WO2011148781A1 - アルミニウム合金製熱交換器の製造方法 - Google Patents
アルミニウム合金製熱交換器の製造方法 Download PDFInfo
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- WO2011148781A1 WO2011148781A1 PCT/JP2011/060729 JP2011060729W WO2011148781A1 WO 2011148781 A1 WO2011148781 A1 WO 2011148781A1 JP 2011060729 W JP2011060729 W JP 2011060729W WO 2011148781 A1 WO2011148781 A1 WO 2011148781A1
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- aluminum alloy
- refrigerant passage
- heat exchanger
- fin
- powder
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Classifications
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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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
- B23P15/26—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass heat exchangers or the like
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing heat exchangers
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/203—Fluxing, i.e. applying flux onto surfaces
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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
- B23K35/001—Interlayers, transition pieces for metallurgical bonding of workpieces
- B23K35/002—Interlayers, transition pieces for metallurgical bonding of workpieces at least one of the workpieces being of light metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B23K35/282—Zn as the principal constituent
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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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/02—Tubular elements of cross-section which is non-circular
- F28F1/022—Tubular elements of cross-section which is non-circular with multiple channels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
- F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
- F28F1/126—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element consisting of zig-zag shaped fins
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2255/00—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
- F28F2255/16—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes extruded
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4935—Heat exchanger or boiler making
- Y10T29/49377—Tube with heat transfer means
- Y10T29/49378—Finned tube
Definitions
- the present invention relates to a method for manufacturing an aluminum alloy heat exchanger.
- aluminum alloys having good lightness and thermal conductivity are used for automotive heat exchangers such as evaporators and condensers.
- a fluoride-based flux is attached to the tube surface of an aluminum alloy extruded material, and a member such as a fin material is assembled into a predetermined structure, and then brazed in a heating furnace in an inert gas atmosphere. The method is generally adopted.
- a multi-hole tube having a plurality of hollow portions partitioned by a plurality of partitions as a refrigerant flow path is used for an extruded tube of an automobile heat exchanger.
- the weight of heat exchangers has been required to improve the fuel efficiency of automobiles, and as a result, the thickness of tubes has been reduced.
- the ratio (container cross-sectional area / extruded cross-sectional area) has increased from several hundred to several thousand, and pure aluminum-based materials having good extrudability are used in consideration of extrudability.
- the thickness of the tube will be further reduced with further weight reduction of the heat exchanger.
- Addition of Si, Cu, Mn, Mg, etc. is effective to increase the strength of the tube material, but if Mg is contained in the material to be brazed, it will melt in the heating process.
- the flux reacts with Mg in the material to produce compounds such as MgF 2 and KMgF 3, and the activity of the flux is lowered and the brazing property is remarkably lowered.
- Cu is added, the extrudability is remarkably lowered, resulting in die breakage and productivity reduction. Therefore, the policy for increasing the strength must be dependent on the addition of Si and Mn.
- extrudability refers to the ram pressure required for extrusion and the maximum extrusion speed (limit extrusion speed) at which the hollow portion of the multi-hole tube is not broken, which is used as an evaluation index. The higher the value or the lower the limit extrusion speed, the worse the extrudability.
- alloys with high concentrations of Mn and Si are more susceptible to ram pressure, die breakage and wear, and lower limit extrusion speed, which increases productivity. descend.
- the extruded tube of the automobile heat exchanger is used as a refrigerant passage tube, if penetration occurs due to corrosion during use, refrigerant leakage occurs and the function as a heat exchanger cannot be achieved.
- Zn is adhered to the surface of the extruded tube in advance by thermal spraying or the like, and Zn is diffused by brazing.
- the Zn diffusion layer formed on the tube surface layer is a sacrificial anode with respect to the deeper portion.
- a Zn deposition process such as Zn spraying is required, and further, it is necessary for brazing.
- a method is proposed in which a brazing filler metal powder and a Zn-containing flux powder are mixed and adhered to the surface of an aluminum alloy extruded refrigerant passage tube.
- the brazing filler metal, Zn, and flux can be deposited simultaneously in a single deposition step, the cost can be reduced, and since the bare fin material can be used as the fin material to be assembled, the cost can be reduced.
- the Zn-containing flux since the Zn-containing flux is used, the Zn concentration of the joint fillet with the fin is increased, preferential corrosion of the fillet occurs during use of the heat exchanger, and the fins peel off at an early stage. .
- the brazing filler metal powder, the Zn-containing flux powder and the flux powder not containing Zn are mixed and adhered to the surface of the aluminum alloy extruded refrigerant passage tube.
- a method has been proposed. However, this method is mainly intended to improve the brazing property.
- the alloy components that affect the corrosion resistance are not defined, and the examples are also included. Since the alloy components are not described, the effect on the corrosion resistance is unclear.
- the ratio of the coating amount of the flux containing Zn to the coating amount of the flux not containing Zn is too large. As a result, the Zn concentration of the fillet becomes high, preferential corrosion of the fillet occurs, and the fin is peeled off early. Will occur.
- the brazing filler metal powder and the flux powder not containing Zn are mixed to the surface of the aluminum alloy extruded refrigerant passage tube.
- a method of attaching is also proposed. In this method, the potential of the fin is made lower than that of the tube, and the tube is anticorrosive by the sacrificial anode effect of the fin. According to this method, the Zn concentration of the fillet can be kept low, and the early peeling of the fin due to the preferential corrosion of the fillet can be suppressed.
- the amount of Si component in the tube is limited, and AlMnSi compound is deposited on the tube surface layer by Si diffusion from the applied Si powder, forming a region with lower Mn solid solubility, that is, a region with a lower potential than the deep portion, on the tube surface layer.
- the potential difference between the tube surface layer and the deep portion is very small, and the corrosion protection is particularly insufficient in a market environment where dry and wet conditions are repeated.
- the present invention has been made to solve the above-described conventional problems in aluminum heat exchangers, particularly automotive heat exchangers, and its purpose is to particularly enhance the strength, extrudability, and corrosion resistance of extruded refrigerant passage tubes.
- An object of the present invention is to provide a method for producing an aluminum alloy heat exchanger having a material structure for improving productivity and realizing cost reduction.
- a method of manufacturing an aluminum alloy heat exchanger according to claim 1 comprises mixing Si powder, flux powder, and a binder on the surface of a flat multi-hole refrigerant passage tube made of an aluminum alloy extruded material.
- Si is limited to less than 0.10%
- Cu is limited to less than 0.10%
- the balance is made of an aluminum alloy extruded material composed of Al and inevitable impurities
- the fin is made of Al—Mn—Zn
- a corrugated fin formed by molding an alloy material, and the coating is composed of a Si-based powder, a Zn-containing compound-based flux powder, a Zn-free compound-based flux powder, and a binder.
- a mixture of a dust, the amount of powder in the paint, Si powder is 1 ⁇ 4g / m 2
- Zn-containing flux is 1 ⁇ 9 g / m 2
- the total amount of the binder is 5 to 20 g / m 2
- the binder is 5 to 40% of the total amount of the paint
- the refrigerant passage pipe deep part of the heat exchanger manufactured by brazing joining has the highest potential, and the refrigerant passage It is characterized in that the potential becomes lower in the order of the tube surface, the fin joint fillet, and the fin.
- alloy component values are expressed in mass%.
- the method for producing an aluminum alloy heat exchanger according to claim 2 is the method according to claim 1, wherein the aluminum alloy extruded material constituting the refrigerant passage tube is further Ti: 0.30% or less, Sr: 0.10% or less, One of Zr: 0.30% or less or two or more are contained.
- a method for producing an aluminum alloy heat exchanger according to claim 3 is characterized in that, in claim 1 or 2, the Si powder has a maximum particle size of 35 ⁇ m or less.
- the method for producing an aluminum alloy heat exchanger according to claim 4 is characterized in that, in any one of claims 1 to 3, the compound-based flux containing Zn is KZnF 3 .
- the method for producing an aluminum alloy heat exchanger according to claim 5 is characterized in that in any one of claims 1 to 4, the composition of the compound-based flux not containing Zn is potassium fluoroaluminate.
- the method for producing an aluminum alloy heat exchanger according to claim 6 is the method according to any one of claims 1 to 5, wherein the aluminum alloy bare fin has Mn: 0.1 to 1.8%, Zn: 0.8 to 3. It is characterized by comprising an aluminum alloy containing 0% and the balance Al and inevitable impurities.
- a method for producing an aluminum alloy heat exchanger according to any one of the first to fifth aspects, wherein the aluminum alloy bare fin has Mn: 0.1 to 1.8%, Zn: 0.8 to 3. Containing 0%, Si: 0.1-1.2%, Fe: 0.01-0.8%, Mg: 0.05-0.5%, Cu: 0.3% or less, Cr : 0.3% or less, Zr: 0.3% or less, Ti: containing one or more of 0.3% or less, and comprising an aluminum alloy composed of the balance Al and inevitable impurities And
- the method for producing an aluminum alloy heat exchanger according to claim 8 is the method according to claim 6 or 7, wherein the aluminum alloy bare fin further comprises In: 0.001 to 0.10%, Sn: 0.001 to 0.10%. It contains 1 type or 2 types of these, It is characterized by the above-mentioned.
- the method for producing an aluminum alloy heat exchanger according to claim 9 is the method according to any one of claims 1 to 8, wherein the extruded aluminum alloy constituting the refrigerant passage tube is formed by casting a cast ingot at a temperature of 400 to 650 ° C. After being subjected to a homogenization heat treatment for 4 hours or more, hot extrusion is performed.
- the method for producing an aluminum alloy heat exchanger according to claim 10 is the method according to any one of claims 1 to 8, wherein the aluminum alloy extruded material constituting the refrigerant passage tube is formed by subjecting the ingot after casting to a temperature of 550 to 650 ° C. After the first-stage heat treatment that is held for 2 hours or more, and then the second-stage heat treatment that is lowered to a temperature of 400 to 550 ° C. and held for 3 hours or more, and then hot extruded. It is characterized by being.
- the method for producing an aluminum alloy heat exchanger according to claim 11 is the method according to any one of claims 1 to 8, wherein the extruded aluminum alloy constituting the refrigerant passage tube is formed by subjecting the ingot after casting to a temperature of 550 to 650 ° C. After performing a first stage heat treatment that is held for 2 hours or more, and then performing a homogenization heat treatment consisting of a second stage heat treatment that is held at a temperature of 400 to 550 ° C. for 3 hours or more after being lowered to 200 ° C. or less. It is an extruded product.
- an aluminum heat exchanger particularly an automobile heat exchanger
- the strength, extrudability, and corrosion resistance of an extruded refrigerant passage pipe are improved, and productivity improvement and cost reduction are realized.
- a method of manufacturing an aluminum alloy heat exchanger having a material structure is provided.
- Mn The aluminum alloy extruded material constituting the refrigerant passage tube contains Mn: 0.5 to 1.7%.
- Mn is solid-solved in the parent phase when brazed to heat exchangers for automobiles, and can be strengthened compared to pure aluminum alloy, which is a conventional extruded multi-hole tube alloy for automobile heat exchangers. Become. When the Mn content is less than 0.5%, the effect of increasing the strength is small, and when the content exceeds 1.7%, the extrudability decreases. A more preferable content of Mn is 0.6 to 1.5%.
- the decrease in extrudability is significantly smaller than when the same amount of Si, Cu or Mg is added. Even when Si, Cu, Mg, or Mn is added so as to have the same strength, the decrease in the critical extrusion rate is the smallest when Mn is added, and Mn exhibits high strength and extrudability, that is, productivity. It is a compatible additive component.
- Si is limited to less than 0.10%.
- the effect is as follows.
- the Si powder applied to the surface of the refrigerant passage tube diffuses into the refrigerant passage tube by brazing heating, and forms and precipitates Mn and an AlMnSi intermetallic compound in the refrigerant passage tube alloy.
- the solid solubility of Mn and Si is reduced in the Si diffusion layer of the refrigerant passage tube alloy, and the potential is lower than that in the region where Si is not diffused deeper than the Si diffusion layer, and the Si diffusion layer starts from the surface.
- it can act as a sacrificial anode layer for deeper parts and improve the corrosion penetration life in the depth direction.
- the Si content is limited to less than 0.05%.
- corrosion protection may be insufficient depending on the environment, but since the Zn-containing flux is further applied in the present invention, the potential lowering effect acts synergistically, and more It becomes possible to prevent corrosion effectively.
- Cu is limited to less than 0.10%.
- the effect is as follows. First, the addition of Cu significantly reduces the extrudability as compared with Mn as described above, so the addition amount needs to be limited also from this viewpoint. Next, it is generally known that when Zn is added, the potential is reduced, and when Cu is added, the potential becomes noble. In the case where the amount is small, the inventors have found that the potential nobleening effect due to Cu acts more remarkably.
- the Zn diffusion layer formed at the time of brazing with flux powder containing Zn has a lower surface layer Zn concentration than the Zn diffusion layer formed at the time of brazing by conventional Zn spraying or the like.
- the surface layer Zn concentration is further reduced.
- the potential lowering effect by the Zn diffusion layer formed by the flux powder containing Zn is the potential noble effect of the contained Cu.
- the potential gradient of the surface layer of the refrigerant passage tube does not become lower, and the potential gradient is such that the surface layer is lower and the deep portion is noble with respect to the thickness direction of the refrigerant passage tube. Can not form.
- the surface of the refrigerant passage tube itself is used as a sacrificial anode to prevent corrosion at the deep part and improve the penetration life.
- the Si diffusion layer also acts in the direction of making the surface potential noble.
- the potential nodifying effect due to Cu becomes more dominant than the potential sacrificing effect due to the Zn diffusion layer, and coupled with the potential noble effect due to the Si diffusion layer, the refrigerant passage tube In the thickness direction, a potential gradient is formed in which the surface layer is noble and the deep portion is base.
- the penetration becomes earlier. It is conceivable to increase the Zn concentration of the surface layer by increasing the amount of flux powder containing Zn, but if this is done, the adhesion film becomes thicker, and the adhesion film thickness decreases due to melting of Si and flux during brazing.
- the distance between the refrigerant passage tube and the fin material is reduced. Since this extends to the entire core, the outer dimensions of the core shrink and become defective. At the same time, the Zn concentration of the fillet at the fin joint increases, and premature peeling of the fin due to preferential corrosion of the fillet occurs.
- the surface layer of the refrigerant passage tube is also subsided even in the low-concentration Zn diffusion layer, and the surface layer is sufficient to prevent corrosion in the deep portion using the surface layer of the refrigerant passage tube as a sacrificial anode. It is possible to form a potential distribution in the thickness direction in which the depth is noble and noble.
- the amount of Cu is more preferably limited to less than 0.05%, and further preferably limited to less than 0.03%.
- the aluminum alloy extruded material constituting the refrigerant passage tube may contain one or more of 0.30% or less of Ti, 0.10% or less of Sr, and 0.30% or less of Zr. it can.
- Ti forms a high-concentration region and a low-concentration region in the refrigerant passage tube, and these regions are alternately distributed in a layered manner in the thickness direction.
- the low-concentration region of Ti is a high-concentration region. Since it corrodes preferentially, the corrosion form becomes layered and the progress of corrosion in the thickness direction is suppressed. This improves pitting corrosion resistance and intergranular corrosion resistance. Further, the addition of Ti improves the strength at normal temperature and high temperature. If the amount of Ti added exceeds 0.30%, giant crystals are produced during casting, making it difficult to produce a sound refrigerant passage tube.
- Sr is a eutectic structure that crystallizes when the Si powder previously applied to the surface of the refrigerant passage tube reacts with Al of the base material during brazing heating to form an Al—Si alloy liquid phase brazing and solidifies during cooling. Is refined and dispersed. Thereby, since the eutectic structure which becomes the anode site on the surface of the material is dispersed, the corrosion is uniformly dispersed to form a planar corrosion form and the corrosion resistance is improved. If the Sr addition amount exceeds 0.10%, the Al—Si—Sr compound is crystallized and the eutectic structure is not refined.
- Zr recrystallizes the refrigerant passage tube alloy during brazing heating, but at this time, the recrystallized grains can be coarsened to reduce the grain boundary density of the base material.
- the Al—Si alloy liquid phase wax produced by the Si powder previously applied to the surface of the refrigerant passage tube can be prevented from penetrating into the crystal grain size of the base material, and preferential corrosion occurs at the grain boundaries. It can be suppressed from occurring.
- the amount of Zr added exceeds 0.30%, a giant crystallized product is generated during casting, making it difficult to produce a sound refrigerant passage tube.
- Ti, Sr, and Zr are added in combination, the effect is also obtained in combination.
- Manufacturing process (1) In the manufacturing step (1), the ingot of the aluminum alloy extrudate having the above-mentioned composition constituting the refrigerant passage tube is subjected to a homogenization treatment for 4 hours or more at a temperature of 400 to 650 ° C. It is characterized by doing. By this treatment, coarse crystals formed during casting solidification can be decomposed or granulated, and a non-uniform structure such as a segregation layer generated during casting can be homogenized. If coarse crystallized material remains, or if a non-uniform structure such as a segregation layer formed during casting remains, these will become resistance during extrusion, lowering the extrudability, The surface roughness is reduced.
- the homogenization temperature is less than 400 ° C.
- the above reaction is difficult to proceed.
- the higher the homogenization temperature is the more the reaction is promoted.
- the upper limit is set to 650 ° C.
- a more preferable homogenization temperature is 430 to 620 ° C.
- the longer the treatment time the more the reaction proceeds. Therefore, the treatment is preferably performed for 10 hours or more. However, even if the treatment is performed for more than 24 hours, it is difficult to obtain a further effect and, on the contrary, it is uneconomical.
- the manufacturing process (2) is a process of combining a high-temperature homogenization process and a low-temperature homogenization process.
- the ingot is held at a temperature of 550 to 650 ° C. for 2 hours or more, followed by 400 It is characterized in that it is subjected to hot extrusion after a homogenization heat treatment comprising a second stage heat treatment in which the temperature is lowered to ⁇ 550 ° C. and held for 3 hours or more.
- a homogenization heat treatment comprising a second stage heat treatment in which the temperature is lowered to ⁇ 550 ° C. and held for 3 hours or more.
- the aluminum residue is a defect that is discharged from the die when the aluminum pieces accumulated in the die during extrusion become a certain size and adheres to the surface of the extruded refrigerant passage tube.
- the high temperature first stage treatment is held at 550 to 650 ° C. for 2 hours or more. By this treatment, the coarse crystallized product formed at the time of casting solidification can be not only decomposed or granulated but also actively re-solidified. If the homogenization temperature is less than 550 ° C., it is difficult for re-solution to proceed. The higher the homogenization treatment temperature is, the more the above reaction is promoted. However, if the temperature is too high, the upper limit is set to 650 ° C.
- a more preferred treatment temperature is 580 to 620 ° C.
- the longer the treatment time the more the reaction proceeds. Therefore, the treatment is preferably performed for 5 hours or longer. However, even if the treatment is performed for more than 24 hours, it is difficult to obtain a further effect and, on the contrary, it becomes uneconomical. Therefore, the treatment is preferably performed for 5 to 24 hours.
- the homogenization heat treatment comprising the second heat treatment in which the temperature is lowered to a temperature of 400 to 550 ° C. and held for 3 hours or more after performing the high temperature first step treatment
- Mn dissolved in the matrix phase is performed.
- the solid solubility of Mn can be reduced, the deformation resistance in the subsequent hot extrusion can be reduced, and the extrudability can be improved. If it is less than 400 degreeC, there will be little precipitation amount and the effect of reducing a deformation resistance will become inadequate. In addition, precipitation does not easily occur at temperatures exceeding 550 ° C., and in this case, the effect of reducing deformation resistance is insufficient.
- the treatment time is less than 3 hours, such precipitation does not occur sufficiently, so that the effect of reducing deformation resistance becomes insufficient.
- the longer the treatment time the more the reaction proceeds.
- the treatment is preferably performed for 5 to 15 hours.
- the above-described two-stage homogenization treatment is for precipitating Mn sufficiently homogeneously dissolved by the first stage treatment by the second stage treatment that is then heat-treated at a specific temperature.
- the second-stage treatment may be performed continuously after the first-stage treatment, or, as the production process (3), a first-stage heat treatment for holding the ingot at a temperature of 550 to 650 ° C. for 2 hours or more, Thereafter, the temperature is once lowered to 200 ° C. or lower, and then subjected to a homogenization heat treatment including a second stage heat treatment that is maintained at a temperature of 400 to 550 ° C. for 3 hours or more, and then hot extrusion can be performed.
- the paint mixed with Si powder, flux powder and binder will be described.
- the flux a compound flux powder containing Zn and a compound flux powder not containing Zn are used.
- the purpose of adhering the mixture of the Si-based powder powder and the Zn-based compound flux powder and the Zn-free compound flux powder and binder to the surface of the refrigerant passage tube extruded material is as follows.
- the Si powder reacts with Al of the base material of the refrigerant passage tube during brazing to produce Al—Si brazing, and the fin material or header material can be joined to the refrigerant passage tube.
- the flux containing Zn is decomposed into flux and Zn at the time of brazing, and the flux removes the oxide film on the aluminum alloy surface to enable brazing, and Zn diffuses into the refrigerant passage tube to form a Zn diffusion layer.
- a potential gradient in which the surface is base and the depth is noble can be formed from the surface of the refrigerant passage tube to the deep portion, and the deep portion can be protected from corrosion by using the surface layer portion as a sacrificial anode.
- the Zn concentration of the joint fillet with the fin is also increased at the same time, and the fin is prematurely peeled off due to the preferential corrosion of the fillet. Therefore, in the present invention, in order to appropriately reduce the Zn ratio in the mixed powder, to ensure the corrosion resistance of the refrigerant passage tube, and to suppress the preferential corrosion of the fillet, it is essential to mix the flux not containing Zn. .
- the flux powder not containing Zn also has the effect of enabling brazing in the same manner as the flux containing Zn decomposed during brazing.
- the binder can improve adhesion when the mixed powder is adhered to the refrigerant passage tube.
- the maximum particle size of the Si powder is preferably 35 ⁇ m or less. This fine powder improves the fluidity of the Al—Si liquid phase brazing that occurs during brazing heating, and also suppresses erosion of the base material. More preferably, it is 15 ⁇ m or less.
- the compound flux powder containing Zn and the compound flux powder not containing Zn those having an average particle size of about 5 ⁇ m are used.
- KZnF 3 is used as the compound-based flux powder containing Zn.
- potassium fluoroaluminate such as KAlF 4 , K 2 AlF 5 or K 3 AlF 6 is used.
- an acrylic resin is used as the binder.
- the coating amount of the Si powder is 1 g / m 2 or more and 4 g / m 2.
- the amount of the Si powder is 1 g / m 2 or more and 4 g / m 2.
- the amount exceeds 4 g / m 2 , the ratio of the flux powder containing Zn and not containing Zn to the entire mixed powder is reduced, so that the amount of Zn diffusing into the refrigerant passage tube is insufficient, and brazing is caused by a decrease in the flux amount.
- Preferably is 2 g / m 2 or more 4g / m 2 or less.
- the coating amount of the flux powder containing Zn is 1 g / m 2 or more and 9 g / m 2 or less, but if it is less than 1 g / m 2, the amount of Zn diffusing into the refrigerant passage tube is insufficient, and the surface layer potential of the refrigerant passage tube However, the corrosion resistance is not sufficiently lowered with respect to the deep part, and the brazing property is deteriorated because the amount of flux is small.
- the amount of Zn diffusing into the refrigerant passage tube is sufficient and the surface potential of the refrigerant passage tube is sufficiently low relative to the depth, but at the same time the Zn concentration in the joint fillet with the fin is also Higher, premature peeling of fins due to preferential corrosion of fillets.
- the Zn concentration in the joint fillet with the fin is also Higher, premature peeling of fins due to preferential corrosion of fillets.
- the flux powder not containing Zn is always mixed, but the flux powder not containing Zn at that time
- the coating amount is set to 1 g / m 2 or more and 9 g / m 2 or less.
- the amount is less than 1 g / m 2
- the ratio of the flux powder containing Zn in the mixed powder becomes high, preferential corrosion occurs due to the high Zn concentration of the fillet, and the brazing property decreases because the total amount of flux is small. .
- the ratio of the flux powder containing Zn in the mixed powder is lowered, the amount of Zn diffusing into the refrigerant passage tube is insufficient, and the corrosion resistance of the refrigerant passage tube is lowered.
- Preferably is 1.5 g / m 2 or more 6 g / m 2 or less.
- the binder ratio with respect to the entire coating is preferably 5 to 40% by weight, and if it is less than 5%, the adhering mixture tends to be peeled off, and if it exceeds 40%, the brazing property is lowered.
- the total coating amount of Si powder, a flux powder composed of a compound flux powder containing Zn and a compound flux powder not containing Zn is appropriately 5 to 20 g / m 2 . If it is less than 5 g / m ⁇ 2 >, bondability will fall and the amount of Zn to adhere will be insufficient. If the amount exceeds 20 g / m 2 , the amount of wax produced increases and the fins and the base metal are likely to melt and dissolve.
- the thickness of the adhesion film between the refrigerant passage tube and the fin material will increase, so if the film thickness decreases due to melting during brazing heating, the entire core Dimensional reduction will occur.
- the paint can be applied to the refrigerant passage tube by roll coating.
- the permutation of the refrigerant passage tube deep portion, the surface, the fin joint fillet, and the fin potential, the refrigerant passage tube deep portion is the most noble, and then the refrigerant passage tube surface, the fin joint fillet , It is characterized by being obscene in the order of fins.
- the deep portion of the refrigerant passage tube is a portion that is not affected by Zn diffusion from the surface.
- the surface of the refrigerant passage tube acts as a sacrificial anode for the deep portion, and the deep portion can be cathodic-protected.
- the fin also acts as a sacrificial anode with respect to the surface and depth of the refrigerant passage tube, and the refrigerant passage tube can be protected from corrosion.
- the fin joint fillet is nobler than the fin and is not the lowest in the entire heat exchanger, so that the preferential corrosion of the fillet is suppressed, and the early peeling of the fin can be suppressed.
- the heat exchanger When the heat exchanger is manufactured using the refrigerant passage tube according to the present invention, it is possible to obtain an effect that it is possible to suppress the brazing failure between the fitting portion of the refrigerant passage tube and the header material.
- the reason for this is as follows. Normally, the fitting portion between the refrigerant passage pipe and the header material is joined mainly by the brazing material applied to the header material, but Si powder is also adhered to the surface of the refrigerant passage pipe, and at the time of brazing the liquid phase Because it is covered with the wax, the wax of the header material is connected to the liquid phase wax on the surface of the refrigerant passage tube and can flow freely.
- the refrigerant passage pipe has a joint portion with the fin on the side opposite to the header, and the brazing of the header material is drawn to the fin joint portion by the surface tension along the surface of the refrigerant passage pipe. For this reason, brazing is insufficient at the header and the refrigerant passage pipe fitting portion, resulting in poor brazing.
- brazing defects occur when a refrigerant passage tube of a conventional pure aluminum alloy or an alloy to which Cu is added is used.
- the alloy of the present invention is used for the refrigerant passage pipe, even when the header material having the same amount of brazing material as the conventional alloy refrigerant passage pipe is used, the refrigerant passage pipe and the header material There is no brazing defect at the mating part.
- Mn increases the strength of the fin material.
- the preferable content range of Mn is 0.1 to 1.8%, and if the content is less than 0.1%, the effect is small. Manufacturing becomes difficult.
- a more preferable content of Mn is in the range of 0.8 to 1.7%.
- Zn functions to lower the potential of the fin material.
- the preferable content range of Zn is 0.8 to 3.0%, and if it is less than 0.8%, a sufficient potential-basing effect cannot be expected, and the fin potential becomes noble than the fin joint fillet and becomes the lowest. Preferential corrosion of the fillet occurs and the resistance to fin peeling is reduced. Further, if the refrigerant passage pipe is made nobler, it acts as a cathode for the refrigerant passage pipe and the corrosion resistance of the refrigerant passage pipe is lowered.
- the potential becomes sufficiently low, but the self-corrosion resistance of the fin material is lowered, and the potential difference between the fin and the fin joint fillet or the refrigerant passage tube is increased, so that a liquid with high conductivity at all times.
- the fin material serving as the anode is quickly corroded and consumed.
- a more preferable content of Zn is in the range of 1.0% to 2.5%.
- Si improves the strength of the fin material.
- the preferred Si content range is 0.1 to 1.2%, and if the content is less than 0.1%, the effect is small. If the content exceeds 1.2%, the melting point of the fin material decreases, and local melting occurs during brazing heating. It tends to occur.
- a more preferable content of Si is in the range of 0.2 to 0.6%.
- Fe improves strength.
- the preferable content range of Fe is 0.01 to 0.8%. If the content is less than 0.01%, the effect is small, and if it exceeds 0.8%, the amount of Al—Fe noble compound increases. The self-corrosion resistance of the material is reduced.
- a more preferable content of Fe is in the range of 0.1 to 0.7%.
- Mg improves the strength of the fin material.
- the preferable range of Mg is 0.05 to 0.5%, and if the content is less than 0.05%, the effect is small.
- Mg reacts with the fluoride-based flux during brazing to produce Mg fluoride, which lowers the brazing property and makes the appearance of the brazed part unclear.
- a more preferable content of Mg is in the range of 0.05 to 0.3%, and a more preferable content is in the range of 0.05 to 0.15%.
- Cu improves the strength of the fin material.
- the preferable content range of Cu is 0.3% or less. If the content exceeds 0.3%, the potential of the fin material becomes noble, and the corrosion resistance and fin peeling resistance of the refrigerant passage pipe are impaired. In addition, the self-corrosion resistance of the fin material also decreases.
- Cr and Zr have the effect of making the crystal grain size after brazing coarse and reducing the buckling of the fin material during brazing heating.
- the preferable content ranges of Cr and Zr are each 0.3% or less. If the content is more than 0.3%, a giant crystallized product is generated during casting, which makes it difficult to produce a sound fin material.
- a high-concentration region and a low-concentration region are formed, and these regions are alternately distributed in the thickness direction of the material, and the low-concentration region of Ti is a high-concentration region. Since it corrodes preferentially, the corrosion form becomes layered and the progress of corrosion in the thickness direction is suppressed. This improves pitting corrosion resistance and intergranular corrosion resistance. Further, the addition of Ti improves the strength at normal temperature and high temperature.
- the preferable content range of Ti is 0.3% or less, and if it exceeds 0.3%, a giant crystallized product is generated at the time of casting, which makes it difficult to produce a sound fin material.
- In and Sn add a small amount to make the potential of the fin material low, and the same effect as Zn addition can be obtained.
- Preferable contents of In and Sn are each in the range of 0.001 to 0.10%. If the content is less than 0.001%, the effect is small, and if it exceeds 0.10%, the self-corrosion resistance of the fin material is lowered.
- the aluminum alloy heat exchanger according to the present invention can be manufactured by combining the refrigerant passage tube having the above composition and the fin material and brazing according to a conventional method, and the manufacturing method is not particularly limited. Further, the heating method in the homogenization treatment of the refrigerant passage tube alloy, the structure of the heating furnace, and the like are not particularly limited. Further, the extrusion shape of the refrigerant passage tube manufactured by extrusion is not particularly limited, and the extrusion shape is selected according to its use, for example, the shape of the heat exchanger. Further, during extrusion, since the extrudability of the aluminum alloy material for the refrigerant passage tube is good, it is possible to extrude well using a hollow-shaped perforated die.
- the atmosphere, heating temperature, and time for brazing are not particularly limited, and the brazing method is not particularly limited, and has good corrosion resistance.
- the brazing method is not particularly limited, and has good corrosion resistance.
- it is mounted on a car in a severe corrosive environment. It is possible to manufacture an aluminum alloy heat exchanger exhibiting good durability.
- Example 1 For refrigerant passage pipes, billets of aluminum alloys AK having the compositions shown in Table 1 were cast, and the following tests 1, 2, and 3 were performed using these billets.
- Comparative Example 1 For refrigerant passage pipes, billets of aluminum alloys L to T having the compositions shown in Table 2 were cast, and the following tests 1, 2, and 3 were carried out using these billets.
- the alloy T is generally widely used as a conventional alloy.
- Test 1 The billet was homogenized at 600 ° C. for 10 hours and then hot extruded into a multi-hole tube. At that time, the limit extrusion speed ratio at the time of extrusion (relative ratio with respect to the limit extrusion speed of the alloy T) was investigated. The results are shown in Tables 3 and 4. Those having a limit extrusion speed ratio exceeding 1.0 were evaluated as having good extrudability ( ⁇ ), and those having less than 1.0 were evaluated as having poor extrudability (x).
- Test 2 The multi-hole tube extruded in Test 1 was brazed and heated. The heating conditions were heating to 600 ° C. at an average rate of 50 ° C./min in a nitrogen gas atmosphere, holding for 3 minutes, and then cooling to room temperature. Thereafter, a tensile test was performed at room temperature. The results are shown in Tables 3 and 4. The case where the tensile strength exceeded the tensile strength of the alloy T was evaluated as good ( ⁇ ), and the case where the tensile strength was less than the tensile strength of the alloy T was evaluated as poor ( ⁇ ).
- Tests 1-3 are shown in Tables 3-6.
- Alloys AK according to the present invention are both in the limiting extrusion rate ratio and strength as compared with Comparative Alloys L-T including the conventional T alloy. Excellent results were obtained.
- the billet of the alloy C according to the present invention all of the billet subjected to the homogenization treatment in accordance with the conditions of the present invention were excellent in the limit extrusion speed ratio as compared with the conventional material alloy T.
- Example 2 For the fin material, slabs of alloys a to l having the compositions shown in Table 7 were cast. These slabs were finished into a fin material having a thickness of 0.1 mm by a predetermined homogenization treatment, hot rolling and cold rolling, and then corrugated with a fin pitch of 3 mm and a fin height of 7 mm.
- a refrigerant passage pipe having a surface coated with a mixture of Si powder, KZnF 3 powder, Zn-free flux powder (Noroclock flux) and an acrylic resin binder mixed so as to have the coating amount shown in Table 9;
- the corrugated fins were combined as shown in Table 9, and a heat exchanger core was produced by brazing to prepare a test material.
- Table 9 shows the production status of the heat exchanger core (test material). Those that were produced without defects were evaluated as good ( ⁇ ), and those with defects were evaluated as defective ( ⁇ ).
- the homogenization treatment of the refrigerant passage pipe is performed by maintaining the temperature at 600 ° C. for 10 hours according to the present invention, and the brazing heating condition is 600 ° C. at a temperature increase rate of 50 ° C./min in a nitrogen gas atmosphere. Until the temperature was lowered to room temperature.
- Comparative Example 2 For the fin material, slabs of alloys mx having the compositions shown in Table 8 were cast. These slabs were finished to a fin material having a thickness of 0.1 mm by a predetermined homogenization treatment, hot rolling and cold rolling as in Example 2, and then corrugated in the same manner as in Example 2.
- the corrugated fins were combined as shown in Table 10, and a heat exchanger core was produced by brazing to prepare a test material.
- the production status of the heat exchanger core (test material) was evaluated in the same manner as in Example 2. The results are shown in Table 10.
- the homogenization process conditions and brazing heating conditions of the refrigerant passage pipe were the same as those in Example 2.
- Test 4 About the heat exchanger core (test material), the leak by the leak test investigated the leakage by the brazing defect of the fitting part of a header and a refrigerant passage pipe. The results are shown in Tables 11 and 12. The case where leakage due to brazing failure did not occur was evaluated as good ( ⁇ ), and the case where leakage occurred was evaluated as poor ( ⁇ ).
- Test 5 The potential of the heat exchanger core (test material) on the surface and the deep part of the refrigerant passage tube and the potential of the fin joint fillet and the fin material were measured.
- the electric potential was measured by grinding the surface of the refrigerant passage tube and the fin material as they were after brazing, the deep portion of the refrigerant passage tube from the surface to a depth of 150 ⁇ m, and the portion where Zn diffusion did not reach.
- For the fin joint fillet only the fillet portion was exposed, and the others were masked with an insulating paint for measurement.
- the measurement was performed by immersing in a 5% NaCl aqueous solution adjusted to pH 3 with acetic acid for 24 hours, and the average of stable measurement values after 10 hours was adopted.
- a saturated calomel electrode was used as the reference electrode.
- the results are shown in Tables 11 and 12. The case where the potential of the tube deep portion, tube surface, fin joint portion fillet, and fin material was precious to noble in this order was evaluated as good ( ⁇ ), and the case where it was not evaluated as poor ( ⁇ ).
- Test 6 With respect to the heat exchanger core (test material), the SWAAT test specified in ASTM-G85-Annex A3 and the CCT test shown below were conducted for 1000 hours.
- the CCT test uses 5% saline adjusted to pH 3 with acetic acid as the test solution, sprays it at an ambient temperature of 35 ° C. for 2 hours, then dries at an ambient temperature of 60 ° C. for 4 hours, and then the atmosphere at a relative humidity of 95% RH or higher. The cycle of wetting at a temperature of 50 ° C. for 2 hours was repeated.
- Tables 13 and 14 show the maximum corrosion depth of the refrigerant passage tube after the test, the peeling state of the fins, and the corrosion state of the fins.
- the maximum corrosion depth of the refrigerant passage tube is 0.05 mm or less, ⁇ 0.05 mm to 0.10 mm or less, 0.10 mm to 0.20 mm or less ⁇ , and 0.20 mm or more x. evaluated.
- As for the corrosion of the fins almost none was evaluated as ⁇ , minor was evaluated as ⁇ , intermediate was evaluated as ⁇ , and remarkable was evaluated as ⁇ .
- Tests 4-7 were as shown in Tables 11-14, with the test materials (heat exchanger core) No. 1-No. As for No. 21, no leak occurred in the header and the refrigerant passage pipe fitting portion in the leak test after brazing. In contrast, test material No. In 42 and 43, since a refrigerant passage pipe containing pure aluminum system and Cu was used, leakage occurred.
- test material (heat exchanger core) No. 1-No. 21 the surface of the refrigerant passage tube has a base potential with respect to the deep portion, the potential of the fin joint fillet is lower than the surface of the refrigerant passage tube, and the potential of the fin material is lower than the potential of the fin joint fillet. It was.
- the test material (heat exchanger core) No. 22-No. 43 a sufficient Zn diffusion layer is not formed on the surface portion of the refrigerant passage tube, and a sufficient potential difference cannot be obtained between the surface of the refrigerant passage tube and the deep portion, or the fin joint fillet has the lowest potential.
- the fin material potential was the lowest, there was a case where the fin material potential was significantly lower than the refrigerant passage tube potential and the fin joint fillet potential.
- the test material heat exchanger core No. 1-No. In No. 21, since a sufficient potential difference was obtained between the surface of the refrigerant passage tube and the deep portion, the maximum corrosion depth was shallow and excellent corrosion resistance was exhibited. Further, the potential of the fin joint fillet showed a value between the surface of the refrigerant passage tube and the fin material, and was not the lowest in the core, so that the fin peeling due to the preferential corrosion of the fillet did not occur.
- the corrosion consumption of the fin material varies depending on the potential difference between the surface of the refrigerant passage tube and the fin material.
- both are appropriate.
- the fin material was slightly corroded.
- the potential of the fin material is lower than that of the deep portion of the refrigerant passage tube, and the fin material does not act as a cathode to promote corrosion of the refrigerant passage tube.
- test material heat exchanger core
- test material No. 22-No. In No. 43 a test material No. in which a sufficient potential difference is not obtained between the surface of the refrigerant passage tube and the deep portion, or the potential of the fin material is noble from the deep portion of the refrigerant passage tube.
- the maximum corrosion depth of the refrigerant passage pipes 24, 30, and 36 was increased.
- the test material (heat exchanger core) no. 1-No. No. 21 has a sufficient potential difference between the surface and the deep part of the refrigerant passage tube, so that the maximum corrosion depth of the refrigerant passage tube is shallow, and excellent corrosion resistance was exhibited as in the SWAAT test. Also, no fin peeling due to preferential corrosion of the fillet occurred. There was almost no corrosion of the fin material. In contrast, the test material (heat exchanger core) No. 22-No. In No.
- the maximum corrosion depth of the refrigerant passage tube was deep in the test material in which the potential difference between the surface of the refrigerant passage tube and the deep portion was insufficient.
- the results of the SWAAT test were the same with respect to the fin peeling and the corrosion of the fin material.
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Abstract
Description
Mn:
冷媒通路管を構成するアルミニウム合金押出材はMn:0.5~1.7%を含有する。Mnは、自動車用熱交換器をろう付け加熱接合した場合、母相中に固溶し、従来の自動車熱交換器用押出多穴管合金である純アルミニウム系合金と比べて高強度化が可能となる。Mn含有量が0.5%未満では高強度化効果は小さく、1.7%を超えて含有すると押出性が低下する。Mnのより好ましい含有量は0.6~1.5%である。
Siは0.10%未満に制限される。その効果はつぎのとおりである。冷媒通路管表面へ塗布されたSi粉末は、ろう付け加熱により冷媒通路管に拡散し、冷媒通路管合金中のMnとAlMnSi系金属間化合物を形成し析出する。このため、冷媒通路管合金のSi拡散層内ではMn及びSiの固溶度が低下し、Si拡散層よりも深くSiが未拡散の部位と比べて電位が卑化して、表面からSi拡散層深さまでは、それより深い部位に対して犠牲陽極層として作用し、深さ方向への腐食貫通寿命を向上させることができる。
Cuは0.10%未満に制限される。その効果はつぎのとおりである。まず、Cuの添加は、前記のようにMnと比べて著しく押出性を低下させるため、この観点からも添加量は制限する必要がある。つぎに、一般的にZnを添加すると電位は卑化し、Cuを添加すると電位は貴化することが知られているが、発明者らはZnとCuが共存する場合について、特にZn含有量が少ない場合にはCuによる電位貴化効果の方が顕著に作用することを見出した。本発明の場合、Znを含有するフラックス粉末によりろう付け時に形成されるZn拡散層は、従来のZn溶射等によりろう付け時に形成されるZn拡散層と比べて、表層Zn濃度が低くなる。さらに本発明においてはZnを含有しないフラックスも混合するため、表層Zn濃度はさらに低くなる。このため、もし冷媒通路管にCuが0.10%以上含有されている場合、前記のZnを含有するフラックス粉末により形成されたZn拡散層による電位卑化効果を、含有Cuの電位貴化効果が相殺してしまい、Zn拡散層が存在するにもかかわらず、冷媒通路管表層の電位が卑化せず、冷媒通路管の板厚方向に対して表層が卑で深部が貴になる電位勾配を形成することができない。これでは冷媒通路管自体で表層を犠牲陽極にして深部を防食し、貫通寿命を向上させることができず、また、実際には塗布されたSi粉末により冷媒通路管表層にはSi拡散層が存在し、このSi拡散層も表層電位を貴化する方向に作用する。
冷媒通路管を構成するアルミニウム合金押出材には、0.30%以下のTi、0.10%以下のSr、0.30%以下のZrのうちの1種または2種以上を含有させることができる。
Tiは、冷媒通路管中にTiの高濃度の領域と低濃度の領域を形成し、これらの領域が肉厚方向に交互に層状に分布し、Tiが低濃度の領域は高濃度の領域に比べて優先的に腐食するために、腐食形態が層状になり肉厚方向への腐食の進行が抑制される。これにより耐孔食性および耐粒界腐食性が向上する。さらに、Ti添加により常温及び高温での強度が向上する。Ti添加量が0.30%を超えると、鋳造時に巨大晶出物が生成し、健全な冷媒通路管の製造が困難となる。
製造工程(1)は、冷媒通路管を構成する前記の組成を有するアルミニウム合金押出材の鋳塊に400~650℃の温度で4時間以上保持する均質化処理を施した後、熱間押出加工することを特徴とする。この処理により、鋳造凝固時に形成される粗大な晶出物を分解あるいは粒状化させ、鋳造時に生じた偏析層などの不均一な組織を均質化させることができる。粗大な晶出物が残存していたり、鋳造時に形成される偏析層などの不均一組織が残存していると、それらが押出時の抵抗になり押出性を低下させたり、押出後の製品の表面粗度の低下を招く。均質化処理温度が400℃未満では上記の反応が進み難い。均質化処理温度が高温であればあるほど、このような反応は促進されるが、高すぎると溶融のおそれがあるため上限は650℃とする。より好ましい均質化処理温度は430~620℃である。また、処理時間は長い方が反応が進むため、好ましくは10時間以上処理を行うのがよい。しかし24時間を超えて処理を行っても、それ以上の効果は得られ難く逆に不経済となるため、10~24時間処理を行うのが好ましい。
製造工程(2)は、高温の均質化処理と低温の均質化処理を組み合わせて実施する工程であり、鋳塊を550~650℃の温度で2時間以上保持する第1段熱処理と、その後400~550℃の温度に降温して3時間以上保持する第2段熱処理からなる均質化熱処理した後に、熱間押出加工することを特徴とする。この工程により、熱間押出性がさらに向上し、熱間押出時のアルミカスの発生を低減させることが可能となる。アルミカスとは押出時にダイス内に堆積したアルミニウム片がある程度の大きさになった時にダイスから排出され、押出された冷媒通路管の表面に付着する欠陥のことをいう。高温の第一段処理は、550~650℃で2時間以上保持を行う。この処理により、鋳造凝固時に形成される粗大な晶出物を分解あるいは粒状化だけでなく、積極的に再固溶させることができる。均質化処理温度が550℃未満では再固溶が進み難い。均質化処理温度は高温であればあるほど、上記の反応は促進されるが、高すぎると溶融するおそれがあるため上限は650℃とする。より好ましい処理温度は580~620℃である。また、処理時間は長い方が反応が進むため、好ましくは5時間以上処理を行うのがよい。しかし24時間を超えて処理を行っても、それ以上の効果は得られ難く逆に不経済となるため、好ましくは5~24時間処理を行うのが好ましい。
なお、上記の二段均質化処理は、第1段処理により十分に均質固溶したMnを、その後特定温度で熱処理を行う第2段処理により析出させるものであり、これら二段階の均質化処理を連続的に行うかどうかは特に限定されない。すなわち、第2段処理は第1段処理後に連続して行ってもよく、あるいは、製造工程(3)として、鋳塊を550~650℃の温度で2時間以上保持する第1段熱処理と、その後一旦200℃以下まで降温した後、400~550℃の温度で3時間以上保持する第2段熱処理からなる均質化熱処理を行った後、熱間押出加工することもできる。
Mn:
Mnはフィン材の強度を高める。Mnの好ましい含有範囲は0.1~1.8%であり、0.1%未満ではその効果が小さく、1.8%を超えると、鋳造時に巨大晶出物が生成し健全なフィン材の製造が困難となる。Mnのさらに好ましい含有量は0.8~1.7%の範囲である。
Znはフィン材の電位を卑化するよう機能する。Znの好ましい含有範囲は0.8~3.0%であり、0.8%未満では十分な電位卑化効果が期待できず、フィン電位がフィン接合部フィレットより貴化し、最卑となったフィレットの優先腐食が生じ耐フィン剥がれ性が低下する。さらに、冷媒通路管より貴化した場合には、冷媒通路管に対してカソードとして作用し冷媒通路管の耐食性が低下する。3.0%を超えると、電位は十分に卑になるが、フィン材の自己耐食性が低下するとともに、フィンとフィン接合部フィレットあるいは冷媒通路管との電位差が大きくなり、常時高導電率の液体に曝されるような使用環境においては、アノードとなるフィン材が早期に腐食消耗してしまう。Znのさらに好ましい含有量は1.0%~2.5%の範囲である。
Siはフィン材の強度性を向上させる。Siの好ましい含有範囲は0.1~1.2%であり、0.1%未満ではその効果が小さく、1.2%を超えるとフィン材の融点が低下し、ろう付け加熱時に局部溶融が生じ易くなる。Siのさらに好ましい含有量は0.2~0.6%の範囲である。
冷媒通路管用として、表1に示す組成を有するアルミニウム合金A~Kのビレットットを鋳造し、これらのビレットを用いて、以下の試験1、2、3を実施した。
冷媒通路管用として、表2に示す組成を有するアルミニウム合金L~Tのビレットットを鋳造し、これらのビレットを用いて、以下の試験1、2、3を実施した。合金Tは従来合金として一般的に広く使用されているものである。
ビレットを600℃で10h均質化処理した後、多穴管に熱間押出加工した。その際、押出時の限界押出速度比(合金Tの限界押出速度に対する相対比)を調査した。その結果を表3及び表4に示す。限界押出速度比が1.0を超えるものは押出性良好(○)、1.0未満のものは押出性不良(×)と評価した。
試験1で押出した多穴管について、ろう付け加熱を実施した。加熱条件は窒素ガス雰囲気中で平均50℃/minの昇温速度で600℃まで加熱し、3分間保持した後、室温ま
で降温した。その後、常温にて引張試験を実施した。その結果を表3及び表4に示す。引張強さが合金Tの引張強さを超えるものは良好(○)とし、引張強さが合金Tの引張強さ未満のものを不良(×)と評価した。
合金C(発明合金)のビレットについて、表5及び表6に示す条件で均質化処理を行った後、同様に多穴管に熱間押出加工し、限界速度比(合金Tの限界押出速度に対する相対比)を調査した。第1段均質化処理温度への昇温速度は50℃/h、第1段から第2段を連続で行う場合の降温速度は25℃/h、第2段終了後の降温速度は炉出放冷とした。その結果を表5及び表6に示す。限界押出速度比が1.0を超えるものは押出性良好(○)、1.0未満のものは押出性不良(×)と評価した。
フィン材用として、表7に示す組成を有する合金a~lのスラブを鋳造した。これらのスラブを所定の均質化処理、熱間圧延及び冷間圧延により0.1mm厚さのフィン材に仕上げた後、フィンピッチ3mm、フィン高さ7mmの寸法のコルゲート加工を施した。表9に示す塗布量となるように混合したSi粉末とKZnF3粉末とZn非含有フラックス粉末(ノコロックフラックス)とアクリル系樹脂バインダの混合物を表面にロールコートにより塗装した冷媒通路管と、前記コルゲート加工を施したフィンとを表9に示すように組み合わせて、ろう付けにより熱交換器コアを作製して試験材とした。熱交換器コア(試験材)作製状況を表9に示す。不具合なく作製できたものを良好(○)とし、不具合が生じたものを不良(×)と評価した。なお、冷媒通路管の均質化処理は本発明に従って600℃の温度に10時間保持することにより行い、ろう付け加熱条件は、窒素ガス雰囲気中で平均50℃/minの昇温速度でて600℃まで加熱し、3分保持後に室温まで降温した。
フィン材用として、表8に示す組成を有する合金m~xのスラブを鋳造した。これらのスラブを実施例2と同じく所定の均質化処理、熱間圧延及び冷間圧延により0.1mm厚さのフィン材に仕上げた後、実施例2と同様にコルゲート加工を施した。表10に示す塗布量となるように混合したSi粉末とKZnF3粉末とZn非含有フラックス粉末(ノコロックフラックス)とアクリル系樹脂バインダの混合物を表面にロールコートにより塗装した冷媒通路管と、前記コルゲート加工を施したフィンとを表10に示すように組み合わせて、ろう付けにより熱交換器コアを作製して試験材とした。熱交換器コア(試験材)作製状況を実施例2と同様に評価した。結果を表10に示す。なお、冷媒通路管の均質化処理条件、ろう付け加熱条件は、実施例2と同一とした。
(試験4)
熱交換器コア(試験材)について、ヘッダと冷媒通路管の嵌合部のろう付け不良による漏れを、リーク試験により調査した。その結果を表11及び表12に示す。ろう付け不良による漏れが発生しなかったものは良好(○)、漏れが発生したものは不良(×)と評価した。
熱交換器コア(試験材)の冷媒通路管表面と深部の電位及びフィン接合部フィレットとフィン材の電位を測定した。電位は、冷媒通路管表面とフィン材はろう付け後そのままの表面を、冷媒通路管深部は表面から150μmの深さまで面削し、Zn拡散の及んでいない部位を測定した。フィン接合部フィレットについてはフィレット部のみを露出し、それ以外を絶縁塗料でマスキングして測定した。測定は、酢酸でpH3に調製した5%NaCl水溶液中に24時間浸漬して行い、10時間以降の安定した測定値の平均を採用した。なお、参照電極は飽和カロメル電極を用いた。その結果を表11及び表12に示す。チューブ深部、チューブ表面、フィン接合部フィレット、フィン材の電位がこの順に貴から卑になっているものは良好(○)、なっていないものは不良(×)と評価した。
熱交換器コア(試験材)について、ASTM-G85-Annex A3に規定されるSWAAT試験と、以下に示すCCT試験をそれぞれ1000h実施した。CCT試験は酢酸でpH3に調整した5%食塩水を試験液とし、雰囲気温度35℃で2時間噴霧した後、雰囲気温度60℃で4時間乾燥させ、その後に95%RH以上の相対湿度で雰囲気温度50℃で2時間湿潤するサイクルを繰り返した。試験後の冷媒通路管の最大腐食深さ、フィンの剥がれ状況、及びフィンの腐食状況を表13及び表14に示す。冷媒通路管の最大腐食深さは、0.05mm以下を◎、0.05mmを超え0.10mm以下を○、0.10mmを超え0.20mm以下を△、0.20mmを超えるものを×と評価した。フィンの剥がれ状況については剥がれの有無を示した。フィンの腐食については、ほとんどなしを◎、軽微を○、中程度を△、顕著を×と評価した。
Claims (11)
- アルミニウム合金押出材からなる偏平多穴状の冷媒通路管の表面に、Si粉末とフラックス粉末とバインダを混合した塗料を塗布し、アルミニウム合金ベアフィンを組み付けてろう付け接合してなるアルミニウム合金製熱交換器を製造する方法であって、前記冷媒通路管は、質量%(以下、合金成分値は質量%で示す)で、Mn:0.5~1.7%を含有し、Siを0.10%未満、Cuを0.10%未満に制限し、残部Alと不可避的不純物からなるアルミニウム合金押出材により構成され、前記フィンはAl-Mn-Zn系合金材を成形してなるコルゲートフィンであり、前記塗料はSi粉末とZnを含有する化合物系フラックス粉末とZnを含有しない化合物系フラックス粉末とバインダを混合したもので、塗料中の各粉末量は、Si粉末が1~4g/m2、Zn含有フラックスが1~9g/m2、Znを含有しないフラックスが1~9g/m2、粉末の合計量が5~20g/m2で、バインダは塗料全体の5~40%の量であり、ろう付け接合により製造される熱交換器の冷媒通路管深部が最も電位が貴で、冷媒通路管表面、フィン接合部フィレット、フィンの順に電位が卑になることを特徴とするアルミニウム合金製熱交換器の製造方法。
- 前記冷媒通路管を構成するアルミニウム合金押出材は、さらにTi:0.30%以下、Sr:0.10%以下、Zr:0.30%以下のうちの1種または2種以上を含有することを特徴とする請求項1記載のアルミニウム合金製熱交換器の製造方法。
- 前記Si粉末は、最大粒径が35μm以下であることを特徴とする請求項1または2記載のアルミニウム合金製熱交換器の製造方法。
- 前記Znを含有する化合物系フラックスはKZnF3であることを特徴とする請求項1~3のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記Znを含有しない化合物系フラックスの組成はフルオロアルミン酸カリウムであることを特徴とする請求項1~4のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記アルミニウム合金ベアフィンは、Mn:0.1~1.8%、Zn:0.8~3.0%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よりなることを特徴とする請求項1~5のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記アルミニウム合金ベアフィンは、Mn:0.1~1.8%、Zn:0.8~3.0%を含有し、さらに、Si:0.1~1.2%、Fe:0.01~0.8%、Mg:0.05~0.5%、Cu:0.3%以下、Cr:0.3%以下、Zr:0.3%以下、Ti:0.3%以下のうちの1種または2種以上を含有し、残部Alと不可避的不純物からなるアルミニウム合金よりなることを特徴とする請求項1~5のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記アルミニウム合金ベアフィンは、さらにIn:0.001~0.10%、Sn:0.001~0.10%のうちの1種または2種を含有することを特徴とする請求項6または7記載のアルミニウム合金製熱交換器の製造方法。
- 前記冷媒通路管を構成するアルミニウム合金押出材は、鋳造後の鋳塊を400~650℃の温度で4時間以上保持する均質化熱処理を行った後、熱間押出加工されたものであることを特徴とする請求項1~8のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記冷媒通路管を構成するアルミニウム合金押出材は、鋳造後の鋳塊を550~650℃の温度で2時間以上保持する第1段熱処理と、その後400~550℃の温度に降温して3時間以上保持する第2段熱処理からなる均質化熱処理を行った後、熱間押出加工されたものであることを特徴とする請求項1~8のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
- 前記冷媒通路管を構成するアルミニウム合金押出材は、鋳造後の鋳塊を550~650℃の温度で2時間以上保持する第1段熱処理と、その後一旦200℃以下まで降温した後、400~550℃の温度で3時間以上保持する第2段熱処理からなる均質化熱処理を行った後、熱間押出加工されたものであることを特徴とする請求項1~8のいずれかに記載のアルミニウム合金製熱交換器の製造方法。
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WO2014065074A1 (ja) * | 2012-10-24 | 2014-05-01 | ハリマ化成株式会社 | ろう付け用組成物、熱交換器用チューブおよび熱交換器 |
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CN115698354A (zh) * | 2020-06-11 | 2023-02-03 | 株式会社Uacj | 换热器用铝合金挤出多孔管及其制造方法 |
WO2021251228A1 (ja) * | 2020-06-11 | 2021-12-16 | 株式会社Uacj | 熱交換器用アルミニウム合金押出多穴チューブ及びその製造方法 |
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CN113692198A (zh) * | 2021-08-26 | 2021-11-23 | 哈尔滨铸鼎工大新材料科技有限公司 | 一种硅铝合金内置冷却结构及其成型方法 |
Also Published As
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DK2578344T3 (en) | 2018-05-22 |
KR20130090767A (ko) | 2013-08-14 |
US20130118013A1 (en) | 2013-05-16 |
ES2668285T3 (es) | 2018-05-17 |
JP5750237B2 (ja) | 2015-07-15 |
CN103038014A (zh) | 2013-04-10 |
CN103038014B (zh) | 2016-03-09 |
EP2578344A1 (en) | 2013-04-10 |
MX361891B (es) | 2018-12-18 |
BR112012029759A2 (pt) | 2016-08-09 |
NO2578344T3 (ja) | 2018-08-04 |
MX2012013541A (es) | 2013-03-25 |
EP2578344B1 (en) | 2018-03-07 |
PL2578344T3 (pl) | 2018-08-31 |
KR101851811B1 (ko) | 2018-04-24 |
EP2578344A4 (en) | 2016-03-09 |
JP2011245499A (ja) | 2011-12-08 |
US9132518B2 (en) | 2015-09-15 |
BR112012029759B1 (pt) | 2018-04-03 |
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