US20120129003A1 - High-strenght aluminum alloy brazing sheet and method of manufacture - Google Patents

High-strenght aluminum alloy brazing sheet and method of manufacture Download PDF

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Publication number
US20120129003A1
US20120129003A1 US13/200,241 US201113200241A US2012129003A1 US 20120129003 A1 US20120129003 A1 US 20120129003A1 US 201113200241 A US201113200241 A US 201113200241A US 2012129003 A1 US2012129003 A1 US 2012129003A1
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Prior art keywords
range
falling
mass
core material
aluminum alloy
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US13/200,241
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Inventor
Makoto Ando
Akio Niikura
Yoichiro Bekki
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Furukawa Sky Aluminum Corp
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Furukawa Sky Aluminum Corp
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Application filed by Furukawa Sky Aluminum Corp filed Critical Furukawa Sky Aluminum Corp
Publication of US20120129003A1 publication Critical patent/US20120129003A1/en
Assigned to FURUKAWA SKYALUMINUM CORP reassignment FURUKAWA SKYALUMINUM CORP ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ANDO, MAKATO, BEKKI, YOICHIRO, NIIKURA, AKIO
Priority to US14/528,930 priority Critical patent/US9878402B2/en
Abandoned legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/001Interlayers, transition pieces for metallurgical bonding of workpieces
    • B23K35/002Interlayers, transition pieces for metallurgical bonding of workpieces at least one of the workpieces being of light metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/0008Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0012Brazing heat exchangers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/20Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • B23K1/203Fluxing, i.e. applying flux onto surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0233Sheets, foils
    • B23K35/0238Sheets, foils layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/28Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286Al as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/016Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/12Alloys based on aluminium with copper as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/12Alloys based on aluminium with copper as the next major constituent
    • C22C21/14Alloys based on aluminium with copper as the next major constituent with silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/043Changing 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 silicon as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00Articles made by soldering, welding or cutting
    • B23K2101/006Vehicles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00Articles made by soldering, welding or cutting
    • B23K2101/04Tubular or hollow articles
    • B23K2101/14Heat exchangers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/084Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/089Coatings, claddings or bonding layers made from metals or metal alloys
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736Al-base component
    • Y10T428/12764Next to Al-base component

Definitions

  • the present invention relates to an aluminum alloy brazing sheet used in a heat exchanger for an automobile. More specifically, the present invention relates to a high strength aluminum alloy brazing sheet which is suitably utilized as a passage-forming member for a compressed air having a high temperature air or a cooling medium, and a method of manufacturing such a brazing sheet.
  • an aluminum alloy exhibits a lightweight nature and a high thermal conductivity, and since a high corrosion-resistant feature can be realized in the aluminum alloy by a suitable processing, it is utilized in a heat exchanger for an automobile, for example, a radiator, a condenser, an evaporator, a heater, an intercooler and so forth.
  • a 2-ply clad material or a 3-ply clad material is used: the 2-ply clad material includes a core material composed of an Al/Mn-based alloy such as JIS3003 alloy and so forth, and an Al/Si-based filler material or an Al/Zn-based sacrificial anode material cladded on one surface of the core material; and the 3-ply clad material includes a core material composed of an Al/Mn-based alloy such as JIS3003 alloy and so forth, an Al—Si-based filler material or an Al/Zn-based sacrificial anode material cladded on one surface of the core material, and an Al/Si-based filler material cladded on the other surface of the core material.
  • the 2-ply clad material includes a core material composed of an Al/Mn-based alloy such as JIS3003 alloy and so forth, and an Al/Si-based filler material or an Al/Zn-based sacrificial anode
  • one of these clad materials is combined with and joined to a corrugated fin by carrying out a brazing process at a high temperature on the order of 600 C, to thereby produce a tube member.
  • the tube members so produced are installed as a heat exchanger in an automobile, when any one of the tube members is broken and pierced, the tube member concerned leaks a cooling water or a cooling medium circulating in an interior of the heat exchanger.
  • an aluminum alloy brazing sheet exhibiting a superior strength after being subjected to a brazing process.
  • a 3-ply tube member has been used, with the 3-ply tube member including a core material composed of an Al/Mn-based alloy or the like, which is represented by JIS 3003, an inner surface of the core material being cladded with a sacrifice material such as Al/Zn-based alloy or the like, an atmosphere-side surface or outer surface of the core material being cladded with a filler material such as Al/Si-based alloy or the like.
  • a strength of the clad material, in which the core material composed of JIS 3003 alloy is used is on the order of 110 MPa after it is subjected to a brazing process, and this strength is insufficient.
  • the core material composed of the Al/Mn-based alloy which covers a major part of the strength of the brazing sheet, is a dispersion strengthened alloy.
  • the core material is strengthened by making the density of particles of intermetallic compounds in the core material high, and making the particles of intermetallic compounds in the core material small.
  • the brazing sheet is heated to a temperature of 600 C, a major part of the fine intermetallic compounds is again subjected to a solid solution.
  • Patent Document 1 it is disclosed that a core material is subjected to a homogenization process at a temperature of at least 570 C over a time period of at least 8 hrs, that the core material is then subjected to a hot rolling process at a temperature within a range of 450-550 C, and that various conditions of other processes are minutely regulated.
  • a metal texture so obtained features that a density of precipitates having a size of at least 1 m is at least 10,000/mm 2 . Nevertheless, no reference is made to the fact that the intermetallic compounds are again subjected to the solid solution during the brazing process.
  • a feature of the present invention is the providing of an aluminum alloy brazing sheet not only has a superior brazing property and a superior corrosion resistance, but also features a large strength.
  • the present invention aims at providing an aluminum alloy brazing sheet, which can be suitably utilized as a passage-forming member for an automobile heat exchanger, and a method of manufacturing the aluminum alloy brazing sheet.
  • the present invention relates to a high strength aluminum alloy brazing sheet having a core material composed of an aluminum alloy; and a filler material cladded on at least one surface of the core material and composed of an Al/Si-based alloy.
  • the core material is an aluminum alloy which contains Si within a range of about 0.05-about 1.2 mass %, Fe within the range of about 0.05-about 1.0 mass %, Cu within the range of about 0.05-about 1.2 mass %, and Mn within the range of about 0.6-about 1.8 mass %, and where the balance is Al and the inevitable impurities;
  • the filler material is an aluminum alloy which contains Si within a range of about 2.5-about 13.0 mass %, and Fe falling within a range of about 0.05-about 1.0 mass %, and where the balance is Al and the inevitable impurities; and that the area percentage, at which an arbitrary cross-section of the core material before a brazing process is occupied with intermetallic compounds having a size falling within a range of about 0.2
  • the present invention relates to a core material that further contains at least one element selected from the group of Mg falling within a range of about 0.05-about 0.5 mass %, Ti falling within a range of about 0.05-about 0.3 mass %, Zr falling within a range of about 0.05-about 0.3 mass %, Cr falling within a range of about 0.05-about 0.3 mass %, and V falling within a range of about 0.05-about 0.3 mass %, in addition to the aforesaid elements.
  • the present invention relates to a filler material cladded to the aforesaid one surface of the core material further contains Zn falling within a range of 0.3-5.5 mass %, in addition to the aforesaid elements.
  • the present invention relates to a high strength aluminum alloy brazing sheet that includes a core material composed of an aluminum alloy; a filler material cladded on a surface of the core material and composed of an Al/Si-based alloy; and a sacrificial anode material cladded on another surface of the core material and composed of an aluminum alloy
  • the core material is an aluminum alloy which contains Si falling within a range of about 0.05-about 1.2 mass %, Fe falling a range of about 0.05-about 1.0 mass %, Cu falling within a range of about 0.05-about 1.2 mass %, and Mn falling within a range of about 0.6-about 1.8 mass %, and where the balance is Al and the inevitable impurities
  • the filler material is an aluminum alloy that contains Si falling within a range of 2.5-13.0 mass %, and Fe falling within a range of 0.05-1.0 mass %, and where the balance is Al and the inevitable impurities
  • the sacrificial anode material is an aluminum alloy
  • the present invention relates to a core material that further contains at least one element selected from the group of Mg falling within a range of about 0.05-about 0.5 mass %, Ti falling within a range of about 0.05-about 0.3 mass %, Zr falling within a range of about 0.05-about 0.3 mass %, Cr falling within a range of about 0.05-about 0.3 mass %, and V falling within a range of about 0.05-about 0.3 mass %, in addition to the aforesaid elements.
  • the present invention relates to a filler material further contains Zn falling within a range of about 0.3-about 5.5 mass %, in addition to the aforesaid elements.
  • the present invention relates to a sacrificial anode material that further contains at least one element selected from the group Mn falling within a range of about 0.05-about 1.8 mass %, Mg falling within a range of about 0.5-about 3.0 mass %, Ti falling within a range of about 0.05-about 0.3 mass %, Zr falling within a range of about 0.05-about 0.3 mass %, Cr falling within a range of about 0.05-about 0.3 mass %, and V falling within a range of about 0.05-about 0.3 mass %, in addition to the aforesaid elements.
  • Mn falling within a range of about 0.05-about 1.8 mass %
  • Mg falling within a range of about 0.5-about 3.0 mass %
  • Ti falling within a range of about 0.05-about 0.3 mass %
  • Zr falling within a range of about 0.05-about 0.3 mass %
  • Cr falling within a range of about 0.05-about 0.3 mass %
  • V falling
  • the present invention relates to a method of manufacturing a high strength aluminum alloy brazing sheet as set forth in any one of aspects 1 to 3.
  • the method entails casting processes for casting the aluminum alloys of the core material and the filler material, respectively; a combining process in which the cast core material is combined with the cast filler material so that the cast filler material is applied to at least one surface of the cast core material, to thereby produce a composite material; a heating process in which the composite material is heated and held after the combining process; and a hot clad rolling process in which the composite material is rolled after the heating process where the casting speed V (mm/min) and an amount of cooling water W (kg/min ⁇ cm) satisfy the following formula (1) in the casting process for the core material:
  • the composite material is held at a temperature falling within a range of about 400-about 500 C over a time period falling within a range of 0-about 10 hrs during the heating process; that a time period, which is counted from a rolling start, and which is taken to reduce a thickness of the composite material by 50 mm, is at most 5 min in the hot clad rolling process; that a temperature of the composite material falls within a range of about 400-about 45° C.
  • the present invention relates to a method of manufacturing a high strength aluminum alloy brazing sheet as set forth in any one of aspects 4 to 7 above entailing: casting processes for casting the aluminum alloys of the core material, the filler material and the sacrificial anode material, respectively; a combining process in which the cast core material is combined with the cast filler material and the cast sacrificial anode material so that the cast filler material is applied to at least one surface of the cast core material, and so that the cast sacrificial anode material to another surface of the cast core material, to thereby produce a composite material; a heating process in which the composite material is heated and held after the combining process; and a hot clad rolling process in which the composite material is rolled after the heating process where a casting speed V (mm/min) and an amount of cooling water W (kg/min ⁇ cm) satisfy the following formula (1) in the casting process for the core material:
  • the composite material is held at a temperature falling within a range of about 400-about 500 C over a time period falling within a range of 0-about 10 hrs during the heating process; that a time period, which is counted from a rolling start, and which is taken to reduce a thickness of the composite material by 50 mm, is at most 5 min in the hot clad rolling process; that a temperature of the composite material falls within a range of about 400-about 45° C.
  • a high strength aluminum alloy brazing sheet exhibiting a high strength after a brazing process, and a method of manufacturing such a brazing sheet. Also, not only can this brazing sheet have superior brazing properties such as a fin joining rate, an erosion resistance and so forth, but also it is possible to attain a superior corrosion resistance, using a filler material composed of suitable components or a sacrificial anode material composed of suitable components, or using a filler material of composed of suitable components and a sacrificial anode material composed of suitable components.
  • the aluminum alloy brazing sheet according to the present invention can be suitably utilized as a tube member in a heat exchanger for an automobile due to not only the aforesaid features but also a lightweight nature and a high thermal conductivity thereof.
  • an aluminum alloy brazing sheet according to the present invention and a method of manufacturing such a brazing sheet will now be explained in detail.
  • performance on a strength and a corrosion resistance is referred to as being obtained after a brazing process.
  • the brazing process is carried out in such a manner that the brazing sheet is heated to a temperature on the order of about 60° C., and is then air-cooled, and thus a heating process, a heating rate, a cooling rate, a heating time, a cooling time and so forth are not especially limited.
  • Si produces Al/Mn/Si-based intermetallic compounds together with Mn, and improves strength of the core material by either a dispersion hardening effect or a solid solution strengthening effect obtained due to a solid solution of Si in the matrix phase of aluminum.
  • the content of Si falls within a range of about 0.05-about 1.2 mass % (which is merely abbreviated to % hereinafter). When the Si content is less than about 0.05%, the aforesaid effect is small. When the Si content exceeds about 1.2%, a melting point of the core material declines, and thus an erosion of the core material by the filler material occurs.
  • the Si content falls within a range of about 0.3-about 1.0%.
  • Fe easily produces intermetallic compounds having a size which can serve as nucleuses for recrystallization, and makes a crystallized grain diameter large after a brazing process.
  • the content of Fe falls within a range of about 0.05-about 1.0%.
  • the Fe content is less than about 0.05%, it is necessary to use a high-purity aluminum metal, resulting in an increase in a manufacturing cost.
  • the Fe content exceeds about 1.0%, the crystallized grain diameter becomes fine after a brazing process, and thus the diffusion of the filler material is caused.
  • the Fe content falls within a range of about 0.1-about 0.5%.
  • Cu improves a strength of the core material by a solid solution strengthening effect.
  • the content of Cu falls within a range of about 0.05-about 1.2%. When the Cu content is less than about 0.05%, the aforesaid effect becomes small. When the Cu content exceeds about 1.2%, a crack occurs in the aluminum alloy during a casting process. Preferably, the Cu content falls within a range about 0.3-about 1.0%.
  • Mn produces Al/Mn/Si-based intermetallic compounds together with Si, and improves strength of the core material by either a dispersion hardening effect or a solid solution strengthening effect obtained due to a solid solution of Mn in the matrix phase of aluminum.
  • the content of Mn falls within a range of about 0.6-about 1.8%. When the Mn content is less than about 0.6%, the aforesaid effect becomes small. When the Mn content exceeds about 1.8%, large intermetallic compounds are easily produced during a casting process so that a plastic-workability deteriorates.
  • the Mn content falls within a range of about 0.8-about 1.6%.
  • Mg improves a strength of the core material by separation of Mg 2 Si, and thus it is preferable that the core material contains Mg.
  • a content of Mg falls within a range of about 0.05-about 0.5%.
  • the Mg content is less than about 0.05%, there may be a case where the aforesaid effect becomes small.
  • the Mg content exceeds about 0.5%, there may be a case where it is difficult to carry out a brazing process. More preferably, the Mg content falls within a range of about 0.15-about 0.4%.
  • Ti improves a strength of the core material by a solid solution strengthening effect, and thus it is preferable that the core material contains Ti.
  • the content of Ti falls within a range of about 0.05-about 0.3%.
  • the Ti content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Ti content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the Ti content falls within a range of about 0.1-about 0.2%.
  • the core material contains Zr.
  • the content of Zr falls within the range of about 0.05-about 0.3%.
  • the Zr content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Zr content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the Zr content falls within a range of about 0.1-about 0.2%.
  • the core material contains Cr.
  • the content of Cr falls within the range of about 0.05-about 0.3%.
  • the Cr content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Cr content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the Cr content falls within a range of about 0.1-about 0.2%.
  • V improves strength of the core material by a solid solution strengthening effect, and thus it is preferable that the core material contains V.
  • the content of V falls within the range of about 0.05-about 0.3%.
  • the V content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the V content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the V content falls within a range of about 0.1-about 0.2%.
  • At least one of the elements Mg, Ti, Zr, Cr and V may be contained in the core material. Also, each of these elements may contain the inevitable impurities of at most 0.05%, and a total content of the inevitable impurities may be at most 0.15%.
  • Si causes a fall of a melting point of the filler material so that the filler material may take on a liquid phase, to thereby make a brazing process possible.
  • the content of Si falls within a range of about 2.5-about 13.0%.
  • the Si content is less than about 2.5%, an amount of the liquid phase becomes small so that a brazing function cannot be sufficiently obtained.
  • the Si content exceeds about 13.0%, an amount of Si which is diffused into a counter-material such as a fin material and so forth is excessive, to thereby cause a melting of the counter-material. It is preferable that the Si content falls within a range of about 3.5-about 12.0%, more preferably, about 7.0-about 12.0%.
  • Fe easily produces Al/Fe-based compounds and Al/Fe/Si-based compounds. Due to the production of the Al/Fe/Si-based compounds, an effective Si amount of the filler material declines. Also, due to the production of the Al/Fe-based compounds and Al/Fe/Si-based compounds, fluidity of the filler material declines during a brazing process, resulting in deterioration in a brazing property.
  • the content of Fe falls within a range of about 0.05-about 1.0%. When the Fe content exceeds about 1.0%, a brazing property deteriorates so that sufficient brazing cannot be obtained. On the other hand, when the Fe content is less than about 0.05%, it is necessary to use a high-purity aluminum metal, resulting in an increase in a manufacturing cost. Preferably, the Fe content falls within a range of about 0.1-about 0.8%.
  • Zn can give a lower potential to the filler material to thereby establish a potential difference between the filler material and the core material whereby it is possible to improve a corrosion resistance due to a sacrificial anode effect, and thus it is preferable that the filler material contains Zn.
  • the content of Zn falls within a range of about 0.3-about 5.5%. When the Zn content is less than about 0.3%, there may be a case where the aforesaid effect is not sufficiently obtained. When the Zn content exceeds about 5.5%, Zn is concentrated in a joining area on a counter-material such as a fin material and so forth, and the concentrated joining area is subjected to a prior corrosion so that the counter-material may be peeled. More preferably, the Zn content falls within the range of about 0.5-about 3.0%.
  • Each of these elements may contain the inevitable impurities in an amount of at most 0.05%, and that a total content of the inevitable impurities may be at most 0.15%.
  • the filler material may be cladded on at least one surface of the core material.
  • Zn can give a lower potential to the sacrificial anode material to thereby establish a potential difference between the sacrificial anode material and the core material whereby it is possible to improve a corrosion resistance by a sacrificial anode effect.
  • the content of Zn falls within a range of about 0.5-about 6.0%. When the Zn content is less than about 0.5%, the aforesaid effect cannot be sufficiently obtained. When the Zn content exceeds about 6.0%, a corrosion rate is accelerated so that the sacrificial anode material prematurely disappears, resulting in deterioration in a corrosion resistance.
  • the Zn content falls within the range of about 1.0-about 5.0%.
  • Si produces Al/Fe/Mn/Si-based compounds together with Fe and Mn, and improves a strength of the sacrificial anode material by either a dispersion hardening effect or a solid solution strengthening effect obtained due to a solid solution of Si in the matrix phase of aluminum. Also, Si reacts with Mg diffused from the core material, to thereby produce Mg 2 Si compounds so that the sacrificial anode material is strengthened.
  • the content of Si falls within a range of about 0.05-about 1.5%. When the Si content is less than about 0.05%, it is necessary to use a high-purity aluminum metal, resulting in an increase in a manufacturing cost.
  • the Si content falls within a range of about 0.05-about 1.2%.
  • Fe produces Al/Fe/Mn/Si-based compounds together with Si and Mn, and improves strength of the sacrificial anode material by a dispersion hardening effect.
  • the content of Fe falls within a range of about 0.05-about 2.0%.
  • the Fe content is less than about 0.05%, it is necessary to use a high-purity aluminum metal, resulting in an increase in a manufacturing cost.
  • the Fe content exceeds about 2.0%, large intermetallic compounds are easily produced during a casting process so that a plastic-workability deteriorates.
  • the Fe content falls within a range of about 0.05-about 1.5%.
  • the sacrificial anode material contains Mn.
  • the content of Mn falls within a range of about 0.05-about 1.8%.
  • the Mn content exceeds about 1.8%, there may be a case where large intermetallic compounds are easily produced during a casting process so that a plastic-workability deteriorates, and where an upper potential is given to the sacrificial anode material so that a sacrificial anode effect is suppressed, resulting in deterioration in a corrosion resistance.
  • the Mn content is less than about 0.05%, there may be a case where the aforesaid effect is not sufficiently obtained. More preferably, the Mn content falls within a range of about 0.05-about 1.5%.
  • Mg improves strength of the sacrificial anode material due to separation of Mg 2 SiMg. Also, not only the strength of the sacrificial anode material per se is improved, but also a strength of the core material is improved due to the fact that Mg is diffused into the core material during a heating process for brazing. For these reasons, it is preferable that the sacrificial anode material contains Mg.
  • the content of Mg falls within a range of about 0.5-about 3.0%. When the Mg content is less than about 0.5%, there may be a case where the aforesaid effect becomes small.
  • the Mg content falls within the range of about 0.5-about 2.0%.
  • Mg retards a brazing property in a Nocolok brazing method when the sacrificial anode material contains Mg in an amount of at most 0.5%, it is impossible to carry out the Nocolok brazing method.
  • a welding method in order to join tube members to each other, it is necessary to utilize, for example, a welding method.
  • Ti improves not only strength of the sacrificial anode material by a solid solution strengthening effect, but also corrosion resistance, and thus it is preferable that the sacrificial anode material contains Ti.
  • the content of Ti falls within a range of about 0.05-about 0.3%.
  • the Ti content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Ti content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates.
  • the Ti content falls within a range of about 0.05-about 0.2%.
  • the sacrificial anode material contains Zr.
  • the content of Zr falls within a range of about 0.05-about 0.3%.
  • the Zr content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Zr content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the Zr content falls within the range of about 0.1-about 0.2%.
  • the sacrificial anode material contains Cr.
  • the content of Cr falls within a range of about 0.05-about 0.3%.
  • the Cr content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the Cr content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates. More preferably, the Cr content falls within the range of about 0.1-about 0.2%.
  • V improves not only a strength of the sacrificial anode material by a solid solution strengthening effect, but also corrosion resistance, and thus it is preferable that the sacrificial anode material contains V.
  • the content of V falls within a range of about 0.05-about 0.3%.
  • the V content is less than about 0.05%, there may be a case where the aforesaid effect is not obtained.
  • the V content exceeds about 0.3%, large intermetallic compounds are easily produced so that there may be a case where a plastic-workability deteriorates.
  • the V content falls within the range of about 0.05-about 0.2%.
  • At least one of the elements Mn, Mg, Ti, Zr, Cr and V may be added to the sacrificial anode material, if necessary.
  • each of these elements may contain the inevitable impurities in an amount of at most 0.05%, and the total content of the inevitable impurities may be at most 0.15%.
  • the sacrificial anode material is cladded on one surface of the core material.
  • the aluminum alloy brazing sheet according to the present invention participates in a metal texture of the core material.
  • a metal texture an area percentage, at which an arbitrary cross-section of the core material before a brazing process is occupied with intermetallic compounds having a size falling within a range of 0.2-0.5 m, is at most 5%, and a solid solution amount of Mn is limited to at least 0.2% in the core material after the brazing process.
  • the ground for this limitation will be explained below.
  • the size of the intermetallic compounds is defined as a projected area diameter.
  • a solid solution amount of Mn becomes large in the core material after a brazing process.
  • the solid solution amount of Mn is at least 0.2% after the brazing process, a solid solution strengthening effect can be sufficiently obtained.
  • the solid solution amount of Mn is less than 0.2% after the brazing process, the solid solution strengthening effect becomes small. Note, although there is no upper limit of the solid solution amount of Mn in view of a high strengthening of the core material, it is difficult to obtain the solid solution amount of Mn having more than 0.8% in the components of the core material according to the present invention.
  • the measurement of the solid solution amount of Mn after the brazing process is carried out by: removing a cladding from the core material with a caustic etching process; resolving the core material in a phenol solution; filtering the un-resolvable intermetallic compounds out of the solution; and by subjecting the intermetallic compounds to a measuring process using an optical emission spectrometer.
  • the intermetallic compounds having a relative large size should become as small as possible in a blank state of the core material before the brazing process.
  • the Mn solid solution amount of at least 0.2% after the brazing process it has been found by the inventors that it is possible to obtain the Mn solid solution amount of at least 0.2% after the brazing process to thereby attain a sufficient solid solution strengthening effect when the area percentage of the intermetallic compound having the size falling within the range of about 0.2-about 0.5 m included in the core material in a blank of the brazing sheet before the brazing process is at most 5% in the arbitrary cross-section of the core material before the brazing process.
  • the area percentage of the intermetallic compound having the size falling within the range of 0.2-0.5 m exceeds 5%, the Mn solid solution amount becomes less than 0.2% after the brazing process, it is extremely difficult to obtain a sufficient solid solution strengthening effect. Since the intermetallic compounds having a size of less than 0.2 m is again subjected to a solid solution during the brazing process so that the solid solution strengthening effect cannot be retarded after the brazing process. Also, the intermetallic compounds having a size of more than 0.5 m are ordinarily Al/Fe/Si-based crystallization products, and do not prevent the solid solution of Mn, so that a decline in the strength is not caused.
  • an amount of heat to be applied to the core material in various processes between a casting process and a hot rolling process should be controlled so as to be small.
  • a cooling rate is significant during a casting process of the core material. The faster the cooling rate, the smaller an amount of the intermetallic compounds.
  • the cooling is carried out by a DC method, and a casting rate V (mm/min) and an amount of cooling water (kg/min ⁇ cm) exert a large influence on the amount of the intermetallic compounds as factors for determining the cooling rate during the casting process.
  • a temperature of a molten metal falls within the range of about 670-about 80° C., and that a height of a metal head falls within a range of about 50-about 150 mm.
  • respective casting processes for sacrificial anode and filler materials are not especially subjected to limitations, it is preferable that each of these processes is carried out by using the DC method, that a temperature of a molten metal falls within a range of about 670-about 80° C., and that a height of a metal head falls within a range of about 50-about 150 mm.
  • each of the composite materials has a thickness falling within a range of about 250-about 800 mm, preferably, a range of about 300-about 600 mm.
  • each of the composite materials is subjected to the heating process.
  • each of the composite materials is held at a heating temperature falling within a range of about 400-about 50° C. over a time period falling within a range of 0- about 10 hrs. Accordingly, it is possible to suppress excess separation of intermetallic compounds during the heating process.
  • the heating temperature is less than about 40° C., since each of the composite materials has a large resistance to deformation during the following hot clad rolling process, there may be a case where it is difficult to carry out the hot clad rolling process.
  • the heating temperature exceeds about 50° C.
  • the heating/holding time is zero, as stated hereinafter. Therefore, as conditions for the heating process prior to the hot clad rolling process, the heating temperature of about 400-about 50° C. and the heating/holding time of 0-10 hrs are selected. As preferable conditions for the heating process, the heating temperature of about 400-about 48° C. and the heating/holding time of about 2-about 5 hrs are selected.
  • the heating time should be set as short as possible.
  • the heating/holding time is defined as zero.
  • each of the composite materials is immediately subjected to the hot clad rolling process.
  • the hot clad rolling process is started.
  • the hot clad rolling process since a separation of the intermetallic compounds is facilitated due to influence of strain exerted on the composite material, it is very significant that the hot clad rolling process is finished at a short time.
  • a time period which is counted from a start of the hot clad rolling process to which each of the composite materials is subjected, and which is taken to reduce an initial thickness of the composite materials falling within the range of 250-800 mm by 50 mm, is defined as a step in which either the core material and the filler material(s) or the core material, the filler material and the sacrificial anode material are pressure-joined to each other to thereby produce a clad material.
  • a control is carried out so that the time period of the aforesaid step is at most 5 min, and a control is carried out so that a temperature of the clad materials falls within the range of about 400-about 45° C.
  • the time period which is counted from the rolling start, and which is taken to reduce the thickness of the clad material by 50 mm, exceeds 5 min, and/or when the temperature of the clad material exceeds 450 C at the time when the thickness of the clad material is reduced by 50 mm, the intermetallic compounds are excessively separated in the core material.
  • the heating temperature in the heating process must be at least 400 C, the temperature of the clad material must not be less than 400 C at the time when the thickness of the clad material is reduced by 50 mm.
  • the time period which is counted from the start of the hot clad rolling process, and which is taken to reduce the thickness of the clad material by 50 mm, is regulated so as to be at most 5 min, and the temperature of the clad material is regulated so as to fall within the range of about 400-about 45° C. at the time when the thickness of the clad material is reduced by 50 mm.
  • a time period between the time when the thickness of the clad material is reduced by 50 mm so that the respective materials of the clad material are sufficiently pressure-joined to each other and a time when the thickness of the clad material is reduced to 20 mm is defined as a step in which a temperature of the clad material is relatively high, and in which an amount of strain exerted on the clad material is very large.
  • a time period which is taken to carry out this step is regulated so as to be at most 10 min, and the temperature of the clad material is regulated so as to fall within a range of about 300-about 40° C. at the time when the thickness of the clad material is reduced to 20 mm, so that it is possible to suppress the excessive separation of the intermetallic compounds in the core material.
  • the time period which is counted from the time when the thickness of the clad material is reduced by 50 mm to the time when the thickness of the clad material is reduced to 20 mm, exceeds 10 min, and/or when the temperature of the clad material exceeds 400 C at the time when the thickness of the clad material is reduced to 20 mm, the intermetallic compounds are excessively separated in the core material.
  • the heating temperature in the heating process must be at least 400 C, it is difficult to set the temperature of the clad material at less than 300 C at the time when the thickness of the clad material is reduced to 20 mm.
  • the time period which is counted from the time when the thickness of the clad material is reduced by 50 mm to the time when the thickness of the clad material is reduced to 20 mm during the hot clad rolling process, is regulated so as to be at most 10 min, and the temperature of the clad material is regulated so as to fall within the range of about 300-about 40° C. at the time when the thickness of the clad is reduced to 20 mm.
  • a time period, which is counted from the rolling start to the rolling end in the hot clad rolling process should be regulated so as to be at most 40 min.
  • the time period, which is counted from the rolling start to the rolling end in the hot clad rolling process is at most 35 min.
  • a specific means for controlling the time period for each of the steps of the hot clad rolling process, the temperature in each of the steps, and the total time period for the steps fall within the aforesaid respective ranges is not especially limited, for example, it is possible to use a feedback means for controlling the rolling rate, the rolling reduction, the amount of rolling oil and so forth so that these parameters fall within the respective ranges.
  • a core material is subjected to a homogenization process after a casting process
  • the clad material is subjected to a cold rolling process, it may be once or twice subjected to an intermediate annealing process until a final thickness is given to the clad material. It is possible to carry out the intermediate annealing process at a temperature of about 150-about 55° C. After the final intermediate annealing process is carried out, a rolling reduction rate, at which the clad material is rolled to a final thickness, ordinarily falls within a range of about 10-about 80%. Usually, the final thickness of the clad material falls within a range of about 0.1-about 0.6 mm.
  • the clad material After the clad material is rolled by the cold rolling process to the final thickness, it may be subjected to a finishing annealing process for improving a formability of the clad material. It is preferable to carry out the finishing annealing process at a temperature falling within the range of about 150-about 55° C.
  • the thickness of the aluminum alloy brazing sheet according to the present invention and clad rates of the brazing and sacrificial anode materials are not especially limited, a thin brazing sheet having a thickness of at most 0.6 mm may be produced when it is used as a tube member for an automobile heat exchanger. Nevertheless, the thickness of the brazing sheet is not limited within this range, and a relatively thick brazing sheet having a thickness falling within a range of about 0.6-about 5.0 mm may be used. Ordinarily, a clad rate, at which either the filler material ply or the sacrificial anode material ply is cladded on one surface of the core material, falls within a range of about 3-about 20%.
  • Core material alloys composed of components as shown in Table 1, filler material alloys composed of components as shown in Table 2, and sacrificial anode material alloys composed of components as shown in Table 3 were cast by using a DC casting process, and then each of the cast alloys was machined and finished so that both surfaces thereof were shaved.
  • each of the core material alloys was combined with a filler material alloy shown in Table 2, so that the filler material alloy concerned was applied as a cladding 1 to one surface of the core material alloy, and/or so that the filler material alloy shown in Table 2 or a sacrificial anode material alloy shown in Table 3 was applied as a cladding 2 to the other surface of the core material alloy, whereby a variety of composite materials was produced.
  • the composite materials there were 2-ply composite materials including no cladding 2.
  • Each of the composite materials was subjected to a heating process and a hot clad rolling process, to thereby produce a 2-ply or 3-ply clad material having a thickness of 3.5 mm.
  • the conditions of the heating and hot clad rolling processes are shown in Table 5.
  • the combinations of the core material alloys, the claddings 1 and the claddings 2 are shown in Tables 6 and 7.
  • Each of the aforesaid clad materials was subjected to an intermediate annealing process at a temperature of 400 C over a time period of 5 hrs, and is then subjected to a final cold rolling process to thereby produce a brazing sheet sample exhibiting an H1n refining and having a thickness of 0.5 mm.
  • brazing sheet samples were estimated in a variety of manners as stated hereinafter. The results are shown in Tables 8 and 9. Note, since a brazing sheet sample could not produced from each of the clad materials estimated as “x”, it was impossible to carry out the estimations on these clad materials.
  • an L-ST face of the core material was exposed by a polishing process, and was observed by a scanning transmission electron microscope (STEM) for a measurement of an area percentage of the intermetallic compounds.
  • STEM scanning transmission electron microscope
  • a film thickness of the core material was measured, using an electron energy-loss spectroscopy (EELS), and only areas having the film thickness falling within a range of 0.1-0.15 m were observed by the STEM.
  • EELS electron energy-loss spectroscopy
  • ten view fields were selected and observed at a 10,000-power. Then, by subjecting each of the STEM photographs of the view fields to an image analysis, an area percentage of the intermetallic compounds having a size falling within a range of 0.2-0.5 m was measured.
  • Each of the brazing sheet samples was subjected to a thermal processing (corresponding to a heating process for brazing) at a temperature of 600 C over a time period of 3 min, and was then subjected to a caustic etching process so that the cladding(s) was removed. Thereafter, the core material was resolved in a phenol solution, and the un-resolvable intermetallic compounds were filtered out of the solution. Then, the intermetallic compounds were subjected to a measuring process using an optical emission spectrometer, so that the Mn solid solution amount was measured.
  • Each of the brazing sheet samples was subjected to a thermal processing (corresponding to a heating process for brazing) at a temperature of 600 C over a time period of 3 min, and was then subjected to a tensile test under the conditions of a tensile speed of 10 mm/min and a gage length of 50 mm in accordance with the JIS Z2241 method, to thereby obtain a stress-strain characteristic curve. Thereafter, a tensile strength of the tested sample was read from the stress-strain characteristic curve. When the sample had a tensile strength of at least 150 MPa, it was estimated as being acceptable ( ⁇ ). When the sample had a tensile strength of less than 150 MPa, it was estimated as being unacceptable (x).
  • JIS 3003 alloy was corrugated and shaped into a fin, and was applied to the filler material surface of each of the brazing sheet samples. Then, the sample was immersed in an aqueous solution containing 5% fluoride flux, and was subjected to a heating process for brazing at a temperature of 600 C over a time period of 3 min.
  • a brazing property was evaluated as being acceptable ( ⁇ ).
  • a brazing property was evaluated as being unacceptable (X).
  • each of the brazing sheet samples was subjected to a thermal processing (corresponding to a heating process for brazing) at a temperature of 600 C over a time period of 3 min, it was cut into sample pieces having a size of 50 mm ⁇ 50 mm.
  • a rear surface which was defined as a surface opposite to a test surface of the sample piece, was masked with a resin. Note, when the sample piece had the filler material containing Zn, the test surface was defined as the surface of the filler material, and, when the sample piece had the cladded sacrificial anode material, the test surface was defined as the surface of the sacrificial anode material.
  • test surface was defined as the surface of the filler material
  • ASTM-G85 an evaluation of corrosion resistance
  • test piece When corrosive pierces occur in the test piece, it was evaluated as being unacceptable (x)
  • test surface was defined as the surface of the sacrificial anode material
  • the test piece concerned was subjected to a 3-month cycle immersion test, in one cycle of which the test piece was immersed in an 88 C hot water containing Cl— 500 ppm, SO 4 2 ⁇ 100 ppm and Cu 2+ 10 ppm over a time period of 8 hrs, and was then left at a room temperature over a time period of 16 hrs.
  • When corrosive pierces occur in the test piece, it was evaluated as being unacceptable (x).
  • Example 1 to 12 and 33 to 43 of the present invention satisfied the requirements regulated by the present invention, and all of the productivity, the area percentage of the intermetallic compounds, the Mn solid solution amount after the brazing, the tensile strength after the brazing, the brazing property and the corrosion depth were evaluated as being acceptable. Note that each of Examples 6 to 8 and 38 to 40 had the filler material containing Zn was especially superior concerning the corrosion depth.
  • the aluminum alloy brazing sheet according to the present invention exhibits a high strength after brazing, and features not only superior brazing properties such as a fin joining rate, an erosion resistance and so forth, but also a superior corrosion resistance.
  • the aluminum alloy brazing sheet can be suitably utilized as a tube member in a heat exchanger for an automobile due to a lightweight nature and a high thermal conductivity thereof.

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