WO2020179467A1 - Matériau d'ailette revêtu d'alliage d'aluminium présentant une excellente résistance à la corrosion, et son procédé de fabrication - Google Patents

Matériau d'ailette revêtu d'alliage d'aluminium présentant une excellente résistance à la corrosion, et son procédé de fabrication Download PDF

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WO2020179467A1
WO2020179467A1 PCT/JP2020/006769 JP2020006769W WO2020179467A1 WO 2020179467 A1 WO2020179467 A1 WO 2020179467A1 JP 2020006769 W JP2020006769 W JP 2020006769W WO 2020179467 A1 WO2020179467 A1 WO 2020179467A1
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aluminum alloy
ingot
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Japanese (ja)
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知浩 小路
中村　真一
淳一 望月
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株式会社Uacj
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working

Definitions

  • the present invention relates to an aluminum alloy clad fin material having excellent self-corrosion resistance used in an aluminum heat exchanger manufactured by brazing.
  • heat exchangers such as those used in automobiles.
  • These heat exchangers have a structure in which a refrigerant such as water is circulated in a flow path composed of a combination of each member to transfer heat and dissipate heat. Then, each member constituting the cooler is metallically joined by brazing.
  • Such a heat exchanger is conventionally assembled by brazing and joining aluminum alloy fins formed in a wavy shape by, for example, corrugated molding with other members.
  • the aluminum alloy fin material a pure aluminum alloy such as JIS 1050 alloy having excellent thermal conductivity or an Al-Mn alloy having excellent strength and buckling resistance such as JIS 3003 alloy has been generally used.
  • sacrificial anode fin that contains Zn in each alloy to prevent corrosion of heat exchanger tubes and plates.
  • sacrificial anode fins are joined to the outer surfaces and inner surfaces of the tubes and plates as needed (for example, Patent Documents 1 and 2).
  • Vacuum brazing is a method in which Mg contained in a brazing material enables brazing by destroying an oxide film on the surface of the material during brazing heat.
  • the fin material plate thickness In order to maintain the sacrificial anode effect for a long time, it is necessary to increase the fin material plate thickness or increase the Zn concentration. However, increasing the fin material plate thickness increases the material cost. Further, when the Zn concentration is increased, the potential becomes low and the corrosion rate increases, and in addition, the fin material penetrates due to pitting corrosion, and a part of the fins partially falls off, resulting in an increase in the amount of self-corrosion. When the amount of self-corrosion increases, clogging due to corrosion products may occur when the fin material is joined to the inner surface side of the tube or plate.
  • an object of the present invention is to provide an aluminum alloy clad fin material as a fin material for a heat exchanger having excellent self-corrosion resistance that can maintain the sacrificial anode effect for a long time.
  • the present inventors clad the skin material on both surfaces of the core material of the fin material and define the difference in Zn content between the skin material and the core material within a specific range. As a result, it was found that the self-corrosion resistance of the fin material was increased, and the present invention was completed.
  • the present invention (1) is a clad material in which a skin material made of an Al—Zn alloy is clad on both sides of a core material made of an Al—Mn alloy.
  • the core material contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5.50% by mass.
  • the balance consists of an aluminum alloy consisting of aluminum and unavoidable impurities
  • the skin material contains 0.01 to 5.50% by mass of Zn, Fe and Si, and the balance is an aluminum alloy composed of aluminum and unavoidable impurities.
  • the Fe content and Si content of the skin material are as follows (i), (ii) and (iii): (I) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is 0.30% by mass or less. (Ii) The Fe content is 0.35% by mass or less, and the Si content is more than 0.3% by mass and 1.20% by mass or less. (Iii) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less. Meet one of the The difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is 0.01% by mass or more.
  • the present invention provides an aluminum alloy clad fin material.
  • the core material further comprises less than 0.05 mass% Cu, 1.00 mass% or less Mg, 0.20 mass% or less Cr, and 0.20 mass% or less Ti. , 0.20% by mass or less Zr, 0.10% by mass or less In, 0.10% by mass or less Sn, and 0.10% by mass or less Bi, or one or more kinds thereof are contained.
  • the present invention provides the aluminum alloy clad fin material according to (1).
  • the skin material further comprises Mn of less than 0.10 mass%, Cu of 0.05 mass% or less, Mg of 1.00 mass% or less, and 0.20 mass% or less.
  • Cr 0.20% by mass or less Ti, 0.20% by mass or less Zr, 0.20% by mass or less Sr, 0.10% by mass or less In, 0.10% by mass or less Sn and 0.10
  • an aluminum alloy clad fin material according to any one of (1) and (2), which contains any one or more of Bi in mass% or less.
  • the clad material is surface-etched by acid cleaning at least after hot working, cold working, intermediate annealing, or final annealing.
  • an aluminum alloy clad fin material is provided according to any one of (1) to (3).
  • the present invention (5) provides the aluminum alloy clad fin material of (4), which is characterized in that the etching treatment by the acid treatment is performed after hot working.
  • the present invention hot working, cold working, and one or both of intermediate annealing and final annealing of a laminate in which an ingot for a skin material is laminated on both sides of an ingot for a core material, or both.
  • This is a method for manufacturing an aluminum alloy clad fin material to obtain an aluminum alloy clad fin material.
  • the core material ingot contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5. The content is limited to 50% by mass or less, the balance is made of an aluminum alloy containing aluminum and inevitable impurities, and the ingot for skin material contains 0.01 to 5.50% by mass of Zn and contains Fe and Si.
  • the Fe content and Si content of the ingot for skin material have the following (i), (ii) and (iii): (i)Fe Content is more than 0.35% by mass and 1.20% by mass or less, Si content is 0.30% by mass or less, and (ii) Fe content is 0.35% by mass.
  • the Si content is more than 0.30% by mass and 1.20% by mass or less, and (iii) the Fe content is more than 0.35% by mass and 1.20% by mass or less.
  • the present invention provides a method for manufacturing an aluminum alloy clad fin material.
  • the ingot for the core material further contains less than 0.05% by mass of Cu, 1.00% by mass or less of Mg, 0.20% by mass or less of Cr, and 0.20% by mass. Any one or more of the following Ti, 0.20% by mass or less of Zr, 0.10% by mass or less of In, 0.10% by mass or less of Sn, and 0.10% by mass or less of Bi. (6), a method for producing an aluminum alloy clad fin material, which is characterized by containing the above.
  • the ingot for skin material further comprises Mn of less than 0.10 mass%, Cu of 0.05 mass% or less, Mg of 1.00 mass% or less, 0.20 mass. % Or less Cr, 0.20 mass% or less Ti, 0.20 mass% or less Zr, 0.20 mass% or less Sr, 0.10 mass% or less In, 0.10 mass% or less Sn and A method for producing an aluminum alloy clad fin material according to (6) or (7), characterized in that it contains one or more of 0.10 mass% or less of Bi. is there.
  • the present invention hot working, cold working, and one or both of intermediate annealing and final annealing of a laminate in which an ingot for a skin material is laminated on both sides of an ingot for a core material, or both.
  • This is a method for manufacturing an aluminum alloy clad fin material to obtain an aluminum alloy clad fin material.
  • the core material ingot contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5. The content is limited to 50% by mass or less, the balance is made of an aluminum alloy containing aluminum and inevitable impurities, and the ingot for skin material contains 0.01 to 5.50% by mass of Zn and contains Fe and Si.
  • the content of Fe and Si of the ingot for a skin material is as follows: (i), (ii) and (iii): (I) Fe content is more than 0.35% by mass and 1.20% by mass or less, Si content is 0.30% by mass or less, and (ii) Fe content is 0. .35% by mass or less, Si content exceeds 0.30% by mass and 1.20% by mass or less, and (iii) Fe content exceeds 0.35% by mass and 1.20 It satisfies any one of the mass% or less and the Si content of more than 0.30 mass% and 1.20 mass% or less, and the Zn content of the ingot for the skin material.
  • the difference (XY) between (X) and the Zn content (Y) of the core ingot is 0.01% by mass or more, Etching the surface by acid cleaning after the hot working, after the cold working, after the intermediate annealing, and after the final annealing.
  • the present invention provides a method for producing a flux-free brazing aluminum alloy clad fin material.
  • the ingot for core material further comprises less than 0.05 mass% Cu, 1.00 mass% or less Mg, 0.20 mass% or less Cr, 0.20 mass%. Any one or more of the following Ti, 0.20 mass% or less Zr, 0.10 mass% or less In, 0.10 mass% or less Sn, and 0.10 mass% or less Bi.
  • the present invention provides a method for producing a flux-free brazing aluminum alloy clad fin material according to (9), which is characterized by containing.
  • the ingot for skin material further comprises Mn of less than 0.10 mass%, Cu of 0.05 mass% or less, Mg of 1.00 mass% or less, 0.20 mass. % Or less Cr, 0.20% by mass or less Ti, 0.20% by mass or less Zr, 0.20% by mass or less Sr, 0.10% by mass or less In, 0.10% by mass or less Sn and (10)
  • the method for producing an aluminum alloy clad fin material for flux-free brazing according to any one of (9) and (10), characterized in that it contains one or more of 0.10 mass% or less of Bi. Is to provide.
  • the present invention (12) also provides the method for producing the flux-free brazed aluminum alloy clad fin material according to (9) to (11), wherein the etching treatment by acid cleaning is performed after the hot working. To do.
  • an aluminum alloy clad fin material as a fin material for a heat exchanger, which can maintain the sacrificial anode effect for a long time and has excellent self-corrosion resistance.
  • the aluminum alloy clad fin material of the present invention is a clad material in which a skin material made of an Al—Zn alloy is clad on both sides of a core material made of an Al—Mn alloy.
  • the core material contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5.50% by mass.
  • the balance consists of an aluminum alloy consisting of aluminum and unavoidable impurities
  • the skin material contains an aluminum alloy containing 0.01 to 5.50% by mass of Zn, Fe and Si, and the balance of aluminum and unavoidable impurities.
  • the Fe content and Si content of the skin material are as follows (i), (ii) and (iii): (I) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is 0.30% by mass or less. (Ii) The Fe content is 0.35% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less. (Iii) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less. Meet one of the The difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is 0.01% by mass or more. Is an aluminum alloy clad fin material.
  • the aluminum alloy clad fin material of the present invention is a clad material in which a skin material made of an Al—Zn alloy is clad on both sides of a core material made of an Al—Mn alloy. That is, the aluminum alloy clad fin material of the present invention includes a core material, a skin material clad on one surface of the core material (skin material 1), and a skin material clad on the other surface of the core material (skin material 2). ) And consist of.
  • the skin material 1 and the skin material 2 may have a coalesced alloy composition or may have different alloy compositions.
  • the core material according to the aluminum alloy clad fin material of the present invention contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, and Si is limited to less than 0.30% by mass.
  • the Zn content is limited to 5.50% by mass or less, and the balance is made of aluminum alloy containing aluminum and unavoidable impurities.
  • the Mn content of the core material is 0.40 to 1.40% by mass, preferably 0.40 to 1.00% by mass.
  • the Mn content of the core material is within the above range, the strength of the aluminum alloy clad fin material is increased.
  • the Mn content of the core material is less than the above range, the effect of improving the strength cannot be sufficiently obtained, and if it exceeds the above range, the self-corrosion resistance becomes low.
  • the Mn content of the core material is preferably 0.40 to 1.00 mass% from the viewpoint of increasing self-corrosion resistance.
  • Fe content of the core material is limited to 0.30 mass% or less, preferably 0.20 mass% or less. Fe contained in the core material easily forms an Al—Fe—Si-based or Al—Fe—Mn-based intermetallic compound, and if the Fe content of the core material exceeds the above range, the self-corrosion resistance becomes low.
  • the Si content of the core material is limited to less than 0.30% by mass, preferably 0.20% by mass or less. Si contained in the core material easily forms an Al-Fe-Si-based or Al-Si-Mn-based intermetallic compound, and if the Si content of the core material exceeds the above range, the self-corrosion resistance becomes low.
  • the core material may or may not contain Zn.
  • the Zn content of the core material is limited to 5.50% by mass or less, preferably less than 2.50% by mass, and particularly preferably less than 1.20% by mass.
  • Zn contained in the heartwood lowers the natural potential of the material and contributes to the sacrificial anticorrosion effect.
  • the core material may or may not contain Zn in the above range. When the Zn content of the core material exceeds the above range, the self-corrosion resistance is lowered.
  • the skin material is preferentially corroded as the sacrificial anode, and then the core material is used as the sacrificial anode. By corroding, a stable sacrificial anode effect can be obtained for a long period of time.
  • the core material can further contain a predetermined amount of any one or more of Mg, Cr, Ti, Zr, Sn, In and Bi.
  • the core material may contain Cu, but in this case, the Cu content of the core material is limited to less than 0.05% by mass, preferably 0.01% by mass or less.
  • the Cu content of the core material is limited to less than 0.05% by mass, preferably 0.01% by mass or less. Cu contained in the core material improves the strength before and after brazing. When the Cu content of the core material exceeds the above range, the self-corrosion resistance becomes low.
  • the Mg content of the core material is 1.00% by mass or less, preferably 0.80% by mass or less. Mg contained in the core material improves the strength before and after brazing. If the Mg content of the core material exceeds the above range, intergranular corrosion occurs and the self-corrosion resistance becomes low.
  • the core material may contain any one or more of Cr, Ti and Zr.
  • the core material contains Cr, the Cr content of the core material is 0.20% by mass or less.
  • the core material contains Ti, the Ti content of the core material is 0.20% by mass or less.
  • the core material contains Zr, the Zr content of the core material is 0.20% by mass or less. If the Cr, Ti or Zr content of the core material exceeds the above range, coarse crystallization is generated during casting, making it difficult to produce a sound plate material.
  • Sn, In and Bi contained in the core material make the natural potential of the material base and contribute to the sacrificial anticorrosion effect.
  • the Sn content of the core material is 0.10% by mass or less, preferably less than 0.05% by mass.
  • the core material contains In the In content of the core material is 0.10 mass% or less, preferably less than 0.05 mass %.
  • the core material contains Bi the Bi content of the core material is 0.10% by mass or less.
  • the skin material related to the aluminum alloy clad fin material of the present invention is made of an aluminum alloy containing 0.01 to 5.50 mass% Zn, Fe and Si, and the balance aluminum and unavoidable impurities.
  • the Fe content and the Si content of the skin material are as follows (i), (ii) and (iii): (I) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is 0.30% by mass or less. (Ii) The Fe content is 0.35% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less. (Iii) The Fe content is more than 0.35% by mass and 1.20% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less. Satisfy any one of them.
  • the Zn content of the skin material is 0.01 to 5.50% by mass, preferably 0.10 to 2.50% by mass, and particularly preferably 0.10 to 1.20% by mass.
  • Zn contained in the skin material lowers the natural potential of the material, contributes to the sacrificial anticorrosion effect, and suppresses the corrosion penetration of the core material.
  • the Zn content of the core material is within the above range, the self-corrosion resistance is increased.
  • the Zn content of the core material exceeds the above range, the self-corrosion resistance becomes low, and if it is less than the above range, the effect of adding Zn cannot be obtained.
  • the skin material contains Fe and Si, and the Fe content and the Si content satisfy any one of the following requirements (i), (ii) and (iii).
  • the Fe content is more than 0.35% by mass and 1.20% by mass or less, preferably 0.40 to 1.00% by mass, and the Si content is 0.30% by mass or less.
  • Fe content is 0.35% by mass or less, and Si content is more than 0.30% by mass and 1.20% by mass or less, preferably 0.35 to 1.00% by mass.
  • the Fe content is more than 0.35% by mass and 1.20% by mass or less, preferably 0.40 to 1.00% by mass, and the Si content is 0.30% by mass. Is more than 1.20% by mass and is preferably 0.35 to 1.00% by mass.
  • the Fe content of the skin material is 0.35 mass% or less and the Si content of the skin material is 0.30 mass% or less, the deformation resistance during hot rolling is low and the core material The difference in deformation resistance from the above becomes large, and the clad rollability decreases. Further, when the Fe content of the skin material exceeds 1.20 mass %, the self-corrosion resistance becomes low. Further, when the Si content of the skin material exceeds 1.20 mass %, the self-corrosion resistance becomes low.
  • the skin material may further contain a predetermined amount of any one kind or two or more kinds of Mn, Cu, Mg, Cr, Ti, Zr, Sr, In, Sn and Bi.
  • the skin material may contain a predetermined amount of Mn, Cr, Ti or Zr in order to adjust the crystal grain size.
  • Mn the Mn content of the skin material is less than 0.10%.
  • Cr the Cr content of the skin material is 0.20% by mass or less.
  • Ti the Ti content of the skin material is 0.20% by mass or less.
  • Zr the Zr content of the skin material is 0.20% by mass or less.
  • the skin material can contain a predetermined amount of Cu, In, Sn or Bi for adjusting the natural electrode potential of the skin material.
  • the skin material contains Cu
  • the Cu content of the skin material is 0.05 mass% or less.
  • the skin material contains In the In content of the skin material is 0.10% by mass or less.
  • the skin material contains Sn the Sn content of the skin material is 0.10 mass% or less.
  • the skin material contains Bi the Bi content of the skin material is 0.10 mass% or less.
  • Mg contained in the skin material reacts with moisture in the usage environment to form a strong oxide film, which improves self-corrosion resistance.
  • the Mg content of the skin material is 1.00% by mass or less, preferably less than 0.80% by mass.
  • the self-corrosion resistance is increased.
  • the Mg content of the skin material exceeds the above range, intergranular corrosion occurs and the self-corrosion resistance becomes low.
  • the skin material may contain 0.20 mass% or less of Sr in order to adjust the size of the dendrite structure when the wax of the mating material to be joined solidifies.
  • the inevitable impurities contained in the core material or the skin material include Ag, B, Be, Ca, Cd, Co, Ga, Ge, Li, Mo, Na, Ni, P, Pb, V, Hg.
  • the aluminum alloy clad fin material of the present invention may contain each of these unavoidable impurities in an amount of 0.05 mass% or less.
  • the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is 0.01% by mass or more, preferably 0. .10% by mass or more.
  • the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is within the above range, the self-corrosion resistance becomes high.
  • the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is less than the above range, the self-corrosion resistance becomes low.
  • the upper limit of the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is preferably 5.50% by mass. ..
  • the (XY) value can be up to 5.50 mass %, and in the aluminum alloy clad fin material of the present invention, the larger the (XY) value is, Corrosion resistance is increased.
  • the composition of the skin material (skin material 1) clad on one surface of the core material and the composition of the skin material (skin material 2) clad on the other surface are
  • the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is 0.01% by mass or more, preferably 0.10% by mass or more. May be the same or different as long as they satisfy the requirement ".”
  • the difference (XY) between the Zn content (X) of the skin material and the Zn content (Y) of the core material is 0.01% by mass or more, preferably 0.10.
  • a potential difference with the core material is formed and a sacrificial anode effect is obtained, so that self-corrosion resistance is enhanced.
  • the Zn content of the skin material is higher than the Zn content of the core material, so that Zn diffusion from the core material to the skin material is prevented during brazing heat addition. Therefore, the potential of the core material does not become lower than the potential of the skin material, and the potential becomes noble as it approaches the core material from the surface of the skin material, so that the sacrificial anode effect can be stably expressed. it can.
  • the aluminum alloy clad fin material of the present invention is used for flux brazing using flux or for flux-free brazing without flux.
  • the aluminum alloy clad fin material of the present invention can be subjected to hot working, cold working, and one or both of intermediate annealing and final annealing.
  • the aluminum alloy clad fin material of the present invention is for flux-free brazing
  • the aluminum alloy clad fin material of the present invention is at least after hot working, after cold working, after intermediate annealing, and after final annealing.
  • it is preferable that the surface is etched by acid cleaning, and it is particularly preferable that the surface is etched by acid cleaning after hot working.
  • the material is washed with a mixed solution of an acid containing a complexing agent such as hydrofluoric acid and an oxidizing acid such as sulfuric acid or nitric acid, It is necessary to remove oxide films and stains that hinder brazing, but acid cleaning a thin plate such as fin material increases cost, so after hot working and as much as possible in the upper process plate thickness. It is preferable to pickle the material in a thick state.
  • the aluminum alloy clad fin material of the present invention may be etched by acid cleaning at a plurality of of hot working, cold working, intermediate annealing and final annealing.
  • the above-mentioned aluminum alloy clad fin material for flux-free brazing is not after the shape of the fin material is processed, but before the fin material is processed. That is, since the surface is etched by acid cleaning after hot working, cold working, intermediate annealing, or final annealing, the cost is low.
  • the aluminum alloy clad fin material of the present invention is preferably manufactured by the method for manufacturing an aluminum alloy clad fin material of the present invention described below. Further, among the aluminum alloy clad fin materials of the present invention, the aluminum alloy clad fin material for flux-free brazing is preferably manufactured by the method for manufacturing an aluminum alloy clad fin material for flux-free brazing of the present invention described below. To.
  • the method for producing the aluminum alloy clad fin material of the present invention is any of hot working, cold working, intermediate annealing and final annealing of a laminate in which an ingot for a skin material is laminated on both sides of an ingot for a core material.
  • the core material ingot contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5.
  • the content is limited to 50% by mass or less
  • the balance is made of an aluminum alloy containing aluminum and inevitable impurities
  • the ingot for skin material contains 0.01 to 5.50% by mass of Zn and contains Fe and Si.
  • the balance is made of an aluminum alloy containing aluminum and unavoidable impurities
  • the Fe content and Si content of the ingot for skin material have the following (i), (ii) and (iii): (i)Fe Content is more than 0.35% by mass and 1.20% by mass or less, Si content is 0.30% by mass or less, and (ii) Fe content is 0.35% by mass.
  • the Si content is more than 0.30% by mass and 1.20% by mass or less, and (iii) the Fe content is more than 0.35% by mass and 1.20% by mass or less. Yes, and the Si content is more than 0.30% by mass and 1.20% by mass or less, whichever is satisfied, and the Zn content (X) of the ingot for the skin material is satisfied.
  • the difference (XY) from the Zn content (Y) of the core ingot is 0.01% by mass or more, And a method for producing an aluminum alloy clad fin material.
  • the method for producing the flux-free brazing aluminum alloy clad fin material of the present invention includes hot working, cold working, and intermediate annealing of a laminate in which an ingot for a skin material is laminated on both sides of an ingot for a core material.
  • a method for producing an aluminum alloy clad fin material which is obtained by performing either one or both of the final annealing and the final annealing to obtain an aluminum alloy clad fin material.
  • the core material ingot contains 0.40 to 1.40% by mass of Mn, Fe is limited to 0.30% by mass or less, Si is limited to less than 0.30% by mass, and Zn is 5.
  • the content is limited to 50% by mass or less
  • the balance is made of an aluminum alloy containing aluminum and inevitable impurities
  • the ingot for skin material contains 0.01 to 5.50% by mass of Zn and contains Fe and Si.
  • the balance is made of an aluminum alloy containing aluminum and unavoidable impurities
  • the Fe content and Si content of the ingot for skin material have the following (i), (ii) and (iii): (i)Fe Content is more than 0.35% by mass and 1.20% by mass or less, Si content is 0.30% by mass or less, and (ii) Fe content is 0.35% by mass.
  • the Si content is more than 0.30% by mass and 1.20% by mass or less, and (iii) the Fe content is more than 0.35% by mass and 1.20% by mass or less. Yes, and the Si content is more than 0.30% by mass and 1.20% by mass or less, whichever is satisfied, and the Zn content (X) of the ingot for the skin material is satisfied.
  • the difference (XY) from the Zn content (Y) of the core material ingot is 0.01% by mass or more, Etching the surface by acid cleaning after the hot working, after the cold working, after the intermediate annealing, and after the final annealing. And a method for producing a flux-free brazing aluminum alloy clad fin material.
  • a laminate in which an ingot for a skin material is laminated on both sides of an ingot for a core material is hot.
  • Manufacture of an aluminum alloy clad fin material by performing hot working for cold working, cold working for cold working, and/or intermediate annealing and/or final annealing to obtain an aluminum alloy clad fin material. Is the way.
  • an aluminum alloy having a desired component composition used for a core material and a skin material is melted.
  • a core material ingot and a skin material ingot are produced by casting.
  • the ingots for skin material are not homogenized, or are homogenized at 600 ° C. or lower, and the ingots for skin material are brought to a predetermined thickness at 400 to 500 ° C. according to a conventional method. Hot rolling. Next, after chamfering the core material ingot and the skin material ingot, the skin material ingot is superposed on both sides of the core material ingot to form a laminate.
  • the ingot for core material according to the method for producing an aluminum alloy clad fin material of the present invention and the flux-free brazing aluminum alloy clad fin material of the present invention contains 0.40 to 1.40 mass% of Mn, and Fe is 0. It is limited to .30% by mass or less, Si is limited to less than 0.30% by mass, Zn is limited to 5.50% by mass or less, and the balance is made of an aluminum alloy consisting of aluminum and unavoidable impurities.
  • the ingot for skin material according to the aluminum alloy clad fin material of the present invention contains 0.01 to 5.50% by mass of Zn, Fe and Si, and the balance is aluminum and unavoidable impurities.
  • the difference between the Zn content (X) of the skin material ingot and the Zn content (Y) of the heart material ingot ( XY) is 0.01% by mass or more, preferably 0.10% by mass or more.
  • the Mn content of the ingot for the core material is 0.40 to 1.40% by mass, preferably 0.40 to 1.00% by mass.
  • the Fe content of the core material ingot is limited to 0.30 mass% or less, preferably 0.20 mass% or less.
  • the Si content of the core material ingot is limited to less than 0.30% by mass, and preferably 0.20% by mass or less.
  • the ingot for the core material may or may not contain Zn. When the ingot for core material contains Zn, the Zn content of the ingot for core material is limited to 5.50% by mass or less, preferably less than 2.50% by mass, and particularly preferably 1.20% by mass. Limited to less than %.
  • the ingot for core material may contain Cu, but the Cu content of the ingot for core material is limited to less than 0.05% by mass, preferably 0.01% by mass or less.
  • the ingot for the core material further includes Mg of 1.00% by mass or less, preferably 0.80% by mass or less, Cr of 0.20% by mass or less, Ti of 0.20% by mass or less, and 0.20% by mass or less.
  • Mg 1.00% by mass or less, preferably 0.80% by mass or less
  • Cr 0.20% by mass or less
  • Ti 0.20% by mass or less
  • 0.20% by mass or less preferably less than 0.05% by mass
  • Sn 0.10% by mass or less
  • 0.10% by mass or less preferably less than 0.05% by mass of In
  • Bi 0.10% by mass or less
  • the Zn content of the ingot for skin material according to the method for producing a flux-free brazing aluminum alloy clad fin material of the present invention is 0.01 to 5.50% by mass, preferably 0.10 to 1.20% by mass. , Particularly preferably 0.10 to 0.80% by mass.
  • the ingot for skin material contains Fe and Si, and the Fe content and the Si content satisfy any one of the following requirements (i), (ii), and (iii).
  • the Fe content is more than 0.35% by mass and 1.20% by mass or less, preferably 0.40 to 1.00% by mass, and the Si content is 0.30% by mass or less. Is.
  • the Fe content is 0.35% by mass or less, and the Si content is more than 0.30% by mass and 1.20% by mass or less, preferably 0.35 to 1.00% by mass.
  • the Fe content is more than 0.35% by mass and 1.20% by mass or less, preferably 0.40 to 1.00% by mass, and the Si content is 0.30% by mass. To 1.20% by mass or less, preferably 0.35 to 1.00% by mass.
  • the skin material further includes Mn of less than 0.10 mass%, Cr of 0.20 mass% or less, Ti of 0.20 mass% or less, Zr of 0.20 mass% or less, and Cu of 0.05 mass% or less. 0.10 mass% or less In, 0.10 mass% or less Sn, 0.10 mass% or less Bi, 1.00 mass% or less, preferably less than 0.80 mass% Mg, and 0.20. Any one or more of Sr of mass% or less can be contained.
  • the aluminum alloy clad fin material of the present invention may contain each of these unavoidable impurities in an amount of 0.05 mass% or less.
  • a laminate in which skin material ingots are laminated on both sides of a core material ingot is hot-rolled.
  • a laminate of the ingot for core material and the ingot for skin material is homogenized at 450 to 650°C for 1 to 20 hours and then at 400 to 550°C. Hot rolling.
  • cold working the hot rolled product obtained by hot working is rolled cold.
  • cold rolling is performed in one or more passes.
  • either one or both of intermediate annealing and final annealing is performed. That is, in the method for producing the aluminum alloy clad fin material of the present invention and the method for producing the flux-free brazing aluminum alloy clad fin material of the present invention, only the intermediate annealing may be performed among the intermediate annealing and the final annealing, and the final annealing may be performed. Only annealing may be performed, or both intermediate annealing and final annealing may be performed. The annealing performed during the cold working pass is the intermediate annealing, and the annealing performed after the final pass of the cold working is the final annealing.
  • intermediate annealing In cold working, when cold rolling is performed in multiple passes, intermediate annealing can be performed between passes.
  • the maximum reached temperature of the intermediate annealing is 150 to 450° C., and the time of the intermediate annealing is 0.5 to 10 hours.
  • final annealing may be performed.
  • the cold rolled product obtained by cold working is annealed at a maximum temperature of 150 to 450 ° C. for 0.5 to 10 hours.
  • the method for producing the aluminum alloy clad fin material for flux-free brazing of the present invention at least after the hot working, after the cold working, after the intermediate annealing, and after the final annealing. In either case, it is preferable to etch the surface by acid cleaning.
  • the method for manufacturing an aluminum alloy clad fin material for flux-free brazing of the present invention in the manufacturing process of the aluminum alloy clad fin material, after hot working, after cold working, or after intermediate annealing. Etching treatment by acid cleaning is performed at least once in the process of either after the final annealing or after the final annealing.
  • the etching treatment by acid cleaning can be performed twice or more.
  • the surface of the material is one of an acid containing a passivation agent such as hydrofluoric acid and an oxidizing acid such as sulfuric acid and nitric acid.
  • a passivation agent such as hydrofluoric acid
  • an oxidizing acid such as sulfuric acid and nitric acid.
  • the cleaning liquid used for acid cleaning examples include an aqueous solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and hydrofluoric acid. From the viewpoint of further enhancing the effect of weakening the oxide film, it is preferable to use an aqueous solution containing hydrofluoric acid as the acid, and an aqueous solution or hydrofluoric acid containing hydrofluoric acid and nitric acid containing an inorganic acid other than hydrofluoric acid. More preferably, an aqueous solution containing and sulfuric acid is used.
  • the inorganic acid for example, one kind or two or more kinds selected from acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid are used. It is particularly preferable to use nitric acid or sulfuric acid as the inorganic acid.
  • the acid cleaning conditions the amount to be etched is preferably 0.05 to 2.00 g / m 2 .
  • the etching amount is 2.00 g / m 2 or less, more preferably 0.50 g / m 2 or less, the oxide film is sufficiently weakened, the time required for etching is shortened, and the productivity is further improved. Can be made to.
  • brazing that does not use flux in an inert gas (flux-free brazing)
  • an aluminum alloy clad fin material is obtained by carrying out the method for producing an aluminum alloy clad fin material of the present invention. Further, by performing the method for producing an aluminum alloy clad fin material for flux-free brazing of the present invention, a more preferable aluminum alloy clad fin material for flux-free brazing can be obtained.
  • the ingot for bare fin which is to be compared with the ingot for core material of clad fin in Table 1, and the ingot for skin material in Table 2, were ingot-cast by continuous casting.
  • the core material is chamfered to a predetermined thickness
  • the skin material is hot-rolled to a predetermined thickness
  • each material is laminated in the combination shown in Table 3, and hot-rolled, cold-rolled 1,
  • the thickness was adjusted to 0.1 mm through intermediate annealing and cold rolling 2.
  • the clad ratio was set to 10%.
  • the core material was Al-0.5Cu-1.2Mn
  • the skin material was Al-10Si
  • the clad ratio of the skin material was 10%.
  • the brazing sheet After masking the core material side of the brazing sheet with a silicone resin, hold it in an aqueous solution containing 975 ppm chloride ion, 300 ppm sulfate ion, 150 ppm iron ion (trivalent), 5 ppm copper ion (divalent) at a temperature cycle of 88°C for 8 hours. After immersing for 240 hours in a cycle of holding at room temperature for 16 hours, the amount of mass loss was measured and the presence or absence of penetration of the brazing sheet was observed. The amount of mass loss is obtained by subtracting the mass of the test piece from which the corrosion products have been removed after the test from the mass of the test piece before the corrosion test and dividing by the test area.
  • Table 3 shows the observation results of the amount of mass reduction and the presence or absence of penetration.
  • the amount of mass reduction and the presence or absence of penetration of the brazing sheet in the examples of the present invention and the comparative examples, those having the same Zn content of the core material and the bare fin material of the clad fin of the present invention are compared with each other. This is because the self-corrosion resistance changes depending on the Zn concentration, and therefore the performance of the clad fin and the bare fin is compared under the same precondition.
  • ⁇ is 70% or less with respect to bare fins having the same Zn content as the core material
  • x is 70% or more.
  • test body C5 did not clad the skin material, the self-corrosion resistance was lowered, and the sacrificial anode effect was not sufficiently exerted, and the brazing sheet was pierced. Since C6 does not clad the skin material, the self-corrosion resistance is lowered.
  • test body C7 the content of Si and Fe in the skin material was out of the range, and the self-corrosion resistance was lowered.
  • C8 the Si content of the core material was out of the range, and the self-corrosion resistance was lowered.
  • C9 the Fe content of the core material was out of the range, and the self-corrosion resistance was lowered.

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Abstract

La présente invention concerne un matériau d'ailette revêtu d'alliage d'aluminium caractérisé en ce qu'il comprend un matériau de revêtement dans lequel les deux surfaces d'un noyau sont revêtues d'un matériau de revêtement, le noyau comprenant un alliage d'aluminium contenant 0,40 à 1,40 % en masse de Mn, Fe étant limité à 0,30 % en masse ou moins, Si étant limité à moins de 0,30 % en masse, Zn étant limité à 5,50 % en masse ou moins, et le reste comprenant de l'aluminium et des impuretés inévitables, le matériau de revêtement comprenant un alliage d'aluminium contenant 0,01 à 5,50 % en masse de Zn, et contenant Fe et Si, le reste comprenant de l'aluminium et des impuretés inévitables, la teneur en Fe dans le matériau de revêtement étant supérieure à 0,35 % en masse et inférieure ou égale à 1,20 % en masse, ou la teneur en Si dans le matériau de revêtement étant supérieure à 0,30 % en masse et inférieure ou égale à 1,20 % en masse, et la différence (X – Y) entre la teneur en Zn (X) du matériau de revêtement et la teneur en Zn (Y) du noyau étant de 0,01 % en masse ou plus.　Grâce à la présente invention, il est possible de fournir un matériau d'ailette revêtu d'alliage d'aluminium en tant que matériau d'ailette d'échange thermique ayant une excellente résistance à la corrosion, ce par quoi un effet d'anode sacrificielle peut être maintenu pendant une longue période.
PCT/JP2020/006769 2019-03-01 2020-02-20 Matériau d'ailette revêtu d'alliage d'aluminium présentant une excellente résistance à la corrosion, et son procédé de fabrication WO2020179467A1 (fr)

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CN112626400B (zh) * 2020-12-10 2022-04-15 中国兵器科学研究院宁波分院 一种高韧性铝合金及其制备方法

Citations (7)

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Publication number Priority date Publication date Assignee Title
JPS60138037A (ja) * 1983-12-26 1985-07-22 Mitsubishi Alum Co Ltd 高温強度および犠牲陽極効果のすぐれた熱交換器用Ａｌ合金製複合フイン材
JPS6254091A (ja) * 1985-08-31 1987-03-09 Furukawa Alum Co Ltd 熱交換器用ブレ−ジングシ−トの製造方法
JPH01102297A (ja) * 1987-10-14 1989-04-19 Mitsubishi Alum Co Ltd ろう付け性と耐食性にすぐれた熱交換器用Ａｌ合金複合フィン材
JPH01198453A (ja) * 1988-02-01 1989-08-10 Furukawa Alum Co Ltd 高熱伝導性アルミニウム合金フィン材の製造方法
JPH03100143A (ja) * 1989-09-14 1991-04-25 Furukawa Alum Co Ltd ろう付け用アルミニウム合金フィン材の製造方法
JPH07207394A (ja) * 1994-01-17 1995-08-08 Mitsubishi Alum Co Ltd ろう付け性に優れたＡｌ合金フィン材
JPH07252566A (ja) * 1994-03-16 1995-10-03 Mitsubishi Alum Co Ltd 高強度を有する熱交換器Ａｌ合金フィン材

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60138037A (ja) * 1983-12-26 1985-07-22 Mitsubishi Alum Co Ltd 高温強度および犠牲陽極効果のすぐれた熱交換器用Ａｌ合金製複合フイン材
JPS6254091A (ja) * 1985-08-31 1987-03-09 Furukawa Alum Co Ltd 熱交換器用ブレ−ジングシ−トの製造方法
JPH01102297A (ja) * 1987-10-14 1989-04-19 Mitsubishi Alum Co Ltd ろう付け性と耐食性にすぐれた熱交換器用Ａｌ合金複合フィン材
JPH01198453A (ja) * 1988-02-01 1989-08-10 Furukawa Alum Co Ltd 高熱伝導性アルミニウム合金フィン材の製造方法
JPH03100143A (ja) * 1989-09-14 1991-04-25 Furukawa Alum Co Ltd ろう付け用アルミニウム合金フィン材の製造方法
JPH07207394A (ja) * 1994-01-17 1995-08-08 Mitsubishi Alum Co Ltd ろう付け性に優れたＡｌ合金フィン材
JPH07252566A (ja) * 1994-03-16 1995-10-03 Mitsubishi Alum Co Ltd 高強度を有する熱交換器Ａｌ合金フィン材

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