WO2015141192A1 - 耐食性及びろう付性に優れたアルミニウム合金クラッド材及びその製造方法 - Google Patents
耐食性及びろう付性に優れたアルミニウム合金クラッド材及びその製造方法 Download PDFInfo
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- WO2015141192A1 WO2015141192A1 PCT/JP2015/001341 JP2015001341W WO2015141192A1 WO 2015141192 A1 WO2015141192 A1 WO 2015141192A1 JP 2015001341 W JP2015001341 W JP 2015001341W WO 2015141192 A1 WO2015141192 A1 WO 2015141192A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0233—Sheets, foils
- B23K35/0238—Sheets, foils layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
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- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing heat exchangers
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- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B23K35/282—Zn as the principal constituent
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- 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
- B23K35/284—Mg as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K35/286—Al as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K35/286—Al as the principal constituent
- B23K35/288—Al as the principal constituent with Sn or Zn
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- 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
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- 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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- 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
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- 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
- C22F1/053—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 of alloys with zinc as the next major constituent
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- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- 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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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- 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
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- 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
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
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- 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
- F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys
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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
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/006—Vehicles
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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
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/04—Tubular or hollow articles
- B23K2101/14—Heat exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/34—Coated articles, e.g. plated or painted; Surface treated articles
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- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2275/00—Fastening; Joining
- F28F2275/04—Fastening; Joining by brazing
Definitions
- the present invention relates to an aluminum alloy clad material used as a constituent member of a heat exchanger such as an automobile and a method for manufacturing the same. More specifically, it is excellent in corrosion resistance and brazing in an alkaline environment, which is used as a material for tubes, headers, or piping materials connected thereto, such as a structural member of an aluminum heat exchanger such as a radiator or a heater core.
- the present invention relates to an aluminum alloy clad material and a manufacturing method thereof.
- a radiator which is one of conventional aluminum heat exchangers for automobiles, is shown in FIGS. 1 (a) and 1 (b).
- the aluminum heat exchanger for an automobile shown in FIG. 1 is obtained by assembling a core 4 by disposing fins 2 on a tube 1 through which cooling water flows and attaching header plates 3 to both ends of the tube 1.
- the resin tanks 5 ⁇ / b> A and 5 ⁇ / b> B are attached to the header plate 3 via the backing 6 to form a radiator.
- As the cooling water for the radiator a weak alkaline aqueous solution containing an antifreeze containing various rust preventives, so-called long life coolant (LLC), or the like is used.
- LLC long life coolant
- a plate material having a thickness of about 0.1 mm obtained by adding Zn to an Al—Mn alloy is used for the fin 2.
- the tube 1 is clad with an Al—Mn alloy as a core material and an Al—Zn alloy as a sacrificial anode material on the cooling water side to prevent the occurrence of through pitting corrosion from the cooling water.
- an aluminum alloy clad material having a thickness of about 0.2 to 0.4 mm clad with an Al—Si alloy as a brazing material is used.
- the header plate 3 is made of an aluminum alloy clad material having a thickness of about 1.0 to 1.3 mm and the same structure as the tube 1.
- the aluminum alloy clad material used for the tube 1 and the header plate 3 is exposed to an atmosphere of about 600 ° C. during brazing addition heat. For this reason, Zn added to the sacrificial anode material forms a Zn diffusion layer in the core material. It is known that the presence of this Zn diffusion layer causes the corrosion generated in the sacrificial anode material in an acidic environment to spread laterally even after reaching the core material, so that no through hole is generated over a long period of time.
- LLC is a weakly alkaline liquid containing a rust preventive material, but in addition to this, crude bad water that does not have a rust preventive effect such as well water and river water may be used as a coolant. These rough waters may be acidic, and in this case, as described above, corrosion is prevented by the sacrificial anode effect of the sacrificial anode material.
- Patent Document 1 in an aluminum alloy clad material in which a brazing material is clad on one surface of a core material and a sacrificial anode material is clad on the other surface, an Al—Ni intermetallic compound containing Ni is dispersed in the sacrificial anode material.
- an aluminum alloy clad material made of an aluminum alloy made of an aluminum alloy.
- This aluminum alloy clad material is a portion where the Al—Ni-based intermetallic compound exists on the surface of the sacrificial anode material, and deposition of aluminum hydroxide, which is a film component, is hindered to suppress film formation.
- small film defects increase and corrosion generation is dispersed. For this reason, compared with the case where the film defects are localized, the progress of the corrosion in the depth direction is suppressed in such dispersed small film defects, and the generation of through holes can be prevented even in an alkaline environment. .
- Patent Document 2 discloses that an Al—Ni—Si intermetallic compound is formed by adding Si together with Ni to the sacrificial anode material, and this is more finely dispersed than the Al—Ni intermetallic compound. For this reason, it shows higher corrosion resistance in an alkaline environment.
- the thinning of the material means the thinning of the sacrificial anode material at the same time.
- the anticorrosive action in an alkaline environment is given only to the sacrificial anode material, and when the corrosion holes partially reach the core material, the corrosion proceeds at a stretch from that point. For this reason, when the sacrificial anode material is thinned, the corrosion resistance in an alkaline environment is significantly reduced.
- Patent Documents 3 and 4 Ni is also added to the core material, and Al—Ni intermetallic compound is uniformly dispersed in the core material, so that some corrosion holes in an alkaline environment are partially formed in the core material.
- a material having a structure capable of exhibiting corrosion resistance even when reaching the above has been proposed.
- JP 2000-34532 A JP 2003-293061 A JP 2000-87170 A JP 2000-96169 A
- the present invention preferentially corrodes the sacrificial anode material even when it is corrosive in an alkaline environment, does not cause a reduction in plate thickness, and has good brazing properties.
- the purpose is to provide.
- the present inventor has found that even when a conventional Al—Ni based sacrificial anode material is used, by appropriately controlling the dispersion state of the core Al—Mn—Si—Fe based intermetallic compound, It was found that the sacrificial anode material was preferentially corroded even in the environment, and as a result, an aluminum alloy clad material having no brazing thickness reduction and excellent brazing properties was obtained.
- the present invention provides an aluminum alloy comprising: an aluminum alloy core material according to claim 1; a sacrificial anode material clad on one surface of the core material; and an Al—Si brazing material clad on the other surface of the core material.
- the core material includes Ti: 0.05 to 0.20 mass%, Zr: 0.05 to 0.20 mass%, and V: 0.05 to 0.20 mass%, Cr. : One or more selected from 0.05 to 0.20 mass% were further contained.
- the crystal grain size of the core material is 150 ⁇ m or more after the brazing heating at 600 ° C. for 3 minutes in the first or second aspect.
- the aluminum alloy clad material according to any one of claims 1 to 3 has a tensile strength of 140 MPa or more after the brazing heating at 600 ° C. for 3 minutes.
- the aluminum alloy clad material according to any one of claims 1 to 4 has an elongation along the rolling direction of 5% or more.
- the present invention provides the method for producing an aluminum alloy clad material according to any one of claims 1 to 5, wherein the aluminum alloys for the core material, the sacrificial anode material, and the brazing material are respectively cast.
- a post-cast heat treatment step in which the core material ingot is subjected to a uniform heat treatment at a high temperature, a sacrificial anode material ingot having a predetermined thickness on one surface of the core material ingot, and a brazing material ingot having a predetermined thickness on the other surface.
- An annealing step of annealing the clad material in at least one of the latter, and the casting step of the core material ingot includes a casting cooling step of cooling the ingot at a rate of 5 ° C./second or more, and after the casting Heat treatment
- the hot-clad rolling comprising: a soaking step for soaking at 550 to 620 ° C. for at least 5 hours; and a cooling step for cooling the soaked ingot at a rate of at least 50 ° C./hour.
- the process includes a heating step before rolling at 400 to 480 ° C. for 5 hours or more, and an annealing temperature in the annealing step is 400 ° C. or less.
- the rolling start temperature of the hot clad rolling is 480 to 350 ° C.
- the rolling end temperature is 350 to 250.
- the aluminum alloy clad material according to the present invention can appropriately control the dispersion state of the Al—Mn—Si—Fe intermetallic compound in the core material even when an Al—Ni based aluminum alloy is used as the sacrificial anode material. Even in an alkaline environment, the sacrificial anode material is preferentially corroded, and the thickness is not reduced and the brazing property is excellent.
- the core material and the sacrificial anode material have a predetermined aluminum alloy composition, and the core material has a specific metal structure in relation to the sacrificial anode material.
- the aluminum alloy clad material which concerns on this invention, and its manufacturing method are explained in full detail.
- the aluminum alloy clad material according to the present invention is a material of a heat exchanger component such as an automobile such as a tube, header, or piping material connected to a structural member of an aluminum heat exchanger such as a radiator or a heater core. Is preferably used.
- Metal structure and mechanical properties 1-1. Reasons for defining the metal structure First, the reason for determining the metal structure of the core alloy according to the present invention will be described. A film defect of aluminum hydroxide occurs in the portion where the Al—Ni intermetallic compound exists, and the occurrence of corrosion is dispersed. This action is not unique to the Al—Ni intermetallic compound, and the same action was confirmed for the Al—Mn—Fe—Si intermetallic compound. Here, the distribution state of the Al—Ni intermetallic compound cannot be adjusted by heat treatment such as soaking. However, the distribution state of the Al—Mn—Fe—Si intermetallic compound can be adjusted.
- the density of the Al—Ni-based intermetallic compound having a circle-equivalent diameter of 1 ⁇ m or more dispersed in the sacrificial anode material is approximately 2.0 ⁇ 10 5 pieces / cm 2 .
- a coarse Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m is more densely dispersed in the core material, so that the starting point of corrosion when the core material is exposed to an alkaline environment.
- the core material is more dispersed than the sacrificial anode material. If the starting point of the corrosion is dispersed, the progress of the corrosion in the thickness direction can be suppressed.
- the corrosion of the sacrificial anode material proceeds preferentially, and the sacrificial anticorrosive effect by the sacrificial anode material is obtained.
- a coarse intermetallic compound is dispersed at a high density in the core material before brazing heating, the crystal grain size after brazing addition heat becomes very fine, which adversely affects brazing properties.
- a fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is dispersed in the core material before brazing heating, and the crystal grain size after the brazing heat is added.
- the equivalent circle diameter means an equivalent circle diameter.
- the density of the Al—Ni intermetallic compound dispersed in the sacrificial anode material is approximately 2.0 ⁇ 10 5 pieces / cm 2 .
- the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was dispersed in the core material by 1.5 times or more of the Al—Ni intermetallic compound density.
- the core material was exposed in an alkaline environment, the starting point of corrosion was significantly more dispersed than the sacrificial anode material.
- corrosion of the sacrificial anode material proceeded preferentially, and the sacrificial anticorrosive effect of the sacrificial anode material was confirmed.
- Such an effect is that the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m in the core corresponds to 1.5 times the density of the Al—Ni intermetallic compound. It indicates that less than 3.0 ⁇ 10 5 pieces / cm 2 is not sufficient. On the other hand, if the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m in the core exceeds 1.0 ⁇ 10 6 pieces / cm 2 , workability is deteriorated.
- the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m in the core is 3.0 ⁇ 10 5 to 1.0 ⁇ 10 6 / cm 2 , preferably 3 It is specified to be 3 ⁇ 10 5 to 9.5 ⁇ 10 5 pieces / cm 2 .
- an Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is finely dispersed in the core material, It is effective to reduce the sites that become the nuclei of recrystallization. Note that Al—Mn—Si—Fe intermetallic compounds having an equivalent circle diameter of less than 0.1 ⁇ m are excluded from the scope because they are dissolved in brazing heat and do not exhibit an effect in reducing recrystallization nuclei. .
- the present invention uses a coarse Al—Mn—Fe—Si intermetallic compound having a circle equivalent diameter of 1 to 20 ⁇ m in the core material as 3.0 ⁇ . It is necessary to disperse at a very high density of 10 5 to 1.0 ⁇ 10 6 pieces / cm 2 . For this reason, there are only relatively fine Al—Mn—Fe—Si intermetallic compounds having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m in the core material of less than 1.0 ⁇ 10 7 / cm 2.
- the density of the Al—Mn—Si—Fe intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m present in the core material is 1.0 ⁇ 10 7 pieces / cm 2 or more, preferably Is defined as 1.5 ⁇ 10 7 pieces / cm 2 or more.
- the upper limit of this density is dependent on a core material composition, a manufacturing method, etc., in this invention, it is 5.0 * 10 ⁇ 9 > piece / cm ⁇ 2 >.
- the density of the Al—Mn—Fe—Si intermetallic compound of each size in the core material was obtained by selecting a plurality of measurement locations in the sample and observing each with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the SEM image was obtained by image analysis.
- the density is obtained as an arithmetic average value of a plurality of measurement results.
- Crystal grain size in core material after brazing is preferably 150 ⁇ m. More preferably, it is 160 ⁇ m or more. Although this upper limit depends on the core material composition and the manufacturing method, it is 300 ⁇ m in the present invention.
- the strength of the clad material after brazing is preferably 140 MPa or more, more preferably 150 MPa or more. Although this upper limit depends on the core material composition, the manufacturing method, etc., it is 220 MPa in the present invention.
- the aluminum alloy clad material according to the present invention has an elongation along the rolling direction of preferably 5% or more, more preferably 8% or more. Although this upper limit depends on the core material composition and the manufacturing method, it is 20% in the present invention.
- the core aluminum alloy contains Si, Fe, Cu, and Mn as essential elements, and Ti, Zr, V, and Cr as selective additive elements.
- Si added to the core material exhibits the effect of improving the strength of the core material.
- the Si content is 0.3 to 1.5 mass% (hereinafter simply referred to as “%”). When the content is less than 0.3%, the above effect is not sufficient. When the content exceeds 1.5%, the melting point of the core material is lowered and local melting is likely to occur during brazing.
- a preferable content of Si is 0.5 to 1.2%.
- Fe added to the core material crystallizes and precipitates as an intermetallic compound with Mn and contributes to dispersion strengthening.
- the Fe content is 0.1 to 1.5%. If the content is less than 0.1%, the above contribution is not sufficient, and if it exceeds 1.5%, the workability decreases.
- a preferable content of Fe is 0.2 to 0.8%.
- Si and Fe added to the core material form various intermetallic compounds with Mn in addition to the above effects, and are effective in improving the corrosion resistance and brazing properties in an alkaline environment.
- Si content + Fe content is 0.8% or more, preferably 0.9% or more. If it is less than 0.8, the above-mentioned effects cannot be obtained sufficiently.
- the upper limit of Si content + Fe content from a viewpoint of exhibiting the said effect shall be 2.5%.
- Cu added to the core material exhibits an effect of greatly improving the strength of the material by dissolving in the matrix.
- the Cu content is 0.2 to 1.0%. When the content is less than 0.2%, the above effect is not sufficient. When the content exceeds 1.0%, an intermetallic compound of Al 2 Cu is precipitated at the grain boundary, and PFZ (no precipitation zone) is formed in the vicinity of the grain boundary. Intergranular corrosion occurs due to the formation.
- a preferable content of Cu is 0.3 to 0.8%.
- Mn added to the core material forms various intermetallic compounds with Si and Fe, contributing to dispersion strengthening and improving corrosion resistance and brazing in an alkaline environment. Further, since Mn has the effect of making the potential of the core material noble, the potential difference from the sacrificial anode material can be increased, and the corrosion resistance under an acidic environment is also improved.
- the Mn content is 1.0 to 2.0%. When the content is less than 1.0%, the above-mentioned effects are not sufficient, and when it exceeds 2.0%, coarse crystallized products are formed and the production yield deteriorates.
- a preferable content of Mn is 1.2 to 1.8%.
- each of Cr and Zr added to the core material produces a fine intermetallic compound in the aluminum alloy and exhibits the effect of improving its strength. If each content is less than 0.05%, the above effect is not sufficient. On the other hand, if it exceeds 0.20%, a coarse intermetallic compound is generated and the formability of the aluminum alloy material is lowered. Accordingly, the Cr and Zr contents are each preferably 0.05 to 0.20%. The more preferable ranges of the Cr and Zr contents are 0.05 to 0.15%, respectively.
- Ti and V added to the core material each produce an fine intermetallic compound in the aluminum alloy and exhibit the effect of improving its strength.
- these intermetallic compounds are dispersed in layers. Since these intermetallic compounds have noble electric potential, the corrosion form in an acidic environment is stratified, and the effect of making it difficult to progress to corrosion in the depth direction is exhibited.
- the content is less than 0.05%, the above effects are not sufficient.
- the content exceeds 0.20%, a coarse intermetallic compound is generated, and the molding processability is lowered.
- the Ti and V contents are each preferably 0.05 to 0.20%. The more preferable ranges of the Ti and V contents are 0.05 to 0.15%, respectively.
- the above Ti, Zr, V and Cr are selectively added as one kind or two or more kinds.
- the core material may contain inevitable impurities such as Zn, Ni, Sn and the like in addition to the essential elements and the selective additive elements, each 0.05% or less, and 0.15% or less in total.
- the aluminum alloy of the sacrificial anode material contains Si, Zn and Ni as essential elements.
- Zn added to the sacrificial anode material lowers the potential of the sacrificial anode material, improves the sacrificial anticorrosion effect on the core material, and exhibits the effect of suppressing the corrosion of the core material in an acidic environment.
- the Zn content is 1.0 to 5.0%. If the content is less than 1.0%, the sacrificial anticorrosive effect is not sufficient. On the other hand, if the content exceeds 5.0%, the corrosion rate increases and, conversely, the corrosion resistance is deteriorated.
- a preferable content of Zn is 2.0 to 5.0%.
- Ni added to the sacrificial anode material forms an Al—Ni intermetallic compound.
- deposition of aluminum hydroxide, which is a film component is hindered, and generation of the film is suppressed.
- small film defects increase and corrosion generation is dispersed.
- the Ni content is 0.1 to 2.0%. If the content is less than 0.1%, the above effect is not sufficient, and if it exceeds 2.0%, the Al—Ni intermetallic compound becomes coarse, and the workability decreases.
- a preferable content of Ni is 0.5 to 1.5%.
- Si added to the sacrificial anode material forms an Al—Si—Ni intermetallic compound together with Ni. Since this Al—Si—Ni intermetallic compound is finely dispersed as compared with the Al—Ni intermetallic compound, the corrosion in an alkaline environment is further dispersed, and the progress of the corrosion in the thickness direction is suppressed. Demonstrate the effect.
- the Si content is 0.1 to 0.6%. If the content is less than 0.1%, the above effect is not sufficient. On the other hand, if the content exceeds 0.6%, the corrosion rate of the sacrificial anode material increases.
- a preferable content of Si is 0.2 to 0.5%.
- the sacrificial anode material may contain inevitable impurities such as Zr, Cr, V, etc., each 0.05% or less, and 0.15% or less in total.
- brazing material As the brazing material used for the aluminum alloy clad material according to the present invention, an aluminum alloy usually used in brazing of an aluminum alloy can be used. Examples of such aluminum alloys include Al-5.0 to 12.0% Si-based alloys, Al-5.0 to 12.0% Si-0.05 to 5.0% Zn-based alloys, Al-- Examples include 5.0 to 12.0% Si-0.05 to 5.0% Mg (Bi) alloy.
- the Al—Mn—Fe—Si intermetallic compound crystallizes at a high density, but the equivalent circle diameter is smaller than usual and less than 1 ⁇ m.
- the cooling rate is high, fine Al—Mn—Fe—Si intermetallic compounds having an equivalent circle diameter of less than 0.1 ⁇ m are also dispersed at a high density.
- a fine Al—Mn—Fe—Si system having an equivalent circle diameter of less than 0.1 ⁇ m is obtained by subjecting the ingot after casting to a soaking treatment at 550 to 620 ° C. for 5 hours or more. It has an equivalent circle diameter of 1 to 20 ⁇ m by promoting the Ostwald growth in which the intermetallic compound is dissolved and the coarse Al—Mn—Fe—Si intermetallic compound exceeding 0.1 ⁇ m is further coarsened.
- the number density of the coarse Al—Mn—Fe—Si intermetallic compound can be set to 3.0 ⁇ 10 5 to 1.0 ⁇ 10 6 pieces / cm 2 .
- the temperature of the soaking is less than 550 ° C.
- a fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of less than 0.1 ⁇ m cannot be completely dissolved in the parent phase, and it is 1 to 20 ⁇ m.
- the number density of coarse Al—Mn—Fe—Si intermetallic compounds having an equivalent circle diameter is less than 3.0 ⁇ 10 5 pieces / cm 2 .
- the soaking temperature exceeds 620 ° C., the core material partially melts and a homogeneous material cannot be produced.
- a preferable soaking temperature is 580 to 610 ° C.
- the soaking time is less than 5 hours, a fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of less than 0.1 ⁇ m cannot be completely dissolved in the matrix phase, and it is 1 to 20 ⁇ m.
- the number density of coarse Al—Mn—Fe—Si intermetallic compounds having an equivalent circle diameter is less than 3.0 ⁇ 10 5 pieces / cm 2 . Therefore, the soaking time is 5 hours or longer, preferably 8 hours or longer.
- the upper limit of the soaking time is not particularly limited, but even if the treatment is performed for 20 hours or more, the effect is saturated and uneconomical, so the upper limit is preferably 20 hours.
- Cooling stage after soaking The ingot after soaking is cooled at a cooling rate of 50 ° C./hour or more. As described above, since the soaking is performed at a high temperature of 550 to 620 ° C., a large amount of the additive element is dissolved in the matrix phase in the soaking step. Such a large amount of solid solution can be maintained by performing cooling after soaking at a high speed. After this cooling step, fine Al—Mn—Fe— having a circle equivalent diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is obtained by a heating step (400 to 480 ° C. for 5 hours or more) before hot clad rolling described later. Si-based intermetallic compounds can be deposited.
- the cooling rate after soaking is preferably 70 ° C./hour or more. Moreover, although the upper limit of this cooling rate is restrict
- the temperature of the heating stage before hot clad rolling which will be described in detail later, is 400 to 480 ° C., but when it exceeds 480 ° C., it has a coarse equivalent diameter of 1 to 20 ⁇ m depending on the additive element dissolved in supersaturation. While the Al—Mn—Fe—Si intermetallic compound further grows, at a temperature of 480 ° C. or less, a fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is formed. Newly dense precipitates.
- the ingots for the sacrificial anode material and the brazing material are cast by a normal DC casting method, and soaking and cooling after casting cooling are not performed.
- the resulting ingots for sacrificial anode material and brazing material are hot-rolled to a predetermined thickness at a temperature of 500 to 250 ° C.
- the sacrificial anode material ingot having a predetermined thickness is clad on one surface of the core material ingot cooled after the soaking, and the brazing material ingot having a predetermined thickness is clad on the other surface.
- Hot clad rolling process 3-4-1 Heating stage before rolling
- the clad material clad in the above-described cladding process is then subjected to a heating stage before rolling in the hot cladding rolling process.
- the ingot is heat-treated at 400 to 480 ° C. for 5 hours or more.
- a fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m in the heating stage before rolling as described above. Does not precipitate.
- the temperature in the pre-rolling heating stage is less than 400 ° C.
- diffusion that causes new precipitates to occur does not occur, and fine Al—Mn—Fe having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m.
- -Si-based intermetallic compound does not precipitate.
- the holding time in the pre-rolling heating stage is less than 5 hours
- the number density of the fine Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is 1.0 ⁇ 10 7.
- the number per piece / cm 2 is not reached.
- the upper limit of the holding time is not particularly limited, but the effect is saturated and uneconomical even if the treatment is performed for 10 hours or more, and the upper limit is preferably 10 hours.
- Hot clad rolling stage After the pre-rolling heating stage described above, the clad material is subjected to hot clad rolling.
- hot clad rolling normal conditions, for example, a rolling start temperature of 480 to 350 ° C. and a rolling end temperature of 350 to 250 ° C. are used.
- the rolled sheet is subjected to a cold rolling process.
- the cold rolling process is performed under normal conditions.
- the clad material is subjected to an annealing process at least one of during the cold rolling process (intermediate annealing) and after the cold rolling process (final annealing).
- the annealing temperature is 200 ° C. or more and 400 ° C. or less.
- the additive element of the core material diffuses into the sacrificial anode material and the brazing material, so that fine Al—Mn—Fe having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m.
- the Si-based intermetallic compound is re-dissolved, and the number density of the intermetallic compound is less than 1.0 ⁇ 10 7 pieces / cm 2 .
- the annealing temperature is less than 200 ° C., the core material structure is not sufficiently softened, and the meaning of performing annealing is lost.
- the annealing time is preferably 1 to 5 hours for batch annealing and 0 to 60 seconds for holding time for continuous annealing.
- the holding time of 0 seconds means that the cooling is started immediately after reaching the desired annealing temperature.
- the aluminum clad material manufactured by the above process exhibits a predetermined effect by creating a heat exchanger by a normal manufacturing method.
- the core ingot was further subjected to soaking treatment under the conditions shown in Table 3. Next, the ingot was cooled at a cooling rate shown in Table 3. Then, the ingot for sacrificial anode material and the ingot for brazing material were hot-rolled at 480 ° C. to a predetermined thickness, and these were combined with the ingot for core material to perform hot clad rolling as a laminated material (rolling) (Start temperature: 470 ° C., rolling end temperature: 300 ° C.). Table 3 also shows the conditions for the pre-rolling heating stage before hot cladding.
- the clad plate thus obtained was sequentially subjected to a cold rolling step, an annealing step (intermediate annealing), and a cold rolling step to obtain a final plate (H14) having a thickness of 0.25 mm.
- the intermediate annealing is batch annealing, and the annealing temperature is shown in Table 3.
- the annealing time was 3 hours.
- the clad rates of the sacrificial anode material and the brazing material were 15% and 10%, respectively.
- a clad material sample was produced as described above.
- the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was measured by SEM observation (magnification: 1000 times) of the core alloy. That is, the core material cross section along the thickness direction of the aluminum alloy clad material after the annealing process produced as described above was exposed by polishing, and this exposed surface was used as a sample of the core material alloy.
- NB equivalent post-TS (MPa) JIS No. 5 TP was cut out from the aluminum alloy clad material sample after the annealing process produced as described above, and the brazing equivalent heating was performed. About this, the tensile strength in normal temperature was measured with the tension tester based on JISZ2241. Three samples were measured for each sample, and their arithmetic average value was used as TS after NB. Note that after NB, TS was 140 MPa or higher, and less than that was defective.
- Corrosion resistance in acidic environment
- Corrosion solution NaCl 226 mg, Na 2 SO 4 89 mg, FeCl 3 ⁇ 6H 2 O 145 mg, CuCl 2 ⁇ 2H 2 O 2.6 mg and distilled water added to adjust to 1 L
- Method Specific liquid volume 10 mL / cm 2 Under the conditions, the immersion test was conducted for 90 days to evaluate the corrosion resistance while adding a temperature cycle in which the sample was immersed in an etching solution of 88 ° C. for 8 hours and then kept in a room temperature atmosphere for 16 hours.
- Corrosion resistance in alkaline environment
- Etchant NaCl 226mg, Na 2 SO 4 89 mg, FeCl 3 ⁇ 6H 2 O 145mg, distilled water CuCl 2 ⁇ 2H 2 O 2.6mg addition, after adjusting to 1L, and the pH was adjusted to 11 with NaOH Liquid method: Under the condition of a specific liquid volume of 10 mL / cm 2 , after being immersed in a caustic solution at 88 ° C. for 8 hours and then being kept in a room temperature atmosphere for 16 hours, an immersion test was conducted for 90 days to improve the corrosion resistance. evaluated.
- the density of the Al—Mn—Fe—Si intermetallic compound having a circle-equivalent diameter of 1 to 20 ⁇ m is 3.0 ⁇ 10 5 to 1.0 ⁇ . 10 6 pieces / cm 2
- the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and less than 1 ⁇ m is 1.0 ⁇ 10 7 pieces / cm 2 or more
- the crystal grain size after the NB equivalent was 150 ⁇ m or more
- the TS after the NB equivalent was 140 MPa or more
- the corrosion resistance in both acidic and alkaline environments was good
- the moldability was also good.
- Comparative Example 26 since the Fe content of the core material was too high, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was too high. As a result, the moldability was poor.
- Comparative Example 35 since the sum of the Si content and the Fe content in the core was too small, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m and 0.1 ⁇ m or more and less than 1 ⁇ m. There were too few of them. As a result, penetration occurred in an alkaline environment, and the corrosion resistance in an alkaline environment was poor.
- Comparative Example 45 since the Si content of the sacrificial anode material was too large, penetration occurred in an acidic environment, and the corrosion resistance in an acidic environment was poor.
- Comparative Example 62 since the casting cooling rate was too slow, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was too small. As a result, penetration occurred in an alkaline environment, and the corrosion resistance in an alkaline environment was poor.
- Comparative Example 63 since the soaking temperature was too low, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was too high. As a result, penetration occurred in an alkaline environment, and the corrosion resistance in an alkaline environment was poor.
- Comparative Example 65 since the soaking time was too short, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 1 to 20 ⁇ m was too small. As a result, penetration occurred in an alkaline environment, and the corrosion resistance in an alkaline environment was poor.
- Comparative Example 68 since the heating temperature before rolling was too high, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and 1 ⁇ m or less was too low. As a result, the crystal grain size after NB was poor.
- Comparative Example 70 since the intermediate annealing temperature was too high, the density of the Al—Mn—Fe—Si intermetallic compound having an equivalent circle diameter of 0.1 ⁇ m or more and 1 ⁇ m or less was too low. As a result, the crystal grain size after NB was poor.
- the aluminum alloy clad material according to the present invention has good corrosion resistance and excellent brazeability even in an alkaline environment.
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Abstract
Description
1-1.金属組織を規定する理由
まず、本発明にかかる心材合金の金属組織を決定した理由について説明する。Al-Ni系金属間化合物が存在する部分で水酸化アルミニウムの皮膜欠陥が発生し、腐食発生が分散する。この作用はAl-Ni系金属間化合物に特有のものではなく、Al-Mn-Fe-Si系金属間化合物でも同様の作用が確認された。ここで、Al-Ni系金属間化合物は均熱処理等の熱処理により、分布状態を調整することができない。しかしながら、Al-Mn-Fe-Si系金属間化合物は分布状態の調整が可能である。以上より、心材のAl-Mn-Fe-Si系金属間化合物の分散状態を規定することにより、犠牲陽極材に添加されたNiによるアルカリ性環境下での耐食性をより向上させることができるものである。
心材中に存在する円相当径1~20μmを有するAl-Mn-Si-Fe系金属間化合物は、主に鋳造の凝固中に形成される晶出物である。このような粗大なAl-Mn-Si-Fe系金属間化合物は前述の通りAl-Ni系金属間化合物と同様に、存在する部分で水酸化アルミニウムの皮膜欠落が発生し、腐食の発生が分散する。そして、これによって板厚方向の腐食の進行を抑制する効果が発揮される。このような効果は、1μm未満の円相当径を有するAl-Mn-Si-Fe系金属間化合物では得ることができないので、1μm未満の円相当径を有するものは対象外とした。また、20μmを超える円相当径を有するAl-Mn-Fe-Si系金属間化合物についても、同様に上記の効果を得ることができないため対象外とした。
一方、1~20μmの円相当径を有する粗大なAl-Mn-Fe-Si系金属間化合物を心材に高密度に分散させると、ろう付加熱時に再結晶の核となり得るサイトが増加し、その結果、ろう付加熱時において結晶粒径が小さくなる。ろう付加熱時において結晶粒が小さいと、ろう付性が低下する。このような結晶粒微細化を抑制する為には、0.1μm以上1μm未満の円相当径を有するAl-Mn-Fe-Si系金属間化合物を心材中に微細に分散させ、ろう付加熱時において再結晶の核となるサイトを低減することが有効である。なお、0.1μm未満の円相当径を有するAl-Mn-Si-Fe系金属間化合物は、ろう付加熱中に固溶してしまうため再結晶核の減少に効果を発揮しないので対象外とした。また、1μm以上の円相当径を有するAl-Mn-Fe-Si系金属間化合物は再結晶核となってしまう為に、再結晶核となるサイトの低減という観点から対象外とした。
本発明に係るアルミニウム合金クラッド材に、ろう付け加熱相当である600℃で3分間の加熱処理を施した際において、心材中の結晶粒径は好ましくは150μm以上、より好ましくは160μm以上である。この上限値は心材組成や製造方法などに依存するが、本発明では300μmである。
本発明に係るアルミニウム合金クラッド材に、ろう付け加熱相当である600℃で3分間の加熱処理を施した際に、その引張強度は好ましくは140MPa以上、より好ましくは150MPa以上である。この上限値は心材組成や製造方法などに依存するが、本発明では220MPaである。
本発明に係るアルミニウム合金クラッド材は、圧延方向に沿った伸びとして、好ましくは5%以上、より好ましくは8%以上の伸びを有する。この上限値は心材組成や製造方法などに依存するが、本発明では20%である。
本発明に係る各部材のAl合金の合金組成について、その添加元素の意義と組成範囲の限定理由について説明する。
心材のアルミニウム合金は、Si、Fe、Cu及びMnを必須元素とし、Ti、Zr、V及びCrを選択的添加元素とする。
心材に添加したSiは、心材の強度を向上させる効果を発揮する。Si含有量は、0.3~1.5mass%(以下、単に「%」と記す)である。この含有量が0.3%未満では上記効果が十分でなく、1.5%を超えると、心材の融点を低下させてろう付時に局部溶融が生じ易くなる。Siの好ましい含有量は、0.5~1.2%である。
犠牲陽極材のアルミニウム合金は、Si、Zn及びNiを必須元素とする。
犠牲陽極材に添加したZnは、犠牲陽極材の電位を卑にし、心材に対する犠牲防食効果を向上させ、酸性環境下において心材の腐食を抑制する効果を発揮する。Znの含有量は1.0~5.0%である。この含有量が1.0%未満では上記犠牲防食効果が十分でなく、一方、5.0%を超えると腐食速度が増大し、逆に耐食性を悪化させる。Znの好ましい含有量は2.0~5.0%である。
本発明に係るアルミニウム合金クラッド材に用いるろう材は、アルミニウム合金のろう付において通常用いられるアルミニウム合金を使用できる。このようなアルミニウム合金としては、たとえば、Al-5.0~12.0%Si系合金、Al-5.0~12.0%Si-0.05~5.0%Zn系合金、Al-5.0~12.0%Si-0.05~5.0%Mg(Bi)系合金等を挙げることができる。
次に、本発明に係る熱交換器用アルミニウム合金クラッド材の製造方法について説明する。
まず、心材用鋳塊の鋳造について説明する。所定の成分組成を有するアルミニウム合金素材を溶融し、DC(Direct Chill)鋳造法により心材の鋳塊を作製する。一般的にDC鋳造法では、溶湯凝固時の鋳造冷却速度は0.5~20℃/秒と非常に速いが、Al-Mn-Fe-Si系金属間化合物を高密度に晶出する為には、この鋳造冷却速度を5℃/秒以上、好ましくは8℃/秒以上に規制する必要がある。なお、冷却速度の上限はスラブサイズなどによって制限されるが、本発明では15℃/秒とするのが好ましい。
3-2-1.均熱処理時の保持段階
そこで、鋳造後の鋳塊を550~620℃で5時間以上の均熱処理を行うことにより、0.1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物を固溶させ、かつ、0.1μmを超える粗大なAl-Mn-Fe-Si系金属間化合物を更に粗大化させるオストワルト成長を促進させることによって、1~20μmの円相当径を有する粗大なAl-Mn-Fe-Si系金属間化合物の数密度を3.0×105~1.0×106個/cm2とすることができる。
均熱処理後の鋳塊は、50℃/時間以上の冷却速度で冷却される。上述のように、均熱処理が550~620℃もの高温で実施される為、均熱処理段階において母相に添加元素が多量に固溶する。このような多量の固溶状態は、均熱処理後の冷却を高速で実施することにより維持可能である。そして、この冷却段階後において、後述の熱間クラッド圧延前の加熱段階(400~480℃で5時間以上)により、0.1μm以上1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物を析出させることができる。なお、均熱処理後の冷却速度は、好ましくは70℃/時間以上である。また、この冷却速度の上限はスラブサイズなどによって制限されるが、本発明では110℃/秒とするのが好ましい。
次に、犠牲陽極材用及びろう材用の鋳塊は、通常のDC鋳造法によって鋳造され、鋳造冷却後の均熱処理とその冷却は実施されない。得られる犠牲陽極材用及びろう材用の鋳塊は、500~250℃の温度で所定の厚さまで熱間圧延される。そして、均熱処理後に冷却された心材鋳塊の一方の面に所定厚さとした犠牲陽極材鋳塊を、他方の面に所定厚さとしたろう材鋳塊をクラッドする。
3-4-1.圧延前の加熱段階
上記クラッド工程でクラッドされたクラッド材は、次いで熱間クラッド圧延工程の圧延前加熱段階にかけられる。圧延前加熱段階では、鋳塊は400~480℃で5時間以上熱処理される。この圧延前の加熱段階の温度が480℃を超えると、前述の通り、この圧延前加熱段階において0.1μm以上1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物が析出しない。また、圧延前加熱段階における温度が400℃未満では、新たな析出物が析出するだけの拡散が生起せず、これまた0.1μm以上1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物が析出しない。また、圧延前加熱段階の保持時間が5時間未満では、0.1μm以上1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物の数密度が1.0×107個/cm2に達しない。なお、この保持時間の上限は特に限定されるものではないが、10時間以上処理しても効果が飽和して不経済となるので、10時間を上限とするのが好ましい。
上述の圧延前加熱段階後に、クラッド材は熱間クラッド圧延にかけられる。熱間クラッド圧延では通常の条件、例えば、480~350℃の圧延開始温度と、350~250℃の圧延終了温度が用いられる。
熱間クラッド圧延工程後に、圧延板は冷間圧延工程にかけられる。冷間圧延工程は、通常の条件下で行われる。また、冷間圧延工程の途中(中間焼鈍)及び冷間圧延工程の後(最終焼鈍)の少なくともいずれか一方において、クラッド材は焼鈍工程にかけられる。ここで、焼鈍温度は200℃以上400℃以下である。中間焼鈍や最終焼鈍の温度が400℃を超えると、心材の添加元素が犠牲陽極材及びろう材へ拡散することにより、0.1μm以上1μm未満の円相当径を有する微細なAl-Mn-Fe-Si系金属間化合物が再固溶し、この金属間化合物の数密度が1.0×107個/cm2未満となってしまう。一方、200℃未満の焼鈍温度では、心材組織が十分に軟化されず、焼鈍を実施する意味がなくなる。なお、焼鈍時間は、バッチ式焼鈍では1~5時間、連続式焼鈍では保持時間を0~60秒とするのが好ましい。ここで、保持時間が0秒とは、所望の焼鈍温度に達した直後に冷却を開始することを意味する。
1~20μmの円相当径を有するAl-Mn-Fe-Si系金属間化合物の密度は、心材合金のSEM観察(倍率:1000倍)によって測定した。すなわち、上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材の厚さ方向に沿った心材断面を研磨によって露出させ、この露出面を心材合金の試料に用いた。SEM観察は各試料について3視野ずつ行い、それぞれの視野のSEM像に画像解析ソフト「A像くん」(旭化成エンジニアリング社製)による粒子解析を行うことにより、ろう付加熱前における上記Al-Mn-Fe-Si系金属間化合物の密度を求めた。なお、上記3視野の算術平均値をもって密度とした。
0.1μm以上1μm未満の円相当径を有するAl-Mn-Fe-Si系金属間化合物の密度は、上記(1)と同様にして、心材合金のSEM観察(倍率:5000倍)を行って画像解析することにより、3視野の算術平均値をもって密度とした。
上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材試料に上記ろう付相当加熱を行った後に、圧延方向に直交し、かつ、板厚方向に沿った心材断面を研磨により露出させ、光学顕微鏡(倍率:100倍)を用いて平均結晶粒径を測定した。各試料について5視野ずつ測定し、それらの算術平均値をもってNB相当後結晶粒径とした。なお、NB相当後結晶粒径は150μm以上を良好とし、それ未満を不良とした。
上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材試料からJIS5号TPを切り出し、上記ろう付相当加熱を行った。これについて、JIS Z2241に準拠して引張試験機にて常温での引張強度を測定した。各試料について3個づつ測定し、それらの算術平均値をもってNB相当後TSとした。なお、NB相当後TSは140MPa以上を良好とし、それ未満を不良とした。
上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材試料からJIS5号TPを切り出し、JIS Z2241に準拠して引張試験機にて常温での伸びを測定した。各試料について3個づつ測定し、それらの算術平均値をもって伸びとし、伸びが5%以上を良好とし、それ未満を不良とした。なお、伸びとは、下記式によって定義される。
伸び(%)={(引張試験後における評点間の長さ-引張試験前における評点間の長さ)/(引張試験前における評点間の長さ)}×100
上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材試料(幅3cm×長さ3cm)に上記ろう付相当加熱を行って、腐食試験試料とした。その後、下記方法により腐食試験を行い、貫通の有無及び粒界腐食の有無を光学顕微鏡(倍率:200倍)によって調べた。貫通が無く、かつ、粒界腐食が無いものを良好とし、それ以外を不良とした。
腐食液:NaCl 226mg、Na2SO4 89mg、FeCl3・6H2O 145mg、CuCl2・2H2O 2.6mgに蒸留水を加え、1Lに調整した液
方法:比液量10mL/cm2の条件で、88℃の腐食液に8時間浸漬した後に、室温雰囲気中で16時間保持するという温度サイクルを加えながら、浸漬試験を90日間行って耐食性を評価した。
上述のようにして作製した焼鈍工程後のアルミニウム合金クラッド材試料(幅3cm×長さ3cm)に上記ろう付相当加熱を行って、腐食試験試料とした。その後、下記方法により腐食試験を行い、貫通の有無及び粒界腐食の有無を光学顕微鏡(倍率:200倍)によって調べた。貫通が無く、かつ、粒界腐食が無いものを良好とし、それ以外を不良とした。
腐食液:NaCl 226mg、Na2SO4 89 mg、FeCl3・6H2O 145mg、CuCl2・2H2O 2.6mgに蒸留水を加え、1Lに調整した後に、NaOHによってpHを11に調整した液
方法:比液量10mL/cm2の条件で、88℃の腐食液に8時間浸漬した後に、室温雰囲気中で16時間保持するという温度サイクルを加えながら、浸漬試験を90日間行って耐食性を評価した。
2・・・フィン
3・・・ヘッダープレート
4・・・コア
5A、5B・・・樹脂タンク
6・・・バッキング
Claims (7)
- アルミニウム合金の心材と、当該心材の一方の面にクラッドされた犠牲陽極材と、前記心材の他方の面にクラッドされたAl-Si系ろう材とを備えるアルミニウム合金クラッド材であって、前記心材が、Si:0.3~1.5mass%、Fe:0.1~1.5mass%、Cu:0.2~1.0mass%、Mn:1.0~2.0mass%を含有し、Si含有量+Fe含有量≧0.8mass%の関係にあり、残部Al及び不可避的不純物からなるアルミニウム合金からなり、1~20μmの円相当径を有するAl-Mn-Si-Fe系金属間化合物の密度が3.0×105~1.0×106個/cm2、且つ、0.1μm以上1μm未満の円相当径を有するAl-Mn-Si-Fe系金属間化合物の密度が1.0×107個/cm2以上であり、前記犠牲陽極材が、Si:0.1~0.6mass%、Zn:1.0~5.0mass%、Ni:0.1~2.0mass%を含有し、残部Al及び不可避的不純物からなるアルミニウム合金からなることを特徴とするろう付性及び耐食性に優れたアルミニウム合金クラッド材。
- 前記心材が、Ti:0.05~0.20mass%、Zr:0.05~0.20mass%、V:0.05~0.20mass%及びCr:0.05~0.20mass%から選択される1種又は2種以上を更に含有する、請求項1に記載のろう付性及び耐食性に優れたアルミニウム合金クラッド材。
- 600℃で3分間のろう付け加熱相当後において、前記心材の結晶粒径が150μm以上である、請求項1又は2に記載のアルミニウム合金クラッド材。
- 600℃で3分間のろう付け加熱相当後において、140MPa以上の引張強度を有する、請求項1~3のいずれか一項に記載のアルミニウム合金クラッド材。
- 5%以上の圧延方向に沿った伸びを有する、請求項1~4のいずれか一項に記載のアルミニウム合金クラッド材。
- 請求項1~5のいずれか一項に記載のアルミニウム合金クラッド材の製造方法であって、前記心材用、犠牲陽極材用及びろう材用のアルミニウム合金をそれぞれ鋳造する工程と、心材鋳塊に高温で均熱処理を行う鋳造後熱処理工程と、心材鋳塊の一方の面に所定厚さとした犠牲陽極材鋳塊と他方の面に所定厚さとしたろう材鋳塊をクラッドするクラッド工程と、クラッド材を熱間圧延する熱間クラッド圧延工程と、熱間クラッド圧延したクラッド材を冷間圧延する冷間圧延工程と、冷間圧延工程の途中及び冷間圧延工程の後の少なくともいずれか一方においてクラッド材を焼鈍する焼鈍工程とを含み、前記心材用鋳塊の鋳造工程が、5℃/秒以上の速度で鋳塊を冷却する鋳造冷却段階を備え、前記鋳造後熱処理工程が冷却した鋳塊を550~620℃で5時間以上均熱処理する均熱処理段階と、均熱処理した鋳塊を50℃/時間以上の速度で冷却する冷却段階とを備え、前記熱間クラッド圧延工程が、400~480℃で5時間以上の圧延前の加熱段階を備え、前記焼鈍工程における焼鈍温度が400℃以下であることを特徴とするアルミニウム合金クラッド材の製造方法。
- 前記熱間クラッド圧延の圧延開始温度が480~350℃であり、圧延終了温度が350~250である、請求項6に記載のアルミニウム合金クラッド材の製造方法。
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- 2015-03-11 US US15/125,968 patent/US10183362B2/en not_active Expired - Fee Related
- 2015-03-11 EP EP15764544.1A patent/EP3121300B1/en not_active Not-in-force
- 2015-03-11 CN CN201580012680.1A patent/CN106068332B/zh not_active Expired - Fee Related
- 2015-03-11 WO PCT/JP2015/001341 patent/WO2015141192A1/ja active Application Filing
- 2015-03-11 JP JP2016508522A patent/JP6407253B2/ja not_active Expired - Fee Related
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CN107498210A (zh) * | 2017-08-16 | 2017-12-22 | 江苏阳明船舶装备制造技术有限公司 | 一种用于紫铜表面改性的Cu基材料及制备和焊接方法 |
Also Published As
Publication number | Publication date |
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CN106068332A (zh) | 2016-11-02 |
CN106068332B (zh) | 2017-10-31 |
US20170080528A1 (en) | 2017-03-23 |
US10183362B2 (en) | 2019-01-22 |
EP3121300A4 (en) | 2017-05-10 |
JP6407253B2 (ja) | 2018-10-17 |
EP3121300A1 (en) | 2017-01-25 |
EP3121300B1 (en) | 2018-08-01 |
JPWO2015141192A1 (ja) | 2017-04-06 |
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