing equivalent heating held at 600 ° C. for 3 minutes in a nitrogen atmosphere or in vacuum (1 × 10 ⁻³ Pa).

  The clad board of the Example and the comparative example was obtained by the above. As shown in Tables 1 to 4, the clad plates of the examples are samples A1 to A12, B1 to B19, C1 to C20, and D1 to D16, and the clad plates of the comparative examples are samples A13 to A20, B20. -B28, C21-C30, D17-D24.

<Evaluation of corrosion resistance>
A circulation cycle test simulating an aqueous refrigerant environment was performed on the produced clad plate to evaluate the corrosion resistance. First, a 50 × 100 mm rectangular plate-shaped test piece was cut out from the produced clad plate. The test surface of the test piece is a surface clad with a sacrificial material layer. The non-test surface and the end surface of the test piece were masked.

Next, an aqueous solution at 88 ° C. containing Cl ⁻ : 195 ppm, SO ₄ ²⁻ : 60 ppm, Cu ²⁺ : 1 ppm, Fe ²⁺ : 30 ppm, a specific liquid amount of 6 mL / cm ² and a flow rate of 2 m with respect to the test surface of the test piece. Per second for 8 hours. Thereafter, the test piece was left for 16 hours. Such a cycle consisting of heating and leaving was performed for 3 months.

  After the cycle test, the corrosion product on the surface of the test piece was removed, and the corrosion depth was measured. The measurement location was 10 locations, and the maximum value was the corrosion depth. Evaluation of corrosion resistance is excellent when the corrosion depth is 60 μm or less (◎), good when the corrosion depth is 60 μm to 75 μm or less (◯), and acceptable when the corrosion depth is 75 μm or more and 100 μm or less (Δ) In the case where the corrosion depth exceeds 100 μm or the test piece penetrates due to corrosion, it was determined as impossible (×).

<Evaluation of manufacturability>
In producing the clad plate, those that had no problem in manufacturability were judged as good (◯), those that were difficult to produce for some reason were judged as bad (x), and the reason is shown in the remarks column of Tables 5 to 8. Was described.

Table 5 shows the evaluation results of the corrosion resistance and manufacturability of samples A1 to A20.
As shown in the table, Samples A1 to A12, which are examples, obtained good results (excellent (◎) or good (○)) in the corrosion resistance evaluation. Of course, the evaluation of manufacturability was also good (◯). On the other hand, Samples A13 to A20, which are comparative examples, did not give good results in the evaluation of corrosion resistance, or the clad plate was difficult to manufacture and were not subject to corrosion resistance evaluation.

  In sample A13, since the Mn content of the core material exceeds 2.0%, coarse crystallized matter was generated during casting, making it difficult to produce. In sample A14, the difference in Mn content between the sacrificial material layer and the intermediate layer and the difference in Mn content between the intermediate layer and the core material are not sufficient, penetration due to corrosion occurs, and corrosion resistance cannot be evaluated ( X). In sample A15, the difference in Mn content between the intermediate layer and the core material was not sufficient, and the corrosion resistance could be evaluated (Δ). In sample A16, the difference in Mn content between the sacrificial material layer and the intermediate layer was not sufficient, and the corrosion resistance could be evaluated (Δ). In Sample A17, since the sacrificial material layer contained too much Mg, it was very difficult to produce a clad plate due to the oxide film formed thick on the surface during production. In sample A18, the sacrificial material layer had too little Mg content, so the sacrificial material layer itself was inferior in corrosion resistance, the sacrificial material layer was consumed in a short period of time, penetration due to corrosion occurred, and corrosion resistance evaluation was impossible (X). In sample A19, since the sacrificial material layer had too much Si, the sacrificial material layer melted during brazing heating, making it difficult to manufacture. In sample A20, the sacrificial material layer had too little Si content, so there was almost no Mg—Si based crystal precipitate, penetration occurred due to corrosion, and corrosion resistance evaluation was impossible (×).

Table 6 shows the evaluation results of the corrosion resistance and manufacturability of samples B1 to B28.
As shown in the table, Samples B1 to B19, which are examples, obtained good results (excellent (◎) or good (○)) in the corrosion resistance evaluation. Of course, the evaluation of manufacturability was also good (◯). On the other hand, Samples B20 to B28, which are comparative examples, did not give good results in the evaluation of corrosion resistance, or were difficult to produce a clad plate, and were not subject to evaluation of corrosion resistance.

  In Sample B20, since the Mg content in the core material was too large, it was very difficult to produce a clad plate due to the oxide film formed thick on the surface during production. In Sample B21, since the Si content of the core material was too large, the core material melted during brazing heating, making it difficult to manufacture. In Sample B22, since the Cu content in the core material was too large, a coarse crystallized product was generated during casting, which made it very difficult to produce. In Sample B23, since the core material had too much Fe content, the corrosion resistance of the core material decreased, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). In Sample B24, since the core material had too much Ni content, the corrosion resistance of the core material was lowered, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). Samples B25 to B28 each contained too much Cr, Zr, Ti, and V, so that coarse crystals were generated during casting, making it difficult to produce.

Table 7 shows the evaluation results of the corrosion resistance and manufacturability of samples C1 to C30.
As shown in the table, Samples C1 to C20, which are examples, obtained good results (excellent (◎) or good (○)) in the corrosion resistance evaluation. Of course, the evaluation of manufacturability was also good (◯). On the other hand, Samples C21 to C30, which are comparative examples, did not give good results in the evaluation of corrosion resistance, or were difficult to produce a clad plate, and were not subject to evaluation of corrosion resistance.

  In Sample C21, since the intermediate layer had an excessively high Mg content, it was very difficult to produce a clad plate due to the oxide film formed thick on the surface during production. In Sample C22, since the Si content in the intermediate layer was too large, the intermediate layer melted during brazing heating, making it difficult to produce. In Sample C23, since the intermediate layer had too much Fe content, the corrosion resistance of the intermediate layer was lowered, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). In Sample C24, since the Ni content in the intermediate layer was too large, the corrosion resistance of the intermediate layer was lowered, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). In Samples C25 to C28, since the contents of Cr, Zr, Ti, and V were too large, coarse crystallized substances were generated during casting, and the productivity was greatly reduced. In addition, as the corrosion progresses, coarse crystallized products are crushed, resulting in penetration due to corrosion, making manufacture difficult. In Samples C29 and C30, the difference in Cu content between the intermediate layer and the core material was not sufficient, and the potential balance was lost, so the corrosion resistance could be evaluated (Δ).

Table 8 shows the evaluation results of corrosion resistance and manufacturability of samples D1 to D24.
As shown in the table, Samples D1 to C16 as examples obtained good results (excellent (◎) or good (○)) in the corrosion resistance evaluation. Of course, the evaluation of manufacturability was also good (◯). On the other hand, samples D17 to D24, which are comparative examples, did not give good results in the evaluation of corrosion resistance, or the clad plate was difficult to manufacture, and were not subject to evaluation of corrosion resistance.

  In sample D17, since the sacrificial material layer had too much Fe content, the corrosion resistance of the sacrificial material layer was lowered, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). In sample D18, the sacrificial material layer had too much Ni content, so the corrosion resistance of the sacrificial material layer was reduced, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). Samples D19 to D22 each contained too much Cr, Zr, Ti, and V, so that coarse crystals were generated during casting, making it difficult to produce. In sample D23, the sacrificial material layer had too much Cu content, so that the corrosion resistance of the sacrificial material layer was lowered, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x). In sample D24, the difference in Cu content between the sacrificial material layer and the intermediate layer was not sufficient, and the potential balance was lost. Therefore, penetration due to corrosion occurred, and the evaluation of corrosion resistance was impossible (x).

  DESCRIPTION OF SYMBOLS 1 ... Clad board made from aluminum alloy, 2 ... Core material, 3 ... Intermediate | middle layer, 4 ... Sacrificial material layer, 21 ... 1st main surface (one side of a core material)

Claims (5)

An aluminum alloy clad plate for a heat exchanger, comprising a core material, an intermediate layer and a sacrificial material layer made of an aluminum alloy, wherein at least one surface of the core material is covered with the sacrificial material layer via the intermediate layer. And
The core material contains Mn: 0.4% (mass%, the same applies below) and 2.0% or less, and the balance is made of an aluminum alloy composed of Al and inevitable impurities,
The intermediate layer contains Mn: 0.2% or more and 1.8% or less, the balance is made of aluminum and inevitable impurities, and the Mn content is 0.2% or less less than the core material. Configured,
The sacrificial material layer contains Mn: 0.05% to 1.6%, Mg: 0.1% to 2.0%, Si: 0.1% to 1.5%, and the remainder It is made of an aluminum alloy composed of Al and unavoidable impurities, and the Mn content is 0.2% or less less than the intermediate layer, or Mg: 0.1% or more and 2.0% or less, Si: Made of an aluminum alloy for heat exchangers, which is made of an aluminum alloy containing 0.1% or more and 1.5% or less, the balance being Al and unavoidable impurities, and containing Mn only as an unavoidable impurity Clad plate.   The core material further includes Mg: 0.05% to 2.0%, Si: 0.05% to 1.5%, Cu: 0.05% to 3.0%, Fe: 0.1 % To 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05% to 0.3%, Ti: 0 The clad plate made of an aluminum alloy for a heat exchanger according to claim 1, comprising one or more selected from 0.05% to 0.3% and V: 0.05% to 0.3%.   The intermediate layer further includes Mg: 0.05% to 2.0%, Si: 0.05% to 1.5%, Fe: 0.1% to 1.0%, Ni: 0.00%. 05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.05% to 0.3%, Ti: 0.05% to 0.3%, V: 1 type or more selected from 0.05% or more and 0.3% or less is contained, and further Cu: 0.05% or more and 2.8% or less is contained, and the Cu content is less than that of the core material. The aluminum alloy clad plate for a heat exchanger according to claim 1 or 2, containing less than 2% or containing Cu only as an inevitable impurity.   The sacrificial material layer further includes Fe: 0.05% to 1.0%, Ni: 0.05% to 0.3%, Cr: 0.05% to 0.3%, Zr: 0.00. It contains at least one selected from 05% to 0.3%, Ti: 0.05% to 0.3%, V: 0.05% to 0.3%, and Cu: Any one of Claims 1-3 which contains 0.05% or more and 1.5% or less, and Cu content is 0.2% or less less than the said intermediate | middle layer, or contains Cu only as an unavoidable impurity. An aluminum alloy clad plate for a heat exchanger according to item 1.   The sacrificial material layer is coated on one surface of the core material through the intermediate layer, and a brazing material layer is coated on the other surface of the core material. Aluminum alloy clad plate for heat exchanger.