US20110114228A1 - Aluminum alloy extruded product exhibiting excellent surface properties, method of manufacturing the same, heat exchanger multi-port tube, and method of manufacturing heat exchanger including the multi-port tube - Google Patents

Aluminum alloy extruded product exhibiting excellent surface properties, method of manufacturing the same, heat exchanger multi-port tube, and method of manufacturing heat exchanger including the multi-port tube Download PDF

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US20110114228A1
US20110114228A1 US12/930,793 US93079311A US2011114228A1 US 20110114228 A1 US20110114228 A1 US 20110114228A1 US 93079311 A US93079311 A US 93079311A US 2011114228 A1 US2011114228 A1 US 2011114228A1
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Prior art keywords
aluminum alloy
heat exchanger
port tube
ingot
temperature
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US12/930,793
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Tomohiko Nakamura
Masaaki Kawakubo
Yoshiharu Hasegawa
Naoki Yamashita
Tatsuya Hikida
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Denso Corp
Sumitomo Light Metal Industries Ltd
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Denso Corp
Sumitomo Light Metal Industries Ltd
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Priority to US12/930,793 priority Critical patent/US20110114228A1/en
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Abandoned legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F1/00Tubular elements; Assemblies of tubular elements
    • F28F1/02Tubular elements of cross-section which is non-circular
    • F28F1/022Tubular elements of cross-section which is non-circular with multiple channels
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/084Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2255/00Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
    • F28F2255/16Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes extruded

Definitions

  • the present invention relates to an aluminum alloy extruded product exhibiting excellent surface properties, a method of manufacturing the same, a heat exchanger multi-port tube, and a method of manufacturing a heat exchanger including the multi-port tube.
  • an aluminum alloy which has a reduced weight and exhibits excellent thermal conductivity has been generally used.
  • an aluminum alloy tube such as an aluminum alloy extruded flat multi-port tube (hereinafter called “multi-port tube”) having a plurality of hollow portions divided by a plurality of partitions, is used as the material for a working fluid passage.
  • the multi-port tube and other members such as a fin material are assembled into a specific structure and joined by brazing in a heating furnace containing inert gas.
  • Mn and Si dissolved in the matrix increase the deformation resistance of the alloy.
  • the extrudability is evaluated using the ram pressure necessary for extrusion and the maximum extrusion rate at which the partition wall of the hollow portion of the multi-port tube is completely formed (i.e. limiting extrusion rate) as indices.
  • a material which requires a high ram pressure or exhibits a low limiting extrusion rate is determined to have a poor extrudability.
  • An alloy containing Mn and Si at high concentrations requires a ram pressure higher than that of a pure Al material, whereby the die tends to break or wear. Moreover, the productivity decreases due to a decrease in the limiting extrusion rate.
  • the film-shaped deposit on the bearing of the die is increased in thickness and amount during continuous extrusion.
  • the deposit is finally removed from the bearing and adheres to the surface of the extruded tube.
  • the deposition, removal, and adhesion process then repeatedly occurs. As a result, the deposit adheres to the surface of the extruded tube at specific intervals.
  • an object of the present invention is to provide an aluminum alloy extruded product which exhibits excellent surface properties, improved strength and excellent extrudability, allows extrusion of a thin multi-port tube at a high limiting extrusion rate, prevents the deposit from adhering to the surface of the extruded tube, and may be suitably used as a constituent member for an aluminum alloy automotive heat exchanger, and a method of manufacturing the same.
  • a first aspect of the present invention provides an aluminum alloy extruded product exhibiting excellent surface properties, comprising 0.8 to 1.6% (mass %; hereinafter the same) of Mn and 0.4 to 0.8% of Si at a ratio of Mn content to Si content (Mn %/Si %) of 0.7 to 2.4, with the balance being Al and inevitable impurities, the number of intermetallic compounds with a diameter (circle equivalent diameter; hereinafter the same) of 0.1 to 0.9 ⁇ m dispersed in a matrix being 2 ⁇ 10 5 or more per square millimeter.
  • This aluminum alloy extruded product may further comprise 0.05% or less of Cu.
  • This aluminum alloy extruded product may further comprise 0.2% or less of Mg.
  • This aluminum alloy extruded product may further comprise 0.3% or less of Ti.
  • a second aspect of the present invention provides a heat exchanger multi-port tube comprising the above aluminum alloy extruded product.
  • a third aspect of the present invention provides a method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties, the method comprising: melting and casting an aluminum alloy having the above composition to obtain an ingot; subjecting the ingot to a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
  • a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more; heating the ingot at
  • a fourth aspect of the present invention provides a method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties, the method comprising: melting and casting an aluminum alloy having the above composition to obtain an ingot; subjecting the ingot to a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
  • a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, maintained at that temperature for
  • a fifth aspect of the present invention provides a method of manufacturing a heat exchanger comprising extruding a heat exchanger multi-port tube using the above method, and joining the multi-port tube to a heat exchanger by brazing.
  • an aluminum alloy extruded product exhibiting excellent surface properties which exhibits improved strength and excellent extrudability, allows extrusion of a thin multi-port tube at a high limiting extrusion rate, prevents the deposit from adhering to the surface of the extruded tube, and may be suitably used as a constituent member for an aluminum alloy automotive heat exchanger, a method of manufacturing the same, a heat exchanger multi-port tube made of the aluminum alloy extruded product, and a method of manufacturing a heat exchanger including the multi-port tube can be provided.
  • FIG. 1 is a cross-sectional view of an aluminum alloy flat multi-port tube extruded in the examples of the present invention.
  • Mn and Si are dissolved in the matrix during heating for brazing to improve the strength of the alloy.
  • the Mn content is preferably 0.8 to 1.6%
  • the Si content is preferably 0.4 to 0.8%. If the content of Mn and Si is greater than the upper limit, the extrudability deteriorates to a large extent to impair the strength improvement effect. If the content of Mn and Si is less than the lower limit, a sufficient strength cannot be obtained.
  • the ratio of the Mn content to the Si content is preferably 0.7 to 2.4. If the ratio of the Mn content to the Si content is within this range, Mn and Si dissolved in the matrix during casting of the alloy can be mainly precipitated as an Al—Mn—Si intermetallic compound during the homogenization of the by ingot, whereby the solid solubility in the matrix can be minimized.
  • the dispersion state in which a number of minute Al—Mn—Si intermetallic compounds are precipitated reduces the deformation resistance of the alloy during hot extrusion performed after homogenization heat treatment, whereby the extrudability of the alloy can be improved.
  • the ratio “Mn %/Si %” is less than 0.7, since Si is contained in the alloy in an amount exceeding the range of the ratio “Mn %/Si %”, which can minimize the solid solubility of Mn and Si in the matrix, Si remains dissolved in the matrix after the homogenization heat treatment, whereby the deformation resistance of the alloy during the subsequent hot extrusion is not reduced. As a result, the extrudability of the alloy cannot be improved.
  • Mn %/Si % exceeds 2.4, since Mn is contained in the alloy in an amount exceeding the range of the ratio “Mn %/Si %”, which can minimize the solid solubility of Mn and Si in the matrix, Mn remains dissolved in the matrix after the homogenization heat treatment, whereby the deformation resistance of the alloy during the subsequent hot extrusion is not reduced. As a result, the extrudability of the alloy cannot be improved.
  • the Cu content is preferably limited to 0.05% or less. This reduces intergranular corrosion during use of an automotive heat exchanger manufactured by brazing the aluminum alloy extruded product according to the present invention. If the Cu content exceeds 0.05%, since the operating temperature of a heat exchanger using carbon dioxide as a refrigerant becomes as high as about 150° C., Al—Mn compounds and the like are significantly precipitated at the grain boundaries, whereby intergranular corrosion susceptibility increases.
  • Mg improves the strength of the alloy when contained in an amount of 0.2% or less. Moreover, when manufacturing an automotive heat exchanger by brazing using a fluoride-type flux containing potassium fluoroaluminate, excellent brazeability can be stably obtained. If the Mg content exceeds 0.2%, when manufacturing an automotive heat exchanger by brazing, a fluoride-type flux containing potassium fluoroaluminate, which melts during heating for brazing, reacts with Mg in the material to produce compounds such as MgF 2 and KMgF 3 . This reduces the activity of the flux, whereby the brazeability deteriorates. Moreover, the extrudability of the alloy decreases when the Mg content exceeds 0.2%.
  • Ti forms a high-Ti-concentration area and a low-Ti-concentration area in the alloy. These areas are alternately distributed in layers in the direction of the thickness of the material. Since the low-Ti-concentration area is preferentially corroded in comparison with the high-Ti-concentration area, corrosion occurs in layers. This prevents corrosion from proceeding in the direction of the thickness of the material. As a result, pitting corrosion resistance and intergranular corrosion resistance are improved. Moreover, the strength of the material at room temperature and a high temperature is improved by adding Ti.
  • the Ti content is preferably 0.06 to 0.3%. If the Ti content is less than 0.06%, the effect is insufficient. If the Ti content exceeds 0.3%, coarse compounds are produced during casting, whereby the workability is impaired.
  • Fe is contained as an inevitable impurity.
  • the Fe content is preferably limited to about 0.7% or less, and still more preferably 0.3% or less.
  • the B content is preferably about 0.01% or less.
  • Impurities such as Cr, Zr, Ni, and Zn may be contained in the alloy in an amount of 0.25% or less in total.
  • intermetallic compounds with a diameter (circle equivalent diameter) of 0.1 to 0.9 ⁇ m be dispersed in the matrix at a number of 2 ⁇ 10 5 or more per square millimeter (mm 2 ).
  • These intermetallic compounds are mainly Al—Mn—Si intermetallic compounds.
  • the above dispersion structure is obtained by homogenizing an unextruded ingot (billet), which reduces the adhesion of the deposit to the surface of the aluminum alloy extruded product and improves the strength of the aluminum alloy extruded product after heating for brazing.
  • the extruded aluminum alloy is deposited on the bearing of the die in the shape of a film.
  • the deposit When extruding a billet in which the above intermetallic compounds are dispersed, since the surface of the film-shaped deposit formed on the bearing of the die is continuously scraped off by the dispersed minute intermetallic compounds during extrusion, the deposit is formed in the shape of a thin uniform film. Since the deposit is maintained in the shape of a thin uniform film during continuous extrusion, removal of the deposit is prevented. As a result, the adhesion of the deposit to the surface of the aluminum alloy extruded product is significantly reduced. Since the deposit is maintained in the shape of a thin uniform film, the extruded product is provided with excellent surface properties and exhibits a gloss.
  • the extruded tube is attached to a heat exchanger (e.g. automotive heat exchanger) and joined by brazing.
  • a heat exchanger e.g. automotive heat exchanger
  • brazing since the Al—Mn—Si intermetallic compounds dispersed in the matrix are redissolved in the matrix, the strength of the tube after joining by brazing is improved due to solid solution hardening. Since the operating temperature is as high as about 150° C. when using carbon dioxide as a refrigerant, the aluminum alloy extruded product is required to exhibit creep strength. Since Mn and Si (solute elements) are redissolved in the matrix after joining by brazing, these elements hinder the motion of dislocation in the matrix to improve the creep strength of the aluminum alloy extruded product.
  • the aluminum alloy extruded product according to the present invention is manufactured by melting an aluminum alloy having the above composition, casting the aluminum alloy by semicontinuous casting or the like to obtain an ingot (billet), and homogenizing and hot-extruding the ingot.
  • a structure in which the above intermetallic compounds are dispersed is obtained by specifying the homogenization conditions, whereby the adhesion of a deposit to the surface of the aluminum alloy extruded product is reduced, and the strength of the aluminum alloy extruded product is improved after heating for brazing.
  • an improved hot extrudability is obtained by combining specific homogenization conditions and hot extrusion conditions.
  • a homogenization step which includes a first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the billet is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more.
  • Homogenization may be performed which includes a first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the billet is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, and maintained at that temperature for three hours or more.
  • Coarse crystals formed during casting/solidification are decomposed, granulated, or redissolved during the first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more. If the temperature is less than 550° C., the above reaction proceeds to only a small extent. The rate of reaction increases as the homogenization temperature becomes higher. On the other hand, local melting occurs when the homogenization temperature is too high. Therefore, the upper limit is preferably set at 650° C.
  • the temperature range of the first-stage heat treatment is still more preferably 580 to 620° C. The reaction proceeds to a larger extent as the treatment time increases. Therefore, it is preferable to set the treatment time at 10 hours or more. On the other hand, a further effect cannot obtained even if the treatment is performed for more than 24 hours. This is disadvantageous from the viewpoint of cost. Therefore, the treatment time is preferably 10 to 24 hours.
  • the first-stage heat treatment performed at a high temperature is effective for decomposing, granulating, or redissolving coarse crystals formed during casting/solidification.
  • the first-stage heat treatment promotes dissolution of Mn and Si (solute elements) in the matrix. If the solid solubility of these solute elements in the matrix is high, the moving speed of dislocations in the matrix decreases, whereby the deformation resistance of the aluminum alloy increases. Therefore, the extrudability of the aluminum alloy decreases when the aluminum alloy is hot-extruded after a homogenization step including only the first-stage heat treatment.
  • the second-stage heat treatment is performed after the first-stage heat treatment at a temperature lower than that of the first-stage heat treatment to precipitate Mn and Si dissolved in the matrix, whereby the solid solubility of Mn and Si is decreased. This reduces the deformation resistance of the aluminum alloy, whereby the extrudability of the aluminum alloy is improved.
  • the second-stage heat treatment is preferably performed at 400 to 500° C. for three hours or more. If the temperature is less than 400° C., only a small amount of Al—Mn—Si intermetallic compounds precipitate, whereby the effect of decreasing the deformation resistance becomes insufficient. If the temperature exceeds 500° C., the intermetallic compounds precipitate to only a small extent, whereby the effect of decreasing the deformation resistance becomes insufficient. If the treatment time is less than three hours, since the precipitation does not sufficiently proceed, the effect of decreasing the deformation resistance becomes insufficient. The reaction proceeds to a larger extent as the treatment time increases. On the other hand, a further effect cannot be obtained even if the treatment is performed for more than 24 hours. This is disadvantageous from the viewpoint of cost. The treatment time is still more preferably 5 to 15 hours.
  • the temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature (the temperature increase rate from room temperature to the second-stage heat treatment temperature when the billet is cooled to room temperature after the first-stage heat treatment) in order to precipitate Mn and Si dissolved in the matrix to decrease the solid solubility of Mn and Si and to achieve the above dispersion state of the intermetallic compounds.
  • the average temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature is preferably 20 to 60° C./h.
  • the average temperature decrease rate is less than 20° C./h, intermetallic compounds are grown to a large extent due to the progress of precipitation, whereby it is difficult to obtain a structure in which intermetallic compounds with a diameter of 0.1 to 0.9 ⁇ m are dispersed at a number of 2 ⁇ 10 5 or more per square millimeter. Moreover, it is not economical because the treatment requires time. If the average temperature decrease rate exceeds 60° C./h, the temperature distribution of the billet becomes nonuniform, whereby precipitation tends to become nonuniform. It is also preferable that the average temperature increase rate to the first-stage heat treatment temperature and the average temperature decrease rate from the second-stage heat treatment temperature to 300° C. be 20 to 60° C./h.
  • the average temperature increase rate is preferably 20 to 60° C./h. If the average temperature increase rate is less than 20° C./h, precipitated intermetallic compounds are grown to a large extent and the number of intermetallic compounds is decreased, whereby the above intermetallic compound dispersion structure may not be obtained. Moreover, it is not economical because heating requires time. If the average temperature increase rate exceeds 60° C./h, it is difficult to obtain the above intermetallic compound dispersion structure since precipitation does not proceed. It is also preferable that the average temperature decrease rate from the second-stage heat treatment temperature to 300° C. be 20 to 60° C./h.
  • the solid solubility of the solute elements in the matrix is decreased by homogenizing the billet by combining the above specific high-temperature heat treatment and low-temperature heat treatment. This reduces the deformation resistance of the aluminum alloy during the subsequent hot extrusion, whereby the extrudability of the aluminum alloy can be improved.
  • the heating temperature of the billet before hot extrusion is preferably 480 to 560° C. If the heating temperature exceeds 560° C., a precipitate mainly containing Al—Mn—Si intermetallic compounds formed during homogenization is redissolved to increase the solid solubility in the matrix. This results in an increase in deformation resistance during hot extrusion, whereby the extrudability of the aluminum alloy is decreased.
  • the heating temperature is less than 480° C., the deformation resistance is increased due to too low a temperature, whereby the extrudability of the aluminum alloy is decreased.
  • the heating temperature is still more preferably 480 to 530° C.
  • the holding time at the above heating temperature is preferably 30 minutes or less. If the holding time exceeds 30 minutes, the intermetallic compounds precipitated during the homogenization step are redissolved to increase the solid solubility in the matrix. This results in an increase in deformation resistance during hot extrusion, whereby the extrudability of the aluminum alloy is decreased.
  • the holding time is still more preferably 10 minutes or less.
  • the aluminum alloy extruded product according to the present invention has been described above taking a tube as an example.
  • the extrusion shape is not particularly limited.
  • the extrusion shape is appropriately selected depending on the application such as the form of the heat exchanger.
  • Multi-port tubes of various shapes may be extruded using a porthole die.
  • the aluminum alloy extruded product and other constituent members e.g. fin material and header material
  • An automotive heat exchanger in which the working fluid passage is formed using the above multi-port tube exhibits excellent corrosion resistance and exhibits excellent durability even under a severe corrosive environment.
  • An aluminum alloy having the composition shown in Table 1 was melted and cast by semicontinuous casting to obtain a billet.
  • the resulting billet was homogenized.
  • the billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature of 600° C. at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature for 15 hours, decreasing the temperature of the billet to a second-stage heat treatment temperature of 450° C. at an average temperature decrease rate of 50° C./h, maintaining the billet at the second-stage heat treatment temperature for 10 hours, and decreasing the temperature of the billet from the second-stage heat treatment temperature to 300° C. at an average temperature decrease rate of 50° C./h.
  • the billet was heated at 510° C. for eight minutes and hot-extruded to obtain a multi-port tube having a shape shown in FIG. 1 .
  • the resulting multi-port tube was used as a test specimen.
  • the extrudability of the aluminum alloy during hot extrusion was evaluated according to the following method. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined.
  • the multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 2. In Tables 1 and 2, values outside the conditions according to the present invention are underlined.
  • the limiting extrusion rate (i.e. the maximum extrusion rate at which the partition wall of the hollow portion of the extruded multi-port tube (see FIG. 1 ) is completely formed) was taken as the extrudability index.
  • the limiting extrusion rate indicates the ratio of the limiting extrusion rate of the aluminum alloy to the limiting extrusion rate of a known alloy (see Table 1) (ratio when the limiting extrusion rate of the known alloy is 1.0).
  • An aluminum alloy with a limiting extrusion rate ratio of 0.9 or more was indicated as “Excellent”, an aluminum alloy with a limiting extrusion rate ratio of 0.8 or more and less than 0.9 was indicated as “Good”, an aluminum alloy with a limiting extrusion rate ratio of 0.7 or more and less than 0.8 was indicated as “Fair”, and an aluminum alloy with a limiting extrusion rate ratio of less than 0.7 was indicated as “Bad”.
  • Measurement of number of deposit portions adhering to surface and observation of gloss of surface of extruded product A portion to which foreign matter adhered was detected using an eddy current test, and the number of portions of the surface of the extruded product to which an aluminum alloy deposit adhered was determined to calculate the number of deposit portions per unit length of the extruded product.
  • the gloss of the surface of the extruded product was evaluated by naked eye observation, and was also taken as the index of adhesion of deposit to the surface of the extruded product.
  • Measurement of tensile strength after heating for brazing The multi-port tube obtained by extrusion was heat-treated at 600° C. for three minutes in a nitrogen atmosphere as simulated heating for brazing, cooled at an average temperature decrease rate of 50 to 250° C./min, and subjected to a tensile test to determine the strength of the multi-port tube. A multi-port tube with a tensile strength of 110 MPa or more was determined to have a sufficient tensile strength.
  • a fluoride-type flux containing potassium fluoroaluminate was applied to the surface of the extruded multi-port tube in an amount of 10 g/m 2 .
  • the multi-port tube and a fin were assembled and joined by brazing by heat-treating the product at 600° C. for three minutes in a nitrogen atmosphere and cooling the product at an average temperature decrease rate of 50 to 250° C./min.
  • the joining state of the multi-port tube with the fin was then observed. A case where the multi-port tube and the fin were sufficiently joined was indicated as “Good”, and a case where the multi-port tube and the fin were not sufficiently joined was indicated as “Bad”.
  • the multi-port tube subjected to the above simulated heating for brazing was heat-treated at 150° C. for 120 hours and immersed for 24 hours in a solution prepared by adding 10 ml/l HCl to a 30 g/l NaCl aqueous solution. The cross section of the multi-port tube was then observed. A multi-port tube in which intergranular corrosion did not occur was indicated as “Good”, and a multi-port tube in which intergranular corrosion occurred was indicated as “Bad”.
  • test specimens 1 to 5 according to the present invention exhibited excellent extrudability, did not show adhesion of deposit to the surface, and exhibited excellent brazeability, intergranular corrosion resistance, and strength.
  • test specimens 6 to 9 and the test specimen 10 (known alloy) were inferior in at least one of extrudability, adhesion of deposit, strength, brazeability, and intergranular corrosion resistance.
  • An aluminum alloy having the composition A shown in Table 1 was melted and cast by semicontinuous casting to obtain a billet.
  • the resulting billet was homogenized under the conditions shown in Table 3.
  • the billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature, decreasing the temperature of the billet to a second-stage heat treatment temperature, maintaining the billet at the second-stage heat treatment temperature, and decreasing the temperature of the billet to 300° C. at an average temperature decrease rate of 50° C./h.
  • Table 3 shows the first-stage heat treatment temperature, the average temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature, and the second-stage heat treatment temperature.
  • the billet was hot-extruded under the conditions shown in Table 3 to obtain a multi-port tube shown in FIG. 1 .
  • the resulting multi-port tube was used as a test specimen.
  • the extrudability of the aluminum alloy during hot extrusion was evaluated in the same manner as in Example 1. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined.
  • the multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 4. In Tables 3 and 4, values outside the conditions according to the present invention are underlined.
  • test specimens 11 to 15 homogenized under the conditions outside the conditions according to the present invention were inferior in at least one of extrudability, number of deposit portions, strength, brazeability, and intergranular corrosion resistance.
  • An aluminum alloy containing 0.6% of Si, 0.2% of Fe, and 1.0% of Mn (Mn %/Si %: 1.7) was melted and cast by semicontinuous casting to obtain a billet.
  • the resulting billet was homogenized under the conditions shown in Table 5.
  • the billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature, decreasing the temperature of the billet to room temperature, increasing the temperature of the billet to a second-stage heat treatment temperature, maintaining the billet at the second-stage heat treatment temperature, and decreasing the temperature of the billet to 300° C. at an average temperature decrease rate of 50° C./h.
  • Table 5 shows the first-stage heat treatment temperature, the second-stage heat treatment temperature, and the average temperature increase rate from room temperature to the second-stage heat treatment temperature.
  • the extrudability of the aluminum alloy during hot extrusion was evaluated in the same manner as in Example 1. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined.
  • the multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 6. In Tables 5 and 6, values outside the conditions according to the present invention are underlined.
  • test specimen 16 according to the present invention exhibited excellent extrudability, did not show adhesion of deposit to the surface, and exhibited excellent brazeability, intergranular corrosion resistance, and strength.
  • test specimens 17 to 21 were inferior in at least one of extrudability, adhesion of deposit, strength, brazeability, and intergranular corrosion resistance.

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Abstract

An aluminum alloy extruded product exhibiting excellent surface properties, contains 0.8 to 1.6% of Mn and 0.4 to 0.8% of Si at a ratio of Mn content to Si content (Mn %/Si %) of 0.7 to 2.4, with the balance being Al and inevitable impurities, the number of intermetallic compounds with a diameter (circle equivalent diameter) of 0.1 to 0.9 μm dispersed in a matrix being 2×105 or more per square millimeter. The aluminum alloy extruded product allows extrusion of a thin multi-port tube at a high limiting extrusion rate, prevents deposits from adhering to the surface of the extruded tube, and may be suitably used as a constituent member for an aluminum alloy automotive heat exchanger.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is a divisional of prior U.S. application Ser. No. 11/489,941, filed Jul. 20, 2006.
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to an aluminum alloy extruded product exhibiting excellent surface properties, a method of manufacturing the same, a heat exchanger multi-port tube, and a method of manufacturing a heat exchanger including the multi-port tube.
  • 2. Description of Related Art
  • As a constituent member for an automotive heat exchanger such as an evaporator and a condenser, an aluminum alloy which has a reduced weight and exhibits excellent thermal conductivity has been generally used. In the manufacture of automotive heat exchangers, an aluminum alloy tube (hereinafter called “tube”), such as an aluminum alloy extruded flat multi-port tube (hereinafter called “multi-port tube”) having a plurality of hollow portions divided by a plurality of partitions, is used as the material for a working fluid passage. After applying a fluoride-type flux to the surface of the multi-port tube, the multi-port tube and other members such as a fin material are assembled into a specific structure and joined by brazing in a heating furnace containing inert gas.
  • In recent years, in order to reduce the fuel consumption of automobiles from the viewpoint of reducing the environmental impact, the weight of heat exchangers has been reduced. Along with this trend, the thickness of the tube has been increasingly reduced. An attempt has also been made to reduce the cross-sectional area of the tube. In this case, since the extrusion ratio (cross-sectional area of container/cross-sectional area of extruded product) of the multi-port tube reaches several hundred to several thousand, a pure Al material exhibiting excellent extrudability has been used for the multi-port tube. It is expected that the weight of heat exchangers and the thickness of the tube will be more and more reduced. Therefore, it is necessary to increase the strength of the tube.
  • It is effective to add Si, Cu, Mn, Mg, and the like in order to increase the strength of the tube. On the other hand, when the Mg content of the brazing target material exceeds 0.2%, a fluoride-type flux containing potassium fluoroaluminate which is melted during heating reacts with Mg in the material to produce compounds such as MgF2 and KM3F3. This reduces the activity of the flux, whereby brazeability deteriorates. The operating temperature of a heat exchanger using a carbon dioxide refrigerant is as high as about 150° C. As a result, intergranular corrosion susceptibility significantly increases when Cu is contained in the material. Therefore, Si and Mn must be necessarily added in order to increase the strength of the tube.
  • In an alloy containing Mn and Si at high concentrations, Mn and Si dissolved in the matrix increase the deformation resistance of the alloy. For example, when the extrusion ratio reaches several hundred to several thousand, such as when manufacturing a multi-port tube, the alloy exhibits significantly inferior extrudability in comparison with a pure Al material. In this case, the extrudability is evaluated using the ram pressure necessary for extrusion and the maximum extrusion rate at which the partition wall of the hollow portion of the multi-port tube is completely formed (i.e. limiting extrusion rate) as indices. A material which requires a high ram pressure or exhibits a low limiting extrusion rate is determined to have a poor extrudability. An alloy containing Mn and Si at high concentrations requires a ram pressure higher than that of a pure Al material, whereby the die tends to break or wear. Moreover, the productivity decreases due to a decrease in the limiting extrusion rate.
  • As a method for improving the extrudability of an aluminum alloy containing Mn and Si, a method has been proposed in which the amount of solute elements dissolved in the matrix is decreased by performing homogenization in which high-temperature heat treatment and low-temperature heat treatment are combined, thereby decreasing the deformation resistance (see JP-A-11-335764). However, the extrudability is not necessarily sufficiently improved when extruding a tube such as a thin multi-port tube. Therefore, a further improvement is required.
  • It was found that a phenomenon occurs in which an aluminum alloy is deposited in the shape of a film on the bearing of the die during extrusion and the deposit adheres to the surface of the extruded tube. A fluoride-type flux is applied to the surface of the extruded tube before brazing by roll coating or the like. In this case, the portion to which the deposit adheres is not provided with the flux. As a result, a brazing failure occurs in the portion which is not provided with the flux. There may be a case where potassium fluorozincate is applied as a flux and Zn produced by the subsequent brazing is diffused in the thickness direction and allowed to function as a sacrificial corrosion protection layer, In this case, a Zn diffusion layer is not formed in the portion which is not provided with the flux, whereby the corrosion protection performance cannot be ensured.
  • The film-shaped deposit on the bearing of the die is increased in thickness and amount during continuous extrusion. The deposit is finally removed from the bearing and adheres to the surface of the extruded tube. The deposition, removal, and adhesion process then repeatedly occurs. As a result, the deposit adheres to the surface of the extruded tube at specific intervals.
  • SUMMARY OF THE INVENTION
  • The present invention was achieved after further experiments and investigations conducted on the relationship among the alloy composition, heat treatment of an unextruded ingot, and extrudability in an attempt to improve the extrudability of an aluminum alloy to which Mn and Si are added to obtain high strength and to solve the problem in which the deposit adheres to the surface of the extruded tube. Accordingly, an object of the present invention is to provide an aluminum alloy extruded product which exhibits excellent surface properties, improved strength and excellent extrudability, allows extrusion of a thin multi-port tube at a high limiting extrusion rate, prevents the deposit from adhering to the surface of the extruded tube, and may be suitably used as a constituent member for an aluminum alloy automotive heat exchanger, and a method of manufacturing the same.
  • In order to achieve the above object, a first aspect of the present invention provides an aluminum alloy extruded product exhibiting excellent surface properties, comprising 0.8 to 1.6% (mass %; hereinafter the same) of Mn and 0.4 to 0.8% of Si at a ratio of Mn content to Si content (Mn %/Si %) of 0.7 to 2.4, with the balance being Al and inevitable impurities, the number of intermetallic compounds with a diameter (circle equivalent diameter; hereinafter the same) of 0.1 to 0.9 μm dispersed in a matrix being 2×105 or more per square millimeter.
  • This aluminum alloy extruded product may further comprise 0.05% or less of Cu.
  • This aluminum alloy extruded product may further comprise 0.2% or less of Mg.
  • This aluminum alloy extruded product may further comprise 0.3% or less of Ti.
  • A second aspect of the present invention provides a heat exchanger multi-port tube comprising the above aluminum alloy extruded product.
  • A third aspect of the present invention provides a method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties, the method comprising: melting and casting an aluminum alloy having the above composition to obtain an ingot; subjecting the ingot to a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
  • A fourth aspect of the present invention provides a method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties, the method comprising: melting and casting an aluminum alloy having the above composition to obtain an ingot; subjecting the ingot to a homogenization step which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
  • A fifth aspect of the present invention provides a method of manufacturing a heat exchanger comprising extruding a heat exchanger multi-port tube using the above method, and joining the multi-port tube to a heat exchanger by brazing.
  • According to the present invention, an aluminum alloy extruded product exhibiting excellent surface properties which exhibits improved strength and excellent extrudability, allows extrusion of a thin multi-port tube at a high limiting extrusion rate, prevents the deposit from adhering to the surface of the extruded tube, and may be suitably used as a constituent member for an aluminum alloy automotive heat exchanger, a method of manufacturing the same, a heat exchanger multi-port tube made of the aluminum alloy extruded product, and a method of manufacturing a heat exchanger including the multi-port tube can be provided.
  • BRIEF DESCRIPTION OF THE DRAWING
  • FIG. 1 is a cross-sectional view of an aluminum alloy flat multi-port tube extruded in the examples of the present invention.
  • DETAILED DESCRIPTION OF THE INVENTION AND Preferred Embodiment
  • The meanings and the reasons for the limitations of the alloy components of the aluminum alloy extruded product according to the present invention are given below. Mn and Si are dissolved in the matrix during heating for brazing to improve the strength of the alloy. The Mn content is preferably 0.8 to 1.6%, and the Si content is preferably 0.4 to 0.8%. If the content of Mn and Si is greater than the upper limit, the extrudability deteriorates to a large extent to impair the strength improvement effect. If the content of Mn and Si is less than the lower limit, a sufficient strength cannot be obtained.
  • The ratio of the Mn content to the Si content (Mn mass %/Si mass %) is preferably 0.7 to 2.4. If the ratio of the Mn content to the Si content is within this range, Mn and Si dissolved in the matrix during casting of the alloy can be mainly precipitated as an Al—Mn—Si intermetallic compound during the homogenization of the by ingot, whereby the solid solubility in the matrix can be minimized. The dispersion state in which a number of minute Al—Mn—Si intermetallic compounds are precipitated reduces the deformation resistance of the alloy during hot extrusion performed after homogenization heat treatment, whereby the extrudability of the alloy can be improved.
  • If the ratio “Mn %/Si %” is less than 0.7, since Si is contained in the alloy in an amount exceeding the range of the ratio “Mn %/Si %”, which can minimize the solid solubility of Mn and Si in the matrix, Si remains dissolved in the matrix after the homogenization heat treatment, whereby the deformation resistance of the alloy during the subsequent hot extrusion is not reduced. As a result, the extrudability of the alloy cannot be improved. If the ratio “Mn %/Si %” exceeds 2.4, since Mn is contained in the alloy in an amount exceeding the range of the ratio “Mn %/Si %”, which can minimize the solid solubility of Mn and Si in the matrix, Mn remains dissolved in the matrix after the homogenization heat treatment, whereby the deformation resistance of the alloy during the subsequent hot extrusion is not reduced. As a result, the extrudability of the alloy cannot be improved.
  • The Cu content is preferably limited to 0.05% or less. This reduces intergranular corrosion during use of an automotive heat exchanger manufactured by brazing the aluminum alloy extruded product according to the present invention. If the Cu content exceeds 0.05%, since the operating temperature of a heat exchanger using carbon dioxide as a refrigerant becomes as high as about 150° C., Al—Mn compounds and the like are significantly precipitated at the grain boundaries, whereby intergranular corrosion susceptibility increases.
  • Mg improves the strength of the alloy when contained in an amount of 0.2% or less. Moreover, when manufacturing an automotive heat exchanger by brazing using a fluoride-type flux containing potassium fluoroaluminate, excellent brazeability can be stably obtained. If the Mg content exceeds 0.2%, when manufacturing an automotive heat exchanger by brazing, a fluoride-type flux containing potassium fluoroaluminate, which melts during heating for brazing, reacts with Mg in the material to produce compounds such as MgF2 and KMgF3. This reduces the activity of the flux, whereby the brazeability deteriorates. Moreover, the extrudability of the alloy decreases when the Mg content exceeds 0.2%.
  • Ti forms a high-Ti-concentration area and a low-Ti-concentration area in the alloy. These areas are alternately distributed in layers in the direction of the thickness of the material. Since the low-Ti-concentration area is preferentially corroded in comparison with the high-Ti-concentration area, corrosion occurs in layers. This prevents corrosion from proceeding in the direction of the thickness of the material. As a result, pitting corrosion resistance and intergranular corrosion resistance are improved. Moreover, the strength of the material at room temperature and a high temperature is improved by adding Ti. The Ti content is preferably 0.06 to 0.3%. If the Ti content is less than 0.06%, the effect is insufficient. If the Ti content exceeds 0.3%, coarse compounds are produced during casting, whereby the workability is impaired.
  • Fe is contained as an inevitable impurity. The Fe content is preferably limited to about 0.7% or less, and still more preferably 0.3% or less. When adding B for ingot grain refinement or the like, the B content is preferably about 0.01% or less. Impurities such as Cr, Zr, Ni, and Zn may be contained in the alloy in an amount of 0.25% or less in total.
  • In the aluminum alloy extruded product according to the present invention, it is important that intermetallic compounds with a diameter (circle equivalent diameter) of 0.1 to 0.9 μm be dispersed in the matrix at a number of 2×105 or more per square millimeter (mm2). These intermetallic compounds are mainly Al—Mn—Si intermetallic compounds. The above dispersion structure is obtained by homogenizing an unextruded ingot (billet), which reduces the adhesion of the deposit to the surface of the aluminum alloy extruded product and improves the strength of the aluminum alloy extruded product after heating for brazing. Specifically, the extruded aluminum alloy is deposited on the bearing of the die in the shape of a film. When extruding a billet in which the above intermetallic compounds are dispersed, since the surface of the film-shaped deposit formed on the bearing of the die is continuously scraped off by the dispersed minute intermetallic compounds during extrusion, the deposit is formed in the shape of a thin uniform film. Since the deposit is maintained in the shape of a thin uniform film during continuous extrusion, removal of the deposit is prevented. As a result, the adhesion of the deposit to the surface of the aluminum alloy extruded product is significantly reduced. Since the deposit is maintained in the shape of a thin uniform film, the extruded product is provided with excellent surface properties and exhibits a gloss.
  • The extruded tube is attached to a heat exchanger (e.g. automotive heat exchanger) and joined by brazing. In this case, since the Al—Mn—Si intermetallic compounds dispersed in the matrix are redissolved in the matrix, the strength of the tube after joining by brazing is improved due to solid solution hardening. Since the operating temperature is as high as about 150° C. when using carbon dioxide as a refrigerant, the aluminum alloy extruded product is required to exhibit creep strength. Since Mn and Si (solute elements) are redissolved in the matrix after joining by brazing, these elements hinder the motion of dislocation in the matrix to improve the creep strength of the aluminum alloy extruded product.
  • The aluminum alloy extruded product according to the present invention is manufactured by melting an aluminum alloy having the above composition, casting the aluminum alloy by semicontinuous casting or the like to obtain an ingot (billet), and homogenizing and hot-extruding the ingot. A structure in which the above intermetallic compounds are dispersed is obtained by specifying the homogenization conditions, whereby the adhesion of a deposit to the surface of the aluminum alloy extruded product is reduced, and the strength of the aluminum alloy extruded product is improved after heating for brazing. Moreover, an improved hot extrudability is obtained by combining specific homogenization conditions and hot extrusion conditions.
  • It is preferable to perform a homogenization step which includes a first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the billet is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more. Homogenization may be performed which includes a first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the billet is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, and maintained at that temperature for three hours or more.
  • Coarse crystals formed during casting/solidification are decomposed, granulated, or redissolved during the first-stage heat treatment in which the billet is maintained at 550 to 650° C. for two hours or more. If the temperature is less than 550° C., the above reaction proceeds to only a small extent. The rate of reaction increases as the homogenization temperature becomes higher. On the other hand, local melting occurs when the homogenization temperature is too high. Therefore, the upper limit is preferably set at 650° C. The temperature range of the first-stage heat treatment is still more preferably 580 to 620° C. The reaction proceeds to a larger extent as the treatment time increases. Therefore, it is preferable to set the treatment time at 10 hours or more. On the other hand, a further effect cannot obtained even if the treatment is performed for more than 24 hours. This is disadvantageous from the viewpoint of cost. Therefore, the treatment time is preferably 10 to 24 hours.
  • The first-stage heat treatment performed at a high temperature is effective for decomposing, granulating, or redissolving coarse crystals formed during casting/solidification. On the other hand, the first-stage heat treatment promotes dissolution of Mn and Si (solute elements) in the matrix. If the solid solubility of these solute elements in the matrix is high, the moving speed of dislocations in the matrix decreases, whereby the deformation resistance of the aluminum alloy increases. Therefore, the extrudability of the aluminum alloy decreases when the aluminum alloy is hot-extruded after a homogenization step including only the first-stage heat treatment. In the present invention, the second-stage heat treatment is performed after the first-stage heat treatment at a temperature lower than that of the first-stage heat treatment to precipitate Mn and Si dissolved in the matrix, whereby the solid solubility of Mn and Si is decreased. This reduces the deformation resistance of the aluminum alloy, whereby the extrudability of the aluminum alloy is improved.
  • The second-stage heat treatment is preferably performed at 400 to 500° C. for three hours or more. If the temperature is less than 400° C., only a small amount of Al—Mn—Si intermetallic compounds precipitate, whereby the effect of decreasing the deformation resistance becomes insufficient. If the temperature exceeds 500° C., the intermetallic compounds precipitate to only a small extent, whereby the effect of decreasing the deformation resistance becomes insufficient. If the treatment time is less than three hours, since the precipitation does not sufficiently proceed, the effect of decreasing the deformation resistance becomes insufficient. The reaction proceeds to a larger extent as the treatment time increases. On the other hand, a further effect cannot be obtained even if the treatment is performed for more than 24 hours. This is disadvantageous from the viewpoint of cost. The treatment time is still more preferably 5 to 15 hours.
  • In order to achieve the above effects during the homogenization step, it is important to control the temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature (the temperature increase rate from room temperature to the second-stage heat treatment temperature when the billet is cooled to room temperature after the first-stage heat treatment) in order to precipitate Mn and Si dissolved in the matrix to decrease the solid solubility of Mn and Si and to achieve the above dispersion state of the intermetallic compounds. The average temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature is preferably 20 to 60° C./h. If the average temperature decrease rate is less than 20° C./h, intermetallic compounds are grown to a large extent due to the progress of precipitation, whereby it is difficult to obtain a structure in which intermetallic compounds with a diameter of 0.1 to 0.9 μm are dispersed at a number of 2×105 or more per square millimeter. Moreover, it is not economical because the treatment requires time. If the average temperature decrease rate exceeds 60° C./h, the temperature distribution of the billet becomes nonuniform, whereby precipitation tends to become nonuniform. It is also preferable that the average temperature increase rate to the first-stage heat treatment temperature and the average temperature decrease rate from the second-stage heat treatment temperature to 300° C. be 20 to 60° C./h.
  • When the billet is cooled to room temperature after the first-stage heat treatment and then heated to the second-stage heat treatment temperature, the average temperature increase rate is preferably 20 to 60° C./h. If the average temperature increase rate is less than 20° C./h, precipitated intermetallic compounds are grown to a large extent and the number of intermetallic compounds is decreased, whereby the above intermetallic compound dispersion structure may not be obtained. Moreover, it is not economical because heating requires time. If the average temperature increase rate exceeds 60° C./h, it is difficult to obtain the above intermetallic compound dispersion structure since precipitation does not proceed. It is also preferable that the average temperature decrease rate from the second-stage heat treatment temperature to 300° C. be 20 to 60° C./h.
  • In the present invention, the solid solubility of the solute elements in the matrix is decreased by homogenizing the billet by combining the above specific high-temperature heat treatment and low-temperature heat treatment. This reduces the deformation resistance of the aluminum alloy during the subsequent hot extrusion, whereby the extrudability of the aluminum alloy can be improved. The heating temperature of the billet before hot extrusion is preferably 480 to 560° C. If the heating temperature exceeds 560° C., a precipitate mainly containing Al—Mn—Si intermetallic compounds formed during homogenization is redissolved to increase the solid solubility in the matrix. This results in an increase in deformation resistance during hot extrusion, whereby the extrudability of the aluminum alloy is decreased. If the heating temperature is less than 480° C., the deformation resistance is increased due to too low a temperature, whereby the extrudability of the aluminum alloy is decreased. The heating temperature is still more preferably 480 to 530° C. The holding time at the above heating temperature is preferably 30 minutes or less. If the holding time exceeds 30 minutes, the intermetallic compounds precipitated during the homogenization step are redissolved to increase the solid solubility in the matrix. This results in an increase in deformation resistance during hot extrusion, whereby the extrudability of the aluminum alloy is decreased. The holding time is still more preferably 10 minutes or less.
  • The aluminum alloy extruded product according to the present invention has been described above taking a tube as an example. Note that the extrusion shape is not particularly limited. The extrusion shape is appropriately selected depending on the application such as the form of the heat exchanger. Multi-port tubes of various shapes may be extruded using a porthole die. When using the aluminum alloy extruded product as a working fluid passage material for a heat exchanger, the aluminum alloy extruded product and other constituent members (e.g. fin material and header material) are assembled and integrally joined by brazing. An automotive heat exchanger in which the working fluid passage is formed using the above multi-port tube exhibits excellent corrosion resistance and exhibits excellent durability even under a severe corrosive environment.
  • EXAMPLES
  • The present invention is described below by way of examples and comparative examples to demonstrate the effects of the present invention. These examples illustrate one aspect of the present invention and should not be construed as limiting the present invention.
  • Example 1 and Comparative Example 1
  • An aluminum alloy having the composition shown in Table 1 was melted and cast by semicontinuous casting to obtain a billet. The resulting billet was homogenized. The billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature of 600° C. at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature for 15 hours, decreasing the temperature of the billet to a second-stage heat treatment temperature of 450° C. at an average temperature decrease rate of 50° C./h, maintaining the billet at the second-stage heat treatment temperature for 10 hours, and decreasing the temperature of the billet from the second-stage heat treatment temperature to 300° C. at an average temperature decrease rate of 50° C./h. After homogenization, the billet was heated at 510° C. for eight minutes and hot-extruded to obtain a multi-port tube having a shape shown in FIG. 1. The resulting multi-port tube was used as a test specimen.
  • The extrudability of the aluminum alloy during hot extrusion was evaluated according to the following method. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined. The multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 2. In Tables 1 and 2, values outside the conditions according to the present invention are underlined.
  • Evaluation of extrudability: The limiting extrusion rate (i.e. the maximum extrusion rate at which the partition wall of the hollow portion of the extruded multi-port tube (see FIG. 1) is completely formed) was taken as the extrudability index. The limiting extrusion rate indicates the ratio of the limiting extrusion rate of the aluminum alloy to the limiting extrusion rate of a known alloy (see Table 1) (ratio when the limiting extrusion rate of the known alloy is 1.0). An aluminum alloy with a limiting extrusion rate ratio of 0.9 or more was indicated as “Excellent”, an aluminum alloy with a limiting extrusion rate ratio of 0.8 or more and less than 0.9 was indicated as “Good”, an aluminum alloy with a limiting extrusion rate ratio of 0.7 or more and less than 0.8 was indicated as “Fair”, and an aluminum alloy with a limiting extrusion rate ratio of less than 0.7 was indicated as “Bad”.
  • Measurement of number of deposit portions adhering to surface and observation of gloss of surface of extruded product: A portion to which foreign matter adhered was detected using an eddy current test, and the number of portions of the surface of the extruded product to which an aluminum alloy deposit adhered was determined to calculate the number of deposit portions per unit length of the extruded product. The gloss of the surface of the extruded product was evaluated by naked eye observation, and was also taken as the index of adhesion of deposit to the surface of the extruded product.
  • Evaluation of distribution (dispersion structure) of intermetallic compounds: the cross-sectional microstructure of the extruded product was observed, and the number of precipitated intermetallic compounds with a diameter (circle equivalent diameter) of 0.1 to 0.9 μm was determined by image analysis.
  • Measurement of tensile strength after heating for brazing: The multi-port tube obtained by extrusion was heat-treated at 600° C. for three minutes in a nitrogen atmosphere as simulated heating for brazing, cooled at an average temperature decrease rate of 50 to 250° C./min, and subjected to a tensile test to determine the strength of the multi-port tube. A multi-port tube with a tensile strength of 110 MPa or more was determined to have a sufficient tensile strength.
  • Evaluation of brazeability: A fluoride-type flux containing potassium fluoroaluminate was applied to the surface of the extruded multi-port tube in an amount of 10 g/m2. The multi-port tube and a fin were assembled and joined by brazing by heat-treating the product at 600° C. for three minutes in a nitrogen atmosphere and cooling the product at an average temperature decrease rate of 50 to 250° C./min. The joining state of the multi-port tube with the fin was then observed. A case where the multi-port tube and the fin were sufficiently joined was indicated as “Good”, and a case where the multi-port tube and the fin were not sufficiently joined was indicated as “Bad”.
  • Evaluation of intergranular corrosion susceptibility: In order to simulate the use at 150° C., the multi-port tube subjected to the above simulated heating for brazing was heat-treated at 150° C. for 120 hours and immersed for 24 hours in a solution prepared by adding 10 ml/l HCl to a 30 g/l NaCl aqueous solution. The cross section of the multi-port tube was then observed. A multi-port tube in which intergranular corrosion did not occur was indicated as “Good”, and a multi-port tube in which intergranular corrosion occurred was indicated as “Bad”.
  • TABLE 1
    Composition (mass %)
    Alloy Si Fe Cu Mn Mg Mn/Si
    Invention A 0.6 0.2 0 1.2 0 2
    B 0.5 0.2 0 1     0.1 2
    C  0.45 0.2 0 1     0.15 2.2
    D 0.7 0.2 0 1.4   0.1 2
    E 0.8 0.2 0 0.8 0 1
    Comparison F 1.5 0.2 0 1.9 0 1.3
    G 0.05 0.2 0 0.1 0 2
    H 0.6 0.2   0.3 1.2 0 2
    I 0.6 0.2 0 1.2   0.6 2
    J 0.05 0.2   0.4 0.1 0 2
  • TABLE 2
    Number of
    intermetallic
    compounds with Number of
    diameter of 0.1 Tensile Intergranular deposit
    Test to 0.9 μm Limiting extrusion strength corrosion portions Surface
    specimen Alloy (105/mm2) rate ratio Brazeability (MPa) susceptibility (/10000 m) gloss
    1 A 3.2  1.0 (Excellent) Good 114 Good 0 Good
    2 B 3.5 0.95 (Excellent) Good 120 Good 0 Good
    3 C 3.1  0.9 (Excellent) Good 110 Good 0 Good
    4 D 3.8  0.8 (Good) Good 130 Good 0 Good
    5 E 4.1 0.85 (Good) Good 110 Good 0 Good
    6 F 5.0  0.4 (Bad) Good 145 Good 0 Good
    7 G 0.5  1.0 (Excellent) Good 68 Good 2.4 Bad
    8 H 2.8  0.7 (Fair) Good 122 Bad 0 Good
    9 I 3.1  0.6 (Fair) Bad 168 Good 0 Good
    10 J 0.5  1.0 (Excellent) Good 72 Bad 3.6 Bad
  • As shown in Table 2, the test specimens 1 to 5 according to the present invention exhibited excellent extrudability, did not show adhesion of deposit to the surface, and exhibited excellent brazeability, intergranular corrosion resistance, and strength. On the other hand, the test specimens 6 to 9 and the test specimen 10 (known alloy) were inferior in at least one of extrudability, adhesion of deposit, strength, brazeability, and intergranular corrosion resistance.
  • Comparative Example 2
  • An aluminum alloy having the composition A shown in Table 1 was melted and cast by semicontinuous casting to obtain a billet. The resulting billet was homogenized under the conditions shown in Table 3. The billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature, decreasing the temperature of the billet to a second-stage heat treatment temperature, maintaining the billet at the second-stage heat treatment temperature, and decreasing the temperature of the billet to 300° C. at an average temperature decrease rate of 50° C./h. Table 3 shows the first-stage heat treatment temperature, the average temperature decrease rate from the first-stage heat treatment temperature to the second-stage heat treatment temperature, and the second-stage heat treatment temperature. After homogenization, the billet was hot-extruded under the conditions shown in Table 3 to obtain a multi-port tube shown in FIG. 1. The resulting multi-port tube was used as a test specimen.
  • The extrudability of the aluminum alloy during hot extrusion was evaluated in the same manner as in Example 1. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined. The multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 4. In Tables 3 and 4, values outside the conditions according to the present invention are underlined.
  • TABLE 3
    Homogenization
    First-stage Second-stage
    heat treatment heat treatment Extrusion
    Test (temperature Average temperature (temperature Billet heating Billet heating
    specimen Alloy (° C.) × time (h)) decrease rate (° C./h) (° C.) × time (h)) temperature (° C.) time (min)
    11 A 530 × 15 50 450 × 10 510 8
    12 A 600 × 15 50 530 × 10 510 8
    13 A 600 × 15 50 450 × 1  510 8
    14 A 600 × 15 15 450 × 10 510 8
    15 A 600 × 15 50 450 × 10 580 35
  • TABLE 4
    Number of
    intermetallic
    compounds with Number of
    diameter of Tensile Intergranular deposit
    Test 0.1 to 0.9 μm Limiting extrusion strength corrosion portions Surface
    specimen Alloy (105/mm2) rate ratio Brazeability (MPa) susceptibility (/10000 m) gloss
    11 A 2.5 0.75 (Fair)  Good 114 Good 0.3 Fair
    12 A 2.1 0.7 (Fair) Good 114 Good 0.3 Fair
    13 A 1.6 0.7 (Fair) Good 115 Good 0.3 Fair
    14 A 3.1 0.75 (Fair)  Good 113 Good 0.3 Fair
    15 A 1.5 0.7 (Fair) Good 114 Good 0.3 Fair
  • As shown in Table 4, the test specimens 11 to 15 homogenized under the conditions outside the conditions according to the present invention were inferior in at least one of extrudability, number of deposit portions, strength, brazeability, and intergranular corrosion resistance.
  • Example 2 and Comparative Example 3
  • An aluminum alloy containing 0.6% of Si, 0.2% of Fe, and 1.0% of Mn (Mn %/Si %: 1.7) was melted and cast by semicontinuous casting to obtain a billet. The resulting billet was homogenized under the conditions shown in Table 5. The billet was homogenized by increasing the temperature of the billet to a first-stage heat treatment temperature at an average temperature increase rate of 50° C./h, maintaining the billet at the first-stage heat treatment temperature, decreasing the temperature of the billet to room temperature, increasing the temperature of the billet to a second-stage heat treatment temperature, maintaining the billet at the second-stage heat treatment temperature, and decreasing the temperature of the billet to 300° C. at an average temperature decrease rate of 50° C./h. Table 5 shows the first-stage heat treatment temperature, the second-stage heat treatment temperature, and the average temperature increase rate from room temperature to the second-stage heat treatment temperature. After homogenization, the billet was hot-extruded under the conditions shown in Table 5 to obtain a multi-port tube shown in FIG. 1. The resulting multi-port tube was used as a test specimen.
  • The extrudability of the aluminum alloy during hot extrusion was evaluated in the same manner as in Example 1. Likewise, the number of deposit portions adhering to the surface of the extruded multi-port tube was calculated, and the gloss of the multi-port tube was observed. The distribution of intermetallic compounds precipitated and dispersed in the matrix was also determined. The multi-port tube was subjected to joining by brazing, and brazeability, tensile strength after heating for brazing, and intergranular corrosion susceptibility were evaluated. The results are shown in Table 6. In Tables 5 and 6, values outside the conditions according to the present invention are underlined.
  • TABLE 5
    Homogenization
    First-stage heat Second-stage heat
    treatment Average temperature treatment Extrusion
    Test (temperature increase (temperature Billet heating Billet heating time
    specimen (° C.) × time (h)) rate (° C./h) (° C.) × time (h)) temperature (° C.) (min)
    16 600 × 15 50 450 × 10 510 8
    17 530 × 15 50 450 × 10 510 8
    18 600 × 15 50 530 × 10 510 8
    19 600 × 15 50 380 × 10 510 8
    20 600 × 15 15 450 × 10 510 8
    21 600 × 15 50 450 × 10 580 20
  • TABLE 6
    Number of intermetallic Number of
    compounds with diameter Tensile Intergranular deposit
    Test of 0.1 to 0.9 μm Limiting extrusion strength corrosion portions Surface
    specimen (105/mm2) rate ratio Brazeability (MPa) susceptibility (/10000 m) gloss
    16 3.0  1.0 (Excellent) Good 113 Good 0 Good
    17 2.5 0.75 (Fair) Good 113 Good 0.2 Fair
    18 2.0 0.75 (Fair) Good 114 Good 0.3 Fair
    19 1.5  0.7 (Fair) Good 116 Good 0.3 Fair
    20 3.0 0.75 (Fair) Good 112 Good 0.4 Fair
    21 1.4  0.7 (Fair) Good 113 Good 0.4 Fair
  • As shown in Table 6, the test specimen 16 according to the present invention exhibited excellent extrudability, did not show adhesion of deposit to the surface, and exhibited excellent brazeability, intergranular corrosion resistance, and strength. On the other hand, the test specimens 17 to 21 were inferior in at least one of extrudability, adhesion of deposit, strength, brazeability, and intergranular corrosion resistance.
  • Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims (4)

1. A method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties and with the number of intermettalic compounds having a circle equivalent diameter of 0.1 to 0.9 μm dispersed in the alloy matrix being at least 2×105 per square millimeter, the method comprising: melting and casting an aluminum alloy having a composition consisting of, in mass %, 0.8-1.6% of Mn and 0.4-0.8% Si, at a Mn/Si content of 0.7-2.4 and, optionally, 0.2% or less of Mg, 0.30% or less of Ti, 0.05% or less of Cu and 0.7% or less of Fe, with the balance being Al, to obtain an ingot; subjecting the ingot to homogenization which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to 400 to 500° C. at an average temperature decrease rate of 20 to 60° C./h and maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
2. A method of manufacturing an aluminum alloy extruded product exhibiting excellent surface properties and with the number of intermetallic compounds having a circle equivalent diameter of 0.1 to 0.9 μm dispersed in the alloy matrix being at least 2×105 per square millimeter, the method comprising: melting and casting an aluminum alloy having a composition consisting of, in mass %, 0.8-1.6% of Mn and 0.4-0.8% Si, at a Mn/Si content of 0.7-2.4 and, optionally, 0.2% or less of Mg, 0.30% or less of Ti, 0.05% or less of Cu and 0.7% or less of Fe, with the balance being Al, to obtain an ingot; subjecting the ingot to homogenization which includes a first-stage heat treatment in which the ingot is maintained at 550 to 650° C. for two hours or more and a second-stage heat treatment in which the ingot is cooled to room temperature, heated to 400 to 500° C. at an average temperature increase rate of 20 to 60° C./h, and maintained at that temperature for three hours or more; heating the ingot at 480 to 560° C.; and extruding the ingot.
3. A method of manufacturing a heat exchanger comprising extruding a heat exchanger multi-port tube using the method according to claim 1, and joining the multi-port tube to a heat exchanger by brazing.
4. A method of manufacturing a heat exchanger comprising extruding a heat exchanger multi-port tube using the method according to claim 2, and joining the multi-port tube to a heat exchanger by brazing.
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