EP1892308A1 - Aluminium piping material for automobile heat exchanger - Google Patents

Aluminium piping material for automobile heat exchanger Download PDF

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Publication number
EP1892308A1
EP1892308A1 EP07016585A EP07016585A EP1892308A1 EP 1892308 A1 EP1892308 A1 EP 1892308A1 EP 07016585 A EP07016585 A EP 07016585A EP 07016585 A EP07016585 A EP 07016585A EP 1892308 A1 EP1892308 A1 EP 1892308A1
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Prior art keywords
mass
balance
good
piping material
corrosion resistance
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EP07016585A
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German (de)
French (fr)
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EP1892308B1 (en
Inventor
Satoshi Tanaka
Junji Ninomiya
Toshiyuki Kakinoki
Kazumi Kato
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Furukawa Sky Aluminum Corp
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Furukawa Sky Aluminum Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions

Definitions

  • 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.
  • JIS 1000-series alloys JIS 3000-series alloys, JIS 6000-series alloys, or the like
  • JIS 1000-series alloys JIS 3000-series alloys
  • JIS 6000-series alloys or the like
  • known as a JIS 6000-series alloy is an aluminum alloy excellent in intergranular corrosion resistance and pitting corrosion resistance, which comprises 0.35 to 1.5 mass% (hereafter simply referred to as %) of Mg, 0.2 to 0.8% of Si, and 0.1 to 0.3% of Zn, further comprises 0.02 to 0.1% of Sn, and 0.15 to 0.4% of Cu (e.g. see JP-B-61-36577 ("JP-B" means examined Japanese patent publication)).
  • a method for producing a tube material for a heat exchanger excellent in tube formability which comprises 0.5 to 2.0% of Mn, 0.25 to 0.75% of Cu, and further comprises one or more elements of 0.05 to 0.2% of Mg, 0.05 to 1.0% of Si, 0.5 to 1.2% of Fe, 0.05 to 0.2% of Ti, 0.05 to 0.2% of Zr, 0.05 to 0.15% of Cr, and 0.05 to 0.15% of V (e.g. JP-A-2001-26850 ("JP-A" means unexamined published Japanese patent application)).
  • this material has a sheet shape, and is a type that is to be subjected to electric resistance welding (ERW or seam welding) or the like for formation of a pipe.
  • an aluminum brazing sheet to be used as a tube material there is a proposal of a material, in which an Al-Si-based alloy filler alloy is clad on one side of a core alloy, and in which a sacrificial anode alloy, such as an Al-Zn-based alloy or an AI-Zn-Mg-based alloy, is clad on the other side (e.g. JP-A-06-073480 ).
  • a sacrificial anode alloy such as an Al-Zn-based alloy or an AI-Zn-Mg-based alloy
  • JIS 3003-series alloys excellent in mechanical strength, workability, weldability, and corrosion resistance are heretofore used for automobile piping materials, but the corrosion resistance is insufficient under severe conditions.
  • perforation corrosion may occur when the alloy is used in an automobile engine room of harsh environment, or when used at high-temperature and high-humidity environments, such as in Southeast Asia.
  • the refrigerant (cooling water) in the piping will leak, resulting in that the cooling function is lost in the case of the piping in an air conditioner or that an engine is burned in the case of the piping in a radiator.
  • the present invention resides in an aluminum piping material for an automobile heat exchanger, which comprises 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, and 0.05 to 0.3 mass% of V, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance.
  • the present invention resides in an aluminum piping material for an automobile heat exchanger, which comprises 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, 0.05 to 0.3 mass% of V, and at least one selected from the group consisting of 0.05 to 0.4 mass% of Mg, 0.05 to 0.2 mass% of Cr, and 0.05 to 0.2 mass% of Zr, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance.
  • the present invention resides in an aluminum piping material for an automobile heat exchanger, which is produced by: subjecting an aluminum alloy ingot having any one of the above-mentioned compositions to hot extrusion, to form a raw pipe for extrusion; and subjecting the resultant raw pipe to drawbench drawing or continuous drawing, to form said aluminum piping material, wherein the aluminum piping material is excellent in corrosion resistance.
  • the inventors of the present invention having conducted intensive study to solve the above-mentioned problems in the conventional technique, found that corrosion resistance is remarkably improved by adding both of Ti and V to an Al-Mn-based alloy.
  • the present invention has been attained based on this finding.
  • Si is an essential alloying element
  • the Si content is 0.05 to 0.4 mass% (hereinafter simply referred to as %).
  • Si has an effect of enhancing the mechanical strength after brazing, by forming a solid solution in a matrix of the aluminum alloy structure and/or by forming an Al-Mn-Si-series compound, and thus Si is an essential alloying element.
  • the Si content needs to be 0.05% or more.
  • the upper limit of the Si content is set to 0.4%.
  • the Si content is more preferably 0.05 to 0.2%.
  • Fe is an essential alloying element, and the Fe content is 0.05 to 0.4%.
  • Fe has an effect of enhancing the mechanical strength, by being crystallized or precipitated as an Al-Fe-series intermetallic compound.
  • the Fe content needs to be 0.05% or more.
  • the upper limit of the Fe content is set to 0.4%.
  • the Fe content is more preferably 0.05 to 0.2%.
  • the Cu content is 0.6% or lower, and Cu is an optional element that may not be added (i.e. the Cu content may be 0%) or may be added, if required.
  • Cu has an effect of enhancing the mechanical strength, by forming a solid solution. To achieve this effect, Cu may be added up to the upper limit of 0.06%, as needed. However, when the Cu content exceeds the upper limit, the corrosion resistance is conspicuously lowered. When corrosion resistance is regarded as the most important property among various properties, it is more preferable to adjust the Cu content to 0.05% or lower.
  • the Mn content is 0.15 to 1.5%, and Mn is an essential alloying element in the present invention. Mn is added in an amount of 0.15 to 1.5% so as to enhance the mechanical strength. When the Mn content is 0.15% or lower, the effect is not sufficiently exhibited, and when the Mn content exceeds 1.5%, extrusion property and drawing workability are lowered.
  • the Mn content is more preferably 0.8 to 1.2%.
  • Ti and V contents is 0.05 to 0.3%, and Ti and V are essential alloying elements in the present invention.
  • Ti and V have an effect of further improving the corrosion resistance. More specifically, Ti and V each are separated into a high concentration region and a low concentration region, to alternately disperse those regions in the direction of the sheet thickness to form layers. Then, the region having low Ti and V concentrations preferentially corrodes as compared with the region having high Ti and V concentrations, to form a layered corrosion state. This prevents corrosion from progressing in the thickness direction, to thereby improve the resistance to pitting corrosion. By adding both of Ti and V, this effect is exhibited more notably.
  • Ti and V can also contribute to enhancement of the mechanical strength, and further higher effects can be obtained by adding a combination of Ti and V.
  • Ti and V each need to be contained in an amount of 0.05% or more. When each content exceeds 0.3% (upper limit), a giant or coarse intermetallic compound is generated at the time of casting, which may adversely affect the extrusion property and/or drawing workability.
  • the Ti and V contents each are more preferably 0.1 to 0.2%.
  • addition may be optionally made of at least one element selected from 0.05 to 0.4% of Mg, 0.05 to 0.2% of Cr, and 0.05 to 0.2% of Zr.
  • These alloying elements contribute to improvement in the mechanical strength of the alloy, by forming a solid solution or a dispersion as minute intermetallic compounds upon homogenization. Therefore, at least one alloying element is contained, if desired.
  • the content of each element is preferably 0.05% or more. When the alloying elements are excessively contained, the extrusion property and/or drawing workability are lowered.
  • the upper limit of each alloying element is defined as mentioned above. It is more preferable that the Mg content be 0.15 to 0.3%, and that the Cr and Zr contents each be 0.05 to 0.15%.
  • the aluminum alloy piping materials of the present invention for automobile heat exchangers can be produced, by processing the aluminum alloy having the aforementioned composition, according to the following procedure.
  • the aluminum alloy for use in the present invention can be produced by melting (to give an ingot) in a usual manner in which the target is set to have the above-mentioned alloying elements, and there is no particular limitation on the production method for the aluminum alloy.
  • a raw pipe for extrusion is produced using the thus-obtained alloy, it is preferable to subject the aluminum alloy (ingot) to homogenization.
  • the homogenization is conducted, by maintaining the aluminum alloy under the conditions in a usual manner of, for example, at 550 to 620°C, preferably 590 to 620°C, for 1 to 10 hours, preferably 2 to 4 hours, in a process of precipitating dispersed particles composed of Si, Mn, or the like, into a matrix uniformly with a high density. Then, the resultant alloy is heated to 450 to 550°C at least before extrusion, and subjected to soaking, followed by hot extrusion. There is no particular limitation on heating methods, heating furnaces, etc., for use in the above-mentioned homogenization and soaking processes.
  • the thus-obtained raw pipe for extrusion is then drawn by drawbench drawing or continuous drawing, followed by working to a product size. Then, the resultant is annealed, for example, by maintaining it at 300 to 520°C for 1 to 10 hours, to give a final product.
  • the above-mentioned extruded materials are to be used as heat exchanger materials, and may be usually used for piping materials for circulating a heating medium and/or piping materials for circulating water in a radiator, a heater core, or the like. Further, the heat exchangers may be used at any places or sites, without particular limitation.
  • an aluminum alloy material whose corrosion resistance is higher than that of JIS 3003 alloy in a single layered form, without cladding, and can be provided an excellent aluminum piping material for an automobile heat exchanger.
  • heat exchanger piping materials having excellent corrosion resistance can be obtained, even if the aluminum alloy piping materials for automobile heat exchangers are not clad materials but single-layer bear materials. Furthermore, according to the present invention, it is possible to eliminate the necessity of forming pipes from a sheet material with electric resistance welding or the like; to provide aluminum alloy piping materials capable of being worked by simple extrusion and drawing; and to reduce the production cost of the resultant heat exchangers. Thus, the present invention exhibits industrially remarkable effects.
  • the conventional example No. 1 is JIS 3003 alloy.
  • the Ti, V, and Mn alloying elements of the samples of Comparative examples 1 and 2 each were outside the range defined in the present invention, and it was impossible to subject those samples for comparison to extrusion and/or drawing, and no product was obtained.
  • the Ti and V contents of the sample of Comparative example 3 were less than the range defined in the present invention, and the corrosion resistance of the sample for comparison was not improved and was inferior to that of the conventional example.
  • the Cu and Fe contents of the samples of Comparative examples 4 and 5 each exceeded the range defined in the present invention, and the corrosion resistance of the samples for comparison was inferior to that of the conventional example.
  • the Si content of the sample of Comparative example 6 exceeded the range defined in the present invention, and the corrosion resistance of the sample for comparison was inferior to that of the conventional example and the extrusion property was poor.
  • each sample was subjected to a CASS test, according to JIS H8601, for 1,500 hours. After the test, surface corrosion products of each sample were removed, and the corrosion state of each sample was evaluated. Evaluation was made, by measuring the maximum pitting corrosion depth by a method using depth of focus with an optical microscope. The results are shown in Table 2.
  • the Ti, V, and Mn alloying elements of the samples of Comparative examples 1 and 2 each were outside the range defined in the present invention, and it was impossible to subject those samples for comparison to extrusion and/or drawing, and no product was obtained.
  • the Ti and V contents of the sample of Comparative example 3 were less than the range defined in the present invention, and the corrosion resistance of the sample for comparison was not improved and was inferior to that of the conventional example.
  • the Cu and Fe contents of the samples of Comparative examples 4 and 5 each exceeded the range defined in the present invention, and the corrosion resistance of the samples for comparison was inferior to that of the conventional example.
  • the Si content of the sample of Comparative example 6 exceeded the range defined in the present invention, and the corrosion resistance of the sample for comparison was inferior to that of the conventional example and the extrusion property was poor.
  • the examples according to the present invention were extremely excellent in the corrosion resistance outside the piping, as compared with that of the comparative examples and conventional example. Further, it is also found that the tensile strength of each example according to the present invention was at least substantially equivalent to or much higher than that of the conventional example.

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Abstract

An aluminum piping material for an automobile heat exchanger, containing 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, and 0.05 to 0.3 mass% of V, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance.

Description

    FIELD OF THE INVENTION
  • 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.
  • BACKGROUND OF THE INVENTION
  • Heretofore, as piping materials for such heat exchangers, JIS 1000-series alloys, JIS 3000-series alloys, JIS 6000-series alloys, or the like, are used in many cases. For example, known as a JIS 6000-series alloy is an aluminum alloy excellent in intergranular corrosion resistance and pitting corrosion resistance, which comprises 0.35 to 1.5 mass% (hereafter simply referred to as %) of Mg, 0.2 to 0.8% of Si, and 0.1 to 0.3% of Zn, further comprises 0.02 to 0.1% of Sn, and 0.15 to 0.4% of Cu (e.g. see JP-B-61-36577 ("JP-B" means examined Japanese patent publication)).
  • With respect to a JIS 3000-series alloy, there is a disclosure of a method for producing a tube material for a heat exchanger excellent in tube formability, which comprises 0.5 to 2.0% of Mn, 0.25 to 0.75% of Cu, and further comprises one or more elements of 0.05 to 0.2% of Mg, 0.05 to 1.0% of Si, 0.5 to 1.2% of Fe, 0.05 to 0.2% of Ti, 0.05 to 0.2% of Zr, 0.05 to 0.15% of Cr, and 0.05 to 0.15% of V (e.g. JP-A-2001-26850 ("JP-A" means unexamined published Japanese patent application)). However, this material has a sheet shape, and is a type that is to be subjected to electric resistance welding (ERW or seam welding) or the like for formation of a pipe.
  • For an aluminum brazing sheet to be used as a tube material, there is a proposal of a material, in which an Al-Si-based alloy filler alloy is clad on one side of a core alloy, and in which a sacrificial anode alloy, such as an Al-Zn-based alloy or an AI-Zn-Mg-based alloy, is clad on the other side (e.g. JP-A-06-073480 ). However, sheet-shaped tube materials and piping materials are utterly different in the casting methods and production processes.
  • Thus, for example, JIS 3003-series alloys excellent in mechanical strength, workability, weldability, and corrosion resistance are heretofore used for automobile piping materials, but the corrosion resistance is insufficient under severe conditions. For example, perforation corrosion may occur when the alloy is used in an automobile engine room of harsh environment, or when used at high-temperature and high-humidity environments, such as in Southeast Asia. When perforation corrosion occurs even in one spot in allocated piping, the refrigerant (cooling water) in the piping will leak, resulting in that the cooling function is lost in the case of the piping in an air conditioner or that an engine is burned in the case of the piping in a radiator. Thus, from the viewpoint of corrosion resistance, not single layer materials as described above but materials in which both or either of inner and outer surfaces of a core alloy, such as a JIS 3003-based alloy, are clad with a JIS 7072-based alloy or the like are commonly used, but such materials pose a problem of high manufacturing cost.
  • SUMMARY OF THE INVENTION
  • The present invention resides in an aluminum piping material for an automobile heat exchanger, which comprises 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, and 0.05 to 0.3 mass% of V, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance.
  • Further, the present invention resides in an aluminum piping material for an automobile heat exchanger, which comprises 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, 0.05 to 0.3 mass% of V, and at least one selected from the group consisting of 0.05 to 0.4 mass% of Mg, 0.05 to 0.2 mass% of Cr, and 0.05 to 0.2 mass% of Zr, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance.
  • Further, the present invention resides in an aluminum piping material for an automobile heat exchanger, which is produced by: subjecting an aluminum alloy ingot having any one of the above-mentioned compositions to hot extrusion, to form a raw pipe for extrusion; and subjecting the resultant raw pipe to drawbench drawing or continuous drawing, to form said aluminum piping material, wherein the aluminum piping material is excellent in corrosion resistance.
  • Other and further features and advantages of the invention will appear more fully from the following description.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The inventors of the present invention, having conducted intensive study to solve the above-mentioned problems in the conventional technique, found that corrosion resistance is remarkably improved by adding both of Ti and V to an Al-Mn-based alloy. The present invention has been attained based on this finding.
  • According to the present invention, there is provided the following means:
    1. (1) An aluminum piping material for an automobile heat exchanger, comprising 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, and 0.05 to 0.3 mass% of V, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance;
    2. (2) An aluminum piping material for an automobile heat exchanger, comprising 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, 0.05 to 0.3 mass% of V, and at least one selected from the group consisting of 0.05 to 0.4 mass% of Mg, 0.05 to 0.2 mass% of Cr, and 0.05 to 0.2 mass% of Zr, with the balance being Al and inevitable impurities, wherein the aluminum piping material is excellent in corrosion resistance;
    3. (3) The aluminum piping material for an automobile heat exchanger according to Item (1) or (2), wherein the Cu content is 0.05 mass% or lower; and
    4. (4) An aluminum piping material for an automobile heat exchanger, which is produced by: subjecting an aluminum alloy ingot having a composition according to any one of Items (1) to (3) to hot extrusion, to form a raw pipe for extrusion; and subjecting the resultant raw pipe to drawbench drawing or continuous drawing, to form said aluminum piping material, wherein the aluminum piping material is excellent in corrosion resistance.
  • Hereinafter, the present invention will be described in detail.
  • First, alloying elements of an aluminum alloy forming the aluminum piping material of the present invention will be described.
  • In the present invention, Si is an essential alloying element, and the Si content is 0.05 to 0.4 mass% (hereinafter simply referred to as %). Si has an effect of enhancing the mechanical strength after brazing, by forming a solid solution in a matrix of the aluminum alloy structure and/or by forming an Al-Mn-Si-series compound, and thus Si is an essential alloying element. To achieve this effect, the Si content needs to be 0.05% or more. When the content exceeds the upper limit, corrosion resistance and extrusion property (the life of a dice to be used) will be lowered. Thus, the upper limit of the Si content is set to 0.4%. The Si content is more preferably 0.05 to 0.2%.
  • In the present invention, Fe is an essential alloying element, and the Fe content is 0.05 to 0.4%. Fe has an effect of enhancing the mechanical strength, by being crystallized or precipitated as an Al-Fe-series intermetallic compound. To achieve this effect, the Fe content needs to be 0.05% or more. However, when Fe is excessively contained, the excessive Fe or compound therefrom is crystallized on the surface, to increase a corrosion speed. Thus, the upper limit of the Fe content is set to 0.4%. The Fe content is more preferably 0.05 to 0.2%.
  • In the present invention, the Cu content is 0.6% or lower, and Cu is an optional element that may not be added (i.e. the Cu content may be 0%) or may be added, if required. Cu has an effect of enhancing the mechanical strength, by forming a solid solution. To achieve this effect, Cu may be added up to the upper limit of 0.06%, as needed. However, when the Cu content exceeds the upper limit, the corrosion resistance is conspicuously lowered. When corrosion resistance is regarded as the most important property among various properties, it is more preferable to adjust the Cu content to 0.05% or lower.
  • The Mn content is 0.15 to 1.5%, and Mn is an essential alloying element in the present invention. Mn is added in an amount of 0.15 to 1.5% so as to enhance the mechanical strength. When the Mn content is 0.15% or lower, the effect is not sufficiently exhibited, and when the Mn content exceeds 1.5%, extrusion property and drawing workability are lowered. The Mn content is more preferably 0.8 to 1.2%.
  • Each of the Ti and V contents is 0.05 to 0.3%, and Ti and V are essential alloying elements in the present invention. Ti and V have an effect of further improving the corrosion resistance. More specifically, Ti and V each are separated into a high concentration region and a low concentration region, to alternately disperse those regions in the direction of the sheet thickness to form layers. Then, the region having low Ti and V concentrations preferentially corrodes as compared with the region having high Ti and V concentrations, to form a layered corrosion state. This prevents corrosion from progressing in the thickness direction, to thereby improve the resistance to pitting corrosion. By adding both of Ti and V, this effect is exhibited more notably.
  • Further, Ti and V can also contribute to enhancement of the mechanical strength, and further higher effects can be obtained by adding a combination of Ti and V. To sufficiently obtain these effects, Ti and V each need to be contained in an amount of 0.05% or more. When each content exceeds 0.3% (upper limit), a giant or coarse intermetallic compound is generated at the time of casting, which may adversely affect the extrusion property and/or drawing workability. The Ti and V contents each are more preferably 0.1 to 0.2%.
  • In the present invention, addition may be optionally made of at least one element selected from 0.05 to 0.4% of Mg, 0.05 to 0.2% of Cr, and 0.05 to 0.2% of Zr. These alloying elements contribute to improvement in the mechanical strength of the alloy, by forming a solid solution or a dispersion as minute intermetallic compounds upon homogenization. Therefore, at least one alloying element is contained, if desired. To sufficiently obtain the above-mentioned functions, the content of each element is preferably 0.05% or more. When the alloying elements are excessively contained, the extrusion property and/or drawing workability are lowered. Thus, the upper limit of each alloying element is defined as mentioned above. It is more preferable that the Mg content be 0.15 to 0.3%, and that the Cr and Zr contents each be 0.05 to 0.15%.
  • The aluminum alloy piping materials of the present invention for automobile heat exchangers can be produced, by processing the aluminum alloy having the aforementioned composition, according to the following procedure.
  • The aluminum alloy for use in the present invention can be produced by melting (to give an ingot) in a usual manner in which the target is set to have the above-mentioned alloying elements, and there is no particular limitation on the production method for the aluminum alloy. When a raw pipe for extrusion is produced using the thus-obtained alloy, it is preferable to subject the aluminum alloy (ingot) to homogenization.
  • The homogenization is conducted, by maintaining the aluminum alloy under the conditions in a usual manner of, for example, at 550 to 620°C, preferably 590 to 620°C, for 1 to 10 hours, preferably 2 to 4 hours, in a process of precipitating dispersed particles composed of Si, Mn, or the like, into a matrix uniformly with a high density. Then, the resultant alloy is heated to 450 to 550°C at least before extrusion, and subjected to soaking, followed by hot extrusion. There is no particular limitation on heating methods, heating furnaces, etc., for use in the above-mentioned homogenization and soaking processes.
  • The thus-obtained raw pipe for extrusion is then drawn by drawbench drawing or continuous drawing, followed by working to a product size. Then, the resultant is annealed, for example, by maintaining it at 300 to 520°C for 1 to 10 hours, to give a final product.
  • The above-mentioned extruded materials are to be used as heat exchanger materials, and may be usually used for piping materials for circulating a heating medium and/or piping materials for circulating water in a radiator, a heater core, or the like. Further, the heat exchangers may be used at any places or sites, without particular limitation.
  • According to the present invention, there can be developed an aluminum alloy material whose corrosion resistance is higher than that of JIS 3003 alloy in a single layered form, without cladding, and can be provided an excellent aluminum piping material for an automobile heat exchanger.
  • Further, according to the present invention, heat exchanger piping materials having excellent corrosion resistance can be obtained, even if the aluminum alloy piping materials for automobile heat exchangers are not clad materials but single-layer bear materials. Furthermore, according to the present invention, it is possible to eliminate the necessity of forming pipes from a sheet material with electric resistance welding or the like; to provide aluminum alloy piping materials capable of being worked by simple extrusion and drawing; and to reduce the production cost of the resultant heat exchangers. Thus, the present invention exhibits industrially remarkable effects.
  • The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.
  • EXAMPLES (Example 1)
  • An AI alloy having the composition, of a number shown in Table 1 (numeric values represent mass%), was molten, and cast, to produce a billet of diameter 219 mm. This billet was maintained at 610°C for 4 hours for homogenization. The resultant billet was cut to a length of 300 mm, to give a billet for extrusion. This billet for extrusion was heated again at 450 to 500°C. Then, the thus-heated billet was extruded with a mandrel dice, to give a raw pipe of outer diameter φ 36 mm and thickness 3 mm. Then, cold-continuous drawing was conducted to the raw pipe at plurality times, to attain the final size of outer diameter φ 17 mm and thickness 1 mm, to thereby obtain a pipe material. Then, the pipe material was maintained at 360°C for 2 hours for annealing, and allowed to cool, to obtain a sample of the number shown in Table 1.
  • The conventional example No. 1 is JIS 3003 alloy.
  • To evaluate the internal corrosion resistance of these samples, the piping of any one of samples was connected to a commercially available aqueous coolant using a cyclic tester. Then, a cycle test in which the samples were maintained at 88°C for 8 hours and then at room temperature for 16 hours was performed for one year. Surface corrosion products of each sample were removed, and the corrosion state of each sample was evaluated. Evaluation was made, by measuring the maximum pitting corrosion depth by a method using depth of focus with an optical microscope. The results are shown in Table 1.
  • Tensile strength was evaluated, by cutting the piping of each sample to form a JIS No. 11 test piece while keeping a circular shape, and a test was conducted at tensile speed 10 mm/min, according to JIS H4080. Table 1
    Categories No Si Fe Cu Mn Ti V Mg Cr Zr Al Tensile strength (MPa) Maximum pitting corrosion depth after internal cyclic test (µm) Extrusion property and drawing property
    This invention 1 0.05 0.05 0.4 0.15 0.05 0.05 - - - Balance 94 245 Good
    2 0.05 0.05 0.02 0.15 0.3 0.3 - - - Balance 100 102 Good
    3 0.05 0.05 0.02 1.1 0.3 0.3 - - - Balance 133 109 Good
    4 0.05 0.05 0.02 1.1 0.05 0.05 - - - Balance 120 144 Good
    5 0.05 0.05 0.02 1.1 0.05 0.3 - - - Balance 124 129 Good
    6 0.05 0.05 0.02 1.1 0.3 0.05 - - - Balance 115 131 Good
    7 0.05 0.05 0.02 0.7 0.15 0.15 - - - Balance 110 184 Good
    8 0.05 0.05 0.02 0.7 0.15 0.05 - - - Balance 106 141 Good
    9 0.05 0.2 0.2 0.7 0.2 0.2 - - - Balance 119 180 Good
    10 0.05 0.4 0.6 1.5 0.2 0.2 - - - Balance 150 327 Good
    11 0.2 0.05 0.01 0.5 0.15 0.15 - - - Balance 108 118 Good
    12 0.2 0.2 0.1 1.1 0.2 0.2 - - - Balance 124 148 Good
    13 0.2 0.3 0.2 1.1 0.05 0.3 - - - Balance 129 155 Good
    14 0.2 0.3 0.2 0.5 0.3 0.05 - - - Balance 119 147 Good
    15 0.2 0.3 0.2 0.7 0.3 0.3 - - - Balance 150 137 Good
    16 0.4 0.05 0.02 0.15 0.15 0.15 - - - Balance 90 114 Good
    17 0.4 0.2 0.3 1.1 0.25 0.05 - - - Balance 138 265 Good
    18 0.4 0.2 0.6 1.1 0.3 0.3 - - - Balance 159 271 Good
    19 0.4 0.4 0.6 1.5 0.3 0.3 - - - Balance 168 286 Good
    20 0.2 0.2 0.1 1.1 0.2 0.2 0.2 - - Balance 139 182 Good
    21 0.2 0.2 0.1 1.1 0.2 0.2 - 0.2 - Balance 135 140 Good
    22 0.2 0.2 0.1 1.1 0.2 0.2 - - 0.2 Balance 131 164 Good
    Comparative example 1 0.2 0.2 0.2 1.1 0.35 0.35 - - - Balance - - Impossible to extrude and draw
    2 0.2 0.2 0.2 1.6 0.05 0.05 - - - Balance - - Impossible to extrude and draw
    3 0.5 0.5 0.2 1.1 0.04 0.04 - - - Balance 123 617 Good
    4 0.2 0.2 0.7 1.1 0.05 0.05 - - - Balance 149 727 Good
    5 0.2 0.5 0.2 1.1 0.05 0.05 - - - Balance 121 596 Good
    6 0.5 0.2 0.3 1.1 0.05 0.05 - - - Balance 130 592 Poor extrusion property
    Conventional example 1 0.1 0.45 0.1 1.0 - - - - - Balance 110 580 Good
  • As is apparent from the results shown in Table 1, the Ti, V, and Mn alloying elements of the samples of Comparative examples 1 and 2 each were outside the range defined in the present invention, and it was impossible to subject those samples for comparison to extrusion and/or drawing, and no product was obtained. The Ti and V contents of the sample of Comparative example 3 were less than the range defined in the present invention, and the corrosion resistance of the sample for comparison was not improved and was inferior to that of the conventional example. The Cu and Fe contents of the samples of Comparative examples 4 and 5 each exceeded the range defined in the present invention, and the corrosion resistance of the samples for comparison was inferior to that of the conventional example. The Si content of the sample of Comparative example 6 exceeded the range defined in the present invention, and the corrosion resistance of the sample for comparison was inferior to that of the conventional example and the extrusion property was poor.
  • Contrary to the above, it is found that the examples according to the present invention were extremely excellent in the corrosion resistance inside the piping, as compared with that of the comparative examples and conventional example.
  • Further, it is also found that the tensile strength of each example according to the present invention was at least substantially equivalent to or much higher than that of the conventional example.
  • (Example 2)
  • An Al alloy having the composition, of a number shown in Table 2 (numeric values represent mass%), was molten, and cast, to produce a billet of diameter 219 mm. This billet was maintained at 610°C for 4 hours for homogenization. The resultant billet was cut to a length of 300 mm, to give a billet for extrusion. This billet for extrusion was heated again at 450 to 500°C. Then, the thus-heated billet was extruded with a mandrel dice, to give a raw pipe of outer diameter φ 36 mm and thickness 3 mm. Then, cold-continuous drawing was conducted to the raw pipe at plurality times, to attain the final size of outer diameter φ 17 mm and thickness 1 mm, to thereby obtain a pipe material. Then, the pipe material was maintained at 360°C for 2 hours for annealing, and allowed to cool, to obtain a sample of the number shown in Table 2.
  • To evaluate the external corrosion resistance of these samples, each sample was subjected to a CASS test, according to JIS H8601, for 1,500 hours. After the test, surface corrosion products of each sample were removed, and the corrosion state of each sample was evaluated. Evaluation was made, by measuring the maximum pitting corrosion depth by a method using depth of focus with an optical microscope. The results are shown in Table 2.
  • Tensile strength was evaluated, by producing test samples in the same manner as in Example 1, and examining under the same conditions as in Example 1, according to JIS H4080. Table 2
    Categories No Si Fe Cu Mn Ti V Mg Cr Zr Al Tensile strength (MPa) Maximum pitting corrosion depth after CASS test (µm) Extrusion property and drawing property
    This invention 1 0.05 0.05 0.4 0.15 0.05 0.05 - - - Balance 94 300 Good
    2 0.05 0.05 0.02 0.15 0.3 0.3 - - - Balance 100 125 Good
    3 0.05 0.05 0.02 1.1 0.3 0.3 - - - Balance 133 133 Good
    4 0.05 0.05 0.02 1.1 0.05 0.05 - - - Balance 120 176 Good
    5 0.05 0.05 0.02 1.1 0.05 0.3 - - - Balance 124 158 Good
    6 0.05 0.05 0.02 1.1 0.3 0.05 - - - Balance 115 160 Good
    7 0.05 0.05 0.02 0.7 0.15 0.15 - - - Balance 110 150 Good
    8 0.05 0.05 0.02 0.7 0.15 0.05 - - - Balance 106 172 Good
    9 0.05 0.2 0.2 0.7 0.2 0.2 - - - Balance 119 220 Good
    10 0.05 0.4 0.6 1.5 0.2 0.2 - - - Balance 150 400 Good
    11 0.2 0.05 0.01 0.5 0.15 0.15 - - - Balance 108 145 Good
    12 0.2 0.2 0.1 1.1 0.2 0.2 - - - Balance 124 181 Good
    13 0.2 0.3 0.2 1.1 0.05 0.3 - - - Balance 129 190 Good
    14 0.2 0.3 0.2 0.5 0.3 0.05 - - - Balance 119 180 Good
    15 0.2 0.3 0.2 0.7 0.3 0.3 - - - Balance 150 168 Good
    16 0.4 0.05 0.02 0.15 0.15 0.15 - - - Balance 90 140 Good
    17 0.4 0.2 0.3 1.1 0.25 0.05 - - - Balance 138 325 Good
    18 0.4 0.2 0.6 1.1 0.3 0.3 - - - Balance 159 332 Good
    19 0.4 0.4 0.6 1.5 0.3 0.3 - - - Balance 168 350 Good
    20 0.2 0.2 0.1 1.1 0.2 0.2 0.2 - - Balance 139 223 Good
    21 0.2 0.2 0.1 1.1 0.2 0.2 - 0.2 - Balance 135 171 Good
    22 0.2 0.2 0.1 1.1 0.2 0.2 - - 0.2 Balance 131 201 Good
    Comparative example 1 0.2 0.2 0.2 1.1 0.35 0.35 - - - Balance - - Impossible to extrude and draw
    2 0.2 0.2 0.2 1.6 0.05 0.05 - - - Balance - - Impossible to extrude and draw
    3 0.5 0.5 0.2 1.1 0.04 0.04 - - - Balance 123 755 Good
    4 0.2 0.2 0.7 1.1 0.05 0.05 - - - Balance 149 890 Good
    5 0.2 0.5 0.2 1.1 0.05 0.05 - - - Balance 121 730 Good
    6 0.5 0.2 0.3 1.1 0.05 0.05 - - - Balance 130 725 Poor extrusion property
    Conventional example 1 0.1 0.45 0.1 1.0 - - - - - Balance 110 710 Good
  • As is apparent from the results shown in Table 2, the Ti, V, and Mn alloying elements of the samples of Comparative examples 1 and 2 each were outside the range defined in the present invention, and it was impossible to subject those samples for comparison to extrusion and/or drawing, and no product was obtained. The Ti and V contents of the sample of Comparative example 3 were less than the range defined in the present invention, and the corrosion resistance of the sample for comparison was not improved and was inferior to that of the conventional example. The Cu and Fe contents of the samples of Comparative examples 4 and 5 each exceeded the range defined in the present invention, and the corrosion resistance of the samples for comparison was inferior to that of the conventional example. The Si content of the sample of Comparative example 6 exceeded the range defined in the present invention, and the corrosion resistance of the sample for comparison was inferior to that of the conventional example and the extrusion property was poor.
  • Contrary to the above, it is found that the examples according to the present invention were extremely excellent in the corrosion resistance outside the piping, as compared with that of the comparative examples and conventional example. Further, it is also found that the tensile strength of each example according to the present invention was at least substantially equivalent to or much higher than that of the conventional example.
  • Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.
  • This non-provisional application claims priority under 35 U.S.C. § 119 (a) on Patent Application No. 2006-228383 filed in Japan on August 24, 2006, which is entirely herein incorporated by reference.

Claims (4)

  1. An aluminum piping material for an automobile heat exchanger, comprising 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, and 0.05 to 0.3 mass% of V, with the balance being AI and inevitable impurities,
    wherein the aluminum piping material is excellent in corrosion resistance.
  2. An aluminum piping material for an automobile heat exchanger, comprising 0.05 to 0.4 mass% of Si, 0.05 to 0.4 mass% of Fe, 0.6 mass% or lower of Cu, 0.15 to 1.5 mass% of Mn, 0.05 to 0.3 mass% of Ti, 0.05 to 0.3 mass% of V, and at least one selected from the group consisting of 0.05 to 0.4 mass% of Mg, 0.05 to 0.2 mass% of Cr, and 0.05 to 0.2 mass% of Zr, with the balance being Al and inevitable impurities,
    wherein the aluminum piping material is excellent in corrosion resistance.
  3. The aluminum piping material for an automobile heat exchanger according to Claim 1 or 2, wherein the Cu content is 0.05 mass% or lower.
  4. An aluminum piping material for an automobile heat exchanger, which is produced by:
    subjecting an aluminum alloy ingot having a composition according to any one of Claims 1 to 3 to hot extrusion, to form a raw pipe for extrusion; and
    subjecting the resultant raw pipe to drawbench drawing or continuous drawing, to form said aluminum piping material,
    wherein the aluminum piping material is excellent in corrosion resistance.
EP07016585A 2006-08-24 2007-08-23 Aluminium piping material for automobile heat exchanger Ceased EP1892308B1 (en)

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JP2006228383A JP5049536B2 (en) 2006-08-24 2006-08-24 Aluminum piping material for automotive heat exchangers

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CN102312134A (en) * 2011-10-20 2012-01-11 银邦金属复合材料股份有限公司 Novel 3003 aluminium alloy
EP2514555A1 (en) 2011-04-21 2012-10-24 Aleris Aluminum Koblenz GmbH Extruded aluminium alloy tube product
EP4004476A4 (en) * 2019-07-22 2023-08-09 Hydro Precision Tubing (Suzhou) Co., Ltd. Long-life aluminum alloy with a high corrosion resistance and helically grooved tube produced from the alloy

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JP5030276B2 (en) * 2007-04-09 2012-09-19 古河スカイ株式会社 Aluminum alloy piping material for heat exchanger and manufacturing method thereof
EP2159528B1 (en) * 2008-09-02 2015-11-04 Calsonic Kansei Corporation Heat exchanger made of aluminum alloy
CN102884393B (en) 2010-03-02 2015-04-15 三菱铝株式会社 Heat exchanger constituted of aluminum alloy
JP5653233B2 (en) * 2011-01-20 2015-01-14 日本軽金属株式会社 Aluminum alloy for microporous hollow material with excellent extrudability and intergranular corrosion resistance and method for producing the same
JP5878235B2 (en) * 2012-04-05 2016-03-08 日本軽金属株式会社 Aluminum alloy for microporous hollow material having excellent extrudability and intergranular corrosion resistance and method for producing the same
JP6066299B2 (en) * 2013-02-14 2017-01-25 日本軽金属株式会社 Aluminum heat exchanger
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US20080050269A1 (en) 2008-02-28

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