WO2021070794A1 - Brazing sheet for heat exchanger and heat exchanger for air conditioning device - Google Patents

Brazing sheet for heat exchanger and heat exchanger for air conditioning device Download PDF

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Publication number
WO2021070794A1
WO2021070794A1 PCT/JP2020/037795 JP2020037795W WO2021070794A1 WO 2021070794 A1 WO2021070794 A1 WO 2021070794A1 JP 2020037795 W JP2020037795 W JP 2020037795W WO 2021070794 A1 WO2021070794 A1 WO 2021070794A1
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WIPO (PCT)
Prior art keywords
sacrificial anode
brazing
brazing sheet
anode material
heat exchanger
Prior art date
Application number
PCT/JP2020/037795
Other languages
French (fr)
Japanese (ja)
Inventor
孝仁 中島
広田　正宣
憲昭 山本
Original Assignee
パナソニックＩｐマネジメント株式会社
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Priority to CN202080015137.8A priority Critical patent/CN113453839B/en
Publication of WO2021070794A1 publication Critical patent/WO2021070794A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286—Al as the principal constituent
    • B23K35/288—Al as the principal constituent with Sn or Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • C23F13/14—Material for sacrificial anodes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D9/02—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the heat-exchange media travelling at an angle to one another
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
    • F28F9/02—Header boxes; End plates
    • F28F9/04—Arrangements for sealing elements into header boxes or end plates
    • F28F9/16—Arrangements for sealing elements into header boxes or end plates by permanent joints, e.g. by rolling
    • F28F9/18—Arrangements for sealing elements into header boxes or end plates by permanent joints, e.g. by rolling by welding
    • 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

Definitions

  • the present disclosure relates to a brazing sheet used for a member constituting a heat exchanger and a heat exchanger for an air conditioner configured by using the brazing sheet.
  • a general heat exchanger is usually provided with a pipe and fins, and has a configuration in which a plurality of fins are attached to the outer circumference of the pipe.
  • As the material of the tube copper (Cu) or an alloy thereof (referred to as “copper material” for convenience) has been used, but in recent years, aluminum (Al) or an alloy thereof (aluminum material) has also been used.
  • As a fin material an aluminum material is generally used.
  • brazing sheet in which a brazing material layer is clad (coated) on at least one surface of a core material made of an aluminum alloy is used.
  • a brazing sheet in which a brazing material is clad on one surface of the core material and a sacrificial anode material layer is clad on the other surface is used.
  • an aluminum-silicon (Si) -based alloy used for brazing an aluminum alloy is generally used, and as a sacrificial anode material, aluminum is generally used in order to make its potential low.
  • An alloy in which zinc (Zn) is added is used.
  • a typical sacrificial anode material a brazing material of a general aluminum-silicon alloy with zinc added can be mentioned. As a result, the sacrificial anode material also functions as a brazing material.
  • Patent Document 1 discloses an aluminum alloy brazing sheet that can be used as a fluid passage component of an automobile heat exchanger.
  • the sacrificial anode material contains Si: 2.5 to 7.0 mass%, Zn: 1.0 to 5.5 mass%, Fe 0.05 to 1.0 mass%, and the balance Al and unavoidable impurities. It is an aluminum alloy made of, and the clad thickness of the sacrificial anode material is 25 to 80 ⁇ m.
  • Patent Document 2 discloses an aluminum alloy brazing fin material for a heat exchanger used, for example, in an air conditioner (room air conditioner, air conditioner) or a heat exchanger for a refrigerator.
  • the sacrificial anode material contains Zn: 7 to 15% by mass, and the balance is composed of an aluminum alloy composed of Al and unavoidable impurities, which is preferable as the clad thickness of the sacrificial anode material. Is 7 ⁇ m or more, more preferably 7 to 40 ⁇ m.
  • the sacrificial anode material has a composition which may contain 8.0% by mass or less of Si from the viewpoint of suppressing excessive coarsening of crystal grains and improving corrosion resistance.
  • the brazing sheet in the heat exchanger for an air conditioner needs to have a higher joint strength than the brazing sheet for an automobile. This is because, in general, the upper limit of the allowable refrigerant pressure (allowable internal pressure) of the heat exchanger for an air conditioner is relatively higher than that of the heat exchanger for an automobile.
  • the sacrificial anode material also serves as a brazing material, of course, the sacrificial anode material is also required to have high bonding strength.
  • the brazing sheet disclosed in Patent Document 1 is for automobiles and must contain iron (Fe).
  • Fe iron
  • the brazing fin material disclosed in Patent Document 2 it is not assumed that the sacrificial anode material also serves as a brazing material, and the inclusion of Si is intended to contribute to the sacrificial anode action.
  • Patent Document 2 it is said that the sacrificial anode action cannot be exhibited unless the Zn content of the sacrificial anode material is 7.0% by mass or more, but according to the study by the present inventors, the Zn content is 7. It can be less than 0% by mass.
  • the sacrificial anode material also serves as a brazing material, it is possible to increase the bonding strength by increasing the Si content, but if the Si content is too large, the fluidity becomes too high. It was also clarified that the corrosion resistance of the brazing sheet was significantly reduced.
  • the present disclosure provides a brazing sheet provided with a sacrificial anode material layer, which is used in a heat exchanger for an air conditioner and can achieve both corrosion resistance and pressure resistance.
  • the brazing sheet according to the present disclosure is a brazing sheet used for a heat exchanger of an air conditioner, and is an aluminum alloy core material made of an aluminum alloy and an aluminum alloy coated on one surface of the core material and containing silicon (Si).
  • a brazing material layer made of a brazing material and a sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si) are provided.
  • the brazing sheet has a silicon content in the sacrificial anode material when the thickness of the sacrificial anode material layer is in the range of 15 to 25 ⁇ m and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C.
  • the brazing sheet according to the present disclosure is a brazing sheet used in a heat exchanger of an air conditioner, which is coated on both surfaces of an aluminum alloy core material and the core material, and zinc (Zn) and silicon (Zn) and silicon (A sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy containing Si) is provided, the thickness of the sacrificial anode material layer is within the range of 15 to 25 ⁇ m, and the temperature T at the time of joining the brazing sheet is 580 to. When the temperature is within the range of 660 ° C., the silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
  • the configuration may be greater than or equal to the value derived from.
  • the sacrificial anode material layer contains silicon within the above range.
  • the silicon content can be optimized in the sacrificial anode material which also serves as a brazing material. Therefore, even if the thickness of the sacrificial anode material layer is within the above range, it is possible to achieve both corrosion resistance and pressure resistance in the bonding structure of the brazing sheet.
  • the present disclosure also includes a heat exchanger for an air conditioner, which is configured by using the brazing sheet having the above configuration.
  • FIG. 1A is a schematic cross-sectional view showing a schematic configuration of a brazing sheet according to a typical embodiment of the present disclosure.
  • FIG. 1B is a schematic cross-sectional view showing a schematic configuration of a joining structure of a brazing sheet according to a typical embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of a header of a plate fin laminated heat exchanger constructed by using the brazing sheet shown in FIG. 1A.
  • FIG. 3 is a schematic cross-sectional view showing an example of a header of a plate fin laminated heat exchanger configured by using a brazing sheet having sacrificial anode material layers on both sides.
  • FIG. 1A is a schematic cross-sectional view showing a schematic configuration of a brazing sheet according to a typical embodiment of the present disclosure.
  • FIG. 1B is a schematic cross-sectional view showing a schematic configuration of a joining structure of a brazing sheet according to a typical embodiment of the present disclosure
  • FIG. 4A is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Comparative Example 1.
  • FIG. 4B is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 1.
  • FIG. 4C is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 2.
  • FIG. 4D is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Comparative Example 2.
  • FIG. 5 is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 3.
  • the brazing sheet according to the present disclosure is used for a heat exchanger of an air conditioner, and is made of an aluminum alloy core material and an aluminum alloy coated on one surface of the core material and containing silicon (Si).
  • a brazing material layer made of a brazing material and a sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si) are provided.
  • the brazing sheet contains the silicon in the sacrificial anode material when the thickness of the sacrificial anode material layer is in the range of 15 to 25 ⁇ m and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C.
  • the quantity X Si is given by the following equation (1).
  • the brazing sheet according to the present disclosure is a brazing sheet used in a heat exchanger of an air conditioner, which is coated on both surfaces of an aluminum alloy core material and the core material, and zinc (Zn) and silicon (Zn) and silicon (A sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy containing Si) is provided, the thickness of the sacrificial anode material layer is within the range of 15 to 25 ⁇ m, and the temperature T at the time of joining the brazing sheet is 580 to. When the temperature is within the range of 660 ° C., the silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
  • the configuration may be greater than or equal to the value derived from.
  • the sacrificial anode material layer contains silicon within the above range.
  • the silicon content can be optimized in the sacrificial anode material which also serves as a brazing material. Therefore, even if the thickness of the sacrificial anode material layer is within the above range, it is possible to achieve both corrosion resistance and pressure resistance in the bonding structure of the brazing sheet.
  • the brazing sheet has a joint portion that constitutes a joint portion by being joined to each other and an inclined portion adjacent to the joint portion, and the inclination angle of the inclined portion with respect to the joint portion is 40 °.
  • the configuration may be as follows.
  • the core material is an aluminum alloy of 3000 series, 5000 series, or 6000 series
  • the sacrificial anode material is a 4000 series aluminum alloy
  • zinc is 2.0 to 6.0.
  • the composition may be such that it is contained within the range of mass%.
  • the brazing material may be a 4000 series aluminum alloy.
  • the heat exchanger for the air conditioner according to the present disclosure may be configured by using the brazing sheet having the above configuration.
  • the heat exchanger for the air conditioner may have a configuration in which plate fins are laminated.
  • the brazing sheet according to the present disclosure is made of an aluminum alloy used for a heat exchanger.
  • the brazing sheet 10 according to the present disclosure includes a core material 11, a brazing material layer 12, and a sacrificial anode material layer 13.
  • the brazing material layer 12 is coated (clad) on one surface of the core material 11, and the sacrificial anode material layer 13 is on the other surface of the core material 11, that is, the surface opposite to the surface on which the brazing material layer 12 is coated. It is covered.
  • the core material 11, the brazing material forming the brazing material layer 12, and the sacrificial anode material forming the sacrificial anode material layer 13 are all aluminum alloys.
  • the brazing sheet 10 may have a core material 11 and a sacrificial anode material layer 13, and may not have a brazing material layer 12.
  • a sacrificial anode material layer 13 is formed on both surfaces of the core material 11.
  • the brazing sheet 10 according to the present disclosure has a joint portion at least on the side of the sacrificial anode material layer 13, and the joint portion is formed by joining the joint surfaces of the joint portions to each other.
  • the structure in which the brazing sheets 10 are joined to each other at the joining site is the joining structure of the brazing sheets 10 according to the present disclosure.
  • the specific shape of the brazing sheet 10 according to the present disclosure is not particularly limited, but a typical example may be a configuration having an inclined portion adjacent to the joint portion and inclined with respect to the joint portion.
  • the joining structure 20 of the brazing sheet 10 is configured by joining the joining portions 10a of the brazing sheet 10 to each other.
  • the inclined portion 10b is adjacent to the joint portion 10a, and the inclination angle ⁇ 1 of the inclined portion 10b with respect to the joint portion 10a is not particularly limited, but the angle ⁇ 2 formed between the inclined portions 10b in the joining structure 20 of the brazing sheet is an acute angle. That is, it may be less than 90 ° ( ⁇ 2 ⁇ 90 °), so the inclination angle ⁇ 1 may be less than 45 °, which is 1/2 of that.
  • fillets 22 are formed between the inclined portions 10b.
  • the fillet 22 is defined as a solidified wax material or sacrificial anode material that has flowed out from the joint portion 10a at the time of joining.
  • the angle ⁇ 2 formed by each inclined portion 10b constituting the joining structure 20 of the brazing sheet is referred to as an “inclined portion forming angle” for convenience of explanation.
  • the inclination angle ⁇ 1 and the inclination portion formation angle ⁇ 2 are shown by dotted lines, but the reference of these angles is an intermediate line of the thickness of the brazing sheet 10 as shown by the dotted line in the figure. (A line having an intermediate thickness (depth) from both one surface and the other surface).
  • the reference of these angles ⁇ 1 and ⁇ 2 is not limited to the intermediate line of the thickness, and may be another known reference (for example, an angle with respect to the surface on the joint side).
  • the inclination angle ⁇ 1 may be less than 45 ° as described above, but the upper limit thereof is preferably less than 40 °, more preferably less than 35 °. Depending on the structure of the heat exchanger for the air conditioner, if the inclination angle ⁇ 1 exceeds 40 °, the brazing sheet 10 may be partially thinned or the core material 11 may be partially eroded during press working. There is a risk of doing so.
  • the fact that the inclination angle ⁇ 1 of the inclined portion 10b with respect to the joint portion 10a is relatively large means that a large processing is applied to the brazing sheet 10 during the press working. As a result, the brazing sheet 10 is partially thinned. When the brazing sheet 10 is partially thinned, stress concentration or insufficient pressure resistance occurs in the thinned portion, so that the portion may be damaged.
  • the diffusion coefficient of silicon from the brazing material layer 12 to the core material 11 becomes large at the portion where the processing is applied, which causes erosion (melting of the core material 11).
  • the risk increases.
  • erosion occurs, zinc contained in the sacrificial anode material layer 13 existing around the molten core material 11 is involved, and a part of the core material 11 becomes a “sacrificial anode material”. As a result, there is a possibility that the brazing sheet 10 penetrates early from the site where the erosion occurs.
  • the brazing sheet 10 when the inclination angle ⁇ 1 is 40 ° or less, the possibility that a large processing is applied to the brazing sheet 10 is reduced. Therefore, it is possible to effectively suppress the possibility that the brazing sheet 10 is partially thinned or the core material 11 is partially eroded.
  • the brazing sheet 10 may be partially thinned during press working, or the core material 11 may be partially eroded. Since the occurrence may be suppressed, the upper limit of the inclination angle ⁇ 1 is not always 40 °.
  • the lower limit of the inclination angle ⁇ 1 is not particularly limited, and a suitable lower limit value may be set according to the structure of the heat exchanger for the air conditioner.
  • a suitable lower limit value may be set according to the structure of the heat exchanger for the air conditioner.
  • the lower limit of the inclination angle ⁇ 1 in the plate fin laminated heat exchanger is preferably 15 ° or more, and more preferably 20 ° or more.
  • the core material 11 included in the brazing sheet 10 according to the present disclosure may be a known aluminum alloy that can realize the physical properties required according to various conditions such as the type or structure of the heat exchanger.
  • the aluminum alloy used as the core material 11 include, in the field of heat exchangers, typically 3000 series (aluminum-manganese (Al-Mn) based alloy) and 5000 series (aluminum-magnesium (Al-Mg)). (Aluminum-based alloy), 6000-based (aluminum-magnesium-silicon (Al-Mg-Si) -based alloy), and the like, but are not limited thereto.
  • the core material 11 may contain an element known to the above-mentioned aluminum alloy at a content (concentration) exceeding the unavoidable impurities.
  • concentration concentration
  • the upper limit of the concentration allowed as an unavoidable impurity varies depending on various conditions, but for example, less than 0.1% by mass in the entire aluminum alloy can be mentioned.
  • the upper limit of the concentration of unavoidable impurities may conform to the alloy composition defined in a known standard such as JIS.
  • the aluminum alloy used as the brazing material may be an alloy containing silicon (silicon, Si), that is, an aluminum-silicon (Al-Si) alloy.
  • the content of Si in the brazing material is not particularly limited, and may be within a range suitable for use as a brazing material. Specifically, for example, the content (concentration) of Si in the brazing material can be in the range of 2.5 to 13% by mass, even if it is in the range of 3.5 to 12% by mass. Good. If the Si content is too low, the Al—Si alloy may not function sufficiently as a brazing material. On the other hand, if the Si content is too high, Si may diffuse into the core material 11 or the mating material and melt the brazing sheet 10 itself. Further, the Al—Si alloy as the brazing material may contain an element other than Si in a content exceeding the unavoidable impurities as long as the function as the brazing material is not affected.
  • the aluminum alloy used as the sacrificial anode material contains zinc (Zn) in the range of 2.0 to 6.0% by mass in order to exert the sacrificial anode action. Further, in the present disclosure, since the sacrificial anode material also serves as a brazing material as described above, Si is contained in the same manner as the brazing material. The Si content (Si concentration) in the sacrificial anode material can be in the range of 3.0 to 6.0% by mass. Therefore, the aluminum alloy used as the sacrificial anode material may be an aluminum-silicon-zinc (Al-Si-Zn) alloy.
  • the sacrificial anode material As the sacrificial anode material, if the Zn content (concentration) is less than 2.0% by mass, a good sacrificial anode action cannot be exhibited. On the other hand, when the Zn content exceeds 6.0% by mass, the sacrificial anode action proceeds too early and the sacrificial anode material layer 13 disappears from the brazing sheet 10 at an early stage, so that the corrosion resistance of the brazing sheet 10 deteriorates. There is a risk of
  • the Si content is less than 3.0% by mass, the amount of Si is too small and the sacrificial anode material does not flow sufficiently, and as a brazing material. There is a risk that good adhesive strength cannot be exhibited.
  • the Si content exceeds 6.0% by mass, the fluidity as the sacrificial anode material is improved, but the fluidity becomes too high and the corrosion resistance may decrease.
  • the brazing sheet 10 is used as a heat exchanger for an air conditioner.
  • the adhesive strength is required to be sufficient to withstand the upper limit of the allowable pressure of the refrigerant.
  • the adhesive strength required for the sacrificial anode material can be appropriately set according to the conditions.
  • the Si content is the adhesion capable of realizing sufficient pressure resistance in the joining structure 20 of the brazing sheets 10.
  • the balance between strength and sufficient corrosion resistance is important.
  • a particularly preferable content of Si in the sacrificial anode material is as follows. It became clear that it can be defined by (1) and Eq. (2).
  • the concentration may be equal to or less than the value derived from the following equation (1) and greater than or equal to the value derived from the following equation (2).
  • T 660-8 ⁇ exp (0.3X Si ) ⁇ ⁇ ⁇ (1)
  • T 580 + 55 ⁇ exp (-0.5 (X Si -1.7)) ⁇ ⁇ ⁇ (2)
  • the content of elements other than Si and Zn exceeds the unavoidable impurities as long as the sacrificial anode action and the function as the brazing material are not affected. It may be contained.
  • the type of aluminum alloy specifically used as the brazing material and the sacrificial anode material is not particularly limited, but typically, 4000 series (aluminum-silicon (Al-Si) based alloy) can be used for both.
  • 4000 series aluminum-silicon (Al-Si) based alloy
  • Si silicon-silicon
  • Zn may be added by a known method so that the content of Zn is also within the above range.
  • the clad ratio of the brazing material and the sacrificial anode material is not particularly limited, and can be mentioned within a general range.
  • the general clad ratio may be, for example, in the range of 2 to 30% by mass, and may be in the range of 3 to 20% by mass.
  • the thickness of the brazing sheet 10 according to the present disclosure and the thicknesses of the core material 11, the brazing material layer 12, and the sacrificial anode material layer 13 are not particularly limited, and the brazing sheet 10 may be configured or manufactured. It can be appropriately set according to the type or parts of the heat exchanger to be used. However, in the present disclosure, the thickness of the sacrificial anode material layer 13 is in the range of 15 to 25 ⁇ m.
  • the thickness of the sacrificial anode material layer 13 can be made thinner than that for an automobile. If the thickness of the sacrificial anode material layer 13 can be reduced, the amount of the sacrificial anode material used can be reduced, so that an increase in the manufacturing cost of the brazing sheet 10 can be suppressed.
  • a plate fin laminated type as a heat exchanger can be mentioned as a preferable example.
  • the plate fin laminated heat exchanger a plurality of plate fins are laminated to form a laminated body, and the laminated body is pressed by a jig to join (braze). Therefore, if the thickness of the sacrificial anode material layer 13 is too large, the dimensional change of the laminated body becomes large, which may affect the bonding structure 20 of the brazing sheet. If the sacrificial anode material layer 13 can be set to 25 ⁇ m or less, such an influence on the joint structure 20 can be effectively suppressed.
  • the sacrificial anode material layer 13 is less than 15 ⁇ m, the absolute amount of the sacrificial anode material with respect to the brazing sheet 10 becomes too small. Therefore, the sacrificial anode material layer 13 may disappear from the brazing sheet 10 at an early stage, and the corrosion resistance of the brazing sheet 10 may decrease.
  • a plurality of brazing sheets 10 are superposed on each other at the joining portions 10a, and the brazing material and the sacrificial anode material are melted and brazed at a high temperature (580 ° C. or higher) to braze the brazing sheets 10 to each other. Be joined.
  • the sacrificial anode of the joint portion 10a is located at a portion adjacent to the joint portion 10a (joint portion 21) between the inclined portions 10b.
  • the sacrificial anode material flowing out of the material layer 13 solidifies to form a fillet 22.
  • the potentials of the joint portion 21 (including the fillet 22), the sacrificial anode material layer 13, and the like may be evaluated (measured) by a known method.
  • a potential measurement sample for example, a brazing sheet 10 or a core material 11, a brazing material, a sacrificial anode material, a fillet 22 or a joint portion 21, or these
  • a potential stat / galvanostat is used in a potential stat / galvanostat.
  • an alloy having a composition simulating a counter electrode, and a reference electrode (for example, a silver / silver chloride (Ag / AgCl) electrode) are connected and immersed in an electrolytic solution (for example, a 5 wt% sodium chloride (NaCl) solution). Then, a method of measuring the potential difference between the sample and the reference electrode can be mentioned.
  • an electrolytic solution for example, a 5 wt% sodium chloride (NaCl) solution.
  • the manufacturing method of the brazing sheet 10 according to the present disclosure is not particularly limited, and a known manufacturing method can be preferably used. Specifically, for example, an aluminum alloy having a desired composition is formed into a plate shape by a known method to obtain a core material 11, and a brazing material of an aluminum alloy containing Si is known for one surface of the core material 11. Clad with the method of, Zn is contained in the range of 2.0 to 6.0% by mass, and Si is contained in the range of 3.0 to 6.0% by mass with respect to the other surface of the core material 11.
  • the sacrificial anode material of the aluminum alloy may be clad by a known method.
  • the conditions for manufacturing the brazing sheet 10 can be appropriately set according to the configuration of the brazing sheet 10 or the type or parts of the heat exchanger for the air conditioner to be manufactured.
  • the brazing sheet 10 according to the present disclosure can be particularly suitably used for manufacturing a heat exchanger for an air conditioner as described above.
  • the joining structure 20 of the brazing sheet formed when the brazing sheet 10 according to the present disclosure is applied to the heat exchanger has a structure as illustrated in FIG. 1B. More specifically, a plate fin laminated heat exchanger having a structure as shown in FIG. 2, an Air To Water laminated heat exchanger having a structure as shown in FIGS. 4A and 4B, and the like can be mentioned. be able to.
  • the plate fin laminated heat exchanger is a plate fin laminated body having a flow path through which a refrigerant, which is a first fluid, flows, and air, which is a second fluid, is flowed between each plate fin laminated body to flow the first fluid. Heat exchange is performed between the fluid and the second fluid.
  • the plate fin included in this heat exchanger has a flow path region having a plurality of first fluid flow paths through which the first fluid flows in parallel, and a header flow path communicating with each first fluid flow path in this flow path region. It has a header area and.
  • FIG. 2 shows a schematic structure of a header portion in the plate fin laminated body 30 as a partial cross section, and a plurality of plate fins 32 are laminated on an end plate 31 located at the uppermost part in the drawing.
  • each of the end plate 31 and the plate fin 32 An opening is provided in each of the end plate 31 and the plate fin 32, and the header opening 33 is formed by laminating these plates to form the plate fin laminated body 30.
  • the refrigerant which is the first fluid
  • each plate fin 32 is provided with the first fluid flow path, so that the refrigerant flowing between the plate fins 32 flows through the first fluid flow path.
  • the air which is the second fluid, flows in the space formed between the plate fins 32 so as to intersect the direction in which the refrigerant flows (the direction of the first fluid flow path). As a result, the air is cooled by the refrigerant.
  • Such a plate fin laminated heat exchanger include, for example, JP-A-2017-180856, JP-A-2018-066531, JP-A-2018-066532, and JP-A-2018-066533. It is described in Japanese Patent Application Laid-Open No. 2018-066534, Japanese Patent Application Laid-Open No. 2018-066535, Japanese Patent Application Laid-Open No. 2018-066536, etc. It shall be a part of the description of the specification.
  • the plate fin laminate 34 constituting the laminated heat exchanger for Air To Water heat pump has a basic configuration of the plate fin laminate of the general plate fin laminated heat exchanger shown in FIG. Similar to body 30.
  • the plate fins 35 (brazing sheet 10 according to the present disclosure) constituting the plate fin laminate 34 have a sacrificial anode material layer 13 on both sides thereof. Therefore, as shown in FIG. 3, the fillet 22 is formed not only at the joint portion 21 located on the header opening 33 side (inside) but also at the joint portion 21 located on the opposite side (outside) of the header opening 33 side. Has been done. Since the configuration shown in FIG. 3 is the same as the configuration shown in FIG. 2 except for the formation positions of the plate fins 35 and the fillets 22, the description thereof will be omitted.
  • the brazing sheet according to the present disclosure is used for a heat exchanger of an air conditioner, and is coated on one surface of an aluminum alloy core material and the core material and contains silicon (Si).
  • a sacrificial anode material layer is coated on both surfaces of the above.
  • the sacrificial anode when the thickness of the sacrificial anode material layer is in the range of 15 to 25 ⁇ m and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C., the sacrificial anode is used.
  • the silicon content X Si in the material is less than or equal to the value derived from the above formula (1) and greater than or equal to the value derived from the above formula (2).
  • the core material is an aluminum alloy of 3003
  • the brazing material layer is an aluminum alloy of 4343
  • the sacrificial anode material layer is silicon (Si) 2.5% by mass and zinc (Zn).
  • An aluminum alloy (Al-2.5% Si-4.0% Zn) having a balance of 4.0% by mass and the balance of aluminum (Al) was used. Further, the inclination angle ⁇ 1 of the inclined portion included in the brazing sheet was about 30 °.
  • This brazing sheet was brazed at each other's joint to form a joint.
  • the joint surface of the joint site was a sacrificial anode material layer. Since the brazing temperature was 610 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.9 to 6.1% by mass from the above formulas (1) and (2). It is within the range of. Visual observation of the joints confirmed that the joints were inadequate.
  • Example 1 As the brazing sheet according to Example 1, an aluminum alloy (Al-2.8% Si) in which the sacrificial anode material layer is silicon (Si) 2.8% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al).
  • the brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was set to 620 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.3 to 5.3% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
  • Example 2 As the brazing sheet according to Example 2, an aluminum alloy (Al-4.4% Si) in which the sacrificial anode material layer is silicon (Si) 4.4% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al).
  • the brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was set to 620 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.3 to 5.3% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
  • Comparative Example 2 As a brazing sheet according to Comparative Example 2, an aluminum alloy (Al-4.4% Si) in which the sacrificial anode material layer is silicon (Si) 7.0% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al).
  • the brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was 610 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.9 to 6.1% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
  • Example 3 As the brazing sheet according to Example 3, brazing in the same manner as in Comparative Example 1 except that a sacrificial anode material layer having the same composition as that in Example 1 was provided on both sides of the core material and no brazing material layer was used. The sheets were brazed together to form a joint. When the joint was visually confirmed, good joint was confirmed.
  • the present disclosure can provide a brazing sheet provided with a sacrificial anode material layer capable of achieving both corrosion resistance and pressure resistance satisfactorily. Therefore, it can be widely and suitably used not only in the field of brazing sheets used for heat exchangers for air conditioners having a sacrificial anode material layer, but also in the field of heat exchangers for air conditioners using the brazing sheets.

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Abstract

A brazing sheet (10) for use in a heat exchanger of an air conditioning device comprises: a core (11) made of an aluminum (Al) alloy; an Al alloy brazing filler layer (12) that covers one surface of the core and contains Si; and an Al alloy sacrificial anode material layer (13) that covers another surface of the core and contains Zn and Si. Where the thickness of the sacrificial anode material layer (13) is in the range 15–25 μm and the temperature T at the time of joining of the brazing sheet (10) is in the range 580–660°C, the Si content XSi does not exceed a value derived from formula (1) T = 660 − 8 × exp (0.3XSi), and is at least a value derived from formula (2) T = 580 + 55 × exp (−0.5 (XSi − 1.7)).

Description

熱交換器用ブレージングシートおよび空気調和装置用熱交換器Brazing sheet for heat exchanger and heat exchanger for air conditioner
　本開示は、熱交換器を構成する部材に用いられるブレージングシートと、当該ブレージングシートを用いて構成される空気調和装置用熱交換器と、に関する。 The present disclosure relates to a brazing sheet used for a member constituting a heat exchanger and a heat exchanger for an air conditioner configured by using the brazing sheet.
　一般的な熱交換器は、通常、管およびフィンを備えており、管の外周に複数のフィンが取り付けられた構成を有している。管の材料としては、銅（Ｃｕ）またはその合金（便宜上「銅材」と称する）が用いられてきたが、近年ではアルミニウム（Ａｌ）またはその合金（アルミニウム材）も用いられている。フィンの材料としては、一般的にはアルミニウム材が用いられている。 A general heat exchanger is usually provided with a pipe and fins, and has a configuration in which a plurality of fins are attached to the outer circumference of the pipe. As the material of the tube, copper (Cu) or an alloy thereof (referred to as "copper material" for convenience) has been used, but in recent years, aluminum (Al) or an alloy thereof (aluminum material) has also been used. As a fin material, an aluminum material is generally used.
　熱交換器の製造に際して、管にフィンを取り付けるためには、一般的にはろう材による接合が用いられる。管およびフィンのいずれもアルミニウム材製であれば、例えば、アルミニウム合金製の心材の少なくとも一方の面にろう材層がクラッド（被覆）されたブレージングシートが用いられる。管およびフィンの防食性を考慮すれば、心材の一方の面にろう材がクラッドされ他方の面に犠牲陽極材層がクラッドされたブレージングシートが用いられる。 When manufacturing a heat exchanger, joining with brazing material is generally used to attach fins to the pipe. If both the pipe and the fin are made of an aluminum material, for example, a brazing sheet in which a brazing material layer is clad (coated) on at least one surface of a core material made of an aluminum alloy is used. Considering the corrosion resistance of the pipe and fins, a brazing sheet in which a brazing material is clad on one surface of the core material and a sacrificial anode material layer is clad on the other surface is used.
　ろう材としては、一般的には、アルミニウム合金のろう付けに用いられるアルミニウム－シリコン（Ｓｉ）系合金が用いられ、犠牲陽極材としては、その電位を卑とするために、一般的にはアルミニウム合金に亜鉛（Ｚｎ）を添加したものが用いられる。代表的な犠牲陽極材としては、一般的なアルミニウム－シリコン系合金のろう材に亜鉛を添加したものが挙げられる。これにより、犠牲陽極材がろう材としても機能することになる。 As the brazing material, an aluminum-silicon (Si) -based alloy used for brazing an aluminum alloy is generally used, and as a sacrificial anode material, aluminum is generally used in order to make its potential low. An alloy in which zinc (Zn) is added is used. As a typical sacrificial anode material, a brazing material of a general aluminum-silicon alloy with zinc added can be mentioned. As a result, the sacrificial anode material also functions as a brazing material.
　ところで、自動車用の熱交換器は、排気ガスに接触する可能性があることから、建築物用の空気調和装置等に用いられる熱交換器に比較してより高い耐食性が求められる。例えば、特許文献１には、自動車用熱交換器の流体通路構成材として使用可能なアルミニウム合金ブレージングシートが開示されている。このブレージングシートでは、犠牲陽極材が、Ｓｉ：２．５～７．０ｍａｓｓ％、Ｚｎ：１．０～５．５ｍａｓｓ％、Ｆｅ０．０５～１．０ｍａｓｓ％を含有し、残部Ａｌと不可避的不純物からなるアルミニウム合金であり、当該犠牲陽極材のクラッド厚さが２５～８０μｍである。 By the way, since heat exchangers for automobiles may come into contact with exhaust gas, higher corrosion resistance is required as compared with heat exchangers used for air conditioners for buildings and the like. For example, Patent Document 1 discloses an aluminum alloy brazing sheet that can be used as a fluid passage component of an automobile heat exchanger. In this brazing sheet, the sacrificial anode material contains Si: 2.5 to 7.0 mass%, Zn: 1.0 to 5.5 mass%, Fe 0.05 to 1.0 mass%, and the balance Al and unavoidable impurities. It is an aluminum alloy made of, and the clad thickness of the sacrificial anode material is 25 to 80 μm.
　一方、特許文献２には、例えば空気調和装置（ルームエアコン、空調機）または冷蔵庫用の熱交換器に用いられる、熱交換器用アルミニウム合金製ブレージングフィン材が開示されている。このブレージングフィン材では、犠牲陽極材が、Ｚｎ：７～１５質量％を含有し、残部がＡｌ及び不可避的不純物からなるアルミニウム合金で構成されており、この犠牲陽極材のクラッド厚さとして、好ましくは７μｍ以上、さらに好ましくは７～４０μｍが挙げられている。また、犠牲陽極材は、結晶粒の過度の粗大化を抑制するとともに耐食性を向上させる観点から、８．０質量％以下のＳｉを含有してもよい組成となっている。 On the other hand, Patent Document 2 discloses an aluminum alloy brazing fin material for a heat exchanger used, for example, in an air conditioner (room air conditioner, air conditioner) or a heat exchanger for a refrigerator. In this brazing fin material, the sacrificial anode material contains Zn: 7 to 15% by mass, and the balance is composed of an aluminum alloy composed of Al and unavoidable impurities, which is preferable as the clad thickness of the sacrificial anode material. Is 7 μm or more, more preferably 7 to 40 μm. Further, the sacrificial anode material has a composition which may contain 8.0% by mass or less of Si from the viewpoint of suppressing excessive coarsening of crystal grains and improving corrosion resistance.
国際公開第２０１１／０３４１０２号公報International Publication No. 2011/034102 特開２０１７－１５５３０８号公報Japanese Unexamined Patent Publication No. 2017-155308
　本発明者らの鋭意検討の結果、空気調和装置用熱交換器におけるブレージングシートでは、自動車用のブレージングシートに比較して接合強度を高める必要があることが明らかとなった。これは、一般に、空気調和装置用熱交換器では、自動車用熱交換器よりも許容される冷媒の圧力（許容内圧）の上限が相対的に高くなるためである。犠牲陽極材がろう材を兼ねる場合には、もちろん犠牲陽極材にも高い接合強度が求められる。 As a result of diligent studies by the present inventors, it has become clear that the brazing sheet in the heat exchanger for an air conditioner needs to have a higher joint strength than the brazing sheet for an automobile. This is because, in general, the upper limit of the allowable refrigerant pressure (allowable internal pressure) of the heat exchanger for an air conditioner is relatively higher than that of the heat exchanger for an automobile. When the sacrificial anode material also serves as a brazing material, of course, the sacrificial anode material is also required to have high bonding strength.
　特許文献１に開示のブレージングシートは、自動車用であり、かつ、鉄（Ｆｅ）を含有することが必須である。一方、特許文献２に開示のブレージングフィン材は、犠牲陽極材がろう材を兼ねることは想定されておらず、Ｓｉの含有は犠牲陽極作用への寄与が目的である。 The brazing sheet disclosed in Patent Document 1 is for automobiles and must contain iron (Fe). On the other hand, in the brazing fin material disclosed in Patent Document 2, it is not assumed that the sacrificial anode material also serves as a brazing material, and the inclusion of Si is intended to contribute to the sacrificial anode action.
　さらに特許文献２では、犠牲陽極材のＺｎの含有量が７．０質量％以上でないと犠牲陽極作用を発揮できないとされるが、本発明者らの検討によればＺｎの含有量は７．０質量％よりも少なくすることが可能である。一方、犠牲陽極材がろう材を兼ねる場合、Ｓｉの含有量を多くすることで接合強度を高めることが可能であるものの、Ｓｉの含有量が多くなり過ぎると、その流動性が高くなり過ぎ、ブレージングシートの耐食性が著しく低下することも明らかとなった。 Further, in Patent Document 2, it is said that the sacrificial anode action cannot be exhibited unless the Zn content of the sacrificial anode material is 7.0% by mass or more, but according to the study by the present inventors, the Zn content is 7. It can be less than 0% by mass. On the other hand, when the sacrificial anode material also serves as a brazing material, it is possible to increase the bonding strength by increasing the Si content, but if the Si content is too large, the fluidity becomes too high. It was also clarified that the corrosion resistance of the brazing sheet was significantly reduced.
　本開示は、空気調和装置用熱交換器に用いられ、耐食性および耐圧性を良好に両立させることが可能な、犠牲陽極材層を備えるブレージングシートを提供する。 The present disclosure provides a brazing sheet provided with a sacrificial anode material layer, which is used in a heat exchanger for an air conditioner and can achieve both corrosion resistance and pressure resistance.
　本開示に係るブレージングシートは、空気調和装置の熱交換器に用いられるブレージングシートであって、アルミニウム合金製の心材と、当該心材の一方の面に被覆され、シリコン（Ｓｉ）を含有するアルミニウム合金のろう材からなるろう材層と、当該心材の他方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、を備える。ブレージングシートは、犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材におけるシリコンの含有量ＸSiは、次式（１）
Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
から導き出される値以下であり、かつ、次式（２）
Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
から導き出される値以上である構成である。 The brazing sheet according to the present disclosure is a brazing sheet used for a heat exchanger of an air conditioner, and is an aluminum alloy core material made of an aluminum alloy and an aluminum alloy coated on one surface of the core material and containing silicon (Si). A brazing material layer made of a brazing material and a sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si) are provided. The brazing sheet has a silicon content in the sacrificial anode material when the thickness of the sacrificial anode material layer is in the range of 15 to 25 μm and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C. X Si is given by the following equation (1)
T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
It is less than or equal to the value derived from, and the following equation (2)
T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
It is a configuration that is greater than or equal to the value derived from.
　あるいは、本開示に係るブレージングシートは、空気調和装置の熱交換器に用いられるブレージングシートであって、アルミニウム合金製の心材と、当該心材の両方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、を備え、犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材における前記シリコンの含有量ＸSiは、次式（１）
Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
から導き出される値以下であり、かつ、次式（２）
Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
から導き出される値以上である構成であってもよい。 Alternatively, the brazing sheet according to the present disclosure is a brazing sheet used in a heat exchanger of an air conditioner, which is coated on both surfaces of an aluminum alloy core material and the core material, and zinc (Zn) and silicon (Zn) and silicon ( A sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy containing Si) is provided, the thickness of the sacrificial anode material layer is within the range of 15 to 25 μm, and the temperature T at the time of joining the brazing sheet is 580 to. When the temperature is within the range of 660 ° C., the silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
It is less than or equal to the value derived from, and the following equation (2)
T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
The configuration may be greater than or equal to the value derived from.
　上記構成によれば、空気調和装置用熱交換器に用いられるブレージングシートにおいて、犠牲陽極材層が上述の範囲内でシリコンを含有している。これにより、ろう材を兼ねる犠牲陽極材において、シリコンの含有量を好適化することができる。そのため、犠牲陽極材層の厚さが上述の範囲内であっても、ブレージングシートの接合構造における耐食性および耐圧性を両立させることが可能になる。 According to the above configuration, in the brazing sheet used for the heat exchanger for the air conditioner, the sacrificial anode material layer contains silicon within the above range. Thereby, the silicon content can be optimized in the sacrificial anode material which also serves as a brazing material. Therefore, even if the thickness of the sacrificial anode material layer is within the above range, it is possible to achieve both corrosion resistance and pressure resistance in the bonding structure of the brazing sheet.
　本開示には、上記構成のブレージングシートを用いて構成される、空気調和装置用熱交換器も含まれる。 The present disclosure also includes a heat exchanger for an air conditioner, which is configured by using the brazing sheet having the above configuration.
図１Ａは、本開示の代表的な実施の形態に係るブレージングシートの概略構成を示す模式的断面図である。FIG. 1A is a schematic cross-sectional view showing a schematic configuration of a brazing sheet according to a typical embodiment of the present disclosure. 図１Ｂは、本開示の代表的な実施の形態に係るブレージングシートの接合構造の概略構成を示す模式的断面図である。FIG. 1B is a schematic cross-sectional view showing a schematic configuration of a joining structure of a brazing sheet according to a typical embodiment of the present disclosure. 図２は、図１Ａに示すブレージングシートを用いて構成されるプレートフィン積層型熱交換器のヘッダの一例を示す模式的断面図である。FIG. 2 is a schematic cross-sectional view showing an example of a header of a plate fin laminated heat exchanger constructed by using the brazing sheet shown in FIG. 1A. 図３は、両面に犠牲陽極材層を備えるブレージングシートを用いて構成されるプレートフィン積層型熱交換器のヘッダの一例を示す模式的断面図である。FIG. 3 is a schematic cross-sectional view showing an example of a header of a plate fin laminated heat exchanger configured by using a brazing sheet having sacrificial anode material layers on both sides. 図４Ａは、比較例１に係るブレージングシートの接合構造の耐食性試験結果を示す図である。FIG. 4A is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Comparative Example 1. 図４Ｂは、実施例１に係るブレージングシートの接合構造の耐食性試験結果を示す図である。FIG. 4B is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 1. 図４Ｃは、実施例２に係るブレージングシートの接合構造の耐食性試験結果を示す図である。FIG. 4C is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 2. 図４Ｄは、比較例２に係るブレージングシートの接合構造の耐食性試験結果を示す図である。FIG. 4D is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Comparative Example 2. 図５は、実施例３に係るブレージングシートの接合構造の耐食性試験結果を示す図である。FIG. 5 is a diagram showing the results of a corrosion resistance test of the joint structure of the brazing sheet according to Example 3.
　本開示に係るブレージングシートは、空気調和装置の熱交換器に用いられるものであって、アルミニウム合金製の心材と、当該心材の一方の面に被覆され、シリコン（Ｓｉ）を含有するアルミニウム合金のろう材からなるろう材層と、当該心材の他方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、を備える。ブレージングシートは、犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材における前記シリコンの含有量ＸSiは、次式（１）
Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
から導き出される値以下であり、かつ、次式（２）
Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
から導き出される値以上である構成である。 The brazing sheet according to the present disclosure is used for a heat exchanger of an air conditioner, and is made of an aluminum alloy core material and an aluminum alloy coated on one surface of the core material and containing silicon (Si). A brazing material layer made of a brazing material and a sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si) are provided. The brazing sheet contains the silicon in the sacrificial anode material when the thickness of the sacrificial anode material layer is in the range of 15 to 25 μm and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C. The quantity X Si is given by the following equation (1).
T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
It is less than or equal to the value derived from, and the following equation (2)
T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
It is a configuration that is greater than or equal to the value derived from.
　あるいは、本開示に係るブレージングシートは、空気調和装置の熱交換器に用いられるブレージングシートであって、アルミニウム合金製の心材と、当該心材の両方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、を備え、犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材における前記シリコンの含有量ＸSiは、次式（１）
Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
から導き出される値以下であり、かつ、次式（２）
Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
から導き出される値以上である構成であってもよい。 Alternatively, the brazing sheet according to the present disclosure is a brazing sheet used in a heat exchanger of an air conditioner, which is coated on both surfaces of an aluminum alloy core material and the core material, and zinc (Zn) and silicon (Zn) and silicon ( A sacrificial anode material layer made of a sacrificial anode material of an aluminum alloy containing Si) is provided, the thickness of the sacrificial anode material layer is within the range of 15 to 25 μm, and the temperature T at the time of joining the brazing sheet is 580 to. When the temperature is within the range of 660 ° C., the silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
It is less than or equal to the value derived from, and the following equation (2)
T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
The configuration may be greater than or equal to the value derived from.
　上記構成によれば、空気調和装置用熱交換器に用いられるブレージングシートにおいて、犠牲陽極材層が上述の範囲内でシリコンを含有している。これにより、ろう材を兼ねる犠牲陽極材において、シリコンの含有量を好適化することができる。そのため、犠牲陽極材層の厚さが上述の範囲内であっても、ブレージングシートの接合構造における耐食性および耐圧性を両立させることが可能になる。 According to the above configuration, in the brazing sheet used for the heat exchanger for the air conditioner, the sacrificial anode material layer contains silicon within the above range. Thereby, the silicon content can be optimized in the sacrificial anode material which also serves as a brazing material. Therefore, even if the thickness of the sacrificial anode material layer is within the above range, it is possible to achieve both corrosion resistance and pressure resistance in the bonding structure of the brazing sheet.
　ブレージングシートにおいては、当該ブレージングシートは、互いに接合されることにより接合部を構成する接合部位と、この接合部位に隣接する傾斜部位と、を有し、接合部位に対する傾斜部位の傾斜角は４０°以下である構成であってもよい。 In the brazing sheet, the brazing sheet has a joint portion that constitutes a joint portion by being joined to each other and an inclined portion adjacent to the joint portion, and the inclination angle of the inclined portion with respect to the joint portion is 40 °. The configuration may be as follows.
　ブレージングシートにおいては、心材は、３０００系、５０００系、または６０００系のいずれかのアルミニウム合金であり、犠牲陽極材は、４０００系のアルミニウム合金であり、かつ、亜鉛を２．０～６．０質量％の範囲内で含有するものである構成であってもよい。 In the brazing sheet, the core material is an aluminum alloy of 3000 series, 5000 series, or 6000 series, the sacrificial anode material is a 4000 series aluminum alloy, and zinc is 2.0 to 6.0. The composition may be such that it is contained within the range of mass%.
　ブレージングシートにおいては、ろう材は、４０００系のアルミニウム合金である構成であってもよい。 In the brazing sheet, the brazing material may be a 4000 series aluminum alloy.
　本開示に係る空気調和装置用熱交換器は、上記構成のブレージングシートを用いて構成されるものであればよい。 The heat exchanger for the air conditioner according to the present disclosure may be configured by using the brazing sheet having the above configuration.
　空気調和装置用熱交換器においては、プレートフィン積層型である構成であってもよい。 The heat exchanger for the air conditioner may have a configuration in which plate fins are laminated.
　以下、本開示の代表的な実施の形態を、図面を参照しながら説明する。なお、以下では全ての図を通じて同一又は相当する要素には同一の参照符号を付して、その重複する説明を省略する。 Hereinafter, typical embodiments of the present disclosure will be described with reference to the drawings. In the following, the same or corresponding elements will be designated by the same reference numerals throughout all the figures, and duplicate description thereof will be omitted.
　本開示に係るブレージングシートは、熱交換器に用いられるアルミニウム合金製である。具体的には、例えば、図１Ａに示すように、本開示に係るブレージングシート１０は、心材１１、ろう材層１２、および犠牲陽極材層１３を備えている。ろう材層１２は、心材１１の一方の面に被覆（クラッド）され、犠牲陽極材層１３は心材１１の他方の面、すなわちろう材層１２が被覆されている面とは反対側の面に被覆されている。心材１１、ろう材層１２を構成するろう材、および、犠牲陽極材層１３を構成する犠牲陽極材はいずれもアルミニウム合金である。 The brazing sheet according to the present disclosure is made of an aluminum alloy used for a heat exchanger. Specifically, for example, as shown in FIG. 1A, the brazing sheet 10 according to the present disclosure includes a core material 11, a brazing material layer 12, and a sacrificial anode material layer 13. The brazing material layer 12 is coated (clad) on one surface of the core material 11, and the sacrificial anode material layer 13 is on the other surface of the core material 11, that is, the surface opposite to the surface on which the brazing material layer 12 is coated. It is covered. The core material 11, the brazing material forming the brazing material layer 12, and the sacrificial anode material forming the sacrificial anode material layer 13 are all aluminum alloys.
　あるいは図示しないが、本開示に係るブレージングシート１０は、心材１１および犠牲陽極材層１３を備え、ろう材層１２を備えていない構成でもよい。このようなブレージングシート１０では、心材１１の両方の面に犠牲陽極材層１３が形成されている。 Alternatively, although not shown, the brazing sheet 10 according to the present disclosure may have a core material 11 and a sacrificial anode material layer 13, and may not have a brazing material layer 12. In such a brazing sheet 10, a sacrificial anode material layer 13 is formed on both surfaces of the core material 11.
　本開示に係るブレージングシート１０は、少なくとも犠牲陽極材層１３の側に接合部位を有しており、この接合部位の接合面同士を互いに接合することで接合部を形成する。ブレージングシート１０同士を接合部位で接合した構造が、本開示に係るブレージングシート１０の接合構造である。本開示に係るブレージングシート１０の具体的な形状は特に限定されないが、代表的には、接合部位に隣接し、当該接合部位に対して傾斜する傾斜部位を有する構成を挙げることができる。 The brazing sheet 10 according to the present disclosure has a joint portion at least on the side of the sacrificial anode material layer 13, and the joint portion is formed by joining the joint surfaces of the joint portions to each other. The structure in which the brazing sheets 10 are joined to each other at the joining site is the joining structure of the brazing sheets 10 according to the present disclosure. The specific shape of the brazing sheet 10 according to the present disclosure is not particularly limited, but a typical example may be a configuration having an inclined portion adjacent to the joint portion and inclined with respect to the joint portion.
　具体的には、例えば、図１Ｂに示すように、本開示に係るブレージングシート１０の接合構造２０は、ブレージングシート１０の接合部位１０ａ同士を接合して構成される。接合部位１０ａには傾斜部位１０ｂが隣接しており、接合部位１０ａに対する傾斜部位１０ｂの傾斜角θ１は特に限定されないが、ブレージングシートの接合構造２０における傾斜部位１０ｂ同士で形成される角度θ２が鋭角すなわち９０°未満であればよい（θ２＜９０°）ので、傾斜角θ１はその１／２である４５°未満であればよい。また、図１Ｂに示すように、傾斜部位１０ｂ同士の間にはフィレット２２が形成される。このフィレット２２は、本実施の形態では、接合時に接合部位１０ａから流出したろう材または犠牲陽極材が固化したものとして定義される。 Specifically, for example, as shown in FIG. 1B, the joining structure 20 of the brazing sheet 10 according to the present disclosure is configured by joining the joining portions 10a of the brazing sheet 10 to each other. The inclined portion 10b is adjacent to the joint portion 10a, and the inclination angle θ1 of the inclined portion 10b with respect to the joint portion 10a is not particularly limited, but the angle θ2 formed between the inclined portions 10b in the joining structure 20 of the brazing sheet is an acute angle. That is, it may be less than 90 ° (θ2 <90 °), so the inclination angle θ1 may be less than 45 °, which is 1/2 of that. Further, as shown in FIG. 1B, fillets 22 are formed between the inclined portions 10b. In the present embodiment, the fillet 22 is defined as a solidified wax material or sacrificial anode material that has flowed out from the joint portion 10a at the time of joining.
　なお、ブレージングシートの接合構造２０を構成する各傾斜部位１０ｂにより形成される角度θ２を、説明の便宜上「傾斜部位形成角」と称する。また、図１Ｂでは、傾斜角θ１、および、傾斜部位形成角θ２は、点線で図示しているが、これら角度の基準は、図中点線で示すように、ブレージングシート１０の厚さの中間線（一方の面と他方の面との双方から中間の厚さ（深さ）となる線）としている。ただし、これら角度θ１およびθ２の基準は厚さの中間線に限定されず、その他の公知の基準（例えば接合側の面を基準とした角度等）であってもよい。 The angle θ2 formed by each inclined portion 10b constituting the joining structure 20 of the brazing sheet is referred to as an “inclined portion forming angle” for convenience of explanation. Further, in FIG. 1B, the inclination angle θ1 and the inclination portion formation angle θ2 are shown by dotted lines, but the reference of these angles is an intermediate line of the thickness of the brazing sheet 10 as shown by the dotted line in the figure. (A line having an intermediate thickness (depth) from both one surface and the other surface). However, the reference of these angles θ1 and θ2 is not limited to the intermediate line of the thickness, and may be another known reference (for example, an angle with respect to the surface on the joint side).
　傾斜角θ１は、前述の通り４５°未満であればよいが、その上限は、好ましくは４０°未満であり、より好ましくは３５°未満であればよい。空気調和装置用熱交換器の構造にもよるが、傾斜角θ１が４０°を超えると、プレス加工時にブレージングシート１０に部分的な減肉が生じたり、心材１１に部分的なエロージョンが生じたりするおそれがある。 The inclination angle θ1 may be less than 45 ° as described above, but the upper limit thereof is preferably less than 40 °, more preferably less than 35 °. Depending on the structure of the heat exchanger for the air conditioner, if the inclination angle θ1 exceeds 40 °, the brazing sheet 10 may be partially thinned or the core material 11 may be partially eroded during press working. There is a risk of doing so.
　接合部位１０ａに対する傾斜部位１０ｂの傾斜角θ１が相対的に大きいということは、プレス加工時にブレージングシート１０に対して大きな加工が加えられていることを意味する。これによりブレージングシート１０に部分的に減肉が発生する。ブレージングシート１０が部分的に減肉すると、減肉部分に応力集中または耐圧不足等が発生するため、当該部分から破損してしまうおそれがある。 The fact that the inclination angle θ1 of the inclined portion 10b with respect to the joint portion 10a is relatively large means that a large processing is applied to the brazing sheet 10 during the press working. As a result, the brazing sheet 10 is partially thinned. When the brazing sheet 10 is partially thinned, stress concentration or insufficient pressure resistance occurs in the thinned portion, so that the portion may be damaged.
　また、大きな加工がブレージングシート１０に加わることにより、当該加工が加えられた部位において、ろう材層１２から心材１１へのシリコンの拡散係数が大きくなり、これによりエロージョン（心材１１の溶融）が生じるおそれが高まる。エロージョンが発生すると、溶融した心材１１の周囲に存在する犠牲陽極材層１３が含有する亜鉛を巻き込むことになり、心材１１の一部が「犠牲陽極材」化する。その結果、エロージョンが発生した部位からブレージングシート１０が早期貫通する可能性が生じる。 Further, when a large processing is applied to the brazing sheet 10, the diffusion coefficient of silicon from the brazing material layer 12 to the core material 11 becomes large at the portion where the processing is applied, which causes erosion (melting of the core material 11). The risk increases. When erosion occurs, zinc contained in the sacrificial anode material layer 13 existing around the molten core material 11 is involved, and a part of the core material 11 becomes a “sacrificial anode material”. As a result, there is a possibility that the brazing sheet 10 penetrates early from the site where the erosion occurs.
　これに対して、傾斜角θ１が４０°以下であれば、ブレージングシート１０に対して大きな加工が加えられるおそれが低減する。それゆえ、ブレージングシート１０に部分的な減肉が生じたり、心材１１に部分的なエロージョンが生じたりするおそれを有効に抑制することができる。もちろん、空気調和装置用熱交換器の構造によっては、傾斜角θ１が４０°を超えていても、プレス加工時のブレージングシート１０の部分的な減肉、または、心材１１の部分的なエロージョンの発生が抑制される場合もあるので、傾斜角θ１の上限は必ずしも４０°とは限らない。 On the other hand, when the inclination angle θ1 is 40 ° or less, the possibility that a large processing is applied to the brazing sheet 10 is reduced. Therefore, it is possible to effectively suppress the possibility that the brazing sheet 10 is partially thinned or the core material 11 is partially eroded. Of course, depending on the structure of the heat exchanger for the air conditioner, even if the inclination angle θ1 exceeds 40 °, the brazing sheet 10 may be partially thinned during press working, or the core material 11 may be partially eroded. Since the occurrence may be suppressed, the upper limit of the inclination angle θ1 is not always 40 °.
　一方、傾斜角θ１の下限も特に限定されず、空気調和装置用熱交換器の構造に応じて好適な下限値を設定すればよい。例えば、後述するプレートフィン積層型熱交換器であれば、構造上、隣接する空気（第２流体）の流路を確保する観点から傾斜角θ１をあまり小さくしない方がよい。プレートフィン積層型熱交換器における傾斜角θ１の下限値としては、好ましくは１５°以上を挙げることができ、より好ましくは２０°以上を挙げることができる。 On the other hand, the lower limit of the inclination angle θ1 is not particularly limited, and a suitable lower limit value may be set according to the structure of the heat exchanger for the air conditioner. For example, in the case of the plate fin laminated heat exchanger described later, it is better not to make the inclination angle θ1 too small from the viewpoint of securing the flow path of the adjacent air (second fluid) due to the structure. The lower limit of the inclination angle θ1 in the plate fin laminated heat exchanger is preferably 15 ° or more, and more preferably 20 ° or more.
　本開示に係るブレージングシート１０が備える心材１１は、熱交換器の種類または構造等の諸条件に応じて求められる物性を実現し得る公知のアルミニウム合金であればよい。心材１１として用いられるアルミニウム合金としては、例えば、熱交換器の分野では、代表的には、３０００系（アルミニウム－マンガン（Ａｌ－Ｍｎ）系合金）、５０００系（アルミニウム－マグネシウム（Ａｌ－Ｍｇ）系合金）、または６０００系（アルミニウム－マグネシウム－シリコン（Ａｌ－Ｍｇ－Ｓｉ）系合金）等を挙げることができるが、これらに限定されない。 The core material 11 included in the brazing sheet 10 according to the present disclosure may be a known aluminum alloy that can realize the physical properties required according to various conditions such as the type or structure of the heat exchanger. Examples of the aluminum alloy used as the core material 11 include, in the field of heat exchangers, typically 3000 series (aluminum-manganese (Al-Mn) based alloy) and 5000 series (aluminum-magnesium (Al-Mg)). (Aluminum-based alloy), 6000-based (aluminum-magnesium-silicon (Al-Mg-Si) -based alloy), and the like, but are not limited thereto.
　あるいは、心材１１は、前述のアルミニウム合金に対して公知の元素を、不可避的不純物を超える含有量（濃度）で添加してもよい。なお、不可避的不純物として許容される濃度の上限は、諸条件によっても異なるが、例えば、アルミニウム合金全体における０．１質量％未満を挙げることができる。あるいは、不可避的不純物の濃度の上限は、ＪＩＳ等の公知の規格に規定される合金組成に準じてもよい。 Alternatively, the core material 11 may contain an element known to the above-mentioned aluminum alloy at a content (concentration) exceeding the unavoidable impurities. The upper limit of the concentration allowed as an unavoidable impurity varies depending on various conditions, but for example, less than 0.1% by mass in the entire aluminum alloy can be mentioned. Alternatively, the upper limit of the concentration of unavoidable impurities may conform to the alloy composition defined in a known standard such as JIS.
　ろう材として用いられるアルミニウム合金は、本開示においては、シリコン（ケイ素、Ｓｉ）を含有するもの、すなわち、アルミニウム－シリコン（Ａｌ－Ｓｉ）系合金であればよい。ろう材におけるＳｉの含有量は特に限定されず、ろう材として好適な使用が可能な程度の範囲内であればよい。具体的には、例えば、ろう材におけるＳｉの含有量（濃度）としては、２．５～１３質量％の範囲内を挙げることができ、３．５～１２質量％の範囲内であってもよい。Ｓｉの含有量が少なすぎると、Ａｌ－Ｓｉ系合金がろう材として十分に機能しなくなるおそれがある。一方、Ｓｉの含有量が多すぎると、心材１１または相手材にＳｉが拡散してブレージングシート１０そのものに溶融が生じるおそれがある。また、ろう材としてのＡｌ－Ｓｉ系合金には、ろう材としての機能に影響を及ぼさない範囲で、不可避的不純物を超える含有量でＳｉ以外の元素を含有してもよい。 In the present disclosure, the aluminum alloy used as the brazing material may be an alloy containing silicon (silicon, Si), that is, an aluminum-silicon (Al-Si) alloy. The content of Si in the brazing material is not particularly limited, and may be within a range suitable for use as a brazing material. Specifically, for example, the content (concentration) of Si in the brazing material can be in the range of 2.5 to 13% by mass, even if it is in the range of 3.5 to 12% by mass. Good. If the Si content is too low, the Al—Si alloy may not function sufficiently as a brazing material. On the other hand, if the Si content is too high, Si may diffuse into the core material 11 or the mating material and melt the brazing sheet 10 itself. Further, the Al—Si alloy as the brazing material may contain an element other than Si in a content exceeding the unavoidable impurities as long as the function as the brazing material is not affected.
　犠牲陽極材として用いられるアルミニウム合金は、犠牲陽極作用を発揮するために、亜鉛（Ｚｎ）を２．０～６．０質量％の範囲内で含有している。また、本開示においては、前述の通り犠牲陽極材がろう材を兼ねているため、ろう材と同様にＳｉを含有している。犠牲陽極材におけるＳｉの含有量（Ｓｉ濃度）は３．０～６．０質量％の範囲内を挙げることができる。したがって、犠牲陽極材として用いられるアルミニウム合金は、アルミニウム－シリコン－亜鉛（Ａｌ－Ｓｉ－Ｚｎ）系合金であればよい。 The aluminum alloy used as the sacrificial anode material contains zinc (Zn) in the range of 2.0 to 6.0% by mass in order to exert the sacrificial anode action. Further, in the present disclosure, since the sacrificial anode material also serves as a brazing material as described above, Si is contained in the same manner as the brazing material. The Si content (Si concentration) in the sacrificial anode material can be in the range of 3.0 to 6.0% by mass. Therefore, the aluminum alloy used as the sacrificial anode material may be an aluminum-silicon-zinc (Al-Si-Zn) alloy.
　犠牲陽極材としてのＡｌ－Ｓｉ－Ｚｎ系合金において、Ｚｎの含有量（濃度）が２．０質量％未満であれば、良好な犠牲陽極作用を発揮することができない。一方、Ｚｎの含有量が６．０質量％を超えると、犠牲陽極作用が早期に進行し過ぎてブレージングシート１０から犠牲陽極材層１３が早期に消失してしまい、ブレージングシート１０の耐食性が低下するおそれがある。 In the Al—Si—Zn-based alloy as the sacrificial anode material, if the Zn content (concentration) is less than 2.0% by mass, a good sacrificial anode action cannot be exhibited. On the other hand, when the Zn content exceeds 6.0% by mass, the sacrificial anode action proceeds too early and the sacrificial anode material layer 13 disappears from the brazing sheet 10 at an early stage, so that the corrosion resistance of the brazing sheet 10 deteriorates. There is a risk of
　また、犠牲陽極材としてのＡｌ－Ｓｉ－Ｚｎ系合金において、Ｓｉの含有量が３．０質量％未満であると、Ｓｉが少なすぎて当該犠牲陽極材が十分に流動せず、ろう材として良好な接着強度を発揮できなくなるおそれがある。一方、Ｓｉの含有量が６．０質量％を超えると、犠牲陽極材としての流動性は向上するものの流動性が高くなり過ぎて耐食性が低下するおそれがある。 Further, in the Al—Si—Zn-based alloy as the sacrificial anode material, if the Si content is less than 3.0% by mass, the amount of Si is too small and the sacrificial anode material does not flow sufficiently, and as a brazing material. There is a risk that good adhesive strength cannot be exhibited. On the other hand, if the Si content exceeds 6.0% by mass, the fluidity as the sacrificial anode material is improved, but the fluidity becomes too high and the corrosion resistance may decrease.
　特に本開示においては、ブレージングシート１０は、空気調和装置用熱交換器に用いられる。ここで、ブレージングシート１０が冷媒の流路を構成する接合構造２０に用いられる場合（後述するプレートフィン積層型熱交換器等）、冷媒の許容圧力の上限に耐え得る程度の接着強度が要求される。なお、この許容圧力は、空気調和装置の種類、用途、性能等の諸条件によって異なるため、犠牲陽極材に求められる接着強度も諸条件に応じて適宜設定することができる。 Particularly in the present disclosure, the brazing sheet 10 is used as a heat exchanger for an air conditioner. Here, when the brazing sheet 10 is used for the bonding structure 20 constituting the flow path of the refrigerant (such as a plate fin laminated heat exchanger described later), the adhesive strength is required to be sufficient to withstand the upper limit of the allowable pressure of the refrigerant. To. Since this allowable pressure varies depending on various conditions such as the type, application, and performance of the air conditioner, the adhesive strength required for the sacrificial anode material can be appropriately set according to the conditions.
　ここで、本開示においては、ブレージングシート１０同士の接合時の温度（ろう付け温度）を考慮すると、Ｓｉの含有量は、ブレージングシート１０の接合構造２０において、十分な耐圧性を実現し得る接着強度と十分な耐食性とのバランスが重要となる。この点について本発明者らが鋭意検討した結果、ブレージングシート１０の接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材におけるＳｉの特に好適な含有量は、下記式（１）および式（２）により定義することが可能であることが明らかとなった。 Here, in the present disclosure, in consideration of the temperature (brazing temperature) at the time of joining the brazing sheets 10 to each other, the Si content is the adhesion capable of realizing sufficient pressure resistance in the joining structure 20 of the brazing sheets 10. The balance between strength and sufficient corrosion resistance is important. As a result of diligent studies by the present inventors on this point, when the temperature T at the time of joining the brazing sheet 10 is in the range of 580 to 660 ° C., a particularly preferable content of Si in the sacrificial anode material is as follows. It became clear that it can be defined by (1) and Eq. (2).
　具体的には、犠牲陽極材において、Ｚｎの含有量（濃度）が２．０～６．０質量％の範囲内であるときに、Ｓｉの含有量（濃度）をＸSiとすると、このＳｉ濃度、次式（１）から導き出される値以下であり、かつ、次式（２）から導き出される値以上であればよい。
Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
　なお、犠牲陽極材としてのＡｌ－Ｓｉ－Ｚｎ系合金においても、犠牲陽極作用およびろう材としての機能に影響を及ぼさない範囲で、ＳｉおよびＺｎ以外の元素を、不可避的不純物を超える含有量で含有してもよい。 Specifically, in the sacrificial anode material, when the Zn content (concentration) is in the range of 2.0 to 6.0% by mass and the Si content (concentration) is X Si , this Si The concentration may be equal to or less than the value derived from the following equation (1) and greater than or equal to the value derived from the following equation (2).
T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
Even in the Al—Si—Zn-based alloy as the sacrificial anode material, the content of elements other than Si and Zn exceeds the unavoidable impurities as long as the sacrificial anode action and the function as the brazing material are not affected. It may be contained.
　ろう材および犠牲陽極材として具体的に用いられるアルミニウム合金の種類は特に限定されないが、代表的には、いずれも４０００系（アルミニウム－シリコン（Ａｌ－Ｓｉ）系合金）を用いることができる。犠牲陽極材では、Ｓｉの含有量が前述の範囲内に入るような４０００系のアルミニウム合金を選択するか、Ｓｉを公知の手法で添加することによって前述の範囲内に入るように調整するとともに、Ｚｎについても含有量が前述の範囲内となるように、公知の手法でＺｎを添加すればよい。 The type of aluminum alloy specifically used as the brazing material and the sacrificial anode material is not particularly limited, but typically, 4000 series (aluminum-silicon (Al-Si) based alloy) can be used for both. For the sacrificial anode material, a 4000 series aluminum alloy having a Si content within the above range is selected, or Si is added by a known method to adjust the content so as to fall within the above range. Zn may be added by a known method so that the content of Zn is also within the above range.
　本開示に係るブレージングシート１０においては、ろう材および犠牲陽極材のクラッド率は特に限定されず、一般的な範囲内を挙げることができる。一般的なクラッド率としては、例えば、２～３０質量％の範囲内を挙げることができ、３～２０質量％の範囲内であってもよい。 In the brazing sheet 10 according to the present disclosure, the clad ratio of the brazing material and the sacrificial anode material is not particularly limited, and can be mentioned within a general range. The general clad ratio may be, for example, in the range of 2 to 30% by mass, and may be in the range of 3 to 20% by mass.
　また、本開示に係るブレージングシート１０の厚さ、並びに、心材１１、ろう材層１２、および犠牲陽極材層１３のそれぞれの厚さについても特に限定されず、当該ブレージングシート１０の構成または製造しようとする熱交換器の種類または部品等に応じて適宜設定することができる。ただし、本開示では、犠牲陽極材層１３の厚さは１５～２５μｍの範囲内である。 Further, the thickness of the brazing sheet 10 according to the present disclosure and the thicknesses of the core material 11, the brazing material layer 12, and the sacrificial anode material layer 13 are not particularly limited, and the brazing sheet 10 may be configured or manufactured. It can be appropriately set according to the type or parts of the heat exchanger to be used. However, in the present disclosure, the thickness of the sacrificial anode material layer 13 is in the range of 15 to 25 μm.
　本開示に係るブレージングシート１０は、空気調和装置用熱交換器に用いられるため、自動車用に比べて犠牲陽極材層１３の厚さをより薄くすることができる。犠牲陽極材層１３の厚さを薄くすることができれば、犠牲陽極材の使用量を低減することができるので、ブレージングシート１０の製造コストの増加を抑制することが可能になる。 Since the brazing sheet 10 according to the present disclosure is used in a heat exchanger for an air conditioner, the thickness of the sacrificial anode material layer 13 can be made thinner than that for an automobile. If the thickness of the sacrificial anode material layer 13 can be reduced, the amount of the sacrificial anode material used can be reduced, so that an increase in the manufacturing cost of the brazing sheet 10 can be suppressed.
　特に、本開示では、後述するように熱交換器としてプレートフィン積層型を好ましい一例として挙げることができる。プレートフィン積層型熱交換器は、複数のプレートフィンを重ねて積層体とし、この積層体を治具で押さえ付けて接合（ろう付け）する。そのため、犠牲陽極材層１３の厚みが大きすぎると積層体の寸法変化が大きくなり、ブレージングシートの接合構造２０に影響を及ぼすおそれがある。犠牲陽極材層１３を２５μｍ以下とすることができれば、このような接合構造２０への影響を有効に抑制することができる。 In particular, in the present disclosure, as will be described later, a plate fin laminated type as a heat exchanger can be mentioned as a preferable example. In the plate fin laminated heat exchanger, a plurality of plate fins are laminated to form a laminated body, and the laminated body is pressed by a jig to join (braze). Therefore, if the thickness of the sacrificial anode material layer 13 is too large, the dimensional change of the laminated body becomes large, which may affect the bonding structure 20 of the brazing sheet. If the sacrificial anode material layer 13 can be set to 25 μm or less, such an influence on the joint structure 20 can be effectively suppressed.
　一方、犠牲陽極材層１３が１５μｍ未満であると、ブレージングシート１０に対する犠牲陽極材の絶対量が少なくなり過ぎる。そのため、ブレージングシート１０から犠牲陽極材層１３が早期に消失してしまい、ブレージングシート１０の耐食性が低下するおそれがある。 On the other hand, if the sacrificial anode material layer 13 is less than 15 μm, the absolute amount of the sacrificial anode material with respect to the brazing sheet 10 becomes too small. Therefore, the sacrificial anode material layer 13 may disappear from the brazing sheet 10 at an early stage, and the corrosion resistance of the brazing sheet 10 may decrease.
　本開示では、複数枚のブレージングシート１０を接合部位１０ａ同士で重ね合わせて、高温（５８０℃以上）の温度でろう材および犠牲陽極材を溶融させてろう付けすることにより、ブレージングシート１０同士が接合される。このようにして製造されるブレージングシート１０の接合構造２０では、図１Ｂに示すように、傾斜部位１０ｂの間で接合部位１０ａ（接合部２１）に隣接する部位には、接合部位１０ａの犠牲陽極材層１３から流出した犠牲陽極材が固化してフィレット２２が形成される。 In the present disclosure, a plurality of brazing sheets 10 are superposed on each other at the joining portions 10a, and the brazing material and the sacrificial anode material are melted and brazed at a high temperature (580 ° C. or higher) to braze the brazing sheets 10 to each other. Be joined. In the joint structure 20 of the brazing sheet 10 manufactured in this manner, as shown in FIG. 1B, the sacrificial anode of the joint portion 10a is located at a portion adjacent to the joint portion 10a (joint portion 21) between the inclined portions 10b. The sacrificial anode material flowing out of the material layer 13 solidifies to form a fillet 22.
　本開示においては、ブレージングシート１０の耐食性を評価する観点から、接合部２１（フィレット２２を含む）、犠牲陽極材層１３等の電位を公知の方法で評価（測定）すればよい。代表的な電位の評価方法としては、ポテンショスタット／ガルバノスタットに、電位測定用の試料（例えば、ブレージングシート１０、もしくは、心材１１、ろう材、犠牲陽極材、フィレット２２または接合部２１、あるいはこれらを模擬した組成の合金等）と、対極と、参照電極（例えば銀／塩化銀（Ａｇ／ＡｇＣｌ）電極）とを接続して電解液（例えば５重量％の塩化ナトリウム（ＮａＣｌ）溶液）に浸漬し、試料と参照電極との電位差を測定する方法を挙げることができる。 In the present disclosure, from the viewpoint of evaluating the corrosion resistance of the brazing sheet 10, the potentials of the joint portion 21 (including the fillet 22), the sacrificial anode material layer 13, and the like may be evaluated (measured) by a known method. As a typical method for evaluating an electric potential, a potential measurement sample (for example, a brazing sheet 10 or a core material 11, a brazing material, a sacrificial anode material, a fillet 22 or a joint portion 21, or these) is used in a potential stat / galvanostat. (For example, an alloy having a composition simulating), a counter electrode, and a reference electrode (for example, a silver / silver chloride (Ag / AgCl) electrode) are connected and immersed in an electrolytic solution (for example, a 5 wt% sodium chloride (NaCl) solution). Then, a method of measuring the potential difference between the sample and the reference electrode can be mentioned.
　このような本開示に係るブレージングシート１０の製造方法は特に限定されず、公知の製造方法を好適に用いることができる。具体的には、例えば、所望の組成のアルミニウム合金を公知の方法で板状に成形して心材１１とし、この心材１１の一方の面に対して、Ｓｉを含有するアルミニウム合金のろう材を公知の方法でクラッドし、心材１１の他方の面に対して、Ｚｎを２．０～６．０質量％の範囲内、および、Ｓｉを３．０～６．０質量％の範囲内で含有するアルミニウム合金の犠牲陽極材を公知の方法でクラッドすればよい。本開示においては、ブレージングシート１０の製造における諸条件は、当該ブレージングシート１０の構成または製造しようとする空気調和装置用熱交換器の種類または部品等に応じて適宜設定することができる。 The manufacturing method of the brazing sheet 10 according to the present disclosure is not particularly limited, and a known manufacturing method can be preferably used. Specifically, for example, an aluminum alloy having a desired composition is formed into a plate shape by a known method to obtain a core material 11, and a brazing material of an aluminum alloy containing Si is known for one surface of the core material 11. Clad with the method of, Zn is contained in the range of 2.0 to 6.0% by mass, and Si is contained in the range of 3.0 to 6.0% by mass with respect to the other surface of the core material 11. The sacrificial anode material of the aluminum alloy may be clad by a known method. In the present disclosure, the conditions for manufacturing the brazing sheet 10 can be appropriately set according to the configuration of the brazing sheet 10 or the type or parts of the heat exchanger for the air conditioner to be manufactured.
　本開示に係るブレージングシート１０は、前述の通り空気調和装置用熱交換器の製造に特に好適に用いることができる。本開示に係るブレージングシート１０を熱交換器に適用した場合に形成されるブレージングシートの接合構造２０は、前述したように、図１Ｂに例示するような構造である。より具体的には、図２に示すような構造を有するプレートフィン積層型熱交換器、あるいは、図４Ａ及び図４Ｂに示すような構造を有するＡｉｒ　Ｔｏ　Ｗａｔｅｒヒートポンプ用積層型熱交換器等を挙げることができる。 The brazing sheet 10 according to the present disclosure can be particularly suitably used for manufacturing a heat exchanger for an air conditioner as described above. As described above, the joining structure 20 of the brazing sheet formed when the brazing sheet 10 according to the present disclosure is applied to the heat exchanger has a structure as illustrated in FIG. 1B. More specifically, a plate fin laminated heat exchanger having a structure as shown in FIG. 2, an Air To Water laminated heat exchanger having a structure as shown in FIGS. 4A and 4B, and the like can be mentioned. be able to.
　プレートフィン積層型熱交換器は、図示しないが、第１流体である冷媒が流れる流路を有するプレートフィン積層体において、各プレートフィン積層間に第２流体である空気を流して、これら第１流体と第２流体との間で熱交換を行うものである。この熱交換器が備えるプレートフィンは、第１流体が並行に流れる複数の第１流体流路を有する流路領域と、この流路領域における各第１流体流路に連通するヘッダ流路を有するヘッダ領域と、を備えている。 Although not shown, the plate fin laminated heat exchanger is a plate fin laminated body having a flow path through which a refrigerant, which is a first fluid, flows, and air, which is a second fluid, is flowed between each plate fin laminated body to flow the first fluid. Heat exchange is performed between the fluid and the second fluid. The plate fin included in this heat exchanger has a flow path region having a plurality of first fluid flow paths through which the first fluid flows in parallel, and a header flow path communicating with each first fluid flow path in this flow path region. It has a header area and.
　プレートフィン積層型熱交換器では、プレートフィン積層体の積層方向の両側に、当該プレートフィンと平面視が略同一形状のエンドプレートが設けられており、これら一対のエンドプレートとこれらの間に介在する複数のプレートフィンとは、積層された状態でろう付けにより接合されて一体化している。図２は、このプレートフィン積層体３０におけるヘッダ部分の概略構造を部分断面として示しており、図中最上部に位置するエンドプレート３１に対して複数のプレートフィン３２が積層されている。 In the plate fin laminated heat exchanger, end plates having substantially the same shape as the plate fins in a plan view are provided on both sides of the plate fin laminated body in the laminating direction, and are interposed between these pair of end plates. The plurality of plate fins to be formed are joined and integrated by brazing in a laminated state. FIG. 2 shows a schematic structure of a header portion in the plate fin laminated body 30 as a partial cross section, and a plurality of plate fins 32 are laminated on an end plate 31 located at the uppermost part in the drawing.
　エンドプレート３１およびプレートフィン３２には、それぞれ開口部が設けられており、これらプレートが積層されてプレートフィン積層体３０を形成することにより、ヘッダ開口３３が形成される。図２に示す構成では、ヘッダ開口３３の外側から図中ブロック矢印で示す方向に第１流体である冷媒が流入し、さらにプレートフィン３２の間に冷媒が流入する。各プレートフィン３２には、前述の通り、第１流体流路が設けられているので、プレートフィン３２の間に流入した冷媒は、第１流体流路を流れる。また、第２流体である空気は、プレートフィン３２の間に形成される空間を、冷媒の流れる方向（第１流体流路の方向）に交差するように流れる。これにより、空気が冷媒により冷却される。 An opening is provided in each of the end plate 31 and the plate fin 32, and the header opening 33 is formed by laminating these plates to form the plate fin laminated body 30. In the configuration shown in FIG. 2, the refrigerant, which is the first fluid, flows in from the outside of the header opening 33 in the direction indicated by the block arrow in the drawing, and further flows in between the plate fins 32. As described above, each plate fin 32 is provided with the first fluid flow path, so that the refrigerant flowing between the plate fins 32 flows through the first fluid flow path. Further, the air, which is the second fluid, flows in the space formed between the plate fins 32 so as to intersect the direction in which the refrigerant flows (the direction of the first fluid flow path). As a result, the air is cooled by the refrigerant.
　このようなプレートフィン積層型熱交換器の具体的な構成例としては、例えば、特開２０１７－１８０８５６号公報、特開２０１８－０６６５３１号公報、特開２０１８－０６６５３２号公報、特開２０１８－０６６５３３号公報、特開２０１８－０６６５３４号公報、特開２０１８－０６６５３５号公報、特開２０１８－０６６５３６号公報等に記載されており、これら公開公報の記載内容は、本明細書で参照することにより本明細書の記載の一部とする。 Specific configuration examples of such a plate fin laminated heat exchanger include, for example, JP-A-2017-180856, JP-A-2018-066531, JP-A-2018-066532, and JP-A-2018-066533. It is described in Japanese Patent Application Laid-Open No. 2018-066534, Japanese Patent Application Laid-Open No. 2018-066535, Japanese Patent Application Laid-Open No. 2018-066536, etc. It shall be a part of the description of the specification.
　Ａｉｒ　Ｔｏ　Ｗａｔｅｒヒートポンプ用積層型熱交換器を構成するプレートフィン積層体３４は、図３に示すように、その基本構成は、図２に示す一般的なプレートフィン積層型熱交換器のプレートフィン積層体３０と同様である。ただし、プレートフィン積層体３４を構成するプレートフィン３５（本開示に係るブレージングシート１０）は、その両面に犠牲陽極材層１３を有する構成となっている。そのため、図３に示すように、フィレット２２は、ヘッダ開口３３側（内側）に位置する接合部２１だけでなく、ヘッダ開口３３側とは反対側（外側）に位置する接合部２１にも形成されている。なお、図３に示す構成は、プレートフィン３５およびフィレット２２の形成位置以外は図２に示す構成と同様であるので、その説明を省略する。 As shown in FIG. 3, the plate fin laminate 34 constituting the laminated heat exchanger for Air To Water heat pump has a basic configuration of the plate fin laminate of the general plate fin laminated heat exchanger shown in FIG. Similar to body 30. However, the plate fins 35 (brazing sheet 10 according to the present disclosure) constituting the plate fin laminate 34 have a sacrificial anode material layer 13 on both sides thereof. Therefore, as shown in FIG. 3, the fillet 22 is formed not only at the joint portion 21 located on the header opening 33 side (inside) but also at the joint portion 21 located on the opposite side (outside) of the header opening 33 side. Has been done. Since the configuration shown in FIG. 3 is the same as the configuration shown in FIG. 2 except for the formation positions of the plate fins 35 and the fillets 22, the description thereof will be omitted.
　このように、本開示に係るブレージングシートは、空気調和装置の熱交換器に用いられるものであって、アルミニウム合金製の心材と、当該心材の一方の面に被覆され、シリコン（Ｓｉ）を含有するアルミニウム合金のろう材層と、当該心材の他方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材層と、を備えるものであるか、あるいは、心材の両方の面に犠牲陽極材層が被覆されたものである。 As described above, the brazing sheet according to the present disclosure is used for a heat exchanger of an air conditioner, and is coated on one surface of an aluminum alloy core material and the core material and contains silicon (Si). An aluminum alloy brazing material layer and a sacrificial anode material layer of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si), or a core material. A sacrificial anode material layer is coated on both surfaces of the above.
　さらに、本開示に係るブレージングシートでは、犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、犠牲陽極材におけるシリコンの含有量ＸSiは前述の式（１）から導き出される値以下であり、かつ、前述の式（２）から導き出される値以上である。これにより、ろう材を兼ねる犠牲陽極材において、亜鉛の含有量だけでなくシリコンの含有量を好適化することができる。そのため、犠牲陽極材層の厚さが前述の範囲内であっても、ブレージングシートの接合構造における耐食性および耐圧性を両立させることが可能になる。 Further, in the brazing sheet according to the present disclosure, when the thickness of the sacrificial anode material layer is in the range of 15 to 25 μm and the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C., the sacrificial anode is used. The silicon content X Si in the material is less than or equal to the value derived from the above formula (1) and greater than or equal to the value derived from the above formula (2). Thereby, in the sacrificial anode material which also serves as a brazing material, not only the zinc content but also the silicon content can be optimized. Therefore, even if the thickness of the sacrificial anode material layer is within the above range, it is possible to achieve both corrosion resistance and pressure resistance in the bonding structure of the brazing sheet.
　本開示について、実施例および比較例に基づいてより具体的に説明するが、本開示はこれに限定されるものではない。当業者は本開示の範囲を逸脱することなく、種々の変更、修正、および改変を行うことができる。なお、以下の実施例および比較例における耐食性試験は次に示すようにして行った。 The present disclosure will be described in more detail based on Examples and Comparative Examples, but the present disclosure is not limited thereto. Those skilled in the art may make various changes, modifications, and modifications without departing from the scope of the present disclosure. The corrosion resistance test in the following Examples and Comparative Examples was carried out as follows.
　［耐食性試験]
　ブレージングシートの接合構造の耐食性は、ＡＳＴＭ　Ｇ８５－Ａ３で規定されるＳＷＡＡＴ試験（Ｓｅａ　Ｗａｔｅｒ　Ａｃｉｄｉｆｉｅｄ　Ｔｅｓｔ）に基づいて評価した。 [Corrosion resistance test]
The corrosion resistance of the bonded structure of the brazing sheet was evaluated based on the SWAAT test (Sea Water Certified Test) defined by ASTM G85-A3.
　（比較例１）
　比較例１に係るブレージングシートとしては、心材が３００３のアルミニウム合金であり、ろう材層が４３４３のアルミニウム合金であり、犠牲陽極材層が、シリコン（Ｓｉ）２．５質量％、亜鉛（Ｚｎ）４．０質量％、残部アルミニウム（Ａｌ）のアルミニウム合金（Ａｌ－２．５％Ｓｉ－４．０％Ｚｎ）であるものを用いた。また、ブレージングシートが備える傾斜部位の傾斜角θ１は約３０°であった。 (Comparative Example 1)
As the brazing sheet according to Comparative Example 1, the core material is an aluminum alloy of 3003, the brazing material layer is an aluminum alloy of 4343, and the sacrificial anode material layer is silicon (Si) 2.5% by mass and zinc (Zn). An aluminum alloy (Al-2.5% Si-4.0% Zn) having a balance of 4.0% by mass and the balance of aluminum (Al) was used. Further, the inclination angle θ1 of the inclined portion included in the brazing sheet was about 30 °.
　このブレージングシートを互いの接合部位でろう付けして接合部を形成した。接合部位の接合面は犠牲陽極材層とした。なお、ろう付け温度は６１０℃としたので、このときの犠牲陽極材におけるＳｉの含有量（濃度）は、前述の式（１）および式（２）から約２．９～６．１質量％の範囲内となる。接合部を目視で観察すると、接合が不十分であることが確認された。 This brazing sheet was brazed at each other's joint to form a joint. The joint surface of the joint site was a sacrificial anode material layer. Since the brazing temperature was 610 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.9 to 6.1% by mass from the above formulas (1) and (2). It is within the range of. Visual observation of the joints confirmed that the joints were inadequate.
　また、ブレージングシート同士の接合部について、前述した腐食試験により耐食性を評価した。その結果、図４Ａの断面写真に示すように、犠牲陽極材層の犠牲陽極作用は確認できたが心材の腐食は確認できなかった。 In addition, the corrosion resistance of the joints between the brazing sheets was evaluated by the corrosion test described above. As a result, as shown in the cross-sectional photograph of FIG. 4A, the sacrificial anode action of the sacrificial anode material layer could be confirmed, but the corrosion of the core material could not be confirmed.
　（実施例１）
　実施例１に係るブレージングシートとして、犠牲陽極材層がシリコン（Ｓｉ）２．８質量％、亜鉛（Ｚｎ）４．０質量％、残部アルミニウム（Ａｌ）のアルミニウム合金（Ａｌ－２．８％Ｓｉ－４．０％Ｚｎ）であるものを用いた以外は、比較例１と同様にしてブレージングシート同士をろう付けして接合部を形成した。なお、ろう付け温度は６２０℃としたので、このときの犠牲陽極材におけるＳｉの含有量（濃度）は、前述の式（１）および式（２）から約２．３～５．３質量％の範囲内となる。接合部を目視で確認すると、良好な接合が確認された。 (Example 1)
As the brazing sheet according to Example 1, an aluminum alloy (Al-2.8% Si) in which the sacrificial anode material layer is silicon (Si) 2.8% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al). The brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was set to 620 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.3 to 5.3% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
　また、ブレージングシート同士の接合部について、前述した腐食試験により耐食性を評価した。その結果、図４Ｂの断面写真に示すように、犠牲陽極材層の犠牲陽極作用は確認できたが心材の腐食は確認できなかった。 In addition, the corrosion resistance of the joints between the brazing sheets was evaluated by the corrosion test described above. As a result, as shown in the cross-sectional photograph of FIG. 4B, the sacrificial anode action of the sacrificial anode material layer could be confirmed, but the corrosion of the core material could not be confirmed.
　（実施例２）
　実施例２に係るブレージングシートとして、犠牲陽極材層がシリコン（Ｓｉ）４．４質量％、亜鉛（Ｚｎ）４．０質量％、残部アルミニウム（Ａｌ）のアルミニウム合金（Ａｌ－４．４％Ｓｉ－４．０％Ｚｎ）であるものを用いた以外は、比較例１と同様にしてブレージングシート同士をろう付けして接合部を形成した。なお、ろう付け温度は６２０℃としたので、このときの犠牲陽極材におけるＳｉの含有量（濃度）は、前述の式（１）および式（２）から約２．３～５．３質量％の範囲内となる。接合部を目視で確認すると、良好な接合が確認された。 (Example 2)
As the brazing sheet according to Example 2, an aluminum alloy (Al-4.4% Si) in which the sacrificial anode material layer is silicon (Si) 4.4% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al). The brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was set to 620 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.3 to 5.3% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
　また、ブレージングシート同士の接合部について、前述した腐食試験により耐食性を評価した。その結果、図４Ｃの断面写真に示すように、犠牲陽極材層の犠牲陽極作用は確認できたが心材の腐食は確認できなかった。 In addition, the corrosion resistance of the joints between the brazing sheets was evaluated by the corrosion test described above. As a result, as shown in the cross-sectional photograph of FIG. 4C, the sacrificial anode action of the sacrificial anode material layer could be confirmed, but the corrosion of the core material could not be confirmed.
　（比較例２）
　比較例２に係るブレージングシートとして、犠牲陽極材層がシリコン（Ｓｉ）７．０質量％、亜鉛（Ｚｎ）４．０質量％、残部アルミニウム（Ａｌ）のアルミニウム合金（Ａｌ－４．４％Ｓｉ－４．０％Ｚｎ）であるものを用いた以外は、比較例１と同様にしてブレージングシート同士をろう付けして接合部を形成した。なお、ろう付け温度は６１０℃としたので、このときの犠牲陽極材におけるＳｉの含有量（濃度）は、前述の式（１）および式（２）から約２．９～６．１質量％の範囲内となる。接合部を目視で確認すると、良好な接合が確認された。 (Comparative Example 2)
As a brazing sheet according to Comparative Example 2, an aluminum alloy (Al-4.4% Si) in which the sacrificial anode material layer is silicon (Si) 7.0% by mass, zinc (Zn) 4.0% by mass, and the balance aluminum (Al). The brazing sheets were brazed to each other to form a joint in the same manner as in Comparative Example 1 except that the one having -4.0% Zn) was used. Since the brazing temperature was 610 ° C., the Si content (concentration) in the sacrificial anode material at this time was about 2.9 to 6.1% by mass from the above formulas (1) and (2). It is within the range of. When the joint was visually confirmed, good joint was confirmed.
　また、ブレージングシート同士の接合部について、前述した腐食試験により耐食性を評価した。その結果、図４Ｄの断面写真に示すように、犠牲陽極材層の犠牲陽極作用だけでなく、心材における粒界腐食の進行が確認された。 In addition, the corrosion resistance of the joints between the brazing sheets was evaluated by the corrosion test described above. As a result, as shown in the cross-sectional photograph of FIG. 4D, not only the sacrificial anode action of the sacrificial anode material layer but also the progress of intergranular corrosion in the core material was confirmed.
　（実施例３）
　実施例３に係るブレージングシートとして、実施例１と同様の組成を有する犠牲陽極材層を心材の両面に備え、ろう材層を備えていないもの用いた以外は、比較例１と同様にしてブレージングシート同士をろう付けして接合部を形成した。接合部を目視で確認すると、良好な接合が確認された。 (Example 3)
As the brazing sheet according to Example 3, brazing in the same manner as in Comparative Example 1 except that a sacrificial anode material layer having the same composition as that in Example 1 was provided on both sides of the core material and no brazing material layer was used. The sheets were brazed together to form a joint. When the joint was visually confirmed, good joint was confirmed.
　また、ブレージングシート同士の接合部について、前述した腐食試験により耐食性を評価した。その結果、図５の断面写真に示すように、犠牲陽極材層の犠牲陽極作用は確認できたが心材の腐食は確認できなかった。 In addition, the corrosion resistance of the joints between the brazing sheets was evaluated by the corrosion test described above. As a result, as shown in the cross-sectional photograph of FIG. 5, the sacrificial anode action of the sacrificial anode material layer could be confirmed, but the corrosion of the core material could not be confirmed.
　なお、本開示は前述の実施の形態の記載に限定されるものではなく、請求の範囲に示した範囲内で種々の変更が可能であり、異なる実施の形態や複数の変形例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施の形態についても本開示の技術的範囲に含まれる。 It should be noted that the present disclosure is not limited to the description of the above-described embodiment, and various changes can be made within the scope of the claims, and the disclosure is disclosed in different embodiments and a plurality of modifications. Embodiments obtained by appropriately combining the above technical means are also included in the technical scope of the present disclosure.
　本開示は、耐食性および耐圧性を良好に両立させることが可能な、犠牲陽極材層を備えるブレージングシートを提供することができる。従って、犠牲陽極材層を有する空気調和装置用熱交換器に用いられるブレージングシートの分野だけでなく、当該ブレージングシートを用いた空気調和装置用熱交換器の分野に広く好適に用いることができる。 The present disclosure can provide a brazing sheet provided with a sacrificial anode material layer capable of achieving both corrosion resistance and pressure resistance satisfactorily. Therefore, it can be widely and suitably used not only in the field of brazing sheets used for heat exchangers for air conditioners having a sacrificial anode material layer, but also in the field of heat exchangers for air conditioners using the brazing sheets.
　１０　　ブレージングシート
　１０ａ　　接合部位
　１０ｂ　　傾斜部位
　１１　　心材
　１２　　ろう材層
　１３　　犠牲陽極材層
　２０　　ブレージングシートの接合構造
　２１　　接合部
　２２　　フィレット
　３０　　プレートフィン積層体
　３１　　エンドプレート
　３２　　プレートフィン
　３３　　ヘッダ開口
　３４　　プレートフィン積層体
　３５　　プレートフィン 10 Brazing sheet 10a Joint part 10b Inclined part 11 Core material 12 Wax layer 13 Sacrificial anode material layer 20 Brazing sheet joint structure 21 Joining part 22 Fillet 30 Plate fin laminate 31 End plate 32 Plate fin 33 Header opening 34 Plate fin laminate 35 plate fins

Claims (7)

  1. 　空気調和装置の熱交換器に用いられるブレージングシートであって、
    　アルミニウム合金製の心材と、
    　当該心材の一方の面に被覆され、シリコン（Ｓｉ）を含有するアルミニウム合金のろう材からなるろう材層と、
    　当該心材の他方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、
    を備え、
    　前記犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、
    　前記ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、
    　前記犠牲陽極材における前記シリコンの含有量ＸSiは、次式（１）
    Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
    から導き出される値以下であり、かつ、次式（２）
    Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
    から導き出される値以上である、
    ブレージングシート。     A brazing sheet used in heat exchangers of air conditioners.
    Aluminum alloy core material and
    A brazing material layer made of an aluminum alloy brazing material coated on one surface of the core material and containing silicon (Si),
    A sacrificial anode material layer composed of a sacrificial anode material of an aluminum alloy coated on the other surface of the core material and containing zinc (Zn) and silicon (Si).
    With
    The thickness of the sacrificial anode material layer is in the range of 15 to 25 μm.
    When the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C.
    The silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
    T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
    It is less than or equal to the value derived from, and the following equation (2)
    T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
    Is greater than or equal to the value derived from
    Blazing sheet.
  2. 　空気調和装置の熱交換器に用いられるブレージングシートであって、
    　アルミニウム合金製の心材と、
    　当該心材の両方の面に被覆され、亜鉛（Ｚｎ）およびシリコン（Ｓｉ）を含有するアルミニウム合金の犠牲陽極材からなる犠牲陽極材層と、
    を備え、
    　前記犠牲陽極材層の厚さが１５～２５μｍの範囲内であり、
    　前記ブレージングシートの接合時の温度Ｔが５８０～６６０℃の範囲内であるときに、
    　前記犠牲陽極材における前記シリコンの含有量ＸSiは、次式（１）
    Ｔ＝６６０－８×ｅｘｐ（０．３ＸSi）　・・・（１）
    から導き出される値以下であり、かつ、次式（２）
    Ｔ＝５８０＋５５×ｅｘｐ（－０．５（ＸSi－１．７））　・・・（２）
    から導き出される値以上である、
    ブレージングシート。     A brazing sheet used in heat exchangers of air conditioners.
    Aluminum alloy core material and
    A sacrificial anode material layer composed of a sacrificial anode material of an aluminum alloy covering both surfaces of the core material and containing zinc (Zn) and silicon (Si).
    With
    The thickness of the sacrificial anode material layer is in the range of 15 to 25 μm.
    When the temperature T at the time of joining the brazing sheet is in the range of 580 to 660 ° C.
    The silicon content X Si in the sacrificial anode material is calculated by the following equation (1).
    T = 660-8 × exp (0.3X Si ) ・ ・ ・ (1)
    It is less than or equal to the value derived from, and the following equation (2)
    T = 580 + 55 × exp (-0.5 (X Si -1.7)) ・ ・ ・ (2)
    Is greater than or equal to the value derived from
    Blazing sheet.
  3. 　前記ブレージングシートは、２枚のブレージングシートが互いに接合されることにより接合部を構成することとなる接合部位と、
    　前記接合部位に隣接する傾斜部位と、を有し、
    　前記接合部位に対する前記傾斜部位の傾斜角は４０°以下である、
    請求項１または２に記載のブレージングシート。     The brazing sheet includes a joining portion in which two brazing sheets are joined to each other to form a joining portion.
    It has an inclined portion adjacent to the joint portion and
    The inclination angle of the inclined portion with respect to the joint portion is 40 ° or less.
    The brazing sheet according to claim 1 or 2.
  4. 　前記心材は、３０００系、５０００系、または６０００系のいずれかのアルミニウム合金であり、
    　前記犠牲陽極材は、４０００系のアルミニウム合金であり、かつ、亜鉛を２．０～６．０質量％の範囲内で含有するものである、
    請求項１または２に記載のブレージングシート。     The core material is an aluminum alloy of any of 3000 series, 5000 series, or 6000 series.
    The sacrificial anode material is a 4000 series aluminum alloy and contains zinc in the range of 2.0 to 6.0% by mass.
    The brazing sheet according to claim 1 or 2.
  5. 　前記ろう材は、４０００系のアルミニウム合金である、
    請求項１に記載のブレージングシート。     The brazing material is a 4000 series aluminum alloy.
    The brazing sheet according to claim 1.
  6. 　請求項１から５のいずれか１項に記載のブレージングシートを用いて構成される、空気調和装置用熱交換器。 A heat exchanger for an air conditioner, which is configured by using the brazing sheet according to any one of claims 1 to 5.
  7. 　前記空気調和装置用熱交換器は、プレートフィン積層型である、
    請求項６に記載の空気調和装置用熱交換器。     The heat exchanger for the air conditioner is a plate fin laminated type.
    The heat exchanger for an air conditioner according to claim 6.
PCT/JP2020/037795 2019-10-11 2020-10-06 Brazing sheet for heat exchanger and heat exchanger for air conditioning device WO2021070794A1 (en)

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