WO2015173984A1 - Matériau d'ailette en alliage d'aluminium pour échangeur de chaleur présentant des capacités exceptionnelles d'aptitude au brasage et de résistance à l'affaissement, et procédé de fabrication dudit matériau - Google Patents

Matériau d'ailette en alliage d'aluminium pour échangeur de chaleur présentant des capacités exceptionnelles d'aptitude au brasage et de résistance à l'affaissement, et procédé de fabrication dudit matériau Download PDF

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WO2015173984A1
WO2015173984A1 PCT/JP2014/080359 JP2014080359W WO2015173984A1 WO 2015173984 A1 WO2015173984 A1 WO 2015173984A1 JP 2014080359 W JP2014080359 W JP 2014080359W WO 2015173984 A1 WO2015173984 A1 WO 2015173984A1
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brazing
aluminum alloy
fin material
mpa
alloy fin
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PCT/JP2014/080359
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English (en)
Japanese (ja)
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鈴木　健太
智浩 佐々木
まさ江 望月
敏也 穴見
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日本軽金属株式会社
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Priority to CN201480059878.0A priority Critical patent/CN105765094B/zh
Publication of WO2015173984A1 publication Critical patent/WO2015173984A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working

Definitions

  • the present invention relates to an aluminum alloy fin material for a heat exchanger, which is used in a heat exchanger such as a radiator for an automobile, and has excellent brazing properties and sag resistance, and a method for producing the same.
  • An aluminum heat exchanger is manufactured by brazing an aluminum alloy fin material formed into a corrugated shape onto a heat medium passage component material made of an aluminum alloy. For this reason, an aluminum alloy fin material used for an aluminum heat exchanger is required to have excellent formability and excellent so-called sag resistance that does not deform during brazing heating.
  • Patent Document 1 discloses that Fe is more than 1.2 mass% and not more than 1.8 mass%, Si that is more than 1.2 mass% and not more than 2.0 mass%, and Mn that is more than 0.3 mass% and not more than 0.9 mass%. 80% or more of the surface area seen from the surface layer after the final annealing performed at a plate thickness of 0.1 mm or less, and having a crystal structure occupied by recrystallized grains having a diameter of 10 mm or more in the rolling direction A brazing fin material produced by cold rolling an aluminum alloy at a sheet thickness reduction of less than 30% is described.
  • Patent Document 2 a) Si is 0.3 to 1.5%, Fe is ⁇ 0.5%, Cu is ⁇ 0.3%, Mn is 1.0 to 2.0%, Mg is ⁇ 0.5%, more preferably ⁇ 0.3%, Zn ⁇ 4.0%, Ni ⁇ 0.5%, dispersion forming elements derived from IVb, Vb, or VIb group respectively ⁇ 0.3% Casting an ingot to obtain an ingot by casting a melt containing 0.05% or less of unavoidable impurity elements and 0.15% or less of the total amount of aluminum, and the balance of aluminum, and b) less than 550 ° C., preferably 400 to 520 Preheating the ingot to form dispersoid particles at a temperature of °C, more preferably from 450 to 520 °C, especially 470 or higher, up to 520 °C; c) hot rolling to obtain a strip; d ) 90% of total reduction of the strip obtained in step (c) Above, preferably cold rolling at> 95% to obtain a strip
  • a sag-resistant strip is described which is produced by a heat treatment to delivery tempering in order to soften the material by tempering without recrystallization of the strip alloy. According to this, high strength is obtained after brazing with a unique combination of excellent brazing performance such as high sag resistance during brazing and low permeability of liquid core and excellent formability in delivery tempering That's it.
  • the fin material for thermal radiation joined to the tube material with the brazing material Comprising:
  • the said fin material is Fe: 0.5% (mass%, the following is similar) or less, Si: 0.3 1.2%, Mn: 0.5-1.7%, Zn: 0.3-1.5%, the balance is made of Al alloy consisting of Al and inevitable impurities, the tube material is Mn : 0.3 to 1.7%, Si: 0.3 to 1.2%, Cu: 0.1 to 1.2%, the balance being made of an Al alloy consisting of Al and inevitable impurities, SWAAT liquid
  • the dissolution loss of the fin material alone is in the range of 20 to 50% of the dissolution loss due to contact with the tube material of the same surface area in the same liquid, and the pitting potential of the fin material
  • the strength, corrosion resistance and brazing can be improved at the same time by setting the Fe content to 0.5% or less. That is, in the aluminum alloy fin material of Patent Document 3, when the Fe content exceeds 0.5%, an intermetallic compound such as Al— (Fe ⁇ Mn) —Si generated during casting tends to be relatively coarse, There is a possibility of increasing the corrosion rate of the fins, and further, since the crystal grains of the recrystallized structure formed at the time of brazing heating become fine, the erosion resistance is deteriorated and the brazing property is lowered.
  • JP 2006-225723 A Japanese Patent Laid-Open No. 2008-190027 Japanese Patent No. 5192718
  • the present invention has been devised in order to solve such problems in the conventional method, and in an aluminum alloy fin material for a heat exchanger, even when the Fe content is 0.5% or more, the cost is low. And it aims at providing the aluminum alloy fin material which has the outstanding brazing property and sag resistance, and its manufacturing method.
  • the solidus temperature can be an indicator of whether or not to generate erosion during brazing heating, but the erosion resistance is not determined solely by the solidus temperature.
  • the brazing property is the metal structure of the fin material before brazing, that is, the density and particle size distribution of Al- (Fe ⁇ Mn) -Si, etc. produced during casting, the amount of Mn solid solution in the matrix, and the cold-rolled annealing material. If present, it is also affected by factors such as the degree of recovery of the processed structure by annealing. That is, it is considered that these factors are intertwined in a complicated manner and affect the brazing property.
  • the molten brazing material permeates into the accumulated dislocations (crystal defects) remaining in the fin material and the crystal grain boundaries generated during brazing heating, thereby generating erosion. Therefore, it can be said that the larger the crystal grain size of the recrystallized grains generated during brazing, the better the fin material has excellent erosion resistance.
  • the sag resistance is lowered when the crystal grain size of the recrystallized grains formed during brazing becomes too large. In other words, in order to improve both the erosion resistance and sag resistance characteristics of the fin material, the crystal grain size of the recrystallized grains should be set to an appropriate size as well as to develop a recrystallized structure during brazing. Technology to control is required.
  • the present inventors conducted a brazing heating test using a corrugated fin material in the process of developing a fin material excellent in brazing property and sag resistance, as described later, before brazing.
  • the present invention was completed by measuring the plate thickness (minimum plate thickness) after brazing with respect to the plate thickness, calculating the plate thickness residual rate, and evaluating the brazing property.
  • the brazing property is understood in a broad sense to include, for example, the form of a fillet formed from a molten brazing material, but in this specification, unless otherwise specified, the erosion resistance of the fin material. And the same meaning.
  • the aluminum alloy fin material for heat exchanger excellent in brazing property and sag resistance of the present invention is Si: 0.6 to 1.6%, Fe: 0.5%. -1.2%, Mn: 1.2-2.6%, Zn: 0.4-3.0%, Cu: less than 0.2%, the balance consists of inevitable impurities and Al, Mg is limited to less than 0.05%, the tensile strength before brazing heating is 160 to 260 MPa, and the difference between the tensile strength before brazing heating and the 0.2% proof stress is 10 to 50 MPa. . Further, the 0.2% proof stress before brazing heating is preferably 140 to 220 MPa. Further, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more in the metal structure is more preferably 70 to 220 particles / mm 2 .
  • the aluminum alloy fin material for heat exchangers with excellent brazing and sag resistance according to the present invention is obtained by continuously applying a molten aluminum alloy having the above composition to a slab having a thickness of 2 to 15 mm using a thin slab continuous casting machine. After casting and winding the slab directly on a roll without hot rolling, cold rolling, intermediate annealing, and cold rolling with a final cold rolling rate of 15 to 60%, Manufactured by final annealing.
  • the aluminum alloy fin material for heat exchangers having excellent brazing and sag resistance according to the present invention is obtained by continuously using a molten aluminum alloy having the above-described composition to a thin slab having a thickness of 2 to 15 mm using a thin slab continuous casting machine. Therefore, the solidification rate during casting is relatively high at 40 to 1000 ° C./second at the slab 1/4 thickness position, and an intermetallic compound such as Al— (Fe ⁇ Mn) —Si is uniformly dispersed. A clump tissue is obtained.
  • this thin slab By subjecting this thin slab to cold rolling, intermediate annealing, final rolling, and final annealing in this order, the tensile strength before brazing heating is 160 to 260 MPa, and the tensile strength before brazing heating and the 0.2% proof stress are The difference is adjusted to 10-50 MPa. Therefore, this cold-rolled annealed material has an appropriate strength, has a small amount of springback during molding, and is excellent in shape freezing property.
  • the final annealing treatment is performed at a relatively low temperature, and the processing strain introduced by the final cold rolling is moderately recovered. Therefore, the recrystallization is completed by brazing heating, and the recrystallization having a grain size of 500 ⁇ m or more is performed.
  • a recrystallized structure consisting of grains can be obtained, and an aluminum alloy fin material excellent in brazing and sag resistance can be obtained. Therefore, according to the present invention, an aluminum alloy fin material for heat exchanger is efficiently produced, and an aluminum alloy fin material excellent in brazing and sag resistance is provided at a low price.
  • Si coexists with Fe and Mn to form an intermetallic compound such as Al- (Fe ⁇ Mn) -Si at the time of casting solidification, and part of Si dissolves in the matrix to improve the strength. Increases sag resistance. In order to obtain this effect, a Si content of 0.6% or more is necessary. When the Si content is less than 0.6%, the high-temperature strength of the fin material is lowered, so that the sag resistance is lowered.
  • the Si content is limited to the range of 0.6 to 1.6%.
  • a preferable Si content is in the range of 0.6 to 1.5%.
  • a more preferable Si content is in the range of 0.6% to 1.4%.
  • Fe coexists with Mn and Si to produce an intermetallic compound such as Al- (Fe ⁇ Mn) -Si at the time of casting solidification, thereby improving the strength and reducing the solid solution amount of Si and Mn. Improve the rate (thermal conductivity).
  • intermetallic compounds such as Al— (Fe ⁇ Mn) —Si produced during casting and solidification, those with an equivalent circle diameter of 3 ⁇ m or more function as nucleation sites for recrystallization during brazing heating.
  • a recrystallized structure having a recrystallized grain size of 500 ⁇ m or more can be developed.
  • an Fe content of 0.5% or more is necessary. If the Fe content is less than 0.5%, the Mn solid solution amount of the matrix cannot be sufficiently reduced, and recrystallization during the brazing heating is delayed, so that the sag resistance is lowered. If the Fe content exceeds 1.2%, the density of intermetallic compounds with an equivalent circle diameter of 3 ⁇ m or more generated during casting solidification increases, and the crystal grain size of recrystallized grains decreases during brazing heating. Too much erosion occurs. Therefore, the Fe content is limited to the range of 0.5 to 1.2%. A preferable Fe content is in the range of 0.6 to 1.2%. A more preferable Fe content is in the range of 0.6 to 1.1%.
  • Mn precipitates at a high density on the matrix as Mn-based precipitates such as submicron-level Al 6 Mn and Al 6 (Fe ⁇ Mn) during brazing heating, and improves the strength of the fin material after brazing. Further, such Mn-based precipitates at the submicron level prevent dislocation and movement of crystal grain boundaries during brazing heating and prevent recrystallization of the metal structure, so that the crystal grain size of the recrystallized structure is 500 ⁇ m. As described above, erosion resistance can be ensured. In order to obtain this effect, a Mn content of 1.2% or more is necessary.
  • the Mn content is limited to the range of 1.2 to 2.6%.
  • a preferable Mn content is in the range of 1.2 to 2.5%.
  • a more preferable Mn content is in the range of 1.3 to 2.5%.
  • Zn 0.4 to 3.0%
  • Zn provides a sacrificial anode effect in order to reduce the natural potential after brazing of the fin material. In order to obtain this effect, a Zn content of 0.4% or more is necessary. When Zn content exceeds 3.0%, the solidus temperature of a fin material will fall, erosion will be generated and brazing property will fall. Therefore, the Zn content is limited to the range of 0.4 to 3.0%. A preferable Zn content is 0.5 to 3.0%. A more preferable Zn content is 0.5 to 2.8%.
  • Cu can improve the strength of the fin material and can also be positively added. If Cu content is less than 0.2%, it will not affect brazing property or sag resistance. However, if the Cu content is 0.2% or more, the solidus temperature of the fin material is lowered, so that the brazing property may be lowered. For this reason, the Cu content is limited to less than 0.2%.
  • Mg as an impurity reacts with the fluoride-based flux used for brazing, and may reduce brazing properties in a broad sense, so the Mg content is limited to less than 0.05%. Since Cr, Zr, Ti, and V lower the electrical conductivity (thermal conductivity) of the material even in a trace amount, the content of these elements is preferably 0.05% or less.
  • Tensile strength before brazing heating is 160 to 260 MPa
  • the final plate is in the state of a coil, but after undergoing slitting with a slit, it is molded into a mold, for example, to form a corrugated molded fin, and this molded fin material is used as a heat exchanger tube material, brazing material, etc. After assembly, insert into the furnace and braze.
  • 160 MPa or more is required as a tensile strength before brazing heating in order to prevent deformation due to a load during assembly.
  • the tensile strength before brazing heating exceeds 260 MPa, the moldability at the time of mold-molding the fin material is lowered. Therefore, the tensile strength before brazing heating is specified in the range of 160 to 260 MPa.
  • 0.2% proof stress before brazing heating is 140 to 220 MPa
  • the aluminum alloy fin material for a heat exchanger that is becoming thinner is required to have a 0.2% proof stress before brazing heating of 140 MPa or more in the same manner as the above-described tensile strength.
  • the 0.2% proof stress before brazing heating exceeds 220 MPa, the moldability when the fin material is molded may be lowered. Therefore, the 0.2% proof stress before brazing heating is preferably in the range of 140 to 220 MPa.
  • the difference between the tensile strength before brazing heating and 0.2% proof stress is 10-50 MPa
  • the number of second phase particles having an equivalent circle diameter of 3 ⁇ m or more in the metal structure is 70 to 220 particles / mm 2.
  • the above characteristics and excellent brazing and sag resistance during brazing heating are manifested by finely adjusting the metal structure of the 3000 series aluminum alloy sheet having the specific component composition.
  • the density of second phase particles having a circle-equivalent diameter of 3 ⁇ m or more in the metal structure is preferably 70 to 220 particles / mm 2 .
  • the density of second-phase particles having a circle-equivalent diameter of 3 ⁇ m or more in the metal structure is less than 70 / mm 2 , the existence density of nucleation sites of recrystallization generated during brazing heating is low, and the grains of recrystallized grains Although the diameter becomes too large, the brazing property is improved, but the sag resistance is lowered.
  • the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more in the metal structure exceeds 220 particles / mm 2 , the density of nucleation sites of recrystallization generated during brazing heating is high, and the recrystallized grains Although the particle size becomes too small, the sag resistance is improved, but the brazing property is lowered.
  • the final annealed plate has a tensile strength of 160 to
  • the aluminum alloy fin material for heat exchangers has a value of 260 MPa, a difference between tensile strength and 0.2% proof stress (UTS-YS) of 10 to 50 MPa, and excellent brazing and sag resistance.
  • the molten aluminum alloy melted in the melting furnace may be cast after it is once transferred to the holding furnace, but may be cast directly from the melting furnace.
  • a more desirable sedation time is 45 minutes or more.
  • in-line degassing or filtering may be performed.
  • In-line degassing is mainly of a type in which an inert gas or the like is blown into a molten aluminum from a rotating rotor, and hydrogen gas in the molten metal is diffused and removed in bubbles of the inert gas.
  • nitrogen gas is used as the inert gas, it is important to control the dew point to, for example, ⁇ 60 ° C. or lower.
  • the amount of hydrogen gas in the ingot is preferably reduced to 0.20 cc / 100 g or less.
  • the reduction rate per pass in the cold rolling process is regulated to, for example, 20% or more to reduce the porosity. It is preferable to crush.
  • the hydrogen gas that is supersaturated in the ingot is deposited at the time of spot welding, for example, even after press forming of the final plate, depending on the heat treatment conditions such as annealing of the cold roll. In some cases, a large number of blow holes are generated. For this reason, the more preferable amount of hydrogen gas in the ingot is 0.15 cc / 100 g or less.
  • Thin slab continuous casting machine includes both twin belt casting machine and twin roll casting machine.
  • the twin belt casting machine includes an endless belt and a pair of rotating belt portions facing each other up and down, a cavity formed between the pair of rotating belt portions, and a cooling means provided inside the rotating belt portion.
  • the molten metal is supplied into the cavity through a nozzle made of a refractory, and a thin slab is continuously cast.
  • the twin roll casting machine includes a pair of rotating roll portions that are provided with endless rolls so as to face each other, a cavity formed between the pair of rotating roll portions, and a cooling unit provided inside the rotating roll portion.
  • the molten metal is supplied into the cavity through a nozzle made of a refractory, and a thin slab is continuously cast.
  • the thin slab continuous casting machine can continuously cast a thin slab having a thickness of 2 to 15 mm. If the slab thickness is less than 2 mm, even if casting is possible, it will be difficult to achieve a final rolling rate of 70 to 95%, which will be described later, depending on the thickness of the final plate. When the slab thickness exceeds 15 mm, it is difficult to wind the slab directly on a roll. In this slab thickness range, the cooling rate of the slab is about 40 to 1000 ° C./second in the vicinity of the slab thickness 1 ⁇ 4, so intermetallic compounds such as Al— (Fe ⁇ Mn) —Si Are uniformly and finely produced. Among these intermetallic compounds produced during casting and solidification, those having an equivalent circle diameter of 3 ⁇ m or more in the final plate function as nucleation sites for recrystallization of the recrystallized structure that appears during brazing heating.
  • a slab is continuously cast using a cold rolling thin slab continuous casting machine, and the slab is directly wound on a roll without hot rolling, and then cold rolled. For this reason, the chamfering process, the homogenization process, and the hot rolling process required for the conventional semi-continuous cast DC slab can be omitted.
  • the roll directly wound with the thin slab is passed through a cold rolling machine and usually subjected to several passes of cold rolling. At this time, since work hardening occurs due to plastic strain introduced by cold rolling, an intermediate annealing treatment is performed as necessary. Usually, the intermediate annealing is also a softening treatment, but depending on the material, a cold rolling roll may be inserted into the batch furnace and held at a temperature of 350 to 450 ° C. for 1 hour or longer.
  • the holding temperature is lower than 350 ° C., softening is not promoted, and if the holding temperature exceeds 450 ° C., coil cooling takes too much time and productivity is lowered, which is not preferable.
  • the intermediate annealing may be held within a period of 30 seconds at a temperature of, for example, 400 ° C. to 500 ° C. by a continuous annealing furnace. If the holding temperature is lower than 400 ° C., softening is not promoted, and even if the holding temperature exceeds 500 ° C., softening is not further promoted.
  • the final cold rolling rate exceeds 50%, the amount of processing strain accumulated during cold rolling is too large, and recovery by final annealing is delayed, and recrystallization during brazing heating becomes insufficient. Adhesiveness and sag resistance are reduced. Therefore, the final cold rolling rate is limited to a range of 15 to 50%. In the case of a cold-rolled material that is not subjected to final annealing, the difference between the tensile strength and the 0.2% proof stress is less than 10 MPa, the shape freezing property is lowered, and, as will be described later, brazing and sag resistance are reduced. Since it falls, it is not preferable.
  • the final annealing performed after the final cold rolling by holding in a batch annealing furnace at a holding temperature of 120 to 200 ° C. for 1 to 8 hours is preferably a batch treatment in which the holding temperature is held at 120 to 200 ° C. for 1 to 8 hours.
  • the holding temperature is less than 120 ° C., it is difficult to recover appropriately during the annealing treatment, recrystallization during brazing heating is delayed, and brazing and sag resistance are reduced.
  • the holding temperature exceeds 200 ° C., the recovery proceeds too much during the annealing process, and the grain size of the recrystallized grains generated during brazing heating becomes too large, so that the sag resistance is lowered.
  • the holding time is less than 1 hour, the actual temperature of the coil does not reach a predetermined temperature, and the annealing process may be insufficient. If the holding time exceeds 8 hours, the process takes too much time, and the productivity is lowered.
  • the final annealing may be a batch treatment with an annealing furnace, but holding at a holding temperature of 150 to 270 ° C. for 5 to 60 seconds with a continuous annealing furnace A continuous annealing treatment is more preferable. If the holding temperature is less than 150 ° C., it is difficult to achieve an appropriate recovery during the annealing treatment, recrystallization during brazing heating is delayed, and brazing and sag resistance are reduced.
  • the holding temperature exceeds 270 ° C.
  • the recovery proceeds too much during the annealing process, and the grain size of the recrystallized grains generated during brazing heating becomes too large, so that the sag resistance is lowered.
  • the holding time is less than 5 seconds, the actual temperature of the coil does not reach a predetermined temperature, and the annealing process may be insufficient. If the holding time exceeds 60 seconds, the process takes too much time and productivity is lowered.
  • final annealing is an indispensable step in the production method of the present invention, and this final annealing brings about an appropriate recovery of the metal structure and expresses a recrystallized grain structure having a crystal grain size of 500 ⁇ m or more during brazing heating. Therefore, it is possible to obtain an aluminum alloy fin material for a heat exchanger that is excellent in brazing and sag resistance.
  • the present invention by performing the final annealing under a predetermined condition, it is possible to appropriately recover the working strain introduced by the final cold rolling, and the brazability during brazing heating and Sag resistance is improved. By passing through the normal continuous casting process and the plate making process as described above, an aluminum alloy fin material for a heat exchanger excellent in brazing and sag resistance can be obtained.
  • SCC material thin slab continuous casting simulation material 5 kg of each ingot blended in the 23 levels of composition shown in Table 1 (Examples 1 to 9, Comparative Examples 1 to 14) was inserted into a # 20 crucible.
  • the crucible was heated with a small electric furnace to melt the ingot.
  • a lance was inserted into the molten metal, and N 2 gas was blown in at a flow rate of 1.0 L / min for 5 minutes for degassing treatment. Thereafter, sedation for 30 minutes was performed, and the soot that floated on the surface of the molten metal was removed with a stirring rod.
  • Both sides of this thin slab are chamfered by 3 mm to a thickness of 10 mm, and then subjected to cold rolling without performing homogenization and hot rolling, and plate thicknesses of 0.125 mm, 0.1 mm, 0 0.083 mm, 0.071 mm, 0.059 mm, and 0.055 mm cold rolled materials were inserted into an annealer and held at 400 ° C. ⁇ 2 hrs for intermediate annealing. Further, these intermediate annealed materials were cold-rolled to a final thickness of 0.050 mm. The final cold rolling rates in this case were 60%, 50%, 40%, 30%, 15%, and 10%, respectively.
  • Table 1 and Table 2 show the chemical composition and plate making conditions of the final plate (test material) obtained in this way as a thin slab continuous casting simulation material (SCC material).
  • a test material having a tensile strength of 160 to 260 MPa was given a good strength, a test material having a tensile strength of less than 160 MPa was considered to be insufficient in strength, and a test material having a tensile strength exceeding 260 MPa was considered to be an excess strength.
  • a specimen having a difference between the tensile strength and 0.2% yield strength of 10 to 50 MPa is considered to have good shape freezing properties, and a specimen having a difference between the tensile strength and 0.2% yield strength of less than 10 MPa is considered to be shape freezing properties. Defective.
  • the evaluation results are shown in Tables 3 and 4.
  • test material with a sag amount of less than 20 mm was considered to have good sag resistance, and the test material with a sag amount of 20 mm or more was considered to have poor sag resistance.
  • the evaluation results are shown in Tables 3 and 4.
  • the final plate (each sample material) obtained was subjected to a brazing property evaluation test.
  • a test piece cut into a length of 140 mm and a width of 20 mm was prepared for each specimen.
  • the corrugated fin formed by corrugated plate of this test piece was placed on a 0.25 mm thick brazing sheet (4045 alloy brazing material, 8% clad rate) and heated and held at 600 ° C. for 3 minutes. Cooled to room temperature.
  • the corrugated fin and brazing sheet after brazing were embedded in a thermoplastic resin, mirror-polished, observed with an optical microscope, and photographed. The thinnest portion of the cross-section of the brazed fin material was measured and used as the remaining plate thickness.
  • the plate thickness remaining rate (%) was calculated as remaining plate thickness / original plate thickness ⁇ 100.
  • a specimen having a sheet thickness remaining rate of 60% or more was regarded as having good brazing properties, and a specimen having a sheet thickness remaining rate of less than 60% was regarded as having poor brazing properties.
  • the evaluation results are shown in Tables 3 and 4. In all Examples and Comparative Examples, Mg was less than 0.05% by mass, so there was no problem due to reaction with the flux, and the brazing property in a broad sense was good.
  • Comparative Example 6 since the Mn content was as high as 3.4% by mass and out of the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 243 particles / mm 2 , and the reference value was Did not meet. In Comparative Example 7, since the Mn content was as low as 1.0% by mass and outside the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 9 / mm 2 , and the reference value was Did not meet.
  • Comparative Example 9 since the Si content was as low as 0.3% by mass and outside the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 63 particles / mm 2 , and the reference value was Did not meet.
  • Comparative Example 10 since the Fe content was as high as 1.5% by mass and out of the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 296 particles / mm 2 , and the reference value was Did not meet.
  • Comparative Example 11 since the Fe content was as low as 0.2% by mass and out of the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 26 particles / mm 2 , and the reference value was Did not meet.
  • Comparative Example 13 since the Mn content was as low as 0.8% by mass and out of the composition range of the present invention, the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 9 / mm 2 , and the reference value was Did not meet.
  • Comparative Examples 8, 12, and 14 were outside the composition range of the present invention, but the density of the second phase particles having an equivalent circle diameter of 3 ⁇ m or more was within the range of 70 to 220 particles / mm 2 , which satisfied the standard value. It was. Since the second phase particles observed with a metallographic microscope do not necessarily specify the type of intermetallic compound, even if it is a test material outside the composition range of the present invention, the second phase particle having an equivalent circle diameter of 3 ⁇ m or more is used. In some cases, the density of phase particles is in the range of 70 to 220 particles / mm 2 .
  • Comparative Example 8 the Si content was as high as 1.7 and was outside the composition range of the present invention, but the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 187 particles / mm 2 , which satisfies the standard value. It was.
  • Comparative Example 12 the Cu content was as high as 0.5 and was outside the composition range of the present invention, but the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 83 particles / mm 2 , which satisfies the standard value. It was.
  • Comparative Example 14 the Zn content was as high as 3.3 and was outside the composition range of the present invention, but the density of second phase particles having an equivalent circle diameter of 3 ⁇ m or more was 83 particles / mm 2 , which satisfied the standard value. It was.
  • Comparative Example 1 in Table 4 showing the results of property evaluation of the test material was within the composition range of the present invention, but was a cold-rolled material with a final cold rolling rate of 15%, so (UTS-YS) is the standard. Although the value was satisfied, the tensile strength was 155 MPa, not satisfying the standard value, insufficient strength ( ⁇ ), and good shape freezing property ( ⁇ ). Comparative Example 2 was within the composition range of the present invention, but was a cold-rolled material with a final cold rolling rate of 30%. Therefore, although the tensile strength satisfied the standard value, (UTS-YS) was 5 MPa. Yes, the reference value was not satisfied, the strength was good ( ⁇ ), and the shape freezing property was poor (x).
  • Comparative Example 3 was within the composition range of the present invention but was a cold-rolled material with a final cold rolling rate of 40%, the tensile strength satisfied the standard value, but (UTS-YS) was 6 MPa. Yes, the reference value was not satisfied, the strength was good ( ⁇ ), and the shape freezing property was poor (x). Since Comparative Example 4 was a cold-rolled annealed material having a final cold-rolling rate of 10%, which was within the composition range of the present invention but less than the specified range of the present invention, (UTS-YS) satisfied the standard value. Although the tensile strength was 154 MPa, the standard value was not satisfied, the strength was insufficient (x), and the shape freezing property was good ( ⁇ ).
  • Comparative Example 5 was within the composition range of the present invention, but was a cold-rolled annealed material having a final cold-rolling rate of 60% exceeding the specified range of the present invention, so (UTS-YS) satisfied the standard value. However, the tensile strength was 265 MPa, which did not satisfy the standard value, the strength exceeded ( ⁇ ), and the shape freezing property was good ( ⁇ ).
  • Comparative Examples 6 to 14 were outside the composition range of the present invention, but were cold-rolled annealed materials, so both the tensile strength and (UTS-YS) satisfied the standard values, the strength was good ( ⁇ ), and the shape was frozen. The property was good ( ⁇ ).
  • Examples 1 to 9 in Table 3 showing the results of property evaluation of the test materials are within the composition range of the present invention, and the sag amount (mm) and the sheet thickness remaining rate (%). Both of them satisfied the standard values, with good sag resistance ( ⁇ ) and good brazing property ( ⁇ ). Specifically, the sag amount: less than 20 mm and the remaining thickness ratio: 60% or more were satisfied.
  • Comparative Examples 1 to 3 in Table 4 showing the property evaluation results of the test materials were within the composition range of the present invention, but were still cold-rolled with a final cold-rolling rate of 15 to 40%. Both the sheet thickness residual ratios did not satisfy the standard values, and were sag resistance failure (x) and brazing property failure (x). In the as-rolled material, dislocations (crystal defects) are introduced due to the accumulation of processing strain due to cold rolling, so the brazing material melted during brazing heating penetrates into the fin material through the accumulated dislocations. It is thought.
  • Comparative Example 4 was within the composition range of the present invention, but was a cold-rolled annealed material having a final cold-rolling rate of 10%, which is less than the specified range of the present invention. They were not satisfied and had poor sag resistance (x) and poor brazeability (x). Since the final cold rolling rate was 10%, the amount of processing strain accumulated during cold rolling was too small, and coupled with recovery by final annealing, the driving force required for recrystallization during brazing heating could not be obtained. It is considered that no recrystallized structure was obtained.
  • Comparative Example 5 was within the composition range of the present invention, but was a cold-rolled annealed material having a final cold-rolling rate of 60% exceeding the specified range of the present invention, so both the sag amount and the sheet thickness remaining rate satisfied the standard values.
  • the sag resistance was poor (x) and the brazeability was poor (x). Since the final cold rolling rate was 60%, the amount of work strain accumulated during cold rolling was too large, and recovery by final annealing was delayed, and recrystallization during brazing heating was insufficient. Conceivable.
  • the Mn content was as low as 1.0% by mass, which was outside the composition range of the present invention, and thus the sag amount was a reference even though it was a cold-rolled annealing material with a final cold-rolling rate of 30%. Although the value was satisfied, the residual thickness ratio did not satisfy the standard value, and the sag resistance was good ( ⁇ ) and the brazing property was poor (x). Since the Mn content was as low as 1.0% by mass, the existence density of intermetallic compounds serving as nucleation sites for recrystallization was low during brazing heating, but the effect of preventing recrystallization of Mn-based precipitates was weakened. Thus, it is considered that the grain size of the recrystallized grains has become too small.
  • Comparative Example 8 had a high Si content of 1.7% by mass and was outside the composition range of the present invention. Therefore, although it was a cold-rolled annealing material having a final cold-rolling rate of 30%, Both the residual thickness ratios did not satisfy the standard values, and were poor sag resistance (x) and poor brazing property (x). It is considered that the solidus temperature of the fin material was lowered because the Si content was as high as 1.7% by mass. In Comparative Example 9, since the Si content was as low as 0.3% by mass and out of the composition range of the present invention, the remaining thickness ratio was a cold rolled annealed material with a final cold rolling rate of 30%.
  • Comparative Example 10 since the Fe content was as high as 1.5% by mass and out of the composition range of the present invention, the sag amount was a reference even though it was a cold-rolled annealing material having a final cold-rolling rate of 30%. Although the value was satisfied, the residual thickness ratio did not satisfy the standard value, and the sag resistance was good ( ⁇ ) and the brazing property was poor (x). Fe content is as high as 1.5% by mass. During brazing heating, the existence density of intermetallic compounds that become nucleation sites for recrystallization is too high, and the grain size of recrystallized grains is considered to be too small. .
  • Comparative Example 11 since the Fe content was as low as 0.2% by mass and outside the composition range of the present invention, the remaining thickness ratio was a cold rolled annealed material with a final cold rolling rate of 40%. Was satisfied with the reference value, but the sag amount did not satisfy the reference value, indicating poor sag resistance ( ⁇ ) and good brazing ( ⁇ ). Fe content is as low as 0.2% by mass, and during brazing heating, the existence density of intermetallic compounds that become nucleation sites for recrystallization is too low, and the particle size of recrystallized grains is considered to be too large. .
  • Comparative Example 13 had a low Mn content of 0.8% by mass and was outside the composition range of the present invention, the amount of sag was a reference even though it was a cold-rolled annealed material with a final cold-rolling rate of 15%. Although the value was satisfied, the residual thickness ratio did not satisfy the standard value, and the sag resistance was good ( ⁇ ) and the brazing property was poor (x). Since the Mn content was as low as 0.8% by mass, the existence density of intermetallic compounds that become nucleation sites for recrystallization was low during brazing heating, but the recrystallization inhibiting action of Mn-based precipitates was weakened. Thus, it is considered that the grain size of the recrystallized grains has become too small.
  • the Zn content was as high as 3.3% by mass, and was outside the composition range of the present invention, so the sag amount was a reference even though it was a cold-rolled annealing material with a final cold-rolling rate of 30%. Although the value was satisfied, the residual thickness ratio did not satisfy the standard value, and the sag resistance was good ( ⁇ ) and the brazing property was poor (x). Since the Zn content was as high as 3.3% by mass, it is considered that the solidus temperature of the fin material was lowered.
  • the final annealed plate has a tensile strength of 160 to 260 MPa and (UTS-YS) of 10 to 50 MPa. It turns out that it becomes the aluminum alloy fin material for heat exchangers which is excellent in brazing property and sag resistance.

Abstract

　La présente invention se rapporte à un matériau d'ailette en alliage d'aluminium pour un échangeur de chaleur présentant des capacités exceptionnelles d'aptitude au brasage et de résistance à l'affaissement, et à un procédé de fabrication dudit matériau. Ce matériau d'ailette en alliage d'aluminium pour un échangeur de chaleur contient, exprimé en % en masse, Si : 0,6 à 1,6 %, Fe : 0,5 à 1,2 %, Mn : 1,2 à 2,6 %, Zn : 0,4 à 3,0 %, et Cu : moins de 0,2 %, le reste étant de l'Al et des impuretés inévitables. Mg en tant qu'impureté est limitée à moins de 0,05 %, la résistance à la traction du matériau avant le réchauffement de brasage est de 160 à 260 MPa, et la différence entre la résistance à la traction avant le réchauffement de brasage et la limite conventionnelle d'élasticité à 0,2 % est de 10 à 50 MPa. La densité de particules de phase secondaire ayant un diamètre circulaire équivalent supérieur ou égal à 3 µm dans la structure métallique est de 70 à 220 particules/mm2. Le procédé de fabrication d'un matériau d'ailette en alliage d'aluminium pour un échangeur de chaleur consiste à utiliser une machine de coulée continue de brames minces pour couler en continu un alliage d'aluminium fondu ayant la composition de composant ci-dessus pour obtenir une brame ayant une épaisseur de 2 à 15 mm, à enrouler la brame directement sur un rouleau sans la soumettre à un laminage à chaud, puis à la soumettre à un laminage à froid, à un procédé de recuit, et à un laminage à froid jusqu'à obtenir une réduction de laminage final de 15 à 50 %, puis à effectuer un recuit final.
PCT/JP2014/080359 2014-05-14 2014-11-17 Matériau d'ailette en alliage d'aluminium pour échangeur de chaleur présentant des capacités exceptionnelles d'aptitude au brasage et de résistance à l'affaissement, et procédé de fabrication dudit matériau WO2015173984A1 (fr)

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