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WO2017007019A1 - Matériau plaqué en alliage d'aluminium ainsi que procédé de fabrication de celui-ci, et échangeur de chaleur mettant en œuvre ce matériau plaqué en alliage d'aluminium - Google Patents

Matériau plaqué en alliage d'aluminium ainsi que procédé de fabrication de celui-ci, et échangeur de chaleur mettant en œuvre ce matériau plaqué en alliage d'aluminium Download PDF

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Publication number
WO2017007019A1
WO2017007019A1 PCT/JP2016/070277 JP2016070277W WO2017007019A1 WO 2017007019 A1 WO2017007019 A1 WO 2017007019A1 JP 2016070277 W JP2016070277 W JP 2016070277W WO 2017007019 A1 WO2017007019 A1 WO 2017007019A1
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Prior art keywords
mass
aluminum alloy
brazing
clad
brazing material
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Ceased
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PCT/JP2016/070277
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English (en)
Japanese (ja)
Inventor
太一 浅野
真樹 原田
手島　聖英
安藤　誠
渉 成田
尚希 山下
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UACJ Corp
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UACJ Corp
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Publication date
Priority claimed from JP2016132727A external-priority patent/JP6713861B2/ja
Application filed by UACJ Corp filed Critical UACJ Corp
Priority to US15/742,418 priority Critical patent/US10625379B2/en
Priority to EP16821487.2A priority patent/EP3321384B1/fr
Priority to CN201680035541.5A priority patent/CN107849645B/zh
Publication of WO2017007019A1 publication Critical patent/WO2017007019A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal

Definitions

  • the present invention relates to a highly corrosion-resistant aluminum alloy clad material suitably used as a refrigerant or high-temperature compressed air passage component in a heat exchanger such as a radiator, and a method for producing the same. Furthermore, the present invention relates to a heat exchanger for an automobile or the like provided with a flow path forming component using the highly corrosion-resistant aluminum alloy clad material.
  • Aluminum alloy is lightweight and has high thermal conductivity, and high corrosion resistance can be realized by appropriate treatment, so it is used for heat exchangers for automobiles, such as radiators, condensers, evaporators, heaters, intercoolers, oil coolers, etc. It has been.
  • a tube material for an automotive heat exchanger an Al—Mn alloy such as 3003 alloy is used as a core material, and an Al—Si alloy brazing material or an Al—Zn alloy sacrificial anode material is provided on one side of the tube material.
  • a two-layer clad material clad with an Al—Si alloy brazing material on the other surface is used.
  • the heat exchanger is usually joined by combining such a clad material and a corrugated fin material and brazing at a high temperature of about 600 ° C.
  • FIG. 1 As a means for forming a cooling water flow path in the heat exchanger, as shown in FIG. 1, a method of laminating a plate 1 that forms a cooling water flow path through a corrugated fin 2 by forming a clad material. There is.
  • This method has an advantage that the degree of freedom in design is high because the size of the heat exchanger can be changed simply by changing the number of stacks.
  • it is necessary to supply the brazing from the plate material itself during brazing.
  • the brazing is supplied to the inner surface of the flow path of the material used for the flow path forming component at the time of brazing, and the holes It is necessary to clad a layer having a plurality of functions such as having a sacrificial anticorrosion function against corrosion and preventing the occurrence of corrosion due to local strong alkalinization.
  • Patent Documents 1 and 2 describe a technique for supplying brazing at the time of brazing and imparting a sacrificial anticorrosion function to pitting corrosion.
  • a liquid phase brazing is formed at the time of brazing to enable bonding, and a part of the cladding layer is made of a solid phase.
  • the solidified structure generated after brazing due to melting of the clad layer becomes a primary phase and a eutectic phase.
  • JP 2010-255013 A International Publication No. 2011/034102
  • brazing is supplied at the time of brazing addition heat, and after sacrificial heating, it has a sacrificial anticorrosion function and is also localized It has been difficult to provide an aluminum alloy clad material that prevents corrosion due to alkalinization by conventional techniques.
  • the present invention has been completed to solve such problems, and in an aluminum alloy clad material, brazing is supplied at the time of brazing addition heat, and after sacrificial heating, it has a sacrificial anticorrosion function, and is also localized.
  • An object of the present invention is to provide a highly corrosion-resistant aluminum alloy clad material that prevents corrosion due to alkalinization, and a flow path forming part for a heat exchanger such as an automobile using the same.
  • the present inventors prepared a core material, a brazing material (first and second), and a sacrificial anode material each having a specific alloy composition and metal structure, and one or both of the core materials.
  • the above-mentioned problem is solved by a clad material in which a first brazing material is clad on one surface and a clad material in which a first brazing material is clad on one surface of a core material and a sacrificial anode material or a second brazing material is clad on the other surface.
  • the present invention has been completed.
  • the core material comprises Si: 0.05 to 1 .50 mass%, Fe: 0.05 to 2.00 mass%, Mn: 0.5 to 2.0 mass%, the balance being made of an aluminum alloy composed of Al and inevitable impurities, wherein the first brazing material is Si : 2.5 to 7.0 mass%, Fe: 0.05 to 1.20 mass%, Zn: 0.5 to 8.0 mass%, Mn: 0.3 to 2.0 mass%, balance Al and inevitable
  • the presence density of the Al—Mn intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more in the first brazing filler metal is 1.0 ⁇ .
  • the presence density of Al—Mn intermetallic compounds having an equivalent circle diameter of 2 ⁇ m or more in the first brazing material after the brazing heat is 300 pieces / mm 2 or more. It was set as the characteristic aluminum alloy clad material.
  • the first brazing material is Cu: 0.05 to 0.60 mass%, Ti: 0.05 to 0.30 mass%, Zr: 0.05 to 0.30 mass. %, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass%, and an aluminum alloy further containing one or more selected from Cr.
  • the first brazing material is one or two selected from Na: 0.001 to 0.050 mass% and Sr: 0.001 to 0.050 mass%. It was made of an aluminum alloy further containing seeds.
  • the core material according to any one of the first to third aspects includes Mg: 0.05 to 0.50 mass%, Cu: 0.05 to 1.50 mass%, and Ti: 0.05.
  • Mg 0.05 to 0.50 mass%
  • Cu 0.05 to 1.50 mass%
  • Ti 0.05.
  • the aluminum alloy contained was used.
  • the present invention provides the method for producing an aluminum alloy clad material according to any one of claims 1 to 4, wherein the aluminum alloy for the core material and the first brazing material are respectively casted.
  • a hot rolling process in which the ingot of the cast first brazing material is hot-rolled to a predetermined thickness, and one or both surfaces of the core material ingot are clad with the first brazing material having a predetermined thickness by hot rolling.
  • One or more annealing steps for annealing the clad material in one or both after the rolling step, and the hot rolling step of the first brazing material includes a heating step, a holding step, and a hot rolling step, and heating In stage 4,
  • the temperature rising rate until reaching 0 ° C. is 30 ° C./h or more, the temperature rising rate from reaching 400 ° C. to reaching the holding temperature in the holding stage is 60 ° C./h or less, and the holding temperature in the holding stage is 450.degree. C.
  • the holding time is 1 hour or longer
  • the time during which the temperature of the first brazing material is 400.degree. C. or higher is 5 minutes or longer during the hot rolling stage.
  • a method for producing a clad material was adopted.
  • the present invention provides, in claim 6, an aluminum alloy clad comprising an aluminum alloy core material, a first brazing material clad on one surface of the core material, and a second brazing material clad on the other surface of the core material.
  • the core material contains Si: 0.05 to 1.50 mass%, Fe: 0.05 to 2.00 mass%, Mn: 0.5 to 2.0 mass%, and the remainder from Al and inevitable impurities
  • the first brazing filler metal is made of an aluminum alloy having the following composition: Si: 2.5 to 7.0 mass%, Fe: 0.05 to 1.20 mass%, Zn: 0.5 to 8.0 mass%, Mn: 0.00.
  • the second brazing filler metal is Si: 2.5 to 13.0 mass%
  • Fe 0.05 to 1.20 m
  • the first brazing material is Cu: 0.05 to 0.60 mass%, Ti: 0.05 to 0.30 mass%, Zr: 0.05 to 0.30 mass. %, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass%, and an aluminum alloy further containing one or more selected from Cr.
  • the first brazing material is one or two selected from Na: 0.001 to 0.050 mass% and Sr: 0.001 to 0.050 mass%. It was made of an aluminum alloy further containing seeds.
  • the core material according to any one of the sixth to eighth aspects includes: Mg: 0.05 to 0.50 mass%, Cu: 0.05 to 1.50 mass%, Ti: 0.05. One or more selected from ⁇ 0.30 mass%, Zr: 0.05 to 0.30 mass%, Cr: 0.05 to 0.30 mass% and V: 0.05 to 0.30 mass% The aluminum alloy contained was used.
  • the second brazing material is Mn: 0.05 to 2.00 mass%, Cu: 0.05 to 1.50 mass%, Ti: One or two selected from 0.05 to 0.30 mass%, Zr: 0.05 to 0.30 mass%, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass%
  • the aluminum alloy further contains the above.
  • the second brazing material is selected from Na: 0.001 to 0.050 mass% and Sr: 0.001 to 0.050 mass%. It was made of an aluminum alloy further containing one or two kinds.
  • the present invention provides the method for producing an aluminum alloy clad material according to any one of claims 6 to 11, wherein the aluminum alloy for the core material, the first brazing material, and the second brazing material is defined in claim 12. , A hot rolling process in which the cast ingots of the first brazing material and the second brazing material are each hot-rolled to a predetermined thickness, and one surface of the core material ingot is predetermined by hot rolling.
  • a clad process in which the first brazing material having a thickness is clad with a second brazing material having a predetermined thickness by hot rolling on the other surface, and a hot clad rolling process in which the clad material is hot-rolled A cold rolling step of cold rolling the clad material that has been hot-clad rolled, and one or more annealing steps of annealing the clad material in one or both of the middle of the cold rolling step and after the cold rolling step;
  • the hot rolling process of the first brazing filler metal includes a heating stage, a holding stage, and a hot rolling stage, and in the heating stage, the rate of temperature rise until reaching 400 ° C. is 30 ° C./h or more, reaching 400 ° C.
  • the heating rate from the time until reaching the holding temperature in the holding stage is 60 ° C./h or less, the holding temperature in the holding stage is 450 ° C. or more and 560 ° C. or less, the holding time is 1 hour or more, and the hot rolling stage
  • the method for producing an aluminum alloy clad material characterized in that the time during which the temperature of the first brazing material is 400 ° C. or higher is 5 minutes or longer.
  • an aluminum alloy clad material comprising: an aluminum alloy core material; a first brazing material clad on one surface of the core material; and a sacrificial anode material clad on the other surface of the core material.
  • the core material contains Si: 0.05 to 1.50 mass%, Fe: 0.05 to 2.00 mass%, Mn: 0.5 to 2.0 mass%, and the balance is Al and inevitable impurities.
  • the first brazing material is Si: 2.5-7.0 mass%, Fe: 0.05-1.20 mass%, Zn: 0.5-8.0 mass%, Mn: 0.3
  • the sacrificial anode material contains Zn: 0.5 to 8.0 mass%, Si: 0.05 to 1.50 m.
  • Al—Mn-based metal having an abundance density of Al—Mn-based intermetallic compound of 1.0 ⁇ 10 5 pieces / mm 2 or more and having an equivalent circle diameter of 2 ⁇ m or more in the first brazing material after the heat of brazing addition
  • An aluminum alloy clad material characterized in that the density of intermetallic compounds is 300 / mm 2 or more.
  • the first brazing material is Cu: 0.05 to 0.60 mass%, Ti: 0.05 to 0.30 mass%, Zr: 0.05 to 0.30 mass. %, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass%, and an aluminum alloy further containing one or more selected from Cr.
  • the first brazing material is one or two selected from Na: 0.001 to 0.050 mass% and Sr: 0.001 to 0.050 mass%. It was made of an aluminum alloy further containing seeds.
  • the core material is Mg: 0.05 to 0.50 mass%, Cu: 0.05 to 1.50 mass%, Ti: 0.05.
  • the aluminum alloy contained was used.
  • the sacrificial anode material includes Ni: 0.05 to 2.00 mass%, Mn: 0.05 to 2.00 mass%, and Mg: 0. .05 to 3.00 mass%, Ti: 0.05 to 0.30 mass%, Zr: 0.05 to 0.30 mass%, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass
  • the aluminum alloy further contains one or more selected from%.
  • the present invention according to claim 18, wherein the aluminum alloy for the core material, the first brazing material, and the sacrificial anode material are respectively casted, and the ingots of the cast first brazing material and sacrificial anode material are each set to a predetermined thickness.
  • One or more annealing steps for annealing the clad material in one or both after the cold rolling step, and the hot rolling step of the first brazing material includes a heating step, a holding step, and a hot rolling step.
  • the rate of temperature rise until reaching 400 ° C. is 30 ° C./h or more, and the rate of temperature rise from reaching 400 ° C. to reaching the holding temperature in the holding stage is 60 ° C./h or less.
  • the temperature is 450 ° C. or more and 560 ° C.
  • the holding time is 1 hour or more
  • the time that the temperature of the first brazing material is 400 ° C. or more is 5 minutes or more.
  • the present invention provides a heat exchanger according to claim 19, wherein the aluminum alloy clad material according to any one of claims 1 to 4 is used for at least a flow path forming component, wherein at least one of the first brazing material surfaces
  • the heat exchanger was characterized by being exposed to a solution having a chloride ion concentration of 1200 ppm or less.
  • the present invention provides a heat exchanger according to claim 20, wherein the aluminum alloy clad material according to any one of claims 6 to 11 and 13 to 17 is used for at least a flow path forming component, wherein the first brazing material
  • the heat exchanger is characterized in that the surface is exposed to a solution having a chloride ion concentration of 1200 ppm or less.
  • an aluminum alloy clad material that supplies brazing at the time of brazing addition heat, has a sacrificial anticorrosion function after brazing heat addition, and prevents corrosion due to local alkalinization, and an automobile using the same
  • a heat exchanger flow path forming component is provided.
  • This clad material is excellent in brazing properties such as erosion resistance, and is suitably used as a flow path forming component material for heat exchangers for automobiles and the like from the viewpoint of light weight and good thermal conductivity.
  • the aluminum alloy clad material of the present invention has brazing properties by appropriately controlling the alloy composition and metal structure of the first brazing material that has both brazing and sacrificial corrosion resistance. In addition, it has excellent corrosion resistance.
  • the first brazing material may be clad on one surface of the core material to form a two-layer clad material, or may be clad on both surfaces of the core material to form a three-layer clad material.
  • a three-layer clad material in which a second brazing material, which is a normal Al—Si alloy brazing material, is clad on the other surface of the core material not clad with the first brazing material may be used.
  • a three-layer clad material clad with an Al—Zn alloy sacrificial anode material may be used.
  • the first brazing material includes: Si: 2.5 to 7.0 mass% (hereinafter simply referred to as “%”), Fe: 0.05 to 1.20%, Zn: 0.5 to 8 An aluminum alloy containing 0.0%, Mn: 0.3 to 2.0% as an essential element, and the balance being Al and inevitable impurities is used.
  • the first brazing filler metal is Cu: 0.05-0.60%, Ti: 0.05-0.30%, Zr: 0.05-0.30%, Cr: 0.05-0.30. % And V: One or more selected from 0.05 to 0.30% may be further contained as the first selective additive element. Furthermore, the first brazing material contains one or two selected from Na: 0.001 to 0.050% and Sr: 0.001 to 0.050% as a second selective additive element. Also good. In addition to the essential elements and the first and second selective additive elements, unavoidable impurities may be contained in amounts of 0.05% or less, respectively, and 0.15% in total. Below, each component is demonstrated.
  • Si By adding Si, the melting point of the brazing material is lowered to form a liquid phase, thereby enabling brazing.
  • a general alloy for brazing filler metals allows an upper limit of up to about 11% if it is a 4045 alloy, but by keeping this low, a certain proportion remains in the solid phase at the time of brazing, and excellent sacrificial corrosion protection Functions can be added.
  • the Si content is 2.5 to 7.0%. If it is less than 2.5%, the resulting liquid phase is small and it becomes difficult to obtain a brazing function. On the other hand, if it exceeds 7.0%, for example, the amount of Si diffused into the counterpart material such as fins becomes excessive, and the counterpart material will melt.
  • a preferable content of Si is 3.5 to 6.0%.
  • Fe Fe easily forms intermetallic compounds of Al-Fe, Al-Fe-Si, Al-Fe-Mn, and Al-Fe-Mn-Si, reducing the amount of Si effective for brazing. Causing a reduction in brazability.
  • the Fe content is 0.05 to 1.20%. If it is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs. On the other hand, if it exceeds 1.20%, the amount of Si effective for brazing is reduced and brazing becomes insufficient.
  • a preferable content of Fe is 0.1 to 0.5%.
  • Zn can lower the pitting corrosion potential, and can improve the corrosion resistance due to the sacrificial anticorrosion effect by forming a potential difference with the core material.
  • the Zn content is 0.5 to 8.0%. If it is less than 0.5%, the effect of improving the corrosion resistance due to the sacrificial anticorrosive effect cannot be sufficiently obtained. On the other hand, if it exceeds 8.0%, the corrosion rate increases, the sacrificial anticorrosion layer disappears early, and the corrosion resistance decreases.
  • a preferable content of Zn is 1.0 to 6.0%.
  • Mn forms Al—Mn, Al—Fe—Mn, and Al—Fe—Mn—Si intermetallic compounds (hereinafter, simply referred to as “Al—Mn intermetallic compounds”).
  • Al—Mn intermetallic compounds By activating the cathode reaction, the corrosion potential can be made noble and pitting corrosion can be easily generated.
  • Mn has the effect of preventing local alkalization and improving corrosion resistance.
  • the Mn content is 0.3 to 2.0%. If it is less than 0.3%, the above effect cannot be obtained sufficiently. On the other hand, if it exceeds 2.0%, a giant intermetallic compound is likely to be formed during casting, and the plastic workability is lowered.
  • the Mn content is preferably 0.4 to 1.8%.
  • Cu Since Cu improves strength by solid solution strengthening, Cu may be contained.
  • the Cu content is 0.05 to 0.60%. If it is less than 0.05%, the above effect is insufficient, and if it exceeds 0.60%, the pitting potential becomes noble, and the sacrificial anticorrosive effect by Zn is lost.
  • the Cu content is preferably 0.10 to 0.50%.
  • Ti may be contained because it improves strength and improves corrosion resistance by solid solution strengthening.
  • the Ti content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Ti content is preferably 0.10 to 0.20%.
  • Zr may be contained because it has the effect of improving the strength by solid solution strengthening and precipitating Al—Zr-based intermetallic compounds to coarsen the crystal grains after the heat of brazing addition.
  • the Zr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Zr content is preferably 0.10 to 0.20%.
  • Cr Cr may be contained because it has the effect of improving strength by solid solution strengthening and precipitating Al—Cr-based intermetallic compounds to coarsen crystal grains after brazing addition heat.
  • the Cr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Cr content is preferably 0.10 to 0.20%.
  • V may be contained because it improves the strength by solid solution strengthening and also improves the corrosion resistance.
  • the V content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the V content is preferably 0.10 to 0.20%.
  • Na, Sr Na and Sr exhibit the effect of refining the Si particles in the first brazing material.
  • the contents of Na and Sr are 0.001 to 0.050%, respectively. If the respective contents are less than 0.001%, the above effects cannot be obtained sufficiently. On the other hand, when each content exceeds 0.050%, an oxide film becomes thick and brazeability is reduced. Each preferable content is 0.003 to 0.020%.
  • Core material contains Si: 0.05 to 1.50%, Fe: 0.05 to 2.00%, Mn: 0.5 to 2.0% as essential elements, the balance Al and inevitable impurities An aluminum alloy is used.
  • the core material is Mg: 0.05 to 0.50%, Cu: 0.05 to 1.50%, Ti: 0.05 to 0.30%, Zr: 0.05 to 0.30%, Cr
  • One or more selected from: 0.05 to 0.30% and V: 0.05 to 0.30% may be further contained as a selective additive element.
  • unavoidable impurities may be contained in amounts of 0.05% or less, respectively, and 0.15% in total.
  • a JIS 3000 series alloy for example, an Al—Mn series alloy such as JIS 3003 alloy is preferably used.
  • JIS 3003 alloy a JIS 3000 series alloy
  • each component is demonstrated in detail.
  • Si forms an Al-Fe-Mn-Si intermetallic compound together with Fe and Mn and improves strength by dispersion strengthening, or improves strength by solid solution strengthening by solid solution in an aluminum matrix. .
  • the Si content is 0.05 to 1.50%. If it is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs. If it exceeds 1.50%, the melting point of the core material is lowered and the possibility of melting is increased.
  • a preferable content of Si is 0.10 to 1.20%.
  • Fe forms an Al—Fe—Mn—Si intermetallic compound together with Si and Mn, and improves the strength by dispersion strengthening.
  • the amount of Fe added is 0.05 to 2.00%. If the content is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs. On the other hand, if it exceeds 2.00%, a giant intermetallic compound is easily formed during casting, and the plastic workability is lowered.
  • a preferable content of Fe is 0.10 to 1.50%.
  • Mn forms an Al—Mn—Si intermetallic compound together with Si, and an Al—Mn—Fe—Si intermetallic compound together with Si and Fe to improve strength by dispersion strengthening, or an aluminum matrix. Strengthened by solid solution in the phase and solid solution strengthening.
  • the Mn content is 0.5 to 2.0%. If the content is less than 0.5%, the above effect is insufficient. If the content exceeds 2.0%, a giant intermetallic compound is easily formed during casting, and the plastic workability is lowered.
  • a preferable content of Mn is 0.8 to 1.8%.
  • Mg may be contained because the strength is improved by precipitation of Mg 2 Si.
  • the Mg content is 0.05 to 0.50%. If it is less than 0.05%, the above effect is insufficient, and if it exceeds 0.50%, brazing becomes difficult.
  • the Mg content is preferably 0.10 to 0.40%.
  • Cu Since Cu improves strength by solid solution strengthening, Cu may be contained.
  • the Cu content is 0.05 to 1.50%. If it is less than 0.05%, the above effect is insufficient, and if it exceeds 1.50%, there is a high risk of cracking of the aluminum alloy during casting.
  • the Cu content is preferably 0.30 to 1.00%.
  • Ti may be contained because it improves the strength by solid solution strengthening.
  • the Ti content is 0.05 to 0.30%. If it is less than 0.05%, the above effect is insufficient. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Ti content is preferably 0.10 to 0.20%.
  • Zr may be contained because it has the effect of improving the strength by solid solution strengthening and precipitating Al—Zr-based intermetallic compounds to coarsen the crystal grains after the heat of brazing addition.
  • the Zr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Zr content is preferably 0.10 to 0.20%.
  • Cr Cr may be contained because it has the effect of improving strength by solid solution strengthening and precipitating Al—Cr-based intermetallic compounds to coarsen crystal grains after brazing addition heat.
  • the Cr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Cr content is preferably 0.10 to 0.20%.
  • V may be contained because it improves the strength by solid solution strengthening and also improves the corrosion resistance.
  • the V content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the V content is preferably 0.10 to 0.20%.
  • Mg, Cu, Ti, Zr, Cr, and V may be added to the core material if necessary.
  • Sacrificial anode material contains Zn: 0.5 to 8.0%, Si: 0.05 to 1.50%, Fe: 0.05 to 2.00% as essential elements, and the balance Al In addition, an aluminum alloy made of inevitable impurities is used.
  • Sacrificial anode materials are Ni: 0.05 to 2.00%, Mn: 0.05 to 2.00%, Mg: 0.05 to 3.00%, Ti: 0.05 to 0.30%
  • One or more selected from Zr: 0.05 to 0.30%, Cr: 0.05 to 0.30 mass%, and V: 0.05 to 0.30 mass% are further added as selective additive elements. You may contain. Furthermore, in addition to the above essential elements and selective additive elements, 0.05% or less each of unavoidable impurities may be contained in total, and 0.15% in total. Below, each component is demonstrated.
  • Zn can lower the pitting corrosion potential, and can improve the corrosion resistance due to the sacrificial anticorrosion effect by forming a potential difference with the core material.
  • the Zn content is 0.5 to 8.0%. If it is less than 0.5%, the effect of improving the corrosion resistance due to the sacrificial anticorrosive effect cannot be sufficiently obtained. On the other hand, if it exceeds 8.0%, the corrosion rate increases, the sacrificial anticorrosion layer disappears early, and the corrosion resistance decreases.
  • a preferable content of Zn is 1.0 to 6.0%.
  • Si forms an Al—Fe—Si based intermetallic compound with Fe, and when it contains Mn at the same time, forms an Al—Fe—Mn—Si based intermetallic compound with Fe and Mn,
  • the strength is improved by dispersion strengthening, or the solid strength is improved by solid solution strengthening in the aluminum matrix.
  • Si makes the potential of the sacrificial anode layer noble, the sacrificial anticorrosive effect is hindered and the corrosion resistance is lowered.
  • the Si content is 0.05 to 1.50%. If the content is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs.
  • a preferable content of Si is 0.10 to 1.20%.
  • Fe forms an Al—Fe—Si intermetallic compound together with Si, and if it contains Mn simultaneously, forms an Al—Fe—Mn—Si intermetallic compound together with Si and Mn, Strength is improved by dispersion strengthening.
  • the amount of Fe added is 0.05 to 2.00%. If the content is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs. On the other hand, if it exceeds 2.00%, a giant intermetallic compound is easily formed during casting, and the plastic workability is lowered.
  • a preferable content of Fe is 0.10 to 1.50%.
  • Ni forms an Al-Ni-based or Al-Fe-Ni-based intermetallic compound together with Fe. Since these intermetallic compounds have a higher corrosion potential than aluminum matrix and are noble, they act as corrosion cathode sites. Therefore, when these intermetallic compounds are dispersed in the sacrificial anode material, the starting point of corrosion is dispersed. As a result, corrosion in the depth direction is difficult to proceed, and the corrosion resistance is improved.
  • the Ni content is 0.05 to 2.00%. If the content is less than 0.05%, the above effect cannot be obtained sufficiently. On the other hand, if it exceeds 2.00%, a giant intermetallic compound is easily formed during casting, and the plastic workability is lowered.
  • the Ni content is preferably 0.10 to 1.50%.
  • Mn may be contained because it improves strength and corrosion resistance.
  • the Mn content is 0.05 to 2.00%. If it exceeds 2.00%, a huge intermetallic compound is likely to be formed during casting, and the plastic workability is lowered. On the other hand, if it is less than 0.05%, the effect cannot be sufficiently obtained.
  • the Mn content is preferably 0.05 to 1.80%.
  • Mg Since Mg improves the strength of the sacrificial anode material by precipitation of Mg 2 Si, it may be contained. In addition to improving the strength of the sacrificial anode material itself, brazing causes Mg to diffuse from the sacrificial anode material to the core material, thereby improving the strength of the core material. For these reasons, Mg may be included.
  • the Mg content is 0.05 to 3.00%. If it is less than 0.05%, the above effect cannot be obtained sufficiently. On the other hand, if it exceeds 3.00%, it becomes difficult to press the sacrificial anode material and the core material in the hot clad rolling process.
  • a preferable content of Mg is 0.10 to 2.00%.
  • Ti may be contained because it improves strength and improves corrosion resistance by solid solution strengthening.
  • the Ti content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Ti content is preferably 0.05 to 0.20%.
  • Zr may be contained because it has the effect of improving the strength by solid solution strengthening and precipitating Al—Zr-based intermetallic compounds to coarsen the crystal grains after the heat of brazing addition.
  • the Zr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Zr content is preferably 0.10 to 0.20%.
  • Cr Cr may be contained because it has the effect of improving strength by solid solution strengthening and precipitating Al—Cr-based intermetallic compounds to coarsen crystal grains after brazing addition heat.
  • the Cr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Cr content is preferably 0.10 to 0.20%.
  • V may be contained because it improves the strength by solid solution strengthening and also improves the corrosion resistance.
  • the V content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the V content is preferably 0.05 to 0.20%.
  • Ni, Mn, Mg, Ti, Zr, Cr, and V may be added to the sacrificial anode material as required, if necessary.
  • Second brazing material contains Si: 2.5 to 13.0%, Fe: 0.05 to 1.20% as essential elements, the balance being Al and unavoidable impurities Is used.
  • the second brazing filler metal is Mn: 0.05 to 2.00%, Cu: 0.05 to 1.50%, Ti: 0.05 to 0.30%, Zr: 0.05 to 0.30. %, Cr: 0.05 to 0.30% and V: 0.05 to 0.30% may be further included as a first selective additive element. Further, the second brazing material contains one or two selected from Na: 0.001 to 0.050% and Sr: 0.001 to 0.050% as a second selective additive element. Also good. In addition to the essential elements and the first and second selective additive elements, unavoidable impurities may be contained in amounts of 0.05% or less, respectively, and 0.15% in total. Below, each component is demonstrated.
  • Si By adding Si, the melting point of the second brazing material is lowered to form a liquid phase, thereby enabling brazing.
  • the Si content is 2.5 to 13.0%. If it is less than 2.5%, the resulting liquid phase is small and it becomes difficult to obtain a brazing function. On the other hand, if it exceeds 13.0%, for example, when this second brazing material is used as a tube material, the amount of Si diffusing into the mating material such as fins becomes excessive, and the mating material will melt.
  • a preferable content of Si is 3.5 to 12.0%.
  • Fe Fe easily forms an Al-Fe-based or Al-Fe-Si-based intermetallic compound, and when it contains Mn at the same time, Al-Fe-Mn-based or Al-Fe-Mn-Si-based Since it is easy to form an intermetallic compound, the amount of Si that is effective for brazing is reduced and brazing properties are reduced.
  • the Fe content is 0.05 to 1.20%. If it is less than 0.05%, high-purity aluminum ingots must be used, resulting in high costs. On the other hand, if it exceeds 1.20%, the amount of Si effective for brazing is reduced and brazing becomes insufficient.
  • a preferable content of Fe is 0.10 to 0.50%.
  • Mn may be contained because it improves the strength and corrosion resistance of the brazing material.
  • the Mn content is 0.05 to 2.00%. If it exceeds 2.00%, a huge intermetallic compound is likely to be formed during casting, and the plastic workability is lowered. On the other hand, if it is less than 0.05%, the effect cannot be sufficiently obtained.
  • the Mn content is preferably 0.05 to 1.80%.
  • Cu may be included because it improves the strength of the second brazing filler metal by solid solution strengthening.
  • the Cu content is 0.05 to 1.50%. If it is less than 0.05%, the above effect is insufficient, and if it exceeds 1.50%, there is a high risk of cracking of the aluminum alloy during casting.
  • the Cu content is preferably 0.30 to 1.00%.
  • Ti may be contained because it improves the strength of the second brazing filler metal by solid solution strengthening and also improves the corrosion resistance.
  • the Ti content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Ti content is preferably 0.10 to 0.20%.
  • Zr may be contained because it has the effect of improving the strength of the second brazing filler metal by solid solution strengthening and precipitating Al—Zr-based intermetallic compounds to coarsen the crystal grains after brazing addition heat. .
  • the Zr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Zr content is preferably 0.10 to 0.20%.
  • Cr Cr may be contained because it has the effect of improving the strength of the second brazing filler metal by solid solution strengthening and precipitating Al—Cr intermetallic compounds to coarsen the crystal grains after brazing addition heat. .
  • the Cr content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the Cr content is preferably 0.10 to 0.20%.
  • V may be contained because it improves the strength of the second brazing filler metal by solid solution strengthening and also improves the corrosion resistance.
  • the V content is 0.05 to 0.30%. If it is less than 0.05%, the above effect cannot be obtained. If it exceeds 0.30%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered.
  • the V content is preferably 0.10 to 0.20%.
  • Na, Sr Na and Sr exhibit the effect of refining the Si particles in the second brazing material.
  • the contents of Na and Sr are 0.001 to 0.050%, respectively. If the respective contents are less than 0.001%, the above effects cannot be obtained sufficiently. On the other hand, when each content exceeds 0.050%, an oxide film becomes thick and brazeability is reduced. Each preferable content is 0.003 to 0.020%.
  • These Mn, Cu, Ti, Zr, Cr, V, Na, and Sr may be added in the second brazing material as required.
  • the aluminum alloy clad material according to the present invention has a density of Al-Mn intermetallic compounds having a circle equivalent diameter of 0.1 ⁇ m or more before the brazing heat of the first brazing material is 1.0.
  • the existence density of the Al—Mn intermetallic compound having a circle equivalent diameter of 2 ⁇ m or more after the heat of brazing addition of the first brazing material is limited to 300 pieces / mm 2 or more to ⁇ 10 5 pieces / mm 2 or more. These limitations are intended to improve the corrosion resistance of the surface on the first brazing material side after the brazing heat.
  • the existence density here refers to the number density per unit area when an arbitrary cross section in the first brazing filler metal layer is observed. The reason for this limitation will be described below.
  • a part of the first brazing material is melted at the time of brazing so that the brazing is supplied and joining is possible, and the first brazing material itself is preferentially corroded to cause the corrosion to progress into a plane, thereby forming a tube.
  • the core material is clad for the purpose of exerting a sacrificial anti-corrosion function for preventing perforation corrosion.
  • a sacrificial anti-corrosion function for preventing perforation corrosion.
  • the present inventors have investigated the cathode during corrosion by dispersing an Al—Mn intermetallic compound in an appropriate size (equivalent circle diameter) and density in the first brazing material after brazing. It was found that the reaction was activated to facilitate pitting corrosion and corrosion penetration due to local alkalinization could be prevented.
  • an Al—Mn-based intermetallic compound having a circle-equivalent diameter of 2 ⁇ m or more has an effect of activating the cathode reaction, and those less than 2 ⁇ m have an insufficient effect. Therefore, in the present invention, Al—Mn intermetallic compounds having an equivalent circle diameter of less than 2 ⁇ m after brazing are excluded. Further, if the existence density of Al—Mn intermetallic compounds having an equivalent circle diameter of 2 ⁇ m or more after brazing is 300 pieces / mm 2 or more, there is a sufficient cathode reaction activation effect, 300 pieces If it is less than / mm 2, the effect is insufficient.
  • the equivalent circle diameter of the Al—Mn intermetallic compound after brazing is preferably 3 ⁇ m or more, and its density is preferably 1000 / mm 2 or more.
  • the upper limit of the equivalent circle diameter of the Al—Mn intermetallic compound after brazing is not limited. However, if a compound exceeding 200 ⁇ m is present, composition workability is reduced and rolling is in progress. There is a risk of breaking. Therefore, the upper limit of the equivalent circle diameter is preferably 200 ⁇ m.
  • the upper limit of the density of Al—Mn intermetallic compounds is not limited, but exceeds 5.0 ⁇ 10 5 pieces / mm 2 from the alloy composition and production method of the present invention. It is difficult to exist. Therefore, the upper limit of the existence density is 5.0 ⁇ 10 5 pieces / mm 2 .
  • Al-Mn intermetallic compounds with an equivalent circle diameter of 0.1 ⁇ m or more before brazing do not dissolve in the matrix during brazing, and form an Al—Mn compound with an equivalent circle diameter of 2 ⁇ m or more after brazing.
  • An Al—Mn intermetallic compound having an equivalent circle diameter of less than 0.1 ⁇ m before brazing is dissolved in the matrix at the time of brazing, or its size is reduced, and after the brazing, an equivalent circle diameter of 2 ⁇ m or more.
  • An Al—Mn intermetallic compound cannot be formed. Therefore, in the present invention, Al—Mn intermetallic compounds having an equivalent circle diameter of less than 0.1 ⁇ m before brazing are excluded.
  • the equivalent circle diameter of the Al—Mn intermetallic compound existing before brazing is preferably 0.2 ⁇ m or more.
  • the density of Al—Mn intermetallic compounds having an equivalent circle diameter of 0.1 ⁇ m or more before brazing is 1 ⁇ 10 5 pieces / mm 2 or more
  • Al—Mn with an equivalent circle diameter of 2 ⁇ m or more after brazing is used.
  • the density of Mn-based intermetallic compounds can be 300 / mm 2 or more.
  • Al— The density of Mn-based intermetallic compounds cannot be 300 / mm 2 or more.
  • the density of Al—Mn compounds having an equivalent circle diameter of 0.1 ⁇ m or more before brazing is preferably 3.0 ⁇ 10 5 pieces / mm 2 or more.
  • the upper limit of the equivalent circle diameter of the Al—Mn intermetallic compound before brazing is not limited. However, if a compound exceeding 200 ⁇ m is present, the composition workability deteriorates and rolling There is a risk of breaking inside. Therefore, the upper limit of the equivalent circle diameter is preferably 200 ⁇ m.
  • the upper limit of the density of Al—Mn compound is not limited, but it exists in excess of 5.0 ⁇ 10 7 / mm 2 from the alloy composition and production method of the present invention. It is difficult to make it. Therefore, the upper limit of the existence density is 5.0 ⁇ 10 7 pieces / mm 2 .
  • the manufacturing method of the aluminum alloy clad material according to the present invention includes a step of casting an aluminum alloy for the core material and the first brazing material, and hot casting the ingot of the cast first brazing material to a predetermined thickness.
  • a rolling step, a cladding step of cladding a first brazing material having a predetermined thickness by hot rolling on one or both surfaces of the core ingot, and a hot cladding rolling step of hot rolling the cladding material A cold rolling process for cold rolling the clad material that has been hot clad rolled, and one or more annealing processes for annealing the clad material in one or both of the cold rolling process and after the cold rolling process. Including. When the first brazing material is clad only on one surface of the core material, the second brazing material or the sacrificial anode material hot-rolled to a predetermined thickness is clad on the other surface of the core material.
  • the aluminum alloy clad material of the present invention realizes excellent corrosion resistance by controlling the structure of the first brazing material.
  • the present inventors have found that the greatest influence on the structure control during the manufacturing process is the hot rolling process of the cast first brazing filler metal. Below, the control method of the hot rolling process of this 1st brazing material is demonstrated.
  • Hot-rolling process of first brazing material In the method for producing an aluminum alloy clad material according to the present invention, after casting the first brazing material, the first brazing material is cast to a predetermined thickness in order to obtain a desired cladding rate. It is characterized by a hot rolling process in which the ingot is hot rolled.
  • the hot rolling process includes a heating stage for heating the ingot, a holding stage following the heating stage, and a hot rolling stage for rolling the heated and held ingot.
  • the rate of temperature rise until reaching 400 ° C. is defined as 30 ° C./h or more
  • the rate of temperature rise from reaching 400 ° C. to reaching the holding temperature in the holding stage is defined as 60 ° C./h or less. .
  • the holding temperature is set to 450 ° C. or more and 560 ° C. or less, and the holding time is set to 1 hour or more. Furthermore, in the hot rolling stage, the time during which the temperature of the rolled material is 400 ° C. or higher is defined as 5 minutes or longer.
  • the aluminum alloy clad material according to the present invention can be obtained between the Al—Mn-based metals defined in the present invention before and after brazing. The distribution of the compound can be obtained, and excellent corrosion resistance can be exhibited after brazing. The reason for this will be described below.
  • the equivalent circle diameter of the Al—Mn intermetallic compound before brazing is 0.1 ⁇ m or more. It needs to be.
  • the holding temperature in the holding stage is lower than 450 ° C.
  • the formation of a relatively large Al—Mn intermetallic compound precipitate is small, and the desired Al—Mn intermetallic compound precipitate distribution is obtained. I can't.
  • the holding time is less than 1 hour, a relatively large Al—Mn-based intermetallic compound precipitate is generated, and the target Al—Mn-based intermetallic compound precipitate distribution cannot be obtained.
  • the heating rate until reaching 400 ° C. is preferably 40 ° C./h or more, and the heating rate from reaching 400 ° C. to reaching the holding temperature in the holding stage is preferably 50 ° C./h or less.
  • the holding temperature in the holding stage is preferably 460 ° C. or more, and the holding time is preferably 2 hours or more.
  • the upper limit of the heating rate until reaching 400 ° C. is not particularly limited, but exceeding 100 ° C./h is difficult in terms of the heat capacity of the ingot. Therefore, in this invention, the upper limit of this temperature increase rate shall be 100 degrees C / h.
  • the lower limit of the rate of temperature rise from the time when reaching 400 ° C. to the time when the holding temperature in the holding stage is reached is not particularly limited. It takes a long time and the economic efficiency is significantly impaired. Therefore, in the present invention, the lower limit of the temperature increase rate is set to 20 ° C./h.
  • the upper limit of the holding temperature is 560 ° C.
  • the upper limit of the holding time is not particularly limited, but if it exceeds 20 hours, the economy is significantly impaired. Therefore, the upper limit of the holding time is preferably 20 hours.
  • the time required for the hot rolling stage is shorter than that of the heating stage and the holding stage, which are the previous stages, but during the hot rolling stage, precipitation of intermetallic compounds is promoted by the introduced strain. Therefore, in this hot rolling stage, a relatively large Al—Mn intermetallic compound precipitate is formed even if the rolling time is short.
  • the temperature of the first brazing filler metal is 400 ° C. or higher during the hot rolling stage is less than 5 minutes, the formation of relatively large Al—Mn intermetallic compound precipitates is small, and the target A distribution of precipitates of the Al—Mn intermetallic compound cannot be obtained.
  • the time during which the temperature of the first brazing material is 400 ° C. or higher is preferably 7 minutes or longer.
  • the upper limit of this time is not particularly limited, but it is difficult to maintain 400 ° C. or more over 30 minutes from the viewpoint of the heat capacity of the ingot. Therefore, in the present invention, the upper limit of this time is 30 minutes.
  • the hot rolling stage in the temperature range where the temperature of the first brazing material is less than 400 ° C., precipitation hardly occurs, and it is not necessary to control the time required during that time.
  • the conditions in the casting process of the first brazing material, core material, second brazing material and sacrificial anode material are not particularly limited, but a water-cooled semi-continuous casting method is usually used.
  • the hot rolling process in which the second brazing material and the sacrificial anode material are each hot-rolled to a predetermined thickness includes a heating and holding stage and a hot rolling stage.
  • the heating conditions in the heating and holding stage are usually 400 to 560.
  • the reaction is preferably carried out at a temperature of 0.5 to 10 hours, more preferably at a temperature of 420 to 540 ° C. for 0.5 to 8 hours.
  • the ingot obtained by casting the core material may be subjected to a homogenization process before the hot clad rolling process.
  • the homogenization treatment step is usually preferably performed at 450 to 620 ° C. for 1 to 24 hours, more preferably at 480 to 620 ° C. for 1 to 20 hours. If the temperature is less than 450 ° C. or the time is less than 1 hour, the homogenization effect may not be sufficient, and if it exceeds 620 ° C., the core material ingot may be melted. Further, if the time exceeds 24 hours, the economic efficiency is remarkably impaired.
  • Hot clad rolling process In the hot clad rolling process, the clad material is heated in the heating stage before the clad rolling stage.
  • the heating temperature is usually preferably 400 to 560 ° C. for 0.5 to 10 hours, more preferably 420 to 540 ° C. for 0.5 to 8 hours. If the temperature is less than 400 ° C., the plastic workability is poor, and cracking may occur during clad rolling. When it exceeds 560 ° C., the ingot may be melted during heating. If the time is less than 0.5 hours, the temperature of the clad material may not be uniform, and if it exceeds 10 hours, the economic efficiency is remarkably impaired.
  • the hot clad rolling process may be divided into a rough rolling process with a rolling reduction of 70 to 95% and a finish rolling process with a subsequent rolling reduction of 70 to 95%.
  • annealing process is performed once or more in the middle of the cold rolling process and one or both after the cold rolling process for the purpose of improving formability. Specifically, (1) one or more intermediate annealings are performed during the cold rolling process, (2) the final annealing process is performed once after the cold rolling process, or (3) (1 ) And (2) are implemented.
  • the clad material is preferably held at 200 to 560 ° C. for 1 to 10 hours. When the temperature is less than 200 ° C. and the holding time is less than 1 hour, the above effect may not be sufficient.
  • the clad material may be melted during heating, and if the holding time exceeds 10 hours, the economical efficiency is remarkably impaired.
  • More preferable annealing conditions are a temperature of 230 to 500 ° C. and a holding time of 1 to 8 hours.
  • count of an annealing process is not specifically limited, In order to avoid the cost increase by the increase in the number of processes, it is preferable to set it as 3 times.
  • Clad rate and plate thickness In the aluminum alloy clad material according to the present invention, the clad rate (one side) of the first brazing material, the second brazing material and the sacrificial anode material is preferably 3 to 25%. If each of these cladding ratios is less than 3%, the material to be clad is too thin, so that it may not be possible to cover the entire core material during hot clad rolling. If each of these cladding ratios exceeds 25%, warpage may occur during hot cladding rolling, and the cladding material may not be manufactured. Each of these cladding rates is more preferably 5 to 20%.
  • the thickness of the aluminum alloy clad material according to the present invention is not particularly limited.
  • a thickness of 0.15 to 0.6 mm is usually used. It is done. It is also possible to use it for a header plate or the like with a plate thickness of about 0.6 to 3 mm.
  • the aluminum alloy clad material according to the present invention is suitably used as a heat exchanger member such as a flow path forming component, a header plate, and a fin material, particularly as a flow path forming component.
  • a heat exchanger member such as a flow path forming component, a header plate, and a fin material, particularly as a flow path forming component.
  • the aluminum alloy clad material is bent, and the overlapping portions at both ends thereof are brazed and joined to produce a flow path forming component for flowing a medium such as cooling water.
  • the heat exchanger according to the present invention has a structure in which, for example, the above-mentioned flow path forming component is combined with a fin material and a header plate, and these are brazed at once.
  • the heat exchanger is assembled by disposing fin materials on the outer surface of the flow path forming component with both end portions attached to the header plate. Next, the overlapping portions on both ends of the flow path forming component, the fin material and the outer surface of the flow path forming component, and both ends of the flow path forming component and the header plate are simultaneously joined by one brazing heating.
  • a flux-free brazing method, a nocolok brazing method, or a vacuum brazing method is used, but the nocolock brazing method is preferable.
  • the brazing is usually performed by heating at a temperature of 590 to 610 ° C. for 2 to 10 minutes, preferably at a temperature of 590 to 610 ° C. for 2 to 6 minutes.
  • the brazed one is usually cooled at a cooling rate of 20 to 500 ° C./min.
  • the aluminum alloy clad material according to the present invention is used as at least a flow path forming component of a heat exchanger.
  • a description will be given of a corrosive environment in which the superiority in terms of corrosion resistance can be exhibited when used as a flow path forming component of a heat exchanger.
  • the superiority of the present invention is exhibited.
  • the corrosion form remains pitting even at high temperatures, and sacrificial corrosion protection continues to act.
  • the superiority of the present invention is not sufficiently exhibited.
  • the chloride ion concentration is less than 5 ppm, corrosion holes are not generated in the first place, so the advantage of the present invention is not particularly exhibited.
  • the aluminum alloy clad material according to the present invention can exhibit superiority in corrosion resistance in an environment where chloride ions are 1200 ppm or less, but as a corrosive environment in which the superiority of the present invention is exhibited, the chloride ion concentration is 5 -1000 ppm is preferable, and 10-800 ppm is more preferable.
  • the aluminum alloy clad material according to the present invention is used at least for the flow path forming component.
  • the first brazing material is used on both surfaces of the core material, at least one surface of the first brazing material surface is used in a state where it is exposed to a solution having a chloride ion concentration of 1200 ppm or less.
  • the surface of the first brazing material is used in a state where it is exposed to a solution having a chloride ion concentration of 1200 ppm or less.
  • the first brazing alloy having the alloy composition shown in Table 1 The first brazing alloy having the alloy composition shown in Table 1, the core alloy having the alloy composition shown in Table 2, the second brazing alloy having the alloy composition shown in Table 3, and the sacrificial anode material having the alloy composition shown in Table 4.
  • Each alloy was cast by DC casting and each side was chamfered and finished.
  • the thickness of the ingot after chamfering was 400 mm in all cases.
  • For the first brazing filler metal, the second brazing filler metal, and the sacrificial anode material calculate the clad ratio to be the desired thickness by the final thickness, and heat at 480 ° C. for 3 hours so as to obtain the required thickness at the time of matching. And then subjected to a hot rolling step to a predetermined thickness.
  • Table 5 shows the conditions for the hot rolling process of the first brazing filler metal.
  • the second brazing material and the sacrificial anode material were both hot-rolled under the conditions of E1 in Table 5.
  • the first brazing material in Table 1 is combined with one side of the core alloy and nothing is combined with the other side of the core material, or the first brazing material in Table 1 or the first brazing material in Table 3 is used.
  • Two brazing materials or sacrificial anode materials from Table 4 were combined.
  • Tables 6 to 9 show combinations of the first brazing material, the core material, the second brazing material, and the sacrificial anode material in each sample.
  • the cladding rates of the first brazing material, the second brazing material, and the sacrificial anode material were all 10% (one side).
  • the clad material was heated and held at 500 ° C. for 3 hours, and then the clad rolling stage was performed to produce a 2-layer or 3-layer clad material having a thickness of 3 mm. Then, after cold rolling in Table 5, (1) cold rolling ⁇ intermediate annealing ⁇ final cold rolling, (2) cold rolling ⁇ final annealing, (3) cold rolling ⁇ intermediate annealing A final clad material sample having a final thickness of 0.4 mm was prepared in any of the order of final cold rolling and final annealing. The conditions for intermediate annealing and final annealing were both 2 hours at 370 ° C., and the rolling ratio in final cold rolling after intermediate annealing was 30%. Table 5 shows the process combinations.
  • the manufacturability is set to “ ⁇ ”, and cracking occurs during casting or rolling to roll to a final thickness of 0.4 mm. If the clad material could not be manufactured due to melting during the heating stage or intermediate annealing process before the hot clad rolling process, or poor crimping during the hot clad rolling stage, It is shown in Tables 6 to 9 as “x”.
  • Tables 6 to 9 show the results obtained by subjecting the above clad material samples to the following evaluations. In addition, since the samples could not be manufactured for those with the productivity “x” in Tables 7 to 9, the following evaluation could not be performed.
  • a fin material having a thickness of 0.07 mm, a tempered H14, and an alloy component of 3003 alloy with 1.0% Zn added thereto was corrugated to obtain a heat exchanger fin material.
  • This fin material is placed on the first brazing filler metal surface or the second brazing filler metal surface of the clad material sample, immersed in a 5% fluoride flux aqueous solution, and subjected to brazing addition heat at 600 ° C. for 3 minutes.
  • a sample was prepared. When the fin joint rate of this mini-core sample is 95% or more and the clad material sample and the fin are not melted, the brazing property is passed (O), while (1) the fin joint rate is 95%. Less than (1) and (2), or (1) or (2) in the case where melting occurs in at least one of the clad material sample and the fin. (X).
  • the L-LT surface of the first brazing filler metal part is ground by polishing, and EPMA is used to determine the Mn element distribution. It was examined by performing mapping. By observing five fields of 500 ⁇ m ⁇ 500 ⁇ m for each sample and analyzing the mapping of Mn in each field, the distribution of Al—Mn intermetallic compounds having an equivalent circle diameter of 2 ⁇ m or more was obtained.
  • the brazing equivalent heating condition in the present invention is that the ultimate temperature is 600 ° C. and the holding time of 580 ° C. or more is 5 minutes.
  • the clad material sample was heated corresponding to the above brazing, then cut into 50 mm ⁇ 50 mm, and the opposite surface of the test surface was masked with resin.
  • the first brazing material surface was used as a test surface
  • the sacrificial anode material surface was also used as a test surface.
  • the test using the second brazing filler metal surface as a test surface was not performed.
  • the test solution when the test surface is the first brazing filler metal is a NaCl aqueous solution (pure water) having a chloride ion concentration of 3 ppm (solution A), 5 ppm (solution B), 1000 ppm (solution C), and 1200 ppm (solution D), respectively.
  • a NaCl aqueous solution pure water having a chloride ion concentration of 3 ppm (solution A), 5 ppm (solution B), 1000 ppm (solution C), and 1200 ppm (solution D), respectively.
  • Each test sample was immersed in these solutions, and a cycle immersion test was performed for 3 hours in 88 ° C high-temperature water for 8 hours and then at room temperature for 16 hours. ( ⁇ ) and the resulting product was rejected ( ⁇ ).
  • test surface is a sacrificial anode material
  • ASTM-G85 SWAAT test based on ASTM-G85
  • Example 1 to 20 and 55 to 59 of the present invention the conditions specified in the present invention were satisfied, and all of the manufacturability, brazing property, tensile strength after brazing, and corrosion resistance were acceptable.
  • Comparative Example 49 there were too many Ti, Zr, Cr and V components in the sacrificial anode material, so that cracking occurred during rolling, and the clad material could not be produced, resulting in rejected productivity.
  • Comparative Example 61 since the temperature increase rate from reaching 400 ° C. in the heating stage of the hot rolling process of the first brazing filler metal to reaching the holding temperature in the holding stage was too high, an appropriate Al—Mn system after the brazing addition heat was used. The distribution of intermetallic compounds could not be obtained, and the corrosion resistance in solutions A and B was unacceptable.
  • the aluminum alloy clad material according to the present invention is excellent in corrosion resistance and excellent in brazing properties such as fin joint ratio and erosion resistance, and therefore is particularly suitably used as a flow path forming part of an automotive heat exchanger.

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Abstract

L'invention concerne un matériau plaqué en alliage d'aluminium ainsi qu'un procédé de fabrication de celui-ci, et un échangeur de chaleur mettant en œuvre ce matériau plaqué en alliage d'aluminium. Plus précisément, l'invention concerne un matériau plaqué en alliage d'aluminium qui est équipé : d'un matériau de noyau en alliage d'aluminium ; et d'un premier métal d'apport de brasage qui est plaqué sur une face ou sur les deux faces dudit matériau de noyau. Lesdits matériau de noyau et premier métal d'apport de brasage sont constitués d'un alliage d'aluminium de composition prédéfinie. La densité d'un composé intermétallique à base de Al-Mn possédant un diamètre de cercle équivalent supérieur ou égal à 0,1μｍ, présent dans le premier métal d'apport de brasage avant chauffage pour brasage, est supérieure ou égale à １,０×１０５／ｍｍ２. La densité d'un composé intermétallique à base de Al-Mn possédant un diamètre de cercle équivalent supérieur ou égal à 2μｍ, présent dans le premier métal d'apport de brasage après chauffage pour brasage, est supérieure ou égale à ３００／ｍｍ２.
PCT/JP2016/070277 2015-07-08 2016-07-08 Matériau plaqué en alliage d'aluminium ainsi que procédé de fabrication de celui-ci, et échangeur de chaleur mettant en œuvre ce matériau plaqué en alliage d'aluminium Ceased WO2017007019A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/742,418 US10625379B2 (en) 2015-07-08 2016-07-08 Aluminum alloy cladding material, manufacturing method therefor, and heat exchanger using said aluminum alloy cladding material
EP16821487.2A EP3321384B1 (fr) 2015-07-08 2016-07-08 Matériau plaqué en alliage d'aluminium ainsi que procédé de fabrication de celui-ci, et échangeur de chaleur mettant en oeuvre ce matériau plaqué en alliage d'aluminium
CN201680035541.5A CN107849645B (zh) 2015-07-08 2016-07-08 铝合金包覆材及其制造方法、以及使用所述铝合金包覆材的热交换器

Applications Claiming Priority (4)

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JP2015137331 2015-07-08
JP2015-137331 2015-07-08
JP2016132727A JP6713861B2 (ja) 2015-07-08 2016-07-04 アルミニウム合金クラッド材及びその製造方法、ならびに、当該アルミニウム合金クラッド材を用いた熱交換器
JP2016-132727 2016-07-04

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Publication number Priority date Publication date Assignee Title
CN117488145A (zh) * 2023-11-09 2024-02-02 魏桥(苏州)轻量化研究院有限公司 一种免热处理压铸铝合金及其制备方法和应用

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JP2008188616A (ja) * 2007-02-02 2008-08-21 Mitsubishi Alum Co Ltd ろう付性と耐食性に優れた熱交換器管用アルミニウム合金ブレージングシートおよび耐食性に優れた熱交換器管
WO2010137649A1 (fr) * 2009-05-27 2010-12-02 株式会社神戸製鋼所 Tôle de brasage en alliage d'aluminium pour échangeurs de chaleur et objet brasé en alliage d'aluminium pour échangeurs de chaleur
JP2013133517A (ja) * 2011-12-27 2013-07-08 Mitsubishi Alum Co Ltd 耐高温３層ブレージングシート
JP2014055326A (ja) * 2012-09-12 2014-03-27 Uacj Corp アルミニウム合金クラッド材、熱交換器、及び熱交換器の製造方法
WO2016080433A1 (fr) * 2014-11-21 2016-05-26 株式会社デンソー Matériau de placage en alliage d'aluminium pour échangeur de chaleur

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Publication number Priority date Publication date Assignee Title
JP2008188616A (ja) * 2007-02-02 2008-08-21 Mitsubishi Alum Co Ltd ろう付性と耐食性に優れた熱交換器管用アルミニウム合金ブレージングシートおよび耐食性に優れた熱交換器管
WO2010137649A1 (fr) * 2009-05-27 2010-12-02 株式会社神戸製鋼所 Tôle de brasage en alliage d'aluminium pour échangeurs de chaleur et objet brasé en alliage d'aluminium pour échangeurs de chaleur
JP2013133517A (ja) * 2011-12-27 2013-07-08 Mitsubishi Alum Co Ltd 耐高温３層ブレージングシート
JP2014055326A (ja) * 2012-09-12 2014-03-27 Uacj Corp アルミニウム合金クラッド材、熱交換器、及び熱交換器の製造方法
WO2016080433A1 (fr) * 2014-11-21 2016-05-26 株式会社デンソー Matériau de placage en alliage d'aluminium pour échangeur de chaleur

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117488145A (zh) * 2023-11-09 2024-02-02 魏桥(苏州)轻量化研究院有限公司 一种免热处理压铸铝合金及其制备方法和应用

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