WO2010150728A1 - Echangeur de chaleur réalisé en un alliage d'aluminium, et procédé de production d'un tube de passage de liquide de refroidissement utilisé dans l'échangeur de chaleur - Google Patents

Echangeur de chaleur réalisé en un alliage d'aluminium, et procédé de production d'un tube de passage de liquide de refroidissement utilisé dans l'échangeur de chaleur Download PDF

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Publication number
WO2010150728A1
WO2010150728A1 PCT/JP2010/060440 JP2010060440W WO2010150728A1 WO 2010150728 A1 WO2010150728 A1 WO 2010150728A1 JP 2010060440 W JP2010060440 W JP 2010060440W WO 2010150728 A1 WO2010150728 A1 WO 2010150728A1
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Prior art keywords
refrigerant passage
aluminum alloy
heat exchanger
passage tube
less
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PCT/JP2010/060440
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English (en)
Japanese (ja)
Inventor
尚希 山下
泰永 伊藤
裕二 久富
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住友軽金属工業株式会社
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Publication of WO2010150728A1 publication Critical patent/WO2010150728A1/fr

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Classifications

    • 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
    • B23K35/3601—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 with inorganic compounds as principal constituents
    • B23K35/3603—Halide salts
    • B23K35/3605—Fluorides
    • 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
    • B23K35/3601—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 with inorganic compounds as principal constituents
    • B23K35/3607—Silica or silicates
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • 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
    • 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
    • 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
    • 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
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/10—Aluminium or alloys thereof
    • 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
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/008—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for vehicles
    • F28D2021/0084—Condensers
    • 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
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/008—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for vehicles
    • F28D2021/0085—Evaporators

Definitions

  • the present invention relates to an aluminum alloy heat exchanger and a method for manufacturing a refrigerant passage tube used in the heat exchanger.
  • aluminum alloys having good lightness and thermal conductivity are used for automotive heat exchangers such as evaporators and condensers.
  • an aluminum alloy extruded tube is used as a refrigerant passage tube, and a fluoride-based flux is attached to the surface of the heat exchanger, and after a member such as a fin material is assembled in a predetermined structure, the inside of a heating furnace in an inert gas atmosphere is used.
  • a method of brazing and joining is employed.
  • an aluminum extruded multi-hole tube having a plurality of hollow portions partitioned by a plurality of partitions is used as a refrigerant flow tube of a heat exchanger for an automobile.
  • the heat exchanger has been required to be lighter in order to improve the fuel efficiency of automobiles, and as a result, the refrigerant passage tube has been made thinner.
  • the extrusion ratio (container cross-sectional area / extruded material cross-sectional area) is several hundred to several thousand. Therefore, so far, pure aluminum-based materials having good extrudability have been used as the tube material in consideration of extrudability.
  • the policy for increasing the strength must be based on the addition of Si and Mn.
  • Mn and Si are added at a high concentration
  • Mn and Si dissolved in the matrix phase increase the deformation resistance.
  • the extrusion ratio increases from several hundred to several thousand like the extruded multi-hole tube.
  • the extrudability is extremely inferior compared with the conventional pure Al-based material.
  • extrudability refers to the ram pressure required for extrusion and the maximum extrusion speed (limit extrusion speed) that can be obtained without causing the loss of the partition of the hollow part of the multi-hole tube.
  • limit extrusion speed the maximum extrusion speed
  • the ram pressure rises and the die breaks and wears compared to the conventional pure Al material. It becomes easy to occur, and the limit extrusion speed is also lowered, so that productivity is lowered.
  • the refrigerant passage tube of the automobile heat exchanger is penetrated by corrosion during use, the refrigerant leaks and cannot function as a heat exchanger.
  • Zn is adhered to the surface of the extruded tube for refrigerant passage in advance by thermal spraying or the like, and Zn is diffused by brazing, and at that time, the Zn diffusion layer formed on the tube surface layer is deeper than that. It acts as a sacrificial anode and suppresses corrosion in the thickness direction, extending the penetration life.
  • Si powder and fluoride-based flux are applied to the surface of an extruded refrigerant passage tube made of pure aluminum-based A1050 alloy or Al-0.4% Cu alloy, It has been proposed to manufacture a heat exchanger by assembling, but when the refrigerant passage tube is made of a pure aluminum alloy, the strength cannot be ensured, and it is impossible to meet the demand for thinning, CO 2. It cannot be applied to a heat exchanger that requires high strength, such as a heat exchanger using a refrigerant.
  • the refrigerant passage tube is made of an Al-0.4% Cu alloy, a higher strength can be obtained as compared with a pure aluminum alloy, but since it contains Cu, it has a high temperature when applied to a heat exchanger using a CO 2 refrigerant. There is concern about intergranular corrosion.
  • the Zn concentration is low, and Cu is contained in the refrigerant passage tube. Therefore, the surface potential of the refrigerant passage tube is not sufficiently reduced, and therefore, in the thickness direction of the refrigerant tube, the surface layer is necessary to prevent corrosion of the refrigerant passage tube itself, and the surface layer is base and the deep portion is not deep. A sufficient potential gradient is not formed. This is because, when the Zn concentration is low and coexists with Cu, the potential noble effect by Cu works more significantly than the potential base effect by Zn.
  • Si applied in advance on the surface layer of the refrigerant passage tube diffuses by brazing to form a diffusion layer, and this diffusion layer also works in a direction to make the surface layer potential noble, and additionally obstructs the formation of the potential gradient. To do.
  • the Si diffusion layer makes the potential of the refrigerant passage tube noble, there is also a corrosion resistance evaluation by the CASS test that can improve the corrosion resistance compared to the refrigerant passage tube without the Si diffusion layer.
  • the cathodic protection effect acts more widely. Since the passage tube can be subjected to cathodic protection, and in most cases, it becomes a dry and wet repetitive environment in an actual use environment, so the range in which the cathodic protection effect acts is limited to a very narrow range. It is difficult to prevent corrosion of the refrigerant passage tube only by cathodic protection by making the potential of the current higher than that of the fin.
  • the evaporator is covered with condensed water due to condensation, and this condensed water has a very low electrical conductivity compared to the CASS test solution, so that even if it is always covered, it acts on a wide range of cathodic protection effects. Therefore, it is difficult to cathodic-protect the refrigerant passage tube.
  • it is necessary to give a sufficient potential gradient to the refrigerant passage pipe itself so that the surface layer is base and the deep portion is noble.
  • the tube is coated with Si powder with a maximum particle size of 30 ⁇ m or less together with a flux that does not contain Zn and fins, and the potential of the tube after brazing is no less than 50 mV higher than the fins, improving the corrosion resistance of the fillet.
  • a heat exchanger is proposed, there is a problem that self-corrosion of the fin is large because it relies on corrosion prevention by using a base fin.
  • the evaporator is covered with low-conductivity condensed water. It is not possible to cathodic-protect the refrigerant passage tube by itself.
  • the present invention uses a fin containing Zn as a technique for solving the above-mentioned conventional problems in a heat exchanger for an automobile and an aluminum refrigerant passage tube, and Zn evaporated from the fin surface during brazing adheres to the surface of the refrigerant passage tube.
  • the pitting corrosion resistance of the refrigerant passage pipe was found to be remarkably improved when a Zn diffusion layer having a concentration gradient is formed in the surface portion of the refrigerant passage pipe by diffusing into the refrigerant passage pipe.
  • An object of the present invention is to provide an aluminum alloy heat exchanger that has high corrosion resistance, can be further reduced in weight and cost, and is particularly suitable as a heat exchanger for automobiles.
  • the other object of this invention is to provide the manufacturing method of the refrigerant path pipe
  • an aluminum alloy heat exchanger a mixture containing Si powder and a fluoride-based flux is applied to the surface of an aluminum alloy refrigerant passage tube, and fins are assembled.
  • the refrigerant passage tube contains 0.5 to 1.7% (mass%, hereinafter the same) of Mn, and the extruded material of the aluminum alloy comprising the balance Al and inevitable impurities
  • the fin is composed of an aluminum alloy containing Zn: 0.3 to 4.0%, Mn 0.8 to 1.7%, the balance Al and unavoidable impurities, A Zn diffusion layer is formed in the surface layer portion.
  • An aluminum alloy heat exchanger according to claim 2 is the heat exchanger made of aluminum alloy according to claim 1, wherein the refrigerant passage tube further includes one or more of Ti 0.30% or less, Sr 0.10% or less, Zr 0.30% or less.
  • the aluminum alloy heat exchanger according to claim 3 is characterized in that, in claim 1 or 2, the refrigerant passage tube is an aluminum alloy extruded material in which the Cu content is regulated to less than 0.10%.
  • An aluminum alloy heat exchanger is characterized in that, in any one of the first to third aspects, the refrigerant passage tube is an aluminum alloy extruded material in which the Si content is regulated to less than 0.10%.
  • An aluminum alloy heat exchanger is the aluminum alloy heat exchanger according to any one of the first to fourth aspects, wherein the fin contains 0.3 to 4.0% Zn, 0.8 to 1.7% Mn, 0.2 to 0.6%, Fe 0.1 to 0.7%, Mg 0.05 to 0.3%, Cu 0.5 or less, Cr 0.3% or less, Zr 0.3% or less, Ti 0.3% or less It contains seeds or two or more, and is composed of the balance Al and inevitable impurities.
  • An aluminum alloy heat exchanger according to claim 6 is the aluminum alloy heat exchanger according to claims 1 to 5, wherein the fin material further contains one or two of In 0.001 to 0.10% and Sn 0.001 to 0.10%. It is characterized by doing.
  • a method for producing a refrigerant passage pipe according to claim 7 is a method for producing the refrigerant passage pipe used in the aluminum heat exchanger according to any one of claims 1 to 6, wherein the refrigerant passage pipe is used in any one of claims 1 to 3.
  • the aluminum alloy ingot constituting the refrigerant passage tube described above is subjected to a homogenization heat treatment at a temperature of 400 ° C. to 650 ° C. for 4 hours or more and then hot extrusion.
  • a method of manufacturing a refrigerant passage tube according to claim 8 is a method of manufacturing the refrigerant passage tube used in the aluminum heat exchanger according to any one of claims 1 to 6, wherein the refrigerant passage tube is used in any one of claims 1 to 3.
  • First-stage heat treatment in which the aluminum alloy ingot constituting the refrigerant passage tube is kept at a temperature of 570 ° C. to 650 ° C. for 2 hours or more, and then the temperature is lowered to a temperature of 400 ° C. to 550 ° C. for 3 hours or more.
  • a hot-extrusion process is performed after the homogenization heat treatment including the second-stage heat treatment to be held.
  • a method of manufacturing a refrigerant passage tube according to claim 9 is a method of manufacturing the refrigerant passage tube used in the aluminum heat exchanger according to any one of claims 1 to 6, wherein the refrigerant passage tube is used in any one of claims 1 to 3.
  • First-stage heat treatment in which the aluminum alloy ingot constituting the refrigerant passage tube is kept at a temperature of 570 ° C. to 650 ° C. for 2 hours or more, and then cooled to room temperature and then a temperature of 400 ° C. to 550 ° C.
  • the material is characterized by being subjected to hot extrusion after being subjected to a homogenization heat treatment comprising a second-stage heat treatment for 3 hours or more.
  • a refrigerant passage tube made of an aluminum alloy having excellent strength and corrosion resistance after brazing and improved extrudability it is possible to achieve high corrosion resistance and further reduce weight and cost.
  • an aluminum alloy heat exchanger suitable as an automotive heat exchanger is provided.
  • tube used for the said heat exchanger is provided.
  • Mn is solid-dissolved in the parent phase after brazing and heat-bonding the heat exchanger, and it becomes possible to increase the strength compared to a pure aluminum alloy that constitutes a conventional extruded multi-hole tube for an automobile heat exchanger. Further, when Mn is added, the decrease in extrudability, particularly the limit extrusion speed, is remarkably small as compared with the case where the same amount of Si, Cu or Mg is added.
  • the addition of Mn has the smallest decrease in the limit extrusion speed, and is an alloy component that can achieve both high strength and extrudability, that is, productivity.
  • the preferred content is in the range of 0.5 to 1.7%. If it is less than 0.5%, the effect of increasing the strength is small, and if it exceeds 1.7%, the extrudability is reduced. A more preferable content range is 0.6% to 1.5%.
  • Si is limited to less than 0.10%. As a result, the following effects are obtained.
  • 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 in the aluminum alloy constituting the refrigerant passage tube and an Al—Mn—Si intermetallic compound. . Due to this precipitation, the solid solubility of Mn and Si decreases in the Si diffusion layer of the refrigerant passage tube, and the potential of the Si diffusion layer is lower than that of a portion deeper than the Si diffusion layer, that is, a portion where Si is not diffused. Turn into. As a result, from the surface to the depth of the Si diffusion layer, it acts as a sacrificial anode layer for deeper portions, and the corrosion penetration life in the depth direction can be improved.
  • the amount of Si is 0.10% or more, an Al—Mn—Si based metal compound is present in the aluminum alloy constituting the refrigerant passage tube from the beginning, so that the Mn solid solubility in the alloy also decreases.
  • the Si powder applied to the surface by brazing heat diffuses into the alloy, the precipitation of Al-Mn-Si intermetallic compounds is reduced, thereby lowering the potential in the Si diffusion layer. Therefore, from the surface to the depth of the Si diffusion layer does not act as a sacrificial anode layer, and the corrosion penetration life is not improved.
  • a more preferable amount of Si for obtaining the above effect is in the range of 0.05% or less.
  • Cu is limited to less than 0.10%. As a result, the following effects (1) to (3) can be obtained.
  • (1) It is possible to suppress intergranular corrosion during use of a heat exchanger for automobiles that has been brazed and heat-joined, particularly during use at high temperatures.
  • the amount of Cu is 0.10% or more, especially when used in a CO 2 refrigerant cycle, the operating temperature becomes a high temperature around 150 ° C., and precipitation of Cu or the like occurs remarkably at the grain boundaries, and the intergranular corrosion sensitivity. Becomes larger.
  • (2) Addition of Cu significantly reduces the extrudability as compared with Mn as described above. From this point as well, the amount added must be limited.
  • the Zn diffusion layer formed by the adhesion and diffusion of Zn evaporated from the fin during brazing to the surface of the refrigerant passage tube is compared with the Zn diffusion layer formed on the surface of the refrigerant passage tube by conventional Zn spraying or the like.
  • the surface Zn concentration is low. For this reason, if Cu is contained in the refrigerant passage tube by 0.10% or more, the potential noble effect of Cu contained in the potential diffusion effect due to the Zn diffusion layer formed by Zn evaporated from the fin is offset.
  • the potential of the surface layer of the refrigerant passage tube does not become lower, and a potential gradient is formed in which the surface layer is lower and the deep portion is noble with respect to the thickness direction of the refrigerant passage tube. It is not possible to prevent the deep portion from being corroded by using the surface layer as a sacrificial anode in the refrigerant passage tube itself, and the penetration life cannot be improved.
  • the potential nomination effect due to Cu is completely more dominant than the potential neutralization effect due to the Zn diffusion layer, and coupled with the potential noble effect due to the Si diffusion layer, A potential gradient is formed in which the surface layer is noble and the deep part is base in the thickness direction. In this case, since the deeper part becomes the anode with respect to the surface layer of the refrigerant passage pipe, the penetration becomes earlier.
  • the Cu content is limited to less than 0.10%, the surface layer of the refrigerant passage tube is obscured even in the low-concentration Zn diffusion layer, the surface layer is base and the deep portion is noble, and the surface of the refrigerant passage tube is used as a sacrificial anode. It is possible to form a potential distribution in the thickness direction sufficient to prevent corrosion at the deep part.
  • a more preferable Cu content range is 0.05% or less, and more preferably 0.03% or less.
  • Ti, Sr, Zr The addition of Ti forms a high-concentration region and a low-concentration region in the alloy, and these regions are distributed alternately in the thickness direction of the material, and the low-concentration region is a high-concentration region. Since corrosion preferentially compared to the region, the corrosion form is layered and progress of corrosion in the thickness direction is suppressed, thereby improving pitting corrosion resistance and intergranular corrosion resistance. Further, the addition of Ti improves the strength at normal temperature and high temperature.
  • the preferable Ti content is in the range of 0.30% or less, and if it exceeds 0.30%, a giant crystallized product is produced at the time of casting, making it difficult to produce a healthy refrigerant passage tube.
  • the addition of Sr is caused by the fact that 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 is crystallized when solidified during cooling. Functions to refine and disperse the crystal structure.
  • the eutectic structure serving as 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.
  • the preferred Sr content is in the range of 0.10% or less, and if it exceeds 0.10%, the Al—Si—Sr compound is crystallized and the eutectic structure is not refined.
  • the preferable content of Zr is in the range of 0.30% or less, and if it exceeds 0.30%, a giant crystallized product is generated at the time of casting, making it difficult to produce a sound refrigerant passage tube.
  • the elements of Ti, Sr, and Zr are added in combination, the effect can be obtained in combination.
  • the preferred production conditions of the aluminum alloy extruded material constituting the refrigerant passage tube of the aluminum alloy heat exchanger of the present invention will be described.
  • the aluminum alloy having the above composition is melted and cast, and the obtained ingot is 400 ° C.
  • hot extrusion is performed.
  • a coarse crystallized product 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.
  • the homogenization treatment temperature is less than 400 ° C., the above effect is difficult to obtain. The higher the homogenization treatment temperature, the more the above effect is promoted. And A more preferable homogenization temperature is 430 to 620 ° C.
  • the homogenization treatment time should be 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 conversely, For economy, it is preferably 10 to 24 hours.
  • the ingot may be combined with a high-temperature homogenization treatment and a low-temperature homogenization treatment, thereby further improving the hot extrudability and reducing the generation of aluminum debris.
  • the aluminum residue refers to 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 aluminum material for refrigerant passage tube.
  • the high-temperature homogenization treatment (first stage heat treatment) is a treatment that is maintained at 570 to 650 ° C. for 2 hours or longer. By this treatment, the coarse crystallized product formed during casting solidification is decomposed or granulated. And can be dissolved again.
  • a more preferable homogenization temperature is 580 to 620 ° C.
  • the treatment time is preferably longer, but 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 temperature range of the homogenization treatment (second stage heat treatment) at a low temperature is 400 to 550 ° C.
  • the temperature is lower than 400 ° C.
  • the amount of precipitation is small, and the effect of reducing deformation resistance is insufficient.
  • the temperature exceeds 550 ° C., precipitation hardly occurs and the effect of reducing deformation resistance becomes insufficient.
  • the processing time is 3 hours or more.
  • the treatment is preferably performed for 5 to 15 hours.
  • the above-mentioned two-stage homogenization treatment is for precipitating Mn sufficiently homogeneously dissolved by the first stage heat treatment by the second stage heat treatment, and whether or not to perform these two-stage homogenization processes continuously?
  • the second-stage heat treatment may be performed continuously after the first-stage heat treatment, or after the first-stage heat treatment, the ingot is once cooled to 200 ° C. or lower and then reheated to perform the second-stage heat treatment. Also good.
  • the mixture containing the Si powder and fluoride flux powder applied to the surface of the refrigerant passage tube extruded material has a maximum particle size of Si powder of 100 ⁇ m or less, and the fluoride flux powder has an average particle size of about 5 ⁇ m. Configured using A preferable range of the maximum particle size of the Si powder is 30 ⁇ m or less, and a more preferable range is 15 ⁇ m or less.
  • Fluoride fluxes include potassium fluoroaluminate fluxes such as KAlF 4 , K 2 AlF 6 , K 2 AlF 5 ⁇ H 2 O, K 3 AlF 6 , AlF 3 , Cs 8 AlF 6 , CsAlF 4 ⁇ 2H Examples thereof include cesium uroaluminate-based fluxes such as 2 O and Cs 2 AlF 5 .H 2 O.
  • Compound fluxes containing Zn, such as ZnF 2 and KZnF 3 diffuse Zn on the surface of the refrigerant passage tube during brazing to form a Zn diffusion layer, so that a refrigerant passage tube with a high sacrificial anode effect is obtained.
  • the present invention even when a flux not containing Zn is used, the same sacrificial anode effect can be obtained by forming the Zn diffusion effect by Zn evaporated from the fin.
  • Si powder: fluoride-based flux 10: 90 to 40:60.
  • Si powder ratio is less than 10%, sufficient brazing is not generated at the time of brazing, and bonding failure is likely to occur.
  • Si powder ratio exceeds 40%, the ratio of the fluoride-based flux powder decreases, and the brazing property is inferior.
  • a binder such as an acrylic resin may be added and applied as a coating agent in order to improve adhesion.
  • the binder ratio should be 5-40% of the total coating material. When the binder ratio is less than 5% of the entire coating agent, peeling of the adhering mixture tends to occur.
  • the appropriate coating amount is 5 to 30 g / m 2 as a mixture of Si powder and fluoride flux powder. If it is less than 5 g / m 2 , the bondability is lowered, and if it exceeds 30 g / m 2 , the amount of brazing produced increases and fins and base materials are likely to melt and dissolve.
  • the heat exchanger is manufactured using the refrigerant passage pipe according to the present invention, it is possible to suppress the brazing failure between the fitting portion of the refrigerant passage pipe and the header material. That is, the fitting portion between the refrigerant passage tube and the header material is joined mainly by the brazing material applied to the header material, but the surface of the refrigerant passage tube is also attached with Si powder, and at the time of brazing, the Si powder and the refrigerant are bonded. Since the surface layer portion of the passage pipe is covered with the liquid phase wax generated by melting, the wax of the header material is connected to the liquid phase wax on the surface of the refrigerant passage pipe and can flow freely.
  • the refrigerant passage pipe has a joint portion with fins on the opposite side of the header, and the solder of the header material travels along the surface of the refrigerant passage pipe and is pulled to the fin joint portion by surface tension. For this reason, brazing is insufficient at the header and the refrigerant passage pipe fitting portion, resulting in poor brazing.
  • brazing occurs when a refrigerant passage pipe made of a conventional pure aluminum alloy or an alloy to which Cu is added is used, brazing failure occurs.
  • the refrigerant passage pipe and the header can be used even when the header material having the same amount of brazing material as that of the conventional alloy refrigerant passage pipe is used.
  • the present invention since a mixture containing Si powder and fluoride-based flux is applied to the surface of the refrigerant passage tube and joined to the fin material, it is compared with the case where conventional Zn spraying is applied to the surface of the refrigerant passage tube.
  • the Zn concentration of the fin material joint fillet can be kept low. Therefore, preferential corrosion of the fin joint fillet can be suppressed, and fin peeling can be suppressed.
  • Zn In the present invention, when a mixture of Si powder and fluoride-based flux powder is applied to the refrigerant passage tube and the fin containing Zn is assembled and brazed, Zn evaporates from the fin surface during brazing and the surface of the refrigerant passage tube The adhered Zn diffuses in the thickness direction of the refrigerant passage tube to form a Zn diffusion layer having a concentration gradient in the surface layer portion of the refrigerant passage tube.
  • This Zn diffusion layer lowers the surface potential of the refrigerant passage tube, and forms a potential gradient in which the surface layer is base and the deep portion is noble with respect to the thickness direction. Therefore, the surface of the refrigerant passage tube is a sacrificial anode. Thus, the deep portion can be cathodic-proofed and penetration due to corrosion can be suppressed.
  • the amount of Zn evaporated from the fins and adhering to the refrigerant passage tube is affected by the shape of the fins to be combined. When the distance from the surface of the refrigerant passage tube to the fin surface is short, more Zn is deposited than when the distance is long.
  • corrugated fins in order to efficiently attach Zn to the refrigerant passage tube.
  • the amount of Zn attached to the refrigerant passage tube varies depending on the fin pitch and fin height.
  • the preferable Zn content in the aluminum alloy constituting the fin is in the range of 0.3 to 4.0%. If the Zn content is less than 0.3%, the fin pitch is made as small as possible or the fin height is made low. However, the amount of Zn adhering to the surface of the refrigerant passage tube is small, and the surface of the refrigerant passage tube is formed by diffusion of the Si powder previously applied to the surface of the refrigerant passage tube in the thickness direction of the refrigerant passage tube during brazing. There is also a potential nobleening effect, and a sufficient potential lowering effect on the surface of the refrigerant passage tube cannot be expected.
  • the amount of Zn in the fin exceeds 4.0%, the amount of Zn adhering to the refrigerant passage tube will be sufficient if the fin shape is normally used as a heat exchanger, but the potential of the fin itself is extremely low. In the use environment where the fins and self-corrosion resistance decrease, the potential difference between the fins and the refrigerant passage pipe increases, and the liquid is constantly exposed to high conductivity liquid, the anode fins are quickly corroded and consumed. End up.
  • a more preferable Zn content range of the fin is 0.5 to 2.5%.
  • Mn increases the strength of the fin material.
  • a preferable content of Mn is in the range of 0.8 to 1.7%. If it is less than 0.8%, the effect is small, and if it exceeds 1.7%, giant crystals are produced during casting, making it difficult to produce a sound fin material.
  • a more preferable content range of Mn is 0.6 to 1.5%.
  • Si improves the strength of the fin material.
  • a preferable content of Si is in the range of 0.2 to 0.6%. If it is less than 0.2%, the effect is small, and if it exceeds 0.6%, the melting point of the fin material is lowered, and local melting is likely to occur during brazing heating.
  • Fe improves strength.
  • a preferable content of Fe is in the range of 0.1 to 0.7%. If it is less than 0.1%, the effect is small, and if it exceeds 0.7%, the amount of noble Al—Fe compound increases, so that the self-corrosion resistance of the fin material decreases.
  • Mg improves the strength of the fin material.
  • a preferable content of Mg is in the range of 0.05 to 0.3%. If the content is less than 0.05%, the effect is small, and if the content exceeds 0.3%, when heat brazing in an inert gas atmosphere using a fluoride-based flux, Mg becomes a fluoride-based flux during brazing. It reacts to produce Mg fluoride, which lowers the brazing property and makes the appearance of the brazed part unclear.
  • a more preferable content range of Mg is 0.05 to 0.15%.
  • a preferable content of Cu is in the range of 0.5% or less. If the content exceeds 0.5%, the potential of the fin material becomes noble, and the corrosion resistance of the refrigerant passage tube is 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 fins during brazing heating.
  • the preferable contents of Cr and Zr are both in the range of 0.3% or less. When both contain more than 0.3%, a giant crystallized product is produced at the time of casting, which makes it difficult to produce a sound fin material.
  • Ti forms a high-concentration region and a low-concentration region, and these regions are distributed alternately in the thickness direction of the material, and the Ti-concentration region corrodes preferentially over the high-concentration region. Therefore, 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 of Ti is in the range of 0.3% or less. If the content 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 lower the potential of the fin material by adding a small amount, exert a sacrificial anode effect on the refrigerant passage tube, and prevent pitting corrosion of the refrigerant passage tube.
  • Preferable contents of In and Sn are both in the range of 0.001 to 0.10%, and if both are less than 0.001%, the effect is small, and if it exceeds 0.10%, the self-corrosion resistance of the fin material decreases. To do.
  • fin materials are produced by semi-continuous casting to produce an ingot, and hot rolling, cold rolling, intermediate annealing, and cold rolling are generally used, but intermediate annealing is omitted. You can also.
  • the method of producing a hot-rolled sheet directly from a molten metal by continuous casting rolling, and manufacturing by cold rolling is also possible.
  • the heat exchanger of the present invention can be manufactured by assembling the refrigerant passage tube having the above composition and the fin material and brazing by a conventional method, and the manufacturing method is not particularly limited.
  • the heat exchanger of the present invention has good corrosion resistance, and can exhibit good durability even when mounted on an automobile in a severe corrosive environment, for example.
  • tube is not specifically limited, The extrusion shape is selected according to the use, for example, the shape of a heat exchanger.
  • a refrigerant passage tube for a heat exchanger is used as a heat exchanger component, it is assembled with other members (for example, fin material or header material) and is usually joined by brazing, but the atmosphere and heating temperature during brazing.
  • the time is not particularly limited, and the brazing method is not particularly limited.
  • Test 1 The ingot 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 a temperature increase rate of 50 ° C./min on average in a nitrogen gas atmosphere, and the temperature was lowered to room temperature after holding for 3 minutes. Thereafter, a tensile test was performed at room temperature. Tables 3 and 4 show the tensile strength. When the tensile strength exceeded that of the alloy T, the strength property after brazing was good ( ⁇ ), and when the tensile strength was less than the tensile strength of the alloy T, the strength property after brazing was evaluated as poor ( ⁇ ).
  • the aluminum alloys A to L for refrigerant passages according to the present invention showed excellent results in both extrusion characteristics and brazing characteristics.
  • the aluminum alloy MS for refrigerant passages outside the conditions of the present invention was inferior in either extrusion characteristics or brazing characteristics.
  • the extruded multi-hole tube is homogenized according to the present invention under the conditions of holding at 600 ° C. for 10 hours.
  • a coating agent obtained by adding a binder to the mixed powder mixed at a ratio of 25:75 was previously applied at 15.5 g / m 2 .
  • the binder was added so that the mass of the binder was 20% of the whole coating agent.
  • Brazing heating conditions were performed under the conditions of heating to 600 ° C. at a temperature increase rate of 50 ° C./min on average in a nitrogen gas atmosphere, and lowering to room temperature after holding for 3 minutes.
  • the following tests 4, 5, and 6 were performed using the produced heat exchanger core.
  • Test 4 The heat exchanger core was subjected to heat treatment at 150 ° C. for 120 hours simulating high temperature use, and then subjected to intergranular corrosion test by the method specified in ISO11846 method B. The results are shown in Table 11 and Table 12.
  • Test 5 Zn concentration on the surface of the refrigerant passage tube of the heat exchanger core, Zn diffusion depth, surface-to-depth potential and surface-to-depth potential difference, fin material potential, refrigerant passage tube surface to fin material potential difference, refrigerant passage tube deep And the potential difference between the fin material was measured.
  • the Zn concentration on the surface of the refrigerant passage tube and the Zn diffusion depth were determined from the results of EPMA line analysis in the thickness direction after filling the cross section of the core with resin.
  • the Zn diffusion depth was a depth at which the Zn concentration became 0.01%.
  • 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.
  • 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 Table 13 and Table 14.
  • Test 6 With respect to the heat exchanger core, the SWAAT test and the CCT test specified in ASTM-G85-Annex A3 were performed for 1000 h, respectively.
  • CCT test 5% saline adjusted to pH 3 with acetic acid is used as a test solution, sprayed at an ambient temperature of 35 ° C. for 2 hours, dried at an ambient temperature of 60 ° C. for 4 hours, and then at a relative humidity of 95% RH or higher. The cycle of wetting for 2 hours at an ambient temperature of 50 ° C. was repeated.
  • Tables 15 and 16 show the maximum corrosion depth of the refrigerant passage tube (tube) after the test 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, ⁇ , 0.20 mm. Those that exceeded were evaluated as x. 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 ⁇ .
  • a sufficient Zn diffusion layer is formed on the surface portion of the refrigerant passage tube, so that the surface of the refrigerant passage tube becomes a base potential with respect to the deep portion,
  • the potential difference between the surface of the passage tube and the deep portion was 95 to 100 mV.
  • the potential of the fin material is also low with respect to the deep part of the refrigerant passage tube.
  • the heat exchanger cores 25 to 43 manufactured under conditions other than the conditions of the present invention there may be cases where a sufficient Zn diffusion layer is not formed on the surface portion of the refrigerant passage tube. A sufficient potential difference could not be obtained between the surface of the refrigerant passage tube and the deep part.
  • the effect of reducing the potential of Zn is offset in the heat exchanger cores 38 to 43 using the alloy T containing Cu as the aluminum alloy for the refrigerant passage.
  • the surface had the same or slightly lower potential than the deep part.
  • the heat exchanger cores 25 to 43 manufactured under conditions other than the conditions of the present invention 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 low.
  • the maximum corrosion depth of the refrigerant passage pipe is deep.
  • the potential of the fin was lower than the potential of the refrigerant passage tube, and the maximum corrosion depth of the refrigerant passage tube was deepened.
  • the core 35, 36, 38, 39, 40, 42, 43 in which the potential of the fin material is significantly lower than the potential of the refrigerant passage tube, and the aluminum alloy having a large amount of Zn, Fe, and Cu as the fin material The fins of the cores 26, 29, and 31 using n, q, and s were inferior in self-corrosion resistance, and corrosion was remarkable.
  • the evaluation becomes close to the actual environment by entering the drying process, but conversely, in the heat exchanger cores 1 to 24 manufactured according to the present invention, it is difficult to obtain the sacrificial anode effect of the fins. Since a sufficient potential difference was obtained between the surface of the refrigerant passage tube and the deep portion, the maximum corrosion depth of the refrigerant passage tube was shallow and showed excellent corrosion resistance as in the SWAAT test. There was almost no corrosion of the fin material.
  • the maximum corrosion of the refrigerant passage tube is caused by insufficient potential difference between the surface and the deep portion of the refrigerant passage tube.
  • the depth was deep.
  • the tendency was the same as the result of the SWAAT test.
  • the cores 27, 28, 30, and 32 to 34 had good corrosion resistance evaluation results. However, as shown in Table 12, problems occurred when the heat exchanger cores were produced. Met.

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Abstract

L'invention porte sur un échangeur de chaleur réalisé en alliage d'aluminium, lequel échangeur de chaleur a une résistance élevée à la corrosion, permet la réduction de poids d'une couche et une réduction de coût, et est particulièrement approprié en tant qu'échangeur de chaleur d'automobile. L'invention porte de manière spécifique sur un échangeur de chaleur réalisé en un alliage d'aluminium, qui est produit par application d'un mélange contenant une poudre de Si et un flux de fluorure sur la surface d'un tube de passage de liquide de refroidissement réalisé en alliage d'aluminium, fixation d'une ailette, et brasage de l'ailette. L'échangeur de chaleur est caractérisé par les éléments suivants : le tube de passage de liquide de refroidissement comprend un matériau d'extrusion réalisé en un alliage d'aluminium comprenant de 0,5 à 1,7 % de Mn, le restant étant du Al et des impuretés inévitables ; l'ailette comprend un alliage d'aluminium comprenant de 0,3 à 4 % de Zn et de 0,8 à 1,7 % de Mn, le restant étant du Al des impuretés inévitables ; et une couche de Zn diffusé est formée sur la couche de surface du tube de passage de liquide de refroidissement.
PCT/JP2010/060440 2009-06-24 2010-06-21 Echangeur de chaleur réalisé en un alliage d'aluminium, et procédé de production d'un tube de passage de liquide de refroidissement utilisé dans l'échangeur de chaleur WO2010150728A1 (fr)

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CN104246417B (zh) * 2012-04-13 2017-02-22 株式会社Uacj 内面带有沟槽的铝合金制导热管
US9631878B2 (en) 2012-08-01 2017-04-25 Uacj Corporation Process for producing aluminum alloy tube having sacrificial anticorrosion layer and joining layer
JP2017036895A (ja) * 2015-08-12 2017-02-16 三菱アルミニウム株式会社 熱交換器用アルミニウム合金チューブ
JP6860968B2 (ja) * 2015-09-25 2021-04-21 三菱アルミニウム株式会社 熱交換器用アルミニウム合金チューブと熱交換器及びその製造方法
JP2023026898A (ja) * 2021-08-16 2023-03-01 株式会社Uacj アルミニウム合金押出チューブ及び熱交換器

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JP2008208416A (ja) * 2007-02-26 2008-09-11 Furukawa Sky Kk 自然冷媒用熱交換器に用いられるアルミニウム合金押出材
JP2009058167A (ja) * 2007-08-31 2009-03-19 Mitsubishi Alum Co Ltd 耐食性に優れたチューブを用いたアルミニウム熱交換器および耐食性に優れたアルミニウム製熱交換器の製造方法

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JP2008208416A (ja) * 2007-02-26 2008-09-11 Furukawa Sky Kk 自然冷媒用熱交換器に用いられるアルミニウム合金押出材
JP2009058167A (ja) * 2007-08-31 2009-03-19 Mitsubishi Alum Co Ltd 耐食性に優れたチューブを用いたアルミニウム熱交換器および耐食性に優れたアルミニウム製熱交換器の製造方法

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